Claims
- 1. An elastomer/filler reinforcement composite comprised of a dispersion of said filler reinforcement formed in-situ within said elastomer host prepared by a method which comprises:
(A) blending an organic solution of a co-solvent and a phase transfer agent with an organic solution of a diene hydrocarbon based elastomer host wherein said elastomer is selected from elastomer host (1) and/or elastomer host (2); (B) thereafter blending therewith a filler precursor; (C) thereafter blending therewith at least one condensation reaction promoter to promote a condensation reaction of said filler precursor; (D) optionally blending therewith an organosilane prior to the completion of said condensation reaction; and (E) recovering the resulting elastomer/reinforcing filler composite; wherein said elastomer host is selected from
(1) at least one of homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with a vinyl aromatic compound, selected from styrene and alpha-methylstyrene and mixtures of such polymers and copolymers; and/or (2) at least one alkoxy metal end functionalized diene-based elastomer having a general formula (I): elastomer-X—(OR)n (I) wherein X is selected from silicon, titanium, aluminum and boron, R is selected from alkyl radicals having from 1 to 4 carbon atoms, and n is 3 for silicon and titanium and is 2 for aluminum and boron, and wherein said elastomer is selected from at least one of homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with styrene and/or alpha-methylstyrene, and mixtures thereof; wherein the solvent for said elastomer is selected from at least one of heptane, toluene, hexane, cyclohexane, xylene and their mixtures and the co-solvent for said transfer agent is selected from at least one of tetrahydrofuran, 1,4-dioxane, 2-ethylfurane, furfurylaldehyde and their mixtures, wherein said phase transfer agent is of the general Formula (II) which is represented in an ionized form: 3wherein R1, R2, R3 ad R4 are alkyl radicals containing from 1 to and including 4 carbon atoms independently selected from methyl, ethyl, n-propyl, sec-propyl, n-butyl and tert-butyl radicals, X is a radical selected from fluorine, chlorine, bromine, iodine, perchlorate, BF4− or PF6− radicals, and tetrabutylammonium fluoride, wherein said filler precursor is selected from at least one material selected from the general formulas (IIIA),(IIIB) and (IIIC): M(OR)x(R′)y (IIIA) (RO)x(R′)yM—O—M′(R′)z(RO)w (IIIB) (RO)x(R′)yM—(CH2)r—M′(R′)z(RO)w (IIIC) wherein M and M′ are the same or different and are selected from silicon, titanium, zirconium, boron and aluminum, where R and R′ are individually selected from alkyl radicals having from 1 to 4 carbon atoms, and wherein the sum of each of x+y and w+z integers is equal to 3 or 4 depending upon the valence of the associated M or M′, as the case may be and is, therefore, 4 except when its associated M or M′ is boron or aluminum for which it is 3, and wherein r is from 1 to 15; wherein said organosilane is at least one material selected from formula (IV), (V) or (VI), namely: an organosilane polysulfide of Formula (IV) as: Z-R1—Sm—R1-Z (IV) wherein m is a number in a range of from 2 to about 8 and the average for m is in a range of
(1) about 2 to about 2.6 or (2) about 3.5 to about 4.5; wherein Z is represented by the following formulas: 4wherein R2 is the same or different radical and is individually selected from alkyl radicals having 1 to 4 carbon atoms and phenyl radical; R3 is the same or different alkoxy groups wherein the alkyl radicals of the alkoxy group(s) are alkyl radicals independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl radicals; and R1 is a radical selected from substituted or unsubstituted alkyl radicals having a total of 1 to 18 carbon atoms and a substituted or unsubstituted aryl radical having a total of 6 to 12 carbon atoms; an alkyl alkoxy silane of Formula (V) as: (OR4)3—Si—R5 (V) where R4 may be the same or different alkyl radical selected from methyl, ethyl, n-propyl and isopropyl radicals and R5 is selected from alkyl radicals having from 1 to 18 carbon atoms and aryl radicals or alkyl substituted aryl radicals having from 6 to 12 carbon atoms; and a functional organosilane of Formula (VI) as: (OR6)3—Si—(CH2)y—Y (VI) wherein R6 is the same or different alkyl radicals selected from methyl, ethyl, n-propyl and isopropyl radicals, y is an integer of from 1 to 12, and Y is selected from primary amino, mercapto, epoxide, thiocyanato, vinyl, methacrylate, ureido, isocyanato and ethylene diamine radicals.
- 2. The elastomer/filler reinforcement composite of claim 1 wherein said co-solvent is selected from heptane, hexane and cyclohexane or their mixtures and said chain transfer agent is tetrabutylammonium fluoride.
