EP1287067A1 - Compositions polymeres a resilience modifiee - Google Patents

Compositions polymeres a resilience modifiee

Info

Publication number
EP1287067A1
EP1287067A1 EP01927943A EP01927943A EP1287067A1 EP 1287067 A1 EP1287067 A1 EP 1287067A1 EP 01927943 A EP01927943 A EP 01927943A EP 01927943 A EP01927943 A EP 01927943A EP 1287067 A1 EP1287067 A1 EP 1287067A1
Authority
EP
European Patent Office
Prior art keywords
composition
composition according
component
contained
amount
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Withdrawn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
EP01927943A
Other languages
German (de)
English (en)
Inventor
Holger Warth
Gerwolf Quaas
Dieter Wittmann
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.)
Styrolution Jersey Ltd
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 EP1287067A1 publication Critical patent/EP1287067A1/fr
Withdrawn legal-status Critical Current

Links

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 invention relates to impact-modified polymer compositions, in particular impact-modified polyamide compositions, and moldings produced therefrom.
  • EP 0 202 214 A discloses polymer blends made from a polyamide, a styrene / acrylonitrile copolymer and a non-digestive agent.
  • a copolymer of a vinyl aromatic monomer and acrylonitrile, methacrylonitrile is used as an excitement agent.
  • nerve tolerance agents increased impact strength is to be achieved.
  • a disadvantage of the polymer blends described in this publication is that they are too stiff and too high for thin-wall applications
  • inorganic materials in certain polymer compositions, in particular in polycarbonate compositions, are also generally known.
  • the inorganic materials are used, for example, as a reinforcing agent to increase the rigidity and tensile strength, to increase the dimensional stability in the event of temperature fluctuations, to improve the surface properties or - in flame-retardant materials - also as a flame retardant synergist.
  • Both mineral and artificially obtained materials are used.
  • Polycarbonate blends which contain certain inorganic fillers to improve stiffness and linear thermal expansion resistance.
  • DE 39 38 421 A1 also describes molding compositions composed of polyamides and special graft polymers containing tert-alkyl esters. These polymers have a high surface gloss and good dimensional stability on. However, it would be desirable to further improve the impact strength required for thin-wall applications.
  • AI rubber-modified polymer compositions which are a terpolymer made of styrene, acrylonitrile and as a non-digestive agent
  • the invention is therefore based on the object of providing polyamide compositions with a reduced coefficient of expansion and increased tensile strength and, at the same time, good processing behavior.
  • the simultaneous use of (a) compatibilizer on the one hand and (b) very finely divided mineral particles with anisotropic particle geometry on the other hand achieves a particularly balanced property profile in impact-modified polyamide compositions can.
  • the polyamide compositions according to the invention have a considerably reduced coefficient of expansion and an increased tensile and tear strength with an outstanding melt volume rate.
  • the moldings produced from the compositions according to the invention have excellent surface properties with extremely low abrasion even in thin-wall applications.
  • special mineral particles are used as component E of the composition. As explained in detail below, these are characterized by an anisotropic particle geometry. According to the invention, particles with anisotropic particle geometry are understood to mean those particles whose so-called aspect ratio, i.e. the ratio of the larger and the smallest particle size is greater than 1, preferably greater than 2 and particularly preferably greater than about 5. Such particles are at least in the broadest sense platelet-shaped or fibrous.
  • Polyamides (component A) which are suitable according to the invention are known or can be prepared by processes known from the literature.
  • 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 azelamic acid and / or adipic acid and / or cyclohexanedicarboxylic acid, the diamine component wholly or partly of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4-trimethylhexamethylenediamine and / or 2,4,4-trimethylhexamethylenediamine and / or isophoronediamine and the composition of which is known in principle.
  • polyamides which are wholly or partly prepared 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-trimethyl hexamethylene diamine, m- and / or p-xylylenediamine, bis- (4-aminocyclohexyl ) - methane, bis (4-aminocyclohexyl) propane, 3,3'-dimethyl-4,4'-diamino-dicyclohexyl-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 oxalic
