BIOBASED MODIFIERS FOR POLYVINYLCHLORIDE BLENDS

• US 20140088233A1
• Filed: 12/02/2013
• Published: 03/27/2014
• Est. Priority Date: 08/17/2012
• Status: Active Grant

• Current Assignee: CJ Cheiljedang Corporation (CJ Group)
• Original Assignee: Metabolix Incorporated
• Inventors: Kann, Yelena
• Granted Patent: US 9,464,187 B2
• Time in Patent Office: Days
• US Class Current: 524/296
• CPC Class Codes: C08J 2327/06 Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: C08J 2367/04 Polyesters derived from hydroxy carboxylic acids, e.g. lactones C08J2367/06 takes precedence
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08K 5/11 of acyclic polycarboxylic acids
• CPC Class Codes: C08K 5/12 of cyclic polycarboxylic acids
• CPC Class Codes: C08L 27/06 Homopolymers or copolymers of vinyl chloride
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence

Abstract

Compositions of polymer blends of polyvinylchloride (PVC), a low molecular weight plasticizer and polyhydroxyalkanoate (PHA) are described. In certain embodiments, the PHA is a poly-3-hydroxybutyrate-co-4-hydroxybutyrate copolymer having a weight percent 4-hydroxybutyrate of 30-45%. In other embodiments the PHA is a multiphase P3HB-4HB copolymer blend having one phase fully amorphous. The PHA is mixed with the PVC and low molecular weight plasticizer to optimize the PVC'"'"'s optical, thermal and mechanical properties. In certain embodiments, the polymer is branched with optionally additives that improve properties. Methods of making the compositions of the invention are also described. The invention also includes articles, films and laminates comprising the compositions.

Claims

1. A composition comprising a polymer blend of a polyvinyl chloride (PVC) polymer, a low molecular weight plasticizer, optionally biobased and a biobased non-extractable nonvolatile plasticizing polyhydroxyalkanoate copolymer or copolymer blend thereof (PHA), wherein the PHA decreases the migration rate of the low molecular weight plasticizer and improves performance of PVC.

2. The composition of claim 1, wherein the PHA copolymer is 3-polyhydroxybutylrate-co-4-polyhydroxybutyrate copolymer, 3-polyhydroxybutylrate-co-5-polyhydroxyvalerate;

or 3-polyhydroxybutylrate-co-6-polyhydroxyhexanoate.

3. The composition of claim 1, wherein the PHA copolymer has a T_g between about −

15°

C. and about −

45°

C. or between about 5°

C. and about −

40°

C. and is between about 5 weight % to about 50 weight % of the total PHA in the composition.

4. The composition of claim 1, wherein the PHA copolymer has a percent crystallinity of about 0.2 to 1% as measured by DSC.

5. The composition of claim 2, wherein the improved performance of the PVC includes having one or more of the following properties selected from:

lower volatile organic carbons, lower liquid extractables, improved permanence, mold and fungal resistance, thermal stability, UV photostability, low temperature flexibility, low temperature tensile elongation, low temperature toughness, low temperature impact strength, heat resistance, improved weathering, puncture resistance plasticization, and melt flow.

6. The composition of claim 1, wherein the PHA is branched or crosslinked.

7. The composition of claim 1, wherein the PHA/PVC blend includes a plasticizer, a barium/zinc stabilizer and an epoxidized soybean oil.

8. The composition of claim 7, wherein the plasticizer is diisononyl adipate, diisodecyl phthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester.

9. The composition of claim 1, wherein the PHA comprises an amorphous rubber phase having 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) co-monomer segments with a weight % 4HB of about 25% to about 40% in the PHA composition.

10. The composition of claim 1, wherein the PHA polymer is included in a PHA masterbatch comprising a PHA crosslinked with a peroxide and a co-agent blended with an acrylonitrile-styrene-acrylate terpolymer or chlorinated polyethylene.

11. The composition of claim 1, wherein the amount of PHA in the polymer composition is about 1% to about 50% by weight of the total composition or 10% to about 40%.

12. The composition of claim 1, further comprising one or more additives, optionally biobased, wherein the additive is selected from plasticizers, peroxide initiators, clarifiers, nucleating agents, thermal or oxidative stabilizers, inorganic fillers, anti-slip agents, compatibilizers, blocking agents or a combination thereof.

