WO1992004410A1 - Films containing polyhydroxy acids and a compatibilizer - Google Patents
Films containing polyhydroxy acids and a compatibilizer Download PDFInfo
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- WO1992004410A1 WO1992004410A1 PCT/US1991/006299 US9106299W WO9204410A1 WO 1992004410 A1 WO1992004410 A1 WO 1992004410A1 US 9106299 W US9106299 W US 9106299W WO 9204410 A1 WO9204410 A1 WO 9204410A1
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- WIPO (PCT)
- Prior art keywords
- film
- composition
- compatibilizer
- acid
- polymer
- Prior art date
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- 229920001273 Polyhydroxy acid Polymers 0.000 title claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 229920001577 copolymer Polymers 0.000 claims description 16
- 150000001261 hydroxy acids Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- -1 polyethylenes Polymers 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 7
- 239000004626 polylactic acid Substances 0.000 claims description 7
- 229920000954 Polyglycolide Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920000578 graft copolymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- YYXLGGIKSIZHSF-UHFFFAOYSA-N ethene;furan-2,5-dione Chemical compound C=C.O=C1OC(=O)C=C1 YYXLGGIKSIZHSF-UHFFFAOYSA-N 0.000 claims 1
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 43
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 208000037534 Progressive hemifacial atrophy Diseases 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012017 passive hemagglutination assay Methods 0.000 description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- OZZQHCBFUVFZGT-UHFFFAOYSA-N 2-(2-hydroxypropanoyloxy)propanoic acid Chemical compound CC(O)C(=O)OC(C)C(O)=O OZZQHCBFUVFZGT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920008712 Copo Polymers 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
Definitions
- compositions useful in making films and their preparation which compositions comprise polyhy ⁇ roxyacid (PHA) and a co patibilizer. It also relates to films comprising such compositions and other polymers- High molecular weight polymers of hydroxy acids and cyclic dimer products of esterification, of 2-hydroxy acids, particularly glycolic acid and lactic acid, are well known to be degradable. These materials can be useful in disposable packaging that will substantially and readily deteriorate to harmless by-products under conditions existing in the natural enviroment or employed in suitable waste treatment facilities. Highly useful films are made from many known polymers, such as polyolefins, polycarbonates, nylon and cellophane.
- polyolefin films pose a waste disposal problem because by themselves they are not degradable in the environment.
- Polyolefin films have been rendered degradable to the extent of degeneration to polyolefin flakes, by incorporating starches into the polymer. While these polyolefin/starch blends have a number of uses such as garbage bags, their utility is limited because they are not transparen .
- compositions comprising a polyhydroxy acid (PHA) and a compatibilizer.
- PHA polyhydroxy acid
- compatibilizer a compatibilizer
- Polyhydroxy acids as used herein means polymers containing at least one hy ⁇ droxy acid unit selected from among:
- the PHA is present in amounts from 5-90 weight percent.
- the compatibilizer is present in amounts from 5 to about 75 weight % of the PHA/compatibilizer composition.
- compatibilizers are compositions that when introduced into a blend of substantially immiscible polymers will bring about an intimate blending of the polymers that does not exhibit gross symptoms of polymer segregation.
- the compatibilizer brings about a compatible blend that is homogeneous on a macroscopic level; a blend that is heterogeneous on a macroscopic level is not compatible.
- a compatibilizer is specific for specific polymer blends because it must contain chemical components that are compatible with each of the other polymers.
- the compatibilizers must all contain a chemical or physical ability to be compatib-ilized with the PHA and also with the other part ⁇ ular polymer component.
- the selection of an e ffective compatibilizer will be made based on the know., chemical and physical characteristics of the other polymer component of the blend. If more than a single polymer is present in the other polymer component, more than one compatibilizer may be required to give a homogeneous blend. Examples of compatibilizers that, when mixed with PHAs will give compatible compositions, are listed in Table I.
- PHA Composition Compatibilizer Other Polymer polyglycolic acid ethylene/vinyl polyethylene homopolymer acetate copo ⁇ lymer
- the amount of compatibilizer needed will vary depending on the relative amounts of PHA and the overall PHA/compatibilizer/polymer blend proportions.
