EP1287075A1 - Polymer blends containing polyamide and rubber modified polymers produced by a mass polymerisation method - Google Patents
Polymer blends containing polyamide and rubber modified polymers produced by a mass polymerisation methodInfo
- Publication number
- EP1287075A1 EP1287075A1 EP01933938A EP01933938A EP1287075A1 EP 1287075 A1 EP1287075 A1 EP 1287075A1 EP 01933938 A EP01933938 A EP 01933938A EP 01933938 A EP01933938 A EP 01933938A EP 1287075 A1 EP1287075 A1 EP 1287075A1
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- European Patent Office
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- polymer blends
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- polymer
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/08—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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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 compatibilizers-containing polymer blends based on polyamide and rubber-modified polymers produced by mass polymerization processes, which have very good mechanical properties such as tensile strength and elongation at break.
- EP-A-202 214 describes polyamide / ABS blends which additionally contain compatibilizers which have functional groups which can react with the amine or acid end groups of the polyamides.
- thermoplastic molding compositions made of polyamides using graft polymers which according to a certain
- Procedure of the redox polymerization are prepared and contain tertiary butyl acrylates in the shell.
- the object of the present invention is to provide polymer blends with excellent mechanical properties such as tensile strength and elongation at break.
- polymer blends based on polyamide and bulk ABS or polyamide and impact-resistant polystyrene, which contain compatibilizers, have the desired properties.
- the invention therefore relates to polymer blends containing
- the invention preferably relates to polymer blends
- component A 10 to 98, preferably 15 to 70, particularly preferably 20 to 60 parts by weight of component A,
- component A 0.5 to 50, preferably 1 to 30, particularly preferably 2 to 10 parts by weight of component C.
- Component A 0.5 to 50, preferably 1 to 30, particularly preferably 2 to 10 parts by weight of component C.
- Suitable polyamides are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and / or amorphous polyamides. Polyamide-6, polyamide-6,6, hybrids and corresponding copolymers of these components are suitable as partially crystalline polyamides.
- 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-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 are to be mentioned, which consist entirely or partially of lactams with 7 to
- 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 aminocyclohexyl) 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 oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and / or 2,4,4-trimethyladipic acid, isophthalic acid and terephthalic acid.
- 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 made from isophthalic acid, hexamethylene diamine and other diamines such as 4,4-diaminodicyclohexylmethane, 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 diammdicyclohexalmethanes 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 is 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-modified graft polymers.
- the rubber-modified graft polymer B comprises a statistical (co) polymer made from monomers according to B1 and B.1.2, as well as a rubber B.2 grafted with the statistical (co) polymer made from B1 and B.1.2, the production of B according to known a bulk or solution or bulk suspension polymerization process, such as in U.S. Patent Nos. 3,243,481, 3,509,237, 3,660,535, 4,221,833 and 4,239,863.
- Examples of monomers B1 are styrene, .alpha.-methylstyrene, halogen- or alkyl nucleus-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (methacrylic acid -C.-alkyl esters such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate.
- Examples of monomers B. .1.2 are unsaturated nitriles such as acrylonitrile, methacrylonitrile,
- (Meth) acrylic acid-CrC 8 -alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures 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, if appropriate, 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 according to 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.
- component B can additionally contain small amounts, usually less than 5% by weight, preferably less than 2
- crosslinking ethylenically unsaturated monomers examples include alkylenediol di (meth) acrylates, polyester di (meth) acrylates, divinylbenzene, tri vinylbenzene, triallyl 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 from B.l.l and B.1.2 is usually in
- graft polymer B) means the product formed from grafted rubber during the graft polymerization and the (co) polymer formed during the graft polymerization.
- the quantities of the (co) polymerizate that necessarily arise during the graft polymerization depend, among other things, on depends on the monomer composition and polymerization method. Since, depending on the type and amount of the (co) polymer D) added separately, it cannot be distinguished from the (co) polymer formed in the polymerization of the graft polymer, the sum of the quantities of component B) and D) corresponds to the sum of the two Graft and (co) polymers.
- the average particle diameter of the resulting grafted rubber particles (determined by counting on electron micrographs) is in the
- Range from 0.5 to 5 ⁇ m, preferably from 0.8 to 2.5 ⁇ m.
- Impact-resistant polystyrene in the sense of the present invention is rubber-modified polystyrene or rubber-containing polystyrene, as described in EP-A 878 506 (incorporated by reference).
- Preferred impact-resistant polystyrene is a graft polymer that generally by polymerizing at least one aromatic vinyl monomer (styrene, ⁇ -alkylstyrene, for example ⁇ -methylstyrene), alkystyrene (for example o-, m- or p-methylstyrene), preferably styrene, in the presence of a Graft base is available in a known manner (bulk, bulk suspension, solution or emulsion polymerization).
- Diene rubbers preferably polybutadiene, polyisoprene, styrene-butadiene copolymers, particularly preferably polybutadiene
- ethylene-vinyl acetate copolymers acrylate rubbers
- EPDM's ethylene-propylene rubbers
- the rubber content in the impact-resistant polystyrene is generally 2 to 30, preferably 5 to 25, in particular 5 to 20% by weight. Copolymers are inevitably obtained in the graft polymerization.
