WO1994019337A1 - Epoxy functional higher alpha-olefin diester copolymer - Google Patents

Epoxy functional higher alpha-olefin diester copolymer Download PDF

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Publication number
WO1994019337A1
WO1994019337A1 PCT/US1994/001424 US9401424W WO9419337A1 WO 1994019337 A1 WO1994019337 A1 WO 1994019337A1 US 9401424 W US9401424 W US 9401424W WO 9419337 A1 WO9419337 A1 WO 9419337A1
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Prior art keywords
glycidyl
copolymer
compound
group
olefin
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PCT/US1994/001424
Other languages
French (fr)
Inventor
Theodore A. Marolewski
Eric W. Burkhardt
Uwe H. Wallfahrer
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Akzo N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo N.V. filed Critical Akzo N.V.
Publication of WO1994019337A1 publication Critical patent/WO1994019337A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
    • C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

  • Copolymers of ⁇ ,/3-unsaturated dicarboxylic acid esters and ⁇ -olefins are useful as lubricant compositions or additives.
  • Some recent examples of disclosures include U.S. Patent No. 4,931,197 to H. Beck et al. and Canadian Patent No. 1,238,448 to Akzo N.V. Copolymers of this type which are butanol esters of ⁇ -olefin-dicarboxylic acid copolymers (average molecular weight of 1200-2500) are, moreover, commercially available under the trademark KETJENLUBE from Akzo Chemicals Inc. and Akzo Chemicals b.v.
  • the present invention relates to epoxy functional copolymers of the previously described type as well as derivatives thereof which can contain such elements as nitrogen, oxygen, phosphorus and/or sulfur which would be useful in lubricant compositions, for example, as anti-wear additives.
  • novel epoxy functionalized copolymers which constitute one embodiment of the present invention, are formed by the copolymerization of a suitable ⁇ -olefin, an unsaturated dicarboxylic acid ester, and an ethylenically unsaturated glycidyl compound.
  • the epoxy-functionalized copolymer which results is then reacted with an epoxy- reactive compound containing the desired elements of the foregoing type (e.g., nitrogen, oxygen, phosphorus and/or sulfur) to form the final desired product.
  • An alternative approach is to form the ultimately desired derivative containing the nitrogen, oxygen, phosphorus and/or sulfur elements directly by copolymerizing the ⁇ -olefin and unsaturated dicarboxylic ester with an ethylenically unsaturated compound which already contains the desired elements identified above.
  • This third comonomer, containing those elements can be formed by reaction of an ethylenically unsaturated glycidyl compound, using the glycidyl functionality as the reaction site, with a compound containing a glycidyl reactive group and the desired element(s) as will be shown in greater detail below.
  • ⁇ -olefin monomers which can be used to form the instant copolymers can be selected from those previously used in synthesizing the known, non-functionalized a , ⁇ - unsaturated dicarboxylic acid ester/ ⁇ -olefin copolymers having lubricant utility.
  • Preferred for use herein are higher ⁇ -olefins having from about ten to about twenty carbon atoms, particularly those of from twelve to about eighteen carbon atoms.
  • the ⁇ ,/3-unsaturated dicarboxylic acid esters which can be used to synthesize the present copolymers also can be selected from those previously used in synthesizing the known copolymers previously described.