  • Copolymers which are obtained by polycondensation of several monomers are also suitable, furthermore copolymers which are prepared with the addition of amino carboxylic acids such as e-amino caproic acid, w-aminoundecanoic acid or w-aminolauric acid or their lactams.
  • amino carboxylic acids such as e-amino caproic acid, w-aminoundecanoic acid or w-aminolauric acid or their lactams.
  • Particularly suitable amorphous polyamides are the polyamides prepared from isophthalic acid, hexamethylenediamine and other diamines such as 4,4-diaminodicyclohexylmethane, isophoronediamine, 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% by weight solution in m-cresol at 25 ° C.) from 2.0 to 5.0, particularly preferably from 2.5 to 4.0.
  • the polyamides can be contained in component A alone or in any hybrid with one another.
  • Component A can be used in the polymer composition according to the invention preferably in an amount of 10 to 98% by weight, in particular 15 to 70% by weight, and particularly preferably 20 to 60 wt .-%, based on the composition.
  • Component B comprises one or more rubber-modified graft polymers.
  • the rubber-modified graft polymer B comprises a statistical (co) polymer from monomers according to B1 and B.1.2, and a rubber B.2 grafted with the statistical (co) polymer from B1 and B.1.2, the production of B in a known manner after a mass or solution or
  • Examples of monomers B1 are styrene, ⁇ -methylstyrene, halogen- or alkyl-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (meth) acrylic acid -CC 8 -alkyl esters such as methyl methacrylate, n-butyl acrylate and tert-butyl acrylate.
  • Examples of monomers B.1.2 are unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) - acrylic acid -CC 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as Maleic anhydride and N-phenyl-maleimide or hybrids thereof.
  • unsaturated nitriles such as acrylonitrile, methacrylonitrile, (meth) - acrylic acid -CC 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as Maleic anhydride and N-phenyl-maleimide or hybrids thereof.
  • Preferred monomers B.l.l are styrene, ⁇ -methylstyrene and / or methyl methacrylate
  • preferred monomers B.1.2 are acrylonitrile, maleic anhydride and / or methyl methacrylate.
  • Particularly preferred monomers are B.l.l styrene and B.1.2 acrylonitrile.
  • Rubbers B.2 suitable for the rubber-modified graft polymers B are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on Ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • Preferred rubbers B.2 are diene rubbers (for example based on butadiene, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example in accordance with B1 and B.1.2), with the proviso that the Glass transition temperature of component B.2 is below 10 ° C, preferably below -10 ° C. Pure polybutadiene rubber is particularly preferred. Further copolymerizable monomers can contain up to 50% by weight, preferably up to 30, in particular up to
  • 20% by weight (based on the rubber base B.2) may be contained in the rubber base.
  • component B can additionally contain small amounts, usually less than 5% by weight, preferably less than 2% by weight, based on B. 2, contain crosslinking ethylenically unsaturated monomers.
  • crosslinking monomers are alkylene diol (mefh) acrylates, polyester di (meth) acrylates, divinylbenzene, trivinylbenzene, tri-allyl cyanurate, allyl (meth) acrylate, diallyl maleate and diallyl furmarate.
  • the rubber-modified graft polymer B is obtained by graft polymerization from 50 to 99, preferably 65 to 98, particularly preferably 75 to 97 parts by weight of a mixture of 50 to 99, preferably 60 to 95 parts by weight of monomers according to B1 and 1 to 50 preferably 5 to 40 parts by weight of monomers according to B.1.2 in the presence of 1 to 50, preferably 2 to 35, particularly preferably 2 to 15, in particular 2 to 13 parts by weight of the rubber component B.2, the graft polymerization after a Bulk or solution or bulk suspension polymerization process is carried out.
  • the statistical copolymer of B.l.l and B.1.2 is usually present in the polymer B in part on the rubber B.2 or grafted on, this graft copolymer forming discrete particles in the polymer B.
  • graft polymer B is used in the
  • the amounts of the (co) polymer inevitably formed in the graft polymerization depend, inter alia, on the monomer composition and polymerization method. Since, depending on the type and amount of the separately added (co) polymer D, this cannot be distinguished from the (co) polymer formed in the polymerization of the graft polymer, the sum of the amounts of components B and D corresponds to the sum of graft and (co) polymers.