- the definition of impact-resistant polystyrene therefore also encompasses the graft polymer and copolymers formed during the graft polymerization.
- thermoplastic polymers with polar groups are preferably used as compatibilizers.
- C.2 at least one monomer selected from the group C2 to -C 2 alkyl methacrylates, C 2 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.
- 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, acrylonitrile and maleic anhydride are preferably 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 0.2-5 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).
- MEK Methyl ethyl ketone
- 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.
- Component C.2 for example the acrylonitrile monomer in the terpolymer, is preferably wise 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 D.
- Suitable as vinyl (co) polymers D are polymers of at least one
- (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 methacrylate), 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 uns
- 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.
- 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 reinforcing materials, and also dyes and pigments.
- 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 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
- phosphorus compounds such as those in the
- EP-A-363 608, EP-A-345 522 or EP-A-640 655 are used.
- the inorganic compounds which can be used include compounds of one or more metals of the 1st to 5th main group and the 1st to 8th subgroup of
- Periodic table preferably the 2nd to 5th main group and the 4th to 8th subgroup, particularly preferably the 3rd to 5th main group and the 4th to 8th subgroup with the elements oxygen, sulfur, boron, phosphorus, carbon, nitrogen , Hydrogen and / or silicon.
- Such compounds are oxides, hydroxides, water-containing oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.
- oxides 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 4 , BaSO 4 , vanadium oxides, zinc borate, silicates such as Al-silicates,
- Mg silicates one, two, three-dimensional silicates, mixtures and doped compounds can also be used.
- these 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 ⁇ m, preferably less than or equal to 150 nm, in particular 1 to 100 nm.
- Particle size and particle diameter always mean the average particle diameter d 50 , determined by Ulfrazentri hypothesis measurements according to W. Scholtan et al. Colloid-Z. and Z. Polymers 250 (1972), pp.782 to 796.
- the inorganic compounds can be in the form of powders, pastes, brine, dispersions or
- Suspensions are present. Precipitation can be used to obtain powders from dispersions, brines or suspensions.
- the powders can be incorporated into the thermoplastic materials by customary methods, for example by direct kneading or extrusion of the
- Components of the molding compound and the very finely divided inorganic powders are preferred methods, 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 very finely divided inorganic materials.
- filling and reinforcing materials come e.g. Glass fibers, optionally cut or ground, glass beads, glass balls, flake-like reinforcing material, such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, wollastonite, 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 moldings of any kind.
- moldings can be produced by injection molding.
- moldings that can be produced are: housing parts of all kinds, for example for household appliances, such as juicers, coffee machines, mixers, for office machines, such as computers, printers, monitors or cover plates for the construction sector and parts for the motor vehicle sector.
- the present invention also relates to the use of the polymer blends according to the invention for the production of moldings and to the moldings themselves.
- the polymer blends are particularly suitable for the production of molded parts which have particularly high demands with regard to elongation at break and tensile strength.
- a polyamide (DURETHAN B30 from Bayer AG, Leverkusen,
- Bl graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60
- Magnum 3504 bulk ABS polymer from DOW Chemical Company Midland, Michigan USA (2) Lustran LTD, from Bayer AG
- 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 Vicat B heat resistance is determined in accordance with
- HDT A was determined at 1.8 MPa.
- the melt volume rate was determined according to ISO 527
- 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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Abstract
The invention relates to polymer blends comprising A) polyamide; B) a graft polymer produced by means of a mass-, solution-, or mass-suspension-polymerisation method from, B1) 50-99 wt. % of one or several vinyl monomers, B2) 50-1 wt. % of one or several graft backbones with a glass transition temperature of <10 DEG C, or impact-resistant polystyrene; C) at least one compatibility mediator comprising at least one thermoplastic polymer with polar groups and, optionally; D) at least one vinyl (co)polymer.
Description
Polymerblends enthaltend Polyamid und Aber Masse-Polymerisationsverfahren hergestellte kautschukmodifizierte PolymerisatePolymer blends containing polyamide and rubber-modified polymers produced by bulk polymerization processes
Die vorliegende Erfindung betrifft Verträglichkeitsvermittler enthaltende Polymer- blends auf Basis Polyamid und über Masse-Polymerisationsverfahren hergestellte kautschukmodifϊzierte Polymerisate, die sehr gute mechanische Eigenschaften wie Zugfestigkeit und Reißdehnung aufweisen.The present invention relates to compatibilizers-containing polymer blends based on polyamide and rubber-modified polymers produced by mass polymerization processes, which have very good mechanical properties such as tensile strength and elongation at break.
In EP-A-202 214 sind Polyamid/ABS-Blends beschrieben, die zusätzlich Verträglichkeitsvermittler enthalten, die funktioneile Gruppen aufweisen, welche mit den Amin- oder Säureendgruppen der Polyamide reagieren können.EP-A-202 214 describes polyamide / ABS blends which additionally contain compatibilizers which have functional groups which can react with the amine or acid end groups of the polyamides.
