EP0894113A2 - Produits alveolaires compostables et pouvant subir un traitement thermoplastique - Google Patents

Produits alveolaires compostables et pouvant subir un traitement thermoplastique

Info

Publication number
EP0894113A2
EP0894113A2 EP97916447A EP97916447A EP0894113A2 EP 0894113 A2 EP0894113 A2 EP 0894113A2 EP 97916447 A EP97916447 A EP 97916447A EP 97916447 A EP97916447 A EP 97916447A EP 0894113 A2 EP0894113 A2 EP 0894113A2
Authority
EP
European Patent Office
Prior art keywords
acids
bifunctional
aliphatic
optionally
alcohols
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
EP97916447A
Other languages
German (de)
English (en)
Inventor
Ernst Grigat
Hanns Peter MÜLLER
Wolfgang Schulz-Schlitte
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of EP0894113A2 publication Critical patent/EP0894113A2/fr
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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • 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
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • 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
    • C08G2101/00—Manufacture of cellular products
    • 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

Definitions

  • thermoplastically processable plastics are known (see Rompp chemistry lexicon, keyword “foam plastics” Vol 5, 9 edition, Thieme Verlag
  • blowing agents see Rompp chemistry lexicon, keyword “blowing agent”, Vol 1, 9 edition, Thieme Verlag 1990.
  • the invention thus relates to foamed moldings produced from polymers selected from the group of the aliphatic or partially aromatic
  • Polyesters thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates and aliphatic polyester amides, which are mixed with blowing agents and processed thermoplastic
  • the invention also relates to a method for producing the objects according to the invention
  • the invention furthermore relates to the use of certain completely compostable, water- and steam-resistant polymers for the production of foamed moldings
  • A) aliphatic bifunctional alcohols preferably linear C 2 -C 10 dialcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably with C 5 -C 6 C atoms in the cycloaliphatic ring like for example cyclohexanedimethanol and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 - C ] 2 -
  • Alkyl diols such as, for example, neopentyl glycol and, if appropriate, small amounts of high-functional alcohols, preferably C 3 -C 12 -alkyl polyols such as, for example, 1,2,3-propanetriol or trimethylol propane, and from aliphatic bifunctional acids, preferably C 2 -C 12 -alkyl dicarboxylic acids such as and preferably succinic acid or
  • Adipic acid and / or optionally aromatic bifunctional acids such as, for example, terephthalic acid or isophthalic acid or naphthandedicarboxylic acid and additionally optionally small amounts of higher-functional acids such as trimellitic acid or
  • acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters,
  • C) aliphatic bifunctional alcohols preferably linear C 2 -C 10 dialcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably with a C 5 -C 6 cycloaliphatic ring such as for example ⁇ as cyclohexanedimethanol and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 -C 12 -alkyldiols such as neopentyl glycol and additionally optionally small amounts of high-functional alcohols, preferably C 3 -C ] 2
  • aromatic acids make up no more than 50% by weight, based on all acids
  • acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters,
  • ethanediol hexanediol, butanediol, cyclohexanedimethanol, and / or optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or highly functional amines and / or amino alcohols with preferably 2 to 12 C atoms of the alkyl chain, e.g. ethylenediamine or aminoethanol, and / or optionally further modified amines or alcohols such as, for example, ethylenediaminoethanesulfonic acid, as the free acid or as a salt,
  • ester content C) and / or D) at least 75 wt .-%, based on the
  • aliphatic bifunctional alcohols preferably linear C 2 -C 10 dialcohols such as, for example, ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms in the cycloaliphatic ring, such as cyclohexanedimethanol and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 -C 12 -alkyldiols such as neopentylglycol and additionally optionally small amounts of high-functional alcohols, preferably C 3 -C 10 dial
  • G from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid or
  • aromatic acids make up no more than 50% by weight, based on all acids
  • acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters,
  • H a carbo fraction which is prepared from aromatic bifunctional phenols, preferably bisphenol-A, and carbonate donors, for example phosgene, or a carbonate fraction which is obtained from aliphatic carboxylic esters or their derivatives such as chlorocarbonic acid esters or aliphatic carboxylic acids or their derivatives like for example
  • Salts and carbonate donors for example phosgene
  • ester fraction F) and / or G) must be at least 70% by weight, based on the sum of F), G) and H),
  • Dialcohols such as ethanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms such as cyclohexanedimethanol and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol,
  • C 12 alkyl polyols such as 1,2,3-propanetriol or trimethylol propane and from aliphatic bifunctional acids, preferably 2 to 12 carbon atoms in the alkyl chain such as and preferably succinic acid or adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid or isophthalic acidic or naphthalenedicarboxylic acid and, if appropriate, small amounts of highly functional acids such as trimellitic acid or
  • K from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the carbon chain, for example hydroxybutyric acid or hydroxyvaleric acid or lactic acid, or their derivatives, for example ⁇ -caprolactone or dilactide,
  • acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters,
  • ester content I) and / or K) must be at least 30% by weight, based on the sum of I), K), L) and M).
  • the proportion by weight of the ester structures is preferably between 30 and 70%, the proportion of the amide structures between 70 and 30%.