  • the average particle diameter of the resulting grafted rubber particles is in the range from 0.5 to 5 ⁇ m, preferably from 0.8 to 2.5 ⁇ m.
  • the graft copolymers can be present in component B alone or in any mixture with one another.
  • Component B in the polymer composition according to the invention is preferably in an amount from 0.5 to 80% by weight, particularly preferably from 1 to 60% by weight and very particularly preferably from 2 to 40% by weight, in particular 8 to 40
  • thermoplastic polymers with polar groups are preferably used as compatibilizers.
  • C.2 at least one monomer selected from the group C 2 to C 1 alkyl methacrylates, C 2 to C 1 alkyl acrylates, methacrylonitriles and acrylonitriles and
  • C.3 contain ⁇ , ⁇ -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.
  • Terpolymers of the monomers mentioned are preferably used as component C.I, C.2 and C.3. Accordingly, terpolymers of styrene preferably
  • Acrylonitrile and maleic anhydride are used. These terpolymers contribute in particular to improving the mechanical properties, such as tensile strength and elongation at break.
  • the amount of maleic anhydride in the terpolymer can vary within wide limits. The amount is preferably 0.2 to 5 mol%. Amounts between 0.5 and 1.5 mol% are particularly preferred. Particularly good mechanical properties with regard to tensile strength and elongation at break are achieved in this area.
  • the terpolymer can be produced in a manner known per se.
  • a suitable method is to dissolve monomer components of the terpolymer, 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 for several hours at elevated temperatures. The solvent and the unreacted monomers are then removed in a manner known per se.
  • the ratio between component C.I (vinyl aromatic monomer) and component C.2, e.g. the acrylonitrile monomer in the terpolymer 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.
  • compatibilizers C which can be used according to the invention are described 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 785 234.
  • the compatibilizers can be contained in component C alone or in any mixture with one another.
  • Another substance which is particularly preferred as a compatibilizer is a terpolymer of styrene and acrylonitrile in a weight ratio of 2.1: 1 containing 1 mol% of maleic anhydride.
  • the amount of component C in the polymer compositions according to the invention is preferably between 0.5 and 50% by weight, in particular between 1 and 30% by weight and particularly preferably between 2 and 10% by weight, based on the composition. Quantities between 5 and 7% by weight are most preferred.
  • Component D comprises one or more thermoplastic vinyl (co) polymers.
  • Suitable vinyl (co) polymers for component D are polymers of at least one monomer from the group of 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-C 8 ) alkyl esters (how
  • Nitriles such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid
  • (-C-Cs) alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate
  • imides of unsaturated carboxylic acids e.g. N-phenylmalein imide
  • 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 D are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights Mw (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • the vinyl (co) polymers can be contained in component D alone or in any mixture with one another.
  • Component D in the polymer composition is preferably in an amount of 0 to 80% by weight, in particular 0 to 70% by weight and particularly preferably 0 to 60% by weight, in particular 5 to 40% by weight. % based on the composition.
  • Very finely divided mineral particles suitable according to the invention are those with anisotropic particle geometry.
  • mineral particles with anisotropic particle geometry are understood to mean those particles whose so-called aspect ratio - ratio of the largest and smallest particle dimensions - is greater than 1, preferably greater than 2 and particularly preferably greater than about 5.
  • Such particles are at least in the broadest sense platelet-shaped or fibrous.
  • Such materials include, for example, certain talcs and certain (alumino) silicates with a layer or fiber geometry such as bentonite, wollastonite, mica (mica), kaolin, hydrotalcite, hectorite or montmorillonite.
  • Inorganic materials with a flaky or flake-like character are preferably used, such as talc, mica / clay layer minerals, montmorrilonite, the latter also in an organophilic form modified by ion exchange, kaolin and vermiculite.
  • Talc is particularly preferred.
  • Talc is understood to mean a naturally occurring or synthetically produced talc.
