US5580919A — Silica reinforced rubber composition and use in t…

Claim 1

Independent Claim 509 words

A process of preparing a rubber composition which comprises the sequential steps of: (A) thermomechanically mixing in at least one preparatory mixing step to a temperature of about 140° C. to about 190° C. for a total mixing time of about 2 to about 20 minutes (i) 100 parts by weight of at least one sulfur vulcanizable elastomer selected from conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene and aromatic vinyl compound, (ii) about 15 to about 100 phr of particulate filler comprised of at least one of precipitated silica, alumina, aluminosilicate and carbon black, wherein said filler contains from about 5 to about to 85 weight percent carbon black, (iii) about 0.05 to about 20 parts by weight per part by weight of said particulate filler of at least one organosilane polysulfide compound having the formula: Z--R.sup.1 --S.sub.n --R.sup.1 --Z wherein n is an integer of from 2 to 8 provided, however, that at least 80 percent of n is 2; wherein Z is selected from the group consisting of: ##STR2## wherein R 2 may be the same or different and is individually selected from the group consisting of alkyl group having 1 to 4 carbons and phenyl; R 3 may be the same or different and is individually selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, phenyl, alkoxy groups having 1 to 8 carbon atoms and cycloalkoxy groups with 5 to 8 carbon atoms; and R 1 is selected from the group consisting of a substituted or unsubstituted alkylene group having a total of 1 to 18 carbon atoms and a substituted or unsubstituted arylene group having a total of 6 to 12 carbon atoms; (iv) at least one additional additive, exclusive of said organosilane polysulfide (iii) having at least 80 percent of n being 2, as a compound selected from (a) a free sulfur source selected from at least one of (1) elemental sulfur and (2) at least one sulfur donor as a polysulfidic organic compound containing sulfur and having a property of releasing at least a portion of said sulfur at a temperature in a range of about 140° C. to about 190° C.; provided, however, that the total free sulfur from said elemental sulfur addition and available from said sulfur donor addition is in a range of about 0.05 to about 2 phr, and (b) about 0.1 to about 0.5 phr of at least one vulcanization accelerator for sulfur vulcanizable elastomers that is not a such a sulfur donor; and (B) subsequently blending therewith, in a final thermomechanical mixing step at a temperature to about 100° C. to about 130° C. for a time of about 1 to about 3 minutes, about 0.4 to about 3 phr of elemental sulfur provided, however that the total of elemental and/or free sulfur introduced in said preparatory mixing steps and elemental sulfur added in said final mixing step is in a range of about 0.45 to about 5 phr, and at least one sulfur vulcanization accelerator.

Claim 2

Dependent Claim 509 words

A process of preparing a rubber composition which comprises the sequential steps of: (A) thermomechanically mixing in at least one preparatory mixing step to a temperature of about 140° C. to about 190° C. for a total mixing time of about 2 to about 20 minutes (i) 100 parts by weight of at least one sulfur vulcanizable elastomer selected from conjugated diene homopolymers and copolymers and copolymers of at least one conjugated diene and aromatic vinyl compound, (ii) about 15 to about 100 phr of particulate filler comprised of at least one of precipitated silica, alumina, aluminosilicate and carbon black, wherein said filler contains from about 5 to about to 85 weight percent carbon black, (iii) about 0.05 to about 20 parts by weight per part by weight of said particulate filler of at least one organosilane polysulfide compound having the formula: Z--R.sup.1 --S.sub.n --R.sup.1 --Z wherein n is an integer of from 2 to 8 provided, however, that at least 80 percent of n is 2; wherein Z is selected from the group consisting of: ##STR2## wherein R 2 may be the same or different and is individually selected from the group consisting of alkyl group having 1 to 4 carbons and phenyl; R 3 may be the same or different and is individually selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, phenyl, alkoxy groups having 1 to 8 carbon atoms and cycloalkoxy groups with 5 to 8 carbon atoms; and R 1 is selected from the group consisting of a substituted or unsubstituted alkylene group having a total of 1 to 18 carbon atoms and a substituted or unsubstituted arylene group having a total of 6 to 12 carbon atoms; (iv) at least one additional additive, exclusive of said organosilane polysulfide (iii) having at least 80 percent of n being 2, as a compound selected from (a) a free sulfur source selected from at least one of (1) elemental sulfur and (2) at least one sulfur donor as a polysulfidic organic compound containing sulfur and having a property of releasing at least a portion of said sulfur at a temperature in a range of about 140° C. to about 190° C.; provided, however, that the total free sulfur from said elemental sulfur addition and available from said sulfur donor addition is in a range of about 0.05 to about 2 phr, and (b) about 0.1 to about 0.5 phr of at least one vulcanization accelerator for sulfur vulcanizable elastomers that is not a such a sulfur donor; and (B) subsequently blending therewith, in a final thermomechanical mixing step at a temperature to about 100° C. to about 130° C. for a time of about 1 to about 3 minutes, about 0.4 to about 3 phr of elemental sulfur provided, however that the total of elemental and/or free sulfur introduced in said preparatory mixing steps and elemental sulfur added in said final mixing step is in a range of about 0.45 to about 5 phr, and at least one sulfur vulcanization accelerator.

