Crosslinked rubber particles and rubber compositions

• US 20040152844A1
• Filed: 01/23/2004
• Published: 08/05/2004
• Est. Priority Date: 04/27/2000
• Status: Active Grant

• Current Assignee: JSR Corporation
• Original Assignee: JSR Corporation
• Inventors: Tadaki, Toshihiro, Akema, Hiroshi, Udagawa, Yoshiyuki, Konno, Tomohisa
• Granted Patent: US 6,977,286 B2
• Time in Patent Office: Days
• US Class Current: 525/329.7
• CPC Class Codes: C08L 15/00 Compositions of rubber derivatives C08L11/00, C08L13/00 take precedence
• CPC Class Codes: C08L 19/006 Rubber characterised by functional groups, e.g. telechelic diene polymers
• CPC Class Codes: C08L 21/00 Compositions of unspecified rubbers
• CPC Class Codes: C08L 2205/22 Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
• CPC Class Codes: C08L 23/16 Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• CPC Class Codes: C08L 2312/00 Crosslinking
• CPC Class Codes: C08L 2666/08 Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof
• CPC Class Codes: C08L 33/066 containing -OH groups
• CPC Class Codes: C08L 9/00 Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• CPC Class Codes: C08L 9/02 Copolymers with acrylonitrile
• CPC Class Codes: C08L 9/06 Copolymers with styrene
• CPC Class Codes: Y10S 525/901 Radial block
• CPC Class Codes: Y10S 525/914 Polymer from conjugated diene hydrocarbon or halohydrocarbons having more than 50 per cent 1,2-microstructure
• CPC Class Codes: Y10S 526/909 Polymerization characterized by particle size of product

Abstract

An objective of the invention is to provide a rubber composition which has satisfactory processability and dimension stability, and the like, gives a vulcanized rubber exhibiting excellent wearing resistance and tensile strength, and the like, and thus is useful in a belt, a hose and a tire and the like, as well as a crosslinked rubber particle for obtaining such rubber composition. A rubber composition of the invention comprises [1] a crosslinked rubber particle comprising as repeating units (a) 30 to 94.89% by weight of a conjugated diene unit, (b) 5 to 69.89% by weight of an aromatic vinyl unit, (c) 0.01 to 10% by weight of a monomer unit having at least two polymerizable unsaturated group, (d)one polymerizable unsaturated group and an amino group, a hydroxyl group and an epoxy group and (e) 0.1 to 30% by weight of a monomer unit having one polymerizable unsaturated group and a carboxylic group and having a particle size of 10 to 500 nm and a toluene-insolubles of 80 by weight or more and [2] a non-crosslinked rubber component whose toluene-insolubles is less than 20% by weight.

Claims

1. A crosslinked rubber particle comprising as repeating units (a) 30 to 94.89% by weight of a conjugated diene unit, (b) 5 to 69.89% by weight of an aromatic vinyl unit, (c) 0.01 to 10% by weight of a monomer unit having at least two polymerizable unsaturated group and (d) 0.1 to 30% by weight of a monomer unit having one polymerizable unsaturated group and at least one functional group selected from an amino group, a hydroxyl group and an epoxy group [the total amount of (a), (b), (c) and (d) is 100% by weight] and having a particle size of 10 to 500 nm and a toluene-insolubles of 80% by weight or more.

2. A crosslinked rubber particle according to claim 1, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and an amino group is at least one selected from dialkylaminoalkyl (meth)acrylates, N-dialkylaminoalkyl group-containing unsaturated amides, dialkylaminoalkyl (meth)acrylate and tertiary amino group-containing vinyl aromatic compound.

3. A crosslinked rubber particle according to claim 1, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and a hydroxyl group is at least one selected from hydroxyalkyl(meth)acrylates, mono(meth)acrylates of polyalkylene glycols (the number of alkylene glycol units is 2 to 23), hydroxyl group-containing unsaturated amides, hydroxyl group-containing vinyl aromatic compounds and (meth)allyl alcohol.

4. A crosslinked rubber particle according to claim 1, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and an epoxy group is at least one selected from (meth)allylglycidylether, glycidyl(meth)acrylate and 3,4-oxycyclohexyl(meth)acrylate.

5. A crosslinked rubber particle according to claim 1, wherein

said conjugated diene forming said conjugated diene unit (a) is at least one selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene and chloroprene;

said aromatic vinyl forming said aromatic vinyl unit (b) is at least one selected from styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, a-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene and tert-butoxystyrene; and

,

said monomer forming said monomer unit (c) having at least two polymerizable unsaturated groups is at least one selected from ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, divinylbenzene, diisopropenylbenzene and trivinylbenzene.

6. A crosslinked rubber particle according to claim 5, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and an amino group is at least one selected from dialkylaminoalkyl(meth)acrylates, N-dialkylaminoalkyl group-containing unsaturated amides, dialkylaminoalkyl(meth)acrylate and tertiary amino group-containing vinyl aromatic compound.

7. A crosslinked rubber particle according to claim 5, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and a hydroxyl group is at least one selected from hydroxyalkyl(meth)acrylates, mono(meth)acrylates of polyalkylene glycols (the number of alkylene glycol units is 2 to 23), hydroxyl group-containing unsaturated amides, hydroxyl group-containing vinyl aromatic compounds and (meth)allyl alcohol.

