EP0986596A1 - Bioabbaubare polyesterurethane, verfahren zu ihrer herstellung sowie ihre verwendung - Google Patents

Bioabbaubare polyesterurethane, verfahren zu ihrer herstellung sowie ihre verwendung

Info

Publication number
EP0986596A1
EP0986596A1 EP98936105A EP98936105A EP0986596A1 EP 0986596 A1 EP0986596 A1 EP 0986596A1 EP 98936105 A EP98936105 A EP 98936105A EP 98936105 A EP98936105 A EP 98936105A EP 0986596 A1 EP0986596 A1 EP 0986596A1
Authority
EP
European Patent Office
Prior art keywords
biodegradable
group
polyester urethanes
unsubstituted
substituted
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.)
Ceased
Application number
EP98936105A
Other languages
German (de)
English (en)
French (fr)
Inventor
Yoon Jick Lee
Hartmut Seliger
Erwin Happ
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.)
Elbe Technologies Ltd
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP0986596A1 publication Critical patent/EP0986596A1/de
Ceased 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31591—Next to cellulosic

Definitions

  • plastics have only been manufactured on a large scale since around 1930, they have become indispensable for modern life. With the rapidly expanding production and the increasing consumption of plastic materials, problems arise. In particular, the focus is on environmental pollution due to plastic waste. From known statistics it can be seen that the proportion of plastic waste is appallingly high: about 18% of the volume of urban waste goes at the expense of plastic materials, with about half of this going to packaging waste. The disposal of plastic materials is still extremely problematic since, for example, the combustion of such materials can produce highly toxic dioxins. About 96% of all plastic waste in the United States ends up in landfills, 3% is incinerated, and only about 1% of it is recycled.
  • EP 0 696 605 AI is a biodegradable multiblock polymer produced by lithium linear polycondensation of two ⁇ , ⁇ -dihydroxypolyesters / - ethers with diisocyanate, diacid halide or phosgene.
  • the ⁇ , ⁇ -dihydroxy polyesters are obtained by transesterification of poly- (R) - (3) -hydroxybutyric acid in the form of Biopol *, so they are broken down by means of transesterification catalysts with the ester bonds broken down.
  • Biopol ® is commercially available and is obtained as a bacterial product.
  • Other ⁇ , ⁇ -dihydroxy polyesters are produced by ring-opening polymerization of cyclic esters or lactones, for example ⁇ -caprolactone with aliphatic diols.
  • the microstructure of the macrodiols produced depends on the monomer distribution, whereby only stereospecific structures are produced.
  • the macrodiol is prepared with and without a catalyst, using SnO (Bu) 2 or dibutyltin dilaurate at temperatures of 100 to 160 ° C.
  • Polyurethanes are also produced by reacting the macrodiols with diisocyanate such as, for example, 1,6-hexamethylene diisocyanate, the block polymers of macrodiol and diisocyanate always having valerate segments in the end product, unlike in the invention.
  • diisocyanate such as, for example, 1,6-hexamethylene diisocyanate
  • biocompatible or biodegradable polymers are used in EP 0 696 605 AI as medical implants; therefore high technical requirements were placed on the material.
  • a particular disadvantage here is that both the starting and the end products are stereospecific, ie only certain configurations (for example, the bacterial product has only the R configuration).
  • bacterial polymers are usually very brittle due to their very regular crystal structure, and are therefore light fragile.
  • the polymeric products of EP 0 696 605 AI are somewhat softer, but some of them still show brittle behavior.
  • the bacterial starting products are also relatively expensive.
  • these block polymers show different discolorations, ie, like their bacterial starting products, are generally milk-colored, which can give them an unsightly appearance.
  • the object is achieved according to the invention by providing biodegradable, linear polyester urethanes, the linear polyester urethanes being composed of units of the general formula (I): (I)
  • R is an unsubstituted or substituted, saturated or unsaturated (C 1 -C 10 ) hydrocarbon group, preferably methyl, ethyl or propyl, and
  • substituents from group A consisting of OH, NH 2 , halogen, pseudohalogen, (C ⁇ -C ⁇ ) alkyl, (C j -C ⁇ ) alkoxy, alyl, vinyl, benzyl, unsubstituted or substituted aryl , such as phenyl or naphthyl, alkenyl, alkynyl, amide, (C j - C 6 ) dialkylamino, unsubstituted or substituted (C 3 - C s ) cycloalkyl, and the aryl or cycloalkyl substituents OH, NH 2 , halogen, pseudohalogen, (C 1 -C 10 ) alkyl, (C ⁇ C ⁇ ) alkoxy, amide, (C x -C 6 ) dialkylamino, alkenyl, alkynyl, allyl and / or vinyl;
  • R is selected from the group consisting of:
  • R and R are, independently of one another, identical or different and from the group consisting of H, OH, NH 2 , -OR, where R is as defined above, halogen, pseudohalogen, benzyl, allyl, vinyl, unsubstituted or substituted aryl, such as phenyl or naphthyl or the like, (C 1 -C 10 ) alkyl, alkenyl, alkynyl, amide, (C ⁇ C g ) dialkylamino, unsubstituted or substituted (C 3 -C 8 ) cycloalkyl with optionally at least one heteroatom, unsubstituted or substituted five-, six- or seven-membered aromatic or heteroaromatic with at least one heteroatom, where the heteroatom is 0, S or N, are selected and the substituents are taken from group A;
