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EP-3916045-B1 - HIGH STRENGTH HYDROGENATED POLYMERS, AND RUBBER COMPOSITIONS INCORPORATING SAME

EP3916045B1EP 3916045 B1EP3916045 B1EP 3916045B1EP-3916045-B1

Inventors

  • BEAULIEU, MICHAEL R.
  • YUKIMURA, Noriaki
  • QIN, ZENGQUAN

Dates

Publication Date
20260506
Application Date
20171221

Claims (8)

  1. A polymer comprising: a functionalized copolymer produced by copolymerization of at least one conjugated diolefin monomer and at least one vinyl monomer, the functionalized copolymer comprising an alkoxysilane functionalized styrene butadiene copolymer derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, or combinations thereof, wherein the functionalized copolymer has a degree of hydrogenation of 90 mol% to 98 mol% as measured using proton nuclear magnetic resonance spectroscopy ( 1 H NMR), and wherein the functionalized copolymer has an initial vinyl content from 10% to 60%.
  2. The polymer of claim 1 wherein the conjugated diolefin monomer comprises 1,3 butadiene, isoprene, myrcene, or combinations thereof, and wherein the vinyl monomer comprise styrene, alpha methyl styrene, or combinations thereof.
  3. A rubber composition comprising: the polymer of any of the preceding claims; at least one curative; and reinforcing filler.
  4. The rubber composition of claim 3, further comprising an additional rubber comprising natural rubber, synthetic rubber, or combinations thereof.
  5. The rubber composition of claims 3-4, wherein the reinforcing filler comprises silica, carbon black, or combinations thereof, and the curative comprises sulfur.
  6. A method of making a hydrogenated functionalized copolymer comprising: introducing an anionic polymerization initiator, at least one conjugated diolefin monomer, at least one vinyl monomer, and solvent to a reactor to produce a living copolymer via anionic polymerization; reacting the living copolymer with a compound comprising an alkoxysilane functionalized styrene butadiene copolymer derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, or combinations thereof, wherein the functionalized copolymer has an initial vinyl content from 10% to 60%; and hydrogenating the functionalized copolymer by mixing the functionalized copolymer with solvent and a hydrogenation catalyst in a hydrogen stream, wherein the hydrogenated functionalized copolymer has a degree of hydrogenation of 90 mol% to 98 mol % as measured using 1 H NMR.
  7. The method of claim 6, wherein the hydrogenation catalyst comprises nickel and aluminum, and the anionic polymerization initiator is a lithium catalyst.
  8. The method of claims 6-7, wherein the hydrogenation catalyst comprises nickel octoate.

Description

TECHNICAL FIELD Embodiments of the present disclosure are generally related to hydrogenated copolymers, and are specifically related to hydrogenated, functionalized copolymers having improved mechanical strength. BACKGROUND Rubber tires employing tire treads have been used for more than a century. Because the tire tread provides the interface between the tire and the road surface, the tire tread performance correlates to the drivability of the vehicle. Accordingly, there is a continual need for improved rubber compositions which increase the performance of the tire treads. EP1245585A2 relates to a hydrogenated modified polymer and a process for producing the same as well as a composition containing the same. EP1293535A2 relates to a resin composition comprising (a) an ionomer resin and (b) an alkoxysilyl group-containing hydrogenated conjugated diene-based polymer and/or an amino group-containing hydrogenated conjugated diene-based polymer. US2005171276A1 relates to a modified polymer and a composition containing the same. EP2272878A1 relates to a coupled copolymer and the manufacturing method thereof. EP2963087A1 relates to a tire member, a hydrogenated conjugated diene polymer, and a polymer composition. SUMMARY Embodiments of the present disclosure are directed to rubber compositions comprising hydrogenated functionalized copolymers, which provide improved mechanical strength, especially in tread tire applications. Specifically, these rubber compositions may demonstrate a significant improvement in elongation and tensile strength at break. By increasing the mechanical strength, these hydrogenated, functionalized copolymers may desirably enable a weight reduction in the tire, which reduces the rolling resistance of the tire. Moreover, while the present disclosure may focus on the utilization of the present rubber compositions in tire tread applications, the present compositions may also be suitable for tire sidewalls, inner liners and bladders, because the hydrogenated, functionalized copolymers have good ozone resistance properties (due to minimal double bonds) and good gas permeability (due to minimal solubility of gases within the polymer). One embodiment of the present disclosure is directed to a polymer comprising a functionalized copolymer produced by copolymerization of at least one conjugated diolefin monomer and at least one vinyl monomer, the functionalized copolymer comprising an alkoxysilane functionalized styrene butadiene copolymer derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, or combinations thereof, wherein the functionalized copolymer has a degree of hydrogenation of 90 mol% to 98 mol% as measured using proton nuclear magnetic resonance spectroscopy (1H NMR), and wherein the functionalized copolymer has an initial vinyl content from 10% to 60%. Another embodiment of the present disclosure is directed to a method of making a hydrogenated functionalized copolymer comprising: introducing an anionic polymerization initiator, at least one conjugated diolefin monomer, at least one vinyl monomer, and solvent to a reactor to produce a living copolymer via anionic polymerization; reacting the living copolymer with a compound comprising an alkoxysilane functionalized styrene butadiene copolymer derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, or combinations thereof, wherein the functionalized copolymer has an initial vinyl content from 10% to 60%; andhydrogenating the functionalized copolymer by mixing the functionalized copolymer with solvent and a hydrogenation catalyst in a hydrogen stream, wherein the hydrogenated functionalized copolymer has a degree of hydrogenation of 90 mol% to 98 mol % as measured using 1H NMR. Additional features and advantages of the embodiments described herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, and the claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a Transmission Electron Microscopy (TEM) micrograph of a styrene butadiene copolymer when hydrogenated to 45.73 mol% with respect to the butadiene (Table 1, Example 4, Sample 5) according to one or more embodiments of the present disclosure.FIG. 1B is a TEM micrograph of a styrene butadiene copolymer when hydrogenated to 57.95 mol% (Table 1, Example 4, Sample 6) according to one or more embodiments of the present disclosure.FIG. 1C is a TEM micrograph of a styrene butadiene copolymer when hydrogenated to 68.72 mol% (Table 1, Example 4, Sam