# US 2019/0169406 A1 · Silane-mediated enhancement of rubber storage stability

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2019/0169406 A1
- Document ID: US20190169406A1
- Status: Published application
- Kind: A1
- Application number: 16/309,200
- Filed: 2017-06-16
- Published: 2019-06-06
- Earliest claimed: 2016-06-17
- Assignees: Trinseo Europe GmbH
- Applicants: Trinseo Europe GmbH
- Inventors: Michael RÖSSLE; Sven THIELE; Helgard EBERT
- Web page: https://patentgrep.com/patent/US20190169406A1

## CPC

- C08L 9/06: Copolymers with styrene
- B60C 1/00: Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- C08C 19/22: Incorporating nitrogen atoms into the molecule
- C08C 19/25: Incorporating silicon atoms into the molecule
- C08C 19/42: reacting with metals or metal-containing groups
- C08C 19/44: of polymers containing metal atoms exclusively at one or both ends of the skeleton
- C08F 236/04: conjugated
- C08F 236/10: with vinyl-aromatic monomers
- C08F 2800/20: as weight or mass percentages
- 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
- C08C: TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

The present invention relates to a process for preparing a branched elastomeric polymer by polymerization of a conjugated diene in the presence of a specific branching agent and a specific stabilizing compound. The branched elastomeric polymer exhibits improved storage stability, as reflected by a constant, or less variable, polymer viscosity over time and with reduced temperature dependence.

## Claims

### Claim 1

A process for preparing a branched elastomeric polymer, said process comprising:
(a) polymerizing at least one conjugated diene and a compound of Formula 1 as defined below, and optionally one or more aromatic vinyl monomers, in the presence of an initiator compound,
(a′) polymerizing at least one conjugated diene and optionally one or more aromatic vinyl monomers in the presence of an initiator compound obtained by reacting a compound of Formula 1 as defined below with an organo-alkali metal compound, or
(a″) reacting a living polymer, obtained by anionically polymerizing at least one conjugated diene and optionally one or more aromatic vinyl monomers, with a compound of Formula 1 as defined below,
(A)-Bn (Formula 1)
wherein
A is an organic group having at least two amino groups;
each B is independently selected from a group —Si(R1)(R2)(R3), wherein R1, R2 and R3 are each independently selected from vinyl, butadienyl, methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl and benzyl, with the proviso that at least one of R1, R2 and R3 is selected from vinyl and butadienyl, wherein each group B is a substituent of an amino group of group A;
at least two of the amino groups of group A are each substituted with at least one group B;
n is an integer of at least 2; and
all amino groups in group A are tertiary amino groups;
wherein (a), (a′) and (a″) is carried out in the presence of a stabilizer compound of Formula 2 as defined below:
wherein
R′ is independently selected from C1-C12 alkyl, C2-C12 alkenyl, C6-C18 aryl and C7-C18 alkylaryl, wherein the two R′ groups may be connected to form a ring and the ring may contain, further to the Si-bonded nitrogen atom, one or more of an oxygen atom, a nitrogen atom, an >N(C1-C6 alkyl, C6-C18 aryl, C7-C18 alkylaryl) group and a sulfur atom;
R″ is selected from C1-C6 hydrocarbyl;
R′″ is independently selected from C1-C18 hydrocarbyl;
Ra, Rb and Rc are independently selected from hydrogen, methyl, ethyl and vinyl;
x is an integer selected from 1 and 2; y is an integer selected from 0, 1 and 2; z is an integer selected from 0, 1 and 2; and x+y+z=3;
m is selected from 0 and 1; with the proviso that, when none of Ra, Rb and Rc is vinyl, then m=0.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the compound of Formula 1 is a compound selected from the following Formulas 1-1 to 1-5:
wherein
each of R11, R12, R13, R14 and R15 is independently selected from group B, C1-C18 alkyl, C6-C18 aryl, optionally C1-C4 alkyl-substituted C3-C12 heteroaryl, C7-C18 aralkyl, (R4)a—O—(R5)b, wherein each of R4 and R5 is independently selected from C1-C6 alkyl and C6-C18 aryl and a and b are each integers independently selected from 0 to 4, and —Si(R6)(R7)(R8), wherein each of R6, R7 and R8 is independently selected from methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl and benzyl;
each of R9 and R10 is independently selected from divalent ethyl, propyl, butyl, phenyl and —(CH2)a—C6H5—(CH2)b′—, wherein each of a′ and b′ is an integer independently selected from 0 and 1; and
c is an integer selected from 0, 1, 2 and 3;
wherein the group —N< >N— is a 5- to 18-membered heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C1-C6 alkyl group, wherein heteroatomic groups other than the two N atoms expressly shown in Formula 1-2 are selected from —N═, >NR16, wherein R16 is selected from group B, C1-C6 alkyl, phenyl and benzyl, —O—, —S— and >SiR17R18, wherein each of R17 and R18 is independently selected from C1-C6 alkyl, phenyl and benzyl;
wherein each of R20, R21 and R22 is independently selected from a single bond and a divalent C1-C10 alkyl group, d is an integer selected from 0, 1 and 2, d′ is an integer selected from 0 and 1, wherein d is 0 when d′ is 0, each group —N< >X— is independently selected from a 5- to 10-membered heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C1-C6 alkyl group, wherein each X is independently selected from —N—, —C═ and —CH—, and heteroatomic groups other than the two groups N and X expressly shown in Formula 1-3 are selected from —N═, >NR16, wherein R16 is selected from C1-C6 alkyl, group B, phenyl and benzyl, —O—, —S— and >SiR17R18, wherein each of R17 and R18 is independently selected from C1-C6 alkyl, phenyl and benzyl;
wherein D is a 5- to 10-membered carbocyclic or heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C1-C6 alkyl group, wherein heteroatomic groups are selected from —N═, >NR16, wherein R16 is selected from C1-C6 alkyl, group B, phenyl and benzyl, —O—, —S— and >SiR17R18, wherein each of R17 and R18 is independently selected from C1-C6 alkyl and phenyl, each group —N< >X— is independently selected from a 5- to 10-membered heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C1-C6 alkyl group, wherein each X is independently selected from —N—, —C═ and —CH—, R23 is selected from a single bond and a divalent C1-C10 alkyl group, and e is an integer selected from 2, 3 and 4;
wherein E is a 6- to 10-membered cycloaliphatic or aromatic group, each R24 is independently selected from a single bond and C1-C2 alkyl, each R is independently selected from B, C1-C6 alkyl and benzyl, and f is an integer selected from 2 and 3.

