EP0697865A4 - Polymeres a base d'acide lactique degradables a l'eau et aux rayons ultraviolets - Google Patents

Polymeres a base d'acide lactique degradables a l'eau et aux rayons ultraviolets

Info

Publication number
EP0697865A4
EP0697865A4 EP19920914551 EP92914551A EP0697865A4 EP 0697865 A4 EP0697865 A4 EP 0697865A4 EP 19920914551 EP19920914551 EP 19920914551 EP 92914551 A EP92914551 A EP 92914551A EP 0697865 A4 EP0697865 A4 EP 0697865A4
Authority
EP
European Patent Office
Prior art keywords
weight
polylactic acid
present
copolymer
range
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP19920914551
Other languages
German (de)
English (en)
Other versions
EP0697865A1 (fr
Inventor
Patrick V Bonsignore
Robert D Coleman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arch Development Corp
Original Assignee
Arch Development Corp
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 Arch Development Corp filed Critical Arch Development Corp
Publication of EP0697865A4 publication Critical patent/EP0697865A4/fr
Publication of EP0697865A1 publication Critical patent/EP0697865A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • 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

Definitions

  • the invention relates to modified polymers and polymer blends useful for waste disposal or for agricultural purposes to provide water or UV degradable materials which are environmentally safe.
  • the materials are designed to degrade upon exposure to water or to UV light to environmentally safe naturally occurring materials.
  • the modified polymers and polymer blends when used are also usable for garbage bags or other waste disposal purposes can be incinerated since upon burning only environmentally safe materials are produced.
  • Another object of the invention is to provide water degradable or UV light degradable polylactic acid polymers and copolymers which may be used as agricultural coatings and mulches which degrade in the field to provide environmentally safe materials as well as plant growth promoters.
  • Another object of the invention is to provide a water degradable modified polylactic acid polymer comprising a copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, p-dioxanone, 1,5 dioxepan-2-one, 1,4 - oxathialan-2-one, 4,4-dioxide and mixtures thereof, wherein the ethylene glycol is present in the range of from about 5% by weight to about 40% by weight, wherein the propylene glycol is present in the range of from about 5% by weight to about 40% by weight, wherein the p-dioxanone, 1,5 dioxepan-2-one or the l,4-oxathialan-2-one, 4,4-dioxide is present in the range of from about 2% by weight to about 40% by weight, the modifying polymer not exceeding about 40% by weight of the modified polylactic acid copolymer.
  • a still further object of the invention is to provide a water and UV degradable polylactic acid polymer comprising a co-polymer of polylactic acid and a modifying monomer selected from the class consisting of p-dioxanone present in an amount up to about 20% by weight, 1,5 dioxepan-2-one present in an amount up to about 20% by weight, and 1,4 oxathialan-2-one, 4,4 dioxide present in an amount up to about 20% by weight, or mixtures thereof, the modifying monomer being present in an amount not greater than about 20% by weight.
  • Still another object of the invention is to provide a water degradable polylactic acid polymer comprising an alloy of polylactic acid and high molecular weight polyethylene oxide wherein the high molecular weight polyethylene oxide is present in the range of from about 2 to about 50% by weight.
  • a final object of the invention is to provide a method of applying an active material selected from the class of seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof of an to agricultural site comprising providing a copolymer of monomers of lactic acid and a modifying monomer selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, p-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 4,4-dioxide and mixtures thereof, wherein the ethylene glycol is present in the range of from about 5% by weight to about 40% by weight, wherein the propylene glycol is present in the range of from about 5% by weight to
  • Polymers and copolymers of lactic acid are transparent, colorless thermoplastics with a wide range of physical properties that mimic those of many conventional thermoplastics. When exposed to moisture or biological fluids, these modified plastics hydrolyze slowly, over a period of several months to natural, harmless, materials such as lactic acid.
  • the copolymers of lactic acid and glycolic acid were originally developed and marketed as an industrial product as resorbable sutures. These polymers and copolymers have high strength and biocompatibility and have controlled degradabilit .
  • Poly (lactic acid) and poly (glycolic acid) can be prepared by either condensation polymerization of the free acids or by catalytic, ring-opening polymerization of the dilactones. Both polylactic acid and polyglycolic acid are environmentally compatible because they degrade respectively to lactic acid and glycolic acid, both natural harmless products. While these polymers degrade primarily by hydrolysis, with the addition of certain other materials, they may degrade also by exposure to sunlight or any other source of UV light. Upon incineration, the polymers burn with a clean blue flame, rather than giving off poisonous or corrosive gases as many plastics do.
  • thermoplastics based on a lactic acid polymer degrade slowly over a period of several weeks up to about one year leads to another important advantage of relatively good shelf life.
  • the modified polylactic acid polymers can be classified as moisture sensitive because they degrade only slowly. For instance, after month's immersion in water, polylactic acid and certain of the copolymers thereof show no degradation of the molecular weight. But after six months, physical properties drop significantly.
  • water degradable modified polylactic acid copolymers may be made from monomers of lactic acid and modifying monomers selected from the class consisting of ethylene and polyethylene glycols, propylene and polypropylene glycols, p-dioxanone, 1,5 dioxepan-2-one, 1,4-oxathialan-2-one, 4,4-dioxide and various mixtures thereof.
  • the physical properties such as crystallinity, melting point, degradation rate, elasticity and the like can be varied depending upon the amount and the type of copolymer formed.
  • the elasticity of the material will vary from glassy materials which are relatively nonelastic to high-modulus elastic materials, and the degradation rates will vary from intermediate to fast to very slow to none depending upon the amounts of polylactic acid or polyglycolic acid utilized.