Claim 3

Dependent Claim 78 words

The process of claim 1 in which a total of about 0.05 to about 5 phr of at least one alkyl silane is added to said preparatory thermomechanical mixing step(s), wherein said alkyl silane has the formula: R'-Si-(OR) 3 , where R is a methyl, ethyl, propyl or isopropyl radical and R' is a saturated alkyl having from 1 to 18 carbon atoms or aryl or saturated alkyl substituted aryl radical having from 6 to 12 carbon atoms.

Claim 4

Dependent Claim 25 words

The process of claim 2 wherein said alkyl silane is selected from one or more of propyltriethoxy silane, methyltriethoxy silane, hexadecyltriethoxy silane and octadecyltriethoxy silane.

Claim 5

Dependent Claim 61 words

The process of claim 1 wherein said preparatory mixing is conducted in at least two thermomechanical mixing steps, wherein at least two of such mixing steps are to a temperature of about 140° C. to about 190° C., with intermediate cooling of the rubber composition between at least two of the said mixing steps to a temperature below about 50° C.

Claim 6

Dependent Claim 31 words

The process of claim 1 which comprises the additional step of vulcanizing the prepared rubber composition at a temperature in a range of from about 140° C. to about 190° C.

Claim 7

Dependent Claim 12 words

A vulcanized rubber composition prepared according to the process of claim 5.

Claim 8

Dependent Claim 48 words

The process of claim 1 which comprises the additional steps of preparing an assembly of a tire of sulfur vulcanizable rubber with a tread comprised of the said rubber composition and vulcanizing the assembly at a temperature in a range of about 140° C. to about 190° C.

Claim 9

Dependent Claim 12 words

A vulcanized rubber tire prepared according to the process of claim 7.

Claim 10

Dependent Claim 31 words

The process of claim 4 which comprises the additional step of vulcanizing the prepared rubber composition at a temperature in a range of from about 140° C. to about 190° C.

Claim 11

Dependent Claim 12 words

A vulcanized rubber composition prepared according to the process of claim 9.

Claim 12

Dependent Claim 48 words

The process of claim 4 which comprises the additional steps of preparing an assembly of a tire of sulfur vulcanizable rubber with a tread comprised of the said rubber composition and vulcanizing the assembly at a temperature in a range of about 140° C. to about 190° C.

Claim 13

Dependent Claim 12 words

A vulcanized rubber tire prepared according to the process of claim 11.

Claim 14

Dependent Claim 33 words

The process of claim 1 where, for said sulfur vulcanizable elastomer, said conjugated dienes are selected from isoprene and 1,3-butadiene and said vinyl aromatic compounds are selected from styrene and alpha methyl styrene.

Claim 15

Dependent Claim 70 words

The process of claim 1 where said sulfur vulcanizable elastomer is selected from at least one of natural and synthetic cis 1,4-polyisoprene rubber, emulsion polymerization prepared styrene/butadiene copolymer rubber, organic solution polymerization prepared styrene/butadiene copolymer rubber, 3,4-polyisoprene rubber, isoprene/butadiene rubber, styrene/isoprene/butadiene terpolymer rubbers, cis 1,4-polybutadiene rubber, medium vinyl polybutadiene rubber (35-50 percent vinyl), high vinyl polybutadiene (50-75 percent vinyl) and emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubber and butadiene/acrylonitrile copolymer rubber.

Claim 16

Dependent Claim 130 words

The process of claim 1 wherein the silica is characterized by having a BET surface area in a range of about 100 to about 300 square meters per gram and a dibutylphthalate (DBP) absorption value in a range of about 150 to about 350, a CTAB value in a range of about 100 to about 220, and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 run and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.

