CN1280596A - Polyolefins containing a polymer blend - Google Patents

Polyolefins containing a polymer blend Download PDF

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Publication number
CN1280596A
CN1280596A CN98811816A CN98811816A CN1280596A CN 1280596 A CN1280596 A CN 1280596A CN 98811816 A CN98811816 A CN 98811816A CN 98811816 A CN98811816 A CN 98811816A CN 1280596 A CN1280596 A CN 1280596A
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weight
acid
aliphatic
preferred
mixture
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R·帝默曼
M·福格特
W·舒尔兹-施利特
G·施文
M·哈穆斯基
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Technical Ltd By Share Ltd
Bayer AG
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Technical Ltd By Share Ltd
Bayer AG
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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
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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

Comprise polyolefinic polyblend
Be that the interest of the high material of vapor permeability grows with each passing day at present to dress material as snug as a bug in a rug.Water vapor permeation rate height, not only to many Application Areass for example clothes and sanitary product (for example diaper) be necessary character, and also be indispensable character to the lining form on roof at building field, this character can highly be brought into play the functions of use of material.
Various material, for example Gore-Tex (poly tetrafluoroethylene of the special reinforcement that Gore Ind. produces) or Sympatex (aliphatic-aromatic polyetherester that Akzo produces) (referring to Lun Pusi R mpps chemistry encyclopedia, Vol.6, P.5000, and Thieme press, Stuttgart, the 9th edition 1992), the water vapor permeation rate is all very high.The shortcoming of these two kinds of materials is to need to use special production method to produce, and raw material is also very expensive.
Therefore, purpose is the high material of a kind of water vapor permeation rate, and it not only produces simple but also have the required mechanical property of various different application of being fit to.
Be surprised to find that the water vapor permeation rate of the mixture of the polyester type carbonic ether of polyester urethane, aliphatic series or the aliphatic-aromatic of the polyester of aliphatic series or partially aromatic, thermoplastic aliphatic series or partially aromatic, aliphatic polyester acid amides and/or polyether ester amides and polyolefine, optional modified polyolefin and optional filler and strongthener is very high.With compare through the pure polyolefin film of filling, the film by mixture according to the present invention is produced also has the character that can stretch extremely thinly.
The present invention relates to a kind of mixture, it comprises:
1) 5-95 weight part, preferred 10-80 weight part, at least a polymkeric substance of preferred especially 15-60 weight part, this polymkeric substance is selected from the polyesteramide and/or the polyether ester amides of polyester type carbonic ether, aliphatic series or partially aromatic of polyester urethane, aliphatic series or the aliphatic-aromatic of the polyester of aliphatic series or partially aromatic, thermoplastic aliphatic series or partially aromatic
2) polyolefine of 5-70 weight part, preferred 7-60 weight part, preferred especially 10-50 weight part,
3) modified polyolefin of 0-25 weight part, preferred 0-20 weight part, preferred especially 0-15 weight part,
4) filler and the strongthener of 0-80 weight part, preferred 0-70 weight part, preferred especially 5-60 weight part.
Wherein 1), 2), 3) and 4) sum total be 100.
Composition 1)
According to composition 1) polymkeric substance, it is polyester, the thermoplastic aliphatic series that is selected from aliphatic series or partially aromatic or the polyesteramide of polyester type carbonic ether, aliphatic series or the partially aromatic of polyester urethane, aliphatic series or the aliphatic-aromatic that comprises aromatics and at least a polymkeric substance in the polyether ester amides.
Suitable polymer blend is as follows:
The polyester of aliphatic series or partially aromatic is formed by following:
A) aliphatic difunctionals group alcohols, preferred straight chain C 2-C 10, preferred C 2-C 6Dibasic alcohol such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol or preferred especially butyleneglycol and/or optional alicyclic difunctionality alcohols, preferably on alicyclic loop chain, have 5 or 6 C atoms, cyclohexanedimethanol for example, and/or based on the monomer polyvalent alcohol that partially or completely replaces dibasic alcohol of ethylene glycol, propylene glycol, tetrahydrofuran (THF) or oligomeric polyvalent alcohol or their its molecular weight up to 8000, preferably up to 4000 multipolymer, and/or the side chain difunctionality alcohols of minor optional, preferred C 3-C 12Alkyl diol, neopentyl glycol for example, the more polyfunctional alcohols that also has minor optional as 1,2,3-glycerol or TriMethylolPropane(TMP) and aliphatic difunctionals group acids, preferred C 2-C 12The alkyl dicarboxylic carboxylic acid, for example with preferred Succinic Acid, hexanodioic acid, and/or optional aromatics bifunctional acids, for example terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids; The more multi-functional acids that also has minor optional, for example polyprotonic acid of trimellitic acid and so on; Or
