Note: Descriptions are shown in the official language in which they were submitted.
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i=UEL COMPOSITIONS EMPLOYING CATALYST COMBUSTION
STRUCTURE
Field of the Invention
The present invention relates to a broad spectrum of pollution reducing,
improved combustion performance, and enhanced stability fuel compositions
for use in jet, aviation, turbine, diesel, gasoline, and other combustion
applications. More particularly, the present invention relates to fuel
compositions employing certain co-combustion agents, including
1 o trimethoxymethylsilane.
Background of the Invention
Growth in environmental concerns related to pollutants generated by
hydrocarbon based fuels, especially emissions related to greenhouse gases,
has given raise to the need to find new fuels and methods of combustion
capable of reducing such emissions, namely carbon dioxide, nitrous oxide
(Nx0), NOx, methane, ozone, CFC's, halons and similar gases. Increases of
nitrous oxide gases occurring post exhaust catalyst have recently been
discovered. Similar to CFC's, nitrous oxides are about a 1000 times more
2 o potent than C02 in their adverse effect. It has been found the effect of
the
exhaust catalyst, itself, may actually tend to increase the concentrations of
nitrous oxides. Thus, there is a current need to reduce overall nitrous oxide
emissions and additionally find a means reducing the effect the exhaust
catalyst has upon increasing said emissions.
International Patent Applications, PCT/US95I02691, PCT/US95/06758,
and PCT/US96109653, incorporated in their entirety herein by reference, speak
to a new form of combustion known as metallic vapor combustion, wherein
combustion does not take place on the surface of the metal, or on andlor
within
the molten layer of oxide covering the metal, typical of heretofore metallic
~mbustion. Rather, combustion is characterized by a luminous reaction zone
extending some distance from the metal's surface and a high burning rate,
wherein metallic oxide particles are formed in the submicron range. It is a
highly
expansive combustion, yielding vastly accelerated exhaust gas velocities
compared to traditional combustion, in turn generating greater amounts of
useable free energy.
Said PCT Applications disclose.fuel compositions and combustion
techniques achieving vapor phase combustion based on an enhanced
combustion structure ("ECS"), which incorporates a free radical generating
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2
oxygenate compound ("ECS oxygenate") and a high energy combustible non-
lead metallic, preferably an "ECS metallic" containing ECS structure.
Applicant's metallic together with an ECS compound yield vapor phase
combustion. In the aforementioned Applications and herein metallic shall mean
at least one non-leaded element or derivative organic or inorganic compound
containing said non-lead element, selected from the group consisting of 1A,
2A,
3B, 4B, 5B, 6B, 7B, 8, 1 B, 2B, 3A, 4A, 5A, 6A, or 7A elements of the Periodic
Chart of Elements (CAS version), and mixture, wherein said element or
derivative compound, is combustible, and optionally has a minimum heating
1 o value of 4,000 Kcallkg, and wherein vapor phase combustion occurs. As
noted,
in the aforementioned Applications and herein, an ECS metallic is a metallic
capable of increasing burning velocity andlor reducing combustion temperature.
It is any non-lead metallic (or non-metallic) which may be employed in the
practice of this invention. Said metallic rnay be employed with hydrogen or a
hydrocarbon fuel, absent an ECS compound.
As set forth herein "ECS metallic" can be read as any non-lead metallic
(and non-metallic as set forth below), or any organic or inorganic derivative
thereof, which accomplishes the vapor phase combustion object of this
invention. As set forth in the disclosure below ECS metallic contemplates any
metallic or non-metallic accomplishing this object. An ECS metallic need not
contain ECS structure (e.g. high kinetic energy free radicals), albeit said
ECS
structure is preferred. A "non-lead element or derivative" herein shall also
be
read as "ECS metallic."
It is noted, a principal ECS metallic of the aforementioned PCT
2 5 applications was manganese, chiefly methylcyclopentadienyl manganese
tricarbonyl. Due to recent concerns over the neurotoxicity of manganese
combustion products, and the potential neurotoxicity of other combustion metal
oxides, a need exists to find a high energy, non-manganese, non-neurotoxic
replacement ECS metallic or group of metallics capable of achieving vapor
3 o phase combustion.
Example A
A fuel composition containing hydrogen or a hydrocarbon fuel and at
35 least one organic or inorganic compound containing a non-lead element,
selected from the group consisting of 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8, 1 B, 2B,
3A, 4A, 5A, 6A, or 7A elements of the Periodic Chart of Elements (CAS
version), wherein said non-lead derivative compound simultaneously increases
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3
combustion burning velocity andlor reduces combustion temperature, wherein
said composition is improved over the hydrogen or the co-fuel alone;
optionally
showing improved thermal efficiency. Said composition optionally containing an
ECS oxygenate.
As noted, in the aforementioned Applications, Applicant has discovered,
under these his combustion conditions, the metallic, itself, becomes an
integral
and powerful agent in the combustion process, improving combustion thermal
efficiencies, translating into improved fuel economy, net available work,
power
1 o generation, thrust, and the like (e.g. increased
miles/gal.(kilometerslliter),
increased flight rangelKg, increased kilowatts generatedlliter), while
simultaneously reducing hazardous pollutants.
In the context of this invention, Applicant generally refers to thermal
efficiency in both its chemical and mechanical context, e.g. the efficiency of
the
chemical reaction and the amount of useful work generated in the system, e.g.
free energy.
Applicant has found, thermal efficiency, particularly as measured as a
function of net useful work generated by the system is increased. Often
substantially.
2 0 For example, Applicant's has discovered thermal efficiency
improvements over existing unadjusted fuels and combustion systems to be on
the order of 1.0%, 2.0%, 3.0%, 4.0%, 5.0% to 20%. And, depending upon the
circumstances (e.g. combustion systems, fuel configurations) average
improvements can range from 2.0% to 5.0%, 5.0% to 10.0% or higher, with
2 5 modest improvements ranging from 0.05% to 1.0% to 2.0%. Exceptional
improvements will range from 10%, 25% to 40%, 30% to 80%, or more.
In the context of this invention "unadjusted" fuels mean conventional
existing hydrocarbon fuels concun-ent to this invention, which have not been
adjusted to improve burning velocity, increase latent heats of vaporization, T-
90
30 temperatures, mid range distillation temperatures, aromatic or sulfur
contents.
These value are variously set forth herein and to the extent they are known in
the industry incorporated herein by reference.
Example B
The compositions of Example A, containing hydrogen or a hydrocarbon,
wherein said composition's burning velocity andlor combustion temperature
permit said non-lead derivative compound to replace need for an ECS
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compound, however, said composition experiencing luminous vapor phase
combustion.
Example C
The aforementioned compositions, wherein said non-lead derivative is a
sodium, potassium, phosphorous, boron, or silicon derivative, including
mixture.
Example D
1 o The aforementioned composition, wherein said non-lead derivative is
trimethoxymethylsilane or homologue, analogue, isomer or derivative.
The aforementioned PCT Applications speak to the use of symmetrical
alkyl carbonates (e.g. dimethyl carbonate "DMC") as a preferred ECS
oxygenate, which the art discloses as having potential hydrolytic or stability
problems when in an acidic or aqueous environments. See for example, EPO
Application # 91306278.2 Karas, which reasonably suggests fuels containing a
symmetrical diakyl-carbonate, like DMC, which have pH's perhaps 11 or lower,
as being potentially problematic. Thus, there is a need to mitigate this
potential
2 0 fuel stability problem.
Additionally, the use of less expensive longer chain or more complex,
viscous fuels, e.g., heavy oils, heavy fuel oils, diesels, etc., have
attendant
handling, emission and combustion problems, which warrant solution,
especially if solved simultaneously with the above related problems.
Summaryr of the Invention
The instant invention is an improvement to the aforementioned PCT
Applications, and simultaneously solves the noted problems. Namely, the
invention reduces combustion greenhouse gases of C02, NOx, ozone,
3 o methane, and problematic chiororfluorocarbons and nitrous oxides. The
invention, is particularly able to control and reduce Nx0 emissions generated
post exhaust emissions catalyst.
The invention also beneficially improves a broad class of combustion
systems and emissions in general, while simultaneously improving fuel
economy, flight range, thrust andlor power.
The invention more particularly relates to discovery of a class of non-
manganese, non-toxic ECS metal and metalloid compounds, including a
combination thereof, capable of achieving vapor phase combustion, but which
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do not have manganese's associated neurotoxicity problem. Metallics of
particular interest include alkall/alkali earth metals, sodium, potassium,
boron,
aluminum, silicon and phosphorus.
The invention also resides in the combination of metallics, which include
combining an ECS metallic with and ECS co-combustion metal, metalloid, or
carbon catalyst structurally similar to triemethoxymethylsilane or dimethyl-
phosphite. Said catalyst is contemplated in combination with Applicant's ECS
metallics to improve vapor phase burning, achieving the objects of this
invention.
10 The invention further resides in discovery of a means of maintaining
stability of fuels containing symmetrical lower dialkyl carbonates, while
simultaneously improving the handling of fuels containing alkalilalkali earth
metals, which can be highly alkaline. In accordance therewith, the fuel
compositions of the present invention exhibits improved stability and handling
15 attributes when the fuel compositions are constructed to a weakly alkaline
(7.5
to 11.0 pH), substantially neutral (6.5 to 7.5 pH), or slightly acidic (4.5 to
6.9 pH)
environments, whether or not water is present. In such cases there is no
handling hazard or hydrolysis problem. Thus, in the case of symmetrical lower
dialkyl carbonate containing fuels, long term storage is possible absent any
20 deterioration of stability. Likewise the handling hazards of strongly
alkaline
compositions due to the presence of alkaline or alkaline earth metals is
additionally controlled.
Additionally, it has been discovered the presence of lower dialkyl
carbonates and ECS metals in the fuel compositions of the present invention
2 5 allow for the use of highly viscous base hydrocarbon fuels, which
otherwise
might not be used.
Detailed Description of the Present Invention
30 ECS COMPONENTS
The free radical generating ECS oxygenates of this invention include
C2 - C12 aldehydes (including aldehydic acids), C2 -C12 ethers (including
ether acids), C3 to C15 di-ethers, C1 - C15 alcohols, C2 - C12 oxides, C3 -
C15 ketones; ketonic acids, C3 - C15 esters (alkyl formates, acetates,
35 diacetates, butyrates, etc.), othroesters, C3 - C12 diesters, C5 -C12
phenols,
C3 - C20 glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbonates, C3 - C20
dialkyl carbonates, C3 - C20 asymmetrical alkylldialkyl carbonates, C3 - C20
di-carbonates, C1 to C20 organic and inorganic peroxides, hydroperoxides,
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carboxylic acids (including formic acids), amines, nitrates, di-nitrates,
oxalates, phenols, glacial acetic acids (including C3 to C8 hyrodoxy esters of
acetic acid, anhydrides, methoxy methyl ester of acetic acid, etc.), boric
acids,
orthoborates, hydroxyacids, orthoacids, anhydrides, acetates, acetyls,
nitrates, di-nitrates, vitro-ethers. Applicant's ECS compounds increasing
burning velocity andlor increase latent heat of vaporization.
Applicant's ECS oxygenated compounds which include one to ten
oxygen atoms are desireable, with to one to three oxygen atoms more
desirable. If organic, those oxygenated compounds having carbon atoms of
10 one to 20 atoms are desireable, with one to ten more desireable, with one
to
five being yet more preferred. Those with three atoms or less are most
preferred. Compounds where oxygen represents 10%, 20%, 30%, 40%, or
more, by weight are desired. Specific oxygenated compounds can be found in
detail in Or4anic Chemistry 6th Ed, T.W.G. Solomons, John Wiley & Sons,
15 N.Y., (1995), Physical Chemistry, 5th Ed, P.W. Atkins, Oxford University
Press, U.K. (1994), Physical Organic Chemistry, 2 Ed, N.S. Issacs, John
Wiley & Sons, N.Y. (1995) and Lan4e's Handbook of Chemistry, 14th Ed, J.A.
Dean, McGraw-Hill, N.Y. (1992).
ECS oxygenates of particular interest (homologues, analogues,
20 derivative, and isomers thereof), include tertiary hydrocarbyl ethers,
including
but not limited to methyl tertiary butyl ethers (MTBE), ethyl tertiary butyl
ether
(ETBE), tertiary methyl amyl ether (TAME), tertiary methyl ethyl ether
(TEME), ethyl tertiary amyl ether; C1 to C6 aliphatic alcohois, including but
not limited to ethanol, methanol; lower diakyl carbonates, including but not
25 ° limited to dimethyl carbonate (DMC), diethyl carbonate (DEC);
ethers having
dual linkage (e.g. diethers), including but not limited to di-ethers,
including
methyal (methylene di methyl ether or dimethoxy methane), ethylal (diethoxy
methane); carbons having multiple alkyloxy groups, including but not limited
to tetramethoxymethane, tetraethoxymethane, anhydrides and hyrodoxy
30 esters of acetic acid, anhydrides, including but not limited to methoxy
methyl
ester of acetic acid, ethoxy methyl ester of acetic acid.
Applicant's ECS oxygenated compounds may be included in weight
percent of the final composition in that amount, which results in optimal
vapor
phase combustion. Concentrations ranging from 0.5, 1.0, 1.5, 2.0, 2.1, 2.2,
35 2.5, 2.7, 3.1, 3.4, 3.5, 3.6, 3.7, 4.0, 4.5, 5.0 percent weight by oxygen
are
contemplated. Other oxygen concentrations range from 0.01 to 3.7, 0.1 to
80.0, 1.0 to 5.0, 1.0 to 10.0, 1.0 to 15.0, 1.0 to 20.0, 1.0 to 30.0, 1.0 to
40.0,
1.0 to 53 percent oxygen by weight in the composition.
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Preferred ECS structurelcomponents (e.g. oxygenates, metallics, and
hydrocarbon base, if any) are characterized as those yielding in
precombustion a significant portion of reactive high kinetic energy free
radicals (e.g. H, H2, O, 00, CO, F, F2, F3, N, B, Be, BO, B2, BF, AL ALO,
CH3, NH3, CH, C2H2, C2H5, l_i, KO, KOO, ONH, ON, NH, NH2, OCH3, OCH,
OCH2, OH, CI, CN, OCOO, COOH, C2H500C, CH3C0, OCH20, OCHCO, or
CONH2), as a weight percent of their total precombustion vapors. Thus,
components containing one or more of these radicals is desired. Preferred
weight percent contributed by the substituent is equal to or greater than 2%,
1 o 5%, 10%, 20%, 30%, 40%, of the precombustion vapors. Similarly Applicant's
ECS compounds should contain one or more radicals of same structure.
The preferred reactive high kinetic energy free radicals of this invention
are those radicals that generate laminar bunsen flame velocities in excess of
40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58,
59,
60, 61, 62, 63, 64, 65, 70, 75, 80, 90 or more, cmlsec. (laminar bunsen
burner flame), more preferably in excess of 50, 60, 65, or 70 cmlsec., and
ideally those having at least one free or unused valency electron; said ideal
radical is characterized as being a chain carrier in the main chain reaction
of
combustion, effectively disassociating and re-associating during combustion.
2 o As used herein flame velocity or propagation is the art definition, which
can
be defined as the volumetric velocity of the stream of the combustible mixture
divided by the surface of the inner cone of a laminar Bunsen flame.
Thus, the preferred ECS oxygenates, metallics, andlor hydrocarbon
bases, if any, have higher relative flame velocities. As a rule, when
2 5 combusted in air (as a function of their own constitution and as measured
in a
laminar Bunsen flame), flame velocities should equal or exceed 32, 33, 34,
35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,
54,
55, 56, 57, 58, 59, 60, 61, 62, 65, 70, 75, 80, 85, 90, 100, 110, 120, 130,
140,
150 cmlsec., with those exceeding 40, 41, 42, 43, 45, 47, or more, preferred.
30 The higher the burning velocity the better. It is recognized individual ECS
oxygenates may have higher burning velocities than individual metallics,
compared to hydrocarbon base fuels. However, ESC oxygenatelmetallic
combinations should have synergistic laminar burning velocities preferably
exceeding 48, 50, 55, 60, 65, 70, or more cmlsec.
35 Preferred latent heats of vaporization of ECS components (e.g.
oxygenates, metallics, andlor hydrocarbon bases) at 60°F are those
equal to
or greater than 60, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130,
135,
140, 145, 150, 155, 150, 160, 165, 170, 180, 190, 200, 210, 220, 230, 240,
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250, 270, 290, 300, 325, 350, 375, 400, 425, 450, 475, 500 btul(b, or more.
Those greater than 100, 115 btu/lb are more desireable. Alternatively,
preferred latent heats of vaporization (enthalpy of vaporization at boiling
point) equal to or greater than 21, 22, 23, 24, 26, 27, 29, 30, 31, 32, 33,
34,
35, 36, 37, 38, 40, 42, 43, 45, 47, or higher, jK mole'' are desireable, with
those no less than 28.0 jK mole'', more desireable. The higher the latent heat
of vaporatization the better. It is an embodiment of this invention to employ
hydrocarbon bases having enhanced l_HV's (see below).
The ECS non-lead metals, metalloids, non-metals (herein "metals or
1 o metallics") are those which are combustible and which having high heating
value, exceeding 2,000 to 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000,
9,500, 10,000, 10,500, 11,000, 12,000, or more, Kcallkg, and which contain
at least one element selected from the group consisting of aluminum, boron,
bromine, bismuth, beryllium, calcium, cesium, chromium, cobalt, copper,
francium, gallium, germanium, iodine, iron, indium, lithium, magnesium,
manganese, molybdenum, nickel, niobium, phosphorus, potassium,
palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium, silicon,
vanadium, strontium, barium, radium, scandium, yttrium, lanthanum, actinium,
cerium, thorium, titanium, zirconium, hafnium, praseodymium, protactinium,
tantalum, neodymium, uranium, tungsten, promethium, neptunium, samarium,
plutonium, ruthenium, osmium, europium, americium, rhodium, iridium,
gadolinium, curium, platinum, terbium, berkelium, silver, gold, dysprosium,
californium, cadmium, mercury, holmium, titanium, erbium, thulium, arsenic,
antimony, ytterbium, selenium, tellurium, polonium, lutetium, astatine,
mixture
thereof, including organic and inorganic derivatives thereof (as set forth in
more detail below).
The preferred metals herein have oxides whose heats of formation are
negative, and should be equal or exceed (e.g. be more negative) about -
10,000 to -75,000 calorieslmole. More preferred are those equal or
exceeding -100,000 to -400,000 gr calorieslmole, and greater (more
negative). Simple oxides containing one or two oxygens may have heats of
formation equal or exceeding -50,000 to -200,000, or greater, calories/mole
are acceptabte.
VAPOR PHASE COMBUSTION
This invention contemplates a vapor phase formlmethod of combusting
a metallic, wherein said method comprises: introducing kinetic free radicals
having enhanced combustion structure (ECS) into a combustion chamber;
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igniting and combusting a flammable metallic or metal compound in presence
of said free radicals at temperature below said metal's oxide boiling point
and
preferably above said metal or metallic compound's boiling point; combusting
said metal wherein accelerated burning occurs, as evidenced by a brilliant
luminous reaction zone extending some distance from the metal's surface;
wherein metallic oxide particles resulting from combustion are in submicron
range andlor remain in a gaseous state.
The composition's ingredients and proportions are tailored to
accomplish this objective. Varying compositions and ingredients will
1 o necessarily yield differing results. However, in the claims below
providing for
vapor phase combustion, the ingredients and ranges are at a minimum
optimizedlarranged to achieve this result.
NON-TOXIC ECS METALS
It is an object of this invention to eliminate neurotoxic manganese or
other hazardous metal oxides of combustion, including concentrations thereof
deemed to be toxic. It is a principal object of this invention to use metals
and
metal combinations, whose combustion products, oxides, carbonates, etc.,
are relatively non-toxic and absent neurotocity.
However, it is expressly recognized differing metals, and metallic
blends yield different combustion products. Differing ECS metallic
applications will results in different combustion products. In some
applications
and compositions the metal combustion products generated may be toxic. Yet
in other compositions, andlor applications, the same metallic or metallics may
2 5 elicit essentially non-toxic combustion products.
Thus, it is expressly contemplated differing applications of the same
metal, or differing metals acting together in combustion may produce non-
toxic combustion products, while in other circumstances would produce toxic
combustion products.
It is contemplated certain risk metals generating potentially toxic
combustion products rnay be employed in applications where risk is
acceptable, e.g. advanced jet, rocket, or outer space applications. Thus,
metallics hazardous on earth could be employed in space.
It is also contemplated manganese containing metallic may be
included in small concentrations in a mixture with non-manganese metallics.
For example, methylcyclopentadienyimanganese tricarbonyl may be added in
small concentrations, perhaps as an anti-knock enhancer in the case of
gasoline. It may be included in other fuels as well.
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In the practice of this invention alkalilalkali earth metals, whose metal
oxides are non-toxic are preferred. Particularly preferred metals include
lithium, sodium, potassium, rubidium, cesium, magnesium, and calcium. More
preferred are lithium, sodium, potassium and magnesium.
5 Other non-lead, non-manganese metals, whose combustion product is
moderately to relatively non-toxic, and desireable in the practice of this
invention, include: aluminum, boron, bismuth, cerium, gallium, lithium,
potassium, sodium, phosphorus, sodium, magnesium, sulfur, chlorine,
indium, iron, copper, zinc, silicon, iodine, cobalt, molybdenum, nitrogen,
10 praseodymium, rhenium, rubidium, fluorine, tin, titanium, chromium,
selenium,
vanadium, boron, nickel, niobium, germanium, ytterbium, yttrium, zirconium.
Blends of these metals, including their derivative compounds are
contemplated.
However, slightly more desirable metals include: aluminum, boron,
bismuth, calcium, cerium, cesium, gallium, lithium, potassium, sodium,
magnesium, iron, copper, zinc, silicon, indium, molybdenum, nitrogen,
potassium, praseodymium, rhenium, rubidium, tin, titanium, selenium, boron,
germanium, ytterbium, yttrium, zirconium.
Even more desirable are aluminum, lithium, potassium, sodium, boron,
2o potassium, magnesium, silicon, nitrogen, selenium, boron, and germanium.
ft is an embodiment of this invention to substitute Applicant's non-toxic
metallics for Mn in the aforementioned PCT Applications.
TESTS
2 5 As a means of illustrating the benefits of Applicant's invention,
Applicant conducted a series of horse power (HP} tests employing an air
cooled honda 75 cc, four stroke engine, rated at 2 horse power on a
DYNOJET MODEL 100 DYNAMOMETER. Increases in HP above the
engine's rate HP is an indication the vapor phase burning. Such an indication
30 would also show improvements in emissions, fuel economy, thrust, flight
range, and the like, if measured. For purpose of this test only HP was
measured. Certain test fuels required blending agents.
The test was conducted to show changes in rated horse power due
only to changes in fuel composition. For purpose of the test the bike's
35 gasoline tank was disconnected. Tests measurements were performed after
the engine had been warmed up. After each test fuel, the carburetor was
drained of excess fuel and flushed to avoid fuel contamination
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After warm up, the test procedure included bringing the warmed bike to
a stop {while engine operating), then shifting the bike into first gear and
engaging the transmission and rear wheel on the dynamometer, with operator
upon the bike. After shifting into second gear, the dynamometer was activated
and the throttle was immediately opened to "wide open." The bike operated
under full throttle until it reached a speed of about 30 mph (in second gear),
when the test was terminated.
The measurement parameters included:
to
A = the speed (mph) which the engine achieved its rated 2 hp.
B = the speed at which the highest rated HP was achieved.
C = the highest rated hp.
D = the speed at which horse power descended back to rated 2 hp.
E = Horse Power Factor [(D-A) x C].
F = Incremental Horse Power Factor [{D-A) x C]] minus Horse Power
Factor of Base Fuel. This is an indication of additional net horse power
attributed to incremental ingredients.
A B C D E F
TEST FUEL
1. Base gasoline 20 21 2.Ohp 23 6
2. Base gasoline with
2.7% 02 wt of MTBE 20 21 2.Ohp 23 6 0
(Oxygen from MTBE is
2.7% weight of composition)
3. Base gasoline with
2.5% 02 wt DMC 20 21 2.Ohp 23.5 7 1
4. Base gasoline with
3.5% 02 wt Ethanol 20 21 2.Ohp 23.5 7 1
7. Base gasoline with 18.5 21.5 2.1 hp 24.5 12.6 6.6
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0.00156% vol. methoxy-
methylsifane
8. Base gasoline with 18 21.5 2.1 25.0 14.7 8.7
hp
0.03125% vol trimethoxy-
methylsilane
9. Base gasoline with 18 16.1 10.1
21.5 2.15hp 25.5
0.125% vol trimethoxy-
l0 methylsilane
10 Base gasoline with 18 1.5 2.15hp 17.2 11.2
2 26.0
0.25% vol trimethoxy-
methylsifane
11 Base gasoline with 17 21.5 2.5hp 27.0 25.0 19.0
0.03125% vol trimethoxy-
methylsilane, 2.5% 02 wt
DMC
2 12 Base gasoline with 16.521.5 2.60hp 27.3 21.3
0 27.0
0.03125% vo1 trimethoxy-
methylsilane, 3.5% 02 wt
Ethanol
13 Base gasoline with 18.521.5 2.1 hp 12.6 6.6
24.5
2 0.00156% vol dimethyl-
5
phosphite
14 Base gasoline with 18.521.5 2.15hp 12.9 6.9
24.5
0.003125% vol dimethyl-
30 phosphite
15 Base gasoline with 18.521.5 2.15hp 14.0 8.0
25.0
0.03125% vol dimethyl-
phosphite
35
16 Base gasoline with 18.521.5 2.2hp 16.5 10.5
26.0
0.125% vol dimethyl-
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phosphite
17 Base gasoline with 18.5 21.5 2.3hp 26.5 18.4 12.4
0.25% vol dimethyl-
phosphite
18 Base gasoline with 17.5 21.5 2.45hp 25.5 19.6 13.6
0.003125% vol dimethyl-
phosphite, 2.7% 02 wt MTBE
19 Base gasoline with 17.0 21.5 2.50hp 26.5 23.8 17.8
0.03125% vol dimethyl-
phosphite, 2.5% 02 wt DMC
20 Base gasoline with 19.5 21.5 2.1 hp 24.0 9.5
3.5
0.003125% wt potassium
ethoxide-
21 Base gasoline with 18.5 21.5 2.2hp 25.0 14.3 8.3
0.0625% wt potassium
ethoxide-
22 Base gasoline with 18.5 21.5 2.2hp 25.5 15.4 9.4
0.125% wt pota$sium
ethoxide-
23 Base gasoline with 17 21 2.5hp 27.0 25.0 19.0
0.0625% wt potassium
ethoxide, 2.7 vol% MTBE
24 Base gasoline with 17.5 21 2.50hp 27.5 25.0 19.0
0.0625% wt potassium
ethoxide, 2.5 vol% DMC
25 Base gasoline with 16.5 21.5 2.55hp 27.5 28.0 22.0
0.03125% wt potassium
ethoxide, 2.7% 02 wt MTBE
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19
26 Base gasoline with 16.5 21.5 2.60hp 27.0 27.0 21.0
0.0625% wt potassium
ethoxide, 2.7% 02 wt MTBE
27 Base gasoline with 16.5 21.5 2.60hp 27.5 28.6 22.6
0.125% wt potassium
ethoxide, 2.5% 02 wt DMC
28 Base gasoline with 19.5 21 2.05hp 24.5 10.2 4.2
0.003125% volume [2-{cyciohexenyl)
ethyl]triethoxysilane
29 Base gasoline with 18.5 21 2.15hp 25.5 15.0 9.0
0.03125% volume [2-(cyclohexenyl)
ethyl]triethoxysilane
30 Base gasoline with 18 21 2.25hp 25.5 16.9 10.9
0.125% volume [2-(cyclohexenyl)
2 o ethylJtriethoxysilane
31 Base gasoline with 16 22 2.6hp 28.0 31.2 25.2
0.0625% volume [2-(cyclohexenyl}
ethylJtriethoxysilane,
2 5 2.7% 02 wt MTBE
32 Base gasoline with 16 22 2.65hp 29.0 34.3 28.3
0.125% volume [2-(cyclohexenyl)
ethyl]triethoxysilane,
30 2.5% 02 wt DMC
33 Base gasoline with 15.5 21.5 2.65hp 28.5 34.5 28.5
0.125% volume [2-(cyclohexenyl}
ethyl]triethoxysilane,
3 5 3.5% 02 wt Ethanol
34 Base gasoline with 19 21 2.05hp 25.0 12.3 6.3
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0.003125% volume [2-(cyclohexenyl}
ethyl]triethoxysiiane, 0.003125 vol%
trimethoxymethylsilane
5 35 Base gasoline with 19 21 2.2 hp 25.5 14.3 8.3
0.03125% volume (2-{cyclohexenyl}
ethyl)triethoxysilane, 0.03125vo1%
trimethoxymethylsilane
10 36 Base gasoline with 19 21 2.25 hp 26.015.8 9.8
0.0625% volume [2-(cyclohexenyl)
ethyl]triethoxysilane, 0.03125vo1%
trimethoxymethylsilane
15 37 Base gasoline with 19 21 2.15hp 26.0 15.0 9.0
0.003125% volume [2-(cyclohexenyl}
ethyl]triethoxysilane, 0.003125 vol%
dimethylphosphite
2 0 38 Base gasoline with 16.5 22 2.8hp 28.5 33.6 27.6
0.03125% volume [2-(cyclohexenyl)
ethyl]triethoxysilane, 0.25 vol%
trimethoxymethylsilane, 2.7% 02 wt MTBE
39 Base gasoline with 17 21 2.75hp 28 30.3 24.3
0.25% volume (2-(cyclohexenyl}
ethyl]triethoxysilane, 0.25 vol%
dimethylphosphite, 2.5% 02 wt DMC
40 Base gasoline with 19 20 2.15hp 25.5 14.0 8.0
0.00625% volume hexamethyldisilane
41 Base gasoline with 18 21 2.25hp 26.5 19.1 13.1
0.0625% volume hexamethyldisilane
42 Base gasoline with 16 23 2.75hp 29 35.8 29.8
0.0625% wt potassium
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ethoxide, 0.03125 vol% trimethoxy
methylsilane, 2.5% 02 wt DMC
43 Base gasoline with 15.5 23 2.80hp 28.5 36.4 30.4
0.0625% wt potassium
ethoxide, 0.03125 vol% trimethoxy
methylsilane, 3.5% 02 wt Ethanol
44 Base gasoline with 16.5 22 2.65hp 28.5 31.8 25.8
0.03125% wt potassium
ethoxide, 0.0625 vol% trimethoxy
methylsilane, 2.0% 02 wt MTBE
45 Base gasoline with 16.5 22 2.65hp 27.0 27.8 21.8
0.03125% wt potassium
ethoxide, 0.003125vo1% dimethyl
phosphate, 2.5% 02 wt DMC
46 Base gasoline with 16.0 22 2.65hp 29.5 35.8 29.8
2 0 0.003125% wt potassium
ethoxide, 0.0625vo1% dimethyl
phosphate, 3.5% 02 wt Ethanol
47 Base gasoline with 16 22 2.75hp 27.5 31.6 25.6
0.125% wt potassium
ethoxide, 0.0625vo1% dimethyl
phosphate, 2.2% 02 wt MTBE
48 Base gasoline with 16.5 21.5 2.65hp 27.5 29.2 23.2
0.03125% wt potassium
phenoxide, 0.03125vo1% dimethyl
phosphate, 2.2% 02 wt MTBE
49 Base gasoline with 17.0 22 2.60hp 26.5 24.7 18.7
0.03125% wt potassium
tert-butoxide, 0.003125vo1% dimethyl
phosphate, 1.5% 02 wt MTBE
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ANALYSIS OF TEST DATA
The above data shows unexpected results and the synergistic nature
of Applicant's ingredients, individually and in combination. For example,
Test 3 shows gasoline with 2.5% 02 wt DMC to have an F value of 1, where
F represents the incremental horse power factor due to the inclusion of DMC
(e.g. [(D-A) x C]] minus horse power Factor of Base Fuel}. Thus, the DMC fuel
has a slightly higher F value than the base fuel.
1 o Test 8, gasoline with 0.03125% wt. trimethoxymethylsilane, shows an
F value of 8.7, which represents an apparent increase in HP as measured by
F.
Test 11 a combination of 0.03125% wt. trimethoxymethylsilane and
2.5% 02 wt DMC in gasoline has an F value of 19.0, or about 10 F numbers
greater than Test 8, which shows a synergism between
trimethoxymethylsilane and DMC. Similar data show similar results with
dimethylphosphite.
[2-(cyclohexenyl)ethyl]triethoxysilane, hexamethyldisilane, potassium
ethoxide, potassium phenoxide, dirnethylphosphite, and
2 o trimethoxymethylsilane generally show improvement alone in gasoline, but
better improvement with MTBE, DMC and Ethanol, and still better
improvement when either dimethylphosphite and trimethoxymethylsilane are
used with the other metallics.
The HP data generally shows Ethanol, MTBE and DMC are generally
2 5 interchangeable achieving similar results. Trimethoxymethylsilane and
dimethoxyphosphite also appear to be similar. It appears [2-
(cyclohexenyl)ethyl]triethoxysilane, hexamethyldisilane, potassium ethoxide
achieve similar results.
30 PRACTICE
Example 1
A non-toxic vapor phase combustion composition comprising: 1 ) an
ECS oxygenate (preferably selected from a hydrocarbyl ether, an alcohol,
35 carbonate, or methylallethylal}, 2) an ECS metallic, preferably a non-
neurotoxic ECS alkalilalkali earth metallic derivative (preferably an
alkyloxide
of potassium or a potassium ferricyanide), or a derivative of lithium, boron,
silicon, or aluminum, optionally; 3} a hydrocarbon, andlor optionally a 4) a
co-
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combustion catalyst (preferably a silicon alkyloxy derivative, like
trimethoxymethylsilane, or an alkylldialkyl phosphite like dimethyiphosphite),
Examale 2
The above examples, wherein the composition constructed to have a
pH ranging from 4.5 to 11.5, more preferably 5.5 to 9.5, even more preferably
6.5 to fi.9.
Example 3
The above examples, wherein the ECS metallic is an alkali/alkali earth
metal (a non-limiting example, potassium ethoxide) and the co-combustion
agent is a phosphorus derivative {non-limiting example dimethyl or diethyl
phosphite), wherein the composition has a pH equal or less than 10.5, 9.5,
8.5, 7.5, but greater than 4.5, 5.5, or 6.0, (substantially neutral is
preferred).
Example 4
The above Examples, wherein the ECS metallic is selected from alkyl
metal and alkyl earth metal salts, naptha's, ferricyanides, organo-metallics
(optionally containing oxygen and/or nitrogen) and derivative compound,
2o including potassium alkanols, potassium alkyl oxides, e.g. potassium
methoxide, potassium ethoxide, potassium propoxide, potassium
isopropoxide, potassium butoxide, potassium sec-butoxide, potassium tert-
butoxide, potassium pentoxide, potassium tert-pentoxide, potassium
phenoxide, etc. Other non-limiting examples of potassium salts include
potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium
acetylenedicarboxylic acid, potassium pyrophosphate, potassium
dihydrogenphosphate, potassium benzoate, potassium chloride, potassium
hexoate (potassium salt hexoic acid), potassium acetates, potassium
formates, potassium diphenylphosphide, potassium trimethylsilonalate,
potassium phthalic acid, P-aminobenzoic acid potassium salt,
monopotassium L-aspartic acid, potassium napthenate. Corresponding
sodium, lithium, rubidium, cesium compounds are contemplated. Mixtures are
contemplated.
Example 4A
The above examples, wherein said ECS metallic is selected from
potassium ethoxide, potassium tert-butoxide, potassium phenoxide,
potassium acetate, potassium napthenate and mixture.
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Example 4B
The above examples, wherein said fuel contains a TMMS co-
combustion catalyst.
Example 4B
The above examples, wherein said fuel contains stabilizer selected
from TMMS, toluene, glycols, glycol ethers and mixture.
1 o Example 4C
The above examples, wherein the ECS component is oxygenated,
selected from C2 - C12 aldehydes (including aldehydic acids), C2 -C12 ethers
(including ether acids), C3 to C15 di-ethers, C1 - C15 alcohols, C2 - C12
oxides, C3 - C15 ketones, ketonic acids, C3 - C15 esters (alkyl formates,
acetates, diacetates, butyrates, etc.), othroesters, C3 - C12 diesters, C5 -
C12
phenols, C3 - C20 glycol ethers, C2 - C12 glycols, C3 - C20 alkyl carbonates,
C3 - C20 dialkyl carbonates, C3 - C20 asymmetrical alkyl/dialkyl carbonates,
C3 - C20 di-carbonates, C1 to C20 organic and inorganic peroxides, hydro-
peroxides, carboxylic acids (including formic acids), amines, nitrates, di-
2 0 nitrates, oxalates, phenols, glacial acetic acids (including C3 to C8
hyrodoxy
esters of acetic acid, anhydrides, methoxy methyl ester of acetic acid, etc.),
boric acids, orthoborates, hydroxyacids, orthoacids, anhydrides, acetates,
acetyls, nitrates, di-nitrates, nitro-ethers, homologues, analogue, derivative
and mixture.
Example 5
The above Examples, wherein the ECS metallic is selected from a
silicon derivative including: (2-(cyclohexenyl)ethyl]triethoxysilane,
cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-(3-
(trimethoxysilyl)propyl)ethylene-diamine, N-1-(3-(trimethoxysilyl)-
propylkliethylenetriamine, N-(3(trimethoxysilyl)propyl)-ethylenediamine; 1-
(trimethyl(silyl)-pyn-olidine, triphenylsilanol, octamethyltrisiloxane,
2,2,4,4,6,6-
hexamethylcyclotrisilazane, hexamethylcyctrisiloxane, hexamethyl-disilane,
1,1,1,3,3,3-hexamethyl disilazane, hexamethyldisiloxane,
hexamethyldisiithiane, allyltributylsilane, tetraalkylsilanes (e.g.
tetraethylsilane, tetrabutylsilane, etc.), 3-aminopropyltriethoxy-siiane,
benzytrimethylsilane, benzytriethylsilane, N-benzyltri-methylsilylamine,
diphenylsilanediol, dihexylsilanediol, (trimethyl-silyl)cyclopentadiene,
including
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homologues, analogues and derivative thereof.
Example 5A
A fuel composition containing an ECS oxygenate increasing burning
5 velocity and/or reducing combustion temperature, optionally selected from
MTBE, ETBE, DMC, DEC, methylal, ethylal, methanol, ethanol, or mixture,
and an ECS metal selected from methylcyciopentadienylmanganese
tricarbonyl, [2-(cyclohexenyl~thyl]triethoxysilane, cyclohexenyl
dimethoxymethylsilane, benzyltrimethylsiiane, N-(3-
10 (trimethoxysilyl)propyl)ethylenediamine, N-1-(3-
(trimethoxysilyl)propyl)diethylenetriamine, N-{3-
(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(silyl)pyrrolidine,
triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,fi,6-
hexamethylcyclotrisilazane,
hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl
15 disilazane, hexamethyldisiloxane, hexamethyldisilthiane,
allyltributylsilane,
tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-
aminopropyitriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-
benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol,
(trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide,
2 o potassium propoxide, potassium isopropoxide, potassium butoxide,
potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide,
potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid,
potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium
acetylenedicarboxylic acid, potassium pyrophosphate, potassium
dihydrogenphosphate, potassium benzoate, potassium chloride, potassium
hexoate (potassium salt hexoic acid), potassium acetate, potassium
diphenylphosphide, potassium trimethylsilonalate, potassium phthaiic acid, P-
aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium
napthenate, potassium hexacyanoferrate {II), potassium hexacyanoferrate
(III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt,
potassium sodium ferricyanide, or mixture.
