JPH01172409A - Polymer amide for multifunctional enhancer - Google Patents

Abstract

PURPOSE: To obtain a hydrocarbon composition, especially an additive to lubricant, which has multifunction including viscosity adjusting performance and sludge dispersibility and comprises three-component polymer of ethylene/ propylene/carboxylic amide.

CONSTITUTION: The three-component polymer shown in formula I or II is used as an additive to hydrocarbon solution. The formula I and II (n=0-12; x = about 15-75 mol.%; y = about 25-85 mol.%; z = about 0.1-10 mol.% ; R₁ and R₃=H, C_1-10 alkyl, aminoalkyl, alkylpolyamino, alkylaminoether, alkylaminoalcohol group; R₂ = alkyl group containing carbon atom of about 1-8. A preferable threecomponent polymer is one which consists of ethylene/ propylene/carboxylic amide and is obtained by the following method. A three- component polymer of ethylene/propylene/carboxylic acid or ester is formed by the Ziegler-Natta polymerization of ethylene, propylene and carboxylic acid or ester. This polymer is subjected to amidation with polyamine or aminoalcohol and the like to form the polymer.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to polymeric viscosity improvers and dispersants for petroleum, particularly lubricating oils. These additives co-react with ethylenically unsaturated carboxylic esters using Ziegler-Natsuta catalysts in a solvent and then further reacted with a polyamine to form an amide and one or more C3-C28a- It consists of a terpolymer of olefins, preferably propylene. The present invention encompasses the use of the above-described terpolymers in oil compositions. Also,
The present invention provides a method for producing the above terpolymer, in particular the use of aluminum alkyl or aluminum alkyl halide as a complexing agent to suppress carboxylic acid ester groups during Ziegler-Natsuta polymerization, and amide formation. It also relates to excellent catalysts for use.

BACKGROUND OF THE INVENTION This invention relates to multifunctional polymeric additives for hydrocarbon compositions, particularly lubricating oils. This additive is an ethylene/propylene/carboxylic acid amide terpolymer.

The present invention primarily concerns polymers known for viscosity control. Various polymers have been used as viscosity modifiers. Terpolymers of vinyl acetate, alkyl hexamalate, and maleic anhydride are taught, for example, in U.S. Pat. No. 408/893, and these terpolymers include
~15 mol% maleic anhydride and 25-50 mol% α
, --alkyl ester of unsaturated dicarboxylic acid and 40~
Copolymers made with out of 70 moles of C, -c@alkylene ester of monocarboxylic acid are mentioned. Techniques for producing polymers are also well known.

For example, a terpolymer of alkyl fumarate, vinyl acetate, and maleic anhydride may be prepared by the method disclosed in U.S. Pat. can be manufactured.

No. 4,637,610 teaches viscosity modifiers that are oil-soluble polymers having free carboxylic acid groups that react with amine-containing polymers.

The concept of incorporating acid moieties into viscosity-enhancing high molecular weight ethylene copolymers and then reacting with amines to create viscosity-enhancing and dispersing agents is known in the art, as exemplified by the following patents: US Pat.

U.S. Pat. No. 3,514,177 teaches ethylene copolymers, such as ethylene-propylene or ethylene-propylene-diene copolymers. These are heated to elevated temperatures in the presence of oxygen to oxidize the polymer and to cause its reaction with the maleic anhydride present during the oxidation. The resulting polymer can then be reacted with an alkylene polyamine.

U.S. Pat. No. 4,326,804 teaches reacting an ethylene copolymer with oxygen or ozone to form a hydroperoxidized polymer, grafting maleic anhydride onto it, and then reacting with a polyalkylene polyamine. There is.

U.S. Pat. No. 4,089,794 teaches that ethylene copolymers are grafted with maleic anhydride using peroxide in a lubricating oil solution (this grafting is preferably carried out under nitrogen) and then the polyamine is reacted. It teaches that.

U.S. Pat. No. 4,137,185 discloses an ethylene copolymer obtained by reacting a ct to cso monocarboxylic anhydride and dicarboxylic anhydride such as acetic anhydride, anophosuccinic acid, etc. with maleic anhydride and a polyalkylene polyamine. It is taught to react to suppress crosslinking and viscosity increase (due to further reaction of initially reacted primary amino groups).

