# US 5,350,532 A · Borated ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives

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- Number: US 5,350,532 A
- Document ID: US5350532A
- Status: Granted
- Kind: A
- Application number: 08/132,028
- Filed: 1993-10-05
- Granted: 1994-09-27
- Earliest claimed: 1988-08-01
- Assignees: Exxon Chemical Patents Inc.
- Inventors: Won R. Song; Albert Rossi; Howard W. Turner; Howard C. Welborn; Robert D. Lundberg; Antonio Gutierrez; Robert A. Kleist
- Web page: https://patentgrep.com/patent/US5350532A

## CPC

- C10M 171/00: Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated (chemically defined ingredients C10M101/00 - C10M169/00; petroleum fractions C10M101/02, C10M121/02, C10M159/04)
- C08F 8/00: Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C)
- C08F 8/46: Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
- C10L 1/143: {mixtures of organic macromolecular compounds with organic non-macromolecular compounds}
- C10L 1/1963: {mono-carboxylic}
- C10L 1/1966: {poly-carboxylic}
- C10L 1/198: obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds {homo- or 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid}
- C10L 1/238: obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds {(C10L1/221 takes precedence)}
- C10L 1/2475: {obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds}
- C10L 1/303: {boron compounds}
- C10L 10/04: for minimising corrosion or incrustation
- C10M 129/93: having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M 129/95: Esters
- C10M 133/52: having a carbon chain of 30 or more atoms
- C10M 133/56: Amides; Imides
- C10M 143/02: Polyethylene
- C10M 159/12: Reaction products
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C10L 1/1608: {Well defined compounds, e.g. hexane, benzene}
- C10L 1/1616: {fractions, e.g. lubricants, solvents, naphta, bitumen, tars, terpentine}
- C10L 1/1817: {Compounds of uncertain formula; reaction products where mixtures of compounds are obtained}
- C10L 1/1832: {mono-hydroxy (C10L1/1802, C10L1/1805, C10L1/1808, C10L1/1811, C10L1/1814, C10L1/1817, C10L1/1828 take precedence)}
- C10L 1/201: {aliphatic bond}
- C10L 1/221: {compounds of uncertain formula; reaction products where mixtures of compounds are obtained}
- C10L 1/2493: {compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds}
- C10L 1/2641: {oxygen bonds only}
- C10L 1/2691: {Compounds of uncertain formula; reaction of organic compounds (hydrocarbons acids, esters) with Px Sy, Px Sy Halz or sulfur and phosphorus containing compounds}
- C10L 1/306: {organo Pb compounds}
- C10M 2205/00: Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M 2207/123: polycarboxylic
- C10M 2207/129: having hydrocarbon chains of thirty or more carbon atoms
- C10M 2207/22: Acids obtained from polymerised unsaturated acids
- C10M 2207/281: of (cyclo)aliphatic monocarboxylic acids
- C10M 2207/282: of (cyclo)aliphatic oolycarboxylic acids
- C10M 2207/283: of polyhydroxy compounds
- C10M 2207/286: of polymerised unsaturated acids
- C10M 2207/288: containing free carboxyl groups
- C10M 2207/289: containing free hydroxy groups
- C10M 2207/34: Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
- C10M 2209/00: Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M 2209/02: Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M 2209/10: Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M 2215/04: having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M 2215/042: containing hydroxy groups; Alkoxylated derivatives thereof
- C10M 2215/08: Amides [having hydrocarbon substituents containing less than thirty carbon atoms]
- C10M 2215/082: containing hydroxyl groups; Alkoxylated derivatives
- C10M 2215/086: Imides [having hydrocarbon substituents containing less than thirty carbon atoms]
- C10M 2215/26: Amines
- C10M 2215/28: Amides; Imides
- C10M 2217/042: between the nitrogen-containing monomer and an aldehyde or ketone
- C10M 2217/043: Mannich bases
- C10M 2217/046: Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
- C10M 2217/06: Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
- C10M 2221/00: Organic macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M 2223/045: Metal containing thio derivatives
- C10N 2010/04: Groups 2 or 12
- C10N 2020/01: {Physico-chemical properties}
- C10N 2040/00: Specified use or application for which the lubricating composition is intended
- C10N 2040/02: Bearings
- C10N 2040/08: Hydraulic fluids, e.g. brake-fluids
- C10N 2040/25: Internal-combustion engines
- C10N 2040/251: {Alcohol-fuelled engines}
- C10N 2040/252: {Diesel engines}
- C10N 2040/253: {Small diesel engines}
- C10N 2040/255: {Gasoline engines}
- C10N 2040/28: Rotary {engines}
- C10N 2040/30: Refrigerators lubricants {or compressors lubricants}
- C10N 2040/32: Wires, ropes or cables lubricants
- C10N 2040/34: Lubricating-sealants
- C10N 2040/36: Release agents {or mold release agents}
- C10N 2040/38: {Conveyors or chain belts}
- C10N 2040/40: {Generators or electric motors in oil or gas winning field}
- C10N 2040/42: {Flashing oils or marking oils}
- C10N 2040/44: {Super vacuum or supercritical use}
- C10N 2040/50: {Medical uses}
- C10N 2070/02: {Concentrating of additives}
- Y10S 526/943: Polymerization with metallocene catalysts
- C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The present invention is directed to an oil-soluble fuel and lubricating oil additive comprising at least one terminally unsaturated ethylene alpha-olefin polymer of 300 to 20,000 number average molecular weight substituted with mono- or dicarboxylic acid producing moieties (preferably dicarboxylic acid or anhydride moieties), wherein the terminal unsaturation comprises terminal ethenylidene unsaturation. The mono- and dicarboxylic acid or anhydride substituted polymers of this invention are useful per se as additives to lubricating oils, and can also be reacted with a nucleophilic reagent, such as amines, alcohols, amino alcohols and reactive metal compounds, to form products which are also useful fuel and lubricating oil additives, e.g., as dispersants.

