CA2251932A1 - Compostable and thermoplastically processable foams - Google Patents
Compostable and thermoplastically processable foams Download PDFInfo
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- CA2251932A1 CA2251932A1 CA 2251932 CA2251932A CA2251932A1 CA 2251932 A1 CA2251932 A1 CA 2251932A1 CA 2251932 CA2251932 CA 2251932 CA 2251932 A CA2251932 A CA 2251932A CA 2251932 A1 CA2251932 A1 CA 2251932A1
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- difunctional
- acids
- aliphatic
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- alcohols
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- 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
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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)
- 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)
- Polyesters Or Polycarbonates (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to foamed mouldings produced from polymers selected from the group of 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 thermoplastically processed. The invention also relates to a process for producing the objects of the invention.
Description
. CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries / KM/by/S-P
I
FILE~ ;,, 7 T~. " ~ ,LJ''.i._ Compostable and melt-processable foams Foamed, melt-processable plastics are known (c.~ Rompp Chemielexikon, "Schaum-kunststoffe" entry, volume 5, 9th edition, Thieme Verlag 1992). They are obtained S inter alia by the use of blowing agents (c.~ Rompp Chemielexikon, "Blahmittel" entry, volume 1, 9th edition, Thieme Verlag 1990).
The object has now arisen of producing completely compostable articles resistant to water and water vapour having a low density. This object has been achieved by 10 processing certain completely compostable polymers resistant to water and water vapour by means of suitable blowing agents to yield the required articles, preferably in a melt processing production process.
The present invention accordingly provides foamed mouldings produced from 15 polymers selected from the group of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyesterurethanes, aliphatic or aliphatic-aromatic polyestercarbonates and aliphatic polyesteramides, which are mixed withblowing agents and melt processed.
20 The present invention furthermore provides a process for the production of the articles according to the invention.
The present invention furthermore provides the use of certain completely compost-able polymers resistant to water and water vapour for the production of foamed 25 mouldings.
The following polymers are suitable:
Aliphatic or partially aromatic polyesters prepared from A) aliphatic difunctional alcohols, preferably linear C2-C1O dialcohols, such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol . , CA 022~1932 1998-10-1~
Le A 31 771 Foreign Countries and/or optionally cycloaliphatic difunctional alcohols, preferably having C5-C6 C atoms in the cycloaliphatic ring, such as for example cyclohexane-dimethanol and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydro-furan or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C,2 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, preferably C3-C12 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolpropane and from aliphatic, difunctional acids, preferably C2-C,2 alkyldicarboxylic acids, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or n~rhth~lenedi-carboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or B) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of A and B, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative 25 to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
30 Aliphatic or partially aromatic polyesterurethanes prepared from CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries C) aliphatic difunctional alcohols, preferably linear C2-C~0 dialcohols, such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol and/or optionally cycloaliphatic difunctional alcohols, preferably having a C5-C6 cyclo~liph~tic ring, such as for exarnple cyclohex~ne~limethanol and/or, S partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C,2 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, preferably C3-C~2 alkylpolyols, such as for example 1,2,3-propall~l.;ol or trimethylolpropane and from aliphatic, difunctional acids, preferably C2-CI2 alkyldicarboxylic acids, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or D) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of C and D, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
- CA 022~1932 1998-10-1~
Le A 31 771-Foreign Countries E) from the reaction product of C and/or D with aliphatic and/or cycloaliphatic difunctional and additionally optionally more highly functional isocyanates, preferably having I to 12 C atoms or 5 to 8 C atoms in the case of cycloaliphatic isocyanates, for example tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally additionally with linear and/or branched and/or cycloaliphatic difunctional and/or more highly functional alcohols, preferably C3-C,2 alkyldi- or polyols or 5 to 8 C
atoms in the case of cycloaliphatic alcohols, for example ethanediol, hex~n~-liol, butanediol, cyclohPx~ne~limethanol, and/or optionally additionally with linear and/or branched and/or cyclo~liph~tic difunctional and/or more highly functional amines and/or aminoalcohols preferably having 2 to 12 C
atoms in the alkyl chain, for example ethylen~di~mine or aminoethanol, and/or optionally further modified amines or alcohols, such as for example ethylçne~ min~ethanesulfonic acid, as the free acid or the salt, wherein the ester fraction C) and/or D) amounts to at least 75 wt.%, relative to the sum of C), D) and E), wherein, in the polymer structure typical of polyurethanesoptionally comprising soft segments C) and D) and hard segments E), a completelyrandom distribution of the raw materials in the polymer is not to be expected;
Aliphatic or aliphatic-aromatic polyestercarbonates prepared from F) aliphatic difunctional alcohols, preferably linear C2-C10 dialcohols, such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol and/or optionally cycloaliphatic difunctional alcohols, preferably having 5 to 8 C atoms in the cycloaliphatic ring, such as for example cyclohexanedimeth-anol and/or, partially or entirely instead of the diols, monomeric or oligo-meric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C12 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, . CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries preferably C3-CI2 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolpropane and from aliphatic, difunctional acids, preferably C2-CI2 alkyldicarboxylic acids, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example S terephthalic acid or isophthalic acid or n~phth~lenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or G) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of F and G, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
H) a carbonate fraction which is produced from aromatic difunctional phenols, preferably bisphenol A, and carbonate donors, preferably phosgene, or a carbonate fraction which is produced from aliphatic carbonic acid esters or the derivatives thereof, such as chlorocarbonic acid esters or aliphatic carboxylic acids or the derivatives thereof, such as for example salts and carbonate donors, for example phosgene.
