EP1287074A1 - Alliages polymeres resistant aux intemperies - Google Patents

Alliages polymeres resistant aux intemperies

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Publication number
EP1287074A1
EP1287074A1 EP01931688A EP01931688A EP1287074A1 EP 1287074 A1 EP1287074 A1 EP 1287074A1 EP 01931688 A EP01931688 A EP 01931688A EP 01931688 A EP01931688 A EP 01931688A EP 1287074 A1 EP1287074 A1 EP 1287074A1
Authority
EP
European Patent Office
Prior art keywords
weight
parts
polymer blends
vinyl
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01931688A
Other languages
German (de)
English (en)
Inventor
Holger Warth
Gerwolf Quaas
Dieter Wittmann
Heinrich Alberts
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE2000124935 external-priority patent/DE10024935A1/de
Priority claimed from DE2000124933 external-priority patent/DE10024933A1/de
Priority claimed from DE2001109225 external-priority patent/DE10109225A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1287074A1 publication Critical patent/EP1287074A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • C08L51/04—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 rubbers
    • 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
    • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to polymer blends based on polyamide and graft polymers selected from the group consisting of silicone, EP (D) M and acrylate rubbers as the graft base, which have very good mechanical properties such as tensile strength and weather stability.
  • EP-A-202 214 describes polyamide / ABS blends which additionally contain ner-inertness mediators which have functional groups which correspond to the
  • Amine or acid end groups of the polyamides can react.
  • thermoplastic molding compositions made from polyamides using graft polymers which are prepared by a certain redox polymerization method and contain tertiary butyl acrylates in the shell.
  • EP-A-785 234 polymer compositions are described, the graft polymers of aromatic vinyl monomers and monomers of alkyl (meth) acrylates or acrylonitrile on a rubber as the first component, a thermoplastic polymer with polar groups as the second component and an excitability mediator as the third Component included.
  • the object of the present invention is to provide polymer blends with excellent mechanical properties such as tensile strength and weather stability. r / I
  • polymer blends based on polyamide and graft polymers selected from the group consisting of silicone, EP (D) M and acrylate rubbers, which contain excipients, have the desired properties.
  • the invention therefore relates to polymer blends containing
  • the invention preferably relates to polymer blends
  • a non-digestive agent containing at least one thermoplastic polymer with polar groups 0.5 to 50, preferably 1 to 30, particularly preferably 2 to 10 parts by weight of a non-digestive agent containing at least one thermoplastic polymer with polar groups.
  • Polyamides suitable according to the invention are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and / or amorphous polyamides.
  • the partially crystalline polyamides are polyamide 6, polyamide 6,6, mixtures and corresponding copolymers of these components are suitable.
  • partially crystalline polyamides the acid component of which is wholly or partly composed of terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component wholly or partly of m- and / or p-xylylene diamine and / or hexamethylene diamine and / or 2,2,4-trimethylhexamethylene diamine and / or 2,4,4-trimethyl hexamethylene diamine and / or isophorone diamine and the composition of which is known in principle.
  • polyamides which are made wholly or in part from lactams with 7 to 12 carbon atoms in the ring, optionally with the use of one or more of the above-mentioned starting components.
  • Particularly preferred partially crystalline polyamides are polyamide-6 and polyamide-6,6 and their mixtures.
  • Known products can be used as amorphous polyamides. They are obtained by polycondensation of diamines such as ethylene diamine, hexamethylene diamine, decamethylene diamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine, m- and / or p-xylylene diamine, bis- (4th -aminocyclo- hexy ⁇ ) methane, bis- (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino-di-cyclohexyl-methane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 2,5- and / or • 2,6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as
  • Copolymers which are obtained by polycondensation of several monomers are also suitable, as are copolymers which are prepared with the addition of aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • aminocarboxylic acids such as ⁇ -aminocaproic acid, ⁇ -aminoundecanoic acid or ⁇ -aminolauric acid or their lactams.
