Note: Descriptions are shown in the official language in which they were submitted.
10~6879
B AC~ GRQU 2; D OF THE INV ENTION
Fleld_of the Invent on
3 In recent ~ears, numerous fuel deterge~ts or "deposit
4 control~ additi~es have been aeveloped. These materials ~hen
added to hydrocarbon fuels employed in internal combustion
6 engines effectively reduce deposit formation which ordinarily
7 occurs in carburetor ports, throttle bodies, venturies, inta~e
8 ports and intake valves. The reduction of these deposit levels
9 has resulted in increased engine efficiency and a reduction ~n
the level of hydrocarbon and car~on monoYide emissions.
11 Thus, the introduction of fuel composi~io~s contairli~g
12 deposit control additives has resulted in many cases in the
13 reductio~ of harmful atmospheric pollutants and, since greater
14 engine efficiencies are maintained, fuel savings.
A complicating factor has, ho~ever, recently arisen.
16 ~ith the advent of automo~ile engines that require the use of non--
17 leaded gasolines (to prevent disablement of catalytic converters
18 used to reduce emissions), a serious problem has arisen in
19 providi~g gasoline of high enough octane to prevent knocking and
~0 the concomitant damage Yhich it causes. The chief problem lies
21 in the area of the degree of octane require~nt i~crease, herein
22 called "ORI", which is caused by deposits formed in the
23 combustio~ chamber ~bile the engine is operating on co~mercial
24 gasoline.
The basis of ~he ORI problem is as ~ollo~s: each
26 engine~ when ne~, requires a certain minimum octane fuel in order
27 to operate satisfactorily ~ithou~ pinging and/or knocking~ As `
28 the engine is operated o~ a~y gasoline, this mi~imu~ octane
29 increases and, in most cases, if the engine is operated on the
same fuel for a prolonged period will reach e~uilibrium. This is
31 apparently caused by an amount of deposits in the combustion
~L
- 2 -
~0"6~379
1 chamber. Equilibrium is typically reached after 5000 to 15,000
2 miles of automobile operatio~.
3 Octane reguirement increases at equilibrium with
4 com~ercial gasolines, in particular engines will vary from 5 or 6
octane units to as high as 12 or 15 units, dependi~g upon the
6 gasoline compositio~s, engine design and type of operation. The
7 seriousness of the problem is thus apparent. A typical 1975 or
8 1976 automobile with a research octane requirement of 85 ~hen new
9 may after a fe~ months of operation require 97 research octane
gasoline for proper operation, and little unleaded gasoline of
11 that octane is available. The ORI pro~lem eYists in some degree
12 with engines operated on leaded fuels. a.s. Patents 3,144,311
13 and 3,146,203 disclose lead-containing fuel compositions having
14 reduced ORI properties.
It is belie~ed, ho~e~er, by many experts that the ORI
16 problem, ~hile present ~ith leaded gasolines, is Duch more
17 serious Yith unleaded fuel because of the different nature of ~he
18 deposits for~ed with the respective f~els, the size of inc ease~
19 a~d because of the lesser availability of high~actan~ non-leaded
fuels. This problem is compounded by the fact that the ~ost
21 common means of enhancing the octa~e of unleaded gasoline,
22 i~creasing its aromatic conte~t, also appears to increase the
23 eventual octane requirement of the engine.
24 The problem is compounded by the recently discovered
fact that sone of the presently used nitrogen-containing deposit
26 control additives and the mi~eral oil or polpmer carriers
27 commonly used ~ith such addi~ives appe r to contribute
28 significantly to the O~I of engines operated on unleaded fuel.~
29 It is, therefore, highly desirable tO provide deposit
control additives which effectively control deposits in intake
31 syste~s (carburetor, valves, etc.~ of engines operated ~lth fuels
10~6879
1 contai~ing them, ~ut do not contribute to the combustio~ chamber
2 deposits which cause increased octane requirements.
3 DESC~IPTION_OF_~HE_PRIOR ART
4 U.S. Pate~t 3,3S9,303 discloses reaction products of
polyalkyleneoxy alkyl 1-aziridine carboxylates ~ith polyamines.