B) composition of acid-functionalized and carbinol-functionalization has 2-12 C atom on the preferred alkyl chain, for example hydroxybutyric acid, hydroxypentanoic acid, lactic acid or their derivative, and for example 6-caprolactone or dilactide,
Or the mixture of A and B and/or multipolymer,
Wherein the aromatic acid share that accounts for total acid preferably is no more than 80% (weight), preferred especially 50% (weight);
The polyester type carboxylamine of aliphatic series or partially aromatic is formed by following:
C) aliphatic difunctionals group alcohols, preferred straight chain C 2-C 10, preferred C 2-C 6Dibasic alcohol such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, preferred especially butyleneglycol and/or optional alicyclic bifunctional alcohols preferably have C 5Or C 6Alicyclic loop chain, for example cyclohexanedimethanol and/or based on the monomer polyvalent alcohol that partially or completely replaces dibasic alcohol of ethylene glycol, propylene glycol, tetrahydrofuran (THF) or oligomeric polyvalent alcohol or their its molecular weight up to 4000, preferably up to 1000 multipolymer, and/or the side chain bifunctional alcohols of minor optional, preferred C 3-C 12Alkyl diol, for example neopentyl glycol and the more multi-functional alcohols of minor optional in addition, preferred C 3-C 12Alkyl polyols, for example 1,2,3-glycerol or TriMethylolPropane(TMP) and aliphatic difunctionals group acids, preferred C 2-C 12The alkyl dicarboxylic aid, for example and preferred Succinic Acid, hexanodioic acid, and/or optional aromatics bifunctional acids such as terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids and also have the more multi-functional acids of minor optional such as trimellitic acid or
D) composition of acid-functionalized and carbinol-functionalization preferably has 2-12 C atom, for example hydroxybutyric acid, hydroxypentanoic acid, lactic acid or their derivative, and for example 6-caprolactone or dilactide,
Or the mixture of C and D and/or multipolymer,
Wherein aromatic acid accounts for total acid and preferably is no more than 80%; (weight), preferred especially 50% (weight);
E) reaction product of more polyfunctional isocyanic ester C and/or D and aliphatic series and/or alicyclic bifunctional and that choose wantonly in addition, the alicyclic isocyanate that preferably has 1-12 C atom or 5-8 C atom, for example tetramethylene diisocyanate, two isocyanic acids, six methylene ester and isophorone diisocyanates, optional in addition have straight chain and/or side chain and/or alicyclic bifunctional and/or more multi-functional alcohols, a preferred C 3-C 12Alkyl diol or alkyl polyols, or has an alicyclic alcohols of 5-8 C atom, for example ethylene glycol, hexylene glycol, butyleneglycol and cyclohexanedimethanol, and/or in addition optional that have straight chain and/or side chain and/or an alicyclic bifunctional and/or more polyfunctional amine and/or alkamine, preferably on alkyl chain, have 2-12 C atom, for example quadrol or monoethanolamine, and/or the amine of optional modification in addition or alcohols are as the compound as quadrol base ethane sulfonic acid of free acid or salt and so on.
Ester C wherein) and/or D) account for C), D) and E) total amount preferably be at least 40% (weight), preferred especially 75% (weight);
Aliphatic series or aliphatic-aromatic polycarbonate are formed by following:
F) aliphatic difunctionals group alcohols, preferred straight chain C 2-C 10Dibasic alcohol such as ethylene glycol, butyleneglycol, hexylene glycol or be preferably butyleneglycol especially and/or optional alicyclic bifunctional alcohols, preferably on alicyclic loop chain, have 5-8 C atom, cyclohexanedimethanol for example, and/or based on the monomer polyvalent alcohol that partially or completely replaces dibasic alcohol of ethylene glycol, propylene glycol, tetrahydrofuran (THF) or oligomeric polyols or their its molecular weight up to 8000, preferably up to 4000 multipolymer, and/or the side chain bifunctional alcohols of minor optional, preferred C 2-C 12The alkyl dicarboxylic carboxylic acid, for example neopentyl glycol and the more multi-functional alcohols that also has minor optional as 1,2,3-glycerol, TriMethylolPropane(TMP) and for example preferred Succinic Acid of aliphatic difunctionals group acids, hexanodioic acid and/or optional aromatics bifunctional acids such as terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids and also have the more multi-functional acids of minor optional, for example trimellitic acid; Or
G) composition of acid-functionalized and carbinol-functionalization has 2-12 C atom on the preferred alkyl chain, for example hydroxybutyric acid, hydroxypentanoic acid, lactic acid or their derivative, and for example 6-caprolactone or dilactide,
Or the mixture of F and G and/or multipolymer,
Wherein aromatic acid accounts for total acid and preferably is no more than 50% (weight),
H) carbonate moiety, by aromatics bifunctional phenol, preferably by dihydroxyphenyl propane and for example carbonyl chloride preparation of carbonate donor, or