  • Particularly suitable amorphous polyamides are the polyamides prepared from isophthalic acid, hexamethylene diamine and other diamines such as 4,4-diaminodicyclohexyl methane, isophorone diamine, 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine, 2,5- and / or 2,6-bis (aminomethyl) norbornene; or from isophthalic acid, 4,4'-diamino-dicyclohexylmethane and -caprolactam; or from isophthalic acid, 3,3'-
  • Positional isomers diamine dicyclohexalmethanes are used, which are composed of
  • the polyamides preferably have a relative viscosity (measured on a 1% strength by weight solution in m-cresol at 25 ° C.) from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.
  • Component B comprises one or more rubber-elastic graft polymers selected from the group consisting of silicone, acrylate and EP (D) M rubbers as the graft base.
  • Component B preferably comprises one or more graft polymers of
  • B.2 95 to 5, preferably 80 to 20, in particular 70 to 20% by weight of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C selected from the group consisting of Silicone, acrylate and EP (D) M rubbers.
  • the graft base B.2 generally has an average particle size (d 50 value) of 0.05 to 5 ⁇ m, preferably 0.10 to 0.5 ⁇ m, particularly preferably 0.20 to 0.40 ⁇ m.
  • Component B1 vinyl monomers which can be used according to the invention are those composed of at least one monomer from the series: vinyl aromatics and / or nucleus-substituted vinyl aromatics (such as, for example, styrene, ⁇ -methylstyrene, p-methyl- • styrene, p-chlorostyrene), methacrylic acid (C 1 -C 8 ) -alkyl esters (such as methyl methacrylate, ethyl methacrylate) (B1) with at least one monomer from the series: vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile), (meth) acrylic acid (-C-C 8 ) alkyl esters ( such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate), derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride
  • Component B.l is preferably a mixture of
  • Thermoplastic (co) polymers with a composition according to component D can be formed as a by-product in the graft polymerization to produce component B, especially when large amounts of monomers are grafted onto small amounts of rubber.
  • graft polymer B is understood to mean the product formed from grafted rubber during the graft polymerization and the (co) polymer formed during the graft polymerization.
  • the amounts of the (co) polymer necessarily formed during the graft polymerization depend, inter alia, on depends on the monomer composition and polymerization method.
  • Particularly preferred vinyl monomers B.l are styrene and acrylonitrile and optionally methyl methacrylate, ⁇ -methylstyrene and acrylonitrile and optionally methyl methacrylate, or styrene, ⁇ -methylstyrene and acrylonitrile and optionally
  • Silicone rubbers B.2 suitable according to the invention consist predominantly of structural units in which
  • RU and Rl2 may be the same or different, and Ci-Cg-alkyl or cycloalkyl or Cß-C 2-aryl and
  • n is an integer.
  • Preferred silicone rubbers B.2 are particulate with an average particle diameter d5Q of 0.09 to 1 ⁇ m, preferably 0.09 to 0.4 ⁇ m and one
  • dihalogenosilanes 2) 0 to 10 mol%, based on 1), trihalosilanes and
  • Ci-Cß-alkenyl preferably vinyl or allyl
  • Preferred silicone rubbers B.2 contain at least as organic residues
  • the end group is generally a diorganyl-hydroxylsiloxy unit, preferably a dimethylhydroxysiloxy unit.
  • Preferred silanes 1) to 4) for the production of the silicone rubbers B.2 contain chlorine as halogen substituents.
  • silicone rubber B.2 does not necessarily have to be produced from the halogen compounds 1) to 4).
  • silicone rubbers B.2 of the same structure consist of silanes with other hydrolyzable groups, e.g. Ci ⁇ Cg alkoxy groups, or have been prepared from cyclic siloxane oligomers, are included.
  • Silicone graft rubbers are mentioned as a particularly preferred component B.2. These can be produced, for example, using a three-stage process.
  • the crosslinked silicone rubbers are obtained from these cyclic oligomers with the addition of mercaptopropylmethyldimethoxysilane by ring-opening cationic polymerization.
  • the silicone rubbers obtained which have graft-active vinyl and mercapto groups, are radically graft-polymerized with vinyl monomers (or mixtures).
