Crosslinked polyester compositions, method of manufacture, and uses thereof
View Patent ↗A composition comprises a thermally crosslinked reaction product of a polyester and a carboxy-reactive material. Methods for the manufacture of the composition and articles derived from the composition are also disclosed.
1. A polymer composition, comprising a polymer and particles of a composition comprising a thermally crosslinked reaction product of a polyester and from 0.1 to 10 wt % based on the weight of the polyester, of a carboxy-reactive material comprising a terminal epoxy group and a terminal silane group; and a compound of the formula
wherein each R′ is independently the same or different C 1-6 alkyl group and each n is independently 1 to 6;
wherein the particles have an average largest diameter of 0.5 to 1200 micrometers and are present in the polymer composition in an amount from 0.1 to 20 wt %, based on the total weight of the composition, effective to adjust the haze and/or clarity of the polymer.
2. The composition of claim 1 , wherein the polyester is selected from the group consisting of poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(ethylene naphthalate), poly(butylene naphthalate), (polytrimethylene terephthalate), poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate), poly(1,4-cyclohexylenedimethylene terephthalate), poly(cyclohexylenedimethylene-co-ethylene terephthalate), poly(butylene-co-poly(oxytetramethylene)terephthalate), poly(butylene-co-poly(oxyethylene)terephthalate), and combinations thereof.
3. The composition of claim 1 , wherein the polyester is selected from the group consisting of poly(butylene terephthalate), poly(ethylene terephthalate), poly(trimethylene terephthalate), a combination of poly(ethylene naphthalate) and poly(butylene naphthalate), and combinations thereof.
4. The composition of claim 1 , wherein the polyester is poly(butylene terephthalate).
5. The composition of claim 1 , wherein the epoxy group is attached to a terminal cycloaliphatic ring system.
6. The composition of claim 5 , wherein the epoxy silane has a general formula
wherein m is an integer of 1-3, n is an integer of 1-6, and X, Y, and Z are each independently a C1-20 alkyl, a C4-10 cycloalkyl, a C7-16 alkylenephenyl, or a C7-16 phenylenealkyl.
7. The composition of claim 6 , wherein m is 2, n is 1 or 2, and X, Y, and Z are the same and are a C 1-3 alkyl.
8. The composition of claim 1 , wherein the epoxy silane is beta-(3,4-epoxycyclohexyl)ethyl triethoxysilane.
9. The composition of claim 1 , wherein the thermally crosslinked reaction product has a gel content of at least 5 weight percent after extraction.
10. The composition of claim 1 , wherein the composition of the particles has a heat deflection temperature at least 5° C. greater than the same composition when it is not crosslinked, wherein each heat deflection temperature is determined at 1.82 MPa in accordance with ASTM D648.
11. The composition of claim 1 , wherein the composition of the particles further comprises an impact modifier, a filler, an antioxidant, a thermal stabilizer, a light stabilizer, an ultraviolet light absorbing additive, a quencher, a plasticizer, a lubricant, a mold release agent, an antistatic agent, a dye, pigment, a visual effect additive, a flame retardant, an anti-drip agent, a radiation stabilizer, or a combination comprising at least one of the foregoing additives.
12. An article comprising the composition of claim 1 .
13. The article of claim 12 , wherein the article is injection molded, rotationally molded, compression molded, blow molded, gas assisted injection molded, extruded, or thermoformed.
14. The composition of claim 1 , wherein the polyester is a poly(1,4-butylene terephthalate), and the carboxy-reactive material is beta-(3,4-epoxycyclohexyl)ethyl triethoxysilane.
15. A method for the manufacture of the thermally crosslinked reaction product of claim 1 , comprising contacting the polyester and the carboxy-reactive material at a temperature and for a time sufficient to crosslink the polyester with the carboxy-reactive material.
16. The method of claim 15 , wherein the contacting is at 140 to 220° C. for 2 to 20 hours.
17. The method of claim 15 , wherein the crosslinking is in the presence of a catalyst.
18. The composition of claim 1 , wherein the composition of the particles has a heat deflection temperature of at least 203° C., wherein the heat deflection temperature is determined at 0.45 MPa in accordance with ASTM D648.
19. The composition of claim 18 , wherein the polyester is a poly(1,4-butylene terephthalate), and the carboxy-reactive material is beta-(3,4-epoxycyclohexyl)ethyl triethoxysilane.
20. A composition comprising a thermally crosslinked reaction product of a polyester and a combination of different carboxy-reactive materials, wherein the reaction product is in the form of particles having an average largest diameter of 10 to 100 micrometers, and wherein a first carboxy-reactive material is an epoxy silane comprising a terminal epoxy group and a terminal silane group and is present in an amount of 0.1 to 10 wt %, based on the weight of the polyester, and wherein the composition further comprises a second carboxy-reactive material that is a silane compound different than the first carboxy-reactive material.