  • Pure talc has the chemical composition 3MgO'4SiO 'H 2 O and therefore an MgO content of 31.9% by weight, an SiO content of 63.4% by weight and a content of chemically bound water of 4%. 8% by weight. It is a silicate with a layer structure.
  • Talktypes of high purity are preferred. These contain, for example, an MgO content of 28 to 35% by weight, preferably 30 to 33% by weight, particularly preferably 30.5 to 32% by weight and an SiO 2 content of 55 to 65% by weight , preferably 58 to 64% by weight, particularly preferably 60 to 62.5% by weight.
  • Preferred talc types are further characterized by an Al 2 O 3 content of ⁇ 5% by weight, particularly preferably ⁇ 1% by weight, in particular ⁇ 0.7% by weight.
  • talc in the form of finely ground types with an average largest particle size d o 5 microns of ⁇ 10, preferably ⁇ 5 micrometers, more preferably ⁇ 2.5 microns, very preferably ⁇ 1.5 microns.
  • very finely divided particles in the context of the invention means particles with a particle size of 0.01 to 200 nm, preferably ⁇ 50 nm and in particular ⁇ 20 nm.
  • the materials are preferably in the form of nanoscale particles.
  • Particle size and particle diameter in the sense of this invention means the average particle diameter d J0 , determined by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z. and Z. Polymers 250 (1972), pp. 782-796.
  • the mineral particles can be surface-modified with organic molecules, for example silanized, in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
  • the inorganic materials described in US Pat. Nos. 5,714,537 and 5,091,461 are also particularly suitable mineral particles with anisotropic particle geometry that are particularly suitable for use in the composition according to the invention.
  • talc and clay filler materials have been found to be particularly suitable.
  • elongated or plate-shaped materials with the specified small particles are particularly suitable, compared to fibril-shaped or spherical fillers. Those are highly preferred
  • D / T ratio it has been found desirable to have a value up to and including 30, preferably up to and including 24, more preferably up to and including 18, even more preferably up to and including 13 and most preferably up to and including 10.
  • Mineral particles to be used with preference are the known minerals talc and clay types.
  • the non-calcined types of talc and clays which have a very low content of free metal oxide are particularly preferred.
  • Types of talc and clay are well-known fillers for various polymeric resins. These materials and their suitability as fillers for polymeric resins are generally described in US Pat. Nos. 5,091,461, 3,442,703 and EP 391,413.
  • the most suitable types of the mineral talc are hydrated magnesium silicates, as generally represented by the theoretical formula:
  • compositions of the talc can vary somewhat with the location where they are mined. For example, talcum varieties from Montana largely correspond to this theoretical composition. Suitable grades of the mineral talc of this type are commercially available as Mikrotalk MP 25-38 and Mikrotalk
  • the most suitable types of clay are water-containing compounds of the aluminosilicate type, which are generally represented by the formula:
  • Suitable clay materials are commercially available as Tex 10R clay from Anglo American Clay Co. These mineral particles preferably have a number average particle size, measured by Coulter Counter, of less than or equal to 10 micrometers ( ⁇ m), more preferably less than or equal to 2 ⁇ m, even more preferably less than or equal to 1.5 ⁇ m and most preferably less than or equal to 1.0 ⁇ m. Depending on the type of grinding or production, such fillers can have number average particle sizes of at least 0.05 ⁇ m, preferably at least 0.1 ⁇ m and more preferably at least 0.5 ⁇ m. The smaller particle sizes, if available, can generally be used to advantage, but it has been found difficult to obtain fillers of this type commercially with an average particle size less than 1.5 microns.
  • these mineral particles generally have a maximum particle size of less than or equal to 50 ⁇ m, preferably less than or equal to 30 ⁇ m, more preferably less than or equal to 25 ⁇ m, even more preferably less than or equal to 20 ⁇ m and most preferably less than or equal to 15 ⁇ m.
  • Another way of specifying the desired uniform small particle size and the particle size distribution of the mineral particles preferably used in the practice of the present invention is to state that at least 98% by weight, preferably at least 99% by weight, of the Particles thereof in the finished mixture have an equivalent spherical volume diameter of less than 44 ⁇ m, preferably less than 20 ⁇ m.
  • the weight percentage of the filler particles with such diameters can likewise be measured by particle size analysis using a Coulter Counter.
