Rubber composition

Patent metadata

Field	Value
Publication number	US-2016237259-A1
Application number	US-201415031391-A
Country	US
Kind code	A1
Filing date	Oct 23, 2014
Priority date	Oct 24, 2013
Publication date	Aug 18, 2016
Grant date	—

Abstract

The invention relates to vulcanizable rubber compositions comprising at least the following components:
a) at least one functionalized polymer, b) at least one modified polybutadiene having a proportion of cis-1,4 units of >95% by weight and a proportion of 1,2-vinyl content of <1% by weight, the polybutadiene having been modified by means of sulphur chlorides after the polymerization, c) at least one silica, d) at least one further filler, e) at least one vulcanizing agent, f) at least one oil and g) optionally at least one further rubber additive.

First claim

1 . Vulcanizable rubber composition comprising:
a) at least one functionalized polymer, b) at least one modified polybutadiene having a proportion of cis-1,4 units of >95% by weight and a 1,2-vinyl content of <1% by weight, the polybutadiene having been modified by means of sulphur chlorides after the polymerization, c) at least one silica, d) at least one further filler, e) at least one vulcanizing agent, and f) at least one oil.

2 . The vulcanizable rubber composition according to claim 1 , wherein the functionalized polymer comprises at least one of:
functionalized diene polymers, and functionalized diene copolymers
obtained by copolymerization of dienes with vinylaromatic monomers.

3 . The vulcanizable rubber composition according to claim 1 , wherein the functionalized polymer is at least one of: a polybutadiene, a polyisoprene, a butadiene-isoprene copolymer, a butadiene-styrene copolymer, an isoprene-styrene copolymer and a butadiene-isoprene-styrene terpolymer.

4 . The vulcanizable rubber composition according to claim 1 , wherein the functionalized polymer comprises end group-functionalized butadiene-styrene copolymers prepared by solution polymerization.

5 . The vulcanizable rubber composition according to claim 4 , wherein the end group-functionalized butadiene-styrene copolymers have Mooney viscosities (ML 1+4 (100° C.)) of 10 to 200 Mooney units.

6 . The vulcanizable rubber composition according to claim 5 , wherein the end group-functionalized butadiene-styrene copolymers have mean molar masses (number-average, Mn) of 10,000 to 2,000,000 g/mol.

7 . The vulcanizable rubber composition according to claim 6 , wherein the end group-functionalized butadiene-styrene copolymers have glass transition temperatures of −110° C. to +20° C.

8 . The vulcanizable rubber composition according to claim 1 , wherein the modified polybutadiene is obtained by solution polymerization in the presence of at least one inert organic solvent and in the presence of at least one catalyst based on neodymium compounds within a temperature range of −20° C. to 150° C., stopping the polymerization by adding protic compounds, and modifying the polymer with sulphur chlorides to increase the Mooney viscosity thereof.

9 . The vulcanizable rubber composition according to claim 8 , wherein, prior to modifying the polymer with sulphur chlorides, the sulphur chlorides are treated with a carboxylic acid, fatty acid and/or fatty acid ester.

10 . The vulcanizable rubber composition according to claim 9 , wherein the sulphur chlorides are disulphur dichloride, sulphur chloride, sulphur bromide, sulphur dichloride, thionyl chloride, disulphur dibromide and/or thionyl bromide.

11 . The vulcanizable rubber composition according to claim 10 , wherein the modified polybutadiene, after modification with the sulphur chlorides, has a Mooney viscosity (ML 1+4 at 100° C.) at least 50% greater than the Mooney viscosity (ML 1+4 at 100° C.) of the polybutadiene prior to modification with the sulphur chlorides.

12 . The vulcanizable rubber composition according to claim 11 , wherein the polybutadiene, before modification with the sulphur chlorides has a Mooney viscosity (ML 1+4 at 100° C.) of at least 20 MU, and the modified polybutadiene after the modification with sulphur chlorides has a Mooney viscosity (ML 1+4 at 100° C.) of at least 30 MU, and a gel content less than 1% by weight.