The ester fraction F) and/or G) must amount to at least 70 wt.%, relative to the sum of F), G) and H);
Aliphatic or partially aromatic polyesteramides plel)aled from CA 022~1932 1998-10-1~
Le A 31 771-Foreign Countries I) aliphatic difunctional alcohols, preferably linear C2-C~0 dialcohols, such as for example ethanediol, butanediol, hex~ne~liol, particularly preferably butanediol and/or optionally cyclo~liph~tic difunctional alcohols, preferably having 5 to 8 carbon atoms, such as for example cyclohex~n~.1imethanol and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C,2 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, preferably C3-C,2 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolplopalle and from aliphatic, difunctional acids, preferably having 2 to 12 C atoms in the alkyl chain, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or K) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the carbon chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of I) and K), wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
CA 022~1932 1998-10-1~
Le A 31 771,Forei~n Countries L) an amide fraction prepared from aliphatic and/or cyclo~liph~tic difunctional and/or optionally small quantities of branched difunctional ~mines, linear aliphatic C2-C~0 diamines being preferred, and additionally optionally small quantities of more highly functional amines, hexamethylene~i~mine, S isophorone~ mine being preferred among the amines and hexamethylene-diamine being particularly preferred, and from linear and/or cycloaliphatic difunctional acids, preferably having 2 to 12 C atoms in the alkyl chain or a C5-C6 ring in the case of cyclo~lirh~tic acids, preferably adipic acid and/or optionally small quantities of branched, difunctional and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, preferably having 2 to 10 C
atoms or 15 M) from an amide fraction prl pal~d from acid- and amine-functionalised structural units, preferably having 4 to 20 C atoms in the cycloaliphatic chain,preferably ci)-laurolactam and ~-caprolactam, particularly preferably ~-caprolactam, or a mixture of L) and M) as the amide fraction.
The ester fraction I) and/or K) must amount to at least 30 wt.%, relative to the sum of I), K), L) and M). The fraction by weight of the ester structures is preferably between 30 and 70%, the fraction of the amide structures between 70 and 30%.
The biodegradable polyesteramides according to the invention may be syntheci.~e~l both in accordance with the "polyamide method" by stoichiometric mixing of the starting components optionally with the addition of water and subsequent removalof water from the reaction mixture and in accordance with the "polyester method"by stoichiometric mixing of the starting components together with the addition of an excess of diol with esterification of the acid groups and subsequent tr~n~esterification or transamidation of these esters. In this second case, the excess of diol is distilled - CA 022~1932 1998-10-1~
Le A 31 771 Forei~n CoullLIies off again together with the water. Synthesis in accordance with the deseribed "polyester method" is preferred.
The polyesters, polyesterurethanes, polye~lelc~l.onates or preferably polyesteramides 5 according to the invention may furthermore contain 0.1 to 5 wt.%, preferably 0.1 to 1 wt.% of br~nching agents. These branching agents may be, for exarnple, trifunctional alcohols, such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citrie aeid. Thebr~nrhing agents inerease the melt viseosity of the polye~le.dll,ides aeeording to the 10 invention to sueh an extent that extrusion blow moulding is possible with these polymers. Biodegradation of these materials is not hindered as a eonsequence.
Polycon(ien~tion may furthermore be accelerated by the use of known catalysts.