  • the mineral particles can be present as powders, pastes, brine dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions.
  • thermoplastic molding compositions can be incorporated into the thermoplastic molding compositions by conventional methods, for example by direct kneading or extrusion of molding compounds and the finely divided inorganic powders.
  • Preferred methods are the production of a masterbatch, e.g. B. in flame retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-precipitation of a thermoplastic component and the very finely divided inorganic powders, for example by co-precipitation of an aqueous
  • Emulsion and the finely divided inorganic powders optionally in the form of dispersions, suspensions, pastes or sols of the finely divided inorganic materials.
  • the mineral particles of component E can be present in the composition according to the invention in an amount of preferably 0.1 to 50% by weight, particularly preferably 0.2 to 20% by weight and most preferably 0.5 to 15% % By weight, based on the mass of the composition, may be present.
  • the polymer compositions 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 reinforcing materials, and also dyes and pigments.
  • the compositions according to the invention can generally contain 0.01 to 20% by weight, based on the total composition, of flame retardants.
  • flame retardants examples include 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-Al-hydroxide, inorganic compounds such as aluminum oxides, titanium dioxide, antimony oxides, barium metaborate, Hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, tin borate, ammonium borate and tin oxide as well as siloxane compounds.
  • 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-Al-
  • EP-A 363 608 phosphorus compounds as described in EP-A 363 608, EP-A 345 522 and / or EP-A 640 655 can be used as flame retardant compounds.
  • filling and reinforcing materials that can be used are those that differ from component E).
  • glass fibers optionally cut or ground, glass beads, glass balls, kaolins, talk, mica, silicates, quartz, talc, titanium dioxide, wollastonite, mica, carbon fibers or mixtures thereof are suitable. 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 sum of the percentages by weight of all the constituents contained in the compositions is 100.
  • compositions according to the invention are prepared by mixing the respective constituents in a known manner and at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and double wave screws melt-compounded and melt-extruded, the mold release agent being used in the form of a coagulated mixture.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • the polymer compositions according to the invention can be used to produce moldings of any kind.
  • moldings can be produced by injection molding.
  • molded articles are: housing parts of all kinds, for example for household appliances such as electric shavers, flat screens, monitors, printers, copiers or cover plates for the construction sector and parts for motor vehicles and rail vehicles. They can also be used in the field of electrical engineering because they have very good electrical properties.
  • polymer compositions according to the invention can be used, for example, to produce the following moldings or moldings:
  • Another form of processing is the production of shaped bodies by deep drawing from previously produced sheets or foils.
  • Another object of the present invention is therefore the use of the compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the compositions according to the invention.
  • Polyamide (Durethan ® B30 from Bayer AG, Germany).
  • Graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60 parts by weight of particulate crosslinked polybutadierikautscb.uk (average particle diameter d 50 0.28 ⁇ m), produced by emulsion polymerization.
  • Styrene / acrylonitrile copolymer with a styrene-acrylic-NiMl weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl g (measurement in dimethylformamide at 20 ° C).
  • Aminosilane-coated aluminum silicate with a particle size d 5 o 1.4 ⁇ m (Burgess ® 2211 from Omya GmbH, Cologne, Germany).
  • compositions are mixed on a 3-1 internal kneader.
  • the moldings are made on an Arburg injection molding machine
  • the heat resistance according to Vicat B is determined in accordance with DIN 53 460 (ISO 306) on rods measuring 80 x 10 x 4 mm 3 .
  • the melt volume rate (MVR) is determined according to ISO 1133 at 240 ° C using a stamp load of 5 kg.
  • the tensile strength and the elongation at break are determined in accordance with DIN 53457 / ISO 527.
  • the longitudinal expansion coefficient (pm x K - " u) was determined in accordance with ASTM E 831.

