Extruded foams made with polylactides that have high molecular weights and high intrinsic viscosities
View Patent ↗This invention provides an economical process for extruding a PLA resin into a low density foam with a high closed cell content. Excellent quality, low density foam is produced easily and reproducibly. The PLA resin in the foam has a weight average molecular weight of at least 500,000 and an intrinsic viscosity of at least 1.4 deciliters/gram.
1. A process that comprises forming a pressurized, molten mixture of a melt-processable branched polylactide (PLA) resin containing about 3 to about 25% by weight of a blowing agent, based on the weight of the PLA resin, and extruding the molten mixture through a die to a region of reduced pressure such that the blowing agent expands and the PLA resin simultaneously cools to form a stable foam, wherein the PLA resin in the foam (1) is the reaction product of a linear PLA resin having a number average molecular weight of at least 80,000 with a reactive branching agent which contains multiple functional groups that can react with hydroxyl and/or carboxylic acid groups that terminate the PLA polymer chains, (2) has an absolute weight average molecular weight of from 550,000 to 1,500,000 as determined by dissolving 0.5 g samples of the PLA resin in 9.6 mL of methylene chloride, transferring 0.25 mL of the PLA resin solution into a 20 mL vial and diluting it with 9.75 mL tetrahydrofuran, filtering the diluted sample, measuring the refractive index, right angle light scatter and low angle light scatter using a multi-detector gel permeation chromatography (GPC) system comprised of a Viscotek GPCmax VE2001 GPC solvent/sample module, a Viscotek TDA 302 triple detector array module, a computer running Viscotek OmniSEC version 4.5 software, a Viscotek low molecular weight mixed-bed GPC column, and a Viscotek high molecular weight mixed-bed GPC column, and calculating the polymer concentration from the refractive index using a dn/dc of 0.045 ml/g for the PLA resin sample, and determining the absolute molecular weight from the right angle light scatter and the low angle light scatter in combination with the polymer concentration, (3) has an intrinsic viscosity of from 1.570 to 1.8 deciliters/gram, and (4) has an average of at least 10 branches/molecule.
2. The process of claim 1 wherein the blowing agent is a physical blowing agent.
3. The process of claim 2 , wherein the foam has a density of no greater than 5 pounds/cubic foot (80 kg/m 3 ).
4. The process of claim 3 , wherein the foam has a closed cell content of at least 90%.
5. The process of claim 3 wherein the PLA resin in the foam has an M w of at least 700,000, an intrinsic viscosity of 1.585 to 1.8 deciliters/gram, and an average of at least 10 branches/molecule.
6. The process of claim 3 wherein the PLA resin in the foam has an M w of 700,000 to 1,100,000, an intrinsic viscosity of 1.4 to 1.7 deciliters/gram, and an average of at least 10 branches/molecule.
7. The process of claim 6 wherein the PLA resin as an intrinsic viscosity of from 1.585 to 1.7 deciliter/gram.
8. The process of claim 3 wherein the PLA resin contains at least 3 weight percent of a high molecular weight fraction that consists of PLA molecules of 3 million or higher molecular weight.
9. The process of claim 3 wherein the blowing agent is carbon dioxide.
10. The process of claim 1 wherein the branching agent is an epoxy-functional acrylate polymer or copolymer characterized in being a solid at 23° C., containing an average of from about 3 to about 10 free epoxide groups/molecule, and being a polymerization product of at least one epoxy-functional acrylate or methacrylate monomer.