IP Library Granted Patent US 10,053,603
Granted Patent B2
US 10,053,603 · App. 14/243,083 · Granted Aug 21, 2018

Block copolymers containing a copolymer myrcene block

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Quick Facts
Patent No.
US 10,053,603
App. No.
14/243,083
Granted
Aug 21, 2018
Kind
B2
Abstract

A block copolymer comprising: at least one monoalkenyl arene monomer polymer block (A) and copolymer block (B) containing myrcene, said copolymer block B also including: a) at least one conjugated diene monomer having a lower molecular weight than myrcene, or b) at least one monoalkenyl arene monomer, or c) a mixture of a) and b). The polymer block A may be a copolymer block. When the polymer block A is a copolymer block, both block A and the copolymer myrcene block copolymer B can have a random, tapered or a controlled distribution configuration of comonomers. The block copolymer can be selectively or exhaustively hydrogenated. The block copolymer may be used in making adhesives and vibration damping compositions.

Claims (35)

1. A block copolymer comprising: at least one monoalkenyl arene monomer polymer block (A) and copolymer block (B) containing myrcene, said copolymer block (B) further comprising:

a) at least one conjugated diene monomer having a lower molecular weight than myrcene, or

b) at least one monoalkenyl arene monomer, or

c) a mixture of (a) and (b),

wherein the copolymer block B has a vinyl content from about 5 to about 80 mol. %,

wherein the block (A) has a molecular weight of from 3 kg/mol to about 60 kg/mol and the copolymer block (B) has a molecular weight of from about 10 kg/mol to about 500 kg/mol,

wherein the block copolymer has a structure according to the following general formulae: A-B, A-B-A, A-B-A′, (A-B) n , (A-B) n -A, (A-B-A) n X, (A-B) n X, (A-B-A′) n X, (A-B-A′) n X, (A-B-B′) n X and A-B-A′-B-A, wherein X is the residue of a coupling agent, n is an integer and ranges from 2 to 5, A and A′ are polymer blocks of monoalkenyl arene(s) and A and A′ may differ with regard to molecular weight or composition, B and B′ are copolymer blocks of myrcene and at least one other monomer and B and B′ may differ with regard to molecular weight or composition, and

wherein the myrcene content of the B block is from 25 to 85 mol. %.

2. The block copolymer of claim 1 , wherein said monoalkenyl arene monomer is selected from styrene, methyl-styrene, p-tert-butylstyrene, dimethylstyrene, alpha-methylstyrene, diphenyl ethylenes, and mixtures of these.

3. The block copolymer of claim 1 , wherein said at least one conjugated diene monomer having a lower molecular weight than myrcene selected from butadiene, isoprene, piperylene, 1,3-hexadiene, or a mixture thereof.

4. The block copolymer of claim 1 wherein the monoalkenyl arene content is at least 10 wt. % based on the total weight of the block copolymer.

5. The block copolymer of claim 1 wherein the A blocks comprise styrene and the B blocks comprise myrcene and isoprene.

6. The block copolymer of claim 1 wherein the A blocks comprise styrene and the B blocks comprise myrcene and butadiene.

7. The block copolymer of claim 1 wherein the A blocks comprise styrene and the B blocks comprise myrcene and styrene.

8. The block copolymer of claim 1 , where the structure of the copolymer block B may have a random, tapered or controlled distribution configuration of comonomers.

9. A block copolymer comprising at least one monoalkenyl arene polymer block A and at least one copolymer block B comprising myrcene, said copolymer block B further comprising:

a) at least one conjugated diene monomer having a lower molecular weight than myrcene, or

b) at least one monoalkenyl arene monomer, or

c) a mixture of (a) and (b),

wherein said block copolymer has been selectively or exhaustively hydrogenated,

wherein the copolymer block B has a vinyl content from about 5 to about 80 mol. %,

wherein the block (A) has a molecular weight of from 3 kg/mot to about 60 kg/mol and the copolymer block (B) has a molecular weight of from about 10 kg/mol to about 500 kg/mol,

wherein the block copolymer has a structure according to the following general formulae: A-B, A-B-A, A-B-A′, (A-B) n , (A-B) n -A, (A-B-A) n X, (A-B) n X, (A-B-A′) n X, (A-B-A′) n X, (A-B-B′) n X and A-B-A′-B-A, wherein X is the residue of a coupling agent, n is an integer and ranges from 2 to 5, A and A′ are polymer blocks of monoalkenyl arene(s) and A and A′ may differ with regard to molecular weight or composition, B and B′ are copolymer blocks of myrcene and at least one other monomer and B and B′ may differ with regard to molecular weight or composition, and

wherein the myrcene content of the B block is from 25 to 85 mol. %.

10. The block copolymer of claim 9 wherein the block copolymer has been selectively hydrogenated such that at least about 60 mol. % of the double bonds of the conjugated diene units have been reduced and between 0 and 10 mol. % of the arene double bonds present in the polymerized monoalkenyl arene units have been reduced.

11. An adhesive formulation comprising:

a) 100 parts by weight of said block copolymer of claim 1 and;

b) from about 30 to 250 parts by weight of a tackifier, based on 100 parts of said block copolymer where the tackifier is selected from the group consisting of C 5 hydrocarbon resins, C 5 /C 9 hydrocarbon resins, hydrogenated or partially hydrogenated C 9 hydrocarbon resins, rosin esters, rosin derivatives, and mixtures thereof; and

c) from about 0 to 80 parts by weight of a plasticizer, based on 100 parts of said block copolymer; and

d) from about 0.1 to 3 parts by weight of a stabilizer, based on 100 parts of said block copolymer.

12. The adhesive formulation of claim 11 , wherein said monoalkenyl arene is selected from styrene, methylstyrene, p-tert-butylstyrene, dimethylstyrene, alpha-methylstyrene, diphenyl ethylenes and mixtures of these.

13. The adhesive formulation of claim 11 , wherein said at least one conjugated diene monomer having a lower molecular weight than myrcene may be selected from butadiene, isoprene, piperylene, 1,3-hexadiene, or a mixture thereof.

14. A vibration damping composition comprising: 100 parts by weight of the block copolymer of claim 1 , from about 0 to about 150 wt. parts of tackifier, and optionally up to about 800 wt. parts filler.

15. The vibration damping composition of claim 14 wherein the filler is selected from the group consisting of mica, talc, flaked aluminum, flaked lead, graphite, clay, calcium carbonate, barytes, silica and iron powder.

16. The vibration damping composition of claim 14 wherein the block copolymer is selectively hydrogenated.

Assignments (10)
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 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NO. 8837224 TO PATENT NO. 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded Jun 11, 2022
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 060344/0919 →
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 →
RELEASE OF SECURITY INTEREST Recorded Mar 15, 2022
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
To: KRATON POLYMERS U.S. LLC
Reel/Frame 059366/0611 →
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 →
PATENT SECURITY AGREEMENT Recorded Jan 7, 2016
From: KRATON POLYMERS U.S. LLC
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 037457/0843 →
CORRECTIVE ASSIGNMENT TO CORRECT THE PATENT NUMBER 8837224 TO PATENT NUMBER 7737224 PREVIOUSLY RECORDED AT REEL: 037448 FRAME: 0453. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded Jan 6, 2016
From: KRATON POLYMERS U.S. LLC; ARIZONA CHEMICAL COMPANY, LLC
To: BANK OF AMERICA, N.A.
Reel/Frame 037448/0453 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 2, 2014
From: STOL, MARIANNE; DUPONT, MARTINE
To: KRATON POLYMERS U.S. LLC
Reel/Frame 032580/0637 →