US4690995A — Copolymers containing high concentrations of phen…

Claim 1

Independent Claim 218 words

The process of producing an oxidation resistant composition of matter comprising a polymer derived from emulsion polymerizing at a pH lower than about 5.0 a monomer system comprising (a) 20 to 50 parts by weight per hundred parts by weight of total monomer of at least one hindered phenol antioxidant monomer having an addition polymerizable double bond of the formula: Ph-A1-D wherein Ph is a hindered phenol group having at least one branched or cyclic lower alkyl substituent of at least 3 carbon atoms ortho to the hydroxyl group; A1 is --(CH 2 ) k --, --S--, --O--, --CH 2 O--, --CH 2 S--, where k is 1 or 2; and D is an acyclic substituent of the formula: --(CR'.sub.2).sub.m --A2--(CR'.sub.2).sub.n --A3--(CR'.sub.2).sub.p --A4--(CR'.sub.2).sub.q --A5--E wherein each A2, A3, A4 and A5 is independently selected from the group consisting of a thioether, ether, carboxylic acid ester, thioester, carboxylic acid amide, urethane-type linkage and nothing; m, n, p, and q are independently integers of zero to 4, but where A1 is --O-- or --S--, m is not zero; each R' is independently H or a (substituted) alkyl group; and E is a group having addition polymerizable unsaturation, and (b) at least 15 to 60 parts by weight of at least one 3 to 8 carbon α,β-ethylenically unsaturated carboxylic acid monomer.

Claim 2

Dependent Claim 218 words

The process of producing an oxidation resistant composition of matter comprising a polymer derived from emulsion polymerizing at a pH lower than about 5.0 a monomer system comprising (a) 20 to 50 parts by weight per hundred parts by weight of total monomer of at least one hindered phenol antioxidant monomer having an addition polymerizable double bond of the formula: Ph-A1-D wherein Ph is a hindered phenol group having at least one branched or cyclic lower alkyl substituent of at least 3 carbon atoms ortho to the hydroxyl group; A1 is --(CH 2 ) k --, --S--, --O--, --CH 2 O--, --CH 2 S--, where k is 1 or 2; and D is an acyclic substituent of the formula: --(CR'.sub.2).sub.m --A2--(CR'.sub.2).sub.n --A3--(CR'.sub.2).sub.p --A4--(CR'.sub.2).sub.q --A5--E wherein each A2, A3, A4 and A5 is independently selected from the group consisting of a thioether, ether, carboxylic acid ester, thioester, carboxylic acid amide, urethane-type linkage and nothing; m, n, p, and q are independently integers of zero to 4, but where A1 is --O-- or --S--, m is not zero; each R' is independently H or a (substituted) alkyl group; and E is a group having addition polymerizable unsaturation, and (b) at least 15 to 60 parts by weight of at least one 3 to 8 carbon α,β-ethylenically unsaturated carboxylic acid monomer.

Claim 3

Dependent Claim 30 words

The process of claim 1 wherein there are at least 25 parts by weight per hundred parts by weight of total monomer of at least one unsaturated carboxylic acid monomer.

Claim 4

Dependent Claim 39 words

The process of claim 1 or 2 wherein Ph is ##STR3## wherein R 2 is an alkyl group; R 3 is a hydrogen or an alkyl group such that the hydroxyl group is sufficiently hindered to have antioxidant function.

Claim 5

Dependent Claim 14 words

The process of claim 1 or 2 wherein Ph is a 2,6-di-tert-butyl phenol group.

Claim 6

Dependent Claim 15 words

The process of claim 2 wherein A1 is --S-- or --(CH 2 ) 2 --.

Claim 7

Dependent Claim 95 words

The process of claim 1 wherein E is an alkenyl group of the formula: --R 4 --CR 5 ═CH 2 wherein R 4 is a divalent alkyl group of 1 to 4 carbon atoms or when at least one of A2, A3, A4, or A5 is an ether, a thioether, a carboxylic ester, a thioester, a carboxylic acid amide, or a urethane-type linkage, R4 may be nothing; and R 5 is chosen from the group consisting of H or alkyl group of 1 to 4 carbon atoms such that the double bond is addition polymerizable.

Claim 8

Dependent Claim 15 words

The process of claim 1 wherein A1 is --S-- or --(CH 2 ) 2 --.

