WO1991006601A1 - Matieres polymeres biodegradables et articles fabriques a partir de celles-ci - Google Patents

Matieres polymeres biodegradables et articles fabriques a partir de celles-ci Download PDF

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Publication number
WO1991006601A1
WO1991006601A1 PCT/US1990/006363 US9006363W WO9106601A1 WO 1991006601 A1 WO1991006601 A1 WO 1991006601A1 US 9006363 W US9006363 W US 9006363W WO 9106601 A1 WO9106601 A1 WO 9106601A1
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WIPO (PCT)
Prior art keywords
poly
materials
biodegradable
safening
composition according
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PCT/US1990/006363
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English (en)
Inventor
Ronald P. Rohrbach
Paul Allenza
Julie Schollmeyer
Harold D. Oltmann
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Allied-Signal Inc.
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Publication of WO1991006601A1 publication Critical patent/WO1991006601A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033—Additives activating the degradation of the macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • This invention relates to biodegradable polymeric compositions and to articles fabricated therefrom. More par icularly, this invention relates to such compositions which exhibit improved biodegradability when exposed to environmental effects such as sunlight, heat, water, oxygen, pollutants, microorganisms, insects, animals and mechanical forces such as wind and rain.
  • a biodegradable composition which comprises a synthetic resin, a biodegradable granular filler such as natural starch, and a substance which is autooxidizable to yield a peroxide which attacks the carbon to carbon linkages of the resin.
  • PCT Appln. WO 88/09354 describes a degradable polymer composition which is a blend of a normally stable chemically saturated polymer such as polyethylene, a less stable chemically unsaturated polymer or copolymer such as a styrene/butadiene block copolymer, or natural rubber, an anti-oxidant active over a limited period and a latent pro-oxidant such as an organic salt of a transition metal, e.g. cobalt naphthenate, which may optionally include filler particles of a directly biologically sensitive material such as a natural starch, a derivative of natural starch, a natural protein, a natural cellulose or a sugar.
  • a directly biologically sensitive material such as a natural star
  • the present invention is directed to biodegradable polymer composition which obviates one or more of the defects of conventional biodegradable resins.
  • the composition of this invention comprises and intimate mixture of:
  • Another aspect of this invention relates to an article of manufacture fabricated totally or in part from the biodegradable composition of this invention.
  • the invention Several beneficial effects are provided by the invention. For example, low concen rations of the particulate filler are required in order to provide an acceptable level of disintegration of the composition within a reasonable period of time.
  • the degradation enhancing material is released when the composition is exposed to environmental (biodegradation) conditions, and is not time dependent. Thus, there is no danger or substantially reduced danger of premature degradation and associated shelf life problems.
  • a wide variety of degradation enhancing materials and safening materials having a wide /ariety of properties can be used, which facilitates the use of the invention with a wide variety of polymers and environmental conditions. Some useful degradation enhancing materials not only cause failure of the polymer due to their own activity, but also promote further biodegradation of the safening material and/or other biodegradable additives that may be in the composition, causing a cascading effect.
  • Figure 1 is a graph indicating the degree to which high density polyethylene is protected by beta- cyclodextrin.
  • Figure 2 is a graph indicating the conductance of the formation and degradation of a beta-cyclodextrin sodium dodecyl sulfate complex.
  • Figure 3 is a graph indicating the conductance of the formation of a beta-cyclodextrin cetyl pyrdinium chloride complex and of a starch/cetyl pyridinium chloride complex.
  • Figure 4 is a graph indicating the conductance of the formation and degradation of a corn starch/sodium dodecyl sulfate complex.
  • the composition of this invention comprises two essential ingredient.
  • One essential ingredient is a polymeric resin.
  • the type of polymeric resin used may vary widely.
