Plasticized poly(hydroxyalkanoic acid) composition
View Patent ↗Disclosed is a composition comprising poly(hydroxyalkanoic acid), plasticizer, and optionally a nucleator, an impact modifier, or both. Also disclosed is a process for producing a thermoformed two-dimensional article having a surface area to thickness ratio greater than about 200:1 inch.
1. A composition comprising or produced from poly(hydroxyalkanoic acid) (PHA), a nucleator, an ethylene copolymer, and optionally a plasticizer wherein
the plasticizer includes phthalate, trimellitate, adipate, sebacate, maleate, epoxidized fatty acid, sulfonamide, organophosphate, polyether, organic compound having more than two methylene linkage acid radicals, amide or oligomers of the PHA, alkanediol, alkanediol derivative, alkanetriol, alkanetriol derivative, polyoxyalkylene diol, or combinations of two or more thereof;
the ethylene copolymer comprises repeat units derived from ethylene, a glycidyl-containing olefin, and a butyl acrylate or carbon monoxide; and
the nucleator includes one or more carboxylic acids or, if the composition comprises the ethylene copolymer, an alkyl ester of the carboxylic acid, alkyl amide of the carboxylic acid, or combinations thereof; and the carboxylic acid includes aromatic carboxylic acid, aliphatic carboxylic acid, polycarboxylic acid, aliphatic hydroxycarboxylic acid, or combinations of two or more thereof.
2. The composition of claim 1 wherein
the plasticizer includes bis(2-ethylhexyl)phthalate, diisononyl phthalate, bis(n-butyl)phthalate, butyl benzyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, diethyl phthalate, diisobutyl phthalate, di-n-hexyl phthalate, trimethyl trimellitate, tri-(2-ethylhexyl)trimellitate, tri-(n-octyl,n-decyl)trimellitate, tri-(heptyl,nonyl)trimellitate, n-octyl trimellitate, bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, bis(capryl lactate)sebacate, dibutyl sebacate, acetyl glycol monolaurate, octyl lactate, 2-ethylhexyl lactate, di(2-ethylhexyl)adipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipate, dibutyldiglycol adipate, di(2-ethylhexyl)adipate, di(2-ethylhexyl)sebacate, methyl acetylricinoleate, butyl acetylricinoleate, acetyltributylcitric acid, diethyl bishydroxymethyl malonate, bis(2-ethyl lactate)adipate, bis(octyl lactate)sebacate, glycol, polyethylene glycol, polyethylene glycol ester, polypropylene glycol, polypropylene glycol ester, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monopropionate, diethylene glycol dipropionate, diethylene glycol monobutyrate, diethylene glycol dibutyrate, diethylene glycol monovalerate, diethylene glycol divalerate, triethylene glycol monoacetate, triethylene glycol diacetate, triethylene glycol monopropionate, triethylene glycol dipropionate, triethylene glycol monobutyrate, triethylene glycol dibutyrate, triethylene glycol monovalerate, triethylene glycol divalerate, glycerol tripropionate, poly(1,3-butanediol), diglycerol triacetate, glycerol monostearate, dibutyl maleate, diisobutyl maleate, benzoate, N-ethyl toluene sulfonamide, N-(2-hydroxypropyl)benzene sulfonamide, N-(n-butyl)benzene sulfonamide, tricresyl phosphate, tributyl phosphate, triethylene glycol dihexanoate, tetraethylene glycol diheptanoate, or combinations of two or more thereof;
the plasticizer is present in the composition from about 0.01 to about 10%; and
the nucleator is present in the composition from about 0.1 to about 4%; each based on the total weight of the composition.
