IP Library Granted Patent US 11,279,817
Granted Patent B2
US 11,279,817 · App. 16/564,424 · Granted Mar 22, 2022

Rubber composition and method for making thereof

Inventors: Neil Riddle (Almere, NL); Noriko Yagi (Tokyo, JP); Jeremie G Pichereau (Almere, NL)
Assignee: KRATON POLYMERS LLC
C08L9/00B60C1/0016C08K5/0016C08K5/101C08L7/00C08L15/005C08L23/16C08L53/025C08K3/013C08K3/36C08K2003/265C08L2205/03
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Quick Facts
Patent No.
US 11,279,817
App. No.
16/564,424
Granted
Mar 22, 2022
Kind
B2
Abstract

A rubber composition is disclosed. The composition comprises a blend based on 100 parts by weight (phr) of diene elastomers: 5 to 95 phr of a first diene elastomer, 5 to 50 phr of a hydrogenated styrenic block copolymer (HSBC), 50 to 200 phr of a filler, up to 25 phr of a plasticizer. The HSBC has a melt flow ratio of 1.0 to 50.0 measured according to ASTM D-1238 at 230° C. and 2.16 kg load, a Shore A hardness of 40 to 80 measured according to ASTM D-2240, a DMA peak tan delta temperature of 0° C. to 40° C. at 1 Hz measured according to ASTM D-4065, and an order-disorder transition temperature of 200° C. to 300° C. The composition does not comprise a resin, a plasticizer, or comprises a resin or a plasticizer in an amount of less than 20 phr.

Claims (50)

1. A tire composition comprising, based on 100 parts total diene elastomers:

a first diene elastomer in an amount of 5 to 95 phr, selected from polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures thereof;

a second diene elastomer in an amount of 5 to 50 phr, comprising a hydrogenated styrenic block copolymer (HSBC);

from 50 to 200 phr of a filler; and

from 0-70 phr of a resin, a plasticizer, or combinations thereof;

wherein the HSBC has a general configuration A-B-A, (A-B-) n , (A-B-A-) n , (A-B-A) n X, (A-B-) n X, or mixtures thereof, where n is an integer from 2 to 30, and X is residue of a coupling agent,

wherein prior to hydrogenation,

each A block is a monoalkenyl arene homopolymer block having a true peak molecular weight of 5 kg/mol to 15 kg/mol,

each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one monoalkenyl arene, and has a true peak molecular weight of 30 kg/mol to 200 kg/mol;

wherein the HSBC has a midblock monoalkenyl arene blockiness index of 3% to 15%, wherein the mono alkenyl arene blockiness index is the proportion of mono alkenyl arene units in the block B having two mono alkenyl arene neighbors on the polymer chain;

wherein subsequent to hydrogenation, 0-10% of the arene double bonds have been reduced, and at least 90% of the conjugated diene double bonds have been reduced;

wherein the HSBC has a midblock poly(monoalkenyl arene) content of 20 wt. % to 50 wt. % based on the total weight of the midblock;

and wherein the HSBC has a melt flow ratio of 1.0 to 50.0 measured according to ASTM D-1238 at 230° C. and 2.16 kg load, a Shore A hardness of 40 to 80 measured according to ASTM D-2240, a DMA peak tan delta temperature of 0° C. to 40° C. at 1 Hz measured according to ASTM D-4065, and an order-disorder transition temperature of 200° C. to 300° C.

2. The tire composition of claim 1 , wherein the composition comprises less than 20 phr of a resin selected from substituted or unsubstituted cyclopentadiene (CPD) homopolymer or copolymer resins, substituted or unsubstituted dicyclopentadiene (DCPD or (D)CPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, rosin derived resins, rosin esters, pinene homopolymer or copolymer resins, C5 fraction homopolymer or copolymer resins, C9 fraction homopolymer or copolymer resins, alpha-methylstyrene homopolymer or copolymer resins, (D)CPD/vinylaromatic copolymer resins, (D)CPD/terpene copolymer resins, terpene/phenol copolymer resins, (D)CPD/pinene copolymer resins, pinen/phenol copolymer resins, (D)CPD/C5 fraction copolymer resins, (D)CPD/C9 fraction copolymer resins, terpene/vinyl aromatic copolymer resins, terpene/phenol copolymer resins, pinene/vinylaromatic copolymer resins, pinene/phenol resins, C5 fraction/vinylaromatic copolymer resins, and combinations thereof.