  • the biodegradable polyesteramides according to the invention can be synthesized either by the "polyamide method” by stoichiometric mixing of the starting components, if appropriate with the addition of water and subsequent removal of water from the reaction mixture, or by the “polyester method” by stoichiometric mixing of the starting components and additions of an excess of diol with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In this second case, the excess diol is distilled off in addition to water. Preference is given to synthesis by the "polyester method” described.
  • polyesters, polyester urethanes, polyester carbonates or preferably polyester amides according to the invention can furthermore 0.1 to 5 wt .-%, preferably 0.1 to
  • branching 1 wt .-% of branching contain.
  • These branchers can e.g. trifunctional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid.
  • the branching agents increase the melt viscosity of the polyester amides according to the invention to such an extent that extrusion blow molding with these polymers is possible. This does not hinder the biodegradation of these materials.
  • the polycondensation can also be accelerated by using known catalysts. Both the known phosphorus compounds that accelerate polyamide synthesis and acidic or organometallic catalysts for the esterification, as well as combinations of the two, are used
  • polycondensation to polyester amides can be influenced by the use of lysine, lysine derivatives or other amidic branching products such as aminoethylaminoethanol, which both the condensate Accelerate sation as well as lead to branched products (see for example DE 38 31 709).
  • the fully compostable polyester urethanes, polyesters, polyester carbonates and polyester amides according to the invention can be equipped with fillers and reinforcing materials and / or with processing aids such as, for example, nucleation aids, mold release aids or stabilizers, it being important to ensure that the complete compostability is not impaired or the remaining ones Substances, such as mineral aids, are harmless in the compost.
  • processing aids such as, for example, nucleation aids, mold release aids or stabilizers
  • Fillers and reinforcing materials suitable according to the invention can be minerals such as kaolin, chalk, gypsum ( ⁇ - or ⁇ -modification), lime or talc or natural substances such as starch or modified starch, cellulose or cellulose derivatives or cellulose products, wood flour or natural fibers such as hemp, Flax, rapeseed or ramie.
  • minerals such as kaolin, chalk, gypsum ( ⁇ - or ⁇ -modification), lime or talc or natural substances such as starch or modified starch, cellulose or cellulose derivatives or cellulose products, wood flour or natural fibers such as hemp, Flax, rapeseed or ramie.
  • the completely compostable polyester urethanes, polyester carbonates and polyester amides according to the invention can also be mixed with other blend partners, it being important to ensure that the full compostability is not impaired or that the remaining substances, for example mineral auxiliaries, are harmless in the compost.
  • Blowing agents which can be used according to the invention can be thermoplastic
  • Gaseous substances for example nitrogen, water or compounds which release carbon dioxide, vaporizable compounds or reaction products of several compounds which are gaseous under thermoplastic processing conditions.
  • the group of blowing agents which release gaseous substances, for example nitrogen, water or carbon dioxide, under thermoplastic processing conditions includes, for example, azo compounds such as, for example, and preferably hydrazides such as, for example and particularly preferably, toluenesulfonic acid hydrazide, or carbonates such as, for example, calcium carbonate or sodium carbonate or preferably hydrogen carbonates, such as sodium hydrogen carbonate, or water-releasing mineral salts.
  • the group of blowing agents, which consist of vaporizable compounds includes, for example, pentane, cyclopentane or C, -halohydrocarbons
  • the group of reaction products consisting of several compounds which are gaseous under thermoplastic processing conditions includes, for example and preferably, mixtures of acids, among the acids preferably lactic acid,
  • blowing agents are generally used in an amount of 0.1 to 30, preferably 0.5 to 15, particularly preferably 1 to 8% by weight, based on the mixture as a whole
  • the invention furthermore relates to a process for producing the articles according to the invention, characterized in that the mixture of the completely compostable, water- and steam-resistant polymers according to the invention is mixed with the blowing agents and the mixture is processed thermoplastic.
  • the thermoplastic processing can be extrusion, for example foamed profiles
  • the thermoplastic processing can also be injection molded into foamed moldings such as bowls or cups.
  • the thermoplastic processing can also be intensive mixing below the foaming temperature, for example on a kneader, and subsequent tempering above the foaming temperature to parts such as semi-finished products
  • the invention furthermore relates to the use of the fully compostable, water- and steam-resistant polymers according to the invention for the production of foamed moldings
  • a biodegradable polyester amide composed of 60% by weight of polycaprolactam and 40% by weight of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1% by weight solution in meta-
  • Cresol at 20 ° C. is extruded with 5% by weight (based on the entire mixture) of toluenesulfonic acid hydrazide at 145 ° C.
  • a foamed extrudate with a bulk density of 0.6 g / cm 3 is obtained
  • a biodegradable polyester amide composed of 60% by weight of polycaprolactan and 40% by weight of an ester of adipic acid and butanediol (relative solution viscosity 2.5, measured on a 1% by weight solution in meta-cresol at 20 ° C.) is also included 0.5% by weight (based on the entire mixture) of sodium hydrogen carbonate extruded at 135 ° C.
  • a foamed extrudate with a bulk density of 0.7 g / cm is obtained

