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WO1994010238A1 - Procede d'augmentation de la biodegradabilite des esters de cellulose - Google Patents

Procede d'augmentation de la biodegradabilite des esters de cellulose Download PDF

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Publication number
WO1994010238A1
WO1994010238A1 PCT/US1993/009140 US9309140W WO9410238A1 WO 1994010238 A1 WO1994010238 A1 WO 1994010238A1 US 9309140 W US9309140 W US 9309140W WO 9410238 A1 WO9410238 A1 WO 9410238A1
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WO
WIPO (PCT)
Prior art keywords
cellulose
promoter
calcium
sodium
potassium
Prior art date
Application number
PCT/US1993/009140
Other languages
English (en)
Inventor
Charles Michael Buchanan
Robert Marshall Gardner
Alan Wayne White
Original Assignee
Eastman Kodak Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Company filed Critical Eastman Kodak Company
Publication of WO1994010238A1 publication Critical patent/WO1994010238A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • This invention concerns a method for increasing the biodegradability of cellulose esters.
  • This invention also concerns dimensionally stable articles consisting of environmentally nonpersistent cellulose esters.
  • cellulose esters are useful as coatings, fibers, films, and other shaped articles of dimensional stability.
  • these articles are formed either by a solution casting or spinning process or via a thermal extrusion or molding process.
  • processing aids and plasticizers are often added to the formulations.
  • These additives typically serve two general functions, i.e., to improve processing and to modify the properties of the final object.
  • plasticizers with cellulose esters
  • Patent 4,094,695, 1978 describes the use poly (alkylene glycols) as plasticizers for cellulose esters.
  • the poly (alkylene glycols) Sanders discloses, i.e.,
  • poly (tetramethylene glycol), poly(ethylene-co-propylene glycol) , and poly (propylene glycol) are in the molecular weight range of 800-1200. They lower the melt
  • resins and/or additives should be compatible with the normal processing conditions used to make a dimensionally stable shaped articles and should not negatively impact the physical properties of these articles. These resins and/or additives should not result in storage instability of the shaped article nor should the final shaped object be so hydrophilic that they can no longer be used for their intended function due to water solubility or dispersibility.
  • the present invention concerns the combined use of cellulose esters having an intermediate degree of substitution per anhydroglucose unit (DS/AGU) with additives which alter the hydrophilicity,
  • the invention is directed to dimensionally stable shaped articles prepared by a method for increasing the biodegradability of ester(s) of cellulose comprising an alkanoyl chain having from 1 to 10 carbon atoms and having a DS/AGU of 1.5 to 2.7 and an inherent viscosity (I.V.) of 0.2 to 3.0
  • cellulose derivatives with a low degree of substitution i.e., less than one, are biodegradable.
  • Cellulose is degraded in the environment by both anaerobic or aerobic microorganisms.
  • Typical endproducts of this microbial degradation include cell biomass, methane (anaerobic only), carbon dioxide, water, and other fermentation products. The ultimate endproducts will depend upon the type of environment as well as the type of microbial population that is present. However, it has been reported that cellulose esters with a DS/AGU greater than one are completely resistant to attack by
  • biodegradable materials are those which, because of their chemical structure are susceptible to being assimilated by microorganisms such as molds, fungi, and bacteria, when buried in the ground or otherwise contacted with the organisms under
  • biodegradable is often used indiscriminately to refer to various types of environmental degradation, including photodegradation. Though a polymeric material may be degraded by sunlight and oxygen, this does not
  • biodegradable as used herein, is reserved for that type of degrad-ability which is brought by living organisms, usually microorganisms. It thus requires the direct interaction of microorganisms and/or their enzymes with the
  • the present invention provides a method for increasing the biodegradability of esters of cellulose comprising an alkanoyl chain having from 1 to 10 carbon atoms and having a DS/AGU of 1.5 to 2.7 and an inherent viscosity of 0.2 to 3.0 deciliters/gram as measured at a temperature of 25°C for a 0.5 g sample in 100 ml of a 60/40 parts by weight solution of
  • the alkanoyl chain present in said ester of cellulose can be either straight-chained or branched.
  • the alkanoyl chain preferably comprises a straight-chain alkyl group.
  • Examples of representative alkyl chains are methyl, ethyl, propyl, isopropyl, t-butyl, butyl, hexyl, isohexyl, heptyl, nonyl, isononyl, and decyl.
