Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof

A composition of matter suitable for use as a fuel or lubricant additive consisting essentially of an olefinic hydrocarbon polymer having a nitrogenous head group, said polymer being derived from at least one polymerizable olefinic monomer selected from the group consisting of ethylene, C.sub.3 -C.sub.20 .alpha.-olefins and a mixture of C.sub.3 -C.sub.20 .alpha.-olefins, said mixture selected from the group consisting of C.sub.3, C.sub.4 and C.sub.5 refinery or steam cracker feedstreams and raffinate derivatives thereof, said polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least about 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,000;
• and
• (f) substantial solubility in hydrocarbon and/or synthetic base oil.

A process for continuously producing monounsaturated olefinic hydrocarbon polymer suitable for use as a fuel or lubricant additive, said polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least about 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,000;
• and
• (f) substantial solubility in hydrocarbon and/or synthetic base oil;
• said polymer derived from at least one polymerizable olefinic monomer selected from the group consisting of ethylene, C.sub.3 -C.sub.20 .alpha.-olefins and a mixture of C.sub.3 -C.sub.20 .alpha.-olefins and polymerized in the presence of a late-transition-metal catalyst system in a reaction zone containing liquid phase, said process further comprising:
• (A) when at least one .alpha.-olefin monomer is selected, continuously providing said .alpha.-olefin as a dilute, liquefied .alpha.-olefin feed stream from a refinery or steam cracker, said feed stream containing diluent admixed therewith wherein the amount of diluent in said feed stream is at least 30 wt. % thereof, and wherein at least 50 wt. % of the constituents of said diluent possess a boiling point under reaction conditions within .+-.20.degree. C. of the average boiling point of the .alpha.-olefin constituents of the feed stream;
• (B) when ethylene is selected, continuously providing a feed stream comprising ethylene in liquid, vapor, or liquid/vapor form;
• (C) when a mixture of ethylene and an .alpha.-olefin is selected, admixing the feed streams of steps (A) and (B) to provide a reactant feed stream having an .alpha.-olefin/ethylene weight ratio effective to yield a polymer containing an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (D) continuously introducing said feed stream or said reactant feed stream derived in accordance with steps (A), (B) or (C) and late-transition-metal catalyst system into the liquid phase of the reaction zone in a manner and under conditions sufficient to:
• (i) polymerize the ethylene and/or .alpha.-olefin to polymer product having a number average molecular weight of not greater than 10,000;
• (ii) obtain an .alpha.-olefin conversion, when an .alpha.-olefin is used as a monomer, of at least 30%;
• (iii) obtain an ethylene conversion, where ethylene is used as a monomer, of at least 70%
• (E) continuously withdrawing said polymer from the reactor.

A reaction product of a functional compound with a monounsaturated olefinic hydrocarbon polymer by the ene reaction, wherein said monounsaturated olefinic hydrocarbon polymer has the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,000;
• and
• (f) substantial solubility in hydrocarbon and/or base oil.

A reaction product of a functional compound with a monounsaturated olefinic hydrocarbon polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn of from about 300 to about 10,000;
• and
• (f) substantial solubility in hydrocarbon and/or base oil,
• wherein said reaction is initiated using one or more free radical generating compounds and wherein said reaction product contains an average of at least 2 of said polymer chains linked to said functional compound.

The functionalized polymer reaction product of at least one member selected from the group consisting 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 with a monounsaturated olefinic hydrocarbon polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least about 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,000;
• and
• (f) substantial solubility in hydrocarbon and/or synthetic base oil.

A functionalized polymer comprising an oxidized polymer, wherein said oxidized polymer is the reaction product of a monounsaturated olefinic hydrocarbon polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least about 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,000;
• (f) substantial solubility in hydrocarbon and/or synthetic base oil;
• and
• (g) a gas selected from the group consisting of an oxygen-containing gas, an ozone-containing gas and mixtures thereof.

A derivatized polymer comprising the reaction product of:

• (a) at least one alkyl-substituted hydroxyaromatic compound formed by the alkylation of at least one hydroxy aromatic compound with a monounsaturated olefinic hydrocarbon polymer having the following characteristics:
• (i) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (ii) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (iii) at least about 50% of said branches being methyl and/or ethyl branches;
• (iv) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (v) a number average molecular weight, Mn, of from about 300 to about 10,000;
• (vi) substantial solubility in hydrocarbon and/or synthetic base oil;
• (b) at least one aldehyde reactant;
• and
• (c) at least one nucleophilic reactant.

The reaction product of a monounsaturated olefinic hydrocarbon polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least about 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,0000;
• and
• (f) substantial solubility in hydrocarbon and/or synthetic base oil;
• with a phenol in the presence of an acid catalyst.

A lubricating oil composition comprising a major amount of basestock lubricating oil of lubricating viscosity and from 0.01 to 5 wt. % of lubricating oil flow improver and from 0.1 to 20 wt. % of a viscosity modifier comprising a monounsaturated olefinic hydrocarbon polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 3.0;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least about 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 300 to about 10,000;
• and
• (f) substantial solubility in hydrocarbon and/or synthetic base oil.

An oil additive concentrate comprising hydrocarbon mineral oil diluent and about 2 to 50 wt. % based on the total amount of hydrocarbon mineral oil diluent of a monounsaturated olefinic hydrocarbon polymer having the following characteristics:

• (a) an average ethylene sequence length, ESL, of from about 1.0 to less than about 1.5;
• (b) an average of at least 5 branches per 100 carbon atoms of the polymer chains comprising said polymer;
• (c) at least 50% of said branches being methyl and/or ethyl branches;
• (d) at least about 30% of said polymer chains terminated with a vinyl or vinylene group;
• (e) a number average molecular weight, Mn, of from about 15,000 to 500,000;
• and
• (f) substantial solubility in hydrocarbon and/or base oil.