  • Illustrative of useful resins are aromatic, aliphatic and cycloalipha ic polyamides such as poly(m-xylylene adipa ide) , poly(p-xylylene sebacamide), poly 2,2,2-trimethyl-hexamethylene terephthalamide), poly (piperazine sebacamide), poly (metaphenylene isophthalamide) (Nomex), poly (p-phenylene terephthalamide) (Kevlar); the copolyamide of 30% hexamethylene diammonium isophthalate and 70% hexamethylene diammonium adipate, the copolyamide of up to 30% bis-(-amidocyclo-hexyl)methylene, terephthalic acid and caprolactam, polyhexamethylene adipamide (nylon 66), poly(butyrolactam
  • 4-cyclohexane dimethylene terephthalate) (trans), poly(decamethylene terephthalate), poly(ethylene terephthalate), poly(ethylene isophthalate) , poly(ethylene oxybenozoate) , poly(para-hydroxy benzoate), poly(dimethylpropiolactone) , poly(decamethylene adipate), poly(ethylene succinate), poly(ethylene azelate), poly(decamethylene sebacate) , poly( 6, -dimethyl- propiolactone) , and the like.
  • R. R 2 -C CH.
  • R and R are the same or different and are hydrogen,hydroxy, halogen, alkylcarbonyl, carboxy, alkoxycarbonyl, heterocycle or alkyl or aryl either unsubs ituted or substituted with one or more substituents selected from the group consisting of alkoxy, cyano, hydroxy, alkyl and aryl.
  • polymers of L.B-unsaturated monomers are polymers including polystyrene, polyethylene, plypropylene, poly( 1-octadence) , polyisobutylene, poly(1-pentene) , poly(2-methylstyrene) , poly(4-methylstyrene) , poly(1-hexene) , poly( 1-pentene) , poly(4-methoxystrene), poly(5-methyl-l-hexene) , poly(4-methylpentene) , poly (1-butene), polyvinyl chloride, polybutylene, polyacrylonitrile, ⁇ oly(methyl pentene-1), poly(vinyl alcohol), poly(vinylacetate) , poly(vinyl butyral), poly(vinyl chloride), poly(vinylidene chloride), vinyl chloride-vinyl acetate chloride copolymer, poly(vinylidene
  • Preferred resins for use in the composition of this invention are resins which are commonly used in the fabrication of packaging materials such as polyethylene, polyethylene terephthalate, polystyrene, polyurethane, polyvinyl chloride, polypropylene, polycarbonate and blends of such materials.
  • packaging materials such as polyethylene, polyethylene terephthalate, polystyrene, polyurethane, polyvinyl chloride, polypropylene, polycarbonate and blends of such materials.
  • the resins of choice are polyethylene (high density, low density and linear low density), polyethylene terephthalate, polyvinyl chloride, polyurethane and blends of such polymers.
  • the second essential ingredient of the composition of this invention is an effective amount of a particulate filler.
  • the filler is a material which is designed to be inactive during the use of the composition and which enhances the degradation of the polymer on exposure of the composition of this invention to a suitable environment,as for example a garbage dump or landfill.
  • the filler is comprised of a degradation enhancing material which is effective to enhance the degradation of the polymeric material and a biodegradable safening agent which inhibits the act. ? ity of the enhancing material.
  • the safening material associates with the degradation enhancing agent, thereby completely or partially inhibiting its activity during the association.
  • the activity of the enhancing material is competely or partially restored, which results in an enhancement of degradation of the polymer.
  • association is any chemical, physical or like interaction between the biodegradable safening material and the degradation enhancing material which completely or partially inhibits the biodegradation enhancing characteristics of the degradation enhancing material, and which allows a complete or partial restoration of such characteristics on the biodegradation of the biodegradable safening material.
  • the nature of the association between the biodegradable safening material and the degradation enhancing material may vary widely and essentially depends on the properties of these two materials. The only requirement is that this association inhibits the activity of the enhancing material during the association, and that this activity is totally or partially restored on biodegradation of the safening material.
  • Certain representative associations include ionic and covalent bonding as for example in the case of the ionic bonding of a metal with cellulose as in sodium cellulose, the ionic bonding of metal salts and ionic species such as metal salts of fatty acids as for example sodium stearate and various covalent fatty acid derivatives such as fatty acid derivatives of proteins or carbohydrates.
  • Other forms of association include non covalent associations such as intercalation, inclusion complexation, chelation and non-specific adsorption as for example the inclusion of a hydrophobic surfactant or stress cracking agent within the cavity of a cyclodextrin molecule.
