Note: Descriptions are shown in the official language in which they were submitted.
2~377~
MULTIFUNCTIONAL FUEL ADDITIVES
FIELD OF THE INVENTION
This invention is directed to
multifunctional additives which improve the low-
temperature properties of distillate fuels and to
fuel compositions containing minor amounts thereof
BACKGROUND OF THE INVENTION
Traditionally, the low-temperature
properties of distillate fuels have been improved
by the addition of kerosene, sometimes in very
large amounts (5-70 wt %). The kerosene dilutes
the wax in the fuel, i.e., lowers the overall
weight fraction of wax, and thereby lowers the
cloud point, filterability temperature, and pour
point simultaneously. The additives of this
invention effectively lower both the cloud point
and CFPP (Cold Filter Plugging Point) of distillate
fuel without any appreciable dilution of the wax
component of the fuel.
Other additives known in the art have
been used in lieu of kerosene to improve the low-
temperature properties of distillate fuels. Many
such additives are polymeric materials with pendent
fatty hydrocarbon groups, and are usually derived
2 ~3 3 rl r~
from the free radical polymerization of unsaturated
hydrocarbons (olefins, acry]ates, fumarates, etc.).
These additives are limited in their range of
activity, however; most improve fuel properties by
lowering the pour point and/or filterability
temperature. These same additives have little or
no effect on the cloud point of the fuelO
U.S. Patents 3,910,987 and 3,910,981
disclose the use of certain aminodiols in the
preparation of petroleum additives. U.S. Patent
4,524,007 discloses the use of polycarboxylic
acids/anhydrides such as pyromellitic dianhydride
reacted with ether capped alcohols to provide
demulsifying additives for lubricants.
S~RY OF THE INVBNTION
The additives of this invention are
substantially difPerent from the prior art both in
terms of structure and function (activity). They
are oligomeric and/or polymeric materials obtained
via condensation reactions, e.g. the reaction of
diols, aminodiols or diaminodiols with acids and/or
anhydrides. In terms of activity, these additives
effectively lower distillate fuel cloud point, thus
providing improved low-temperature fuel properties,
and offering a unique and useful advantage over
known distillate fuel additives.
The novel additives of this invention
have been found to be surprisingly active wax
crystal modifier additives for distillate fuels.
Distillate fuel compositions containing minor
amounts, such as less than 0~1 wt%, of such
additives demonstrate significantly improved low-
temperature flow properties, with lower cloud point
and lower CFPP filterability temperature.
2~7~
The additlves of this invention, which
improve the low-temperature properties of
distillate fuels, are the reaction products of (1)
diols~ aminodiols or diaminodiols, and (2) the
product of benzophenone tetracarboxylic dianhydride
(BTDA) or pyromellitic dianhydride (PMDA) and
aminoalcohols and/or amines, the reaction product
having long-chain hydrocarbyl groups attached.
Long-chain hydrocarbyl groups may be
introduced into the final reaction product via (1)
the various substituted diol comonomers ~diols,
aminodiols or diaminodiols) or (2) the substituted
amino alcohol and/or amine precursors to the
derivatized BDTA or PMDA comonomers or (3) some
combination of (1) and (2).
These new additives are especially
effective in lowering the cloud point of distillate
fuels, and thus improve the low-temperature flow
properties of such fuels without the use of any
light hydrocarbon diluent, such as kerosene. In
addition, the filterability properties are improved
as demonstrated by lower CFPP temperatures. Thus,
the additives of this invention demonstrate
multifunctional activity in distillate fuels.
This invention is also directed to fuel
compositions comprising minor amounts of these
multifunctional additives.
The additive compositions, described in
this application, have cloud point activity, and
CFPP activity and are unique in structure and
activity. Additive concentrates and fuel
compositions containing such additives are also
unique. Similarly, the processes for making these
additives, additive concentrates, and fuel
compositions are uni~le. Accordingly, it is not
~ ~ 3 ~
believed that these novel additive products and
fuel compositions thereof were heretofore known or
used in the prior art.
These oligomeric/polymeric additives are
reaction products derived f r om two types of monomer
components. (1) The first monomer type i5 a diol,
aminodiol or dlaminodiol, either alone or in
combination with other diols, aminodiols or
diaminodiols. (2) The second monomer type is a
reactive acid/anhydride product, either alone or in
combination with other such monomers, derived from
the reaction of BTDA or its acid equivalent or PMDA
or its acid equivalent with either ~a~ an
aminoalcohol, the product of an amine and an
epoxide, or (b) a combination of an aminoalcohol
(above, a) and an amine.
The additives of this invention
accordingly, have oligomeric (i.e., dimers,
trimers, etc.) and/or polymeric structures.
Various hydrocarbyl groups, especially groups with
linear paraffinic substructures attached or
containing linear paraffinic substructures, are
distributed along the backbone of the oligomer
and/or polymer, and may be carried by either or
both of the comonomers used.
Diols
Any diol, either alone or in combination,
may be used in this invention. Such diols may
encompass, but are not limited to, examples of the
following types: 1,2-diols, 1,3-diols, lf4 diols,
alpha-omega-diols, ether diols, polyether diols,
glyceryl monoesters, and any other hydrocarbyl
diol. However, 1,2-octadecanediol, 1,4-butanediol,
1,12-dodecanediol, poly(ethyleneglycol) and
2 C~ 3~ r~ r~
poly(propyleneglycol) are among the preferred
reactants.
Aminodiols
Any aminodiol, either alone or in
combination, may be used in this invention and may
include, but is not limited by, examples given
below.
Such aminodiols are those diols derived
from the reaction of a primary amine with two or
more equivalents of an epoxide:
R-NH2 + R1Rl-C~o~C~R1Rl >
H-[O-C(R1R~)-C~R1Rl)~V~ [C(R1R1)-c(R1R1)-o]~-H
R
The reaction conditions for the
preparation of the aminodiols is as follows: 80-
250C for 1-24 hrs., under autogenous pressure to
25 atmospheres.
The temperature chosen will depend upon
for the most part on the particular reactants and
on whether or not a solvent is usedc Solvents used
will typically be hydrocarbon solvents such as
xylene, but any non-polar, unreactive solvent can
be used including benzene and toluene and/or
mixtures thereof.
Molar ratios of epoxide/primary amine are
generally 2:1, but may also include ratios greater
than 2:1.
The amine used above may be any primary
amine, with each substituent being independently C1-
~37~
C100 hydrocarbyl, or hydrocarbyl containing O, N, S,P.
Diaminodiols
One of the comonomers, alone or in
combination, used in the synthesis of these
additives may be a diaminodiol. The diaminodiols
of this invention are the reaction products of (1)
a diepoxide ard a secondary amine, or (2) an
epoxide and a bis secondary amine. These
diepoxides include but are not limited to terminal
hydrocarbyl diepoxides and diglycidyl ethers. Such
a diaminodiol provides the capability of
introducing additional linear hydrocarbyl groups
along the oligomer/polymer backbone, thus
increasing the overall density of linear
hydrocarbyl groups in the final additive structure.
However, any diaminodiol may be used in this
invention and may include, but is not limited by,
examples given below.
In the first class, the diaminodiols are
those diols, for example, derived from the reaction
of two equivalents of a secondary amine and a
diglycidyl ether, according to the following
general scheme:
2 H-N(R2R3) + H2C\ ~CH-CH2-o-R4-O-CH2-HC ~ /CH2
(R2R3) N-cH2-~H-cH2-o-R4-o-cH2-cH-cH2-N (R2R3
OH 1H
In a one-pot synthesis the diaminodiol is
prepared by suitably reacting an amine or mixture
of amines with a diglycidyl ether.
