EP1036107A1 - Polyether ester amides - Google Patents

Polyether ester amides

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Publication number
EP1036107A1
EP1036107A1 EP98956937A EP98956937A EP1036107A1 EP 1036107 A1 EP1036107 A1 EP 1036107A1 EP 98956937 A EP98956937 A EP 98956937A EP 98956937 A EP98956937 A EP 98956937A EP 1036107 A1 EP1036107 A1 EP 1036107A1
Authority
EP
European Patent Office
Prior art keywords
polyether ester
ester amides
acids
mixtures
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98956937A
Other languages
German (de)
French (fr)
Inventor
Ralf Timmermann
Wolfgang Schulz-Schlitte
Michael Voigt
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
BASF SE
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Filing date
Publication date
Priority claimed from DE1997153534 external-priority patent/DE19753534A1/en
Priority claimed from DE1997153532 external-priority patent/DE19753532A1/en
Application filed by BASF SE filed Critical BASF SE
Publication of EP1036107A1 publication Critical patent/EP1036107A1/en
Withdrawn legal-status Critical Current

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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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances

Definitions

  • DE-A 25 23 991, DE-A 28 02 989, DE-A 28 56 787 describe copolyether ester amides which, starting from short-chain, acid-terminated polyamide units, preferably based on PA 11, are prepared by condensation with hydroxyl-functional polyethers and monofunctional acids become.
  • DE-A 31 45 998 describes polyether ester amides from aminocarboxylic acids, dicarboxylic acids and long-chain polyethers.
  • the polymers obtained are characterized by low molecular weights and are not suitable, e.g. To extrude foils.
  • EP-A 0 163 902 and EP-A 0 095 893 describe polyether ester amides from lactams or aminocarboxylic acids, dicarboxylic acids and long-chain polyethers.
  • US-A 4 230 838 describes polyether ester amides from an acid-terminated polyamide, dicarboxylic acids and polytetramethylene glycol.
  • EP-A 0 378 015 describes polyether ester amides with good water vapor permeability, which in turn have a block-like structure and are acid-terminated
  • Polyamides and hydroxyl-functional polyethers are produced. It is difficult rigorous adherence to stoichiometry to obtain high molecular weight polymers. Polymers with lower molecular weights are poorly suited for film extrusion.
  • the object of the invention is to provide polyether ester amides which have a high water vapor permeability, are suitable for use in film extrusion and are simple and safe to produce and are fast-crystallizing.
  • polyether ester amides according to the invention are also biodegradable or compostable.
  • polyester amides are much simpler than the methods described so far, since a multi-stage procedure is not necessary (prior synthesis of acid-terminated short-chain polyamides) and the stoichiometry of the synthesis can be maintained very well by the additional use of short-chain diol compounds and very high molecular weight polyether ester amides are thus obtained that are ideal for extrusion applications.
  • the invention therefore relates to polyether ester amides which have a statistical arrangement of the ester and amide segments and where the alcohol component consists of monomeric and oligomeric diols.
  • the content of oligomeric diol, based on the total content of the alcohol component, is generally 3 to 99, preferably 5 to 80 mol%, particularly preferably 15 to 80 mol%, in particular 15 to 50 mol%.
  • the polyether ester amides are preferably composed of the following monomers:
  • Oligomeric polyols consisting of polyethylene glycols, polypropylene glycols, randomly or block-like polyglycols from mixtures of ethylene oxide or propylene oxide, or polytetrahydrofurans with molecular weights (weight average) between 100 and 10,000 and
  • monomeric diols preferably C2-C j 2-alkyldiols, in particular C 2 -C, 5-alkyldiols, for example and preferably ethylene glycol, 1,4-butanediol, 1,3-propanediol,
  • Dicarboxylic acids preferably C2-C12-, particularly preferably C2-Cö-alkyldicarboxylic acids, for example and preferably oxalic acid, succinic acid, adipic acid, also in the form of their respective esters (methyl, ethyl, etc.),
  • Alkylhydroxycarboxylic acids with preferably 2 to 12 carbon atoms in the alkyl chain and lactones such as and preferably caprolactone and others,
  • Amino alcohols preferably having 2 to 12 carbon atoms in the alkyl chain, for example and preferably ethanolamine, propanolamine,
  • Cyclic lactams preferably having 5 to 12, preferably 6 to 11 carbon atoms. such as and preferably ⁇ -caprolactam or laurolactam etc.,
  • ⁇ -aminocarboxylic acids preferably having 6 to 12 carbon atoms in the alkyl chain, such as, for example, and preferably aminocaproic acid, etc.
  • both hydroxyl- or acid-terminated polyesters with molecular weights between 300 and 10,000 can be used as the ester-forming component.
  • the polyether ester amides according to the invention can further contain 0.05 to 5% by weight, preferably 0.1 to 1% by weight, of branching agents.
  • branching agents can e.g. trifunctional alcohols such as trimethylolpropane or glycerin, tetrafunctional
  • Alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid or tri- or tetrafunctional hydroxycarboxylic acids.
  • the branching agents increase the melt viscosity of the polyether ester amides according to the invention to such an extent that extrusion blow molding is possible with these polymers.