Possible catalysts for accelerating polycon~en~tion are not only known phosphorus 15 compounds, which accelerate polyamide synthesis, and acidic or organometallic esterification catalysts, but also combinations of the two types.
Care must be taken to ensure that the catalysts have a negative effect neither on biodegradability or compostability nor on the quality of the resultant compost.
Polycondensation to yield polyesteramides may furthermore be influenced by the use of lysine, lysine derivatives or other amide br~n~hing products, such as for example aminoethylaminoethanol, which both accelerate contlen~tion and give rise to branched products (c.~ for example DE 38 31 709).
The completely compostable polyesterurethanes, polyesters, polye~l~rc~l,onates and polyesteramides according to the invention may be provided with fillers and reinforcing materials and/or with processing auxiliaries, such as for example nucleating auxiliaries, mould release auxiliaries or stabilisers, wherein care must be 30 taken to ensure that complete compostability is not impaired or the rem~iningsubstances, for example mineral auxiliaries, are innocuous in the compost.
CA 022~1932 1998-10-1~
Le A 31 771-Foreign Countries Fillers and reinforcing materials suitable according to the invention may be minerals, such as for example kaolin, chalk, gypsum (a or ~3 modification), lime or talc or natural substances, such as for example starch or modified starch, cellulose or cellulose derivatives or cellulose products, wood flour or natural fibres, such as for 5 example hemp, flax, rape or ramie.
The completely compostable polyesterurethanes, polyestercarbonates and polyester-amides according to the invention may also be mixed with further blend components, wherein care must be taken to ensure that complete compostability is not inlpailed 10 or the rem~ining substances, for example mineral auxiliaries, are innocuous in the compost.
Blowing agents usable according to the invention may be substances which are gaseous under melt processing conditions, for example compounds which elimin~te 15 nitrogen, water or carbon dioxide, vaporisable compounds or reaction products of two or more compounds which are gaseous under melt processing conditions.
The group of blowing agents elimin~ting gaseous subst~nre~, for example nitrogen, water or carbon dioxide under melt processing conditions includes, for example, azo 20 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,among these preferably sodium hydrogen carbonate, or mineral salts which elimin~te water.
The group of blowing agents con~i~ting of vaporisable compounds includes, for example, pentane, cyclopentane or C, halogenated hydrocarbons.
The group of reaction products of two or more compounds, which are gaseous under30 melt processing conditions, includes for example and preferably mixtures of acids, among the acids preferably lactic acid, oxalic acid and particularly preferably citric acid, and CO2 donors, such as for example carbonates and bicarbonates.
CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries The blowing agents are generally used in a quantity of 0.1 to 30, preferably of 0.5 to 15, particularly preferably of 1 to 8 wt.%, relative to the entire llli~Ule.
The present invention furthermore provides a process for the production of the S articles according to the invention, characterised in that the lllixlufe of the completely compostable polymers resistant to water and water vapour according to the invention is mixed with the blowing agents and the mixture is melt processed. Melt processing may comprise extrusion, for example to yield foamed profiles. Melt processing may also c~lllpl,se injection moulding to yield foamed mo~ inEs, such as for example10 dishes or cups. Melt processing may also comprise vigorous mixing below the foaming telllyel~ule, for example in a kne~(lçr, and subsequent heat treatment at above the foaming temperature to yield components, such as for example semi-finished products.
lS The present invention furthermore provides the use of the completely compostable polymers resistant to water and water vapour according to the invention for the production of foamed mouldings.
CA 022~1932 1998-10-1~
Le A 31 771 Forei~n Countries Examples Example 1 A biodegradable polyesteramide comprising a 60 wt.% fraction of polycaprolactam and a 40 wt.% fraction of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1 wt.% solution in meta-cresol at 20~C) is extruded at 145~C with 5 wt.% (relative to the entire ~ lu~e) of tol~len~s.llfonic acid hydrazide.
A foamed extrudate having a bulk density of 0.6 g/cm3 is obtained.
Example 2 20 g of a biodegradable polyesteramide comprising a 60 wt.% fraction of polycapro-lactam and a 40 wt.% fraction of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1 wt.% solution in meta-cresol at 20~C) are intim~tely mixed with 1 g of azodicarbonamide at 150~C in a kne?~er, transferredinto an open, heat-resistant mould and then heated for 30 minutes at 200~C in anoven. A coarse-cell foam having a bulk density of 0.07 g/cm3 is obtained.