In der DE-A-39 38 421 werden thermoplastische Formmassen aus Polyamiden unter Verwendung von Pfropfpolymerisaten beschrieben, die nach einer bestimmtenDE-A-39 38 421 describes thermoplastic molding compositions made of polyamides using graft polymers, which according to a certain
Verfahrensweise der Redoxpolymerisation hergestellt werden und in der Hülle tertiäre Butylacrylate enthalten.Procedure of the redox polymerization are prepared and contain tertiary butyl acrylates in the shell.
In der EP-A-785 234 sind schließlich Polymerzusammensetzungen beschrieben, die Pfropfpolymerisate von aromatischen Vinylmonomeren und Monomeren ausFinally, in EP-A-785 234 polymer compositions are described which graft polymers from aromatic vinyl monomers and monomers
Alkyl(meth)acrylaten oder Acrylnitril auf einem Kautschuk als erste Komponente, ein thermoplastisches Polymer mit polaren Gruppen als zweite Komponente sowie einen Verträglichkeitsvermittler als dritte Komponente enthalten.Contain alkyl (meth) acrylates or acrylonitrile on a rubber as the first component, a thermoplastic polymer with polar groups as the second component and a compatibilizer as the third component.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Polymerblends mit ausgezeichneten mechanischen Eigenschaften wie Zugfestigkeit und Reißdehnung.The object of the present invention is to provide polymer blends with excellent mechanical properties such as tensile strength and elongation at break.
Es wurde nun gefunden, dass Polymerblends auf Basis Polyamid und Masse-ABS bzw. Polyamid und schlagzähem Polystyrol, die Verträglichkeitsvermittler enthalten, die gewünschten Eigenschaften aufweisen.
Gegenstand der Erfindung sind daher Polymerblends enthaltendIt has now been found that polymer blends based on polyamide and bulk ABS or polyamide and impact-resistant polystyrene, which contain compatibilizers, have the desired properties. The invention therefore relates to polymer blends containing
A) Polyamid,A) polyamide,
B) mittels Masse-, Lösungs- oder Masse-Suspensions-Polymerisationsverfahrens hergestelltes Pfropfpolymerisat von,B) graft polymer prepared by bulk, solution or bulk suspension polymerization process,
B 1) 50-99 Gew.-% eines oder mehrerer Vinylmonomere auf,B 1) 50-99% by weight of one or more vinyl monomers,
B2) 50-1 Gew.-% einer oder mehrerer Pfropfgrundlagen mit einer Glasumwandlungstemperatur < 10°C,B2) 50-1% by weight of one or more graft bases with a glass transition temperature <10 ° C,
oder schlagzähem Polystyrol,or impact-resistant polystyrene,
C) mindestens einen Verträglichkeitsvermittler enthaltend mindestens ein thermoplastisches Polymer mit polaren Gruppen und gegebenenfallsC) at least one compatibilizer containing at least one thermoplastic polymer with polar groups and optionally
D) mindestens ein Vinyl(co)polymerisat.D) at least one vinyl (co) polymer.
Gegenstand der Erfindung sind vorzugsweise Polymerblends enthaltendThe invention preferably relates to polymer blends
10 bis 98, bevorzugt 15 bis 70, besonders bevorzugt 20 bis 60 Gew.-Teile der Komponente A,10 to 98, preferably 15 to 70, particularly preferably 20 to 60 parts by weight of component A,
- 0,5 bis 80, bevorzugt 10 bis 70, besonders bevorzugt 20 bis 65 Gew.-Teile eines Gemischs bestehend aus den Komponenten B und gegebenenfalls D, bzw.0.5 to 80, preferably 10 to 70, particularly preferably 20 to 65 parts by weight of a mixture consisting of components B and optionally D, or
0,5 bis 50, bevorzugt 1 bis 30, besonders bevorzugt 2 bis 10 Gew.-Teile der Komponente C.
Komponente A0.5 to 50, preferably 1 to 30, particularly preferably 2 to 10 parts by weight of component C. Component A
Geeignete Polyamide sind bekannte Homopolyamide, Copolyamide und Mischungen dieser Polyamide. Es können dies teilkristalline und/oder amorphe Polyamide sein. Als teilkristalline Polyamide sind Polyamid-6, Polyamid-6,6, Mischlingen und entsprechende Copolymerisate aus diesen Komponenten geeignet. Weiterhin kommen teilkristalline Polyamide in Betracht, deren Säurekomponente ganz oder teilweise aus Terephthalsäure und/oder Isophthalsäure und/oder Korksäure und/oder Sebacinsäure und/oder Azelainsäure und/oder Adipinsäure und/oder Cyclohexandicarbonsäure, deren Diaminkomponente ganz oder teilweise aus m- und/oder p-Xylylen-diarnin und/oder Hexamethylendiamin und/oder 2,2,4-Trimethylhexamethylendiamin und/oder 2,4,4-Trimethylhexamethylendiamin und/oder Isophorondiamin besteht und deren Zusammensetzung prinzipiell bekannt ist.Suitable polyamides are known homopolyamides, copolyamides and mixtures of these polyamides. These can be partially crystalline and / or amorphous polyamides. Polyamide-6, polyamide-6,6, hybrids and corresponding copolymers of these components are suitable as partially crystalline polyamides. Also suitable are 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-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.