  • the invention further relates to biodegradable crosslinked polyester urethanes which result from the linear polyester urethanes with units of the formula (I) in that they are crosslinked by diisocyanate bridges and contain fragments of the general formula (II):
  • R, R, R, R, R and x, y, z, 1 and m are as defined above.
  • the physical, chemical and biological properties of the polyester urethane can be set in a targeted manner; in particular, its biodegradability rate can be varied, since the degree of crosslinking means that the biodegradation takes place more slowly.
  • the polyester urethanes according to the invention are transparent and also elastic.
  • the deformability of the polyester urethanes according to the invention can be varied continuously from the linear to a partially cross-linked to a fully cross-linked product.
  • highly elastic, easily deformable to gui-like and less deformable, rubber-like polymers can be produced in a targeted manner.
  • linear polyester urethanes can be processed thermoplastically.
  • the crosslinked polyester urethanes cannot be processed thermoplastically, but can be brought into the desired shape, for example by injection molding and, if appropriate, further processing steps, such as cutting or the like.
  • the linear and cross-linked polymers are soluble in organic solvents, but not in water. They are also completely transparent.
  • the invention also relates to a process for producing biodegradable polyester urethanes with the following steps:
  • R is an unsubstituted or substituted, saturated or unsaturated (C 1 -C 10 ) hydrocarbon group, preferably methyl, ethyl or propyl, and
  • Aryl such as phenyl or naphthyl, alkenyl, alkynyl, amide, (C : - C 6 ) -dialkylamino, unsubstituted or substituted (C 3 - C ") -cycloalkyl, and the aryl or cycloalkyl-substituents OH, NH 2 , halogen, pseudohalogen, (C 1 -C 10 ) alkyl, (C j -C ⁇ ) alkoxy, amide, (C x -C 6 ) dialkylamino, alkenyl, alkynyl, allyl and / or vinyl;
  • R and R are as defined above;
  • R, R and R are as defined above and 0 ⁇ x + y ⁇ 60 and 2 ⁇ 1 + m ⁇ 60;
  • aliphatic diols such as ethylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanedi
  • Lactones which may be mentioned as examples are: ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone or an N-protected D, L-serine lactone, it being understood that any protective group X known to the person skilled in the art can of course be used here .
  • the lactones can be used not only unsubstituted but also mono- or poly-substituted, the substituents being selected from group A defined above.
  • the specified temperature and time intervals of the individual reaction stages are to be understood as ranges from which the appropriate parameters can be selected depending on the selected pressure conditions and reaction products of the reaction to be carried out.
  • tin complex can be used as the tin catalyst to be used, such as, for example, dibutyltin oxide, di- butyltin dilaurate or the like.
  • tin catalyst any tin complex can be used, such as, for example, dibutyltin oxide, di- butyltin dilaurate or the like.
  • the compound with the following chemical formula (E) can advantageously be used:
  • the tin catalyst complex of steps (ii) and (iii) is the dimer of 2,2-di-n-butyl-1,3,2-dioxastannolane with the following chemical formula (F):
  • Step (ii) for the preparation of the oligodiol is carried out in the process according to the invention with a tin catalyst. Without a catalyst, the transesterification reaction works in this step, i.e. the splitting off of ethanol, practically not.
  • step (iii) for the preparation of the macrodiol can be carried out both with and without a tin catalyst.
  • the step (iii) reaction can be continued directly after the step (ii) reaction without purification of the product (oligodiol) formed. Since the step (ii) product then still contains the catalyst, step (iii) is carried out automatically with the catalyst.
  • the reaction of step (iii) also works without a catalyst.
  • step (ii) product After purification of the oligodiol (step (ii) product), e.g. precipitated twice from a chloroform solution with cyclohexane, the conversion to macrodiol then takes place, in which case the reaction proceeds more slowly.
  • the polyester urethanes according to the invention are obtained by reaction with at least one compound having at least two isocyanate groups.
  • the diisocyanates which can be used in the context of the invention are known to the person skilled in the art; Examples include: pentamethylene-1, 5-diisocyanate, hexamethylene-1, 6-diisocyanate, hepta-methylene-1, 7-diisocyanate, 2,2, 4-trimethylhexamethylene diisocyanate or any polydiisocyanate which meets the above requirements fulfill.
  • the diisocyanates can also be used appropriately substituted, where the substituents from the group, H, OH, NH 2 , -OR, where R is as defined above, halogen, pseudohalogen, benzyl, allyl, vinyl, unsubstituted or substituted aryl, such as phenyl or naphthyl, (C ⁇ C ⁇ ) alkyl, alkenyl, alkynyl, amide, (C ⁇ C -di- alkylamino, unsubstituted or substituted (C 3 -C 8 ) cycloalkyl with optionally at least one heteroatom, unsubstituted or substituted five-, six- or seven-membered aromatic or heteroaromatic with at least one heteroatom, where the heteroatom is 0, S or N, and the substituents are selected from group A.
  • R is as defined above, halogen, pseudohalogen, benzyl, allyl, vinyl, unsubstituted or substituted