  • the esters of maleic, fumaric, citraconic, mesaconic, or itaconic can be chosen, with the first two being preferred.
  • esters having a straight-chain and/or branched chain monoalcohol component of from three to ten carbon atoms can be used.
  • an additional ethylenically unsaturated monomer is copolymerized with the foregoing comonomers.
  • This additional monomer is either: (a) an ethylenically unsaturated glycidyl compound, in those instances where an epoxy-functional copolymer is desired; or (b) an ethylenically unsaturated compound containing at least one of the previously enumerated elements (nitrogen, oxygen, phosphorus and/or sulfur) where the final derivative is desired, and it is intended that a one step copolymerization process by used to effectuate its formation.
  • third monomer (a) will contain ethylenic unsaturation and a glycidyl group. This type of compound can be envisioned as having the structure
  • G is a glycidyl group
  • R is hydrogen or methyl
  • L is an organo group linking the ethylenic unsaturation and glycidyl group, such as -C(O))-.
  • Representative compounds which can be employed include the glycidyl acrylates and methacrylates.
  • the glycidyl group is available for reaction with the glycidyl-reactive compounds to be described below. If the third monomer (b) is chosen, this can be a reaction product of monomer (a) with a glycidyl reactive compound which also contains the desired elements in the ultimate final product.
  • the glycidyl-reactive compounds enumerated hereinbelow should be understood as being useful. For example, a dialkyl dithioacid phosphate of the formula
  • R is alkyl, such as C ⁇ -C 10 alkyl
  • R can be a source of both phosphorus and sulfur with the group -SH providing for reaction with the glycidyl moiety.
  • a glycidyl-reactive dialkyl acid phosphate compound of the following formula can be chosen for reaction with the glycidyl moiety, under conditions as previously described:
  • R is alkyl, such as alkyl, or aryl.
  • Sulfur and nitrogen atoms can be analogously provided by use of a glycidyl-reactive dimercapto thiadiazole, such as
  • R is hydrogen or alkyl, such as c ⁇ c ⁇ .
  • Nitrogen atoms can be provided by use of the a ino carbazole compounds, for example, illustrated in European Patent Publication No. 414,343.
  • This Example illustrates the incorporation of epoxide side chains into an ⁇ -olefin dibutylmaleate copolymer.
  • This Example illustrates the incorporation of sulfur and phosphorus functionality into the epoxy functionalized copolymer of Example 1.
  • This Example illustrates preparation of a sulfur and phosphorus-containing monomer for reaction with an epoxy functionalized- ⁇ -olefin-dibutyl aleate copolymer.
  • Glycidyl methacrylate was dosed continuously to one mole of dibutyldithiophosphate at 80°C within one hour.
  • the reaction mixture was stirred at this temperature until the concentration of free dibutyldithiophosphate had diminished below 2%.
  • the reaction product was a faint yellow, non- smelling liquid.
  • This Example illustrates the incorporation of the sulfur and phosphorus monomer of Example 3 into an ⁇ -olefin- dibutylmaleate copolymer.
  • Two moles of C 14 /C 16 ⁇ -olefin mixture and two moles of dibutylmaleate were heated to 160°C.
  • 0.2 mole of the monomer from Example 3 and 16 g of di-tert- butylperoxide were added within three hours. After a further hour of stirring at this temperature, the volatiles were removed in vacuo.
  • the reaction product showed similar analytical and wear properties to the product of Example 2.