Claim 17

Dependent Claim 51 words

The process according to claim 15 in which said filler is comprised of about 15 to about 95 weight percent precipitated silica and, correspondingly, from 5 to about 85 weight percent carbon black; wherein said carbon black is has a CTAB value in a range of about 80 to about 150.

Claim 18

Dependent Claim 31 words

The process according to claim 16 wherein the filler is comprised of about 60 to about 95 weight percent silica and, correspondingly, about 40 to about 5 weight percent carbon black.

Claim 19

Dependent Claim 137 words

The process of claim 1 wherein said filler is comprised of about 15 to about 100 weight percent alumina and, correspondingly, from 5 to about 85 weight percent carbon black; wherein said carbon black has a CTAB value in a range of about 80 to about 150 and said alumina has a CTAB value in a range of about 100 to about 220 and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.

Claim 20

Dependent Claim 32 words

The process according to of claim 18 wherein said filler is comprised of about 60 to about 95 weight percent alumina and, correspondingly, about 40 to about 5 weight percent carbon black.

Claim 21

Dependent Claim 138 words

The process of claim 1 wherein said filler is comprised of about 15 to about 100 weight percent aluminosilicate and, correspondingly, from about 5 to about 85 weight percent carbon black; wherein said carbon black has a CTAB in a range of about 80 to about 150 and wherein said aluminosilicate has a CTAB value in a range of about 100 to about 220 and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.

Claim 22

Dependent Claim 31 words

The process according to claim 20 wherein said filler is comprised of about 60 to about 95 weight percent aluminosilicate and, correspondingly, about 40 to about 5 weight percent carbon black.

Claim 23

Dependent Claim 70 words

The process of claim 1 where said aluminosilicate is selected from at least one of at least one of (a) natural aluminosilicates selected from Muscovite, Beryl, Dichroite, Sepiolite and Kaolinire and (b) synthetic aluminosilicates prepared by (i) coprecipitation by pH adjustment of a basic solution, or mixture of silicate and aluminate or by (ii) a chemical reaction between silanols at the surface of a silicon dioxide and NaAlO 2 .

Claim 24

Dependent Claim 42 words

The process according to claim 22 where for said synthetic coprecipitated aluminosilicate about 5 to about 95 percent of its surface is composed of silica moieties and, correspondingly, about 95 to about 5 percent of its surface is composed of aluminum moieties.

Claim 25

Dependent Claim 51 words

The process according to claim 20 wherein said synthetic aluminosilicate is represented by the formula selected from: [(Al 2 O 3 ) x .(SiO 2 ) y .(H 2 O) z ] and/or [(Al 2 O 3 ) x .(SiO 2 ) y . MO]; where M is magnesium or calcium.

Claim 26

Dependent Claim 29 words

The process of claim 1 wherein said sulfur donor additional additive is selected from at least one of dimorpholine tetrasulfide, tetramethyl thiuram tetrasulfide, benzothiazyl-2,N dithiomorpholide, thioplasts, dipentamethylenethiuramhexasulfide and disulfidecaprolactame.

Claim 27

Dependent Claim 56 words

The process of claim 1 wherein said vulcanization accelerator for sulfur vulcanizable elastomers additional additive is selected from at least one of mercaptobenzothiazole, tetramethyl thiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate, N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N diphenylthiourea, dithiocarbamylesulfenamide, N,N diisopropylbezothiozole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N methyl piperazine), dithiobis(N beta hydroxy ethyl piperazine) and dithiobis(dibenzyl amine).

Claim 28

Dependent Claim 56 words

The process of claim 1 wherein said sulfur donor additional additive (iv) is exclusive of said organosilane polysulfide (iii) having at least 80 percent of n being 2 and is selected from at least one of 3,3'-bis(trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3 '-bis(triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylethyl tolylene) trisulfide and tetrasulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) trisulfide and tetrasulfide.

Claim 29

Dependent Claim 32 words

The process of claim 1 wherein for the said organosilane polysulfide compound, said R 2 radicals are alkyl radicals and said R 1 radicals are selected from alkaryl, phenyl and haloaryl radicals.

Claim 30

Dependent Claim 49 words

The process according to claim 28 wherein said alkyl radicals are selected from methyl, ethyl, n-propyl and n-decyl radicals; said aralkyl radicals are selected from benzyl and alpha, alpha dimethylbenzyl radicals; said alkaryl radicals are selected from p-tolyl and p-nonylphenol radicals; and said haloaryl radical is a p-chlorophenol radical.

