Styrene-butadiene block copolymers for tubing applications

Patent metadata

Field	Value
Publication number	US-2016264773-A1
Application number	US-201514645658-A
Country	US
Kind code	A1
Filing date	Mar 12, 2015
Priority date	Mar 12, 2015
Publication date	Sep 15, 2016
Grant date	—

Abstract

Conjugated diene monovinylarene block copolymers having superior kink resistance properties are disclosed. These copolymers can be used to produce tubing and other end-use articles, and can be a replacement for flexible PVC.

First claim

We claim:

1 . A conjugated diene monovinylarene block copolymer comprising from about 35 phm to about 75 phm monovinylarene monomer, and comprising polymer chains containing a block structure having formula I:
S 1 —(S/B) 1 —(S/B) 2   (I); wherein:
S 1 is a monoblock of the monovinylarene monomer, wherein S 1 is from about 10 phm to about 45 phm of the copolymer; (S/B) 1 is a mixed block of the conjugated diene monomer and the monovinylarene monomer, wherein the monovinylarene monomer content is from about 30 wt. % to about 80 wt. %, based on the total weight of (S/B) 1 ; and (S/B) 2 is a mixed block of the conjugated diene monomer and the monovinylarene monomer, wherein the conjugated diene monomer content is from about 70 wt. % to about 99 wt. %, based on the total weight of (S/B) 2 ; and wherein a kink resistance of tubing produced from the copolymer and tested in accordance with DIN EN 13868 is less than or equal to about 32 mm.

2 . The copolymer of claim 1 , wherein S 1 is in a range from about 20 phm to about 40 phm.

3 . The copolymer of claim 1 , wherein the monovinylarene monomer content in (S/B) 1 is in a range from about 35 wt. % to about 65 wt. %, based on (S/B) 1 .

4 . The copolymer of claim 1 , wherein the conjugated diene monomer content in (S/B) 2 is in a range from about 70 wt. % to about 85 wt. %, based on (S/B) 2 .

5 . The copolymer of claim 1 , wherein the copolymer comprises monovinylarene monomer in a range from about 58 phm to about 68 phm.

6 . The copolymer of claim 1 , wherein:
the monovinylarene monomer is styrene; the conjugated diene monomer is a butadiene; and the kink resistance is in a range from about 10 to about 24 mm.

7 . The copolymer of claim 1 , wherein:
the monovinylarene monomer is from about 57 phm to about 67 phm of the copolymer; S 1 is from about 25 phm to about 38 phm of the copolymer; the monovinylarene monomer content is from about 40 wt. % to about 60 wt. % of (S/B) 1 ; and the conjugated diene monomer content is from about 72 wt. % to about 90 wt. % of (S/B) 2 .

8 . The copolymer of claim 7 , wherein the conjugated diene monovinylarene block copolymer is a styrene butadiene block copolymer.

9 . The copolymer of claim 1 , wherein S 1 is two or more monoblocks of the monovinylarene monomer.

10 . The copolymer of claim 1 , wherein the copolymer further comprises polymer chains containing a block structure having formula II:
S 2 —(S/B) 1 —(S/B) 2   (II); wherein:
S 2 is a monoblock of the monovinylarene monomer, wherein S 2 is from about 5 phm to about 30 phm of the copolymer.

11 . The copolymer of claim 10 , wherein S 2 is in a range from about 12 phm to about 25 phm.

12 . The copolymer of claim 10 , wherein the copolymer further comprises polymer chains containing a block structure having formula IA and/or IIA:
S 1 —(S/B) 1 —(S/B) 2 —S T1   (IA)
S 2 —(S/B) 1 —(S/B) 2 —S T2   (IIA); wherein:
S T1 and S T2 independently are monoblocks of the monovinylarene monomer, wherein S T1 and S T2 independently are from about 0.5 phm to about 5 phm of the copolymer.

13 . The copolymer of claim 1 , wherein (S/B) 1 is two mixed blocks of the conjugated diene monomer and the monovinylarene monomer having formula III:
—(S/B) 1A —(S/B) 1B —  (III); wherein:
the monovinylarene monomer content is from about 30 wt. % to about 80 wt. % of (S/B) 1A , and the monovinylarene monomer content is from about 30 wt. % to about 80 wt. % of (S/B) 1B .

