US4433114A
Expired / Lapsed
US
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Diene rubber and method and composition for rubber treatment
Assignee: Monsanto Co
•
Filing: 1982-05-20
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Granted: 1984-02-21
•
Expires: 2002-05-20
Abstract
Abstract Improved tack, green strength or non-black filler interaction capability are realized in a treated diene rubber. The method of treating diene rubber to achieve the improvements is shown, together with a composition in which maleamic acid or derivatives of maleamic acid are combined with sulfur or an organic sulfur compound capable of generating a thiyl radical.
Inventors
- 👤 Aubert Y. Coran
- 👤 Chester D. Trivette, Jr.
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 07:31
CPC Classifications
C; C08; C08C; C08C19/00; C08C19/28; C08K; C08K5/00; C08K5/16; C08K5/20
Claims Analysis
Total Claims: 64
Claim 1
Independent Claim
206 words
A composition comprising diene rubber treated, in the presence of a modification promoting amount of (A) sulfur or an organic sulfur compound capable of generating thiyl radicals, by (B) a compound of the formula ##STR13## n being an integer of 1-3, wherein R 1 is hydrogen or alkyl of 1-10 carbon atoms and, if n=1, R 2 is selected from hydrogen, alkyl of 1-10 carbon atoms, optionally forming a heterocyclic moiety with the N atom of the formula and R 1 , either with or without an added N or O atom, ##STR14## wherein Y is an oxygen or sulfur atom, x is an integer of 1-12, R 3 is: hydrogen, --COOH, alkoxy of 1-5 carbon atoms or ##STR15## R 4 and R 5 are the same or different selected from: hydrogen, phenyl and alkyl of 1-10 carbon atoms; if n=2, R 2 is selected from phenylene, divalent aliphatic hydrocarbon radicals of 2-20 carbon atoms and ##STR16## and if n=3, R 2 is s-triazinyl or a trivalent aliphatic hydrocarbon of 2-20 carbon atoms, said composition having been treated at a temperature of from 160° to 210° C. for a long enough time to impart to the compositin improved green strength, tack or non-black filler interaction capability.
Claim 2
Dependent Claim
206 words
A composition comprising diene rubber treated, in the presence of a modification promoting amount of (A) sulfur or an organic sulfur compound capable of generating thiyl radicals, by (B) a compound of the formula ##STR13## n being an integer of 1-3, wherein R 1 is hydrogen or alkyl of 1-10 carbon atoms and, if n=1, R 2 is selected from hydrogen, alkyl of 1-10 carbon atoms, optionally forming a heterocyclic moiety with the N atom of the formula and R 1 , either with or without an added N or O atom, ##STR14## wherein Y is an oxygen or sulfur atom, x is an integer of 1-12, R 3 is: hydrogen, --COOH, alkoxy of 1-5 carbon atoms or ##STR15## R 4 and R 5 are the same or different selected from: hydrogen, phenyl and alkyl of 1-10 carbon atoms; if n=2, R 2 is selected from phenylene, divalent aliphatic hydrocarbon radicals of 2-20 carbon atoms and ##STR16## and if n=3, R 2 is s-triazinyl or a trivalent aliphatic hydrocarbon of 2-20 carbon atoms, said composition having been treated at a temperature of from 160° to 210° C. for a long enough time to impart to the compositin improved green strength, tack or non-black filler interaction capability.
Claim 3
Dependent Claim
39 words
The composition of claim 1 wherein the treatment time is from 0.1 to 20 minutes and (A) and (B) are present in amounts of from 0.01-15 and 0.1-20 parts by weight, respectively, per 100 parts diene rubber by weight.
Claim 4
Dependent Claim
38 words
The composition of claim 2 wherein the time is from 0.5 to 15 minutes and (A) and (B) are present in amounts of from 0.02-4 and 0.2-8 parts by weight, respectively, per 100 parts diene rubber by weight.
Claim 5
Dependent Claim
36 words
The composition of claim 3 wherein the time is from 1-10 minutes and (A) and (B) are present in amounts of from 0.05-2.5 and 0.25-5 parts by weight, respectively, per 100 parts diene rubber by weight.
