Star-shaped polymer reacted with dicarboxylic acid and amine as dispersant viscosity index improver

• US 4,141,847 A
• Filed: 05/11/1977
• Issued: 02/27/1979
• Est. Priority Date: 05/11/1977
• Status: Expired due to Term

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Kiovsky, Thomas E.
• Primary Examiner(s): Gantz, Delbert E.
• Assistant Examiner(s): Thierstein, Joan
• Application Number:
  US05/795,675
• Time in Patent Office: 657 Days
• Field of Search: 252/51.5 A, 260/879, 260/880 B
• US Class Current: 508/233
• CPC Class Codes: C08C 19/00 Chemical modification of rubber
• CPC Class Codes: C08C 19/44 of polymers containing metal atoms exclusively at one or both ends of the skeleton
• CPC Class Codes: C08G 81/021 Block or graft polymers containing only sequences of polymers of C08C or C08F
• CPC Class Codes: C08G 81/022 containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
• CPC Class Codes: C10M 143/12 containing conjugated diene
• CPC Class Codes: C10M 2203/10 Petroleum or coal fractions, e.g. tars, solvents, bitumen
• CPC Class Codes: C10M 2205/00 Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
• CPC Class Codes: C10M 2205/026 Butene
• CPC Class Codes: C10M 2205/04 containing aromatic monomers, e.g. styrene
• CPC Class Codes: C10M 2205/06 containing conjugated dienes
• CPC Class Codes: C10M 2207/022 containing at least two hydroxy groups
• CPC Class Codes: C10M 2207/023 having hydroxy groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C10M 2207/024 having at least two phenol groups but no condensed ring
• CPC Class Codes: C10M 2207/281 of (cyclo)aliphatic monocarboxylic acids
• CPC Class Codes: C10M 2207/282 of (cyclo)aliphatic oolycarboxylic acids
• CPC Class Codes: C10M 2207/283 of polyhydroxy compounds
• CPC Class Codes: C10M 2207/286 of polymerised unsaturated acids
• CPC Class Codes: C10M 2207/287 Partial esters
• CPC Class Codes: C10M 2207/288 containing free carboxyl groups
• CPC Class Codes: C10M 2207/289 containing free hydroxy groups
• CPC Class Codes: C10M 2207/32 : of carbonic acid
• CPC Class Codes: C10M 2207/34 : Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
• CPC Class Codes: C10M 2209/00 : Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions oxidised hydrocarbons C10M2205/12
• CPC Class Codes: C10M 2209/02 : Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2209/08 : containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
• CPC Class Codes: C10M 2209/084 : Acrylate; Methacrylate
• CPC Class Codes: C10M 2209/086 : polycarboxylic, e.g. maleic acid
• CPC Class Codes: C10M 2209/10 : Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2209/103 : Polyethers, i.e. containing di- or higher polyoxyalkylene groups
• CPC Class Codes: C10M 2209/104 : of alkylene oxides containing two carbon atoms only
• CPC Class Codes: C10M 2209/12 : Polysaccharides, e.g. cellulose, biopolymers
• CPC Class Codes: C10M 2211/02 : containing carbon, hydrogen and halogen only
• CPC Class Codes: C10M 2215/00 : Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
• CPC Class Codes: C10M 2215/04 : having amino groups bound to acyclic or cycloaliphatic carbon atoms
• CPC Class Codes: C10M 2215/065 : Phenyl-Naphthyl amines
• CPC Class Codes: C10M 2215/08 : Amides
• CPC Class Codes: C10M 2215/082 : containing hydroxyl groups; Alkoxylated derivatives
• CPC Class Codes: C10M 2215/086 : Imides
• CPC Class Codes: C10M 2215/22 : Heterocyclic nitrogen compounds
• CPC Class Codes: C10M 2215/221 : Six-membered rings containing nitrogen and carbon only
• CPC Class Codes: C10M 2215/225 : the rings containing both nitrogen and oxygen
• CPC Class Codes: C10M 2215/226 : Morpholines
• CPC Class Codes: C10M 2215/26 : Amines
• CPC Class Codes: C10M 2215/28 : Amides; Imides
• CPC Class Codes: C10M 2215/30 : Heterocyclic compounds
• CPC Class Codes: C10M 2217/00 : Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
• CPC Class Codes: C10M 2217/02 : Macromolecular compounds obtained from nitrogen containing monomers by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2217/04 : Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10M 2217/046 : Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
• CPC Class Codes: C10M 2217/06 : Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
• CPC Class Codes: C10M 2219/046 : Overbasedsulfonic acid salts
• CPC Class Codes: C10M 2219/087 : containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
• CPC Class Codes: C10M 2219/088 : Neutral salts
• CPC Class Codes: C10M 2219/089 : Overbased salts
• CPC Class Codes: C10M 2223/04 : Phosphate esters
• CPC Class Codes: C10M 2223/041 : Triaryl phosphates
• CPC Class Codes: C10M 2223/042 : Metal salts thereof
• CPC Class Codes: C10M 2223/045 : Metal containing thio derivatives
• CPC Class Codes: C10M 2229/02 : Unspecified siloxanes; Silicones
• CPC Class Codes: C10M 2229/05 : containing atoms other than silicon, hydrogen, oxygen or carbon
• CPC Class Codes: C10N 2010/04 : Groups 2 or 12
• CPC Class Codes: C10N 2040/04 : Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
• CPC Class Codes: C10N 2040/042 : for automatic transmissions
• CPC Class Codes: C10N 2040/044 : for manual transmissions
• CPC Class Codes: C10N 2040/046 : for traction drives
• CPC Class Codes: C10N 2070/02 : Concentrating of additives

