Oil extended functionalized styrene-butadiene copolymer

Patent metadata

Field	Value
Publication number	US-9902837-B2
Application number	US-201414785002-A
Country	US
Kind code	B2
Filing date	Apr 16, 2014
Priority date	Apr 18, 2013
Publication date	Feb 27, 2018
Grant date	Feb 27, 2018

Abstract

The present invention refers to an oil extended functionalized styrene-butadiene copolymer wherein the functionalized styrene-butadiene copolymer comprises 15 to 50 wt. %, based on 100 wt. % of the copolymer, of repeating units based on styrene, 42 to 80 wt. %, based on 100 wt. % of the copolymer, of repeating units based on butadiene, and 5 to 43 wt. %, based on 100 wt. % of the copolymer, of units based on at least one functional monomer and wherein at least one extender oil is based on vegetable oils, preferably epoxidized vegetable oil.

First claim

What is claimed is:

1. An oil extended, functionalized styrene-butadiene copolymer comprising:
functionalized styrene-butadiene copolymer comprising 15 to 50 wt. % of repeating units based on styrene, 42 to 80 wt. % of repeating units based on butadiene, and 5 to 43 wt. % of units based on at least one functional monomer; and
at least one extender oil comprising a transesterified vegetable oil, wherein the extender oil comprises a mixture of 35 to 48 wt. % fatty acid ethyl ester, 50 to 75 wt. % diglyceride, and 0.01 to 50 wt. % triglyceride, based on 100 wt. % of the mixture.

2. The oil extended functionalized styrene-butadiene copolymer according to claim 1 , wherein the functionalized copolymer is a functionalized terpolymer comprising the functional monomer is polymerized with the units based on styrene and the units based on butadiene.

3. The oil extended functionalized styrene-butadiene copolymer according to claim 2 , wherein the functionalized copolymer comprises 0.3 to 10 wt. % of the units based on the functional monomer.

4. The oil extended functionalized styrene-butadiene copolymer according to claim 3 , wherein the functionalized copolymer has a Mooney viscosity (ML 1+4 at 100° C.) of 35 to 65, and an average molecular weight (Mw) of 100,000 to 2,200,000 g/mol.

5. The oil extended functionalized styrene-butadiene copolymer according to claim 1 , wherein the functionalized copolymer comprises the functional monomer grafted to the copolymer.

6. The oil extended functionalized styrene-butadiene copolymer according to claim 1 , wherein the functional monomer comprises an acrylate based monomer.

7. The oil extended functionalized styrene-butadiene copolymer according to claim 1 , wherein the transesterified vegetable oil is a transesterified oil derived from an oil selected from the group consisting of soybean, cottonseed, castorbean, palm, linseed, coconut, sunflower, pine, corn, olive, peanut, rapeseed, canola, sesame, rice bran, jatropha oils and mixtures thereof.

8. The oil extended functionalized styrene-butadiene copolymer according to claim 7 , comprising 25 to 42 phr of the extender oil.

9. A process for producing the oil extended functionalized styrene-butadiene copolymer according to claim 1 , the process comprising:
(1) producing the functionalized styrene-butadiene copolymer by at least one of:
(1a) emulsion polymerization of the units based on styrene, the units based on butadiene and the functional monomer using a buffering system and controlling the pH in the range of 8.5 to 9.5, wherein the buffering system is selected from the group consisting of disodium hydrogen phthalate/sodium dihydrogen orthophosphate, acetic acid/sodium acetate, boric acid/sodium tetraborate, sodium phosphate disubstituted sodium hydroxide, monosodium phosphate/phosphoric acid, potassium dihydrogen orthophosphate/sodium hydroxide, disodium phosphate/phosphoric acid, monosodium phosphate/sodium hydroxide, boric acid/sodium hydroxide, dipotassium hydrogen phtalate/potassium dihydrogen orthophosphate, potassium dihydrogen orthophosphate/sodium hydroxide, sodium tetraborate/hydrochloric acid, sodium carbonate/sodium hydrogen carbonate, disodium phosphate/phosphoric acid, potassium phosphate/potassium hydroxide, sodium tetraborate/sodium hydroxide, sodium bicarbonate/sodium hydroxide, sodium hydrogen orthophosphate/sodium hydroxide, and potassium chloride/sodium hydroxide, or
(1b) grafting a styrene-butadiene copolymer obtained by emulsion polymerization of the units based on styrene and the units based on butadiene with the functional monomer, or
(1c) directly functionalizing the polymeric chain of an Emulsion Styrene-Butadiene Rubber with epoxide groups, and

(2) blending the functionalized styrene-butadiene copolymer obtained by (1a), (1b) and/or (1c) with the at least one extender oil.