~37~ ~
A second class of aminodiols are those
diols derived from the reaction of a bis-secondary
amine with two or more equivalents of an epoxide:
R-NH-R'-NH-R + R1R1-C~ ~ -R1Rl - - >
H-tO-C~R~R~)-C(R~R1)]v-N--Rl--N-[~(R1R1~-c(R1R1)-o]~-H
,!~
Molar ratios of epoxide/secondary amine
are generally 1:1 for each reactive amine group but
may include ratios greater than 1:1.
The amine used above may be any secondary
amine, with each substituent being independently C1-
C1~ hydrocarbyl, or hydrocarbyl containing 0, N, S,
P.
Reactive Acid and/or Anhvdride
The other comonomer, alone or in
combination, used in the synthesis of these
additives is a reactive acid and/or anhydride
derived from the reaction of BTDA or its acid
equivalent or PMDA or its acid equivalent and
alcohols and/or amines to introduce suitable
pendant groups derived from the aminoalcohols
and/or amines. The pendant groups are some
combination of hydrocarbyl, preferably linear
hydrocarbyl groups attached to the esters and/or
amides of the derivitized dianhydride (DA)~ As
used herein "DA" refers generically to either BTDA
or PMDA or their acid equivalents.
~7~
The pendant groups include (a) esters
derived from aminoalcohols, which may be derived
fr~m a secondary amine capped with an olefin
epoxide, (b) combinations of esters and amides
derived from the aminoalcohol from (a) and an
amine, and (c) combinations of esters derived from
two or more different aminoalcohols. These pendant
ester and/or amide groups usually contain from 8 to
about 100 carbon atoms or more, preferably from
about 28 or 30 to 100 carbon atoms or more. The
aminoalcohol used above is the reaction product of
an epoxide and a secondary amine, in substantially
1:1 molar ratio. Preferred amines are secondary
amines such as di(hydrogenated tallow) amine.
Preferred epoxides are such epoxides as 1,2-
epoxyoctadecane.
In a one-pot synthesis process the
aminodiol is first prepared by suitably reacting an
amine or mixture of amines with an epoxide or
mixture thereof and then reacting the resultant
product with BTDA or PMDA or its acid equivalent.
The reactions can be carried out under widely
varying conditions.
Reaction with Acid/AnhYdride to Produce the
Multifunctional Additiv_
The additives of this invention are the
reaction products obtained by combining the two
monomer types described above in differing ratios
using standard esterification techniques according
to the following stepwise procedures:
(1) DA + HO-~H-CH2-~-R~ + optionally H-N-R2
R
Reactive Acid/Anhydride
2~7~
(2a~ Reactive Acid/Anhydride and Diol
Reactive AcidJAnhydride + HO-R~-OH -
Oligomer/Polymex
(2b) Reactive Acid Anhydride and Aminodiol
Reactive Acid/Anhydride + HO-R~-OH
Oligomer/Polymer
2(c) Reactive Acid/Anhydride and Diaminodiol
Reactive Acid/Anhydride + HO-R7-OH
~ ~ Oligomer/Polymer
Structure of Acid/Anhydride Reaction Products
A general structure for the
oligomers/polymers derived from BTDA or PMDA
partial ester and diol is as follows:
-[(~A)-(o-lcH-cH2-~-R2)x]-t
R2
A general structure for the
oligomers/polymers derived from BTDA or PMDA mixed
partial ester and diol is as follows:
-[(DA)-~O-~CH-CH2-l-~2)y(0-~H CH2-l-R2)~]-[O-~-O]~-
R2 R 1 R
A general structure for the
oligomers/polymers derived from BTDA or PMDA
partial ester~amide and diol is as ollows:
2 ~ 3 7 r~ ~ ~
-[(DA)-(O-CH-CH2-~-R2)y(l~R2)~] [-Rs~],~
~2 R R
A general structure, for example, for
oligomers/polymers derived from BTDA or PMDA
partial ester and aminodiol is as follows:
-~(DA)-(O-~CH-CH2-~-R2)X] [o R~ o]~
R2
A g e n e ral s t ru c tu re fo r
oligomers/polymers derived from BTDA or PMDA mixed
partial ester and aminodiol is as follows:
-[(DA)-(O-~H-CH2-~-R2)y(0~clH-cH2-~-R3~z]-[o-R
R2 R1 R
A g e n e ral st ru ct u re f or
oligomers/polymers derived from BTDA or PMDA
partial ester/amide and aminodiol is as follows:
--[ (DA)-(o-lcH-cH2-l-R2)y( ~-R2)z]-[o-R6 - o]~ -
R2 R R
A general structure for the
oligomers/polymers derived from BTDA or PMD~
partial ester and diaminodiol is as follows:
[(DA)-(O-CIH-cH2-~-R2)x] [o-c~H-cH2-o-R~-o-cH2-clH-O]~-
R2 R H2-N(R2R3) C H 2 ~
N(R2R3)
Also, oligomers~polymers analogous to these may be
derived from DA mixed partial ester, i.e., DA
2~337~
derivatlves where the pendant aminoalcohols are
different from one another.
A general structur~ for the
oligomers~polymers derived from BTDA or PMDA
partial ester/amide and diaminodiol is as follows:
-[ (DA)-(O-CH-C~I2-~ -R2)y~N-R2);~]-[o-cH - cH2-o-R~-o-cH2
~2 R ~ CH2-N(R2R3)
--C~--O ] ~,--
~H2-N ( ~2R3 )
Definitions
In the above formulas,
v + w > 2;
x = y+z = 0.5 to 3.5, preferably from 1 to about 3;
a is 0.25 to about 2, preferably from 0.5 to about
1.25;
R is C1 to about C10O hydrocarbyl, or C1 to about C100
hydrocarbyl containing phosphorus, nitrogen, sulfur
andjor oxygen;
R' is a divalent group corresponding to R, i.e., a
divalent C1 to C100 hydrocarbyl or a divalent C1 to
C10O hydrocarbyl containing phosphorus, nitrogen,
sulfur and/or oxygen;
R1, which each may be the same or different, is
hydrogen, Cl to about C100 hydrocarbyl or C1 to about
C100 hydrocarbyl containing phosphorus, nitrogen,
sulfur and/or oxygen;
R2, which each can be the same or different, is C8
to about C50 hydrocarbyl group, preEerably linear
either saturated or unsaturated;
R3 is Cl to about C100 hydrocarbyl or C1 to about C100
hydrocarbyl containing phosphorus, nitrogen, sulfur
and/or oxygen;
~77~
12
R4 - C1 to about Cl00 hydrocarbyl, or Cl to about C
hydrocarbyl containing nitrogen, sulfur,
phosphorus, boron, silicon and/or oxygen;
F~ is C2-C100 hydrocarbyl; and
R6 is the sub-structure of the aminodiol(s) defined
above; and
R7 is one of the two diaminodiol sub-structures
defined above.
The phrase "long-chain hydrocarbyl group"
as used in this application means linear or near
linear alkyl or alkenyl groups. Each individual
long-chain hydrocarbyl group is usually a C8 to C30
hydrocarbyl group, preferably a C14 to Cz2
hydrocarbyl group.
Amines
Any suitable amine may be used.
When used to prepare an amino diol, the
amine is preferably any primary amine such as n-
octylamine, hydrogenated ~allow amine and aniline.
When the amine is used to prepare a
diaminodiol by reaction with a diepoxide, the amine
is any secondary amine such as di(hydrogenated
tallow) amine and methyl octadecylamine.
When the amine is used to prepare a
diaminodiol by reaction with an epoxide, the amine
is any bis secondary amine such as piperazine.