  • the proportion of ether and ester fractions in the polymer is generally 5 to 85, preferably 20 to 80,% by weight, based on the total polymer.
  • the polyetheresteramides according to the invention generally have an average molecular weight (Mw determined according to gel chromatography in cresol against standard polystyrene) from 10,000 to 300,000, preferably from 15,000 to 150,000, in particular 15,000 to 100,000.
  • Mw average molecular weight
  • the synthesis can be carried out 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 adding an excess of diol with esterification of the acid groups and subsequent transesterification or unamidation these esters are made. In this second case, the excess glycol is distilled off in addition to water.
  • the reaction generally takes place at temperatures of 180 up to 280 ° C and under reduced pressure, preferably ⁇ 5 mbar, in particular ⁇ 1 mbar.
  • suitable catalysts can be used to catalyze the esterification or amidation reactions.
  • Titanium compounds for the esterifications or phosphorus compounds for the amidation reactions include e.g. Titanium compounds for the esterifications or phosphorus compounds for the amidation reactions. These catalysts are known from the prior art.
  • polyether ester amides according to the present invention can be filled and
  • Reinforcing materials and common additives are mixed. As a rule, up to 80% by weight (based on polyetheresteramide) of fillers and reinforcing materials can be added.
  • inorganic materials are used as fillers and reinforcing materials.
  • fibrous reinforcing materials such as glass and carbon fibers and mineral fillers, e.g. Talc, mica, chalk, kaolin, wollastonite, gypsum, quartz, dolomite, silicates.
  • the fillers and reinforcing materials can also be surface-treated.
  • Glass fibers generally have a fiber diameter between 8 and 14 ⁇ m and can be used as continuous fibers or as cut or ground glass fibers, the fibers being able to be equipped with a suitable sizing system and an adhesion promoter or adhesion promoter system based on silane.
  • the polyetheresteramides may further contain 1 to 90, preferably 10 to 60, in particular 15 to 50 parts by weight (based on polyetheresteramide) of starch, modified starch, cellulose and / or modified cellulose.
  • starch described in WO 96/31 561 can be used as starch.
  • Other possible additives are:
  • UV stabilizers antioxidants, pigments, dyes, nucleating agents, crystallization accelerators and retarders, flow aids, lubricants, mold release agents, flame retardants, water repellents. Plasticizers and / or impact modifiers can also be added.
  • polyether ester amides according to the invention can also be used as a blend with biodegradable polymers.
  • biodegradable polymers include e.g. aliphatic polyesters such as polycaprolactone, aliphatic-aromatic polyesters from e.g. Terephthalic acid, butanediol and adipic acid, polyhydroxybutyric acid, polylactides and copolymers thereof,
  • Polyester urethanes e.g. EP-A 593 975.
  • mixtures according to the invention of polyether ester amide and fillers and reinforcing materials and, if appropriate, further additives can be prepared by mixing the respective constituents in a known manner and in the customary manner
  • Temperatures e.g. at 180 ° C to 300 ° C, in conventional units such as internal kneaders, extruders, twin-screw extruders, melt-compounded or melt-extruded.
  • polyether ester amides of the present invention and their mixtures mentioned above can be used in injection molding, as a fiber or film or in the non-woven sector
  • melt-blown can be used in particular for the production of films, for example by bubble extrusion.
  • caprolactam 28.2 g of adipic acid, 29.5 g of butanediol and 78.4 g of polyethylene glycol 200 are combined with titanium tetraisopropylate as a catalyst and heated to 240 ° C. under nitrogen. After water has been removed, the pressure is gradually reduced to 1 mbar.
  • caprolactam 256.6 g of caprolactam, 66.0 g of adipic acid, 20.4 g of 1,4-butanediol, 108.0 g of polyethylene glycol (PEG 400, from BASF) and 3.03 g of trimethylolpropane are used with titanium tetraisopropylate as a catalyst under nitrogen heated to 250 ° C. With easing the distillation rate is slowly applied to a water jet vacuum, followed by an oil pump vacuum (approx. 1 mbar). It is polycondensed at this temperature for 3 h and cooled.
  • PEG 400 polyethylene glycol
  • an oil pump vacuum approximately 1 mbar
  • is obtained 3.0 (1% by weight in m-cresol at 25 ° C).
  • the melting point is 155.4 ° C, the crystallization temperature 92.9 ° C (DS C measurements).
  • caprolactam 253 g of adipic acid, 156 g of 1,4-butanediol and 1,380 g of PEG 400 are heated to 250 ° C. in trimethylolpropane using titanium tetraisopropylate as a catalyst under nitrogen.
  • water jet vacuum is slowly applied, followed by an oil pump vacuum (approx. 1 mbar). It is polycondensed at this temperature for 3 h and cooled.
  • a high molecular weight polymer with ⁇ re ⁇ 3.0 (1% by weight in m-cresol at 25 ° C.) is obtained.
  • the melting point is 118J ° C, the crystallization temperature 73.3 ° C (according to DSC).
  • a high molecular weight polymer with ⁇ re j 2.8 (1% by weight in m-cresol at 25 ° C.) is obtained.
  • the melting point is 118J ° C, the crystallization temperature 41.4 ° C (DSC measurements).
  • Example 1 420
  • Example 2 1120
  • Example 3 780
  • Example 4 920 Comparative example: 210

