CA2312489A1 - Polyolefins containing a polymer blend - Google Patents
Polyolefins containing a polymer blend Download PDFInfo
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- CA2312489A1 CA2312489A1 CA002312489A CA2312489A CA2312489A1 CA 2312489 A1 CA2312489 A1 CA 2312489A1 CA 002312489 A CA002312489 A CA 002312489A CA 2312489 A CA2312489 A CA 2312489A CA 2312489 A1 CA2312489 A1 CA 2312489A1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
- C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- 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
Abstract
The invention relates to mixtures containing the following: 1) 5 to 95 parts by weight of at least one polymer selected from the group of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides and/or polyether ester amides; 2) 5 to 70 parts by weight polyolefins; 3) 0 to 25 parts by weight modified polyolefins and 4) 0 to 80 parts by weight fillers and reinforcing agents.
Description
Polymer blend containing polyolefins Interest is increasingly being shown in materials which are very comfortable to wear, i.e. materials which exhibit elevated water vapour permeability. 'This elevated water vapour permeability is a property necessary to many areas of use, such as clothing and sanitary products (e.g. nappies) but also in the building sector for roof lining membranes, allowing the achievement of a high level of functional efficiency.
High water vapour permeability levels are exhibited by various materials, e.g.
Gore-Tex~ (specially stretched polytetrafluoroethylene films made by Gore Ind.) or Sympatex~ (aliphatic-aromatic polyether esters made by Akzo) (c.f. Rompps Chemie-Lexikon, Vol. 6, p. 5000, Thieme Verlag Stuttgart, 9th Edition 1992).
Both materials exhibit the disadvantage of requiring special production methods and in addition the raw materials are very expensive.
The object therefore arose of achieving high water vapour permeability levels with materials which are easy to produce and exhibit the mechanical properties required for the various applications.
It was surprisingly found that blends of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic polyester amides and/or polyether ester amides with polyolefins, optionally modified polyolefins, together optionally with fillers and reinforcing materials, exhibit very high levels of water vapour permeability. Films made from the blend according to the invention additionally exhibit the property that they may be drawn out very thinly, in contrast to pure filled polyolefin films.
The invention relates to mixtures containing 1 ) 5 to 95, preferably 10 to $0, in particular 1 S to 60 parts by weight of at least one polymer selected from the group consisting of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides and/or polyether ester amides, 2) 5 to 70, preferably 7 to 60, in particular 10 to 50 parts by weight of polyolefins, 3) 0 to 25, preferably 0 to 20, in particular 0 to 15 parts by weight of modified polyolefins and 4) 0 to 80, preferably 0 to 70, in particular 5 to 60 parts by weight of fillers and reinforcing materials, wherein the sum of 1), 2), 3) and 4) is 100.
Component 1) The polymers according to component 1 ) are selected from at least one polymer from the group consisting of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides and polyether ester amides.
The following polymers are suitable:
Aliphatic or partially aromatic polyesters from A) aliphatic bifunctional alcohols, preferably linear CZ to C,o, preferably Cz dialcohols such as, for example, ethanediol, propanediol, butanediol, hexanediol or particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 or 6 C atoms in the cycloaliphatic ring, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 8000, preferably up to 4000, and/or optionally small amounts of branched bifunctional alcohols, preferably C3 -C,, alkyl diols, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols such as for example 1,2,3-propanetriol or trimethylolpropane, as well as from aliphatic bifunctional acids, preferably Cz - C,z alkyl dicarboxylic acids, such as for example and preferably succinic acid, adipic acid, and/or optionally aromatic bifunctional acids, such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or B) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example E-caprolactone or dilactide, or a mixture and/or copolymer of A and B, wherein the aromatic acids preferably constitute a fraction of no more than 80, in particular 50 wt.%, relative to all the acids;
aliphatic or partially aromatic polyester urethanes from C) aliphatic bifunctional alcohols, preferably linear CZ to C,o, preferably Cz dialcohols such as, for example, ethanediol, propanediol, butanediol, hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with a CS or C6 cycloaliphatic ring, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000, preferably up to 1000, and/or optionally small amounts of branched bifunctional alcohols, preferably C3 -C,Z alkyl diols, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols, preferably C3 -C,Z alkyl polyols, such as for example 1,2,3-propanetriol or trimethylolpropane, as well as from aliphatic bifunctional acids, preferably CZ - C,z alkyl dicarboxylic acids, such as for example and preferably succinic acid, adipic acid, and/or optionally aromatic bifunctional acids, such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or D) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example s-caprolactone or dilactide, or a mixture and/or copolymer of C and D, wherein the aromatic acids preferably constitute a fraction of no more than 80, in particular 50 wt.%, relative to all the acids;
E) from the reaction product of C and/or D with aliphatic and/or cycloaliphatic bifunctional and additionally optionally more highly functional isocyanates, with preferably 1 to 12 C atoms or 5 to 8 C atoms in the case of p0 cycloaliphatic isocyanates, e.g. tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally additionally with linear and/or branched and/or cycloaliphatic bifunctional and/or more highly functional alcohols, preferably C3 - C,Z alkyl di- or polyols or 5 to 8 C
atoms , in the case of cycloaliphatic alcohols, e.g. ethanediol, hexanediol, butanediol, cyclohexane-dimethanol, and/or optionally additionally with linear and/or branched and/or cycloaliphatic bifunctional and/or more highly functional amines and/or amino alcohols with preferably 2 to 12 C atoms in the alkyl chain, e.g. ethylene diamine or aminoethanol, and/or optionally further modified amines or alcohols such as for example ethylenediaminoethanesulfonic acid, as a free acid or salt, wherein the ester fraction C) and/or D) preferably amounts to at least 40, in particular 75 wt.%, relative to the sum of C), D) and E);
aliphatic or aliphatic-aromatic polyester carbonates from F) aliphatic bifunctional alcohols, preferably linear CZ to C,°