  • mixtures of cyclic siloxane oligomers such as octamethylcyclotetrasiloxane and tetramethyltetravinylcyclotetrasiloxane in an emulsion are preferably cationically polymerized in a ring-opening manner.
  • the silicone rubbers are particulate as an emulsion.
  • alkylbenzenesulfonic acids which are both catalytically active and emulsifiers. After the polymerization, the acid is neutralized.
  • alkylbenzenesulfonic acids n-alkylsulfonic acids can also be used. It is also possible to use co-emulsifiers in addition to the sulfonic acid.
  • Co-emulsifiers can be nonionic or anionic. Particularly suitable anionic co-emulsifiers are salts of n-alkyl- or alkylbenzenesulfonic acids.
  • Nonionic co-emulsifiers are polyoxyethylene derivatives of fatty alcohols and fatty acids. Examples are POE (3) lauryl alcohol, POE (20) oleyl alcohol, POE (7) nonyl alcohol or POE ( ⁇ ) stearate. (The notation POE (number) alcohol means that the number of units of ethylene oxide added to a molecule .... alcohol corresponds to the number. POE stands for polyethylene oxide. The number is an average.)
  • crosslinking and grafting groups (vinyl and mercapto groups, cf. organic residues ⁇ and ⁇ ) can be inserted into the silicone rubber by using appropriate siloxane oligomers.
  • siloxane oligomers such are, for example, tetramethyltetravinylcyclotetrasiloxane, or ⁇ -mercaptopropylmethyldimethoxysiloxane or its hydrolyzate. They are added to the main oligomer, for example octamethylcyclotetrasiloxane, in the desired amounts in the second stage.
  • Adequate crosslinking of the silicone rubber can already be achieved if the residues ⁇ and ⁇ react with one another in the emulsion polymerization, so that the addition of an external crosslinker can be unnecessary.
  • a crosslinking silane can be added in the second reaction step to increase the degree of crosslinking of the silicone rubber.
  • Branches and cross-links can be achieved by adding e.g. Tetraethoxysilane or a silane of the formula
  • X is a hydrolyzable group, in particular an alkoxy or halogen radical
  • y is an organic residue
  • Preferred silanes y-SiX3 are methyltrimethoxysilane and phenyltrimethoxysilane.
  • the gel content is determined at 25 ° C. in acetone (cf. DE-AS 2 521 288, SP. 6, lines 17 to 37).
  • silicone rubbers according to the invention it is at least 70% by weight, preferably 73 to 98% by weight.
  • Grafted silicone rubbers B can be produced by radical graft polymerization, for example analogously to DE-PS 2 421 288.
  • the graft monomers can be graft-polymerized radically in the presence of the silicone rubber, in particular at 40 to 90 ° C.
  • the graft polymerization can be carried out in suspension, dispersion or emulsion. Continuous or discontinuous emulsion polymerization is preferred.
  • This graft polymerization is carried out using free radical initiators (e.g. peroxides, azo compounds, hydroperoxides, persulfates, perphosphates) and, if appropriate, under
  • anionic emulsifiers e.g. Carboxonium salts, sulfonic acid salts or organic sulfates.
  • the silicone rubber has graft-active residues, so that special measures for heavy grafting are unnecessary.
  • the grafted silicone rubbers can be prepared by graft polymerization from 5 to 95 parts by weight, preferably 20 to 80 parts by weight of a vinyl monomer or a vinyl monomer mixture to 5 to 95, preferably 20 to 80 parts by weight of silicone rubber.
  • a particularly preferred vinyl monomer is styrene or methyl methacrylate.
  • Suitable vinyl monomer mixtures consist of 50 to 95 parts by weight of styrene, ⁇ -methylstyrene (or other alkyl- or halogen-substituted styrenes) or methyl methacrylate on the one hand and from 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, acrylic acid-Ci-Cig -alkyl esters, Ci-Ciss-alkyl alkyl, maleic anhydride or substituted maleimides on the other hand.
  • Acrylic acid esters of primary or secondary aliphatic C 2 -C 10 alcohols preferably n-butyl acrylate or acrylic or methyl acrylate esters of tert-butanol, preferably t-butyl acrylate, may additionally be present as further vinyl monomers in smaller amounts.