When the amine is used as a structural
fragment of the reactive anhydride acid, the amine
may be any suitable aliphatic or aromatic,
arylalkyl or alkylaryl having from 1 to about l00
carbon atoms secondary amine. A highly preferred
amine is di(hydrogenated tallow) amine. Other
suitable amines include, but are not limited to,
ditallow amine, dioctadecylamine, methyl octadecyl
amine, and other secondary amines.
~3~7~
13
Die~oxides
Included within the scope of diepoxides
are any diglycidyl ethers and any diepoxide
reaction products derived ~Erom any diol, and two
molar amounts of epichlorohydrin (or synthetic
equivalents) such as 2,2-dimethyl-1,3-propane diol
diglycidyl ether.
Epoxides
Included within the scope of the epoxides
used in preparing aminoalcohols from amines as set
forth above, are ethylene oxide, l,2-epoxides,
including, for example, 1,2-epoxydecane, 1,2-
epoxydodecane, 1,2-epoxytetradecane, 1,2-
epoxypentadecane, 1,2-epoxyhexadecane, 1,2-
epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-
epoxyeicosane and mixtures thereof. Especially
preferred are 1,2-epoxyoctadecane and ethylene
oxide.
Reaction conditions
In general, the additive reaction product
can be synthesized under widely varying conditions
which are not believed to be critical. The
reaction temperature can vary from S0 to 250C,
preferably 100 to 250C, mor~ preferably from 150
to 200C, under ambient or autogenous pressure.
However, slightly higher pressures may be used if
desired. The pressure may vary from 0.001 atm to
lo atm and preferably 0.001 atm to 1 atm. The
temperature chosen will depend for the most part on
the particular reactants and on whether or not a
solvent is used. Solvents when used will typically
be hydrocarbon solvents such as xylene, but any
non-polar, unreactive solvent can be used including
benzene, toluene or mixtures thereof.
2~3~7~
14
Molar ratios, less than molar ratios or more
than molar ratios of the comonomer reactants can be
used. Preferentially, a molar ratio of diol,
aminodiol or diaminodiol to reactive acid/anhydride
of 1:2 to 3.5:1, more preferentially 1:1.25 to
1.5:1 is used.
The times for the reactions are also not
believed to be critical. The process is generally
carried out in about 1 to about 24 hours to 36 to
48 hours or more.
Fuel Com~ositions
In generall the reaction products of ~he
present invention may be employed in any amount
effective for imparting the desired degree of
activity necessary to improve the low temperature
characteristics of distillate fuels. In many
applications the products are effectively employed
in amounts from about 0.001% to about 10% by wPight
and preferably from less than about 0.1% to about
5~ of the weight of the total composition. These
additives may be used in conjunction wit~ other
known low-temperature fuel additives (dispersants,
etc.) being used for their intended purpose.
The fuels contemplated are liquid
hydrocarbon combustion fuels, including the
dist~llate fuels and fuel oils. Accordingly, the
fuel oils that may be improved in accordance with
the present invention are hydrocarbon fractions
having an initial boiling point of at least about
250F (121C) and an end-boiling point no higher
than about 750F (399C) and boiling substantially
continuously throughout their distillation range.
Such fuel oils are generally known as distillate
fuel oils. It is to be understood, however, that
~ ~ 3 7 ~
this term i5 not restricted to straight run
distillate fractions. The distillate fuei oils can
be straight run distillate fuel oil~, catalytically
or thermally crac~ed (including hydrocracked)
distillate fuel oils, or mixtures of straight run
distillate fuel oils, naphthas and the like, with
cracked distillate stocks. Moreover, such fuel
oils can be treated in accordance with well-known
commercial methods, such as, acid or caustic
treatment, hydrogenation, solvent refining, clay
treatment, etc.
The distillate fuel oils are
characterized by their relatively low viscosities,
pour points, and the like. The principal property
which characterizes the contemplated hydrocarbons,
however, is the distillation range. As mentioned
hereinbefore, this range will ~enerally lie between
about 250F (121C) and about 750F (400C).
Obviously, the distillation range of each
individual fuel oil will cover a narrower boiling
range falling, nevertheless, within the above-
specified limits. Likewise, each fuel oil will
boil substantially continuously throughout its
distillation range.
Contemplated among the fuel oils are Nos.
1, 2 and 3 fuel oils used in heating and as diesel
fuel oils, and the jet combustion fuels. The
domestic fuel oils generally conform to the
specification set forth in A.S.T.M. Speci~ications
D396-48T. Specifications for diesel fuels are
defined in A.S.T.M. Specification D975-48T.
Typical jet fuels are defined in Military
Specification MIL-F-5624B.
7 ~
16
EXAMPLES
The following examples are illustrative
only and are not meant to limit the scope of the
invention.
Example 1
Preparation of Additive 1
Di(hydrogenated tallow) amine (50.0 grams,
0.10 mol; from Akzo Chemie), and 1,2-
epoxyoctadecane (33.6 grams, 0.125 mol; e.g.
Vikolox 18 from Viking Chemical) were combined and
heated at 170~ for 16-18 hours. Benzophenone
tetracarboxylic dianhydride (17.7 grams, 0.055 mol;
e.g. BTDA from Allco Chemical Corporation), 1,12
dodecanediol (5.06 grams, 0.025 mol; e.g. from
Aldrich Chemical Company), and xylene
(approximately 50 ml) were added and heated at
reflux (190-200C) with azeotropic removal of water
for 24 hours. Volatiles were then removed from the
reaction medium at 190-200-C, and the reaction
mixture was hot filtered through diatomaceous earth
to give 92.5 grams of the final product.
Example 2
Preparation of Additive 2
According to the procedure used for Example 1
(above~, di(hydrogenated tallow) amine (50.0 grams,
0.10 mol), and 1,2-epoxyoctadecane (33.6 grams,
0.125 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (17.7 grams 0.055 mol~,
1,12 dodecanediol (9.11 grams, 0.045 mol), and
xylene (approximately 50 ml) were added and allowed
to react. Excess ~ylene was added to facilitate
filtration, and was subsequently removed by
evaporative distillation. After isolation, 102.0
grams of the final product was obtained.
~37~
17
~xample 3
Preparation of Additive 3
According to the proceclure used for Example 1
(above), di(hydrogenated tallow) amine (50.0 grams,
0.10 mol), and 1,2-epoxyoctadecane (33.6 grams,
0.125 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (17.7 gram~ 0.055 mol),
poly(propyleneglycol) with avg. M.W. 400 (10.0
grams, 0.025 mol; from Texaco Chemical Company),
and xylene (approximately 50 ml) were added and
allowed to react. After isolation, 97.8 grams of
the final product was obtained.
Example 4
Preparation of Additive 4
According to the procedure used for Example 1
(above), di(hydrogenated tallow) amine (50.0 grams,
0.10 mol), and 1,2-epoxyoctadecane ~33.6 grams,
0.125 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (17.7 grams 0.055 mol),
poly(propyleneglycol) with avg. M.W. 400 (21.0
grams, 0.052 mol), and xylene (approximately 50 ml)
were added and allowed to react. After isolation,
111. 2 grams of the final product was obtained.
Example 5
Preparation of Additive 5
According to the procedure used for Example 1
(above), di(hydrogenated tallow) amine (40.0 grams,
0.08 mol), and 1,2-epoxyoctadecane ~26.8 grams,
O.10 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (14.2 grams 0.044 mol),
poly(propyleneglycol) with avg. M.W. 2000 (40.0
grams, O A O20 mol; from Texaco Chemical Company),
and xylene (appr~ximately 50 ml~ wexe added and
~37~
18
allowed to react. After lsolation, 109.7 grams of
the ~inal product was obtained.