8. A crosslinked rubber particle according to claim 5, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and an epoxy group is at least one selected from (meth)allylglycidylether, glycidyl(meth)acrylate and 3,4-oxycyclohexyl(meth)acrylate.

9. A rubber composition comprising:

[1] at least one crosslinked rubber particle selected from;

(1) a crosslinked rubber particle comprising as repeating units (a) 30 to 94.89% by weight of a conjugated diene unit, (b) 5 to 69.89% by weight of an aromatic vinyl unit, (c) 0.01 to 10% by weight of a monomer unit having at least two polymerizable unsaturated group and (d) 0.1 to 30% by weight of a monomer unit having one polymerizable unsaturated group and at least one functional group selected from an amino group, a hydroxyl group and an epoxy group [the total amount of (a), (b), (c) and (d) is 100% by weight] and having a particle size of 10 to 500 nm and a toluene-insolubles of 80% by weight or more;

(2) a crosslinked rubber particle comprising as repeating units (a) 30 to 94.89% by weight of a conjugated diene unit, (b) 5 to 69.89% by weight of an aromatic vinyl unit, (c) 0.01 to 10% by weight of a monomer unit having at least two polymerizable unsaturated group and (e) 0.1 to 30% by weight of a monomer unit having one polymerizable unsaturated group and a carboxylic group (CO₂H and/or CO₂⁻

) [the total amount of (a), (b), (c) and (e) is 100% byweight] and having a particle size of 10 to 500 nm and a toluene-insolubles of 80% by weight or more; and

,

(3) a crosslinked rubber particle comprising as repeating units (a) 30 to 94.99% by weight of a conjugated diene unit, (b) 5 to 69.99% by weight of an aromatic vinyl unit and (c) 0.01 to 10% by weight of a monomer unit having at least two polymerizable unsaturated group [the total amount of (a), (b) and (c) is 100% by weight] and having a particle size of 10 to 500 nm and a toluene-insolubles of 80% by weight or more; and

,

[2] a non-crosslinked rubber component whose toluene-insolubles is less than 20% by weight,

wherein said non-crosslinked rubber component is at least one selected from (A) a polymer consisting of as a repeating unit only a conjugated diene unit, (B) a polymer which comprises as repeating units a conjugated diene unit and an aromatic vinyl unit and whose conjugated diene unit has a 1,4-trans content of 55% or less, (C) a polymer comprising as repeating units a conjugated diene unit and an α

,β

-unsaturated nitrile unit, (D) an acrylic rubber and (E) a polymer comprising as repeating units an ethylene unit and an a-olefin unit having 3 to 12 carbon atoms.

10. A rubber composition according to claim 9, wherein

said conjugated diene forming said conjugated diene unit (a) is at least one selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene and chloroprene;

said aromatic vinyl forming said aromatic vinyl unit (b) is at least one selected from styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α

-methylstyrene, 2,4-demethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene and tert-butoxystyrene; and

,

said monomer forming said monomer unit (c) having at least two polymerizable unsaturated groups is at least one selected from ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, divinylbenzene, diisopropenylbenzene and trivinylbenzene.

11. A rubber composition according to claim 10, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and an amino group is at least one selected from dialkylaminoalkyl (meth)acrylates, N-dialkylaminoalkyl group-containing unsaturated amides and tertiary amino group-containing vinyl aromatic compound.

12. A rubber composition according to claim 10, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and a hydroxyl group is at least one selected from hydroxyalkyl(meth)acrylates, mono (meth)acrylates of a polyalkylene glycol (the number of alkylene glycol units is for example 2 to 23), hydroxyl group-containing unsaturated amides, hydroxyl group-containing unsaturated vinyl aromatic compounds and (meth)allyl alcohol.

13. A rubber composition according to claim 10, wherein

said monomer forming said monomer unit (d) having one polymerizable unsaturated group and an epoxy group is at least one selected from (meth)allylglycidylether, glycidyl(meth)acrylate and 3,4-oxycyclohexyl(meth)acrylate.

14. A rubber composition according to claim 9, wherein

said monomer forming said monomer unit (e) having one polymerizable unsaturated group and a carboxylic group (CO₂H and/or CO₂⁻

) is at least one selected from unsaturated carboxylic acids, free carboxyl group-containing esters and their salts.

15. A rubber composition according to claim 9, further comprising at least one selected from a silica and a carbon black.

16. A rubber composition according to claim 15, wherein

said conjugated diene forming said conjugated diene unit (a) is at least one selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene and chloroprene;

said aromatic vinyl forming said aromatic vinyl unit (b) is at least one selected from styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α

-methylstyrene, 2,4-demethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene and tert-butoxystyrene; and

,

said monomer forming said monomer unit (c) having at least two polymerizable unsaturated groups is at least one selected from ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, divinylbenzene, diisopropenylbenzene and trivinylbenzene.

17. A rubber composition according to claims 16, wherein

said monomer forming said monomer unit (e) having one polymerizable unsaturated group and a carboxylic group (CO₂H and/or CO₂⁻

) is at least one selected from unsaturated carboxylic acids, free carboxyl group-containing esters and their salts.

18. A rubber composition according to claim 15, further comprising a silane coupling agent.