3. The tire composition of claim 2 , wherein the composition comprises 0-10 phr of the resin.

4. The tire composition of claim 1 , wherein the composition comprises less than 35 phr of a plasticizer selected from aliphatic acid esters, hydrocarbonprocessing oils, tall oil pitch, modified tall oil pitch, and combinations thereof.

5. The tire composition of claim 1 , wherein the composition comprises 5-25 phr of the plasticizer.

6. The tire composition of claim 1 , wherein the second diene elastomer is present in an amount of at least 10 phr.

7. The tire composition of claim 1 , wherein the HSBC has a general configuration (A-B-A) n X, (A-B) n X, or mixtures thereof, and a coupling efficiency of 30-90%.

8. The tire composition of claim 1 , wherein the second diene elastomer comprises:

a linear HSBC having a general configuration A-B-A, (A-B-)n, (A-B-A-)n, or combinations thereof and a total apparent number average molecular weight from 70 to 150 kg/mol; and

a branched HSBC having a general configuration (A-B-A-) n X, (A-B-) n X, or combinations thereof and a total apparent number average molecular weight from 35 to 75 kg/mol per arm.

9. The tire composition of claim 1 , wherein each B block has

terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units,

10 to 40 wt. % of polymerized mono alkenyl arene units,

a styrene blockiness index of less than 10%; and

a vinyl content of at least 40 mole percent.

10. The tire composition of claim 1 , wherein the HSBC has a midblock vinyl content from 30 mol percent to 90 mol percent.

11. The tire composition of claim 1 , wherein the HSBC has a total poly(monoalkenyl arene) content of 30 wt. % to 70 wt. %.

12. The tire composition of claim 1 , wherein the first diene elastomer is end-group functionalized.

13. The tire composition of claim 12 , wherein the first diene elastomer is end-group functionalized with a C—Sn bond, an amino group, a silanol group, a polysiloxane group, or an epoxy group.

14. The tire composition of claim 1 , wherein the HSBC has a tensile strength of 10 MPa to 30 Mpa.

15. The tire composition of claim 1 , wherein the HSBC has a rate of change of elastic modulus (ΔG 0° C.-40° C. ) from −9 MPa/° C. to −25 MPa/° C. over a temperature range from 0° C. to 40° C. measured according to ASTM 1640-99.

16. The tire composition of claim 1 , wherein the HSBC has an elongation of 500% to 1000%.

17. The tire composition of claim 2 , wherein the HSBC has an order-disorder temperature (ODT) in the range of 200° C.-300° C.

18. The tire composition of claim 1 , wherein the first diene elastomer is selected from natural rubber (NR), butadiene rubber (BR), synthetic polyisoprene rubber, epoxylated natural rubber, polybutadiene rubber, nitrile-hydrogenated butadiene rubber NHBR, hydrogenated styrene-butadiene rubber HSBR, ethylene propylene diene monomer rubber, ethylene propylene rubber, maleic acid-modified ethylene propylene rubber, butyl rubber, isobutylene-aromatic vinyl or diene monomer copolymers, brominated-NR, chlorinated-NR, brominated isobutylene p-methylstyrene copolymer, chloroprene rubber, epichlorohydrin homopolymers rubber, epichlorohydrin-ethylene oxide or allyl glycidyl ether copolymer rubbers, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer rubbers, chlorosulfonated polyethylene, chlorinated polyethylene, maleic acid-modified chlorinated polyethylene, methylvinyl silicone rubber, dimethyl silicone rubber, methylphenylvinyl silicone rubber, polysulfide rubber, vinylidene fluoride rubbers, tetrafluoroethylene-propylene rubbers, fluorinated silicone rubbers, fluorinated phosphagen rubbers, styrene elastomers, thermoplastic olefin elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, and mixtures thereof.