## Claims

### Claim 1

A boron-containing oil soluble dispersant mixture useful as an additive in oleaginous compositions comprising an adduct of:
(A) ethylene alpha-olefin polymer substituted with monounsaturated mono- or dicarboxylic acid producing moieties, the starting polymer from which the substituted polymer is derived comprising monomer units derived from ethylene and at least one alpha-olefin of the formula H.sub.2 C.dbd.CHR.sup.1 wherein R.sup.1 is an alkyl group of from 1 to 18 carbon atoms, and wherein said starting polymer has a number average molecular weight of from about 300 to 20,000 and an average of at least about 30% of said polymer chains contain terminal ethenylidene unsaturation, said acid producing moieties being derived from at least one monounsaturated carboxylic reactant selected from the group consisting of (i) monounsaturated C.sub.4 to C.sub.10 dicarboxylic acids wherein (a) the carboxyl groups are attached to adjacent carbon atoms and (b) at least one of said adjacent carbon atoms is part of said monounsaturation; (ii) anhydride or C.sub.1 to C.sub.5 alcohol derived mono- or di-ester derivatives of (i); (iii) monounsaturated C.sub.3 to C.sub.10 monocarboxylic acids wherein the carbon-carbon double bond is allylic to the carboxy group; and (iv) C.sub.1 to C.sub.5 alcohol derived monoester derivatives of (iii); and
(B) at least one nucleophilic reagent selected from the group consisting of amines, alcohols and mixtures thereof; and
wherein said adduct is borated.

### Claim 2 (depends on 1)

The boron-containing dispersant mixture according to claim 1 wherein the acid producing moieties comprise at least one member selected from the group consisting of succinic anhydride, succinic acid and propionic acid; and wherein the substituted polymer has a VR value of less than about 4.1 and the adduct has a VR' value of less than about 4.1.

### Claim 3 (depends on 2)

The boron-containing dispersant mixtures according to claim 2 wherein the dispersant mixture has a VR'/VR ratio of less than about 1.11.

### Claim 4 (depends on 1)

The boron-containing dispersant mixture according to claim 1 wherein the nucleophilic reagent comprises an amine containing from 2 to 60 carbon atoms and from 1 to 12 nitrogen atoms per molecule, and wherein the adduct contains from about 0.05 to 2.0 weight percent boron.

### Claim 5 (depends on 4)

The boron-containing dispersant mixture according to claim 4 wherein said amine comprises a polyalkylenepolyamine wherein said alkylene group contains 2 to 60 carbons and said polyalkylenepolyamine contains from 2 to about 9 nitrogen atoms per molecule; and wherein the substituted polymer has a VR value of less than about 4.1 and the adduct has a VR' value of less than about 4.1.

