US4229333A
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US
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Cross-linkable rubber mixtures containing silicate fillers and process for cross-linking
Assignee: Evonik Operations GmbH
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Filing: 1979-04-27
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Granted: 1980-10-21
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Expires: 1999-04-27
Abstract
Abstract Sulfur containing organosilicon compounds having the formula: Z--Alk--S.sub.x --Alk--Z in which Z is: ##STR1## where R 1 is alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 8 carbon atoms or phenyl and R 2 is alkoxy of 1 to 4 carbon atoms, cycloalkoxy of 5 to 8 carbon atoms or phenoxy. Alk is a divalent aliphatic hydrocarbon or a cyclic hydrocarbon group containing 1 to 8 carbon atoms and x is a number from 2 to 6 are used as cross-linking agents in rubber mixtures containing conventional vulcanization accelerators and a siliceous filler, and optionally carbon black. No sulfur is present.
Inventors
- 👤 Siegfried Wolff
- 👤 Ewe H. Tan
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 08:54
CPC Classifications
C; C08; C08K; C08K5/00; C08K5/54; C08K5/548; C08K3/00; C08K3/34
Claims Analysis
Total Claims: 85
Claim 1
Independent Claim
203 words
An elemental sulfur free cross-linkable rubber composition comprising a rubber capable of being cross-linked by sulfur, a siliceous filler in an amount of 1 to 300 parts per 100 parts by weight of the rubber, carbon black in an amount of 0 to 300 parts by 100 parts by weight of the rubber, the total of siliceous filler and carbon black not exceeding about 300 parts per 100 parts by weight of the rubber, a vulcanization accelerator for a sulfur cross-linkable rubber in an amount of 0.02 to 10 parts per 100 parts by weight of the rubber and a sulfur containing organosilicon compound having the formula: Z--Alk--S.sub.x --Alk--Z in which Z is: ##STR7## where R 1 is alkyl of 1 to 4 carbon atoms, cycloaklyl of 5 to 8 carbon atoms or phenyl, R 2 is alkoxy of 1 to 4 carbon atoms, cycloalkoxy of 5 to 8 carbon atoms or phenoxy, Alk is a divalent aliphatic hydrocarbon or a cyclic hydrocarbon group containing 1 to 8 carbon atoms and x is a number from 2 to 6 in an amount of 0.2 to 40 parts per 100 parts of siliceous filler, said sulfur containing organosilane compound being the sole vulcanizing agent.
Claim 2
Dependent Claim
203 words
An elemental sulfur free cross-linkable rubber composition comprising a rubber capable of being cross-linked by sulfur, a siliceous filler in an amount of 1 to 300 parts per 100 parts by weight of the rubber, carbon black in an amount of 0 to 300 parts by 100 parts by weight of the rubber, the total of siliceous filler and carbon black not exceeding about 300 parts per 100 parts by weight of the rubber, a vulcanization accelerator for a sulfur cross-linkable rubber in an amount of 0.02 to 10 parts per 100 parts by weight of the rubber and a sulfur containing organosilicon compound having the formula: Z--Alk--S.sub.x --Alk--Z in which Z is: ##STR7## where R 1 is alkyl of 1 to 4 carbon atoms, cycloaklyl of 5 to 8 carbon atoms or phenyl, R 2 is alkoxy of 1 to 4 carbon atoms, cycloalkoxy of 5 to 8 carbon atoms or phenoxy, Alk is a divalent aliphatic hydrocarbon or a cyclic hydrocarbon group containing 1 to 8 carbon atoms and x is a number from 2 to 6 in an amount of 0.2 to 40 parts per 100 parts of siliceous filler, said sulfur containing organosilane compound being the sole vulcanizing agent.
Claim 3
Dependent Claim
11 words
The composition of claim 1 wherein the siliceous filler is silica.
Claim 4
Dependent Claim
17 words
The composition of claim 2 wherein the siliceous filler is finely divided precipitated silica or pyrogenic silica.
Claim 5
Dependent Claim
12 words
The composition of claim 1 wherein Z is (1), (2) or (3).
Claim 6
Dependent Claim
11 words
The composition of claim 1 where n is 2 to 4.
Claim 7
Dependent Claim
11 words
The composition of claim 5 where n is 3 to 4.
Claim 8
Dependent Claim
18 words
The composition of claim 1 where Alk is a saturated aliphatic hydrocarbon of 1 to 8 carbon atoms.
Claim 9
Dependent Claim
13 words
The composition of claim 7 where alk has 2 to 3 carbon atoms.
Claim 10
Dependent Claim
9 words
The composition of claim 8 wherein Z is (3).