Abstract

Epoxy functional copolymers of a higher α-olefin, and an unsaturated dicarboxylic acid ester formed by copolymerization of olefin, acid ester and ethylenically unsaturated glycidyl compound can be used to form nitrogen, oxygen, phosphorus and/or sulfur-containing lubricant additives by reaction of the epoxy functionality in such a copolymer with glycidyl-reactive compounds containing nitrogen, oxygen, phosphorus and/or sulfur atoms. Alternatively, the copolymerization reaction can utilize the olefin, unsaturated acid ester, and an ethylenically unsaturated compound containing the nitrogen, phosphorus and/or sulfur atom, which compound is formed by reaction of ethylenically unsaturated glycidyl compound and an epoxy-reactive nitrogen, phosphorus, and/or sulfur-containing compound.

Description

"EPOXY FUNCTIONAL HIGHER ALPHA-OLEFIN DIESTER COPOLYMER"
BACKGROUND OF THE INVENTION
Copolymers of α,/3-unsaturated dicarboxylic acid esters and α-olefins are useful as lubricant compositions or additives. Some recent examples of disclosures include U.S. Patent No. 4,931,197 to H. Beck et al. and Canadian Patent No. 1,238,448 to Akzo N.V. Copolymers of this type which are butanol esters of α-olefin-dicarboxylic acid copolymers (average molecular weight of 1200-2500) are, moreover, commercially available under the trademark KETJENLUBE from Akzo Chemicals Inc. and Akzo Chemicals b.v.
DESCRIPTION OF THE INVENTION
The present invention relates to epoxy functional copolymers of the previously described type as well as derivatives thereof which can contain such elements as nitrogen, oxygen, phosphorus and/or sulfur which would be useful in lubricant compositions, for example, as anti-wear additives.
The novel epoxy functionalized copolymers, which constitute one embodiment of the present invention, are formed by the copolymerization of a suitable α-olefin, an unsaturated dicarboxylic acid ester, and an ethylenically unsaturated glycidyl compound. The epoxy-functionalized copolymer which results is then reacted with an epoxy- reactive compound containing the desired elements of the foregoing type (e.g., nitrogen, oxygen, phosphorus and/or sulfur) to form the final desired product. An alternative approach is to form the ultimately desired derivative containing the nitrogen, oxygen, phosphorus and/or sulfur elements directly by copolymerizing the α-olefin and unsaturated dicarboxylic ester with an ethylenically unsaturated compound which already contains the desired elements identified above. This third comonomer, containing those elements, can be formed by reaction of an ethylenically unsaturated glycidyl compound, using the glycidyl functionality as the reaction site, with a compound containing a glycidyl reactive group and the desired element(s) as will be shown in greater detail below. The types of α-olefin monomers which can be used to form the instant copolymers can be selected from those previously used in synthesizing the known, non-functionalized a , β- unsaturated dicarboxylic acid ester/α-olefin copolymers having lubricant utility. Preferred for use herein are higher α-olefins having from about ten to about twenty carbon atoms, particularly those of from twelve to about eighteen carbon atoms.
The α,/3-unsaturated dicarboxylic acid esters which can be used to synthesize the present copolymers also can be selected from those previously used in synthesizing the known copolymers previously described. The esters of maleic, fumaric, citraconic, mesaconic, or itaconic can be chosen, with the first two being preferred. For example, esters having a straight-chain and/or branched chain monoalcohol component of from three to ten carbon atoms can be used.
In order to achieve either epoxy-functional copolymers which can be further derivatized or the final, derivatized species, an additional ethylenically unsaturated monomer is copolymerized with the foregoing comonomers. This additional monomer is either: (a) an ethylenically unsaturated glycidyl compound, in those instances where an epoxy-functional copolymer is desired; or (b) an ethylenically unsaturated compound containing at least one of the previously enumerated elements (nitrogen, oxygen, phosphorus and/or sulfur) where the final derivative is desired, and it is intended that a one step copolymerization process by used to effectuate its formation.
