Improved viscosity modifier polymers

Claim 2

Copolymer of ethylene and at least one other alpha-olefin monomer, said copolymer comprising intramolecularly heterogeneous copolymer chains containing at least one crystallizable segment of methylene units and at least one low crystallinity ethylene-alpha-olefin copolymer segment, wherein said crystallizable segment comprises at least 10 weight percent of said copolymer chain and contains an average ethylene content of at least 57 weight percent, wherein said low crystallinity segment contains an average ethylene content not greater than 53 weight percent, and wherein said copolymer has a molecular weight distribution (MWD) characterized by at least one of a ratio of M w/ M n of less than 2 and a ratio of M z/ M w of less than 1.8, and wherein at least two portions of an individual intramolecularly heterogeneous chain, each portion comprising at least 5 weight percent of said chain, differ in composition from one another by at least 7 weight percent ethylene.

Claim 3

The copolymer according to Claim 1, wherein said copolymer has an intermolecular compositional dispersity such that 95 weight % of said copolymer chains have a composition 15 weight % or less different from said average ethylene composition.

Claim 4

The copolymer according to claim 2, wherein said intermolecular compositional dispersity of said copolymer is such that 95 weight % of said copolymer chains have a composition 13 weight % or less different from said average ethylene composition.

Claim 5

The copolymer according to Claim 3, wherein said intermolecular compositional dispersity of said copolymer is such that 95 weight % of said copolymer chains have a composition of 10 wt % or less different from said average ethylene composition.

Claim 6

The copolymer according to any of claims 1 to 4, wherein said low crystallinity segment comprises an average ethylene content of from 20 to 53 wt %.

Claim 7

The copolymer according to Claim 5, wherein said low crystallinity segment comprises an average ethylene content of from about 30 to 50 weight %.

Claim 8

The copolymer according to any of Claims 1 to 6, wherein said crystallizable segment comprises an average ethylene content of at least 62 wt. %.

Claim 9

The copolymer according to any of Claims 1 to 7, which has a weight-average molecular weight of from 2,000 to 12,000,000.

Claim 10

The copolymer according to Claim 8, which has a weight average molecular weight of from 10,000 to 1,000,000

Claim 11

The copolymer according to Claim 9, which has a weight average molecular weight of from 20,000 to 750,000.

Claim 12

The copolymer according to Claim 1, which has a MWD characterized by at least one of a ratio of M w/ M n of less than 1.5 and a ratio of M z/ M w of less than 1.5.

Claim 13

The copolymer according to Claim 11 wherein said portions differ in composition from one another by at least 10 wt. % ethylene.

Claim 14

The copolymer according to Claim 12, wherein said portions differ in composition by at least 20 wt. % ethylene.

Claim 15

The copolymer according to any of Claims 11 to 13 which has a MWD characterized by both a ratio of M w/ M n of less than 1.5 and a ratio of M z/ M w of less than 1.5.

Claim 16

The copolymer according to any of Claims 11 to 14, which has a MWD characterized by at least one of a ratio of M w/ M n of less than 1.25 and a ratio of M z/ M w of less than 1.2.

Claim 17

The copolymer according to Claim 15 which has a MWD characterized by both of a ratio of M w/ M n of less than 1.25 and a ratio of M z/ M w of less than 1.2.

Claim 18

The copolymer according to any of Claims 1 to 16, having a total maximum ethylene content of 90% on a weight basis, and wherein said portions differ in composition from one another by at least 40 wt. % ethylene.

Claim 19

The copolymer according to Claim 17, having a total minimum ethylene content of 20 % on a weight basis.

Claim 20

The copolymer according to any of Claims 1 to 18, having a total ethylene content of greater than 35 % on a weight basis.

Claim 21

The copolymer according to Claim 19, wherein the total ethylene content is from 35 to 75 % on a weight basis.

Claim 22

The copolymer according to any of Claims 1 to 20, wherein said copolymers chain segment sequences are characterized by at least one of the structures: (I)      M - T (II)      T¹ - (M - T²) x (III)      T¹ - (M¹ - T²) y - M² wherein x and y are each integers of 1 to 3, M comprises said crystallizable segment, T comprises said low crystallinity segment, M¹ and M² are the same or different and each comprises an M segment, and T¹ and T² are the same or different and each comprises a T segment.

Claim 23

The copolymer according to Claim 20, wherein x is one.

Claim 24

The copolymer according to Claim 21 or Claim 22, wherein said T¹ and T² segments are of substantially the same weight-average molecular weight.

Claim 25

The copolymer according to Claim 23, wherein the sum of the weight average molecular weights of said T¹ and T² segments is substantially equal to the weight-average molecular weight of said M segment.

Claim 26

The copolymer according to any of Claims 1 to 24, further comprising diene.