Landscapes

  • 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 une composition polymère à résilience modifiée qui contient : (A) au moins un polyamide ; (B) au moins un copolymère greffé, la base de greffe étant à base d'un caoutchouc diénique ; (C) au moins un médiateur de compatibilité ; (D) au moins un copolymère vinylique et (E) des particules minérales à très fines particules à géométrie anisotrope. L'invention concerne en outre des corps moulés produits à partir de cette composition polymère.
EP01927943A 2000-05-19 2001-05-07 Compositions polymeres a resilience modifiee Withdrawn EP1287067A1 (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
DE2001109225 DE10109225A1 (de) 2001-02-26 2001-02-26 Schlagzähmodifizierte Polymer-Zusammensetzungen
DE10109225 2001-02-26
PCT/EP2001/005137 WO2001090241A1 (fr) 2000-05-19 2001-05-07 Compositions polymeres a resilience modifiee

Publications (1)

Publication Number Publication Date
EP1287067A1 true EP1287067A1 (fr) 2003-03-05

Family

ID=27213870

Family Applications (3)

Application Number Title Priority Date Filing Date
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

Family Applications Before (2)

Application Number Title Priority Date Filing Date
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

Country Status (12)

Country Link
US (3) US20030153677A1 (fr)
EP (3) EP1287074A1 (fr)
JP (3) JP2003534432A (fr)
KR (3) KR20030001517A (fr)
CN (3) CN1430647A (fr)
AR (3) AR033370A1 (fr)
AU (3) AU2001258394A1 (fr)
BR (3) BR0110853A (fr)
CA (3) CA2409011A1 (fr)
MX (3) MXPA02011394A (fr)
TW (1) TWI281484B (fr)
WO (3) WO2001090246A1 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6925513B1 (en) * 1999-05-04 2005-08-02 Apple Computer, Inc. USB device notification
EP1430100A1 (fr) * 2001-09-21 2004-06-23 Bayer Aktiengesellschaft Compositions polymeres a resistance aux chocs modifiee
US7135520B2 (en) * 2002-07-01 2006-11-14 Lanxess Corporation Glass fiber filled thermoplastic compositions with good surface appearance
DE10231001A1 (de) * 2002-07-09 2004-02-12 Volkswagen Ag Aus Kunststoff bestehendes Werkzeug
DE10233170A1 (de) * 2002-07-22 2004-02-12 Bayer Ag Polymerblends auf Basis Polyamid
JP2006507401A (ja) * 2002-11-25 2006-03-02 ランクセス ドイチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング 衝撃抵抗が改善されたポリマー組成物
DE10254877A1 (de) * 2002-11-25 2004-06-03 Bayer Ag Schlagzähmodifizierte Polymer-Zusammensetzungen
DE10310693A1 (de) * 2003-03-12 2004-09-23 Bayer Ag Schlagzähmodifizierte Polymer-Zusammensetzungen
EP1678257A1 (fr) * 2003-10-10 2006-07-12 Basf Aktiengesellschaft Compositions a mouler thermoplastiques
JP2008505199A (ja) * 2004-07-02 2008-02-21 エルジー・ケム・リミテッド ナノ複合体難燃性熱可塑性樹脂組成物
JP5221876B2 (ja) * 2004-11-04 2013-06-26 ライオン株式会社 導電性マスターバッチ及びそれを含む樹脂組成物
KR100616723B1 (ko) 2005-04-15 2006-08-28 주식회사 이폴리머 재생 폴리아미드 나노복합체 조성물
CN101787205B (zh) * 2009-10-28 2012-07-04 上海锦湖日丽塑料有限公司 一种改善皮纹制件表面闪光点的pa6/苯乙烯类树脂共混物
KR20140117459A (ko) 2012-01-11 2014-10-07 스티롤루션 유럽 게엠베하 스티렌 공중합체 및 폴리아미드를 기재로 한 향상된 인성을 갖는 내후성 열가소성 성형 배합물
WO2015134922A1 (fr) * 2014-03-07 2015-09-11 Invista North America S.A R.L. Résines de polyamide à additifs minéraux
EP3256516B1 (fr) * 2015-02-13 2019-12-25 EMS-Patent AG Composition de moulage à base de polyamide et objet moulé fabriqué à partir de cette composition de moulage
US10676577B2 (en) 2015-12-02 2020-06-09 Toyobo Co., Ltd. Glass-fiber-reinforced polyamide resin composition
CN105860512A (zh) * 2016-04-28 2016-08-17 苏州新区华士达工程塑胶有限公司 一种多功能防老化塑料
US11193019B2 (en) 2016-09-08 2021-12-07 Ineos Styrolution Group Gmbh Thermoplastic polymer powder for selective laser sintering (SLS)
CN109135277A (zh) * 2018-08-28 2019-01-04 安徽江淮汽车集团股份有限公司 一种pa66复合材料及其制备方法
CN109897331A (zh) * 2019-02-28 2019-06-18 金发科技股份有限公司 一种高极性阻燃苯乙烯类组合物、制备方法及其应用