If third monomer (a) is chosen for use it will contain ethylenic unsaturation and a glycidyl group. This type of compound can be envisioned as having the structure
Figure imgf000005_0001
where G is a glycidyl group, R is hydrogen or methyl, and L is an organo group linking the ethylenic unsaturation and glycidyl group, such as -C(O))-. Representative compounds which can be employed include the glycidyl acrylates and methacrylates. The glycidyl group is available for reaction with the glycidyl-reactive compounds to be described below. If the third monomer (b) is chosen, this can be a reaction product of monomer (a) with a glycidyl reactive compound which also contains the desired elements in the ultimate final product. The glycidyl-reactive compounds enumerated hereinbelow should be understood as being useful. For example, a dialkyl dithioacid phosphate of the formula
RO S
\" PSH /
RO
where R is alkyl, such as Cι-C10 alkyl, can be a source of both phosphorus and sulfur with the group -SH providing for reaction with the glycidyl moiety. If phosphorus and oxygen atoms are desired in the ultimate final product, a glycidyl-reactive dialkyl acid phosphate compound of the following formula can be chosen for reaction with the glycidyl moiety, under conditions as previously described:
RO O
\" POH
/ RO
where R is alkyl, such as
Figure imgf000006_0001
alkyl, or aryl.
Sulfur and nitrogen atoms can be analogously provided by use of a glycidyl-reactive dimercapto thiadiazole, such as
2,5-dimercapto-l,3,4-thiadiazole compound which is described in U.S. Patent No. 5,110,491:
N - N
II II C C
/ \ / \ HS S SR
where R is hydrogen or alkyl, such as c^c^.
Nitrogen atoms can be provided by use of the a ino carbazole compounds, for example, illustrated in European Patent Publication No. 414,343.
The present invention is further illustrated by the Examples which follow.
EXAMPLE 1
This Example illustrates the incorporation of epoxide side chains into an α-olefin dibutylmaleate copolymer.
Dibutylmaleate (1 mole) and a C14/C16 α-olefin mixture (0.9 mole) were heated to 160°C and, at this temperature, glycidyl methacrylate (0.1 mole) and di-tert-butylperoxide (8 g) were added continuously to that reaction mixture within three hours. After a further twenty minutes at this temperature, the volatiles were distilled off in vacuo. The resulting polymer was a colorless viscous liquid which contained 3% epoxy side chains and had an average molecular weight of 2400.
EXAMPLE 2
This Example illustrates the incorporation of sulfur and phosphorus functionality into the epoxy functionalized copolymer of Example 1.
Seventy grams of the copolymer from Example 1 and a stoichiometric amount (3.7 g) of dibutyldithiophosphate was heated to 80°C until the content of free epoxy groups decreased below 0.1% (about two hours). The reaction product was a yellowish, bad smelling viscous oil. This oil, when present as a 10% solution in 150 N mineral oil, gave an abrasion of 2.3 mm2 in a REICHERT wear tester. For comparison, a copolymer of dibutylmaleate and C14-C16 α-olefin of similar viscosity without the sulfur and phosphorus functionality yielded a worse abrasion value of 9 mm2. EXAMPLE 3
This Example illustrates preparation of a sulfur and phosphorus-containing monomer for reaction with an epoxy functionalized-α-olefin-dibutyl aleate copolymer. Glycidyl methacrylate was dosed continuously to one mole of dibutyldithiophosphate at 80°C within one hour. The reaction mixture was stirred at this temperature until the concentration of free dibutyldithiophosphate had diminished below 2%. The reaction product was a faint yellow, non- smelling liquid.
EXAMPLE 4
This Example illustrates the incorporation of the sulfur and phosphorus monomer of Example 3 into an α-olefin- dibutylmaleate copolymer. Two moles of C14/C16 α-olefin mixture and two moles of dibutylmaleate were heated to 160°C. At this temperature, 0.2 mole of the monomer from Example 3 and 16 g of di-tert- butylperoxide were added within three hours. After a further hour of stirring at this temperature, the volatiles were removed in vacuo. The reaction product showed similar analytical and wear properties to the product of Example 2.
The foregoing Examples are presented for illustrative purposes only and should therefore not be construed in a limiting sense. The scope of protection sought is set forth in the claims which follow.