EXAMPLE 6
The above examples, wherein the ECS metallic is selected from a
spiral compound based upon ferricyanhydric acid derivatives, namely
ferricyanides. See Dictionary of Chemical Solubilties, supra, pages 334-342,
which lists various ferrocyanides (as herein provided ferrocyanides include
cyanofemates, ferricyanides, and the like), incorporated herein by reference.
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2Z
Alkali and alkali earth metal ferrocyanides are desireable. Transition metal
ferrocyanides are desireable. Nitrogen ferrocyanides are desireable. Non-
limiting examples include: potassium hexacyanoferrate (ll) and potassium
hexacyanoferrate (III) are desireable. Non-limiting examples include
potassium hexacyanocobalt I I- fen-ate, potassium Hexacyanocobalt II I,
potassium hexachloroosmate (IV), potassium hexachloroplatinate (IV),
potassium hexafluorosilicate, potassium hexafluoromanganate (IV),
potassium Hexaflourozirconate. potassium hexathiocyanatoplatinate (IV),
potassium sodium ferricyanide, potassium hexacyanoplatinate, potassium
to hexacyanoruthinate (//)hydrate, potassium hexacyanoplatinate (IV),
potassium hexafluoroaluminate, potassium hexafluoroarsenate, potassium
hexafluorophosphite, potassium hexafluorophosphite, potassium
hexafluorosilicate, potassium hexahydroxyantimonate, potassium hexafluoro
titante, Potassium copper ferracyanide, potassium cyanide, iron (III)
ferrocyanide, sodium ferrocyanide decahydrate, magnesium ferrocyanide,
magnesium potassium ferrocyanide. Naturally other cyano-spiral, including
hexacyano compounds are contemplated. Substitutions for potassium and/or
iron are also contemplated. Examples of such substitution include potassium
hexacyanocobaltate (III}, sodium hexacyanocobaltate (III}, etc. Structurally
2o similar compounds, analogues, and homologues, etc., are incorporated
herein by reference and contemplated.
Example 6a
The example of 5, 5A, 6, wherein said composition contains a solvent
is selected from alkyl ketones (acetone, etc.), alkyl alcohols (methanol,
ethanol, isobut-anol), alkyl ethers, glycerols, alkanol amines (ethanolamine,
etc.), and other solvent known in the art and soluble with said hexacyanides
(herein incorporated by reference), Applicant's ECS oxygenates, and
optionally with a hydrocarbon (incorporated herein by refer ence). or other
known solvent is employed capable of creating a solution, which is soluble in
ECS oxygenate and/or a hydrocarbon base.
Example 6b
The example of 6 and 6a, containing an ECS oxygenate in a
combustion improving amount, and
It) a combustion improving amount of a ferricyanide; and optionally: III)
a co-combustion catalyst, IV) hydrogen or a hydrocarbon base fuel, V) an
oxidizer, VI) a solvent;
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wherein said composition is optionally VII) characterized as having a
pH of from 4.5 to 10.5; and
VIII) wherein said fuel is a vapor phase composition characterized
upon combustion as having a luminous reaction zone extending from surface
of said element.
Example 6c
The example 6, 6a and 6b, wherein the ECS oxygenate is selected
from the group consisting of MTBE, ETBE, TAME, ethanol, methanol, DMC,
1 o EMC or mixture; the ferricyanide is optionally a potassium based; the
composition comprises a hydrocarbon base; and the composition optionally
contains a mutual solvent.
Example 7
The example of 6, wherein said hexacyanide is preferably potassium
hexacyanoferrate (II) or (III), and optionally contains a mutual solvent,
optionally containing a co-combustion catalyst.
EXAMPLE 8
The Examples above, wherein the ECS oxygenated is methyl tertiary
butyl ethers (MTBE), ethyl tertiary butyl ether (ETBE), tertiary methyl amyl
ether (TAME), tertiary methyl ethyl ether (TEME), ethyl tertiary amyl ether;
C1
to C6 aliphatic alcohols, including but not limited to ethanol, methanol;
lower
diakyl carbonates, including but not limited to dimethyl carbonate (DMC),
diethyl carbonate (DEC); ethers having dual linkage, including but not limited
to methyal (methylene di methyl ether or dimethoxy methane), ethylal
(diethoxy methane); carbons having multiple alkyloxy groups, including but
not limited to tetramethoxymethane, anhydrides and hyrodoxy esters of acetic
acid, including but not limited to methoxy methyl ester of acetic acid, ethoxy
methyl ester of acetic acid.
Example 9
A fuel composition comprising: I) an ECS oxygenate in a combustion
improving amount, and
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II) a combustion improving amount of at least one combustible element
or compound containing at least one element selected from the group
consisting of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium,
chromium, cobalt, copper, francium, gallium, germanium, iodine, iron, indium,
lithium, magnesium, manganese, molybdenum, nickel, niobium, phosphorus,
potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium,
silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum,
actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium,
protactinium, tantalum, neodymium, uranium, tungsten, promethium,
1o neptunium, samarium, plutonium, ruthenium, osmium, europium, americium,
rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver,
gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium,
thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium,
lutetium,
astatine, mixture thereof, including organic and inorganic derivatives, and
I I I ) a co-combustion catalyst, and
IV) optionally hydrogen or a hydrocarbon base fuel, and
V) optionally an oxidizer, and
VI) optionally wherein said fuel composition has a pH of from 4.5 to
10.5, and
VII) wherein said fuel is a vapor phase composition characterized upon
combustion as having a luminous reaction zone extending from surface of
said element.
Example 10
The fuel of Example 9, wherein the ECS oxygenate is selected from
the group consisting of methyl tertiary butyl ethers, ethyl tertiary butyl
ether,
tertiary methyl amyl ether, tertiary methyl ethyl ether, ethyl tertiary amyl
ether,
C1 to C6 aliphatic alcohols, dimethyl carbonate, diethyl carbonate, and
mixture.
CO-COMBUSTION AGENTICATALYST
As evident in the tests above, it has been found the combustion activity
employing Applicant's ECS oxygenated compounds and metallics is
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unexpectedly improved by the combination of a co-combustion catalyst, such
as trimethoxymethylsilane or dimethyl-phosphite.
As contemplated in the claims hereto, co-combustion agents may
serve a multiple role, including acting as a stabilizing agents. As set forth
in
greater detail below TMMS and other co-catalysts acts in combination with
certain beneficial components to stabilize the fuel composition. Thus, as set
forth herein a co-combustion catalyst can serve as a stabilizing agent.
The co-combustion catalyst (combustion co-catalyst) is a combustible
compound generally having a structure of M-r~, wherein M is a metal,
metalloid, or non-metal. Selected M include, but are not limited to, carbon,
silicon, germanium, tin, boron, aluminum, gallium, indium, nitrogen,
phosphorus, arsenic, antinomy, bismuth, sulfur, and wherein r is either an
alkyloxy, hydroxy, oxy, or carboxyl radical, and wherein n is the number up to
the number of valence electrons of M or the total possible number of radicals
available.
If n is greater than one, then r1, r2, etc., may be a heterogeneous or
homogenous, an alkyloxy, vitro, or other radical, including an alkyl or aryl
radical. If n is greater than 1, one or more r may be alkyl or cyclomatic
radicals may be substituted. However, compounds with at least one alkyloxy,
2 o hydroxy, oxy, or carboxyl radical are desired. Compounds containing a
blend
of alkyl or alkyloxy, hydroxy, oxy, carboxyl radicals are contemplated. Thus,
alkyfoxymetallics and polyalkyfoxymetallics are expressly contemplated.
If r is greater than one, then one or more r may be substituted for direct
or indirectly connected ring systems, for example r1 may be a phenyl radical
connected directly, or indirectly connected through an alkyl group to M, where
r2, r3, etc., may be an alkyloxy or alkyl radical. Likewise, when more than
one
r may be substituted for sulfur, nitrogen, chlorine, fluorine, or other metal,
metalloid or non-metal of this invention.
Preferred co-combustion catalysts have one or more alkyioxy,
3o carboxyl, oxy, or hydroxy radicals. More preferred catalysts have one or
more
alkyloxy, oxy, carboxyl, hydroxy, radicals, and at least one alkyl radical. A
ring
system radical may be substituted for the alkyl radical.
Non-limiting examples of co-combustion catalyst, including derivative,
analogue, homologue and isomers thereof, include polyalkyloxysilanes:
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trimethoxymethyisilane, ethoxytrimethylsilane, isobutyltriethoxy-silane,
tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-
aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane,
vinyltrimethoxysilane, diethoxydi-methylsilane, dimethoxydimethylsilane,
5 vinyltris(2-butyldenamino-oxy)silane, tetraalkyloxysilanes (e.g.
tetramethoxysilane, tetraethoxysilane, tetrapropyloxysilane,
tetraisopropylsilane, tetraisobutylsilane, etc.); alkylphosphites,
polyalkylphosphites (e.g. dimethyl-phosphite, diethylphosphite,
dipropylphosphite, dibutylphosphite, di-tert-butylphosphite,
1o trimethylphosphite, triethylphosphite, tripropylphosphite,
triisopropylphosphite,
tributylphosphite), dimethylmethylphos-phonate, diethylmethylphosphonate,
P-pyrophosphate, alkylphosphoramides, polyalkylphosphoramides (e.g.
hexamethylphosphoramide, hexamethylphosphorus diamide,
hexamethylphosphorus triamide, hexamethylphospophorimidic triamide,
15 triethylphosphoramide, trimethylphosphoramide, tripropylphosphoramide,
triisopropylphosphoramide, tributylphosphoramide, triisobutylphosphoramide,
tri-sec-butylphosphoramide, tri-tert-butylphosphoramide,
triphenylphosphoramide, dimethoxyphosphorusamide (CH30)2PNH2),
diethoxyphosphorusamide, dipropoxyphosphorusamide,
2 o diisopropoxyphosphorusamide, dibutoxyphosphorusamide, di-
isobutoxyphosphorusamide, di-sec-butoxyphosphorusamide, di-tert-
butoxyphosphorusamide, diphenoxyphosphorusamide, dimethyiphosphor-
amide (CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide,
diisopropyfphosphoramide, dibutylphosphoramide, diisobutylphosphoramide,
2 5 di-sec-butylphosphoramide, di-tert-butylphosphoramide,
diphenylphosphoramide, dimethylethylphosphoramide, diethylmethyl-
phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-
phosphoramide, di-butyl-methylphosphoramide, di-iso-butyfmethyl-
phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-
methyiphosphoramide, diphenylmethyl phosphoramide), trimethyl-
orthoacetate, trimethylorthovalerate, trimethylorthobutyrate,
trimethylorthoformate; alkyloxymethanes (tetramethoxy-methane,
tetraethoxymethane, tetrapropoxymethane, tetraisopropoxy-methane,
tetratertbutoxy-methane, etc.), polyalkyloxymethanes; potassium
pryophosphite, trimethylorthoacetate, triethylorthoacetate, trimethylortho-
butyrate, triethylortho-butyrate, trimethylorthovalerate,
trimethylorthoformate,
dimethoxymethane, diethoxyethane, tetramethoxymethane, tri-
methoxymethylmethane, tetraethoxymethane, trimethoxymethylethane,
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triethoxymethylethane, trimethoxymethylmethane, triethoxy-methylmethane,
glacial acetic acids, including but not limited to acetic anhydrides,
(acetyloxy)
acid, ethyl ester (acetyloxy) acetic acid, aminooxo acetic acid, aminooxo
acetic acid hydrazide, ammonium acetate, acetoacetic acid, hydroxyacetic
acid (glycolic acid), methoxyacetic acid, ethoxyacetic acid, methoxy ethyl
ester of acetic acid, methoxy methyl ester of acetic acid, ethoxy methyl ester
of acetic acid, ethoxy ethyl ester of acetic acid, propoxy methyl ester of
acetic
acid, oxoacetic acid, alkylhydroxyesters of acetic acid (including but not
limited to methylesterhydro-xyacetic acid, ethylesterhydroxy-acetic acid,
propylesterhydro-xyacetic acid, alkyl acetates (including methyl ester acetic
acid), ethyl arsenate, ethyl arsenite, methyl ester of botanic acid, ethyl
ester
of botanic acid, 2-hydroxybutanic acid, 3-hydroxybutanic acid, 3-hydroxy-
ethylester of botanic acid, 2-hydroxyethylester of botanic acid, diphenyl
carbonate, dipropyl carbonate, ethyimethyl carbonate, dibutyl carbonate,
tetranitromethane, triethylphosphine oxide, triethylphosphine oxide,
triethylphosphine, diethyl-phosphinic acid, dimethylphosphinic acid, ethyl
diethylphosphinic acid, diethylphosphonic chloride, dibutyl ester phosphonic
acid, (1,1-dimethylethyl) phosphonic acid, ethenyl diethyl ester phosphoric
acid, diethyl ethylphosphonate, ethyl dimethylester phosphonic acid, methyl
2 o dimethylester phosphonic acid, methyl monoethylester phosphonic acid,
methyl monomethylester phosphonic acid, methyl-O,O-dimethylester
phosphonothioic acid, diethyl ester phosphoric acid, dimethyl ester
phosphoric acid, tributyl phosphate, ethylphosphate, trimethyl ester
phosphoric acid, triethyl ester phosphoric acid, tripropyl phosphate, 0,0,0,-
methyl ester phosphorothioic acid, diethylester phosphorous acid,
dimethylester phosphorous acid, tributyi ester phosphorous acid, triphenyl
ester phosphorous acid, O,O,S-tiethyl ester phosphorodithioic acid, 2-methyl-
1,2,propanediol, 2-methyl-2-vitro-1,3; propanediol, 2-methyl-2-propyl-1,3,-
propanediol, 1-nitrate-1,2,propanediol, 1,1',1",1'"-
[methanetetrayltetrakis{oxy)]-tetrakis propane, methyl propyl ether,
isopropylmethyl ether, isobutyl methyl ether, ethyl propyl ether, propylmethyl
ether, butyl methyl ether, tertiary butyl methyl ether, 1,1'-
[methylenebis(oxy)]bis[2-methyl-propane, 1-(1-methylethoxy)-propane,
2,2',2"-[methylidyne-tris(oxy)]tris propane, 1,1',1"-
[methylidynetris(oxy)]tris[2-
methyl propane, 2-methyl-1-vitro propane, 2-methyl-2-vitro propane,
hyd racrylonitrile, 1,1,1-triethoxy-propane, 1,1,3-triethoxy-propane, 1,1,1-
trimethoxy-propane, 1,1,3-trimethoxy-propane, 1,1,1-trifluoro-3-vitro-propane,
2-pyrrolidinone, and phenol. Similar structured compounds of aluminum,
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27
gallium, germanium, nitrogen, and sulfur are contemplated and incorporated
by reference.
It is to be appreciated not every possible combination of this invention
is available due to potential incompatibilities, and certain combinations are
more effective than others. Thus, it is contemplated a wide range of
substitution be made to best practice the invention. Where necessary mutual
solvents are contemplated.
As contemplated herein and in the claims below, any reference to
trimethoxymethylsilane ('TMMS") or dimethylphosphite or co-combustion
catalyst contemplates substitution with one or more the above disclosed co-
combustion catalysts, or any structurally similar compound. It is contemplated
the majority of the Applicant's ECS metallics (including those disclosed
herein), including contemplated cyclornatic metallics, alkali/alkali earth
metals,
metal alkanols, metallic hexacyanides, inorganic metallics and non-metals
alike, which achieve vapor phase combustion on their own, can be benefited
from simultaneous use of co-combustion agent. Thus, it is an
embodiment of this invention, and the aforementioned PCT Applications,
wherever an ECS metallic is disclosed, that a co-combustion agent be
additionally added.
Example 11
A fuel composition comprising: 1 ) an ECS oxygenate, 2) a co-
combustion catalyst, and optionally: 3) a hydrocarbon or 4) an ECS metallic;
said fuel optionally having a pH range of 10.5 to 4.0, 9.5 to 5.0, 8.5 to 6.0,
8.0
to 6.3, 7.8 to 6.2, 7.6 to 6.2; or optionally a pH less than 10.5, 10.0, 9.5,
9.0,
8.5, 8.0, 7.9, 7.8, 7.7., 7.6, 7.5, 7.4, 7.3, 7.2, 7.0, 6.9, 6.8, but greater
than a
pH of 4.0, 4.5, 5.0, 5.5, 6.0, 6.2, or 6.5,
Example 11A
A fuel composition comprising: 1 ) a hydrocarbon, 2) a co-combustion
catalyst, and optionally: 3) an ECS oxygenate, or 3) an ECS metallic; said
fuel
optionally having a pH range of 10.5 to 4.0, 9.5 to 5.0, 8.5 to 6.0, 8.0 to
6.3,
7.8 to 6.2, 7.6 to 6.2; or optionally a pH less than 10.5, 10.0, 9.5, 9.0,
8.5, 8.0,
7.9, 7.8, 7.7., 7.6, 7.5, 7.4, 7.3, 7.2, 7.0, 6.9, 6.8, but greater than a pH
of 4.0,
4.5, 5.0, 5.5, 6.0, 6.2, or 6.5,
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26
Example 11 B
A fuel composition comprising: 1 ) an ECS metallic; 2) a co-combustion
catalyst, and optionally: 3) a hydrocarbon, 4) an ECS oxygenate, said fuel
optionally having a pH range of 10.5 to 4.0, 9.5 to 5.0, 8.5 to 6.0, 8.0 to
6.3,
7.8 to 6.2, 7.6 to 6.2; or optionally a pH less than 10.5, 10.0, 9.5, 9.0,
8.5, 8.0,
7.9, 7.8, 7.7., 7.6, 7.5, 7.4, 7.3, 7.2, 7.0, 6.9, 6.8, but greater than a pH
of 4.0,
4.5, 5.0, 5.5, 6.0, 6.2, or 6.5,
Example 12
The composition of Example 11, 11A, 11 B, wherein the a co-
combustion catalyst is selected from group consisting of
trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane,
tetramethylsiiane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-
aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane,
vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethyfsilane,
vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysifane,
tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane,
dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-
2 o tert-butylphosphite, trialkylphosphites trimethylphosphite,
triethylphosphite,
triisopropylphosphite, tributylphosphite), dimethylmethylphosphonate,
diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate,
triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate,
trimethylorthovalerate, trimethylorthoformate, including homolgues,
2 5 analogues, isomers, derivatives, and mixture thereof.
Example 12
The fuel composition of Example 11, 11 A, 19 B, wherein the co-
combustion catalyst is~ selected from group consisting of
3o trimethoxymethylsilane, dimethylphosphite, diethyphosphite,
tetramethoxymethane, tetraethoxymethane, trimethoxymethylmethane,
triethoxymethylmethane, methoxy methyl ester of acetic acid,
tetranitromethane, and mixture.
3 5 Example 13
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29
The fuel composition of Example 11, 11 A, 11 B, wherein the ECS
oxygenate is optionally selected from MTBE, ETBE, DMC, methanol, ethanol,
methylal, or mixture, and the ECS metal is a combustible compound is
selected from [2-(cyclohexenyl)ethyl]triethoxysilane, cyclohexenyl
dimethoxymethylsilane, benzyltrimethylsilane, N-(3-
(trimethoxysilyl)propyl)ethylenediamine, N-1-(3-
(trimethoxysilyl)propyl)diethylenetriamine, N-(3-
(trimethoxysilyl)propyl)ethylenediamine, 1-(trimethyl(siiyl)pyrrolidine,
triphenylsilanol, octamethyltrisiloxane, 2,2,4,4,6,6-
hexamethylcyclotrisilazane,
1o hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl
disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane,
tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-
aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-
benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol,
(trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide,
potassium propoxide, potassium isopropoxide, potassium butoxide,
potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide,
potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid,
potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium
2 o acetylenedicarboxylic acid, potassium pyrophosphate, potassium
dihydrogenphosphate, potassium benzoate, potassium chloride, potassium
hexoate (potassium salt hexoic acid), potassium acetate, potassium
diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-
aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium
napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate
(III}, potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt,
potassium sodium ferricyanide, or mixture.
Example 14
3 o A luminous combustion composition comprising:
I) a combustion improving amount of at least one ECS compound, said
compound characterized as reducing combustion temperature and/or
increasing burning velocity, having a minimum latent heat of evaporation of
21 kJ mol-' at its boiling temperature, and a minimum burning rate (as
measured by laminar Bunsen flame) of 40 cmlsec, said compound optionally
selected from the group consisting of alcohols, afdehydes, amines, carbonic
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esters, carboxylic acids, carbonates, di-carbonates, esters, di-esters,
ethers,
di-ethers, glycols, glycol ethers, ketones, nitrates, di-nitrates, peroxides,
hydroperoxides, phenols, said compound optionally containing at least one
alkyl, alkyloxy, dialkyl, dialkyloxy, polyalkyl, polyalkyioxy, aryl, amide,
acetate,
5 aldehyde, carbethoxy, carbomethoxy, carbonyl, carbonyldioxy, carboxyl,
ethoxalyl, ethoxy, formyl, glycolyl, glyoxylyl, hydroxyl, imide, methoxy,
methyfenedioxy or nitrosyl radical, including derivatives, analogues, and
homologues, and mixture;
II} a combustion improving amount of at least one non-leaded element
10 or derivative organic or inorganic compound containing said non-lead
element, selected from the group consisting of 1A, 2A, 3B, 4B, 5B, 6B, 7B, 8,
1 B, 2B, 3A, 4A, 5A, 6A, or 7A elements of the Periodic Chart of Elements
(CAS version), and mixture, wherein said element or derivative compound, is
combustible and optionally has a minimum heating value of 4,000 Kcal/kg;
15 III) a combustion co-catalyst; optionally a:
IV} stabilizer,
V) a co-fuel andlor oxidizer;
VI} wherein a luminous reaction zone extends from the surface of said
non-lead element or derivative compound in combustion, optionally, where
20 resultant oxides of said non-lead element are formed in the submicron
range;
and
V11) wherein said composition has a thermal efficiency of at least 2%
greater than unadjusted co-fuel (if any).
25 Example 15
A fuel composition comprising:
I) a hydrocarbon fuel base; and
II) an ECS oxygenate selected from the group consisting of C2 - C12
aldehydes, aldehydic acids, C2 -C12 ethers, ether acids, C1 - C15 alcohols,
30 C2 - C12 oxides, C3 - C15 ketones, ketonic acids, C3 - C15 esters,
othroesters, C3 - C12 diesters, C5 -C12 phenols, C3 - C20 glycol ethers, C2 -
C12 glycols, C3 - C20 alkyl carbonates, C3 - C20 dialkyl carbonates, C3 -
C20 asymmetrical alkyl carbonates, C3 - C20 di-carbonates, C1 to C20
organic and inorganic peroxides, hydroperoxides, carboxylic acids, amines,
nitrates, di-nitrates, oxalates, phenols, glacial acetic acids, C3 to C8
hyrodoxy
esters of acetic acid, methoxy methyl ester of acetic acid,acetic acid
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31
anhydrides, methoxy methyl ester of acetic acid, boric acids, orthoborates,
hydroxyacids, orthoacids, anhydrides, acetates, acetyls, formic acids,
nitrates,
di-nitrates, nitro-ethers; and
III} an ECS metallic selected from the group consisting of [2-
(cyclohexenyl)ethyljtriethoxysilane, cyclohexenyl dimethoxymethylsilane,
benzyltrimethylsilane, N-(3-(trimethoxysilyl)propyl)ethyienediamine, N-1-(3-
(trimethoxysilyi)propyl)diethylenetriamine, N-(3-
(trimethoxysilyl)propyl)ethylenediamine, 1-{trimethyl(silyl)pyrrolidine,
triphenylsilanol, octamethyltrisiioxane, 2,2,4,4,6,6-
hexamethylcyclotrisilazane,
1 o hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl
disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane,
tetraalkylsilanes {e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-
aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-
benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol,
(trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide,
potassium propoxide, potassium isopropoxide, potassium butoxide,
potassium sec-butoxide, potassium tert-butoxide, potassium pentoxide,
potassium tert-pentoxide, potassium phenoxide, potassium salt of acetic acid,
potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium
acetylenedicarboxyiic acid, potassium pyrophosphate, potassium
dihydrogenphosphate, potassium benzoate, potassium chloride, potassium
hexoate (potassium salt hexoic acid), potassium acetate, potassium
diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-
aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium
napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate
(III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt,
potassium sodium ferricyanide, or mixture; and,
IV) optionally a co-combustion catalyst; and
V) optionally a hydrocarbon base; and
VI) optionally an oxider, and
VII) wherein said fuel is a vapor phase composition characterized upon
combustion as having a luminous reaction zone extending from surface of
said element.
3 5 Example 15A
The above examples, wherein said fuel optionally contains a viscous
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32
hydrocarbon base andlor an oxidizer. Said fuel further characterized as
having a pH of 10.5 or less. When this fuel composition contains a
hydrocarbon base, said base may have a viscosity outside normal industry
standards (as set forth above). However, resultant fuel's viscosity is within
industry standards.
Example 16
The example compositions above, wherein the oxygenate is selected
from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and
1 o said ESC metal is optionally hexamethyldisilane.
Example 17
The example compositions above, wherein the oxygenate is selected
from MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and
said ECS metallic is optionally potassium ethoxide.
Example 18
The fuel compositions above, wherein the oxygenate is selected from
MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said
2o ECS metallic is optionally [2-(cyclohexenyl)ethyl)triethoxysilane.
Example 19
The fuel compositions above, wherein the oxygenate is selected from
MTBE, ETBE, TAME, methanol, ethanol, DMC, DEC, or mixture, and said
ECS metallic is optionally potassium hexacyanoferrate (II), potassium
hexacyanoferrate (I I I ), potassium hexacyanocobalt II- ferrate, potassium
hexacyanocobalt, potassium sodium ferricyanide, or mixture.
Examplg 20
3o The above compositions, wherein the oxygenate is a dialkyl carbonate
and the pH is substantially neutral.
Example 21
A fuel composition comprising:
I) a hydrocarbon fuel base, and
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33
II) a co-combustion agent selected from the group consisting of
trimethoxymethylsilane, ethoxytrimethylsilane, isobutyltriethoxysilane,
tetramethylsilane, dimethoxy-methyl-vinyl-silane, methyltriethoxysilane, 3-
aminopropyl-triethoxysilane, 3-aminopropyl-trimethoxysilane,
vinyltrimethoxysilane, diethoxydimethylsilane, dimethoxydimethylsilane,
vinyltris(2-butyldenaminooxy)silane, tetramethoxysilane, tetraethoxysilane,
tetrapropyloxysilane, tetraisopropylsilane, tetraisobutylsilane,
dimethylphosphite, dipropylphosphite, diethylphosphite, dibutylphosphite, di-
tert-butylphosphite, trialkylphosphites trimethylphosphite, triethylphosphite,
triisopropylphosphite, tributylphosphite), dirnethylmethylphosphonate,
diethylmethylphosphonate, potassium pryophosphite, trimethylorthoacetate,
triethylorthoacetate, trimethylorthobutyrate, triethylorthobutyrate,
trimethylorthovalerate, trimethylorthoformate, including homolgues,
analogues, isomers, derivatives, and mixture thereof.
Example 22
A fuel composition comprising: a hydrocarbon base; a combustion
improving amount of an ECS metal is a combustible compound is selected
from methylcyclopentadienylmanganese tricarbonyl, [2-(cyclohexenyl)ethyl]tri-
ethoxysilane, cyclohexenyl dimethoxymethylsilane, benzyltrimethylsilane, N-
(3-{trimethoxysilyl)propyl)ethylenediamine, N-1-(3-
(trimethoxysilyl)propyl}diethylenetriamine, N-(3-
(trimethoxysilyl)propyl)ethylenediamine, 1-{trimethyi(silyl)pyrrolidine,
triphenylsilanol; octamethyltrisiloxane, 2,2,4,4,6,6-
hexamethylcyclotrisilazane,
2 5 hexamethylcyctrisiloxane, hexamethyldisilane, 1,1,1,3,3,3-hexamethyl
disilazane, hexamethyldisiloxane, hexamethyldisilthiane, allyltributylsilane,
tetraalkylsilanes (e.g. tetraethylsilane, tetrabutylsilane, etc.), 3-
aminopropyltriethoxysilane, benzytrimethylsilane, benzytriethylsilane, N-
benzyltrimethylsilylamine, diphenylsilanediol, dihexylsilanediol,
3o (trimethylsilyl)cyclopentadiene, potassium methoxide, potassium ethoxide,
potassium propoxide, potassium isopropoxide, potassium butoxide,
potassium sec-butoxide, potassium tart-butoxide, potassium pentoxide,
potassium tart-pentoxide, potassium phenoxide, potassium salt of acetic acid,
potassium hydrogenphthalate, potassium hydrogensulfate, monopotassium
35 acetylenedicarboxylic acid, potassium pyrophosphate, potassium
dihydrogenphosphate, potassium benzoate, potassium chloride, potassium
hexoate (potassium salt hexoic acid), potassium acetate, potassium
diphenylphosphide, potassium trimethylsilonalate, potassium phthalic acid, P-
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39
aminobenzoic acid potassium salt, monopotassium L-aspartic acid, potassium
napthenate, potassium hexacyanoferrate (II), potassium hexacyanoferrate
(III), potassium hexacyanocobalt II- ferrate, potassium hexacyanocobalt,
potassium sodium ferricyanide, or mixture; optionally a combustion improving
amount of an ECS oxygenate selected from MTBE, ETBE, DMC, methanol,
ethanol, or mixture; optionally a co-combustion catalyst.
Example 23
The composition of 21, wherein the ECS metallic is selected from
1 o potassium ethoxide, [2-(cyclohexenyl}ethylJtriethoxysilane, potassium
hexacyanoferrate (II), potassium hexacyanoferrate (III}, potassium
hexacyanocobalt I I- ferrate, potassium hexacyanocobalt, potassium sodium
ferricyanide, or mixture.
Example 24
The composition of 21, wherein an ESC oxygenate is employed.
Example 25
The composition of 21, containing a co-combustion agent iselected
2 0 from the group consisting of trimethoxymethylsilane,
ethoxytrimethylsilane,
isobutyltriethoxysilane, tetramethylsilane, dimethoxy-methyl-vinyl-silane,
methyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-
trimethoxysilane, vinyltrimethoxysilane, diethoxydimethylsilane,
dimethoxydimethylsilane, vinyltris(2-butyldenaminooxy)silane,
2 5 tetramethoxysilane, tetraethoxysilane, tetrapropyioxysilane,
tetraisopropylsilane, tetraisobutylsilane, dimethylphosphite,
dipropyiphosphite,
diethylphosphite, dibutylphosphite, di-tert-butylphosphite, trialkylphosphites
trimethylphosphite, triethylphosphite, triisopropylphosphite,
tributylphosphite),
dimethyimethylphosphonate, diethylmethylphosphonate, potassium
3 o pryophosphite, trimethylorthoacetate, triethylorthoacetate,
trimethytorthobutyrate, triethylorthobutyrate, trimethylorthovaferate,
trimethylorthoformate, including homolgues, analogues, isomers, derivatives,
and mixture thereof.
35 Example 26
The example of various fuel compositions contained herein, containing
a hydrocarbon base, whose viscosity is greater than acceptable industry
standards (as set forth above); wherein the resultant fuel composition has a
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pH of less than 11 (more preferrable less than 10.5, 10.0, 9.5, 9.0, 8.5, 8.0,
7.5, 7.0, 6.9, 6.8, but a above 4.5, 5.5, fi.0, 6.3, 6.5 or the other ranges
set
forth herein, and wherein the resultant fuel meets acceptable industry
standards for viscosity.
5
Example 27
An improved fuel composition containing an alkyl carbonate (dimethyl
andlor diethyl carbonate) an ECS metal selected from an alkali/alkali earth
1o metal derivative, and optionally a co-combustion catalyst, a hydrocarbon
base
or co-fuel(propellant}, andlor oxidizer, wherein the pH is less than about
10.5,
9.0, 8.0, 7.5, 7.0, 6.9, or less, but greater than 4.5, 5.5, or 6.3.
STABILIZERS
In the practice of this invention, certain metallic (non-metallic)
formulations are hydroscopic or tend to destabilize particularly when in
combination with hydrocarbon co-fuels. For example, Applicant has found
alkali/alkali earth metals to be particularly susceptible to destabilization,
especially where there is a presence of water. Other formulations need to be
stabilized due to the presence of Applicant's ingredients. Fuel
destabilization
can be undetectable, to mild, to severe, and ultimately result in the complete
fuel oxidation.
Thus, it is an embodiment to employ certain classes of stabilizers.
Several are also act as co-combustion agents andlor ECS compounds.
Principal stabilizers include ployalkyloxysilanes, glycols, glycol ethers,
including alkylene glycols, glycol esters, glycol acetates, and aromatic
hydrocarbons, aromatic solvents, including toluenes, naphthalenes, napthas
and the like.
Non-limiting examples of contemplated polyalkyioxysilanes include
trimethoxymethylsilane, and those compounds, including homologue,
analogue, isomers, and derivative, which are set forth above in co-
combustion catalyst. Applicant has found TMMS is be particularly useful.
Non-limiting examples of glycols and glycol ethers contemplated
include C3 to C15 alkylene glycol monolpoly alkylethers, including ethylene
glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, ethylene glycol
polyalkyl ethers, diethylene glycol poiyalkyl ethers. Other non-limiting
examples of glycols and related compounds include alkyioxy polyethylene
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36
glycols, alkyloxypolyglycols, alkyloxypolyglycol ethers, alkylene glycol
acetates, alkylene glycolslesters/etherslacetatesl
diacetateslamineslglycerols/formateslcarbinols/carbitolsl
nitrites, and the like, and polyalkylene glycolslesters/ethersl
acetatesldiacetateslamineslglycerols/formates/carbinolslcarbitolslnitriles,
and
the like.
Non-limiting examples include: diethylene glycol dimethyl ether,
diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene
glycol diisopropyl ether, diethylene glycol dibutyl ether, diethyiene glycol
1o dipentyl ether, diethylene glycol dihexyl ether, diethyiene glycol
monomethyl
ether, diethylene glycol monoethyl ether, diethyiene glycol monopropyl ether,
diethylene glycol monoisopropyl ether, diethylene glycol rnonobutyl ether,
diethylene glycol monopentyl ether, diethylene glycol monohexyl ether,
ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol
dipropyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl
ether,
ethylene glycol dipentyl ether, ethylene glycol dihexyl ether, ethylene glycol
monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol
monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol
monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol
2,o monohexyl ether, methoxy diethylene glycol, ethoxy diethylene glycol,
propoxy diethylene glycol, butoxy diethylene glycol, methoxy ethylene glycol,
ethoxy ethylene glycol, propoxy ethylene glycol, butoxy ethylene glycol,
methoxyglycol, ethoxyglycol, propoxyglycol, butoxyglycol, pentoxyglycol,
methoxydiglycol, ethoxydiglycol, propoxydiglycol, butoxydiglycol,
2 5 pentoxydiglycol, methoxytriglycol, ethoxytriglycol, propoxytriglycol,
butoxytriglycol, pentoxytriglycol, methoxytertglycol, ethoxytertglycol,
propoxytertglycol, butoxytertgiycol, pentoxytertglycol. Also contemplated are
Union Carbide's Cellosolve solvents, including Methyl Cellosoive, Ethyl
Cellosolve, Propyl Cellosolve, Butyl Cellosolve, Pentyl Cellosolve, Hexyl
3o Cellosolve; Union Carbine's Carbitol solvents, including Methyl Carbitol,
Ethyl
Carbitol, Propyl Carbitol, Butyl Carbitol, Pentyl Carbitol, diethyl carbitol
and
the like.
Additional non-limiting examples of other acceptable glycols include:
triethylene glycol, 3-aminopropyl ether triethylene glycol, diacetate
triethylene
35 glycol, monobutyl ether triethylene glycol, monomethyl ether triethylene
glycol,
monopropyl ether triethylene glycol, tetraethylene glycol,
dibutoxytetraethylene glycol, diacetate tetraethylene glycol, aminopropyl
ether
tetraethylene glycols, monobutyl ether tetraethylene glycol, monomethyl ether
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37
tetraethylene glycol, dimethyl ether tetraethylene glycol, diethyl ether
tetraethylene glycol, monoethyl ether tetraethylene glycol, monopropyl ether
tetraethylene glycol, tetraethylenepentamine, tripropylene glycol,
tetrapropylene glycol, dipropylene glycol, propylene glycol monornethyl ether,
propylene glycol monopropyl ether, ethylene glycol monobutyl ether,
propylene glycol monomethyl ether, diethylene glycol monoethyl ether,
diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether,
tripropylene glycol monomethyl ether, propylene glycol, ethylene glycol,
hexylene glycol, dipropylene glycol, diethylene glycol, triproylene glycol,
tetraethyiene glycol, tetramethylene glycol, tetrapropylene glycol,
polyethylene
glycol (200, 300, 400, 600, 1000, 1500, 1540, 4000, 6000 Ashland Chemical),
polyethylene glycol 3350 (Spectrum), polypropylene glycol (P400, P1200,
P2000, P4000 Ashland Chemical), diacetate diethylene glycol, diethyl ether
diethylene glycol, dioleate diethylene glycol, mono (2 hydroxylpropyl) ether
diethylene glycol, monomethyl ether acetate diethylene glycol. In the practice
of this invention, homologues, analogues, isomers and derivative of the above
stabilizers are contemplated.
Other non-limiting stabilizers include nonvolatile, nonion compounds,
including alkylanoic acids (ethanoic, propanoic, butanoic, pentanoic, and
2 o hexanoic acids), their acetates, esters and ethers. Related ethenes,
butenes,
propenes, hexenes, pentenes are acceptable.