6 These materials are disclosed as being curing agents (cross-
7 linking agents~ for epoxy resins. The alkylenaoxy chains cont3i~
8 a maYimum of 20 alkyleneoxy units.
9 U.S~ Pate~t 3,6S8,882 discloses certai~ aryl carbamates
and quaternary derivatives thereof useful as antistatic agents.
11 SU~ARY_OP THE_INYENT_ON
12 Deposit control additives are provided ~h-ich maintaln
13 cleanliness of enqine intake systems and do not themselves
14 contribute to combustion chamber deposits. The deposit cont~ol
additi~es are poly(~xyalkylene) car~amates soluble in a hydro-
16 carbon fuel boiling in the gasoline range. The carbamates
17 comprise at least one hydroxy- or hydrocarbyloxy-terminated
18 poly(oxyal~yle~e) chain of from 21 to 30 oxyalkylene u~its
19 co~taining 2 to 5 carbon atoms per unit bonded through an
oxycar~onyl group t~ a nitrogen atom of ethylenediaminP. The
21 hydrocarbyloxy group preferably will contain ~rom 1 to 30,
22 preferably 2 to 20, carbon atoms.
23 The preferred compounds may be described by the
24 following general formula:
- R-NH-C~2-CH2-NHz
26 in ~hich R is a,group of the formula
O
_c-o[C(H)~ )h (Cll~)l ~ [C~gl(~l ~ (Cl~2) ~ ]j,
~~C(H)g~ , (CH~) ~ } ~ Z
.. .. . .
27 i~ which g, g' a~d g" are integers 1 to 2; h' and h" are 0 or 1;
28 i, i' and i" are integers 1 to 3; the sum of q and h is 2; ~ is
29 methyl or ethyl; j, j' and j" are integ2rs and the sum of j~j'~;"
.
10~687~
1 is an integer 21 to 30, pref~rably 22 to 28; z is ~ or
2 hydrocarbyl of 1 to 30 carbons. Sufficient of the oxyaikylene
3 units i~ R are other than ethyleneoxy to render the compound
4 soluble in hydrocarbon fuel ~oiling in the gasoline range.
The additi~es are usually prepared by the reaction of a
6 suitable polyether alcohol with phosgene to form a chloroformate
7 follo~ed by reaction of the chloroformate Hith ethylenediamine to
8 form the active carbamate.
9 DETAILED DESCRIPTION_O~_THE_INYENTION
~he Polvethers-
11 The polyethers or poly(o~yalkyler.e) materials which are
12 utilized in preparing the polyether carbamates are condensation
13 polymers of the lo~er aliphatic oxides such as ethyle~e oxide,
14 propylene oxide, the butylene oxides and the pentylene oxidas.
The preferred materials are the propyle~e oxide polymers or
16 poly(propylene ~lycol~ . These materials may be terminated or
17 capped on one end by a suitable hydrocarbyl group. ~or example,
18 particularly preferred materials are capped with a butyl, oleyl
19 groups, etc. Also suitable are materials ~hich are capped ~ith
mixtures of alkyl groups, i.e., ~ith a mi~ture of Cl6, Cl8 a~d
21 C2~ alkyls~ ~ryloxy termination is also suitable. ~hus, phenols
22 and substituted phenols such as 4-t-butyl phenol, 4-tetrapropenyl
~3 phe~ol, or 2-n-propyl phenol, etc., may be used. ~hile materials
24 vith two terminal hydroxyl groups can be employed, the use of a
material contai~ing but one is preferred since chloroformylation
26 ~ill produce a prefe~red monochloroformate ~hich can then be
27 reacted ~ith a suita~le amine to produce the preferred carbamyl~
28 material. Ho~e~er, e~en though some dicarbamate ~ill be formed
29 ~ith the dihydroxy materials, the presemce of small amounts of
these materials are, though ~ot preferred, not detrimental to the
31 performance of the materials.
6879
1 ~he materlals may be prepared from ~i~t ~e of oYide
2 mo~omers, i.e. Yhen the reactivities of ~he oYides are relati~ely
3 equal, ra~dom polymers can be prepared. In certai~ Cases, with
4 ethylene oxide, in combination with other oxides, the ethylene
oxide reaction rate is ~uch greater, and random polymers cannot
6 be easily prepared. In those cases, ~lock copoly~ers are
7 prepared.
