WO1999035179A1 - Biologisch abbaubare polyesteramide mit blockartig aufgebauten polyester- und polyamid-segmenten - Google Patents
Biologisch abbaubare polyesteramide mit blockartig aufgebauten polyester- und polyamid-segmenten Download PDFInfo
- Publication number
- WO1999035179A1 WO1999035179A1 PCT/EP1998/008489 EP9808489W WO9935179A1 WO 1999035179 A1 WO1999035179 A1 WO 1999035179A1 EP 9808489 W EP9808489 W EP 9808489W WO 9935179 A1 WO9935179 A1 WO 9935179A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ester
- block
- amide
- acid
- polyester
- Prior art date
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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Definitions
- Compostable aliphatic polyester amides are known (e.g. EP-A 641 817). Compostable aliphatic-aromatic polyester amides are also described
- Block-shaped polyester amides are also known.
- EP-A 717 064, JP 0 430 6229, JP 0 701 0988 and JP 0 715 7557 describe block-like polyesteramides by transesterification-zumamidation reactions of higher molecular weight polyamides with higher molecular weight polyesters. Such reactions are difficult to reproduce, since the degree of the reactions depends very much on the processing conditions. However, the block-like polyesteramides produced by this reaction are not sufficiently biodegradable.
- the object of the present invention is to provide block-like segmented polyester amides which are completely biodegradable and enzymatically degradable.
- the invention therefore relates to block-like polyesteramides with an amide or ester structure, which can be built up from the following monomers: aliphatic dialcohols with preferably 2 to 12 carbon atoms such as ethylene glycol, diethylene glycol, 1, 4-butanediol, 1,3-propanediol, 1,6-hexanediol or cycloaliphatic diols such as cyclohexanedimethanol, and / or
- Oxalic acid, succinic acid, adipic acid, etc. also in the form of their respective esters (methyl, ethyl, etc.), and / or
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and others, also in the form of their respective esters (methyl, ethyl, etc.), and / or
- Hydroxy carboxylic acids with preferably 2 to 12 carbon atoms, and / or lactones such as caprolactone and others, and / or
- Amino alcohols with preferably 2 to 12 carbon atoms such as ethanolamine
- cyclic lactams such as ⁇ -caprolactam or laurolactam etc., and / or
- polyesteramides are obtainable by polycondensation of a hydroxyl-, acid- or ester-terminated ester block and an amino acid- or ester-terminated amide block and wherein the ester content of the polyesteramide is from 20 to 80, preferably 30 to 70% by weight and the amide content is 80 to 20, preferably 70 to
- Caprolactam or AH salt or mixtures thereof with butanediol and / or diethylene glycol and terephthalic acid (ester) and adipic acid (ester) are preferably used in the synthesis of the polyester amides.
- the short blocks made from amide or ester units are produced by known polymer-chemical methods by selecting the monomer composition from the monomers. For example, from 3 mol of adipic acid and 2 mol of hexamethylenediamine, a polyamide block with the molecular weight 598 with acid end groups can be produced.
- polyester block with a molecular weight of 490 from 2 mol of adipic acid and 3 mol of butanediol. If these two blocks are now reacted in a stoichiometric ratio, block-like polyester amides with short amide and ester segments are obtained which do not interfere with the biodegradation.
- suitable catalysts can be used to catalyze the esterification or amidation reaction.
- These include e.g. Titanium compounds for the esterifications or phosphorus compounds for the amidation reactions.
- These catalysts correspond to the state of the art. However, they must not subsequently impair the use of the degradable polymer in the compost and must not interfere with the biodegradability. Therefore, catalysts based on heavy metals such as antimony or lead are used e.g. completely dispensed with.
- the polyester amides produced in this way are completely biodegradable and compostable in accordance with DIN 54 900 and have very good mechanical properties.
- the property of a polymer to be degraded by enzymes is said to be enzymatically degradable.
- the bonds by which the polymer building blocks are linked to one another are split.
- the degradation products are the monomers of the polymer and their oligomers.
- the enzymatic degradation of the polymer leads to a reduction in its molecular weight.
- Degradation differs from biodegradation in that it does not usually lead to naturally occurring metabolic products.
- the degradation is carried out in an aqueous solution, which can be buffered.
- the pH can be between 3 and 11, preferably between 5 and 9 and particularly preferably between 6 and 8.
- the temperature at which the enzymatic degradation is carried out can be between 5 and 95 ° C., preferably between 20 and 70 ° C and particularly preferably between 30 and 50 ° C.
- buffers can be used according to the invention, for example: citrate, acetate, phosphate, formate, carbonate, trishydroxymethylaminomethate, triethanolamine,
- Imidazole oxalate, tartrate, fumarate, maleinate, phthalate, succinate, ethylenediamine and mixtures of several of them.
- Acetate, phosphate and citrate are preferably used as buffers.