Example 3 A biodegradable polyesteramide comprising a 60 wt.% fraction of polycaprolactam and a 40 wt.% fraction of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1 wt.% solution in meta-cresol at 20~C) is extruded at 135~C with 0.5 wt.% (relative to the entire mixture) of sodium hydrogen carbonate.
A foamed extrudate having a bulk density of 0.7 g/cm3 is obtained.
Le A 31 771-Forei~n Countries / KM/by/S-P
I
FILE~ ;,, 7 T~. " ~ ,LJ''.i._ Compostable and melt-processable foams Foamed, melt-processable plastics are known (c.~ Rompp Chemielexikon, "Schaum-kunststoffe" entry, volume 5, 9th edition, Thieme Verlag 1992). They are obtained S inter alia by the use of blowing agents (c.~ Rompp Chemielexikon, "Blahmittel" entry, volume 1, 9th edition, Thieme Verlag 1990).
The object has now arisen of producing completely compostable articles resistant to water and water vapour having a low density. This object has been achieved by 10 processing certain completely compostable polymers resistant to water and water vapour by means of suitable blowing agents to yield the required articles, preferably in a melt processing production process.
The present invention accordingly provides foamed mouldings produced from 15 polymers selected from the group of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyesterurethanes, aliphatic or aliphatic-aromatic polyestercarbonates and aliphatic polyesteramides, which are mixed withblowing agents and melt processed.
20 The present invention furthermore provides a process for the production of the articles according to the invention.
The present invention furthermore provides the use of certain completely compost-able polymers resistant to water and water vapour for the production of foamed 25 mouldings.
The following polymers are suitable:
Aliphatic or partially aromatic polyesters prepared from A) aliphatic difunctional alcohols, preferably linear C2-C1O dialcohols, such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol . , CA 022~1932 1998-10-1~
Le A 31 771 Foreign Countries and/or optionally cycloaliphatic difunctional alcohols, preferably having C5-C6 C atoms in the cycloaliphatic ring, such as for example cyclohexane-dimethanol and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydro-furan or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C,2 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, preferably C3-C12 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolpropane and from aliphatic, difunctional acids, preferably C2-C,2 alkyldicarboxylic acids, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or n~rhth~lenedi-carboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or B) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of A and B, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative 25 to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
30 Aliphatic or partially aromatic polyesterurethanes prepared from CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries C) aliphatic difunctional alcohols, preferably linear C2-C~0 dialcohols, such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol and/or optionally cycloaliphatic difunctional alcohols, preferably having a C5-C6 cyclo~liph~tic ring, such as for exarnple cyclohex~ne~limethanol and/or, S partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C,2 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, preferably C3-C~2 alkylpolyols, such as for example 1,2,3-propall~l.;ol or trimethylolpropane and from aliphatic, difunctional acids, preferably C2-CI2 alkyldicarboxylic acids, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or D) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of C and D, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
- CA 022~1932 1998-10-1~
Le A 31 771-Foreign Countries E) from the reaction product of C and/or D with aliphatic and/or cycloaliphatic difunctional and additionally optionally more highly functional isocyanates, preferably having I to 12 C atoms or 5 to 8 C atoms in the case of cycloaliphatic isocyanates, for example tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally additionally with linear and/or branched and/or cycloaliphatic difunctional and/or more highly functional alcohols, preferably C3-C,2 alkyldi- or polyols or 5 to 8 C
atoms in the case of cycloaliphatic alcohols, for example ethanediol, hex~n~-liol, butanediol, cyclohPx~ne~limethanol, and/or optionally additionally with linear and/or branched and/or cyclo~liph~tic difunctional and/or more highly functional amines and/or aminoalcohols preferably having 2 to 12 C
atoms in the alkyl chain, for example ethylen~di~mine or aminoethanol, and/or optionally further modified amines or alcohols, such as for example ethylçne~ min~ethanesulfonic acid, as the free acid or the salt, wherein the ester fraction C) and/or D) amounts to at least 75 wt.%, relative to the sum of C), D) and E), wherein, in the polymer structure typical of polyurethanesoptionally comprising soft segments C) and D) and hard segments E), a completelyrandom distribution of the raw materials in the polymer is not to be expected;
Aliphatic or aliphatic-aromatic polyestercarbonates prepared from F) aliphatic difunctional alcohols, preferably linear C2-C10 dialcohols, such as for example ethanediol, butanediol, hexanediol, particularly preferably butanediol and/or optionally cycloaliphatic difunctional alcohols, preferably having 5 to 8 C atoms in the cycloaliphatic ring, such as for example cyclohexanedimeth-anol and/or, partially or entirely instead of the diols, monomeric or oligo-meric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C12 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, . CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries preferably C3-CI2 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolpropane and from aliphatic, difunctional acids, preferably C2-CI2 alkyldicarboxylic acids, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example S terephthalic acid or isophthalic acid or n~phth~lenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or G) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the alkyl chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of F and G, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
H) a carbonate fraction which is produced from aromatic difunctional phenols, preferably bisphenol A, and carbonate donors, preferably phosgene, or a carbonate fraction which is produced from aliphatic carbonic acid esters or the derivatives thereof, such as chlorocarbonic acid esters or aliphatic carboxylic acids or the derivatives thereof, such as for example salts and carbonate donors, for example phosgene.