Carbonate moiety, by aliphatic carbonic acid lipid or derivatives thereof chloro-formic ester and so on for example, or by aliphatic carboxylic acid or derivatives thereof salt and so on for example, with for example carbonyl chloride preparation of carbonate donor, wherein
Ester F) and/or G) account for F), G) and H) total amount preferably be at least 40% (weight), preferred especially 70% (weight);
The polyesteramide of aliphatic series or partially aromatic or polyether ester amides are formed by following:
I) aliphatic difunctionals group alcohols, preferred straight chain C 2-C 10, preferred C 2-C 6Dibasic alcohol such as ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, preferred especially butyleneglycol, and/or optional alicyclic bifunctional alcohols, preferably have 5-8 C atom, for example cyclohexanedimethanol and/or based on the monomer polyvalent alcohol that partially or completely replaces dibasic alcohol of ethylene glycol, propylene glycol, tetrahydrofuran (THF) or oligomeric polyvalent alcohol or their its molecular weight up to 10,000, preferably up to 8000, especially preferably up to 5000 multipolymer, and/or the side chain bifunctional alcohols of minor optional, preferred C 3-C 12Alkyl diol, for example neopentyl glycol and the more multi-functional alcohols of minor optional in addition, for example 1,2,3-glycerol, TriMethylolPropane(TMP) and aliphatic difunctionals group acids, preferably on alkyl chain, have 2-12 C atom, for example preferred Succinic Acid, hexanodioic acid and/or optional aromatics bifunctional acids such as terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids and also have the more multi-functional acids of minor optional, for example trimellitic acid or
K) acid-functionalized functionalized composition has 2-12 C atom on the preferred alkyl chain, for example hydroxybutyric acid, hydroxypentanoic acid, lactic acid or their derivative, and for example 6-caprolactone or three rac-Lactides,
Or I) and mixture K) and/or multipolymer,
Wherein aromatic acid accounts for total acid and preferably is no more than 80% (weight), preferred especially 50% (weight);
L) amide moieties of the amine of the side chain bifunctional of aliphatic series and/or alicyclic bifunctional and/or minor optional, linear aliphatic two-C 2-C 10Alkylamine is preferred, the more polyfunctional amine that also has minor optional, wherein preferred hexamethylenediamine, isophorone diamine and preferred especially hexamethylenediamine, and straight chain and/or alicyclic bifunctional acids, preferably on alkyl chain, have 2-12 C atom, or have C 5Or C 6The alicyclic acids of ring, preferred hexanodioic acid, and/or the side chain bifunctional acids of minor optional and/or optional aromatics difunctionality acids such as terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids and also have the more polyfunctional acids of minor optional, preferably have 2-10 C atom; Or
M) amide moieties of acid-functionalized and amine-functionalized composition preferably has 4-20 C atom on the alicyclic ring chain, preferred omega-lauric lactam, ε-Ji Neixianan, preferred especially 'epsilon '-hexanolactam.
Or L) or mixture M) as amide moieties, wherein
Ester I) and/or K) account for I), K), L) and M) preferred at least 30% (weight) of total amount, the weight of ester structure part is preferably 30-80% (weight), amide structure partly is 70-20% (weight).
Also can adopt molecular weight (weight-average molecular weight) is 300-10, and the polyester of 000 hydroxyl terminalization or acid endization is as the composition that generates ester.
All acids also can be for example use as the form of the analog derivative of the acid chloride of monomeric ester and oligomeric ester class or ester.
Polyether ester amides is particularly preferred, wherein the arrangement of ester and acid amides segmental is random, pure composition wherein is made up of monomer dibasic alcohol and oligomeric dibasic alcohol, and the content of oligomeric dibasic alcohol generally accounts for the 10-99% (mole) of pure composition total content, preferred 15-80% (mole).
Polyether ester amides specifically is made up of following monomer:
The oligomeric polyols of forming by polyoxyethylene glycol, polypropylene glycol, polyoxyethylene glycol random or the blocked structure, by oxyethane or propylene oxide or the preparation of polytetrahydrofuran mixture, its molecular weight (weight-average molecular weight) is 100-10,000 and
The monomer dibasic alcohol, preferred C 2-C 12Alkyl diol, preferred especially C 2-C 6Alkyl diol, ethylene glycol, 1 for example, 4-butyleneglycol, 1, ammediol and 1, the 6-hexylene glycol,
With at least a monomer, it is selected from:
Di-carboxylic acid, preferred C 2-C 12, preferred especially C 2-C 6The alkyl dicarboxylic carboxylic acid, for example oxalic acid, Succinic Acid and hexanodioic acid also can be the forms of their corresponding ether (methyl ether, ethyl ether etc.).
C 2-C 12Alkyl hydroxy carboxylic acid and lactone, for example caprolactone etc. particularly.
The alkamine that on alkyl chain, has 2-12 C atom, for example thanomin and Propanolamine
Have 5-12 C atom, the cyclic lactames of preferred 6-11 C atom, for example ε-Ji Neixianan or laurolactam etc.
The omega-amino acid that on alkyl chain, has 6-12 C atom, for example hexosamine etc.
C 2-C 12The alkyl dicarboxylic carboxylic acid is hexanodioic acid and Succinic Acid and C for example 2-C 12Alkyl diamine is the mixture (1: 1 salt) of hexamethylenediamine and diaminobutane for example.