Claim 11
Dependent Claim
12 words
The composition of claim 9 wherein all R 2 groups are ethoxy.
Claim 12
Dependent Claim
34 words
The composition of claim 1 wherein there are 10 to 150 parts of siliceous filler per 100 parts of rubber and 1 to 20 parts of organosilicon compound per 100 parts of siliceous filler.
Claim 13
Dependent Claim
15 words
The composition of claim 1 wherein the polymer is a polymer of a conjugated diene.
Claim 14
Dependent Claim
29 words
The composition of claim 12 wherein the polymer is natural rubber, polybutadiene, polyisoprene, butadienestyrene copolymer, butadiene-acrylonitrile copolymer, polychlorobutadiene, butyl rubber, chlorobutyl rubber, bromobutyl rubber or ethylene-propylene non-conjugated polyene terpolymer.
Claim 15
Dependent Claim
15 words
The composition of claim 13 wherein the polymer is natural rubber, polybutadiene or butadienestyrene copolymer.
Claim 16
Dependent Claim
20 words
The composition of claim 14 where Z is (3), x is 2 to 4 and Alk is 2 to 3.
Claim 17
Dependent Claim
10 words
The composition of claim 15 where R 2 is ethoxy.
Claim 18
Dependent Claim
134 words
The composition of claim 1 including 0.01 to 10 parts per 100 parts by weight of the rubber of a triazine sulphenimide of the formula ##STR8## in which ##STR9## R 1 , R 2 , R 3 and R 4 are hydrogen or alkyl with 1 to 4 carbon atoms; Y is --CH 2 --CH 2 --; --CH 2 --CH 2 --CH 2 --; --CH(CH 3 )--CH 2 --; ##STR10## ##STR11## where R 5 and R 6 are hydrogen, alkyl with 1 to 8 carbon atoms, alkylthioalkyl with a total of 2 to 8 carbon atoms, CH 3 --S--, alkoxyalkyl with a total of 2 to 8 carbon atoms, CH 3 O-- or phenyl, or ##STR12## where R 7 and R 8 are hydrogen, alkyl with 1 to 8 carbon atoms, allyl or phenyl.
Claim 19
Dependent Claim
9 words
The composition of claim 17 where Y is ##STR13##
Claim 20
Dependent Claim
9 words
The composition of claim 18 where X is Y.
Claim 21
Dependent Claim
14 words
The composition of claim 19 where R 1 and R 2 are both ethyl.
Claim 22
Dependent Claim
14 words
The composition of claim 17 where the polymer is natural rubber, polybutadiene or butadienestyrene.
Claim 23
Dependent Claim
22 words
The composition of claim 17 including 0.05 to 5 parts per 100 parts by weight of the rubber of a vulcanization retarder.
Claim 24
Dependent Claim
22 words
The composition of claim 1 including 0.05 to 5 parts per 100 parts by weight of the rubber of a vulcanization retarder.
Claim 25
Dependent Claim
29 words
The composition of claim 23 including 0.05 to 10 parts of zinc oxide and 0.05 to 10 parts of stearic acid per 100 parts by weight of the rubber.
Claim 26
Dependent Claim
29 words
The composition of claim 17 including 0.05 to 10 parts of zinc oxide and 0.05 to 10 parts of stearic acid per 100 parts by weight of the rubber.
Claim 27
Dependent Claim
29 words
The composition of claim 1 including 0.05 to 10 parts of zinc oxide and 0.05 to 10 parts of stearic acid per 100 parts by weight of the rubber.
Claim 28
Dependent Claim
21 words
The composition of claim 26 including 5 to 100 parts of plasticizer oil per 100 parts by weight of the rubber.
Claim 29
Dependent Claim
21 words
The composition of claim 1 including 5 to 100 parts of plasticizer oil per 100 parts by weight of the rubber.
Claim 30
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 28 until cross-linking occurs.
Claim 31
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 27 until cross-linking occurs.
Claim 32
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 26 until cross-linking occurs.
Claim 33
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 25 until cross-linking occurs.
Claim 34
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 24 until cross-linking occurs.
Claim 35
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 23 until cross-linking occurs.
Claim 36
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 21 until cross-linking occurs.
Claim 37
Dependent Claim
16 words
The cross-linked product of claim 35 where Z is (3) and Alk is 2 to 3.
Claim 38
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 20 until cross-linking occurs.
Claim 39
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 19 until cross-linking occurs.
Claim 40
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 18 until cross-linking occurs.
Claim 41
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 17 until cross-linking occurs.
