Biobased modifiers for polyvinylchloride blends

• US 9,464,187 B2
• Filed: 12/02/2013
• Issued: 10/11/2016
• Est. Priority Date: 08/17/2012
• Status: Active Grant

• Current Assignee: CJ Cheiljedang Corporation (CJ Group)
• Original Assignee: Metabolix Incorporated
• Inventors: Kann, Yelena
• Primary Examiner(s): CHIN, HUI H
• Application Number:
  US14/094,150
• Publication Number:
  US 20140088233A1
• Time in Patent Office: 1,044 Days
• Field of Search: 525/55
• US Class Current: 1/1
• 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 primary plasticizer, optionally biobased; and

polyhydroxyalkanoate (PHA) composition comprising one or more biobased non-extractable nonvolatile plasticizing polyhydroxyalkanoate polymers,

wherein the PHA composition decreases the migration rate of the primary plasticizer and improves performance of the polymer blend,

where the PHA composition includes poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer, poly(3-hydroxybutyrate-co-5-hydroxyvalerate) copolymer;

or poly(3-hydroxybutyrate-co-6-hydroxyhexanoate) copolymer.

3. The composition of claim 1, wherein the improved performance of the polymer blend includes having one or more of the following properties selected from:

lower volatile organic carbons, lower liquid extractables, improved permanence, improved mold and fungal resistance, improved thermal stability, improved UV photostability, imroved low temperature flexibility, improved low temperature tensile elongation, improved low temperature toughness, improved low temperature impact strength, improved heat resistance, improved weathering, improved puncture resistance plasticization, and improved melt flow, wherein the polymer blend is compared to a corresponding blend without the PHA composition.

4. The composition of claim 1, wherein the polymer blend includes a secondary plasticizer, a barium/zinc stabilizer and an epoxidized soybean oil.

5. The composition of claim 4, wherein the primary plasticizer is diisononyl adipate, diisodecyl phthalate or 1,2-cyclohexane dicarboxylic acid diisononyl ester.

6. The composition of claim 1, wherein at least one of the one or more PHA copolymers comprises an amorphous rubber phase having 3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB) co-monomer segments, having the 4HB content of about 25% to about 40% by weight of the at least one PHA copolymer.

7. The composition of claim 1, wherein at least one copolymer in the PHA composition is crosslinked with a peroxide and a co-agent blended with an acrylonitrile-styrene-acrylate terpolymer or chlorinated polyethylene.

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

9. The composition of claim 1, wherein the PHA composition comprises a poly(3-hydroxybutyrate) homopolymer, a poly(3-hydroxybutyrate-co-3-hydroxyvalerate), or a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).

10. The composition of claim 1, wherein the PHA composition comprises:

a poly(3-hydroxybutyrate) homopolymer;

a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% 4-hydroxybutyrate content by weight;

a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with 5% to 15% 5-hydroxyvalerate content by weight;

or

a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with 3% to 15% 3-hydroxyhexanoate content by weight.

11. The composition of claim 1, wherein the PHA composition 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).

12. The composition of claim 1, wherein the PHA composition comprises:

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with the content of 4-hydroxybutyrate at 5% to 15% by weight of b);

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with the content of 3-hydroxyvalerate at 5% to 22% by weight of b);

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with the content of 3-hydroxyhexanoate at 3% to 15% by weight of b);

a blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with the content of 4-hydroxybutyrate at 5% to 15% by weight of a) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with the content of 3-hydroxyvalerate at 5% to 22% by weight of b);

a blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with the content of 4-hydroxybutyrate at 5% to 15% by weight of a) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with the content of 3-hydroxyhexanoate at 3% to 15% by weight of b);

or

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with the content of 3-hydroxyvalerate at 5% to 22% by weight of a) blended with b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with the content of 3-hydroxyhexanoate at 3% to 15% by weight of b).

13. The composition of claim 1, wherein the PHA composition comprises:

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and the content of polymer a) in the blend is 5% to 95% by weight of the blend;

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and the content of polymer a) in the blend is 5% to 95% by weight of the blend;

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the content of polymer a) in the blend is 5% to 95% by weight of the blend;

a blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and b) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and the content of polymer a) in the blend is 5% to 95% by weight of the blend;

a blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the content of polymer a) in the blend is 5% to 95% by weight of the blend;

or

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and the content of polymer a) in the blend is 5% to 95% by weight of the blend.

14. The composition of claim 1, wherein the PHA composition comprises:

a blend of a) poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% by weight of b) 4-hydroxybutyrate content;

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% by weight of b) 5-hydroxyvalerate content;

a blend of a) a poly(3-hydroxybutyrate) homopolymer and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% by weight of b) 3-hydroxyhexanoate content;

a blend of a) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15% by weight of a) 4-hydroxybutyrate content and b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% by weight of b) 4-hydroxybutyrate content;

a blend of a) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 5% to 15% by weight of a) 4-hydroxybutyrate content and b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% by weight of b) 5-hydroxyvalerate content;

a blend of a) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with 5% to 15% by weight of a) 4-hydroxybutyrate content and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% by weight of b) 3-hydroxyhexanoate content;

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22% by weight of a) 3-hydroxyvalerate content and b) poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% by weight of b) 4-hydroxybutyrate content;

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22% by weight of a) 3-hydroxyvalerate content and b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% by weight of b) 5-hydroxyvalerate content;

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with a 5% to 22% by weight of a) 3-hydroxyvalerate content and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% by weight of b) 3-hydroxyhexanoate content;

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15% by weight of a) 3-hydroxyhexanoate content and b) a poly(3-hydroxybutyrate-co-4-hydroxybutyrate) with a 20-50% by weight of b) 4-hydroxybutyrate content;

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15% by weight of a) 3-hydroxyhexanoate content and b) a poly(3-hydroxybutyrate-co-5-hydroxyvalerate) with a 20% to 50% by weight of b) 5-hydroxyvalerate;

or

a blend of a) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) with a 3% to 15% by weight of a) 3-hydroxyhexanoate content and b) a poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) having a 5%-50% by weight of b) 3-hydroxyhexanoate content.

15. The composition of claim 1, wherein the PHA composition comprises:

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

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

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

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

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

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

a blend of 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) in the blend is 5% to 95% by weight of the blend;

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

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

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

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

or

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

16. The composition of claim 1, wherein the impact resistance of the polymer blend as measured by notched izod impact is 3 to at least 18 ft lb/in.

17. A film comprising the composition of claim 1.

2. A composition, comprising a polymer blend of:

a polyvinyl chloride (PVC) polymer;

a primary plasticizer, optionally biobased; and

polyhydroxyalkanoate (PHA) composition comprising one or more biobased non-extractable nonvolatile plasticizing polyhydroxyalkanoate polymers,

wherein the PHA composition decreases the migration rate of the primary plasticizer and improves performance of polymer blend,

wherein the PHA composition has a percent crystallinity of about 0.2 to 1% as measured by DSC.