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3120803A1 (de) * 1981-05-25 1982-12-16 Basf Ag, 6700 Ludwigshafen Schlagzaehne thermoplastische formmassen
US4713415A (en) * 1985-05-10 1987-12-15 Monsanto Company Rubber modified nylon composition
US5227428A (en) * 1985-05-10 1993-07-13 Monsanto Company Rubber modified nylon composition
EP0272241A3 (fr) * 1986-12-19 1989-10-18 Monsanto Company Mélange polymère à couleur stable
NL8603246A (nl) * 1986-12-20 1988-07-18 Stamicarbon Thermoplastische polymeermengsels.
US4824905A (en) * 1987-02-13 1989-04-25 Sumitomo Naugatuck Co., Ltd. Thermoplastic resin composition comprising polyamide, aromatic vinyl/unsaturated nitrile/rubbery polymer graft copolymer and aromatic vinyl/unsaturated nitrile/α-unsaturated carboxylic acid copolymer
DE3801537A1 (de) * 1988-01-20 1989-07-27 Bayer Ag Mit silikon-pfropfkautschuken modifizierte, schlagzaehe polyamidformmassen
JP2715499B2 (ja) * 1988-12-15 1998-02-18 住友化学工業株式会社 熱可塑性樹脂組成物
IT1237127B (it) * 1989-11-09 1993-05-18 Montedipe Srl Composizioni termoplastiche a base di un copolimero vinil aromatico e di una resina poliammidica.
JPH0481460A (ja) * 1990-07-24 1992-03-16 Mitsubishi Rayon Co Ltd 耐衝撃性、耐熱安定性に優れた樹脂組成物
DE4114589A1 (de) * 1991-05-04 1992-11-05 Bayer Ag Polycarbonat/polyamid-formmassen
JPH08143768A (ja) * 1994-11-16 1996-06-04 Kanegafuchi Chem Ind Co Ltd 耐熱性熱可塑性樹脂組成物
BE1009904A3 (nl) * 1995-12-29 1997-10-07 Dsm Nv Rubber gemodificeerde polyamide polymeersamenstelling.
BE1009903A3 (nl) * 1995-12-29 1997-10-07 Dsm Nv Rubber gemodificeerde polymeersamenstelling.
JPH09217006A (ja) * 1996-02-10 1997-08-19 Kanegafuchi Chem Ind Co Ltd 耐熱性熱可塑性樹脂組成物
WO1998036022A1 (fr) * 1997-02-17 1998-08-20 Basf Aktiengesellschaft Matieres de moulage thermoplastiques ignifugees
JP4124854B2 (ja) * 1998-02-25 2008-07-23 本田技研工業株式会社 車輛用外装プラスチック部品
WO1999045069A1 (fr) * 1998-03-05 1999-09-10 Basf Aktiengesellschaft Matieres moulables en polyamide-polyphenylenether comportant des charges minerales
JP4250220B2 (ja) * 1998-03-31 2009-04-08 日本エイアンドエル株式会社 熱可塑性樹脂組成物および塗装成形品
JP4433512B2 (ja) * 1998-04-28 2010-03-17 東レ株式会社 ポリアミド樹脂組成物およびその製造方法
JP4433515B2 (ja) * 1998-06-11 2010-03-17 東レ株式会社 自動車電装部品ハウジング用ポリアミド樹脂組成物
CA2320888A1 (fr) * 1998-12-17 2000-06-22 Montell Technology Company B.V. Melange de copolymere greffe de polyolefine et de polyamide
JP3715813B2 (ja) * 1999-01-22 2005-11-16 日本エイアンドエル株式会社 車両用外装部品
EP1200523A1 (fr) * 1999-08-02 2002-05-02 E.I. Du Pont De Nemours And Company Compositions de polyamide destinees au moulage