Example 6
Preparation of Additive 6
According to the procedure used for Example 1
~ab~ve), di(hydrogenated tallow) amine (35.0 grams,
0.07 mol), and 1,2-epoxyoctadecane (23.5 grams,
0.088 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (12.4 qrams 0.038 mol),
poly(propyleneglycol) with avg. M.W. 2000 (73.5
grams, 0.037 mol; and xylene (approximately 50 ml)
were added and allowed to react~ After isolation,
131.4 grams of the final product was obtained.
Exam~le 7
Preparation of Additive ~
According to the procedure used for
Example 1 (above), di(hydrogenated tallow) amine
(51.0 grams, 0.10 mol), and 1,2-epoxyoctadecane
(14.2 grams, 0.050 mol) were combined. Then,
benzophenone tetracarboxylic dianhydride (16.1
grams 0.050 mol), poly(propyleneglycol) with avg.
M.W. 400 (20.0 grams, 0.050 mol; and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 90.7 grams of the final
product was obtained.
Example 8
Preparation of Additive 8
Piperazine (1.44 g, 0.017 mol; e.g. from
Aldrich Chemical Company), di(hydrogenated tallow)
amine (50.0 g, 0.10 mol; e.g. Armeen 2HT from Akzo
Chemie), and 1,2-epoxyoctadecane (44.8g, 0.167 mol;
e.g. Vikolox 18 from Viking Chemical) were combined
~ ~ ~ r) 7
19
and heated at 160 to 190C for 18 to 24 hours.
Benzophenone tetracarboxylic dianhydride (11.8 g,
0.037 mol; e.g. BTDA from Allco Chemical
Corporation) and xylen~ (approximately 50 ml) were
added and heated at reflux (180 to 200-C) with
azeotropic removal of water for 24 hours.
Volatiles were then removed from the reaction
medium at 190 to 200 C, and the reaction mixture
was hot filtered through diatomaceous earth to give
97.5 g of the final product.
Example 9
_eParation of Additive g
According to the procedure used for
Example 8, piperazine (3.45 g, 0.040 mol),
di(hydrogenated tallow) amine (40.0 g, 0.080 mol),
and 1,2-epoxyoctadecane (53.7 g, 0.200 mol) were
combined. Then, benzophenone tetracarboxylic
dianhydride (7.85 g, 0.036 mol) and xylene
~approximately 50 ml) were added and allowed to
react. After isolation, 105.9 g of the final
product was obtained.
Example 10
Preparation_of Additive 10
~ ccording to the procedure used for Example 8,
n-octylamine (2.75 g, 0.017 mol; e.g. fxom Aldrich
Chemical Company, di(hydrogenated tallow) amine
(50.0 g, 0.100 mol), and 1,2-epoxyoctadecane ~44.8
g, 0.167 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (11.8 g, 0.037 mol) and
xylene (approximately ~0 ml) were added and allowed
to react. After isolation, 98.2 g of the final
product was obtained.
~377~'~
Example 11
~Paration_of Additive 11
According to the procedure used for
Example 8, n-octylamine (6.61 g, 0.040 mol,
di(hydrogenated tallow) amine (40.0 g, 0.080 mol),
and 1,2-epoxyoctadecane (64.7 g, 0.200 mol) were
combined. Then, benzophenone tetracarboxylic
dianhydride (14.2 g, 0.044 mol) and xylene
(approximately ~0 ml) were added and allowed to
react. After isolation, 103.0 g of the final
product was obtained.
Example 12
Pre~aration of Additive 12
According to the procedure used for Example 8,
hydrogenated tallow amine (4.31 g, 0.017 mol; e.g.
Armeen HT from Akzo Chemie), di(hydrogenated
tallow) amine (50.0 g, 0.100 mol), and 1,2-
epoxyoctadecane (44.8 g, 0.16~ mol) were combined.
Then, benzophenone tetracarboxylic dianhydride
(11.8 g, 0.037 mol) and xylene (approximately 50
ml~ were added and allowed to react. After
isolation, 103.4 g of the final product was
obtained.
Example 13
Preparation of Additive 13
According to the procedure used for
Example 8, hydrogenated tallow amine (10.3 g, 0.040
mol, di(hydrogenated tallow) amine (40.0 g, 0.080
mol), and l,2-epoxyoctadecane ~53.7 g, 0.200 mol)
were combined. Then, benzophenone tetracarboxylic
dianhydride (14.2 g, 0.044 mol) and xylene
(approximately 50 ml) were added and allowed to
2 ~ 3 r~ 7 ~ ~
21
react. After isolation, 108.2 g of thQ final
product was obtained.
Example 14
Preparation of Additive 14
According to the procedure used for
Example 8, di(hydrogenated tallow) amine (50.0 g,
0.100 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125
mol) were combined. Then, Ethomeen T/12 (8.66 g,
0.025 mol; an aminodiol derived from tallow amine
and two equivalents of ethylene oxide, e.g. from
Akzo Chemie), benzophenone tetracarboxylic
dianhydride (17.7 g, 0.055 mol~ and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 100.5 g of the final
product was obtained.
Example 15
Preparation of Additive 15
According to the procedure used for
Example 8, di(hydrogenated tallow) amine ~50.0 g,
0.100 mol) and 1,2-epoxyoctadecane (33.6 g, 0.125
mol) were combined. Then, Ethomeen T/12 (18.2 q,
0.052 mol) benzophenone tetracarboxylic dianhydride
(17.7 g, 0.055 mol) and xylene (approximately 50
ml) were added and allowed to react. After
isolation, 109.2 g of the final product was
obtained.
ExamPle 16
Preparation of Additive 16
According to the procedure used for
Example 8, di(hydrogenated tallow) amine (5000 g,
0.100 mol), and 1,2-epoxyoctadecane (33.6 g, 0.125
mol) were combined. Then, Ethomeen T/12 (12.0 g,
C~ ~ 3 ~) r~
22
0.025 mol); an aminodiol derived from tallow amine
and five equivalents of ethylene oxide, e.g. from
Akzo Chemie), benzophenone tetracar~oxylic
dianhydride (17.7 g, 0.055 mol) and xylene
(approximately 50 ml) were added and allowed to
react. Af er isolation, 89.2 g of the final
product was obtained.
Example 17
Preparation of Additive 17
According to the procedure used for Exa~ple 8,
di(hydrogenated tallow) amine (50.0 g, 0.100 mol)
and 1,2-epoxyoctadecane (33.6 g, 0.125 mol~ were
combined. Then, Ethomeen T/15 (25.1 g, 0.052 mol),
benzophenone tetracarboxylic dianhydride (17.7 g,
0.055 mol) and xylene (approximately 50 ml) were
added and allowed to react. After isolation, 86.7
g of the final product was obtained.
Exam~le 18
Preparation of Additive 18
a-Octylamine (5.17 g, 0.040 mol), and
1,2-epoxyoctadecane (34.2 g~ 0.12 mol) were
combined and were reacted together at 140 to 170C
for 23 hours. Di(hydrogenated tallow) amine (40.8
g, 0.80 mol) was added to the reaction mixture and
was heated at 170C for six to seven hours. Then,
benzophenone tetracarboxylic dianhydride (12.9 g,
0.040 mol) and xylene (approximately 50 ml) were
added and heated at reflux (190C) with azeotropic
removal of water for 24 hours. Volatiles were then
removed from the reaction medium at 199 to 200 C,
and the reaction mixture was hot filtered through
diatomaceous earth to give 84.8 g of the final
product.