Other stabilizers of this invention may be selected from alcohols,
ketones, ethers, esters, phenols, acetals, acid azides, acid halides, acids
and
acid derivatives (aldehydic, aliphatic dicaroxylic, alipatic monocarboxylic,
aliphatic polycarboxylic, amino acids, hydroamic, hydroxyacids, imidic,
ketonic, nitrolic, orthoacids, peracid, etc.), acetic acids, acetic
anhydrides,
acetic acid esters, aldehydes, aliphatic hydrocarbons (including high boiling
point material), amides, amidines, amidoximes, anhydrides, aromatic
hydrocarbons, azides, azines, azelates, azo compounds, betaines,
bromoactealdehydes, bromoethanes, bromoethylenes, bromoacetic acids,
bromobutanes, bromobutenes, bromobutylenes, bromo ethers, di bromo
compounds, butyric acids, butanoic acids, butanoic esters, esters,
orthoesters, acetates, ethylene acetates, esters, hydrates, hydrides,
hydroperoxides, hydroxamic acids, hydroxyacids, imides, imidic acids, imines,
ketenes, lactams, lactones, glycolic acids, butyric acids, heptic acids,
valeric
acids, isocaproic acids, nitrolic acids, nitrosolic acids, octanoic acids,
esters of
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octanoic acids, opium compounds, orthoacids, ortho borates, octynes,
octenes, octanones, oximes, esters of oxalic acid, oxalic acids, ethanoic
acids, esters of ethanoic acids, esters of nonanoic acids, propanoic acids,
esters of propanoic acid, pentanoic acids, propanediones, propanones,
ethenes, propenes, butenes, pentanes, petenes, hexenes, esters of
pentanoic acids, butanoic acids, oxalic esters, esters of butanoic acids,
pentaneoic acids, esters of pentaneoic acids, pentanedioic acids, esters of
pentanedioic acids, 2- or 3-pentanones, hexanoic acids, esters of hexnoic
acids, heptanoic acids, esters of heptanoic acids, esters of formic acid,
glycol
1o esters, octenes, octanone(s), oxalic acids, esters of oxalic acids, esters
of
hexanoic acid, hexanones, pentanedials, peroxides, furans, esters of 2-
furancarboxylic acids, furfurals, propenes, propenoic acids, esters of
propenoic acids, ethers, butenedioc acids, bromo-alcohols, ethanetriols,
propanetriols, butanetriols, pentanetriols, naphthalenes, hexanetriols,
septanetriols, octanetriols, nitrobenzene, iodobenzene, 2-nitrophenol,
cyclohexylamine, dibutylamine, diethylamine, diethylenetriamine,
diethylethanolamine, diisopropanolamine, morpholine, triethylamine,
triethylenetetramine, triisopropanolamine, amino methyl propanol, propylene
oxide, propylene glycol, 1,2 propanediol carbonate, salicylic acid, succinic
2 o acid, tartaric acid, tannic acid, 2,2,4-trimethylpentane,
dimethylbenezenes,
dimethyl formamide, n-methyl-2 pyrrolidone, amyl alcohol (primary),
cyclohexanol, 2-ethylhexanol, methyl amyl alcohol, tetrahydrofurfuryl alcohol,
TEXANOL ester alcohol (Eastman Chemical), UCAR Filmer IBT (Union
Carbide Corp.), amyl acetate, dibase ester, ester solvent EEP (Ashland
Chemical), 2-ethylexyi acetate, glycol ether acetates (DB, DE, DPM, EB, EE,
PM, Ashland Chemical), isobutyl acetate, isobutyl isobutyrate, n-pentyl
propionate, cyclohexanone, 2-hexanone, 3-hexanone, 2-methyl-3-pentanone,
3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone,
diactone alcohol, diisobutyl ketone, ethyl methyl ketone, pinacolone,
3o methone, 3,3-Biphenyl 2-butanone, 1-hydroxy 2-butanone, 3-hydroxy-(dl) 2-
butanone, 3-methyl 2-butanone, oxime 2-butanone, 2-butanone, 2-methyl
proponoic acid, cyclopentanone, cyclopropyl methyl ketone, 2-
tetrahdrofurylmethanol, cyclohexanone, isophorone, methyl amyl ketone,
methyl isoamyl ketone, acetonylacetone, acetic anhydride, benzyl alcohol (a-
hydroxytoluene) and variations, triisobutylene, tetraisobutylene, allylidene
diacetate, acetol, 1 (4-methyoxyphenyl~2- propanone, isobutyrophenone,
acetonylbenzene, butyl acetate, aliphatic alcohols, n-butyibutyrate, cetyl
alcohol, cyclohexane, cyclohexanol, cyclohexanone, diethylphthalate, 2,5
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dimethoxytetrahydofuran, p-dioxane, 1,3-dioxane, 1,4-dioxane, 5-hydroxy-2-
methyl-1,3-dioxane, glycol methylene ether, propylene carbonate,
isopropylene carbonate, glycerin, 1,2,3-propanetriol, heptane, n-hexane, 2-
methylpentane, 3-methylpentane, methycyclopentane, 1,4-benzenediol,
isopentyl alcohol, methyl ethyl ketone, 4-methyl-2-pentanone, methyl propyl
ketone, diisopropyl ketone, 1- or 3- or 4- or 5 hydroxy 2- pentanone,
diisopropyl ketone, methyl propyl ketone, diacetone alcohol, isopentyl phenyl
ketone, 2-pentanone, diacetone alcohol, isopentyl phenol ketone, n-butyl
phenol ketone, i-butyl phenol ketone, 2-butyl phenol ketone, isopropyl
acetone, 2- or 3- or 4-methoxy phenol, dehydrate oxalic acid, pentane,
phenol, 3-methoxy phenol, 1,2 or 1,3 or 1,4 or 2,4 or 2,5 or 2,6 or 3,4 or 3,5
dimethyphenol, 1-octene, isobutyl 2-methylpropanate, 2-phenoxyethanol,
ethylene acetate, ethyl acetate, acetonphenone, benzyl acetate, 1,3 or 1,4 or
2,3 butanediol, formaldehyde, formamide, triethyl ester orthoacetic acid,
trimethyl ester orthoacetic acid, oxalic ester (diethyl ester oxalic acid),
methyl
hydroperoxide, ethyl hydroperoxide, acetyl peroxide, ethyl peroxide, di(tert-
butyl) peroxide, acetic anhydride, 2-ethyl butyl ester acetic acid, cresyl
acetates, methylglycolate, methylester phenoxy acetic acid, nitrite acid,
butyric acid, butanoic acid, 2-butyl butanoic acid, 2-ethyl butanoic acid,
tert-
2o butyl butanoic acid, butyl nitril, propyl ester butanic acid, diethyl
acetic acid,
acetonacetic acid, allyl acetoneacetate, diacetylacetone, acetylacetone, ethyl
ester benzoic acid, butanic methyl ester, butanic ethyl ester, butanic propyl
ester, isoamyl butyrate, propyl ester butanoic acid, hexyl ester butanoic
acid,
2-methyl-{d) butanoic acid, 2-methyl-{dl) butanoic acid, ethyl ester 3-methyl
butanoic acid, methyl ester 3-methyl butanoic acid, isopropyl ester 3-methyl
butanoic acid, 2, 2-dimethyl butanoic acid, allyl ester butanoic acid, amide
butanoic acid, N,N-dimethyl butanoic acid, anhydride butanoic acid, butyl
ester butanoic acid, pentyl ester butanoic ester, propyl ester butanoic acid,
diethylacetic acid, 2-methyl-(d) butanic acid, methyl acetoacetate, ethyl
3o acetoacetate, diethyl acetal, acetate, acetyl acetone, 2,2-dimethyl ether
ester
propanoic acid, 2-oxo ethyl ester propanoic acid, 2-oxo methyl ester
propanoic acid, 2-oxo isobutyt propanoic acid, 2-oxo-isopropyl propanoic acid,
methyl ester propanoic acid, ethyl ester propanoic acid, propyl ester
propanoic acid, propanoic acid, giyceric acid, 1, 2 dimethoxethane, 1,2
3 5 ethanediol, 1,3 butanediol, 2,3 butanedione, 1,2,3 butanetriol, 1,2,4
butanetriol, glutaric acid, glutaric anhydride, glutaronitrile, 1,5
pentanedial,
glutaraldehyde, 2,4 pentadione (CH3COCH2COCH3), pentanic acid, levulinic
acid, {CH3COCH3COC02H), dimethyl suberate, octanedioc acid, i,2,3
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pentanetriol, 2,3,4 pentanetriol, formamide, bromoacetic acid, acetamide,
pyruvic acid, methyloxyacetic acid, propionamide, allyl bromide, diethyl
acetal
propenal, diacetate propenal, propenal, 1,2 propanediol, 1,3 propanediol,
glycerol, trimethyl ether glycerol, acetylpropionyl, acetylacetone, propionic
5 acid, methyloxyacetic acid, propionamide, malefic anhydride, eis-crotonic
acid,
dimethyl oxalate, isobutyric acid, hydroxyisobutyric acid, ethanetriols,
propanetriols, butanetciols, pentanetriols, hexanetriols, septanetriols, 1,2,3
butanetriol, 2,3,4 pentanetriol, 1,2,3 pentanetriol, 1,2,3 propanetriol,
dioxypentane, 2,4-dioxypentane, hexantriols, monobutyl ether triethylene
l0 glycol, propanoic acid, anhydride propanoic acid, butyl ester propanoic
acid,
ethyl ester propanoic acid, pentyl ester propanoic acid, octyl ester propanoic
ester, pimelic acid, suberic acid, azelaic acid, methacrylic acid,
dibromobutanes (e.g. 1,2; dl-2,3; 1,4; meso-2,3; etc), tribromobutanes (e.g.
1,1,2; 1,2,2; 2,2,3; etc.), diacetamide, di(2-bromoethy!) ether, 2-
ethylhexanol,
15 furfuryl alcohol, 2-propanone, 2-propen-1-ol, ethyl methanate, methyl
ethanate, pentadioic acid, pentadioic acid diethyl ester, pentadioic acid
dimethyl ester, pentadioic acid dinitril, 2,3-pentaedione, 2,4-pentadione,
1,2,3-
pentanetriol, pentanoic acid, pentanoic acid methyl ester, pentanoic acid
butyl
ester, pentanoic acid ethyl ester, pentanoic acid furfuryl ester, pentanoic
acid
2 o hexyl ester, pentanoic acid nitrite, pentanoic acid octyi ester, pentanoic
acid
pentyl ester. Also included are alkyllpolyalkyl/alkylene/ polyalkylene
carbinols
(non-limiting examples include, carbinol, methyl carbinol, ethyl carbinol,
propyl
carbinol, methyl ethyl carbinol, butyl carbinol, diethyl carbinol, methyl n-
propyl
carbinol, dimethyl isobutyl carbinol, ethyl isopropyl carbinol, ethyl
isopropyl
2 5 methyl carbinol, diisopropyl carbinol, triethyl carbinol, isoamyl
carbinol,
dimethyl n-propyl carbinol, 2-butyl methyl carbinol, methyl isobutyl carbinol,
diethyl methyl carbinol), methyl propyl ketone, methyoxacetic acid,
acetoacetic acid, methyl acetate, tert-amyl acetate, ethyl acetate, glycol
diacetate, 1,2-propendiol carbonate, 1,2-propanediol, 1,3-propanediol,
30 adiponitrile, 2-amino-2-methyl-1-propanol, triethyienetetrarnine, butyl
acetate,
dimethylaniline, di-n-propylaniline, methyl isobutyl ketone, n-amyl cyanide,
di-
n-butyl carbonate, diethylacetic acid, diethyl formamide, diisobutyl ketone,
ethyl benzoate, ethyl phenylacetate, heptadecanol, 3-heptanol, n-heptyl
acetate, n-hexy ether, methyl isopropyl ketone, 4-methyl-n-valeric acid, o-
35 phenetidine, tetradecanol, triethylenetetramine, 2,fi,8-trimethyl 4-
nonanone,
ethanedial, carbonate 1,2-ethanediol, diacetate 1,2-ethanediol, dimethyl ether
1,2-ethanediol, dinitrate 1,2-ethanediol, n,n-di-methyl formic acid, n,n-di-
ethyl
formic acid, butyl ester formic acid, isoamyl formate, octyl ester formic
acid,
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41
pentyl ester formic acid, propyl ester formic acid, isobutyl ester formic
acid,
propargl acetate, 2-methoxyethanol, cyclopentanone, cyclopropyl methyl
ketone, ethyl propenoate, 3-methyl-2-butanone, phenol, 2-or 3-or 4-
methoxyphenol, propanoic anhydride, cyclohexanone, 4-methyl-3-penen-2-
one, 2- or3- Hexanone, [2, 3 or 4]-methyl-[2 or3]-pentanone, 2-heptanone,
methyl phenyl ketone, diethyl benzene, and azulene.
Fuel soluble aromatic hydrocarbons are acceptable stabilizers.
Benzene ring compounds and derivative are contemplated (including toluene,
phenyl and derivative). Toluene is a preferred. Non-limiting examples of
1 o aromatic hydrocarbon stabilizers include benzene, toluene, benzaldehyde,
benzin, benzl alcohol, toluene bromides, toluene cresols, toluene dimethyl
amino compounds, toluene ethers, toluene oxyls, toluene alcohols. For other
example, see the benzene ring compounds and derivative in CRC Handbook
in Chemistry and Physics. 75th Ed, Lide, CRC Press (1994-1995), "Phyical
Constants of Organic Compounds," Oroanic Chemistry 6th Ed, T.W.G.
Solomons, John Wiley & Sons, N.Y., (1995), Physical Chemistry, 5th Ed,
P.W. Atkins, Oxford University Press, U.K. (1994), Ph sly cal Organic
Chemistry, 2 Ed, N.S. Issacs, John Wiley & Sons, N.Y. (1995) and Lan e's
Handbook of Chemistry, 14th Ed, J.A. Dean, McGraw-Hill, N.Y. (1992}, are
hereby incorporated herein by reference.
Examples 27A
The above compositions containing an ECS metallic selected from
2 5 group of alkali or alkali earth metals, including derivative compounds,
said
composition additionally containing a stabilizer selected from the group of
trimethoxysilane, toluene, a glycol, a glycol ether (including
mono/polyalkylene glycol monolpolyalkylethers), including homologue,
analogue and derivative compounds and mixture.
pH MODIFICATION
A desirable pH range of the fuel composition of the present invention,
3 5 particularly when DMC is employed, is from approximately 4.5 to
approximately 10.5, with a more desirable pH range of from approximately 4.5
to approximately 9.5. An even more desireable pH range is from
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approximately 4.5 to 9Ø Another highly preferred pH range is from
approximately 5.5. to 8Ø A preferred pH range is from approximately 4.5 to
approximately 6.5. The most preferred pH range for the fuel composition of
the present invention is from approximately 6.3 to approximately 6.8. It is an
object of this invention to keep pH as close to neutral as possible, such that
if
alkaline, it is only weakly alkaline (i.e., preferably equal or less than
11.0,
10.5, 10.0, 9.5, 9.0, 8.5, 8.0 pH), but that it preferably be either
substantially
neutral (i.e., 6.5 to 7.5) or slightly acidic (6.3 to 6.9 pH).
When the pH of the fuel composition of the present invention is less
l0 than 11.0, preferably 10.5 or below, 9.5 or below, and more preferably 8.5
or
below, the fuel, whether anhydrous or hydrous, may be stored at ambient
temperature (65°F) and as high as 95°F for up to 6 months, or
more, absent
hydrolysis.
For example, Applicant tested a fuel containing 5% by volume dimethyl
carbonate, 95% by volume unleaded regular grade commercially available 87
octane (R+M)12, 118 gram Mnlgal of methylcyclopentadienyl manganese
tricarbonyl, a pH of 7.0, and 5% by volume of water, which was stored for six
months at temperature ranging from 65°F to 90°F. Afterwards, the
fuel
exhibited no hydrolysis.
2 o The same fuel composition was subsequently titrated with glacial
acetic acid to a pH of 6.4, still containing 5% by volume of water and was
then
stored for sax months under the same conditions. After which period the fuel
exhibited no signs of hydrolysis.
However, the same fuel composition was prepared with a pH of
approximately 11.0, and contained 5% by volume of water and was stored for
six months under the same conditions. The fuel showed slight evidence of
hydrolysis. The same fuel with an adjusted a pH of 12.5, however, showed
even stronger evidence of hydrolysis.
It should be appreciated that although acetic acid was used to acidify
the pH of the fuel in the present test case, other fuel soluble acids,
including
but not limited to benzoic acid derivatives e.g. 2,4-dimethyl benzoic acid,
methyl red, p-tert-butylbenzoic acid, 2-(1-methylethyl) benzoic acid, benzoic
acid anhydride, 4-benzoyl benzoic acid, 2,4-dihdroxy benzoic acid, 2,4-
dimethyl-benzoic acid, 3-ethoxy benzoic acid, 2-hydroxy-4-methyl benzoic
acid, 2-hydroxy benzontrile, 4-methoxy benzotrile, acetic acid derivatives,
e.g.
anhydride acetic acid, chloroacetic acid, decyl ester acetic acid,
dibromoacetic acid, and the like, may be employed. Fuel soluble acids are
incorporated by reference. See for example CRC Handbook of Chemistry and
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43
Physics. 75th Ed, Lide, CRC Press (1994-1995) "Dissociation Constants for
Inorganic Acids and Bases," and "Dissociation Constants for Organic Acids
and Bases," incorporated herein by reference. If an additive acid is employed,
it is preferred it be compatible with the base fuel, the metallic and have low
toxicity, low corrosivity, and be as envimomentally friendly as possible.
Naturally, acidic fuel components, which are indigenous to the fuel
composition, e.g. base fuel, ECS metallic, ECS oxygenate, or an additional
co-combustion catalyst, or ECS component (e.g. aldehydic acids, ketonic
acids, carboxylic acids, hydroxyacids, orthoacids, formic acids, and the like)
should be ultilized to achieve target pH's, prior to addition of an additive
acid.
Individual circumstances will dictate proper approach and additive. Acidic
metals of this invention may be used individually andlor in conjunction with
one or more other metallics to reduce pH. Non-limiting examples of such
acidic metallics include binary, ternary and higher metallic acid salts,
hydroxy
acids, phosphoric acids, etc., oxamic acid, lithium acetate acid, lithium salt
acetic acid, propanoic acid lithium salt, cyclohexanebutyric acid lithium
salt,
aminobenzole acid lithium salt, borate ester, dimethyl borate, di-n-butyl
borate, dicyclohexyl borate, didodecylborate, di-p-cresyl borates, boric
acids,
orthoborates, phenylboronic acid, diphenylboronic acid, o-tolylboronic acid, p-
2 o tolylboronic acid, m-tolylboronic acid, cylohexylboronic acid,
cylohexenylboronic acid, cyclopentylboronic acid, methylphenylboronic acid,
methylcylohexylboronic acid, methylcyclopentylboronic acid,
methylbenzylboronic acid, dimethylphenylboronic acid,
dimethylcylohexylboronic acid, dimethylcyclopentylboronic acid,
dimethylbenzylboronic acid, diphenylboronic acid, dibenzylboronic acid,
dicylohexylboronic acid, dicylohexenylboronic acid, dicyclopentylboronic acid,
methyldiphenylboronic acid, bis[(methyl)cylohexyl]boronic acid,
bis[(methyl)cyclopentyl]boronic acid, bis[(methyl)benzyl]boronic acid,
bis[(dimethyl)phenyl]boronic acid, bis[(dimethyl)cylohexyl]boronic acid,
bis[(dimethyl)cyclopentyl]boronic acid, or bis[(dimethyl)benzyl]boronic acid.
Other acidic metallics are set forth below and contemplated.
Example 28
A method of minimizing hydrolysis of a vapor phase combustion fuel
composition comprising the steps of:
providing a symmetrical lower dialkyl carbonate;
providing an combustion improving amount of at least one combustible
compound containing at least one element selected from the group consisting
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of aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium,
cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium,
magnesium, manganese, molybdenum, nickel, niobium, phosphorus,
potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium,
silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum,
actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium,
protactinium, tantalum, neodymium, uranium, tungsten, promethium,
neptunium, samarium, plutonium, ruthenium, osmium, europium, americium,
fiodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver,
1o gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium,
thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium,
lutetium,
astatine, mixture thereof, including their organic and inorganic derivative
compounds;
providing a hydrocarbon;
mixing said carbonate, said combustible compound, and said
hydrocarbon so as to produce a fuel composition having a pH of from 4.5 to
9.5, and
store said composition at a temperature of no more than 90°F for up tp
6 months, or longer, and,
2o combusting said fuel in an engine or combustor, wherein vapor phase
composition occurs characterized as having a luminous reaction zone
extends from surtace of said element.
Example 29
The method of Example above, wherein said fuel is stored at an
average temperature of 65EF for 6 months, prior to combustion.
Example 30
A method of mitigating handling hazards of an alkali/alkali earth metal
3 o based vapor phase combustion fuel composition, comprising the steps of:
providing an combustion improving amount of a combustible
compound containing at least one element selected from an alkali metal or
alkali earth metal, and mixture; and a stabilizer.
3 5 Example 30A
The method of example 30, optionally providing an acidic ECS
metallic; and
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optionally providing a hydrocarbon; and
optionally providing an ECS oxygenate; and
mixing said composition.
5 Example 30B
The method of examples 30, 30A, wherein the composition's target pH
ranges up to 9.5.
Example 30C
10 A method of mitigating handling hazards of an alkalilalkaii earth metal
based vapor phase combustion fuel composition, comprising the steps of:
providing an combustion improving amount of at least one combustible
compound containing at least one element selected from an alkali metal or
alkali earth metal; and
15 optionally providing an acidic ECS metallic; and
optionally providing a hydrocarbon; and
optionally providing an ECS oxygenate, and
mixing said composition, said combustible compound, and said
hydrocarbon so as to produce a fuel composition having a pH of from 4.5 to
2 0 9.5, and
combusting said fuel in an engine or combustor, wherein vapor phase
composition occurs characterized as having a luminous reaction zone
extends from surface of said element.
2 5 Example 31
The above example 30, wherein the target pH is ranges from 6.0 to
8Ø
Example 32
3o The above example 30, wherein the target pH is achieved by providing
at least one acidic ECS metallic or acidic ECS oxygenate.
Example 33
35 The above example 30, wherein the acidic ECS metallic is a
phosphorus derivative.
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Anhydrous fuels or substantially anhydrous fuels are contemplated and
particularly preferred when employing water reactive group la, Ila, Ilb, IIIA
metals and derivative compounds. Circumstances where hydrocarbon bases
require anhydrous compositions are contemplated, e.g. jet aviation
applications, etc.
Although anhydrous fuels are preferable, fuel compositions of the
present invention may contain water.
It is noted, acidity level of Applicant's fuels may be measured in terms
of equivalents, e.g., equivalents of KOH required to neutralize the fuel
l0 composition. The fuels of the present invention show improved operation at
acidity levels which are 100%, 150%, 200%, 300%, or more, above such
standards. Acidity levels below such standards, including those at least 50%
less, are expressly contemplated.
Also by way of example, when the fuel compositions of the present
invention are used in jet turbine engines, such fuels typically must meet
ASTM D 1655 specifications (incorporated herein by reference) or other
international specifications, including maximum acidity levels ASTM D 3242
and IP 354 standards. However, it is believed that the increased efficiency of
the fuels of the present invention are less destructive to engines during
2 o combustion, and operation with lower pH's than presently acceptable.
International, industry and government fuel standards, including ASTM, IP,
GOST, DERD, MIL, AN, U.S. Clean Air Act, California Air Resources Board,
and SwedishlEuropean EPEFET standards, etc., governing hydrocarbon
fuels containing applicant's ECS oxygenateslmetallics are incorporated herein
2 5 by reference.
It is an embodiment, especially when employing DMC, to
maintain a pH in the desired target range and store said fuel at temperatures
at or below 90° F.
3 o Example 34
A method of maintain fuel stability, said method comprising:
mixing a fuel composition containing an ECS metallic and a dialkyl
carbonate (preferably DMC), and adjusting pH of the fuel composition to less
than 10.5 pH.
In addition to the preferred pH ranges described above, it is further
contemplated that Applicant's pH adjusted hydrocarbon based fuels will
additionally contain known additive, including but not limited to
antioxidants,
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co-solvents, metal deactivators, detergents, dispersants, corrosion
inhibitors,
mutual solvents, oxygenated anti-knock compound (e.g. hydrocarbyl ethers,
alcohols, etc.), conventional combustion catalysts including ferrous picrate,
Li
and LH promoters, other additive, and additive set forth in incorporated PCT
Applications. The metal deactivators contemplated in this invention are known
in the art and incorporated herein by reference.
A preferred fuel of the present invention comprises 1 ) dimethyl
carbonate or dimethyl carbonate, representing 0.1 % to 99.5% wt of
composition; 2) at least one metal as set forth below, representing 0.01 % to
99.5% wt of composition; optionally a metal deactivator representing
0.00001 % to 10.0% wt of composition, or an antioxidant representing
0.00001 % to 10.0% wt, or a detergent/dispersant representing 0.00001 % to
10.0% wt, or an ignition promoter representing 0.000001 % to 20.0% wt, or a
demuisifier representing 0.00001 % to 10.0% wt, or a co-solvent or salt
representing 0.000001 % to 40.0% wt, or a hydrocarbon representing 0.1 % to
99.0% volume of the composition, or a co-combustion catalyst (described
below) representing 0.000001 % to 80.0% wt, or mixture. Said fuel is
constructed with a pH no greater than 11.0 or 10.5, and preferably less than
9.5. More preferably, the pH is from 6.3 to 6.8. When such fuel is a jet
aviation turbine hydrocarbon based-fuel, preferred acidity does not exceed
equivalent of 0.1 mg KOHIg.
As described in the aforementioned PCT applications, the presence of
a co-solvent is also preferred, so long as pH is maintained. Co-solvents that
enhance mutual solubility of fuel components, fuel stability, water tolerance
are preferred (e.g. C1 to C12 alcohols, alkanolamines, etc.). These are known
in the art and incorporated herein by reference. Additionally, co-solvents
that
increase flash point or reduce vapor pressure are contemplated. Non-limiting
examples include, ethanetriols, propanetriols, butanetriols, 1,2,3
butanetriol,
pentanetriols, 1,2,3 pentanetriol, 2,3,4 pentanetriol, hexanetriols,
septanetriols, octanetriols, or tertraethylene glycol, triethylene glycol, 1-
octene, high flash point ketone, naphthalenes, triethylene glycol,
trimethylene
glycol, isopropyl acetone, diisopropyl acetone, diisopropyl diacetone,
diethylene acetate, diethylene diacetate, ethylene acetate compound, phenol,
or other flash point temperature reducing co-solvent set forth in
aforementioned PCT Applications. Co-solvents should not be corrosive or
hazardous to fuel systems.
It is desirable the resultant fuel be constructed to have an average
latent heat of vaporization (LHV) no less than typical industry standards.
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Preferred LHV's are generally greater. For example, the latent heat of
vaporization or enthalpy of vaporization ("apH(Tb)IkJ mol-') for commercial
grade diesel, gas turbine, or fuel oils range from about 90 to 105 btullb (at
60°F) or 18 to 21 jK/mole or (at boiling temperatures). Likewise,
commercial
motor gasolines have a LHV ranging from 135 to 145 btullb or 27 to 29
jKlmole, aviation gasolines about 130 to 150 btullb or 26 to 30 jklmole, and
aviation jet fuels about 105 to 115 btulfb or 21 to 23 jKlmole.
Thus, it is preferred that the LHV for commercial grade diesel, gas
turbine, or fuel oils at 60°F exceed 105 btullb or 21 jKlmole (at
boiling
1o temperatures), for commercial motor gasolines LHV's should exceed 145
btullb or 29 jKlmole, for aviation gasolines LHV's should exceed 150 btullb or
30 jklmole, and for aviation jet fuels LHV's should exceed 115 btu/lb or 23
jKlmole. LHV's at least 2%, 5%, 10%, 20%, 30% or greater than these
amounts are however preferred.
The burning velocities {as measured by laminar Bunsen burner flame)
for commercial grade diesel, gas turbine, and fuel oils range from about 32-34
cmlsec, kerosine about 36 cmlsec, benzene about 44, automotive gasoline
about 44-46 cmlsec, aviation gasoline about 44-45 cmlsec, aviation jet fuels
about 32-34 cmlsec. Methanol is reported at about 57 cmlsec.
2 o Thus, in Applicant's fuels it is desireable that burning velocities for
commercial grade diesel, gas turbine, and fuel oils exceed 33, 34, 35, 36, 37,
38, 40, 41, 42, 43 cmlsec, kerosine exceed 35, 36, 37, 39, 40, 41, 42, 43, 44
cmlsec, automotive gasoline exceed 44, 45, 46, 47, 48, 49, 50, 51, 52, 53,
54, 55, 56 cmlsec, aviation gasoline exceed 44, 45, 46, 47, 48, 49, 50, 51,
52,
2 5 53, 54, 55, 56 cmlsec, and aviation jet fuels exceed 35, 36, 37, 38, 39,
40, 41,
42, 43, 44 cm/sec. However, BV's at least 2%, 5%, 10%, 20%, 30%, or
greater than the burning velocity of the unadjusted base fuel or conventional
fuel is preferred.
It is also desirable that the hydrocarbon based fuels have high possible
3 o allowable densities. High densities of base fuels permit higher
concentrations
of metallics and dialkyl carbonates. For example, aviation turbine densities
equal or exceeding 841 kglma @ 15° C are contemplated. More generally,
the fuel compositions of the present invention allow for base fuel densities
of
from 840 to 1200 kglm3 @ 15° C, and even 900 to over 1200 kgl m3 @
15° C.
35 Moderate, low, to very low densities are also contemplated so long as the
increased burning velocity object of above PCT Applications is accomplished
and a pH is not greater than 10.5, preferably below 9.0, and most preferably
from 6.3 to 6.8 is maintained.
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Moreover, highly viscous hydrocarbon fuel bases with viscosities above
fuel specification, are unexpectedly brought to within fuel viscosity limits
by
the addition of dialkyl carbonates and metal. For example, is has been found
that a diesel fuel oil having a viscosity of 2.6 mmZIS at 40° C was
acceptably
combined with dimethyl carbonate representing 5% volume of the
composition, and 2.0 grs Mn/gal of methylcyclopentadienyl manganese
tricarbonyl (MMT) or alternative non-toxic metallic. The resultant fuel
composition had a lower viscosity of 2.4 mm2lS at 40° C.
In this way, highly viscous fuels can be adapted by the addition of
applicant's ingredients, whereby non-conforming highly viscous fuels can be
made less viscous and brought into compliance with ASTM International,
industry and government fuel standards, including ASTM, IP, GOST, DERD,
MIL, AN, U.S. Clean Air Act, California Air Resources Board, and
SwedishlEuropean EPEFET standards, or other specification (herein
incorporated by refererence).
Also by way of example, Jet A hydrocarbon bases having a viscosity of
8.1 to 15.0 or more, (ASTM 445) can be adapted to meet the current 8.0
mm2/s~ at -20°C standard by addition of the components described above.
Alternatively, base fuel viscosity of from 13.5 to 23.0 Cs at -30EF, or more,
2 o may be met by the addition of the components described above.
Similarly, a gas oil turbine hydrocarbon base may have maximum
kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater,
mmZls
for ASTM D 445 No. 1-GT fuels, and be adapted to meet the 2.4 standard, by
addition of the components described herein. Alternatively, base fuel kinetic
2 5 viscosities of 4.15 to 6.0, or more, mrn2/s for ASTM D 445 No. 2-GT fuels,
may be adapted to meet the 4.1 standard by addition of applicant=s additives,
as described herein.
In an analogous manner, a diesel fuel oil base may have maximum
kinetic viscosities at 40°C equal or exceeding 2.45 to 7.0, or greater,
mm2/s
3o for ASTM D 445 low sulfur or regular No. 1-D fuels, and be adapted to meet
the 2.4 standard by addition of applicant=s additives. Alternatively, a diesel
fuel oil base having maximum kinetic viscosities of 4.15 to 9.0, or more,
mm2ls for ASTM D 445 low sulfur or regular No. 2-D fuels, and be adapted to
meet the 4.1 standard, by addition of applicant=s additives. Similarly, fuels
3 5 having a maximum kinetic viscosity of 24.5 to 60.0, or more, mm2/s for
ASTM
D 445 No. 4-D fuels, and be adapted to meet 24.0 mm2ls by addition of
applicant=s additives. Additionally, a low emission diesel base may have
viscosities exceeding 2.45 to 5.5, or more, cSt at 40°C (where 1 mm2ls
=
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1 cSt), and be adapted to meet the 2.4 standard.
Furthermore, a fuel oil base may have kinetic viscosities equal or
exceeding 2.15 10.0, or more, mm2ls at 40°C ASTM D 445 for No. 1 fuels,
and can be adapted to the 2.1 standard by addition of applicant=s additives.
5 A fuel base having kinetic viscosities of from 3.45 to 10,0, or more, mm2ls
at
40°C ASTM D 445 for No. 2 fuels can be similarly adapted to meet 3.4. A
fuel base having kinetic viscosities of 5.55 to 25.0 or more, mm2ls at
40°C
ASTM for D 445 No. 4 fuels (Light), may be similarly adapted to meet 5.5. A
fuel base having kinetic viscosities of from 24.5 to 40.0, or more, mm2/s at
10 40°C ASTM D 445 for No. 4 fuels (regular), may be adapted to meet
24. A
fuel base having kinetic viscosities of from 8.95 to 25.0, or more, mm3ls at
100°C ASTM D 445 for No. 5 fuels (Light), may be adapted to meet 8.9. A
fuel base having kinetic viscosities of from 15.0 to 30.0, or more, mm3ls at
100°C ASTM D 445 for No. 5 fuels (Heavy), may be adapted to meet 14.9.
A
15 fuel base having kinetic viscosities of from 50.5 to 80.0, or more, mm3/s
at
100°C STM D 445 for No. 6 fuel oils, and adapted to meet 50.0 mm3ls.
Similarly, a heavy diesel, locomotive or marine engine base fuel,
exceeding ISO DIS 8217, BS MA 100, government andlor other industry
viscosity specifications, but adapted to meet such standards (incorporated by
2 o reference), typically uncorrected viscosity exceeds such standards by 1.0,
2.0,10.0, 50.0, or more centistokes at 50°C. Applicant has discovered
by
incorporating his lower dialkyl carbonates and metals, fuels having excessive
viscosities can meet government, or other viscosity standards.
By way of further example, an enhanced combustion aviation turbine
2 5 fuel composition of the present invention includes an ECS oxygenate
(preferably a dialkyl carbonate andlor dialkyl dicarbonate),.an ECS metal
(preferably an alkalilalkali earth metal, or silicon), optionally a co-
combustion
catalyst, an aviation turbine hydrocarbon base having a viscosity of from 8.1
to 9.0 MM2/S (ASTM 445); optionally one or more of the following: a salt, a
30 co-solvent, antioxidant, freeze point additive, anti-icing additive, metal
deactivator, corrosion inhibitor, hydroscopic control additive, lubricity
agent,
lubricant or friction modifier, anti-wear additive, combustion chamber or
deposit control additive, any other recognized additive, additive disclosed in
aforementioned PCT Applications, or mixture thereof. The resultant fuel is
35 characterized as being slightly alkaline, substantially neutral or acidic,
and
having a maximum viscosity equal or less than 8.2 MMZIS~ (ASTM 445). The
fuel preferably has a density of from 840.5 to 850, or greater, kglm3 @
15° C,
a flash point of at least 38°C, a maximum vapor pressure of 21 kPa @
38°C,
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51
minimum thermal stability meeting ASTM D 1655 standards, a heat of
combustion or equivalent equal to or exceeding 42.8 MJlkg (lower heats of
combustion are contemplated, including those less than or equal to 42.5, 42,
41, 40, 39, 38, 37, 36 MJlkg, based upon additive heats of individual
components), and a maximum freezing temperature of from -40 to -50°C,
optionally a LHV not less than 115 btullb or 23 jKlmole, optionally a burning
velocity exceeding 37 cm/sec.
Example 34A
1o This composition may be summarized as an enhanced aviation turbine
fuel composition wherein aviation turbine hydrocarbon base has a viscosity
equal or exceeding 8.1 MM2/S, a C3 to C7 symmetrical dialkyl dicarbonate,
said fuel optionally characterized as being slightly acidic not exceeding
equivalent of 0.1 mg KOH/g.
A diesel fuel, fuel oil, turbine gas oil composition of the present
invention includes dimethyl carbonate representing 0.01 % to 40.0% oxygen
by weight of the fuel; a compound or element containing a combustion
improving amount of transition metal, alkaline metal, alkaline earth, group
Illa,
IVa, Va, Vla, Vlla element or derivative compound, or mixture, optionally a co-
combustion agent, optionally in an concentration of 0.001 to about 100.0 gr
elementlgal, preferably 2.0 to 20.0 gr elementlgal; and a No. 1 (ASTM) diesel
fuel base having a viscosity of from 2.45 to 3.0, MM2lS at 40°C,; said
fuel
base optionally characterized as having one or more of the following: a
density ranging from 880 to 800 kg/m3 , a cetane index of 40 to ?0, an
aromatic content by vol. ranging from approximately 0 to 35%,preferably 0%
to 10%, provided that 3-ring + aromatics not to exceed 0.16 volume %; a T10
fraction temperature of about 190 to 230°C, a T 50 fraction temperature
of
about 220 to 280°C, a T90 fraction of about 260 to 340°C, a
cloud point
temperature of °C -10, -28, -32 or 6°G above tenth percentile
minimum
3o ambient temperature, a sulfur content preferably not greater than 250 ppm,
more preferably not greater than 50 ppm, most preferably not exceeding 5
ppm, a Bunsen laminar burning velocity of at preferably greater than 37, more
preferably greater than 44, most preferably 50 ore more, cmlsec, a latent heat
of vaporization of preferably at least 105, more preferably at least 120, most
preferably 130 or more, BTUIIb. The resultant fuel is characterized as having
a pH less than 10.5 and a viscosity equal to or less than 2.4 MM2lS at
40°C,
optionally a LHV at 60°F equal or in excess of 105 btullb or 21, 22,
23, 25, 27
jKlmole (at boiling temperatures), optionally a minimum laminar Bunsen
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52
burner flame of 37, 39, 40, 41 cmlsec.
Example 34B
A composition, wherein the fuel composition is a diesel fuel oil, the
ECS oxygenate is dimethyl carbonate representing 0.01 % to 40.0% oxygen
by wt. of the fuel, the hydrocarbon base fuel has a viscosity equal to or
greater than 2.5, MMZIS at 40°C, and the fuel composition is
characterized as
having a pH less than 10.5 and a viscosity equal to or less than 2.4 MM2/S at
40°C.
An aviation gasoline fuel composition of the present invention includes
an ECS oxygenate (preferably a hydrocarbyl ether, including MTBE, ETBE,
etc.) andlor dialkyl carbonate, an ECS metal {preferably an alkalilalkali
earth
metal, or silicon), optionally a co-combustion catalyst, and an aviation
gasoline base. The resultant fuel is characterized as having a pH less than
7.0 and a minimum octane or performance number of from 87 to 130 (ASTM
909). It is further characterized as having a distillation fraction wherein
the
sum of the T-10 plus T-50 fractions are 307° F, the T-40 temperature is
167°
F and the T-90 temperature is less than 250° F, a maximum sulfur
content of
2 0 0.05 wt%, or sulfur free, a latent heat of vaporization preferably
exceeding
120, more preferably exceeding 150, most preferably exceeding 160 BTUIIb,
a laminar bunsen burning velocity preferably equal to or in excess of 40, more
preferably greater than 48, most preferably greater than 52 cmlsec, a heat of
combustion (as measured by the sum of fuel ingredients) equal or less than
43.0 kJlkg, or equal or less than from 18,720 to 15,000, or less, BTUIIb.
Examale 34C
A gasoline composition of the present invention includes an a
hydrocarbyl ether (MTBE, ETBE, etc.) andlor dialkyi carbonate, an ECS metal
(preferably an alkalilalkali earth metal, or silicon), optionally a co-
combustion
catalyst, and an unleaded base fuel composition. The resultant composition
is characterized as having a pH less than 10.5, and optionally being
phosphorus free hydrocarbons, a maximum Reid Vapor Pressure of from 6.0
to 12.0 psi, 6.0 to 10 psi, 6.0 to 9.0 psi; a maximum of 12% to 5.0% by
volume, or less of olefins, a maximum of 30% to 20% or less by volume of
aromatics (more preferably 15% to 10%, or less), a maximum of 2.0% to
0.8% or less benzene, a maximum of 40 ppm sulfur, most preferably sulfur
free, a total 02 concentration ranging of 0.5% to 10.0% wt of dimethyl
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S3
carbonate, a manganese tricarbonyl compound at 1/64 to 3116 gr. Mnlgal
(preferably 1132 gr. Mn) or other metallic in a combustion improving amount, a
maximum T-90 temperature of 330°F to 280°F, a T-50 temperature
of approx.
170°F to 230°F., 175°F preferred, a minimum (R+M)12
octane of 85, to 92, a
bromine number of 20 or less, an average latent heat of vaporization of 880
to 920, or more, BTU/gal at 60°F; a heating value greater than 106,000
btu/gal at 60°F (more preferably greater than 108,000, 114,000
btulgal), as
measured by the sum of individual fuel substituents.
1 o Example 34D
A fuel composition, wherein said composition is a gasoline comprising
an ECS oxygenate selected from MTBE, ETBE, DMC, or ethanol,
characterized as having a pH ranging form 8.5 to 5.5, optionally a maximum
Reid Vapor Pressure of 12.0 psi or 8.0 psi, a maximum of 12% voi. olefins, a
maximum of 30% vol. aromatics, a maximum of 1.0% vol. benzene, a
maximum of 50 ppm sulfur or sulfur free, a total 02 concentration ranging
from 0.5% to 4.0% wt of the composition, a maximum T-90 temperature of
330°F to 280°F, a T-50 temperature of approx. 170°F to
230°F., a minimum
(R+M)/2 octane of 85, to 92, a bromine number of 20 or less, an average
2 0 latent heat of vaporization of 880 to 920 BTU/gal at 60°F, a
heating value
greater than 106,000 btu/gal at 60°F.