dialcohols such as, for example, ethanediol, butanediol, hexanediol or particularly preferably butanediol, andlor optionally cycloaliphatic bifunctional alcohols, preferably with 5 to 8 C atoms in the cycloaliphatic ring, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 8000, preferably up to 4000, and/or optionally small amounts of branched bifunctional alcohols, preferably CZ - C,z alkyldicarboxylic acids, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane, as well as from aliphatic bifunctional acids, such as for example and preferably succinic acid, adipic acid and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or G) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example s-caprolactone or dilactide, or a mixture and/or copolymer of F and G, wherein the aromatic acids preferably constitute a fraction of no more than SO
wt.%, relative to all the acids;
H) a carbonate fraction, which is produced from aromatic bifunctional phenols, preferably bisphenol A and carbonate donors, for example phosgene, or a carbonate fraction, which is produced from aliphatic carbonic acid esters or derivatives thereof, such as for example chloroformic acid esters or aliphatic carboxylic acids or derivatives thereof such as for example salts and carbonate donors, for example phosgene, wherein the ester fraction F) and/or G) preferably amounts to at least 40, in particular 70 wt.%, relative to the sum of F), G) and H);
aliphatic or partially aromatic polyester amides or polyether ester amides from I) aliphatic bifunctional alcohols, preferably linear CZ to C,°, preferably Cz - C6 dialcohols such as, for example, ethanediol, propanediol, butanediol, hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 to 8 C atoms, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 10,000, preferably up to 8000, in particular up to _ '7 _ 5000, and/or optionally small amounts of branched bifunctional alcohols, preferably C3 - C,z alkyl diols, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane, as well as from aliphatic bifunctional acids, preferably with 2 to 12 C atoms in the alkyl chain, such as for example and preferably succinic acid, adipic acid, and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or K) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example s-caprolactone or dilactide, or a mixture and/or a copolymer of I) and K), wherein the aromatic acids preferably constitute a fraction of no more than 80, in particular 50 wt.%, relative to all the acids;
L) an amide fraction of aliphatic and/or cycloaliphatic bifunctional and/or optionally small amounts of branched bifunctional amines, linear aliphatic di-CZ - C,o alkyl amines being preferred, and additionally optionally small amounts of more highly functional amines, preferably hexamethylenediamine, isophorone diamine and particularly preferably hexamethylenediamine, as well as from linear and/or cycloaliphatic bifunctional acids, preferably with 2 to 12 C atoms in the alkyl chain or CS
or C~ ring in the case of cycloaliphatic acids, preferably adipic acid, and/or optionally small amounts of branched bifunctional and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic _g_ acid, naphthalene dicarboxylic acid and additionally optionally small amounts of more highly functional acids, preferably with 2 to 10 C atoms, or M) from an amide fraction of acid- and amine-functionalised units, preferably with 4 to 20 C atoms in the cycloaliphatic chain, preferably w-laurolactam, E-caprolactam, particularly preferably E-caprolactam, or a mixture of L) and M) as amide fraction, wherein the ester fraction I) and/or K) preferably amounts to at least 30 wt.%, relative to the sum of I), K), L) and M), the proportion by weight of the ester structures preferably amounting to 30 to 80 wt.% and the proportion of the amide structures preferably amounting to 70 to 20 wt.%.
Hydroxyl- or acid-terminated polyester with molecular weights (weight average) of from 300 to 10,000 may likewise be used as ester-forming component.
All the acids may also be used in the form of derivatives such as for example acid chlorides or esters, both as monorneric and oligomeric esters.
Polyether ester amides are particularly preferred which exhibit a random arrangement of ester and amide segments and wherein the alcohol component consists of monomeric and oligomeric diols and the content of oligomeric diol, relative to the total content of alcohol component, amounts in general to 10 to 99, preferably 15 to 80 mol%.
The polyether ester amides are composed in particular of the following monomers:
oligomeric polyols consisting of polyethylene glycols, polypropylene glycols, polyglycols, of random or block-type structure, from mixtures of ethylene oxide or propylene oxide or polytetrahydrofuranswith molecular weights (weight average) of between 100 and 10,000 and monomeric diols, preferably Cz - C,2 alkyl diols, in particularly Cz - C6 alkyl diols, for example ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, and at least one monomer selected from the group consisting of dicarboxylic acids, preferably Cz - C,z, particularly preferably CZ - C6 alkyl dicarboxylic acids, for example oxalic acid, succinic acid, adipic acid, also in the form of the respective ethers thereof (methyl, ethyl etc.) Cz - C,Z alkylhydroxycarboxylic acids and lactones such as caprolactone inter alia amino alcohols with 2 to 12 carbon atoms in the alkyl chain, for example ethanolamine, propanolamine cyclic lactams with 5 to 12, preferably 6 to 11, C atoms, such as s-caprolactam or laurolactam etc.
c~-aminocarboxylic acids with 6 to 12 C atoms in the alkyl chain such as aminocaproic acid etc.
mixtures (1:1 salts) of CZ - C,z alkyl dicarboxylic acids, for example adipic acid, succinic acid and Cz - C,2 alkyl diamines, for example hexamethylenediamine, diaminobutane.
Likewise, both hydroxyl- or acid-terminated polyesters with molecular weights of between 300 and 10,000 may be used as ester-forming component.
The proportion of the ether and ester fractions in the polymer amounts in general to to 85 wt.%, relative to the total polymer.
The polyether ester amides according to the invention in general have an average 5 molecular weight (Mw determined by gel chromatography in cresol relative to a polystyrene standard) of from 10,000 to 300,000, preferably 15,000 to 150,000, in particular 15,000 to 100,000.
The synthesis of the polyester amides or polyether ester amides according to the invention may be performed both by the "polyamide method", entailing stoichiometric mixing of the starting components optionally with the addition of water and then removal of water from the reaction mixture, and by the "polyester method", entailing stoichiometric mixing of the starting components together with the addition of an excess of diol with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In this second instance, not only the water but also the excess diol is distilled off again.