- the polymer other than those of formalae (i) to (v) in the preferred compositions is present in amounts up to about 90 weight % of the final 3 or more component product.
- the F ./compatibilizer compositions of this invention are p-...-.pared by dry mixing or melt blending the PHA with a compatibilizer that is compatbile with the PHA and the particular 3rd component other polymer.
- the films of this invention are prepared by melt processing the PHA/compatibilizer/polymer compositions under sufficient mechanical agitation to obtain a uniform composition that is a solution or intimately homogeneous small particle blend.
- the film product is ther ormed by conventional techniques, such as solution casting, extruding, or tubular blowing, to produce a film of uniform thickness normally from about 0.01 to 2 mm.
- non-hydroxy acid comonomers include those capable of condensation pol ⁇ aerization with ?- .-ctide or lactic acid; i.e., lactones such as epsilon-caprolactone, beta-propiolactone; alpha-dimethyl-beta-propiolactcne; glycolide; and dodecanola ⁇ tone and lactams.
- lactones such as epsilon-caprolactone, beta-propiolactone
- alpha-dimethyl-beta-propiolactcne glycolide
- dodecanola ⁇ tone and lactams dodecanola ⁇ tone and lactams.
- Polyhydroxy acid containing compositions of this invention have average molecular weights at le ⁇ st high enough to provide sufficient viscosity and strength to form sustainable film from the total polymer melt.
- weight average molecular weights from about 2,000 to about 600,000 can be used.
- a molecular weight of the PHA from about 20,000 to about 450,000 is used where the PHA comprises over half of the polymer content of the final film produc containing the other compatibilizer polymer; and 4,00-. ro 20,000 where the PHA comprises less than half of the polymer content of the final film product.
- degradation as used here with respect to the polyhydroxy acids means that the polyhydroxy acid portion of the degradable material is biodegradable and, more importantly, degradable by hydrolysis.
- the degradation rate is consistent with its intended usage, i.e., the product does not degrade significantly in normal storage and usage, but will degrade in a reasonable time, after discarding.
- hydrolytic degradation of a polymer can be tailored readily to meet the requirements of use and disposal of the film. It depends primarily on the nature of groups in the chains.
- Certain conditions such as moisture, pH, temperature, ion strength, sunlight, enzymes, polymer crystallinity and hydrophilicity of the polymer affect degradation of the polymer, as is well known.
- Rate of degradation of polyhydroxy polymers can be too great for many typical packaging applications (i.e., the packaging film will deteriorate excessively in less time than the expected shelf-life of the package, which includes the warehousing time of the packaging film between its production and application of the product) .
- the reduced tensile strength of the film caused by the deterioration results in film ruptures while being processed on shrink-wrap machinery and would be unacceptable for commercial packaging applications.
- the amount of shrinkage or the resistance of the films may be inappropriate for particular uses.
- Preferred non-polyhydroxy r lymers of this invention include polyolefins, polyet rs, polyesters, polyamides, polyvinyl chlorides, polycarbonates, polysulfones, copolyetheresters, polyurethanes, ethylene/vinyl alcohol copolymers, copolyamidoetheresters, ethylene/vinyl ester copolymers and terpolymers,ethylene/acrylic acid and terpolymers and their metal salts, ethylene-carbon monoxide copolymers, and copolyetherimidoesters.
- "Hazy" products outside the scope of this invention, have impaired transparency caused by insufficient compatibilization, extruding of low molecular weight plasticizer to the surfaces of the films, high crystalline content of the starting polymer, and the like.
- ambient temperature means the highest temperature at which the film product will be exposed during use or storage. Normally, this will range from room temperature (20"C) or below when under refrigeration, up to 40 ⁇ C or more when in warehouse storage.
- Preferred polyhydroxy acids of this invention are those wherein 50-99 mol% is the PHA component composed of hydroxy acid units (i) wherein R' is hydrogen and R" is the methyl radical, and having 80-97 mol% of asymmetric carbon atoms R- configuration and 3-20 mol% S- configuration or 80-97 mol% S- configuration and 3-20 mol% R- configuration; and wherein 1-45 mol% is tfc-> minor component composed of either h ydroxy acid unit (i) of such asymmetric carbon content that the total R- or S- configuration in major and minor components do not exceed 97 mol% of asymmetric carbon atoms, or any hydroxy acid units (ii) to (iv) or suitable non-hydroxy acid comonomers.