19. An extruded, compression-molded, blow-molded, injection-molded, or laminated rubber part comprising:

a first diene elastomer in an amount of 5 to 95 phr, selected from polybutadienes, natural rubber, synthetic polyisoprenes, butadiene copolymers, isoprene copolymers and mixtures thereof;

a second diene elastomer in an amount of 5 to 50 phr, comprising a hydrogenated styrenic block copolymer (HSBC);

from 50 to 200 phr of a filler; and

from 0-70 phr of a resin, a plasticizer, or combinations thereof;

wherein the HSBC has a general configuration A-B-A, (A-B-) n , (A-B-A-) n , (A-B-A-) n X, (A-B-) n X, or mixtures thereof, where n is an integer from 2 to 30, and X is residue of a coupling agent,

wherein prior to hydrogenation,

each A block is a monoalkenyl arene homopolymer block having a true peak molecular weight of 5 kg/mol to 15 kg/mol,

each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one monoalkenyl arene, and has a true peak molecular weight of 30 kg/mol to 200 kg/mol;

wherein the HSBC has a midblock monoalkenyl arene blockiness index of 3% to 15%, wherein the mono alkenyl arene blockiness index is the proportion of mono alkenyl arene units in the block B having two mono alkenyl arene neighbors on the polymer chain;

wherein subsequent to hydrogenation, 0-10% of the arene double bonds have been reduced, and at least 90% of the conjugated diene double bonds have been reduced;

wherein the HSBC has a midblock poly(monoalkenyl arene) content of 20 wt. % to 50 wt. % based on the total weight of the midblock;

and wherein the HSBC has a melt flow ratio of 1.0 to 50.0 measured according to ASTM D-1238 at 230° C. and 2.16 kg load, a Shore A hardness of 40 to 80 measured according to ASTM D-2240, a DMA peak tan delta temperature of 0° C. to 40° C. at 1 Hz measured according to ASTM D-4065, and an order-disorder transition temperature of 200° C. to 300° C.

20. The rubber part of claim 19 , wherein the rubber part comprises less than 20 phr of a resin selected from substituted or unsubstituted cyclopentadiene (CPD) homopolymer or copolymer resins, substituted or unsubstituted dicyclopentadiene (DCPD or (D)CPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, rosin derived resins, rosin esters, pinene homopolymer or copolymer resins, C5 fraction homopolymer or copolymer resins, C9 fraction homopolymer or copolymer resins, alpha-methylstyrene homopolymer or copolymer resins, (D)CPD/vinylaromatic copolymer resins, (D)CPD/terpene copolymer resins, terpene/phenol copolymer resins, (D)CPD/pinene copolymer resins, pinen/phenol copolymer resins, (D)CPD/C5 fraction copolymer resins, (D)CPD/C9 fraction copolymer resins, terpene/vinyl aromatic copolymer resins, terpene/phenol copolymer resins, pinene/vinylaromatic copolymer resins, pinene/phenol resins, C5 fraction/vinylaromatic copolymer resins, and combinations thereof.

Assignments (5)
RELEASE OF SECURITY INTEREST IN PATENTS Recorded Jul 24, 2024
From: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
To: KRATON CHEMICAL, LLC; KRATON CORPORATION
Reel/Frame 068671/0836 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059525/0804 →
SECURITY INTEREST Recorded Mar 18, 2022
From: KRATON CHEMICAL, LLC; KRATON POLYMERS LLC; KRATON POLYMERS U.S. LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 059864/0455 →
RELEASE OF SECURITY INTEREST Recorded Mar 16, 2022
From: BANK OF AMERICA, N.A.
To: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION; KRATON CHEMICAL B.V.
Reel/Frame 059910/0017 →
SECURITY INTEREST Recorded Apr 16, 2020
From: KRATON POLYMERS U.S. LLC; KRATON CHEMICAL, LLC F/K/A ARIZONA CHEMICAL COMPANY, LLC; KRATON POLYMERS LLC; KRATON CORPORATION
To: BANK OF AMERICA, N.A.
Reel/Frame 053020/0101 →
Continuity (2)
Provisional Application 62729065 · Sep 10, 2018
Related Publication 20200079935A1 · Mar 12, 2020
Cited By (2)
US 12,522,021 US 12,558,920