U.S. Pat. No. 4,144,181 teaches the use of sulfonic acid to deactivate residual primary amine 7 groups when reacting maleic anhydride-grafted ethylene-propylene copolymers with polyamines. This is similar to U.S. Pat. No. 4,137,185.

U.S. Pat. No. 4,169,065 discloses reacting an ethylene copolymer with chlorine and maleic anhydride at a temperature of 150-250 DEG C. in the absence of oxygen and then reacting with a polyamine.

A number of prior art disclosures avoid the use of polyamines with two primary amino groups and thereby avoid crosslinking problems (which increase the number of amine moieties added to the polymer molecule to improve dispersibility). (which also raises other issues as the situation progresses).

German Published Application No. P5025274.5 teaches ethylene copolymers reacted with maleic anhydride in oil using long-chain alkyl hetero or oxygen-containing amines.

US Pat. No. 4,132.6tS1 uses peroxide and/or air blowing to graft maleic anhydride onto an ethylene copolymer and then react with a primary tertiary diamine.

U.S. Pat. No. 4,160,739 teaches an ethylene copolymer grafted with another maleic anhydride and a second polymerizable monomer such as methacrylic acid using free radical techniques, and this material It has been reacted with an amine having a single primary or a single secondary amino group.

U.S. Pat. No. 4,171,273 discloses the addition of maleic anhydride to an ethylene copolymer in the presence of a free radical initiator followed by N-
A mixture of a C4-2n-alcohol and an amine, such as aminopropylmorpholine or dimethylamylablepylamine, is reacted to form a dispersant-pour point depressant.

U.S. Pat. No. 4,219,432 discloses maleic anhydride-grafted ethylene in which a mixture of amines having only one primary amino group is reacted with a secondary amine having two or more primary amino groups. teaches copolymers.

DE 2755569.9 discloses ethylene copolymers which are reacted by free radical techniques with maleic anhydride and then with amines having a single primary amine 7 group.

DE 2.845.288 grafts maleic anhydride onto an ethylene-propylene copolymer by thermal grafting at high temperatures and then reacts it with an amine having one primary amino group.

French Publication No. 2.424530 discloses that an ethylene copolymer is thermally reacted with maleic anhydride at 150 DEG to 210 DEG C. and then reacted with an amine having one primary or secondary amino group.

U.S. Pat. No. 4,518,757 teaches heterogeneously catalyzed copolymers of alpha-olefins and alpha-olefin ester complexes to reduce frictional drag.

U.S. Pat. No. 449.lambda.277 teaches a functionalized olefin copolymer prepared by reacting a polar monomer with an organoaluminium compound by heating at 60-150C.

U.S. Pat. No. 431 to 177 and U.S. Pat. No. 3,524,804
Early patent literature, such as No. 1, teaches the general concept of grafting maleic anhydride onto an ethylene-propylene copolymer and then reacting with a polyalkylene polyamine such as polyethylene amine. Subsequently, US Pat. No. 4,089,794 was directed to grafting maleic anhydride onto an engineered tyrene copolymer and then reacting with a polyamine, using an oil solution for the free radical peroxide. This concept was developed by using oil so that the entire reaction could be carried out in oil solution to prepare oil concentrates (which is the commercial form in which such additives are sold). It brought a profit.

This was an advantage over using volatile solvents in the reaction. These volatile solvents must subsequently be removed and replaced by oil in order to make the concentrate. Subsequently, operating at higher polyamine levels to further improve the dispersion efficiency results in a number of problems associated with cross-linking of unreacted amine groups, which increases the viscosity of the oil concentrate during storage and the subsequent development of haze. If so, gelation was caused. Even when more than one mole of ethylene polyamine was used per mole of maleic anhydride during imide formation, crosslinking problems caused further problems as the nitrogen content of the polymer increased.

One solution is to use a polyamine and then react the remaining primary amino groups with an acid anhydride of U.S. Pat. No. 413/185, preferably acetic anhydride or a sulfonic acid of U.S. Pat. No. 4,144,181. there were. Also, crosslinking avoids ethylene polyamine and instead 1 anhydride! This could be minimized by using amines that have one primary amine group that reacts with leic acid and the other 7ξ groups are essentially non-reactive tertiary amino groups. . Patent documents showing the use of such primary tertiary amines as described above include U.S. Pat. No. 4,132.461, No. 4160,739, No. 4171273, German Patent No. P 27555
69. ? , French Patent No. 2.84 to 288 and French Patent No. 2.43 to 530.