23
~xam~le 19
Pre~arat~on o~j~dditive 19
Di(hydrogenated tallow) amine (60.0 g,
O.12 mol; e.g. Armeen 2HT from ~kzo Chemie), 2,2-
dimethyl-1,3-propaned~ol diglycidyl ether ~10.9 g,
o.osO mol; e.g. Azepoxy N form AZS Corporation),
and 1,2-epoxyoctadecane (14.2 g, 0.053 mol; e.g.
Vikolox 18 for Viking Chemical) were combined and
heated at 140 to 150C for three hours, and at 165
to 170~C for 16 to 20 hours. Benzophenone
tetracarboxylic dianhydride (17.0 g, 0.053 mol;
e.g. BTDA from Allco Chemical Corporation) and
xylene (approximately S0 ml) were added and heated
at reflux (180 to 190C) with azeotropic removal of
water for 24 hours. Volatiles were then removed
from the reaction medium at l90-C, and the reaction
mixture was hot filtered through diatomaceous earth
to give 90.2 g of the final producS.
Exam~le 20
Preparation of Additive 20
According to the procedure used for Example
19, di(hydrogenated tallow) amine (60.0 g, 0.12
mol), 2,2-dimethyl-1,3-propanediol diglycidyl ether
(6.29 g, 0.029 mol), and 1,2-cpoxyoctadecane (24.4
g, 0.091 mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (12.9 g, 0.040 mol)- and
xylene (approximately 50 ml) were added and allowed
to react. After isolation, 95.0 g of the final
product was obtained.
Example 21
Preparation of Additive 21
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (60.0 g,
2~37 l~i~
24
0.12 mol), 1,4-butanediol diglycidyl ether (~.38 g,
0.029 mol; e.g. Araldite RD-2 from Ciba-Geigy
Company), and 1,2-epoxyoctadecane (24.4 g, 0.091
mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (12.9 g, 0.040 mol) and
xylene (approximately 50 ml) were added and allowed
to react. After isolation, 96.8 g of the final
product was obtained.
Example_22
Preparation of Additive 22
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (60.0 g,
0.12 mol), a polyetherglycol diglycidyl ether with
an average molar weight of 380 (11.0 g, 0.029 mol;
e.g. DER 736 from Dow Chemical Company), and 1,2-
epoxyoctadecane (24.4 g, 0.091 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride
(12.9 g, 0.040 mol) and xylene (approximately 50
ml) were added and allowed to react. After
isolation, 98.0 g of the final product was
obtained.
Example 23
Preparation of Additive 23
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (60.0 g,
0.12 mol), a polyetherglycol diglycidyl ether with
an average molar weight of 630 (15.3 g, 0.024 mol;
e.g. DER 732 from Dow Chemical Company), and 1,2-
epoxyoctadecane (20.3 g, 0.076 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride
(10.7 g, 0.033 mol) and xylene (approximately 50
ml) were added and allowed to react. After
isolation, 88.9 g of the ~inal product was
obtained.
Exam~le 24
Pre~aration of Additive 24
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (60.0 g,
0.12 mol), 2,2-dimethyl-1,3-propanediol diglycidyl
ether (10.2 g, 0.047 mol), and 1,2-epoxyoctadecane
(14.4 g, 0.054 mol) were combined. Then,
benzophenone tetracarboxylic dianhydride (7.60 g,
0.024 mol), phthalic anhydride (3.49 g, 0.024 mol;
e.g. from Aldrich Chemical Company), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 87.5 g of the final
product was obtained.
26
Example 25
Preparation~ Additive 25
According to thle procedure used for
Example 19, di~hydrogenatedl tallow) amine (60.0 g,
0.12 mol), 1,4-butanediol diglycidyl ether (13.6 g,
0.047 mol), and 1,2-epoxyoctadecane (14.4 g, 0.054
mol) were combined. Then, benzophenone
tetracarboxylic dianhydride (7.60 g, 0.024 mol),
phthalic anhydride (3.49 g. 0.024 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 88.6 g of the final
product was obtained.
Example 26
Preparation of Additive 26
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (60.0 g,
0.12 mol), DER 736 (17.9 g, 0.047 mol), and 1,2-
epoxyoctadecane ~14.4 g, 0.054 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride
(7.60 g, 0.024 mol), phthalic anhydride (3.49 g,
0.024 mol), and xylene ~approximately 50 ml) were
added and allowed to react. After isolation, 93.0
g of the final product was obtained.
Example 27
Preparation of Additive 27
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (50.0 g,
0.10 mol), DER 732 (24.8 g, 0.039 mol), and 1,2-
epoxyoctadecane (12.0 g, 0.045 mol) were combined.
Then, benzophenone tetracarboxylic dianhydride
(6.33 g, Q.020 mol), phthalic anhydride (2.91 g,
0.020 mol), and xylene (approximately 50 ml) were
r~ 7
27
added and allowed to react. After isolation, 87.2
g of the final product was obtained.
Example 28
PreParatio~ of Additive 28
According to the procedure used for
Example 19, di(hydrogenated tallow) amine (61.2 g,
0.12 mol), 2,2-dimethyl-1,3-propanediol diglycidyl
ether (6.49 g, 0.030 mol), and 1,2-epoxyoctadecane
(8.55 g, 0.030 mol) were combined. Then,
benzophenone tetracarboxylic dianhydride (9.67 g,
0.030 mol) and xylene ~approximately 50 ml) were
added and allowed to react. After isolation, 76.4
g of the final product was obtained.
xample 29
Preparation of Additive 29
Di(hydrogenated tallow) amine (49.9 g, o.$o
mol; e.g. Armeen 2HT from Akzo Chemie), and 1,2-
epoxyoctadecane (33.6 g, 0.125 mol; e.g. Vikolox 18
from Viking Chemical) were combined and heated at
165~C for 18 hours. Pyromellitic dianhydride (6.23
g, 0.028 mol; e.g. PMDA from Allco Chemical Corp.),
1,2-octadecanediol (2.05 g, 0.007 mol; e.g. Vikinol
18 from Viking Chemical), and xvlene (approximately
50 ml) were added and heated at reflux (180 to
240~C) with azeotropic removal of water for 24 to
36 hours. Volatiles were then removed from the
reaction medium at 190 to 200C, and the reaction
mixture was hot filtered through diatomaceous earth
to give 82.7 g of the final product.
~ 7~i~
28
xample 30
~reParation o~ Additive 30
According to the procedure used for Example
29, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, pyromellitic dianhydride
(7.27 g, 0.033 mol), 1,2-octadecanediol (4.78 g.
0.017 mol), and xylene (approximately 50 ml) were
added and allowed to react. After isolation, 85.0
g of the final product was obtained.
Example 31
Preparation of Additive 31
According to the procedure used for Example
29, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and l,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, pyromellitic dianhydride
(8.72 g, 0.040 mol), 1,2-octadecanediol (8.60 g,
0.030 mol), and xylene (approximately 50 ml) were
added and allowed to react. After isolation, 90.5
g of the final product was obtained.
ExamPle 32
Preparation of Additive 32
According to the procedure used for Example
29, di(hydrogenated tallow) amine (49.9 g, 0~10
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, pyromellitic dianhydride
(7.27 g, 0.033 mol), 1,4-butanediol (1.50 g, 0.017
mol; e.g. from Aldrich Chemical Company), and
xylene (approximately 50 ml) were added and allowed
to react. After isolation, 81.6 g of the final
product was obtained.
29
ExamP~~ 33
Preparation of Add~tiv~ 33
According to the procedure used for Example
29, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, pyxomellitic dianhydride
(8.72 g, 0.040 mol), 1,4-butanediol (2.70 g, 0O030
mol), and xylene (approximately 50 ml) were added
and allowed to react. After isolation, 84.3 g of
the final product was obtained.