Claim 31

Dependent Claim 96 words

The process of claim 1 wherein organosilane disulfides of said organosilane polysulfide compounds are selected from at least one of: 2,2'-bis(trimethoxysilylethyl) disulfide; 3,3'-bis(trimethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 2,2'-bis(triethoxysilylpropyl) disulfide; 2,2'-bis(tripropoxysilylethyl) disulfide; 2,2'-bi(tri-sec.butoxysilylethyl) disulfide; 3,3'-bis(tri-t-butoxyethyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; 3,3'-bis(trimethoxysilylethyl tolylene) disulfide; 3,3'-bis(triisopropoxypropyl) disulfide; 3,3'-bis(trioctoxypropyl) disulfide; 2,2'-his(2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis(dimethoxy ethoxysilylethyl) disulfide; 3,3'-bis(methoxyethoxypropoxysilylpropyl) disulfide; 3,3'-bis(methoxy dimethylsilylpropyl) disulfide; 3,3'-bis(cyclohexoxy dimethylsilylpropyl) disulfide; 4,4'-bis(trimethoxysilylbutyl) disulfide; 3,3'-bis(trimethoxysilyl-3-methylpropyl) disulfide; 3,3'-bis(tripropoxysilyl-3-methylpropyl)disulfide; 3,3 '-bis(dimethoxy methylsilyl-3-ethylpropyl) disulfide; 3,3 '-bis(trimethoxysilyl-2-methylpropyl) disulfide; 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,3'-bis (trimethoxysilylcyclohexyl) disulfide; 12,12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18,18'-his (trimethoxysilyloctadecyl) disulfide; 18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2-'-his (trimethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (tripropoxysilyl-2-methylethyl) disulfide; and

Claim 32

Dependent Claim 2 words

2'-bis(trioctoxysilyl-2-methylethyl) disulfide.

Claim 33

Dependent Claim 2 words

2'-bis(trioctoxysilyl-2-methylethyl) disulfide.

Claim 34

Dependent Claim 31 words

The process of claim 1 where organosilane disulfides of said organosilane polysulfide compounds are selected from at least one of: 3,3'-bis(trimethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) disulfide.

Claim 35

Dependent Claim 52 words

The process of claim 1 where, for said organosilane polysulfide, at least 95 percent of n is 2; where said R 2 radicals are alkyl radicals selected from methyl, ethyl, n-propyl and n-decyl radicals; and where said R 1 radicals are selected from benzyl, alpha, alpha dimethylbenzyl, p-tolyl, p-nonylphenol and p-chlorophenol radicals.

Claim 36

Dependent Claim 33 words

The process according to claim 32 where the organosilane disulfides of said organosilane polysulfide compounds are selected from at least one of: 3,3'-bis(trimethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) disulfide.

Claim 37

Dependent Claim 286 words

The process of claim 1 wherein said organosilane disulfide of said organosilane polysulfide compound (iii) is selected from at least one of 3,3'-bis(trimethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) disulfide; where said carbon black has a CTAB value in a range of about 80 to about 150 and said silica, alumina and aluminosilicate have a BET surface area in a range of about 100 to about 300 square meters per gram, a dibutylphthalate (DBP) absorption value in a range of about 150 to about 350, a CTAB value in a range of about 100 to about 220 and has a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.; wherein said sulfur donor additional additive is selected from at least one of dimorpholine disulfide, dimorpholine tetrasulfide, tetramethyl thiuram tetrasulfide, benzothiazyl-2,N dithiomorpholide, thioplasts, dipentamethylenethiuramhexasulfide and disulfidecaprolactame; wherein said vulcanization accelerator for sulfur vulcanizable elastomers additional additive is selected from at least one of mercaptobenzothiazole, tetramethyl thiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate, N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N diphenylthiourea, dithiocarbamylesulfenamide, N,N diisopropylbezothiozole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N methyl piperazine), dithiobis(N beta hydroxy ethyl piperazine) and dithiobis(dibenzyl amine); and wherein said organosilane polysulfide additional additive is selected from at least one of 3,3'-bis(trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylethyl tolylene) trisulfide and tetrasulfide; and 3,3 '-bis(trimethoxysilylethyl tolylene) trisulfide and tetrasulfide.

Claim 38

Dependent Claim 32 words

The process according to claim 34 which comprises the additional step of vulcanizing the prepared rubber composition at a temperature in a range of from about 140° C. to about 190° C.