13. The composition of claim 1, wherein the PVC polymer and PHA polymer are miscible.

14. The composition of claim 1, wherein the biobased PHA further comprises a poly(3-hydroxybutyrate) homopolymer, a poly(3-hydroxybutyrate-co-4-hydroxybutyrate), a poly(3-hydroxybutyrate-co-3-hydroxyvalerate), a poly(3-hydroxybutyrate-co-5-hydroxyvalerate), or a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with the proviso that the PHA composition is not 100% poly(3-hydroxybutyrate) homopolymer or 100% poly(3-hydroxybutyrate-co-3-hydroxyvalerate).

15. The composition of claim 1, wherein the biobased PHA further comprises a poly(3-hydroxybutyrate) homopolymer, a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content,) with 5% to 22% 3-hydroxyvalerate content, a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with 5% to 15% 5-hydroxyvalerate content, or a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content.

16. The composition of claim 1, wherein the biobased PHA further comprises a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate);

a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate);

a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate);

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate));

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanote, or a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate),) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).

17. The composition of claim 1, wherein the biobased PHA further comprises a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15% 4-hydroxybutyrate content;

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

a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15% 3-hydroxyhexanoate content;

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15% 4-hydroxybutyrate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22% 3-hydroxyvalerate content;

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) with a 3% to 15% 3-hydroxyhexanoate content or a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22% 3-hydroxyvalerate content blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15% 3-hydroxyhexanoate content.

18. The composition of claim 1, wherein the biobased PHA further comprises a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and the weight of polymer a) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight of polymer a) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate) homopolymer blended to with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of polymer a) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and the weight of polymer a) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of polymer a) can be 5% to 95% of the combined weight of polymer a) and polymer b);

or a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the weight of polymer a) can be 5% to 95% of the combined weight of polymer a) and polymer b).

19. The composition of claim 1, wherein the biobased PHA further comprises a) poly(3-hydroxybutyrate) homopolymer blended with b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% 4-hydroxybutyrate content;

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

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

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

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

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;

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

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

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

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

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

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

20. The composition of claim 1, wherein the biobased PHA further comprises a) 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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 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) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 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) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 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) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 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) can be 5% to 95% of the combined weight of polymer a) and polymer b);

or a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 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) can be 5% to 95% of the combined weight of polymer a) and polymer b).

21. The composition of claim 1, wherein the impact resistance of the PVC-PHA polymer blends as measured by notched izod impact is 3 to at least 18 ft lb/in.

22. A film comprising the composition of claim 1.

23. An article comprising the composition of claim 1.

24. The article of claim 23, wherein the article having greater tensile elongation with greater tensile toughness than a corresponding polymer article consisting of PVC polymer with PHA.

25. The film of claim 22, wherein the film has increased tensile elongation and toughness according ASTM D822 relative to a corresponding polymer blend film without a copolymer of 3-polyhydroxybutylrate and one more monomers selected from lactic acid, 3-hydroxypropionic acid (3HP), 4-hydroxybutyrate (4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH), 6-hydroxyhexanoate (6HH) and 3-hydroxyoctanoate (3HO), wherein the monomer content is about 25-90% of the weight of the PHA.

26. The composition of claim 1, wherein the PHA is selected from a blend of 55-65% P3HB and 35-45% P3HB-4HB copolymer with 8-14% 4HB by weight, a blend of 18-22% P3HB, 77-83% P3HB-4HB copolymer with 8-14% 4HB by weight, a blend of 34-38% P3HB, 22-26% P3HB-4HB copolymer with 8-14% 4HB by weight and 38-42% P3HB-4HB copolymer with 25-33% 4HB by weight, and Tianjin SOGREEN®

P3HB-4HB copolymer with 30% 4HB.

27. The composition of claim 1, wherein an article made from the composition has one or more of the following properties improved, low temperature tensile elongation, low temperature toughness, low temperature impact strength, plasticization, tear resistance, heat resistance, mold and fungal resistance, thermal stability, UV photostability, melt flow or puncture resistance relative to a corresponding article made from a composition with the copolymer of 3-polyhydroxybutylrate and one more monomers selected from lactic acid, 3-hydroxypropionic acid (3HP), 4-hydroxybutyrate (4HB), 5-hydroxyvalerate (5HV), 3-hydroxyhexanoate (3HH), 6-hydroxyhexanoate (6HH) and 3-hydroxyoctanoate (3HO), wherein the monomer content is about 25-90% of the weight of the PHA.

28. A method of preparing a polyvinyl chloride (PVC)/polyhydroxyalkanoate (PHA) polymer blend composition, comprising

melt ending the composition of claim 1, using a single or twin screw extruder, two-roll mill, Banbury mixer or the like, thereby forming a polymer composition of PVC and PHA.