EP0441485A2
Expired / Lapsed
EP
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Vulcanizable liquid copolymer
Assignee: Mobil Oil AS
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Filing: 1991-01-16
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Granted: —
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Expires: 2011-01-16
Abstract
Abstract There is disclosed a linear block copolymer comprising at least one triblock I-B-I, wherein I is a block of at least one polymerized conjugated diene of at least five (5) carbon atoms, such as isoprene, and B is a block of a polymer of at least one conjugated diene, different from that used to polymerize the block I, of at least four (4) carbon atoms, such as 1,3-butadiene. The B block is selectively hydrogenated, while each of the I blocks is hydrogenated and therefore retains a sufficient amount of its original unsaturation to vulcanize the copolymer. There is also disclosed an alternative linear block copolymer containing at least one triblock of the first polymer block made from a minor proportion of at least one aryl-substituted olefin, such as styrene, and a major proportion of at least one conjugated diene used to polymerize the block I, the second middle polymer block of at least one diene used to polymerize the block B, and the third polymer block which is the same as the first polymer block. In this alternative copolymer, the middle block is also selectively hydrogenated, thereby leaving the terminal polymer blocks with a sufficient amount of their original unsaturation to vulcanize the copolymer. The polymers can be crosslinked or functionalized through the terminal blocks containing the vinyl unsaturation. There are also disclosed random linear and star-branched block and random copolymers made from the same monomers as the linear block copolymers. Also disclosed are methods of producing the polymers and selectively hydrogenating the aforementioned polymerized dienes.
Inventors
- 👤 Thomas Smith Coolbaugh
- 👤 Frederick Charles Loveless
- 👤 Demetreos Nestor Matthews
- 👤 Leslie Robert Rudnick
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-28 16:36
CPC Classifications
C; C08; C08F; C08F297/00; C08F297/02; C08F293/00; C08F236/00; C08F236/02; C08F236/04; C08F8/00; C08F8/04; C08F8/08
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
89 words
A liquid, vulcanisable copolymer comprising at least two, copolymerised monomers which: (i) when the copolymerised monomers are disposed as an at least tri-, or as a star-branched, block copolymer, has a middle block which is selectively and substantially completely hydrogenatable while each terminal block, which may be the same or different, contains sufficient unsaturation for vulcanisation; or (ii) when the copolymerised monomers are disposed as a random (including star-branched random) copolymer, has a backbone which is selectively and substantially completely hydrogenatable while pendant groups contain sufficient unsaturation for vulcanisation.
Claim 2
Dependent Claim
315 words
A liquid block copolymer according to claim 1 which comprises at least three alternating blocks of the formula: (I) x -(B) y -(I) x′ wherein: (I) represents a block comprising at least one polymerized conjugated diene I having at least five (5) carbon atoms and the formula: in which: R¹ to R⁶, which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that: (a) at least one of R¹ to R⁶ represents a hydrocarbyl group; and (b) the structure of the residual double bond in the polymerized block has the formula: in which: R I , R II , R III and R IV , which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that both R I and R II represent hydrocarbyl groups and/or both R III and R IV represent hydrocarbyl groups; (B) represents a block comprising at least one conjugated diene B, different from the diene I, having at least four (4) carbon atoms and the formula: in which: R⁷ to R¹², which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that the structure of the residual double bond in the polymerized block has the formula: in which: R a , R b , R c and R d , which may be the same or different, each represents a hydrogen atom or a hydrocarbyl group, provided that: (c) one of R a or R b represents a hydrogen atom; (d) one of R c or R d represents a hydrogen atom; and (e) at least one R a , R b , R c or R d represents a hydrocarbyl group; x and x′, which may be the same or different, each represents a number of at least 1, and y represents a number of at least 25.
Claim 3
Dependent Claim
95 words
A liquid star-branched block polymer according to claim 1 of the formula: [P] i Q in which: P comprises blocks of the formula: (I) x and (B) y wherein: I is defined in claim 2; x is defined in claim 2; the values for each block being the same or different; B is defined in claim 2; y is defined in claim 2, the values for each block being the same or different, each free end of P being an (I) block; Q represents a coupling moiety; and i represents the number of star branches.
Claim 4
Dependent Claim
39 words
A liquid random copolymer according to claim 1 which comprises at least one polymerised conjugated diene I and at least one polymerised conjugated diene B wherein: I is defined in claim 2; and B is defined in claim 2.
Claim 5
Dependent Claim
40 words
A liquid star-branched random copolymer according to claim 1 which comprises at least one polymerized conjugated diene I and at least one polymerized conjugated diene B, wherein: I is defined in claim 2; and B is defined in claim 2.
Claim 6
Dependent Claim
33 words
A liquid copolymer according to any preceding claim which comprises at least one polymerised arylsubstituted olefin and which, in a block copolymer, may be contained, randomly or block copolymerised, in an (I) block.
Claim 7
Dependent Claim
42 words
A liquid copolymer according to claim 6 wherein the aryl-substituted olefin has the formula: wherein Ar represents a phenyl, alkyl-substituted phenyl, naphthyl, or alkyl-substituted naphthyl group; and R e represents a hydrogen atom or a methyl, ethyl, propyl, butyl or aryl group.
Claim 8
Dependent Claim
37 words
A liquid block copolymer according to claim 1, 2, 3, 6 or wherein at least one of the (I) blocks, which may be the same or different, comprises at least 30 molar percent of the arylsubstituted olefin.
Claim 9
Dependent Claim
25 words
A liquid block copolymer according to claim 6, 7 or 8 wherein the (B) block(s) comprise from 96 to 40 weight percent of the copolymer.