  • the various physical attributes discussed above can be varied among a wide range of physical properties depending upon the types and amounts of copolymers used for the final material, it being important that depending upon the end usage desired that the modifying polymer for the polylactic acid be present in the range from about 5% by weight to about 40% by weight so as to provide a water degradable modified polylactic acid copolymer which has suitable physical properties for the end use selected.
  • the various copolymers of polylactic acid may be useful for a variety of agricultural and waste management uses.
  • the copolymers may be used as coatings on or as matrices for seeds, seedlings, pesticides, herbicides, fertilizers and mixtures thereof, wherein the coating or matrices provide a controlled release of the coated or embedded material depending upon the thickness of the coating or percent of active ingredient embedded in the matrix.
  • the coatings may have a thickness in the range of from about 0.25 microns to about 4 microns, so that release rates can be varied as required.
  • the active ingredients such as seeds, pesticides, herbicides, fertilizers or mixtures thereof also may be mixed with the copolymer and extruded as pellets, with the active ingredient dispersed in a matrix of the copolymer.
  • the release of active ingredients will be controlled by varying the type of copolymer and the amount thereof present. It is preferred that where the copolymer is used as a matrix for an active ingredient, it is present in the range of from about 2% to about 40% by weight, that is, the active ingredient is present in the range of from about 60% to about 98%.
  • fertilizers for instance such as urea or other nitrogen rich fertilizers can be coated with various thicknesses of coating or dispersed in a matrix to provide a continuing release of the coated or dispersed materials over a wide range of time so as to prevent crop burning and other undesirable side effects when too much urea or other fertilizer is released at any one time.
  • the copolymers of lactic acid are useful with molecular weights in a range of from about 20,000 to about 100,000 for the uses aforesaid as coatings or matrices.
  • molecular weights of greater than about 25,000 are preferred and in particular, molecular weights in the range from 25,000 to 100,000 are preferred for agricultural mulches which upon time and exposure to moisture and UV light will degrade to the constituent lactic acid and other monomers.
  • the copolymer particularly for agricultural use will often be present as a matrix or as a coating for the active material.
  • polylactic acid has been used as an encapsulator in the medical field and preparation of encapsulated active materials with polylactic acid coatings has been taught by Ogawa et al. in a paper entitled New Technique to Efficiently Entrap Leuprolide Acetate into Microcapsules of Polylactic Acid or COPOIV (Lactic/Glycolic) Acid in Chem. Pharm. Bull. 36(3) 1095-1103 (1988), the disclosure of which is incorporated herein by reference. Further, a process of preparing microcapsules of lactides or lactide copolymers has been patented by Gardner, January 20, 1987, U.S. Patent No.
  • the various modifying monomers which form the new copolymers hereinbefore disclosed provide a wide range of physical properties from highly crystalline to amorphous materials and from high to low melting point materials, thereby providing controlled degradation rates upon exposure to either UV light or to moisture or to both.
  • Sinclair in an article entitled Slow-Release Pesticide System, Polymers of Lactic and Glycolic Acids as Ecologically Beneficial. Cost-Effective Encapsulating Materials, teaches the use of combinations of glycolic and lactic acids as a matrixes for a pesticide, Sinclair does not show or suggest the use of the modified copolymers of lactic acid of this invention. Specifically, the polypropylene glycol and polyethylene glycol used as modifiers are a different class of materials than the glycolic acid taught by Sinclair.
  • the present invention permits a copolymer to be designed to control the release rate of the active material to the environment.
  • the active material is a high urea content fertilizer
  • the controlled degradation of the matrix permits the urea to be released at a rate which prevents crop burning and other undesirable side effects.
  • the active material is a herbicide or pesticide
  • the controlled degradation of the matrix permits continual application of the pesticide or herbicide over a prolonged period of time, thereby permitting fewer applications by the farmer and ultimately, releasing less of the active material into the environment since only so much as needed is added at any one time.
  • modified polylactic polymers as matrixes or coatings for seeds or seedlings which when germinating or growing are provided with a concentration of growth promoting oligomers of polylactic acid or the disclosed copolymers as the modified polylactic acid copolymer degrades in situ.
  • the disclosed copolymers degrade in an agricultural site, there will be a variety of oligomers of polylactic acid and copolymers thereof present in a wide variety of chain lengths or molecular weights. Some of these materials are proven growth promoters.
  • plastic materials for a wide variety of products including, inter alia, agricultural mulches and garbage bags, which depending on the polymers selected, degrade over a wide range of time.
  • an agricultural mulch may be designed to degrade fron a few days to a few months.
  • a plastic garbage bag certainly will not be designed to degrade over a few days.
  • a preferred blend is polylactic acid and high molecular weight polyethylene oxide. It has been found that a high molecular weight polyethylene oxide of greater than about 100,000 molecular weight blended with a polylactic acid having a molecular weight in the range of from about 25,000 to approximately 100,000 provides a superior film.
  • the high molecular weight polyethylene oxide is present as a blend or alloy in the range of from about 2% by weight to about 50% by weight of the total polymer material, a superior film occurs. It should be understood that this is not a copolymer as previously discussed, but rather is a - physical blend or alloy of polylactic acid and a high molecular weight polyethylene oxide wherein a copolymer is not formed. However, these particular blends of polylactic acid, modified as previously taught or with the addition of a glycolic acid monomer or unmodified and high molecular weight polyethylene oxide provide films having superior physical properties.
  • the film when used as a film for trash bags and the like, can be designed so as to degrade without the presence of UV light such as in conditions which occur in landfills.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Fertilizers (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Protection Of Plants (AREA)