  • Still other forms of association includes incapsulation where the enhancing material is physically encapsulated and surrounded by the safening material.
  • Suitable safening agents may vary widely. Any material which is degradable and which is capable of inhibiting the biodegradation enhancing activity of the enhancing material can be used. As used herein, a material is "degradable” where it degrades as a result of exposure to the environmental effects of sunlight, heat, water, oxygen, pollutants, microorganisms, insects and/or animals. Usually such materials are naturally occurring and are usually “biodegradable”. As used herein,
  • biodegradable materials are those which are degraded by microorganisms or by enzymes and the like produced by such microorganisms.
  • suitable safening materials are starches and starch derivatives such as rice and maize starch, dextrin, cyclodextrin, a ylose, amylopec in, defatted or solvent extracted starch, and the like.
  • sugars and derivatives thereof such as sucrose, dextrose, maltose, mannose, galactose, lactose, fructose, glucose, glyamic acid, gluconic acid, maltobionic acid, lactobionic acid, lactosazone, glucosazone, and the like.
  • Still other useful safening materials are cellulose and derivatives thereof such as esters of cellulose as for example, triacetate cellulose, acetate cellulose, acetate- butyrate cellulose, nitrate cellulose and sulfate cellulose, ethers of cellulose as for example, ethyl ether cellulose, hydroxymethyl ether cellulose, hydroxypropyl ether cellulose, carboxymethyl ether cellulose, ethylhydroxy ether cellulose, and cyanoethylether ether cellulose, ether-esters of cellulose as for example, acetoxyethyl ether cellulose, propionoxypropyl cellulose, and benzoyloxypropyl cellulose and urethane cellulose as for example, phenyl urethane cellulose.
  • esters of cellulose as for example, triacetate cellulose, acetate cellulose, acetate- butyrate cellulose, nitrate cellulose and sulfate cellulose
  • useful safening agents include proteins such as zein, soy protein or protein hydrolysates, casein, collagen, elastin, albumins and the like and lignins.
  • Useful biodegradable safening materials also include fats and fatty acids such as mono-, di- and tri-glycerides derived from animal or plant material and the common derivatives of these fats such as fats obtained from peanut oil, corn oil, coconut oil, cottonseed oil, palm oil and tallow, and fatty acids such as oleic acid, stearic acid, lauric acid, myristic acid and palmitic acid; biodegradable anti-oxidants such as tocophenols, rosemary (rosemari-quinone) and mustard seed extracts, ascorbic acid and compounds closely related to vitamin C such as ascorbic acid-2-phosphates and ascorbic acid-6-fatty acid esters propionic acid; and biodegradable polymers such as poly(glycolide) , poly(tetramethylene carbonate), poly(
  • Preferred biodegradable safening materials are starch and starch derivatives such as cyclodextrins, fats, fatty acids and biodegradable polymers such as poly(carbonates) , and homopolymers and copolymers derived from the polymerization of hydroxy alkanoic acids and their derivatives such as poly(B -hydroxy butyrate), poly(lactide) , polyglycolic acid and copolymers thereof, and particularly preferred biodegradable safening materials are starches and starch derivatives and biodegradable polymers derived from the polymerization of hydroxyalkanoic acids and their derivatives.
  • biodegradable safening agents are cyclodextrins, poly(beta-hydroxybutyrate) , poly(lactides) , poly(glycolide) and block copolymers containing g -hydroxybutyrate glycolide and/or lactide recurring monomeric units.
  • Useful degradation enhancing materials include any material which in an unassociated form is capable of directly or indirectly enhancing the degradation of a polymeric material to some extent and which is capable of association with a biodegradable safening material which inhibits the activity of the enhancing material, such activity being restored on biodegradation of the biodegradable safening material.
  • Useful enhancing materials may vary widely.
  • Illustrative of useful materials are stress cracking agents as for example, surfactants.
  • Useful surfactants include, anionic, cationic, zwitterionic and nonionic surfactants.
