US4417012A
Expired / Lapsed
US
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Organic thiosulphates and thiosulphonates useful as stabilising agents for rubber vulcanisates
Assignee: Flexsys NV SA
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Filing: 1982-06-30
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Granted: 1983-11-22
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Expires: 2002-06-30
Abstract
Abstract Additives for rubber compositions, giving vulcanisates having improved retention of optimum physical properties, are compounds containing two or more groups of the formula -S-SO2R linked by an organic bridging group, or polymers containing two or more groups of the formula -S-SO2R attached to an organic polymer chain, where R represents (a) a radical OM where M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a nitrogenous base, or the equivalent of a multivalent ion derived by the addition of two or more protons to a nitrogenous base, or (b) an organic radical selected from aliphatic, cycloaliphatic, aromatic and heterocyclic radicals, and radicals which are combinations of any two or more such radicals.
Inventors
- 👤 Philippe G. Moniotte
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 01:35
CPC Classifications
C; C08; C08K; C08K5/00; C08K5/36; C08K5/41; C07; C07C; C07C381/00; C07C381/02; C08K5/42
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
167 words
A vulcanisable rubber composition comprising a diene rubber, sulphur and vulcanisation accelerator, characterised in that the composition also comprises a stabilizer material which is a compound having the formula ##STR34## where X' represents an alkylene radical or a radical comprising two or more alkylene units, pairs of such units being linked through an oxygen or sulphur atom, rhrough a group --SO 2 --, --NH--, --NH 2 + --, --N(C 1-16 alkyl)- or --COO--, or through an arylene or cycloalkylene radical, X is the trivalent or tetravalent analogue of X1 and in addition may contain one or more Si groups to link pairs of alkylene radicals, n' has an integral value of at least 1, n" has the value 3 or 4, and M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a nitrogenous base, or the equivalent of a multivalent ion derived by the addition of two or more protons to a nitrogenous base.
Claim 2
Dependent Claim
167 words
A vulcanisable rubber composition comprising a diene rubber, sulphur and vulcanisation accelerator, characterised in that the composition also comprises a stabilizer material which is a compound having the formula ##STR34## where X' represents an alkylene radical or a radical comprising two or more alkylene units, pairs of such units being linked through an oxygen or sulphur atom, rhrough a group --SO 2 --, --NH--, --NH 2 + --, --N(C 1-16 alkyl)- or --COO--, or through an arylene or cycloalkylene radical, X is the trivalent or tetravalent analogue of X1 and in addition may contain one or more Si groups to link pairs of alkylene radicals, n' has an integral value of at least 1, n" has the value 3 or 4, and M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a nitrogenous base, or the equivalent of a multivalent ion derived by the addition of two or more protons to a nitrogenous base.
Claim 3
Dependent Claim
26 words
A composition according to claim 1 wherein, in a stabiliser compound, each group --S--SO 3 M is attached to a primary carbon of a bridging group.
Claim 4
Dependent Claim
17 words
A composition according to claim 1 wherein the stabiliser material is a compound having the formula I.
Claim 5
Dependent Claim
17 words
A composition according to claim 1 wherein the stabiliser material is a compound having the formula II.
Claim 6
Dependent Claim
88 words
A composition according to claim 1 wherein X represents a C 2 or a C 5-16 alkylene radical or a radical having the formula ##STR35## wherein each a independently represents an integer of from 3 to 8, b represents an integer of from 1 to 4, c represents an integer of from 3 to 12, Y represents a group --(CH 2 ) c -- or a group --(CH 2 CH 2 O) d CH 2 CH 2 -- where d represents an integer of from 1 to 5.
Claim 7
Dependent Claim
34 words
A composition according to claim 1 in which M represents an alkali metal or an equivalent of magnesium, calcium, barium, zinc, cobalt or nickel, and the stabiliser material may also contain water of crystallisation.
Claim 8
Dependent Claim
11 words
A composition according to claim 6 in which M represents sodium.
Claim 9
Dependent Claim
84 words
A composition according to claim 1 in which M represents an ammonium ion or an ion R.sup.2 NH.sub.3.sup.+, R.sup.2 R.sup.3 NH.sub.2.sup.+ or R.sup.2 R.sup.3 R.sup.4 NH.sup.+ where each of R 2 , R 3 and R 4 independently represents a C 1-20 alkyl group, a C 5-9 cycloalkyl or alkylcyloalkyl group, a benzyl group, a phenyl group or a substituted phenyl group, provided that not more than one of R 2 , R 3 and R 4 is a phenyl or substituted phenyl group.
Claim 10
Dependent Claim
62 words
A composition according to claim 8 in which M represents an ion R 2 R 3 NH + where one of R 2 and R 3 is a C 4-12 tert-alkyl group and the other is a benzyl group; or where one of R 2 is a C 3-12 sec-alkyl group or a cyclohexyl group and the other is a 4-phenylaminophenyl group.
Claim 11
Dependent Claim
79 words
A composition according to claim 1 in which M represents a guanidinium or substituted guanidinium ion of the formula ##STR36## or a substituted isothiouronium ion of the formula ##STR37## where each R 2 independently represents hydrogen, a C 1-20 alkyl group, a C 5-9 cycloalkyl or alkylcycloalkyl group, a benzyl group, a phenyl group or a substituted phenyl group, and R 5 represents a C 1-20 alkyl group, a C 5-9 cycloalkyl or alkylcycloalkyl group or a benzyl group.
Claim 12
Dependent Claim
15 words
A composition according to claim 1 in which M represents an optionally ring-substituted 1,2-dihydroquinolinium ion.