Abstract

Lubricating oil additives having both dispersant and viscosity index-improving properties are prepared by reacting a selectively hydrogenated star-shaped polymer having at least four arms of polymers or copolymers of dienes and monoalkenyl arenes with an alpha-beta unsaturated carboxylic acid or derivative, and then reacting the resulting intermediate with an amine.

Claims

1. The oil-soluble product prepared by the process comprising:

a. reacting a selectively hydrogenated star-shaped polymer with an excess of an alpha-beta unsaturated carboxylic acid, anhydride or ester at a temperature of between about 150°

C. and about 300°

C. for between about 1 hour and about 20 hours wherein said star-shaped polymer comprises a poly (polyalkenyl coupling agent) nucleus and between about 7 and about 15 polymeric arms linked to said nucleus wherein said polymeric arms are selected from the group consisting of;

i. hydrogenated homopolymers and hydrogenated copolymers of conjugated dienes;

ii. hydrogenated copolymers of conjugated dienes and monoalkenyl arenes; and

iii. mixtures thereof;

and wherein at least about 80% of the aliphatic unsaturation of the star-shaped polymer has been reduced; and

b. reacting the product of step (a) with a C₁ to C₁₈ amine containing 1 to 8 nitrogen atoms at a temperature of between about 150°

C. and about 250°

C. wherein the molar ratio of amine to carboxylic acid, anhydride or ester is between about 0.1;

1 and about 2;

1.

2. A product, according to claim 1, wherein the polyalkenyl coupling agent is a polyvinyl aromatic compound.

3. A produt, according to claim 1, wherein the polyalkenyl coupling agent is divinyl benzene.

4. A product, according to claim 1, wherein the number average molecuar weight of each polymeric arm is between about 5,000 and about 150,000.

5. A product, according to claim 1, wherein the peak molecular weight of the hydrogenated star-shaped polymer is between about 100,000 and about 500,000.

6. A product, according to claim 1, wherein between about 90 and 98% of the aliphatic unsaturation has been reduced by hydrogenation.

7. A product, according to claim 3, wherein each polymeric arm is a hydrogenated polyisoprene homopolymer.

8. A product, according to claim 1, wherein said star-shaped copolymer and said carboxylic acid, anhydride or ester are reacted in the presence of a solvent in a ratio of moles of carboxylic acid, anhydride or ester to olefinic double bonds remaining in the selectively hydrogenated star-shaped polymer of between about 1:

1 and about 2;

1.

9. A product, according to claim 8, wherein said star-shaped polymer and said carboxylic acid, anhydride or ester are reacted in the presence of a solvent and chlorine in a molar ratio of chlorine to said carboxylic acid, anhydride or ester of between about 0.3:

1 and about 1.5;

1.

10. A product according to claim 1 wherein the amine has the formula:

space="preserve" listing-type="equation">NH.sub.2 (CH.sub.2).sub.n [NH(CH.sub.2).sub.n ].sub.m NH.sub.2

wherein n is 2 to 4 and m is 0 to 6.

11. A product, according to claim 10, wherein the amine is tetraethylenepentamine and the molar ratio of amine to carboxylic acid, anhydride or ester is between about 0.5:

1 and about 2;

1.

12. A product, according to claim 1, wherein the polymer is reacted with between about 0.5 and 3.0 moles of chlorine per 100 carbon atoms of the star-shaped polymer prior to reaction with the unsaturated carboxylic acid, anhydride, or ester.

13. A lubricating composition comprising a major amount of a lubricating oil and from 0.1 to about 15.0 weight percent of the oil-soluble product of claim 1.

14. A concentrated lubricating composition comprising a lubricating oil and from 15 to 45 weight percent of the oil-soluble product of claim 1.