HETEROATOM CONTAINING MODIFIED DIENE POLYMERS

Abstract

Modified diene polymers containing heteroatoms are disclosed, as is their production, rubber mixtures comprising these modified diene rubbers, and to their use for the production of rubber vulcanizates, which serve, in particular, for the production of rubber moldings and the production of tires.

Claims

1. A modified diene polymer comprising: an in-chain substructure according to formula (X) ##STR00016## and/or a terminal end-chain substructure according to formula (XI),
SR.sup.1(XI) where for formula (X), X is a halogen, and for formulae (X) and (XI), R.sup.1 is selected from a group consisting of an aromatic amide moiety of the formula (II)
C.sub.6(R.sup.2).sub.5(C?O)N(R.sup.3)C.sub.5(R.sup.2).sub.4 (II) where R.sup.2 and R.sup.3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a dithiazyl disulphide moiety of the formula (III) ##STR00017## where R.sup.4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxy, a linear or branched alkyl moiety having 1 to 12 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together form the cyclic moiety of the formula (IV); ##STR00018## where R are identical or different and are a hydrogen moiety, hydroxy, a linear or branched alkyl moiety having 1 to 12 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a bistrialkoxysilylalkyl polysulphide moiety of the formula (V)
(R.sup.6O).sub.3Si(CH.sub.2).sub.n(Y).sub.m(V) where n is an integer 1 to 12; m is an integer 0 to 4; R.sup.6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; Y is sulphur, a group of the formula (Via), (VIb), (Vic), (Vid), or (Vie) ##STR00019## where x is an integer 1 to 8; p is an integer 1 to 12; R.sup.8 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, an alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a phenoxy moiety; thiuram moiety of the formula (VII)
(R.sup.9).sub.2N(C?Z)(VII) where Z is sulphur or oxygen, R.sup.9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a dithioxanthogenate moiety according to the formula (VIII)
R.sup.10OC(?S)(VIII) where R.sup.10 are identical or different and are a hydrogen atom, linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a phosphonate moiety according to the formula (IX)
(R.sup.11O)(R.sup.11O)P(Z)(IX) where Z is a sulphur or oxygen atom, and R.sup.11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms.

2. The modified polymer according to claim 1, further comprising a sulfur bridge between polymeric chains according to formula (XII) ##STR00020##

3. The modified polymer according to claim 1, wherein the polymer is a diene homopolymer or a diene copolymer obtained via copolymerization of conjugated diene monomers, or copolymerization of conjugated diene monomers with vinylaromatic co-monomers.

4. The modified polymer according to claim 1, wherein the polymer is a polybutadiene or a polybutadiene-styrene copolymer.

5. A process for producing a modified polymer, the process comprising reacting a diene polymer with at least one halogenated sulphidic organic compound, wherein the halogenated sulphidic organic compound is formed by reacting a halogen with a sulphidic compound with the general formula (I-a) and/or (I-b) and/or (I-c):
R.sup.1SSR.sup.1(I-a),
R.sup.1S(S).sub.nSR.sup.1, where 1?n?8(I-b),
R.sup.1SH(I-c), where R.sup.1 are identical or different and selected from a group consisting of: an aromatic amide moiety of the formula (II)
C.sub.6(R.sup.2).sub.5(C?O)N(R.sup.3)C.sub.6(R.sup.3).sub.4(II) where R.sup.2 and R.sup.3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 18 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a dithiazyl disulphide moiety of the formula (III) ##STR00021## where R.sup.4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxy, a linear or branched alkyl moiety having 1 to 12 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together form the cyclic moiety of the formula (IV); ##STR00022## where R.sup.5 are identical or different and are a hydrogen moiety, hydroxy, a linear or branched alkyl moiety having 1 to 12 C atoms, a linear or branched alkoxy moiety having 1 to 12 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a bistrialkoxysilylalkyl polysulphide moiety of the formula (V)
(R.sup.6O).sub.3Si(CH.sub.2).sub.n(Y).sub.m(V) where n is an integer 1 to 12; m is an integer 0 to 4; R.sup.6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms; Y is sulphur, a group of the formula (Via), (VIb), (Vic), (Vid), or (Vie) ##STR00023## where x is an integer 1 to 8; p is an integer 1 to 12; R.sup.8 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, an alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a phenoxy moiety; a thiuram moiety of the formula (VII)
(R.sup.9).sub.2N(C?Z)(VII) where Z is sulphur or oxygen, R.sup.9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a dithioxanthogenate moiety according to the formula (VIII)
R.sup.10OC(?S)(VIII) where R.sup.10 are identical or different and are a hydrogen atom, linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a phosphonate moiety according to the formula (IX)
(R.sup.11O)(R.sup.11O)P(Z)(IX) where Z is a sulphur or oxygen atom, and R.sup.11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms.