8 A particular type of polymer that can be prepared and
9 has been commercially prepared are represented by materials vhich
are prepared by polymerizi~g propylene oxide to ~orm a first
11 material and then polymerizing ethylene oYide on one or both ends
12 of the poly(oYypropylene). Materials of this type are marketed
13 by ~yandotte Che_icals as "Plu~onics". Block copolymers of
14 propyleneoxy and butyleneoxy groups are also suitabie.
PreParAaAtion of tha Polyether_Ca~bamates
16 The additives of this invention may be most
17 convenie~tly prepared, as has bee~ previously noted, by reaction
18 of phosgene ~ith the poly(oxyalkylene~ compound followed by
19 reaction of the proauct with ethylenediamine
The reaction of the poly(oxyalkylene) ~aterial is
21 carr~ed out on an esse~tially equimolar basis utili2ing only a
22 slight e~cess of phosgene, although a~ e~cess of phosgene is not
23 detri~e~tal. ~he reaction may be carried ou$ a~ ~emperatures
24 from -10 to 100C, preferably in the range o~ 0 to 30c. The
reaction will usually be complete ~ithin 1/4 to 5 hours. Ti~es
26 of reac~io~ ~ill usually be i~ the range of from 1/2 to 3 hours.
27 ~ sol~ent may be used in the chloroformylation
28 reactio~. Su~table solvents include benzene, toluene, etc. It
29 is preferred that the phosge~e be dlssolved in a suitable solvent
before reaction ~ith tbe poly(o~yalkylene) material.
* T~ 1q~ .
.
~Q"6879
1 The reaction of the chloroIormate with the
2 ethylenediamine may be carried out neat or in solution. The
3 molar ratio of amine to chlorof ormate ~ill usually be i~ the
4 range o~ 0.5 to 5. ~emperatures of from -10 to ~oooc may be
utilized. ~he desired product may be obtained by ~ater ~ash a~d
6 stripping, usually by the aid of vacuum, oî any residmal solvent.
7 The mol ratio o~ the polysther chloroforma~es to a~ine
8 ~ill generally be in the ra~ge from about 0.2 to 20 mols of amine
9 per mol oî chloroformate, and more usually O.S to 5 mols of a~ne
~.
per mol o~ chloroformate. The mol ratio will depend upon the
11 particular chloroformate and the desired ratio of polyether to
12 amine. If suppressio~ of polysubstitution of the ethylen~diamine
13 is desired, large mol excesses of the amine will be used.
14 The reactio~ or reactions ~ay be conducted with or
without the presence of a reaction solvent. A reaction sol~ent
16 is ge~erally employed whenever necessary to reduce the viscosity
17 of the reaction product. ~hese solvents should be stable and
18 inert to the reactants and reaction produ~t. Preferred solvents
19 include aliphatic or aromatic hydrocarbons. Depending o~ the
temperature of the reaction, the particular chloroformate used,
21 the mol ratios as ~ell as the reactant concentrations, the time
22 may varg fro~ 1/4 to 24 hours, more usually from abou~ 2 to 3
23 hours. Times greatly in excess of 3 hours do no~ particularly
24 e~bance the yield a~d may lead to undesirable degradation,
especially at higher temperatures. It is therefore preferred to
26 limit the reaction time to le~s than 3 hours.
27 ~fter the reaction has been carried out for a
28 sufficie~t length of time, the reaction mi~ture may bs subjected
"`O~
- 29 to eYtraction with a hydrocarbon or hydrocarbon-alcohol medium to
free the product from any lo~-molecular-~eight amine saits which
31 have formed and a~y unreacted ethyle~ediamine. The product may
11~"6879
1 t~e~ be isolated by evaporation of the solvent. Small amounts of
2 halogen may be p~esent as the hydrohalide salt of the poly~ther
3 carbamates.
4 Dependinq on the particular application of the
composition of this invention, the reaction ~ay be carried out in
6 the medium in which it will ultimately find use, e.g. polyether
7 carriers and be formed at concentrations ~hich provide a
8 concentrate of the detergent co~position. Thus, the final
9 mixture may be in a for~ to be used directly for blending in
fuels.