  • cycloalkyl substituents are cyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl, etc.
  • Heterocycles which are suitable according to the invention are, for example, furyl, thienyl, pyrryl, pyridyl, morpholino, pyrazolyl, imidazolyl, pyrimidinyl, pyrazinyl, tetrahydrofuryl, tetr ahydrothienyl and similar compounds.
  • crosslinked polyester urethanes by using equimolar amounts of a compound with at least two isocyanate groups, linear polyester urethanes and through an excess of a compound with at least two isocyanate groups with diisocyanate bridges, crosslinked polyester urethanes can be are formed, which show different properties depending on the degree of cross-linking set.
  • the polyester urethane of the invention is generally not degradable as quickly as the block polymer from EP 0 696 605 A1, which is produced with bacteriological starting products and which degrades very quickly. This is of particular advantage in long-term applications; moreover, the products according to the invention produced are not stereospecific.
  • polyester urethanes are impermeable to water and water vapor, and are aroma and greaseproof.
  • a particularly important sector in which the polyester urethanes according to the invention can be used is galenics.
  • the dosage form of a drug influences the type, duration, direction and strength of the action of the drug.
  • the polyester urethanes the biodegradability of which, for example, can be lengthened or shortened in the cross-linked product, can therefore be used for oral or rectal administration.
  • Powders, granules, tablets, pills, lozenges, dragees, capsules or suppositories come into question here, the drug contained therein being intended to be released with a delay within a certain period of time.
  • the connections according to the invention are of particular importance, particularly for implants of all types or also for sutures which are to dissolve over time. It goes without saying that It is possible to manufacture common items such as bags, bags, cans, bottles, book covers or the like.
  • the desired properties can also be achieved by adjusting the degree of crosslinking.
  • hard or soft rubber-like polymers are obtained which are versatile, for example usable as auxiliaries or thickeners, but are always biodegradable.
  • the crosslinked polyester urethanes can be designed such that they can be used, for example, as tires for cars, bicycles or the like, which, like all the other polymers according to the invention, are even completely transparent.
  • the crosslinked polyester urethanes according to the invention can also be used as adhesives.
  • This type of all-purpose adhesive is solvent-free, completely toxicologically safe and completely biodegradable.
  • Adhesive tapes can be produced here in a simple manner with the polyester urethanes according to the invention. These also have an optically good appearance, since both the adhesive layer and the coated layer - both of which can be produced from the material according to the invention - are transparent.
  • the polyester urethanes according to the invention can be added to any material in any mixing ratio, for example to impart hydrophobic properties and / or to obtain biodegradable polymer blends with advantageous properties.
  • Such polymer blends can contain the biodegradable linear and / or cross-linked polyester urethanes in an appropriate amount, depending on the field of application, it being possible for additional biodegradable polymers to be incorporated.
  • Biodegradable polymers that can be used are, for example, bacterially produced poly-3-hydroxyalkanoates. In mixtures with starch and / or cellulose powder and / or biodegradable compound materials, so-called composite materials can also be obtained which have the advantages of the compounds according to the invention already described.
  • polymer blends according to the invention can be used in the same areas and applications as have already been described for the linear or crosslinked polyester urethanes, which is why further explanations for avoiding repetitions can be omitted here.
  • biodegradable cross-linked polyester urethanes for example with the building blocks 3-hydroxybutyric acid / ⁇ -caprolactone / dianhydro-D-glucite / hexamethylene diisocyanate, representative of all other cross-linked polyester urethanes according to the invention, were represented according to the following general reaction scheme:
  • FIG. 1 An IR film spectrum of a crosslinked polyester urethane according to the invention is shown as an example in FIG. It is a cross-linked polyester urethane from the building blocks 3-hydroxybutyric acid / ⁇ -caprolactone / dianhydro-D-glucite, cross-linked with 1, 6-hexamethylene diisocyanate.
  • the reaction product was dissolved in chloroform and 5 to 10 times the amount of the precipitant (cyclohexane, diethyl ether) was precipitated.
  • the precipitant cyclohexane, diethyl ether
  • Tacky crosslinked polymer with a low degree of crosslinking was swollen in a small amount of acetone or chloroform and applied thinly to the polyester urethane film according to Example 4 or paper. After the solvent has evaporated, the adhesive adheres well to the film or paper, just like known adhesive tapes.
  • Solvent was evaporated at room temperature. The result was a slightly beige, largely transparent, elastically deformable film.
  • Example 7 Manufacture of a composite material