Example 34
Preparation of Additive 34
Di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and 1~2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined and heated at 170-C ~or 18 hours.
Pyromellitic dianhydride (8.00 g, 0.037 mol~, 1,12-
dodecanediol (3.37 g, 0.017 mol: e.g. from Aldrich
Chemical Company), and xylene (approximately 50 ml)
were added and heated at reflux (190 to 200-C) with
a2eotropic removal of water for 24 hours.
Volatiles were then removed from the reaction
medium at 190 to 200C, and the reaction mixture
was hot filtered through diatomaceous earth to give
87.1 g of the final product.
Example 35
Pre~aration of Additive 35
According to the procedure used for Example
34, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, pyromellitic dianhydride
(12.0 g, 0.055 mol, 1,12-dodecanediol (9.11 g,
0.045 mol), and xylene (approximately 50 ml) were
~ ~ 3 ~
added and allowed to react. After isolation, 91.4
g of the final product wa~ obtalned.
Example 36
Pre~aration o~ Additive 36
According to the procedure used for Example
34, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and l,2-epoxyoctadecane ~33.6 g, 0.125 mol)
were comhined. Then, pyromellitic dianhydride
(8.00 g, 0.037 mol, poly~ethyleneglycol with
average M.W. 400 (6.67 g, 0.017 mol; e.g. from
Aldrich Chemical Company), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 84.7 g of the final
product was obtained.
Exam~le 37
_eparation of Additive 37
According to the procedure used for Example
34, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, pyromellitic dianhydride
(12.0 g, 0.055 mol, poly(ethyleneglycol with
average M.W. 400 (22.0 g, 0.055 mol, and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 78.0 g of the final
product was obtained.
Example 38
Preparation of Additive 38
According to the procedure used for Example
34, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and l,2-epoxyoctadecane (33.6 g, 0.12S mol)
were combined. Then, pyromellitic dianhydride
(8.00 g, 0.037 mol, poly(propyleneglycol with
7 ~ i~
31
averaye M.W. 400 (6.67 g, 0.017 mol; e.g. JEFFOX
PPG 400 from Texaco Chemical Company), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 88.2 g of the final
product was obtained.
Example 39
Pre~aration of Additive 39
According to the procedure used for Example
34, di(hydrogenated tallow) amine (49.9 g, 0.10
mol), and 1,2-epoxyoctadeCane (33.6 g, 0.12S mol)
were com~ined. Then, pyromellitic dianhydride
(12.0 g, 0.055 mol, poly(propyleneglycol with
average M.W. 400 (22.0 g, 0.055 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 112.6 g of the final
product was obtained.
Example 4Q
Preparation of Additive 40
According to the procedure used for Example
34, di(hydrogenated tallow) amine (40.0 g, 0.08
mol), and 1,2-epoxyoctadecane (26.8 g, 0.10 mol)
were combined. Then, pyromellitic dianhydride
(9.60 g, 0.044 mol, poly(propyleneglycol with
average M.W. 2000 (40.0 g, 0.020 mol; JEFFOX PPG-
2000 from Texaco Chemical Company), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 105.0 g of the final
product was obtained.
Example ~1
Preparation of Additive 41
According to the procedure used for Example
34, di~hydrogenated tallow) amine (35.0 g, 0O07
7 1~ ~
32
mol), and 1,2-epoxyoctadecane (23.5 g, 0.088 mol)
were combined. Then, pyromellitic dianhydride
(8.40 g, 0.038 mol, poly(propyleneglycol with
average M.W. 2000 (73.5 g, 0.037 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 131.7 g of the final
product was obtained.
Example 42
Preparation of Additive 42
According to the procedure used for Example
34, di(hydrogenated tallow) amine (51.0 g, 0.10
mol), and 1,2-epoxyoctadecane (14.2 g, 0.050 mol)
were combined. Then, pyromellitic dianhydride
(10.9 g, 0.050 mol, 1,12-dodecanediol (9.11 g,
0.045 mol),Jand xylene (approximately 50 ml) were
added and allowed to react. After isolation, 71.6
g of the final product was obtained.
Exam~le 43
Pre~aration of Additive 43
According to the procedure used for Example
34, di(hydrogenated tallow) amine (40.8 q, 0.080
mol), and 1,2-epoxyoctadecane (11.4 g, 0.040 mol)
were combined. Then, pyromellitic dianhydride
(8.72 g, 0.040 mol, poly(propyleneglycol with
average M.W. 2000 (40.0 g, 0.020 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 89.5 g of the final
product was obtained.
Example 44
Preparation of Additive 44
Aniline (1.55 g, 0.017 mol; e.g. from Aldrich
Chemical Company), and 1,2-epoxyoctadecane ~33.6 g,
2 0 3 7 r;~
33
0.125 mol: e.g. Vikolox 18 from Viking Chemical)
were combined and heated at 160 to 190~C for 18 to
24 hour~. Di(hydrogenated tallow) amine (50.0 g,
0.10 mol; e.g. Armeen 2 HT form Akzo Chemie) was
added to the reaction mixture at 120'C, and then
heated at 165 to 185-C for 18 to 24 hours.
Pryromellitic dianhydride (7.27 g, 0.033 mol: e.g.
PMDA from Allco Chemical Corporation) and xylene
(approximately 50 ml) were added and heated at
reflux (140 to 230-C), with azeotropic removal of
water for 24 hours. Volatiles were then removed
from the reaction medium at 190 to 200C, and the
reaction mixture was hot filtered through
diatomaceous earth to give 93.4 g of the final
product.
Example 45
Preparation of Additive 45
According to the procedure used for Example
44, aniline (2.51 g, 0.027 mol), and 1,2-
epoxyoctadecane (48.3 g, 0.180 mol) were combined.
Di(hydrogenated tallow) amine (45.0 q, 0.090 mol)
was then added and reacted. Pyromellitic
dianhydride (7.85 g, 0.036 mol) and xylene
(approximately 50 ml) were added to the mixture and
allowed to react. After isolation, 92.3 q of the
final product was obtained.
Example 46
Preparation of Additive 46
According to the procedure used for Example
44, piperazine (1.44 g, 0.017 mol, e.g. from
Aldrich Chemical Company) and 1,2-epoxyoctadecane
(44.8 g, 0.167 mol) were combined. Di(hydrogenated
tallow) amine ~50.0 g, 0.100 mol) was added and
7 ~ '~
34
reacted. Then, pyromellitiG dianhydride (7.27 g,
0.033 mol) and xylene (approximately 50 ml) were
added and allowed to react. After isolation, 96.9
g of the final product wa~ obtained.
Example_47
Preparation of Additive 47
According to the procedure used for Example
44, piperazine (3.88 g, 0.045 mol), and 1,2-
epoxyoctadecane (60.4 g, 0.225 mol) were combined.
Di(hydrogenated tallow) amine (45.0 g, 0.090 mol)
was added and reacted at 200~C. Then, pyromellitic
dianhydride (10.8 g, 0.050 mol) and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 99.2 g of the final
product was obtained.
Example 48
Preparation of Additive 48
According to the procedure used for Example
44, n-octylamine (2.15 g, 0.017 mol; e.g. ALdrich
Chemical Company), and 1,2-epoxyoctadecane (44.8 g,
0.167 mol) were combined. Di(hydrogenated tallow)
amine (50.0 g, 0.100 mol) was added and reacted.
Then, pyromellitic dianhydride (7.27 g, 0.033 mol)
and xylene (approximately 50 ml) were added and
allowed to react. After isolation, 93.9 g of the
final product was obtained.
Example 49
Preparation of Additive 49
According to the procedure used for Example
44, n-octylamine (5.82 g, 0.045 mol), and 1,2-
epoxyoctadecane (60.4 g, 0.225 mol~ were combined.