Yet another problem that has arisen when using free radical initiators with mineral oil as a grafting medium is that as the grafting level is increased to improve the dispersibility level, the majority of the oil molecules are converted to maleic anhydride. It was to be in a grafted state. Then, upon subsequent reaction with the amine, these grafted oil products tended to become insoluble and form a haze. [To avoid using initiators such as peroxides and to avoid the use of oils for grafting, some of the above-mentioned patents utilize thermal grafting in a solvent and preferably In this case an ethylene copolymer containing a diene monomer was used to achieve a 1-ene'' type reaction between the unsaturation arising from the diene moiety and the maleic anhydride. , such a 1-ene'' reaction is slower than peroxide grafting.

U.S. Pat. No. 451/104 allows the use of generally inexpensive polyalkylene polyamines having two primary amino groups, yet achieves good dispersion levels, inhibits crosslinking, and provides It provides an improvement over the prior art in allowing grafting and performing grafting in oil.

The present invention is conventional in that it produces carboxyl-containing ethylene terpolymers in a single process step, whereas the prior art requires both a polymerization reaction and a separate grafting reaction. The present invention provides an additional benefit in that no harmful by-products such as acid-functionalized solvents are formed.

Such acid-functionalized solvent by-products are a significant problem and are only overcome in US Pat. No. 4,517.104 by the addition of significant amounts of high molecular weight polyisobutylene succinic anhydride. The present invention is further advantageous in that the dispersant functionality, ie, the amine, is attached to the polymer backbone via amide bridges, thereby providing much better viscosity stability during storage compared to prior art imide bridges. bring about.

SUMMARY OF THE INVENTION The present invention relates to a hydrocarbon solution additive comprising a terpolymer having multifunctional properties including viscosity control and sludge dispersibility, and the terpolymer of the present invention is a non-polar hydrocarbon. It is also a viscosity modifier for liquids.

GENERAL DESCRIPTION OF THE INVENTION The present invention relates to a hydrocarbon solution additive consisting of an ethylene/propylene/carboxylic acid amide terpolymer having multifunctional properties including viscosity control and sludge dispersibility; The terpolymers of the invention are also viscosity control agents for non-polar hydrocarbon liquids such as jet fuels.

The terpolymer of the present invention is an ethylene/propylene/carboxylic acid amide terpolymer. The terpolymer of the present invention is obtained by forming a terpolymer of ethylene, propylene, and carboxylic acid or ester by Ziegler-Natsuta polymerization of ethylene, propylene, and carboxylic acid or ester. This terpolymer is then reacted with a polyamine or amino alcohol to form a terpolymer of ethylene, propylene, and carbonamide.

Suitable hydrocarbon-soluble water-soluble terpolymers of the present invention have the formula:
most preferably from about 30 to about 65 mol%, and y from about 25 to about 85 mol%, preferably from about 33 to about 70 mol%, and most preferably from about 37 to about 70 mol%. , 2 is about 11 to about 10 mol%, preferably about [L2 to
About 9 mol% a'), n=0-12, R, and R3 are H
Sc1 to cto are equivalent to alkyl, alkylamino, alkylpolyamino, alkylaminoether, alkylaminoalcohol groups, and R1 is an alkyl group having 1 to 8 carbon atoms.

Although the preferred monomer is propylene, suitable or terpolymers may be substituted for propylene to form the copolymer.
α-olefins suitable for use in combination with ethylene and propylene to form quaternary polymers, etc. include:
Examples include 1-butene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-butene, 4-methyl-1-
Hexene, 5-methyl is 4,4-dimethyl-
Also included are branched a-olefins such as 1-benthene, 6-methylhebutene-1, etc., and mixtures thereof.