Synthesis by the above-described "polyester method" is preferred.
Polycondensation may additionally be accelerated by the use of known catalysts.
Both the known phosphorus compounds which accelerate polyamide synthesis and acidic or organometallic catalysts for esterification as well as combinations of the two may be used to accelerate polycondensation.
Furthermore, polycondensation to produce polyester amides may be influenced by the use of lysine, lysine derivatives or other amidically branching products such as for example aminoethylaminoethanol, which both accelerate condensation and result in branched products (see for example DE-3 831 709).
The production of polyesters, polyester carbonates and polyester urethanes is 3() generally known or is performed in a manner similar to known methods (c.f.
for example EP-A-304 787, WO 95/12629, WO 93/13154, EP-A-682 054, EP-A-593 975).
The polyesters, polyester urethanes, polyester carbonates, polyester amides and polyether ester amides according to the invention may additionally contain 0.1 to 5 wt.%, preferably 0.1 to 1 wt.%, of branching agents (c.f. also description of polymers). These branching agents may for example be trifunctional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid.
The polymers cited as component 1 ) have as a rule a molecular weight of at least 10,000 g/mol, preferably 10,000 to 100,000, in particular 15,000 to 60,000 g/mol and generally have a random distribution of starting substances in the polymer.
When the polymer is synthesised in the manner typical of polyurethanes, optionally from C) and D) as well as from E), completely random distribution of the monomeric units cannot always be expected.
Component 2) Polyolefins suitable according to the invention are polymers of aliphatically unsaturated hydrocarbons, such as for example ethylene, propylene, butylene or isobutylene, which are obtained by conventional methods, e.g. free radical polymerisation or by means of metallocene catalysis. The polyolefins as a rule have average weight average molecular weights M W (measured by gel chromatographic methods) of from 5000 to 3,000,000. Both high density polyolefin and low density polyolefin, e.g. LDPE, LLDPE, MDPE, may be used.
WO 99/28384 PCT/EP98/0'7459 The polyolefins are generally known and are described for example in Ullman's Encyclopedia of industrial chemistry, Vol. A21, pp. 487-577, 5th compl. rev.
ed.
1992, VCH Verlag, Weinheim.
Component 3) Modified polyolefins are polyolefins which may be obtained either by grafting of the above-mentioned polyolefms or by copolymerisation of the monomers mentioned under component 2), preferably ethylene and/or propylene, with other monomers, preferably vinyl monomers, with reactive groups, e.g. anhydride, amino, acid, epoxy, ester or keto groups or salts of carboxylic acids. Preferred copolymerisable monomers are acrylic acid and its alkyl esters of mono- and/or di-C, - C,Z-, preferably C2 - C6-alkanols, together with malefic anhydride.
The modified polyolefins used in the present invention are preferably of the following composition:
a) 40 to 99.9, preferably 88 to 99.9 wt.%, of at least one or more a-olefins with 2 to 8 C atoms, b) 0 to 50 wt.% of a dime, c) 0 to 45 wt.% of a primary or secondary C, - C,2 alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters, d) 0 to 45 wt.% of an olefinically unsaturated mono- or dicarboxylic acid, e.g.
malefic anhydride, which may also be present partially or completely as a salt and/or a functional derivative of such an acid, e) 0 to 40 wt.% of an epoxy group-containing monomer, e.g. glycidyl methacrylate or glycidyl acrylate, f) 0 to 75 wt.% of a vinyl ester, e.g. vinyl acetate or saponified products thereof (vinyl alcohols) wherein at least one of the components b, c, d, a and f is included.
Grafted or copolymerised ethylene/acrylic acid (t-alkyl) esters, ethylene/glycidyl acrylate (or allylglycidic ether)/acrylic acid (t-alkyl) esters, ethylene/acrylic acid (ester)/maleic anhydride or ethylene/maleic anhydride are particularly preferred.
The molecular weight (weight average) of the modified polyolefins amounts in general to 5000 to 3,000,000, preferably 10,000 to 1,000,000 (measured by gel chromatographic methods).
The modified polyolefins are known or may be produced by known methods (e.g.
EP-A-77 415).
Component 4) Inorganic materials are generally used as fillers and reinforcing agents.
These are fibrous reinforcing materials such as glass and carbon fibres and mineral fillers, e.g.
talc, mica, chalk, kaolin, wollastonite, gypsum, quartz, dolomite, silicates.
Mineral fillers are preferred, in particular chalk.
The fillers and reinforcing materials may also be surface-treated.
Glass fibres generally have a fibre diameter of between 8 and 14 pm and may be used in the form of continuous filaments or cut or ground glass fibres, wherein the fibres may be provided with a suitable sizing system and a coupling agent or coupling agent system on the basis of silane.
The mixtures according to the invention may additionally contain conventional S additives such as UV stabilisers, antioxidants, pigments, dyestuffs, nucleating agents, crystallisation accelerators or retarders, flow auxiliaries, lubricants, mould release agents and flame retardants.
The mixtures according to the invention and optionally other additives may be produced by mixing the respective constituents in a known way and melt-compounding or melt-extruding them at conventional temperatures, e.g.
150°C to 300°C, in conventional units such as internal mixers, extruders, twin-screw extruders.
The mixture according to the invention may be used for injection moulding, in fibre or film form or in the nonwoven sector (spun-bond or melt-blown).
Use in film form is preferred. The films may be used alone or as a composite component in conjunction with other nonwovens, woven fabrics, knitted fabrics or other films.
Preferred areas of use are: sanitary products (e.g. nappies, sanitary towels, incontinence pads for adults); packaging in general, clothing, e.g. also in the medical field, building, e.g. roof lining membranes.