Außerdem sind Polyamide zu nennen, die ganz oder teilweise aus Lactamen mit 7 bisIn addition, polyamides are to be mentioned, which consist entirely or partially of lactams with 7 to
12 C- Atomen im Ring, gegebenenfalls unter Mitverwendung einer oder mehrerer der obengenannten Ausgangskomponenten, hergestellt werden.12 carbon atoms in the ring, optionally using one or more of the above-mentioned starting components.
Besonders bevorzugte teilkristalline Polyamide sind Polyamid-6 und Polyamid-6,6 und ihre Mischungen. Als amorphe Polyamide können bekannte Produkte eingesetzt werden. Sie werden erhalten durch Polykondensation von Diaminen wie Ethylen- diamin, Hexamethylendiamin, Decamethylendiamin, 2,2,4- und/oder 2,4,4-Tri- methylhexamethylendiamin, m- und/oder p-Xylylen-diamin, Bis-(4-aminocyclo- hexyl)-methan, Bis-(4-aminocyclohexyl)-propan, 3,3 '-Dimethyl-4,4'-diamino-di- cyclohexyl-methan, 3-Aminomethyl-3,5,5-trimethylcyclohexylamin, 2,5- und/oderParticularly 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 aminocyclohexyl) 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)-norbornan und/oder 1,4-Diaminomethylcyclohexan mit Dicarbonsäuren wie Oxalsäure, Adipinsäure, Azelainsäure, Decandicarbonsäure, Heptadecandicarbonsäure, 2,2,4- und/oder 2,4,4-Trimethyladipinsäure, Isophthalsäure und Terephthalsäure.
Auch Copolymere, die durch Polykondensation mehrerer Monomerer erhalten werden, sind geeignet, ferner Copolymere, die unter Zusatz von Aminocarbonsäuren wie ε-Aminocapronsäure, ω-Aminoundecansäure oder ω-Aminolaurinsäure oder ihren Lactamen, hergestellt werden.2,6-bis (aminomethyl) norbornane and / or 1,4-diaminomethylcyclohexane with dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and / or 2,4,4-trimethyladipic acid, isophthalic acid and terephthalic acid. 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 ε-aminocaproic acid, ω-aminoundecanoic acid or ω-aminolauric acid or their lactams.
Besonders geeignete amorphe Polyamide sind die Polyamide hergestellt aus Isophthalsäure, Hexamethylendiamin und weiteren Diaminen wie 4,4-Diaminodicy- clohexylmethan, Isophorondiamin, 2,2,4- und/oder 2,4,4-Trimethylhexamethylen- diamin, 2,5- und/oder 2,6-Bis-(aminomethyl)-norbornen; oder aus Isophthalsäure, 4,4'-Diamino-dicyclohexylmethan und -Caprolactam; oder aus Isophthalsäure, 3,3'-Particularly suitable amorphous polyamides are the polyamides made from isophthalic acid, hexamethylene diamine and other diamines such as 4,4-diaminodicyclohexylmethane, 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'-
Dimethyl-4,4'-diamino-dicyclohexylmethan und Laurinlactam; oder aus Terephthalsäure und dem Isomerengemisch aus 2,2,4- und/oder 2,4,4-Trimethylhexamethylen- diamin.Dimethyl-4,4'-diamino-dicyclohexylmethane and laurolactam; or from terephthalic acid and the isomer mixture of 2,2,4- and / or 2,4,4-trimethylhexamethylene diamine.
Anstelle des reinen 4,4'-Diaminodicyclohexylmethans können auch Gemische derInstead of the pure 4,4'-diaminodicyclohexylmethane, mixtures of
Stellungsisomeren Diammdicyclohexalmethane eingesetzt werden, die sich zusammensetzen ausPositional isomers diammdicyclohexalmethanes are used, which are composed of
70 bis 99 mol-% des 4,4'-Diamino-Isomeren 1 bis 30 mol-% des 2,4'-Diamino-Isomeren70 to 99 mol% of the 4,4'-diamino isomer 1 to 30 mol% of the 2,4'-diamino isomer
0 bis 2 mol-% des 2,2'-Diamino-Isomeren0 to 2 mol% of the 2,2'-diamino isomer
gegebenenfalls entsprechend höher kondensierten Diaminen, die durch Hydrierung von Diaminodiphenylmethan technischer Qualität erhalten werden. Die Isophthal- säure kann bis zu 30 % durch Terephthalsäure ersetzt sein.if appropriate, correspondingly more highly condensed diamines obtained by hydrogenating technical-grade diaminodiphenylmethane. Up to 30% of the isophthalic acid can be replaced by terephthalic acid.