13 . Vulcanizable rubber composition comprising:
a) 50 to 90 parts by weight of at least one functionalized solution butadiene-styrene copolymer (SSBR) (oil-free) having a glass transition temperature (Tg) between −110° C. to 20° C., based on the oil-free SSBR, b) 10-50 parts by weight of at least one modified neodymium-catalysed polybutadiene (NdBR) having a Mooney viscosity (ML 1+4 at 100° C.) of at least 30 MU, c) 50-120 parts by weight of at least one silica, d) 2-25 parts by weight of at least one further filler, e) 1-5 parts by weight of at least one vulcanizing agent, and f) 5-50 parts by weight of at least one oil,
where the parts by weight figures for components c)-f) are each based on 100 parts by weight of rubber (sum total of a) and b)).

14 . The vulcanizable rubber composition according to claim 13 , wherein the composition comprises:
a) 60 to 70 parts by weight of the at least one functionalized solution butadiene-styrene copolymer (SSBR) (oil-free) having a glass transition temperature (Tg) between −110° C. to 20° C., based on the oil-free SSBR, b) 20 to 40 parts by weight of the at least one modified neodymium-catalysed polybutadiene (NdBR) having a Mooney viscosity (ML 1+4 at 100° C.) of at least 30 MU, c) 60-100 parts by weight of the at least one silica, d) 5-10 parts by weight of the at least one further filler, wherein the further filler is carbon black, e) 2-4 parts by weight of the at least one vulcanizing agent, f) 10-40 parts by weight of at least one oil, and g) 2-5 parts by weight, of at least one rubber additive,
where the parts by weight figures for components c)-g) are each based on 100 parts by weight of rubber (sum total of a) and b)).

15 . Process for producing the vulcanizable rubber compositions according to claim 1 , the process comprising mixing components a) to f) with one another in one or more stages comprising:
a three-stage mixing operation with two mixing stages in an internal mixer and a final mixing stage on a roller, with cooling of the mixture to temperatures of <120° C., preferably <110° C., prior to addition of those components which are added on the roller, or a two-stage mixing operation in which the 1st mixing stage is effected in an internal mixer and the 2nd mixing stage on a roller, or a two-stage mixing operation in which both mixing stages are effected in an internal mixer.

16 . Process for producing vulcanizates from the rubber compositions of claim 1 , the process comprising subjecting the vulcanizable rubber compositions according to claim 1 to a crosslinking reaction at a temperature of 100 to 250° C., under a pressure of 1 to 200 bar.

17 . The process according to claim 16 , further comprising a shaping operation, wherein the crosslinking takes place in the course of shaping operation.

18 . Vulcanizates obtained by the process according to claim 16 .

19 . The vulcanizable rubber composition according to claim 1 , wherein:
the functionalized polymer comprises end group-functionalized butadiene-styrene copolymers prepared by solution polymerization, wherein the end group-functionalized butadiene-styrene copolymers have Mooney viscosities (ML 1+4 (100° C.)) of 30 to 150 Mooney units, mean molar masses (number-average, Mn) of 100,000 to 1,000,000 g/mol, and glass transition temperatures of −110° C. to 0° C.; and the modified polybutadiene is obtained by solution polymerization in the presence of at least one inert organic solvent and in the presence of at least one catalyst based on neodymium compounds within a temperature range of −20° C. to 150° C., stopping the polymerization by adding protic compounds to produce polybutadiene, and modifying the polybutadiene with sulphur chlorides to increase the Mooney viscosity thereof, wherein the polybutadiene, before modification with the sulphur chlorides has a Mooney viscosity (ML 1+4 at 100° C.) of at least 20 MU, and the modified polybutadiene after the modification with the sulphur chlorides has a Mooney viscosity (ML 1+4 at 100° C.) of at least 30 MU.

20 . The vulcanizable rubber composition accord

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Hardy David John
• Kloppenburg Heike
• Lucassen Alex
• Steinhauser Norbert
• Zhang Yan

Classifications

• C08L2205/06

  having improved processability or containing aids for moulding methods · CPC title

• C08L2205/02

  containing two or more polymers of the same C08L -group · CPC title

• C08L15/00 Primary

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title

• C08L9/00 Primary

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• C08K3/36

  Silica · CPC title