- the procedure is such that enzyme and polymer are added to the aqueous solution.
- the biodegradable polymer can be added as a film, foil or granulate. Shaped bodies can be added as a whole or crushed. Coated or bonded materials or materials in which coatings have been applied with biodegradable polymers or bonds have been produced, such as paper or cardboard and coated paper or coated cardboard can be added as a whole or crushed to the enzyme-containing solution.
- aqueous enzyme-containing solution can be applied or sprayed onto the coating to be broken down or the molded body to be broken down by spraying.
- Lipolytic and / or proteolytic enzymes can be used as enzymes.
- lipases For the purposes of this invention, lipases, cutinases,
- the lipolytic enzymes preferably come from microorganisms. In particular, they come from bacteria, fungi or yeast. Furthermore, the lipolytic enzymes can also be of plant or animal origin.
- proteolytic enzymes are referred to as proteolytic enzymes for the purposes of this invention. These preferably originate from bacteria of the genus Bacillus; proteases of the organisms Bacillus alcalophilus and Bacillus licfheniformis are particularly preferred. They can also come from mushrooms or plants.
- the joint use of lipolytic and proteolytic enzymes and lipolytic enzymes of different specificity which can lead to synergistic effects.
- metal ions such as sodium or calcium ions, which accelerate the enzymatic degradability, is according to the invention.
- auxiliaries such as anionic or nonionic surfactants such as sec. Alcohol ethoxylates according to the invention.
- Compostability is the property of a polymeric material to be biodegraded during a composting process.
- standard methods must be used to demonstrate that the polymer material material in a composting system can be biodegraded and high quality compost can be produced (according to DIN 54 900).
- the biodegradation of a material is a process caused by biological activity, which leads to naturally occurring metabolic end products by changing the chemical structure of the material (according to DIN 54 900).
- a polymeric material is biodegradable if all organic components are subject to complete biodegradation, which is determined in standardized processes (according to DIN 54 900).
- the mixtures according to the invention can additionally contain from 0 to 80% by weight of customary additives, for example inorganic fillers or reinforcing materials (for example glass fibers, carbon fibers) and mineral fillers (for example talc, mica, chalk, kaolin, wollastonite, gypsum) , Quartz, dolomite, etc.)
- customary additives for example inorganic fillers or reinforcing materials (for example glass fibers, carbon fibers) and mineral fillers (for example talc, mica, chalk, kaolin, wollastonite, gypsum) , Quartz, dolomite, etc.)
- UV stabilizers antioxidants, pigments, dyes, nucleating agents, crystallization accelerators and retarders, flow aids, lubricants, mold release agents, flame retardants.
- the polyester amides according to the invention can furthermore contain 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight, in particular 0.1 to 1% by weight, of branching agents.
- branching agents can be, for example, trifunctional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid or tri- or tetrafunctional hydroxycarboxylic acids. Examples
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000527574A JP2002500252A (ja) | 1998-01-10 | 1998-12-29 | ポリエステルセグメントとポリアミドセグメントをブロック型で有する生分解性ポリエステルアミド |
AU24175/99A AU2417599A (en) | 1998-01-10 | 1998-12-29 | Biodegradable polyester amides with block-shaped polyester and polyamide segments |
EP98966684A EP1045874A1 (de) | 1998-01-10 | 1998-12-29 | Biologisch abbaubare polyesteramide mit blockartig aufgebauten polyester- und polyamid-segmenten |
CA 2317747 CA2317747A1 (en) | 1998-01-10 | 1998-12-29 | Biodegradable polyester amides with block-shaped polyester and polyamide segments |
KR1020007007562A KR20010033975A (ko) | 1998-01-10 | 1998-12-29 | 폴리에스테르 세그먼트 및 폴리아미드 세그먼트를 갖는블록형 생분해성 폴리에스테르 아미드 |
NO20003469A NO20003469L (no) | 1998-01-10 | 2000-07-05 | Biologisk nedbrytbare polyesteramider med blokkformet oppbygde polyester- og polyamidsegmenter |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1998100698 DE19800698A1 (de) | 1998-01-10 | 1998-01-10 | Biologisch abbaubare Polyesteramide mit blockartig aufgebauten Polyester- und Polyamid-Segmenten |