The polymers of the present invention generally have about -000 to about soo, o
oo preferably an IC of 1,000 to 20Q, 000, optimally a number average molecular weight of about 20,000 to 10Q, 000 (
Mn). The multifunctional viscosity modifier of the present invention generally has a weight average molecular weight ffi (MY) and a log average molecular weight (M
have a narrow range of molecular weights as measured by the ratio of n). A polymer having a (My/Mn) of 10 or less, preferably 7 or less, and more preferably 4 or less is most desirable.

(Tel n ) and (My) used herein are
''C is determined by the well known techniques of membrane osmometry and gel permeation chromatography.

The terpolymer of ethylene/a)''syn/carboxylic acid or ester is prepared in the presence of a polyamine, amine, aminoalfur or amine ether and a catalyst from about 100 to about 2
The reaction is carried out at a temperature of 60° C. for a time sufficient to form an ethylene/propylene/carboxylic acid amide terpolymer.

Examples of suitable polyamines include ethylenediamine, lyethylenetriamine, triethylenetetramine, tetraethylene amine, N,N-dimethylethylenediamine SN, N-'; ethylethylenecyamine, N,N-dimethyltrimethylenediamine 7SN, N-'; Examples include ethyltrimethylenediamine.

Amino alcohols and ethers are also suitable.

Examples of these include 2-aminoethanol, jetanolamine triethanolamine, N-aminomethylmorpholine, N-aminoethylmorpholine, N-aminodia? 'lumorpholine, trishydroxymethylaminomethane (THAM), azadioxabicyclooctane (DOBO), aminomethylpyridine, aminoethylpyridine, aminopropylpyridine, aminothiazole, pi-butane, aminobi-butane, their hydroxy derivatives and similar Other amines with functional groups may be mentioned.

A suitable catalyst for the amidation process is a tin gold 14 salt such as stannous octoate (2-ethyl hekylate).

Other suitable catalysts for the reaction of carboxylic acid polymer functionality with amines to form amides include silica gel, tetraalkyl or tetraaryl pyrophosphites, trialkyl or triaryl phosphites. Triarylphosphites are the preferred phosphite catalysts. Polyphosphoric acid and boric acid are also catalysts for the formation of amide polymer derivatives.

The concentration of the terpolymers of the present invention in the hydrocarbon liquid is from about [1L001 to about 25fii1%, and the oil composition ranges from gasoline fraction to oil.

The additives of the present invention may also be used alone or in combination with other hydrocarbon soluble additives as detergent and/or rust inhibitor additives in jet fuels and gasoline at concentrations within the range of about 100 to tO weight. Can be used.

In controlling the viscosity of non-polar hydrocarbon liquids, the terpolymers of the present invention can be used at a concentration of from about 1001 to about 25% by weight - preferably from about 105 to about 15% by weight, and most preferably from about 17 to about 14% by weight. % concentration to nonpolar hydrocarbon liquids.

The following examples are illustrative of the invention and are not intended to limit it.

Example 1 Into a reactor containing 4000 dehydrated n-heptane, ethylene was added at 209/hrs propylene was added at 409/hrs methyl undecylenate (7,5-methyl undecylenate + 675-diethyl aluminum chloride + 19-
n-hexane) at 22 d/hr.

VCl4 (1005d (DVC14+ 90 mf)
cyclo"'Psan) at 12 m/hr, and diethylaluminum chloride (25% DKAC + 75% n-
Hexane) was fed at 25 lI//hr, respectively.

The reaction temperature was 15°C. The reaction time was 2 hours. The polymer was precipitated in 55 gallons of acetone, washed in acetone + 10 - concentrated HCl + 90 + d H,O,
Then again add acetone + 2g of “Irganox 10”
The yield of polymer was 80 g.

The polymer purified by reprecipitation contained 19 mmol of ester/10 (1 polymer).

Example 2 3. Into a reactor containing dehydrated n-hebutane of OOO-, 209/hr of ethylene and 409/hr of propylene were added.
Methyl undecylenate (8゜5-ester of 10-complexed with ethylaluminum chloride + 25.5-
of hexane) at 28 d/hr for a total of 42-1 VC14
(10 me of VC14 + 90 ships of cyclohexane) were fed at 12 rd/hr for a total of 21 m and diethylaluminium chloride (25% DEAC1 + 75% n-hexane) for a total of 63 - each at 56 m/hr.