Examples Example 1 40 wt.% of a polyester amide of adipic acid, butanediol and caprolactam with an ester/amide ratio of 40/60, randomly copolycondensed (with a relative solution viscosity of 2.5, measured using a 1 wt.% solution in meta-cresol at 20°C) are compounded with 40 wt.% of a finely divided chalk produced by Omya (Cologne, Germany (Hydrocarb 95T)) and 20 wt.% Lupolen~, an LDPE produced by BASF
(Ludwigshafen, Germany) in a twin-screw extruder (ZSK) at 170°C. The blend may be pelletised without difficulty.
Subsequent processing in a blown film installation results in white-coloured films with a thickness of 10 pm. The water permeability of these films in accordance with the DIN standard using the Mocon method amounts to 770 g/mz'd.
Example 2 30 wt.% of a polyether ester amide of AH salt, adipic acid, diethylene glycol and polyethylene glycol 400 with an ester/amide ratio of 70/30 are compounded with 40 wt.% of a finely divided chalk produced by Omya (Cologne, Germany (Hydrocarb 95T)) and 30 wt.% Lupolen~, an LLDPE produced by BASF, Ludwigshafen, Germany, in a twin-screw extruder (ZSK) at 180°C. The blend may be pelletised without difficulty.
Subsequent processing in a blown film installation results in white-coloured films with a thickness of 8 pm.
s0 The water permeability of these films in accordance with the DIN standard using the Mocon method amounts to 1030 g/m''d.
Production of the polyether ester amide in Example 2:
710 g AH salt, 253 g adipic acid, 184 g diethylene glycol and 1380 g polyethylene glycol 400 are mixed together with titanium(IV) isopropylate as catalyst and heated under nitrogen to 240°C. When the water has been distilled off, the pressure is reduced in stages to I mbar. After 3 hours of polycondensation, a colourless, high molecular weight material is obtained (relative viscosity of 3.2 measured in 1 wt.%
solution in m-cresol at 25°C) with a melting point of 186°C.
Example 3 35 wt.% of a polyether ester amide of AH salt, adipic acid, diethylene glycol and polyethylene glycol 1000 with an ester/amide ratio of 60/40 are compounded with 30 wt.% of the above-mentioned finely divided chalk produced by Omya, 30 wt.%
Lupolen, an LLDPE produced by BASF and 5 wt.% of an ethylene/acrylic acid ester copolymer (Lucalen~, BASF, Ludwigshafen, Germany) using a twin-screw extruder (ZSK) at 180°C. The blend may be pelletised without difficulty.
Subsequent processing in a blown film installation results in white-coloured films with a thickness of 10 pm. The water permeability of these films in accordance with the DIN standard using the Mocon method amounts to 9230 g/mz'd.
High water vapour permeability levels are exhibited by various materials, e.g.
Gore-Tex~ (specially stretched polytetrafluoroethylene films made by Gore Ind.) or Sympatex~ (aliphatic-aromatic polyether esters made by Akzo) (c.f. Rompps Chemie-Lexikon, Vol. 6, p. 5000, Thieme Verlag Stuttgart, 9th Edition 1992).
Both materials exhibit the disadvantage of requiring special production methods and in addition the raw materials are very expensive.
The object therefore arose of achieving high water vapour permeability levels with materials which are easy to produce and exhibit the mechanical properties required for the various applications.
It was surprisingly found that blends of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic polyester amides and/or polyether ester amides with polyolefins, optionally modified polyolefins, together optionally with fillers and reinforcing materials, exhibit very high levels of water vapour permeability. Films made from the blend according to the invention additionally exhibit the property that they may be drawn out very thinly, in contrast to pure filled polyolefin films.
The invention relates to mixtures containing 1 ) 5 to 95, preferably 10 to $0, in particular 1 S to 60 parts by weight of at least one polymer selected from the group consisting of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides and/or polyether ester amides, 2) 5 to 70, preferably 7 to 60, in particular 10 to 50 parts by weight of polyolefins, 3) 0 to 25, preferably 0 to 20, in particular 0 to 15 parts by weight of modified polyolefins and 4) 0 to 80, preferably 0 to 70, in particular 5 to 60 parts by weight of fillers and reinforcing materials, wherein the sum of 1), 2), 3) and 4) is 100.
Component 1) The polymers according to component 1 ) are selected from at least one polymer from the group consisting of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides and polyether ester amides.