Claim 6
Dependent Claim
11 words
The composition of claim 2 wherein the diene rubber comprises polyisoprene.
Claim 7
Dependent Claim
9 words
The composition of claim 5 wherein (A) is sulfur.
Claim 8
Dependent Claim
17 words
The composition of claim 5 wherein (A) is an organic sulfur compound capable of generating thiyl radicals.
Claim 9
Dependent Claim
130 words
The composition of claim 7 wherein (A) is selected from polymeric polysulfides and compounds of the formula (R 6 S z ) y R 7 , wherein z is an integer of 1-5, y is an integer of from 1-4, R 7 is selected from aliphatic hydrocarbon radicals of 3-18 carbon atoms optionally containing one or more ether or ester linkages and optionally substituted by one or more nitro, amino or carboxyl groups; cycloalkyl of 3-10 carbon atoms; benzyl or phenyl optionally ring-substituted by one or more nitro, amino, carboxyl, or 1-5 carbon-atom alkyl groups; or benzothiazyl, dialkylthiocarbamoyl; alkylamino of 4-12 carbon atoms; morpholino; or dialkylthiophosphoroyl; R 7 having a valence of y; and R 6 is hydrogen or a radical selected from the same group as R 7 .
Claim 10
Dependent Claim
9 words
The composition of claim 8 where (A) is 2,2'-dithiobisbenzothiazole.
Claim 11
Dependent Claim
11 words
The composition of claim 8 wherein (A) is a phenyl mercaptan.
Claim 12
Dependent Claim
9 words
The composition of claim 8 wherein (A) is 2-mercaptobenzothiazole.
Claim 13
Dependent Claim
18 words
The composition of claim 7 wherein n is one, R 1 is hydrogen and R 2 is ##STR17##
Claim 14
Dependent Claim
9 words
The composition of claim 12 wherein Y is oxygen.
Claim 15
Dependent Claim
26 words
The composition of claim 2 wherein the diene rubber comprises polyisoprene, (A) is 2,2'-dithiobisbenzothiazole, n is one, R 1 is hydrogen and R 2 is ##STR18##
Claim 16
Dependent Claim
11 words
The composition of claim 14 wherein the polyisoprene comprises natural rubber.
Claim 17
Dependent Claim
14 words
The composition of claim 14 wherein the diene rubber includes polybutadiene or styrene-butadiene rubber.
Claim 18
Dependent Claim
15 words
The composition of claim 4 wherein the diene rubber comprises polyisoprene and (A) is 2,2'-dithiobisbenzothiazole.
Claim 19
Dependent Claim
10 words
The composition of claim 17 wherein (B) is maleamic acid.
Claim 20
Dependent Claim
18 words
The composition of claim 17 wherein n is one, R 1 is hydrogen and R 2 is ##STR19##
Claim 21
Dependent Claim
11 words
The composition of claim 17 wherein (B) is N-carbamoyl maleamic acid.
Claim 22
Dependent Claim
11 words
The composition of claim 17 wherein (B) is N-carboxymethyl maleamic acid.
Claim 23
Dependent Claim
11 words
The composition of claim 17 wherein (B) is N-carboxyphenyl maleamic acid.
Claim 24
Dependent Claim
10 words
The composition of claim 17 wherein (B) is N,N'-(4,4'-dithiophenyl)bismaleamic acid.
Claim 25
Dependent Claim
13 words
The composition of claim 20 wherein carbon black is present during the treatment.
Claim 26
Dependent Claim
11 words
The composition of claim 20 wherein the polyisoprene comprises natural rubber.
Claim 27
Dependent Claim
14 words
The composition of claim 20 wherein the diene rubber includes polybutadiene or styrene-butadiene rubber.
Claim 28
Dependent Claim
14 words
The composition of claim 20 wherein a non-black filler is present during the treatment.
Claim 29
Dependent Claim
15 words
The composition of claim 27 wherein the filler is clay, talc, calcium carbonate or silica.
Claim 30
Dependent Claim
10 words
The composition of claim 4 wherein the treatment comprises mastication.
