Biobased rubber modified biodegradable polymer blends

• US 10,113,060 B2
• Filed: 06/05/2013
• Issued: 10/30/2018
• Est. Priority Date: 06/05/2012
• Status: Active Grant

• Current Assignee: CJ Cheiljedang Corporation (CJ Group)
• Original Assignee: CJ Cheiljedang Corporation (CJ Group)
• Inventors: Krishnaswamy, Rajendra K., van Walsem, Johan, Peoples, Oliver P., Shabtai, Yossef, Padwa, Allen R.
• Primary Examiner(s): Woodward, Ana L.
• Application Number:
  US14/406,131
• Publication Number:
  US 20150132512A1
• Time in Patent Office: 1,973 Days
• Field of Search: None
• CPC Class Codes: C08J 2367/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds; C08J2367/06 takes precedence
• CPC Class Codes: C08J 2367/04 Polyesters derived from hydroxy carboxylic acids, e.g. lactones C08J2367/06 takes precedence
• CPC Class Codes: C08J 2467/04 Polyesters derived from hydroxy carboxylic acids, e.g. lactones C08J2467/06 takes precedence
• CPC Class Codes: C08J 3/246 Intercrosslinking of at least two polymers
• CPC Class Codes: C08J 5/18 Manufacture of films or sheets
• CPC Class Codes: C08L 2201/06 Biodegradable
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2205/025 containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• CPC Class Codes: C08L 2205/24 Crystallisation aids
• CPC Class Codes: C08L 2207/02 Heterophasic composition
• CPC Class Codes: C08L 67/02 Polyesters derived from dicarboxylic acids and dihydroxy compounds C08L67/06 takes precedence
• CPC Class Codes: C08L 67/04 Polyesters derived from hydroxycarboxylic acids, e.g. lactones C08L67/06 takes precedence
• CPC Class Codes: Y10T 428/1334 Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
• CPC Class Codes: Y10T 442/3146 Strand material is composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
• CPC Class Codes: Y10T 442/637 Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material

Abstract

Compositions of biobased polymer blends of polymers and a polyhydroxyalkanoate copolymer are described. In certain embodiments, the copolymer is a multiphase copolymer blend having one phase a glass transition temperature of about −5° C. to about −50° C. Methods of making the compositions of the invention are also described. Also articles, films and laminates made from the compositions are described.

Claims

1. A composition, comprising a biodegradable branched polymer blend formed by reactive blending of:

a. polylactic acid (PLA); and

b. a biodegradable polyhydroxyalkanoate (PHA) polymer having a glass transition temperature (Tg) of between −

5°

C. and −

50°

C. and a weight average molecular weight from 500,000 Daltons to 2,000,000 Daltons, wherein the PHA polymer is a copolymer of;

3-hydroxybutyrate and 4-hydroxybutyrate, wherein the content of 4-hydroxybutyrate in the PHA polymer is from about 25% to about 85% by weight of the PHA polymer;

wherein the copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate is the sole PHA polymer in the polymer blend,

wherein the content of the PHA polymer in the biodegradable branched polymer blend is between about 3% and about 40% by weight of the blend, and

wherein the renewable carbon content of the biodegradable branched polymer blend is at least 95% by weight of the blend,

wherein the biodegradable branched polymer blend was formed by reactive blending of the PLA and the PHA polymer with a branching agent.

2. The composition of claim 1, wherein the renewable carbon content of the biodegradable branched polymer blend is at least 99% by weight of the blend.

3. The composition of claim 1, wherein the branching agent is selected from:

dicumyl peroxide, t-amyl-2-ethylhexyl peroxycarbonate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, 2,5-dimethyl-2,5-di(t-amyl peroxy) hexane, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 2,5-dimethyl-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, benzoyl peroxide, di-t-amyl peroxide, t-butyl cumyl peroxide, n-butyl-4,4-bis(t-butylperoxy)valerate, 1,1-di(t-butylperoxy)-3,3,5-trimethyl-cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-amylperoxy)-cyclohexane, 2,2-di(t-butylperoxy)butane, ethyl-3,3-di(t-butylperoxy)butyrate, 2,2-di(t-amylperoxy)propane, ethyl-3,3-di(t-amylperoxy)butyrate, t-butylperoxy-acetate, t-amylperoxyacetate, t-butylperoxybenzoate, t-amylperoxybenzoate, and di-t-butyldiperoxyphthalate or combinations thereof.

4. The composition of claim 1, wherein the PLA and the PHA polymer were reactively blended with a branching agent in the presence of a co-agent.

5. The composition of claim 4, wherein the co-agent is diallyl phthalate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, diethylene glycol dimethacrylate, bis (2-methacryloxyethyl) phosphate, or combinations thereof.

6. The composition of claim 4, wherein the co-agent is an epoxy-functional styrene-acrylic polymer, an epoxy-functional acrylic copolymer, an epoxy-functional polyolefin copolymer, an oligomer comprising a glycidyl group with an epoxy functional side chain, an epoxy-functional poly(ethylene-glycidyl methacrylate-co-methacrylate), or an epoxidized oil or combinations thereof.

7. The composition of claim 1, wherein the content of 4-hydroxybutyrate (4HB) in the PHA polymer is from 30% to 65% by weight of the PHA polymer.

8. The composition of claim 1, wherein the content of 4-hydroxybutyrate (4HB) in the PHA polymer is from 45% to 65% by weight of the PHA polymer.

9. The composition of claim 1, wherein the PHA polymer comprises an amorphous rubber phase having no melting point.

10. A film or multilayer laminate comprising at least one film layer comprising the composition of claim 1.

11. An article made with the laminate of claim 10, wherein the film has a thickness of about 1 to about 2 microns.

12. The article of claim 11, wherein the article is a bag, a packaging film or an agricultural mulch film.

13. A resin composition made from the composition according to claim 1.

14. A finished article made by extrusion processing of the resin composition of claim 13, wherein the article is an injection molded part, a thermoformed part, a film or a coating.

15. An article made with the composition of claim 1, wherein the article is a foam, a woven or nonwoven fiber, or a thermoformed part.

16. A method of preparing a polylactic acid (PLA)/polyhydroxyalkanoate (PHA) polymer blend, comprising reactively blending in the presence of a branching agent,

a. polylactic acid (PLA);

and

b. a biodegradable polyhydroxyalkanoate (PHA) polymer having a glass transition temperature (Tg) of between −

5°

C. and −

50°

C. and a weight average molecular weight from 500,000 Daltons to 2,000,000 Daltons, wherein the PHA polymer is a copolymer of;

3-hydroxybutyrate and 4-hydroxybutyrate, wherein the content of 4-hydroxybutyrate in the PHA polymer is about 25% to about 85% of the weight of the PHA polymer;

wherein the copolymer of 3-hydroxybutyrate and 4-hydroxybutyrate is the sole PHA polymer in the polymer blend;

wherein the content of the PHA polymer in the PLA/PHA polymer blend is from about 3% to about 40% by weight of the PLA/PHA polymer blend, and

wherein the renewable carbon content of the PLA/PHA polymer blend is at least 95% by weight of the PLA/PHA polymer blend;

thereby forming a PLA/PHA polymer blend.