  • Useful anionic surfactants include alkali metal, ammonium and amine soaps and alkali metal salts of alkyl-aryl sulfonic acids, sodium dialkyl sulfosuccinate, sulfated or sulfonated oils such as glycocholic acid sodium salt, glycodeoxycholic acid sodium salt, sodium dioxychalate, cholic acid sodium salt, 1-deconesulfonic acid sodium salt, caprylic acid sodium salt, sodium dodecyl sulfate, taurocholic acid sodium salt, taurodeoxycholic acid sodium salt, sodium decyl sulfate, sodium octyl sulfate, sodium hexyl carboxylate, sodium heptyl carboxylate, sodium octyl carboxylate, sodium nonyl carboxylate, sodium decyl carboxylate and sodium dodecyl carboxylate, disodium dodcyl phosphate, disodium 4-alkyl
  • Useful cationic surfactants include salts of long chain primary, secondary and tertiary amines such as oleylamine acetate, cetylamine acetate, didodecylamine lactate, the acetate of aminoethyl-amino ethyl stearamide, dilauroyl triethylene tetramine diacetate, and l-aminoethyl-2-heptadecenyl imidazoline acetate; quaternary salts such as cetylpyridinium bromide, hexodecyl ethyl morpholinium chloride, didodecyl ammonium chloride, cetylpyridinium chloride, dodecyltrimethyl- ammonium bromide, hexadecyl trimethylammonium bromide, te radecyl tri ethylammonium bromide, dodecyl ammonium chloride, cetyl tri
  • Useful zwitterionic surfactants include N-alkyl-N,N- dimethyl-3-ammonio-l-propane sulfonates such as N-decyl-
  • N,N-dimethyl-3-ammonio-l-propane N-dodecyl-N,N-dimethyl-3- ammonio-l-propane, N-hexadecyl-N,N-dimethyl-3-ammonio-l- propane, N-octyl-N,N-dimethyl-3-ammonio-l-propane, and
  • Useful nonionic surfactants include n-alkyl-D- glucopyranosides and n-alkyl-D-maltosides such as decyl-D-glucopyranoside, dodecyl-D-glucopyranoside, heptyl-D-glucopyranoside, octyl-D-glucopyranoside, nonyl-D-glucopyranoside, decyl-D-maltoside, dodecyl-D- maltoside, heptyl-D-maltoside, octyl-D-maltoside, and nonyl-D-maltoside, condensation products of higher fatty alcohols with alkylene oxides, such as the reaction product of oleyl alcohol with 10 ethylene oxide units; condenstation products of alkylphenols with alkylene oxides, such as the reaction products of isooctylphenol, octylphenol and nonylphenol with from abut 12 to about 30
  • a combination of two or more of these surfactants may be used.
  • a cationic surfactant may be blended with a nonionic surfactant, or an anionic surfactant with a nonionic surfactant.
  • Other useful degradation enhancing material include olefins especially mono, di and tri unsaturated fatty acids, triglycerides and derivatives such as lipoproteins and lipopolysacharides; agents capable of a change in physical properties upon exposure to environmental conditions such as moisture, for example, bentonite clay; oxidizing agents such as halogens and heterosubs ituted anions, especially tri iodide (I ); strong acids, strong bases and certain salts such as trifluoroacitic acid, dichloroacetic acid, hydrochloric acid, lithium bromide, zinc cloride, sodium cyanide, phosphoric acid, nitric acid, sulfuric acid, sodium hydroxide, lithium hydroxide, and sodium alkoxide; and transition metal salts (cobalt, copper, nickel, zinc, manganese, cadmium, iron) alone or in combination with organic compounds such as fatty acids (e.g. stearate or naphthenate, and the like) as salt complexes.