Claim 42
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 16 until cross-linking occurs.
Claim 43
Dependent Claim
10 words
The cross-linked product of claim 41 where Alk is 3.
Claim 44
Dependent Claim
11 words
The cross-linked product obtained by heating the composition of claim 15.
Claim 45
Dependent Claim
11 words
The cross-linked product obtained by heating the composition of claim 14.
Claim 46
Dependent Claim
11 words
The cross-linked product obtained by heating the composition of claim 13.
Claim 47
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 12 until cross-linking occurs.
Claim 48
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 11 until cross-linking occurs.
Claim 49
Dependent Claim
12 words
The cross-linked product of claim 47 which is free of carbon black.
Claim 50
Dependent Claim
20 words
The cross-linked product of claim 47 which contains 1 to 150 parts of carbon black per 100 parts of rubber.
Claim 51
Dependent Claim
26 words
The cross-linked product of claim 46 wherein the total of the siliceous filler and carbon black is not over 150 parts per 100 parts by rubber.
Claim 52
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 10 until cross-linking occurs.
Claim 53
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 9 until cross-linking occurs.
Claim 54
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 8 until cross-linking occurs.
Claim 55
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 7 until cross-linking occurs.
Claim 56
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 6 until cross-linking occurs.
Claim 57
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 5 until cross-linking occurs.
Claim 58
Dependent Claim
10 words
The cross-linked product of claim 55 where n is 2.
Claim 59
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 4 until cross-linking occurs.
Claim 60
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 3 until cross-linking occurs.
Claim 61
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 2 until cross-linking occurs.
Claim 62
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 1 until cross-linking occurs.
Claim 63
Dependent Claim
19 words
A process of preparing the product of claim 61 consisting of heating said composition at 100° to 200° C.
Claim 64
Dependent Claim
14 words
The process of claim 62 wherein the heating is for 3 to 200 minutes.
Claim 65
Dependent Claim
15 words
The composition of claim 1 wherein there are 10 to 250 parts of siliceous filler.
Claim 66
Dependent Claim
14 words
The cross-linked product obtained by heating the composition of claim 64 until cross-linking occurs.
Claim 67
Dependent Claim
12 words
A composition consisting essentially of the materials set forth in claim 1.
Claim 68
Dependent Claim
12 words
A composition according to claim 66 wherein the rubber is diene elastomer.
Claim 69
Dependent Claim
11 words
A composition according to claim 66 consisting of the stated materials.
Claim 70
Dependent Claim
11 words
The composition of claim 1 where Alk is a saturated aliphatic.
Claim 71
Dependent Claim
13 words
The composition of claim 69 wherein Alk has 2 to 4 carbon atoms.
Claim 72
Dependent Claim
11 words
The composition of claim 70 wherein Alk has 4 carbon atoms.
Claim 73
Dependent Claim
20 words
The composition of claim 71 where Z is (3), x is 2 to 4 and Alk is 2 to 5.
Claim 74
Dependent Claim
11 words
The composition of claim 72 where Alk is 2 to 4.
Claim 75
Dependent Claim
294 words
An elemental sulfur free cross-linking rubber composition consisting of (A) (1) a rubber capable of being cross-linked by sulfur and which is a halogen free rubber, (2) a siliceous filler in an amount of 1 to 300 parts per 100 parts by weight of the rubber, (3) carbon black in an amount of 0 to 300 parts by 100 parts by weight of the rubber, the total of siliceous filler and carbon black not exceeding about 300 parts per 100 parts by weight of the rubber, (4) a vulcanization accelerator for a sulfur cross-linkable rubber in an of 0.02 to 10 parts per 100 parts by weight of the rubber and (5) a sulfur containing organosilicon compound having the formula: Z--Alk--S.sub.x --Alk--Z in which Z is: ##STR14## where R 1 is alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 8 carbon atoms or phenyl, R 2 is alkoxy of 1 to 4 carbon atoms, cycloalkoxy of 5 to 8 carbon atoms or phenoxy, Alk is a divalent aliphatic hydrocarbon or a cyclic hydrocarbon group containing 1 to 8 carbon atoms and x is a number from 2 to 6 in an amount of 0.2 to 40 parts per 100 parts of siliceous filler, or (B) a composition including (A) and at least one of (b) zinc oxide in an amount of 0.05 to 10 parts per 100 parts by weight of the rubber, (7) stearic acid in an amount of 0.05 to 10 parts per 100 parts by weight of the rubber, (8) 5 to 100 parts of plasticizer oil per 100 parts by weight of the rubber, (9) a vulcanization retarder in an amount of 0.05 to 5 parts per 100 parts by weight of rubber and (10) an antiager.