DE19800698.5 | 1998-01-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999035179A1 true WO1999035179A1 (de) | 1999-07-15 |
Family
ID=7854307
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/008489 WO1999035179A1 (de) | 1998-01-10 | 1998-12-29 | Biologisch abbaubare polyesteramide mit blockartig aufgebauten polyester- und polyamid-segmenten |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1045874A1 (de) |
JP (1) | JP2002500252A (de) |
KR (1) | KR20010033975A (de) |
CN (1) | CN1285853A (de) |
AU (1) | AU2417599A (de) |
CA (1) | CA2317747A1 (de) |
DE (1) | DE19800698A1 (de) |
NO (1) | NO20003469L (de) |
WO (1) | WO1999035179A1 (de) |
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WO2001094468A2 (de) * | 2000-06-06 | 2001-12-13 | Bayer Aktiengesellschaft | Biologisch abbaubare formmasse |
WO2007099397A2 (en) * | 2005-06-16 | 2007-09-07 | Dow Global Technologies Inc. | Aliphatic polyester-amide compositions and a process for producing the same |
EP3228651A1 (de) | 2016-04-08 | 2017-10-11 | Nanjing Tech University | Verfahren zur herstellung von polyesteramiden durch organische katalyse |
CN107383368A (zh) * | 2017-08-18 | 2017-11-24 | 浙江心源科技有限公司 | 一种含有酰胺基聚酯多元醇及在制备聚氨酯上的应用 |
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WO2023023446A1 (en) | 2021-08-19 | 2023-02-23 | Solutia Inc. | High molecular weight polyesteramides |
Citations (4)
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JPS54119594A (en) * | 1978-03-09 | 1979-09-17 | Agency Of Ind Science & Technol | Biodegradable film |
JPH0710988A (ja) * | 1993-06-24 | 1995-01-13 | Agency Of Ind Science & Technol | 生分解性ポリエステルアミド共重合体の製造方法 |
US5446109A (en) * | 1993-02-23 | 1995-08-29 | Teijin Limited | Polyamide/aliphatic polyester block copolymer, process for the production thereof, and blend containing the same |
EP0717064A1 (de) * | 1994-12-16 | 1996-06-19 | Ems-Inventa Ag | Teilkristalline Block-Copolyesterpolyamide |
-
1998
- 1998-01-10 DE DE1998100698 patent/DE19800698A1/de not_active Withdrawn
- 1998-12-29 CN CN98813012A patent/CN1285853A/zh active Pending
- 1998-12-29 JP JP2000527574A patent/JP2002500252A/ja active Pending
- 1998-12-29 KR KR1020007007562A patent/KR20010033975A/ko not_active Application Discontinuation
- 1998-12-29 EP EP98966684A patent/EP1045874A1/de not_active Ceased
- 1998-12-29 AU AU24175/99A patent/AU2417599A/en not_active Abandoned
- 1998-12-29 WO PCT/EP1998/008489 patent/WO1999035179A1/de not_active Application Discontinuation
- 1998-12-29 CA CA 2317747 patent/CA2317747A1/en not_active Abandoned
-
2000
- 2000-07-05 NO NO20003469A patent/NO20003469L/no not_active Application Discontinuation
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JPS54119594A (en) * | 1978-03-09 | 1979-09-17 | Agency Of Ind Science & Technol | Biodegradable film |
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JPH0710988A (ja) * | 1993-06-24 | 1995-01-13 | Agency Of Ind Science & Technol | 生分解性ポリエステルアミド共重合体の製造方法 |
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DATABASE WPI Section Ch Week 9512, Derwent World Patents Index; Class A23, AN 95-085494, XP002101374 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001094468A2 (de) * | 2000-06-06 | 2001-12-13 | Bayer Aktiengesellschaft | Biologisch abbaubare formmasse |
WO2001094468A3 (de) * | 2000-06-06 | 2002-05-02 | Bayer Ag | Biologisch abbaubare formmasse |
WO2007099397A2 (en) * | 2005-06-16 | 2007-09-07 | Dow Global Technologies Inc. | Aliphatic polyester-amide compositions and a process for producing the same |
WO2007099397A3 (en) * | 2005-06-16 | 2007-11-29 | Dow Global Technologies Inc | Aliphatic polyester-amide compositions and a process for producing the same |
US8080617B2 (en) | 2005-06-16 | 2011-12-20 | Dow Global Technologies Llc | Aliphatic polyester-amide compositions and a process for producing the same |
EP3228651A1 (de) | 2016-04-08 | 2017-10-11 | Nanjing Tech University | Verfahren zur herstellung von polyesteramiden durch organische katalyse |
CN107383368A (zh) * | 2017-08-18 | 2017-11-24 | 浙江心源科技有限公司 | 一种含有酰胺基聚酯多元醇及在制备聚氨酯上的应用 |
Also Published As
Publication number | Publication date |
---|---|
AU2417599A (en) | 1999-07-26 |
CA2317747A1 (en) | 1999-07-15 |
EP1045874A1 (de) | 2000-10-25 |
NO20003469D0 (no) | 2000-07-05 |
DE19800698A1 (de) | 1999-07-15 |
CN1285853A (zh) | 2001-02-28 |
JP2002500252A (ja) | 2002-01-08 |
NO20003469L (no) | 2000-07-05 |
KR20010033975A (ko) | 2001-04-25 |
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