IP Library Granted Patent US 8,487,023
Granted Patent B2
US 8,487,023 · App. 12/988,175 · Granted Jul 16, 2013

Nucleating agents for polyhydroxyalkanoates

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Quick Facts
Patent No.
US 8,487,023
App. No.
12/988,175
Granted
Jul 16, 2013
Kind
B2
Abstract

Provided herein are nucleating agent compositions for use in nucleating polymers during processing. Methods for making and using the nucleating agent compositions are also provided. The nucleating agent in dry powder form is wet milled in a liquid carrier, such as a plasticizer, surfactant, or lubricant.

Claims (79)

1. A nucleating composition comprising

a wet-milled nucleating agent, and

a liquid carrier, wherein the nucleating agent is cyanuric acid or boron nitride and is dispersed and wet-milled in the liquid carrier and wherein at least 50% of the cumulative solid volume of the nucleating agent exists as particles with a particle size of 2 microns or less.

2. The composition of claim 1 , wherein the liquid carrier is CITROFLEX A4® citric acid ester or dibutoxyethoxyethyl adipate.

3. The composition of claim 1 , wherein the wet-milled nucleating agent exists as particles with a particle size of one micron or less.

4. The composition of claim 1 , further comprising a surfactant selected from the group consisting of TRITON X™-100 surfactant, TWEEN®-20 polysorbate surfactant, TWEEN®-65 polysorbate surfactant, SPAN™-40 sorbitan monopalmitate and SPAN™ 80 sorbitan monooleate.

5. The composition of claim 4 , wherein the nucleating agent is cyanuric acid, the liquid carrier is CITROFLEX A4® citric acid ester and the surfactant is Span 80 sorbitan monoleate.

6. The composition of claim 1 , wherein the amount of nucleating agent in the liquid carrier is from 5% to 50% by weight.

7. A method for preparing a nucleating composition, comprising:

dispersing a nucleating agent in dry powder form in a liquid carrier to form a nucleant-liquid mixture; and

wet milling the nucleant-liquid mixture until at least 50% of the cumulative solid volume of the nucleating agent exists as particles with a particle size of 2 microns or less to form a nucleating composition, wherein the nucleating agent is cyanuric acid or boron nitride.

8. A polymer composition, comprising: a polymer and the composition of claim 1 , wherein in the polymer is a) poly(3-hydroxybutyrate) homopolymer blended with a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

a poly(3-hydroxybutyrate) homopolymer blended with a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content;

a poly(3-hydroxybutyrate) homopolymer blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content;

a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content; a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate;

a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with b) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with b) poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with b) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); or

a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b).

9. The composition of claim 8 , wherein the weight of polymer a) is 20% to 60% of the combined weight of polymer a) and polymer b) and the weight of polymer b is 40% to 80% of the combined weight of polymer a) and polymer b).

10. The composition of claim 8 , wherein the polymer is further blended with polymer c) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) 20% to 50% 4-hydroxybutyrate content.

11. The composition of claim 8 , wherein the polymer is further blended with c) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) 20% to 50% 5-hydroxyvalerate content.

12. The composition of claim 8 , wherein the polymer is further blended with c) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 5% to 50% 3-hydroxyhexanoate content.

13. The composition of claim 10 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

14. The composition of claim 10 , wherein the weight of polymer c) is 5% to 40% of the combined polymer weight of polymer a), polymer b) and polymer c).

15. The composition of claim 8 , wherein the polymer is further blended with c) selected from the group, a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) 20% to 50% 4-hydroxybutyrate content, a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) 20% to 50% 5-hydroxyvalerate content and a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 5% to 50% 3-hydroxyhexanoate content.

16. The composition of claim 15 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

17. The composition of claim 11 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

18. The composition of claim 12 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

19. The composition of claim 15 , wherein the weight of polymer c) is 5% to 40% of the combined polymer weight of polymer a), polymer b) and polymer c).

20. A polymer composition, comprising: a polymer and the composition of claim 5 , wherein in the polymer is a) poly(3-hydroxybutyrate) homopolymer blended with a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

a poly(3-hydroxybutyrate) homopolymer blended with a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content;

a poly(3-hydroxybutyrate) homopolymer blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content;

a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content; a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate;

a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content;

a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with b) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with b) poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with b) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with 5% to 22% 3-hydroxyvalerate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b);

a polymer blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% 5-hydroxyvalerate and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b); or

a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% 3-hydroxyhexanoate content and the weight of polymer a) is 5% to 95% of the combined weight of polymer a) and polymer b).

21. The composition of claim 20 , wherein the weight of polymer a) is 20% to 60% of the combined weight of polymer a) and polymer b) and the weight of polymer b is 40% to 80% of the combined weight of polymer a) and polymer b).

22. The composition of claim 20 , wherein the polymer is further blended with polymer c) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) 20% to 50% 4-hydroxybutyrate content.

23. The composition of claim 20 , wherein the polymer is further blended with c) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) 20% to 50% 5-hydroxyvalerate content.

24. The composition of claim 20 , wherein the polymer is further blended with c) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 5% to 50% 3-hydroxyhexanoate content.

25. The composition of claim 22 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

26. The composition of claim 22 , wherein the weight of polymer c) is 5% to 40% of the combined polymer weight of polymer a), polymer b) and polymer c).

27. The composition of claim 20 , wherein the polymer is further blended with c) selected from the group, a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) 20% to 50% 4-hydroxybutyrate content, a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) 20% to 50% 5-hydroxyvalerate content and a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 5% to 50% 3-hydroxyhexanoate content.

28. The composition of claim 27 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

29. The composition of claim 23 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

30. The composition of claim 24 , wherein the weight of polymer c) is 5% to 95% of the combined polymer weight of polymer a), polymer b) and polymer c).

31. The composition of claim 27 , wherein the weight of polymer c) is 5% to 40% of the combined polymer weight of polymer a), polymer b) and polymer c).

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 30, 2017
From: CJ RESEARCH CENTER LLC
To: CJ CHEILJEDANG CORPORATION
Reel/Frame 043723/0517 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 3, 2017
From: METABOLIX, INC.
To: CJ RESEARCH CENTER LLC
Reel/Frame 041234/0890 →
ADDRESS CHANGE Recorded May 2, 2016
From: METABOLIX, INC.
To: METABOLIX, INC.
Reel/Frame 038665/0359 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 3, 2010
From: WHITEHOUSE, ROBERT S.; PADWA, ALLEN R.
To: METABOLIX, INC.
Reel/Frame 025448/0195 →