14 . The copolymer of claim 13 , wherein the monovinylarene monomer content, independently, is from about 35 wt. % to about 65 wt. %, based on (S/B) 1A , and from about 35 wt. % to about 65 wt. %, based on (S/B) 1B .

15 . The copolymer of claim 1 , wherein the copolymer has:
a melt flow rate in a range from about 3 to about 20; a kink resistance in a range from about 9 mm to about 20 mm; and a Shore A hardness in a range from about 50 to about 90.

16 . The copolymer of claim 15 , wherein the copolymer has:
a pellet blocking force of less than or equal to about 120 lb f ; and a re-kink resistance in a range from about 10 mm to about 30 mm.

17 . The copolymer of claim 1 , wherein the copolymer has:
a melt flow rate in a range from about 4 to about 18; a kink resistance in a range from about 10 mm to about 24 mm; and a Shore A hardness in a range from about 60 to about 80.

18 . An article of manufacture comprising the copolymer of claim 1

19 . A tubing product comprising the copolymer of claim 1 .

20 . A composition comprising:
(a) a conjugated diene monovinylarene block copolymer; and (b) a second polymer;
wherein the conjugated diene monovinylarene block copolymer comprises from about 35 phm to about 75 phm monovinylarene monomer, and comprises polymer chains containing a block structure having formula I:
S 1 —(S/B) 1 —(S/B) 2   (I); wherein:

S 1 is a monoblock of the monovinylarene monomer, wherein S 1 is from about 10 phm to about 45 phm of the copolymer;
(S/B) 1 is a mixed block of the conjugated diene monomer and the monovinylarene monomer, wherein the monovinylarene monomer content is from about 30 wt. % to about 80 wt. %, based on the total weight of (S/B) 1 ; and
(S/B) 2 is a mixed block of the conjugated diene monomer and the monovinylarene monomer, wherein the conjugated diene monomer content is from about 70 wt. % to about 99 wt. %, based on the total weight of (S/B) 2 ; and
wherein a kink resistance of tubing produced from the copolymer and tested in accordance with DIN EN 13868 is less than or equal to about 32 mm.

21 . The composition of claim 20 , wherein the second polymer comprises a styrene butadiene polymer, a polystyrene polymer, or a combination thereof.

22 . The composition of claim 20 , wherein the composition further comprises an additive.

23 . The composition of claim 20 , wherein a kink resistance of tubing produced from the composition and tested in accordance with DIN EN 13868 is from about 10 to about 28 mm.

24 . A tubing product comprising the composition of claim 23 .

25 . A process to produce a conjugated diene monovinylarene block copolymer comprising from about 35 phm to about 75 phm monovinylarene monomer, and comprising polymer chains containing a block structure having formula I:
S 1 —(S/B) 1 —(S/B) 2   (I); wherein:
S 1 is a monoblock of the monovinylarene monomer, wherein S 1 is from about 10 phm to about 45 phm of the copolymer; (S/B) 1 is a mixed block of the conjugated diene monomer and the monovinylarene monomer, wherein the monovinylarene monomer content is from about 30 wt. % to about 80 wt. %, based on the total weight of (S/B) 1 ; and (S/B) 2 is a mixed block of the conjugated diene monomer and the monovinylarene monomer, wherein the conjugated diene monomer content is from about 70 wt. % to about 99 wt. %, based on the total weight of (S/B) 2 ; and wherein a kink resistance of tubing produced from the copolymer and tested in accordance with DIN EN 13868 is less than or equal to about 32 mm; the process comprising contacting: (i) a first initiator charge and a first charge of the monovinylarene monomer and allowing polymerization to occur until minimal free monomer is present; thereafter contacting all products of step (i) with (ii) a second initiator charge and a second charge of the monovinylarene monomer and allowing polymerization to occur

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Zhou Jinping Joe
• Pace Walter H
• Young David A

Classifications

• C08F236/10 Primary

  with vinyl-aromatic monomers · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08L53/02 Primary

  of vinyl-aromatic monomers and conjugated dienes · CPC title