11 The polyether carbamates will generally be employed in
12 a hydrocarbon distillate fuel. The proper concentration of
13 additive necessary in order to achieve the desired deterge~c~ and
14 dispersancy varies depending upon the ~ype of fuel employed, the
S presence of other detergents, dispersants and other additives,
16 etc. Generally, ho~ever, from 30 to 2000 ~eight parts per
17 million, prefetably from 100 to 700 ppm of polyethercarbamate per
18 part of base fuel is needed to achieve the best results. ~hen
19 other de~ergents are present, a lesser amount of polyether
carbamate may be used. For performance as a carburetor detergen-t
21 only, lo~er concentrations, for exa~ple 30 to 70 parts per
22 ~illio~ may be preferred.
23 The detergent-dispersant additive may be formulated as
24 a concentrate, using an inert stable oleophilic organic solvent
boiling in the range of about 150 to 400F. Preferably, an
26 aliphatic or an aromatic hydrocarbon solYent is used, such as
27 ~e~zene, tolue~e, xylene or higher boiling aromatics or aromatic
28 thianers. Aiiphatic alcohols of about 3 to 8 carbon atoms, such
29 as isopropanol, isobutylcarbinol, n-butanol and the li~e, in
co~bination ~ith hydrocarbon solvents are also suitable for use
31 Yith the detergent-dispersant additive. In the concentrate, the
~96879
1 amount of the additive ~ill be ordi~arily at least 10 percent by
2 ~eight and generally not exceed 70 percent by ~eight and
3 preerably from 20 to 60 ~eight percent.
4 In gasoli~e fuels, other fuel additives may also be
S included such as antiknock agents, e.g., methylcyclopentadienyl
m~nga~ese tricarbonyl, tetramethyl or tetraethyl lead, or other
7 dispersants or deterg~nts such as ~arious substituted
8 succinimides, amines, etc. Also included ~ay be lead scavengers
9 such as aryl halides, e.g., dichlorobe~zene or alkyl halides,
e.g., ethylene dibro~ide. ~dditionally, antioxidants, me~al
11 deactivators and demulsifiers ~ay be present.
12 A particularly useful additive is a fuel-soluble
13 carrier oil. Exemplary caIrler oils include nonvolatile
14 poly(oxyalkyle~e3s; other synthetic lubricants or lubricating
1S mineral oil. Particularly preferred carrier oils are poly(oxy-
16 alkylene) mo~o a~d polyols, such as the Pluronics ~arketed by
17 BA5F ~yandotte Corp., and the UCON LB-series fluids marketed ~y
18 Union Car~ide Corp. ~hese materials have been found to exhibit a
19 synergistic deposit-control effect in combination with the
polyether amines. ~he~ used, these oils are believed to act as a
21 carrier for the detergent and assist in removing a~d retardi~g
22 deposits. They a~e employed in amounts fro~ about 0.05 to 0.5
23 perce~t by volume, based on tbe final gasoline compositio~.
24 The ollo~ing exampl~s are presented to illustrate
specific embodiments of the practice of t~is invention a~d should
26 not be interpret~ed as limitations upon the scope of the
27 i~vention.
28 ~3~1e 1_-- Pr~ration of Polyl~x~E~PYleneL_Chloroformatel
29 Phosge~e (298 g, 3.0 mols) was condensed into toluene
~2.5 liters~ at 0C. Poly(oYypropylene) ~5.0 kg~ 2.78 mols~ ~ith
31 a molecular ~eight of about 1800 ~as added to the phosgene
lOg6~7g
1 solution in a rapid stream, ~ith stirring. The mixture Yas
2 stirred an additional 30 minutes after completion of the
3 addition, and eYcess phosgene was removed by purging ~ith
4 nitroge~ while the temperature rose to ambient (about 2 hours).
S The product sho~ed a strong chloroformate absorption at 1790
6 cm-l.