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyamides (AREA)

Abstract

The invention relates to polyether ester amides which present a static arrangement of the ester and amide segments, the alcohol component consisting of monomeric and oligomeric diols. The invention also relates to a method for producing the polyether ester amides and to items produced from the same.

Description

PolyetheresteramidePolyetheresteramides
DE-A 25 23 991, DE-A 28 02 989, DE-A 28 56 787 beschreiben Copolyetherester- amide, die ausgehend von kurzkettigen, säureendständigen Polyamideinheiten, bevorzugt auf Basis PA 11 , durch Kondensation mit hydroxylfunktionellen Poly- ethern und monofunktionellen Säuren hergestellt werden.DE-A 25 23 991, DE-A 28 02 989, DE-A 28 56 787 describe copolyether ester amides which, starting from short-chain, acid-terminated polyamide units, preferably based on PA 11, are prepared by condensation with hydroxyl-functional polyethers and monofunctional acids become.
Diese Herstellmethode ist sehr aufwendig und unsicher, da die Herstellung mehr- stufig ist und die Stöchiometrie nur schwer eingehalten werden kann, um wirklich hochmolekulare Polymere (M w > 15.000) zu erhalten.This production method is very complex and unsafe, since the production is multi-stage and the stoichiometry can only be adhered to with difficulty in order to obtain really high molecular weight polymers (M w> 15,000).
DE-A 31 45 998 beschreibt Polyetheresteramide aus Aminocarbonsäuren, Dicarbon- säuren und langkettigen Polyethern. Die erhaltenen Polymere zeichnen sich durch geringe Molekulargewichte aus und sind nicht geeignet, daraus z.B. Folien zu extru- dieren.DE-A 31 45 998 describes polyether ester amides from aminocarboxylic acids, dicarboxylic acids and long-chain polyethers. The polymers obtained are characterized by low molecular weights and are not suitable, e.g. To extrude foils.
EP-A 0 163 902 und EP-A 0 095 893 beschreiben Polyetheresteramide aus Lactamen oder Aminocarbonsäuren, Dicarbonsäuren und langkettigen Polyethern.EP-A 0 163 902 and EP-A 0 095 893 describe polyether ester amides from lactams or aminocarboxylic acids, dicarboxylic acids and long-chain polyethers.
US-A 4 230 838 beschreibt Polyetheresteramide aus einem säureterminierten Polyamid, Dicarbonsäuren und Polytetramethylenglykol.US-A 4 230 838 describes polyether ester amides from an acid-terminated polyamide, dicarboxylic acids and polytetramethylene glycol.
Die obengenannten Anmeldungen und das US-Patent beschreiben blockartig aufge- baute Polyetheresteramide, die hohe Elastizitäten aufweisen, die Eigenschaften der hohen Wasserdampfdurchlässigkeit dieser Polyetheresteramide wird jedoch nicht erwähnt.The above-mentioned applications and the US patent describe block-like polyether ester amides which have high elasticities, but the properties of the high water vapor permeability of these polyether ester amides are not mentioned.
In EP-A 0 378 015 werden Polyetheresteramide mit guter Wasserdampfdurchlässig- keit beschrieben, die wiederum blockartig aufgebaut sind und aus säureterminiertenEP-A 0 378 015 describes polyether ester amides with good water vapor permeability, which in turn have a block-like structure and are acid-terminated
Polyamiden und hydroxylfunktionellen Polyethern hergestellt werden. Es ist schwie- rig, die Stöchiometrie genau einzuhalten, um Polymere mit hohen Molekulargewichten zu erhalten. Polymere mit niedrigeren Molekulargewichten sind für Folienextrusion nur schlecht geeignet.Polyamides and hydroxyl-functional polyethers are produced. It is difficult rigorous adherence to stoichiometry to obtain high molecular weight polymers. Polymers with lower molecular weights are poorly suited for film extrusion.
Die Aufgabe der Erfindung ist die Bereitstellung von Polyetheresteramiden, die eine hohe Wasserdampfdurchlässigkeit aufweisen, für den Einsatz in der Folienextrusion geeignet sind und einfach und sicher herstellbar sowie schnell kristallisierend sind.The object of the invention is to provide polyether ester amides which have a high water vapor permeability, are suitable for use in film extrusion and are simple and safe to produce and are fast-crystallizing.
Die erfindungsgemäßen Polyetheresteramide sind weiterhin auch biologisch ab- baubar bzw. kompostierbar.The polyether ester amides according to the invention are also biodegradable or compostable.
Es wurde gefunden, daß Polyetheresteramide aufgebaut aus Lactamen, Dicarbonsäuren und einem Gemisch aus kurzkettigen und langkettigen Diolen, die eine statistische Anordnung der Ester- und Amidsegmente aufweisen, diesen Anforde- rungen genügen.It has been found that polyether ester amides composed of lactams, dicarboxylic acids and a mixture of short-chain and long-chain diols, which have a statistical arrangement of the ester and amide segments, meet these requirements.
Die Herstellung dieser Polyesteramide ist wesentlich einfacher als die bisher beschriebenen Methoden, da keine mehrstufige Fahrweise notwendig ist (vorherige Synthese von säureterminierten kurzkettigen Polyamiden) und die Stöchiometrie der Synthese durch den zusätzlichen Einsatz von kurzkettigen Diolverbindungen sehr gut einzuhalten ist und damit sehr hochmolekulare Polyetheresteramide erhalten werden, die hervorragend für Extrusionsanwendungen geeignet sind.The preparation of these polyester amides is much simpler than the methods described so far, since a multi-stage procedure is not necessary (prior synthesis of acid-terminated short-chain polyamides) and the stoichiometry of the synthesis can be maintained very well by the additional use of short-chain diol compounds and very high molecular weight polyether ester amides are thus obtained that are ideal for extrusion applications.
Gegenstand der Erfindung sind daher Polyetheresteramide, die eine statistische Anordnung der Ester- und Amidsegmente aufweisen und wobei die Alkoholkomponente aus monomeren und oligomeren Diolen besteht.The invention therefore relates to polyether ester amides which have a statistical arrangement of the ester and amide segments and where the alcohol component consists of monomeric and oligomeric diols.
