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## where X is a halogen, and R.sup.1 is selected from a group consisting of an aromatic amide moiety of formula (II):
C.sub.6(R.sup.2).sub.5(CO)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 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a dithiazyl disulphide moiety of formula (III): ##STR00017## where R.sup.4a and R.sup.4b are identical or different and are a hydrogen moiety, a halogen, a nitro, a hydroxy, a linear or branched alkyl moiety having 1 to 12 carbon atoms, a linear or branched alkoxy moiety having 1 to 12 carbon atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 carbon atoms, or together form the cyclic moiety of formula (IV): ##STR00018## where R.sup.5a, R.sup.5b, R.sup.5c, and R.sup.5d are identical or different and are a hydrogen moiety, a hydroxy, a linear or branched alkyl moiety having 1 to 12 carbon atoms, a linear or branched alkoxy moiety having 1 to 12 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a thiuram moiety of formula (VII): ##STR00019## where Z is sulphur or oxygen, R.sup.9a and R.sup.9b are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a dithioxanthogenate moiety according to formula (VIII):
R.sup.10OC(S)(VIII) where R.sup.10 is a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; and a phosphonate moiety according to formula (IX):
(R.sup.11aO)(R.sup.11bO)P(Z)(IX) where Z is a sulphur or oxygen atom, and R.sup.11a and R.sup.11b are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms.

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

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

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

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

6. The rubber mixture according to claim 5, further comprising at least one of one or more of a rubber auxiliary and at least one further rubber different from the modified diene polymer.

7. A vulcanizable composition comprising: the rubber mixture according to claim 5, and at least one crosslinking system comprising at least one crosslinker and optionally one or more crosslinking accelerators.

8. A process for producing vulcanizates, the process comprising vulcanizing the vulcanizable composition according to claim 7.

9. The process according to claim 8, wherein the vulcanizing is performed at a temperature of 100 C. to 200 C.

10. The process according to claim 8, wherein the vulcanizing is performed at a temperature of 120 C. to 190 C.

11. A vulcanizate obtained by the process according to claim 8.

12. The vulcanizate according to claim 11, wherein the vulcanizate is in the form of a shaped body, a drive belt, a roller covering, a seal, a cap, a stopper, a hose, a floor covering, a sealing mat, a sealing sheet, a sealing profile, or a sealing membranes.

13. The vulcanizate according to claim 11, wherein the vulcanizate is in the form of a tire, a tire tread or a layers of a tire tread.

14. The modified diene polymer according to claim 1, comprising: the in-chain substructure according to formula (X): ##STR00021## where X is selected from a chlorine atom, a bromine atom, and an iodine atom, and R.sup.1 is selected from: an aromatic amide moiety of formula (II):
C.sub.6(R.sup.2).sub.5(CO)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 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a dithiazyl disulphide moiety of formula (III): ##STR00022## where R.sup.4a and R.sup.4b are identical or different and are a hydrogen moiety, a halogen, a nitro, a hydroxy, a linear or branched alkyl moiety having 1 to 8 carbon atoms, a linear or branched alkoxy moiety having 1 to 8 carbon atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 carbon atoms, or together form the cyclic moiety of formula (IV): ##STR00023## where R.sub.5a, R.sub.5b, R.sub.5c, and R.sub.5d are identical or different and are a hydrogen moiety, a hydroxy, a linear or branched alkyl moiety having 1 to 8 carbon atoms, a linear or branched alkoxy moiety having 1 to 8 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a thiuram moiety of formula (VII): ##STR00024## where Z is sulphur or oxygen, R.sup.9a and R.sup.9b are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a dithioxanthogenate moiety according to formula (VIII):
R.sup.10OC(S)(VIII) where R.sup.10 is a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; and a phosphonate moiety according to formula (IX):
(R.sup.11aO)(R.sup.11bO)P(Z)(IX) where Z is a sulphur or oxygen atom, R.sup.11a and R.sup.11b are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 8 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms.