Can adopt molecular weight equally is 300-10, and the polyester of 000 hydroxyl terminalization or acid endization is as the composition that generates ester.
Ether and ester generally account for the 5-85% (weight) of total polymer in the polymkeric substance.
Polyether ester amides molecular-weight average of the present invention (Mw adopts cresols gel chromatography method, be with the polystyrene standard test) is generally 10,000-300, and 000, preferred 15,000-150,000, preferred especially 15,000-100,000.
The synthetic of polyesteramide of the present invention or polyether ester amides can adopt " polymeric amide method " and " polyester process " to carry out, " polymeric amide method " need make original composition by stoichiometric, also can add, mix, from reaction mixture, remove then and anhydrate, and " polyester process " need make original composition be mixed together by the excess glycol of stoichiometric and adding, and the esterification of acidic-group takes place earlier, the transesterify of these ester classes takes place then or change the amido exchange.Under second kind of situation, not only to distill water outlet, but also will distill out excessive dibasic alcohol.Preferably synthetic by above-mentioned " polyester process ".
Also can adopt known catalyzer to quicken polycondensation.Can adopt the acidity quickening the known P contained compound of polymeric amide synthetic and be used for esterification or organo-metallic catalyst and the combination of the two to quicken polycondensation.
In addition, for example aminoethyl base ethanol is to influence the polycondensation of polyesteramide also can to adopt Methionin, lysine derivative or the amino branched product of other band, and aminoethyl base ethanol can quicken condensation can produce branched product (referring to for example German Patent-3831709) again.
The production method of polyester, polyester type carbonic ether and polyester urethane is well-known, or adopts the similar mode of known method (referring to for example English Patent-A-304787, WO95/12629, WO 93/13154, English Patent-A-682054 and A-593975) to produce.
Polyester of the present invention, polyester urethane, polyester type carbonic ether, polyesteramide and polyether ester amides also can comprise 0.1-5% (weight), the branching agent (referring to the explanation to polymkeric substance) of preferred 0.1-1% (weight).These branching agents can be for example trifunctional alcohols such as TriMethylolPropane(TMP) or glycerol, four-functional group alcohols such as tetramethylolmethane, trifunctional carboxylic-acid such as citric acid.
As composition 1) polymkeric substance enumerated, molecular weight is generally at least 10, and 000g/mol is preferred 10,000-100,000, preferred especially 15,000-60,000g/mol, the raw material distribution in polymkeric substance generally is random.When the polymkeric substance that adopts polyurethanes is synthetic, also can be by C) and D) and by E) when synthetic, can not always expect that chain link is random distribution fully.
Composition 2)
According to the present invention, suitable polyolefine is for example polymkeric substance of ethene, propylene, butylene or iso-butylene and so on of aliphatic unsaturated hydrocarbon, and they are to adopt for example radical polymerization or adopt the method preparation of metallocene catalyst of ordinary method.Polyolefinic average weight-average molecular weight Mw (being measured by the gel chromatography method) is generally 5000-3,000,000.Can adopt high pressure polyolefin and low pressure polyolefine, for example LDPE, LLDPE and MDPE.
Polyolefine is well-known, for example in horse Germania (Ullman) technical chemistry complete works, Vol.A21, P 487-577 (the 5th additional revised edition, 1992, VCH press, Wei Yin Haimu) in existing narration.
Composition 3)
Modified polyolefin is by the said polyolefins grafting or by composition 2) described in monomer, optimal ethylene and/or propylene and other monomer preferably have active group for example acid anhydrides, amino, acidic group, oxygen support base, the vinyl monomer of ester group ketone group or the polyolefine of carboxylate salt copolymerization.But the monomer of preferred copolymerization is vinylformic acid and its single alkanol and/or two-C 1-C 12Alkanol, preferred C 2-C 6The alkyl ester of alkanol and maleic anhydride.
The modified polyolefin of Cai Yonging is preferably following in the present invention forms:
A) 40-99.9% (weight), at least a or multiple alpha-olefin of preferred 88-99.9% (weight) with 2-8 C atom,
B) diolefine of 0-50% (weight),
C) C of the acrylic or methacrylic acid of 0-45% (weight) 1-C 12The mixture of uncle or secondary alkyl ester or these esters.
D) unsaturated monobasic of ethylenic or the di-carboxylic acid of 0-45% (weight), maleic anhydride for example, they also can be partly or entirely exist with salt and/or these sour functional group derivants' form,
E) 0-40% (weight) contains the monomer of oxygen support base, for example glycidyl methacrylate or glycidyl acrylate,
F) vinyl ester of 0-75% (weight), for example vinyl-acetic ester or its saponified product (vinyl alcohol)
Comprising at least a composition among b, c, d, e and the f.