7 E~ample 2 -^ Reactlon of Poly(oxy-
8 pEop~le~eL-chl-r-f-rm-te wl-h-Ethylenedlamlne
9 The chloroformate solution from Example 1 was di~idad
in half, diluted with toluene (6 liters), and each half ~as added
11 to ethylenediamine (527 g, 8.6 mol~ in toluene (1 liter~ at 0C,
12 vith vigorous stirring. Immediate precipitation of
13 ethylenediamine hydrochloride occurred. The reaction temperature
14 ~as kept belov 25C and stirring ~as continued for one hour-after
addition. n-Butanol (5 liters) ~as added, and t~e mixture was
16 extracted ~ith hot water (appro~imately 15 liters~. The t~o
17 batches were combined a~d sol~ent was remoYed OD a 5-gallon
18 rotary evaporator. The product (5050 g~ contained 1.12~ nitrogen
19 and 0.46% basic nitrogen by ~STM D-2896, I~frared analysis
revealed a typical carbamate absorption at 1725 c~
21 The polyether carbamates were blended in gasoline and
22 their deposit reducing capacity tested in an ~ST~/CPR Single-
23 Cylinder Engi~e Test.
24 In carrying out the tests, a ~aukesha CFR single-
cylinder cngine is used. The run is carried out .or 15 hours, at
26 the end of ~hich time the intake val~e is remoYed, ~ashed ~ith
27 heYane and ~eighed. The previously de~er~ined ~eigh+ of the
28 clean Yalve is substracted from the weight o~ the valve~ ~he
29 differe~ces bet~een~the t~o veights-~s the ~eig~t of the deposit
~ith a lesser amount of deposit measured con~oting a superior
31 additive. The operating conditions of the test are as follows:
-- 1 0 -- ,
~6879
1 water jacket temperature 100C (212P); ma~ifold vacuum of 12 iG
2 Hg~ intake miXture temperatUre of 50.2C (125F); air-fuel ratio
3 of 12; ignition spark timing of 40 ~TC; engine speed is 1800
4 rpm the crankcase oil is a commercial 30~ oil. The amount of
carbonaceous deposit in milligrams on the intake valves is
6 measured and reported in the following ~able I.
7 l~he base fuel tested i~ the above exte~ded detergency
8 test is a regular octane unleaded gasoline contai~ing no fuel
9 detergent. The base fuel is admixed ~ith varying amounts of
detergent additi~es.
11 TABLE I
12 INTAKE ~ALVE_DEPOSIT TESTS1
13 Average ~ashed
14 Additive Carrier _____Demosit,_mg __
_Descr Ptmom __ Ppm 11A_Enqine 12A ~ine
16 Base ~uel ~ 2592 1023
17 PPG-1800~ EDA
18 Carbamates 333 12 6
19 PPG-1~00~ 167
P~G-1800~ ED~ -
21 Carbamate5 200 33 18
22 PP~~1450~ 300
23 lSi~gle evaluatio~s unless noted
24 2Average of 8 runs
3Average of 4 runs
26 ~The designation PPG~x refers to a monobutyl-
27 capped poly(oxypropylene~ glycol of about
28 ~ molecular ~eight.
29 SPrepared as in Example 1.
The t~ndency of the additives to contribute to ORI ~as
31 e~aluated in a laboratory engine test. The test engine is a CLR `
32 single-cylinder, balanced, high-speed, four-cycle engine design~d
33 primarily fo~ oil test a~d research wor~. It is ma~ufactured ~y
34 t~e Laboratory Equipment Corporation of ~ooresville, Indiana.
The major e~gine dimensions are:
36 Bore 3.8~ In.
37 ` Stroke 3.75 In.
38 Displaceme~t 42.5 Cu. I~.
39 Co~pression Ratio 8:1
- 11 -
~09~37g
1 The carburetor, i~take manifold, a~d distri~utor ~ave
2 been slightly modified to facilitate our test procedure~ ~hese
3 modifications have made the engine~s ORI characteristics
4 comparable to modern day automo~iles.