### Claim 3 (depends on 1)

The process according to claim 1, wherein the compound of Formula 1 is selected from
wherein each R is independently selected from B, C1-C6 alkyl and benzyl;
wherein R is a C1-C6 alkyl group; and

### Claim 4 (depends on 1)

The process according to claim 1, wherein R′″ in Formula 2 is independently selected from C1-C18 alkyl, C2-C18 alkenyl, C6-C18 aryl and C7-C18 alkylaryl.

### Claim 5 (depends on 1)

The process according to claim 1, wherein R′ in Formula 2 is independently selected from methyl, ethyl, n-propyl, n-butyl, isobutyl, pentyl, hexyl, octyl and benzyl, or the two R′ groups are connected to form, together with the Si-bonded nitrogen atom, a 5- to 12-membered ring.

### Claim 6 (depends on 1)

The process according to claim 1, wherein R″ in Formula 2 is selected from C1-C6 alkyl and phenyl.

### Claim 7 (depends on 1)

The process according to claim 1, wherein Ra, Rb and Rc in Formula 2 are identical.

### Claim 8 (depends on 1)

The process according to claim 1, wherein in Formula 2
(i) x, y and z are each 1 and m=0,
(ii) x=2, y=0, z=1 and m=0, or
(iii) x=1, y=0, z=2 and m=1 and
at least one of Ra, Rb and Rc is vinyl.