  • a particularly preferred monomer mixture is 30 to 40 Parts by weight of ⁇ -methylstyrene, 52 to 62 parts by weight of methyl methacrylate and 4 to 14 parts by weight of acrylonitrile.
  • the thus grafted silicone rubbers can be worked up in a known manner, e.g. by coagulation of the latices with electrolytes (salts, acids or
  • free polymers or copolymers of the graft monomers forming the graft shell are generally also formed to a certain extent in addition to the actual graft copolymer.
  • grafted silicone rubber is the product obtained by polymerizing the graft monomers in the presence of the silicone rubber, that is to say strictly speaking a mixture of graft copolymer and free (co) polymer of the graft monomers.
  • Graft polymers based on acrylate are preferably made of
  • the acrylate rubbers (a) are preferably polymers made from acrylic acid alkyl esters, optionally with up to 40% by weight, based on (a), of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include C 1 -C 6 -alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen-Cj-Cg-alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.
  • Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
  • crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as, for example, ethylene glycol dimethacrylate, Allyl methacrylate; polyunsaturated heterocyclic compounds, such as, for example, trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers trialyll cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
  • the amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the rubber base.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic esters, can optionally be used to prepare the graft base B.2 are, for. B. acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-Ci- C 6 alkyl ether, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as graft base layer B.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • the acrylate-based polymers are generally known, can be prepared by known processes (for example EP-A 244 857) or are commercially available products.
  • the gel content of the graft base is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg
  • the average particle size d 0 is the diameter above and below which 50% by weight of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-796).
  • the EP (D) M graft base used is at least one copolymer or terpolymer containing ethylene and propylene with only a small number of double bonds (cf. EP-A 163 411, EP-A 244 857).
  • EP (D) M rubbers used are those which have a glass transition temperature in the range from -60 to -40 ° C.
  • the rubbers have only a small number of double bonds, ie fewer than 20 double bonds per 1000 carbon atoms, in particular 3 to 10 double bonds per 1000 carbon atoms.
  • Examples of such rubbers are copolymers consisting of ethylene-propylene and ethylene-propylene terpolymers. The latter are produced by polymerizing at least 30% by weight of ethylene, at least 30% by weight of propylene and 0.5 to 15% by weight of a non-conjugated diolefinic component.
  • Diolefins with at least 5 carbon atoms such as 5-ethylidene norbornene, dicyclopentadiene, 2,2,1-dicyclopentadiene and 1,4-hexadiene, are generally used as the ter component.
  • polyalkylene amers such as polypentenamer, polyoctenamer, polydodecanamer or mixtures of these substances.
  • Partially hydrogenated polybutadiene rubbers in which at least 70% of the residual double bonds are hydrogenated are also suitable.
  • EPDM rubbers generally have a Mooney viscosity ML1.4 (100 ° C) of 25 to 120. They are commercially available.
  • the EP (D) M-based graft polymer can be prepared in various ways
  • a solution of the EP (D) M elastomer (rubber) is preferably prepared in the monomer mixture and (if appropriate) indifferent solvents and the grafting reaction is carried out at higher temperatures by radical initiators, such as azo compounds or peroxides.
  • radical initiators such as azo compounds or peroxides.
  • DE-AS 23 02 014 and DE-A 25 33 991 may be mentioned as examples. It is also possible - as described in US Pat. No. 4,202,948 - to work in suspension.
  • thermoplastic polymers with polar groups are preferably used as compatibilizers.
  • C.2 at least one monomer selected from the group C2 to C12 alkyl methacrylates, C2 to C ⁇ ⁇ alkyl acrylates, methacrylonitriles and acrylonitriles and
  • C.3 contain ⁇ -, ß-unsaturated components containing dicarboxylic anhydrides.
  • Styrene is particularly preferred as the vinyl aromatic monomer C.I.
  • Acrylonitrile is particularly preferred for component C.2.
  • Maleic anhydride is particularly preferred for ⁇ -, ⁇ -unsaturated components containing dicarboxylic anhydrides C.3.