Di(hydrogenated tallow) amine ~45.0 g, OOO90 mol)
7 ~ ~
wa~ added and reacted. Then, pyromellitic
dianhydride (10.8 g, 0.050 mol) and xylene
(approximately 50 ml) were added and allowed to
react at 200 C. After isolation, 107.0 g of the
final product was obtained.
ExamPle 5 0
Preparation of Additive 50
According to the procedure used for Example
44, hydrogenated tallow amine (4.31 g, 0.017 mol:
Armeen HT from Akzo Chemie), and 1,2-
epoxyoctadecane (44.8 g, 0.167 mol) were combined.
Di(hydrogenated tallow) amine (50.0 g, 0.100 mol)
was added and reacted. Then, pyromellitic
dianhydride (7.27 g, 0.033 mol) and xylene
(approximately 50 ml) were added and allowed to
react at 200C. After isolation, 95.9 g of the
final product was obtained.
Exam~le 51
Preparation of Additive 51
According to the procedure used for Example
44, hydrogenated tallow amine (11.6 g, 0.045 mol~,
and 1,2-epoxyoctadecane (60.4 g, 0.225 mol) were
cambined. Di(hydrogenated tallow~ amine (45.~ g,
0.090 mol) was added and reacted. Then,
pyromellitic dianhydride (10.8 g, 0.050 mol) and
xylene (approximately 50 ml) were added and allowed
to react at 200C. After isolation, 116.1 g of the
final product was obtained.
Exam~le 52
Preparation of Additive 52
According to the procedure used for Example
44, di(hydrogenated tallow) amine (50.0 y, 0.100
~77~'~
36
mol), and 1~2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, Ethomeen T/12 (5.77 g, 0.017
mol; an aminodiol derlved from tallow amine and two
equivalents of ethylene oxide, e.g. from Akzo
Chemie), pyromellitic dianhydride (8.00 g, 0.037
mol) and xylene (approximately 50 ml) were added
and allowed to react at 200-C. After isolation,
90.7 g of the final product was obtained.
Example 53
Preparation of Additive 53
According to the procedure used for Example
44, di(hydrogenated tallow) amine (50.0 g, 0.100
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, Ethomeen T/12 (19.0 g, 0.055
mol), pyromellitic dianhydride (12.0 g, 0.055 mol)
and xylene (approximately 50 ml) were added and
allowed to react at 200 C. After isolation, 102.0
g of the final product was obtained.
Example 54
Pre~aration of Additive 54
According to the procedure used for Example
44, di(hydrogenated tallow) amine (50.0 g, 0.100
mol), and 1,2-epoxyoctadecane (33.6 g, 0.125 mol)
were combined. Then, Ethomeen T/15 (7.98 g, 0.017
mol; an aminodiol derived from tallow amine and
five equivalents of ethylene oxide, e.g. from Akzo
Chemie), pyromellitic dianhydride (8.00 g, 0.037
mol) and xylene (approximately 50 ml) were added
and allowed to react at 200C. After isolation,
90.1 g of the final product was obtained.
~ ~J ~
Example S5
Preparation of Additive 5~
According to the procledure used for Example
44, di(hydrogenated tallow~ amine (50.0 g, 0.100
mol), and 1~2-epoxyoctadecane (33.6 ~, 0.125 mol3
were combined. Then, Ethom~een T/15 (26.3 g, 0.055
mol), pyromellitic dianhydride (12.0 g, 0.055 mol~
and xylene (approximately 50 ml) were added and
allowed to react at 200-C. After isolation, 108.7
g of the final product was obtained.
Example 56
Preparation of Additive 56
According to the procedure used for Example
44, piperazine (3.88 q, 0.045 mol), and 1,2-
epoxyoctadecane (38~5 g, 0.135 mol) were combined.
Di(hydrogenated tallow) amine (45.9 g, 0.090 mol),
was added and reacted. Then pyromellitic
dianhydride (9.82 g, 0.045 mol) and xylene
(approximately 50 ml) were added and allowed to
react at 200 C. After isolation, 87.9 g of the
final product was obtained.
Example 57
Preparation of Additive 57
Di(hydrogenated tallow) amine ~60.0 g, 0.12
mol; e.g. Armeen 2HT from Akzo Chemie), 2,2-
dimethyl-1,3--propanediol diglycidyl ether (6.29 g,
0.029 mol; e.g. Azepoxy N from AZS Corporation),
and 1,2-epoxyoctadecane (24.4 g, 0.091 mol; e~g.
Vilolox 18 for Viking Chemical) were combined and
heated at 140C for three hours, and at 165 to
170-C for 16 to 20 hour~. Pyromellitic dianhydride
(8.72 g, 0.040 mol; e.g. PMDA from Allco Chemical
Corporation and xylene (approximately 50 ml) were
r~
3~
added and heated at reflux ~180 to l90 C) with
azeotropic removal of water for 24 hours.
Volatiles were then removed from the reaction
medium at 190C, and the reaction mixture was hot
filtered through diatomaceous earth to give 89.1 g
of the final product.
Example 5~
Preparation of Additive 58
According to the procedure used for Example
57, di(hydrogenated tallow) amine (60.0 g, 0.12
mol), 2,2'dimethyl-1,3-propanediol diglycidyl ether
(10.9 g, O.OS0 mol), and 1,2-epoxyoctadecane (14.2
g, 0.053 mol) were combined. Then, pyromellitic
dianhydride (11.5 g, 0.053 mol) and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 84.7 g of the final
product was obtained.
Example 59
preparation of Additive 59
According to the procedure used for Example
57, di~hydrogenated tallow) amine (60.0 g, 0.12
mol), 1,4-butanediol diglycidyl ether (8.38 g,
O.029 mol; e.g. Araldite RD-2 from Ciba-Geigy
Company), and 1,2-epoxyoctadecane (24.4 g, 0.091
mol) were combined. Then, pyromellitic dianhydr~de
(8.72 g, 0.040 mol) and xylene (approximately 50
ml) were added and allowed to react. After
isolation, 93.7 g of the final product was
obtained.
2~37rl6a~
39
Example 60
Preparation 0~ Additive 60
According to the procedure used for Example
57, di(hydrogenated tallow) amine (60.0 g, 0.12
mol3, 1,4-butanediol diglycidyl ether (14.5 g,
0.050 mol), and ~,2-epoxyoctadecane (14.2 g, 0.053
mol) were combined. Then, pyromellitic dianhydride
(11.5 g, 0.053 mol) and xylene (approximately 50
ml) were added and allowed to react. Excess xylene
solvent was added to facilitate filtration of the
final reaction product, and then was removed under
reduced pressure. After isolation, 107.4 g of the
final product was obtained.
Example 61
P e~aration of Additive 61
According to the procedure used for Example
57, di~hydrogenated tallow~ amine (60.0 g, 0.12
mol), a polyetherglycol diglycidyl ether with an
average molar weight of 380 (11.0 g, 0.029 mol;
e.g. DER 736 from Dow Chemical Company), and 1,2-
epoxyoctadecane (24.4 g, 0.091 mol) were combined.
Then, pyromellitic dianhydride (11.5 g, 0.040 mol)
and xylene (approximately 50 ml) were added and
allowed tD react. After isolation, 90.2 g of the
final product was obtained.
Example 62
Preparation of Additive 62
According to the procedure used for Example
57, di~hydrogenated tallow) amine (60.0 g, 0.12
mol), DER 736 (19.2 g, 0.050 mol), and 1,2-
epoxyoctadecane (14.2 g, 0.053 mol) were combined.