  • Still other useful degradation enhancing materials include solvents and other materials which enhance the degradation of specific polymers as for example n-hexane/n heptane (1:1), isobutyl acetate, 5-methyl-2-hexanone, 2-pentanone, 3-pentanone, toluene, cyclohexane, and tetrahydrofuran which are detrimental to ⁇ oly(butadienes) ; xylene, p-xylene, tetralin, decalin, tetrachloroethylene, n-butyl acetate, diphenyl ether, butyl sterate, squalene, glycol dipalmitate, tripalmitin which are detrimental to polyethylene, poly(propylene) and poly(tetrafluoro- ethylene); N,N-dimethylformamide, N,N-dimethylacetamide,
  • Y-butyrolactone nitric acid, hydroxyacetonitrile, dimethylformamide, ethylene carbonate, propylene carbonate, malonitrile, succinonitrile, sulfuric acid, which are detrimental to polyacrylonitrile; cyclohexanone, cyclopentanone, and tetrahydrofuran which are detrimental to poly(vinyl chloride); acetonitrile, heptanone-4, isoamyl acetate, n-butyl chloride, heptanone-3, n-propanol, acetone, benzene, n-butyl acetate, n-butyl chloride, and chloroform which are detrimental to poly(methylmethacrylate) ; benzene, toluene, butanone, and cyclohexanone which are detrimental to poly(styrene) ; phenol, o-chlorophenol, aniline, cyclopentanone, ethylene carbonate
  • Preferred degradation enhancing materials are stress cracking agents which are materials which cause the polymer composition to crack, and particularly preferred degradation enhancing materials are surfactants. More preferred surfactants are capable of not only degrading the plastic but also exhibit a beneficial effect by enhancing the biodegradation of any biodegradable component incorporated into the plastic. Most preferred for use in the practice of this invention as degradation enhancing materials are nonionic surfactants, or mixtures of nonionic surfactants and other types of surfactants.
  • nonionic surfactants such surfactants are capable of not only degrading the polymers but also exhibit a beneficial effect by enhancing the biodegradation of any biodegradable component in the polymer.
  • Preferred nonionic surfactants for use in the practice of this invention are alkylarylpolyethers, such as the condensation products of alkylphenols, such as octylphenol, nonylphenol and isooctyphenol, and alkylene oxides, such as ethylene oxide; fatty acid alkanol amides; poly-alkoxylated alcohols, such as polyethoxylated tridecanol, idotridecyl alcohol adduct with ethylene oxide; and fatty alcohol polyethers.
  • the particularly biodegradation safening materials and degradation enhancing material selected in any particular situation will depend on a number of factors including the capability of the biodegradation safening material for inhibiting the activity of the degradation enhancing material, the level and nature of the activity of the degradation enhancing material, the polymeric material stability of the complex, especially as it pertains to processing conditions for the polymeric mateial and the effect that the degradation enhancing material has upon the biodegradation of incorporated components of the polymer, the proposed use of the composition and article fabricated therefrom, the cost of the composition and article fabricated therefrom, the usable lifetime of the composition and article fabricated therefrom, the time after exposure to biodegradation
  • the biodegradation safening material is preferably a carbohydrate such as starch or a starch derivative including a ylose, linear polysaccharides and cyclic polysaccarides such as cyclodextrins which function to form an inclusion complex and encapsulate the surfactant and protect the polymeric material from the deteriorating effects of the surfactant. Biodegradation of the carbohydrate releases the surfactnat which can enhance the degradation of the polymeric material.
  • the biodegradable safening material is preferably a polysaccharide such as a starch which is capable of complexing the salt which functions to prevent or retard the formation of the halogen, I_ which adversely affects the polymeric material.
  • a polysaccharide such as a starch which is capable of complexing the salt which functions to prevent or retard the formation of the halogen, I_ which adversely affects the polymeric material.
  • the I is released to enhance the degradation of the polymeric material.
  • the composition of the invention includes an "effective amount" of the particulate filler.
  • an "effective amount” is an amount which when activated is sufficient to enhance the biodegradation of the polymeric material to any extent. This amount may vary widely and depends on a number of factors such as the amount and activity of the degradation enhancing material in the filler and the like.
  • the amount of filler employed is at least about 0.001 weight percent based on the total weight of the composition.
  • the amount of the filler is from about 0.05 to about 40 weight percent based on the total weight of the composition, and in the particularly preferred embodiments of the invention is from about 0.01 to about 20 weight percent on the aforementioned basis. Amongst these particularly preferred embodiments, most preferred are those embodiments in which the amount of the filler is from about 1 to about 10 weight percent based on the total weight of the composition.