Abstract

Copolymère dégradable à l'eau et à la lumière ultraviolette, contenant des monomères d'acide lactique ainsi qu'un monomère modificateur choisi dans la catégorie composée d'éthylène et de polyéthylène glycols, de propylène et de polypropylène glycols, de p-dioxanone, de 1,5-dioxépan-2-one, de 1,4-oxathialan-2-one, de 1,4-dioxyde et de mélanges de ces éléments. Ces copolymères peuvent être utilisés à des fins d'élimination de déchets et à des fins agricoles. L'invention se rapporte également à un mélange, dégradable à l'eau, d'acide polylactique ou d'acide polylactique modifié et d'un oxyde de polyéthylène de masse moléculaire élevée, cet oxyde de polyéthylène étant présent en une teneur comprise entre environ 2 et environ 50 pourcent en poids et ce mélange convenant à la fabrication de films. Un procédé d'application d'une matière active, choisie parmi les catégories des graines, des semis, des pesticides, des herbicides, des engrais et des mélanges de ceux-ci dans un site agricole, est également décrit.
EP92914551A 1992-06-05 1992-06-05 Polymeres a base d'acide lactique degradables a l'eau et aux rayons ultraviolets Withdrawn EP0697865A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1992/004684 WO1993025202A1 (fr) 1992-06-05 1992-06-05 Polymeres a base d'acide lactique degradables a l'eau et aux rayons ultraviolets

Publications (2)