15. A process for producing a modified diene polymer, the process comprising reacting a diene polymer with at least one halogenated sulphidic organic compound, wherein the at least one halogenated sulphidic organic compound is formed by reacting a halogen with at least one sulphidic compound having at least one of formula (I-a), (I-b), and (I-c):
R.sup.1aSSR.sup.1b(I-a),
R.sup.1aS(S).sub.nSR.sup.1b, where 1n8(I-b),
R.sup.1aSH(I-c), where R.sup.1a and R.sup.1b are identical or different and selected from a group consisting of: an aromatic amide moiety of formula (II):
C.sub.6(R.sup.2).sub.5(CO)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 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a dithiazyl disulphide moiety of formula (III): ##STR00025## where R.sup.4a and R.sup.4b are identical or different and are a hydrogen moiety, a halogen, a nitro, a hydroxy, a linear or branched alkyl moiety having 1 to 12 carbon atoms, a linear or branched alkoxy moiety having 1 to 12 carbon atoms, a phenyl moiety, a cycloalkyl moiety having 5 to 8 carbon atoms, or together form the cyclic moiety of formula (IV): ##STR00026## where R.sup.5a, R.sup.5b, R.sup.5c, and R.sup.5d are identical or different and are a hydrogen moiety, a hydroxy, a linear or branched alkyl moiety having 1 to 12 carbon atoms, a linear or branched alkoxy moiety having 1 to 12 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a thiuram moiety of formula (VII): ##STR00027## where Z is sulphur or oxygen, R.sup.9a and R.sup.9b are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a dithioxanthogenate moiety according to formula (VIII):
R.sup.10OC(S)(VIII) where R.sup.10 is a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms; a phosphonate moiety according to formula (IX):
(R.sup.11aO)(R.sup.11bO)P(Z)(IX) where Z is a sulphur or oxygen atom, and R.sup.11a and R.sup.11b are identical or different and are a hydrogen atom, a linear or branched alkyl moiety having 1 to 16 carbon atoms, a phenyl moiety, or a cycloalkyl moiety having 5 to 8 carbon atoms.

16. The process according to claim 15, wherein the modified 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.

17. The process according to claim 15, further comprising reacting the diene polymer with a Mooney jump functionalization reagent.

18. The process according to claim 17, wherein the Mooney jump functionalization reagent is S.sub.2Cl.sub.2.

19. A modified diene polymer obtained according to the process of claim 15.

Description

EXAMPLES

I. Polymers

Inventive Example 1

(1) Preparation of Fx-PBR1

(2) 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.

(3) 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.

(4) 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

(5) Preparation of Fx-PBR2

(6) 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.

(7) 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:

(8) 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

(9) 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:

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

Inventive Example 4

(11) Preparation of Moony Jumped Fx-PBR2

(12) 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:

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

II: Vulcanizate Tests

(14) The following properties were determined on the vulcanizates in accordance with the stated standards: DIN 53505: Shore A hardness at 60 C. DIN 53512: rebound resilience at 60 C. DIN 53504: tensile test with stress values at 100% and 300% (S100 and S300) 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. The method was used to obtain the following variables, the terminology here being in accordance with ASTM 5992-96: tan (60 C.): loss factor (E/E) at 60 C. 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. 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 206 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%. The method was used to obtain the following variables, the terminology here being in accordance with ASTM 5992-96: G* (15%): dynamic modulus at 15% amplitude sweep tan (max): maximum loss factor (G/G) of entire measuring range at 60 C. 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.

(15) Comparison of polymer Mooney of various modified NdBRs according to the invention and standard NdBRs

(16) 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)

(17) Following substances were used in the compounds:

(18) 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)

(19) 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:

(20) 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

(21) The following are comparative results for the compounded materials and vulcanizates of the BR/carbon black mixtures

(22) 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

(23) 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:

(24) 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

(25) The following are comparative results for the compounded materials and vulcanizates of the BR/carbon black mixtures

(26) 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

(27) 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.