Der Gehalt an oligomerem Diol, bezogen auf den Gesamtgehalt der Alkoholkomponente beträgt im allgemeinen 3 bis 99, vorzugsweise 5 bis 80 Mol-%, besonders bevorzugt 15 bis 80 Mol-%, insbesondere 15 bis 50 Mol-%. Die Polyetheresteramide sind vorzugsweise aufgebaut aus den folgenden Monomeren:The content of oligomeric diol, based on the total content of the alcohol component, is generally 3 to 99, preferably 5 to 80 mol%, particularly preferably 15 to 80 mol%, in particular 15 to 50 mol%. The polyether ester amides are preferably composed of the following monomers:
Oligomere Polyole bestehend aus Polyethylenglykolen, Polypropylenglykolen, statis- tisch oder blockartig aufgebauten Polyglykolen aus Mischungen aus Ethylenoxid oder Propylenoxid, oder Polytetrahydrofurane mit Molekulargewichten (Gewichtsmittel) zwischen 100 und 10.000 undOligomeric polyols consisting of polyethylene glycols, polypropylene glycols, randomly or block-like polyglycols from mixtures of ethylene oxide or propylene oxide, or polytetrahydrofurans with molecular weights (weight average) between 100 and 10,000 and
monomere Diole, vorzugsweise C2-Cj2-Alkyl-Diole, insbesondere C2-C,5-Alkyl- diole, beispielsweise und bevorzugt Ethylengykol, 1 ,4-Butandiol, 1,3-Propandiol,monomeric diols, preferably C2-C j 2-alkyldiols, in particular C 2 -C, 5-alkyldiols, for example and preferably ethylene glycol, 1,4-butanediol, 1,3-propanediol,
1 ,6-Hexandiol,1, 6-hexanediol,
und mindestens einem Monomer ausgewählt aus der Gruppe derand at least one monomer selected from the group of
Dicarbonsäuren, vorzugsweise C2-C12-, besonders bevorzugt C2-Cö-Alkyldicarbon- säuren, beispielsweise und bevorzugt Oxalsäure, Bernsteinsäure, Adipinsäure, auch in Form ihrer jeweiligen Ester (Methyl-, Ethyl- usw.),Dicarboxylic acids, preferably C2-C12-, particularly preferably C2-Cö-alkyldicarboxylic acids, for example and preferably oxalic acid, succinic acid, adipic acid, also in the form of their respective esters (methyl, ethyl, etc.),
Alkylhydroxycarbonsäuren mit vorzugsweise 2 bis 12 Kohlenstoffatomen in der Alkylkette und Lactone wie beispielsweise und bevorzugt Caprolacton u.a.,Alkylhydroxycarboxylic acids with preferably 2 to 12 carbon atoms in the alkyl chain and lactones such as and preferably caprolactone and others,
Aminoalkohole vorzugsweise mit 2 bis 12 Kohlenstoffatomen in der Alkylkette, beispielsweise und bevorzugt Ethanolamin, Propanolamin,Amino alcohols preferably having 2 to 12 carbon atoms in the alkyl chain, for example and preferably ethanolamine, propanolamine,
cyclische Lactame vorzugsweise mit 5 bis 12, bevorzugt 6 bis 11 C-Atomen. wie beispielsweise und bevorzugt ε-Caprolactam oder Laurinlactam usw.,Cyclic lactams preferably having 5 to 12, preferably 6 to 11 carbon atoms. such as and preferably ε-caprolactam or laurolactam etc.,
ω -Aminocarbonsäuren vorzugsweise mit 6 bis 12 C-Atomen in der Alkylkette wie beispielsweise und bevorzugt Aminocapronsäure usw., Mischungen (1 :1 Salze) aus C2-Cj2 _Alkyldicarbonsäuren, beispielsweise und bevorzugt Adipinsäure, Bernsteinsäure und C2-Ci2-Nlkyldiaminen, vorzugsweise C4-C6- Dialkylaminen, beispielsweise und bevorzugt Hexamethylendiamin, Diaminobutan.ω-aminocarboxylic acids, preferably having 6 to 12 carbon atoms in the alkyl chain, such as, for example, and preferably aminocaproic acid, etc., Mixtures (1: 1 salts) of C2-Cj 2 _ alkyldicarboxylic acids, for example and preferably adipic acid, succinic acid and C2-Ci 2 -alkyldiamines, preferably C 4 -C 6 -dialkylamines, for example and preferably hexamethylenediamine, diaminobutane.
Ebenso können sowohl hydroxyl- oder säureterminierte Polyester mit Molekulargewichten zwischen 300 und 10.000 als esterbildende Komponente eingesetzt werden.Likewise, both hydroxyl- or acid-terminated polyesters with molecular weights between 300 and 10,000 can be used as the ester-forming component.
Die erfindungsgemäßen Polyetheresteramide können weiterhin 0,05 bis 5 Gew.-%, bevorzugt 0,1 bis 1 Gew.-% an Verzweigern enthalten. Diese Verzweiger können z.B. trifunktionelle Alkohole wie Trimethylolpropan oder Glycerin, tetrafunktionelleThe polyether ester amides according to the invention can further contain 0.05 to 5% by weight, preferably 0.1 to 1% by weight, of branching agents. These branchers can e.g. trifunctional alcohols such as trimethylolpropane or glycerin, tetrafunctional
Alkohole wie Pentaerythrit, trifunktionelle Carbonsäuren wie Citronensäure oder auch tri- oder tetrafunktionelle Hydroxycarbonsäuren sein. Die Verzweiger erhöhen die Schmelzviskosität der erfindungsgemäßen Polyetheresteramide soweit, daß Extrusionsblasformen mit diesen Polymeren möglich wird.Alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid or tri- or tetrafunctional hydroxycarboxylic acids. The branching agents increase the melt viscosity of the polyether ester amides according to the invention to such an extent that extrusion blow molding is possible with these polymers.
Der Anteil der Ether- und Esteranteile im Polymer beträgt im allgemeinen 5 bis 85, vorzugsweise 20 bis 80 Gew.-%, bezogen auf das Gesamtpolymer.The proportion of ether and ester fractions in the polymer is generally 5 to 85, preferably 20 to 80,% by weight, based on the total polymer.
Die erfindungsgemäßen Polyetheresteramide haben im allgemeinen ein mittleres Molekulargewicht (Mw ermittelt nach Gelchromatographie im Kresol gegen Standard Polystyrol) von 10.000 bis 300.000, vorzugsweise von 15.000 bis 150.000, insbesondere 15.000 bis 100.000.The polyetheresteramides according to the invention generally have an average molecular weight (Mw determined according to gel chromatography in cresol against standard polystyrene) from 10,000 to 300,000, preferably from 15,000 to 150,000, in particular 15,000 to 100,000.