Claim 10
Dependent Claim
25 words
A liquid random copolymer according to claim 1, 4, 5, 6 or 7 which comprises from 0.3 to 15 molar percent of the aryl-substituted olefin.
Claim 11
Dependent Claim
25 words
A liquid random copolymer according to claim 10 which comprises from 1 to 25 molar percent of I wherein I is defined in claim 2.
Claim 12
Dependent Claim
34 words
A liquid random copolymer according to claim 11 which comprises from 1.0 to 10 molar percent of the conjugated diene I, and, correspondingly from 90 to 99 molar percent of the conjugated diene B.
Claim 13
Dependent Claim
16 words
A liquid copolymer according to any preceding claim having a molecular weight of at least 2,000.
Claim 14
Dependent Claim
15 words
A liquid copolymer according to claim 13 having a molecular weight of 5,000 to 10,000.
Claim 15
Dependent Claim
27 words
A liquid block copolymer according to any of claims 1, 2, 3, 6 to 14 wherein x represents 1 to 30 and y represents 30 to 275.
Claim 16
Dependent Claim
33 words
A liquid copolymer according to any preceding claim wherein the diene I comprises isoprene, 2,3-dimethyl-butadiene, 2-methyl-1,3-pentadiene, myrcene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2-phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene, or a mixture thereof.
Claim 17
Dependent Claim
13 words
A liquid copolymer according to claim 16 wherein the diene I comprises isoprene.
Claim 18
Dependent Claim
32 words
A liquid copolymer according to any preceding claim wherein the diene B comprises 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4-nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, 3,5-decadiene, or a mixture thereof.
Claim 19
Dependent Claim
13 words
A liquid copolymer according to claim 18 wherein the diene B comprises 1,3-butadiene.
Claim 20
Dependent Claim
35 words
A liquid copolymer according to any preceding claim wherein the or each of the (B) blocks, or the polymerised conjugated diene B, prior to the selective hydrogenation reaction, is a mixture of 1,4- and 1,2-units.
Claim 21
Dependent Claim
36 words
A liquid copolymer according to claim 20 wherein the or each of the (B) blocks, or the polymerised conjugated diene B, prior to the selective hydrogenation reaction, has at least 25 weight percent of the 1,2-units.
Claim 22
Dependent Claim
50 words
A liquid polymer according to any preceding claim which has been selectively hydrogenated so that the or each of the blocks (B), or the polymerised conjugated diene B, has been substantially completely hydrogenated while each of the blocks (I), or the polymerized conjugated diene I, retains sufficient unsaturation for vulcanisation.
Claim 23
Dependent Claim
39 words
A liquid copolymer according to claim 22 wherein, after the hydrogenation reaction, the Iodine Number for the blocks (I), or the polymerised conjugated diene I, is from 20 to 100% of the Iodine Number prior to the hydrogenation reaction.
Claim 24
Dependent Claim
39 words
A liquid copolymer according to claim 22 or 23 wherein, after the hydrogenation reaction, the Iodine Number for the blocks (B), or the polymerised diene B, is 0 to 10% of the Iodine Number prior to the hydrogenation reaction.
Claim 25
Dependent Claim
12 words
A halogenated derivative of the copolymer of any of the preceding claims.
Claim 26
Dependent Claim
12 words
A maleated derivative of the copolymer of any of the preceding claims.
Claim 27
Dependent Claim
70 words
A process for the production of a liquid block copolymer according to claim 1, 2, or 3, which process comprises: polymerising the conjugated diene I, under anionic polymerisation conditions, to form (I); adding the conjugated diene B to the reaction mixture and polymerising it to block (B); and repeating the sequential addition of monomer feed to provide the liquid block copolymer, wherein: I and B are defined in claim 2.
Claim 28
Dependent Claim
107 words
A process for the production of a liquid block copolymer according to claim 1, 2 or 3, which process comprises: polymerising the conjugated diene I, under anionic polymerisation conditions, to form (I); separately polymerising the conjugated diene, under anionic polymerisation conditions, to form (I)¹; adding the conjugated diene B to the reaction mixture containing (I)¹ and polymerising it to (B) thereby forming diblock (B) y -(I) x′ ; and subsequently coupling the or each block (I) to the diblock (B) y -(I) x′ to provide the liquid block copolymer (I) x -(B) y -(I) x′ , wherein: I,x, x′, B and y are defined in claim 2.
Claim 29
Dependent Claim
30 words
A process according to claim 28 wherein the coupling agent comprises an ester, carbon dioxide, iodine, a dihaloalkane, silicon tetrachloride, an alkyltrichlorosilane, a dialkyldichlorosilane, a Lewis base or divinyl benzene.
Claim 30
Dependent Claim
40 words
A process for the production of a liquid random copolymer according to claim 1, 4 or 5, which process comprises: polymerising the conjugated diene I with the conjugated diene B under anionic polymerisation conditions to provide the liquid random copolymer.
Claim 31
Dependent Claim
24 words
A process according to claim 30 wherein the polymerised conjugated diene B comprises from 75 to 90 molar percent of the liquid random copolymer.
Claim 32
Dependent Claim
27 words
A process according to any of claims 27 to 31 wherein at least one monomer feed comprises an aryl-substituted olefin as defined in claims 6 to 8.
Claim 33
Dependent Claim
51 words
A process according to any claims 27 to 32 wherein the liquid polymer is selectively hydrogenated so that each of the blocks (B), or the polymerised conjugated diene B, has been substantially completely hydrogenated while each of the blocks (I), or the polymerised conjugated diene I, retains sufficient unsaturation for vulcanisation.
References Cited (Backward Citations)
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