Nucleating agents for polyhydroxyalkanoates
View Patent ↗The present invention provides a process for crystallizing a polymer having at least 20 mole percent of hydroxyalkanoate repeat units, comprising admixing the polymer and a compound of the formula R 1 —C(O)N(R 2 ) 2 , R 1 —C(O)NH—(R 3 )—NHC(O)—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)NH—R 1 , R 1 —NHC(O)—R 2 , R 1 —NHC(O)—(R 3 )—C(O)NH—R 1 , R 1 —C(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)—R 1 , or a combination thereof, at a first temperature, which is from about 5° C. to about 15° C. above the melting point of the polymer; and cooling the polymer at a second temperature, which is from about the glass transition temperature of the polymer to about the melting point of the compound. The present invention also provides a composition comprising a polymer having at least about 20 mole percent of hydroxyalkanoate repeat units, and a compound of the formula R 1 —C(O)N(R 2 ) 2 , R 1 —C(O)NH—(R 3 )—NHC(O)—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)NH—R 1 , R 1 —NHC(O)—R 2 , R 1 —NHC(O)—(R 3 )—C(O)NH—R 1 , R 1 —C(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)—R 1 , or a combination thereof.
1. A process for crystallizing a polymer that is copolymer of a first repeat units which has a structure:
and a second repeat unit that has a structure:
in which R is independently a C 3 to C 19 alkyl group, the poloymer having at least 20 mole percent of hydroxyalkanoate repeat units, comprising
a) admixing the polymer and a compound of the formula:
R 1 —C(O)N(R 2 ) 2 , R 1 —C(O)NH—(R 3 )—NHC(O)—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)NH—R 1 , R 1 —NHC(O)—R 2 , R 1 —NHC(O)—(R 3 )—C(O)NH—R 1 , R 1 —C(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)—R 1 , or a combination thereof at a first temperature, which is from about 5° C. to about 15° C. above the melting point of the polymer; and
b) cooling the polymer at a second temperature, which is from about the glass transition temperature of the polymer to about the melting point of the compound; wherein
each R 1 is independently C 6 -C 30 alkyl;
each R 2 is C 1 -C 20 alkyl; and
each R 3 is independently C 2 -C 10 alkylene.
2. The process of claim 1 , wherein the compound is (C 6 -C 30 alkyl)C(O)NH 2 .
3. The process of claim 1 , wherein the first temperature is from about 100° C. to about 190° C.
4. The process of claim 1 , wherein the second temperature is from about 50° C. to about 90° C.
5. The process of claim 1 , wherein the cooling occurs for a time of from about 3 to about 30 seconds.
6. The process of claim 1 , wherein the admixing comprises melt blending, solution blending, dry mixing, extrusion mixing, injection molding, pelleting, blow molding, extrusion sheet forming, inflation forming, contour extrusion forming, vacuum pressure forming, blown film processing, extrusion coating, fiber spinning, or a combination thereof.
7. The process of claim 1 , wherein the polymer comprises at least about 50 mol % hydroxyalkanoate repeat units.
8. The process of claim 7 , wherein the repeat units are 3-hydroxybutyrate repeat units.
9. The process of claim 1 , wherein the polymer has a melting point of from about 80° C. to about 160° C.
10. The process of claim 1 , wherein the polymer has a glass transition temperature of from about −30° C. to about 10° C.
11. The process of claim 1 , wherein the compound has a melting point of from about 60° C. to about 150° C.
12. A process for crystallizing a polymer that is copolymer of a first repeat unit which has a structure:
and a second repeat unit has a structure:
in which R is independently a C 3 to C 19 alkyl group, the polymer having at least 20 mole percent of hydroxyalkanoate repeat units, comprising
a) admixing the polymer and wherein the compound is behenamide; and
b) cooling the polymer at a second temperature, which is from about the glass transition temperature of the polymer to about the melting point of the behenamide.