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Biological Depolymerization Polymers (AREA)
EP98936105A 1997-06-06 1998-06-06 Bioabbaubare polyesterurethane, verfahren zu ihrer herstellung sowie ihre verwendung Ceased EP0986596A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19723895A DE19723895C2 (de) 1997-06-06 1997-06-06 Bioabbaubare Polyesterurethane, Verfahren zu ihrer Herstellung sowie ihre Verwendung
DE19723895 1997-06-06
PCT/DE1998/001539 WO1998055527A1 (de) 1997-06-06 1998-06-06 Bioabbaubare polyesterurethane, verfahren zu ihrer herstellung sowie ihre verwendung

Publications (1)

Publication Number Publication Date
EP0986596A1 true EP0986596A1 (de) 2000-03-22

Family

ID=7831682

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98936105A Ceased EP0986596A1 (de) 1997-06-06 1998-06-06 Bioabbaubare polyesterurethane, verfahren zu ihrer herstellung sowie ihre verwendung

Country Status (9)

Country Link
US (1) US6228969B1 (ja)
EP (1) EP0986596A1 (ja)
JP (1) JP2002504939A (ja)
KR (1) KR20010013503A (ja)
AU (1) AU8529998A (ja)
CA (1) CA2292564A1 (ja)
DE (1) DE19723895C2 (ja)
IL (1) IL133328A0 (ja)
WO (1) WO1998055527A1 (ja)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6423850B1 (en) * 1999-06-18 2002-07-23 E.I. Du Pont De Nemours And Company Preparation and use of gamma-butyrolactones as cross-linking agents
WO2001019887A1 (fr) * 1999-09-10 2001-03-22 Mitsui Chemicals, Inc. Resine de polyuretane biodegradable
EP1301551A2 (en) 2000-07-14 2003-04-16 Metabolix, Inc. Polyurethanes obtained from hydroxyalkanoates and isocyanates
KR100396937B1 (ko) * 2000-07-29 2003-09-02 정효식 생분해성 및 가수분해성을 갖는 수지 조성물
US6514193B2 (en) * 2000-11-16 2003-02-04 Microspherix Llc Method of administering a therapeutically active substance
US7776310B2 (en) 2000-11-16 2010-08-17 Microspherix Llc Flexible and/or elastic brachytherapy seed or strand
KR100401184B1 (ko) * 2001-01-18 2003-10-10 바이오리플라 주식회사 폴리우레탄 생붕괴성 캡슐 및 그 제조방법
KR20020065180A (ko) * 2001-02-06 2002-08-13 엘베테크놀로지 주식회사 생분해성 폴리에스테르 우레탄 및 그의 제조방법
KR20030000345A (ko) * 2001-06-23 2003-01-06 엘베테크놀로지 주식회사 생분해성 막대풍선
JP2003034734A (ja) * 2001-07-23 2003-02-07 Sony Corp 生分解性樹脂の分解速度をコントロールする方法および分解速度がコントロールされた生分解性樹脂
GB0207345D0 (en) * 2002-03-28 2002-05-08 Unichema Chemie Bv Polyurethane
DE102004027673B3 (de) * 2004-06-07 2006-01-19 Universität Ulm Biodegradables Verbundsystem und dessen Verwendung sowie Verfahren zur Herstellung eines bioabbaubaren Block-copolyesterurethans
US7736293B2 (en) * 2005-07-22 2010-06-15 Biocompatibles Uk Limited Implants for use in brachytherapy and other radiation therapy that resist migration and rotation
US8187159B2 (en) 2005-07-22 2012-05-29 Biocompatibles, UK Therapeutic member including a rail used in brachytherapy and other radiation therapy