The ester fraction F) and/or G) must amount to at least 70 wt.%, relative to the sum of F), G) and H);
Aliphatic or partially aromatic polyesteramides plel)aled from CA 022~1932 1998-10-1~
Le A 31 771-Foreign Countries I) aliphatic difunctional alcohols, preferably linear C2-C~0 dialcohols, such as for example ethanediol, butanediol, hex~ne~liol, particularly preferably butanediol and/or optionally cyclo~liph~tic difunctional alcohols, preferably having 5 to 8 carbon atoms, such as for example cyclohex~n~.1imethanol and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000, preferably of up to 1000, and/or optionally small quantities of branched, difunctional alcohols, preferably C3-C,2 alkyldiols, such as for example neopentyl glycol and additionally optionally small quantities of more highly functional alcohols, preferably C3-C,2 alkylpolyols, such as for example 1,2,3-propanetriol or trimethylolplopalle and from aliphatic, difunctional acids, preferably having 2 to 12 C atoms in the alkyl chain, such as for example and preferably succinic acid or adipic acid and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, such as for example trimellitic acid or K) from acid- and alcohol-functionalised structural units, preferably having 2 to 12 C atoms in the carbon chain, for example hydroxybutyric acid or hydroxy-valeric acid or lactic acid, or the derivatives thereof, for example ~-capro-lactone or dilactide, or a mixture and/or a copolymer of I) and K), wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids.
All the acids may also be used in the form of derivatives, such as for example acid chlorides or esters, both as monomeric and as oligomeric esters;
CA 022~1932 1998-10-1~
Le A 31 771,Forei~n Countries L) an amide fraction prepared from aliphatic and/or cyclo~liph~tic difunctional and/or optionally small quantities of branched difunctional ~mines, linear aliphatic C2-C~0 diamines being preferred, and additionally optionally small quantities of more highly functional amines, hexamethylene~i~mine, S isophorone~ mine being preferred among the amines and hexamethylene-diamine being particularly preferred, and from linear and/or cycloaliphatic difunctional acids, preferably having 2 to 12 C atoms in the alkyl chain or a C5-C6 ring in the case of cyclo~lirh~tic acids, preferably adipic acid and/or optionally small quantities of branched, difunctional and/or optionally aromatic difunctional acids, such as for example terephthalic acid or isophthalic acid or naphthalenedicarboxylic acid and additionally optionally small quantities of more highly functional acids, preferably having 2 to 10 C
atoms or 15 M) from an amide fraction prl pal~d from acid- and amine-functionalised structural units, preferably having 4 to 20 C atoms in the cycloaliphatic chain,preferably ci)-laurolactam and ~-caprolactam, particularly preferably ~-caprolactam, or a mixture of L) and M) as the amide fraction.
The ester fraction I) and/or K) must amount to at least 30 wt.%, relative to the sum of I), K), L) and M). The fraction by weight of the ester structures is preferably between 30 and 70%, the fraction of the amide structures between 70 and 30%.
The biodegradable polyesteramides according to the invention may be syntheci.~e~l both in accordance with the "polyamide method" by stoichiometric mixing of the starting components optionally with the addition of water and subsequent removalof water from the reaction mixture and in accordance with the "polyester method"by stoichiometric mixing of the starting components together with the addition of an excess of diol with esterification of the acid groups and subsequent tr~n~esterification or transamidation of these esters. In this second case, the excess of diol is distilled - CA 022~1932 1998-10-1~
Le A 31 771 Forei~n CoullLIies off again together with the water. Synthesis in accordance with the deseribed "polyester method" is preferred.