Die Synthese kann sowohl nach der „Polyamidmethode" durch stöchiometrisches Mischen der Ausgangskomponenten gegebenenfalls unter Zusatz von Wasser und anschließendem Entfernen von Wasser aus dem Reaktionsgemisch als auch nach der „Polyestermethode" durch Zugabe eines Überschusses an Diol mit Veresterung der Säuregruppen und nachfolgender Umesterung bzw. Unamidierung dieser Ester erfolgen. In diesem zweiten Fall wird neben Wasser auch der Überschuß an Glykol wieder abdestilliert. Die Reaktion findet im allgemeinen bei Temperaturen von 180 bis 280°C und unter vermindertem Druck, vorzugsweise < 5 mbar, insbesondere < 1 mbar statt.The synthesis can be carried out 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 adding an excess of diol with esterification of the acid groups and subsequent transesterification or unamidation these esters are made. In this second case, the excess glycol is distilled off in addition to water. The reaction generally takes place at temperatures of 180 up to 280 ° C and under reduced pressure, preferably <5 mbar, in particular <1 mbar.
Bei der Herstellung der erfmdungsgemäßen Polyetheresteramide kann man geeignete Katalysatoren zur Katalyse der Veresterungs- bzw. Amidierungsreaktionen einsetzen.In the preparation of the polyether ester amides according to the invention, suitable catalysts can be used to catalyze the esterification or amidation reactions.
Dazu gehören z.B. Titanverbindungen für die Veresterungen bzw. Phosphorverbindungen für die Amidierungsreaktionen. Diese Katalysatoren sind aus dem Stand der Technik bekannt.These include e.g. Titanium compounds for the esterifications or phosphorus compounds for the amidation reactions. These catalysts are known from the prior art.
Die Polyetheresteramide gemäß vorliegender Erfindung können mit Füll- undThe polyether ester amides according to the present invention can be filled and
Verstärkungsstoffen und üblichen Additiven gemischt werden. In der Regel können bis zu 80 Gew.-% (bezogen auf Polyetheresteramid) Füll- und Verstärkungsstoffe zugesetzt werden.Reinforcing materials and common additives are mixed. As a rule, up to 80% by weight (based on polyetheresteramide) of fillers and reinforcing materials can be added.
Als Füll- und Verstärkungsstoffe werden im allgemeinen anorganische Materialien eingesetzt. Dies sind faserige Verstärkungsstoffe, wie Glas und Kohlenstoffasern, und mineralische Füllstoffe, z.B. Talkum, Glimmer, Kreide, Kaolin, Wollastonit, Gips, Quarz, Dolomit, Silikate.In general, inorganic materials are used as fillers and reinforcing materials. These are fibrous reinforcing materials such as glass and carbon fibers and mineral fillers, e.g. Talc, mica, chalk, kaolin, wollastonite, gypsum, quartz, dolomite, silicates.
Die Füll- und Verstärkungsstoffe können auch oberflächenbehandelt sein.The fillers and reinforcing materials can also be surface-treated.
Glasfasern haben im allgemeinen einen Faserdurchmesser zwischen 8 und 14 μm und können als Endlosfasern oder als geschnittene oder gemahlene Glasfasern eingesetzt werden, wobei die Fasern mit einem geeigneten Schlichtesystem und einem Haftvermittler bzw. Haftvermittlersystem auf Silanbasis ausgerüstet sein können.Glass fibers generally have a fiber diameter between 8 and 14 μm and can be used as continuous fibers or as cut or ground glass fibers, the fibers being able to be equipped with a suitable sizing system and an adhesion promoter or adhesion promoter system based on silane.
Die Polyetheresteramide können weiterhin 1 bis 90, vorzugsweise 10 bis 60, insbesondere 15 bis 50, Gew. -Teile (bezoden auf Polyetheresteramid) Stärke, modifizierte Stärke, Cellulose und/oder modifizierte Cellulose, enthalten. Als Stärke kann bei- spielsweise die in WO 96/31 561 beschriebene Stärke eingesetzt werden. Als übliche Additive kommen ferner in Fage:The polyetheresteramides may further contain 1 to 90, preferably 10 to 60, in particular 15 to 50 parts by weight (based on polyetheresteramide) of starch, modified starch, cellulose and / or modified cellulose. For example, the starch described in WO 96/31 561 can be used as starch. Other possible additives are:
UV-Stabilisatoren, Antioxidantien, Pigmente, Farbstoff, Nukleiermittel, Kristallisationsbeschleuniger bzw. -verzögerer, Fließhilfsmittel, Gleitmittel, Entformungs- mittel, Flammschutzmittel, Hydrophobierungsmittel. Weiterhin können Weich- macher und/oder Schlagzähmodifikatoren zugesetzt werden.UV stabilizers, antioxidants, pigments, dyes, nucleating agents, crystallization accelerators and retarders, flow aids, lubricants, mold release agents, flame retardants, water repellents. Plasticizers and / or impact modifiers can also be added.
Die erfindungsgemäßen Polyetheresteramide können auch mit biologisch abbaubaren Polymeren als Blend eingesetzt werden. Dazu zählen z.B. aliphatische Polyester wie Polycaprolacton, aliphatisch-aromatische Polyester aus z.B. Terephthalsäure, Butan- diol und Adipinsäure, Polyhydroxybuttersäure, Polylactide und Copolymere daraus,The polyether ester amides according to the invention can also be used as a blend with biodegradable polymers. These include e.g. aliphatic polyesters such as polycaprolactone, aliphatic-aromatic polyesters from e.g. Terephthalic acid, butanediol and adipic acid, polyhydroxybutyric acid, polylactides and copolymers thereof,
Polyesterurethane (z.B. EP-A 593 975).Polyester urethanes (e.g. EP-A 593 975).
Die erfindungsgemäßen Mischungen aus Polyetheresteramid und Füll- und Verstärkungsstoffen und gegebenenfalls weiteren Additiven können hergestellt werden, indem man die jeweiligen Bestandteile in bekannter Weise mischt und bei üblichenThe mixtures according to the invention of polyether ester amide and fillers and reinforcing materials and, if appropriate, further additives can be prepared by mixing the respective constituents in a known manner and in the customary manner
Temperaturen, z.B. bei 180°C bis 300°C, in üblichen Aggregaten wie Innenknetern, Extrudern, Doppelwellenschnecken, schmelzcompoundiert oder schmelzextrudiert.Temperatures, e.g. at 180 ° C to 300 ° C, in conventional units such as internal kneaders, extruders, twin-screw extruders, melt-compounded or melt-extruded.
Die Polyetheresteramide der vorliegenden Erfindung und deren obengenannten Mischungen können im Spritzguß, als Faser oder Folie oder im Non-woven-BereichThe polyether ester amides of the present invention and their mixtures mentioned above can be used in injection molding, as a fiber or film or in the non-woven sector
(spun-bond oder melt-blown) insbesondere zur Herstellung von Folien, beispielsweise durch Blasextrusion, verwendet werden. (spun-bond or melt-blown) can be used in particular for the production of films, for example by bubble extrusion.