The test procedure i~volves engine operatio~ ror 80
6 h~urs l24 hours a day) on a prescribed load and speed schedule
7 representative of typical vehicle drivi~g co~ditions. The cycle
8 for e~gine operation during the test is as ~ollo~s:
9 TAsI. E II
DeP--lt-Accu~ulatlon C~cl_CLR Slllq~ nder
11 Time in ~Sanifold Engine
12 ~ode, Yacu~m, Speed,
13________Mod e _ _____ ____Sec . __ In~ Hq_ _EPm_~
14 1. Idle 140 16 900
2. ~eaYy cruise, Lo~ Speed 70 7 2000
16 3. Light Cruise, Lo~ Speed140 13 2000
17 4. ~eceleration 140 18 1800
18 5. Heavy Cr~ise, Low Speed 70 7 2000
19 6. Light Cruise, Low Speed140 13 2000
7. Idle 210 16 900
21 8. HeaYy Cruise, Low Speed 70 7 2000
22 9. Ligh~ Cruise, Lov Spaed 70 13 2000
23 10. Heavy Cruise, High Speed70 9 2500
24 11. Light Cruise, ~igh Speed140 15 2599
12. Deceleratio~ 140 18 ~1800
26 All of the test runs were made ~ith the same base gasoline,
27 ~hich ~as representati~e of commercial un~eaded fuel. ~he
28 results are set forth i~ Table IV.
~096~7g
TABLE III
2 L aborator Y ORI_Test_Re sults
3 Combustion
4Additive, Carrier Conce~- Chamber
S Descr~tion tration~_PPm ~osits~_~
_ _ _ ___ __ _ _ ~ ____ _ ~ ___
6 -- -- -- 3.4
7 Commerciallg available
8 nitrogen-containing
9 ~ DC additi~e 467 -~ 7.1
Mineral carrier oil 1600
11 PPG-1800 EDA Carbamat6~ ~86 1.3 2~5
12 PPG- 1450~ 214
~ .
13 PPG-1800 EDA Carbamate~ 286 1~6 2.4
14 PPG-1450* 214
*See Table I
16 Si~ple arithmetic averages of the results indicate:
17 base fuel gives an ORI of 3.1 and combustion chamber deposits
18 weigh.ing 1.3 g, the commercial additi~es averaged 6.3 units .ORI
19 and had combustion chamber deposits weighing 2.1 g, and the
polyether carbamates gave an OBI of 2.5 and combustion chamber
21 deposits averaging 1.5 g. Generally, these results indicate that
22 the polyether carbamates, Yhich have been demonstrated to be .
23 excellent inlet system deposit control additives, do not
24 contribute significantly to increasing octane requireme~ts (over
base fuell of the enginos in which they are employed.
: 26 The test for eva}uating the ability of fuel additives
27 to control carburetor deposits employs a 1973 model year, 240
: :28 CID~ 6-cyli~der Ford engine~ The internal bore of the carburetor
.
29 throttle body is eguipped ~ith a thin, removable alumi~um sleeve.
: ~30 Tha difference between sleeve ~eights determined hefore and after
~ 31 a~ engine run represents the change in amount of surface deposit
-- : 32 occurring auring that run. "~
33 For additive eYaluation, t~o test phases are run as set
34 forth in Table IV.
- ?3 - `
~L09~ii879
T~BLE IV
2 Carburetor DePoslt Test Procedure
3 1. Dirty-Up Phase (starting
4 ~ithClean slee Ye ___
ObjectiYe: Establish d~posits on carburetor sleeve.
6 Duration: 15 hours.
7 Operating Cycle: 7 minutes moderate load and speed, 4
8 minutes idle.
9 Engine Setup: Crankcase blowby gases routad to
carburetor air inlet.
11 Fuel: Deposit-forming fuel containing heaYy
12 ~CC component.
13 Evaluation: Sleeve weights are deter~ined at the
14 begi~ning and e~d of the dirty-up p~aset
and sleeve deposits are rated visually
16 on a-scâle of 0 to 10 ~10 = clean~.
17 2. Clea~up Phase (Begins vith Sleeve
18 DePosits_Formed Durinq Dirty-UP Ph~se
19 Ob~ective: ~easure additive perfor~ance in cleaning
up deposits.
21 Duration: 4 hours.
22 Operating Cycle: Same as dirty-up phase.
23 Engine Setup: Crankcase ~lowby cases div~rted from
24 carburetor inlet - EGR shutoff.
Fuel: Commercial-type gasoli~e containi~g
26 additi~e under test.