The polyesters, polyesterurethanes, polye~lelc~l.onates or preferably polyesteramides 5 according to the invention may furthermore contain 0.1 to 5 wt.%, preferably 0.1 to 1 wt.% of br~nching agents. These branching agents may be, for exarnple, trifunctional alcohols, such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citrie aeid. Thebr~nrhing agents inerease the melt viseosity of the polye~le.dll,ides aeeording to the 10 invention to sueh an extent that extrusion blow moulding is possible with these polymers. Biodegradation of these materials is not hindered as a eonsequence.
Polycon(ien~tion may furthermore be accelerated by the use of known catalysts.
Possible catalysts for accelerating polycon~en~tion are not only known phosphorus 15 compounds, which accelerate polyamide synthesis, and acidic or organometallic esterification catalysts, but also combinations of the two types.
Care must be taken to ensure that the catalysts have a negative effect neither on biodegradability or compostability nor on the quality of the resultant compost.
Polycondensation to yield polyesteramides may furthermore be influenced by the use of lysine, lysine derivatives or other amide br~n~hing products, such as for example aminoethylaminoethanol, which both accelerate contlen~tion and give rise to branched products (c.~ for example DE 38 31 709).
The completely compostable polyesterurethanes, polyesters, polye~l~rc~l,onates and polyesteramides according to the invention may be provided with fillers and reinforcing materials and/or with processing auxiliaries, such as for example nucleating auxiliaries, mould release auxiliaries or stabilisers, wherein care must be 30 taken to ensure that complete compostability is not impaired or the rem~iningsubstances, for example mineral auxiliaries, are innocuous in the compost.
CA 022~1932 1998-10-1~
Le A 31 771-Foreign Countries Fillers and reinforcing materials suitable according to the invention may be minerals, such as for example kaolin, chalk, gypsum (a or ~3 modification), lime or talc or natural substances, such as for example starch or modified starch, cellulose or cellulose derivatives or cellulose products, wood flour or natural fibres, such as for 5 example hemp, flax, rape or ramie.
The completely compostable polyesterurethanes, polyestercarbonates and polyester-amides according to the invention may also be mixed with further blend components, wherein care must be taken to ensure that complete compostability is not inlpailed 10 or the rem~ining substances, for example mineral auxiliaries, are innocuous in the compost.
Blowing agents usable according to the invention may be substances which are gaseous under melt processing conditions, for example compounds which elimin~te 15 nitrogen, water or carbon dioxide, vaporisable compounds or reaction products of two or more compounds which are gaseous under melt processing conditions.
The group of blowing agents elimin~ting gaseous subst~nre~, for example nitrogen, water or carbon dioxide under melt processing conditions includes, for example, azo 20 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,among these preferably sodium hydrogen carbonate, or mineral salts which elimin~te water.
The group of blowing agents con~i~ting of vaporisable compounds includes, for example, pentane, cyclopentane or C, halogenated hydrocarbons.
The group of reaction products of two or more compounds, which are gaseous under30 melt processing conditions, includes for example and preferably mixtures of acids, among the acids preferably lactic acid, oxalic acid and particularly preferably citric acid, and CO2 donors, such as for example carbonates and bicarbonates.
CA 022~1932 1998-10-1~
Le A 31 771-Forei~n Countries The blowing agents are generally used in a quantity of 0.1 to 30, preferably of 0.5 to 15, particularly preferably of 1 to 8 wt.%, relative to the entire llli~Ule.
The present invention furthermore provides a process for the production of the S articles according to the invention, characterised in that the lllixlufe of the completely compostable polymers resistant to water and water vapour according to the invention is mixed with the blowing agents and the mixture is melt processed. Melt processing may comprise extrusion, for example to yield foamed profiles. Melt processing may also c~lllpl,se injection moulding to yield foamed mo~ inEs, such as for example10 dishes or cups. Melt processing may also comprise vigorous mixing below the foaming telllyel~ule, for example in a kne~(lçr, and subsequent heat treatment at above the foaming temperature to yield components, such as for example semi-finished products.
lS The present invention furthermore provides the use of the completely compostable polymers resistant to water and water vapour according to the invention for the production of foamed mouldings.
CA 022~1932 1998-10-1~
Le A 31 771 Forei~n Countries Examples Example 1 A biodegradable polyesteramide comprising a 60 wt.% fraction of polycaprolactam and a 40 wt.% fraction of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1 wt.% solution in meta-cresol at 20~C) is extruded at 145~C with 5 wt.% (relative to the entire ~ lu~e) of tol~len~s.llfonic acid hydrazide.
A foamed extrudate having a bulk density of 0.6 g/cm3 is obtained.