BeispieleExamples
Beispiel 1example 1
246,6 g Caprolactam, 28,2 g Adipinsäure, 29,5 g Butandiol und 78,4 g Polyethylen- glykol 200 werden mit Titantetraisopropylat als Katalysator zusammengegeben und unter Stickstoff auf 240°C erhitzt. Nach dem Abdestülieren von Wasser wird der Druck stufenweise bis auf 1 mbar abgesenkt.246.6 g of caprolactam, 28.2 g of adipic acid, 29.5 g of butanediol and 78.4 g of polyethylene glycol 200 are combined with titanium tetraisopropylate as a catalyst and heated to 240 ° C. under nitrogen. After water has been removed, the pressure is gradually reduced to 1 mbar.
Nach 3 h Polykondensationszeit erhält man ein farbloses hochmolekulares MaterialAfter 3 h of polycondensation, a colorless, high molecular weight material is obtained
(relative Viskosität von 2,9 gemessen in 1 gew.-%iger Lösung in m-Kresol bei 25°C) mit einem Schmelzpunkt von 134°C. M w = 25.000, gemessen mittels GPC in Kresol gegen Polystyrol als Standard(Relative viscosity of 2.9 measured in 1% by weight solution in m-cresol at 25 ° C) with a melting point of 134 ° C. M w = 25,000, measured by means of GPC in cresol against polystyrene as standard
Beispiel 2Example 2
710 g AH-Salz, 253 g Adipinsäure, 184 g Diethylenglykol und 1380 g Polyethylen- glykol 400 werden mit Titantetraisopropylat als Katalysator zusammengegeben und unter Stickstoff auf 240°C erhitzt. Nach dem Abdestülieren von Wasser wird der Druck stufenweise bis auf 1 mbar abgesenkt.710 g of AH salt, 253 g of adipic acid, 184 g of diethylene glycol and 1380 g of polyethylene glycol 400 are combined with titanium tetraisopropylate as a catalyst and heated to 240 ° C. under nitrogen. After water has been removed, the pressure is gradually reduced to 1 mbar.
Nach 3 h Polykondensationszeit erhält man ein farbloses hochmolekulares Material (relative Viskosität von 3,2, gemessen in 1 gew.-%iger Lösung in m-Kresol bei 25°C) mit einem Schmelzpunkt von 186°C. M w = 28.000, gemessen mittels GPC in Kresol gegen Polystyrol als StandardAfter a polycondensation time of 3 h, a colorless, high molecular weight material (relative viscosity of 3.2, measured in 1% strength by weight solution in m-cresol at 25 ° C.) with a melting point of 186 ° C. is obtained. M w = 28,000, measured by means of GPC in cresol against polystyrene as standard
Beispiel 3Example 3
256,6 g Caprolactam, 66,0 g Adipinsäure, 20,4 g 1 ,4-Butandiol, 108,0 g Poly- ethylenglykol (PEG 400, Fa. BASF), 3,03 g Trimethylolpropan werden mit Titantetraisopropylat als Katalysator unter Stickstoff auf 250°C erwärmt. Bei nachlassen- der Destillationsgeschwindigkeit wird langsam Wasserstrahlvakuum, anschließend Ölpumpenvakuum (ca. 1 mbar) angelegt. Es wird bei dieser Temperatur 3 h polykondensiert und abgekühlt.256.6 g of caprolactam, 66.0 g of adipic acid, 20.4 g of 1,4-butanediol, 108.0 g of polyethylene glycol (PEG 400, from BASF) and 3.03 g of trimethylolpropane are used with titanium tetraisopropylate as a catalyst under nitrogen heated to 250 ° C. With easing the distillation rate is slowly applied to a water jet vacuum, followed by an oil pump vacuum (approx. 1 mbar). It is polycondensed at this temperature for 3 h and cooled.
Man erhält ein hochmolekulares Polymer mit ηre| 3,0 (1 gew.-%ig in m-Kresol bei 25°C). Der Schmelzpunkt beträgt 155,4°C, die Kristallisationstemperatur 92,9°C (DS C-Messungen) .A high molecular polymer with η re | is obtained 3.0 (1% by weight in m-cresol at 25 ° C). The melting point is 155.4 ° C, the crystallization temperature 92.9 ° C (DS C measurements).
Beispiel 4Example 4
653 g Caprolactam, 253 g Adipinsäure, 156 g 1,4-Butandiol und 1 380 g PEG 400 werden in Trimethylolpropan mit Titantetraisopropylat als Katalysator unter Stickstoff auf 250°C erwärmt. Bei nachlassender Destillationsgeschwindigkeit wird langsam Wasserstrahlvakuum, anschließend Ölpumpenvakuum (ca. 1 mbar) angelegt. Es wird bei dieser Temperatur 3 h polykondensiert und abgekühlt.653 g of caprolactam, 253 g of adipic acid, 156 g of 1,4-butanediol and 1,380 g of PEG 400 are heated to 250 ° C. in trimethylolpropane using titanium tetraisopropylate as a catalyst under nitrogen. When the distillation speed decreases, water jet vacuum is slowly applied, followed by an oil pump vacuum (approx. 1 mbar). It is polycondensed at this temperature for 3 h and cooled.
Man erhält ein hochmolekulares Polymer mit ηreι 3,0 (1 gew.-%ig in m-Kresol bei 25°C).A high molecular weight polymer with η re ι 3.0 (1% by weight in m-cresol at 25 ° C.) is obtained.
Der Schmelzpunkt eträgt 118J°C, die Kristallisationstemperatur 73,3°C (lt. DSC). The melting point is 118J ° C, the crystallization temperature 73.3 ° C (according to DSC).
VergleichsversuchComparison test
557 g Caprolactam, 287,8 g Adipinsäure, 221,0 g 1 ,4-Butandiol und 6,6 g Trimethylolpropan werden mit Titantetraisopropylat als Katalysator unter Stickstoff auf 250°C erwärmt. Bei nachlassender Destillationsgeschwindigkeit wird langsam Wasserstrahlvakuum, anschließend Ölpumpenvakuum (ca. 1 mbar) angelegt. Es wird bei dieser Temperatur 3 h polykondensiert und abgekühlt.557 g of caprolactam, 287.8 g of adipic acid, 221.0 g of 1,4-butanediol and 6.6 g of trimethylolpropane are heated to 250 ° C. using titanium tetraisopropoxide as a catalyst under nitrogen. When the distillation speed decreases, water jet vacuum is slowly applied, followed by an oil pump vacuum (approx. 1 mbar). It is polycondensed at this temperature for 3 h and cooled.
Man erhält ein hochmolekulares Polymer mit ηrej 2,8 (1 gew.-%ig in m-Kresol bei 25°C).A high molecular weight polymer with η re j 2.8 (1% by weight in m-cresol at 25 ° C.) is obtained.
Der Schmelzpunkt eträgt 118J°C, die Kristallisationstemperatur 41,4°C (DSC- Messungen).The melting point is 118J ° C, the crystallization temperature 41.4 ° C (DSC measurements).
Die Wasserdampfdurchlässigkeit bei 23°C/85 % relativer Feuchte, gemessen an einerThe water vapor permeability at 23 ° C / 85% relative humidity, measured on a
20 μm dicken Folie nach DIN 53 122 Teil 1 beträgt:20 μm thick film according to DIN 53 122 part 1 is:
Beispiel 1: 420 Beispiel 2: 1120 Beispiel 3: 780Example 1: 420 Example 2: 1120 Example 3: 780
Beispiel 4: 920 Vergleichsbeispiel: 210 Example 4: 920 Comparative example: 210

