# US 4,400,485 A · Rubber composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,400,485 A - Document ID: US4400485A - Status: Granted - Kind: A - Application number: 06/297,175 - Filed: 1981-08-28 - Granted: 1983-08-23 - Earliest claimed: 1981-08-28 - Assignees: Standard Oil Company (Indiana) - Inventors: Harold Mukamal; Richard S. Lamar; Laurence E. Ferreira - Web page: https://patentgrep.com/patent/US4400485A ## CPC - C08K 3/34: Silicon-containing compounds - C08K 9/06: with silicon-containing compounds - Y10T 428/2995: Silane, siloxane or silicone coating - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract A rubber composition containing a phyllosilicate mineral filler is disclosed. ## Claims ### Claim 1 A rubber composition formed according to an improved rubber compounding process, wherein the improvement comprises vulcanizing natural rubber, polybutadiene rubber, polyisoprene rubber, or styrene-butadiene rubber containing a substantially uniform dispersion of: A. 1. particulate Agent E at a level of from about 5 to about 200 phr, 2. Agent F at a level of from about 0.005 to about 15 phr, and 3. Agent G at a level of from about 0.005 to about 15 phr; or B. 1. a particulate adduct of Agents E and F having a median particle size in the range of from about 0.01 to about 20 microns and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr and the portion thereof contributed from Agent F is at a level of from about 0.005 to about 15 phr, and 2. Agent G at a level of from about 0.005 to about 15 phr; or C. 1. a particulate adduct of Agents E and G having a median particle size in the range of from about 0.01 to about 20 microns and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr and the portion thereof contributed from Agent G is at a level of from about 0.005 to about 15 phr, and 2. Agent F at a level of from about 0.005 to about 15 phr; or D. a particulate adduct of Agents E, F, and G having a median particle size in the range of from about 0.01 to about 20 and present at a level such that the portion thereof contributed from Agent E is at a level of from about 5 to about 200 phr, the portion thereof contributed from Agent F is at a level of from about 0.005 to about 15 phr and the portion thereof contributed from Agent G is at a level of from about 0.005 to about 15 phr; wherein Agent E comprises phyllosilicate mineral particles having a median particle size in the range of from about 0.01 to about 20 microns; wherein Agent F comprises an organosilane of formula I ##STR3## wherein X is a group which is, or which upon hydrolysis forms a group which is, capable of reacting with a reactive site on the phyllosilicate mineral particles so as to form a bond between the organosilane of formula I and the phyllosilicate mineral particles, wherein Y is an alkyl, aryl or alkyl-substituted aryl group containing from 1 to 20 carbon atoms and bears a functional group capable of reacting with a reactive site on the rubber so as to form a bond between the organosilane of formula I and the rubber, and wherein R.sub.1 and R.sub.2 are the same or different and are each selected from the group consisting of the groups described by X and Y, an alkyl group containing from 1 to 20 carbon atoms, an aryl group, and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms; and wherein Agent G comprises an amine of formula II ##STR4## wherein Z is zero or a positive integer from 1 to 12, wherein R.sub.3, R.sub.4, R.sub.6 and R.sub.7 are the same or different and are each selected from the group consisting of hydrogen, an alkyl group containing from 1 to 20 carbon atoms, an aryl group and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms, wherein R.sub.5 is an alkylene group containing from 2 to 16 carbon atoms, wherein, when Z is zero, at least one of R.sub.3, R.sub.4 and R.sub.7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and at least one of R.sub.3, R.sub.4 and R.sub.7 bears a second functional group which is, or which upon hydrolysis forms a group which is selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is located at a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and wherein, when Z is not zero, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, a group hydrolyzable to a hydroxy group, and, in addition, when R.sub.5 contains more than 3 carbon atoms, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is attached to a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II. ### Claim 2 (depends on 1) The rubber composition of claim 1 wherein a sulfur or sulfur-donating curing agent is employed. ### Claim 3 (depends on 1) The rubber composition of claim 1 wherein the phyllosilicate mineral is selected from the group consisting of a member of the kaolin group, a member of the mica group, a member of the group characterized by a primitive three-layer structure, a member of the group characterized by an expandable three-layer structure and a member of the group characterized by a four-layer structure. ### Claim 4 (depends on 3) The method of claim 3 wherein the phyllosilicate mineral is selected from the group consisting of kaolinite, muscovite, pyrophyllite, talc, vermiculite and chlorite. ### Claim 5 (depends on 4) The rubber composition of claim 4 wherein the phyllosilicate