Example 34E
Another gasoline composition of the present invention includes an ECS
2 5 oxygenate (preferably a dialkyl carbonate andlor dialkyl Bicarbonate,
MTBE,
ETBE, Ethanol, or methanol), an ECS metal (preferably an alkalilalkali earth
metal, or silicon), optionally a co-combustion catalyst, and an unleaded base
fuel composition, characterized as having a pH less than 10.5, and optionally
characterized as having one or more of the following: being phosphorus free
3o hydrocarbons, with a maximum Reid Vapor Pressure of 12.0 psi, a maximum
of 12% olefins, a maximum of 30% aromatics, a maximum of 2.0% benzene,
a maximum of 50 ppm sulfur or sulfur free, a total O2 concentration ranging
from 0.5% to 10.0% wt of dialkyl carbonate, a combustible metal or non-metal
selected from groups set forth below including (but not limited to) those
35 consisting of the preferred manganese, silicon, potassium, and iron
compounds, or mixture, a maximum T-90 temperature of 330°F to
280°F, a T-
50 temperature of approx. 170°F to 230°F., a minimum (R+M}l2
octane of
85, to 92, a bromine number of 20 or less, an average latent heat of
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54
vaporization of 880 to 920 BTU/gal at 60°F, a heating value greater
than
106,000 btulgal at 60°F (as measured by the sum of individual fuel
substituents), a burning velocity exceeding 50 cmlsec, a latent heat of
vaporization exceeding 29 jKlmole (or equivalent).
Example 34F
A similar gasoline composition comprises an ECS oxygenate selected
from MTBE, ETBE, DMC, or ethanol, is characterized as having a pH ranging
form 8.5 to 5.5, and optionally with a maximum Reid Vapor Pressure of 12.0
1 o psi or 8.0 psi, a maximum of 12% olefins, a maximum of 30% aromatics, a
maximum of 1.0% benzene, a maximum of 50 ppm sulfur or sulfur free, a
total 02 concentration ranging from 0.5% to 4.0% wt of the composition, a
maximum T-90 temperature of 330°F to 280°F, a T-50 temperature
of approx.
170°F to 230°F., a minimum (R+M)/2 octane of 85, to 92, a
bromine number
of 20 or less, an average latent heat of vaporization of 880 to 920 BTUlgal at
60°F, a heating value greater than 106,000 btulgal at 60°F.
Example 34G
Another gasoline composition would include the aforementioned ECS
oxygenates and an ECS metallic (including a combustible alkalilalkali earth
metal, preferably a potassium derivative, and MTBE, ETBE, ethanol,
methanol, DMC, or EMC, or substitutes as provided herein), and a gasoline
base, wherein the resultant composition has one or more of the following
characteristics: a RVP of 6.4 to 10.0 psi, aromatics content of 0% to 50%,
more preferably no greater than 22%, 25%, 30%, or 35% vol., a benzene
content of 0% to 2.0%, preferably no greater than 0.8%, 1.Q%, 1.2% vol., an
olefin content of 0% to 25%, preferably no greater than 15%, 12%, 10%, 8%
vol., an distillation evaporation point where 30% to 70% of the fuel has
distilled by 200°F, an distillation evaporation point where 70% to 100%
of the
fuel has distilled by 300°F, a T50 distillation temperature ranging
from 200°F
to 220°F, maximum T90 distillation temperature of 290°F to
310°F, oxygen by
wt% ranging from 0% to 5.0%, 0.001 % to 4.0%, 0.1 % to 4.0% to preferably
1.8% to 2.2%., sulfur, ppm, wt. ranging from 0 to 500 ppm, more preferably
30 to 80 ppm.
Example 34H
Another gasoline composition would include the aforementioned
gasoline composition, wherein the resultant composition has one or more of
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the following characteristics: a maximum summer RVP of 8.1, 8.0, 7.5, 7.2,
7.1, 7.0 psi, maximum aromatics of 22%, 25%, or 30% vol., max, benzene of
0.8%, 1.0%, 1.2% vol., T50 distillation temperature ranging from 200°F
to
220°F, a maximum T50 distillation temperature ranging from 200°F
to 220°F,
5 minimum T50 distillation temperature greater than 175°F, maximum T90
distillation temperature of 290°F to 310°F, oxygen by wt% 1.8%
to 2.2%.,
sulfur, ppm, wt. 30 to 80.
Example 35
10 A gasoline composition including a combustion improving amount of
potassium ethoxide and an ECS oxygenate selected from MTBE, ETBE,
ethanol, DMC, or EMC, wherein the composition has one or more of the
following characteristics: a RVP no greater than 7.5, 7.1, 7.0 psi, maximum
aromatics of 22%, 25%, or 30% vol., max. benzene of 1.0% vol., a minimum
15 T50 distillation temperature ranging of 175°F, maximum T90
distillation
temperature of 290°F to 310°F, oxygen by wt% 1.8% to 2.2%., and
a sulfur
content of 0 to 80 wt. ppm, 30 ppm or less preferred.
The invention achieves unexpected reduction of nitrous oxides in
2o combustion after emissions pass through a catalytic exhaust converter. As
noted above, reductions of nitrous oxides is important for purpose of reducing
global warming gases, but catalytic converters tend to increase the amount of
said oxides during their catalytic activity. Applicant has discovered that
combusting his ECS oxyenate andlor metallic containing fuels, particularly
2 5 those containing alkalilalkali earth metals, and emitting them through a
catalytic converter, he is able to no only reduce the nitrous oxide flowing
into
the converter, but is able to reduce total oxides, which otherwise would be
emitted from the converter. Thus, reducing the harmful effect the exhaust
catalyst has in increasing nitrous oxides.
Example 36
A method of reducing green house nitrous oxide gases, comprising:
mixing a combustion improving amount of a combustion improving
amount of an ECS metallic, optionally a combustion improving amount of an
ECS oxygenate, together with a gasoline; and
combusting resultant fuel composition in an automotive engine; and
exhausting resultant emissions through an exhaust catalyst; emitting
catalyst reacted emissions into the atmosphere; whereby exhaust nitrous
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oxide emissions are reduced.
56
Example 37
The Example above, wherein the ESC metal is an alkali or alkali earth
metal (preferably a potassium derivative) and the oxygenate is MTBE, ETBE,
ethanol, methanol, DMC, and wherein the fuel optionally contains a co-
combustion catalyst.
Example 38
The Example of 36, wherein also mixed into the composition is a co-
combustion catalyst.
Example 39
The Example of 36, wherein said method incorporates mixing a metal
only.
Example 40
The Example of 36 or 39, wherein said metal is absent manganese.
2 0 Example 41
The Example of 36, wherein said fuel composition is includes a
combustible alkalilalkafi earth metal, and an ECS oxygenate selected from
MTBE, ETBE, ethanol, methanol, DMC, EMC, and mixture, having one or
more of the following characteristics: a RVP of 6.4 to 10.0 psi, aromatics
content of 0% to 50%, a benzene content of 0% to 2.0%, an olefin content of
0% to 25%, an distillation evaporation point where 30% to 70% of the fuel has
distilled by 200°F, an distillation evaporation point where 70% to 100%
of the
fuel has distilled by 300°F, a minimum T50 distillation temperature of
175°F
and a maximum T50 distillation temperature ranging from 200°F to
220°F,
3o maximum T90 distillation temperature of 290°F to 310°F,a co-
combustion
catalyst, oxygen by wt% ranging from 0.1 % to 4.0%, sulfur, ppm, wt. ranging
from 0 to 500 ppm; or a fuel composition of the character of Examples 34A
through 34E and 35.
Example 42
The Example of 36 to 41, wherein the fuel composition has a pH
ranging from 10.0 to 4Ø, more preferably 9.0 to 5.0, 8.0 to 6.0, 7.7 to 6.3,
or
6.9 to 6.3, or other range or amount set forth herein.
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Example 43
The above examples additionally containing an nitrogen based
enhancer, or compound containing nitrogen, a nitrogenloxygen combination,
or a NH, NH2, NH3, NH4, NO, NN, OON, OONH, ONH, ONH2, ONH3,
ONH4, CON, CONH, CONH2, CONH3, COON, COONH, MNH, MON,
MONH, MONH2, MONH3, MOON radical (where M is a metal as set forth
herein). Non-limiting examples also include fuel soluble andlor combustible
amines, amides/imides, such as vitro compounds, nitric compounds,
1 o tetranitromethanes, nitromethanes, nitroethanes, nitropropanes, nitrous
oxides, dinitrous oxides, nitric oxides, nitrates, and di-nitrates. Other non-
limiting examples include, alkylmetallicamides, polyalkylmetallicamides,
alkylphosphoramides, polyalkylphosphoramides (e.g.
hexamethylphosphoramide, hexamethylphosphorus diamide,
hexamethylphosphorus triamide, hexamethylphospophorimidic triamide,
triethylphosphoramide, trimethylphosphoramide, tripropylphosphoramide,
triisopropylphosphoramide, tributylphosphoramide, triisobutylphosphoramide,
tri-sec-butylphosphoramide, tri-tert-butylphosphoramide,
triphenylphosphoramide, dimethoxyphosphorusamide (CH30)2PNH2),
2 0 diethoxyphosphorusamide, dipropoxyphosphorusamide,
diisopropoxyphosphorusamide, dibutoxyphosphorusamide, di-
isobutoxyphosphorusarnide, di-sec-butoxyphosphorusamide, di-tert-
butoxyphosphorusamide, diphenoxyphosphorusamide, dimethylphosphor-
amide (CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide,
diisopropylphosphoramide, dibutylphosphoramide, diisobutylphosphoramide,
di-sec-butylphosphoramide, di-tert-butylphosphoramide,
diphenylphosphoramide, dimethylethylphosphoramide, diethyimethyl-
phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-
phosphoramide, di-butyl-methylphosphoramide, di-iso-butylmethyl-
phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-
methyiphosphoramide, diphenylmethyl phosphoramide).
Phosphoramides are particularly desired.
In the practice of this invention it is contemplated at least one
combustible reactive non-lead transition metal, alkaline metal, alkaline
earth,
group Illa, IVa (except carbon), Va, Vla (except oxygen), Vlfa element, or
derivative thereof, as set forth herein, or mixture (herein referred to as
"metal"
or "metallic") be together with at least one C3 to C13 symmetrical dialkyl
ester
of carbonic acid, and mixture, in a fuel stable composition; said composition
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58
optionally containing a combustion catalyst as set forth below, a hydrocarbon,
andlor an oxidizer; resultant composition as having a pH slightly alkaline,
neutral or acidic.
Non-limiting examples of suitable dialkyl carbonates include, dimethyl
carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate,
dibutyl carbonate, diisobutyl carbonate, ditertiary butyl carbonate, diisoamyl
carbonate, methyl ethyl carbonate, diphenyl carbonate, or mixture. C3 to C8
symmetrical dialkyl carbonates are more desirable, with C3 to C5 being
preferred. It is contemplated that such carbonates will be introduced into the
l0 composition in concentrations of 0.01 to 100.0 volume percent in an amount
sufficient to improve combustion. The carbonates may be additionally
combined with one or more oxygenated compounds, including but not limited
to alkyl butyl ethers (e.g. MTBE, ETBE, TAME, ETAME, etc.), alkyl alcohols,
and/or known co-solvents. In the practice of this invention methylal, ethylal,
C1 to C6 aliphatic alcohols, may be substituted for dialkyl cartaonates,
absent
compromise of vapor phase combustion. Examples of ECS compounds are
presented in the aforementioned PCT Applications.
Non-limiting examples of the optional hydrocarbon bases contemplated
herein, include any hydrocarbon, including but not limited to carbonaceous
liquid or solid fuels, alternative fuels, gaseous fuels (including hydrogen,
natural gas, methane, ethane, propane, butane, etc.), automotive gasolines,
diesel fuel oils, heavy diesel fuel oils, aviation gasoline, gas oils, fuel
oils,
aviation jet turbine oils, coal, coat oils, coal liquids, and the like.
Industry
specifications, including ASTM, IP, GOST, DERD, MIL, AN, U.S. Clean Air
2 5 Act, California Air Resources Board, and SwedishlEuropean EPEFET
standards, EU Standards, and other reported industry or government
standards known in the art, and Criteria for Quality of Petroleum Products,
J.P. Allison, 1973 (and subsequent editions), all hereby incorporated herein
by reference.
METALS PRACTICE
In the practice of this invention, as set forth in the aforementioned PCT
Applications, contemplated metallics include all non-lead metals, metalloids,
and non-metals (herein "metals" or "metallics"}, their derivative compounds
3 5 (organic or inorganic}, whose combustion product accomplishes primary
object of vapor phase combustion, which is evidenced by a brilliant luminous
reaction zone extending some distance from the metal's surface. Such
combustion does not take place on the surface of the metal, or on andlor
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59
within the molten layer of oxide covering the metal, typical of heretofore
metallic combustion. Distinguishing vapor phase combustion is that its
combustion is expansive with elevated exhaust velocities, and resultant
metallic oxide particles are formed in the submicron range. Typically fuel
economy, power output, exhaust emissions, combustion temperatures are
materially improved.
Thus, a very wide range of acceptable metals and derivative
compounds are contemplated. Group IA (alkali metals), IIA (alkaline earths)
elements, the transition elementslmetals of group Illb, IVb, Vb, Vlb, Vllb,
Vlllb
l0 [8, 9, 10), the elements of group Ib, Ilb, Illa, IVa (absent carbon), and
group
Va, Vla, Vlla elements are contemplated. Non-limiting examples include
aluminum, boron, bromine, bismuth, beryllium, calcium, cesium, chromium,
cobalt, copper, francium, gallium, germanium, iodine, iron, indium, lithium,
magnesium, manganese, molybdenum, nickel, niobium, phosphorus,
potassium, palladium, rubidium, sodium, tin, zinc, praseodymium, rhenium,
silicon, vanadium, strontium, barium, radium, scandium, yttrium, lanthanum,
actinium, cerium, thorium, titanium, zirconium, hafnium, praseodymium,
protactinium, tantalum, neodymium, uranium, tungsten, promethium,
neptunium, samarium, plutonium, ruthenium, osmium, europium, americium,
rhodium, iridium, gadolinium, curium, platinum, terbium, berkelium, silver,
gold, dysprosium, californium, cadmium, mercury, holmium, titanium, erbium,
thulium, arsenic, antimony, ytterbium, selenium, tellurium, polonium,
lutetium,
and astatine, including their organic and inorganic derivative compounds,
which are capable of vapor phase combustion, are contemplated in the claims
hereto and incorporated herein by reference. Applicant's metals, including
derivative compound, may be organo-metallic or inorganic. Accordingly, the
inorganic and organic compounds of CRC Handbook of Chemistr~r and
Ph~rsics, Lide, 75th (1994-1995) and earlier editions, Ann Arbor, CRC Press;
Sigma-Aldrich Chemical Directory, Aldrich Chemical Company (1997),
Chemical Abstract Service~CAS), on line Registry File [1], American
Chemical Society, Chemical Abstract Service, Ohio State University, A
Manual of Inorclanic Chemistry, Thorpe, N.Y., Putnam & Son's (1896),
Inor4anic Materials, 2 ed., Ducan, N.Y. J.Wlley 8~ Son (1996), Handbook of
Inorganic Compounds, Peny, Phillips, CRC Press, Boco Raton, (1995),
Inorganic Chemistry, Phillips, Wllliams, N.Y. Oxford University Press (1965-
1966), Inorganic Materials Chemistry, D. Seneeta, G.E. R & D Center, N.Y.,
CRC Press (1997), _Inorganometallic Chemistry, Fehlner, N.Y., Plenum
(1992), Nontransition-Metal Compounds, Eisch, N.Y., Academic Press
CA 02310056 2000-OS-16
WO 99/66009 PCTNS99/13751
(1981 ), Metal & Metalloid Amides, Horwood, N.Y., Halsted Press (1980), Kirk-
Othmer Encycloaedia of Chemical Technology, 2nd and subsequent editions,
John Wiley & Sons (1963), Dictionary of Chemical Names & Synonyms,
Howard, Neal, Lewis Publishers, Ann Arbor, {1992), Hawley's Condensed
5 Chemical Dictionary, 12th Edition, Richard J. Lewis, Sr., Van Nostrad
Reinhold Company, N.Y. {1993), Dictionary of Chemical Solubilities.
Inorganic, Convey, MacMiilian Press (1921 ), Solubilities of Inorganic and
Metal Organic Substances, Seidell, N.Y., Van Nostrand (1940-1941 ),
Solubility of Inorganic and Metal-Organic Compounds, Like, Princeton N.J.,
10 Van Nostrand (1958-1965), Or anometallics (cite omitted}, Oraano Metallic
Chemistry, F.G.A. Stone, Academic Press (1972 and subsequent years),
Oraano Metallic Compounds. 2 Ed, Michael Dub, Springer-Verlag, New York
Inc. (1966 Vol. 1 to 3, and subsequent volumeslsupplments}, Oraano-metallic
Compounds, Coates, Edward, New York, Wiley (1960), Comprehensive
15 Org~anometallic Chemistry II (A Review of the Literature 1982-1994), Abel,
Stone, Wilkinson, EI Sevier Science Ltd {1995}, Handbook of Oraanometallic
Compounds, Kaufman, D. Van Nostranl Company Inc. (1961 ), Handbook of
Oraanometallic Compounds, Hagihara, Kumanda, Okawars, W.A. Benjamin
Inc (1968), Oraanometallic Chemistry, Mehrotra, Singh, John Wiley and Sons,
20 (1991 ), Organometallic Chemistry, Chemical Society {1971 and all
subsequent publications), London, Metal-Organic Compounds, American
Chemical Society (1959 to present}, Chemical Abstracts, American Chemical
Society, Chemical Abstract Service, Ohio State University, {From 1907 to
present), Structure Reports 1913 to 1973 (Metals and Inorganic Compounds),
25 International Union of Crystallography, Bohn, Scheltena & Hellema (volumes
1-40), The Merck Index, 12th Ed., Budavari, O'Neil, Merck Research
Laboratories, N.J. {1996), which are capable of vapor phase combustion,
together with said publications (including all relatedlsubsequent editions,
volumes, supplements, updates, or related publications) are incorporated
3 0 herein by reference.
However, it is an object of this invention to ultilize where possible those
ECS metallics which are not nuerotoxic, especially where human ingestion is
possible.
In the practice of this invention, cyclomatic compounds are particularly
35 desireable. Non-limiting examples of cyclomatic compounds include
compounds with one or more rings systems, including alicyclic or aromatic
ring systems. Ring systems which rnay be wholely organic, wholely inorganic,
or heterocyclic. Such ring systems may include cyclic borons (bvrazoles),
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61
cyclic silanes (silacyclobutane, 2,4,6,8,10-pentamethylcyclopentasilazane,
cyclohexasilanes, cyclopropenyl silanes, etc.), cyclic nitrogens (pyrazoles,
pyridines, pyrroles, piperazines, imidazals, etc.), cyclic oxygens (benzoyls,
furans, pyrans, e.g. tetrahydropyran, pyrones, dioxins, etc,), cyclic sulfurs
(thiophens, dithiles, etc.) or other cyclic inorganics. Cyclomatic organic
ring
systems include saturated rings (cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cyclooctyl, etc.), unsaturated rings, rings with one or more
multiple
or double bonds (cyclohexadiene, cyclopentadiene, cyclotetraene, etc.),
aromatic ringslcycloalkyl radicals (phenyl, benzyl, styryl, etc.), fused
rings,
to fused aromatic rings (naphthls, naphthenates, etc.), fused ring with
cyclopentadienyl moiety, rings containing oxygen or a hydroxyl (phenol, etc.).
The disclosed metallic cyclomatics contained in Heterocyclic Chemistry,
Katritzy, Boulton, Academic Press (1966 to 1997 all volumes), Benzenoid-
Metal Complexes, Zeiss, Wheatley, Winkler, The Ronald Press Co (1966),
The Rina Index 2 Ed, Patterson, Capell, American Chemical Society,
Reinhold Publishing Corp (1960 and subsequent editions), Ring Enlar eq ment
of Organic Chemist, Hesse, VCH Publishers (1991 ), Rinqs. Cluster. and
Plymers of Main Group Elements, Cowley, American Chemical Society
(1983), which are capable of vapor phase combustion, together with said
publications (including subsequent editions, volumes, or supplements), are
incorporated herein by reference.
Desireable metal containing cyclomatic compounds are those with
cyclic rings having high burning velocities. The higher the burning the
velocity,
generally the higher the preference. Generally larger rings have higher
burning velocities compared to smaller rings. Thus, a cyclooctane ring is
generally preferred over cyclohexane, which is preferred over a cyclobutane
ring. Saturated rings are normally more preferred over unsaturated rings. The
more saturated the ring the more preferred. Thus, cyclohexane is preferred
over benzene. Ring systems where the metal is in turn attached to one or
more a hydroxyl, carbonyl, an alkyloxy radicals is generally preferred.
Variations to this general rule are expected.
Non-limiting examples of desireable ring systemslcompiexes include:
cyclohexane, cyclohexene, cyclopentane, cyclobutane, cyclopentadiene,
phenyl, benzene, and naphthalene. More desireable are cyclohexane,
cyclohexene, and cyclopentadienyl. It is contemplated each elemental metal
of this invention can be employed in a cyclomatic compound.
Transition metal ring systems are well known in the art and highly
desireable. See U.S. Patents Nos. 2,818,416, 3,127,351, 2,818,417,
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2,839,552, 2,680,_; 2,804,468; 3,341,311, 3,272,606, 3,718,444), Canadian
Patent #1073207, European Patent Application # 93303488.6, pages 6-8
(1993), incorporated herein by reference. As contemplated herein, ring
system attachment may be direct or indirect. Attachment may be via
molecular bond, ionic bond, coordination bond or other bond known in the art.
Indirect attachment may be via one or more radical or element, or be via other
bond as described below or known in the art. See The Chemisty of
Orpanometallic Compounds, Rochow, Hurd, Lewis, New York, John Wiley &
Sons, Inc. (latest edition), incorporated by reference.
One or more radicals (including cyclic radicals), side chains, saturated
or unsaturated, may be attached to one or more locations on the ring, andlor
to one or more locations of each metal. Thus, the metal may contain between
one to as many radicals as available valence electrons (oxidation states)
permit. See Handbook of Data on Organic Compounds Zed, Weast, Grasselli,
CRC (185).
Non-limiting examples of radicals, include organic or inorganic,
saturated or unsaturated, or combinations thereof, including: hydrogen
(hydride), hydroxyl, hydrocarbyl group radicals, including alkyl radicals
(e.g.
methyl, ethyl, propyl, issopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
amyl,
pentyl, hexyl, etc.), alkyloxy radicals, various positional isomers thereof
(e.g.
1-methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 1,1-dimethyl-propyl, 1,2-
dimethyl-propyl, etc.), corresponding straight and branched chain isomers
(e.g. hexyl, hepyl, octyl, nonyl, decyl, etc.), alkenyl radicals (ethyl, /1'-
propenyl,
I_12-propenyl, isopropenyl, etc.), corresponding branch chain isomers thereof,
other isomers thereof (e.g. heptenyl, octenyl, nonyl, decenyl, etc.),
alkenyloxy
radicals, aryl radicals (e.g. phenyl, a-napthyl, b-naphthyl, a-anthryl, b-
anthryl,
etc.), aryloxy radicals, including monovalent radicals of such aromatics {e.g.
indene, isoindene, acenaphthene, flourene, phenanthrene, naphthacene,
chrysene, pyrene, triphenylene, etc.), aralkyl radicals (e.g. benzyl, a-phenyl-
ethyl, b-phenyl-ethyl, a-phenyl-propyl, etc.), aralkyloxy radicals, various
positional isomers thereof (e.g. derivatives of 1-methyl-butyl, 2-methyl-
butyl,
3-methyl-butyl, 1,1 dimethyl-propyl, etc.), corresponding alkyl derivatives of
phenanthrene, flourene, acenapthene, etc., alkaryl radicals, (e.g. o-tolyl, m-
tolyl, p-tolyl, o-ethylphenyl, etc.), arylalkenyl, cycloalkyl radicals
(benzyl, etc.),
cycloalkyioxy radicals, aliphatic radicals, mesityl. See generally Canadian
Patent 1073207, pages 4-7, European Patent Application # 93303488.6,
pages 6-8, 10/11193), Handbook of Data on Oraanic Compounds 2 Ed,
Weast, Grasselli, CRC 1985, CRC Handbook of Chemistry and Physics, 75th
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63
and earlier editions, sections re: "Nomenclature For Inorganic Ions and
Radicals," "Organic Radicals and Ring Systems," Nomenclature of Inoroanic
Chemistry (Recommendations, Blackwell Scientific Publications, Offord
1990; Richer, J.C., Panico, R., and Powell, W.H. A Guide to IUPAC
Nomenclature of Organic Compounds, Blackwell Scientific Publications,
Offord 1993, Weast, R.C., and Grasselli, J.C., Handbook of Data on Organic
Compounds. 2nd Ed. CRC Press, Boca Raton, FL, 1989; incorporated by
reference.
Hydroxyl, alkanol, alkanolamine, oxy andlor oxygen containing
radicals, including derivatives of thereof and derivative of above radical are
also contemplated. Non-limiting examples include hydroxy, methoxide,
ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, seo-butoxide, tert-
butoxide, pentoxide, amyloxide, phenyloxidesperhydroxy, methoxy, methylol,
methylenedioxy, ethoxy, ethyfol, ethylenedioxy, enanthyl, propoxy, proprylol,
propylenedioxy, isopropoxy, isopropylol, isopropylenedioxy, butoxy,
butylenedioxy, butylol, iso-butoxy, iso-butylol, isobutylenedioxy, isobutyryl,
sec-butoxy, sec-butylol, sec-butylenedioxy, tert-butoxy, tert-butylol, tert-
butylenedioxy, butyryl, caproyl, capryl, caprylrl, pentoxy, pentylol, pent
alenedioxy, amylol, amylenedioxy, phenoxy, phenylol, phenylenedioxy,
2 o phenylmethoxy, diphenylmethoxy, benzoyl, benzyloxy, benzoxy, iso-benzoyl,
napthoxy, napthylol, hexylol, hexamethylol, amylenedioxy, hexadecanoyl,
heptanedioyl, hexylenedioxy, carbomethoxy, carbethoxy, carbobenzoxy,
carbpropoxy, carbisopropoxy, carbutoxy, phenacyl, phenacylidene, propionyl
radicals, methyienedioxyl, carbonyldioxy, etc., including derivatives,
homologes, analoges, and isomers thereof. Additional non-limiting oxygen
containing radicals include acetyl, acetamido, acetoacetyl, acetonyl,
acetonylidene, acrylyl, alanyl, B-alanyl, allophanoyl, anisyl, benzamido,
butryl,
carbonyl, carboxyl, carbazoyl, caproyl, capryl, caprylrl, carbamido,
carbamoyl,
carbamyl, carbazoyl, chromyl, cinnamoyl, crotoxyl, cyanato, decanoly,
disiioxanoxy, epoxy, formamido, formyl, furyl, furfuryl, furfurylidene,
glutaryl,
glycinamido, glycolyl, glycyl, glyocylyl, heptadecanoyl, heptanolyl,
hydroperoxy, hydroxarnino, hydroxylamido, hydrazidolhydrazide, hydroxy,
iodoso, isoccyanato, isonitroso, keto, lactyl, methacrylyl, malonyl,
nitroamino,
vitro, nitrosamino, nitrosimino, nitrosyllnitroso, nitrilo, oxamido, peroxy,
phosphinyl, phosphidelphosphido, phosphitelphosphito, phospho,
phosphono, phosphoryl, seleninyl, selenonyl, siloxy, succinamyl, sulfamino,
sulfamyl, sulfeno, thiocarboxy, toluyl, ureido, valeryl radicals, etc.,
including
derivatives, homologes, analoges, and isomers thereof.
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Additional non-limiting examples of other radicals, include: acetimido,
amidino, amido, amino, aniline, anilino, arsino, azido, azino, azo, azoxy,
benzylidine, benzldyne, biphenylyl, butylene, iso-butylene, sec-butylene, tert-
butylene, cyano, cyanamido, diazo, diazoamino, ethylene, disilanyl, glycidyl,
guanidino, guanyl, heptanamido, hydrazino, hydrazo, hypophosphite
(hypophosphito), imido, isobutylidene, isopropylidene, silyl, silylene,
methylene, mercapto, methylene, ethylene, naphthal, napthobenzyl, naphthyl,
naphthylidene, propylene, propylidene; pryidyl, pynyl, phenethyl, phenylene,
pyridino, sulfinyl, sulfo, sulfonyl, tetramethylene, thenyl, thienyl,
thiobenzyl,
thiocarbamyl, thiocarbonyl, thiocyanato, thionyl, thiuram, toluidino, tolyl, a-
tolyl, tolylene, a-tolylene, tosyl, triazano, ethenyl (vinyl), selenyl,
trihydrocarbyiamino, trihaloamino, trihydrocarbyl phosphite, trihalophosphine,
trimethylene, trityl, vinylidene, xenyl, xylidino, xylyl, xylylene, 1,3-diene,
hydrocarbyl radicals, etc., including derivatives, homologes, analoges, and
isomers thereof. Thus, ring compounds or metals themselves may directly or
indirectly contain one or more chelating radicals (e.g. carbonyl, cyano,
etc.).
One or more of the above radicals may be attached directly or
indirectly to another. Indirect attachment may be via one or more intermediate
atom, including but not limited to carbon, nitrogen, oxygen, phosophorus,
silicon, boron, sulfur, or another metal. Metallic compounds may have
one or more non-ring radicals attached. Desireable metals may for example
have one or more alkyl, alkylene or similar radical attached to the metal, or
one or more hydroxyl, carbonyl, alkyloxy, alkanol radicals, or combination
thereof attached. Examples include
Other metallic compounds may have one or more ring systems
attached directly or indirectly to a metal, with or without an attached non-
ring
radical to the metal.
One or more cyclic rings maybe attached, fused or indirectly attached
together or linked together via one or more radicals, one or more atoms,
including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon,
boron, sulfur, or a metal.
One or more metals may be attached to each other, for example
hexamethyldisilane, which is a preferred metallic. Indirect attachment herein
includes attachment via one or more radicals, andlor one or more atoms,
including but not limited to carbon, nitrogen, oxygen, phosophorus, silicon,
boron, sulfur, or another metal.
As contemplated herein said carbon, nitrogen, oxygen, phosophorus,
silicon, boron, sulfur, or other metal atom, may be attached to itself or to
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another herein, one or more times, with each atom optionally having one or
more hydrogen andlor radical(s). Said attachment may be independent of
attachment to any other radical or metal, or may include an attachment to
another radical or metal.
5 Likewise one or more cyclic rings may be attached directly to the
metal, or indirectly via one or more non-ring radicals, andlor via one or more
intermediate atoms, including but not limited to carbon, nitrogen, oxygen,
phosophorus, silicon, boron, sulfur, or another metal.
Thus, one or more metals may be attached at one, or up to every
10 location possible on the ring system, directly and/or indirectly. Likewise,
one
or more ring systems may be attached at one, or up to every metal location
possible, directly and/or indirectly.
A non-ring radical may be independently attached directly or indirectly
to the metal, absent its attachment of a ring system. In the practice of this
15 invention the attachment of one or more non-ring radicals) to a metal,
absent
a ring system is expressly contemplated.
Contemplated oxygenated metallic compounds include metallic
alkanols, ethers, ketones, hydroxides, alkyloxy, including methoxy, dimethoxy,
trimethoxy, ethoxy, diethoxy, triethoxy, oxalate, carbonate, Bicarbonate,
2 o tricarbonate, and similar structured compounds, including mixture thereof.
For
example trimethoxymethylsilane (as set forth below) is desireable. Metallic
carbonates, including dimetallic carbonates, dimetallic Bicarbonates, and the
like, are also contemplated. It is contemplated these oxygenated metallic or
organo-metallic compounds may be employed absent a dialkyl carbonate or
2 5 other oxygenated ECS structure.
Likewise one or more non-ring radicals may be independently attached
directly or indirectly to the ring system, absent attachment of a metal. An
independent attachment of a metal may be via intermediate radical, one or
more intermediate atoms, including but not limited to carbon, nitrogen,
30 oxygen, phosophorus, silicon, boron, sulfur, or another metal.
A cyclic ringlradicallside chain may be indirectly attached to the metal
through one of more atom, including but not limited to carbon, nitrogen,
oxygen, phosophorus, silicon, boron, sulfur, or a metal. Indirect attachment
via oxygen is contemplated but less desireable.
35 Cyclic rings may be attached to one or more non-ring radicals, atoms
andlor ring systems prior to a direct or indirect attachment of the metal. For
example, [2-(cyclohexenyl)ethyljtriethoxysilane contains a ethyl radical
attached to the cyclohexenyl ring, which is then attached to silicon. This is
a
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preferred metallic structure.
66
Thus, cyclomatic compounds may contain one or more ring systems,
optionally with one or more non-ring radicals attached thereto. Said rings)
then may be attached directly or indirectly to a metal, with said metal in
turn
optionally attached directly or indirectly to a radical, with said radical
being
optionally a non-ring radical selected from one or more hydrogen, hydroxyl,
alkyl, aryl, carbonyl, alkanol, alkanolamine, alkyloxy, oxy or oxygen
containing
radical. Non-limiting examples include methylcyclopentadienyl manganese
tricarbonyl, [2-(cyclohexenyl)ethyljtriethoxysilane, and cyclohexenyl
l0 dimethoxymethylsilane.
Another class of desireable metallics include metal hydrides or metallic
hydryls. Examples of metallic hydryls include sodium hydride, lithium hydride,
aluminum hydride, aluminum borohydride; boron hydride, boron anhydride,
beryllium borohydride, lithium borohydride,lithium aluminum hydride, lithium
borohydride, sodium borohydride, transition-metal hydrides, transition-metal
carbonyl hydrides, transition-metal cyclopentadienyf hydrides, and mixture.
Those hydrides known in the art and those disclosed in Metal Hydrides,
Bambakidis, New York, Pienum Press (1981 ), Boron Hydride Chemistr~r,
Muetterties, New York, Academic Press (1975), which accomplish primary
vapor phase combustion object of this invention, are contemplated in the
claims below and incorporated herein by reference.
Organometallic nitrosyls are also desireable. See for example Metal
Nitrosvls, Richter-Addo, Oxford University Press, U.K. (1992), incorporated by
reference. Flammable metal napthenates or metals derivatives of napthenic
acid are desireable, including potassium naphthenate.
Alkalilalkali earth metal carbonates (including organic alkyl aryl
carbonates), alkalilalkali earth formates, alkalilalkali earth etherates,
alkali/alkafi earth alkalates, alkali/alkali earth esters, multi-metal
alkyllalkyl
earth carbonates, or carbonates including those with a hydrogen (e.g.
LiHC03, Na2C03, NaHC03, MnC03, MgCO3, CaC03, CaMg(C03)2, etc.),
alkali metal carbonates; and other metal carbonates (e.g. AgC03, TI2C03,
etc.), including organic derivatives are contemplated. Contemplated salts
also include acid salts containing replaceable hydrogen. Double oxides and
hydroxides are also contemplated.
Transition metals and their known cyclomatic compounds, including
carbonyl compounds are expressly contemplated. See Fundamental
Transition Metal Or9anometallic Chemistry, Lukehart, Monteray, Calif,
BrookslCole (1985), Transition Metat Compounds, King, New York, Academic
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67
Press (1965), Transition-Metal Oraanometallic Chemistry, King, New York,
Academic Press (1969), Fundamental Transition Metal Oraanometallic
Chemistry, lukehart, Monterey, Ca., Brooks/Cole (1985), incorporated herein
by reference. A preferred cyclomatic transition metallic is MMT.
Contemplated herein are non-transition-metal compounds known in the
art. See Nontransition-Metal Compounds, Eisch, New York, Academic Press
{1981 ), incorporated by reference. Non-transition metal compounds that
accomplish primary object of vapor phase combustion are contemplated in
the claims below and incorporated herein by reference.
1 o Likewise known metallocenes are contemplated. Non-iimiting
examples include alkylmetallocenes, arylmetallocenes, including
dicyclopentadienyl-metal with the general formula (C5H5)2M,
dicyclopentadienyl-metal halides with the general formula (C5H5)2MX1-3,
monocyclopentadienyl-metal compounds with the general formula C5H5MR1-
3, where R is CO, NO, halide group, alkyl group, etc. Non-limiting examples
include napthacenes, metallocene, ferrocene, methylferrocene, cobaltocene,
nickelocene, titanocene dichloride, zirconocene dichloride, uranocene,
decamethylferrocene, decamethylsilicocene, decamethyfgermaniumocene,
decamethylstannocene, decamethylphosocene, decamethylosmocene,
2o decamethylruthenocene, decamethylzirconocene, sificocene,
decamethylsilicocene, etc., are also contemplated. Metallocenes that
accomplish primary object of vapor phase combustion are contemplated in
the claims below and incorporated herein by reference. See also Hawle s
Condensed Chemical Dictionary 12th ed, Lewis, Van Nostrand Reinhold
Company, New York (1993), also incorporated by reference.
Carbonyl compounds are expressly contemplated. A limited number of
examples include decacarbonyl dimanganese, (acetylacetonato~ii-
carbonylrhodium. See for example Carbon~yrlation: Direct Synthesis of
Carbon l~pounds, H.M. Colquhoun, Plenum Press (1991 ), incorporated
herein by reference.
As noted above, non-limiting non-leaded simple binary/temary metallic
compounds, including binaryltemary and higher metallic salts, acid salts,
including those with replaceable hydrogen, etc., are contemplated. Hydroxy
acids, perchlorates, sulfates, nitrates, carbonates, hydroxides, methylates,
ethylates, propylates, and others, are also contemplated. Non-limiting
examples include potassium nitrite, sodium nitrite, lithium nitrite, and
hexamethylphosphoric triamide.
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68
It is also within the scope and practice of this invention to employ
oxygenated containing ECS metallic compounds, including oxygenated
organo metallic compounds, which are metallic alcohols, alkanolamines,
ketones, esters, ethers, carbonates, and the like, which are themselves ECS
compounds, in hydrocarbon fuels with or absent additional dialkyl carbonate
or other ECS structure. Those metallics are incorporated herein by reference.
Additionally, this invention contemplates one or more similar organo oxygen
containing metallics, including mixture, with or without an ECS compound, to
act as neat "stand alone" fuel. Thus, it is an express embodiment to use
metallic compounds alone, as singular means of enhancing fuel combustion.
However, it is preferred the metallic be added to the ECS oxygenate,
preferably MTBE, ETBE, DMC, or Ethanol, optionally a co-fuel, an oxidizer,
catalyst, andlor a hydrocarbon. The contemplated oxidizers of this invention
are set forth in the aforementioned PCT applications. Oxidizers, including
those employed in rocket propulsion, which are known in the art are
incorporated by reference.
It is also within the practice of this invention to employ a metallic
compound, including homologue, analogue, isomer, or derivative thereof,
having a structure or structure similar to
2 0 M-R", R"-M-M-R", R"-M-Q-M-R", R"-M-Q'-M-R", R"-M-R'-M-R", wherein M iS
one or more non-leaded metal(s), metalloid(s), or non-metal element(s), and
R is one or more hydrogen, cyclic ring systemlradicallside chain(s), andlor
non-ring radicallside chains) as provided herein above, including but not
limited to alkyl, aryl, alkyloxy, alkylanol (alkanol), hydroxyl, aryloxy,
polyalkyl,
polyaryl, polyalkyloxy, polyalkylanol, polyaryloxy, polyhydroxyl radicals. R'
is
one or more cyclic ring systemlradical/side chain(s), andlor non-ring
radical/side chains) as provided herein. If R is greater than 1, then
subsequent R's may be same or different radical, etc. R also be a single
radical or one radical attached to one or more radicals. "n" is an interger
3o ranging from 1 to the number of valence electrons (or common oxidation
states) available of M. Q is an atom having a minimum oxidation available of
2, including but not limited to carbon, nitrogen, oxygen, phosophonrs,
silicon,
boron, sulfur, or a differing metal than M. Q' is an atom with a minimum
available oxidation state of 2, including but not limited to carbon, nitrogen,
oxygen, phosophorus, silicon, boron, sulfur, or a differing metal than M, also
containing one or more radicals.