Publication Number Publication Date
EP0697865A4 true EP0697865A4 (fr) 1995-09-27
EP0697865A1 EP0697865A1 (fr) 1996-02-28

Family

ID=4154792

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92914551A Withdrawn EP0697865A1 (fr) 1992-06-05 1992-06-05 Polymeres a base d'acide lactique degradables a l'eau et aux rayons ultraviolets

Country Status (5)

Country Link
EP (1) EP0697865A1 (fr)
JP (1) JPH07507827A (fr)
AU (1) AU2234692A (fr)
CA (1) CA2137244A1 (fr)
WO (1) WO1993025202A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661325B1 (fr) * 1993-12-28 2001-10-10 Dainippon Ink And Chemicals, Inc. Procédé pour la préparation continue de copolymère de lactide
JP3391133B2 (ja) 1995-01-27 2003-03-31 株式会社島津製作所 可塑化されたポリ乳酸及びその成型品
EP1215225B9 (fr) * 1999-06-18 2005-03-09 Kanebo Limited Resine d'acide polyactique, articles textiles obtenus a l'aide de cette resine, et procedes de production de ces articles textiles
AU2001261300A1 (en) * 2000-05-09 2001-11-20 Pearl Technology Holdings, Llc Biodegradable fiber optic
JP2005099500A (ja) * 2003-09-25 2005-04-14 Harison Toshiba Lighting Corp レジストおよびリソグラフィー方法
WO2018190769A1 (fr) * 2017-04-14 2018-10-18 Tria Pte. Ltd. Appareil de traitement de déchets mélangés et procédé associé
CN111662725A (zh) * 2020-06-24 2020-09-15 代彦霞 一种降低土壤中迁移态铅离子的修复材料及其制备方法
CN114133293A (zh) * 2021-09-08 2022-03-04 新洋丰农业科技股份有限公司 一种花生专用肥及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2700729A1 (de) * 1976-01-12 1977-07-21 Ethicon Inc Synthetisches, absorbierbares chirurgisches nahtmaterial und verfahren zu seiner herstellung
US4470416A (en) * 1983-06-17 1984-09-11 Ethicon, Inc. Copolymers of lactide and/or glycolide with 1,5-dioxepan-2-one
EP0166596A2 (fr) * 1984-06-26 1986-01-02 Imperial Chemical Industries Plc Copolymères amphiphiles biodégradables
JPH01163135A (ja) * 1987-12-18 1989-06-27 Taki Chem Co Ltd 徐放性基剤の製造方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033938A (en) * 1974-01-21 1977-07-05 American Cyanamid Company Polymers of unsymmetrically substituted 1,4-dioxane-2,5-diones
US4272398A (en) * 1978-08-17 1981-06-09 The United States Of America As Represented By The Secretary Of Agriculture Microencapsulation process
US4767627A (en) * 1985-05-29 1988-08-30 Merck & Co., Inc. Drug delivery device which can be retained in the stomach for a controlled period of time
US4861627A (en) * 1987-05-01 1989-08-29 Massachusetts Institute Of Technology Preparation of multiwall polymeric microcapsules

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2700729A1 (de) * 1976-01-12 1977-07-21 Ethicon Inc Synthetisches, absorbierbares chirurgisches nahtmaterial und verfahren zu seiner herstellung
US4470416A (en) * 1983-06-17 1984-09-11 Ethicon, Inc. Copolymers of lactide and/or glycolide with 1,5-dioxepan-2-one
EP0166596A2 (fr) * 1984-06-26 1986-01-02 Imperial Chemical Industries Plc Copolymères amphiphiles biodégradables
JPH01163135A (ja) * 1987-12-18 1989-06-27 Taki Chem Co Ltd 徐放性基剤の製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 89-225646(31) *
HUFFMAN K.R. ET AL: "Polyesters derived from 1,4-oxathian-2-ones", J. POLYMER SCI. POLYMER CHEM ED., vol. 23, 1985, pages 843 - 849 *
See also references of WO9325202A1 *

Also Published As

Publication number Publication date
AU2234692A (en) 1994-01-04
JPH07507827A (ja) 1995-08-31
WO1993025202A1 (fr) 1993-12-23
EP0697865A1 (fr) 1996-02-28
CA2137244A1 (fr) 1993-12-23

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