Die Polyamide weisen vorzugsweise eine relative Viskosität (gemessen an einer 1 gew.-%igen Lösung in m-Kresol bei 25°C) von 2,0 bis 5,0, besonders bevorzugt von 2,5 bis 4,0 auf.
Komponente BThe 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
Die Komponente B umfasst ein oder mehrere kautschukmodifizierte Pfropfpolymerisate. Das kautschukmodifϊzierte Pfropfpolymerisat B umfasst ein statistisches (Co)polymerisat aus Monomeren gemäß B.l.l und B.1.2, sowie einem mit dem statistischen (Co)polymerisat aus B.l.l und B.1.2 gepfropften Kautschuk B.2, wobei die Herstellung von B in bekannter Weise nach einem Masse- oder Lösungs- oder Masse-Suspensions-Polymerisations verfahren erfolgt, wie z.B. in den US-A 3 243 481, US-A 3 509 237, US-A 3 660 535, US-A 4 221 833 und US-A 4 239 863 beschrieben.Component B comprises one or more rubber-modified graft polymers. The rubber-modified graft polymer B comprises a statistical (co) polymer made from monomers according to B1 and B.1.2, as well as a rubber B.2 grafted with the statistical (co) polymer made from B1 and B.1.2, the production of B according to known a bulk or solution or bulk suspension polymerization process, such as in U.S. Patent Nos. 3,243,481, 3,509,237, 3,660,535, 4,221,833 and 4,239,863.
Beispiele für Monomere B.l.l sind Styrol, α-Methylstyrol, halogen- oder alkylkern- substituierte Styrole wie p-Methylstyrol, p-Chlorstyrol, (Meti jacrylsäure- -Cs- alkylester wie Methylmethacrylat, n-Butylacrylat und t-Butylacrylat. Beispiele für Monomere B.1.2 sind ungesättigte Nitrile wie Acrylnitril, Methacrylnitril,Examples of monomers B1 are styrene, .alpha.-methylstyrene, halogen- or alkyl nucleus-substituted styrenes such as p-methylstyrene, p-chlorostyrene, (methacrylic acid -C.-alkyl esters such as methyl methacrylate, n-butyl acrylate and t-butyl acrylate. Examples of monomers B. .1.2 are unsaturated nitriles such as acrylonitrile, methacrylonitrile,
(Meth)Acrylsäure-CrC8-alkylester wie Methylmethacrylat, n-Butylacrylat, t-Butylacrylat, Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren wie Maleinsäureanhydrid und N-Phenyl-maleinimid oder Mischungen davon.(Meth) acrylic acid-CrC 8 -alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, derivatives (such as anhydrides and imides) of unsaturated carboxylic acids such as maleic anhydride and N-phenyl-maleimide or mixtures thereof.
Bevorzugte Monomere B.l.l sind Styrol, α-Methylstyrol und/oder Methylmethacrylat, bevorzugte Monomere B.1.2 sind Acrylnitril, Maleinsäureanhydrid und/oder Methylmethacrylat.Preferred monomers B.l.l are styrene, α-methylstyrene and / or methyl methacrylate, preferred monomers B.1.2 are acrylonitrile, maleic anhydride and / or methyl methacrylate.
Besonders bevorzugte Monomere sind B.l.l Styrol und B.1.2 Acrylnitril.Particularly preferred monomers are B.l.l styrene and B.1.2 acrylonitrile.
Für die kautschukmodifizierten Pfropfpolymerisate B geeignete Kautschuke B.2 sind beispielsweise Dienkautschuke, EP(D)M-Kautschuke, also solche auf Basis Ethylen/Propylen und gegebenenfalls Dien, Acrylat-, Polyurethan-, Silikon-, Chloropren- und Ethylen/Vinylacetat-Kautschuke.
Bevorzugte Kautschuke B.2 sind Dienkautschuke (z.B. auf Basis Butadien, Isopren etc.) oder Gemische von Dienkautschuken oder Copolymerisate von Dienkautschuken oder deren Gemischen mit weiteren copolymerisierbaren Monomeren (z.B. gemäß B.l.l und B.1.2), mit der Maßgabe, dass die Glasübergangstemperatur der Komponente B.2 unterhalb 10°C, vorzugsweise unterhalb -10°C liegt. Besonders bevorzugt wird reiner Polybutadienkautschuk.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, if appropriate, 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 according to 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.
Die Komponente B kann, falls erforderlich und wenn dadurch die Kautschukeigenschaften der Komponente B.2 nicht beeinträchtigt werden, zusätzlich noch geringe Mengen, üblicherweise weniger als 5 Gew.-%, vorzugsweise weniger als 2If necessary and if this does not impair the rubber properties of component B.2, component B can additionally contain small amounts, usually less than 5% by weight, preferably less than 2
Gew.-%, bezogen auf B.2, vernetzend wirkender ethylenisch ungesättigter Monomeren enthalten. Beispiele für solche vernetzend wirkenden Monomere sind Alkylendiol-di-(meth)-acrylate, Polyester-di-(meth)-acrylate, Divinylbenzol, Tri- vinylbenzol, Triallylcyanurat, Allyl-(meth)-acrylat, Diallylmaleat und Diallyl- furmarat.% By weight, based on B.2, of crosslinking ethylenically unsaturated monomers. Examples of such crosslinking monomers are alkylenediol di (meth) acrylates, polyester di (meth) acrylates, divinylbenzene, tri vinylbenzene, triallyl cyanurate, allyl (meth) acrylate, diallyl maleate and diallyl furmarate.