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Polyamides (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des corps moulés moussés, obtenus à partir de polymères sélectionnés dans le groupe des polyesters aliphatiques ou partiellement aromatiques, des uréthanes de polyester thermoplastiques aliphatiques ou partiellement aromatiques, des carbonates de polyester aliphatiques ou aliphatico-aromatiques et des amides de polyester aliphatiques, qui sont mélangés à des agents gonflants et sont soumis à un traitement thermoplastique. L'invention concerne en outre un procédé de production de tels articles.
EP97916447A 1996-04-18 1997-04-07 Produits alveolaires compostables et pouvant subir un traitement thermoplastique Ceased EP0894113A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19615356 1996-04-18
DE1996115356 DE19615356A1 (de) 1996-04-18 1996-04-18 Kompostierbare und thermoplastisch verarbeitbare Schaumstoffe
PCT/EP1997/001721 WO1997040091A2 (fr) 1996-04-18 1997-04-07 Produits alveolaires compostables et pouvant subir un traitement thermoplastique

Publications (1)

Publication Number Publication Date
EP0894113A2 true EP0894113A2 (fr) 1999-02-03

Family

ID=7791663

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97916447A Ceased EP0894113A2 (fr) 1996-04-18 1997-04-07 Produits alveolaires compostables et pouvant subir un traitement thermoplastique

Country Status (8)

Country Link
EP (1) EP0894113A2 (fr)
JP (1) JP2000508698A (fr)
CN (1) CN1216558A (fr)
AU (1) AU728971B2 (fr)
CA (1) CA2251932A1 (fr)
DE (1) DE19615356A1 (fr)
NZ (1) NZ332356A (fr)
WO (1) WO1997040091A2 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1087800A (fr) * 1975-07-18 1980-10-14 Nelson S. Marans Obtention de mousses de polyurethanne hydrophile et biodegradable
US4049592A (en) * 1975-07-18 1977-09-20 W. R. Grace & Co. Biodegradable hydrophilic foams and method
EP0569149B1 (fr) * 1992-05-08 1998-07-15 Showa Highpolymer Co., Ltd. Articles en polyester moulés par injection
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
US5654380A (en) * 1994-05-23 1997-08-05 Mitsubishi Gas Chemical Company, Inc. Aliphatic polyester carbonate and process for producing the same
FI97726C (fi) * 1994-07-07 1997-02-10 Alko Yhtioet Oy Sulatyöstettävä polyesteriuretaani ja menetelmä sen valmistamiseksi

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9740091A3 *

Also Published As

Publication number Publication date
NZ332356A (fr) 2000-03-27
CN1216558A (zh) 1999-05-12
AU2509297A (en) 1997-11-12
JP2000508698A (ja) 2000-07-11
WO1997040091A3 (fr) 1997-11-27
WO1997040091A2 (fr) 1997-10-30
CA2251932A1 (fr) 1997-10-30
AU728971B2 (en) 2001-01-25
DE19615356A1 (de) 1997-10-23

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