Claims

Patentansprüche claims
1. Polyetheresteramide, die eine statistische Anordnung der Ester- und Amidsegmente aufweisen und wobei die Alkoholkomponente aus monomeren und oligomeren Diolen besteht.1. Polyetheresteramides which have a statistical arrangement of the ester and amide segments and where the alcohol component consists of monomeric and oligomeric diols.
2. Polyetheresteramide gemäß Anspruch 1, wobei der Esteranteil 5 bis 85 Gew.-%, der Amidanteil 15 bis 95 Gew.-%, jeweils bezogen auf das Gesamtpolymer, betragen.2. polyether ester amides according to claim 1, wherein the ester content 5 to 85 wt .-%, the amide content 15 to 95 wt .-%, each based on the total polymer.
3. Polyetheresteramide gemäß Anspruch 1, wobei der Gehalt an oligomerem Diol, bezogen auf den Gesamtgehalt der Alkoholkomponente 3 bis 99 Mol-% beträgt.3. polyether ester amides according to claim 1, wherein the content of oligomeric diol, based on the total content of the alcohol component is 3 to 99 mol%.
4. Polyetheresteramide gemäß Anspruch 1, wobei der Gehalt an oligomerem4. polyether ester amides according to claim 1, wherein the content of oligomeric
Diol 5 bis 50 Mol-% beträgt.Diol is 5 to 50 mol%.
5. Polyetheresteramide gemäß Anspruch 1, aufgebaut aus den folgenden Monomeren:5. Polyetheresteramides according to claim 1, built up from the following monomers:
Oligomere Polyole bestehend aus Polyethylenglykolen, Polypropylengly- kolen, statistisch oder blockartig aufgebauten Polyglykolen aus Mischungen aus Ethylenoxid oder Propylenoxid, oder Polytetrahydrofurane mit Molekulargewichten (Gewichtsmittel) zwischen 100 und 10.000 undOligomeric polyols consisting of polyethylene glycols, polypropylene glycols, randomly or block-like polyglycols from mixtures of ethylene oxide or propylene oxide, or polytetrahydrofurans with molecular weights (weight average) between 100 and 10,000 and
monomere Diolemonomeric diols
und mindestens einem Monomer ausgewählt aus der Gruppe der Dicarbonsäuren, Alkylhydroxycarbonsäuren, Lactone, Aminoalkohole, cyclische Lactame, ω -Aminocarbonsäuren, Mischungen (1:1 Salze) aus C2-C ^-Alkyldicarbonsäuren und C2-C12-Dialkylaminen.and at least one monomer selected from the group of Dicarboxylic acids, alkylhydroxycarboxylic acids, lactones, amino alcohols, cyclic lactams, ω-amino carboxylic acids, mixtures (1: 1 salts) of C2-C ^ -alkyldicarboxylic acids and C2-C 12 -dialkylamines.
6. Polyetheresteramide gemäß Anspruch 5, aufgebaut aus den folgenden6. Polyetheresteramides according to claim 5, constructed from the following
Monomeren:Monomers:
Oligomere Polyole bestehend aus Polyethylenglykolen, Polypropylengly- kolen, statistisch oder blockartig aufgebauten Polyglykolen aus Mischungen aus Ethylenoxid oder Propylenoxid, oder Polytetrahydrofurane mit Molekulargewichten (Gewichtsmittel) zwischen 100 und 10.000 und C2-Ci2- Alkyl-Diole, und mindestens ein Monomer ausgewählt aus der Gruppe der C2-C 12- Alkyldicarbonsäuren, C2-C \ 2-Alkylhydroxycarbonsäuren, Aminoalkohole mit 2 bis 12 C-Atomen in der Alkylkette, cyclische Lactame mit 5 bis 12 C-Atomen, ω -Aminocarbonsäuren mit 6 bis 12 C-Atomen, Mischungen (1:1 Salze) aus C2-C12- Alkyldicarbonsäuren und C2-C12-Dialkylaminen.Oligomeric polyols consisting of polyethylene glycols, polypropylene glycols, randomly or block-shaped polyglycols from mixtures of ethylene oxide or propylene oxide, or polytetrahydrofurans with molecular weights (weight average) between 100 and 10,000 and C 2 -Ci2 alkyl diols, and at least one monomer selected from the group Group of C2-C 1 2 -alkyldicarboxylic acids, C2-C \ 2-alkylhydroxycarboxylic acids, amino alcohols with 2 to 12 C atoms in the alkyl chain, cyclic lactams with 5 to 12 C atoms, ω-amino carboxylic acids with 6 to 12 C atoms , Mixtures (1: 1 salts) of C2-C 12 alkyldicarboxylic acids and C2-C 12 dialkylamines.
7. Mischung aus Polyetheresteramiden gemäß Anspruch 1 mit Füll- und Verstärkungsstoffen und gegebenenfalls üblichen Additiven.7. Mixture of polyether ester amides according to claim 1 with fillers and reinforcing materials and optionally conventional additives.
8. Verwendung der Polyetheresteramide und der Mischungen gemäß Anspruch 1 und 6 zur Herstellung von Spritzgußartikeln, Folien, Fasern oder Non- Woven Material.8. Use of the polyether ester amides and the mixtures according to claims 1 and 6 for the production of injection molded articles, foils, fibers or non-woven material.
9. Spritzgußartikel, Folien, Faser und Non-Woven Material erhältlich aus Polyetheresteramiden gemäß Anspruch 1 bis 7. 9. injection molded articles, films, fibers and non-woven material obtainable from polyether ester amides according to claims 1 to 7.
EP98956937A 1997-12-03 1998-11-20 Polyether ester amides Withdrawn EP1036107A1 (en)

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DE1997153534 DE19753534A1 (en) 1997-12-03 1997-12-03 Biodegradable thermoplastic polyester-amides with good mechanical properties for molding, film and fiber, useful for e.g. compostable refuse bag
DE19753534 1997-12-03
DE19753532 1997-12-03
DE1997153532 DE19753532A1 (en) 1997-12-03 1997-12-03 Easily produced random polyether-ester-amides with high water vapor permeability, suitable for film extrusion
PCT/EP1998/007458 WO1999028371A1 (en) 1997-12-03 1998-11-20 Polyether ester amides

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11242456B2 (en) 2018-01-23 2022-02-08 Solutia Inc. Interlayers comprising polyesteramide compositions