### Claim 6 (depends on 5)

The boron-containing dispersant mixture according to claim 5 wherein said amine comprises polyethylenepolyamine.

### Claim 7 (depends on 5)

The boron-containing dispersant mixture according to claim 5 wherein the adduct has a VR' value of from about 2.5 to 4.0.

### Claim 8 (depends on 1)

The boron-containing dispersant mixture according to claim 1 wherein said alpha-olefin is propylene.

### Claim 9 (depends on 1)

The boron-containing dispersant mixture according to claim 1 wherein said nucleophilic reagent comprises an amido-amine or a thioamide-amine characterized by being a reaction product of at least a polyamine and an alpha, beta-unsaturated compound of the formula: ##STR46## wherein X is sulfur or oxygen, Y is --OR.sup.4, --SR.sup.4, or --NR.sup.4 (R.sup.5), and R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are the same or different and are hydrogen or substituted or unsubstituted hydrocarbyl.

### Claim 10 (depends on 9)

The boron-containing dispersant mixture according to claim 9, wherein said alpha-olefin comprises propylene.

### Claim 11 (depends on 10)

The boron-containing dispersant mixture according to claim 10, wherein said polyamine comprises a polyalkylenepolyamine wherein said alkylene group contains 2 to 40 carbons and said polyalkylenepolyamine contains from 5 to about 9 nitrogen atoms per molecule.

### Claim 12 (depends on 9)

The boron-containing dispersant mixture according to claim 9, wherein said polyamine comprises polyalkylenepolyamine wherein said alkylene groups contain 2 to 6 carbons and said polyalkylenepolyamine contains 5 to 9 nitrogen atoms per molecule, and said alpha, beta-unsaturated compound comprises at least one member selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.

### Claim 13 (depends on 12)

The boron-containing dispersant mixture according to claim 12 wherein said polyamine comprises a polyethylenepolyamine or polypropylenepolyamine and wherein the substituted polymer has a VR value of less than about 4.1 and the adduct has a VR' value of less than about 4.1; and

### Claim 14 (depends on 10)

The boron-containing dispersant mixture according to claim 10 wherein said monounsaturated carboxylic reactant comprises maleic anhydride.

### Claim 15 (depends on 9)

The boron-containing dispersant mixture according to claim 9 wherein said nucleophilic reagent is an amido-amine and about 1 to 5 moles of said producing moieties per primary nitrogen equivalent of said amido-amine are present in said reaction mixture.

### Claim 16 (depends on 12)

The boron-containing dispersant mixture according to claim 12 wherein said polyamine contains an average of at least 2 primary nitrogen atoms per molecule, said X group is oxygen and said polyamine and said alpha, beta-unsaturated compound are contacted in an amount of from about 3 to 5 equivalents of said polyamine (based on said primary amine content) per mole of said alpha, beta unsaturated compound.

### Claim 17 (depends on 1)

A concentrate containing from about 20 to 60 wt. % of the boron-containing dispersant mixture of claim 1.

### Claim 18 (depends on 1)

A lubricating oil composition containing from about 0.1 to 20 wt. % of the boron-containing dispersant mixture of claim 1.

### Claim 19 (depends on 1)

The boron-containing dispersant mixture according to claim 1 wherein said substituted polymer comprises "ene" reacted polymer formed by reacting said starting polymer and said monounsaturated carboxylic reactant under "ene" reaction conditions.

### Claim 20 (depends on 19)

The boron-containing dispersant mixture according to claim 19 wherein said starting polymer has a molecular weight distribution of less than about 4 and a molar ethylene content of about 20 to 80 percent, wherein said starting polymer contains less than 5 wt. percent of a polymer fraction comprising polymer molecules having a number average molecular weight of less than about 300, and wherein said "ene" reacted polymer has a functionality of from about 0.5 to 2.8.

### Claim 21 (depends on 19)

The boron-containing dispersant mixture according to claim 19 wherein the substituted polymer has a chlorine content of less than about 25 wppm.

### Claim 22 (depends on 19)

The boron-containing dispersant mixture according to claim 19 wherein the nucleophilic reagent comprises an amine containing from 2 to 60 carbon atoms and from 1 to 12 nitrogen atoms per molecule, and wherein the adduct contains from about 0.05 to 2.0 weight percent boron.

### Claim 23 (depends on 19)

The boron-containing dispersant mixture according to claim 19 wherein the starting polymer comprises ethylene-propylene copolymer.