Claim 39

Dependent Claim 11 words

A rubber composition prepared according to the process of claim 35.

Claim 40

Dependent Claim 49 words

The process according to claim 34 which comprises the additional steps of preparing an assembly of a tire of sulfur vulcanizable rubber with a tread comprised of the said rubber composition and vulcanizing the assembly at a temperature in a range of about 140° C. to about 190° C.

Claim 41

Dependent Claim 10 words

A tire prepared according to the process of claim 37.

Claim 42

Dependent Claim 34 words

The process according to claim 4 where, for said sulfur vulcanizable elastomer, said conjugated dienes are selected from isoprene and 1,3-butadiene and said vinyl aromatic compounds are selected from styrene and alpha methyl styrene.

Claim 43

Dependent Claim 58 words

The process according to claim 4 where the sulfur vulcanizable elastomer is selected from at least one of natural and synthetic cis 1,4-polyisoprene rubber, emulsion polymerization prepared styrene/butadiene copolymer rubber, organic solution polymerization prepared styrene/butadiene copolymer rubber, 3,4-polyisoprene rubber, isoprene/butadiene rubber, styrene/isoprene/butadiene terpolymer rubbers, cis 1,4-polybutadiene rubber, and emulsion polymerization prepared styrene/butadiene/acrylonitrile terpolymer rubber and butadiene/acrylonitrile copolymer rubber.

Claim 44

Dependent Claim 131 words

The process according to claim 4 wherein the silica is characterized by having a BET surface area in a range of about 100 to about 300 square meters per gram and a dibutylphthalate (DBP) absorption value in a range of about 150 to about 350, a CTAB value in a range of about 100 to about 220, and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.

Claim 45

Dependent Claim 51 words

The process according to claim 41 in which said filler is comprised of about 15 to about 100 weight percent precipitated silica and, correspondingly, from 5 to about 85 weight percent carbon black; wherein said carbon black is has a CTAB value in a range of about 80 to about 150.

Claim 46

Dependent Claim 31 words

The process according to claim 42 wherein the filler is comprised of about 60 to about 95 weight percent silica and, correspondingly, about 40 to about 5 weight percent carbon black.

Claim 47

Dependent Claim 138 words

The process according to claim 4 wherein said filler is comprised of about 15 to about 100 weight percent alumina and, correspondingly, from 5 to about 85 weight percent carbon black; wherein said carbon black has a CTAB value in a range of about 80 to about 150 and said alumina has a CTAB value in a range of about 100 to about 220, and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.

Claim 48

Dependent Claim 31 words

The process according to claim 44 wherein said filler is comprised of about 60 to about 95 weight percent alumina and, correspondingly, about 40 to about 5 weight percent carbon black.

Claim 49

Dependent Claim 139 words

The process according to claim 4 wherein said filler is comprised of about 15 to about 100 weight percent aluminosilicate and, correspondingly, from about 5 to about 85 weight percent carbon black; wherein said carbon black has a CTAB in a range of about 80 to about 150 and wherein said aluminosilicate has a CTAB value in a range of about 100 to about 220, and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.

Claim 50

Dependent Claim 31 words

The process according to claim 46 wherein said filler is comprised of about 60 to about 95 weight percent aluminosilicate and, correspondingly, about 40 to about 5 weight percent carbon black.

Claim 51

Dependent Claim 65 words

The process according to claim 46 where said aluminosilicate is selected from at least one of at least one of (a) natural aluminosilicates selected from Muscovite, Beryl, Dichroite, Sepiolite and Kaolinire and (b) synthetic aluminosilicates prepared by (i) coprecipitation of a basic solution, or mixture of silicate and aluminate or by (ii) a chemical reaction between silanols of a silicon dioxide and NaAlO 2 .

Claim 52

Dependent Claim 41 words

The process according to claim 48 where for said synthetic aluminosilicate about 5 to about 95 percent of its surface is composed of silica moleties and, correspondingly, about 95 to about 5 percent of its surface is composed of aluminum moieties.

Claim 53

Dependent Claim 50 words

The process according to claim 46 where said synthetic aluminosilicate is represented by the formula selected from: [(Al 2 O 3 ) x .(SiO 2 ) y .(H 2 O) z ] and/or [(Al 2 O 3 ) x .(SiO 2 ) y .MO]; where M is magnesium or calcium.

