# US 2019/0375918 A1 · Rubber composition

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- Number: US 2019/0375918 A1
- Document ID: US20190375918A1
- Status: Published application
- Kind: A1
- Application number: 16/301,554
- Filed: 2017-06-07
- Published: 2019-12-12
- Earliest claimed: 2016-06-07
- Assignees: Trinseo Europe GmbH
- Applicants: Trinseo Europe GmbH
- Inventors: Silvia VALENTI; Sven THIELE; Christiane BERNDT
- Web page: https://patentgrep.com/patent/US20190375918A1

## CPC

- C08L 9/00: Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L 9/06: Copolymers with styrene
- B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- C08F 8/34: Introducing sulfur atoms or sulfur-containing groups
- C08F 8/42: Introducing metal atoms or metal-containing groups
- C08F 236/06: Butadiene
- C08F 236/10: with vinyl-aromatic monomers
- C08K 3/06: Sulfur
- C08K 3/22: of metals
- C08K 3/36: Silica
- C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators}
- C08K 5/09: Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K 5/5403: {containing no other elements than carbon or hydrogen}
- C08K 2003/2296: {of zinc}
- C08L 7/00: Compositions of natural rubber
- C08L 91/00: Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- B60C: VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

The present invention relates to polymer blend that includes (a) 50 to 90 percent by weight of a first elastomeric polymer having a high molecular weight, (b) 5 to 50 percent by weight, preferably 5 to 40 percent by weight, more preferably 10 to 35 percent by weight, of a second elastomeric polymer having a low molecular weight and being coupled, wherein the amounts of the components (a) and (b) are based on the total weight of the polymer blend.

## Claims

### Claim 1

A polymer blend, comprising:
(a) 50 to 95 percent by weight of a first elastomeric polymer,
(b) 5 to 50 percent by weight, preferably 5 to 40 percent by weight, more preferably 10 to 35 percent by weight, of a second elastomeric polymer;
wherein the first elastomeric polymer is a random polymer and obtainable by (I) anionic polymerization of at least one conjugated diene monomer and one or more α-olefin monomer(s) in the presence of a polymerization initiator in an organic solvent and (II) optionally coupling of the polymer chains obtained in (I) by a coupling agent;
wherein the second elastomeric polymer is obtainable by (i) anionic polymerization of at least one conjugated diene monomer and one or more α-olefin monomer(s) in the presence of a polymerization initiator in an organic solvent, and (ii) coupling the polymer chains obtained in (i) by a coupling agent;
wherein the first elastomeric polymer (a) has a number average molecular weight (Mn) of 300,000 to 2,000,000 g/mol and a weight-average molecular weight (Mw) of 300,000 to 4,000,000 g/mol;
wherein the second elastomeric polymer (b) has a number average molecular weight (Mn) of 1,000 to 80,000 g/mol, a weight-average molecular weight (Mw) in the range of 1,000-140,000 g/mol, more preferably in the range of 5,000-90,000 g/mol, most preferably in the range of 2,000-40,000 g/mol, and a molecular weight at the maximum of the peak (MP) in the range of 2,000 g/mol to 100,000 g/mol, more preferably in the range of 3,000 to 70,000 g/mol, most preferably in the range of 4,000 to 40,000 g/mol; and
wherein the amounts of the components (a) and (b) are based on the total weight of the polymer blend.

### Claim 2 (depends on 1)

The polymer blend according to claim 1,
wherein (III) the polymer chain ends of the first elastomeric polymer obtained in (I) are modified by addition and reaction of at least one compound represented by any of formula (1) or formula (12), as defined below:
(R***O)x(R**)ySi-A-S—SiR**3 formula (1),
wherein each of R** is independently selected from C1-C16 alkyl or alkylaryl; R*** is independently selected from C1-C4 alkyl; A is selected from C6-C18 aryl, C7-C50 alkylaryl, C1-C50 alkyl and C2-C50 dialkylether; and optionally R**, R***, or A may independently be substituted with one or more groups, selected from C1-C4 alkyl, C1-C4 alkoxy, C6-C12 aryl, C7-C16 alkylaryl, di(C1-C7 hydrocarbyl)amino, bis(tri(C1-C12 alkyl)silyl)amino, tris(C1-C7 hydrocarbyl)silyl and C1-C12 thioalkyl; x is an integer selected from 1, 2 and 3; y is an integer selected from 0, 1 and 2; provided that x+y=3;
wherein R9e, R10e, R11e and R12e are each independently selected from hydrogen, (C1-C16) alkyl, (C6-C16) aryl and (C7-C16) aralkyl, preferably R9e, R10e, R11e are hydrogen and R12e is methyl.