The following polymers are suitable:
Aliphatic or partially aromatic polyesters from A) aliphatic bifunctional alcohols, preferably linear CZ to C,o, preferably Cz dialcohols such as, for example, ethanediol, propanediol, butanediol, hexanediol or particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 or 6 C atoms in the cycloaliphatic ring, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 8000, preferably up to 4000, and/or optionally small amounts of branched bifunctional alcohols, preferably C3 -C,, alkyl diols, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols such as for example 1,2,3-propanetriol or trimethylolpropane, as well as from aliphatic bifunctional acids, preferably Cz - C,z alkyl dicarboxylic acids, such as for example and preferably succinic acid, adipic acid, and/or optionally aromatic bifunctional acids, such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or B) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example E-caprolactone or dilactide, or a mixture and/or copolymer of A and B, wherein the aromatic acids preferably constitute a fraction of no more than 80, in particular 50 wt.%, relative to all the acids;
aliphatic or partially aromatic polyester urethanes from C) aliphatic bifunctional alcohols, preferably linear CZ to C,o, preferably Cz dialcohols such as, for example, ethanediol, propanediol, butanediol, hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with a CS or C6 cycloaliphatic ring, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 4000, preferably up to 1000, and/or optionally small amounts of branched bifunctional alcohols, preferably C3 -C,Z alkyl diols, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols, preferably C3 -C,Z alkyl polyols, such as for example 1,2,3-propanetriol or trimethylolpropane, as well as from aliphatic bifunctional acids, preferably CZ - C,z alkyl dicarboxylic acids, such as for example and preferably succinic acid, adipic acid, and/or optionally aromatic bifunctional acids, such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or D) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example s-caprolactone or dilactide, or a mixture and/or copolymer of C and D, wherein the aromatic acids preferably constitute a fraction of no more than 80, in particular 50 wt.%, relative to all the acids;
E) from the reaction product of C and/or D with aliphatic and/or cycloaliphatic bifunctional and additionally optionally more highly functional isocyanates, with preferably 1 to 12 C atoms or 5 to 8 C atoms in the case of p0 cycloaliphatic isocyanates, e.g. tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally additionally with linear and/or branched and/or cycloaliphatic bifunctional and/or more highly functional alcohols, preferably C3 - C,Z alkyl di- or polyols or 5 to 8 C
atoms , in the case of cycloaliphatic alcohols, e.g. ethanediol, hexanediol, butanediol, cyclohexane-dimethanol, and/or optionally additionally with linear and/or branched and/or cycloaliphatic bifunctional and/or more highly functional amines and/or amino alcohols with preferably 2 to 12 C atoms in the alkyl chain, e.g. ethylene diamine or aminoethanol, and/or optionally further modified amines or alcohols such as for example ethylenediaminoethanesulfonic acid, as a free acid or salt, wherein the ester fraction C) and/or D) preferably amounts to at least 40, in particular 75 wt.%, relative to the sum of C), D) and E);
aliphatic or aliphatic-aromatic polyester carbonates from F) aliphatic bifunctional alcohols, preferably linear CZ to C,°
dialcohols such as, for example, ethanediol, butanediol, hexanediol or particularly preferably butanediol, andlor optionally cycloaliphatic bifunctional alcohols, preferably with 5 to 8 C atoms in the cycloaliphatic ring, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 8000, preferably up to 4000, and/or optionally small amounts of branched bifunctional alcohols, preferably CZ - C,z alkyldicarboxylic acids, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane, as well as from aliphatic bifunctional acids, such as for example and preferably succinic acid, adipic acid and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or G) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example s-caprolactone or dilactide, or a mixture and/or copolymer of F and G, wherein the aromatic acids preferably constitute a fraction of no more than SO
wt.%, relative to all the acids;
H) a carbonate fraction, which is produced from aromatic bifunctional phenols, preferably bisphenol A and carbonate donors, for example phosgene, or a carbonate fraction, which is produced from aliphatic carbonic acid esters or derivatives thereof, such as for example chloroformic acid esters or aliphatic carboxylic acids or derivatives thereof such as for example salts and carbonate donors, for example phosgene, wherein the ester fraction F) and/or G) preferably amounts to at least 40, in particular 70 wt.%, relative to the sum of F), G) and H);
aliphatic or partially aromatic polyester amides or polyether ester amides from I) aliphatic bifunctional alcohols, preferably linear CZ to C,°, preferably Cz - C6 dialcohols such as, for example, ethanediol, propanediol, butanediol, hexanediol, particularly preferably butanediol, and/or optionally cycloaliphatic bifunctional alcohols, preferably with 5 to 8 C atoms, such as for example cyclohexanedimethanol, and/or, partially or completely replacing the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights of up to 10,000, preferably up to 8000, in particular up to _ '7 _ 5000, and/or optionally small amounts of branched bifunctional alcohols, preferably C3 - C,z alkyl diols, such as for example neopentyl glycol, and additionally optionally small amounts of more highly functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane, as well as from aliphatic bifunctional acids, preferably with 2 to 12 C atoms in the alkyl chain, such as for example and preferably succinic acid, adipic acid, and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid and additionally optionally small amounts of more highly functional acids such as for example trimellitic acid or K) from acid- and alcohol-functionalised units, preferably with 2 to 12 C
atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example s-caprolactone or dilactide, or a mixture and/or a copolymer of I) and K), wherein the aromatic acids preferably constitute a fraction of no more than 80, in particular 50 wt.%, relative to all the acids;
L) an amide fraction of aliphatic and/or cycloaliphatic bifunctional and/or optionally small amounts of branched bifunctional amines, linear aliphatic di-CZ - C,o alkyl amines being preferred, and additionally optionally small amounts of more highly functional amines, preferably hexamethylenediamine, isophorone diamine and particularly preferably hexamethylenediamine, as well as from linear and/or cycloaliphatic bifunctional acids, preferably with 2 to 12 C atoms in the alkyl chain or CS
or C~ ring in the case of cycloaliphatic acids, preferably adipic acid, and/or optionally small amounts of branched bifunctional and/or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic _g_ acid, naphthalene dicarboxylic acid and additionally optionally small amounts of more highly functional acids, preferably with 2 to 10 C atoms, or M) from an amide fraction of acid- and amine-functionalised units, preferably with 4 to 20 C atoms in the cycloaliphatic chain, preferably w-laurolactam, E-caprolactam, particularly preferably E-caprolactam, or a mixture of L) and M) as amide fraction, wherein the ester fraction I) and/or K) preferably amounts to at least 30 wt.%, relative to the sum of I), K), L) and M), the proportion by weight of the ester structures preferably amounting to 30 to 80 wt.% and the proportion of the amide structures preferably amounting to 70 to 20 wt.%.
Hydroxyl- or acid-terminated polyester with molecular weights (weight average) of from 300 to 10,000 may likewise be used as ester-forming component.
All the acids may also be used in the form of derivatives such as for example acid chlorides or esters, both as monorneric and oligomeric esters.
Polyether ester amides are particularly preferred which exhibit a random arrangement of ester and amide segments and wherein the alcohol component consists of monomeric and oligomeric diols and the content of oligomeric diol, relative to the total content of alcohol component, amounts in general to 10 to 99, preferably 15 to 80 mol%.