  • C. I, C.2 and C.3 are preferably used as components of components
  • terpolymers of styrene, acrylonitrile and maleic anhydride are preferably used. These polymers in particular contribute to the improvement of the mechanical properties, such as tensile strength and weather stability.
  • the amount of maleic anhydride in the polymer can vary within wide limits. The amount is preferably 0.2-5 mol%.
  • Quantities between 0.5 and 1.5 mol% are particularly preferably contained in component C.I. Particularly good mechanical properties with regard to tensile strength and weather stability are achieved in this area.
  • Te ⁇ olymer can be produced in a manner known per se.
  • a suitable one
  • the method is to dissolve monomer components of the polymer, e.g. of styrene, maleic anhydride or acrylonitrile in a suitable solvent, e.g. Methyl ethyl ketone (MEK).
  • a suitable solvent e.g. Methyl ethyl ketone (MEK).
  • One or optionally several chemical initiators are added to this solution. Suitable initiators are e.g. Peroxides.
  • the mixture is then polymerized at elevated temperature for several hours.
  • the solvent and the unreacted monomers are then removed in a manner known per se.
  • the ratio between the component Cl (vinylaromatic monomer) and the component C.2, for example the acrylonitrile monomer in the polymer, is preferably between 80:20 and 50:50.
  • an amount of vinyl aromatic monomer Cl is preferably selected which corresponds to the amount of the vinyl monomer B1 in the graft copolymer B.
  • the amount of component C in the polymer blends according to the invention is between 0.5 and 50% by weight, preferably between 1 and 30% by weight, particularly preferably between 2 and 10% by weight. Quantities between 5 and 7% by weight are most preferred.
  • Such polymers are described for example in EP-A-785 234 and EP-A-202 214. According to the invention, particular preference is given to the polymers mentioned in EP-A-202 214.
  • Component D comprises one or more thermoplastic vinyl (co) polymers.
  • Suitable as vinyl (co) polymers D are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 -C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides ) unsaturated carboxylic acids.
  • (Co) polymers of are particularly suitable
  • Dl 50 to 99 preferably 60 to 80 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) alkyl esters such as eg methyl methacrylate, ethyl ethacrylate), and
  • D.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C 8 -C 8 ) alkyl esters (such as methyl methacrylate, n-butyl acrylate, t -Butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example
  • vinyl cyanides unsaturated nitriles
  • C 8 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, t -Butyl acrylate
  • unsaturated carboxylic acids such as maleic acid
  • derivatives such as anhydrides and imides
  • the (co) polymers D are resinous, thermoplastic and rubber-free.
  • the copolymer of D.l styrene and D.2 acrylonitrile is particularly preferred.
  • the (co) polymers according to D are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • (Co) polymers according to component D often arise as by-products in the graft polymerization of component B, especially when large amounts of monomers B.l are grafted onto small amounts of rubber B.2.
  • the polymer blends according to the invention can contain conventional additives such as flame retardants, anti-dripping agents, very finely divided inorganic compounds, lubricants and mold release agents, nucleating agents, antistatic agents, stabilizers, fillers and
  • the polymer blends according to the invention can generally contain 0.01 to 20% by weight, based on the total molding composition, of flame retardants.
  • flame retardants are organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg-alhydroxide, inorganic compounds such as aluminum oxides, titanium dioxide, antimony oxides, barium metaborate , Hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdenum dat, tin borate, ammonium borate, barium metaborate and tin oxide as well as siloxane compounds.
  • Phosphorus compounds as described in EP-A-363 608, EP-A-345 522 or EP-A-640 655 can also be used as flame retardant compounds.
  • the inorganic compounds which can be used comprise compounds of one or more metals of the 1st to 5th main group and the 1st to 8th subgroup of the periodic table, preferably the 2nd to 5th main group and the 4th to 8th subgroup, particularly preferably the 3rd to the 5th main group and the 4th to 8th subgroup with the elements oxygen, sulfur, boron, phosphorus, carbon, nitrogen, hydrogen and / or silicon.