### Claim 3 (depends on 2)

The polymer blend according to claim 2, wherein the compound represented by formula (1) is (MeO)3Si—(CH2)3—S—SiMe2C(Me)3, (MeO)2(Me)Si—(CH2)3—S—SiEt3, (MeO)2(Me)Si—(CH2)3—S—Si(tBu)3, (MeO)2(Me)Si—(CH2)3—S—Si(Bz)3 or (MeO)2(Me)Si—(CH2)3—S—SiMe2C(Me)3 and/or wherein the compound represented by formula (12) is N-methyl-2-pyrrolidon.

### Claim 4 (depends on 1)

The polymer blend according to claim 1, wherein the coupling rate of the second elastomeric polymer is at least 50 percent by weight, such as at least 60 percent by weight or 80 percent by weight.

### Claim 5 (depends on 1)

The polymer blend according to claim 1, wherein (III) the polymer chain ends of the first elastomeric polymer obtained in (I) and/or (iii) the polymer chain ends of the second elastomeric polymer obtained in (i) are modified by addition and reaction of at least one compound represented by any of formula (2), as defined below;
((R1O)x2′(R2)y2′Si—R3—S)s2′M*(R4)t2′(X*)u2′ formula (2),
wherein M* is silicon or tin; x2′ is an integer selected from 1, 2 and 3; y2′ is an integer selected from 0, 1, and 2; wherein x2′+y2′=3; s2′ is an integer selected from 2, 3 and 4; t2′ is an integer selected from 0, 1 and 2; u2′ is an integer selected from 0, 1 and 2; wherein s2′+t2′+u2′=4; R1 is independently selected from hydrogen and (C1-C6) alkyl; R2 is independently selected from (C1-C16) alkyl, (C7-C16) alkylaryl and (C7-C16) arylalkyl; R3 is at least divalent and is independently selected from (C1-C16) alkyl, (C8-C16) alkylarylalkyl, (C7-C16) arylalkyl and (C7-C16) alkylaryl, and each group may be substituted with one or more of the following groups: tertiary amine group, silyl group, (C7-C18) aralkyl group and (C6-C18) aryl group; R4 is independently selected from (C1-C16) alkyl and (C7-C16) alkylaryl; X* is independently selected from chloride, bromide and —OR5*; wherein R5* is selected from (C1-C16) alkyl and (C7-C16) arylalkyl.

### Claim 6 (depends on 1)

The polymer blend according to claim 1, wherein the coupling agent is at least one compound represented by any of formula (16), formula (II) or formula (III), as defined below;
(R100)a100(Z**)Xb100 formula (16),
(R100O)a100(Z**)Xb100 formula (II),
(R100O)b100(Z**)(R100)a100 formula (III),
wherein Z** is tin or silicon; Xb100 is independently selected from chlorine, bromine and iodine; R100 is independently selected from the group consisting of (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C16) aryl and (C7-C16) aralkyl; a100 is independently an integer from 0 to 1 and b100 is independently an integer from 3 to 4, provided that a+b=4.

### Claim 7 (depends on 1)

The polymer blend according to claim 1, wherein the coupling agent is selected from the group consisting of SiCl4, Si(OCH3)4 and SnCl4.

### Claim 8 (depends on 1)

The polymer blend according to claim 1, wherein the polymerization initiator used in (i) is selected from the group consisting of n-BuLi, sec-BuLi, or tert-BuLi.

### Claim 9 (depends on 1)

The polymer blend according to claim 1, wherein the polymerization initiator used in (I) is selected from the group consisting of n-BuLi, sec-BuLi, tert-BuLi, Li-(CH2)(Me)2Si—N—(C4H9)2, Li-(CH2)(Me)2Si—N—(C2H5)2, a compound of formula (6) or formula (7), as defined below, or a Lewis base adduct thereof, and/or a mixture thereof;
wherein R3a is independently selected from —N(R28)R29, C1-C18 alkyl, C6-C18 aryl and (C7-C18) aralkyl; R4a is independently selected from —N(R30a)R31a, (C1-C18) alkyl, (C6-C18) aryl and (C7-C18) aralkyl; R5 and R6 are each independently selected from hydrogen, C1-C18 alkyl, C6-C18 aryl and C7-C18 aralkyl; M2 is lithium; R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24 and R25 are each independently selected from hydrogen, C1-C18 alkyl, C6-C18 aryl and C7-C18 aralkyl; R26, R27, R28, R29, R30a and R31a are each independently selected from C1-C18 alkyl, C6-C18 aryl and C7-C18 aralkyl; q is selected from an integer of 1, 2, 3, 4 and 5; r is selected from an integer of 1, 2 and 3; and a1′ is selected from an integer of 0 or 1; preferably a1′ is 1.