Claim 54

Dependent Claim 30 words

The process according to claim 4 wherein said sulfur donor additional additive is selected from at least one of dimorpholine tetrasulfide, tetramethyl thiuram tetrasulfide, benzothiazyl-2,N dithiomorpholide, thioplasts, dipentamethylenethiuramhexasulfide and disulfidecaprolactame.

Claim 55

Dependent Claim 57 words

The process according to claim 4 wherein said vulcanization accelerator for sulfur vulcanizable elastomers additional additive is selected from at least one of mercaptobenzothiazole, tetramethyl thiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate, N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N diphenylthiourea, dithiocarbamylesulfenamide, N,N diisopropylbezothiozole-2-sulfenamide, zinc-2-mercaptotoluimidazole, dithiobis (N methyl piperazine), dithiobis(N beta hydroxy ethyl piperazine) and dithiobis(dibenzyl amine).

Claim 56

Dependent Claim 56 words

The process according to claim 4 wherein said sulfur donor additional additive (iv) is exclusive of said organosilane polysulfide (iii) having at least 80 percent of n being 2 and is selected from at least one of 3,3'-bis(trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylethyl tolylene) trisulfide and tetrasulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) trisulfide and tetrasulfide.

Claim 57

Dependent Claim 33 words

The process according to claim 4 wherein for the said organosilane polysulfide compound, said R 2 radicals are alkyl radicals and said R 1 radicals are selected from alkaryl, phenyl and haloaryl radicals.

Claim 58

Dependent Claim 49 words

The process according to claim 54 wherein said alkyl radicals are selected from methyl, ethyl, n-propyl and n-decyl radicals; said aralkyl radicals are selected from benzyl and alpha, alpha dimethylbenzyl radicals; said alkaryl radicals are selected from p-tolyl and p-nonylphenol radicals; and said haloaryl radical is a p-chlorophenol radical.

Claim 59

Dependent Claim 23 words

The process according to claim 4 wherein organosilane disulfides of said organosilane polysulfide compounds are selected from at least one of: 2,2'-bis(trimethoxysilylethyl) disulfide;

Claim 60

Dependent Claim 74 words

3'-bis(trimethoxysilylpropyl) disulfide; disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 2,2'-bis(triethoxysilylpropyl) disulfide; 2,2'-bis(tripropoxysilylethyl) 2,2'-bi(tri-sec.butoxysilylethyl) disulfide; 3,3'-bis(tri-t-butoxyethyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; 3,3,-bis(trimethoxysilylethyl tolylene) disulfide; 3,3'-bis(triisopropoxypropyl) disulfide; 3,3'-bis(trioctoxypropyl) disulfide; 2,2'-bis(2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis(dimethoxy ethoxysilylethyl) disulfide; 3,3'-bis(methoxyethoxypropoxysilylpropyl) disulfide; 3,3'-bis(methoxy dimethylsilylpropyl) disulfide; 3,3'-bis(cyclohexoxy dimethylsilylpropyl) disulfide; 4,4'-bis(trimethoxysilylbutyl) disulfide; 3,3'-bis(trimethoxysilyl-3-methylpropyl) disulfide; 3,3'-bis(tripropoxysilyl-3-methylpropyl)disulfide; 3,3'-bis(dimethoxy methylsilyl-3-ethylpropyl) disulfide; 3,3'-bis(trimethoxysilyl-2-methylpropyl) disulfide; 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,3'-bis (trimethoxysilylcyclohexyl) disulfide; 12,12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18,18'-bis (trimethoxysilyloctadecyl) disulfide; 18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2-'-bis (trimethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (tripropoxysilyl-2-methylethyl) disulfide; and 2,2'-bis(trioctoxysilyl-2-methylethyl) disulfide.