13. The process of claim 1 , wherein the compound is CH 3 —(CH 2 ) 8 —C(O)NH—CH 2 —CH 2 —NHC(O)—(CH 2 —) 8 —CH 3 or CH 3 —(CH 2 ) 17 —NHC(O)NH—(CH 2 —CH 2 ) 3 —NHC(O)NH—(CH 2 ) 17 —CH3.
14. The process of claim 1 , wherein the amount of the compound is about 0.01% to about 20% by weight of the polymer.
15. The process of claim 1 , wherein the amount of the compound is about 0.5% to about 1.5% by weight of the polymer.
16. The process of claim 1 , wherein the particle size of the polymer and of the compound are similar.
17. The process of claim 1 , wherein at least 90% of the polymer's repeat units are hydroxyalkanoate repeat units.
18. The process of claim 17 , wherein the polymer is a hydroxybutyrate-hydroxyhexanoate copolymer.
19. The process of claim 17 , wherein the hydroxyalkanoate is a D-hydroxyalkanoate.
20. The process of claim 17 , wherein the molecular weight of the polymer is from about 300,000 to about 1,000,000.
21. The process of claim 17 , wherein the polymer has a purity of at least about 90%.
22. The process of claim 1 , wherein
a) the first temperature is from about 130° C. to about 190° C.;
b) the second temperature is from about 50° C. to about 90° C.; and
c) 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; wherein the polymer has from about 75 mol % to about 99 mol % of the first repeat unit and from about 1 mol % to about 25 mol % of the second repeat unit.
23. A composition comprising: a) a polymer that is copolymer of a first repeat unit which has a structure:
and a second repeat unit having the structure:
in which R is independently a C 3 to C 19 alkyl group, the polymer having at least 20 mole percent of hydroxyalkanoate repeat units, and b) a compound of the formula R 1 —C(O)N(R 2 ) 2 , R 1 —C(O)NH—(R 3 )—NHC(O)—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)NH—R 1 , R 1 —NHC(O)—R 2 , R 1 —NHC(O)—(R 3 )—C(O)NH—R 1 , R 1 —C(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—C(O)NH—R 1 , R 1 —NHC(O)NH—(R 3 )—NHC(O)—R 1 , or a combination thereof; wherein each R 1 is independently C 6 -C 30 alkyl; each R 2 is C 1 -C 20 alkyl; and each R 3 is independently C 2 -C 10 alkylene.
24. The composition of claim 23 , wherein the compound is (C 6 -C 30 alkyl)C(O)NH 2 .
25. The composition of claim 23 , wherein the polymer is a hydroxybutyrate-hydroxyhexanoate copolymer.
26. The composition of claim 25 , wherein the hydroxybutyrate-hydroxyhexanoate copolymer is a D-3-hydroxybutyrate-D-3-hydroxyhexanoate copolymer.
27. A composition comprising: a) a polymer that is copolymer of a first repeat unit which has a structure:
and a second repeat unit that has a structure:
in which R is independently a C 3 to C 19 alkyl group, the polymer having at least 20 mole percent of hydroxyalkanoate repeat units, and b) behenamide.
28. The composition of claim 23 , 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; wherein the polymer has from about 75 mol % to about 99 mol % of the first repeat unit and from about 1 mol % to about 25 mol % of the second repeat unit.
29. The composition of claim 23 , the polymer has a melting point of from about 80° C. to about 160° C.
30. The composition of claim 24 , wherein the polymer has a glass transition temperature of from about −30° C. to about 10° C.
31. The composition of claim 23 , wherein the compound has a melting point of from about 60° C. to about 150° C.
32. The composition of claim 23 , wherein the compound is CH 3 —(CH 2 ) 8 —C(O)NH—CH 2 —CH 2 —NHC(O)—(CH 2 ) 8 —CH 3 or CH 3 —(CH 2 ) 17 —NHC(O)NH—(CH 2 —CH 2 ) 3 —NHC(O)NH—(CH 2 ) 17 —CH 3 .
33. The composition of claim 23 , wherein the amount of the compound is about 0.01% to about 20% by weight of the polymer.
34. The composition of claim 23 , wherein the molecular weight of the polymer is from about 300,000 to about 1,000,000.