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0190241A1 *

Also Published As

Publication number Publication date
AU2001258394A1 (en) 2001-12-03
JP2003534432A (ja) 2003-11-18
CA2409011A1 (fr) 2002-11-15
TWI281484B (en) 2007-05-21
KR20030001519A (ko) 2003-01-06
EP1287075A1 (fr) 2003-03-05
US20030153677A1 (en) 2003-08-14
US20030181591A1 (en) 2003-09-25
CA2409013A1 (fr) 2002-11-15
CA2409012A1 (fr) 2002-11-15
BR0110823A (pt) 2003-02-11
CN1244636C (zh) 2006-03-08
JP2003534429A (ja) 2003-11-18
CN1429250A (zh) 2003-07-09
MXPA02011371A (es) 2003-06-06
EP1287074A1 (fr) 2003-03-05
KR20030001517A (ko) 2003-01-06
AU2001254829A1 (en) 2001-12-03
BR0110873A (pt) 2003-02-11
CN1429254A (zh) 2003-07-09
JP2003534433A (ja) 2003-11-18
WO2001090247A1 (fr) 2001-11-29
AR033369A1 (es) 2003-12-17
CN1430647A (zh) 2003-07-16
AR033370A1 (es) 2003-12-17
WO2001090241A1 (fr) 2001-11-29
AR033368A1 (es) 2003-12-17
KR20030001518A (ko) 2003-01-06
BR0110853A (pt) 2003-02-11
WO2001090246A1 (fr) 2001-11-29
MXPA02011394A (es) 2003-06-06
AU2001260282A1 (en) 2001-12-03
MXPA02011369A (es) 2003-06-06
US20030181582A1 (en) 2003-09-25

Similar Documents

Publication Publication Date Title
WO2001090241A1 (fr) Compositions polymeres a resilience modifiee
EP1567591B1 (fr) Compositions a base de polymeres presentant une resilience modifiee
EP1525263A1 (fr) Melanges polymeres a base de polyamide
DE102004004230A1 (de) Thermoplastische Formmassen auf Basis von Styrolcopolymeren und Polyamiden
EP1430100A1 (fr) Compositions polymeres a resistance aux chocs modifiee
DE10024935A1 (de) Witterungsstabile Polymerblends
DE102005036981A1 (de) Thermoplastische Formmassen mit reduziertem Durchgangswiderstand und erhöhter Stabilität
EP1030888B1 (fr) Matieres moulables thermoplastiques indeformable
DE10254877A1 (de) Schlagzähmodifizierte Polymer-Zusammensetzungen
EP0248255B1 (fr) Polymère greffé thermoplastique
DE10109225A1 (de) Schlagzähmodifizierte Polymer-Zusammensetzungen
US20030073773A1 (en) Impact-modified polymer compositions
DE10149152A1 (de) Schlagzähmodifizierte Polymer-Zusammensetzungen
DE10310693A1 (de) Schlagzähmodifizierte Polymer-Zusammensetzungen
WO2006061154A1 (fr) Matieres de moulage a base de copolymeres de styrene, contenant une charge
DE10024933A1 (de) Polymerblends enthaltend Polyamid und über Masse-Polymerisationsverfahren hergestellte kautschukmodifizierte Polymerisate
DE10257077A1 (de) Schlagzähmodifizierte Polymer-Zusammensetzungen
EP1129136A1 (fr) Matieres moulables thermoplastiques antistatiques a proprietes ameliorees
WO2000064978A1 (fr) Matieres moulables thermoplastiques a base de polycetones

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20021219

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LANXESS DEUTSCHLAND GMBH

17Q First examination report despatched

Effective date: 20071008

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: INEOS ABS (JERSEY) LIMITED

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20080419