Additional oxygenated-organo or oxygenated metallic structure
includes M1-O(CO)O-M2, wherein M1 or M2 are the same or different metal
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or element. M1 may be a double valence cation, wherein M2 is absent from
above structure, unless additional carbonate is included. Preferred M
valences are 1 or 2. M valences or multiple M1 M2 combinations having
combined valence greater than two are acceptable. In which case, additional
carbonate structure would be added, e.g. CaMg(C03)2.
In the immediate structure above, M11M2 valence's may be greater
than one, wherein excess valence is occupied by same or additional metal
{element), and/or wherein M1 or M2 are substituted for a single or double
bond oxygen, andlor by one or more radicals. M1 or M2 also may be
1o substituted for single bond oxygen, or nitrogen, andlor by one or more
radicals, including methyl, hydrogen, hydroxy, ethoxy, carbethoxy,
carbomethoxy, carbonyl, carbonyldioxy, carboxyl, methyoxy, isonitro,
isonitroso, or methylenedioxyl radical. Non-limiting examples include
carbonates of lithium [Li202(CO)], ammonium manganese, potassium
[K2O2(CO)], sodium, calcium, cesium, copper, rubidium, lithium hydrogen,
sodium hydrogen, potassium hydrogen, potassium sodium, magnesium, and
the like.
It is contemplated that C2 to C8 metallic ethers, C2 to C41C51C6
metallic ethers being more desireable, will be used as metallic structure in
this
invention. For example, M'1-CH2-CH2-O-CH2-CH2-M'2 structure is
contemplated wherein M'1 and M'2 may be same or different metallic or
wherein one M'1 or M'2 may be hydrogen, or other atom, or radical with one
available valence.
Other contemplated structure include metallic ketones, esters (esters
2 5 of boric acid), alcohols, acids, and the tike. Non-limiting examples
include
M'1-C-OH3-R, wherein M'1 is one or more metallic comprising valence of 3 or
greater, and R is radical, whereby resulting structure is ketone, ester, acid,
alcohol; or ether. Other structure include M'1-C204, wherein M'1 has a
valence of 2. M1-C-C-O-C-C-M2 structure is also contemplated wherein M1
3o and M2 may be same or different metallic or wherein M2 may be hydrogen or
atom of one valence. Other structure includes RO-M, where RO is an alkanol
and M is a metal. Similar structure is contemplated for M have available
valence greater than 1.
As in the case of ECS oxygenates, the carbon chains of organo-ECS
35 metallics are preferably shorter than longer. For example, a 5 carbon atom
straight chain, which is immediately antecedent to a metal atom, is less
preferred than a 4 carbon straight carbon atom chain. A three carbon chain is
more preferred over a 4 carbon atom chain, and a two more preferred than a
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3. Generally the longer the chain, the less desireable. An exception would be
where the chain length and character positively increases burning velocity.
Where there is an intermediate oxygen or nitrogen atom between the
carbon chain and the metal atom, particularly if the oxygen or nitrogen atom
is
5 attached to the metal, a chain of two carbon atoms is generally preferred
over
a single carbon atom. In such cases an ethyl radical is generally preferred
over propyl, which is preferred over butyl radicals. Branch chains are
prefer-ed over straight chains with the same number of carbon atoms.
Chains greater than 10 carbon atoms long are less desireable and not
1o normally contemplated. Thus, the oil soluble metal soap of aluminum
stearate, which has three separate 17 carbon chains each connected to the
aluminum atom through an intermediate oxygen atom [CH3(CH2)~6COOJ3AL,
is not an effective ECS metallic and is excluded. Poorly combustible long
chain metal soaps are excluded from the ECS metallics contemplated herein.
15 Also excluded is cety! pyrdrium chloride,
Non limiting examples of lithium derivative compounds of this
invention, include: lithium bis(dimethylsilyl)amide, lithium bis(trimethyl-
silyl)amide, oxamic acid, P-aminosalicylic acid lithium salt, lithium salt 5-
nitroorotic acid, lithium D-gluconate, lithium hexacyanoferrate(III)
20 {Li3Fe(CN)6), lithium diphenylphosphide, lithium acetate, lithium acetate
acid,
lithium salt acetic acid, lithium acetamide, lithium anilide, lithium azide,
lithium
benzamide, lithium antimonide, lithium orthoarsenate, lithium orthoarsenite,
lithium meta-arsenite, lithium diborane, lithium pentaborate, lithium
dihydroxy
diborane, lithium borohydride, lithium cadium iodide, lithium chloride,
lithium
25 calcium chloride, lithium carbide, lithium carbonate, lithium hydrogen
carbonate, lithium carbonate, alkyl lithium carbonates, lithium methyl
carbonate, lithium ethyl carbonate, lithium carbonyl, lithium cobalt (II)
cyanide,
lithium cobalt (111) cyanide, lithium cobaltinitrite, lithium cynomanganate
(II),
lithium cynomanganate (III), lithium citrate, lithium ferricyanide, lithium
3o ferrocyanide, lithium formate, lithium hydride, lithium hydroxide, lithium
manganate, lithium permanganate, lithium methionate, lithium napthenate,
lithium nitride, lithium nitrate, lithium nitrite, lithium nitrobenzene (e.g.
lithium-
p-nitrobenzene), lithium nitrophenoxide, lithium etherate, lithium chromate,
lithium oleate, lithium oxalate, lithium oxalatoferrate (II), lithium
oxalatoferrate
35 (III), lithium monoxide, lithium oxide, lithium peroxide, lithium mono-
orthophosphate, lithium hypophosphite, lithium orthophosphite, lithium
hydroxoplumbate, lithium rhodium cyanide, lithium selenide, lithium selenite,
lithium selenocynate, lithium selenocyanoplatinate, lithium disilicate,
lithium
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metasilicate, lithium sodium carbonate, lithium sodium ferricyanide, lithium
hydroxostannate, lithium disufide, lithium hydrosulfide, lithium pentasulfide,
lithium tetrasulfide, lithium trisulfide, lithium telluride, lithium
thioarsenate,
lithium thioarsenite, lithium trithiocarbonate, lithium thiocyanate, lithium
amide, lithium salt (E,E}-2,4-hexadienoic acid, dilithium fluorophosphate,
dilithium fluorophosphite, trilithium phosphate, trilithium phosphite, lithium
perchlorate, propanoic acid lithium salt, lithium formats, lithium cyanate,
lithium hexacyanocobaltate (111), lithium hypophosphite, lithium hexa-
flurorsilicate, lithium nitroprusside, lithium phenoxide, lithium phosphate
(dibasic, monobasic, tribasic), lithium salicylate, lithium selenide, lithium
tetracyanonickelate (II}, lithium tetrafluoroborate, lithium xanthogenate,
lithium
-p-aminobenzoate, lithium copper ferrocynanide, lithium cupric ferrocyanide,
lithium hexafluorophosphate, lithium hexanitricobaltate III, lithium
naphthenate, lithium -B-naphthoxide, lithium polysulfide, lithium -sodium
phosphate, lithium stearate, lithium sulfide, lithium sulfite, lithium
sulfate,
lithium thiocyanate, lithium xanthate, lithium fluorosilicate, N-
lithiumethylenediamine, oxalic acid dilithium salt, lithium beta-hydropyruvic
acid, lithium 1,1-dimethylurea, lithium 1,1-diethyfurea, lithium 1,1-
diepropylurea, lithium xanthate, lithium ethylxanthate, lithium
methylxanthate,
lithium salt thiophenol, lithium triphenylmethyllithium, methyllithium,
ethyllithium, lithiumethynyl(acetylide), propyllithium, isopropyllithium,
butyllithium, isobutyllithium, secbutyllithium, tertbutyllithium,
pentalithium,
hexyllithium, heptalithium, amyllithium, isoamyllithium, benzyllithium,
dirnethylbenzyl-lithium, tolyllithium, dodecyllithium,
cyclopentadienyllithium,
methylcycfopentadienyllithium, cyclohexyllithium, lithiumheptyl,
Iithiumdodecyl,
lithium tetradecyl, lithium hexadecyl, lithium octadecyl, phenyllithium,
lithium
o-tolyl, lithium m-tolyl, lithium p-tolyl, lithium-p-chlorophenyl, lithium p-
bromophenyl, lithium o- anisyl, lithium m-anisyl, lithium p-anisyl, lithium
diethoxyphenyl, lithium dimethoxyphenol, lithium m-cumyl, lithium p-
ethoxyphenyl, lithium m-dimethylaminophenyl, lithium 9-flourene, lithium a-
napthyl, lithium b-napthyl, lithium p-phenylphenyl, lithium 9-phenylanthryl,
lithium 9-anthryl, lithium 9-methylphenanthryl, lithium pyridyl, lithium 2-
pyridyl,
lithium 3-pyridyl, lithium 6-bromo-2-pyridyl, lithium 5-bromo-2-pyridyl,
lithium
dibenzofuryl, lithium 3-quinoyl, lithium 2-lepidyl, lithium triphenylmethyl,
lithium
2,4,6-trimethylphenyl, lithium 2,4,6-triisopropylphenyl, lithium 2,3,5,6-
tetraisopropylphenyl, lithium tetrabutylphenyl, thiophenedilithium,
toluenedilithium, diphenylethylenedilithium, lithiumamylethynyl, lithiumphenyl-
ethynyl, lithiummethoxybromophenyl, lithium phenylisopropyl, lithium
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tetraphenylboron, lithium tetramethylboron, lithium a-thienyl, lithium m-
trifluoromethylphenyl, phenylethynyllithium, 3-furyllithium,
phenylisopropyllithium, dibenzofuranyllithium, lithium dimethylbenzyl, lithium
selenocyanate, lithium trimethyl-silanolate, diphenylphosphide, lithium
benzoate, lithium tert-butyl carbonate, lithium azide, di-lithiumcyanamide,
lithium cyanide, lithium dicyanamide, cyclohexanebutyric acrd lithium salt,
cyclohexane acid lithium salt, cyclopentadientyllithium, lithium tri-tert-
butoxy-
aluminum hydride, lithium triethyl-borohydride, lithium trimethylborohydride,
lithium tripropyl-borohydride, lithium triisopropylborohydride, lithium
tributylborohydride, lithium triisobutylborohydride, lithium tri-sec-
butylborohydride, lithium tri-tert-butylborohydride, lithium
trisiamylborohydride,
lithium chlorate, lithium tert-butoxide, lithium sec-butoxide, iso-butoxide,
lithium antimonate, lithium diphenylphosphide, lithium bis(trismethylsilyl)
amide, trilithium phosphite, lithium selenocyanate, lithium tri-sec-
butylborohydride, lithium triethylsilanotate, lithiumthiocyanate, lithium
acetylide, lithium chlorate, lithium salicylate, lithium di-lithium
tetracarbonylferrate, lithium tetraphenylborate, lithium triethylborohydride,
lithium triacetoxy-borohydride, lithium triphenylborane, lithium hydroxide,
lithium diphenylphosphide, lithium methoxide, lithium ethoxide, lithium tri-
sec-
2 0 butylborohydride, tri-tert-butylborohydride, lithium triethylborohydride,
lithium
triphenylborohydride, lithium trisiamylborohydride, lithium metavanadate,
lithium cyclohexanebutyrate, lithium hexachloroplatinate, lithium thiocyanate,
lithium selenocyanate, lithium cyanate, lithium floride, lithium hexafluoroan-
timonate, lithium hexafluoroaluminate, lithiumaluminate, lithiumaluminum-tri-
tert-butoxide, lithium hexafluoroarsenate, lithium hexafluorosilicate, lithium
hexacyanocobalt(ll)ferrate(II), lithium ferrosilicon,
dilithiumhexacyanocobalt(li)ferrate(II), lithium hexafluorotitanate, lithium
hexafluorozirconate, lithium hexahydroxyantimonate, lithium
hexachlororuthenate, lithium hexachloropalladate, lithium formats, lithium
tetracyanonickelate, lithium tetrafluoroaluminate, lithium tetrafluoroborate,
lithium thioacetate, L-glutamic acid monolithium salt, fumaric acid lithium
salt,
oxamic acid lithium salt, lithium salt diphenyl-phospane, P-aminobenzoic
lithium salt, aminobenzole acid lithium salt, alpha-napthaieneacetic acid
lithium salt, dilithium salt 2,6-naphthalenedicarboxlic acid, lithium
cyclcohexanetherate, lithium phthalimide, P-aminosalicylic acid lithium salt,
lithium salt 3,5-dimethylcyclohexyl sulfate, indolebutyric acid lithium
salt,indole-3-butyric acid Lithium salt, diphenylphosphide, lithium dimethyl-
silanolate, lithium triethylborohydride, lithium propoxide, lithium
isopropoxide,
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lithium butoxide, lithium sec-butoxide, lithium pentoxide, lithium tert-
pentoxide, lithium hydrogenphthalate, lithium oxalate, lithium
hydrogensulfate,
monolithium acetylenedicarboxylic acid, lithium pyrophosphate, lithium
dihydrogenphosphate, lithium hexoate (lithium salt hexoic acid), lithium
diphenylphosphide, lithium trimethylsilonalate, lithium phthalic acid, P-
aminobenzoic acid lithium salt, monolithium L-aspartic acid,
tetraphenyldilithium (C6H5)2CLi2C(C6H5)2, lithiumethylphenyl (LiCH2C6H5),
lithium bromate, lithium hydrogenphospate, monlithium salt D-shaccharic
acid, DI-asparatic lithium salt, (R}-alpha-hyroxymethylaspartic acid lithium
salt,
lithium fluoride, lithium iodate, lithium salt ethyl malonate, lithium
thioacetate,
lithium phenol, lithium salt aminobenzoic acid, lithium aminophenol salt,
lithium cyclohexenol, lithium methylcyclohexenol, lithium cyclopropanol,
lithium methylcyclopropanol, lithium cyclobutanol, lithium methylcyclobutanol,
lithium methylcyclopentanol, lithium cyclopentanol, lithium cyclohexenol,
lithium methyicyclohexenol, lithium dimethyicyclohexenols (e.g. lithium 3,5
dimethylcyclo-hexanol, lithium 2,3-dimethylcyclohexanol, lithium 2,6
dimethylcyclohexanol, lithium 2,5-dimethylcyclohexanol, 3,5-
dimethylcyclohexanol), lithium o-ethylxanthic acid, monolithium salt 2
ketoglutaric acid, difithium salt, ketomalonic acid, lithium salt lactic acid,
2o dilithium thiosulfate, lithium antimony tartrate, lithium dichloroacetate,
lithium
dimethylacetate, lithium diethylacetate, lithium dipropylacetate, lithium
metaborate, lithium tetraborate, lithium tetrachlorocuprate, lithium
acetoacetate, lithium diisopropylamide, lithium diethylamide, lithium
dimethylamide, lithium bis(dimethylsilyl)amide, dilithium phthalocyanine,
dilithiumtetra-bromocuprate, dilithium tetrabromonickelate, dilithiumtetra-
chioromanganate, dilithiumbutadiyne, lithium cyclopentadienide, lithium
dicyclohexylamide, lithium diethylamide, lithium dimethylamide, lithium
dipropylamide, lithium diisopropylamide, lithium thexylborohydride, lithium
tri-
tert-butoxyaluminohydride, lithium trimethylsilyl)acetylide, lithium
triethylsilyl)-
acetylide, lithium tris[(3-ethyl-3-pentyl)oxy]aluminohydride,
(phenylethynyl)lithium, 2-thienyllithium, lithium diethyldihydro-aluminate,
lithium dimethyldihydroaluminate, lithium aluminum hydride, lithium
bifluoride,
lithium biphenyl, lithium bis-elenite, lithium bis(2-methoxyethoxy)aluminum
hydride, lithium bismuthate, lithium borate, lithium chlorite, lithium cobalt-
nitrite, lithium cyanoborohydride, lithium cyclopentadienide, lithium
dicyanamide, lithium hexametaphosphate, lithium hexanitrocolbaltate, lithium
hydrogenphosphite, lithium hydrogenselenite, lithium hydrogensulfite, lithium
hydrosulfite, lithium hypochloride, lithium metaarsenite, lithium
metabisulfide,
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lithium metaperiodate, lithium methacrylate, lithium nitroferricyanide,
oxybate,
lithium pentamethylcyclo-pentadienide, lithium phenofate, polyphosphate,
lithium polypho-sphite, lithium propionate, lithium pyrophosphate, lithium
selenate, lithium selenite, lithium tetrachloroafuminate, lithium
thiomethoxide,
lithium thiosulfate, lithium thiosulfide, lithium thiosulfite, lithium tri-
actoxyborohydride, lithium trimethylsilonate, lithium triethylsilonate,
lithium
tris(1-pyrazoly)borohydride, including analogues, homologue, isomers and
derivatives thereof. See Lithium Chemistry: A Theorical and Experimental
Overview, Sapse, Schleyer, John Wiley & Sons, N.Y. (1995), incorporated
1 o herein by reference. Non limiting examples of the boron derivative
compounds of this invention include: alkyl boron compounds, aryl boron
compounds, 1,3,2-benzodioxaborole, diisopropoxymethylborane, ethylborane,
diethylborane, diemthylborane, dicyclohexylborane, boric acid esters (e.g.
borate ester, dimethyl borate, di-n-butyl borate, dicyclohexyl borate,
didodecylborate, di-p-cresyi borates), phenylboronic acid, 2-phenyl-1,3,2-
dioxborinane, pyrrolyboranes (e.g. 1-pyrrolyborane, 2-pyrrolyborane), tetra-
butylammonium borohydride, tetramethylammonium borohydride,
tetraisoproplyammonium borohydride, tetrapropylammonium borohydride,
tetraethylammonium borohydride, tetraisobutyiammonium borohydride, tetra-
2o tert-butylammonium borohydride, tetra-sec-butylammonium borohydride,
tetrabutylammonium cyanoborohydride, tetramethylammonium cyano-
borohydride, tetraisoproplyammonium cyanoborohydride, tetra-
propylammonium cyanoborohydride, tetraethylammonium cyanoborohydride,
tetraisobutylammonium cyanoborohydride, tetra-tert-butylammonium
2 5 cyanoborohydride, tetra-sec-butyfammonium cyanoborohydride,
tetramethylammonium triacetoxyborohydride, thiopheneboric acid, 2-
thiopheneboric acid, 3-thiopheneboric acid, tolylboronic acid (e.g. o-
tolylboronic acid, p-tolylboronic acid, m-tolylboronic acid), tributoxyborane,
tributylborane, tri-sec-butylborane, tri-tert-butylborane, tributylborate, tri-
tert-
3o butylborate, trimethoxyboroxine, trimethylamineboran, trimethylborate,
trimethylboroxine, trimethylborazine, trimethylene borate, triphenylborate,
triphenylborane, tribenzyl borate, borate, trisiamylborane, tris(2-
methoxyethyl)borate, boron hydride, lithium borohydride, sodium borohydride,
boron hydrate, boron hydride, boron anhydride, triethylboron (C2H5)3,
35 decaborane, borazoles, aluminimum borohydride, beryllium borohydride,
lithium borohydride, hexamethyldiamineborane (CH3)3NBH(CH3)3),
(CH3)2B1, berylliumborohydride (Be(BH4)2), trimethoxytriborate
(BO)3{OCH3)3, C4H9B{OH)2, AI(BH4)2, Be(BH4)2, LiBH4, B(OC2H5)3,
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B(OCH3)3, trimethoxytriborane, 3-bromophenylboronic acid, trimethoxy
borate, triethoxy borate, triproxyborate, tributoxyborate, triisobutoxyborate,
tri-
tert-butoxyborate, tri-sec-butoxyborate, tri-phenoxyborate, tri-
phenoxyboroamine, tri-phenoxyborane, phenylboronic acid, benzylboronic
5 acid, cylohexylboronic acid, cylohexenylboronic acid, cyclopentylboronic
acid,
methyiphenylboronic acid, methylcylohexylboronic acid, methyfcyclopentyl-
boronic acid, rnethylbenzylboronic acid, dimethylphenylboronic acid,
dimethylcylohexylboronic acid, dimethylcyclopentylboronic acid,
dimethylbenzylboronic acid, diphenylboronic acid, dibenzylboronic acid,
10 dicylohexylboronic acid, dicylohexenylboronic acid, dicyclopentylboronic
acid,
methyldiphenylboronic acid, bis[(methyl)cylohexyl]boronic acid,
bis[(methyl)cyclopentyl]boronic acid, bis[(methyl)benzyl]boronic acid,
bis[(dimethyl)phenyl]boronic acid, bis[(dimethyl)cylohexyl]boronic acid,
bis[(di-
methyl)cyclopentyl]boronic acid, bis[(dimethyl)benzyl]boronic acid,
15 phenylboroncarbonyl, benzylboroncarbonyl, cylohexylboroncarbonyl,
cylohexenylboroncarbonyl, cyclopentylboroncarbonyl,
methylphenylboroncarbonyl, methylcyfohexylboroncarbonyl,
methylcyclopentylboroncarbonyl, methylbenzylboroncarbonyl, phenylboronic
acid carbonyl, benzylboronic acid carbonyl, cylohexylboronic acid carbonyl,
20 cylohexenylboronic acid carbonyl, cyclopentylboronic acid carbonyl,
methylphenylboronic acid carbonyl, methylcylohexylboronic acid carbonyl,
methylcyclopentylboronic acid carbonyl, methylbenzylboroncarbonyl,
dimethyiphenylboroncarbonyl, dimethylcyiohexylboroncarbonyl, dimethyl-
cyclopentylboroncarbonyl, dimethylbenzylboroncarbonyl,
25 diphenylboroncarbonyl, dibenzylboroncarbonyl, dicylohexylboron-carbonyl,
dicylohexenylboroncarbonyl, dicyclopentylboroncarbonyl,
methyldiphenylboroncarbonyl, di[(methyl)cylohexyl]boroncarbonyl,
di[{methyl)cyclopentyl]boroncarbonyl, di[(methyl)benzyl]boroncarbonyl,
di[(dimethyl)phenyl]boroncarbonyl, di[(dimethyl)cylohexyl]boroncarbonyl,
30 di[(dimethyl)cyclopentyl]boroncarbonyl, di[(dimethyl)benzyl]boroncarbonyl,
phenylboromethoxide (phenylborodimethoxide C6H5B(OCH3)2),
benzylboromethoxide, cylohexylboromethoxide, cylohexenylboromethoxide,
cyclopentylboro-methoxide, methylphenylboromethoxide,
methylcylohexylboro-methoxide, methylcyclopentylboromethoxide,
35 methylbenzyl-boromethoxide, methylphenylboromethoxide,
dimethylphenylboromethoxide, methylcylohexylboromethoxide,
dimethylcylohexylboromethoxide, methylcyclopentylboromethoxide,
dimethylcyclopentylboromethoxide, methylbenzylboromethoxide,
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dimethylbenzylboromethoxide, diphenylboromethoxide,
dibenzylboromethoxide, dicylohexylboromethoxide, dicylohexenyl-
boromethoxide, dicyclopentylboromethoxide, di(methylphenyl)boromethoxide,
di(methylcylohexyl)boromethoxide, di(methylcyclopentyl)boromethoxide,
di(methylbenzyl)boromethoxide, di(dimethylphenyl)boromethoxide,
di(dimethylcylohexyl)boromethoxide, di(dimethylcyclopentyl)boromethoxide,
di(dimethylbenzyl)boromethoxide, phenylboroethoxide (phenylborodiethoxide
C6H5B(OCH3)2), benzylboroethoxide, cylohexylboroethoxide,
cylohexenylboroethoxide, cyclopentylboroethoxide,
l0 methylphenylboroethoxide, methylcyfohexylboroethoxide,
methylcyclopentylboroethoxide, methylbenzylboroethoxide,
methylphenylboroethoxide, dimethyiphenylboroethoxide,
methylcylohexylboroethoxide, dimethylcylohexylboroethoxide,
methylcyclopentylboroethoxide, dimethylcyclopentylboroethoxide,
methylbenzylboroethoxide, dimethylbenzylboroethoxide, diphenyl-
boroethoxide, dibenzylboroethoxide, dicylohexylboroethoxide,
dicylohexenylboroethoxide, dicyclopentylboroethoxide, di(methyl-
phenyl)boroethoxide, di(methylcylohexyl}boroethoxide, di(methyl-
cyclopentyl)boroethoxide, di(methylbenzyl)boroethoxide, di(di-
methylphenyl)boroethoxide, di(dimethylcylohexyl)boroethoxide,
di(dimethylcyclopentyl)boroethoxide, di(dimethylbenzyl)boroethoxide,
phenylboric acid, benzylboric acid, cylohexylboric acid, cylohexenylboric
acid,
cyclopentylboric acid, methylphenylboric acid, methylcylohexylboric acid,
methylcyclopentylboric acid, methylbenzylboric acid, dimethylphenylboric
acid, dimethylcylohexylboric acid, dimethylcyclopentylboric acid,
dimethylbenzylboric acid, dibenzylboric acid, dicylohexylboric acid, dicylo-
hexenylboric acid, dicyclopentylboric acid, methyldiphenylboric acid,
bis(methylcylohexyl)boric acid, bis[methylcyclopentyl]boric acid, bis[methyl-
benzylJboric acid, bis[dimethylphenyl]boric acid, bis[dimethylcylohexyl]boric
acid, bis[dimethylcyclopentyl]boric acid, bis[dimethylbenzyl]boric acid,
aminophenylboronic acid,3-aminophenylboronic acid, diborane,
tetramethoxydiborane, tetraethoxydiborane, boric acid, borazine, borocar
bonate, borane-tert-butylamine, tetraethylammonium borohydride, tetraethyl-
ammonium tetrafluoroborate, tetrapropylammonium tetrafluoroborate,
naphthylboronic acids (e.g. 1-naphthylboronic acid, 2-naphthylboronic acid, 3-
naphthylboronic acid, 4-naphthylboronic acid}, methylnaphthlboronic acid,
biphenylboronic acid, carborane, cyclohexylamine diborane,
methylbenzeneboric acid, dimethylbenzeneboric acids (e.g. 3,5-
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dimethylbenzeneboric acid), hexadecaneboronic acid, tetreadecaneboronic
acide, phenylethylboroamine, methylborazine, dimethylborazine,
trimethylborazine, ethylborazine, diethylborazine, triethylborazine,
carboborazine, dicarboborazine, tricarboborazine, triisopropoxyboroxine,
tripropoxyboroxine, trimenthyl borate, trimenthyl bovine, trimenthyl borane,
trimethallyl borate, trimethallyl bovine, tripentyl borate, tripentyl bovine,
tripentyl borane, trimethyl borate, trimethylborine, triethylborine,
triethylborane, triethylborate, tripropylborane, tripropylborine,
tripropylborate
(tripropoxyborane), triisopropylborane, triisopropylborate,
triisopropylborine,
1 o tri-iso-butylborane, tri-iso-butylborate, tri-sec-borane, tri-sec-borate,
tri-sec-
borine, tributyl borate, tributyl bovine, tributyl borane, tri-tert-butyl
borate, tri-
tert-butyl bovine, tri-tert-butyl borane, triphenyl borate, triphenyl borane,
tricyclohexylborate, tricyclohexylborane, dimethyl boric acid, diethylboric
acid,
dipropylboric acid, diisopropylboric acid, di-iso-butylboric acid, di-sec-
boric
acid, dibutylboratic acid, di-tert-butylboric acid, diphenylboric acid,
dicyclohexylboric acid, boron tribromide, sodium tetrafluoroborane, sodium
trimethylborohydride, triethylborohydride, sodium tripropylborohydride, sodium
triisopropylborohydride, sodium tributylborohydride, sodium triisobutyl-
borohydride, sodium-tert- butylborohydride, sodium-sec-butylborohydride,
2o sodiumphenylborohydride, potassium tetrafluoroborane, potassium
trimethylborohydride, triethylborohydride, potassium tripropylborohydride,
potassium triisopropylborohydride, potassium tributylborohydride, potassium
triisobutylborohydride, potassium-tert- butylborohydride, potassium-sec-
butylborohydride, potassium phenylborohydride, butylboronic acid,
sodiumborohydride,
methyldichloroborane, ethyldichloroborane, propyldichloroborane,
isopropyldichloroborane, butyldichloroborane, isobutyldichloroborane,
tertbutyldichloroborane, secbutyldichloroborane, phenyldichloroborane,
methylboric acid, ethylboric acid, trichloroborazine, borane-tetrahydrofuran,
3 o tetrafluoroboric acid, boron trichloride, tre-sec-butylborane, boran-
trimethylamine, borane-triethylamine, borane-N,N-diethylaniline, boran-
pyridine, borane-tert-butylamine, borane-morpholine, borane-dimethylamine,
borane-diethylamine, trisiamylborane, trisiamylborate, disiamylborane,
disiamylborate, trimesitylborane, sodium metaborate, lithium metaborate,
potassium metaborate, sodium metaborane, borane-tributylphosphine,
lanthanum hexaboride, boran-triphenylphosphine, boran-tributylphosphine,
cyclopentadienylboran, methyicyclopentadienylboran, boran-N,N-
diisopropylborohydride, N,N'-bis(monoisoipinocampheylborane~N,N,N'N'-
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tetramethylethylenediamine, boron nitride, 4-{borane-dimethylamine)benzene,
4-(borane-dimethylamine)pyridyl, 3-(methylthio)proplyborane,
tris(dimethylamino)borane, butyldiisopropoxyborane, triphenyl borane sodium,
sodiumtetraphenylborane, sodiumtetraphenylborane, sodium tetrakis(1-
imidazolyl)borane, sodium tetrakis(1-imidazolyl)borate, diisopro-
poxyphenylborate, diisopropoxymethylborate, diisopropoxyethylborate, boron-
ammonia, borontrifluoride, diethyl(3-pyridyl)borane, dimethyl(3-
pyridyl)borane,
lithium thexylborohydride, dichloromethyldiisopropylborate, diethyl-
methoxyborane, dipropylmethoxyborane, diisopropylmethoxyborane,
to diethylethoxyborane, dipropylethoxyborane, diisopropylethoxyborane, boran-
piperidine, diphenylborinic anhydride, tris(trimethylsilyl)borate, tris(tri-
methylsilyl)borane, trimethylacetic acid with diethylboinic acid, (2-
methylpropyl)borinic acid, boroglycine, boron alchols, boron etherates, boron
acetates {e.g. propylborodiacetate, phenylborodiacetate, boron tris(trifluoro)-
acetate), sodium tris{1-pyrazolyl)borohydride, sodium perborate, tolylboronic
acid, aluminum diboride, chlorodicyclohexylborane, methyldicyclohexyl-
borane, ethyldicyclohexylborane, propyldicyclohexylborane,
isopropyldicyclohexylborane, dimethyicyclohexylborane, diethyl-
cyclohexyfborane, dipropylcyclohexylborane, diisopropylcyclohexylborane,
lithium tetramethyfboron, lithium tetraethylboron, lithium tetrapropyllboron,
lithium tetraisopropylboron, tetrabutylboron, lithium tetraisobutylboron,
lithium
tetra-sec-butylboron, tetra-tart-butylboron, lithium tetraphenylboron,
potassium hydroxide with trimethylboron, potassium hydroxide with
triethylboron, potassium hydroxide with tripropyliboron, potassium hydroxide
with triisopropylboron, tributylboron, potassium hydroxide with tri-
isobutylboron, potassium hydroxide with tri-sec-butylboron, tri-tart-
butylboron,
potassium hydroxide with triphenylboron, vinylphenylboronic acid, 4-
vinylphenylboronic acid, boron phosphide, boron carbide, borinoaminoborine,
boroethane, pentaborane, hexaborane, decaborane, triselenideborane,
3o hexasilicide borane, trisilicide borane, trichloroborine dimethyletherate,
trichloroborine trimethlyammine, trimethylborine trimethlyammine, trimethyl-
borine triethlyammine, triethylborine trimethlyammine, tricyclohexylborine,
tri-
n-hexyltriborine trioxane, triisoamylborate, triisoamylborine, tri-p-
anisylborine,
trimethoxyboroxine, trimethylamminoborine, triethylamminoborine,
tripropylamminoborine, triisopropylamminoborine, triisobutylamminoborine,
tributylamminoborine, tri-sec-butylamminoborine, tri-tart-butylamminoborine,
triphenylamminoborine, tribenzylamminoborine, trimethylamminoboric acid,
triethylamminoboric acid, tripropylamminoboric acid, triisopropylamminoboric
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acid, triisobutylamminoboric acid, tributylamminoboric acid, tri-sec-butylam-
minoboric acid, tri-tart-butylamminoboric acid, triphenylamminoboric acid,
tribenzylamminoboric acid, trimethyldiborane, triethyldiborane, tripropyl-
diborane, trimethyltriborinetriamine (B), triethyltriborinetriamine (B),
trimethylt-
riborinetriamine (N), triethyltriborinetriamine (N),
trimethyltriborinetriamine
(N-B-B'), triethyltriborinetriamine (N-B-B'), tri-B-naphthylborate, tri-a-
naphthaborate, trlpehnylborineammine, tri-p-tolyborine, tri-p-xylxborine,
including analogues, homologues, isomers and derivatives thereof.
Corresponding compounds of aluminum, gallium, indium, and thallium are
to contemplated. See Organv Boron Chemistry, Volumes I & II (and subsequent
volumes, editions, or supplements), Howard Steinberg, InterScience
Publishers (1966), Boron-Nitrogen Gompounds, Niedenzu, Dawson, New
York, Academic Press (1965), The Or4anic Compounds of Boron. Aluminum.
Gallium. Indium, and Thallium, Nesmeianov, Nikolaevich, Amterdam, North-
Holland Pub. Co. (1967), Peroxides. Superperoxides. and azomides of Alkali
and Alkali Earth Metals, Perekisi, N.Y., Plenum Press (19966), incorporated
herein by reference.