3. The composition of claim 2 wherein
the composition comprises the nucleator;
the PHA comprises repeat units derived from hydroxyalkanoic acids having five or fewer carbon atoms;
the plasticizer includes bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, bis(capryl lactate) sebacate, dibutyl sebacate, acetyl glycol monolaurate, octyl lactate, 2-ethylhexyl lactate, di(2-ethylhexyl)adipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipate, dibutyldiglycol adipate, di(2-ethylhexyl)adipate, di(2-ethylhexyl)sebacate, methyl acetylricinoleate, butyl acetylricinoleate, acetyltributylcitric acid, diethyl bishydroxymethyl malonate, bis(2-ethyl lactate)adipate, bis(octyl lactate)sebacate, glycol, polyethylene glycol, polyethylene glycol ester, polypropylene glycol, polypropylene glycol ester, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monopropionate, diethylene glycol dipropionate, diethylene glycol monobutyrate, diethylene glycol dibutyrate, diethylene glycol monovalerate, diethylene glycol divalerate, triethylene glycol monoacetate, triethylene glycol diacetate, triethylene glycol monopropionate, triethylene glycol dipropionate, triethylene glycol monobutyrate, triethylene glycol dibutyrate, triethylene glycol monovalerate, triethylene glycol divalerate, glycerol tripropionate, poly(1,3-butanediol), diglycerol triacetate, glycerol monostearate, or combinations of two or more thereof; and
the plasticizer is present in the composition from 0.1 to about 5%; and the nucleator is present in the composition from about 0.5 to about 4%.
4. The composition of claim 3 wherein
the PHA comprises repeat units derived from glycolic acid, lactic acid, 3-hydroxypropionic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, or combinations of two or more thereof;
the plasticizer includes bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, bis(capryl lactate)sebacate, dibutyl sebacate, polyethylene glycol, polyethylene glycol ester, polypropylene glycol, polypropylene glycol ester, or combinations of two or more thereof; and
the plasticizer is present in the composition from about 0.5 to about 4; and the nucleator is present in the composition from about 1 to about 4%; each based on the total weight of the composition.
5. The composition of claim 4 wherein
the PHA comprises poly(glycolic acid), poly(lactic acid), poly(hydroxy-butyric acid), poly(hydroxy-butyrate-valerate) copolymer, copolymer of glycolic acid and lactic acid, hydroxyvaleric acid, 5-hydroxyvaleric acid, or combinations of two or more thereof;
the nucleator includes aliphatic, mono-functional carboxylic acid; the plasticizer includes bis(2-ethylhexyl)adipate, bis(capryl lactate)sebacate, polyethylene glycol, polyethylene glycol ester, or combinations thereof; and
the plasticizer is present in the composition from about 1 to about 3%; and the nucleator is present in the composition from about 0.5 to about 3%; each based on the total weight of the composition.
6. The composition of claim 5 wherein the PHA comprises the poly(lactic acid) and the nucleator includes aliphatic, mono-functional carboxylic acid; the plasticizer is present in the composition from about 0.5 to about 3%; and the nucleator is present in the composition from about 1 to about 2%; each based on the total weight of the composition.
7. The composition of claim 6 wherein the nucleator includes lauric acid, palmitic acid, stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, behenamide, ethylene bis-stearamide, or combinations of two or more thereof; the plasticizer is present in the composition from about 1 to about 2%; and the nucleator is present in the composition from about 1 to about 2%; each based on the total weight of the composition.
8. The composition of claim 7 wherein the ethylene copolymer is terpolymer of ethylene, butyl acrylate, and glycidyl methacrylate.
9. The composition of claim 7 wherein the nucleator is stearic acid or behenamide.
10. The composition of claim 8 wherein the nucleator is stearic acid or behenamide.
11. The composition of claim 1 further comprising the plasticizer.
12. The composition of claim 11 wherein the ethylene copolymer is terpolymer of ethylene, butyl acrylate, and glycidyl methacrylate.
13. The composition of claim 2 wherein the composition is a concentrated master batch comprising about 25 to about 50% of stearic acid, behenamide, or both and about 50 to about 75% of PHA.