Then, pyromellitic dianhydride (11.5 g, 0.053 mol)
and xylene (approximately 50 ml) were added and
c,~ r~
4n
allowed to reactO After :isolation~ 88.4 g of the
final product was obtained.
Examp~
Preparation of Addi~ive 63
According to the procedure used for Example
57, di(hydrogenated tallow) amine (50.0 g, 0.10
mol), a polyetherylycol diglycidyl ether with an
average molar weight of 630 (15.3 g, 0.024 mol;
e.g. DER 736 from Dow Chemical Company), and 1,2-
epoxyoctadecane ~20.3 g, 0.076 mol) were combined~
Then, pyromellitic dianhydride (7~27 g, 0.033 mol)
and xylene (approximately 50 ml) were added and
allowed to react. After isolation, 84.0 g of the
final product was obtained.
Example 64
Preparation of Additive 64
According to the procedure used for Example
57, di(h~drogenated tallow) amine (60.0 g, 0.12
mol), 2,2~dimethyl-1,3-propanediol diglycidyl ether
(10.2 g, 0.047 mol), and 1,2-epoxyoctadecane (14.4
g, 0.054 mol) were combined. Then, pyromellitic
dianhydride (5.14 g, 0.024 mol), phthalic anhydride
(3.49 g, 0.024 mol; e.g. from Aldrich Chemical
Company), and xylene (approximately 50 ml) were
added and allowed to react. After isolati~n, 82.2
g of the final product was obtained.
Example 65
Preparation of Additive 65
~ ccording to the procedure used for Example
57, di(hydrogenated tallow~ amine (60.0 g, 0.12
mol), 1,4-butanediol diglycidyl ether (13.6 g,
0.047 mol), and 1,2-epoxyoctadecane (5.14 g, 0.0~4
~7~
~1
mol~ were combined. Then, pyromellitic dianhydride
(11.5 g, 0.053 mol~, phthalic anhydride (3.49 g,
0.024 mol~, and xylene (approximately 50 ml) were
added and allowed to react. After isolation, 88.8
g of the final product was obtained.
Example 66
Prepara ion of Additive 66
According to the procedure used for Example
57, di(hydrogenated tallow) amine (60.0 g, 0.12
mol), DER 736 (17.9 g, 0.047 mol), and 1,2-
epoxyoctadecane (14.4 g, 0.054 mol) were combined.
Then, pyromellitic dianhydride (5.14 g, 0.024 mol),
phthalic anhydride (3.49 g, 0.024 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 89.4 g of the final
product was obtained.
Example 67
Preparation of Additive 67
According to the procedure used for Example
57, di(hydrogenated tallow) amine (50.0 g, 0.10
mol), DE~ 736 (24.8 g, 0.039 mol), and 1,2-
epoxyoctadecane (12.0 g, 0.045 mol) were combined.
Then, pyromellitic dianhydride (4.28 g, 0~020 mol),
phthalic anhydride (2.91 q, 0.020 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 84.5 g of the final
product was obtained.
Exam~le 68
Preparation of Additive 68
According to the procedure used for Example
57, di(hydrogenated tallow) amine (61.2 g, 0.12
mol), 2,2-dimethyl-1,3-propanediol diglycidyl ether
2~3r~)7~4
42
(6.49 g, 0.030 mol), and 1,2-epoxyoctadecane (8.55
g, 0.030 mol) were combined. Then, pyromellitic
dianhydride (6.54 g, 0.030 mol), and xylene
(approximately 50 ml) were added and allowed to
react. After isolation, 74.2 g of the ~inal
product was obtained.
Preparation of Additive Concentrate
A concentrate solution of 100 ml total volume
was prepared by dissolving 10 grams of additive in
mixed xylenes solvent. Any insoluble particulates
in the additive concentrate were removed by
filtration before use.
Test Procedures
The cloud point of the additized
distillate fuel was determined using two
procedures:
(a) an automatic cloud point test based
on the equipment/procedure detailed
in U.S. 4,601,303; the test
designation (below) is "AUT0 CP",
(b) an automatic cloud point test based
on the commercially available Herzog
cloud point tester; the test
designation (below) is "HERZOG".
The low-temperature filterability was
determined using the Cold Filter Plugging Point
(CFPP~ test. This test procedure is described in
"Journal of the Institute of Petroleum," Volume 52,
Number 510, June 1966, pp. 173-185.
~77~
43
Test Fuel Characteristiçs
FUEL A F~ 1
API ~ravity 35. 5 34 .1
Cloud Point, ' F
Auto CP 15 22
Herzog 16 . 4 23 . 4
CFPP, F 9 16
Pour Point, F 10 0
TABLE
Additive Effects on the Cloud Point and
Filterability (CFPP) of Distillate Fuel
(Additive Concentration = O. 1 W~ %)
IMPROVEMENT IN PERFORMANCE TEMPERATURE ( F)
Diesel Fuel A Diesel Fuel B
Cloud Point Cloud Point
Addltive Auto CP Herzoq CFPP Auto CP Herzoq CFPP
1 2.4 4 7.7 4
2 1.8 6 6.7 4
3 3.3 6 6.7 2
4 2.7 6 6.1 4
3.6 4 7 6
6 3.4 6 5.8 4
7 2.1 4.3 7
8 1.5 4 6.3 9
9 1.6 6 6.7 7
1.8 6 6.3 9
11 2.0 6 7.4 11
12 1.6 6 6.1 6
13 1.6 6 6.1 7
14 2.7 4 7.9 6
2.2 4 7.6 7
3776~
4~
16 1.6 6 7.011
17 1.8 6 7.011
18 2.1 7.4 6
19 5 3.4 4 11 5.8 4
1.8 6 6.7 9
21 1.5 -6 6.7 9
22 1.8 4 7.6 6
23 2 6 7.6 6
24 3 2.4 4 8 6.3 7
1 2.2 4 7.2 4
26 2 2.5 4 5.4 o
27 3 2.5 4 6.5 4
28 1.2 7.4 7
29 4 2 4 6 5.9 4
4 2.2 4 7 5.9 2
31 3 2.4 6 8 5.4 4
32 4 2.2 4 6 4.9 2
33 3 2.4 4 7 5.9 2
34 2 6 7 11
1.8 6 6.7 7
36 1.6 6 6.1 9
37 1.5 4 4.7 6
38 2 6 6.511
39 2 4 7.4 6
3.8 4 7.2 6
41 3.3 6 6.3 6
42 1.6 7.0 9
43 2.7 4.3 6
44 3 2.2 4 7 6.7 9
3 2.5 6 7 7 6
46 1.8 6 6.8 9
47 2 6 7.211
48 3 2.2 6 7 6.8 9
49 1.8 6 6.811
2 2 6 7 6.5 7
~Y~7~
51 1.8 ~ 5.97
52 2 1.6 ~ 7 6.39
53 2 2 4 7 6.611
54 3 1.8 ~ 7 6.111
2 2 ~6 6 6.111
56 1.8 8.113
57 2.2 ~ ~-0 9
58 4 3.4 4 11 6.64
59 1.6 6 6.79
3.1 4 6.74
61 2.2 6 7.74
62 3.6 4 6.84
63 1.8 6 7.411
64 3 2.~ 4 1~ 5~09
3 ~.0 4 8 5.~7
66 3 2.0 4 8 5.~2
67 4 2.0 4 9 5.02
68 1.2 7.96
The test data clearly show that minor
amounts of the additives of the present invention
improve low-temperature characteristics of
distillate fuels.
Although the present invention has been
described with preferred embodiments, it is to be
understood that modifications and variations may be
utilized without departing from the spirit and
scope of this invention, as those skilled in the
art will readily understand. Such modifications
and variations are considered to be within the
purview and scope of the appended claims.
