IP Library Granted Patent US 9,994,694
Granted Patent B2
US 9,994,694 · App. 14/510,202 · Granted Jun 12, 2018

Olefinically unsaturated radial styrenic block copolymer and an improved vulcanizer-free latex comprising water and said radial styrenic block copolymer

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Quick Facts
Patent No.
US 9,994,694
App. No.
14/510,202
Granted
Jun 12, 2018
Kind
B2
Abstract

The invention concerns an olefinically unsaturated radial styrenic block copolymer having the general formula A-B—Y—(B-A) n wherein each A is independently a polymer block composed of at least 90 mol. % of an alkenyl aromatic hydrocarbon, each B is independently a polymer block composed of at least 90 mol. % of one or more conjugated dienes, Y is the remnant of a coupling agent, and n is an integer from 2 to 5. The invention is also an improved vulcanizer-free latex comprising water and the olefinically unsaturated radial styrenic block copolymer. Moreover, the invention concerns a process for preparing articles by coagulation dipping from the improved latex and dipped goods made from such latex.

Claims (31)

1. An olefinically unsaturated radial styrenic block copolymer of the general formula:

A-B—Y—(B-A) n

wherein

each A is independently a polymer block composed of at least 90 mol. % of an alkenyl aromatic hydrocarbon;

the content of A by weight of the total weight of the polymer (PSC) is in the range of 9-12%;

Y is the remnant of a coupling agent having a functionality greater than 2;

the degree of branching (DoB) is n+1, wherein n is an integer from 2 to 4;

each B is independently an olefinically unsaturated polymer block composed of at least 90 mol. % of one or more conjugated dienes;

the styrenic block copolymer has a coupling efficiency (CE) in the range of 84 to 100%;

each A block independently has a weight average molecular weight (MW A) ranging from 10,000 to 12,000;

each B Block independently has a weight average molecular weight (MW B) ranging from 80,000 to 120,000, wherein the molecular weights are determined pursuant to ASTM 3536 using mono-dispersed polystyrene standards;

a film prepared from the olefinically unsaturated radial styrenic block copolymer has tensile strength of greater than or equal to 19 MPa, 10% Young's modulus smaller than 0.25 MPa and complex modulus at 120° C. of 5.6×10 5 Pas or higher.

2. The radial styrenic block copolymer of claim 1 , wherein each B is a polymer block composed of at least 90 mol. % of isoprene.

3. The radial styrenic block copolymer of claim 2 , wherein at least one B comprises at most 10 mol. % butadiene with at least 1 butadiene unit directly connected to the remnant of the coupling agent Y.

4. The radial styrenic block copolymer of claim 1 , wherein each A is a polymer block composed of at least 90 mol. % of styrene.

5. The radial styrenic block copolymer of claim 1 , wherein Y is the remnant of gamma-glycidoxy-propyltrimethoxysilane.

6. A vulcanizer-free artificial latex comprising water and one or more styrenic block copolymers as defined in claim 1 dispersed in said water in an amount of 20 to 80% by weight of the combination of water and styrenic block copolymer and said latex being free from vulcanizer.

7. The artificial latex of claim 6 , comprising said one or more styrenic block copolymers in an amount of 50 to 70% by weight of the combination of water and styrenic block copolymer.

8. The artificial latex of claim 6 , comprising

(a) a thio-functionalized phenolic antioxidant, or

(b) an antioxidant package comprising a primary phenolic antioxidant and a thioester as secondary antioxidant; or

(c) a combination of (a) and (b).

9. The artificial latex of claim 6 comprising a primary phenolic antioxidant selected from 2,6-di-t-butyl-4-methylphenol, 2,6,-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, butyl hydroxyanisole, 2,6-di-t-butyl-α-dimethylamino-p-cresol, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, styrenated phenol, 2,2′-methylenebis(6-α-methylbenzyl-p-cresol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 3,3′,3′,5,5′,5′-hexa-tert-butyl-a,a′,a′-(mesitylene-2,4,6-triyl)6-tril)tri-p-cresol, alkylated bisphenol, the butylation reaction product of p-cresol and dicyclopentadiene, or a mixture of two or more thereof, and comprising a thioester selected from dilauryl thiodipropionate and distearyl thiodipropionate.

10. The artificial latex of claim 6 comprising a thio-functionalized phenolic antioxidant selected from thiobisphenolic antioxidants.

11. The artificial latex of claim 10 , wherein said thiobisphenolic antioxidants are selected from 2,2′-thiobis(4-methyl-6-t-butylphenol), 4,4′-thiobis(6-t-butyl-o-cresol), 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxy-phenyl)propionate], or 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol.

12. The artificial latex of claim 6 comprising a thio-functionalized phenolic antioxidant, and/or a combination of a primary phenolic antioxidant and a thioester wherein the amount of the thio-functionalized phenolic antioxidant is within a range of from 0.1 to 3.0 parts by weight, per 100 parts by weight of the rubber constituting the rubber latex (phr), and/or wherein the amount of the primary antioxidant and the thioester are each independently within a range of from 0.1 to 3.0 parts by weight, per 100 parts by weight of the rubber constituting the rubber latex (phr).

13. A process for preparing articles by coagulation dipping from the artificial latex according to claim 6 , wherein a film is made from the latex and said film is allowed to dry and wherein said film is annealed for at least 10 minutes at an annealing temperature within the range of 100-130° C.

14. The process of claim 13 , wherein said film is annealed at about 120° C.

15. The method of claim 13 further comprising subjecting the articles to irradiation.

16. Dipped goods comprising a film composed of the olefinically unsaturated radial styrenic block copolymer of claim 1 .

17. The radial styrenic block copolymer of claim 1 , wherein the coupling efficiency (CE) is in the range of 90 to 100%; and wherein the complex modulus is 6.4×10 5 Pas or higher.

Assignments (7)
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 →