Claim 31
Dependent Claim
22 words
The composition of claim 4 additionally incorporating from 10 to 1,000 parts by weight of diene rubber not present during the treatment.
Claim 32
Dependent Claim
5 words
Vulcanized composition of claim 4.
Claim 33
Independent Claim
212 words
A method of treating diene rubber comprising treating the rubber, in the presence of a modification promoting amount of (A) sulfur or an organic sulfur compound capable of generating thiyl radicals, with (B) a compound of the formula: ##STR20## n being an integer of 1-3, wherein R 1 is hydrogen or alkyl of 1-10 carbon atoms and, if n=1, R 2 is selected from hydrogen, alkyl of 1-10 carbon atoms, optionally forming a heterocyclic moiety with the N atom of the formula and R 1 , either with or without an added N or O atom, ##STR21## wherein Y is an oxygen or sulfur atom, x is an integer of 1-12, R 3 is: hydrogen, --COOH, alkoxy of 1-5 carbon atoms or ##STR22## R 4 and R 5 are the same or different selected from: hydrogen, phenyl and alkyl of 1-10 carbon atoms, including cycloalkyl of from 3 to 10 carbon atoms; if n=2, R 2 is selected from phenylene, divalent aliphatic hydrocarbon radicals of 2-20 carbon atoms and ##STR23## and if n=3, R 2 is s-triazinyl or a trivalent aliphatic hydrocarbon of 2-20 carbon atoms, at a temperature of from 160° to 210° C. for sufficient time to impart to the composition improved green strength, tack or non-black filler interaction capability.
Claim 34
Independent Claim
212 words
A method of treating diene rubber comprising treating the rubber, in the presence of a modification promoting amount of (A) sulfur or an organic sulfur compound capable of generating thiyl radicals, with (B) a compound of the formula: ##STR20## n being an integer of 1-3, wherein R 1 is hydrogen or alkyl of 1-10 carbon atoms and, if n=1, R 2 is selected from hydrogen, alkyl of 1-10 carbon atoms, optionally forming a heterocyclic moiety with the N atom of the formula and R 1 , either with or without an added N or O atom, ##STR21## wherein Y is an oxygen or sulfur atom, x is an integer of 1-12, R 3 is: hydrogen, --COOH, alkoxy of 1-5 carbon atoms or ##STR22## R 4 and R 5 are the same or different selected from: hydrogen, phenyl and alkyl of 1-10 carbon atoms, including cycloalkyl of from 3 to 10 carbon atoms; if n=2, R 2 is selected from phenylene, divalent aliphatic hydrocarbon radicals of 2-20 carbon atoms and ##STR23## and if n=3, R 2 is s-triazinyl or a trivalent aliphatic hydrocarbon of 2-20 carbon atoms, at a temperature of from 160° to 210° C. for sufficient time to impart to the composition improved green strength, tack or non-black filler interaction capability.
Claim 35
Dependent Claim
39 words
The method of claim 32 wherein the treatment time is from 0.1 to 20 minutes and (A) and (B) are present in amounts of from 0.01-15 and 0.1-20 parts by weight, respectively, per 100 parts diene rubber by weight.
Claim 36
Dependent Claim
38 words
The method of claim 33 wherein the time is from 0.5 to 15 minutes and (A) and (B) are present in amounts of from 0.02-4 and 0.2-8 parts by weight, respectively, per 100 parts diene rubber by weight.
Claim 37
Dependent Claim
36 words
The method of claim 34 wherein the time is from 1-10 minutes and (A) and (B) are present in amounts of from 0.05-2.5 and 0.25-5 parts by weight, respectively, per 100 parts diene rubber by weight.
Claim 38
Dependent Claim
11 words
The method of claim 33 wherein the diene rubber comprises polyisoprene.
Claim 39
Dependent Claim
9 words
The method of claim 36 wherein (A) is sulfur.
Claim 40
Dependent Claim
17 words
The method of claim 33 wherein (A) is an organic sulfur compound capable of generating thiyl radicals.