The polyether ester amides are composed in particular of the following monomers:
oligomeric polyols consisting of polyethylene glycols, polypropylene glycols, polyglycols, of random or block-type structure, from mixtures of ethylene oxide or propylene oxide or polytetrahydrofuranswith molecular weights (weight average) of between 100 and 10,000 and monomeric diols, preferably Cz - C,2 alkyl diols, in particularly Cz - C6 alkyl diols, for example ethylene glycol, 1,4-butanediol, 1,3-propanediol, 1,6-hexanediol, and at least one monomer selected from the group consisting of dicarboxylic acids, preferably Cz - C,z, particularly preferably CZ - C6 alkyl dicarboxylic acids, for example oxalic acid, succinic acid, adipic acid, also in the form of the respective ethers thereof (methyl, ethyl etc.) Cz - C,Z alkylhydroxycarboxylic acids and lactones such as caprolactone inter alia amino alcohols with 2 to 12 carbon atoms in the alkyl chain, for example ethanolamine, propanolamine cyclic lactams with 5 to 12, preferably 6 to 11, C atoms, such as s-caprolactam or laurolactam etc.
c~-aminocarboxylic acids with 6 to 12 C atoms in the alkyl chain such as aminocaproic acid etc.
mixtures (1:1 salts) of CZ - C,z alkyl dicarboxylic acids, for example adipic acid, succinic acid and Cz - C,2 alkyl diamines, for example hexamethylenediamine, diaminobutane.
Likewise, both hydroxyl- or acid-terminated polyesters with molecular weights of between 300 and 10,000 may be used as ester-forming component.
The proportion of the ether and ester fractions in the polymer amounts in general to to 85 wt.%, relative to the total polymer.
The polyether ester amides according to the invention in general have an average 5 molecular weight (Mw determined by gel chromatography in cresol relative to a polystyrene standard) of from 10,000 to 300,000, preferably 15,000 to 150,000, in particular 15,000 to 100,000.
The synthesis of the polyester amides or polyether ester amides according to the invention may be performed both by the "polyamide method", entailing stoichiometric mixing of the starting components optionally with the addition of water and then removal of water from the reaction mixture, and by the "polyester method", entailing stoichiometric mixing of the starting components together with the addition of an excess of diol with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In this second instance, not only the water but also the excess diol is distilled off again.
Synthesis by the above-described "polyester method" is preferred.
Polycondensation may additionally be accelerated by the use of known catalysts.
Both the known phosphorus compounds which accelerate polyamide synthesis and acidic or organometallic catalysts for esterification as well as combinations of the two may be used to accelerate polycondensation.
Furthermore, polycondensation to produce polyester amides may be influenced by the use of lysine, lysine derivatives or other amidically branching products such as for example aminoethylaminoethanol, which both accelerate condensation and result in branched products (see for example DE-3 831 709).
The production of polyesters, polyester carbonates and polyester urethanes is 3() generally known or is performed in a manner similar to known methods (c.f.
for example EP-A-304 787, WO 95/12629, WO 93/13154, EP-A-682 054, EP-A-593 975).
The polyesters, polyester urethanes, polyester carbonates, polyester amides and polyether ester amides according to the invention may additionally contain 0.1 to 5 wt.%, preferably 0.1 to 1 wt.%, of branching agents (c.f. also description of polymers). These branching agents may for example be trifunctional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid.
The polymers cited as component 1 ) have as a rule a molecular weight of at least 10,000 g/mol, preferably 10,000 to 100,000, in particular 15,000 to 60,000 g/mol and generally have a random distribution of starting substances in the polymer.
When the polymer is synthesised in the manner typical of polyurethanes, optionally from C) and D) as well as from E), completely random distribution of the monomeric units cannot always be expected.
Component 2) Polyolefins suitable according to the invention are polymers of aliphatically unsaturated hydrocarbons, such as for example ethylene, propylene, butylene or isobutylene, which are obtained by conventional methods, e.g. free radical polymerisation or by means of metallocene catalysis. The polyolefins as a rule have average weight average molecular weights M W (measured by gel chromatographic methods) of from 5000 to 3,000,000. Both high density polyolefin and low density polyolefin, e.g. LDPE, LLDPE, MDPE, may be used.
WO 99/28384 PCT/EP98/0'7459 The polyolefins are generally known and are described for example in Ullman's Encyclopedia of industrial chemistry, Vol. A21, pp. 487-577, 5th compl. rev.
ed.
1992, VCH Verlag, Weinheim.
Component 3) Modified polyolefins are polyolefins which may be obtained either by grafting of the above-mentioned polyolefms or by copolymerisation of the monomers mentioned under component 2), preferably ethylene and/or propylene, with other monomers, preferably vinyl monomers, with reactive groups, e.g. anhydride, amino, acid, epoxy, ester or keto groups or salts of carboxylic acids. Preferred copolymerisable monomers are acrylic acid and its alkyl esters of mono- and/or di-C, - C,Z-, preferably C2 - C6-alkanols, together with malefic anhydride.
The modified polyolefins used in the present invention are preferably of the following composition:
a) 40 to 99.9, preferably 88 to 99.9 wt.%, of at least one or more a-olefins with 2 to 8 C atoms, b) 0 to 50 wt.% of a dime, c) 0 to 45 wt.% of a primary or secondary C, - C,2 alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters, d) 0 to 45 wt.% of an olefinically unsaturated mono- or dicarboxylic acid, e.g.
malefic anhydride, which may also be present partially or completely as a salt and/or a functional derivative of such an acid, e) 0 to 40 wt.% of an epoxy group-containing monomer, e.g. glycidyl methacrylate or glycidyl acrylate, f) 0 to 75 wt.% of a vinyl ester, e.g. vinyl acetate or saponified products thereof (vinyl alcohols) wherein at least one of the components b, c, d, a and f is included.