- 3. The elastomer/filler reinforcement composite of claim 1 wherein said elastomer is elastomer (1) selected from at least one of homopolymers and copolymers of 1,3-butadiene and isoprene, copolymers of styrene with at least one of 1,3-butadiene and isoprene styrene, tin coupled polymers and copolymers of 1,3-butadiene and isoprene and tin coupled copolymers of styrene with at least one of 1,3-butadiene and isoprene, and mixtures thereof
- 4. The method of claim 1 wherein said elastomer is at least one elastomer (2) and wherein elastomer (2) has a general formula (I) of
- 5. The elastomer/filler reinforcement composite of claim 1 wherein said elastomer is said elastomer (2) selected from at least one of homopolymers and copolymers of 1,3-butadiene and isoprene and copolymers of 1,3-butadiene and/or isoprene with styrene and where said end functionalization is an alkoxysilane wherein the alkyl radicals of said alkoxysilane are selected from at least one of ethyl, methyl, n-propyl and isopropyl radicals, and mixtures thereof
- 6. The elastomer/filler reinforcement composite of claim 1 wherein said filler precursor is selected from at least one of tetraethoxy ortho silicate, titanium ethoxide, titanium n-propoxide, aluminum tri-sec butoxide, zirconium t-butoxide, zirconium n-butoxide, tetra-n-propoxy zirconium and boron ethoxide, methyl triethoxy silicate or dimethyl diethoxy silicate.
- 7. The elastomer/filler reinforcement composite of claim 1 wherein said filler precursor is selected from di-s-butoxyaluminoxy triethoxysilane and hexaethoxydisiloxane.
- 8. The elastomer/filler reinforcement composite of claim 1 wherein said organosilane polysulfide material is a bis-(3-triethoxysilylpropyl) disulfide having an average of from 2 to 2.6 or from 3.5 to 4 sulfur atoms in its polysulfidic bridge.
- 9. The elastomer/filler reinforcement composite of claim 1 wherein said alkyl alkoxy silane (VI) is selected from at least one of propyltriethoxysilane, methyltriethoxysilane, hexadecyltriethoxysilane or octadecyltriethoxysilane.
- 10. The elastomer/filler reinforcement composite of claim 1 wherein said functional organosilane of formula (VI) is selected from 3-amino propyl triethoxysilane, 2-aminoethyl triethoxysilane, 4-aminobutyltriethoxysilane, 3-mercapto propyl triethoxysilane, 2-mercaptoethyl triethoxysilane, 4-mercaptobutyl triethoxysilane, (3-glycidoxypropyl) triethoxysilane, 3-thiocyanato propyl triethoxysilane, vinyltriethoxysilane, ureidopropyltriethoxysilane, 3-isocyanatopropyl triethoxysilane, or N(3-triethoxysilyl) propyl ethylenediamine
- 11. The elastomer/filler reinforcement composite of claim 1 wherein said elastomer (1) is selected from cis 1,4-polyisoprene, cis 1,4-polybutadiene, isoprene/butadiene copolymers, styrene/butadiene copolymers including emulsion polymerization prepared copolymers and organic solvent solution polymerization prepared copolymers, styrene/isoprene copolymers, 3,4-polyisoprene, trans 1,4-polybutadiene, styrene/isoprene/butadiene terpolymer, high vinyl polybutadiene having from about 35 to about 90 percent vinyl groups and their mixtures.
- 12. The elastomer/filler reinforcement composite of claim 1 wherein the elastomer component of elastomer (2) is an organic solvent polymerization prepared elastomer selected from at least one of cis 1,4-polyisoprene, cis 1,4-polybutadiene, isoprene/butadiene copolymers, styrene/butadiene copolymers including emulsion polymerization prepared copolymers and organic solvent solution polymerization prepared copolymers, styrene/isoprene copolymers, 3,4-polyisoprene, trans 1,4-polybutadiene and styrene/isoprene/butadiene terpolymers and their mixtures.
- 13. The elastomer/filler reinforcement composite of claim 1 wherein said tin coupled elastomer is the product of reacting at least one conjugated diene or by reacting styrene together with at least one conjugated diene, wherein said diene is selected from 1,3-butadiene and isoprene, in an organic solvent solution and in the presence of an organolithium based catalyst followed by reacting the live polymer with at least one compound having the formula R74—SnXn, wherein n is an integer from 1 to and including 4, X is chlorine; and R7 is an alkyl radical selected from methyl, ethyl, propyl or butyl radicals.
- 14. An elastomer composition comprised of, based upon 100 parts by weight elastomers,
(A) about 10 to about 90 phr of at least one diene-based elastomer, (B) about 90 to about 10 phr of the elastomer/filler reinforcement composite of claim 1, (C) at least one additional reinforcing filler, wherein the total of said in situ formed filler and said additional reinforcing filler are present in an amount of from about 5 to about 120 phr and where said additional reinforcing filler is selected from precipitated silica, aluminosilicate as a co-precipitate of an aluminate and a silicate, carbon black, and modified carbon black having hydroxyl groups on its surface prepared by treatment of reinforcing carbon black with an organosilane at an elevated temperature or by co-fuming an organosilane and oil at an elevated temperature and their mixtures and (D) optionally a coupling agent additive having a moiety reactive with said additional reinforcing filler and another moiety interactive with said elastomer(s).