Claim 9

Dependent Claim 24 words

The process of claim 1 wherein at least two of A2, A3, A4, A5 are carboxylic acid ester, thioester, carboxylic amide, or urethane-type linkages.

Claim 10

Dependent Claim 11 words

The process of claim 8 wherein A3 is a urethane-type linkage.

Claim 11

Dependent Claim 23 words

The process of claim 9 wherein A2 and A4 are independently chosen from the group consisting of carboxylic amides, carboxylic esters and nothing.

Claim 12

Dependent Claim 21 words

The process of claim 10 wherein A1 is --S-- and m is 2 or A1 is --(CH 2 ) 2 --.

Claim 13

Dependent Claim 24 words

The process of claim 1 or 2 wherein the hindered phenol antioxidant monomer having an addition polymerizable double bond is 2-(((2-(3-((3,5-bis (1,1-dimethyl)-4-hydroxyphenyl)thio)-1-oxopropoxy) ethoxy)carbonyl)amino)ethyl-2-methyl 2-propenoate.

Claim 14

Dependent Claim 74 words

The process of claim 1 or 2 wherein the α,β-ethylenically unsaturated carboxylic acid monomer is of the formula: RCH═CR'--COOH wherein R is H and R' is H or a 1 to 4 carbon alkyl group, or --CH 2 COOX; or R is --CH 2 COOX and R' is H or --CH 2 COOX; or R is --CH 3 and R' is H; and X is H or a 1 to 4 carbon alkyl group.

Claim 15

Dependent Claim 26 words

The process of claim 1 or 2 wherein the α,β-ethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid and methacrylic acid.

Claim 16

Dependent Claim 21 words

The process of claim 1 or 2 wherein the emulsion polymerization takes place at a pH of less than about 5.0.

Claim 17

Dependent Claim 222 words

An oxidation resistant composition of matter comprising a polymer derived from the emulsion polymerization of a monomer system comprising (A) 20 to 50 parts by weight per hundred parts by weight of total monomer of at least one hindered phenol antioxidant monomer having an addition polymerizable double bond of the formula: Ph--A1--D wherein Ph is a hindered phenol group having at least one branched or cyclic lower alkyl substituent of at least 3 carbon atoms ortho to the hydroxyl group; A1 is --(CH 2 ) k --, --S--, --O--, --CH 2 O--, --CH 2 S--, where k is 1 or 2; and D is an acyclic substituent of the formula: --(CR'.sub.2).sub.m --A2--(CR'.sub.2).sub.n --A3--(CR'.sub.2).sub.p --A4--(CR'.sub.2).sub.q --A5--E wherein each A2, A3, A4 and A5 is independently selected from the group consisting of a thioether, ether, carboxylic acid ester, thioester, carboxylic acid amide, urethane-type linkage and nothing; m, n, p, and q are independently integers of zero to 4, but where A1 is --O-- or --S--, m is not zero; each R' is independently H or a (substituted) alkyl group; and E is a group having addition polymerizable unsaturation, and (b) at least 15 to 60 parts by weight of at least one 3 to 8 carbon α,β-ethylenically unsaturated carboxylic acid monomer, said monomer system having been polymerized at a pH lower than about 5.0.

Claim 18

Dependent Claim 222 words

An oxidation resistant composition of matter comprising a polymer derived from the emulsion polymerization of a monomer system comprising (A) 20 to 50 parts by weight per hundred parts by weight of total monomer of at least one hindered phenol antioxidant monomer having an addition polymerizable double bond of the formula: Ph--A1--D wherein Ph is a hindered phenol group having at least one branched or cyclic lower alkyl substituent of at least 3 carbon atoms ortho to the hydroxyl group; A1 is --(CH 2 ) k --, --S--, --O--, --CH 2 O--, --CH 2 S--, where k is 1 or 2; and D is an acyclic substituent of the formula: --(CR'.sub.2).sub.m --A2--(CR'.sub.2).sub.n --A3--(CR'.sub.2).sub.p --A4--(CR'.sub.2).sub.q --A5--E wherein each A2, A3, A4 and A5 is independently selected from the group consisting of a thioether, ether, carboxylic acid ester, thioester, carboxylic acid amide, urethane-type linkage and nothing; m, n, p, and q are independently integers of zero to 4, but where A1 is --O-- or --S--, m is not zero; each R' is independently H or a (substituted) alkyl group; and E is a group having addition polymerizable unsaturation, and (b) at least 15 to 60 parts by weight of at least one 3 to 8 carbon α,β-ethylenically unsaturated carboxylic acid monomer, said monomer system having been polymerized at a pH lower than about 5.0.