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10027905A1 (en) * 2000-06-06 2001-12-13 Bayer Ag Biodegradable molding composition, useful for the production of plant covers, disposable cutlery, casings or packaging, comprises a biodegradable polymer and a mineral and/or a renewable material,
US7776314B2 (en) 2002-06-17 2010-08-17 Grunenthal Gmbh Abuse-proofed dosage system
DE10336400A1 (en) * 2003-08-06 2005-03-24 Grünenthal GmbH Anti-abuse dosage form
DE102005005446A1 (en) 2005-02-04 2006-08-10 Grünenthal GmbH Break-resistant dosage forms with sustained release
DE102004032051A1 (en) * 2004-07-01 2006-01-19 Grünenthal GmbH Process for the preparation of a secured against misuse, solid dosage form
US20070048228A1 (en) 2003-08-06 2007-03-01 Elisabeth Arkenau-Maric Abuse-proofed dosage form
DE102004020220A1 (en) * 2004-04-22 2005-11-10 Grünenthal GmbH Process for the preparation of a secured against misuse, solid dosage form
DE10361596A1 (en) 2003-12-24 2005-09-29 Grünenthal GmbH Process for producing an anti-abuse dosage form
BR122018068298B8 (en) * 2003-08-06 2021-07-27 Gruenenthal Gmbh process for producing an abuse-safe thermoformed tablet by extrusion without bleaching
US8075872B2 (en) * 2003-08-06 2011-12-13 Gruenenthal Gmbh Abuse-proofed dosage form
US8685431B2 (en) * 2004-03-16 2014-04-01 Advanced Cardiovascular Systems, Inc. Biologically absorbable coatings for implantable devices based on copolymers having ester bonds and methods for fabricating the same
PT1602600T (en) * 2004-06-03 2020-01-24 Novamont Spa Ventilated system for the collection of organic waste
DE102004032103A1 (en) * 2004-07-01 2006-01-19 Grünenthal GmbH Anti-abuse, oral dosage form
DE102004032049A1 (en) * 2004-07-01 2006-01-19 Grünenthal GmbH Anti-abuse, oral dosage form
DE102005005449A1 (en) * 2005-02-04 2006-08-10 Grünenthal GmbH Process for producing an anti-abuse dosage form
US20070106034A1 (en) * 2005-11-03 2007-05-10 Annett Linemann Process to make copolymers having polyamide blocks and polyether blocks
DE102007011485A1 (en) * 2007-03-07 2008-09-11 Grünenthal GmbH Dosage form with more difficult abuse
KR100909749B1 (en) * 2007-11-19 2009-07-29 도레이새한 주식회사 Vehicle coating film protective cover processed from non-woven tissue material and manufacturing method thereof
US8383152B2 (en) 2008-01-25 2013-02-26 Gruenenthal Gmbh Pharmaceutical dosage form
HUE030803T2 (en) * 2008-05-09 2017-06-28 Gruenenthal Gmbh Process for the preparation of an intermediate powder formulation and a final solid dosage form under usage of a spray congealing step
FR2936803B1 (en) * 2008-10-06 2012-09-28 Arkema France BLOCK COPOLYMER DERIVED FROM RENEWABLE MATERIALS AND METHOD FOR MANUFACTURING SUCH A BLOCK COPOLYMER.
AR077420A1 (en) 2009-07-22 2011-08-24 Gruenenthal Gmbh DOSAGE METHOD RESISTANT TO HANDLING FOR OXIDATION SENSITIVE OPTIONS
EP2456427B1 (en) 2009-07-22 2015-03-04 Grünenthal GmbH Hot-melt extruded controlled release dosage form
EP2531176B1 (en) * 2010-02-03 2016-09-07 Grünenthal GmbH Preparation of a powdery pharmaceutical composition by means of an extruder
ES2486791T3 (en) 2010-09-02 2014-08-19 Grünenthal GmbH Tamper resistant dosage form comprising an inorganic salt
JP5933553B2 (en) 2010-09-02 2016-06-15 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Tamper resistant dosage forms containing anionic polymers
RS56527B1 (en) 2011-07-29 2018-02-28 Gruenenthal Gmbh Tamper-resistant tablet providing immediate drug release
LT2736495T (en) 2011-07-29 2017-11-10 Grünenthal GmbH Tamper-resistant tablet providing immediate drug release
CN102382301B (en) * 2011-08-11 2013-05-08 浙江雅迪纤维有限公司 Melt-spinnable spandex resin and production method thereof
CA2864949A1 (en) 2012-02-28 2013-09-06 Grunenthal Gmbh Tamper-resistant dosage form comprising pharmacologically active compound and anionic polymer
EP2838512B1 (en) 2012-04-18 2018-08-22 Grünenthal GmbH Tamper resistant and dose-dumping resistant pharmaceutical dosage form
US10064945B2 (en) 2012-05-11 2018-09-04 Gruenenthal Gmbh Thermoformed, tamper-resistant pharmaceutical dosage form containing zinc
JP6466417B2 (en) 2013-05-29 2019-02-06 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング A tamper-resistant dosage form with a bimodal release profile
MX371432B (en) 2013-05-29 2020-01-30 Gruenenthal Gmbh Tamper-resistant dosage form containing one or more particles.
MX368846B (en) 2013-07-12 2019-10-18 Gruenenthal Gmbh Tamper-resistant dosage form containing ethylene-vinyl acetate polymer.
CN103524732B (en) * 2013-09-22 2015-12-09 株洲时代新材料科技股份有限公司 The production method of polyether ester amides and the application of polyether ester amides obtained thus
EP3073994A1 (en) 2013-11-26 2016-10-05 Grünenthal GmbH Preparation of a powdery pharmaceutical composition by means of cryo-milling
EP3142646A1 (en) 2014-05-12 2017-03-22 Grünenthal GmbH Tamper resistant immediate release capsule formulation comprising tapentadol
AU2015266117A1 (en) 2014-05-26 2016-11-24 Grunenthal Gmbh Multiparticles safeguarded against ethanolic dose-dumping
CN104479127B (en) * 2014-12-12 2016-10-19 东华大学 A kind of caprolactam hydrating polymer and hydrolytic polymerization method thereof
EA035434B1 (en) 2015-04-24 2020-06-15 Грюненталь Гмбх Tamper-resistant dosage form with immediate release and resistance against solvent extraction
JP2018526414A (en) 2015-09-10 2018-09-13 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Protection against oral overdose with abuse-inhibiting immediate release formulations
CN105646876B (en) 2016-04-08 2018-06-19 南京工业大学 A kind of method that organic catalysis prepares polyesteramide
CN109897370A (en) 2019-02-25 2019-06-18 佛山金万达科技股份有限公司 It is a kind of biology based elastomeric compositions and its preparation film and laminates

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE793293A (en) * 1971-12-23 1973-06-22 Bayer Ag ANTISTATIC POLYAMIDE MASSES AND THEIR PREPARATION PROCESS
FR2273021B1 (en) 1974-05-31 1977-03-11 Ato Chimie
FR2378058A1 (en) 1977-01-24 1978-08-18 Ato Chimie HYDROLYSIS STABLE COPOLYETHERESTERAMIDES
DE2712987C2 (en) * 1977-03-24 1981-09-24 Chemische Werke Hüls AG, 4370 Marl Process for the production of thermoplastic polyetheresteramides with units of the starting components randomly distributed in the polymer chain
FR2413417A1 (en) 1977-12-30 1979-07-27 Ato Chimie CONTINUOUS SYNTHESIS OF POLY SEQUENCE COPOLYCONDENSATES (ETHER-ESTER-AMIDE)
JPS5790017A (en) 1980-11-25 1982-06-04 Toray Ind Inc Production of polyether-ester-amide
JPS58206628A (en) 1982-05-27 1983-12-01 Toray Ind Inc Preparation of polyether ester amide
JPS60228533A (en) 1984-04-27 1985-11-13 Toray Ind Inc Production of polyether-ester-amide
JPS6445429A (en) * 1987-08-13 1989-02-17 Toray Industries Production of polyether ester amide
JPH02235045A (en) 1989-03-08 1990-09-18 Konica Corp Reflective support for photography

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9928371A1 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11242456B2 (en) 2018-01-23 2022-02-08 Solutia Inc. Interlayers comprising polyesteramide compositions
US11578207B2 (en) 2018-01-23 2023-02-14 Solutia Inc. Interlayers comprising polyesteramide compositions
US11767429B2 (en) 2018-01-23 2023-09-26 Eastman Chemical Company Polyesteramides, processes for the preparation thereof, and polyesteramide compositions
US11845864B2 (en) 2018-01-23 2023-12-19 Solutia Inc. Interlayers comprising polyesteramide compositions

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