The ethylene/acrylic acid of grafting or copolymerization (tertiary alkyl) ester, ethylene/propene acid glycidyl ester (or glycidyl allyl ether)/vinylformic acid (tertiary alkyl) ester, ethylene/acrylic acid (ester)/maleic anhydride or ethene/maleic anhydride are particularly preferred.
The molecular weight of modified polyolefin (weight-average molecular weight) is generally 5000-3, and 000,000, preferred 10,000-1,000,000 (measuring) by the gel chromatography method
Modified polyolefin is known, or can be by known method production (for example EP-A-77415).
Composition 4)
The general inorganic materials that adopts is as filler and toughener.These materials are as fiber reinforced material of glass and carbon fibre and so on and mineral filler, for example talcum, mica, chalk, kaolin, wollastonite, gypsum, quartz, rhombspar and silicate.Mineral filler is preferred, preferred especially chalk.
Filler and strongthener are also surface treated.
The Fibre diameter of glass fibre is generally 8-14 μ m, can adopt with the successive fibers form, also can adopt with chopping or ground form of glass fibers, and wherein these fibers have suitable screening system and based on the coupler or the coupler system of silane.
Mixture of the present invention also can comprise conventional additive, for example ultra-violet stabilizer, antioxidant, pigment, dyestuff, nucleator, crystallization promoter or delayer, flow promotor, lubricant, releasing agent and fire retardant.
Other additive that can prepare mixture of the present invention and also can have, can adopt known method that corresponding composition is mixed, can for example carry out melt compounded or melt extruded in the formula kneader, extrusion machine, double-screw extrusion machine at conventional equipment in for example under 150 ℃-300 ℃ in conventional temperature.
Mixture of the present invention can injection molding, makes the form of fiber or film, or is used for nonwoven field (spun-bond process or the molten method of blowing).
Preferably use with the form of film.This class film can use separately, also can be used as composite parts and uses with other non-woven fleece, yarn fabric, tricot or other film.
Preferred field of using is: sanitary product (for example diaper, sanitary towel and adult incontinence pad); General wrapping material, clothes for example also are used in medical field, material of construction for example as the roof lining form.
Embodiment
Embodiment 1
The Lupolen that the broken chalk and 20% (weight) of the fine powder that to make 40% (weight) be 40/60 polyesteramide (adopt the m-cresol solution of 1% (weight) to measure down at 20 ℃, the relative viscosity of solution is 2.5) by the ester/acid amides ratio of the random copolycondensation of hexanodioic acid, butyleneglycol and hexanolactam preparation is produced by Omya (Cologne, Germany (Hydrocarb95T)) with 40% (weight) is produced by BASF (Ludwigshafen, Germany) -LDPE, under 170 ℃ in double-screw extrusion machine (ZSK) chemical combination.Reaction mixture there is not difficulty ground granulation.
Adopt the blown film apparatus processing then, make the thick white films of 10 μ m.Measure with health (Mocon) method not according to the DIN-standard, the water rate of permeation of these films reaches 770g/m 2*D.
Embodiment 2
The broken chalk and 30% (weight) of the fine powder that to make 30% (weight) be 70/30 polyether ester amides and 40% (weight) by the ester/acid amides ratio of AH salt, hexanodioic acid, glycol ether and poly(oxyethylene glycol) 400 preparation is produced by Omya (Cologne, Germany (Hydrocarb95T)) is by the Lupolen of BASF (Ludwigshafen, Germany) production -LLDPE, under 180 ℃ in double-screw extrusion machine (ZSK) chemical combination.Reaction mixture there is not difficulty ground granulation.
Use the blown film apparatus processing then, make the thick white films of 8 μ m.
Measure with Kang Fangfa not according to the DIN-standard, the water rate of permeation of these films reaches 1030g/m 2*D.
The production of polyether ester amides among the embodiment 2:
710gAH salt, 253g hexanodioic acid, 184g glycol ether and 1380g poly(oxyethylene glycol) 400 and catalyzer titanium isopropylate (IV) are mixed together, and under nitrogen atmosphere, are heated to 240 ℃.After the distillation water outlet, pressure classification is dropped to 1mbar.After 3 hours, make colourless high molecular weight material (m-cresol solution with 1% (weight) is measured down at 25 ℃, and relative viscosity is 3.2) in polycondensation, fusing point is 186 ℃.
Embodiment 3
Making 35% (weight) is 60/40 polymeric amide ether-ether by the ester/acid amides ratio of AH salt, hexanodioic acid, glycol ether and cetomacrogol 1000 preparation, the ethene/acrylic ester multipolymer (Lucalen of the Lupolen-LLDPE and 5% (weight) that is produced by BASF with the broken chalk, 30% (weight) of the above-mentioned above-mentioned fine powder of being produced by Omya of 30% (weight) , produce by Ludwigshafen, Germany BASF), adopt double-screw extrusion machine (ZSK) chemical combination down at 180 ℃.Reaction mixture there is not difficulty ground granulation.
Adopt the blown film apparatus processing then, make the thick white films of 10 μ m.Measure with Kang Fangfa not according to the DIN-standard, the water rate of permeation of these films reaches 9230g/m 2*D.