Das kautschukmodifizierte Pfropfpolymerisat B wird erhalten durch Pfropfpolymerisation von 50 bis 99, bevorzugt 65 bis 98, besonders bevorzugt 75 bis 97 Gew.- Teilen eines Gemischs aus 50 bis 99, bevorzugt 60 bis 95 Gew.-Teilen Monomeren gemäß B.l.l und 1 bis 50, bevorzugt 5 bis 40 Gew.-Teilen Monomeren gemäß B.1.2 in Gegenwart von 1 bis 50, vorzugsweise 2 bis 35, besonders bevorzugt 2 bis 15, insbesondere 2 bis 13 Gew.-Teilen der Kautschukkomponente B.2, wobei die Pfropfpolymerisation nach einem Masse- oder Lösungs- oder Masse-Suspensions-Poly- merisationsverfahren durchgeführt wird.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.
Wesentlich bei der Herstellung des kautschukmodifizierten Pfropfpolymerisats B ist, dass die Kautschukkomponente B.2 vor der Pfropφolymerisation im Gemisch der Monomeren B.l.l und B.1.2 in gelöster Form vorliegt. Die Kautschukkomponente B.2 darf also weder so stark vernetzt sein, dass eine Lösung in B.l.l und B.1.2 unmöglich wird, noch darf B.2 zu Beginn der Pfropfpolymerisation bereits in Form diskreter Teilchen vorliegen. Die für die Produkteigenschaften von B wichtige
Teilchenmorphologie und zunehmende Vernetzung von B.2 bildet sich erst im Verlauf der Pfropfpolymerisation aus (siehe hierzu beispielsweise Lπimann, Encyclo- pädie der technischen Chemie, Bd. 19, S.284 ff., 4. Auflage 1980).It is essential in the production of the rubber-modified graft polymer B that the rubber component B.2 is present in dissolved form before the graft polymerization in a mixture of the monomers B1 and B.1.2. The rubber component B.2 must therefore not be so strongly crosslinked that a solution in B1 and B.1.2 becomes impossible, and B.2 must not be present in the form of discrete particles at the start of the graft polymerization. The important for the product properties of B. Particle morphology and increasing crosslinking of B.2 only develop in the course of the graft polymerization (see, for example, Lπimann, Encyclopedia of Industrial Chemistry, Vol. 19, pp. 284 ff., 4th edition 1980).
Das statistische Copolymerisat aus B.l.l und B.1.2 liegt üblicherweise imThe statistical copolymer from B.l.l and B.1.2 is usually in
Polymerisat B zu einem Teil auf dem Kautschuk B.2 oder eingepfropft vor, wobei dieses Pfropfmischpolymerisat diskrete Teilchen im Polymerisat B ausbildet. Der Anteil des auf- oder eingepfropften Copolymerisats aus B.l.l und B.1.2 am gesamten Copolymerisat aus B.l.l und B.1.2 - also die Pfropfausbeute (=Gewichts- Verhältnis der tatsächlich gepfropften Pfropfmonomeren zu den insgesamt verwendeten Pfropfmonomeren x 100, angegeben in %) - sollte dabei 2 bis 40 %, vorzugsweise 3 bis 30 %, besonders bevorzugt 4 bis 20 % betragen.Part of polymer B on the rubber B.2 or grafted in front, this graft copolymer forming discrete particles in the polymer B. The proportion of the grafted-on or grafted-in copolymer from B1 and B.1.2 in the total copolymer from B1 and B.1.2 - i.e. the grafting yield (= weight ratio of the grafting monomers actually grafted to the total grafting monomers used x 100, stated in%) should be 2 to 40%, preferably 3 to 30%, particularly preferably 4 to 20%.
Im Sinne der vorliegenden Erfindung wird unter Pfropfpolymerisat B) das bei der Pfropφolymerisation entstandene Produkt aus gepfropftem Kautschuk und das bei der Pfropφolymerisation entstehende (Co)Polymerisat verstanden. Die Mengen des bei der Pfropφolymerisation zwangsläufig entstehenden (Co)Polyrnerisats hängen u.a. von der Monomerzusammensetzung und Polymerisationsmethode ab. Da sich je nach Art und Menge des separat zugesetzten (Co)Polymerisats D), dieses nicht von dem bei der Polymerisation des Pfropφolymeren entstehende (Co)Polymerisat unterscheiden lässt, entspricht die Summe der Mengen an Komponente B) und D) gleich der Summe aus Pfropf- und (Co)Polymeren.For the purposes of the present invention, graft polymer B) means the product formed from grafted rubber during the graft polymerization and the (co) polymer formed during the graft polymerization. The quantities of the (co) polymerizate that necessarily arise during the graft polymerization depend, among other things, on depends on the monomer composition and polymerization method. Since, depending on the type and amount of the (co) polymer D) added separately, it cannot be distinguished from the (co) polymer formed in the polymerization of the graft polymer, the sum of the quantities of component B) and D) corresponds to the sum of the two Graft and (co) polymers.