Grafted or copolymerised ethylene/acrylic acid (t-alkyl) esters, ethylene/glycidyl acrylate (or allylglycidic ether)/acrylic acid (t-alkyl) esters, ethylene/acrylic acid (ester)/maleic anhydride or ethylene/maleic anhydride are particularly preferred.
The molecular weight (weight average) of the modified polyolefins amounts in general to 5000 to 3,000,000, preferably 10,000 to 1,000,000 (measured by gel chromatographic methods).
The modified polyolefins are known or may be produced by known methods (e.g.
EP-A-77 415).
Component 4) Inorganic materials are generally used as fillers and reinforcing agents.
These are fibrous reinforcing materials such as glass and carbon fibres and mineral fillers, e.g.
talc, mica, chalk, kaolin, wollastonite, gypsum, quartz, dolomite, silicates.
Mineral fillers are preferred, in particular chalk.
The fillers and reinforcing materials may also be surface-treated.
Glass fibres generally have a fibre diameter of between 8 and 14 pm and may be used in the form of continuous filaments or cut or ground glass fibres, wherein the fibres may be provided with a suitable sizing system and a coupling agent or coupling agent system on the basis of silane.
The mixtures according to the invention may additionally contain conventional S additives such as UV stabilisers, antioxidants, pigments, dyestuffs, nucleating agents, crystallisation accelerators or retarders, flow auxiliaries, lubricants, mould release agents and flame retardants.
The mixtures according to the invention and optionally other additives may be produced by mixing the respective constituents in a known way and melt-compounding or melt-extruding them at conventional temperatures, e.g.
150°C to 300°C, in conventional units such as internal mixers, extruders, twin-screw extruders.
The mixture according to the invention may be used for injection moulding, in fibre or film form or in the nonwoven sector (spun-bond or melt-blown).
Use in film form is preferred. The films may be used alone or as a composite component in conjunction with other nonwovens, woven fabrics, knitted fabrics or other films.
Preferred areas of use are: sanitary products (e.g. nappies, sanitary towels, incontinence pads for adults); packaging in general, clothing, e.g. also in the medical field, building, e.g. roof lining membranes.
Examples Example 1 40 wt.% of a polyester amide of adipic acid, butanediol and caprolactam with an ester/amide ratio of 40/60, randomly copolycondensed (with a relative solution viscosity of 2.5, measured using a 1 wt.% solution in meta-cresol at 20°C) are compounded with 40 wt.% of a finely divided chalk produced by Omya (Cologne, Germany (Hydrocarb 95T)) and 20 wt.% Lupolen~, an LDPE produced by BASF
(Ludwigshafen, Germany) in a twin-screw extruder (ZSK) at 170°C. The blend may be pelletised without difficulty.
Subsequent processing in a blown film installation results in white-coloured films with a thickness of 10 pm. The water permeability of these films in accordance with the DIN standard using the Mocon method amounts to 770 g/mz'd.
Example 2 30 wt.% of a polyether ester amide of AH salt, adipic acid, diethylene glycol and polyethylene glycol 400 with an ester/amide ratio of 70/30 are compounded with 40 wt.% of a finely divided chalk produced by Omya (Cologne, Germany (Hydrocarb 95T)) and 30 wt.% Lupolen~, an LLDPE produced by BASF, Ludwigshafen, Germany, in a twin-screw extruder (ZSK) at 180°C. The blend may be pelletised without difficulty.
Subsequent processing in a blown film installation results in white-coloured films with a thickness of 8 pm.
s0 The water permeability of these films in accordance with the DIN standard using the Mocon method amounts to 1030 g/m''d.
Production of the polyether ester amide in Example 2:
710 g AH salt, 253 g adipic acid, 184 g diethylene glycol and 1380 g polyethylene glycol 400 are mixed together with titanium(IV) isopropylate as catalyst and heated under nitrogen to 240°C. When the water has been distilled off, the pressure is reduced in stages to I mbar. After 3 hours of polycondensation, a colourless, high molecular weight material is obtained (relative viscosity of 3.2 measured in 1 wt.%
solution in m-cresol at 25°C) with a melting point of 186°C.
Example 3 35 wt.% of a polyether ester amide of AH salt, adipic acid, diethylene glycol and polyethylene glycol 1000 with an ester/amide ratio of 60/40 are compounded with 30 wt.% of the above-mentioned finely divided chalk produced by Omya, 30 wt.%
Lupolen, an LLDPE produced by BASF and 5 wt.% of an ethylene/acrylic acid ester copolymer (Lucalen~, BASF, Ludwigshafen, Germany) using a twin-screw extruder (ZSK) at 180°C. The blend may be pelletised without difficulty.
Subsequent processing in a blown film installation results in white-coloured films with a thickness of 10 pm. The water permeability of these films in accordance with the DIN standard using the Mocon method amounts to 9230 g/mz'd.
Claims (6)
1. Mixtures containing 1) 5 to 95 parts by weight of at least one polymer selected from the group consisting of aliphatic or partially aromatic polyesters, thermoplastic aliphatic or partially aromatic polyester urethanes, aliphatic or aliphatic-aromatic polyester carbonates, aliphatic or partially aromatic polyester amides and/or polyether ester amides, 2) 5 to 70 parts by weight of polyolefins, 3) 0 to 25 parts by weight of modified polyolefins and 4) 0 to 80 parts by weight of fillers and reinforcing materials.
2. Mixtures according to claim 1 containing additives selected from at least one from the group consisting of UV stabilisers, antioxidants, pigments, dyestuffs, nucleating agents, crystallisation accelerators or retarders, flow auxiliaries, lubricants, mould release agents and flame retardants.
3. Use of the mixtures according to claim 1 for producing injection moulded articles, fibres, films, nonwoven material.
4. Use according to claim 3 in the sanitary sector, as packaging material, in the clothing sector or in the building sector.