6. The process according to claim 5, wherein the diene polymer is formed via polymerization of at least one conjugated diene monomer, or polymerization of at least one conjugated diene monomer with at least one vinylaromatic co-monomer.

7. The process according to claim 5, further comprising reacting the diene polymer with a moony jump functionalization reagent.

8. The process according to claim 7, wherein the moony jump functionalization reagent is S.sub.2Cl.sub.2.

9. A modified polymer obtained according to the process of claim 5.

10. A rubber mixture comprising: the modified polymer according to claim 1; and 10 to 500 parts by weight of filler, based on 100 parts by weight of the modified polymer.

11. The rubber mixture according to claim 10, further comprising: one or more of a rubber auxiliary, and/or at least one further rubber different from the modified polymer.

12. A vulcanizable composition comprising: the rubber mixture according to claim 10, and at least one crosslinking system comprising at least one crosslinker, and optionally one or more crosslinking accelerators.

13. A process for producing vulcanizates, the process comprising vulcanizing the vulcanizable composition according to claim 12.

14. The process according to claim 13, wherein the vulcanizing is performed at a temperature of 100? C. to 200? C., preferably 120? C. to 190? C.

15. A vulcanizate obtained by the process according to claim 13.

16. The vulcanizate according to claim 15, wherein the vulcanizate is in the form of shaped bodies, more preferably in the form of a drive belt, of roller coverings, of a seal, of a cap, of a stopper, of a hose, of floor covering, of sealing mats or sheets, profiles or membranes.

17. The vulcanizate according to claim 15, wherein the vulcanizate is in the form of tires, tire treads, or layers thereof.

18. The modified diene polymer according to claim 1, comprising: the in-chain substructure according to formula (X) ##STR00024## and/or the terminal end-chain substructure according to formula (XI),
SR.sup.1(XI) where for formula (X), X is selected from Cl, Br, and I, and for formulae (X) and (XI), R.sup.1 is selected from: an aromatic amide moiety of the formula (II)
C.sub.6(R.sup.2).sub.5(C?O)N(R.sup.3)C.sub.6(R.sup.2).sub.4 (II) where R.sup.2 and R.sup.3 are identical or different and are a hydrogen moiety, a linear or branched alkyl moiety having 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a dithiazyl disulphide moiety of the formula (III) ##STR00025## where R.sup.4 are identical or different and are a hydrogen moiety, a halogen, nitro, hydroxy, a linear or branched alkyl moiety having 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 8 C atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms, or together form the cyclic moiety of the formula (IV); ##STR00026## where R.sup.5 are identical or different and are a hydrogen moiety, hydroxy, a linear or branched alkyl moiety having 1 to 8 C atoms, a linear or branched alkoxy moiety having 1 to 8 C atoms, or a phenyl moiety, a cycloalkyl moiety having 5 to 8 C atoms; a bistrialkoxysilylalkyl polysulphide moiety of the formula (V)
(R.sup.6O).sub.3Si(CH.sub.2).sub.n(Y).sub.m(V) where n is an integer 1 to 6; m is an integer 0 to 2; R.sup.6 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; Y is sulphur, a group of the formula (Via), (VIb), (Vic), (Vid), or (Vie) ##STR00027## where x is an integer 2 to 6; p is an integer 1 to 6; R.sup.8 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 C atoms, an alkyl moiety having 1 to 8 C atoms, or a phenyl moiety, a phenoxy moiety; thiuram moiety of the formula (VII)
(R.sup.9).sub.2N(C?Z)(VII) where Z is sulphur or oxygen, R.sup.9 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a dithioxanthogenate moiety according to the formula (VIII)
R.sup.10OC(?S)(VIII) where R.sup.10 are identical or different and are a hydrogen atom, linear or branched alkyl moiety having 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms; a phosphonate moiety according to the formula (IX)
(R.sup.11O)(R.sup.11O)P(Z)(IX) where Z is a sulphur or oxygen atom, R.sup.11 are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 C atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 C atoms.