Der mittlere Teilchendurchmesser der resultierenden gepfropften Kautschukteilchen (ermittelt durch Auszählung an elektronenmikroskopischen Aufnahmen) liegt imThe average particle diameter of the resulting grafted rubber particles (determined by counting on electron micrographs) is in the
Bereich von 0,5 bis 5 μm, vorzugsweise von 0,8 bis 2,5 μm.Range from 0.5 to 5 μm, preferably from 0.8 to 2.5 μm.
Schlagzähes Polystyrol im Sinne der vorliegenden Erfindung ist Kautschuk modifiziertes Polystyrol bzw. Kautschuk enthaltendes Polystyrol, wie es in EP-A 878 506 beschrieben ist (incorporated by reference).
Bevorzugtes schlagzähes Polystyrol ist ein Pfropφolymer, dass im Allgemeinen durch Polymerisation wenigstens eines aromatischen Vinylmonomeren (Styrol, α- Alkylstyrole, z.B. α-Methylstyrol), Alkystyrole (z.B. o-, m- oder p-Methylstyrol), bevorzugt Styrol, in der Gegenwart einer Pfropfgrundlage in bekannter Weise (Masse-, Masse-Suspensions-, Lösungs- oder Emulsions-Polymerisation) erhältlich ist.Impact-resistant polystyrene in the sense of the present invention is rubber-modified polystyrene or rubber-containing polystyrene, as described in EP-A 878 506 (incorporated by reference). Preferred impact-resistant polystyrene is a graft polymer that generally by polymerizing at least one aromatic vinyl monomer (styrene, α-alkylstyrene, for example α-methylstyrene), alkystyrene (for example o-, m- or p-methylstyrene), preferably styrene, in the presence of a Graft base is available in a known manner (bulk, bulk suspension, solution or emulsion polymerization).
Als Pfropfgrundlage kommen Dien-Kautschuke (bevorzugt Polybutadien, Poly- isopren, Styrol Butadien-Copolymere, besonders bevorzugt Polybutadien), Ethylen- Vinylacetat-Copolymere, Acrylatkautschuke, Ethylen-Propylen-Kautschuke (EPDM's) allein oder in Mischung eingesetzt werden. Besonders bevorzugt sindDiene rubbers (preferably polybutadiene, polyisoprene, styrene-butadiene copolymers, particularly preferably polybutadiene), ethylene-vinyl acetate copolymers, acrylate rubbers, ethylene-propylene rubbers (EPDM's) are used alone or in a mixture as the graft base. Are particularly preferred
Polybutadien und Styrol/Butadien-Copolymere als Pfropfgrundlage. Der Kautschukgehalt im schlagzähen Polystyrol beträgt im Allgemeinen 2 bis 30, bevorzugt 5 bis 25, insbesondere 5 bis 20 Gew.-%. Bei der Pfropφolymerisation fallen zwangsläufig Copolymerisate an. Die Definition von schlagzähem Polystyrol umfasst daher auch das Pfropφolymerisat und bei der Pfropφolymerisation entstehendes Copofymer.Polybutadiene and styrene / butadiene copolymers as a graft base. The rubber content in the impact-resistant polystyrene is generally 2 to 30, preferably 5 to 25, in particular 5 to 20% by weight. Copolymers are inevitably obtained in the graft polymerization. The definition of impact-resistant polystyrene therefore also encompasses the graft polymer and copolymers formed during the graft polymerization.
Einzelheiten sind EP-A 878 506 zu entnehmen.Details can be found in EP-A 878 506.
Komponente CComponent C
Als Verträglichkeitsvermittler werden erfindungsgemäß vorzugsweise thermoplastische Polymeren mit polaren Gruppen eingesetzt.According to the invention, thermoplastic polymers with polar groups are preferably used as compatibilizers.
Erfindungsgemäß kommen demgemäss Polymere zum Einsatz, dieAccording to the invention, polymers are accordingly used that
C.1 ein vinylaromatisches Monomer,C.1 a vinyl aromatic monomer,
C.2 wenigstens ein Monomer ausgewählt aus der Gruppe C2 bis Cι2-Alkylmethacrylate, C2 bis C^-Alkylacrylate, Methacrylnitrile und Acrylnitrile und
C.3 α-, ß-ungesättigte Komponenten enthaltend Dicarbonsäureanhydride enthalten.C.2 at least one monomer selected from the group C2 to -C 2 alkyl methacrylates, C 2 to C ^ alkyl acrylates, methacrylonitriles and acrylonitriles and C.3 contain α-, ß-unsaturated components containing dicarboxylic anhydrides.