5. Moulded articles or mouldings produced from mixtures according to claims 1 and 2.
6. Injection-moulded articles, fibres, films, nonwoven material, packaging material, produced from mixtures according to claims 1 and 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19753531.3 | 1997-12-03 | ||
| DE19753531A DE19753531A1 (en) | 1997-12-03 | 1997-12-03 | Polymer blend containing polyolefins |
| PCT/EP1998/007459 WO1999028384A1 (en) | 1997-12-03 | 1998-11-20 | Polyolefins containing a polymer blend |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2312489A1 true CA2312489A1 (en) | 1999-06-10 |
Family
ID=7850548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002312489A Abandoned CA2312489A1 (en) | 1997-12-03 | 1998-11-20 | Polyolefins containing a polymer blend |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1036113A1 (en) |
| JP (1) | JP2001525437A (en) |
| KR (1) | KR20010032722A (en) |
| CN (1) | CN1280596A (en) |
| AU (1) | AU1756099A (en) |
| CA (1) | CA2312489A1 (en) |
| DE (1) | DE19753531A1 (en) |
| NO (1) | NO20002674D0 (en) |
| WO (1) | WO1999028384A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910645B2 (en) | 2001-08-01 | 2011-03-22 | H.B. Fuller Company | Breathable biodegradable hot melt composition |
Families Citing this family (10)
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| JP3297033B2 (en) * | 2000-02-02 | 2002-07-02 | オリンパス光学工業株式会社 | Endoscope |
| JP2001253979A (en) * | 2000-03-09 | 2001-09-18 | Asahi Kasei Corp | Urethane-based elastomer composition |
| DE10037434A1 (en) * | 2000-07-24 | 2002-02-14 | Gerhard Behrendt | Thermoplastic compatible homogeneous polymer blends useful for production of e.g. automobile components comprises polyalkylene terephthalate, olefinic polymers and compatibility agents. |
| JP2006036883A (en) * | 2004-07-26 | 2006-02-09 | El & Chem Corp | Reclaimed frp-based thermoplastic composite composition |
| JP2006077063A (en) * | 2004-09-08 | 2006-03-23 | Kaneka Corp | Composition and its molded article |
| CN1847296B (en) * | 2005-03-14 | 2010-12-01 | 住友化学株式会社 | Polyolefin resin composition |
| EP2110407A1 (en) * | 2008-04-16 | 2009-10-21 | Total Petrochemicals Research Feluy | Blends of polar low density ethylene copolymers and poly(hydroxy carboxylic acid)s |
| CN101724238B (en) * | 2008-10-24 | 2012-05-23 | 比亚迪股份有限公司 | Makrolon/polyethylene alloy material and preparation method thereof |
| CN105440654B (en) * | 2015-12-09 | 2018-07-24 | 东莞市精伦实业有限公司 | A kind of thermoplastic polyurethane elastomer and preparation method thereof of soft high intensity |
| JP2018076413A (en) * | 2016-11-08 | 2018-05-17 | 三菱ケミカル株式会社 | Moisture-permeable film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901838A (en) * | 1972-07-28 | 1975-08-26 | Union Carbide Corp | Environmentally degradable biodegradable blends of a dialkanoyl polymer and an environmentally degradable ethylene polymer |
| CA1111179A (en) * | 1978-02-17 | 1981-10-20 | Eric G. Kent | Polymeric casts |
| DE3220324C2 (en) * | 1981-06-03 | 1994-02-03 | Daicel Chem | Mass containing polycaprolactone |
| JPS58125735A (en) * | 1981-09-14 | 1983-07-26 | Toray Ind Inc | Resin composition |
| FR2519034A1 (en) * | 1981-12-29 | 1983-07-01 | Ato Chimie | TEXTILE MATERIALS BASED ON POLYOLEFINS |
| JPH0757832B2 (en) * | 1987-12-18 | 1995-06-21 | 東レ株式会社 | Thermoplastic resin composition |
| JPH05230301A (en) * | 1992-02-19 | 1993-09-07 | Toray Ind Inc | Thermoplastic resin composition |
| JP3496991B2 (en) * | 1994-11-15 | 2004-02-16 | 東燃ゼネラル石油株式会社 | Thermoplastic resin composition |
| US5648088A (en) * | 1995-03-06 | 1997-07-15 | Ethicon, Inc. | Blends of absorbable polyoxaesters containing amines and/or amide groups |
| US5952088A (en) * | 1996-12-31 | 1999-09-14 | Kimberly-Clark Worldwide, Inc. | Multicomponent fiber |
-
1997
- 1997-12-03 DE DE19753531A patent/DE19753531A1/en not_active Withdrawn
-
1998
- 1998-11-20 EP EP98962367A patent/EP1036113A1/en not_active Withdrawn
- 1998-11-20 WO PCT/EP1998/007459 patent/WO1999028384A1/en not_active Application Discontinuation
- 1998-11-20 CA CA002312489A patent/CA2312489A1/en not_active Abandoned
- 1998-11-20 JP JP2000523271A patent/JP2001525437A/en active Pending
- 1998-11-20 KR KR1020007006011A patent/KR20010032722A/en not_active Application Discontinuation
- 1998-11-20 AU AU17560/99A patent/AU1756099A/en not_active Abandoned
- 1998-11-20 CN CN98811816A patent/CN1280596A/en active Pending
-
2000
- 2000-05-25 NO NO20002674A patent/NO20002674D0/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7910645B2 (en) | 2001-08-01 | 2011-03-22 | H.B. Fuller Company | Breathable biodegradable hot melt composition |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1036113A1 (en) | 2000-09-20 |
| CN1280596A (en) | 2001-01-17 |
| NO20002674L (en) | 2000-05-25 |
| WO1999028384A1 (en) | 1999-06-10 |
| NO20002674D0 (en) | 2000-05-25 |
| AU1756099A (en) | 1999-06-16 |
| JP2001525437A (en) | 2001-12-11 |
| DE19753531A1 (en) | 1999-06-10 |
| KR20010032722A (en) | 2001-04-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |