Patent US4934962A successfully refreshed from Google Patents.
Patent US4357432A successfully refreshed from Google Patents.
US4357432A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Vulcanizates
Assignee: Polysar Ltd
•
Filing: 1981-05-11
•
Granted: 1982-11-02
•
Expires: 2001-05-11
Abstract
Abstract A process, and the product of the process, is provided for the production of improved rubbery vulcanizates which contain both of silica or calcium silicate and carbon black as the fillers and two polymers one of which contains hydroxy or epoxy groups. Such vulcanizates may be used in tires, general purpose goods such as belting, and the like.
Inventors
- 👤 Douglas C. Edwards
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 08:39
CPC Classifications
C; C08; C08L; C08L9/00; C08L9/06; C08K; C08K3/00; C08L19/00; C08L19/006; C08L21/00; C08K3/02; C08K3/04; C08K3/34; C08K3/36
Claims Analysis
Total Claims: 13
Claim 1
Independent Claim
443 words
An improved rubbery vulcanizate is provided by the vulcanization of a mixture comprising vulcanization active agents, at least two synthetic polymers and at least two fillers, said at least two fillers being one of silica or calcium silicate and the other being carbon black, said at least two synthetic polymers being (A) a C 4 -C 6 conjugated diolefin containing polymer which contains, per 100 grams of polymer, chemically bound in the polymer from about 1.5 to about 80 millimoles of hydroxy groups or from about 4 to about 60 millimoles of epoxy groups and selected from styrene-butadiene-hydroxyethyl acrylate, styrene-butadiene-hydroxyethyl methacrylate, styrene-butadiene-glycidyl acrylate, styrene-butadiene-glycidyl methacrylate and styrene-butadiene-methallyl glycidyl ether polymers, which polymer is mixed with said silica or calcium silicate and optionally other compounding ingredients, and (B) a C 4 -C 6 conjugated diolefin containing polymer which is mixed with said carbon black and optionally other compounding ingredients prior to being mixed with the polymer A-filler mixture, the mixture comprising, per 100 parts by weight of total polymers, from about 20 to about 80 parts by weight of polymer A, from about 20 to about 80 parts by weight of polymer B, from about 5 to about 100 parts by weight of silica or calcium silicate, from about 5 to about 100 parts by weight of carbon black to provide a weight ratio of silica or calcium silicate to carbon black of from about 20:80 to about 65:35 and optionally an additive selected from (i) 0.5 to 5 parts by weight of an amine of the formula R--NH.sub.2, R--NHR' or R--NR"R''' where R is a C 4 -C 30 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group or a C 4 -C 30 cycloalkyl group or a C 7 -C 20 alkaryl group connected to the nitrogen atom through the alkyl component of the alkaryl group, R' is a C 1 -C 30 linear or branched alkyl or alkylene group and R" and R''', which may be the same or different, is a C 1 -C 10 alkyl group, or (ii) from about 1 to about 5 parts by weight of an organic acid or salt thereof selected from the C 15 -C 20 saturated or unsaturated fatty acids or the alkali metal, alkaline earth metal or ammonium salts thereof, or (iii) from about 1 to about 10 parts by weight of magnesium oxide, said silica or calcium silicate having been mixed with said polymer A and said additive under conditions of shear at a temperature of from about 100° C. to about 190° C. prior to being mixed with the polymer B-carbon black mixture.
Claim 2
Dependent Claim
443 words
An improved rubbery vulcanizate is provided by the vulcanization of a mixture comprising vulcanization active agents, at least two synthetic polymers and at least two fillers, said at least two fillers being one of silica or calcium silicate and the other being carbon black, said at least two synthetic polymers being (A) a C 4 -C 6 conjugated diolefin containing polymer which contains, per 100 grams of polymer, chemically bound in the polymer from about 1.5 to about 80 millimoles of hydroxy groups or from about 4 to about 60 millimoles of epoxy groups and selected from styrene-butadiene-hydroxyethyl acrylate, styrene-butadiene-hydroxyethyl methacrylate, styrene-butadiene-glycidyl acrylate, styrene-butadiene-glycidyl methacrylate and styrene-butadiene-methallyl glycidyl ether polymers, which polymer is mixed with said silica or calcium silicate and optionally other compounding ingredients, and (B) a C 4 -C 6 conjugated diolefin containing polymer which is mixed with said carbon black and optionally other compounding ingredients prior to being mixed with the polymer A-filler mixture, the mixture comprising, per 100 parts by weight of total polymers, from about 20 to about 80 parts by weight of polymer A, from about 20 to about 80 parts by weight of polymer B, from about 5 to about 100 parts by weight of silica or calcium silicate, from about 5 to about 100 parts by weight of carbon black to provide a weight ratio of silica or calcium silicate to carbon black of from about 20:80 to about 65:35 and optionally an additive selected from (i) 0.5 to 5 parts by weight of an amine of the formula R--NH.sub.2, R--NHR' or R--NR"R''' where R is a C 4 -C 30 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group or a C 4 -C 30 cycloalkyl group or a C 7 -C 20 alkaryl group connected to the nitrogen atom through the alkyl component of the alkaryl group, R' is a C 1 -C 30 linear or branched alkyl or alkylene group and R" and R''', which may be the same or different, is a C 1 -C 10 alkyl group, or (ii) from about 1 to about 5 parts by weight of an organic acid or salt thereof selected from the C 15 -C 20 saturated or unsaturated fatty acids or the alkali metal, alkaline earth metal or ammonium salts thereof, or (iii) from about 1 to about 10 parts by weight of magnesium oxide, said silica or calcium silicate having been mixed with said polymer A and said additive under conditions of shear at a temperature of from about 100° C. to about 190° C. prior to being mixed with the polymer B-carbon black mixture.