Claims

We Claim:
1. An epoxy functional copolymer of: (1) a higher α-olefin; (2) an unsaturated dicarboxylic acid ester; and (3) an ethylenically unsaturated glycidyl compound.
2. A copolymer formed by reaction of the epoxy functional copolymer of Claim 1 with an epoxy reactive compound containing at least one element selected from the group consisting of nitrogen, phosphorus, and sulfur.
3. A copolymer as claimed in Claim 2 wherein the epoxy reactive compound is a dithiophosphate.
4. A copolymer as claimed in Claim 1 wherein the α- olefin contains from about ten to about twenty carbon atoms and the acid ester contains from about three to about ten carbon atoms in the monoalcohol component thereof.
5. A copolymer as claimed in Claim 1 wherein the α- olefin contains from about ten to about twenty carbon atoms, the acid ester contains from about three to about ten carbon atoms in the monoalcohol component thereof, and the glycidyl compound is of the formula
Figure imgf000009_0001
where G is a glycidyl group, R is hydrogen or methyl, and L is an organo group linking the ethylenic unsaturation and glycidyl group.
6. A copolymer as claimed in Claim 5 wherein the glycidyl compound is selected from the group consisting of the glycidyl acrylates and the glycidyl ethacrylates.
7. A copolymer as claimed in Claim 4 wherein the
■ glycidyl compound is selected from the group consisting of the glycidyl acrylates and the glycidyl methacrylates.
8. A copolymer of: (1) a higher α-olefin; (2) an unsaturated dicarboxylic acid ester; and (3) an ethylenically unsaturated compound containing at least one element selected from the group consisting of nitrogen, phosphorus and sulfur.
9. A copolymer as claimed in Claim 8 wherein compound (3) comprises a moiety derived from a dithiophosphate.
10. A copolymer as claimed in Claim 8 wherein the α- olefin contains from about ten to about twenty carbon atoms, the acid ester contains from about three to about ten carbon atoms, and the ethylenically unsaturated compound is formed by reaction of a glycidyl compound of the formula
Figure imgf000010_0001
where G is a glycidyl group, R is hydrogen or methyl, and L is an organo group linking the ethylenic unsaturation and glycidyl group with a glycidyl reactive compound containing at least one element selected from the group consisting of nitrogen, oxygen, phosphorus, and sulfur.
11. A copolymer as claimed in Claim 10 wherein the glycidyl reactive compound is a dialkyl dithioacid phosphate.
12. A copolymer as claimed in Claim 10 wherein the glycidyl reactive compound is a dialkyl acid phosphate.
13. A copolymer as claimed in Claim 10 wherein the glycidyl reactive compound is a dimercapto thiadiazole.
14. A copolymer as claimed in Claim 10 wherein the glycidyl reactive compound is an amino carbazole compound.
15. A copolymer as claimed in Claim 10 wherein the glycidyl compound is selected from the group consisting of the glycidyl acrylates and glycidyl methacrylates and the glycidyl reactive compound is selected from the group consisting of a dialkyl dithioacid phosphate, a dialkyl acid phosphate, a dimercapto thiadiazole and an amino carbazole.
PCT/US1994/001424 1993-02-19 1994-02-08 Epoxy functional higher alpha-olefin diester copolymer WO1994019337A1 (en)

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US08/019,498 1993-02-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019115398A1 (en) 2017-12-11 2019-06-20 Total Marketing Services Grease composition having improved adhesiveness

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5446105A (en) * 1994-02-18 1995-08-29 Akzo Nobel N.V. Functionalized copolymer of higher α-olefin and unsaturated dicarboxylic acid ester and derivatives thereof
US5863818A (en) * 1996-10-08 1999-01-26 Advanced Micro Devices, Inc. Multilevel transistor fabrication method having an inverted, upper level transistor
US5872029A (en) * 1996-11-07 1999-02-16 Advanced Micro Devices, Inc. Method for forming an ultra high density inverter using a stacked transistor arrangement
US5926700A (en) 1997-05-02 1999-07-20 Advanced Micro Devices, Inc. Semiconductor fabrication having multi-level transistors and high density interconnect therebetween
US5888872A (en) 1997-06-20 1999-03-30 Advanced Micro Devices, Inc. Method for forming source drain junction areas self-aligned between a sidewall spacer and an etched lateral sidewall
US5818069A (en) 1997-06-20 1998-10-06 Advanced Micro Devices, Inc. Ultra high density series-connected transistors formed on separate elevational levels
US7553020B2 (en) * 2006-09-29 2009-06-30 Welch Allyn, Inc. Medical diagnostic instrument with variable focus liquid lens
WO2012087781A1 (en) * 2010-12-21 2012-06-28 The Lubrizol Corporation Functionalized copolymers and lubricating compositions thereof
US9624380B2 (en) 2011-12-15 2017-04-18 Sun Chemical Corporation Sulfide extended epoxy resins and barrier coating applications thereof
CN106753688B (en) * 2016-12-30 2021-01-29 天津南开大学蓖麻工程科技有限公司 Biodegradable chain oil special for electric chain saw

