EP1036113A1 - Polyolefins containing a polymer blend - Google Patents

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

There is an increasing interest in materials with high wearing comfort, i.e. materials that have increased water vapor permeability. This increased water vapor permeability is a necessary property in many application areas such as clothing, hygiene area (e.g. diapers) but also in the construction area in the use of roofing membranes in order to achieve a high level of functionality.

High water vapor permeability of different materials, e.g. Gore-Tex ^® (specially stretched polytetrafluoroethylene films from Gore Ind.) Or Sympatex ^® (aliphatic-aromatic polyether esters from Akzo) (see Römpps Chemie-Lexikon, Vol. 6, p. 6) 5000, Thieme Verlag Stuttgart, 9th edition 1992). Both materials have the disadvantage of special manufacturing methods, and the raw materials are economically very expensive.

The task now was to achieve high water vapor permeability with materials that are easy to manufacture and have the necessary mechanical properties in various applications.

Surprisingly, it was 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 and optionally fillers and reinforcing materials have very high water vapor permeability . The films made from the blends according to the invention also have the property of being able to be drawn out very thinly, in contrast to pure filled polyolefin films.

The invention relates to mixtures 1) 5 to 95, preferably 10 to 80, in particular 15 to 60 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, 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 filling and

Reinforcing materials,

where 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 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 polyester A) aliphatic bifunctional alcohols, preferably linear C ₂ -C ₁₀ -, preferably C2-Cö-dialcohols such as ethanediol, propanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 carbon atoms in the cycloaliphatic ring, such as cyclohexanedimethanol, and / or partially or completely instead of the diols, monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 8000, preferably up to 4000, and / or small amounts of branched bifunctional ones Alcohols, preferably C ₃ -C ₂ alkyldiols, such as neopentyl glycol, and additionally optionally small amounts of higher functional alcohols such as 1,2,3-propanetriol or trimethylolpropane, and from aliphatic bifunctional acids, preferably C ₂ -C ₁₂ alkyldi - Carboxylic acids, such as ise and preferably succinic acid, adipic acid and / or optionally aromatic bifunctional acids such as for example terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or

B) from acid and alcohol functionalized building blocks, preferably with 2 to

12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of A and B,

wherein the aromatic acids preferably make up no more than 80, in particular 50,% by weight, based on all acids;

aliphatic or partially aromatic polyester urethanes C) aliphatic bifunctional alcohols, preferably linear C ₂ to C ₁₀ -, preferably C2-Cö-dialcohols such as ethanediol, propanediol, butanediol, hexanediol, particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably with C ₅ - or C ₆ -cycloaliphatic ring, such as cyclohexanedimethanol, and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or small amounts of branched bifunctional ones Alcohols, preferably C ₃ -C ₂ alkyldiols, such as neopentyl glycol, and additionally optionally small amounts of higher functional alcohols, preferably C ₃ -C ₂ alkyl polyols, such as 1,2,3-propanetriol or trimethylolpropane, and from aliphatic bifunctional acids, preferably C ₂ -C ₁₂ -A Alkyl dicarboxylic acids, such as and preferably succinic acid, adipic acid, and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or

D) from acid- and alcohol-functionalized building blocks, preferably with 2 to

12 carbon atoms, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of C and D,

wherein the aromatic acids preferably make up no more than 80, in particular 50,% by weight, based on all acids;

E) from the reaction product of C and / or D with aliphatic and / or cycloaliphatic bifunctional and, if appropriate, tional isocyanates, preferably having 1 to 12 carbon atoms or 5 to 8 carbon atoms in the case of cycloaliphatic isocyanates, for example tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, optionally additionally with linear and / or branched and / or cycloaliphatic bifunctional and / or higher functional alcohols, preferably C ₃ -C _{] 2} -

Alkyl di- or polyols or 5 to 8 carbon 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 higher functional amines and / or amino alcohols with preferably 2 to 12

C atoms in the alkyl chain, e.g. Ethylenediamine or aminoethanol, and / or optionally further modified amines or alcohols such as, for example, ethylenediaminoethanesulfonic acid, as the free acid or as a salt,

the ester portion C) and / or D) preferably at least 40, in particular

75% by weight, based on the sum of C), D) and E), is;

aliphatic or aliphatic-aromatic polyester carbonates

F) aliphatic bifunctional alcohols, preferably linear C ₂ to C ₁₀ -

Dialcohols such as ethanediol, butanediol, hexanediol or particularly preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms in the cycloaliphatic ring, such as cyclohexanedimethanol, and / or partially or completely instead of the diols on monomeric or oligomeric polyols Base

Ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 8000, preferably up to 4000, and / or optionally small amounts of branched bifunctional alcohols, preferably with C ₂ -C ₁₂ -alkyl dicarboxylic acids, such as neopentyl glycol and additionally small amounts of higher-functional alcohols such as for example 1,2,3-propanetriol, trimethylolpropane and aliphatic bi-functional acids such as and preferably succinic acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or

G) from acid and alcohol-functionalized building blocks, preferably with 2 to 12 carbon atoms in the alkyl chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of F and G,

the aromatic acids preferably making up no more than 50% by weight, based on all 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 derived from aliphatic carbonic acid esters or their derivatives such as chlorocarbonic acid esters or aliphatic carboxylic acids or their derivatives such as salts and carbonate donors, for example phosgene is produced, wherein

the ester fraction F) and / or G) is preferably at least 40, in particular 70,% by weight, based on the sum of F), G) and H);

aliphatic or partially aromatic polyester amides or polyether ester amides I) aliphatic bifunctional alcohols, preferably linear C ₂ to C, ₀ -, preferably C2-C6-dialcohols such as ethanediol, propanediol, butanediol, hexanediol, more preferably butanediol, and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 C -Atoms, such as cyclohexanedimethanol, and / or partially or completely branched instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 10,000, preferably up to 8,000, in particular up to 5,000, and / or optionally small amounts bifunctional alcohols, preferably C ₃ -C ₁₂ alkyldiols, such as neopentyl glycol and additionally, if appropriate, small amounts of higher functional alcohols, preferably C ₃ -C ₁₂ alkyl polyols, such as 1,2,3-propanetriol, trimethylolpropane and aliphatic bifunctional acids, preferably with 2 to 12 carbon atoms omen in the alkyl chain, such as and preferably succinic acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or

K) from acid- and alcohol-functionalized building blocks, preferably with 2 to

12 carbon atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,

or a mixture and / or a copolymer of I) and K),

wherein the aromatic acids preferably make up no more than 80, in particular 50% by weight, based on all acids,

L) an amide portion of aliphatic and / or cycloaliphatic bifunctional and / or optionally small amounts of branched bifunctional Amines are preferred, linear aliphatic di-C ₂ to C ₀ -alkylamines, and in addition, if appropriate, small amounts of higher-functional amines, among the amines preferably hexamethylenediamine, isophoronediamine and particularly preferably hexamethylenediamine, and from linear and / or cycloaliphatic bifunctional acids, preferably With 2 to 12 carbon atoms in the alkyl chain or C ₅ or C ₆ ring in the case of cycloaliphatic acids, preferably adipic acid, and / or possibly small amounts of branched bifunctional and / or optionally aromatic bifunctional acids such as, for example, terephthalic acid, isophthalic acid , Naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids, preferably with 2 to 10 carbon atoms, or

M) from an amide portion of acid- and amine-functionalized building blocks, preferably with 4 to 20 carbon atoms in the cycloaliphatic chain, preferably ω-laurolactam, ε-caprolactam, particularly preferably ε-caprolactam,

or a mixture of L) and M) as an amide component, wherein

the ester fraction I) and / or K) is preferably at least 30% by weight, based on the sum of I), K), L) and M), preferably the weight fraction of the ester structures is 30 to 80% by weight, the fraction of the amide structures is 70 to 20% by weight.

Hydroxyl- or acid-terminated polyesters with molecular weights (weight average) of 300 to 10,000 can also be used as the ester-forming component.

All acids can also be used in the form of derivatives such as acid chlorides or esters, both as monomeric and as oligomeric esters. Particularly preferred are 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 and the content of oligomeric diol, based on the total content of the alcohol component in general 10 to 99, preferably 15 is up to 80 mol%.

The polyether ester amides are composed in particular of the following monomers:

Oligomeric polyols consisting of polyethylene glycols, polypropylene glycols. random 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 C ₂ -C _j 2-alkyl diols, especially diols C ₂ -C 6 alkyl, for example, of ethylene glycol, 1, 4-butanediol, 1,3-propanediol, 1, 6-hexanediol,

and at least one monomer selected from the group of

Dicarboxylic acids, preferably C2-C12, particularly preferably C2-Cg-alkyldicarboxylic acids, for example oxalic acid, succinic acid, adipic acid, also in the form of their respective ethers (methyl, ethyl, etc.)

C ₂ -C _{j 2} alkyl hydroxycarboxylic acids and lactones such as caprolactone and others

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, carbon atoms, such as ε-caprolactam or laurolactam etc. ω-aminocarboxylic acids with 6 to 12 carbon atoms in the alkyl chain such as aminocaproic acid etc.