  • the filler is in particulate form to allow dispersion of the filler in the polymeric material.
  • the particle size is equal to or less than about 1000 ⁇ m.
  • the lower limit in particle size is not critical, and in the preferred embodiments of the invention, the size of the particles is as small as possible which facilitates the dispersion of the filler in the polymeric material.
  • the particle size is from about 0.1 to about 500 um, and in the most preferred embodiments of the invention, particle size is from about 1 to about 300 ⁇ m. Amongst the most preferred embodiments of the invention, those in which the particle size is from about 2 to about 200 ym are the embodiments of choice.
  • composition of this invention can include various optional components which are additives commonly employed with polymers.
  • Optional components include fillers, nucleating agents, plasticizers, impact modifiers, chain extenders, pigments, colorants, mold release agents, antioxidants, ultra violet light stabilizers, lubricants, antistatic agents, fire retardants, and the like. These optional components are well known to those of skill in the art, and accordingly, will not be described herein in detail.
  • the composition may further comprise .additional particulate biodegradable fillers which further enhance the rate of biodegradation of the composition.
  • additional particulate biodegradable fillers are those materials described as useful for biodegradable safening materials.
  • Preferred fillers are starches.
  • the amount of biodegradable filler may vary widely and amounts normally used in the art may be used. However, in the preferred embodimets of the invention, the amount of such biodegradable filler is not more than about 30 weight percent based on the total weight of the composition and more preferably not more than about 20 weight percent and most preferably not more than about 10 weight percent.
  • composition of this invention can be prepared by blending or mixing the essential ingredients, and other optional components, as uniformly as possible employing any conventional blending means.
  • Appropriate blending means such as melt extrusion, batch melting and the like, are well known in the art and will not be described herein in greater detail.
  • the blending procedure can be carried out at elevated temperatures above the melting point of the polymer and the nucleating agent either preformed, or as individual components of the agent separately or as a combination of the components in a suitable form as for example, granules, pellets and preferably powders is added to the melt with vigorous stirring. Alternatively, all or a portion of the var .
  • us components of the filler can be masterbatched or preblended with the polymer in the melt and this premixed or masterbatch added to the polymer in the melt in amounts sufficient to provide the desired amount of the filler in the polymer product. Stirring is continued until a homogeneous composition is formed. Blending temperatures and blending pressures, and the order of addition of the various components are not critical and may be varied as desired provided that a substantially homogeneous composition results. The blending procedure can be carried out at elevated temperatures, in which case the polymer component is melted and the filler and other optional ingredients are admixed therewith by vigorously stirring the melt. Similarly, the various solid components can be granulated, and the granulated components mixed dry in a suitable blender, or for example, a Banbury mixer, as uniformly as possible, then melted in an extruder and extruded with cooling.
  • compositions according to the invention are thermoplastic biodegradable materials from which molded articles of manufacture can be produced by te conventional shaping processes, such as melt spinning, casting, injection molding and extruding.
  • the compositions of this invention are especially useful for fabrication of extruded films, as for example, films for use in food packaging. Such films can be fabricated using conventional fil extrusion techniques.
  • Such films formed from the composition of this inven ion are biodegradable such as being buried or composted with other garbage, the film degraded by evironmental effects such as sunlight, heat, water, oxygen, pollutants, microorganisms, and the like.
  • a known weight of complex was subjected to extensive acid hydrolysis so as to fully degrade the cyclodextrin to its component glucose units, which could then be measured using a glucose analyzer (Beck an Instruments) .
  • the amount of cyclodextrin in the complex can thus be determined (7 glucose molecules per 1 ⁇ -cyclodextrin molecule) with the remainder of the weight of the complex due to the Igepal.
  • 150 mg of the complex was hydrolyzed by refluxing for 1.5 hours at 100°C in 100 ml of 1 M HC1. The glucose produced was measured and accounted for 115.3 mg of the sample wtih 38 mg representing the contribution of the Igepal.
  • the ratio of cyclodextrin to Igepal in the complex was determined to be approximately 1.6 to 1.