Non-limiting examples of sodium derivative compounds of this
invention include: sodium bis(dimethylsilyl~mide, sodium bis(trimethyl-
2o silyl)amide, oxamic acid, P-aminosalicylic acid sodium salt, sodium salt 5-
nitroorotic acid, sodium D-gluconate, sodium hexacyanoferrate(III)
{Li3Fe(CN)6), sodium diphenylphosphide, sodium acetate, sodium acetate
acid, sodium salt acetic acid, sodium acetamide, sodium anilide, sodium
azide, ammonium diisodium amminepentacyanoferrate, sodium benzamide,
sodium antimonide, sodium orthoarsenate, sodium orthoarsenite, sodium
meta-arsenite, sodium diborane, sodium pentaborate, sodium dihydroxy
diborane, sodium borohydride, sodium cadium iodide, sodium chloride,
sodium calcium chloride, sodium carbide, sodium carbonate, sodium
hydrogen carbonate, sodium alkyl carbonates, sodium aryl carbonates,
sodium methyl carbonate, sodium ethyl carbonate, sodium carbonyl, sodium
cobalt (II) cyanide, sodium cobalt (III) cyanide, sodium cobaltinitrite,
sodium
cynomanganate (II), sodium cynomanganate (lll), sodium citrate, sodium
ferrosilicon, sodium ferricyanide, sodium ferrocyanide, sodium
nitroferricyanide, sodium aminepentacyanide, sodium formates, sodium
hydride, sodium hydroxide, sodium manganate, sodium permanganate,
sodium methionate, sodium napthenate, sodium nitride, sodium nitrate,
sodium nitrite, sodium nitrobenzene (e.g. sodium-p-nitrobenzene), sodium
nitrophenoxide, sodium etherate, sodium chromate, sodium oleate, sodium
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oxalate, sodium oxalatoferrate (II), sodium oxaiatoferrate (III), sodium
monoxide, sodium oxide, sodium peroxide, sodium, sodium mono-
orthophosphate, sodium hypophosphite, sodium orthophosphite, sodium
hydroxoplumbate, sodium rhodium cyanide, sodium selenide, sodium
5 selenite, sodium selenocynate, sodium seienocyanoplatinate, sodium
disilicate, sodium metasilicate, lithium sodium carbonate, lithium sodium
ferricyanide, sodium hydroxostannate, sodium disufide, sodium hydrosulfide,
sodium pentasulfide, sodium tetrasulfide, sodium trisulfide, sodium telluride,
sodium thioarsenate, sodium thioarsenite, sodium trithiocarbonate, sodium
to thiocyanate, sodium amide, sodium salt (E,E)-2,4-hexadienoic acid, disodium
fluorophosphate, disodium fluorophosphite, trisodium phosphate, trisodium
phosphite, sodium perchlorate, propanoic acid sodium salt, sodium formate,
sodium cyanate, sodium hexacyanocobaltate (III), sodium hypophosphite,
sodium hexaflurorsilicate, sodium nitroprusside, sodium phenoxide, sodium
15 phosphate (dibasic, monobasic, tribasic), sodium salicylate, sodium
selenide,
sodium tetracyanonickelate (II), sodium tetrafluoroborate, sodium
xanthogenate, sodium -p-aminobenzoate, sodium copper ferrocynanide,
sodium cupric ferrocyanide, sodium hexafluorophosphate, sodium
hexanitricobaltate lll, sodium naphthenate, sodium -B-naphthoxide, sodium
20 polysulfide, lithium -sodium phosphate, sodium stearate, sodium sulfide,
sodium sulfite, sodium sulfate, sodium thiocyanate, sodium xanthate, sodium
fluorosilicate, N-sodiumethylenediamine, oxalic acid disodium salt, sodium
beta-hydropyruvic acid, sodium 1,1-dimethylurea, sodium 1,1-diethylurea,
sodium 1,1-diepropylurea, sodium xanthate, sodium ethylxanthate, sodium
25 rnethylxanthate, sodium salt thiophenol, sodium triphenylmethylsodium,
methylsodium, ethylsodium, sodiumethynyl(acetylide), propylsodium,
isopropylsodium, butylsodium, isobutylsodium, secbutylsodium,
tertbutylsodium, pentasodium, hexylsodium, heptasodium, amylsodium,
isoamylsodium, benzylsodium, dimethylbenzyisodium, tolylsodium,
30 dodecylsodium, cyclopentadienylsodium, methylcyclopentadienylsodium,
cyclohexylsodium, sodiumheptyl, sodiumdodecyl, sodium tetradecyl, sodium
hexadecyl, sodium octadecyl, phenylsodium, sodium o-tolyl, sodium m-tolyl,
sodium p-tolyl, sodium-p-chlorophenyl, sodium p-bromophenyl, sodium o-
anisyl, sodium m-anisyl, sodium p-anisyl, sodium diethoxyphenyl, sodium
35 dimethoxyphenol, sodium m-cumyl, sodium p-ethoxyphenyl, sodium m-
dimethylaminophenyl, sodium 9-flourene, sodium a-napthyl, sodium b-
napthyl, sodium p-phenylphenyl, sodium 9-phenyianthryl, sodium 9-anthryl,
sodium 9-methylphenanthryl, sodium pyridyl, sodium 2-pyridyl, sodium 3-
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pyridyl, sodium 6-bromo-2-pyridyl, sodium 5-bromo-2-pyridyl, sodium
dibenzofuryl, sodium 3-quinoyl, sodium 2-lepidyl, sodium triphenylmethyl,
sodium 2,4,6-trimethylphenyl, sodium 2,4,6-triisopropylphenyl, sodium
2,3,5,6-tetraisopropylphenyl, sodium tetrabutylphenyl, thiophenedisodium,
toluenedisodium, diphenylethylenedisodium, sodiumamylethynyl,
sodiumphenylethynyl, sodiummethoxybromophenyl, sodium phenylisopropyl,
sodium tetraphenylboron, sodium tetramethylboron, sodium a-thienyl, sodium
m-trifluoromethylphenyl, phenylethynylsodium, 3-furylsodium,
phenylisopropylsodium, dibenzofuranylsodium, sodium dimethylbenzyl,
l0 sodium selenocyanate, sodium trimethylsilanolate, diphenylphosphide,
sodium benzoate, sodium tert-butyl carbonate, sodium azide, di-sodium-
cyanamide, sodium cyanide, sodium dicyanamide, cyclohexanebutyric acid
sodium salt, cyclohexane acid sodium salt, cyclopentadientylsodium, sodium
tri-tert-butoxyaluminum hydride, sodiumaluminum-tri-tert-butoxide, sodium
triethylborohydride, sodium trimethylborohydride, sodium tripropylborohydride,
sodium triisopropylborohydride, sodium tributylborohydride, sodium
triisobutylborohydride, sodium tri-sec-butylborohydride, sodium tri-tert-
butylborohydride, sodium trisiamylborohydride, sodium chlorate, sodium tert-
butoxide, sodium sec-butoxide, iso-butoxide, sodium antimonate, sodium
diphenylphosphide, sodium bis(trismethylsilyl) amide, trisodium phosphate,
sodium selenocyanate, sodium tri-sec-butylborohydride, sodium triethylsilano-
late, sodium thiocyanate, sodium acetylide, sodium chlorate, sodium
salicylate, sodium di-sodium tetracarbonylferrate, sodium tetraphenylborate,
sodium triethylborohydride, sodium triacetoxyborohydride, sodium
triphenylborane, sodium hydroxide, sodium diphenylphosphide, sodium
methoxide, sodium ethoxide, sodium tri-sec-butylborohydride, tri-tert-
butylborohydride, sodium triethylborohydride, sodium triphenylborohydride,
sodium trisiamylborohydride, sodium metavanadate, sodium cyclohexane-
butyrate, sodium hexachloroplatinate, sodium thiocyanate, sodium
selenocyanate, sodium cyanate, sodium floride, sodium hexafluoro-
antimonate, sodium hexafluoroaluminate, sodium hexafluoroarsenate, sodium
hexafluorosilicate, sodium hexacyanocobalt(Il~errate(II),
disodiumhexacyanocobalt(Il~errate(II), sodium hexafluorotitanate, sodium
hexafluorozirconate, sodium hexahydroxyantimonate, sodium
hexachlororuthenate, sodium hexachloropalladate, sodium formate, sodium
tetracyanonickelate, sodium tetrafluoroaluminate, sodium tetrafluoroborate,
sodium thioacetate, L-glutamic acid monosodium salt, fumaric acid sodium
salt, oxamic acid sodium salt, sodium salt Biphenyl-phospane, P-
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aminobenzoic sodium salt, aminobenzole acid sodium salt, alpha-
napthaleneacetic acid sodium salt, disodium salt 2,6-naphthaienedicarboxlic
acid, sodium cyclcohexanetherate, sodium phthalimide, P-aminosalicylic acid
sodium salt, sodium salt 3,5-dimethylcyclohexyl sulfate, indolebutyric acid
sodium salt,indole-3-butyric acid sodium salt, diphenylphosphide, sodium
dimethylsilanolate, sodium triethylborohydride, sodium propoxide, sodium
isopropoxide, sodium butoxide, sodium sec-butoxide, sodium pentoxide,
sodium tert-pentoxide, sodium hydrogenphthalate, sodium oxalate, sodium
hydrogensulfate, monosodium acetylenedicarboxylic acid, sodium
1o pyrophosphate, sodium dihydrogenphosphate, sodium hexoate (sodium salt
hexoic acid), sodium diphenylphosphide, sodium trimethylsilonalate, sodium
phthalic acid, P-aminobenzoic acid sodium salt, monosodium L-aspartic acid,
tetraphenyldisodium (C6H5)2CLi2C(C6H5)2, sodiumethylphenyl
(LiCH2C6H5), sodium bromate, sodium hydrogenphospate, monsodium salt
D-shaccharic acid, DI-asparatic sodium salt, (R)-alpha-hyroxymethylaspartic
acid sodium salt, sodium fluoride, sodium iodate, sodium salt ethyl malonate,
sodium thioacetate, sodium phenol, sodium salt aminobenzoic acid, sodium
aminophenol salt, sodium cyclohexenol, sodium methylcyclohexenol, sodium
cyclopropanol, sodium methylcyclopropanol, sodium cyclobutanol, sodium
2o methylcyclobutanol, sodium methylcyclopentanol, sodium cyclopentanol,
sodium cyclohexenol, sodium methylcyclohexenol, sodium
dimethylcyclohexenols (e.g. sodium 3,5-dimethylcyclohexanol, sodium 2,3-
dimethylcyclohexanol, sodium 2,6-dimethylcyclohexanol, sodium 2,5-
dimethylcyclohexanol, 3,5-dimethylcyclohexanol), sodium o-ethylxanthic acid,
2 5 monosodium salt 2-ketoglutaric acid, disodium salt, ketomalonic acid,
sodium
salt lactic acid, disodium thiosulfate, sodium antimony tartrate, sodium
dichloroacetate, sodium dimethylacetate, sodium diethylacetate, sodium
dipropylacetate, sodium metaborate, sodium tetraborate, sodium
tetrachlorocuprate, sodium acetoacetate, sodium diisopropylamide, sodium
3o diethylamide, sodium dimethylamide, sodium bis(dimethylsilyl)amide,
disodium phthalocyanine, disodiumtetrabromocuprate, disodium
tetrabromonickelate, disodiumtetrachloromanganate, disodiumbutadiyne,
sodium cyclopentadienide, sodium dicyclohexylamide, sodium diethylamide,
sodium dimethylamide, sodium dipropylamide, sodium diisopropylamide,
35 sodium thexylborohydride, sodium tri-tert-butoxyaluminohydride, sodium
trimethylsilyl)acetylide, sodium triethylsilyl}acetylide, sodium tris[(3-ethyl-
3-
pentyl~xy)aluminohydride, (phenylethynyl}sodium, 2-thienylsodium, sodium
diethyldihydroaluminate, sodium dimethyldihydroaluminate, sodium
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aluminum hydride, sodium bifluoride, sodium biphenyl, sodium biselenite,
sodium bis{2-methoxyethoxy~luminum hydride, sodium bismuthate, sodium
borate, sodium chlorite, sodium cobaltnitrite, sodium cyanoborohydride,
sodium cyclopentadienide, sodium dicyanamide, sodium
hexametaphosphate, sodium hexanitrocofbaltate, sodium hydrogenphosphite,
sodium hydrogenselenite, sodium hydrogensuifite, sodium hydrosulflte,
sodium hypochloride, sodium metaarsenite, sodium metabisulfide, sodium
metaperiodate, sodium methacrylate, sodium nitroferricyanide, oxybate,
sodium pentamethylcyclopentadienide, sodium phenolate, polyphosphate,
to sodium polyphosphite, sodium propionate, sodium pyrophosphate, sodium
selenate, sodium selenite, sodium tetrachloroaluminate, sodium
thiomethoxide, sodium thiosulfate, sodium thiosulfide, sodium thiosulfite,
sodium triactoxyborohydride, sodium trimethylsilonate, sodium
triethylsilonate, sodium tris(1-pyrazoly)borohydride, including analogues,
homologues, isomers and derivatives thereof.
The non limiting examples of aluminum derivative compounds of this
invention include: diisobutylaluminum hydride, dimethylaluminum hydride,
dimethylaluminum hydride, dipropylaluminumhydride,
diisopropylaiuminumhydride, dibutylaluminumhydride, di-tart-butylaluminum
hydride, di-sec-butylaluminum hydride, diisobutylaluminum chloride,
ethylaluminum sesquichloride, lithium aluminum hydride, lithium tri-tert-
butoxyaluminum hydride, lithium-aluminum alloy, aluminum triethoxide,
aluminum trimethoxide, aluminum tripropoxide, aluminum triisopropoxide,
aluminum tri-tart-butoxide, aluminum tri-sec-butoxide (aluminum sec-
butoxide), aluminum tri-isobutoxide, aluminum tributoxide, aluminum
pentoxide, diethylaluminum ethoxide, aluminum phosphate, diethylaluminum
chloride, diethylaluminum cyanide, diethylaluminum ethoxide,
diethylaluminum methoxide, diisobutylaluminum hydride, diisobutylaluminum
chloride, diisobutyalumnum fluoride, tetraisobutyldialuminoxarie,
3o triethylaluminum, trimethylaluminum, tributylaluminum, triisobutylaluminum,
tri-sec-butylaluminum, tri-tart-butylaluminum, tripentaluminum,
triphenylaluminum, triamylaluminum, triisoamylaluminum, tripropylaiuminum,
triisopropylaluminum, triisobutylaluminum, triisobutyldialuminoxane,
trioctylaluminum, sodium aluminum hydride, bis{2-methoxyethoxy}aluminum
hydride, aluminum borohydride, aluminum hydride, dimethlylberyllium,
potassium tri-tart-butoxyaluminum hydride, sodium tri-tart-butoxyaiuminum
hydride, lithium tri-tart-butoxyaluminum hydride, aluminum sec butoxide,
aluminum tart-butoxide, aluminum acetylacetone, aluminum ethoxide,
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aluminum methoxide, aluminum propoxide, aluminum isopropoxide,
aluminum butoxide, aluminum isobutoxide, aluminum pentoxide, aluminum
metaphosphate, aluminum hydroxide, aluminum metaphosphite, aluminum
hydroxystearate, aluminum monostearate, aluminum nitrate, aluminum
fluoride, aluminum fluoride trihydrate, sodium diethyldihydroaluminate,
sodium hexafluoroaluminate, aluminum hexafluorosilicate, lithium aluminum
hydride, lithium aluminum hydride bis(tetrahydrofuran), lithium tris((3-thyl-3-
pentyl)oxy)aluminohydride, lithium tri-tart-aluminohydride, aluminum-nickel
catalyst, aluminum silicate, aluminum silicate hydroxide, aluminum chloride
1 o hydrate, diethylaiuminum chloride, sodium bis(2-methoxyethoxy)aluminum
dihydride, aluminum carbide, aluminum phosphate, aluminum acetate
(aluminum diacetate hydroxide), dihydroaluminum acetate, aluminum
formoacetate, lithium aluminate, aluminum salt lactic acid,
tetramethyllithiumaluminum salt (LiAI(CH3}4), tetaethyllithiumaluminum salt,
tetrapropyllithiumaluminurn salt, tetraisopropyllithiumaluminum salt, tetra-
butyllithiumaluminum salt, tetraisobutyllithiumaluminum salt, tetra-sec-
butyllithiumaluminum salt, tetra-tart-butyllithiumaluminum salt,
tetraphenyilithium aluminum salt, aluminum tririconoleate, aluminum
metaphosphate, sodium aluminum hydride, aluminum dodecaboride,
aluminum diboride, aluminum arsenide, aluminum lactate, aluminum titanium
chloride, tri(N-nitroso-N-phenylhydroxylaminoato)aluminum, aluminum
acetylacetonate, methylaluminum dichloride, ethylaluminum dichloride,
propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum
dichloride, sec-butylaluminum dichloride, tart-butylaluminum dichloride,
isobutylaluminum dichloride, phenylaluminum dichloride, ethylaluminum
sesquichloride, methylaluminum sesquichloride, methylaluminoxane,
propylaluminum sesquichloride, ethylaiuminoxane, sodium bis(2-
rnethoxyethoxy)aluminum, aluminum magnesium silicate, aluminum
hydroxychloride, aluminum phosphide, aluminum potassium sulfide,
3o aluminum octoate (aluminum ethylhexonate), aluminum diformate, aluminum
triformate, aluminum chromate, aluminum napthenate, aluminum oleate,
aluminum palmite, aluminum pictrate, aluminum sodium silicate, aluminum
sodium chloride, aluminum isopropylate, aluminum magnesium ethoxide,
trimethylaluminum etherate, triethylaluminum etherate, including analogues,
homologues, isomers and derivatives thereof. Corresponding compounds of
gallium, indium, thallium are contemplated in the practice of this invention.
The non-limiting examples of silicon derivative compounds of this
invention include: dimethoxymethylsilane, dimethoxyethylsilane,
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diethoxymethylsilane, dipropoxymethylsilane, diisopropoxymethylsiiane,
dibutoxymethylsilane, diisobutoxyrnethylsilane, di-sec-butoxymethylsilane, di-
sec-butoxyrnethylsifane, diethoxyethylsilane, dipropoxyethylsilane, diisoprop-
oxyethylsilane, dibutoxyethylsilane, diisobutoxyethylsilane, di-sec-
butoxyethyl-
5 silane, di-sec-butoxyethylsilane, diethoxydimethylsilane, dimethoxydi-
methylsilane, dipropoxydimethylsilane, diisopropoxydimethylsilane,
dibutoxydimethylsilane, diisobutoxydimethylsilane, di-sec-butoxydi-
methylsilane, di-sec-butoxydimethylsilane, diethoxymethylethylsilane,
ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytripropylsilane,
1 o ethoxytriispropylsilane, methoxytrimethylsilane, propoxytrimethylsilane,
iso-
propoxytrimethylsilane, butoxytrimethylsilane, isobutoxytrimethylsilane, sec-
butoxytrimethylsilane, sec-butoxytrimethylsilane, phenoxytrimethylsilane,
ethoxydiethylsilane, isobutyldiethoxysilane, sec-butyldiethoxysilane, butyl
diethoxysilane, tertbutyldiethoxysilane, pentyldiethoxysilane, isobutyl-
15 dimethoxysilane, secbutyldimethoxysilane, butyldimethoxysilane,
tertbutyltri-
methoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
pentyldimethoxysilane, diethylsilandiol, tripropylsilandiol,
triisopropylsilandiol,
tertbutyldimethylsilane, diethylsilanediol (C2H5Si(OH)2), methyl-
tripropoxysilane, methyl-tris(dimethylsiloxy)silane, 1,1-
20 diphenylsilacyclohexane, pentamethylsilanime, 1,1,1-trimethyl-N-phenyl-N-
silanamine, hexamethyldisilazane, [1,1'-biphenyl]-4-yltrichlorosilane, (bromo-
methyl)chlorodimethylsilane, bromomethyltrimethylsilane, (4-
bromophenoxy}trimethylsilane, butylchlorodimethylsilane, trichlorobutylsilane,
trimethylbutylsilane, chloro(chloromethylklimethylsilane,
25 chloro(dichloromethyl)dimethylsilane, chlorodimethylphenylsilane,
chlorodimethyl-2-propenylsilane, chloroethenyldimethyisilane,
chloromethylsilane, (chloromethyl)dimethylphenylsilane, chlorome-
thyldiphenylsiiane, chloromethylphenylsilane, (chloromethyl~rimethylsllane,
(4-chloropehoxy}trimethylsilane, phenylchlorosilane, (3-
30 chlorophenyl}trimethylsilane, (3-chloropropyl~rimethylsilane,
chlorotriethoxysilane, chlorotriethylsilane, trimethylchlorosilane,
dichloro(chloromethyl)methylsilane, dichloro(dichioromethyl)methylsilane,
dichlorodiethoxysiiane, dichlorodiethylsilane, dichlorodimethylsilane,
dichlorodiphenylsilane, dichloroethenylmethylsilane,
35 methylethyldichlorosilane, dichloromethylsiiane, dichloromethyl(1-
methylethyl)silane, dichloromethyl{4-methylphenyl)silane,
dichloromethylphenylsilane, dichloromethyl-2-
propenylsilane,dichlorophenylsilane, diethenyldiphenylsilane,
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diethoxydimethylsilane, diphenyldiethoxysilane, diethoxymethylphenylsilane,
diethyloxymethyl-2-propenylsiiane, diethylsilane, diethyldifluorosilane,
difluorodiphenylsilane, dimethyoxydimethylsilane, dimethoxydiphenylsilane,
dimethylsilane, dimethyldiphenoxysilane, dimethyldiphenylsilane, dimethyl-2-
propenylsilane, dimethylphenylsilane, dimethyl-diacetatesilane,
diphenylsilane, 1,2,-ethenediylbis[trimethyl-(E)]silane (C8H20Si2),
ethenyldiethoxymethylsilane, ethenylethoxydimethylsilane, ethenyl-
triethoxysilane, ethenyltrimethylsilane, ethenyltris(1-methylethoxyrsilane,
ethenyitris(2-propenyloxy)silane, ethoxytriethytsilane, ethoxytrifluorosilane,
ethoxytrimethylsilane, ethoxytriphenylsilane, ethyltrifluorosilane,
ethyltrimethoxysilane, 1,2,-ethynediylbis[trimethyl]silane, ethynylsilane,
methoxysilane, methylsilane, methyldiphenylsilane, methylenebissilane,
methylenebis[trichloro]silane, (2-methylphenoxy)triphenylsilane, methyl-
phenylsilane, methyltriphenoxysilane, methyltriphenylsilane, methyltri-p-toly-
silane, phenylsilane, [1,3-phenylenebis(oxy)]bis[trimethyl]silane,
phenyltripropylsilane, tetraethenylsilane; tetraethylsilane,
tetraethoxysilane,
tetramethylsilane, tetramethoxysilane, tetrapropylsilane, tetrapropoxysilane,
tetraisopropylsilane, tetraisopropoxysilane, tetrabutylsilane,
tetrabutoxysilane,
tetra-sec-butylsilane, tetra-sec-butoxysilane, tetra-tert-butylsilane, tetra-
tert-
butoxysilane, tert-iso-butylsilane, tetra-iso-butoxysilane, tetraphenylsilane,
tetraphenoxysilane, triethylsilane, triethoxysilane, trimethylsilane,
trimethoxysilane, tripropylsilane, tripropoxysilane, triisopropylsilane,
triiso-
propoxysilane, tributylsilane, tributoxysilane, tri-sec-butylsilane, tri-sec-
butoxysilane, tri-tert-butylsilane, tri-tert-butoxysiiane, tert-iso-
butylsilane, tri-
iso-butoxysilane, triphenylsilane, triphenoxysilane, triethylmethylsilane,
triethoxymethylsilane, trimethoxymethylsilane, tripropylmethylsilane, tripro-
poxymethylsilane, triisopropylmethylsilane, triisoproxymethylsilane,
tributylmethylsilane, tributoxymethylsilane, tri-sec-butylmethylsiiane, tri-
sec-
butoxymethylsilane, tri-tert-butylmethylsilane, tri-tert-butoxymethylsilane,
tert-
iso-butylmethylsilane, tri-iso-butoxymethylsilane, triphenylmethylsilane,
triphenoxymethylsilane, diethylsilane, diethoxysilane, dimethylsilane,
dimethoxysilane, dipropylsilane, dipropoxysilane, diisopropylsilane,
diisopropoxysilane, dibutylsilane, dibutoxysilane, di-sec-butylsilane, di-sec-
butoxysilane, di-tert-butyisilane, di-tert-butoxysilane, tert-iso-butylsilane,
di-
iso-butoxysilane, diphenylsiiane, diphenoxysilane, ethylsilane, ethoxysilane,
rnethylsilane, methoxysilane, propylsilane, propoxysilane, isopropylsilane,
isoproxysilane, butylsilane, butoxysilane, sec-butylsilane, sec-butoxysilane,
tert-butylsilane, tert-butoxysilane, iso-butylsilane, iso-butoxysilane,
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phenylsilane, phenoxysilane, tribromomethylsilane, tributylsilane,
tributylphenylsilane, trichloro(chloromethyl)silane, trichloro(4-
chlorophenyl)silane, trichloro(3-chforopropyl)silane, trichloro(di-
chloromethyl)silane, trichlorododecylsilane, trichloroethenylsilane,
trichloroethoxysilane, trichloroethylsilane, trichlorohexylsilane,
trichloromethy-
Isilane, trichloro(1-methylethyl}silane, trichloro(2-methylphenyl)silane,
trichloro(3-methylphenyl)silane, trichloro(2-methylpropyl)silane,
trichlorootadectylsilane, trichlorooctylsilane, trichloropentylsilane,
trichlorophenylsilane, trichloro(2-phenylethyl)silane, trichloro-2-
propenylsilane,
l0 trichloropropylsilane, triethoxysilane, triethoxyethylsilane,
triethoxyethylsilane,
triethoxyphenylsilane, triethoxypentylsilane, triethoxy-2-propenylsilane,
triethylsilane, triethylfluorosilane, triethylphenylsilane,
trifluorophenylsilane,
trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane,
trimethoxyisopropylsilane, trimethoxybutylsilane, trimetho-
xyisobutylsilane,trimethoxy-sec-butylsilane, trimethoxy-tert-butylsilane,
trimethoxyphenylsilane, trimethylsilane, trimethyl(4-methylphenyl}silane, tri-
methyl(2-methylpropyl)silane, trimethylphenoxysilane, trimethylphenylsilane,
trimethyl(phenyimethyl)silane, trimethyl(cyclohexylmethyl)silane, trimethyl-2-
propenylsilane, trimethylpropylsilane, trimethyl[4-
[(trimethylsifyl)oxy]phenyl]silane, ethenyl-triacetatesilanetriol, methyl-
triacetatesilantriol, tripropylsilane, ethyldimethylsilanol,
methyldiphenylsilanol,
triethylsilanol, triphenylsilanol, tetrabutyl ester silicic acid (C16H3604Si),
tetraethyl ester silicic acid, tetrakis(2-ethylbutyl) ester silicic acid,
methylsilicate (C4H12Si04), tetraphenyl ester silicic acid, tetrapropyl ester
2 5 silicic acid, triethyl phenyl ester silicic acid, 1,2-dichloro-1,1,2,2-
tetramethyldisilane, 1,2,-difluorotetramethyldisiiane, hexamethyldisiiane, 1,3-
diethenyl-1,1,3,3-tetramethyfdisiloxane, 1,3-diethenyl-1,1,3,3-
tetramethyldisilazane, bis(methoxydimethylsilyl)oxide, 1,1,1,3,3,3-
hexaethyldisiloxane, 1,1,1,3,3,3=hexaethyldisilazane, hexamethyldisiloxane,
3 o hexamethyldisilazane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetramethyl-
disilazane, 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane, 1,1,3,3-tetramethyl-
1,3-
diphenyldisilazane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 1,1,1-trimethyl-
3,3,3-triphenyldisilazxane, docosamethyfdecasiloxane,
docosamethyldecasilazane, ethenylheptamethylcyctetrasiloxane,
35 ethenylheptamethylcyctetrasilazane, heptamethylcyclotetrasiloxane,
heptamethylcyclotetrasilazane, octaphenylcyclotetrasiloxane,
butylmethyl(cyclic tetramer)siloxane, 2,4,6,8-tetraethenyl-2,4,6,8-
tetramethylcyclotetrasiloxane (C12H2404Si4), 2,4,6,8-tetraethyl-2,4,6,8-
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cyclotetrasiloxane, 2,4,6,8-tetraethyl-2,4,6,8-cyclotetrasilazane, 2,4,6,8-
tetra-
ethyl-2,4,6,8-cyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane,
2,4,6,8-tetramethylcyclotetrasilazane, 2,4,6,8-tetramethyl-2,4,6,8-
tetraphenylcyclotetrasiloxane, 2,2,4,4,6,6-hexamethylcyclotrisilazane,
hexamethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiioxane,
2,4,6-
methyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-methyl-2,4,6-
triphenylcyclotrisiloxane, 2,4,6-mmethyl-2,4,6-tripehnylcyclotrisiloxane,
decamethylcyclopentasiloxane, decamethylcyciopentasilazane, 2,4,6,8,10-
pentamethylcyclopentasiloxane, 2,4,6,8,10-pentamethylcyclopentasilazane,
l0 octademethylcyclononasiloxane, octademethyicyclononasilazane,
hexadecamethylcyclooctasiloxane, hexadecamethylcyclooctasilazane,
dodecamethylcyclohexasiloxane, dodecamethylcyclohexasilazane,
hexamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, tetra-
decamethylcycloheptasilazane, decamethyltetrasiloxane, 1,1,1,3,5,7,7,7-
octamethyltetrasiloxane, aminotrisilane, benzyltriethoxysilane,
butyltrifluorosilane, carboxyethyldimethylsilane, chloromethylsilicane,
chlorotriisocyanatesilane, dichloromethylsilicane, diethoxydibutoxysilane,
diethylanilinefluorosilicate, diethyldichlorosilane, [2-
(cyclohexenyl)ethyl]tri-
ethoxysilane, [2-(cyclohexenyl)ethyl]methyldiethoxysilane, [2-
(cyclohexenyl)ethyl]dimethylethoxysilane, [2-(cyclohexenyl~
ethyl]trimethylsilane, [2-(cyclohexenyl)ethyl]triethylsilane,
cyclohexyldimethoxymethylsilane, cyclohexylmethoxydimethylsilane,
cyclohexyltrimethylsilane, cyclohexyltriethylsiiane,
dicyclohexyldimethylsilane,
cyclohexyldimethylsilane, cyclohex-1-enyl-trimethylsilane,
benzyltrimethylsilane, (1-cyclohexen-1-ylethynyl)trimethylsilane, 1-
cyclohexenyltrimethylsilane, cyclohexenyloxytrimethylsilane,
cyclohexyltrichlorosilane, 1-cyclopropyl-1-(trimethylsilyloxy}ethylene,
phenyldimethylsilanol, phenylsilandiol, cyclohexylsilandiol,
cyclohexylethylsilandiol, tert-butylsilandiol, cyclohexyldimethylsilanol,
3 o cyclohexyldiethylsilanol, benzyltrimethylsilane, N-
benzyltrimethylsilylamine,
phenyl dimethylsilanol, phenyl diethylsilanoi,
cyclohexylethylenetrimethylsiiane, N-cyclohexylethylenetrimethylsilyiamine,
cycloethylenetrimethylsilane, diphenyldiethoxysilane,
diphenyldimethoxysilane, diphenyl-methyl-ethoxysiiane, diphenylmethylsilane,
diphenylmethylsilandiol, diphenylsilandiol, methyl-phenyl-diethoxysilane,
methyl-phenyl-dimethoxysilane, methyl-phenyl-dichiorosiiane, octadecyltri-
methoxysilane, octyltriethoxysilane, octyltrimethoxysilane, 1,3-bis(3-
aminopropyl}-1,1,3,3-tetramethyldisiloxane, 1,3-bis{3-aminopropyl)-1,1,3,3-
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tetramethyldisilazane, tertbutyldimethylsilandiol,
hydroxymethylenetrimethylsilane (CH3)3CH24H), hydro-
xyethylenetrimethylsilane, hydroxymethyltriethylsilane, hydrox~
ethyltriethylsilane,diethylsilanediol, dimethylsilanediol, dipropylsilanediol,
diisopropylsilanediol, dibutylsflanediol, di-tert-butylsilanediol, di-iso-
butylsilanediol, di-sec-butylsilanediol, diphenylsilanediol,
dicyclohexyfsilanediol, cyclohexylmethylsilanediol, cyclohexylethylsilanediol,
dimethoxydichforosilane, dimethylanilineflourosilicate, dimethyldi(B-
chloroethoxy)silane, dimethylflourochiorosilane, dimethylsilicane, di-a-
1o napthylamineflourosilicate, di-b-napthylamineflourosilicate, di-m-
nitranilineflourosilicate, dinitrosodiphenylamine, diphenylar-
sinophenylenetriethylsilane, diphenyldichlorophenoxysilane, di-o-
toluidinefluorosilicate, di-m-toluidinefluorosilicate, di-p-
toluidinefluorosilicate,
docosamethyldecasiloxane, dodecamethylcyclohexasiloxane, dodecamethyl-
pentasiloxane, eicosamethylnonasiloxane, silanesifanesilane-
docosamethyldecasifazane, dodecamethylcyclohexasilazane,
dodecamethylpentasilazane, eicosamethylnonasilazane, ethyl-
diethoxyacetoxysilane, ethyldiethoxychlorosilane, ethylisocyanatesilane,
ethyltriethoxysilane, ethyltriphenylsilicane, hexadacamethylcyclooctasiloxane,
2 o hexadacamethylcyclooctasiiazane, hexamethylsilicane (hexamethyldisilane),
hexamethylmethylenedislane, hydroxyrnethyltrimethylsilane, methylsilicane,
methyltriphenylsilicane, octadecamethylcotasiloxane, octamethyl-
cyclotetrasiloxane, octamethyltrisiloxane, octadecamethylcotasilazane,
octamethylcyclotetrasilazane, octamethyltrisilazane, tetraphenylenesilane,
2 5 phenylenediamineflourosilicate, phenylisocyanatesifane,
phenyltrichlorosilicane, silicobenzoic acid, tetra-m-aminophenylsilane,
tetrabenzylsilicane, tetra-p-biphenylylsilane, tetradecamethylcyclohep-
tasiloxane, tetradecamethylcycloheptasilazane, tetradecamethylhexasiloxane,
tetradecamethylhexasilazane, tetraethylsilane, tetraethylthiosilane,
30 tetrahexyfoxysilane, tetraisopropylmercaptane silicon, tetramethoxysifane,
tetramethylmercaptanesilicon, tetramethylsilane, tetraphenoxysifane,
tetraphenylsilane, tertapropoxysilane, tetratriethylsiloxysilane,
thioisocyanatotriethylsilane, tolidinefluorosilicate(o), tri-p-
Biphenylylphenyl-
silane, trichloromethyltriethoxysifane, triethylbromosilane,
triethylchlorosilane,
35 triethylfluorosilane, triethylphenylsilane, trimethylchloromethylsilane,
trimethylethoxysilane, triphenylacetoxysifane, vinyltriphenoxysilane,
vinyltriethoxysilane, silicane cyanate, dibromosilane, dibromodichlorosilane,
dichlorosilane, dichlorodifluorosifane, hexaoxocyclosilane, hexacycl~ilazane,
CA 02310056 2000-OS-16
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monooiodosilane, (tri-)nitrilostlane (silicylamine), trichlorosilane,
trifluorosilane,
siticane diimide (Si(NH)2), silicane tetramide, silicane isocyanate, silicon
tetracetate, tetrabromosilane, silicon hex(di-)bromide, silcon carbide,
tertachlorosilane, hexachlorodisilane, tetrafluorosilane, hexa-fluorodisilane,
5 silicon hydride (SiH4), disilane (Si2H6), trisilanepropane, tetrasilane
butane,
silicon nitride, silicon thiocyanate, disilicic acid, silicon cyanate, allyl-
chlorodimethylsilane, allylchloromethyldimethylsitane, allyl-
dichtorodimethylsilane, altyl(diisoproprylamino)dimethylsilane, allyloxy-tert-
butyldimethylsilane, allytoxy-sec-butyldimethylsilane, allyfoxy-iso-butyl-
1 o dimethylsilane, allylchlorodiethytsilane, allylchloromethyldiethylsilane,
allyldichlorodiethylsilane, allyl(diisoproprylamino)diethylsilane, allyloxy-
tert-
butyldiethylsilane, allyloxy-sec-butykiiethylsilane, allyloxy-iso-butyldiethyl-
silane, allyloxybutyldimethylsilane, allyloxytrimethylsilane, allyloxy
triethylsilane, diallyloxydimethylsilane, triallyloxymethylsilane,
15 diallyloxydiethylsilane, triallyloxyethylsilane,
diallyloxydimethoxylsilane, trtal-
lyloxymethoxylsilane, diallyloxydiethoxylsilane, trialtyloxyethoxylsilane,
allyltri-
chlorosilane, allyltriethoxysilane, allyltriisopropylsilane,
allyltripropylsilane, al-
lyltriisopropyloxysilane, allyltripropyloxysilane, atlyltrimethoxysilane,
allyltri-
methylsilane, allyltriethylsilane, allyltriphenylsilane, 3-
aminopropyltriethoxy
2 o silane, 3-aminopropyltrimethoxysilane, 3-aminoethyltriethoxysilane, 3-
aminoethyltrimethoxysilane, 3-aminomethyltriethoxysilane, 3-aminomethyltri-
methoxysilane, 3-aminotrimethoxysilane, 3-aminotriethoxysilane, 3-
amino(cyclohexyl)propyltriethoxysitane, 3-amino(cyclohexyt)pro-
pyltrimethoxysilane, 3-amino(cyclohexyl)ethyltriethoxysilane, 3-
25 amino(cyclohexyl)ethyltrimethoxysilane,
3-amino(cyclohexyl)methyltriethoxysilane, 3-amino(cyclohexyl}-
methyltrimethoxysilane, 3-amino(cyclohexyl)trimethoxysilane, 3-
amino(cylcohexyl)triethoxysilane, trimethoxypropylsilane, trte-
thoxypropylsilane, trimethoxysitane, 3-amtnopropyltrimethoxysilane, N-[3-
3 o (trimethoxysilyl)propyl]aniline, N-[3-(triethoxysityl)propyl]aniline, N-[3-
(triethoxysilyl)ethyt]aniline, N'-[3-
(trimethoxysilyl)propyl]diethylenetriamine, N-
[3-(trimethoxysilyl)propyl]ethylenediamine, N-[3-(triethoxysilyl)propyl]ethyl-
enediamine, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl
methacrylate, aminotriphenylsilane, azidotrimethylsifane, azidotriethylsilane,
35 azidotripropylsilane, azidotributylsilane, azidotrimethoxysilane,
azidotriethoxysilane, azidotripropoxysitane, azidotributoxysilane, bis[3-
(trimethoxysilyl)propyl]amine, N,O-bis(trimethylsilyl)acetamide, bis(trimethyl-
silyl)acetylene, bis(trimethylsilylkyclopentadiene, 1,4-
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bis(trimethylsilyl)benzene, N,O-bis(trimethylsilyl)hydroxylamine,
bis(trimethylsilyl)methane, 2,3-bis(trimethylsilyloxyr1,3-butadiene, 1,2-
bis(trimethylsilyloxy)cyclobutene, 1,2-bis(trimethylsilyl)cyclobutene, 1,2,3-
bis(trimethylsilyl)cyclobutene, 1,2,3,4-bis(trimethylsilyl)cyclobutene,
bis(trimethylsilyl)cyclobutene, 1,2-bis(trimethylsilyloxy)ethane, 2,3-bis(tri-
methylsilyl~1-propene, 2,4-bis(trimethylsilyloxy)pyrimidine, 1,3-
bis(trimethylsilyl)urea, O,O'-bis(trimethyisilyl)uracil,
bis(trimethylsilyl)trifluoroacetamide, (1-cyclohexenyl-1-
ethynyl)trimethylsilane,
1-cyclohexenyloxytrimethylsilane, 1-cyclohexyltrimethylsilane,
to cyclohexyldimethoxysilane, cyclohexyftrimethoxysilane,
cyclohexyldiethoxysilane, cyclohexyltriethoxysilane,
cyclohexyldimethoxymethylsilane, cyclohexyltrimethoxysilane,
cyclohexyldiethoxymethylsifane, cyclohexyltriethoxysiiane,
cyclohexyldimethoxysilandiol, cyclohexyldiethoxysilandiol,
cyclohexyldipropxymethylsilane, cyclohexyldipropxymethylsilandiol,
cyclohexyltrichlorosilane, [(1-cyciopropyletheneyl)oxy]trimethylsilane,
diallyldimethylsilane,
diethoxymethylphenylsilane, 3-(diethoxymethylsilyl)propyiamine,
diethoxymethylsilane, dimethyloctadecyline, ethyltriacetoxysilane,
2 o methyltriacetoxysilane, propyltriacetoxysilane, isopropyltriacetoxysilane,
butyltriacetoxysilane, isobutyltriacetoxysilane, sec-butyltriacetoxysilane,
tert-
butyltriacetoxysilane, benzyltriacetoxysilane, phenyltriacetoxysilane, cycl-
pentadienyltriacetoxysilane, cyclohexyltriacetoxysilane,
isopropoxytrimethylsilane, isopropylaminotrimethylsilane, lithium
bis(trimethylsilyl)arnide,
methoxydimethyloctylsilane, methylbis(trimethylsilyloxy)vinylsilane,
octyltriethoxysilane, octyltrimethoxysilane,
(phenylthiomethyl)trimethylsilane, phenyltriethoxysilane, phenyl-
trimethoxysilane, poly(dimethylsiloxane) silicon hexaboride, silicon nitride,
3o silicon tetracetate, silicon tetrachloride, silicon tetrafluoride, sodium
bis(trimethylsilyl)amide, -tetrakis(trimethylsilyl)silane, tetravinylsilane,
trichloro-
3-chloropropylsilane, trichlorocyclopentysilane, cyclohexyltrichlorosilane,
trichlorovinylsilane, 3-(triethoxysilyl~ropionitrile, 3-(tri-
methoxysilyl)propylamine, 3-(trimethoxysilyl)propyl isocyanate, 3-
(trimethoxysilyl)propyl thiocyanate, trihexylsilane, triisopropylsilane,
(triisopropylsilyl)acetylene (chforotriisopropylsilane),
triisopropylsilylchloride, 1-
(triisopropylsilyl)pyrrole, trimethylsilylacetate, (trimethylsilyl)acetic
acid,
(trimethylsilyl)acetylene, trimethylsilyl cyanide,
(trimethylsilylkliazomethane, b-
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(trimethylsilyl)-1,3-cyclopentadiene, 1-(trimethylsilyl)imidazole, 1-(trimethy-
Isilyl)pyrrolidine, triphenylsilane, 1,1,1-triphenylsilylamine,
triphenylsilylchloride, tris(2-methoxyethoxy~inylsilane, 2,5,5-
tris(trimethylsilyl~
1,3-cylcopentadiene, tris(trimethylsilyf)borate, tris(trimethylsilyl)amine,
tris(tri-
methylsilyl)germaniumhydride, tris{trimethylsilyl)methane,
tris(trimethylsilylmethyl)borane, tris(trimethylsilyloxy)silane,
vinyltrimethoxysilane, vinyltrimethylsilane, trimethylsilyl N-(trimethylsilyl)-
car
bamate, triphenylsilylamine, triethoxysilylamine, tributoxysilyamine,
tripropoxysilylamine, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-
1 o triisopropoxsilane, vinyltrimethoxysifane, vinyltriethoxysilane,
dimethoxymethylvinylsilane, diethoxymethylvinylsilane,
dimethoxyethylvinylsilane, diethoxyethylvinylsilane,
dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, di-
methylpropoxyvinylsilane, dimethylisopropoxyvinyfsilane,
diethylmethoxyvinylsilane, diethylethoxyvinylsilane,
diethylpropoxyvinylsiiane,
diethyiisopropoxyvinylsilane, dirnethylethoxy(methylvinyl)silane,
dimethoxymethyl(ethylvinyl)silane, diethoxymethyl(propylvinyl)silane,
vinyltrimethylsiiane, vinyltriethylsiiane, vinyltriphenylsilane, vinyltris(2-
butyiidenaminooxy)silane, vinyltris(2-methoxyethoxy)silane, vinyltris{2-methyl-
2 0 ethoxy)silane, vinyltris(2-ethoxy)silane,
vinyltris(trimethylsiloxy)silane, 3-(2-
aminoethylamino)propyltrimethoxysilane, 3-arninopropyl-methyl-
diethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,
3-aminomethyltriethoxysifane, 3-aminoethyltriethoxysilane, 3-
aminopropyltrimethoxysilane, 3-aminomethyltrimethoxysilane, 3-
aminoethyltrimethoxysilane, (3-aminopropyl)tris[2-(2-
methoxyethoxy)ethoxysilane, amyltriethoxysilane, 1,3-bis{chloromethyl~
1,1,3,3-tetramethyldisilazane, 1,3-bis(chloromethyl)-1,1,3,3-
tetramethyldisiloxane, 1,2-bis(chlorodimethylsilyl)ethane, 1,3-bis(3-
cyanopropyl}tetramethyldisiioxane, 1,3-bis(3-cyano-
3o propyl)tetramethyldisilazane, bis(diethylamino)dimethylsilane,
bis(dimethylaminoklimethylsilane, bis( diethylamino)diethylsilane,
bis(dimethylamino)diethylsilane, 1,2-bis[(dimethylamino)dimethylsilyl]ethane,
1,2-bis(dimethylsilyl}benzene, 1,2-bis(dimethylsilyl)cyclohexene, 1,4-
bis(dimethylsilyl)benzene, 1,4-bis(dimethylsilyl)cyclohexene, 1,3-bis(4-
3 5 hydroxybutyl)-1,1,3,3-tetramethyldisiloxane, 1,3-bis(4-hydroxybutyl)-
1,1,3,3-
tetramethyldisilazane, bis(N-methylbenzamido)methylethoxysilane, 1,4-
bis(trirnethylsilyl)butadiyne, N,O-bis(trimethylsilyl)acetimide, N,N-bis(tri-
rnethylsilyl)methylamine, N,N-bis(trimethylsilyl}amine, N,N-bis(tri-
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ethylsilyl)amine, N,N'-bis(trimethylsilyl)urea, bis(trimethylsilyl)phosphite,
N,O-
bis(trimethylsilyl)trifluoroacetirnide, tert-butyldimethylsilane, tert-
butyldimethylsilanol, (tert-butyldimethsilyl)acetylene, tert-
butyldimethylsilyl
cyanide, N-(tert-butyldimethylsilyl)dimethylamine, butyldimethylchlorosilane,
tert-butyldimethylchlorosilane, O-(tert-butyldimethylsilyl)hydroxylamine, 1-
(tert-
butyldimethylsilyl)imidazole, tert-butyldiphenylsilyl cyanide, tert-
butyldicyclohexylsilyl cyanide, N-tert-butyltrimethylsilylamine, tert-butyl-
trimethylsilyi peroxide, tert-butyl-trimethylsilyl acetate, [2-
(cyclohexenyl)ethyl]triethoxysilane, N,N-diethyltrimethylsilylamine, N,N-
to diethyltriethylsilylamine, N,N-diethyl(trimethylsilylmethyl}amine, diethyl
trimethylsilyl phosphite, diphenylmethylsilane, dicyclohexylmethylsilane,
diphenylethylsilane, dicyclohexylethylsilane,
diphenylsilane, dicyclohexylsilane, dicyclohexylsiladiol, 1,3-diphenyl-1,1,3,3-
tertamethyldisilazane, 1,3-diphenyl-1,1,3,3-tertamethyldisiloxane, 1,3-
dicyclohexyl-1,1,3,3-tertamethyldisilazane, 1,3-dicyclohexyl-1,1,3,3-
tertamethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-
1,1,3,3-tetramethyldisiloxane, dodecyltriethoxysiiane, 1,1,3,3,5,5-
hexamethyltrisilazane, 1,1,3,3,5,5-hexamethyltrisiloxane, methyl-
triethoxysilane, ethyltriethoxysilane, propyltriethoxysilane,
2 0 isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane,
isobutyltriethoxysilane, sec-butyltriethoxysilane, tert-butyltriethoxysilane,
hexyltriethoxysilane, (3-isocyanatropropyl)triethoxysilane,
(isopropenyloxy)trimethylsilane, isopropyldimethylchlorosilane, lithium
bis(trimethylsilyl)amide, potassium bis(trimethylsilyl)amide, (3-men;,ap-
topropyl)methyldimethoxysilane, (3-mercaptopropyl)triethoxysilane, (3
mercaptopropyl)trimethoxysilane, (methoxymethyl)trimethylsilane,
methoxytrimethylsilane, ethoxytrimethylsilane, [3-
(methylamino}propyl]trimethoxysilane, methyldiethoxysilane, 2-
methylbenzosilylazole, methyl-octadecyl-dichlorosilane, methyl-
octyldimethoxysilane, methyl-octyldichlorositane, methyl-phenyl-chlorosilane,
methyl-phenyl-dichlorosilane, methyl-phenyl-diethoxysilane, methyl-phenyl-
dimethoxysilane, (methylthio)trimethylsilane, methyltriactoxysilane, methyltri-
chforosilane, ethyltrichlorosilane, methylethoxysilane, ethylethoxysilane,
methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, N-methyl-N-
trimethylsilylacetamide, methylvinyldiethoxysilane, phenyltriethoxysilane,
cyclohexyltriethoxysilane, Phenyltrimethoxysilane, cyclohexyltrimethoxysilane,
Phenyl(methylene)triethoxysilane, cyclohexyl(methylene)triethoxysilane,
pheny!(methylene)trimethoxysilane, cyclohexyl(methylene)trimethoxysilane,
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Phenyl(ethylene)triethoxysilane, cyclohexyl(ethylene)triethoxysilane,
phenyl{ethylene)trimethoxysilane, cyclohexyl(ethylene)trimethoxysilane,
phenyltrimethylsilane, phenyltriethylsilane, phenyltripropylsiiane,
phenyltriisopropylsilane, phenyltributylsilane, phenyltri-sec-butylsilane,
phenyltri-tert-butylsilane, phenyltriisobutylsilane,
cyclohexyltrimethylsilane,
cyclohexyitriethylsilane, cyclohexyltripropylsilane,
cyclohexyltriisopropylsilane,
cyclohexyltributylsilane, cyclohexyltri-sec-butylsilane, cyclohexyltri-tert-
butylsilane, cyclohexyltriisobutylsilane,
Phenyltriethoxysilanediol, cyclohexyltriethoxysilanediol, Phenyl-
1o trimethoxysilanediol, cyclohexyltrimethoxysilanediol,
phenyltrimethylsilanediol, phenyltriethylsilanediol,
phenyltripropylsilanediol,
phenyltriisopropylsilanediol, phenyltributylsilanediol, phenyltri-sec-
butylsilanediol, phenyltri-tert-butylsilanediol, phenyltriisobutylsilanediol,
cyclohexyltrimethylsilanediol, cyclohexyltriethylsilanediol,
cyclohexyltripropy~
silanediol, cyclohexyltriisopropylsilanediol, cyclohexyltributylsilanediol,
cyclohexyltri-sec-butylsilanediol, cyclohexyltri-tert-butylsilanediol,
cyclohexyltriisobutylsilanediol, propyltrimethoxysilane, tetramethylsilane,
2,4,fi,8-tetramethylcyclotetrasilazane, 1,1,3,3-tetramethyldisilazane, 1,1,3,3-
tetramethyldisiloxane, tetramethyltetrasilylfulvalene, trimethylethoxysilane,
2o N-(trimethylsilyl)acetamide, trimethylphenoxylsilane, 1-(trimethy-
Isiloxy)cyciopentene, 1-(trimethylsiloxy)cyclohexene.