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4790948A (en) * 1986-10-14 1988-12-13 Texaco Inc. Lubricating oil containing dispersant viscosity index improver
US4904403A (en) * 1989-06-12 1990-02-27 R. T. Vanderbilt Company, Inc. Polyalkylated 1,3,4-thiadiazoles and lubricating compositions containing same
US5176841A (en) * 1989-11-17 1993-01-05 Akzo N.V. Compositions from α,β-unsaturated dicarboxylic acid esters and olefinically unsaturated compounds which are particularly suitable for use as lubricants and lubricant additives and a process for the preparation of such compositions

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2543964A (en) * 1947-07-09 1951-03-06 Socony Vacuum Oil Co Inc Mineral oil compositions containing copolymers of olefins and esters of alpha, beta-unsaturated polybasic acids
US2615845A (en) * 1948-08-02 1952-10-28 Standard Oil Dev Co Lubricating oil additives
US3194763A (en) * 1962-12-18 1965-07-13 California Research Corp Polymeric composition and lubricant containing it
US3314908A (en) * 1964-07-01 1967-04-18 Exxon Research Engineering Co Emulsion polymers of a 2-methyl alpha olefin and a dialkyl fumarate
US3304261A (en) * 1966-01-24 1967-02-14 Exxon Research Engineering Co Mineral lubricating oil compositions containing terpolymer viscosity index improvers
DE3136931A1 (en) * 1981-09-17 1983-04-07 Akzo Gmbh, 5600 Wuppertal COPOLYMERS FROM (ALPHA) - (BETA) -UNSATURED DICARBONIC ACID ESTERS, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS A LUBRICANT FOR THE PLASTIC PROCESSING
DE3223694A1 (en) * 1981-09-17 1983-03-24 Akzo Gmbh, 5600 Wuppertal COPOLYMERS FROM (ALPHA) - (BETA) -UNSATURED DICARBONIC ACID ESTERS PROCESS FOR THE PRODUCTION AND USE THEREOF
US4732942A (en) * 1986-09-02 1988-03-22 Texaco Inc. Hydrocarbon compositions containing polyolefin graft polymers
US4826613A (en) * 1986-09-22 1989-05-02 Texaco Inc. Lubricating oil containing dispersant viscosity index improver
US4842756A (en) * 1987-03-23 1989-06-27 Texaco Inc. Multifunctional viscosity index improver
US4812261A (en) * 1987-08-12 1989-03-14 Texaco Inc. Lubricating oil containing viscosity index improver
US5110491A (en) * 1991-04-22 1992-05-05 Texaco Inc. Oligomeric lubricant additive designed to enhance antioxidancy and corrosion resistance in railway diesel crankcase lubricants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4790948A (en) * 1986-10-14 1988-12-13 Texaco Inc. Lubricating oil containing dispersant viscosity index improver
US4904403A (en) * 1989-06-12 1990-02-27 R. T. Vanderbilt Company, Inc. Polyalkylated 1,3,4-thiadiazoles and lubricating compositions containing same
US5176841A (en) * 1989-11-17 1993-01-05 Akzo N.V. Compositions from α,β-unsaturated dicarboxylic acid esters and olefinically unsaturated compounds which are particularly suitable for use as lubricants and lubricant additives and a process for the preparation of such compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019115398A1 (en) 2017-12-11 2019-06-20 Total Marketing Services Grease composition having improved adhesiveness

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