Claim 76
Dependent Claim
294 words
An elemental sulfur free cross-linking rubber composition consisting of (A) (1) a rubber capable of being cross-linked by sulfur and which is a halogen free rubber, (2) a siliceous filler in an amount of 1 to 300 parts per 100 parts by weight of the rubber, (3) carbon black in an amount of 0 to 300 parts by 100 parts by weight of the rubber, the total of siliceous filler and carbon black not exceeding about 300 parts per 100 parts by weight of the rubber, (4) a vulcanization accelerator for a sulfur cross-linkable rubber in an of 0.02 to 10 parts per 100 parts by weight of the rubber and (5) a sulfur containing organosilicon compound having the formula: Z--Alk--S.sub.x --Alk--Z in which Z is: ##STR14## where R 1 is alkyl of 1 to 4 carbon atoms, cycloalkyl of 5 to 8 carbon atoms or phenyl, R 2 is alkoxy of 1 to 4 carbon atoms, cycloalkoxy of 5 to 8 carbon atoms or phenoxy, Alk is a divalent aliphatic hydrocarbon or a cyclic hydrocarbon group containing 1 to 8 carbon atoms and x is a number from 2 to 6 in an amount of 0.2 to 40 parts per 100 parts of siliceous filler, or (B) a composition including (A) and at least one of (b) zinc oxide in an amount of 0.05 to 10 parts per 100 parts by weight of the rubber, (7) stearic acid in an amount of 0.05 to 10 parts per 100 parts by weight of the rubber, (8) 5 to 100 parts of plasticizer oil per 100 parts by weight of the rubber, (9) a vulcanization retarder in an amount of 0.05 to 5 parts per 100 parts by weight of rubber and (10) an antiager.
Claim 77
Dependent Claim
25 words
The composition of claim 74 wherein the rubber is natural rubber, polybutadiene, polyisoprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butyl rubber or ethylene-propylene non conjugated polyene terpolymer.
Claim 78
Dependent Claim
31 words
The composition of claim 75 wherein when the antiager is present it is present in an amount of about 2 to 3 parts per 100 parts by weight of the rubber.
Claim 79
Dependent Claim
27 words
The composition of claim 74 wherein the antiager is present in an amount of about 2 to 3 parts per 100 parts by weight of the rubber.
Claim 80
Dependent Claim
24 words
The composition of claim 74 wherein the antiager is present in an amount of 3 parts per 100 parts by weight of the rubber.
Claim 81
Dependent Claim
24 words
The composition of claim 74 wherein the antiager is present in an amount of 2.3 parts per 100 parts by weight of the rubber.
Claim 82
Dependent Claim
11 words
The composition of claim 74 wherein the vulcanization accelerator is tetramethylthiuramdisulfide.
Claim 83
Dependent Claim
26 words
The composition of claim 75 wherein the tetramethylthiuramdisulfide is present in an amount of 0.2 to 1 part per 100 parts by weight of the rubber.
Claim 84
Dependent Claim
42 words
The composition of claim 74 wherein the vulcanization accelerator is a tetraalkylthiuram monosulfide, a thiourea, a dithiocarbamate, a xanthogenate, a mercapto thiazole, a mercapto thiazoline, a mercaptotriazine, a sulfenamide, an amine, an amine-aldehyde, a guanidine, a bis triazine disulfide or dibenzothiazyl disulfide.
Claim 85
Dependent Claim
26 words
The composition of claim 82 wherein the accelerator is 2-[bis-(2-hydroxyethyl)-amine]-4,6-bis-mercaptotriazine,bis-1,2-ethylamino-4-diethylamino-triazinyl-6-yl)-disulfide; di-2-benzothiazyldisulfide; tetramethylthiurammonosulfide; N,N'-diphenylguanidine; N-cyclohexyl-2-benzothiazolsulfenamide; 2-mercaptobenzothiazole; zinc-N-diethyldithiocarbamate; 2-ethylamino-4-diethylamine-6-mercapto-s-triazine; 2-dimethylamino-4,6-bis-dimethylamino-thiotriazine; ethylene thiourea; butyraldehydeaniline or hexamethylene-tetramine; benzothiazyl-N-sulfen-morpholide; or N-cyclohexyl-2-benzothiazole-sulfenamide.
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) | 1983-10-21 | 1984-04-21 | 1984-10-21 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-10-21 | 1988-04-21 | 1988-10-21 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-10-21 | 1992-04-21 | 1992-10-21 | $7700.00 | Window Closed / Lapsed |