Claim 61

Dependent Claim 74 words

3'-bis(trimethoxysilylpropyl) disulfide; disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 2,2'-bis(triethoxysilylpropyl) disulfide; 2,2'-bis(tripropoxysilylethyl) 2,2'-bi(tri-sec.butoxysilylethyl) disulfide; 3,3'-bis(tri-t-butoxyethyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; 3,3,-bis(trimethoxysilylethyl tolylene) disulfide; 3,3'-bis(triisopropoxypropyl) disulfide; 3,3'-bis(trioctoxypropyl) disulfide; 2,2'-bis(2'-ethylhexoxysilylethyl) disulfide; 2,2'-bis(dimethoxy ethoxysilylethyl) disulfide; 3,3'-bis(methoxyethoxypropoxysilylpropyl) disulfide; 3,3'-bis(methoxy dimethylsilylpropyl) disulfide; 3,3'-bis(cyclohexoxy dimethylsilylpropyl) disulfide; 4,4'-bis(trimethoxysilylbutyl) disulfide; 3,3'-bis(trimethoxysilyl-3-methylpropyl) disulfide; 3,3'-bis(tripropoxysilyl-3-methylpropyl)disulfide; 3,3'-bis(dimethoxy methylsilyl-3-ethylpropyl) disulfide; 3,3'-bis(trimethoxysilyl-2-methylpropyl) disulfide; 3,3'-bis(dimethoxyphenylsilyl-2-methylpropyl) disulfide; 3,3'-bis (trimethoxysilylcyclohexyl) disulfide; 12,12'-bis (trimethoxysilyldodecyl) disulfide; 12,12'-bis (triethoxysilyldodecyl) disulfide; 18,18'-bis (trimethoxysilyloctadecyl) disulfide; 18,18'-bis (methoxydimethylsilyloctadecyl) disulfide; 2,2-'-bis (trimethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (triethoxysilyl-2-methylethyl) disulfide; 2,2'-bis (tripropoxysilyl-2-methylethyl) disulfide; and 2,2'-bis(trioctoxysilyl-2-methylethyl) disulfide.

Claim 62

Dependent Claim 32 words

The process according to claim 4 where organosilane disulfides of said organosilane polysulfide compounds are selected from at least one of: 3,3'-bis(trimethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) disulfide.

Claim 63

Dependent Claim 54 words

The process according to claim 4 where, for said organosilane polysulfide compound, at least 95 percent of n is 2; where said R 2 radicals are alkyl radicals selected from methyl, ethyl, n-propyl and n-decyl radicals; and where said R 1 radicals are selected from benzyl, alpha, alpha dimethylbenzyl, p-tolyl, p-nonylphenol and p-chlorophenol radicals.

Claim 64

Dependent Claim 32 words

The process according to claim 58 where organosilane disulfides of said organosilane polysulfide compounds are selected from at least one of: 3,3'-bis(trimethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) disulfide.

Claim 65

Dependent Claim 288 words

The process according to claim 4 wherein said organosilane disulfide of said organosilane polysulfide compound (iii) is selected from at least one of 3,3 '-bis(trimethoxysilylpropyl) disulfide; 3,3 '-bis(triethoxysilylpropyl) disulfide; 3,3'-bis(triethoxysilylethyl tolylene) disulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) disulfide; where said carbon black has a CTAB value in a range of about 80 to about 150 and said silica, alumina and aluminosilicate have a BET surface area in a range of about 100 to about 300 square meters per gram, a dibutylphthalate (DBP) absorption value in a range of about 150 to about 350, a CTAB value in a range of about 100 to about 220 and a mercury porosimetry pore size distribution of: five percent less of its pores with a diameter of less than about 10 nm; 60 to 90 percent of its pores with a diameter of about 10 to about 100 nm; 10 to 30 percent of its pores with a diameter of about 100 to about 1000 nm and 5 to 20 percent of its pores with a diameter of greater than about 1000 nm.; wherein said sulfur donor additional additive is selected from at least one of dimorpholine disulfide, dimorpholine tetrasulfide, tetramethyl thiuram tetrasulfide, benzothiazyl-2,N dithiomorpholide, thioplasts, dipentamethylenethiuramhexasulfide and disulfidecaprolactame; wherein said vulcanization accelerator for sulfur vulcanizable elastomers additional additive is selected from at least one of mercaptobenzothiazole, tetramethyl thiuram disulfide, benzothiazole disulfide, diphenylguanidine, zinc dithiocarbamate, alkylphenoldisulfide, zinc butyl xanthate, N-dicyclohexyl-2-benzothiazolesulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N diphenylthiourea, dithiocarbamylesulfenamide, N,N diisopropylbezothiozole-2-sulfenamide, zinc-2-mercaptotoluinfidazole, dithiobis (N methyl piperazine), dithiobis(N beta hydroxy ethyl piperazine) and dithiobis(dibenzyl amine); and wherein said organosilane polysulfide additional additive is selected from at least one of 3,3 '-bis(trimethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylpropyl) trisulfide and tetrasulfide; 3,3'-bis(triethoxysilylethyl tolylene) trisulfide and tetrasulfide; and 3,3'-bis(trimethoxysilylethyl tolylene) trisulfide and tetrasulfide.