mineral is talc. ### Claim 6 (depends on 1) The rubber composition of claim 1 wherein X is a group which upon hydrolysis forms a hydroxyl group. ### Claim 7 (depends on 1) The rubber composition of claim 1 wherein X is selected from the group consisting of a halogen radical and --OR.sub.8 and wherein R.sub.8 is an alkyl group containing from 1 to 20 carbon atoms. ### Claim 8 (depends on 7) The rubber composition of claim 7 wherein X is --OR.sub.8 and R.sub.8 contains from 1 to 7 carbon atoms. ### Claim 9 (depends on 1) The rubber composition of claim 1 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, and an amino group having an active hydrogen atom. ### Claim 10 (depends on 9) The rubber composition of claim 9 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of a mercapto group, a vinyl group and an amino group having an active hydrogen atom. ### Claim 11 (depends on 10) The rubber composition of claim 10 wherein Y contains from 1 to 6 carbon atoms. ### Claim 12 (depends on 1) The rubber composition of claim 1 wherein R.sub.1 and R.sub.2 are the same or different and are each selected from the group consisting of the group described by X. ### Claim 13 (depends on 12) The rubber composition of claim 12 wherein R.sub.1 and R.sub.2 are the same or different and are each selected from the group consisting of a halogen radical and --OR.sub.8 and wherein R.sub.8 is an alkyl group containing from 1 to 20 carbon atoms. ### Claim 14 (depends on 13) The rubber composition of claim 13 wherein X, R.sub.1 and R.sub.2 are the same. ### Claim 15 (depends on 1) The rubber composition of claim 1 wherein the organosilane of formula I is selected from the group consisting of 3-aminopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane and vinyl-tri-(2-methoxyethoxy) silane. ### Claim 16 (depends on 1) The rubber composition of claim 1 wherein the alkoxy group is --OR.sub.8 wherein R.sub.8 is an alkyl group containing from 1 to 20 carbon atoms. ### Claim 17 (depends on 1) The rubber composition of claim 1 wherein, when Z is not zero, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 bears said second functional group. ### Claim 18 (depends on 1) The rubber composition of claim 1 wherein Z in formula II is 0 or 1. ### Claim 19 (depends on 1) The rubber composition of claim 1 wherein R.sub.5 contains 2 or 3 carbon atoms. ### Claim 20 (depends on 1) The rubber composition of claim 1 wherein the amine of formula II is triethanolamine and N,N,N',N'-tetra-(2-hydroxypropyl) ethylenediamine. ### Claim 21 (depends on 1) The rubber composition of claim 1 wherein the median particle size of Agent E and of the adducts is in the range of from about 0.1 to about 1 micron. ### Claim 22 (depends on 1) The rubber composition of claim 1 wherein Agent E and the portions of the adducts contributed from Agent E are each at a level of from about 50 to about 150 phr. ### Claim 23 (depends on 1) The rubber composition of claim 1 wherein Agent F and the portions of the adducts contributed from Agent F are each at a level of from about 0.25 to about 3 phr. ### Claim 24 (depends on 1) The rubber composition of claim 1 wherein Agent G and the portions of the adducts contributed from Agent G are each at a level of from about 0.25 to about 3 phr. ### Claim 25 A rubber composition comprising phyllosilicate mineral particles substantially uniformly distributed in natural rubber, polybutadiene rubber, polyisoprene rubber or styrene-butadiene rubber at a level of from about 5 to about 200 phr and having a median particle size of from about 0.01 to about 20 microns, and (1) an Adduct A of the rubber and phyllosilicate mineral particles with an organosilane of formula I ##STR5## wherein X is a group which is, or which upon hydrolysis forms a group which is, capable of reacting with a reactive site on the phyllosilicate mineral particles so as to form a bond between the organosilane of formula I and the phyllosilicate mineral particles, wherein Y is an alkyl, aryl or alkyl-substituted aryl group containing from 1 to 20 carbon atoms and bears a functional group capable of reacting with a reactive site on the rubber so as to form a bond between the organosilane of formula I and the rubber, and wherein R.sub.1 and R.sub.2 are the same or different and are each selected from the group consisting of the groups described by X and Y, an alkyl group containing from 1 to 20 carbon atoms, an aryl group, and an alkyl-substituted aryl group wherein the alkyl substituents contain a total of from 1 to 20 carbon atoms, the portion of Adduct A contributed from the organosilane of formula I being at a level of from about 0.005 to about 15 phr; and (2) an Adduct B of the rubber and phyllosilicate mineral particles with an amine of formula II ##STR6## wherein Z is zero or a positive integer from 1 to 12, wherein R.sub.3, R.sub.4, R.sub.6 and R.sub.7 are the same or different and are each selected from the group consisting of hydrogen, an alkyl group containing from 1 to 20 carbon atoms, an aryl group and an alkyl-substituted aryl group wherein the aryl substituents contain a total of from 1 to 20 carbon atoms, wherein R.sub.5 is an alkylene group containing from 2 to 16 carbon atoms, wherein, when Z is zero, at least one of R.sub.3, R.sub.4 and