Claim 3
Dependent Claim
21 words
The vulcanizate of claim 1 wherein the styrene content of polymer A is from about 18 to about 30 weight percent.
Claim 4
Dependent Claim
25 words
The vulcanizate of claim 1 wherein polymer B is a styrene-butadiene polymer having a styrene content of from about 18 to about 30 weight percent.
Claim 5
Dependent Claim
55 words
The vulcanizate of claim 1 wherein the fillers are silica in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer A and carbon black in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer B.
Claim 6
Dependent Claim
194 words
The vulcanizate of claim 1 wherein polymer A is a styrene-butadiene-hydroxyethyl methacrylate polymer containing from about 18 to about 30 weight percent of styrene and from about 2 to about 60 millimoles of hydroxy groups per 100 grams of polymer, polymer B is a styrene-butadiene polymer containing from about 18 to about 30 weight percent of styrene, the fillers are silica in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer A and carbon black in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer B, the additive for the mixing of the polymer A and silica is an amine of formula R--NH 2 or R--NHR' wherein R is a C 10 -C 20 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group and R' is a C 10 -C 20 linear or branched alkyl or alkylene group and the polymer A, silica and additive are mixed under conditions of shear at from about 120° to about 180° C. for from about 0.5 to about 5 minutes.
Claim 7
Dependent Claim
422 words
A process for the production of improved rubbery vulcanizates which process comprises the steps of (1) mixing for from about 0.25 to about 10 minutes under conditions of shear at a temperature of from about 100° to about 190° C. from about 20 to about 80 parts by weight of polymer A, said polymer A being a C 4 -C 6 conjugated diolefin containing polymer which contains, per 100 grams of polymer, chemically bound in the polymer from about 1.5 to about 80 millimoles of hydroxy groups or from about 4 to about 60 millimoles of epoxy groups, with from about 5 to about 100 parts by weight per 100 parts by weight of polymer A of silica or calcium silicate and optionally an additive selected from (i) 0.5 to 5 parts by weight of an amine of the formula R--NH.sub.2, R--NHR' or R--NH"R''' where R is a C 4 -C 30 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group or a C 4 -C 30 cycloalkyl group or a C 7 -C 20 alkaryl group connected to the nitrogen atom through the alkyl component of the alkaryl group, R' is a C 1 -C 30 linear or branched alkyl or alkylene group and R" and R''', which may be the same or different, is a C 1 -C 10 alkyl group, or (ii) from about 1 to about 5 parts by weight of an organic acid or salt thereof selected from the C 15 -C 20 saturated or unsaturated fatty acids or the alkali metal, alkaline earth metal or ammonium salts thereof, or (iii) from about 1 to about 10 parts by weight of magnesium oxide, (2) allowing the mixture to cool and incorporating vulcanization active agents and optionally other compounding ingredients, (3) mixing from about 20 to about 80 parts by weight of polymer B, said polymer B being a C 4 -C 6 conjugated diolefin containing polymer, with from about 5 to about 100 parts by weight per 100 parts by weight of polymer B of carbon black, (4) allowing the mixture to cool and incorporating vulcanization active agents and optionally other compounding ingredients, (5) mixing together the products from steps (2) and (4), the weight ratio therein of silica or calcium silicate to carbon black being from about 20:80 to about 65:35, shaping the mixture from step (5) and vulcanizing it by heating to a temperature of from 125° to about 200° C. for 1 minute to about 10 hours.