CA2843110A1 (en) * 2005-09-13 2007-03-22 Dow Global Technologies Llc Distannoxane catalysts for silane crosslinking and condensation reactions
JP5386798B2 (ja) * 2007-06-22 2014-01-15 東ソー株式会社 ポリ３−ヒドロキシブチレート系複合体
US8182647B2 (en) 2007-07-23 2012-05-22 Cohera Medical, Inc. Hydrophilic biodegradable adhesives
JP4539688B2 (ja) * 2007-07-24 2010-09-08 Ｂａｓｆコーティングスジャパン株式会社 熱硬化性塗料組成物を改質する反応性希釈剤及びそれを用いた塗料組成物
US7923486B2 (en) * 2007-10-04 2011-04-12 Board Of Regents, The University Of Texas System Bio-polymer and scaffold-sheet method for tissue engineering
DE102007057768A1 (de) * 2007-11-30 2009-06-04 Universität Ulm Biodegradables Verbundsystem und dessen Verwendung
AU2014268199B2 (en) * 2008-10-11 2015-11-26 Rutgers, The State University Of New Jersey Biocompatible Polymers for Medical Devices
WO2010042918A1 (en) * 2008-10-11 2010-04-15 Rutgers, The State University Of New Jersey Biocompatible polymers for medical devices
US9080015B2 (en) 2009-07-31 2015-07-14 Rutgers, The State University Of New Jersey Biocompatible polymers for medical devices
CA2777234C (en) 2009-10-11 2019-02-26 Rutgers, The State University Of New Jersey Biocompatible polymers for medical devices
JP5459111B2 (ja) * 2010-07-02 2014-04-02 東ソー株式会社 樹脂組成物、該樹脂組成物の製造方法及び射出成形体
JP5993862B2 (ja) * 2010-11-15 2016-09-14 コヘラ メディカル インコーポレイテッド 感圧性接着特性を有する生分解性組成物
US11472918B2 (en) 2012-02-03 2022-10-18 Rutgers, The State University Of New Jersey Polymeric biomaterials derived from phenolic monomers and their medical uses
CA3069030C (en) 2012-02-03 2021-11-16 Rutgers, The State University Of New Jersey Polymeric biomaterials derived from phenolic monomers and their medical uses
WO2014184792A1 (en) * 2013-05-14 2014-11-20 Eco Sports Llc. Controllably degradable thermoplastic polyurethane and overgrips made therefrom
US10774030B2 (en) 2014-12-23 2020-09-15 Rutgers, The State University Of New Jersey Polymeric biomaterials derived from phenolic monomers and their medical uses
EP3237487B1 (en) 2014-12-23 2021-02-17 Rutgers, the State University of New Jersey Biocompatible iodinated diphenol monomers and polymers
CN114276512A (zh) * 2022-01-14 2022-04-05 南京先进生物材料与过程装备研究院有限公司 一种可回收聚酯型聚氨酯及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3079716B2 (ja) * 1991-11-26 2000-08-21 昭和高分子株式会社 ウレタン結合を含むポリラクタイドの製造方法
FI97726C (fi) * 1994-07-07 1997-02-10 Alko Yhtioet Oy Sulatyöstettävä polyesteriuretaani ja menetelmä sen valmistamiseksi
ATE196486T1 (de) * 1994-08-10 2000-10-15 Peter Neuenschwander Biokompatibles blockcopolymer
EP0723983B1 (en) * 1995-01-26 2001-08-08 Takasago International Corporation Biodegradable composition
DE19508627A1 (de) * 1995-03-10 1996-09-12 Buna Sow Leuna Olefinverb Gmbh Verfahren zur Herstellung biologisch abbaubarer Polyurethanester

