US 5,229,022 A · Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920)

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.

Claims94

Dependent claims

Functionalized ethylene alpha-olefin "ene" reacted polymer useful in preparing dispersant additives for oleaginous compositions, which comprises ethylene alpha-olefin polymer substituted with at least one of C.sub.3 to C.sub.10 monounsaturated monocarboxylic acid producing moieties and C.sub.4 to C.sub.10 monounsaturated dicarboxylic acid producing moieties, the starting polymer from which the functionalized 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, wherein said starting polymer has a number average molecular weight of from about 700 to 15,000, a molecular weight distribution of less than about 4, and a molar ethylene content between about 20 to 80 percent, wherein an average of at least about 30% of said starting polymer chains contain terminal ethenylidene unsaturation, wherein said starting polymer contains less than 5 wt. percent of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300, and wherein said functionalized polymer has a functionality of from about 0.5 to 2 and a VR value of less than about 4.1.

A process for producing an additive useful in oleaginous compositions, which comprises contacting:

(A) ethylene alpha-olefin starting polymer 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, said starting polymer having a number average molecular weight of between about 700 to 15,000, a molar ethylene content of from about 20 to about 80 percent, and less than about 5 percent by weight of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300, and wherein an average of at least about 30% of said starting polymer chains contain terminal ethenylidene unsaturation;
with
(B) 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 mono- or di-ester derivatives of (iii) under thermal "ene" reaction conditions and for a time sufficient to form a product mixture containing an ethylene alpha-olefin polymer substituted with said carboxylic acid moieties, wherein said product mixture has a VR value of not greater than about 4.1.

3 more elements

A process for producing an additive useful in oleaginous compositions, which comprises:

(A) treating ethylene alpha-olefin polymer 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 containing at least about 5 wt % of a low molecular weight polymer fraction comprising polymer chains having a molecular weight of less than about 300 under conditions and for a time sufficient to remove at least a portion of said low molecular weight fraction, to provide a treated polymer containing less than about 5 wt % of said low molecular weight fraction, said treated polymer having a number average molecular weight of between about 700 and 15,000, a molar ethylene content of from about 20 to about 80 percent, and wherein an average of at least about 30% of the polymer chains of the starting ethylene alpha-olefin polymer contain terminal ethenylidene unsaturation;
and
(B) contacting said treated polymer with 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 mono- or di-ester derivatives of (iii) under thermal "ene reaction conditions and for a time sufficient to form a product mixture containing ethylene alpha-olefin polymer substituted with said carboxylic acid producing moieties, wherein said product mixture has a VR value of not greater than about 4.1.

3 more elements

Functionalized ethylene alpha-olefin polymer additive useful in oleaginous compositions, said additive being prepared by a process which comprises:

(A) contacting ethylene alpha-olefin polymer with a halogenating reactant under halogenating reaction conditions to form halogenated ethylene alpha-olefin polymer, wherein the starting ethylene alpha-olefin polymer comprises 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, said starting polymer having a number average molecular weight of between about 700 to 15,000, a molar ethylene content of from about 20 to about 80 percent, and less than about 5 percent by weight of a low molecular weight polymer fraction comprising polymer molecules having a molecular weight of less than about 300, and wherein an average of at least about 30% of said starting polymer chains contain terminal ethenylidene unsaturation;
and
(B) contacting said halogenated ethylene alpha-olefin polymer 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-esters 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 mono- or di-ester derivatives of (iii) under reaction conditions effective to form a product mixture containing an ethylene alpha-olefin polymer substituted with said carboxylic acid moieties, wherein said product mixture has a VR value of not greater than about 4.1 and wherein the functionality of the acid substituted polymer is from about 0.5 to 2.

3 more elements

Functionalized ethylene alpha-olefin polymer additive useful in oleaginous compositions, said additive being prepared by contacting, simultaneously, (a) ethylene alpha-olefin starting polymer, (b) halogenating reactant, and (c) monounsaturated carboxylic acid producing reactant under reaction conditions effective to from a product mixture containing ethylene alpha-olefin polymer substituted with carboxylic moieties, said starting polymer (i) 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, (ii) having a number average molecular weight of from about 700 to 15,000, (iii) having a molar ethylene content between about 20 to 80 percent, (iv) having an average of at least about 30% of polymer chains containing terminal ethenylidene unsaturation, and (v) having less than 5 wt. percent of a polymer fraction comprising polymer molecules having a molecular weight of less than about 300;

and said functionalized polymer having a functionality of from about 0.5 to 2 and a VR value of less than about 4.1.

A process for producing an additive useful in oleaginous compositions which comprises:

(I) contacting (A) ethylene alpha-olefin starting polymer 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, said polymer having a number average molecular weight of between about 700 to 15,000, a molar ethylene content of from about 20 to about 80 percent, and less than about 5 percent by weight of a low molecular weight polymer fraction comprising polymer molecules having a molecular weight of less than about 300, and wherein an average of at least about 30% of said starting polymer chains contain terminal ethenylidene unsaturation;
with (B) halogenating reactant under conditions effective to form an intermediate mixture containing halogenated starting polymer;
and then
(II) contacting said intermediate mixture with 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 mono- or di-ester derivatives of (iii) under reaction conditions effective to form a product mixture containing ethylene alpha-olefin polymer substituted with carboxylic acid moieties, wherein said product mixture has a VR value of not greater than about 4.1 and the functionality of the substituted polymer is from about 0.5 to 2.

4 more elements

A process for producing an additive useful in oleaginous compositions which comprises:

simultaneously contacting ethylene alpha-olefin starting polymer, halogenating reactant and monounsaturated carboxylic acid producing reactant under reaction conditions effective to form a product mixture containing ethylene alpha-olefin polymer substituted with carboxylic acid moieties;
wherein said ethylene alpha-olefin starting polymer (i) comprises 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, (ii) contains less than about 5 wt % of a low molecular weight polymer fraction comprising polymer chains having a molecular weight of less than about 300, (iii) has a number average molecular weight of about 700 to about 15,000, (iv) has a molar ethylene content of from about 20 to about 80 percent and, (v) contains an average of at least about 30% of polymer chains having terminal ethenylidene unsaturation;
wherein said monounsaturated carboxylic producing reactant comprises a member 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 mono- or di-ester derivatives of (iii);
wherein said product mixture has a VR value of not greater than about 4.1;
and wherein said polymer substituted with carboxylic acid moieties has a functionality of about 0.5 to 2.

5 more elements

Dependencies are inferred from the claim text.

Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920)

Life of this patent

Ethylene alpha-olefin polymer substituted mono- and dicarboxylic acid dispersant additives (PT-920)

Life of this patent

Abstract

Claims94