The reaction temperature was 10°C and the total reaction time was 3 hours. 55g of acetone + 10Wd of MCI and P
Precipitated in od of H,0. The yield of polymer was 108 ml. The intrinsic viscosity at 135℃ in decalin is α
It was 97. The polymer purified by reprecipitation is 1
&7 mmol of ester/1001m combination.

Example 3 In a reactor containing 4000 - dehydrated butane, 20 g/hr of ethylene and 409 g/hr of propylene were added.
.

Phenyl undecylenate (ester complexed with ethylaluminum sesquichloride) at 18 ef/hr.

VCI, (10d VCl4 + 90d (7) Schiff 1"'
l? 4111 g/hr of ethylaluminum sesquichloride (25% EtsA 1 g/hr)
+ 75% hexane) at 40 sd/hr. The reaction temperature was 10°C and the reaction time was 4 hours. The polymer was precipitated in 55 gallons of acetone containing 20 - of concentrated HCl + 100 - of H,0. The above operation was repeated until the yield of polymer reached 7709. The intrinsic viscosity at 135° C. in decalin was t45. The polymer purified by reprecipitation contained 1a7-limos ester/10 (1 polymer).

Example 4 In a reactor containing dehydrated n-hebutane, ethylene was added at 209/hr, propylene was added at 709/hr,
Thioethyl undecylenate (7,55 m ester complexed with 4-diethylaluminum chloride)
8 d/hr SVC14 (10-VCl4+90-
cyclohexane) at 8 ml/hr and diethylaluminum chloride (25% DEAC + 75% n-
Hexane) was supplied at a rate of 40 m/hr. The reaction temperature was 10°C. Total reaction time was 5 hours.

Add 55 gallons of polymer to 30 ml (7
) Precipitated in HCI + 70 dH. The yield of polymer was 126 g. 13 in decalin
The intrinsic viscosity at 5°C was α97.0 The polymer purified by reprecipitation contained 10 mmol of Este/I//100
g polymer.

Example 5 In a reactor containing 4,000 liters of dehydrated n-heptane, 1 ethylene was added at 20 liters/br, and propylene was added at 4°9/hrS.
) Limethylsilyl undecylenate (ester of 8,25-
of hexane) at 52 d/hr %VCl4 (10-
VCl4-)-90-Schiff tetrahexane) at 8d/h
r, and diethylaluminum chloride (25% D
EACI+75% hexane) were each fed at 40 td/br. The polymerization temperature was 10° C. and the polymerization time was 3 hours. After 3 hours of polymerization, 44 liters of NAPM (N-
aminopropylmorpholine) was added. The temperature was increased to 85°C for 112 hours. The polymer was precipitated once in acetone-isopropanol+30-HCl and then reprecipitated from acetone-isopropanol+27"IRGlolo". The yield of polymer was 143 g. The intrinsic viscosity at 135° C. in decalin was t15. The nitrogen content of the polymer was α315%. Based on nitrogen, the polymer contained 113 mmol of amide/1009 polymer.

Example 6 The electric combination 159 of Example 1 was placed in 859 5100N lubricating oil.
Dissolved at 70"C. After the polymer was dissolved, α5 of NAPM (N-aminopropylmorpholine) was added and the temperature was maintained at 170"C for 24 hours. Unreacted NAPM was removed with N! bath topping. The weight percent nitrogen incorporated into the polymer was α091. Based on nitrogen, the polymer contained 2 mmol NAPM/100 g polymer.

Example 7 Same as Example 6 except that Q, 1 stannous octoate was added along with NAPM. The weight percent nitrogen incorporated into the polymer was α282. Based on nitrogen, the polymer contained 1α1 ml of NAPM/1DOg polymer.

Example 8 5 g of the polymer from Example 2 were dissolved in 10-hydro-7 run. 15 g of NAPM was added to the above solution. The tetrahydro7rane was carefully removed by evaporation. The remaining contents in the test tube were heated to 240° C. in an oil bath under a nitrogen blanket for 6 hours. Unreacted NAPM was removed by nitrogen stripping. The weight percent of nitrogen incorporated into the polymer was α123. Based on nitrogen, the polymer contained 4.4 mmol NAPM/100 q polymer.

Example 9 Same as Example 8 except that n, 1 g of stannous octoate was added along with the NAPM. The weight percent nitrogen incorporated into the polymer was α914.