27 Evaluation: ~he sleeve is reweighed and rerated
28 ~isually~ Differences bet~ee~ i~itial
29 a~d final values represent additiYe
effectiveness.
31 Table V prese~ts average values for the performance of
32 PPG-amine carbamate,additives. ~lso,-presented are values for a
33 commercial,deposit control additive havi~g recognized perfor~ance
34 i~ the field. Deposit level changes with a com~ercial-type
unleaded gasoline without additive are,also shown.
-
- - 14 -
1~6879
1 TABLE ~
2 Càrburetor ~_st Results
3 Averaqe_Additive Performa~ce
4 Deposit
Concen- ~eight Visual Deposit
6 tration, Reduc- Rati~gsl
7 Runs __yPm tion,_~ Inlt~al Fmnal _~_
8 PPG-1800 EDA
9 Carbamatel 4 200 88 4.93 -~ 8.13 3~23
Commercial
11 Additive 8 150 91 5. 3 _> 8.4 3,1
12 None 2 - 63 4.6 -> 6~0 1~4
13 ~Visual Deposit rating ~10 = clean); see Table I
14 2Similar to product of Example 4
3Data for 3 runs only
16 T~ese data show that the polyether carbamates are as
17 effective carburetor deposit control additives as the recognized
18 commercial additiYe.
19 The previously mentioned U.s. Patent 3,359,303
discloses compounds similar i~ structure to the current
21 compounds. ~owever, by their nature they are limited to amines
22 containing at least two alkylene groups, e.g., the derivative of
23 diethylenetriamine. It has been found that the ethylenediamine
24 deriYative of this inven+ion shows unexpectedly superior water-
toierance properties, a~ important co~sideration for use in
26 fuels.
27 The follo~i~g table shows the comparative water-
28 tolerance properties for the ethylenediaminP and
29 diethyle~etriamine compou~ds. ~lso, the water~tolerance
properties of the 1,2-propylenediamine and di-(1,2-propylene~
.
3~ triamine derivatives are sho~n. The polyether in each case ~as
32 butyl-capped polyo~ypropyle~e material having a molecular ~eight
33 of about 1483 and containing 25 oxypropylene units. The ~ater-
34 tolera~ce test is a modified Enjay ~aring Ble~der ~aze ~est
wherein 300 ml of fueI and 3 ml of water are mixed at 13,000 rpm
.
_ 15 _
1096879
1 for 30 seconds. The samples of ~oth the ~ater and fuel phases
2 are rated from 1 to 5. Por the ~ater phase, 1 indicates free
3 ~ater after 30 minutes; 5 is total emulsion at 20 hours. ~or the
4 fuel phase, 1 is bright and clear; 5 is extreme haze (no light
passing through bottle). ~ rating of 3 is co~sidered a marginal
6 pass. The tests ~ere run Yith and without a commercial
7 demulsifier. The demulsifier was used at 5 ppm conce~tration.
8 ~able VI shows the results without demulsifier.
9 ~ABL~ V
water Tolerance_of P_lVetheE_SL~g~3~
11 ~ater Fuel Phase_
12 _ _ _ _ _ Amin_ _ _ _ Ph3se 3 hrs 20 hrs
13 Ethylenediamine 3 2
14 Ethyle~ediamine* 1 3
Diethylenetriamine 3 4
16 Diethylenetriamine~ 1 4
17 1,2-Propylenediamine 1 ~ t
18 1,2-Propylenediamine* 1 3
19 di-(1,2-propylenetriamine~ 1 2 1
di-(1,2-prop~le~etriamine)* 1 3
21 *Contai~s 5 ppm of commercial demulsifier
22 This sho~s that the ethylenediamine derivative is
23 surprisingly superior to the diethyle~etriamine derivatiYe. Note
24 that the propylenediamine and dipropylenetriamines were
equivalent. ~ote also that the diethylenetriami~e deri~ative
26 fails to pass eve~ ~ith a de~ulsifier present.
27 All specific embodiments of the invention have been
28 described in detail, and it should be u~derstood that the inve~-
29 tion is to be giYen the broadest possible interpretation ~ithin
the terms of the following claims.
- 16 -