Claim 8
Dependent Claim
422 words
A process for the production of improved rubbery vulcanizates which process comprises the steps of (1) mixing for from about 0.25 to about 10 minutes under conditions of shear at a temperature of from about 100° to about 190° C. from about 20 to about 80 parts by weight of polymer A, said polymer A being a C 4 -C 6 conjugated diolefin containing polymer which contains, per 100 grams of polymer, chemically bound in the polymer from about 1.5 to about 80 millimoles of hydroxy groups or from about 4 to about 60 millimoles of epoxy groups, with from about 5 to about 100 parts by weight per 100 parts by weight of polymer A of silica or calcium silicate and optionally an additive selected from (i) 0.5 to 5 parts by weight of an amine of the formula R--NH.sub.2, R--NHR' or R--NH"R''' where R is a C 4 -C 30 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group or a C 4 -C 30 cycloalkyl group or a C 7 -C 20 alkaryl group connected to the nitrogen atom through the alkyl component of the alkaryl group, R' is a C 1 -C 30 linear or branched alkyl or alkylene group and R" and R''', which may be the same or different, is a C 1 -C 10 alkyl group, or (ii) from about 1 to about 5 parts by weight of an organic acid or salt thereof selected from the C 15 -C 20 saturated or unsaturated fatty acids or the alkali metal, alkaline earth metal or ammonium salts thereof, or (iii) from about 1 to about 10 parts by weight of magnesium oxide, (2) allowing the mixture to cool and incorporating vulcanization active agents and optionally other compounding ingredients, (3) mixing from about 20 to about 80 parts by weight of polymer B, said polymer B being a C 4 -C 6 conjugated diolefin containing polymer, with from about 5 to about 100 parts by weight per 100 parts by weight of polymer B of carbon black, (4) allowing the mixture to cool and incorporating vulcanization active agents and optionally other compounding ingredients, (5) mixing together the products from steps (2) and (4), the weight ratio therein of silica or calcium silicate to carbon black being from about 20:80 to about 65:35, shaping the mixture from step (5) and vulcanizing it by heating to a temperature of from 125° to about 200° C. for 1 minute to about 10 hours.
Claim 9
Dependent Claim
107 words
The process of claim 6 wherein polymer A is selected from styrene-butadiene-hydroxyethyl acrylate, styrene-butadiene hydroxyethyl methacrylate, styrene-butadiene-glycidyl acrylate, styrene-butadiene-glycidyl methacrylate and styrene-butadiene-methallyl glycidyl ether polymers wherein the styrene content is from about 18 to about 30 weight percent, polymer B is a styrene-butadiene polymer having a styrene content of from about 18 to about 30 weight percent and the fillers are silica in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer A and carbon black in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer B.
Claim 10
Dependent Claim
94 words
The process of claim 7 wherein the additive for the mixing of the polymer A and silica is an amine of formula R--NH 2 or R--NHR' wherein R is a C 10 -C 20 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group and R' is a C 10 -C 20 linear or branched alkyl or alkylene group and the polymer A, silica and additive are mixed under conditions of shear at from about 120° to about 180° C. for from about 0.5 to about 5 minutes.
Claim 11
Dependent Claim
37 words
The process of claim 6 wherein the mixtures from step (2) and from step (4) both contain all compounding ingredients and vulcanization active agents and are mixed together in step (5) at a temperature below 75° C.
Claim 12
Dependent Claim
35 words
The process of claim 9 in which the final mixture from step (5) is vulcanized by heating at a temperature of from about 150° to about 170° C. for about 3 to about 60 minutes.
Claim 13
Dependent Claim
221 words
The process of claim 6 wherein polymer A is a styrene-butadiene-hydroxyethyl methacrylate polymer containing from about 18 to about 30 weight percent of styrene and from about 2 to about 60 millimoles of hydroxy groups per 100 grams of polymer, polymer B is a styrene-butadiene polymer containing from about 18 to about 30 weight percent of styrene, the fillers are silica in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer A and carbon black in an amount of from about 30 to about 75 parts by weight per 100 parts by weight of polymer B, the additive for the mixing of polymer A and silica is an amine of formula R--NH 2 or R--NHR' wherein R is a C 10 -C 20 linear or branched alkyl or alkylene group which may contain one NH 2 or NH group and R' is a C 10 -C 20 linear or branched alkyl or alkylene group, the polymer A, silica and additive are mixed under conditions of shear at from about 120° to about 180° C. for from about 0.5 to about 5 minutes and the final mixture from step (5) is vulcanized by heating at a temperature of from about 150° to about 170° C. for about 3 to about 60 minutes.
References Cited (Backward Citations)
US3704196A
Cited
US3696061A
Cited
US3700620A
Cited
US3700621A
Cited
US4169822A
Cited
US4229333A
Cited
US4150015A
Cited
US4150014A
Cited
US4152308A
Cited
US4179421A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-11-01 | 1986-05-03 | 1986-11-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-11-01 | 1990-05-03 | 1990-11-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-11-01 | 1994-05-03 | 1994-11-02 | $7700.00 | Window Closed / Lapsed |