trimethoxylphenylsilane, 1-(trimethoxylsilylxyclopentene, 1-
(trimethoxylsilyl)cyclohexene, triethoxylphenylsilane, 1-(tri-
ethoxylsilyl)cyclopentene, 1-(triethoxylsilyl)cyclohexene,
2 5 trimethoxylcyclohexylsilane, (trimethoxylsilyl)cyclopentane,
(trimethoxylsilyl)cyclohexane, triethoxylcyclohexylsilane,
(triethoxylsilylkyclopentane, (triethoxylsilylkyclohexane,
trimethylsilyl azide, triethylsilyl azide, tripropylsilyl azide,
triisopropylsilyl azide,
tributyl azide, triisobutyl azide, tri-tert-butyl azide, tri-sec-butyl azide,
triphenyl
30 azide,
trimethoxylsilyl azide, triethoxylsilyl azide, tripropoxylsilyl azide,
triisopropoxylsilyl azide, tributoxyl azide, triisobutoxyl azide, tri-tert-
butoxyl
azide, tri-sec-butoxyl azide,
(trimethylsiiyl)cyclopentadiene, trimethylsilyl cyanide,
(trimethylsilyl)acetontrile,
35 traps-3-(trimethylsilyl)allyl alcohol, 2-{trimethylsilyl)methanol, 2-
(triethylsilyl)ethanol, (trimethylsilyl)methanol, (triethylsilyl)ethanol,
triisobutyl-
silane, 2-(trimethylsilyl)methanol, 2-{trimethytsilyl)ethanol, O-{trimethy-
Isilyl)hdroxylamine, 1-{trimethylsilyl)imidazole, trimethylsilylisocyanate,
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(trimethylsilyl)methyl acetate, trimethylsilyl methacrylate,
(trimethylsilyl)methylamine, N-(trimethylsilylmethyl)urea, 4-
(trimethylsilyl)morpholine, 4-(triethoxysilyl)butyronitrile, 1-
(trimethylsilyl)pryrrolide, 1-trimethylsilyl-1,2,4-triazole, triphenyisilane,
5 triphenylsilandiol, triphenylsilylamine, tricyclohexylsilylamine, phenyl-
dimethoxysilylamine, methylphenyldimethoxysilane, phenyldiethoxysifylamine,
cyclohexyldimethoxysilylamine, cyclohexyldiethoxysilyiamine, dipheny-
Imethoxysilylamine, diphenylethoxysilylamine, dicyclohexylmethoxysilylamine,
dicyclohexylethoxysilylamine, cyclohexylsilyltriamine,
cyclohexyl(ethyl)silyltri-
1 o amine, cyclohexyl(methyl)silyltriamine, benzylsilyltriamine,
benzyl(methyl)silyltriamine, diphenytsilyldiarnine, phenylethoxysilyldiamine,
cyclohexylethoxysilyldiamine, cyclohexyldiethoxysilylamine,
cyclohexylmethoxysilyldiamine, cyclohexyl(ethyl)ethoxysilyldiamine,
cyclohexyl(methyl)ethoxysilyldiamine, benzylmethoxysilyldiamine, benzyl-
15 dimethoxysilylamine, tris{trimethylsilyl)amine,
tris(trimethoxylsilyl)amine,
tris(triethoxylsilyl}amine, tris(trimethylsilyl)borate,
tris{trimethylsilyl)methane,
tris(trimethylsilyl}ethane, tris(trimethylsilyl)phosphate,
tris(trimethylsilyl)phosphine, tris(trimethylsilyl)silane,
vinyltriethoxysilane,
vinyltrichlorosilane, vinyl-triisopropylsilane, vinyltrimethylsilane, vinyltri-
2 0 phenylsilane, vintris(2-buytlidenaminooxy)silane, vinyltris(2-
methoxyethoxy~
silane), vinyltris(trimethylsiloxy)silane,
allyldimethylsilane, allyldiethylsilane, diallyldimethylsilane,
diallyldiethylsilane,
allyoxytrimethylsilane, allyoxytriethylsilane, allylphenylsilicon,
tripropylsilane,
tris(trimethylsilyl)silane, pentamethylcyclopentasiloxane, 2,4,6,8,10-
2 5 pentamethylcyclopentasiloxane, pentamethyldisiloxane, amyltriethoxysilane,
vinyltricholorsilane, vinyltriethylsilane, vinyltrimethylsilane,
vinyltriphenylsilane,
vinyltriethoxysilane, vinyltripropyoxysilane, vinyltrisopropyoxysilane,
vinyitri-
methoxylsilane, vinyltriphenoxysilane, vinyltributoxysilane,
vinyltriisobutoxysilane, vinyltrisecbutoxysilane, vinyltri-tert-butoxysilane,
3 o vinyltris(2-butylidenaminooxy)silane, vinyltris(2-methoxyethoxy)silane,
vinyltris(trimethoxysiloxy)silane, N,N-dimethyitrimethylsilyamine, N,N-
diethyltrimethylsilyamine, 3,3-dimethyl-1-trimethylsily-1-butyne, 3,3-diethyl-
1-
trimethylsily-1-butyne, dimethyltrimethylsifylmethylphosphonate, dimethyltri-
methylsilylphosphite, dimethyltritylbromosilane, dimethyl-vinyl-ethoxysilane,
35 dimethylvinylchlorosilane, diphenylmethylchlorosilane,
diphenylethylchlorosilane, phenyldimethylchlorosilane,
phenyldiethylchlorosilane, diphenyldi(M-tolyl)silane, 1,2-dimethylsilane, 1,2-
diethylsilane, 2,2,4,4,6,6-hexamethylcyclotrisilazane, N-
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benzyltrimethylsilylamine,
96
chlorodimethyloctylsilane, trimethyloctylsilane, disiloxane, silicori nitride,
disilane, dimethylsilanediol, trichlorocyclopentysilane,
tris(isopropylthio)silane,
chlorotrimethylsilane, chlorodimethylsilane, bis{chloromethyl)dimethylsilane,
propyltrichlorosilane, trimethyl(pentafluorophenyl)silane, trichloro(1 H,1 H,-
2H,2H-perfluorooctyl)silane, silicon tetraboride, silicon hexaboride,
trimethyl-
2-thienylsilane, (4-bromophenyl)trimethylsilane, 4-(trtmethylsilyl)phenol, 5-
(trimethylsilyi}-1,3-cyclopentadiene, trimethylsilylmethylmagnesiumchloride,
N,N-diisopropyltrimethylsilylamine, dicyclohexyl-methyl-silane,
1 o tetracyclohexysilane, 1,1,2,2,3,3,4,4,5,5-decaphenyl-6,6-
dimethylcyclohexasilane, trimethylsilylpolyphosphate, trimethyl-
silylpolyphosphite, including analogues, homologues, isomers and derivatives
thereof.
Additional examples of acceptable silicon derivatives can be found in Silicon
Compounds. Reaister and Review, Petrarch Systems, Inc. (1984), Frontiers
of Organosilicon Chemistry, Bassindale, Gaspar, The Royal Society of
Chemistry, (1991 ), incorporated herein by reference. Corresponding
compounds of germanium, tin, titanium, zirconium, selenium, tellurium, are
contemplated in the practice of this invention.
Non-limiting germanium derivative compounds include:
decamethylgermaniumocene {bis(pentamethylcyclopentadienyl)germanium),
tertbutylgermanium, tetramethylgermanium, tetraethylgermanium,
tetrapropylgermanium, tetraisopropylgermanium, tetrabutylgermanium,
tetraisobutylgermanium, tetra-tert-butylgermanium, tetra-sec-butylgermanium,
tetra-phenylgermanium, phenylgermanium, methylphenylgermanium,
methylphenolgermanium, including analogues, homologues, isomers and
derivatives thereof.
Non-limiting derivative tin compounds include: decamethylstannocene
(bis(pentamethylcyclopentadienyl)tin),
dibutyltin bis{2-ethylhexanoate), dibutyltin diacetate, dibutyloxotin
(dibutyltin
oxide), dimethyltin, diethyltin, dipropyltin, diisopropyltin, dibutyltin,
diisobutyltin, di-tert-butyltin, di-sec-butyltin, di-phenyltin,
tetramethyltin,
tetraethyltin, tetrapropyltin, tetraisopropyltin, benzltriphenyltin,
allyltributyltin,
tetrabutyltin, tetraisobutyltin, tetra-tert-butyltin, tetra-sec-butyltin,
3 5 tetraphenyltin, tetramethoxytin, tetraethoxytin, tetrapropoxytin,
tetraisopropoxytin, tetrabutoxytin, tetraisobutoxytin, tetra-tert-butoxytin,
tetra-
sec-butoxytin, tetraphenoxytin, trimethoxymethyltin, triethoxymethyltin,
tripropoxymethyltin, triisopropoxymethyltin, tributoxymethyltin,
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triisobutoxymethyltin, tri-tent-butoxymethyltin, tri-sec-butoxymethyltin,
triphenoxymethyltin, dibutyltin dichloride, dibutyltin dilaurate, dibutyltin
dimethoxide, dibutyltin diethoxide, dibutyltin methoxide, dibutyltin ethoxide,
tetrabutyltin, tetramethyltin, tetraethyltin, tetrapropyltin, tetra-tent-
butyltin,
allyldibutyltin, allyldiphenyltin, allyldiphenylstannane, dichlorodiphenyltin,
diphenyltin acetate, tributyltineacetate, tributyltinechloride,
tributyltincyanide,
tributyltin ethoxide, tributyltin methoxide, tributyltinhydride,
tributylvinyltin,
triphenyltinchloride, triphenyltinhydroxide, triphenyltinhydride, tributyltin
ethoxide, including analogue, homologue, isomer, and derivative thereof.
1o Non-limiting examples of phosphorus derivative compounds of this
invention include: phosphoric acid esters, othrophosphoric acid esters,
nuetral
phosphate esters, tetrabutylphosphonium hydroxide, allyldiphenylphospine,
diphenylphosphine, phenylphosphine, diphenyl phosphate,
diphenylphosphine, diphenylphosphinic acid, diphenylethoxyphospine,
diphenylmethoxyphospine, diphenylpropoxyphospine,
diphenylisopropoxyphospine, diphenylbutoxyphospine, diphenyl-sec-
butoxyphospine, diphenyl-tert-butoxyphospine, diphenyl-iso-butoxyphospine,
dicyclohexylethoxyphospine, dicyclohexylmethoxyphospine,
dicyclohexyipropoxyphospine, dicyclohexyfisopropoxyphospine,
2 o dicyclohexylbutoxyphospine, dicyclohexyl-sec-butoxyphospine, dicyclohexyl-
tert-butoxyphospine, dicyclohexyl-iso-butoxyphospine,
dicyclopentyiethoxyphospine, dicyclopentylmethoxyphospine,
dicycfopentylpropoxyphospine, dicyclopentylisopropoxyphospine,
dicyclopentylbutoxyphospine, dicyclopentyl-sec-butoxyphospine,
2 5 dicyclopentyl-tert-butoxyphospine, dicyclopentyl-iso-butoxyphospine,
dicyclohexyl(ethyl)ethoxyphospine, dicyclohexyl(ethyl)methoxyphospine,
dicyclohexyl(ethyl)propoxyphospine, dicyclohexyl(ethyl)isopropoxyphospine,
dicyclohexyl(ethyl)butoxyphospine, dicyciohexyl(ethyl)-sec-butoxyphospine,
dicyclohexyl(ethyl)-tert-butoxyphospine, dicyclohexyl(ethyl)-iso-
~ o butoxyphospine, phenyldiethoxyphospine (diethylphenylphosphonite),
phenyldimethoxyphospine, phenyldipropoxyphospine,
phenyldiisopropoxyphospine, phenyldibutoxyphospine, phenyidi-sec-
butoxyphospine, phenyldi-tert-butoxyphospine, phenyldiisobutoxyphospine,
cyclohexyldiethoxyphospine, cyclohexyldimethoxyphospine, cyclohexyl-
3 5 dipropoxyphospine, cyclohexyldiisopropoxyphospine, cyclohexyl-
dibutoxyphospine, cyclohexyldi-sec-butoxyphospine, cyclohexyldi-tert-
butoxyphospine, cyclohexyldi-iso-butoxyphospine, cyclopen-
tyldiethoxyphospine, cyclopentyldimethoxyphospine, cyclopentyl-
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dipropoxyphospine, cyclopentyldiisopropoxyphospine, cyclopentyl-
dibutoxyphospine, cyclopentyldi-sec-butoxyphospine, cyclopentyldi-tert-
butoxyphospine, cyclopentyldiiso-butoxyphospine,
cyclohexyl(ethyl)diethoxyphospine, cyclohexyl(ethyl}dimethoxyphospine,
cyclohexyl(ethyl)dipropoxyphospine, cyclohexyl(ethyl)diisopropoxyphospine,
cyclohexyl(ethyl)dibutoxyphospine, cyclohexyl(ethyl)di-sec-butoxyphospine,
cyclohexyl(ethyl)ditert-butoxyphospine, cyclohexyl(ethyl)diiso-butoxyphos-
pine, dimethyimethylphosphate, diethylmethylphosphate, diethylethyl-
phosphate, dimethylethylphosphate, ethylenebis(diphenylphosphine), methyl-
1 o dichlorophosphite, methyldichlorophosphate, methyldichlorophosphine,
methyldiphenylphosphine, propylphosphonic anhydride, dimethylphosphine,
diethylphosphine, dimethylphosphine, dipropylphosphine, diisopropyl-
phosphine, dibutylphosphine, diisobutylphosphine, disecbutylphosphine, di-t-
butylphosphine, diphenylphosphine, diphenylphosphate,
diphenylphosphineoxide, diphenylphosphine oxide, diphenyl-
phosphineselenide, dis(diethylamino)phosphine, dis(dimethylamino)phospine,
dis(2-ethylhexyl)phosphate, dis(dimethylsilyl)phosphate, dis(dimethylsil-
yl)phosphite, di(toly)phosphine, di(o-toly)phosphine, di(m-toly)phosphine,
di(p-
toly)phosphine, di(toly)phosphite, di(o-toly)phosphite, di(m-toly)phosphite,
2 o di(p-toly)phosphite, di(toly)phosphate, di(toly)hydrophosphate,
di(toly)phosphonic acid [(CH3C6H4)2P(OH)], mono{toly)phosphonic acid
[(CH3C6H4)P(OH)2], diethylphenylphosphine, diethylphenylphosphite,
dipropylphosphite, diisopropylphosphite, dibutylphosophite,
diisobutylphosophite, di-sec-butylphosophite, di-tert-butylphosophite,
2 5 diphenylphosphite, allydiphenylphosphonium, allydiphenyfphosphonium
hydride, allydiphenylphosphonium hydroxide, allydiphenylphosphonium
chloride,
dimethylphosphoramidous dichloride, hexamethylphosphoramide,
hexamethylphosphorus diamide, hexamethylphosphorus triamide,
3o hexamethylphospophorimidic triamide, trimethylphosphine, trimethylphospate,
trimethylphosphite, triethylylphosphite, tripropylphosphite,
triisopropylphosphite, tri-butyl-phosphite, tri-iso-butylphosphite, tri-sec-
butylphosphite, tri-tert-butylphosphite, triphenylphosphite,
dimethylphosphite,
diethylphosphite, dipropylphosphite, diisopropylphosphite, dibutylphosphite,
35 diisobutylphosphite, di-sec-butylphosphite, di-tert-butylphosphite,
diphenyl-
phosphite, dimethyiethylphosphine, dimethylethylphosphate,
dimethylethylphosphite, diethylmethylphosphite, dipropylmethylphosphite,
diisopropylmethylphosphite, di-butyl-methylphosphite, di-iso-
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butylmethylphosphite, di-sec-butylmethylphosphite, di-tert-
butylmethylphosphite, diphenylmethyl phosphate, dimethylphosphonate,
diethylphosphonate, dipropylphosphonate, diisopropylphosphonate, di-butyl-
phosphonate, di-iso-butylphosphonate, di-sec-butylphosphonate, di-tert-
butylphosphonate, diphenylphosphonate, dimethylmethylphosphonate,
dimethylethylphosphonate, diethylmethylphosphonate,
dipropylmethylphosphonate, diisopropylmethylphosphonate, di-butyl-
methylphosphonate, di-iso-butylmethylphosphonate, di-sec-
butylmethylphosphonate, di-tert-butyfmethylphosphonate, diphenylmethyl
1 o phosphonate, diethylethylphosphonate, dipropylethylphosphonate,
diisopropylethylphosphonate, di-butyl-ethylphosphonate, di-iso-
butylethylphosphonate, di-sec-butylethylphosphonate, di-tert-
butylethylphosphonate, diphenylethyl phosphonate,
dimethylcarbophosphonate, diethylcarbophosphonate, dipropyl-
carbophosphonate, diisopropylcarbophosphonate, di-butyl-phosphonate, di-
iso-butylcarbophosphonate, di-sec-butylcarbophosphonate, di-tert-
butylcarbophosphonate, diphenylcarbophosphonate, dimethyl-
methylcarbophosphonate, dimethylethylcarbophosphonate, diethyl-
methylcarbophosphonate, dipropylmethylcarbophosphonate, diisopro-
2 o pyimethylcarbophosphonate, di-butyl-methylcarbophosphonate, di-iso-
butylmethylcarbophosphonate, di-sec-butylmethylcarbophosphonate, di-tert-
butylmethylcarbophosphonate, diphenyimethyl phosphonate,
diethylethylcarbophosphonate, dipropylethylcarbophosphonate,
diisopropylethylcarbophosphonate, di-butyl-ethytcarbophosphonate, di-iso-
2 5 butylethylcarbophosphonate, di-sec-butylethylcarbophosphonate, di-tert-
butylethylcarbophosphonate, diphenylethyl phosphonate, dimethylphospite,
dimethylphosphite,
trimethyl phosphonoacetate, trimethyl 2-phosphonoacrylate, trimethyf
phosphonoformate, trioctylphosphine oxide, triphenyl phospate,
3 o triphenylphosphine, triphenylphosphine oxide, triphenylphosphine-copper
hydride, triphenylphosphine hydrobromide, triphenylphosphine dibromide,
triphenylphosphine oxide, triphenylphosphine selenide, triphenylphosphine
sulfide,
tripiperidinophosphine oxide, tris(2-ethyihexyl)phosphate,
35 tris(dimethylamino)phosphine, tris(hydroxymethyl)aminomethane phosphate,
tris(trimethylsilyl)phosphate, tris(trimethylsilyl)phosphite,
tri(toly)phosphines
(e.g. tri(o toly)phosphine, trim-toly)phosphine, trip-toly)phosphine),
tri{toly)phosphite (e.g. tri(o-toly)phosphite, tri{m-toly)phosphite, trip-to-
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ly)phosphite), tri(toly)phosphate, tri(toly)hydrophosphate,
tri(toly)phosphonic
acid [(CH3C6H4)3P(OH)2], bis(2-ethylhexel) phosphate, diallyphenyl-
phosphine, dibenzylphosphite, dibenzylphosphate, dibutyl phosphate, dimethyl
methylphosphonate, dimethyl methylphosphine, dimethyl methylphosphonite,
dimethylphenylphosphine, dimethylphenylphosphonite, dimethylphenyl-
phosphite, dimethylphosphinic acid, dimethyl(trimethylsilyl-
methyl)phosphonate, dimethyl trimethylsilyl phosphate, dimethyl trimethylsilyl
phosphonate, ethyldiphenylphosphonite, diphenyl(2-
methoxyphenyl)phosphine,
to manganese (II) hydrogen phosphate, disodium fluorophosphate, disodium
fluorophosphite, disodiumhydrogenphosphite, trisodium phosphate, trisodium
phosphate, dipotassiium fluorophosphate, dipotassium fluorophosphite,
tripotassium phosphate, tripotassium phosphate, ethyldiphenylphosphine,
ethyldiphenylphosphinite, ethyldiphenylphosphonate,
methyldiphenylphosphine, methyldiphenylphosphinite,
methyldiphenylphosphonate, phenylphosphine, phenylphosphonic acid,
phenylphospate phosphorus acid, phosphoric acid, phosphorus trichloride,
phosurea, phosphorus trisulfide, tributyl phosphate, tributylphosphine, tri-
tert-
butylphosphine, tributylphosphine oxide, tributylphosphite, tris(2,4-di-tert-
2 o butylphenyl)phosphite, tris(nonlphenyl)phosphite, phosphorous acid
triphenylester with propane 1,3-diol, tris(2,2,2-trifluoroethyl)phosphite,
tris(2-
chloroethyl)phosphite, tris(1-chloroethyl)phosphite, trichlorophosphite,
tris(tridecyl)phosphite, isooctyldiphenylphosphite, diisodecylphenylphosphite,
triethyl 4-phosphonocrotonate, trimethyl 4-phosphonocrotonate, triethyl-
2 5 phosphonoacetate, trimethylphosphonoacetate, trimethyl 2-phosphono-
butyrate, triethyl 2-phosphonobutyrate, trimethylphosphonoformate,
triethylphosphonoformate, trimethylphosponopropionate, trimethyl-
phosponopropionate, tricyclohexylphosphite, tricyclohexylphophine,
triethylphosphine, triethylphosphite, trimethylphosphine, triethylphosphate,
tri-
3 o methylphosphate, tripropylphosphate, triisopropylphosphate, tributyl-
phosphate, triisobutylphosphate, tri-sec-butylphosphate, tri-tert-
butylphosphate, triphenylphosphate, dimethyfphosphate, diethylphosphate,
dipropylphosphate, diisopropylphosphate, dibutylphosphate,
diisobutylphosphate, di-sec-butylphosphate, di-tert-butylphosphate,
35 diphenyimethylphosphate, diphenylethylphosphate, diphenylpropylphosphate,
diphenylisopropylphosphate, dimethylethylphosphate,
diethylmethyfphosphate, dipropyimethylphosphate,
diisopropylmethylphosphate, di-butyl-methylphosphate, di-iso-
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butylmethyiphosphate, di-sec-butylmethylphosphate, di-tert-
butylmethylphosphate, diphenylmethyl phosphate, triethylphosphoramide,
trimethylphosphoramide, tripropylphosphoramide, triisopropylphosphoramide,
tributylphosphoramide, triisobutylphosphoramide, tri-sec-butylphosphoramide,
tri-tert-butylphosphoramide, triphenylphosphoramide, dimethoxyphosphorus-
amide (CH30)2PNH2), diethoxyphosphorusamide, dipropoxyphosphorus-
amide, diisopropoxyphosphorusamide, dibutoxyphosphorusamide, di-
isobutoxyphosphorusamide, di-sec-butoxyphosphorusamide, di-tert-
butoxyphosphorusamide, diphenoxyphosphorusamide, dimethylphosphor-
lo amide (CH30)2PONH2), diethylphosphoramide, dipropylphosphoramide,
diisopropylphosphoramide, dibutylphosphoramide, diisobutylphosphoramide,
di-sec-butylphosphoramide, di-tert-butylphosphoramide,
diphenylphosphoramide, dimethylethylphosphoramide, diethylmethyl-
phosphoramide, dipropylmethylphosphoramide, diisopropylmethyl-
phosphoramide, di-butyl-methylphosphoramide, di-iso-butylmethyl-
phosphoramide, di-sec-butylmethylphosphoramide, di-tert-butyl-
methylphosphoramide, diphenylmethyl phosphoramide, triethylcar-
bophosphate, trimethylcarbophosphate, tripropylcarbophosphate,
triisopropylcarbophosphate, tri-butyl-phosphate, tri-iso-butylcarbophosphate,
2 o tri-sec-butylcarbophosphate, tri-tart-butylcarbophosphate, triphenylcar-
bophosphate, dimethylcarbophosphate, diethylcarbophosphate,
dipropylcarbophosphate, diisopropylcarbophosphate, dibutylcarbophosphate;
diisobutylcarbophosphate, di-sec-butylcarbophosphate, di-tert-
butylcarbophosphate, diphenylcarbophosphate,
dimethylethylcarbophosphate, diethylmethylcarbophosphate, dipropyl-
methylcarbophosphate, diisopropylmethyicarbophosphate, di-butyl-
methylcarbophosphate, di-iso-butyimethylcarbophosphate, di-sec-
butylmethylcarbophosphate, di-tart-butylmethylcarbophosphate,
diphenylmethyl phosphate, dimethylvinylphosphate, diethylvinylphosphate,
3o dipropylvinylphosphate, diisopropylvinylphosphate, dibutyivinyiphosphate,
diisobutylvinylphosphate, di-sec-butylvinylphosphate, di-tert-
butyfvinyiphosphate, diphenylvinylphosphate, triisobutylphosphine,
triisodecylphosphite, triisopropylphosphite, dibenzyldiethylphosphoramidite,
dibenzyldiisopropylphosphoramidite, dibenzylphosphite, dibenzylphosphate,
tris(tridecyl)phosphite, tritolylphosphate, tritolyphophine, tritolyphosphite,
tricyclohexylphosphine, aliminum phosphate, 1,2-bis(diphenylphos
phino)propane, trioctylphosphine oxide, trioctylphosphine,
dichloromethylphosphine, dichlorophosphineoxide (C12P0),
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ethyidichlorophosphite, tetraethylpyrophosphite, benzyldiethylphosphite,
benzyldiethoxyphosphorus, cyclohexyldiethoxyphosphorus,
dibenzyldiisopropylphosphoramite (dissopropyl-phosphoraramidous acid
dibenyl ester), di-tert-butyl diisopropylphosphoramidite, tert-butyl
tetraisopropylphosphorodiamidite, (+I-)-1-amino-cis-3-
phosphonocyciopentanecarboxlic acid, diallyl diisopropylphosphoramide, tert-
butyl tetraisopropylphosphorodiamite, (1-amino-butyl)-phosponic acid, 6-
amino-1-hexyl phosphate, 1-aminoethylphosponic acid, 2-aminoethyl
dihydrogenphosphate, 2-aminoethylphosponic acid, methyl N,N,N'-
to tetraisopropylphosphordiamidite, hexamethylphosphoramide [(CH3)2N]3P0,
hexamethylphosphortriamidite [(CH3)2N]3P, diethyl 4-
aminobenzylphosphonate, diethyl 4-aminobenzylphosphite,
diethyibenzylphosphonate, diethylbenzylphosphite,
tetraethylbenzylphosphonate, diethyl (pyrrolidinomethyl)phosphonate,
diethyloxyphosphinyl isocyanate, 6-amino-1-hexylphosphate, diethyloxyphinyl
isocyanate, diethylcyanomethylphosphonate, diethyfveinylphosphonate,
dioctylphenylphosphonate, ethylphenylphosphinate, ethylphenylphosphonic
acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid,
isopropylphosphonic acid, butylphosphonic acid, sec-butylphosphonic acid,
2 o tert-butylphosphonic acid, isobutylphosphonic acid, phenylphosphonic acid,
phenylphosphoric acid, phenylphosphinic acid, methylphenylphosphinate,
methylphenylphosphine, aminomethylphosphonic acid, vinylphosphonic acid,
hypophosphorus acid, sodium hypophosphate, sodium
dihydrogenphosphate, fluorophosphoric acid, ammonium
hydrogenphosphate, ammonium hydrogenphosphite, ammonium hydrogen-
phosphine, lithiumdihydrogenphosphate, triphenylphosphineselenide,
phosphoric acid, phosphorus oxychloride, phosphorus pentasuifide,
metaphosphoric acid, phenylphosphate disodium salt,
nitrilotris(methylene)triphosphonic acid, ethylenephosphite,
3o ammonium salt benzylphosphite, potassiumhexafluorophosphate,
diethyltrimethylsilylphosphite, diethyl(trichloroethyl)phosponate,
dimethyl(trimethylsilyl)phosphite, tris(trimethylsilyl)phosponate,
2-chloro-1,3,2-dioxaphospoJane, 2-chloro-1,3,2-dioxaphosphoiane-2-oxide,
dimethylmethylphosphonate, diethylmethylphosphonate,
3 5 dimethylethylphosphonate, diethylethylphosphonate, ethylmethyl-
phosphonate, 2-carboxyehtylphosphonic acid, 2,2,2-trichloro-1,1-
dimethylethyldichlorophosphite, bis(2-chloroethyt)phosphoramidic dichloride,
butyldichlorophosphite, butylphosphonic dichloride, tert-butylphosphonic
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dichloride, tent-butyldichlorophosphine, trimethylphosphonoformate,
trimethylprapionamtde, trimethylpropionanilide, diethylchlorophosphate,
diethytchtorophosphite, chlorodiethylphosphine, diethylphosphoramidous
dichloride, diethylthiophosphate, sodium salt diethylthiophosphate, diethyl-
phosphoramidate, dimethylphosphoramidate, tetramethylphosophorodiamidic
chloride, tetramethylphosphonium chloride, diethylcyanophosphate,
diethylcyanophosphonate, diethylcyanomethylphosphonate,
diethoxyphosphinyl isocyanate, O,O'-diethytmethylphosphonothioate,
diethytmethylphosphonate, diethyl(hydroxymethyl)phosphonate,
to dimethyltrimethylsilylphosphite, 1-ethyl-3-methyl-1H-imidzolium
hexaflurophosphite, diethylcyanmethylphosphonate, phosphorus napthenate,
methylphenylphospholene, methylphenylphosolenedichloride, (aminobe-
nzyl)phosphonic acid (e.g. (4-aminobenzyl)phosphonic acid),
cyclophosphamide, pinacolytmethylphosphonate, diethyl(ethylthio-
methyl)phosphonate, 2-furyl tetramethylphosphorodiamidite,
diisopropylcyanomethylphosphate, 1,3,5-tris(2-hydroxyethyl}cyanuric acid,
tris(2,4,-di-tert-butylphenyl)phosphite, tris(tridecyl)phosphite,
tris(nonylphenyl)phosphite, phosphorus anyhydride, phospham, phosphonium
chloride, phosphoniumsulfide, phosphoniumsulfate, phosphoramide, phor-
2o phoramidite, metaphosphoramide, phosphorus chloride(di)nitride, phosphorus
cyanide, phosphorus trifluoride, phosphorus pentafluoride, phosphorus
oxybromide, phosphorus pentaselenide, phosphorus trioxide, phosphorus
sesquioxide, phosphorus tri(tetra-)selenide, phosphorus thiochloride,
phosphorus thiocyanate, hypophosphorus acid, metaphosphorus acid,
2 5 orthophosphorus acid, pyrophosphorus acid, phosphine, phosphorus nitride,
phosphorus sesquisulfide, including analogues, homologues, isomers and
derivatives thereof. The corresponding compounds of arsenic, antimony and
bismuth are contemplated.
Non-limiting antimony derivative compounds include:
3 o alkyl antimony compounds, trialkyl compounds, cyclomaticlring system
compounds, including, trimethylantimony, triethylantimony, tripropylantimony,
triisopropylantimony, tributylantimony, triisobutylantimony, tri-tert-
butylantimony, tri-sec-butylantimony, tri-phenylantimony, phenylantimony,
tri(methylphenyl)antimony, triphenylantimony oxide,
35 tri(methylphenot)antimony, antimony ethoxide, pentamethytantimony,
phenyldimethylantimony, phenylstibinic acid, tetramethyldistibyl,
tributylstibene, triethylantimony, triethylantimony chloride,
trimethylantimony,
triphenylantimony, triphenylantimony dichloride, triphenylantimony sulfide,
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including analogue, homologue, isomers and derivative thereof.
Non-limiting arsenic derivative compounds include:
alkyl arsenic compounds. dialkyl compounds, cyciomaticlring system
compounds including, diethylarsine, dimethylarsine, diphenylarsine,
ethylarsine, methyiarsine. oxophenylarsine, triethylarsine, triethylarsine,
tripropylarsine, triisopropylarsine, tributylarsine, triisobutylarsine, tri-
tert-
butylarsine, tri-sec-butylarsine, tri-phenylarsine, phenylarsine, tri(methyl-
phenyl)arsine, triphenylarsine oxide, tri(methylphenol)arsine, phenylarsenic
acid, phenylcyclotetramethylenearsine, arsenobenzene, cacodylic acid,
1 o cacodyl oxide, cacodyl amide, carbasone, arsanilic acid, ethanearsonic
acid,
methanearsonic acid, nitarsone, benzenearsonic acid, propyl arsonic acid,
dimethylchlor-arsine, dimethylcyanoarsine, diphenylarsinic acid,
diphenylchloro-arsine, ethylarsonic acid, methylarsine, methyldichloroarsine,
phenylarsine, phenyldimethylarsine, tetraethyldiarsine, tetramethylbiarsine,
tribenzylarsine, trimethylarsine, triethylarsine, tributyl arsine, tri-
isobutyl
arsine, triphenyl arsine, including analogue, homologue, isomers and
derivative thereof. See Orpano Arsenial Compounds, Raiziss, Gavron,
American Chemical Society (1923) and relatedlsubsequent editions, volumes
or supplements, incorporated by reference. Corresponding compounds of
2o phosporus, antimony, bismuth are also contemplated herein and incorporated
by reference.
Non-limiting bismuth derivative compounds include: alkyl bismuth
compounds, dialkyl compounds, cyclomaticlring system compounds including,
triphenylbismuth, triphenylbismuth carbonate, diphenylbismuthine,
2 5 methylbismuthine, triethyibismthine, trimethylbismthine,
triphenylbismuthine,
tri-n-propyibismuth, including analogue, homologue, isomers and derivative
thereof.