Claim 13
Dependent Claim
85 words
A composition according to claim 1 in which M represents the equivalent of a divalent ion of the formula ##STR38## where A represents a radical --(CH 2 ) c -- where c has a value from 2 to 20 or a phenylene radical, and each R 2 independently represents a C 1-20 alkyl group, a C 5-9 cycloalkyl or alkylcycloalkyl group, a benzyl group or a phenyl or substituted phenyl group, provided that neither R 2 is phenyl or substituted phenyl when A represents phenylene.
Claim 14
Dependent Claim
23 words
A composition according to claim 12 in which A represents a para-phenylene radical and each R 2 represents a C 3-12 sec-alkyl group.
Claim 15
Dependent Claim
29 words
A composition according to claim 1 in which M represents the equivalent of a divalent ion of the formula ##STR39## where c is an integer from 2 to 20.
Claim 16
Dependent Claim
50 words
A composition according to claim 2 wherein the stabiliser material is a compound having the formula MOO.sub.2 S--S--X'--S--SO.sub.2 OM where X' represents a C 5-16 alkylene radical and M represents sodium or an equivalent of magnesium, calcium, barium, zinc, cobalt or nickel, which compound may also contain water of crystallisation.
Claim 17
Dependent Claim
38 words
A composition according to claim 15 wherein X' in the formula represents a C 5-10 alkylene radical and M represents sodium or an equivalent of zinc, cobalt or nickel, and the compound may also contain water of crystallisation.
Claim 18
Dependent Claim
19 words
A composition according to claim 16 wherein the stabiliser compound is hexamethylene bis(thiosulphate) sodium salt or a hydrate thereof.
Claim 19
Dependent Claim
42 words
A composition according to claim 2 wherein the stabiliser material is a compound having the formula MOO.sub.2 S--S--X'--S--SO.sub.2 OM where X represents a C 5-16 alkylene radical and M represents an N-tertiary(C 4-12 alkyl)-N-benzylammonium ion or an N(4-phenylaminophenyl)-N-(C 3-12 sec-alkyl) ammonium ion.
Claim 20
Dependent Claim
67 words
A composition according to claim 2 wherein the stabiliser material is a compound having the formula MOO.sub.2 S--S--X'--S--SO.sub.2 OM where X' represents a radical --(CH.sub.2).sub.C --COO(CH.sub.2).sub.a -- where a represents an integer from 3 to 8, c represents an integer from 3 to 12, and M represents sodium or an equivalent of magnesium, calcium, barium, zinc, cobalt or nickel, which compound may also contain water or crystallisation.
Claim 21
Dependent Claim
26 words
A composition according to claim 19 wherein the stabiliser compound is NaO.sub.3 S.sub.2 (CH.sub.2).sub.3 COO(CH.sub.2).sub.4 S.sub.2 O.sub.3 Na or NaO.sub.3 S.sub.2 (CH.sub.2).sub.5 COO(CH.sub.2).sub.4 S.sub.2 O.sub.3 Na.
Claim 22
Dependent Claim
28 words
A composition according to claim 1 wherein the diene rubber is natural or synthetic cis-polyisoprene or a blend of rubbers containing at least 25% by weight of cis-polyisoprene.
Claim 23
Dependent Claim
29 words
A composition according to claim 1 in which the amount of the stabiliser compound is from 1 to 5 parts by weight per 100 parts by weight of rubber.
Claim 24
Dependent Claim
14 words
A composition according to claim 1 in which the vulcanisation accelerator is a benzothiazole-2-sulphenamide.
Claim 25
Dependent Claim
17 words
A vulcanisate that has been obtained by heating a composition according to claim 1 at vulcanisation temperature.
Claim 26
Independent Claim
185 words
A method of preparing a rubber vulcanisate having improved physical properties, which comprises incorporating sulphur and vulcanisation accelerator into a diene rubber together with an vulcanisate-stabilising amount of a stabiliser material which is a compound having the formula ##STR40## where X' represents an alkylene radical or a radical comprising two or more alkylene units, pairs of such units being linked through an oxygen or sulphur atom, through a group --SO 2 --, --NH--, --NH 2 + --, --N(C 1-16 alkyl)- or --COO--, or through an arylene or cycloalkylene radical, X is the trivalent or tetravalent analogue of X' and in addition may contain one or more Si groups to link pairs of alkylene radicals, n' has an integral value of at least 1, n" has the value 3 or 4, and M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a nitrogenous base, or the equivalent of a multivalent ion derived by the addition of two or more protons to a nitrogenous base, and heating the mixture thus obtained at vulcanisation temperature.
Claim 27
Independent Claim
185 words
A method of preparing a rubber vulcanisate having improved physical properties, which comprises incorporating sulphur and vulcanisation accelerator into a diene rubber together with an vulcanisate-stabilising amount of a stabiliser material which is a compound having the formula ##STR40## where X' represents an alkylene radical or a radical comprising two or more alkylene units, pairs of such units being linked through an oxygen or sulphur atom, through a group --SO 2 --, --NH--, --NH 2 + --, --N(C 1-16 alkyl)- or --COO--, or through an arylene or cycloalkylene radical, X is the trivalent or tetravalent analogue of X' and in addition may contain one or more Si groups to link pairs of alkylene radicals, n' has an integral value of at least 1, n" has the value 3 or 4, and M is a monovalent metal, the equivalent of a multivalent metal, a monovalent ion derived by the addition of a proton to a nitrogenous base, or the equivalent of a multivalent ion derived by the addition of two or more protons to a nitrogenous base, and heating the mixture thus obtained at vulcanisation temperature.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-11-21 | 1987-05-23 | 1987-11-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-11-21 | 1991-05-23 | 1991-11-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-11-21 | 1995-05-23 | 1995-11-22 | $7700.00 | Window Closed / Lapsed |