Claim 27

The copolymer according to Claim 25, comprising ethylene, propylene and 5-ethyldiene-2-­norbornene.

Claim 28

The copolymer according to any of Claims 1 to 26 which is cured.

Claim 29

A polymerization process for producing copolymer in the form of copolymer chains, from a reaction mixture comprising catalyst, ethylene and at least one other alpha-olefin, characterized by: (a) introducing an initial feed to a polymerization reaction zone in such a manner and under conditions sufficient to initiate propagation of essentially all copolymer chains simultaneously, said initial feed comprising said catalyst, ethylene and at least one other alpha-olefin, said polymerization reaction zone comprising at least one mix-free reactor; (b) introducing at least one additional monomer feed into said polymerization reaction zone after initiation of said copolymer chains, said additional monomer feed comprising at least one of ethylene and one or more other alpha-olefin; and (c) conducting the polymerization in said reactor; (i) with essentially one active catalyst species; (ii) using at least one reaction mixture which is essentially transfer agent-free; and (iii) in such a manner and under conditions sufficient to form intramolecularly heterogeneous copolymer chains containing at least one crystallizable segment of methylene units and at least one low crystallinity ethylene-alpha-­olefin copolymer segment, wherein said at least one crystallizable segment comprises at least 10 weight percent of said copolymer chain and contains an average ethylene content of at least 57 weight percent, and wherein said low crystallinity segment contains an average ethylene content of from 20 to 53 weight percent, and wherein said copolymer has a molecular weight distribution characterized by at least one of a ratio of M w/ M n of less than 2 and a ratio of M z/ M w of less than 1.8, and wherein at least two portions of an individual intramolecularly heterogeneous chain, each portion comprising at least 5 weight percent of said chain, differ in composition from one another by at least 7 weight percent ethylene.

Claim 30

A polymerization process for producing copolymer in the form of copolymer chains, from a reaction mixture comprising catalyst, ethylene and at least one other alpha-olefin, characterized by: (a) introducing an initial feed to a polymerization reaction zone in such a manner and under conditions sufficient to initiate propagation of essentially all copolymer chains simultaneously, said initial feed comprising said catalyst, ethylene and at least one other alpha-olefin, said polymerization reaction zone comprising at least one mix-free reactor; (b) introducing at least one additional monomer feed into said polymerization reaction zone after initiation of said copolymer chains, said additional monomer feed comprising at least one of ethylene and one or more other alpha-olefin; and (c) conducting the polymerization in said reactor; (i) with essentially one active catalyst species; (ii) using at least one reaction mixture which is essentially transfer agent-free; and (iii) in such a manner and under conditions sufficient to form intramolecularly heterogeneous copolymer chains containing at least one crystallizable segment of methylene units and at least one low crystallinity ethylene-alpha-­olefin copolymer segment, wherein said at least one crystallizable segment comprises at least 10 weight percent of said copolymer chain and contains an average ethylene content of at least 57 weight percent, and wherein said low crystallinity segment contains an average ethylene content of from 20 to 53 weight percent, and wherein said copolymer has a molecular weight distribution characterized by at least one of a ratio of M w/ M n of less than 2 and a ratio of M z/ M w of less than 1.8, and wherein at least two portions of an individual intramolecularly heterogeneous chain, each portion comprising at least 5 weight percent of said chain, differ in composition from one another by at least 7 weight percent ethylene.

Claim 31

The process according to Claim 28, wherein the catalyst comprises a Ziegler catalyst.

Claim 32

The process according to Claim 29, wherein the catalyst comprises hydrocarbon-soluble vanadium compound and organo-aluminium compound which react to form essentially one active catalyst species, at least one of the vanadium compound and organo-aluminium compound containing a valence-bonded halogen.

Claim 33

The process according to Claim 30, wherein the catalyst comprises: (a) hydrocarbon-soluble vanadium compound selected from where x=0-3 and R=hydrocarbon radical; VCl₄; VO(AcAc)₂, where AcAc=acetyl acetone; V(AcAc)₃, where AcAc=acetyl acetonate; VOCl x (AcAc)₃-x, where x=1 or 2 and AcAc=acetyl acetonate; and VCl₃·nB, where n=2-3 and B-Lewis base capable of forming hydrocarbon-soluble complexes with VCl₃; V(dicarbonyl moiety)₃; wherein "dicarbonyl moiety" is derived from a compound of the formula wherein R, is divalent alkylene of 1 to 6 carbon atoms, and R in each instance in which it appears is independently selected from the group consisting of C₁ to C₁₀ alkyl, C₃ to C₁₀ cycloalkyl and C₆ to C₁₀ aryl; and V(dicarbonyl moiety)₃Cl, wherein "dicarbonyl moiety" is as defined above; (b) organo-aluminium compound selected from the group consisting of: AlR₃, AlR₂Cl, Al₂R₃Cl₃, AlRCl₂ AlR′RCl, Al(OR′)R₂, R₂Al-OA1R₂, and AlR₂I, where R and R, are hydrocarbon radicals.

