Crystal nucleating agents for polyhydroxyalkanoates
This invention relates to compositions and methods for increasing the crystallization rate and/or processing speed of polyhydroxyalkanoate (PHA) polymers. PHA polymers are notorious for slow crystallization rates, reducing the practicality for using PHA for consumer products. Compounds that have similar crystal structures to PHA and have a melting point higher than that of the PHA, such as pentaerythritol, as well as compounds that undergo a crystal structure change at or below the melting point of the polymer, such as sulfur or selenium, act as good crystal nucleators for PHA.
1. A polymeric composition comprising:
a polymer including at least 20 mole percent hydroxyalkanoate repeat units, and
a nucleating agent, in an amount from about 0.01% to about 20% by weight of the polymer, wherein the nucleating agent is selected from the group consisting of dipentaerythritol, anatase, wulfenite, aragonite, sulfur, selenium, phosphorous, benzamide, and mixtures thereof.
2. The polymeric composition of claim 1 , wherein the nucleating agent is present in an amount from about 0.5% to about 5% by weight of the polymer.
3. The polymeric composition of claim 1 , wherein the polymer is hydroxybutyrate-hydroxyhexanoate copolymer.
4. The polymeric composition of claim 1 , wherein the polymer has a first repeat unit having the structure:
and a second repeat unit having the structure:
wherein each R is independently a C 3 to C 19 alkyl group, and
wherein the polymer includes from about 75 mole percent to about 99 mole percent of the first repeat unit and from about 1 mole percent to about 25 mole percent of the second repeat unit.
5. The polymeric composition of claim 1 , wherein the polymer has a weight average molecular weight from about 10,000 to about 3,000,000 daltons.
6. The polymeric composition of claim 1 , wherein the polymer has a melting point from about 100° C. to about 150° C.
7. The polymeric composition of claim 1 , wherein the polymer has a glass transition temperature from about −30° C. to about 10° C.
8. A process for crystallizing a polymer, comprising the steps of:
admixing a polymer including at least 20 mole percent of hydroxyalkanoate repeat units with a nucleating agent, in an amount from about 0.01% to about 20% by weight of the polymer, at a first temperature, which is from about 5° C. to about 15° C. above the melting point of the polymer; and
cooling the mixture to a second temperature, which is from about the glass transition temperature of the polymer to about the melting point of the nucleating agent,
wherein the nucleating agent is selected from the group consisting of dipentaerythritol, anatase, wulfenite, aragonite, sulfur, selenium, phosphorous, benzamide, and mixtures thereof.
9. The method of claim 8 , wherein the first temperature is from about 100° C. to about 190° C.
10. The method of claim 8 , wherein the second temperature is from about 50° C. to about 90° C.
11. The method of claim 8 , wherein the nucleating agent is present in an amount from about 0.5% to about 5% by weight of the polymer.
12. The method of claim 8 , wherein the polymer is hydroxybutyrate-hydroxyhexanoate copolymer.
13. The method of claim 8 , wherein the polymer has a weight average molecular weight from about 10,000 to about 3,000,000 daltons.
14. The method of claim 8 , wherein the polymer has a melting point from about 100° C. to about 150° C.
15. The method of claim 8 , wherein the polymer has a glass transition temperature from about −30° C. to about 10° C.
16. The method of claim 8 , wherein the polymer has a first repeat unit having the structure:
and a second repeat unit having the structure:
wherein each R is independently a C 3 to C 19 alkyl group, and
wherein the polymer includes from about 75 mole percent to about 99 mole percent of the first repeat unit and from about 1 mole percent to about 25 mole percent of the second repeat unit.
17. The method of claim 8 ,
wherein the nucleating agent transitions from a crystalline form which is not orthorhombic, hexagonal, or tetragonal to a crystalline form which is orthorhombic, hexagonal, or tetragonal during the cooling step.