### Claim 10 (depends on 1)

The polymer blend according to claim 1, wherein
the conjugated diene monomer is selected from 1,3-butadiene, 2-alkyl-1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene and/or 1,3-cyclooctadiene, preferably 1,3-butadiene, and/or 2-methyl-1,3-butadiene; and/or
the α-olefin monomer is selected from styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, stilbene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, vinyl benzyl dimethylamine, (4-vinylbenzyl)dimethyl aminoethyl ether, N,N-dimethylaminoethyl styrene, N,N-bis-(trialkylsilyl)aminostyrene, tert-butoxystyrene, vinylpyridine, divinylbenzene, and/or mixtures thereof; preferably styrene, α-methylstyrene, and/or divinylbenzene; and/or
the first elastomeric polymer (a) is a styrene-butadiene-copolymer and the second elastomeric polymer (b) is a styrene-butadiene-copolymer; and/or
the α-olefin content of the first elastomeric polymer is in the range of 10-50% and the vinyl content of the diene fraction of the copolymers is in the range of 10-70%; and/or
the α-olefin content of the second elastomeric polymer is in the range of 5-50% and the vinyl content of the diene fraction of the copolymers is in the range of 30-75%; and/or
the degree of branching of the second elastomeric polymer is more than 2.

### Claim 11 (depends on 1)

The polymer blend according to claim 1, wherein the anionic polymerization (I) and/or (i) is performed in the presence of at least one randomizer, such as ditetrahydrofuyl-propane (DTHFP) and tetramethylene-ethylene-diamine (TMEDA).

### Claim 12 (depends on 1)

The polymer blend according to claim 1, further comprising (c) 0 to 13 percent by weight of one or more extender oil(s), wherein the amounts of the components (a), (b) and (c) are based on the total weight of the polymer blend.

### Claim 13 (depends on 1)

A non-cured polymer composition, comprising the polymer blend according to claim 1 and optionally further comprising one or more additional components selected from the group consisting of (i) components which are added to or formed as a result of the polymerization process used for preparing the first and second elastomeric polymers; (ii) components which remain after solvent removal from the polymerization process; and (iii) components which are added to the polymer prior to completion of the polymer manufacturing process.

### Claim 14 (depends on 1)

A method for preparing the polymer blend according to claim 1, comprising the following steps:
preparing the first elastomeric polymer by (I) anionic polymerization of at least one conjugated diene monomer and one or more α-olefin monomer(s) in the presence of a polymerization initiator in an organic solvent and (II) optionally coupling the polymer chains obtained in (I) by a coupling agent; and
preparing the second elastomeric polymer by (i) anionic polymerization of at least one conjugated diene monomer and one or more α-olefin monomer(s) in the presence of a polymerization initiator in an organic solvent and (ii) coupling the polymer chains obtained in (i) by a coupling agent;
blending the first and second elastomeric polymer and optionally one or more extender oil(s);
removing solvent to provide a resulting polymer; and
drying of the resulting polymer blend under heating.

### Claim 15 (depends on 1)

A method for preparing the polymer blend according to claim 1, comprising the following steps:
in situ-preparing the polymer blend by (i) anionic polymerization of at least one conjugated diene monomer and one or more α-olefin monomer(s) in the presence of a polymerization initiator in an organic solvent and (ii) coupling the polymer chains obtained in (i) by a coupling agent, thereby preparing the second elastomeric polymer, and (I) addition of at least one conjugated diene monomer and one or more α-olefin monomer(s) and (II) optionally coupling the polymer chains obtained in (II) by a coupling agent, thereby preparing the first elastomeric polymer;
optionally blending one or more extender oil(s) with the in situ-prepared polymer blend;
removing solvent to provide a resulting polymer; and
drying of the resulting polymer blend under heating.

### Claim 16 (depends on 14)

A polymer blend obtainable according to claim 14.

### Claim 17 (depends on 15)

A polymer blend obtainable according to claim 15.