Example 2 20 g of a biodegradable polyesteramide comprising a 60 wt.% fraction of polycapro-lactam and a 40 wt.% fraction of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1 wt.% solution in meta-cresol at 20~C) are intim~tely mixed with 1 g of azodicarbonamide at 150~C in a kne?~er, transferredinto an open, heat-resistant mould and then heated for 30 minutes at 200~C in anoven. A coarse-cell foam having a bulk density of 0.07 g/cm3 is obtained.
Example 3 A biodegradable polyesteramide comprising a 60 wt.% fraction of polycaprolactam and a 40 wt.% fraction of an ester of adipic acid and butanediol (relative solution viscosity: 2.5, measured on a 1 wt.% solution in meta-cresol at 20~C) is extruded at 135~C with 0.5 wt.% (relative to the entire mixture) of sodium hydrogen carbonate.
A foamed extrudate having a bulk density of 0.7 g/cm3 is obtained.
Claims (4)
1. Foamed mouldings produced from biodegradable polymers selected from the group of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyesterurethanes, aliphatic or aliphatic-aromatic polyester-carbonates, aliphatic polyesteramides, which are mixed with blowing agents and optionally conventional additives and melt processed.
2. Foamed mouldings according to claim 1, wherein the polymers used are:
Aliphatic or partially aromatic polyesters prepared from A) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or B) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of A and B, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
Aliphatic or partially aromatic polyesterurethanes prepared from C) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic, difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or D) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of C and D, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
E) from the reaction product of C and/or D with aliphatic and/or cycloaliphatic difunctional and additionally optionally more highly functional isocyanates, optionally additionally with linear and/or branched and/or cycloaliphatic difunctional and/or more highly functional alcohols, and/or optionally additionally with linear and/or branched and/or cycloaliphatic difunctional and/or more highly functional amines and/or aminoalcohols and/or optionally further modified amines or alcohols, wherein the ester fraction C) and/or D) amounts to at least 75 wt.%, relative to the sum of C), D) and E);
Aliphatic or aliphatic-aromatic polyestercarbonates prepared from F) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic, difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or G) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of F and G, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
H) a carbonate fraction which is produced from aromatic difunctional phenols and carbonate donors or a carbonate fraction which is produced from aliphatic carbonic acid esters or the derivatives thereof or aliphatic carboxylic acids or the derivatives thereof and carbonate donors, wherein the ester fraction F) and/or G) amounts to at least 70 wt.%, relative to the sum of F), G) and H);
Aliphatic or partially aromatic polyesteramides prepared from I) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic, difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or K) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of I) and K), wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
L) an amide fraction- prepared from aliphatic and/or cycloaliphatic difunctional and/or optionally small quantities of branched difunctional amines and additionally optionally small quantities of more highly functional amines and from linear and/or cycloaliphatic difunctional acids and/or optionally small quantities of branched, difunctional and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or M) from an amide fraction prepared from acid- and amine-functionalised structural units, or a mixture of L) and M) as the amide fraction, wherein the ester fraction I) and/or K) amounts to at least 30 wt.%, relative to the sum of I), K), L) and M), and wherein all the acids may also be used in the form of derivatives, both as monomeric and as oligomeric esters.
Aliphatic or partially aromatic polyesters prepared from A) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or B) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of A and B, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
Aliphatic or partially aromatic polyesterurethanes prepared from C) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic, difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or D) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of C and D, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
E) from the reaction product of C and/or D with aliphatic and/or cycloaliphatic difunctional and additionally optionally more highly functional isocyanates, optionally additionally with linear and/or branched and/or cycloaliphatic difunctional and/or more highly functional alcohols, and/or optionally additionally with linear and/or branched and/or cycloaliphatic difunctional and/or more highly functional amines and/or aminoalcohols and/or optionally further modified amines or alcohols, wherein the ester fraction C) and/or D) amounts to at least 75 wt.%, relative to the sum of C), D) and E);
Aliphatic or aliphatic-aromatic polyestercarbonates prepared from F) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic, difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or G) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of F and G, wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
H) a carbonate fraction which is produced from aromatic difunctional phenols and carbonate donors or a carbonate fraction which is produced from aliphatic carbonic acid esters or the derivatives thereof or aliphatic carboxylic acids or the derivatives thereof and carbonate donors, wherein the ester fraction F) and/or G) amounts to at least 70 wt.%, relative to the sum of F), G) and H);
Aliphatic or partially aromatic polyesteramides prepared from I) aliphatic difunctional alcohols and/or optionally cycloaliphatic difunctional alcohols and/or, partially or entirely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof having molecular weights of up to 4000 and/or optionally small quantities of branched, difunctional alcohols and additionally optionally small quantities of more highly functional alcohols and from aliphatic, difunctional acids and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or K) from acid- and alcohol-functionalised structural units or the derivatives thereof, or a mixture and/or a copolymer of I) and K), wherein the aromatic acids constitute a fraction of no more than 50 wt.%, relative to all the acids;
L) an amide fraction- prepared from aliphatic and/or cycloaliphatic difunctional and/or optionally small quantities of branched difunctional amines and additionally optionally small quantities of more highly functional amines and from linear and/or cycloaliphatic difunctional acids and/or optionally small quantities of branched, difunctional and/or optionally aromatic difunctional acids and additionally optionally small quantities of more highly functional acids or M) from an amide fraction prepared from acid- and amine-functionalised structural units, or a mixture of L) and M) as the amide fraction, wherein the ester fraction I) and/or K) amounts to at least 30 wt.%, relative to the sum of I), K), L) and M), and wherein all the acids may also be used in the form of derivatives, both as monomeric and as oligomeric esters.