Based on nitrogen, the polymer contains 69 mmol NAPM/1
It contained 00g polymer.

Example 10 The terpolymer 320 of Example 5 was combined with 2.8809 S-100.
Added to N# lubricant. The reaction was carried out at 170℃ with nitrogen sparging.
The polymer was dissolved by heating for 5 hours. After adding 52" of stannous octoate at 170° C. under a nitrogen blanket, 213 g of N-aminopropylmorpholine (NA
PM) was added over 15 minutes. Stir the reaction;
Heat at 170°C for 5 hours, heat again to 170°C, and add 6 portions of NAPM. The mixture was heated again for 2 hours.

The mixture was then heated to 180° C. for 3 hours during which excess NAPM was stripped. cooling the reactants;
The material was then removed for analysis. The purified polymer contained α416% N. Based on nitrogen, the polymer has 14.9 mmol NAPM/100
Based on the amide IR peak at ◇1670-, which contained 9 polymers, the polymer contained 142 mmol of NA.
Contained PM/1009 polymer.

Example 11 An oil solution containing 75% of the polymer of Example 4 was heated to 170° C. for 24 hours with a stannous octoate catalyst and NAPM. The obtained polymer had 1t2 mmol of NAPM/1
009 polymer.

Example 12 Table I illustrates the ability of catalysts such as stannous octoate to significantly accelerate the conversion of esters to ami v. The Wheat I data also illustrate the superiority of phenyl esters compared to methyl esters in conversion to amides.

Table ■ Ester example 1 Methi/I/19 None 52
Example 6 Example 1 Methyl 19 Yes 1α1
Example 7 Example 2 Methyl 15.7 None
4.4 Example 8 Example 2 Methyl 1 & 7
Yes 69 Example 9 Example 3 Phenyl 1
8.7 Yes 14.9 Example 10 Example 13 Table 1 shows the remarkable stability of the amide polymer of Example 10 compared to a typical succinimide multifunctional viscosity modifier (Comparative Example A) with respect to viscosity increase during heated storage. For example:

Table ■ Example 10 891 888 877 841 Comparative example A 1580 1815 2156 2757
The polymer of Comparative Example A is an ethylene-tetrapyrene copolymer reacted with the same amine as in Example 4, and the maleic anhydride is a ruoxide graft polymer, which is the same as in Example 4.
, 031.

Example 14 Multifunctional viscosity modifiers with attached amine functionality via succinimide linkages are known to interact with polar additives commonly found in lubricating oils. This interaction, which results in and is manifested by an increase in viscosity, is disadvantageous. The amide polymer of the present invention is shown in Table ■
has a significantly reduced interaction with polar lubricant additives as shown by the data.

Table ■ Viscosity, centistokes (100℃ change, 60℃ storage M)
Comparative example Human polymer (IX2) 1S, 1
15.8(1) 14.6% by weight of polymer (Example 10 or Comparative Example A) and 77.7% by weight of 814ON mineral oil;7.
5% cleaning agent, zinc dialkyldithiophosphate, a, double! Oil blend with 1% pour point depressant.

(2) Comparative Example The human polymer was the same as the polymer used in Table 3.

Example 15 The ability of the polymer of Example 1o to loosen sludge and control varnish is illustrated in Table IV.

Table ■ Polymer SIB results VIB result example 1
0 40 2 Comparative example 1)
112 1・paratone
715・(2)15.0 5 none
145 11 (1) Comparative Example A is the same nitrogen-containing polymer used in Table ■.

(2) "Paraton 715" is a nitrogen viscosity modifier available from Exxon Chemical Company.

The efficacy of the derivatized copolymers of the present invention as dispersants in lubricating oils is illustrated in a sludge inhibition bench-top (SIB) test. S
The IB test has been found to be an excellent test for evaluating the dispersing ability of lubricating oil dispersants after numerous evaluation experiments.

The medium selected for the SIB test was a used crankcase mineral lubricant composition (1) used in a taxi normally driven for short distances, which caused the build-up of high concentrations of sludge precursor materials. This smells at 38℃ [
The oil used contained a refined pace mineral lubricating oil, a viscosity index improver, a pour point depressant and a zinc dialkyldithiophosphate antiwear additive. was. This oil did not contain any sludge dispersant. A predetermined amount of used oil was obtained by draining and filling the crankcase of a taxi at intervals of 1,000 to 2,000 miles.