Description

EXAMPLES

I. Polymers

Inventive Example 1

Preparation of Fx-PBR1

[0155] Preparation of the modification reagent #1: Perkacit? TBzTD (109 g) was dispersed in dry hexane (330 g) at 50? C. Chlorine gas (17 g) is introduced. The reaction mixture was stirred for 30 min at 50? C. This gave a clear, yellow solution. The quantity needed for functionalization was then charged directly from this solution to a polymerization reactor with the below living polymer cement.

[0156] 71.4 kg of an 18.2% living polymer solution (cement) are charged under inert conditions of dry nitrogen into a 160 L steal reactor, that is equipped with an agitator, temperature control and a burette. To control the cement Mooney viscosity, about 300 g of the cement was transferred under nitrogen to a 1 L bottle, short stopped with 100 g of ethanol, stabilized with 0.2 g Irganox? 1520 and dried at 100? C. on a hot mill to get a solid sample. The resulting cement Mooney viscosity (ML 1+4@ 100? C.) was found to be 42.4 MU.

[0157] 243 g of the modification reagent #1 was placed in the burette and added under mixing at 58? C. to the reactor. The reaction mixture is stirred for 30 min. The mixture is then stabilized with 0.2 phr of Irganox? 1520. The polymer solution is stripped (pH 8-9), and the rubber is dried in dried in vacuo at 65? C. for 48 hours to a residual moisture level of <0.5% and found to have the following analytic data: Mooney viscosity (ML 1+4@ 100? C.): 52.5 MU, Mooney Stress Relaxation MSR 0.58; Solution viscosity 200 mPas; and Microstructure by FT-IR: 1,4-cis-BR: 97.7%, 1,4-trans-BR: 1.8%, 1.2-vinyl-BR: 0.5%.

Inventive Example 2

Preparation of Fx-PBR2

[0158] Preparation of the modification reagent #2: Vulkacit? DM (50 g) was dispersed in cyclohexane (400 g) at 50? C. Chlorine gas (12.8 g) was introduced and the reaction mixture was stirred for 30 min at 50? C. This gave a clear solution. The quantity needed for functionalization was charged directly from this solution to a polymerization reactor with living polymer cement below.

[0159] 68.1 kg of an 18.2% living polymer solution cement were charged into a reactor in a manner analogous to example 1. The cement Mooney viscosity (ML 1+4@ 100? C.) was 46.4 MU. 462 g of the modification reagent #2 was added at 63? C. thereto, and the reaction mixture stirred for 30 min. The mixture was then stabilized with 0.2 phr of Irganox? 1520. The polymer solution was stripped (pH 8-9), and the rubber was dried in vacuo at 65? C. for 48 hours to a residual moisture level of <0.5% and found to have the following analytic data:

[0160] Mooney viscosity (ML 1+4@ 100? C.): 43.5 MU, Mooney Stress Relaxation MSR 0.75; Solution viscosity 184 mPas; Microstructure by FT-IR: 1,4-cis-BR: 97.7%, 1,4-trans-BR: 1.8%, 1.2-vinyl-BR: 0.5%.

Reference Example 3

[0161] 71.4 kg of an 18.2% living polymer solution cement are charged into a reactor in a manner analogous to example 1 and short stopped by the addition of 300 g iso-propanol. The reactor was stirred for 1 hour. The cement Mooney viscosity (ML 1+4@ 100? C.) was 33.0 MU. 3.9 g lauric acid dissolved in 100 g of hexane were added and the reactor was stirred for 30 minutes. 26 g of S.sub.2Cl.sub.2 were added at 60? C. thereto, and the reaction mixture was stirred again for 30 min. The mixture was then stabilized with the addition of 0.2 phr of Irganox? 1520. The polymer solution was stripped (pH 8-9), and the rubber dried in vacuo at 65? C. for 48 hours to a residual moisture level of <0.5% and found to have the following analytic data:

[0162] Mooney viscosity (ML 1+4@ 100? C.): 43.2 MU, Mooney Stress Relaxation MSR 0.55; Solution viscosity 157 mPas.