21. The composition of claim 20 , wherein the polyester is of the formula
wherein each T is independently a divalent C 2-20 aliphatic group, C 5-20 cycloaliphatic group, or C 6-20 aromatic group derived from a dicarboxylic acid or a chemical equivalent thereof; and each D is independently a divalent C 2-20 alkylene group, C 6-20 alicyclic group, C 6-20 aromatic group, or poly(C 2-6 oxyalkylene) group derived from a dihydroxy compound or a chemical equivalent thereof.
22. The composition of claim 20 , wherein the polyester is selected from the group consisting of poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(ethylene naphthalate), poly(butylene naphthalate), (polytrimethylene terephthalate), poly(1,4-cyclohexylenedimethylene 1,4-cyclohexanedicarboxylate), poly(1,4-cyclohexylenedimethylene terephthalate), poly(cyclohexylenedimethylene-co-ethylene terephthalate), poly(butylene-co-poly(oxytetramethylene)terephthalate), poly(butylene-co-poly(oxyethylene)terephthalate), and combinations thereof.
23. The composition of claim 20 , wherein the polyester is selected from the group consisting of poly(butylene terephthalate), poly(ethylene terephthalate), poly(trimethylene terephthalate), a combination of poly(ethylene naphthalate) and poly(butylene naphthalate), and combinations thereof.
24. The composition of claim 20 , wherein the polyester is poly(butylene terephthalate).
25. The composition of claim 20 , wherein the composition has 10 to 320 milliequivalents epoxy group per 1.0 kg of the polyester.
26. The composition of claim 20 , wherein the epoxy group in the first carboxy-reactive material is attached to a terminal cycloaliphatic ring system.
27. The composition of claim 26 , wherein the first carboxy-reactive material is a epoxy silane that has a general formula
wherein m is an integer of 1-3, n is an integer of 1-6, and X, Y, and Z are each independently a C1-20 alkyl, a C4-10 cycloalkyl, a C7-16 alkylenephenyl, or a C7-16 phenylenealkyl.
28. The composition of claim 27 , wherein m is 2, n is 1 or 2, and X, Y, and Z are the same and are a C 1-3 alkyl.
29. The composition of claim 20 , wherein the epoxy silane is beta-(3,4-epoxycyclohexyl)ethyl triethoxysilane.
30. The composition of claim 20 , wherein the second carboxy-reactive material has the following structure:
wherein each R′ is independently the same or different C 1-6 alkyl group and each n is independently 1 to 6.
31. The composition of claim 20 , wherein the polyester is a poly(1,4-butylene terephthalate), and the carboxy-reactive material is beta-(3,4-epoxycyclohexyl)ethyl triethoxysilane.
32. The composition of claim 20 , further comprising an antioxidant, a thermal stabilizer, a light stabilizer, an ultraviolet light absorbing additive, a quencher, a plasticizer, a lubricant, a mold release agent, or a combination comprising at least one of the foregoing additives.
33. The composition of claim 20 , wherein the thermally crosslinked reaction product has a gel content of at least 5 weight percent after extraction.
34. An article comprising the composition of claim 20 .
35. The article of claim 34 , wherein the article is injection molded or extruded.
36. A composition comprising a polymer and the particles of claim 20 in an amount effective to adjust the haze and/or clarity of the polymer.
37. A polymer composition comprising poly(butylene terephthalate) and particles comprising a thermally crosslinked reaction product of a polyester and a combination of different carboxy-reactive materials, a first carboxy-reactive material that is an epoxy silane comprising a terminal epoxy group and a terminal silane group, present in an amount of 0.1 to 10 wt %, based on the weight of the poly(butylene terephthalate), and a second carboxy-reactive material that is a silane compound different than the first carboxy-reactive material, wherein the particles have an average largest diameter of 0.5 to 1200 micrometers and wherein the amount of particles, effective to adjust the haze and/or clarity of the polymer composition, is from 0.001 to 20 wt %, based on the total weight of the polymer composition.
38. An article comprising the composition of claim 37 .
39. A method for the manufacture of the thermally crosslinked polyester composition of claim 20 , comprising:
contacting the polyester and the carboxy-reactive materials at a temperature and for a time sufficient to crosslink the polyester with the carboxy-reactive material; and
comminuting the crosslinked thermally crosslinked polyester composition to form the particles.
40. The method of claim 39 , wherein the contacting is at 140 to 220° C. for 2 to 20 hours.
41. The method of claim 39 , wherein the contacting is in the presence of a catalyst.
42. The method of claim 39 , wherein the contacting is at 140 to 220° C. for 2 to 20 hours in the presence of a catalyst.
43. A composition comprising poly(butylene terephthalate)polymer and a thermally crosslinked reaction product of a polyester and a carboxy-reactive material, wherein the reaction product is in the form of particles having an average largest diameter of 0.5 to 1200 micrometers, wherein the particles are present in an amount, from 0.001 to 20 wt %, based on the total weight of the composition, effective to adjust the haze and/or clarity of the polymer.
44. An article comprising the composition of claim 43 .