### Claim 9 (depends on 1)

The process according to claim 1, wherein the initiator compound in step (a) or the organo-alkali metal compound in step (a′) is selected from methyllithium, ethyllithium, n-butyllithium, s-butyllithium, tert-butyllithium, tert-octyllithium, isopropyllithium, phenyllithium, cyclohexyllithium, 2-butyllithium, 4-phenylbutyllithium, t-butyldimethylsilyloxypropyllithium, dialkylaminopropyllithium, N-morpholinopropyllithium, sodium biphenylide, sodium naphthalenide, potassium naphthalenide, 1,3-bis(1-(phenyl)1-lithiohexyl)benzene, 1,3-bis(1-(4-ethylphenyl)1 dithiohexyl)benzene, 1,3-bis(1-(4-methyl-phenyl)1-lithiohexyl)benzene, 1,3-bis(1-(4-propylphenyl)1-lithiohexyl)benzene, 1,3-bis(1-(4-(tert-butyl)phenyl)1 dithiohexyl)-benzene, 1,3-bis(1-(4-(diethylamino)phenyl)1-lithiohexyl)-benzene, 1,3-bis(1-(4-(dimethylamino)phenyl)1-lithiohexyl)benzene, 1,3-bis(1-(4-ethoxy-phenyl)1-lithiohexyl)benzene, 1,3-bis(1-(4-(dimethoxy)phenyl)1 dithiohexyl)benzene, (((dimethylamino)dimethylsilyl)methyl)lithium, (((diethylamino)dimethylsilyl)methyl)lithium, (((dibutylamino)dimethylsilyl)methyl)lithium, (((dihexylamino)dimethylsilyl)methyl)lithium, (((dioctylamino)dimethylsilyl)methyl)lithium, (((dibenzylamino)dimethylsilyl)methyl)lithium, ((dimethyl(piperidin-1-yl)silyl)methyl)lithium, ((dimethyl(morpholino)silyl)methyl)lithium, ((dimethyl(4-methylpiperazin-1-yl)silyl)methyl)lithium, ((dimethyl(4-ethylpiperazin-1-yl)silyl)methyl)lithium, and ((dimethyl(4-benzylpiperazin-1-yl)silyl)methyl)lithium.

### Claim 10 (depends on 1)

The process according to claim 1, wherein the stabilizer of Formula 2 is used in an amount of 0.01 to 100 equivalent per equivalent of initiator or living polymer chain end.

### Claim 11 (depends on 1)

A branched elastomeric polymer obtained by a process as defined in claim 1.

### Claim 12 (depends on 11)

A non-vulcanized polymer composition comprising the branched elastomeric polymer as defined in claim 11 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for making said polymer, (ii) components which remain after solvent removal from the polymerization process, and (iii) components which are added to the polymer after completion of the polymer manufacturing process, wherein said composition optionally comprises one or more fillers.

### Claim 13 (depends on 12)

The non-vulcanized polymer composition according to claim 12, which comprises one or more extender oils.

### Claim 14 (depends on 12)

The non-vulcanized polymer composition according to claim 12, which comprises one or more vulcanizing agents.

### Claim 15 (depends on 14)

A vulcanized polymer composition which is obtained by vulcanizing the non-vulcanized polymer composition as defined in claim 14.

### Claim 16 (depends on 14)

A process for preparing a vulcanized polymer composition, said process comprising vulcanizing the non-vulcanized polymer composition as defined in claim 14.

### Claim 17 (depends on 15)

An article comprising at least one component formed from the vulcanized polymer composition as defined in claim 15, which article is selected from a tire, a tire tread, a tire side wall, a tire carcass, a belt, a gasket, a seal, a hose, a vibration damper, a footwear component, a golf ball and a hose.

### Claim 18 (depends on 5)

The process according to claim 5 wherein the 5- to 12-membered ring is a cyclopentylamine group, cyclohexylamine group, a cycloheptylamine group, a cyclooctylamine group, a cyclododecylamine group, a morpholine group, an oxazolidine group, a thiazolidine group, a thiamorpholine group, a 4-methylpiperazine group, a 4-ethylpiperazine group, a 4-propylpiperazine group, a 4-butylpiperazine group or a 4-benzylpiperazine group.