- 15. A method of preparing an elastomer/filler reinforcement composite which comprises:
(A) blending an organic solution of a co-solvent and a phase transfer agent with an organic solution of a diene hydrocarbon based elastomer host wherein said elastomer is selected from elastomer host (1) and/or elastomer host (2); (B) thereafter blending therewith a filler precursor; (C) thereafter blending therewith at least one condensation reaction promoter to promote a condensation reaction of said filler precursor; (D) optionally blending therewith an organosilane prior to the completion of said condensation reaction; and (E) recovering the resulting elastomer/reinforcing filler composite; wherein said elastomer host is selected from
(1) at least one of homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with a vinyl aromatic compound, selected from styrene and alpha-methylstyrene and mixtures of such polymers and copolymers; and/or (2) at least one alkoxy metal end functionalized diene-based elastomer having a general formula (I): elastomer-X—(OR)n (I) wherein X is selected from silicon, titanium, aluminum and boron, R is selected from alkyl radicals having from 1 to 4 carbon atoms, and n is 3 for silicon and titanium and is 2 for aluminum and boron, and wherein said elastomer is selected from at least one of homopolymers of conjugated dienes, copolymers of conjugated dienes, copolymers of conjugated diene with styrene and/or alpha-methylstyrene, and mixtures thereof; wherein the solvent for said elastomer is selected from at least one of heptane, toluene, hexane, cyclohexane, xylene and their mixtures and the co-solvent for said transfer agent is selected from at least one of tetrahydrofuran, 1,4-dioxane, 2-ethylfurane, furfurylaldehyde and their mixtures, wherein said phase transfer agent is of the general Formula (II) which is represented in an ionized form: 5wherein R1, R2, R3 ad R4 are alkyl radicals containing from 1 to and including 4 carbon atoms independently selected from methyl, ethyl, n-propyl, sec-propyl, n-butyl and tert-butyl radicals, X is a radical selected from fluorine, chlorine, bromine, iodine, perchlorate, BF4− or PF6− radicals, and tetrabutylammonium fluoride, wherein said filler precursor is selected from at least one material selected from the general formulas (IIIA),(IIIB) and (IIIC): M(OR)x(R′)y (IIIA) (RO)x(R′)yM—O—M′(R′)z(RO)w (IIIB) (RO)x(R′)yM—(CH2)r—M′(R′)z(RO)w (IIIC) wherein M and M′ are the same or different and are selected from silicon, titanium, zirconium, boron and aluminum, where R and R′ are individually selected from alkyl radicals having from 1 to 4 carbon atoms, and wherein the sum of each of x+y and w+z integers is equal to 3 or 4 depending upon the valence of the associated M or M′, as the case may be and is, therefore, 4 except when its associated M or M′ is boron or aluminum for which it is 3, and wherein r is from 1 to 15; wherein said organosilane is at least one material selected from formula (IV), (V) or (VI), namely: an organosilane polysulfide of Formula (IV) as: Z-R1—Sm—R1-Z (IV) wherein m is a number in a range of from 2 to about 8 and the average for m is in a range of
(1) about 2 to about 2.6 or (2) about 3.5 to about 4.5; wherein Z is represented by the following formulas: 6wherein R2 is the same or different radical and is individually selected from alkyl radicals having 1 to 4 carbon atoms and phenyl radical; R3 is the same or different alkoxy groups wherein the alkyl radicals of the alkoxy group(s) are alkyl radicals independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl radicals; and R1 is a radical selected from substituted or unsubstituted alkyl radicals having a total of 1 to 18 carbon atoms and a substituted or unsubstituted aryl radical having a total of 6 to 12 carbon atoms; an alkyl alkoxy silane of Formula (V) as: (OR4)3—Si—R5 (V) where R4 may be the same or different alkyl radical selected from methyl, ethyl, n-propyl and isopropyl radicals and R5 is selected from alkyl radicals having from 1 to 18 carbon atoms and aryl radicals or alkyl substituted aryl radicals having from 6 to 12 carbon atoms; and a functional organosilane of Formula (VI) as: (OR6)3—Si—(CH2)y—Y (VI) wherein R6 is the same or different alkyl radicals selected from methyl, ethyl, n-propyl and isopropyl radicals, y is an integer of from 1 to 12, and Y is selected from primary amino, mercapto, epoxide, thiocyanato, vinyl, methacrylate, ureido, isocyanato and ethylene diamine radicals.
- 16. An article of manufacture having at least one component comprised of the elastomer/filler reinforcement composite of claim 1.
- 17. A tire having at least one component comprised of the elastomer/filler reinforcement composite of claim 1.
- 18. A tire having a tread comprised of the elastomer/filler reinforcement composite of claim 1.
- 19. A tire having a tread comprised of the elastomer/filler reinforcement composite of claim 2.
- 20. A tire having a tread comprised of the elastomer/filler reinforcement composite of claim 14.
Parent Case Info
[0001] The Applicants hereby incorporate by reference prior U. S. Provisional Application Serial No. 60/322,065, filed on Sep. 14, 2001.
Provisional Applications (1)
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Number |
Date |
Country |
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60322065 |
Sep 2001 |
US |