Claim 34

The process according to Claim 31, wherein the catalyst comprises VC1₄ and A1₂R₃C1₃.

Claim 35

The process according to any of Claims 28 to 32, wherein the mole ratio of aluminium to vanadium in the catalyst is from 2 to 25.

Claim 36

The process according to Claim 33, wherein the mole ratio of aluminium to vanadium in the catalyst is from 4 to 15.

Claim 37

The process according to Claims 28 to 34, wherein the catalyst components are premixed, and wherein the polymerization is a solution polymerization.

Claim 38

The process according to Claim 35, wherein the catalyst components are aged for at least 0.5 seconds.

Claim 39

The process according to Claim 36, wherein the catalyst comprises components that are premixed and then aged for from 1 to 50 seconds.

Claim 40

The process according to any of Claims 35 to 37, wherein the reaction mixture leaving the reactor has a copolymer concentration of from 3 to 15% on a weight of copolymer per weight of solvent basis.

Claim 41

The process according to Claim 38, wherein the reaction mixture leaving the reactor has a copolymer concentration of from 3% to 10% on a weight of polymer per weight of solvent basis.

Claim 42

The process according to any of Claims 28 to 39, wherein the inlet temperature of the reaction mixture is from -50°C to 150°C.

Claim 43

The process according to Claim 40, wherein the maximum outlet temperature of the reaction mixture is 200°C.

Claim 44

The process according to Claim 41, wherein the maximum outlet temperature of the reaction mixture is 70°C.

Claim 45

The process according to Claim 42, wherein the maximum outlet temperature of the reaction mixture is 50°C.

Claim 46

The process according to Claim 43, wherein the polymerization is adiabatic.

Claim 47

The process according to any of Claims 28 to 44, wherein the catalyst comprises one active species which provides for at least 65% of the total copolymer produced.

Claim 48

The process according to Claim 35, which is continuous and is conducted in hexane solvent.

Claim 49

The process according to any of Claims 28 to 46, wherein said copolymer product is cured.

Claim 50

The process according to any of Claims 28 to 47 wherein said polymerization is conducted in at least one tubular reactor.

Claim 51

The process according to Claim 48, wherein said reaction mixture further comprises diene, and wherein at least one of said ethylene, other alpha-olefin monomer and diene are fed to said tubular reactor at multiple feed sites.

Claim 52

The process according to any of Claims 28 to 49, wherein said copolymer product is blended with basestock lubricating oil.

Claim 53

The process according to Claim 50, wherein said copolymer product is blended with basestock lubricating oil in an amount of from .001 to 49 wt. %.

Claim 54

The process according to Claim 50, wherein said copolymer product is blended with hydrocarbon mineral oil diluent in an amount of from 5 to 50 wt. %.

Claim 55

A lubricating oil composition comprising a major amount of basestock lubricating oil, of lubricating viscosity, containing an effective amount of a viscosity modifier comprising a copolymer as claimed in any of Claims 1 to 27.

Claim 56

The lubricating oil composition according to Claim 53, containing from .001 to 49 wt. % of said copolymer.

Claim 57

The lubricating oil composition according to Claim 54, wherein said copolymer has a weight-average molecular weight of from 50,000 to 500,000.

Claim 58

The lubricating oil composition according to Claim 55, wherein said weight-average molecular weight is less than 300,000.

Claim 59

The lubricating oil composition according to Claim 56, wherein said weight-average molecular weight is less than 250,000.

Claim 60

The lubricating oil composition according to any of Claims 53 to 57 wherein said copolymer comprises ethylene and propylene.

Claim 61

The lubricating oil composition according to any of Claims 53 to 58, having a MRV viscosity of less than 30,000 cP at the maximum SAE borderline pumping temperature for the oil.

Claim 62

The lubricating oil composition according to Claim 59, having an MRV viscosity of less than 20,000 cP at the maximum SAE borderline pumping temperature for the oil.

Claim 63

The lubricating oil composition according to Claim 60, having an MRV viscosity of less than 10,000 cP at the maximum SAE borderline pumping temperature for the oil.

Claim 64

An oil additive concentrate composition comprising hydrocarbon mineral oil diluent and about 2 to 50 wt. % based on the total amount of hydrocarbon mineral oil diluent of a copolymer as claimed in any of Claims 1 to 27.

Claim 65

The oil additive concentrate composition according to Claim 62, wherein said copolymer is as defined in any of Claims 55 to 58.

Claim 66

The use in a lubricant of a copolymer as claimed in any of Claims 1 to 27.