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9855527A1 *

Also Published As

Publication number Publication date
US6228969B1 (en) 2001-05-08
CA2292564A1 (en) 1998-12-10
DE19723895A1 (de) 1998-12-10
KR20010013503A (ko) 2001-02-26
JP2002504939A (ja) 2002-02-12
IL133328A0 (en) 2001-04-30
WO1998055527A1 (de) 1998-12-10
DE19723895C2 (de) 1999-06-02
AU8529998A (en) 1998-12-21

Similar Documents

Publication Publication Date Title
DE19723895C2 (de) Bioabbaubare Polyesterurethane, Verfahren zu ihrer Herstellung sowie ihre Verwendung
EP1074570B1 (de) Biologisch abbaubare Polymere, Verfahren zu deren Herstellung sowie deren Verwendung zur Herstellung bioabbaubarer Formkörper
EP0802939B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
EP0802941B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
EP0927212B1 (de) Biologisch abbaubare polyester
EP0792310B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
EP0802940B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
EP2268702B1 (de) Verfahren zur kontinuierlichen herstellung von biologisch abbaubaren polyestern
DE60029289T2 (de) Biologisch abbaubare Polyesterharzzusammensetzung und ihre Verwendung
EP0802942B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
EP0792311B1 (de) Biologisch abbaubare polymere, verfahren zu deren herstellung sowie deren verwendung zur herstellung bioabbaubarer formkörper
EP3713987A1 (de) Kontinuierliches verfahren zur herstellung eines aliphatischen polyesters
DE19753534A1 (de) Schnell kristallisierende, biologisch abbaubare Polyesteramide
EP0828788A1 (de) Stärke und polyurethane enthaltende polymerblends
DE4444948C2 (de) Teilkristalline Block-Copolyesterpolyamide und Verwendung
DE4235135A1 (de) Verwendung thermoplastischer Poly(ester-urethane) als kompostierbare Kunststoffe
DE60106591T2 (de) Herstellungsverfahren für aliphatische polyestercarbonate
EP2247637A1 (de) Thermoplastisches polyurethan mit verminderter belagsbildung
EP2217635B1 (de) Biodegradables verbundsystem und dessen verwendung
DE19508627A1 (de) Verfahren zur Herstellung biologisch abbaubarer Polyurethanester
EP0894118A1 (de) Kompostierbarer wasserfester überzug
DE3236521A1 (de) Thermoplastische formmassen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20000107

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LEE, YOON JICK

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ELBE TECHNOLOGIES LTD

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20010323

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20010921