  • Starch Complexes with Sodium Dodecyl Sulfate Using the procedure of Example I, the complexation and degradation of corn starch (Pearl Starch) was demonstrated with sodium dodecyl sulfate. As shown by monitoring conductivity changes ( Figure 4) starch can complex a stress-cracking surfactant (SDS), and release it upon enzymatic degradation. Since starch has been widely used as an additive to plastics, it follows that the starch/surfactant complex could be added then the surfactant released upon exposure to conditions which promote biodegradation.
  • SDS stress-cracking surfactant

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Abstract

Composition comprenant un ou plusieurs polymères aisni qu'une matière de remplissage composée d'une ou de plusieurs matières facilitant la dégradation, lesquelles facilitent la biodégradation des polymères en association avec une ou plusieurs matières neutralisantes biodégradables inhibant l'activité favorable des matières facilitant la dégradation, de sorte que lors de la dégradation des matières neutralisantes, l'activité est complètement ou partiellement rétablie.
PCT/US1990/006363 1989-11-02 1990-11-01 Matieres polymeres biodegradables et articles fabriques a partir de celles-ci WO1991006601A1 (fr)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5142023A (en) * 1992-01-24 1992-08-25 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
EP0540641A1 (fr) * 1990-07-25 1993-05-12 Ici America Inc Melange polymere biodegradable contenant un copolymere de 3-hydroxybutyrate/3-hydroxyvalerate.
US5247058A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247059A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
US5258488A (en) * 1992-01-24 1993-11-02 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
EP0596123A1 (fr) * 1991-10-31 1994-05-11 Kabushiki Kaisha Kobe Seiko Sho Plastique biodegradable
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
EP0708148A1 (fr) 1994-10-21 1996-04-24 Ems-Inventa Ag Compositions à mouler à base de polyesters aliphatiques dégradables aptes à produire des feuilles soufflées
DE19513237A1 (de) * 1995-04-07 1996-12-05 Biotec Biolog Naturverpack Biologisch abbaubare Polymermischung
US5665474A (en) * 1992-10-02 1997-09-09 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
US5807973A (en) * 1992-10-02 1998-09-15 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US6005067A (en) * 1992-01-24 1999-12-21 Cargill Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6326458B1 (en) 1992-01-24 2001-12-04 Cargill, Inc. Continuous process for the manufacture of lactide and lactide polymers
US8796362B2 (en) 2008-12-16 2014-08-05 Carlsberg A/S Cellulose based polymer material
WO2021211715A1 (fr) 2020-04-15 2021-10-21 3M Innovative Properties Company Compositions compostables, articles, et procédés de fabrication d'articles compostables
CN114957799A (zh) * 2022-05-27 2022-08-30 华东师范大学 一种具有可视化稳定期的降解塑料的功能填料及制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2393126B (en) 2002-09-18 2004-11-03 Joseph Anthony Griffiths High G oxygen mask for aircrew
US7713561B2 (en) 2006-02-17 2010-05-11 Diamond Foods, Inc. Oil resistant packaging
AU2007245266B2 (en) * 2006-05-01 2013-11-14 Bnt Force Biodegradable Polymers Pvt Ltd. Novel biodegradable polymer composition useful for the preparation of biodegradable plastic and a process for the preparation of said composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006609A1 (fr) * 1987-02-27 1988-09-07 Amrotex Ag Compositions de matieres plastiques degradables
WO1988009354A1 (fr) * 1987-05-21 1988-12-01 Epron Industries Limited Plastiques degradables

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988006609A1 (fr) * 1987-02-27 1988-09-07 Amrotex Ag Compositions de matieres plastiques degradables
WO1988009354A1 (fr) * 1987-05-21 1988-12-01 Epron Industries Limited Plastiques degradables

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Mark S. M. Alger "Polymer science dictionary", 1989, Elsevier Applied Science, (London,GB), see page 148 under "environment stress cracking". *

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0540641A1 (fr) * 1990-07-25 1993-05-12 Ici America Inc Melange polymere biodegradable contenant un copolymere de 3-hydroxybutyrate/3-hydroxyvalerate.
EP0540641A4 (en) * 1990-07-25 1993-09-01 Ici Americas Inc. Biodegradable polymer blend containing 3-hydroxybutyrate/3-hydroxyvalerate copolymer
EP0596123A1 (fr) * 1991-10-31 1994-05-11 Kabushiki Kaisha Kobe Seiko Sho Plastique biodegradable
EP0596123A4 (fr) * 1991-10-31 1995-03-29 Kobe Steel Ltd Plastique biodegradable.
US5274073A (en) * 1992-01-24 1993-12-28 Cargill, Incorporated Continuous process for manufacture of a purified lactide
US5258488A (en) * 1992-01-24 1993-11-02 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5142023A (en) * 1992-01-24 1992-08-25 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5247059A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for the manufacture of a purified lactide from esters of lactic acid
US6326458B1 (en) 1992-01-24 2001-12-04 Cargill, Inc. Continuous process for the manufacture of lactide and lactide polymers
US5357035A (en) * 1992-01-24 1994-10-18 Cargill, Incorporated Continuous process for manufacture of lactide polymers with purification by distillation
US5247058A (en) * 1992-01-24 1993-09-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6277951B1 (en) 1992-01-24 2001-08-21 Cargill, Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US6005067A (en) * 1992-01-24 1999-12-21 Cargill Incorporated Continuous process for manufacture of lactide polymers with controlled optical purity
US5763564A (en) * 1992-10-02 1998-06-09 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US6207792B1 (en) 1992-10-02 2001-03-27 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5536807A (en) * 1992-10-02 1996-07-16 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US5539081A (en) * 1992-10-02 1996-07-23 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US6355772B1 (en) 1992-10-02 2002-03-12 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
US5585191A (en) * 1992-10-02 1996-12-17 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5665474A (en) * 1992-10-02 1997-09-09 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
US5338822A (en) * 1992-10-02 1994-08-16 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US5773562A (en) * 1992-10-02 1998-06-30 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US5798436A (en) * 1992-10-02 1998-08-25 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5807973A (en) * 1992-10-02 1998-09-15 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
US5852166A (en) * 1992-10-02 1998-12-22 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
US5981694A (en) * 1992-10-02 1999-11-09 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US6005068A (en) * 1992-10-02 1999-12-21 Cargill Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US5484881A (en) * 1992-10-02 1996-01-16 Cargill, Inc. Melt-stable amorphous lactide polymer film and process for manufacturing thereof
US6093791A (en) * 1992-10-02 2000-07-25 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US6111060A (en) * 1992-10-02 2000-08-29 Cargill, Incorporated Melt-stable lactide polymer nonwoven fabric and process for manufacture thereof
US6121410A (en) * 1992-10-02 2000-09-19 Cargill, Incorporated Melt-stable semi-crystalline lactide polymer film and process for manufacture thereof
US6143863A (en) * 1992-10-02 2000-11-07 Cargill, Incorporated Melt-stable lactide polymer composition and process for manufacture thereof
US5475080A (en) * 1992-10-02 1995-12-12 Cargill, Incorporated Paper having a melt-stable lactide polymer coating and process for manufacture thereof
DE4437792A1 (de) * 1994-10-21 1996-04-25 Inventa Ag Formmassen auf der Basis von aliphatischen Polyestern
EP0708148A1 (fr) 1994-10-21 1996-04-24 Ems-Inventa Ag Compositions à mouler à base de polyesters aliphatiques dégradables aptes à produire des feuilles soufflées
DE19513237A1 (de) * 1995-04-07 1996-12-05 Biotec Biolog Naturverpack Biologisch abbaubare Polymermischung
US8796362B2 (en) 2008-12-16 2014-08-05 Carlsberg A/S Cellulose based polymer material
US9428635B2 (en) 2008-12-16 2016-08-30 Carlsberg A/S Coating of hydroxylated surfaces by gas phase grafting
WO2021211715A1 (fr) 2020-04-15 2021-10-21 3M Innovative Properties Company Compositions compostables, articles, et procédés de fabrication d'articles compostables
CN114957799A (zh) * 2022-05-27 2022-08-30 华东师范大学 一种具有可视化稳定期的降解塑料的功能填料及制备方法

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