  • Examples of such compounds are oxides, hydroxides, water-containing oxides,
  • These include, for example, TiN, TiO 2 , SnO 2 , WC, ZnO, Al 2 O 3 , AIO (OH), ZrO 2 , Sb 2 O 3 , SiO 2 , iron oxides, NaSO, BaSO, vanadium oxides, zinc borate, silicates such as Al Silicates, Mg silicates, one, two, three-dimensional silicates, mixtures and doped
  • nanoscale particles can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
  • the average particle diameters are less than or equal to 200 n, preferably less than or equal to 150 nm, in particular 1 to 100 nm.
  • Particle size and particle diameter always means the mean particle diameter d 50 , determined by ultracentrifuge measurements according to W. Scholtan et al.
  • the inorganic compounds can be in the form of powders, pastes, brine, dispersions or suspensions. Powder can be obtained from dispersions, brines or suspensions by precipitation.
  • the powders can be incorporated into the thermoplastic materials by customary methods, for example by direct kneading or extruding the constituents of the molding composition and the very finely divided inorganic powders.
  • Preferred methods are the preparation of a master batch, e.g. in flame retardant additives, other additives, monomers, solvents, in component A or the co-precipitation of dispersions of components B or C with dispersions, suspensions, pastes or sols of the finely divided inorganic materials.
  • Filling and reinforcing materials e.g. Glass fibers, optionally cut or ground, contain glass beads, glass balls, flake-like reinforcing material, such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, wool astonite, mica, carbon fibers or a mixture thereof. Cut or ground glass fibers are preferably used as the reinforcing material.
  • Preferred fillers which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc, titanium dioxide, wollastonite.
  • the polymer blends of the present invention can be used to produce molded articles of any kind.
  • molded bodies can be produced by injection molding.
  • moldings that can be produced are: Housing parts of all types, e.g. for household appliances, such as juicers, coffee machines, blenders, for
  • Office machines such as computers, printers, monitors or cover plates for the construction sector and parts for the motor vehicle sector.
  • the polymer blends are particularly suitable for the production of molded parts to which particularly high demands are made with regard to weather resistance, tensile strength and stress crack resistance.
  • the use of the polymer blends for the production of moldings and the moldings obtainable therefrom are also the subject of the present invention.
  • a polyamide (DURETHAN B30 from Bayer AG, Leverkusen,
  • Styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight of particulate cross-linked polybutadiene rubber (average particle diameter d 50 0.28 ⁇ m), produced by emulsion polymerization B2 acrylonitrile-ethylene-styrene copolymer (AES) with an EPDM
  • Blendex WX270 from General Electric B3 acrylate-styrene-acrylonitrile copolymer (ASA) with a rubber content of approx. 60% by weight
  • Blendex WX160 from General Electric B4 Silicon Acrylate Chew Scb.uk with core-shell structure from one
  • Metablen S2001 Metaln Company B.N., Nlissingen, The Netherlands.
  • the polymer blends according to the invention are produced by mixing the respective constituents in a known manner and melt-compounding or melt-extruding them at temperatures of 200 to 300 ° C. in conventional units, such as internal kneaders, extruders and twin-screw screws, the fluorinated polyolefins preferably in the form of the coagulated mixture already mentioned be used.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at an elevated temperature.
  • the heat resistance according to Vicat A and B is determined according to DI ⁇ 53 460 (ISO 306).
  • HDT A was determined at 1.8 MPa according to ISO75.
  • the melt volume rate was determined according to ISO 527.
  • Weathering was determined according to SAE J 1885:
  • the modulus of elasticity was determined in accordance with DIN 53 457 / ISO 527.
  • the elongation at break was determined in accordance with ISO 527.

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

Abstract

L'invention concerne des alliages polymères résistant aux intempéries, contenant A) un polyamide, B) au moins un polymère greffé présentant l'élasticité du caoutchouc, sélectionné dans le groupe comprenant le caoutchouc silicone, le caoutchouc EP(D)M et le caoutchouc acrylate, comme base de greffe, C) au moins un agent de compatibilité contenant au moins un polymère thermoplastique à groupes polaires et D) éventuellement au moins un (co)polymère de vinyle.