  • esters of cellulose of the present invention generally comprise repeating units of the structure:
  • R 1 , R 2 , and R 3 are selected independently from the group consisting of hydrogen or straight chain alkanoyl having from 1 to 10 carbon atoms.
  • the cellulose ester useful in the invention will be a secondary cellulose ester.
  • secondary cellulose esters include cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate.
  • inventions can be prepared using techniques known in the art or are commercially available from Eastman Chemical Company, Inc., Kingsport, TN, U.S.A.
  • the cellulose esters useful in the invention have an inherent viscosity (IV) of 0.2 to 3.0 deciliters/gram, preferably 1 to 1.6, as measured at a temperature of 25 °C for a 0.5 gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane.
  • Preferred esters of cellulose include cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose propionate butyrate (CPB), and the like.
  • Cellulose acetates or cellulose acetate propionates having a DS/AGU of 1.7 to 2.6 are more preferred
  • a preferred ester of cellulose is cellulose acetate having a DS/AGU of 1.8 to 2.5 and an I.V. of 1.1 to 1.5.
  • a more preferred cellulose ester is cellulose acetate propionate having a DS/AGU of 1.8 to 2.2 in which acetyl comprises 1-90% of the acyl substituents.
  • the even more preferred cellulose ester of the invention is cellulose acetate having a DS/AGU of 1.8 to 2.2 and an I.V. of 1.1 to 1.5.
  • the degradable resins of this invention can be formed into a shaped article either by a solvent casting process or by a thermal process.
  • a solvent process include spinning of fibers or casting of film from the appropriate solvent (e.g., acetone, tetrahydrofuran, CH 2 Cl 2 /MeOH, CHCl 3 , dioxane, DMF, DMSO, AcOMe, AcOEt, pyridine).
  • the choice of solvent depends upon the type of ester substituent and upon the DS/AGU.
  • the preferred solvent for cellulose esters is acetone containing 0-30% water or methylene chloride containing 0-20% MeOH.
  • the preferred solvent is acetone containing less than 2% water.
  • the preferred solvent is acetone containing 5-15% water.
  • the preferred solvent is acetone containing
  • the cellulose ester or pla ⁇ ticized cellulose ester have a melt temperature of 120°C to 250°C.
  • a more preferred melt temperature is from 180°C to 220°C.
  • plasticizers for use in a thermal process include, but are not limited to, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, triacetin, diethyl acetyl citrate or dioctyl adipate.
  • Preferred plasticizers are dibutyl phthalate or dioctyl adipate.
  • additives which can serve dual functions.
  • additives such as polyethylene glycol having a weight average molecular weight in the range of 200 - 600, are preferred for the practice of this invention as they can both serve as plasticizers and as additives which are particularly useful in modifying the surface or bulk water content of the biodegradable resin.
  • the blend components can be mixed by thermally compounding.
  • the most preferred method is by thermally compounding in an apparatus such as a torque rheometer, a single screw extruder, or a twin screw extruder.
  • the resins produced by thermally compounding can be converted to thin films by a number of methods known to those skilled in the art.
  • thin films can be formed by dipcoating as described in U.S. Patent 4,372,311, by compression molding as described in U.S. Patent 4,427,614, by melt extrusion as described in U.S. Patent 4,880,592, by melt blowing, or by other similar methods.
  • the resins can be converted to molded plastic objects by injection molding as well as by extrusion into a sheet from which an object is cut or stamped.
  • the thermally compounded resins can be used for melt extrusion of fiber as well.
  • the resins used to prepare biodegradable shaped articles can consist of cellulose esters containing additives effective at promoting biodegradation. These additives generally can be divided into two classes; (i) hydrophilic modifiers and (ii) hydrolysis promoters. Hydrophilic modifiers generally consist of plasticizers or polymers which are themselves very hydrophilic. When added to cellulose esters, they increase the bulk water content or modify the surface hydrophilicities of the resulting biodegradable resin.
  • Hydrolysis promoters are additives which promote the base, acid, or oxidative catalyzed hydrolysis of the cellulose ester acyl substituents when the shaped article is placed in an environment suitable for biodegradation. By promoting the hydrolysis of the cellulose substituents, the DS/AGU is lowered and the rate of biodegradation is increased. It is of course understood that using the hydrophilic modifiers and hydrolysis promoters in combination gives resins and shaped articles with the highest rate of biodegradation.
  • the hydrophilic modifiers can be divided into glycols, polyethers, and polyalcohols.