- a preferred polyhydroxy acid may, for example, contain a major component of 67 mol% hydroxy acid unit (i) in which 90 mol% of asymmetric carbon atoms are S- configuration.
- the minor polyhydroxy acid component will be 35 mol%, and might be completely composed of hydroxy acid unit (ii) or a suitable non-hydroxy acid comonomer.
- the minor component of the PHA might be additional hydroxy acid unit (i) but the fraction of asymmetric carbon atoms which are S- configuration component can be no greater than that which when added to the S- atoms of the PHA component does not raise the S- atom content of the total above 97 mol%.
- the range of R- and S- asymmetric carbon atoms in the polyhydroxy acid is 85-96 mol%.
- R- and S- refer to the standard nomenclature for identifying stereoisomer configurations on the asymmetrical carbon.
- the percentages of R- and S- carbons indicated herein refer only to fractions of asymmetrical carbon atoms in the PHA polymer chains and not to total carbon atoms in the polymer chains.
- Asymmetrical carbon atoms are those having less than four different substituent radical groups attached to them.
- the preferred compositions have narrow ranges of selected asymmetrical carbon atoms because polymers containing more equal fractions of R- and S- carbon atoms demonstrate accelerated degradation by hydrolysis, produce films adjacent layers of which often adhere to each other and which are prone to degradation during processing to form film.
- films made outside these ranges may be hazy and/or brittle.
- polymer films having fractions above the S- carbon atom range are substantially crystalline after hot processing, such as in film production. Crystallinity is detrimental to film-forming capability, and to optical clarity of films formed from crystalline polymers.
- a method for reducing the negative effects of highly crystalline polymer on film properties is to plasticize the polymer by incorporating and dispersing monomeric, low molecular weight oligomeric ' species within the polymer matrix.
- Plasticizers for polyhydroxy acids of this invention are monomeric hydroxy acids, lactides of monomeric hydroxy acids, lactyl lactate non-cyclic dimers of monomeric hydroxy acids and other oligomers of monomoric hydroxy acids up to molecular weight of about 450.
- amounts of plasticizers produces films of uneven thickness. Where films are made by casting onto drums, excessive plasticizer may separate from the film, stick to and foul the drum, or may cause the film to stick to the drum. Thus, it has been found necessary to use polymer containing a minimal 3mount of plasticizer.
- the amount of plasticizers need ; to obtain useful films of this invention is from about 0.10 to about 8 wt%, and preferably from about 0.2 to 6 wt%.
- a highly preferable composition range is from about 0.2 to 0.4 wt% plasticizer. These plasticizer levels are based upon the concentrations of the polyhydroxy acid and plasticizer in the feedstock to the film production process and not necessarily to the concentrations of the plasticizer in the film produced from compositions of this invention. Plasticizer content may be determined by lactide content analysis methods taught in Journal of Applied Polymer Science, Kohn, Van den Berg, Van de Ridder and Feyen, volume 29, pages 4265-4277 (1984) . When necessary to reduce the concentration of plasticizers in a plasticizer-rich composition, a devolatilizing extruder can be used either as a separate step or during film extrusion.
- the compatibilizers used in these Examples are: TRX-101 HFTM (Du Pont Co.), aleic anhydride grafted on ethylene-propylene copolymer; ElvaxTM 360 (Du Pont Co.), a copolymer of ethylene and vinyl acetate; FusabondTM D-100 and FusabondTM D-111 (Du Pont Co.), maleic anhydride grafted on PE; and NucrelTM 0407 (Du Pont Co.) and NucrelTM 0903(Du Pont Co.) copolymer of ethylene and acrylic acid.
- SurylnTM Ionomer #1650 and #1601 (Du Pont Co.) are NucrelTM salts.