Claim 19

Dependent Claim 30 words

The composition of claim 16 wherein there are at least 25 parts by weight per hundred parts by weight of total monomer of at least one unsaturated carboxylic acid monomer.

Claim 20

Dependent Claim 38 words

The composition of claims 16 or 22 wherein Ph is ##STR4## wherein R 2 is an alkyl group; R 3 is a hydrogen or alkyl group such that the hydroxyl group is sufficiently hindered to have antioxidant function.

Claim 21

Dependent Claim 12 words

The composition of claim 18 wherein Ph is a 2,6-di-tert-butyl phenol group.

Claim 22

Dependent Claim 17 words

The composition of claim 16, or 17 wherein A1 is --S-- or --(CH 2 ) 2 --.

Claim 23

Dependent Claim 96 words

The composition of claim 16 wherein E is an alkenyl group of the formula: --R 4 --CR 5 ═CH 2 wherein R 4 is a divalent alkyl group of 1 to 4 carbon atoms or when at least one of A2, A3, A4 or A5 is an ether, thioether, a carboxylic acid ester, a thioester, a carboxylic acid amide or a urethane-type linkage, R 4 may be nothing; and R 5 is chosen from the group consisting of H or alkyl group of 1 to 4 carbon atoms such that the double bond is addition polymerizable.

Claim 24

Dependent Claim 15 words

The composition of claim 16 wherein A1 is --S-- or --(CH 2 ) 2 --.

Claim 25

Dependent Claim 24 words

The composition of claim 16 wherein at least two of A2, A3, A4, A5 are carboxylic acid ester, thioester, carboxylic amide, or urethane-type linkages.

Claim 26

Dependent Claim 11 words

The composition of claim 23 wherein A3 is a urethane-type linkage.

Claim 27

Dependent Claim 23 words

The composition of claim 24 wherein A2 and A4 are independently chosen from the group consisting of carboxylic amides, carboxylic esters and nothing.

Claim 28

Dependent Claim 21 words

The composition of claim 25 wherein A1 is --S-- and m is 2 or A1 is --(CH 2 ) 2 --.

Claim 29

Dependent Claim 24 words

The composition of claim 16 or 17 wherein the hindered phenol antioxidant monomer having an additional polymerizable double bond is 2-(((2-(3-((3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl) thio)-1-oxopropoxy)ethoxy)carbonyl)amino)ethyl 2-methyl 2-propenoate.

Claim 30

Dependent Claim 74 words

The composition of claim 16 or 17 wherein the α,β-ethylenically unsaturated carboxylic acid monomer is of the formula: RCH═CR'--COOH wherein R is H and R' is H or a 1 to 4 carbon alkyl group, or --CH 2 COOX; or R is --CH 2 COOX and R' is H or --CH 2 COOX; or R is --CH 3 and R' is H; and X is H or a 1 to 4 carbon alkyl group.

Claim 31

Dependent Claim 26 words

The composition of claim 16 or 17 wherein the α,β-ethylenically unsaturated carboxylic acid monomer is selected from the group consisting of acrylic acid and methacrylic acid.

Claim 32

Dependent Claim 32 words

The process of claim 1 wherein the urethane-type linkage is formed by reaction of an isocyanate with a compound selected from the group consisting of amines, alcohols, thiols, carboxylic acids and carboxamides.

Claim 33

Dependent Claim 32 words

The process of claim 16 wherein the urethane-type linkage is formed by reaction of an isocyanate with a compound selected from the group consisting of amines, alcohols, thiols, carboxylic acids and carboxamides.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1990-08-31	1991-03-02	1991-09-01	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1994-08-31	1995-03-02	1995-09-01	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	1998-08-31	1999-03-02	1999-09-01	$7700.00	Window Closed / Lapsed

Copolymers containing high concentrations of phenol antioxidant units

Abstract

Inventors

Bibliographic Details

Claims Analysis

References Cited (Backward Citations)

USPTO Annuity & Maintenance Windows

Assigned Categories & Tags

Assign Category Tag