  • glycols include, but are not limited to, glycerol, diethylene glycol, triethylene glycol, and tetraethylene glycol.
  • the preferred glycol is glycerol.
  • polyethers include polyethylene glycol in which the end groups are hydroxyl or hydroxyl substituted with methyl, ethyl, propyl, butyl, acetyl, propionyl, or butyryl.
  • the preferred polyether is polyethylene glycol with a degree of polymerization (DP) of 5-600.
  • polyalcohol polyvinyl alcohol with a DP of 10 to 500,000, preferably 10 to 10,000, and more preferably, 10 to 2,000.
  • the polyvinyl alcohol can optionally contain 0-10% of other substituents such as acetyl or sulfonyl.
  • the preferred polyalcohol is polyvinyl alcohol having a DP of 50-500.
  • Hydrolysis promoters can be divided into basic, acidic, or oxidative promoters.
  • Examples of basic promoters include, but are not limited to, potassium, sodium, calcium, or barium carbonate or combinations thereof.
  • acidic promoters include, but are not limited to, (i) potassium, sodium, calcium, or barium sulfate, nitrate, or phosphate citrate; (ii) potassium, sodium, calcium, or barium acetate, propionate, or butyrate; (iii) potassium, sodium, calcium, or barium citrate or oxylate.
  • oxidative promoters include, but are not limited to, potassium, sodium, calcium, or barium peroxides, preferably coated with a water soluble substrate such as starch or polyvinyl alcohol.
  • Preferred basic promoters are calcium or potassium carbonate.
  • Preferred acidic promoters are sodium acetate or sodium citrate.
  • a preferred oxidative promoter is calcium peroxide.
  • Any of the cellulose esters or fibers of the invention can optionally additionally comprise 0.001 to 50 weight per cent, based on the total weight of the composition, of at least one additional additive
  • a plasticizer selected from a plasticizer, a thermal stabilizer, an antioxidant, a pro-oxidant, an acid scavenger,
  • the method of this invention can be used to prepare shaped articles such as films, fibers, etc., which are dimensionally stable.
  • Films made from the resins have good tensile properties and can be very flexible depending upon the type of cellulose ester selected. Many of the films have good optical properties, e.g., are preferably
  • the films can also contain
  • colorant i.e., pigment or dye
  • the resins of this invention are particularly useful as thin barrier films where they must function as a barrier and/or be biodegradable.
  • these resins are useful as protective barrier films and may be used in disposable absorbent articles such as infant diapers, incontinence briefs, sanitary napkins, tampons, bed liners, bedpan liners, bandages, food packaging, and the like.
  • the films of the invention have a tangent modulus of 2.5 ⁇ 10 5 psi to 0.01 ⁇ 10 5 psi, a tensile strength of at least 0.5 ⁇ 10 3 psi, an average tear force of at least 7.0 g/mil, and an elongation at break of at least 10%.
  • said films have a thickness of 0.1 mil to 20 mil and a water vapor transmission rate less than 500 g mil/m 2 -24 hours.
  • the resins of this invention can also be used in the other parts of disposable diapers.
  • these blends can be used as tabs, nonwovens, fibers, tape, and other parts needed in the construction of a diaper.
  • the resins of this invention are also useful as molded plastic parts or as solid, foamed plastic
  • plastic parts especially those made by a foamed method which gives the plastic part increased surface area, of this invention are particularly useful in applications were it is desired that the plastic part be environmentally non-persistent. Shaped articles made by the process of the invention can be injected molded.
  • Injection molding bars made from the resins of the invention typically have a flexural modulus of 5.0 X 10 5 psi to 0.1 X 10 5 psi, a flexural strength of 13 X 10 3 psi to 0.1 X 10 3 psi, and a notched Izod (23°C) of 1.0 to 25 ft-lb/in. (53.4 to 1,335 J/m).
  • the molding bars have a flexural modulus of 3.8 X 10 5 psi to 1.5 X 10 5 psi, a flexural strength of 11.4 X 10 3 psi to 4 X 10 3 psi, and a notched Izod (23 °C) of 2 to 15 ft-lb/in. (106.8 to 801 J/m).
  • the resins of this invention are also useful as fibers. Examples of fiber applications include
  • the fibers can be oriented by drawing the fiber after spinning or by orientation during the spinning (cabinet orientation).
  • Fibers produced from the resins have excellent shape retention even for fibers with complex
  • Fiber produced from the resins typically have a denier/filament (DPF) of 30-0.1 (33.33-0.11 dtex).