R.sub.7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and at least one of R.sub.3, R.sub.4 and R.sub.7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is located at a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and wherein, when Z is not zero, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 bears a first functional group which is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group, hydroxy group, and a group hydrolyzable to a hydroxy group, and, in addition, when R.sub.5 contains more than 3 carbon atoms, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 bears a second functional group which is, or which upon hydrolysis forms a group which is, selected from the group consisting of a hydroxy group, an alkoxy group, a mercapto group, and a sulfide group and which second functional group is attached to a carbon atom which is beta or gamma to the nearest tertiary nitrogen atom in formula II, and the portion of Adduct B contributed from the amine of formula II being at a level of from about 0.005 to about 15 phr. ### Claim 26 (depends on 25) The rubber composition of claim 25 formed by a vulcanization process employing a sulfur or sulfur-donating curing agent. ### Claim 27 (depends on 25) The rubber composition of claim 25 wherein the phyllosilicate mineral is selected from the group consisting of a member of the kaolin group, a member of the mica group, a member of the group characterized by a primitive three-layer structure, a member of the group characterized by an expandable three-layer structure and a member of the group characterized by a four-layer structure. ### Claim 28 (depends on 27) The rubber composition of claim 27 wherein the phyllosilicate mineral is selected from the group consisting of kaolinite, muscovite, pyrophyllite, talc, vermiculite and chlorite. ### Claim 29 (depends on 28) The rubber composition of claim 28 wherein the phyllosilicate mineral is talc. ### Claim 30 (depends on 25) The rubber composition of claim 25 wherein X is a group which upon hydrolysis forms a hydroxyl group. ### Claim 31 (depends on 25) The rubber composition of claim 25 wherein X is selected from the group consisting of a halogen radical and --OR.sub.8 and wherein R.sub.8 is an alkyl group containing from 1 to 20 carbon atoms. ### Claim 32 (depends on 31) The rubber composition of claim 31 wherein X is --OR.sub.8 and R.sub.8 contains from 1 to 7 carbon atoms. ### Claim 33 (depends on 25) The rubber composition of claim 25 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of a mercapto group, allyl group, vinyl group, epoxy group, methacryloxy group, acryloxy group and an amino group having an active hydrogen atom. ### Claim 34 (depends on 33) The rubber composition of claim 33 wherein the functional group on Y which is capable of reacting with a reactive site on the rubber is selected from the group consisting of mercapto, vinyl and an amino group having an active hydrogen atom. ### Claim 35 (depends on 34) The rubber composition of claim 34 wherein Y contains from 1 to 6 carbon atoms. ### Claim 36 (depends on 25) The rubber composition of claim 25 wherein R.sub.1 and R.sub.2 are the same or different and are each selected from the group consisting of the group described by X. ### Claim 37 (depends on 36) The rubber composition of claim 36 wherein R.sub.1 and R.sub.2 are the same or different and are each selected from the group consisting of a halogen radical and --OR.sub.8 and wherein R.sub.8 is an alkyl group containing from 1 to 20 carbon atoms. ### Claim 38 (depends on 37) The rubber composition of claim 37 wherein X, R and R.sub.2 are the same. ### Claim 39 (depends on 25) The rubber composition of claim 25 wherein the agent of formula I is 3-aminopropyl-triethoxysilane, 3-mercaptopropyl-trimethoxysilane, and vinyl-tri-(2-methoxyethoxy) silane. ### Claim 40 (depends on 25) The rubber composition of claim 25 wherein the alkoxy group is --OR.sub.8 wherein R.sub.8 is an alkyl group containing from 1 to 20 carbon atoms. ### Claim 41 (depends on 25) The rubber composition of claim 25 wherein, when Z is not zero, at least one of R.sub.3, R.sub.4, R.sub.6 and R.sub.7 bears said second functional group. ### Claim 42 (depends on 25) The rubber composition of claim 25 wherein Z in formula II is 0 or 1. ### Claim 43 (depends on 25) The rubber composition of claim 25 wherein R.sub.5 contains from 2 or 3 carbon atoms. ### Claim 44 (depends on 25) The rubber composition of claim 25 wherein the amine of formula II is triethanolamine and N,N,N',N'-tetra-(2-hydroxypropyl) ethylenediamine. ### Claim 45 (depends on 25) The rubber composition of claim 25 wherein the phyllosilicate mineral median particle size is in the range of from about 0.1 to about 1 micron. ### Claim 46 (depends on 25) The rubber composition of claim 25 wherein the phyllosilicate mineral particles are at a level of from about 50 to about 150 phr. ### Claim 47 (depends on 25) The rubber composition of claim 25 wherein the portion of Adduct A contributed from the organosilane of formula I is at a level of from about 0.25 to about 3 phr. ### Claim 48 (depends on 25) The rubber composition of claim 25 wherein the portion of Adduct B contributed from the amine of formula II is at a level of from about 0.25 to about 3 phr.