14. An article comprising or produced from a composition wherein the composition is as recited in claim 1 .
15. The article of claim 14 wherein
the composition comprises the plasticizer;
the PHA comprises repeat units derived from hydroxyalkanoic acids having five or fewer carbon atoms;
said plasticizer includes bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, bis(capryl lactate)sebacate, dibutyl sebacate, acetyl glycol monolaurate, octyl lactate, 2-ethylhexyl lactate, di(2-ethylhexyl)adipate, diisobutyl adipate, dibutyl adipate, diisodecyl adipate, dibutyldiglycol adipate, di(2-ethylhexyl)adipate, di(2-ethylhexyl)sebacate, methyl acetylricinoleate, butyl acetylricinoleate, acetyltributylcitric acid, diethyl bishydroxymethyl malonate, bis(2-ethyl lactate)adipate, bis(octyl lactate)sebacate, glycol, polyethylene glycol, polyethylene glycol ester, polypropylene glycol, polypropylene glycol ester, diethylene glycol monoacetate, diethylene glycol diacetate, diethylene glycol monopropionate, diethylene glycol dipropionate, diethylene glycol monobutyrate, diethylene glycol dibutyrate, diethylene glycol monovalerate, diethylene glycol divalerate, triethylene glycol monoacetate, triethylene glycol diacetate, triethylene glycol monopropionate, triethylene glycol dipropionate, triethylene glycol monobutyrate, triethylene glycol dibutyrate, triethylene glycol monovalerate, triethylene glycol divalerate, glycerol tripropionate, poly(1,3-butanediol), diglycerol triacetate, glycerol monostearate, or combinations of two or more thereof; and
the plasticizer is present in the composition from 0.1 to about 5%; and the nucleator is present in the composition from about 0.5 to about 4%.
16. The article of claim 15 wherein
the PHA comprises poly(glycolic acid), poly(lactic acid), poly(hydroxy-butyric acid), poly(hydroxy-butyrate-valerate) copolymer, copolymer of glycolic acid and lactic acid, hydroxyvaleric acid, 5-hydroxyvaleric acid, or combinations of two or more thereof;
the nucleator includes aliphatic, mono-functional carboxylic acid; the plasticizer includes bis(2-ethylhexyl)adipate, bis(capryl lactate)sebacate, polyethylene glycol, polyethylene glycol ester, or combinations thereof; and
the plasticizer is present in the composition from about 1 to about 3%; and the nucleator is present in the composition from about 0.5 to about 3%; each based on the total weight of the composition.
17. The article of claim 16 wherein the ethylene copolymer is terpolymer of ethylene, butyl acrylate, and glycidyl methacrylate and the nucleator is stearic acid or behenamide.
18. A process comprises contacting a poly(hydroxyalkanoic acid) (PHA) composition or the PHA with a plasticizer and, 0.01 to about 4%, based on the weight of the composition or the PHA, of a nucleator to produce a compound; producing a film or sheet from the compound;
thermoforming the film or sheet in a heated mold at a temperature of from about 50° C. to about 140° C. to produce a thermoformed article; heat setting the article for 1 to about 20 seconds to produce a heat set-article; recovering the heat set-article wherein the plasticizer is as recited in claim 2 ; and the nucleator includes lauric acid, palmitic acid, stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid, behenamide, or combinations of two or more thereof.
19. The process of claim 18 wherein the PHA comprises poly(lactic acid); the nucleator includes stearic acid, behenic acid, behenamide, ethylene bis-stearamide, or combinations of two or more thereof; the contacting is carried out at a temperature from about 60° C. to about 130° C.; and the heat setting is carried out at about 90° C. to about 135° C. for about 1 to about 20 seconds.
20. The process of claim 19 wherein the plasticizer is bis(2-ethylhexyl)adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, bis(capryl lactate)sebacate, dibutyl sebacate, polyethylene glycol, polyethylene glycol ester, polypropylene glycol, polypropylene glycol ester, or combinations of two or more thereof; the nucleator is stearic acid or behenamide; the contacting is carried out at a temperature from about 65° C. to about 120° C.; the heat setting is carried out at about 90° C. to about 120° C. for about 1 to about 10 seconds; and the heat set-article is substantially clear.