EP01931688A 2000-05-19 2001-05-07 Alliages polymeres resistant aux intemperies Withdrawn EP1287074A1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE2000124935 DE10024935A1 (de) 2000-05-19 2000-05-19 Witterungsstabile Polymerblends
DE2000124933 DE10024933A1 (de) 2000-05-19 2000-05-19 Polymerblends enthaltend Polyamid und über Masse-Polymerisationsverfahren hergestellte kautschukmodifizierte Polymerisate
DE10024933 2000-05-19
DE10024935 2000-05-19
DE10109225 2001-02-26
DE2001109225 DE10109225A1 (de) 2001-02-26 2001-02-26 Schlagzähmodifizierte Polymer-Zusammensetzungen
PCT/EP2001/005141 WO2001090247A1 (fr) 2000-05-19 2001-05-07 Alliages polymeres resistant aux intemperies

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EP1287074A1 true EP1287074A1 (fr) 2003-03-05

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EP01931688A Withdrawn EP1287074A1 (fr) 2000-05-19 2001-05-07 Alliages polymeres resistant aux intemperies
EP01933938A Withdrawn EP1287075A1 (fr) 2000-05-19 2001-05-07 Alliages polymeres contenant un polyamide et des polymeres modifies avec du caoutchouc et obtenus par polymerisation en masse
EP01927943A Withdrawn EP1287067A1 (fr) 2000-05-19 2001-05-07 Compositions polymeres a resilience modifiee

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EP01933938A Withdrawn EP1287075A1 (fr) 2000-05-19 2001-05-07 Alliages polymeres contenant un polyamide et des polymeres modifies avec du caoutchouc et obtenus par polymerisation en masse
EP01927943A Withdrawn EP1287067A1 (fr) 2000-05-19 2001-05-07 Compositions polymeres a resilience modifiee

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US (3) US20030181591A1 (fr)
EP (3) EP1287074A1 (fr)
JP (3) JP2003534429A (fr)
KR (3) KR20030001518A (fr)
CN (3) CN1429250A (fr)
AR (3) AR033368A1 (fr)
AU (3) AU2001258394A1 (fr)
BR (3) BR0110823A (fr)
CA (3) CA2409013A1 (fr)
MX (3) MXPA02011371A (fr)
TW (1) TWI281484B (fr)
WO (3) WO2001090246A1 (fr)

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WO2001090241A1 (fr) 2001-11-29
BR0110853A (pt) 2003-02-11
AR033369A1 (es) 2003-12-17
BR0110873A (pt) 2003-02-11
AR033370A1 (es) 2003-12-17
EP1287067A1 (fr) 2003-03-05
US20030181582A1 (en) 2003-09-25
MXPA02011394A (es) 2003-06-06
CA2409012A1 (fr) 2002-11-15
WO2001090247A1 (fr) 2001-11-29
BR0110823A (pt) 2003-02-11
CN1430647A (zh) 2003-07-16
JP2003534432A (ja) 2003-11-18
AU2001258394A1 (en) 2001-12-03
EP1287075A1 (fr) 2003-03-05
MXPA02011371A (es) 2003-06-06
AU2001260282A1 (en) 2001-12-03
CN1244636C (zh) 2006-03-08
CN1429254A (zh) 2003-07-09
TWI281484B (en) 2007-05-21
AU2001254829A1 (en) 2001-12-03
US20030153677A1 (en) 2003-08-14
CA2409013A1 (fr) 2002-11-15
JP2003534433A (ja) 2003-11-18
AR033368A1 (es) 2003-12-17
CN1429250A (zh) 2003-07-09
KR20030001518A (ko) 2003-01-06
CA2409011A1 (fr) 2002-11-15
KR20030001517A (ko) 2003-01-06
KR20030001519A (ko) 2003-01-06
JP2003534429A (ja) 2003-11-18
US20030181591A1 (en) 2003-09-25
MXPA02011369A (es) 2003-06-06
WO2001090246A1 (fr) 2001-11-29

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