Mixtures (1: 1 salts) of C2-C ₂ alkyl dicarboxylic acids, for example adipic acid, succinic acid and C2-C ₂ -alkyldiamines, for example hexamethylenediamine, diaminobutane.

Likewise, both hydroxyl- or acid-terminated polyesters with molecular weights between 300 and 10,000 can be used as the ester-forming component.

The proportion of ether and ester fractions in the polymer is generally 5 to 85% by weight, based on the total polymer.

The polyether ester amides according to the invention generally have an average molecular weight (Mw determined after gel chromatography in cresol against

Standard polystyrene) from 10,000 to 300,000, preferably from 15,000 to 150,000, in particular from 15,000 to 100,000.

The synthesis of the polyester amides or polyether ester amides according to the invention can be carried out either by the "polyamide method" by stoichiometric mixing of the starting components, if appropriate with addition of water and subsequent removal of water from the reaction mixture, or by the "polyester method" by stoichiometric mixing of the starting components and An excess of diol is added with esterification of the acid groups and subsequent transesterification or transamidation of these esters. In this second

In addition to water, the excess diol is distilled off again. The synthesis according to the described “polyester method” is preferred.

The polycondensation can also be accelerated by using known catalysts. Both the well-known phosphorus compounds that the

Polyamide synthesis accelerate as well as acidic or organometallic catalysts for the esterification as well as combinations of the two are possible to accelerate the polycondensation.

Furthermore, the polycondensation to polyesteramides can be influenced by the use of lysine, lysine derivatives or other amidically branching products such as, for example, aminoethylaminoethanol, which both accelerate the condensation and lead to branched products (see, for example, DE-3 831 709).

The production of polyester, polyester carbonates and polyester urethanes is generally known or is carried out analogously by known processes (cf. 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 can furthermore contain 0.1 to 5% by weight, preferably 0.1 to

1% by weight of branching agents (see also description of the polymers). These branchers can e.g. trifunctional alcohols such as trimethylolpropane or glycerol, tetrafunctional alcohols such as pentaerythritol, trifunctional carboxylic acids such as citric acid.

The polymers mentioned as component 1) generally have 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 statistical distribution of the starting materials in the polymer. In the case of a typical polymer structure, possibly from C) and D) and from E), a completely statistical distribution of the monomer units is not always to be expected.

Component 2)

Polyolefins suitable according to the invention are polymers of aliphatically unsaturated

Hydrocarbons such as ethylene, propylene, butylene or iso- butylene, which are obtained by customary processes, for example radical polymerization or else via metallocene catalysis. The polyolefins generally have average weight-average molecular weights M _w (measured by gel chromatography methods) of 5,000 to 3,000,000. Both high-pressure polyolefin and low-pressure polyolefin, for example LDPE, LLDPE, MDPE, can be used.

The polyolefins are generally known and described, for example, in Ullmann'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 are obtained either by grafting the above-mentioned polyolefins or by copolymerizing the monomers mentioned in component 2), preferably ethylene and / or propylene, with other monomers, preferably vinyl monomers, with reactive groups, for example anhydride, amino or acid -, Epoxy, ester, keto groups or salts of carboxylic acids are available. Suitable copolymerizable monomers are preferably acrylic acid and its alkyl esters of mono- and / or di-C _j ^ -C -, C ₂ -C 6 alkanols and preferably maleic anhydride.

The modified polyolefins used in the present invention are preferably constructed as follows:

a) 40 to 99.9, preferably 88 to 99.9% by weight of at least one or more α-olefins having 2 to 8 C atoms,

b) 0 to 50% by weight of a diene,

c) 0 to 45 wt .-% of a primary or secondary the

Acrylic acid or methacrylic acid or mixtures of such esters, d) 0 to 45% by weight of an olefinically unsaturated mono- or dicarboxylic acid, for example maleic anhydride, which can also be partially or completely in the form of a salt and / or a functional derivative of such an acid,

e) 0 to 40% by weight of a monomer containing epoxy groups, e.g. Glycidyl methacrylate or glycidyl acrylate,

f) 0 to 75% by weight of a vinyl ester e.g. Vinyl acetate or its saponified products (vinyl alcohols)

at least one of components b, c, d, e and f is contained.

Grafted or copolymerized ethylene-acrylic acid (t-alkyl) esters, ethylene glycidyl acrylate (or allyl glycidyl ether) -acrylic acid (t-alkyl) esters, ethylene-acrylic acid (ester) -maleic anhydride or ethylene-maleic acid are particularly preferred - anhydride.

The molecular weight (weight average) of the modified polyolefins is generally 5,000 to 3,000,000, preferably 10,000 to 1,000,000 (measured by gel chromatography methods).

The modified polyolefins are known or can be prepared by known methods (e.g. EP-A-77 415).

Component 4)

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. Mineral fillers, in particular chalk, are preferred.

The fillers and reinforcing materials can also be surface-treated.

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.

The mixtures according to the invention can furthermore contain customary additives such as UV stabilizers, antioxidants, pigments, dyes, nucleating agents, crystallization accelerators or retarders, flow aids, lubricants, mold release agents, flame retardants.

The mixtures according to the invention and optionally other additives can be prepared by mixing the respective constituents in a known manner and at conventional temperatures, e.g. at 150 ° C to 300 ° C, in conventional units such as internal kneaders, extruders, twin-screw extruders, melt compounded or melt extruded.

The mixture according to the invention can be used in injection molding, as a fiber or film or in the non-woven sector (spun-bond or melt-blown).

It is preferably used as a film. The films can be used alone or as a composite component in conjunction with other nonwovens, woven fabrics, knitted fabrics or other films. Preferred areas of application are: hygiene area (eg diapers, sanitary napkins, incontinence diapers for adults), packaging in general, clothing, eg also in the medical field, construction, eg roofing membranes.

Examples

example 1

40% by weight of a polyester amide from adipic acid, butanediol and caprolactam with an ester / amide ratio of 40/60, randomly copolycondensed (with a relative solution viscosity of 2.5, measured on a 1% by weight solution in meta-cresol 20 ° C) with 40 wt .-% of a fine chalk from Omya (Cologne, Germany (Hydrocarb 95 T)) and 20 wt .-% Lupolen® an LDPE from BASF (Ludwigshafen, Germany) on a twin-screw extruder

(ZSK) compounded at 170 ° C. The blend can be granulated easily.

The subsequent processing on a blown film line produces white colored films with a thickness of 10 μm. The water permeability of these films according to the DIN standard according to the Mocon method is 770 g / m ² * d.

Example 2

30 wt .-% of a polyether ester amide from AH salt, adipic acid, diethylene glycol and polyethylene glycol 400 with an ester / amide ratio of 70/30 are with

40% by weight of a finely divided chalk from Omya (Cologne, Germany (Hydrocarb 95 T)) and 30% by weight Lupolen®, an LLDPE from BASF, Ludwigshafen, Germany, on a twin-screw extruder (ZSK) at 180 ° C compounded. The blend can be granulated easily.

The subsequent processing on a blown film line produces white colored films with a thickness of 8 μm.

The water vapor permeability of these films is 1030 g / m ² * d according to the DIN standard using the Mocon method. Preparation of the polyether ester amide in Example 2:

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 tetraisopropoxide as a catalyst and heated at 240 ° C. under nitrogen. After the water has been distilled off, the pressure is gradually reduced to 1 mbar. After a polycondensation time of 3 h, a colorless, high molecular weight material (relative viscosity of 3.2 measured in 1% by weight solution in m-cresol at 25 ° C.) with a melting point of 186 ° C. is obtained.

Example 3

35% by weight of a polyether ester amide from AH salt, adipic acid, diethylene glycol and polyethylene glycol 1000 with an ester / amide ratio of 60/40 are mixed with 30% by weight of the above-mentioned fine-particle chalk from Omya, 30% by weight

Lupolen, an LLDPE from BASF and 5% by weight of an ethylene-acrylic acid ester copolymer (Lucalen®, from BASF, Ludwigshafen, Germany) compounded with a twin-screw extruder (ZSK) at 180 ° C. The blend can be granulated easily.

The subsequent processing on a blown film line produces white colored films with a thickness of 10 μm. The water vapor permeability of these films is 9230 g / m ² * d according to the DIN standard using the Mocon method.

Claims

claims 1. Containing mixtures 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 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 of UV stabilizers, antioxidants, pigments, dyes, nucleating agents, crystallization accelerators or retarders, flow aids, lubricants, mold release agents, flame retardants. 3. Use of the mixtures according to claim 1 for the production of injection molded articles, fibers, films, non-woven material. 4. Use according to claim 3 in the hygiene sector, as packaging material, in the clothing sector or in the construction sector. 5. molded body or molded parts made from mixtures according to claim 1 and 2. 6. Injection molded article, fibers, films, non-woven material, packaging material, made from mixtures according to claims 1 and 2.