Claims (6)

1. mixture, it comprises:
1) 5-95 (weight) part at least a polymkeric substance, this polymkeric substance is selected from the polyesteramide and/or the polyether ester amides of polyester type carbonic ether, aliphatic series or partially aromatic of polyester urethane, aliphatic series or the aliphatic-aromatic of the polyester of aliphatic series or partially aromatic, thermoplastic aliphatic series or partially aromatic
2) polyolefine of 5-70 weight part,
3) modified polyolefin of 0-25 weight part and
4) filler of 0-80 weight part and strongthener.
2. according to the mixture of claim 1, it comprises at least a additive that is selected from ultra-violet stabilizer, antioxidant, pigment, dyestuff, nucleator, crystallization promoter or delayer, flow promotor, lubricant, releasing agent and the fire retardant.
3. according to the application of mixture in injection molded article, fibre product, film and nonwoven production of claim 1.
According to claim 3 at health field as wrapping material, in the application of garment industry or building field.
5. by moulded product or the molded parts produced according to the mixture of claim 1 and 2.
6. by injection molded article, fiber, film, non-woven material and the wrapping material produced according to the mixture of claim 1 and 2.
CN98811816A 1997-12-03 1998-11-20 Polyolefins containing a polymer blend Pending CN1280596A (en)

Applications Claiming Priority (2)

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DE19753531A DE19753531A1 (en) 1997-12-03 1997-12-03 Polymer blend containing polyolefins

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CN105440654A (en) * 2015-12-09 2016-03-30 东莞市精伦实业有限公司 Low-hardness and high-strength thermoplastic polyurethane elastomer and preparation method thereof

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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
CN105440654A (en) * 2015-12-09 2016-03-30 东莞市精伦实业有限公司 Low-hardness and high-strength thermoplastic polyurethane elastomer 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

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WO1999028384A1 (en) 1999-06-10
NO20002674L (en) 2000-05-25
CA2312489A1 (en) 1999-06-10
KR20010032722A (en) 2001-04-25
DE19753531A1 (en) 1999-06-10

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