  • the preferred denier is 10-1.5 DPF (11.11 to 1.67 dtex).
  • IV inherent viscosity
  • g is gram
  • psi pounds per square inch (kilopascal)
  • cc is cubic centimeter
  • m is meter
  • rpm revolutions per minute
  • DSAc degree of substitution per anhydroglucose unit for acetyl
  • BOD biochemical oxygen demand
  • vol. or v is volume
  • wt. is weight
  • mm is micrometer
  • NaOAc sodium acetate; “nm” is not measured; “CE” is cellulose ester; “mil” is 0.001 inch. Relative to naming of the cellulose ester, “CA” is cellulose acetate and “CAP” is cellulose acetate propionate.
  • PEG poly (ethylene glycol).
  • PEG 400 is poly (ethylene glycol) having a molecular weight of 400.
  • the tensile strength, break to elongation, and tangent modulus of the films are measured by ASTM method D882; the tear force is measured by ASTM method D1938.
  • the tensile strength and elongation at break for molded pieces are measured by ASTM method D638; the flexural strength and modulus by ASTM method D790; the Izod impact strength by ASTM method D256; the heat deflection temperature (HDT) by ASTM method D648.
  • viscosities are measured at a temperature of 25°C for a 0.5 gram sample in 100 ml of a 60/40 by weight solution of phenol/tetrachloroethane (PM95). Molecular weight was measured by gel permeation chromatography using tetrahydrofuran as the eluding solvent. The molecular weight is reported in polystyrene equivalents.
  • the resins were prepared by two general methods: (i) the components are shaken together before compounding at the appropriate temperature in a Rheometrics Mechanical Spectrometer. The resulting resin is typically ground to 5 mm particle size; (ii) resins were prepared by compounding on a 30 mm Werner-Pfliderer twin screw extruder.
  • the typical procedure is as follows: Two separate feed systems, one for the cellulosic and one for the hydrophobic modifier were utilized for this method of melt blending. The cellulosic was added as a dry powder in Zone 1 while the hydrophobic modifier were typically added as a liquid.
  • the production rate of the extruder is in the range of 10-50 pounds/hr (4.54-22.68 kg/hr).
  • the zone temperatures are set depending on the exact nature of the cellulose ester and generally vary in the range of 100°C to 250°C.
  • the two strands of material exiting the extruder were quenched in water and chopped with a CONAIR (trademark) JETRO pelletizer.
  • CONAIR trademark
  • JETRO pelletizer JETRO pelletizer
  • the material can optionally be allowed to age 0.5 to 500 h before adding to the extruder.
  • the dry blend was added at the desired rate using an AccuRate feeder through a hopper into the barrel of the extruder.
  • the production rate of the extruder is in the range of 10-50 pounds/hr.
  • the zone temperatures are set depending on the exact nature of the cellulose ester and generally vary in the range of 100°C to 250°C. Afterwards, the two strands of material exiting the extruder were quenched in water and chopped with a CONAIR JETRO pelletizer.
  • Fresh composite samples of activated sludge are obtained from the A 03 aeration basins in the Tennessee Eastman (Kingsport, TN, U.S.A.) wastewater treatment plant which has a design capacity of receiving 25 million gallons (94.6 million liters) of waste per day with BOD concentration up to 200,000 pounds (90,718 kg) per day.
  • the major waste components consist largely of methanol, ethanol, isopropanol, acetone, acetic acid, butyric acid, and propionic acid.
  • the sludge operating temperatures vary between 35°C to 40°C.
  • a dissolved oxygen concentration of 2.0 to 3.0 and a pH of 7.1 are examples of water.
  • the activated sludge serves as the starting inoculum for the stable mixed population of microbes used in this invention.
  • Cellulose ester film degrading enrichments are initiated in a basal salts medium containing the following ingredients per liter: 50 ml of Pfennig's Macro-mineral solution, 1.0 ml of Pfennig's trace element solution, 0.1% (wt/vol) Difco yeast extract, 2 mM Na 2 SO 4 , 10 mM NH 4 Cl which supplements the ammonia levels provided by Pfennig's Macro-mineral solution, 0.05% (wt/vol) cellobiose, 0.05% (wt/vol) NaOAc.
  • This solution is adjusted to pH 7.0 and a final volume of 945 ml before being autoclaved at 121°C at 15 psi (103.42 kPa) for 15 minutes.
  • 50 ml of sterile 1 M phosphate buffer and 5 ml of a complex vitamin solution which has been filtered through a 0.2 mm filter are added.
  • the test cellulosic film is then added and the flask is inoculated (5% v/v) with a stable mixed population enrichment.
  • the flask is placed in a New Brunswick incubator and held at 30°C and 250 rpm for the appropriate period.
  • Typical radiochemistry experiments consisted of eight 250 ml test flasks, each of which received 70 ml of the complete media, approximately 1-2 mCi of 14 C cellulose acetate, and 10 ml inoculum. In each
  • Flasks were sealed and incubated in a shaking water bath at 30°C and approximately 250 rpm. Samples were taken at four hour intervals for 28 days by trapping the 14 CO 2 on a cooled column of methoxy ethylamine. Radioactivity, in counts per minute (CPM), were determined by standard techniques.
  • Composting can be defined as the microbial degradation and conversion of solid organic waste into soil.
  • compost piles are self heating; heat is a natural by-product of the metabolic break down of organic matter. Depending upon the size of the pile, or its ability to insulate, the heat can be trapped and cause the internal temperature to rise.
  • thermophilic species on one hand (optimal growth range between 45-60°C), while inhibiting the mesophiles on the other.
  • temperature profiles are often cyclic in nature, alternating between mesophilic and thermophilic populations, municipal compost facilities attempt to control their operational temperatures between 55-60°C in order to obtain optimal degradation rates.
  • Municipal compost units are also typically aerobic processes, which supply sufficient oxygen for the metabolic needs of the microorganisms permitting accelerated biodegradation rates.
  • small-scale compost units were employed to simulate the active treatment processes found in a municipal solid waste composter. These bench-scale units displayed the same key features that distinguish the large-scale municipal compost plants.
  • the starting organic waste was formulated to be representative of that found in municipal solid waste streams: a carbon to nitrogen of 25:1 ratio, a 55% moisture content, a neutral pH, a source of readily degradable organic carbon (eg. cellulose, protein, simple carbohydrates, and lipids), and had a particle size that allowed good air flow through the mass.
  • a carbon to nitrogen of 25:1 ratio a carbon to nitrogen of 25:1 ratio
  • a 55% moisture content e. cellulose, protein, simple carbohydrates, and lipids
  • a source of readily degradable organic carbon eg. cellulose, protein, simple carbohydrates, and lipids
  • Example 1 Materials were harvested after 10 or 15 days of incubation and carefully washed, dried, and weighed to determine weight loss.
  • Cellulose acetate with different DS/AGU were prepared via hydrolysis of cellulose acetate with a DS/AGU of 2.5. Typically, 29 lbs (13.15 kg) of
  • samples 1, 2, and 3 show that as the amount of the hydrophobic additive increases from 10 to 30%, the contact angle decreases indicating that the film surface is becoming progressively hydrophilic.
  • Samples 5, 1, and 4 demonstrate that as the weight average molecular weight of the polyethylene glycol (PEG) is decreased from 600 to 200 the contact angle decreases and hence, the hydrophilic character of the film increases.
  • PEG polyethylene glycol
  • Cellulose 1- 14 C-triacetate prepared by the general method of Buchanan et al. Macromolecules, 1991, 24, 3050 was hydrolyzed by a method similar to example 1 to provide 1- 14 C-acetylcellulose with the following degrees of substitution: 1.85, 2.0, and 2.5.
  • the specific activities of the starting materials were 4.46 ⁇ Ci/g, 5.73 ⁇ Ci/g, and 7.16 ⁇ Ci/g, respectively.
  • Approximately 1 ⁇ Ci of the respective esters were individually incubated in an in vitro enrichment assay at 30°C for
  • Figure 1 illustrates the microbial production of 14 CO 2 from labelled the 1- 14 C-cellulose acetates.
  • Resins were prepared by thermal compounding according to the method generally described in Example 2 of this application using the plasticizers disclosed by Sanders (U. S. Patent 4,094,695) and a cellulose acetate having a DS/AGU of 2.06.
  • a resin consisting of the CA and 30% poly(propylene glycol) was a gray-brown resin that was very hard and brittle and is not useful for the purposes of this invention.
  • a resin consisting of CA and 30% poly(ethylene-co-propylene glycol) [12/88] was a white, hard, brittle resin which is not useful for the purposes of this invention; a resin consisting of CA and 30% poly(tetramethylene glycol) was very similar to the poly(ethylene-co-propylene glycol) resin and is also not useful for this invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention se rapporte à un procédé visant à augmenter la biodegradabilité d'esters C1-C10 de cellulose présentant un degré de substitution par unité d'anhydroglucose (DS/AGU) de 1,5 à 2,7 et une viscosité inhérente de 0,2 à 3,0 décilitres/gramme mesurée à une température de 25 °C pour un échantillon de 0,5 g dans 100 ml d'une solution de 60/40 parties en poids de phénol/tétrachloroéthane consistant à mettre en contact l'ester C1-C10 de cellulose avec 0,1 à 40 % en poids d'un agent modifiant hydrophile ou d'un promoteur d'hydrolyse, ou d'une combinaison de ceux-ci. L'invention se rapporte également à des articles façonnés préparés par le procédé mentionné ci-dessus.
PCT/US1993/009140 1992-10-26 1993-09-27 Procede d'augmentation de la biodegradabilite des esters de cellulose WO1994010238A1 (fr)

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US96621692A 1992-10-26 1992-10-26
US966,216 1992-10-26

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000075259A1 (fr) * 1999-06-07 2000-12-14 Eastman Chemical Company Films de paillage pour l'agriculture a degradation declenchee
WO2001060437A1 (fr) * 2000-02-18 2001-08-23 Boo Yoon Tech, Inc. Seringue jetable biodegradable
WO2010043293A1 (fr) * 2008-10-14 2010-04-22 Rhodia Acetow Gmbh Matière plastique biodégradable et son utilisation
EP2368915A1 (fr) * 2010-03-26 2011-09-28 Taiwan Textile Research Institute Mélange maître à base de cellulose doté d'une meilleure élongation à la rupture, son application et son procédé de préparation
TWI399399B (zh) * 2010-03-30 2013-06-21 Taiwan Textile Res Inst 網狀結構纖維素母粒之製備方法與應用
KR101328141B1 (ko) * 2011-10-26 2013-11-13 재단법인대구경북과학기술원 안경테용 셀룰로오스 에스테르계 복합소재
KR101449466B1 (ko) * 2013-02-25 2014-10-14 재단법인대구경북과학기술원 복합 가소제를 이용한 안경테용 셀룰로오스 에스테르계 조성물, 이를 이용한 안경테 다리의 제조 방법 및 이로부터 제조된 안경테 다리
EP3031847A1 (fr) 2014-12-11 2016-06-15 Solvay Acetow GmbH Composition de polymère comprenant un additif basique, procédé et articles comprenant ladite composition de polymère

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US3406129A (en) * 1965-02-15 1968-10-15 Celanese Corp Oxymethylene polymer-cellulose compound blended moldable compositions
US4094695A (en) * 1976-08-05 1978-06-13 Eastman Kodak Company Plasticized cellulose ester compositions
EP0394803A1 (fr) * 1989-04-28 1990-10-31 Battelle Memorial Institute Matière plastique biodégradable
US4983730A (en) * 1988-09-02 1991-01-08 Hoechst Celanese Corporation Water soluble cellulose acetate composition having improved processability and tensile properties
WO1992009654A2 (fr) * 1990-11-30 1992-06-11 Eastman Kodak Company Melanges de copolyesters aliphatiques aromatiques et d'esters/de polymeres de cellulose
WO1992020738A1 (fr) * 1991-05-21 1992-11-26 Battelle Memorial Institute Polymeres de cellulose degradables

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Publication number Priority date Publication date Assignee Title
US3406129A (en) * 1965-02-15 1968-10-15 Celanese Corp Oxymethylene polymer-cellulose compound blended moldable compositions
US4094695A (en) * 1976-08-05 1978-06-13 Eastman Kodak Company Plasticized cellulose ester compositions
US4983730A (en) * 1988-09-02 1991-01-08 Hoechst Celanese Corporation Water soluble cellulose acetate composition having improved processability and tensile properties
EP0394803A1 (fr) * 1989-04-28 1990-10-31 Battelle Memorial Institute Matière plastique biodégradable
WO1992009654A2 (fr) * 1990-11-30 1992-06-11 Eastman Kodak Company Melanges de copolyesters aliphatiques aromatiques et d'esters/de polymeres de cellulose
WO1992020738A1 (fr) * 1991-05-21 1992-11-26 Battelle Memorial Institute Polymeres de cellulose degradables

Cited By (25)

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