3. Process for the production of foamed mouldings according to claim 1, wherein the biodegradable polymers are mixed with the blowing agents and the mixture is melt processed.
4. Use of biodegradable polymers according to claims 1 and 2 for the production of foamed mouldings using blowing agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1996115356 DE19615356A1 (en) | 1996-04-18 | 1996-04-18 | Compostable and thermoplastically processable foams |
| DE19615356.5 | 1996-04-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2251932A1 true CA2251932A1 (en) | 1997-10-30 |
Family
ID=7791663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2251932 Abandoned CA2251932A1 (en) | 1996-04-18 | 1997-04-07 | Compostable and thermoplastically processable foams |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0894113A2 (en) |
| JP (1) | JP2000508698A (en) |
| CN (1) | CN1216558A (en) |
| AU (1) | AU728971B2 (en) |
| CA (1) | CA2251932A1 (en) |
| DE (1) | DE19615356A1 (en) |
| NZ (1) | NZ332356A (en) |
| WO (1) | WO1997040091A2 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1087800A (en) * | 1975-07-18 | 1980-10-14 | Nelson S. Marans | Biodegradable hydrophilic polyurethane foams and method |
| US4049592A (en) * | 1975-07-18 | 1977-09-20 | W. R. Grace & Co. | Biodegradable hydrophilic foams and method |
| EP0569143B1 (en) * | 1992-05-08 | 1998-03-18 | Showa Highpolymer Co., Ltd. | Polyester tying tape-like materials |
| JPH0710988A (en) * | 1993-06-24 | 1995-01-13 | Agency Of Ind Science & Technol | Production of biodegradable polyester amide copolymer |
| US5654380A (en) * | 1994-05-23 | 1997-08-05 | Mitsubishi Gas Chemical Company, Inc. | Aliphatic polyester carbonate and process for producing the same |
| FI97726C (en) * | 1994-07-07 | 1997-02-10 | Alko Yhtioet Oy | Meltable polyester urethane and method for its preparation |
-
1996
- 1996-04-18 DE DE1996115356 patent/DE19615356A1/en not_active Withdrawn
-
1997
- 1997-04-07 AU AU25092/97A patent/AU728971B2/en not_active Ceased
- 1997-04-07 WO PCT/EP1997/001721 patent/WO1997040091A2/en not_active Application Discontinuation
- 1997-04-07 JP JP9537660A patent/JP2000508698A/en active Pending
- 1997-04-07 NZ NZ33235697A patent/NZ332356A/xx unknown
- 1997-04-07 CN CN 97193929 patent/CN1216558A/en active Pending
- 1997-04-07 EP EP97916447A patent/EP0894113A2/en not_active Ceased
- 1997-04-07 CA CA 2251932 patent/CA2251932A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JP2000508698A (en) | 2000-07-11 |
| WO1997040091A3 (en) | 1997-11-27 |
| NZ332356A (en) | 2000-03-27 |
| AU728971B2 (en) | 2001-01-25 |
| EP0894113A2 (en) | 1999-02-03 |
| CN1216558A (en) | 1999-05-12 |
| DE19615356A1 (en) | 1997-10-23 |
| WO1997040091A2 (en) | 1997-10-30 |
| AU2509297A (en) | 1997-11-12 |
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