The sludge suppression bench test is conducted in the following manner.

Add the above crankcase oil (which is a milky brown color) to about 59. Centrifuge for 1 hour at OO0 gravity (g-) to remove the sludge from it. The resulting clear bright red supernatant is then decanted and thereby separated from the insoluble sludge particles. However, the skim oil still contains oil-soluble sludge precursor material, which tends to form additional sludge oil-insoluble adducts when heated under the conditions used by this test. The sludge control properties of the additive to be tested are determined based on the active ingredient in each portion of the used oil supernatant.
It is determined by adding a small amount, such as % by weight, of the particular additive being tested. 109 of each mixture to be tested
is placed in a stainless steel centrifuge tube and heated at 138° C. for 16 hours in the presence of air. After heating, the tube containing the oil to be tested is cooled and then heated to about 39.00 ml at room temperature.
Centrifuge at 0 gm for approximately 30 minutes. The new sludge deposits that form in this step are separated from the oil. this is,
Decant the supernatant oil and remove the sludge deposits.
5- Carefully wash with hebutane and remove from the sludge.
Removal of residual oil and further centrifugation are carried out by K. The weight of the new solid sludge formed in this test, 11 (cape), is determined by drying the residue and weighing it. The results are reported as the percentage of sludge dispersed by comparison to a blank test that did not contain any additional additives. The less fresh sludge precipitated in the presence prior to addition, the greater the percentage value of sludge dispersed, and the more effective the additive is as a sludge dispersant.

In other words, if an additive is effective, it
At least a portion of the new sludge that forms during heating and oxidation is kept in stable suspension in the oil so that it does not settle during centrifugation.

Fez Suppression Test Each test sample consisted of 109 lubricating oil and either 1% or 2% by weight neutralized polymer. The test oil into which the additive was mixed was a commercially available lubricant obtained from a taxi after approximately 2,000 miles.

Each 10 g sample is heat soaked overnight at about 140'C and then centrifuged to remove the sludge. Approximately α7 volume% SO2 and t4 volume% N were applied in the test sample between heating stages.

A gas consisting of a mixture of and the remaining air was bubbled. At the end of the test period (this test cycle may be optional additive) the wall of the test flask containing one sample is visually assessed for fest inhibition. A score of 1 to 11 is given to the amount of fest attached to the wall soil. Larger classes, more festivals.

Claims (7)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, n = 0 to 12, x is about 15 to about 75 mol%, y is about 25 to about 85 mol%, and z is about 0.1 to about 85 mol%
approximately 10 mol%, R_1 and R_3 are H, C_1~
A terpolymer having C_1_0 alkyl, alkylamino, alkyl polyamino, alkylamino ether, alkylamino alcohol group and R_2 is an alkyl group having from about 1 to about 8 carbon atoms. (2) (a) Nonpolar hydrocarbon liquid, and (b) formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, n = 0 to 12, x is from about 15 to about 75 mol%, y from about 25 to about 85 mol%, and z from about 0.1 to about 85 mol%.
about 10 mole %, R_2 is an alkyl group having about 1 to about 8 carbon atoms, and R_1 and R_3 are H, C_1-C_1_0 alkyl, alkylamino, alkyl polyamino, alkylamino ether, alkylamino alcohol a terpolymer having a group equal to about 0
．． 1 to about 30% by weight. (3) Using a Ziegler-Natta catalyst, ethylene and
The C_3-C_1_0 α-olefin is reacted with an unsaturated C_4-C_2_1 ester complexed with an aluminum alkyl or aluminum alkyl halide (the ester may contain other elements such as sulfur and silicon), and then the alkyl A process consisting of reacting amines, alkylpolyamines, alkylaminoethers or alkylaminoalcohols. (4) The method according to claim 3, wherein the ester is a phenyl ester. (5) The method according to claim 3, wherein the ester is a methyl ester. (6) Methods of using catalysts to enhance the conversion of esters to amides. (7) The method according to claim 6, wherein the catalyst is stannous octoate.