10. The process according to claim 9 , wherein the functional monomer comprises an acrylate based monomer.

11. The process according to claim 9 , wherein the transesterified vegetable oil is a transesterified oil derived from an oil selected from the group consisting of soybean, cottonseed, castorbean, palm, linseed, coconut, sunflower, pine, corn, olive, peanut, rapeseed, canola, sesame, rice bran, jatropha and mixtures thereof.

12. The process according to claim 11 , wherein the transesterified vegetable oil comprises epoxidized oil having a degree of epoxidation of 2.5 to 4.5%.

13. A rubber composition comprising the oil extended functionalized styrene-butadiene copolymer according to claim 1 and at least one carbon black and/or at least one silica.

14. The oil extended functionalized styrene-butadiene copolymer according to claim 1 , wherein:
the oil extended functionalized styrene-butadiene copolymer comprises 25 to 42 phr of the extender oil; and
the transesterified vegetable oil is a transesterified oil derived from an oil selected from the group consisting of soybean, cottonseed, castorbean, palm, linseed, coconut, sunflower, pine, corn, olive, peanut, rapeseed, canola, sesame, rice bran, jatropha oils and mixtures thereof.

15. The oil extended functionalized styrene-butadiene copolymer according to claim 14 , wherein:
the functionalized copolymer is a functionalized terpolymer comprising the functional monomer polymerized with the units based on styrene and the units based on butadiene;
the functionalized copolymer comprises 0.3 to 10 wt. % of the units based on the functional monomer;
the functionalized copolymer has a Mooney viscosity (ML 1+4 at 100° C.) of 35 to 65, and an average molecular weight (Mw) of 100,000 to 2,200,000 g/mol;
the functional monomer comprises an acrylate based monomer; and
the extender oil comprises a mixture of 40 to 44 wt. % fatty acid ethyl ester, 56 to 60 wt. % diglyceride, and 0.01 to 4 wt. % triglyceride, based on 100 wt. % of the mixture.

16. The oil extended functionalized styrene-butadiene copolymer according to claim 15 , wherein:
the functionalized copolymer comprises 0.7 to 3.5 wt. %, of the units based on the functional monomer;
the functionalized copolymer has a Mooney viscosity (ML 1+4 at 100° C.) of 40 to 60, and an average molecular weight (Mw) of 200,000 to 900,000 g/mol;
the functional monomer is an acrylate based monomer selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, hydroxypopyl methacrylate, hydroxyethyl methacrylate, acrylonitrile, methacryimpropyltrimethoxysilane, methacryloxypropyltrilsopropoxysilane, methacryloxysilane, and mixtures thereof;
the oil extended functionalized styrene-butadiene copolymer comprises 375 phr of the extender oil; and
the extender oil comprises epoxidized oil having a degree of epoxidation of 3.3 to 3.5%.

17. The process according to claim 16 , wherein:
the functional monomer is selected from the group consisting of glycidyl methacrylate, glycidyl acrylate, hydroxypopyl methacrylate, hydroxyethyl methacrylate, methacryloxypropyltrimethoxysilane, methacryloxypropyltriisopropoxysilane, methacryloxysilane, and mixtures thereof;
the extender oil comprises 40 to 44 wt. % fatty acid ethyl ester, 56 to 60 wt. % diglyceride, and 0.01 to 4 wt. % triglyceride, based on 100 wt. % of the mixture;
the transesterified vegetable oil is a transesterified oil derived from an oil selected from the group consisting of soybean, cottonseed, castorbean, palm, linseed, coconut, sunflower, pine, corn, olive, peanut, rapeseed, canola, sesame, rice bran, jatropha and mixtures thereof; and
extender oil comprises epoxidized oil having a degree of epoxidation of 3.3 to 3.5%.

Assignees

• Lanxess Deutschland Gmbh
• Lanxess Elastomeros Do Brasil S A
• Arlanxeo Deutschland Gmbh
• Arlanxeo Brasil S A

Inventors

• Moutinho Marcus Tadeus De Moura
• Remigio Dos Santos Manoel
• Hardy Dave

Classifications

• C08F257/02

  on to polymers of styrene or alkyl-substituted styrenes · CPC title

• C08F2/32

  Polymerisation in water-in-oil emulsions · CPC title

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title

• C08F279/02

  on to polymers of conjugated dienes · CPC title

• C08K5/01

  Hydrocarbons {(C08K5/0091 takes precedence)} · CPC title