Claim 66

Dependent Claim 32 words

The process according to claim 4 which comprises the additional step of vulcanizing the prepared rubber composition at a temperature in a range of from about 140° C. to about 190° C.

Claim 67

Dependent Claim 12 words

A vulcanized rubber composition prepared according to the process of claim 61.

Claim 68

Dependent Claim 49 words

The process according to claim 60 which comprises the additional steps of preparing an assembly of a tire of sulfur vulcanizable rubber with a tread comprised of the said rubber composition and vulcanizing the assembly at a temperature in a range of about 140° C. to about 190° C.

Claim 69

Dependent Claim 12 words

A vulcanized rubber tire prepared according to the process of claim 63.

Claim 70

Dependent Claim 19 words

The process according to claim 60 wherein, for said organosilane compound, at least 95 percent of n is 2.

Claim 71

Dependent Claim 32 words

The process according to claim 65 which comprises the additional step of vulcanizing the prepared rubber composition at a temperature in a range of from about 140° C. to about 190° C.

Claim 72

Dependent Claim 12 words

A vulcanized rubber composition prepared according to the process of claim 66.

Claim 73

Dependent Claim 49 words

The process according to claim 65 which comprises the additional steps of preparing an assembly of a tire of sulfur vulcanizable rubber with a tread comprised of the said rubber composition and vulcanizing the assembly at a temperature in a range of about 140° C. to about 190° C.

Claim 74

Dependent Claim 12 words

A vulcanized rubber tire prepared according to the process of claim 68.

Claim 75

Dependent Claim 59 words

The process of claim 4 wherein said preparatory steps (A) are composed of at least two sequential mixing steps in which said elastomer, said particulate filler and said organosilane polysulfide compound are added to one or more of said sequential mixing steps and wherein said sulfur source and/or vulcanization accelerator is/are added in a subsequent sequential preparatory mixing step.

Claim 76

Dependent Claim 64 words

The process of claim 4 wherein said preparatory steps (A) are composed of at least two sequential mixing steps in which about 20 to about 60 weight percent of the silica, the said organosilane disulfide compound and said sulfur source and/or vulcanization accelerator are added in one or more mixing steps and the remainder thereof added in at least one subsequent preparatory mix step.

Claim 77

Dependent Claim 60 words

The process of claim 1 wherein said organosilane polysulfide compound, in which at least 80 percent of n is 2, is added to said thermomechanical preparatory mixing in a form of a particulate comprised of about 25 to about 75 weight percent of said organosilane polysulfide compound and, correspondingly, about 75 to about 25 weight percent of particulate carbon black.

Claim 78

Dependent Claim 60 words

The process of claim 4 wherein said organosilane polysulfide compound, in which at least 80 percent of n is 2, is added to said thermomechanical preparatory mixing in a form of a particulate comprised of about 25 to about 75 weight percent of said organosilane polysulfide compound and, correspondingly, about 75 to about 25 weight percent of particulate carbon black.

Claim 79

Dependent Claim 60 words

The process of claim 60 wherein said organosilane polysulfide compound, in which at least 80 percent of n is 2, is added to said thermomechanical preparatory mixing in a form of a particulate comprised of about 25 to about 75 weight percent of said organosilane polysulfide compound and, correspondingly, about 75 to about 25 weight percent of particulate carbon black.

Claim 80

Dependent Claim 59 words

The process of claim 60 wherein said organosilane polysulfide compound, wherein at least 95 percent of n is 2, is added to said thermomechanical preparatory mixing in a form of a particulate comprised of about 25 to about 75 weight percent of said organosilane polysulfide compound and, correspondingly, about 75 to about 25 weight percent of particulate carbon black.

Claim 81

Dependent Claim 105 words

The process according to claim 60 which comprises the additional steps of preparing an assembly of a tire of sulfur vulcanizable rubber with a tread comprised of the said rubber composition and vulcanizing the assembly at a temperature in a range of about 140° C. to about 190° C.; and wherein the organosilane polysulfide compound, for which at least 80 percent of n is 2, is added to said thermomechanical preparatory mixing in a form of a particulate comprised of about 40 to about 60 weight percent of said organosilane polysulfide compound and, correspondingly, about 60 to about 40 weight percent of particulate carbon black.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1999-12-03	2000-06-03	2000-12-03	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2003-12-03	2004-06-03	2004-12-03	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2007-12-03	2008-06-03	2008-12-03	$7700.00	Window Closed / Lapsed

Silica reinforced rubber composition and use in tires

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