Inventive Example 4

Preparation of Moony Jumped Fx-PBR2

[0163] 1 kg of the functionalized NdBR of example 2 (Fx-PBR2) was dissolved in 9 kg of hexane under inert atmosphere. 0.20 phr of lauric acid was added and the reaction mixture was heated to 65? C. 3 g of S.sub.2Cl.sub.2 were slowly added and the reaction mixture was stirred for 30 minutes. The reaction was cooled to ambient temperature and a mixture of 0.5 phr of epoxidized soja beanoil (ESBO) and 0.5 phr of Vulkanox? 4020 were added. The procedure was repeated a second time and both solutions were finished together. The product was precipitated in 60 L of ethanol and was dried in vacuo at 65? C. for 48 hours to a residual moisture level of <0.5% and found to have the following analytic data:

[0164] Mooney viscosity (ML 1+4@ 100? C.): 65.7 MU, Mooney Stress Relaxation MSR 0.42.

II: Vulcanizate Tests

[0165] The following properties were determined on the vulcanizates in accordance with the stated standards: [0166] DIN 53505: Shore A hardness at 60? C. [0167] DIN 53512: rebound resilience at 60? C. [0168] DIN 53504: tensile test with stress values at 100% and 300% (S100 and S300) [0169] DIN 53513: dynamic damping via Eplexor equipmentEplexor equipment (Eplexor 500 N) from Gabo-Testanlagen GmbH, Ahlden, Germany was used to determine dynamic properties (temperature dependency of storage modulus E in the temperature range from ?60? C. to 0? C. and also tan ? at 60? C.). The values were determined in accordance with DIN53513 at 10 Hz on Ares strips in the temperature range from ?100? C. to +100? C. at a heating rate of 1 K/min. [0170] The method was used to obtain the following variables, the terminology here being in accordance with ASTM 5992-96: [0171] tan ? (60? C.): loss factor (E/E) at 60? C. [0172] tan ? (60? C.) is a measure of hysteresis loss from the tyre under operating conditions. As tan ? (60? C.) decreases, the rolling resistance of the tyre decreases. [0173] DIN53513-1990: Elastic propertiesAn MTS elastomer test system (MTS Flex Test) from MTS was used to determine the elastic properties. The measurements were carried out in accordance with DIN53513-1990 on cylindrical samples (2 samples each 20?6 mm) with a total 2 mm compression at a temperature of 60? C. and a measurement frequency of 1 Hz in the range of amplitude sweep from 0.1 to 40%. [0174] The method was used to obtain the following variables, the terminology here being in accordance with ASTM 5992-96: [0175] G* (15%): dynamic modulus at 15% amplitude sweep [0176] tan ? (max): maximum loss factor (G/G) of entire measuring range at 60? C. [0177] tan ? (max) is a measure of the hysteresis loss from the tire under operating conditions. As tan ? (max) decreases, the rolling resistance of the tire decreases.

[0178] Comparison of polymer Mooney of various modified NdBRs according to the invention and standard NdBRs

TABLE-US-00001 Polymer ML (1 + 4).sub.100? C. MSR [MU] [MU s.sup.?1] Fx-PBR 1 (Inventive Example 1) 52.5 0.58 Fx-PBR 2 (Inventive Example 2) 43.5 0.75 Buna? CB24 (Reference) 43.7 0.62 Reference Example 3 43.6 0.59 Example 4 (Ex 2 + Mooney Jump) 65.7 0.42 (Inventive)

[0179] Following substances were used in the compounds:

TABLE-US-00002 Tradename Producer BUNA? CB 24 (Nd-Polybutadiene) Lanxess Deutschland GmbH CORAX? N 326 (Carbon Black) Evonic Degussa GmbH VIVATEC? 500 (oil) Hansen und Rosenthal KG ROTSIEGEL? ZINC WHITE Grillo Zinkoxid GmbH (Zinc oxide) EDENOR? C 18 98-100 Caldic Deutschland GmbH (stearic acid) VULKANOX? 4020/LG (Stabilizer) Lanxess Deutschland GmbH VULKANOX? HS/LG (Stabilizer) Lanxess Deutschland GmbH VULKACIT? CZ/EGC (Accelerator) Lanxess Deutschland GmbH RHENOGRAN? IS 90-65 (Sulfur) RheinChemie Rheinau GmbH TSR/RSS 3 DEFO 700 Natural Rubber Defo 700 (Natural rubber)

[0180] All quantities mentioned below are provided in phr (parts per hundred) of rubber. The following substances were used for the mixture studies on modified NdBR (Fx-PBR1 and 2), on reference example 3 and on standard NdBR Buna? CB 24 with Carbon Black:

TABLE-US-00003 BR Rubber 100 CORAX? N 326 50 VIVATEC? 500 4 EDENOR? C 18 98-100 3 VULKANOX? 4020/LG 2 VULKANOX? HS/LG 3 ROTSIEGEL? ZINC WHITE 2 VULKACIT? CZ/EGC 1.4 RHENOGRAN? IS 90-65 2.72

[0181] The following are comparative results for the compounded materials and vulcanizates of the BR/carbon black mixtures

TABLE-US-00004 Rubber Used Buna? Fx-PBR 1 Fx-PBR 2 Reference CB24 Example 1 Example 2 Example 3 Compounded material 56.8 58.6 64.7 56.8 ML 1 + 4 Hardness [Shore A] 60.9 63.6 64.07 60.6 Rebound 60? C. [%] 64.5 67.5 67.5 60.23 Amplitude sweep 60? C. 10 Hz (MTS) G* (15%) [MPa] 1.29 1.,29 1.34 1.23 tan ? (max.) 0.131 0.12 0.114 0.119 Dynamic damping (Eplexor) tan ? (60? C.) 0.071 0.069 0.057 0.066 Tensile test S100 [MPa] 2.0 2.1 2.2 1.9 S300 [MPa] 7.8 8.1 8.6 7.5

[0182] The following substances were used for the mixture studies modified NdBR (Fx-PBR2 and Example 4) and on standard NdBR Buna? CB 24 with natural rubber and Carbon Black:

TABLE-US-00005 BR 70 TSR/RSS 3 DEFO 700 30 CORAX? N 326 50 VIVATEC? 500 4 EDENOR? C 18 98-100 3 VULKANOX? 4020/LG 2 VULKANOX? HS/LG 3 ZINKWEISS ROTSIEGEL 2 RHENOGRAN? IS 90-65 2.7 VULKACIT? CZ/EGC 1.4

[0183] The following are comparative results for the compounded materials and vulcanizates of the BR/carbon black mixtures

TABLE-US-00006 Buna? CB24 Example 2 Example 4 Compounded material ML 1 + 4 61.2 62.5 71.3 Hardness [Shore A] 60.9 64.1 60.6 Rebound 60? C. [%] 66.0 67.3 67.5 Amplitude sweep 60? C. 10 Hz (MTS) G* (15%) [MPa] 1.17 1.19 1.19 tan ? (max.) 0.129 0.129 0.121 Dynamic damping (Eplexor) tan ? (60? C.) 0.065 0.061 0.056 Tensile test S300 [MPa] 8.9 9.0 9.,8

[0184] In both compound studies above, the modified polymers from the inventive examples 1 and 2 and the modified and Mooney jumped polymer from the inventive example 4 show an improved rolling resistance tendency over the reference rubber, that is indicated by an increased rebound resilience at 60? C., a lower tan d (max) at the amplitude sweep at 60? C. and for example 2 and 4 also a lower tan ? (60? C.) in the dynamic damping in the Eplexor. In addition, the inventive examples 1, 2 and 4 have a higher S300 modulus in the tensile test at room temperature and a higher dynamic modulus G* at 15% amplitude sweep, that indicate a stronger network formation due to increased interactions between the polymer and the filler.