- EMATM 2205 and 2207 are ethylene and methylacrylic acid copolymers. These compatibilizers all have both hydrophyllic and hydrophobic end groups. Examples 1-5
- a 50% polylactic acid/50% polyglycolic acid (PLA/PGA) copolymer is prepared by heating a mixture of 1667g of crystalline glycolic acid, 1894g of R-lactic acid, and 3.3g of stannous octoate. The reaction is heated from room temperature to 136 ⁇ C under atmospheric pressure. The pressure is then reduced to 100mm. while heating over 3 hrs. to 190 ⁇ C. -li ⁇ lt is then heated for an additional 5 hours at 190°C under 2mm v ⁇ ⁇ u . There is produced a 50/50 copolymer with an average molecular weight of 6000 with a softening point of about 120"C.
- Blends as shown in Table I, are then prepared using low-density polyethylene (LDPE) , Exxon #3060, with a melt index of 2.0; and the compatibilizers listed in Table I.
- LDPE low-density polyethylene
- Exxon #3060 Exxon #3060
- melt index of 2.0 melt index of 2.0
- compatibilizers listed in Table I The above described 50/50 copolymer, the LDPE, and the compatibilizer are mixed together in a Banbury mixer above the melting points of the three ingredients and then is crushed to 1/4" average diameter particles. The particles are then dried in an oven.
- blown films are prepared as follows: The particles are then fed to a screw feeder having a 1" dia eter die. It is maintained at 175-225*C in tht- heating and melt zones. The screw is run at 32 rpm. Films are tnen extruded ar. - conventionally blown to 2-4 mil. (.05-.lmm) thickness.
- Examples 1, 4 and 5 are first tested and then are heated in distilled water for 28 days at 70°C. Table II shows the results of these tensile tests in PSI before and after the water treatment. MD is the extrusion direction; TD is the transverse or circumferential direction.
- Examples 4 and 5 this invention show high strengths as blown compared to Example 1 (100% PE) , and also shows lower strengths (degradation) after water treatment. Similar films are prepared by casting the film directly without blowing. These films have similar properties of strength, clarity and degradability.
- Example 7 Several films are blown on commercial equipment .04-.05mm thickness from a blend containing 10% of 50/50% PLA/PGA copolymer, 10% of ElvaxTM 360, and 80% of LDPE (Exxon 3060) . These films of the present invention are clear and flexible and have elongations at break and tensile strengths ' comparable to a 100% LDPE control. Accelerated tests are run on these films simulating exposure to municipal sewage in a treatment plant bio-digester. After 5 days exposure a biological oxygen demand is (BOD) of 300ppm is obtained. After 20 days the BOD is increased further to 1400ppm. The films are completely broken down by the biological degradation of + ⁇ e PLA/PGA component of the films.
- BOD biological oxygen demand
- Comparative film of 100% LDPE has inferior strength and elongation properties and does not degrade in the simulated sewage test.
- Example 1 PLA of inherent viscosity of 1.1 is blended in a Banbury mixer in a 1:2 ratio with FusabondTM D-111. The resulting blend is crushed to 1/4" average diameter particles and blown films are made as in Example 1. The resulting films are significantly degradable.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US58052790A | 1990-09-11 | 1990-09-11 | |
US580,527 | 1990-09-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992004410A1 true WO1992004410A1 (en) | 1992-03-19 |
Family
ID=24321463
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1991/006299 WO1992004410A1 (en) | 1990-09-11 | 1991-09-09 | Films containing polyhydroxy acids and a compatibilizer |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0548209A4 (en) |
JP (1) | JPH06500819A (en) |
CN (1) | CN1059919A (en) |
AU (1) | AU8611391A (en) |
IE (1) | IE913195A1 (en) |
MX (1) | MX9101008A (en) |
PT (1) | PT98914A (en) |
WO (1) | WO1992004410A1 (en) |
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- 1991-09-09 WO PCT/US1991/006299 patent/WO1992004410A1/en not_active Application Discontinuation
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Also Published As
Publication number | Publication date |
---|---|
CN1059919A (en) | 1992-04-01 |
EP0548209A1 (en) | 1993-06-30 |
IE913195A1 (en) | 1992-03-11 |
JPH06500819A (en) | 1994-01-27 |
AU8611391A (en) | 1992-03-30 |
PT98914A (en) | 1992-07-31 |
EP0548209A4 (en) | 1993-09-01 |
MX9101008A (en) | 1992-05-04 |
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