Non-limiting potassium derivative compounds of this invention include:
potassium bis(dimethylsilyl)amide, potassium acetamide, potassium
3o bis(trimethylsilyl)amide, oxamic acid, P-aminosalicylic acid potassium
salt,
potassium salt 5-nitroorotic acid, potassium D-gluconate, potassium
hexacyanoferrate(III) (K3Fe(CN)6), potassium diphenylphosphide,
potassiumetherate, potassium acetate, potassium acetate acid, potassium
salt acetic acid, potassiumbenzamide, potassium azide, potassium
35 antimonide, potassium orthoarsenate, potassium orthoarsenite, potassium
meta-arsenite, potassium diborane, potassium pentaborate, potassium
dihydroxy diborane, potassium borohydride, potassium anilide, potassium
radium iodide, potassium chloride, potassium calcium chloride, potassium
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carbide, potassium carbonate, potassium hydrogen carbonate, potassium
carbonate, potassium alkyl carbonates (alkyl potassium carbonates),
potassium methyl carbonate, potassium ethyl carbonate, potassium propyl
carbonate, potassium isopropyl carbonate, potassium carbonyl, potassium
s cobalt (II) cyanide, potassium cobalt (III) cyanide, potassium
cobaltinitrite,
potassium cynomanganate (ll), potassium cynomanganate (III), potassium
citrate, potassium ferricyanide, potassium ferrocyanide, potassium hydride,
potassium hydroxide, potassium manganate, potassium permanganate,
potassium methionate, potassium napthenate, potassium nitride, potassium
1 o nitrate, potassium nitrite, potassium nitrophenoxide, potassium
nitrobenzene
(e.g. potassium-p-nitrobenzene)potassium oleate, potassium oxalate,
potassium oxalatofen-ate (II), potassium oxalatoferrate {III), potassium
monoxide, potassium oxide, potassium peroxide, potassium mono-
orthophosphate, potassium hypophosphite, potassium orthophosphate,
i5 potassium hydroxoplumbate, potassium rhodium cyanide; potassium
selenide, potassium selenite, potassium selenocynate, potassium
selenocyanoplatinate, potassium disilicate, potassium metasilicate, potassium
sodium carbonate, potassium sodium ferricyanide, potassium
hydroxostannate, potassium disufide, potassium hydrosulfide, potassium
2 o pentasulfide, potassium tetrasulfide, potassium trisulfide, potassium
telluride,
potassium thioarsenate, potassium thioarsenite, potassium trithiocarbonate,
potassium thiocyanate, potassium amide, potassium salt (E,E)-2,4-
hexadienoic acid, dipotassium fluorophosphate, dipotassium fluorophosphite,
tripotassium phosphate, tripotassium phosphate, potassium perchlorate,
2 5 propanoic acid potassium salt, potassium formate, potassium cyanate,
potassium hexacyanocobaltate (III), potassium hypophosphite, potassium
hexaflurorsilicate, potassium nitroprusside, potassium phenoxide, Shell
Chemical's "SparkAid or SparkAde," potassium phosphate (dibasic,
monobasic, tribasic), potassium salicylate, potassium selenide, potassium
3o tetracyanonickelate (II), potassium tetrafluoroborate, potassium
xanthogenate, potassium -p-aminobenzoate, potassium copper
ferrocynanide, potassium cupric ferrocyanide, potassium
hexafluorophosphate, potassium hexanitricobaltate lli, potassium
naphthenate, potassium-B-naphthoxide,potassium polysulfide, potassium
35 sodium phosphate, potassium stearate, potassium sulfide, potassium sulfite,
potassium sulfate, potassium thiocyanate, potassium xanthate, potassium
fluorosilicate, N-potassiumethylenediamine, oxalic acid dipotassium salt,
potassium beta-hydropyruvic acid, potassium 1,1-dimethylurea, potassium
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1,1-diethylurea, potassium 1,1-diepropylurea, potassium xanthate; potassium
ethylxanthate, potassium methyfxanthate, potassium salt thiophenol, potas-
siumaluminum-tri-tert-butoxide, potassium ferrosilicon, tri-
phenyimethylpotassium, methylpotassium, ethylpotassium, potas-
siumethynyl(acetylide), propylpotassium, isopropylpotassium, butylpotassium,
isobutylpotassium, secbutylpotassium, tertbutylpotassium, pentapotassium,
hexylpotassium, heptapotassium, amylpotassium, isoamylpotassium,
benzylpotassium, dimethylbenzylpotassium, tolylpotassium,
dodecylpotassium, cyclopentadienylpotassium,
1 o methylcyclopentadienylpotassium, cyclohexylpotassium, potassiumheptyl,
potassiumdodecyl, potassium tetradecyl, potassium hexadecyl, potassium
octadecyl, phenylpotassium, potassium o-tolyl, potassium m-tolyl, potassium
p-tolyl, potassium-p-chlorophenyl, potassium p-bromophenyl, potassium
potassium o- anisyl, potassium m-anisyl, potassium p-anisyl, potassium
diethoxyphenyl, potassium dimethoxyphenol, potassium m-cumyl, potassium
p-ethoxyphenyl, potassium m-dimethyfaminophenyl, potassium 9-flourene,
potassium a-napthyl, potassium b-napthyl, potassium p-phenylphenyl,
potassium 9-phenylanthryl, potassium 9-anthryl, potassium 9-methylphen-
anthryl, potassium pyridyl, potassium 2-pyridyl, potassium 3-pyridyl,
2 o potassium 6-bromo-2-pyridyl, potassium 5-bromo-2-pyridyl, potassium diben-
zofuryl, potassium 3-quinoyl, potassium 2-lepidyl, potassium triphenylmethyl,
potassium 2,4,6-trimethylphenyl, potassium 2,4,6-triisopropylphenyl,
potassium 2,3,5,6-tetraisopropylphenyi, potassium tetrabutylphenyl,
thiophenedipotassium, toluenedipotassium, diphenylethyienedipotassium,
2 5 potassiumamylethynyl, potassiumphenylethynyl,
potassiummethoxybromophenyl, potassium phenylisopropyl, potassium
tetraphenylboron, potassium tetramethylboron, potassium a-thienyl,
potassium m-trifluoromethylphenyl, phenylethynylpotassium, 3-
furylpotassium, phenylisopropylpotassium, dibenzofuranylpotassium,
3 o potassium dimethylbenzyl, potassium selenocyanate, potassium
trimethylsilanolate, diphenylphosphide, potassium benzoate, potassium tert-
butyl carbonate, potassium azide, di-potassiumcyanamide, potassium
cyanide, potassium dicyanamide, cyclohexanebutyric acid potassium salt,
cyclohexane acid potassium salt, cyclopentadientylpotassium, potassium tri-
35 tert-butoxyaiuminum hydride, potassium triethylborohydride, potassium
trirnethylborohydride, potassium tripropylborohydride, potassium
triisopropylborohydride, potassium tributylborohydride, potassium
triisobutylborohydride, potassium tri-sec-butylborohydride, potassium tri-tert-
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butylborohydride, potassium trisiamylborohydride, potassium chlorate,
potassium tert-butoxide, potassium sec-butoxide, iso-butoxide, potassium
antimonate, potassium diphenylphosphide, potassium bis(trismethylsilyl)
amide, tripotassium phosphite, potassium selenocyanate, potassium tri-sec-
butylborohydride, potassium triethylsilanolate, potassium thiocyanate,
potassium acetylide, potassium chlorate, potassium salicylate, potassium di-
potassium tetracarbonylferrate, potassium tetraphenylborate, potassium
triethylborohydride, potassium triacetoxyborohydride, potassium
triphenylborane, potassium hydroxide, potassium diphenylphosphide,
to potassium methoxide, potassium ethoxide, potassium tri-sec-
butylborohydride, tri-tert-butylborohydride, potassium triethylborohydride,
potassium triphenylborohydride, potassium trisiamylborohydride, potassium
metavanadate, potassium cyclohexanebutyrate, potassium hexachloro-
platinate, potassium thiocyanate, potassium selenocyanate, potassium
cyanate, potassium floride, potassium hexafluoroantimonate, potassium
hexafluoroaluminate, potassium hexafluoroarsenate, potassium
hexafluorosilicate, potassium hexacyanocobalt(II)ferrate(II),
dipotassiumhexacyanocobalt(II)ferrate(II), potassium hexafluorotitanate,
potassium hexafluorozirconate, potassium hexahydroxyantimonate,
2 o potassium hexachlororuthenate, potassium hexachloropalladate, potassium
formate, potassium tetracyanonickelate, potassium tetrafluoroaluminate,
potassium tetrafluoroborate, potassium thioacetate, L-glutamic acid mono-
potassium salt, fumaric acid potassium salt, oxamic acid potassium salt,
potassium salt Biphenyl-phospane, P-aminobenzoic potassium salt,
aminobenzole acid potassium salt, alpha-napthaleneacetic acid potassium
salt, dipotassium salt 2,6-naphthalenedicarboxlic acid, potassium
cyclcohexanetherate, potassium phthalimide, P-aminosalicylic acid
potassium salt, potassium salt 3,5-dimethylcyclohexyl sulfate, indolebutyric
acid potassium salt,indole-3-butyric acid potassium salt, potassium
3o diphenylphosphide, potassium dimethylsilanolate, potassium
triethylborohydride, potassium propoxide, potassium isopropoxide, potassium
butoxide, potassium sec-butoxide, potassium pentoxide, potassium tert-
pentoxide, potassium hydrogenphthalate, potassium oxalate, potassium
hydrogensulfate, monopotassium acetylenedicarboxylic acid, potassium
3 5 pyrophosphate, potassium dihydrogenphosphate, potassium hexoate
(potassium salt hexoic acid), potassium diphenylphosphide, potassium
trimethylsifonalate, potassium phthalic acid, P-aminobenzoic acid potassium
salt, monopotassium L-aspartic acid, tetraphenyldipotassium (C6H5)2CK2-
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C(C6H5)2, potassiumethylphenyl (KCH2C6H5), potassium bromate,
potassium chromate, potassium hydrogenphospate, monpotassium salt D-
shaccharic acid, DI-asparatic potassium salt, (R)-alpha-hyroxymethylaspartic
acid potassium salt, potassium fluoride, potassium iodate, potassium salt
ethyl malonate, potassium thioacetate, potassium phenol, potassium salt
aminobenzoic acid, potassium arninophenol salt, potassium cyclohexenol.
potassium methylcyciohexenol, potassium cyclopropanol, potassium methyl-
cyclopropanol, potassium cyclobutanol, potassium methylcyclobutanol.
potassium methylcyclopentanol, potassium cyclopentanol, potassium
1 o cyclohexenol, potassium methylcyclohexenol, potassium
dimethylcyclohexenols (e.g. potassium 3,5-dimethylcyclohexanol, potassium
2,3-dimethylcyclohexanol, potassium 2,6-dimethylcyclohexanol, potassium
2,5-dimethylcyclohexanol, 3,5-dimethylcyclohexanol), potassium o-
ethylxanthic acid, monopotassium salt 2-ketoglutaric acid, dipotassium salt,
ketomalonic acid, potassium salt lactic acid, dipotassium thiosulfate,
potassium antimony tartrate, potassium dichloroacetate, potassium dimethyl-
acetate, potassium diethylacetate, potassium dipropylacetate, potassium
metaborate, potassium tetraborate, potassium tetrachlorocuprate, potassium
acetoacetate, potassium diisopropylamide, potassium diethylamide,
2o potassium dimethylamide, potassium bis(dimethylsilyl)amide, dipotassium
phthalocyanine, dipotassiumtetrabromocuprate, dipotassium
tetrabromonickelate, dipotassiumtetrachloromanganate,
dipotassiumbutadiyne, potassium cyclopentadienide, potassium
dicyclohexylamide, potassium diethyiamide, potassium dimethylamide,
potassium dipropylamide, potassium diisopropylamide, potassium
thexylborohydride, potassium tri-tert-butoxyaluminohydride, potassium
trimethylsilyl)acetyfide, potassium triethylsilyl)acetylide, potassium tris[(3-
ethyl-3-pentyl)oxyJaluminohydride, (phenylethynyl)potassium, 2-
thienylpotassium, potassium diethyldihydroaluminate, potassium
3o dimethyldihydroaluminate, potassium aluminum hydride, potassium bifluoride,
potassium biphenyl, potassium biselenite, potassium bis(2-methoxyethoxy)-
aluminum hydride, potassium bismuthate, potassium borate, potassium
chlorite, potassium cobaltnitrite, potassium cyanoborohydride, potassium
cyclopentadienide, potassium dicyanamide, potassium hexametaphosphate,
potassium hexanitrocolbaltate, potassium hydrogenphosphite, potassium
hydrogenselenite, potassium hydrogensulfite, potassium hydrosulfite,
potassium hypochloride, potassium metaarsenite, potassium rnetabisuifide,
potassium metaperiodate, potassium methacrylate, potassium
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nitroferricyanide, oxybate, potassium pentamethylcyclopentadienide,
potassium phenolate, polyphosphate, potassium polyphosphite, potassium
propionate, potassium pyrophosphate, potassium selenate, potassium
selenite, potassium tetrachloroaluminate, potassium thiomethoxide,
potassium thiosulfate, potassium thiosulfide, potassium thiosulfite, potassium
triactoxyborohydride, potassium trimethylsilonate, potassium triethylsilonate,
potassium tris(1-pyrazoly)borohydride, including analogues, homologues,
isomers and derivatives thereof. Corresponding compounds of rubidium,
caesium (cesium ), francium are contemplated in the practice of this
invention.
to Non-limiting derivative magnesium compounds contemplated by this
invention include: alkyl manganese compounds, dialkyl magnesium
compounds, magnesium ethylate (ethoxide), magnesium methoxide,
dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
diisopropylmagnesium, dibutylmagnesium, ditertbutyimagnesium, di-iso-
butylmagnesium, di-sec-butylmagnesium, diphenylmagnesium,
methylmagnesium chloride, methylmagnesium iodide, magnesium
methylcarbonate, magnesium hydroxide, magnesium anthracene dianion,
bromomagnesium isopropylcyclohexylamide, methylmagnesium bromide,
methylmagnesium chloride, ethylmagnesium chloride, magnesium floride,
2 o magnesium chloride, butylmagnesium chloride, isopropylmagnesium chloride,
cyclopentylmagnesiumhydride, cyclopentylmagnesiumhydroxide, cyclopentyl-
magnesiumchloride, cyclopentylmagnesiummethyl, cyclopentylmag-
nesiumethyl, cyclopentylmagnesiummethylol, cyclopentylmagnesiumethylol,
cyclopentylmagnesiummethoxy, cyclopentylmag-
nesiumethoxy,cyclohexylmagnesiumhydride, cyclohexylmagnesiumhydroxide,
cyclohexylmagnesiumchloride, cyclohexylmagnesiummethyl, cyclohexylmag-
nesiumethyl, cyclohexylmagnesiummethylol, cyclohexylmagnesiumethylol,
cyclohexylmagnesiummethoxy, cyclohexylmagnesiumethoxy, tert-
butyimagnesium chloride, isobutyl-magnesium chloride, allymagnesium
3o chloride, benzylmagnesium chloride, benzylmagnesium hydride,
benzylmagnesium ethylate, benzylmagnesium methylate, benzylmagnesium
ethoxy, benzyl-magnesium methoxy, magnesium acetate, magnesium alkyl
carbonates, magnesium methyl carbonate, magnesium ethyl carbonate,
magnesium isopropyl carbonate, trimethyisilylmethyl magnesium chloride,
3 5 magnesium acetate tetrahydrate, methylmagnesium isopropylcyclo-
hexylamide, magnesium pyrophosphate, phenylethynylmagnesium bromide,
methylphenylmagnesiumchloride, methylmagnesium, ethylmagnesium,
propylmagnesium, isopropylmagnesium, butylmagnesium,
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isobutylmagnesium, tert-butylmagnesium, sec-butylmagnesium,
phenylmagnesium, magnesium acetate, magnesium hydrogenphosphate,
cyclopentylmagnesium, cyclopentylmagnesiumhydroxide,
cyclopentylmethylmagnesium, methylcyclopentylmethylmagnesium,
allylmagnesium, benzylmagnesium, pentylmagnesium, 1,1-
dimethylpropylmagnesiumhydroxide, 1,1-dimethylpropylmethylmagnesium,
phenylmagnesium, phenolmagnesium, magnesium hydroxide,
magnesiumcarbonate, magnesiumsilicide, magnesium phosphate,
magnesium phosphite, magnesium bisulfite, L-aspartic acid magnesium, DL-
1 o aspartic acid magnesium, including analogue, homologue, isomer, and
derivative thereof. Corresponding beryllium, calcium, strontium, barium,
radium and zinc compounds are contemplated in the practice of this
invention. See The Organic Compounds of Magnesium Beryllium Calcium
Strontium. and Barium, loffe, Nesmeyanov, Amsterdam (1967),
Orpanomagnesium Methods in Or~c~anic Synthesis, Wakefield, Academic
Press, FL (1995), incorporated by reference. The mixture of dialkyl
magnesium compounds with pyrophoric metallics is specifically contemplated.
Non-limiting selenium derivative compounds include: alkyl and dialkyl
selenium compounds, dimethylselenium, dimethyl selenide, diethylselenium,
2 o dipropylselenium, diaisopropylselenium, diabutylselenium,
diaisobutylselenium, dip-tert-butylselenium, dip-sec-butylselenium, di-
phenylselenium, tetramethylselenium, tetraethylselenium,
tetrapropylselenium, tetraisopropylselenium, tetrabutylselenium, tetraisobutyl-
selenium, tetra-tert-butylselenium, tetra-sec-butylselenium, tetra-
2 5 phenylselenium, phenylselenium, methylphenylselenium,
methylphenylselenide, methylphenolselenium, zinc selenite, di-n-
butylphosphane selenide, selenanthrene, selenourea, selenophene,
allylphenylselenide, 1,3-dihydro-benzoimid-; 2,3-dihydro-3-methyl-, 1,1-
dimethyl-2-selenourea, dipheny! diselenide, phenylselenyl chloride,
3 o benzeneseleninic acid, sodium selenite, benzeneseninic anhydride,
potassium selenocyanate, selenourea, sodium hydrogenselenite, 4-
chiorobenzeneseleninide, 4-(methylseleno)butyrate, benzyl selenide, alkyl
selenium, including dimethylselenide, diethylselenide, dipropylseienide, etc.,
ally phenyl selenide, benzeneselenol, benzyl selenide,
35 (phenylselenomethyl)trimethylsilane, potassium selenate, potassium
selenite,
selenic acid, dibenzyl diselenide, p-tolyl selenide, triphenylphosphine
selenium, seleno-DL-methionine, P-tolyl selenide, including analogue,
homologue, isomer, and derivative thereof. See Organoselenium Chemistry,
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Liotta, John Wiiey & Sons, N.Y. (1987), incorporated herein by reference.
Non-limiting telluride derivative compounds include: di-n-
butylphosphane selenide, selenanthrene, selenourea, selenophene,
allylphenylselenide, dimethyltelluride, diethyltelluride, dipropyltelluride,
diisopropyltelluride, dibutyltelluride, diaisobutyltelluride, dia-tent-
butyltelluride,
dia-sec-butyltelluride, di-phenyltelluride, tetramethyltelluride,
tetraethyltel-
luride, tetrapropyltelluride, tetraisopropyltelluride, tetrabutyltelluride,
tetraisobutyltelluride, tetra-tart-butyltelluride, tetra-sec-butyltelluride,
tetra-
phenyltelluride, phenyltelluride, methylphenyltelluride,
methylphenoltelluride,
1 o zinc selenite, di-n-butylphosphane telluride, diphenyl ditelluride,
dimethyltel-
luride, diethyltelluride, dipropylteliuride, diisopropyltelluride,
dibutyltelluride,
diisobutyltelluride, di-tart-butyltelluride, di-sec-butyltelluride, di-
phenyltelluride,
dimethylditelluride, diethylditelluride, dipropyiditelluride,
diisopropylditelluride,
dibutylditelluride, diisobutylditelluride, di-tart-butylditelluride, di-sec-
butylditelluride, di-phenylditelluride, including analogue, homologue, isomer,
and derivative thereof.
Non-limiting iron derivative compounds include: [cyclopentadienyl]
methylcyclopentadienyl iron, ferrocene, methylferrocene, and butadiene iron
tricarbonyl, [butadiene iron tricarbonyl,] dicyclopentadienyl iron and
2 o dicyclopentadienyl iron compounds;ferrocene, rnethylferrocenes,
decamethylferrocene (bis(pentamethyicyclopentadienyl)iron), 1,1'-
diacetylferrocene, ferrocenecarboxylic acid, 1,1'-ferrocenecarboxylic acid,
ferroceneacetic acid, ferroceneacetronitrile, 1,1'-ferrocene-
bis(diphenylphosphine), ferrocenecarbonxaldehyde, ferrocenecarboxylic acid,
2 5 1,1'ferrocenedicarboxylic acid, 1,1'ferrocenedimethanol,
ferrocenedimethanol,
diiron nonacarbonyl, di-irondodecacarbonyl, di-ironnonacarbonyl,
ironpentacarbonyl, triiron dodecacarbonyl, vinylferrocene, biscyclopentadienyl
iron (ferrocene), cyclopentadienyl methylcyclopentadienyi iron, bis(methyl-
cyclopentadienyl)iron, cyclopentadienyl ethylcyclopentadienyl iron,
3o bis(ethylcyclopentadienyl)iron,
bis(dimethylcyclopentadienyl)iron,bis(trimethyl-
cyclopentadienyl)iron, cyclopentadienyl tart-butylcyclopentadienyl iron,
bis(pentamethylcyclopentadienyl)iron, methylcyclopentadienyl
ethylcyclopentadienyl iron, bis(hexylcyclopentadienyl)iron, bisindenyl iron,
butadiene iron tricarbonyl, dicyclopentadienyl iron, cyclopentadienyl iron (di
3s carbonyl) (iodide), cyciopentadienyl iron (carbonyl) (iodide) (methyltetra-
hydrofuran), iron (III} ferrocyanide, ammonium hexacyanoferrate (II) hydrate,
cyclopentadienyliron dicarbonyl dimer, cyclopentadienyliron dicarbonyl iodide,
iron pentacarbonyl, diiron nonacarbonyl, ferroceneacetic acid, ferro-
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ceneacetonitrile, ferrocenemethanol, acetylferrocene, including analogue,
homologue, isomer, and derivative thereof. Other examples are set forth U.S.
Patents 2,680,; 2,804,468; 3,341,311, The Organic Chemistry of Iran,
Koemer, New York, Academic Press (1978), incorporated herein by
reference.
Non-limiting nickel derivative compounds include:
alkyl, aryl, alkyloxy, alkylanol, aryloxy, diltriaikyl, diltriaryl,
diltrialkyloxy,
diltrialkylanol, diltriaryloxy, andlor cyclomatic complexes, including, bis-
cyciopentadienyl nickel, cyclopentadienyl methylcyclopentadienyl nickel,
1o bis(methylcyclopentadienyl) nickel, bis(triphenylphosphine)dicarbonyi
nickel,
bis(isopropylcyclopentadienyl) nickel, bisindenyl nickel, cyclopentadienyl
nickel nitrosyl, methyfcyclopentadienyl nickel nitrosyl, including analogue,
homologue, isomer, and derivative thereof.
Non-limiting cobalt derivative compounds include: biscyclopentadienyl
cobalt, bis(methylcyclopentadienyl) cobalt, bis(dimethylcyclopentadienyl)
cobalt, cyclopentadienyl cobalt, dicarbonyl, cobalt(ous)
hexamethylenetetramine, cobalt(ous) hydroxyquinone, cyclopentadienylcobalt
dicarbonyf, including analogue, homologue, isomer, and derivative thereof.
Non-limiting zinc derivative compounds include: alkyl zinc, aryl zinc,
2 o alkyloxy zinc, aryloxy zinc, dialkyl zinc, diaryl zinc, dialkyloxy zinc,
diaryloxy
zinc, cyclomatic zinc complexes, including, dimethylzinc, diethylzinc,
dipropylzinc, diisopropylzinc, dibutylzinc, diisobutylzinc, di-tert-butylzinc,
di-
sec-butylzinc, di-phenylzinc, zinc acetate, zinc ethoxide, zinc arsenide, zinc
hydroxide, zinc selenide, zinc selenite, zinc flouride, zinc chloride, zinc
2 s cyanide, zinc floride, zinc chloride, zinc undecylenate, zinc nitrate,
zinc
acrylate, zinc methacrylate, methyl zinc chloride, isobutylzinc chloride, zinc
stearate, zinc dimethyldiethiocarbamate, di-n-propylzinc, di-o-tolyzinc,
isobutylzinc chloride, methylzinc chloride, zinc methacrlate, zinc acrylate,
zinc
hexaflourosilicate, zinc nitrate, zinc hydroxide, zinc undecylenate, zinc
3 o selenite, zinc cyanide, isobutylzinc chloride, methyl zinc chloride,
L(+)lactic
acid hemizinc, including analogues, homologues, isomers and derivatives
thereof. Corresponding magnesium compounds are contemplated. See Zinc.
The Science and Technology of the Metal. Its Alloys & Compounds,
Mattewson, N.Y., Reinhold (1959), incorporated by reference.
35 Non-limiting examples of transition metal derivative compounds, e.g.
metals of scandium, titanium, vanadium, chromium, manganese, iron, cobalt,
nickel, and their respective chemical groups, include transition metal alkyl,
aryl, alkyloxy, aryloxy, andlor ring system type compounds. Multiple alkyl,
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alkyloxy radicals per metal are contemplate. Cyclomatic transition metal
compounds are expressly contemplated. See Oraanometaliic Chemistry of
Transition Metals, 2 Ed, Crabtree, John Wiley & Sons, N.Y. (1994),
incorporated herein by reference.
Non-limiting examples of manganese compounds include
benzyleyelopentadienyl manganese tricarbonyl; 1.2-dipropyl 3-
cyclohexylcyclopentadienyl manganese tricarbonyl; 1.2-diphenyl-
cyclopentadienyl manganese tricarbonyl; 3-propenylienyl manganese
tricarbonyl; 2-tolyindenyl manganese tricarbonyl; fluorenyl manganese
1 o tricarbonyl; 2.3.4.7 - propyflourentyl manganese tricarbonyl; 3-
naphthylfluorenyl manganese tricarbonyl; 4.5.6.7-tetrahydroindenyl
manganese tricarbonyl; 3-3ethenyl-4, 7-dihydroindenyl manganese
tricarbonyl; 2-ethyl 3 (a-phenylethenyl) 4,5,6;7 tetrahydroindenyl manganese
tricarbonyl; 3 - (a-cyclohexylenthenyl) -4.7 - dihydroindenyl manganese
tricarbonyl; 1,2,3,4,5,6,7,8 - octahydrofluorenyl manganese tricarbonyl and
the like. A preferred cyclomatic manganese tricarbonyl is cyclopentadienyl
manganese tricarbonyl. A more preferred cyclomatic manganese tricarbonyl
is methyl cyclopentadienyl manganese (MMT).
Non-limiting examples of acceptable substitutes include the alkyl, aralkyl,
2 o aralkenyl, cycloalkyl, cycloalkenyl, aryl and alkenyl groups. The above
compounds can be generally prepared by methods that are known in the art.
Corresponding compounds of technetium and rhenium (see Canadian Patent
#1073207) are contemplated.
Non-limiting nitrogen derivative compounds include:
2-methoxybenzyfamine, 2-methoxybenzylarnine, 2-(4-methoxyben-
zylamino)pyridine, nitroanline, 1-nitroanline, 2-nitroanline, 3-nitroanline, 4-
nitroanline, nitroanisole, 1-nitroanisole, 2-nitroanisole, 3-nitroanisole, 4-
nitroanisole, aniline, 2-anilinoethanol, anisamide, anisonitrile,
acetonitrile,
nitromethane, nitroethane, picoline, 1-picoline, 2-picofine, 3-picoline, 4-
3o picoline, tetramethylammoniumhydroxide, dimethylolurea, 1,1-dibutylurea,
tetraethylammoniumhydroxide, N,N,N',N'-tetramethylethylenediamine, toluic
hydazide, toluidine, m-toluidine, o-toluidine, p-toluidine, tolunitrile, o-
tolunitrile,
p-tolunitrile, triazacyclononane, triazole, 1,2,4-triazole, triazine, 1,3,5-
triazine,
tributylamine, triethanofamine, trimethanolamine, tripropanolamine,
trimethoxypyrimidine, 2,4,6-trimethoxypyrimidine, tetramethylammonium,
trimethylpyrazine, urea, urazole, guanidine nitrate, guandine acetatic acid,
thiophenol, sodium salt thiophenol, thiourea, cumidine, diphenylamine, m-
xylidine, monmelthylanine, toluidine, amylaminobenzene, ethyiaminobenzene,
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aminophenyl, methyl-o-toluidine, n-butylaminobenzene, n-propyl-
aminobenzene, monoethylaniline, mon-n-propylanifine, ethyldiphenylamine,
mono-n-butylaniline, diethylamine, di-n-propylaniline, mono-isoamylaniline,
diethyianiline, dimethylaniline, ethylamine, triethylamine, triphenylamine,
s isopropylnitrite, ammonia, including analogues, homologues, isomers and
derivatives thereof.
Non-limiting titanium derivative compounds include: titanium
diisopropoxide bis(2,4-pentanedionate), titanium methoxide, titanium
ethoxide, titanium (IV) 2-ethylexoxide, titanium isopropoxide,
1 o tetraethylorthotitanate, including analogues, homologues, isomers and
derivatives thereof.
Non-limiting zirconium derivative compounds include: zirconium
carbide, zirconium propoxide, zirconium ethoxide, decamethyfzirconocene,
decamethylzirconocene dichloride, bis-cyclopentadienyl zirconium, including
15 analogues, homologues, isomers and derivatives thereof.
Non-limiting molybdenum derivative compounds include: molyb-
denumcarbonyl, molybdenum hexacarbonyl, tripyridine tricarbonyl-
molybdenum, molybdenumoxytetrachloride, cyclopentadienyl molybdenum
carbonyls, including but not limited to benzenemolybdenumtricarbonyl,
2 o bicycloheptadienemolybdenum tetracarbonyl, cycloheptatrienmolybdenum
tricarbonyl, bis-cyclopentadienylbimolybdenum pentacarbonyl,
mesitylenemolybdenum tricarbonyl, tropeniummolybdenum tricarbonyl
fluoroborate, cyclopentadienylmolybdenum tricarbonyl dimer,
methylcyclopentadienylmolybdenum tricarbonyl dimer, anisoie molybdenum
2 s tricarbonyl, mesitylene molybdenum tricarbonyl, including analogue,
homologue, isomers and derivative thereof. See U.S. Patents 3,272,606, and
3,718,444, incorporated by reference. Corresponding chromium and tungsten
compounds are contemplated in the practice of this invention.
Non-limiting copper derivative compounds include: alkyl copper
3o compounds, bis(ethylenediamine)copper(II) hydroxide, copper carbonate,
cyclopentadienyltriethylphosphine copper, diazoaminobenzene (ous), copper
acetate, copper acetylacetonate, copper aminoacetate, copper ethylacetate,
copper ferrocyanide, copper potassium ferrocyanide, copper nathenate,
copper nitrate, copper phosphide, copper phthalate, including analogue,
3 5 homologue, isomers and derivative thereof. See Copper. The Science and
Technology of the Metal. Its Alloys & Comaounds, Butts, N.Y., Reinhold
(1954), incorporated by reference.
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Other contemplated organometailic compounds are metallocenes, non-
limiting example compounds include, ferrocene, cobaltocene, nickelocene,
titanocene dichloride, zirconocene dichloride, uranocene,
decamethyfferrocene, decamethylsificocene, decamethylgermaniumocene,
decamethylstannocene, decamethylphosocene, decamethyiosmocene,
decamethylruthenocene, decamethyizirconocene, including analogue,
homologue, isomers and derivative thereof.
It is to be noted the above list is not exhaustive. The metals and their
derivative compounds of this invention include every metal, metalloid, andlor
1 o non-metal (herein "metal" or "metallic") capable of acheiving vapor phase
combustion, individually or incombination with Applicant's said ECS oxygen-
ates.
Applicant's invention contemplates wide variation in metal substitution
and mixing practice. Thus, it is expressly contemplated the non-lead organo-
metallics, non-lead inorganic metallics, andlor their related high heat
releasing compounds, including those set forth above may be mixed in
varying proportions, andlor substituted andlor replaced by any non-lead
metallic or non-metallic (organic or inorganic [atom, molecule or compound,
including those containing nitrogen, sulfur, chlorine, fluorine, helium, neon,
2o argon, krpton, xenon, or radon atoms]) accomplishing the object of this
invention.
Metal derivative compounds and combinations may be entirely or may
contain in part or whole non-metal atoms, e.g. nitrogen, sulfur, chlorine,
fluorine, helium, neon, argon, krpton, xenon, or radon, etc., so long as
primary
object of vapor phase combustion is accomplished. It is contemplated
Applicant's metals are substitutents in the fuel, itself, which may also
contain
certain non-metals and their derivative compounds, including but not limited
to nitrogen, sulfur, fluorine, chlorine, helium, neon, argon, krpton, xenon,
or
radon, in combination with dialkyl carbonates. These non-metals, and their
3 o derivative compound, may be employed with or without any other
contemplated metals. It is further contemplated to substitute or mix these non-
metallics with non-metallics, with metallics, or to mix metallics with
metallics,
etc., to achieve synergistic improvements in heat releases, burning velocity,
thermal efficiency, emission reductions, power generation, and the like.
It is contemplated said non-metals will employed in varying proportions
within the compound or combination compounds to achieve synergistic
improvements in heat releases, burning velocity, thermal efficiency,
emissions, power generation, and the like. For example,
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hexamethylphosphoric triamide, N,N,N',N'-hexamethylsilanediamine,
bis(diethylamono}-dimethylsilane may be added as a co-metallic or as a
secondary co-combustion agent to the co-combustion agents set forth above.
Concentrations will be minor, but sufficient to further improve vapor phase
combustion (e.g further enhancing fuel ecomony or power, etc.).
Ranges vary depending upon the specific metallic, fuels, fuel weight,
regulations, advance applications, thermodynamics, and the extent
combustion systems are modified to enhance the accelerated low
temperature high energy nature of Applicant's invention. Thus, metallic
1o concentrations that maximize combustion velocity andlor the vapor phase
combustion object of this invention are expressly contemplated.
However, it is contemplated that Applicant's fuel also be absent any
metal or non-metal. That is, Applicant's invention, by accelerating burning
velocity and/or increasing latent heat of vaporization, andlor reducing
combustion temperatures by fuel substituent tailoring, chemical andlor
mechanical means, as set forth herein or in the afforementioned PCT Applica-
tions, said fuel can be employed absent either an ECS oxygenate or a
metallic or non-metallic.
In accordance with this invention, Applicant's fuels will contain that
2 o amount of at least non-lead metallic, which constitutes a combustion
improving amount consistent with the fuel composition, stoichiometry,
combustion system, efficiencies, fuel economy and power desired, as well as
legal and/or environmental considerations.
1t is expressly contemplated that Applicant's metallics be incorporated
2 5 into liquid fuel systems by means of mutual solvents, mutual
dispersentslsolvents, colloidal media, suspension media, or other known
means, or being separately injected. Metallic's, which are solid at ambiant
temperatures may be introduced into the combustorlcombustion chamber by
liquidification or gasification means.
3 o It is preferred the metailics of this invention be relatively inexpensive
to
manufacture on a mass production basis.
The metal and concentration amounts are to be optimized, such that
vapor phase combustion results. Thus, the metal and its optimum
concentration amount, is an amount that results in vapor phase combustion,
35 which is evidenced by improved fuel economy, emissions, power, etc. In the
practice of this invention, the ratio of oxygenated ECS compound by weight to
elemental metal by weight in the composition is equal to or less than 10,000:1
(parts) to equal or greater than 1:1. Other ratios include from 1,000,000:1 to
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100,000:1; 100,000:1 to 50,000:1; 50,000:1 to 25,000:1; 25,000:1 to
15, 000:1; 15, 000:1 to 12, 000:1, 12, 000:1 to 11. 000:1, 11, 000:1 to 10,
000:1,
9, 000:1, 8, 000:1. 7, 000:1, 6, 000;1, 5, 000:1, 4, 000:1, 1, 000:1, 900:1,
500:1,
300:1, 200:1, 150:1, 100:1, 90:1, 80:1, 75:1, 70:1, 60:1, 50:1, 40:1, 30:1,
20:1, 10:1, 5:1 to 3:1, or interval ratio contained therein (e.g. 50:1 to 30:1
) and
also 1:1 to 1:20, or any other ratio that maximizes vapor phase combustion.
Every concentration which maximizes vapor phase combustion is
contempated in the claims hereto.
Metallic salts may be employed in fuels at 0.01 to 4000.0 parts metallic
to per million fuel, 1.0 to 150 ppm metallic being contemplated, with
concentrations equal or less than 50.0, 40.0, 30.0, 20.0, 16.0, 10.0, 5.0 ppm
metallic also contemplated. Other salt concentrations will vary from 0.10 to
75.0 ppm metal per million, from 30.0 to 2000.0 per million, from 25 to 750
parts metallic or salt per million fuel. In the application of Applicant's
invention
elemental metal concentrations from 3.0 to 500.0 ppm metal are expressly
contemplated and desirable. Concentrations outside these ranges are
contemplated.
It has been found that higher oxygen weight concentrations in fuel
compositions, particularly with higher concentrations of enhanced combustion
2o properties, permit higher acceptable metallic concentrations. Higher
average
fuel densities are also associated with higher acceptable metallic
concentrations and higher exhaust velocities, and are preferred. Engine
combustion thermal dynamics and stoichiometry dictate upper metallic limits.
As noted above, elemental metallic concentrations will vary
substantially. Non-limiting examples include elemental metallic
concentrations equal to or greater than 1164, 1132, 1116, 3/32, 118, 5132,
3116,
114, 5116, 318, 7116, 1/2, 518, 314, 718, 1, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5,
2.75,
3.0, 3.25, 3.5, 3.75, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0,
9.5, 10.0
gramslgal. In advance aviation, rocket andlor propellant and other
3 o applications, elemental metal concentrations can be on the order of 10 to
25,
20 to 40, 20 to 50, 20 to 100, even 50 to 1000, or more, gramslgal, especially
in hypergolic conditions. Concentrations both above and below these ranges
are contemplated. A11 combustion improving or stoichiometric amounts of
elemental metal are contemplated, which maximize combustion so long as
the resultant fuel's burning velocity increases compared to fuel absent
metallic.
Thus, those metallic concentrations that maximize combustion velocity
andlor other objects of this invention are expressly contemplated. Ranges
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will vary depending upon the specific metallic, its concentration,
concentration
and type of ECS oxygenates, the concentration and nature of hydrocarbon
fuel composition, including its density, the intended application, relevant
thermodynamics, extent combustion systems are modified to enhance the
accelerated low temperature high energy nature of Applicant's invention,
environmental regulation, and the like.
Metallics used in the fuel compositions of the present invention should
be fuel soluble generally having melting and boiling ranges compatible with
liquid hydrocarbons, or be incorporated into liquid fuel systems by means of
1o mutual solvents, dispersants, or other means, as required. Alternatively,
the
metallics may be introduced into the combustorlcombustion chamber of
liquide or gaseous fuels (e.g. natural gas) by separate means, including
separate injection, liquidification or gasification, colloidal media,
suspension
media. Metallics may be introduced into the combustor in an atomized,
vaporized, or gasified form, separately andlor in combination with the other
ingredients of the invention.
In solid fuel applications, the metallic may be introduced as a solid. In
hybrid applications, it may be introduced as either as solid, liquid or gas,
together with the balance of the invention's ingredients. Most preferably, the
2 o metallic is employed as a propellant or co-propellant, or jointly together
with a
propellant. Hydrogen content of the metallic andlor metallic containing fuel
should be maximized, to the extent possible.
Those skilled in the art will appreciate that many variations and
modifications of the invention disclosed herein may be made without
2 5 departing from the spirit and scope thereof.