Claim 41
Dependent Claim
130 words
The method of claim 38 wherein (A) is selected from polymeric polysulfides and compounds of the formula (R 6 S z ) y R 7 , wherein z is an integer of 1-5, y is an integer of from 1-4, R 7 is selected from aliphatic hydrocarbon radicals of 3--18 carbon atoms optionally containing one or more ether or ester linkages and optionally substituted by one or more nitro, amino or carboxyl groups; cycloalkyl of 3-10 carbon atoms; benzyl or phenyl optionally ring-substituted by one or more nitro, amino, carboxyl, or 1-5 carbon-atom alkyl groups; or benzothiazyl; dialkylthiocarbamoyl; alkylamino of 4-12 carbon atoms; morpholino; or dialkylthiophosphoroyl; R 7 having a valence of y; and R 6 is hydrogen or a radical selected from the same group as R 7 .
Claim 42
Dependent Claim
9 words
The method of claim 38 wherein (A) is 2,2'-dithiobisbenzothiazole.
Claim 43
Dependent Claim
11 words
The method of claim 38 wherein (A) is a phenyl mercaptan.
Claim 44
Dependent Claim
9 words
The method of claim 38 wherein (A) is 2-mercaptobenzothiazole.
Claim 45
Dependent Claim
18 words
The method of claim 40 wherein n is one, R 1 is hydrogen and R 2 is ##STR24##
Claim 46
Dependent Claim
9 words
The method of claim 43 wherein Y is oxygen.
Claim 47
Dependent Claim
26 words
The method of claim 34 wherein the diene rubber comprises polyisoprene, (A) is 2,2'-dithiobisbenzothiazole, n is one, R 1 is hydrogen and R 2 is ##STR25##
Claim 48
Dependent Claim
11 words
The method of claim 45 wherein the polyisoprene comprises natural rubber.
Claim 49
Dependent Claim
14 words
The method of claim 45 wherein the diene rubber includes polybutadiene or styrene-butadiene rubber.
Claim 50
Dependent Claim
15 words
The method of claim 35 wherein the diene rubber comprises polyisoprene and (A) is 2,2'-dithiobisbenzothiazole.
Claim 51
Dependent Claim
10 words
The method of claim 48 wherein (B) is maleamic acid.
Claim 52
Dependent Claim
17 words
The method of claim 48 wherein n is one, R is hydrogen and R 2 is ##STR26##
Claim 53
Dependent Claim
11 words
The method of claim 50 wherein (B) is N-carbamoyl maleamic acid.
Claim 54
Dependent Claim
11 words
The method of claim 48 wherein (B) is N-carboxymethyl maleamic acid.
Claim 55
Dependent Claim
11 words
The method of claim 48 wherein (B) is N-carboxyphenyl maleamic acid.
Claim 56
Dependent Claim
10 words
The method of claim 48 wherein (B) is N,N'-(4,4'-dithiophenyl)bismaleamic acid.
Claim 57
Dependent Claim
13 words
The method of claim 51 wherein carbon black is present during the treatment.
Claim 58
Dependent Claim
11 words
The method of claim 55 wherein the polyisoprene comprises natural rubber.
Claim 59
Dependent Claim
14 words
The method of claim 55 wherein the diene rubber includes polybutadiene or styrene-butadiene rubber.
Claim 60
Dependent Claim
14 words
The method of claim 51 wherein a non-black filler is present during the treatment.
Claim 61
Dependent Claim
15 words
The method of claim 58 wherein the filler is clay, talc, calcium carbonate or silica.
Claim 62
Dependent Claim
10 words
The method of claim 35 wherein the treatment comprises mastication.
Claim 63
Dependent Claim
22 words
The method of claim 35 additionally incorporating from 10 to 1,000 parts by weight of diene rubber not present during the treatment.
Claim 64
Dependent Claim
14 words
The method of claim 35 and the additional step of vulcanizing the diene rubber.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-02-20 | 1987-08-22 | 1988-02-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-02-20 | 1991-08-22 | 1992-02-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-02-20 | 1995-08-22 | 1996-02-21 | $7700.00 | Window Closed / Lapsed |