Als vinylaromatische Monomere C.l ist Styrol besonders bevorzugt.Styrene is particularly preferred as the vinyl aromatic monomer C.I.
Für die Komponente C.2 ist besonders bevorzugt Acrylnitril.Acrylonitrile is particularly preferred for component C.2.
Für α-, ß-ungesättigte Komponenten enthaltend Dicarbonsäureanhydride C.3 ist besonders bevorzugt Maleinsäureanhydrid.Maleic anhydride is particularly preferred for α-, β-unsaturated components containing dicarboxylic anhydrides C.3.
Vorzugsweise werden als Komponente C.l, C.2 und C.3 Terpolymere der genannten Monomeren eingesetzt. Demgemäss kommen vorzugsweise Terpolymere von Styrol, Acrylnitril und Maleinsäureanhydrid zum Einsatz. Diese Terpolymere tragen insbesondere zur Verbesserung der mechanischen Eigenschaften, wie Zugfestigkeit und Reißdehnung bei. Die Menge an Maleinsäureanhydrid in dem Terpolymer kann in weiten Grenzen schwanken. Vorzugsweise beträgt die Menge 0,2-5 mol-%. Besonders bevorzugt sind Mengen zwischen 0,5 und 1,5 mol-%. In diesem Bereich werden besonders gute mechanischen Eigenschaften bezüglich Zugfestigkeit und Reißdehnung erzielt.Terpolymers of the monomers mentioned are preferably used as component C.I, C.2 and C.3. Accordingly, terpolymers of styrene, acrylonitrile and maleic anhydride are preferably 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 0.2-5 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.
Das Terpolymer kann in an sich bekannter Weise hergestellt werden. Eine geeignete Methode ist das Lösen von Monomerkomponenten des Terpolymers, z.B. des Styrols, Maleinsäureanhydrids oder Acrylnitrils in einem geeigneten Lösemittel, z.B. Methylethylketon (MEK). Zu dieser Lösung werden ein oder gegebenenfalls mehrere chemische Initiatoren hinzugesetzt. Geeignete Initiatoren sind z.B. Peroxide. Sodann wird das Gemisch für mehrere Stunden bei erhöhter Temperaturen polymerisiert. Anschließend werden das Lösemittel und die nicht umgesetzten Monomere in an sich bekannter Weise entfernt.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). 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.
Das Verhältnis zwischen der Komponente C.1 (vinylaromatiscb.es Monomer) und derThe ratio between component C.1 (vinylaromatiscb.es monomer) and the
Komponente C.2, z.B. dem Acrylnitrilmonomer in dem Terpolymer liegt Vorzugs-
weise zwischen 80:20 und 50:50. Um die Mischbarkeit des Te olymers mit dem Pfropfcopolymer B zu verbessern wird vorzugsweise eine Menge an vinylaroma- tischen Monomer C.l ausgewählt, die der Menge des Vinylmonomeren B.l in dem Pfropfcopolymer B entspricht.Component C.2, for example the acrylonitrile monomer in the terpolymer, is preferably wise between 80:20 and 50:50. In order to improve the miscibility of the polymer with the graft copolymer B, 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.
Die Menge der Komponente C in den erfindungsgemäßen Polymerblends liegt zwischen 0,5 und 50 Gew.-%, vorzugsweise zwischen 1 und 30 Gew.-%, besonders bevorzugt zwischen 2 und 10 Gew.-%. Höchst bevorzugt sind Mengen zwischen 5 und 7 Gew.-%.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.
Solche Polymere sind beispielsweise in der EP-A-785 234 und der EP-A-202 214 beschrieben. Erfindungsgemäß bevorzugt sind insbesondere die in der EP-A-202 214 genannten Polymere.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.
Komponente DComponent D
Die Komponente D umfasst ein oder mehrere thermoplastische Vinyl(co)poly- merisate D.Component D comprises one or more thermoplastic vinyl (co) polymers D.
Geeignet sind als Vmyl(co)Polymerisate D Polymerisate von mindestens einemSuitable as vinyl (co) polymers D are polymers of at least one
Monomeren aus der Gruppe der Vinylaromaten, Vinylcyanide (ungesättigte Nitrile), (Meth)Acrylsäure-(C1-C8)-Alkylester, ungesättigte Carbonsäuren sowie Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren. Insbesondere geeignet sind (Co)Polymerisate ausMonomers 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) of unsaturated carboxylic acids. (Co) polymers of are particularly suitable
D.l 50 bis 99, vorzugsweise 60 bis 80 Gew.-Teilen Vinylaromaten und/oder kernsubstituierten Vinylaromaten wie beispielsweise Styrol, α-Methylstyrol, p- Methylstyrol, p-Chlorstyrol) und/oder Methacrylsäure-(C1-C8)-Alkylester wie z.B. Methylmethacrylat, Ethylmethacrylat), und
D.2 1 bis 50, vorzugsweise 20 bis 40 Gew.-Teilen Vinylcyanide (ungesättigte Nitrile) wie Acrylnitril und Methacrylnitril und/oder (Meth)Acrylsäure-(Cι- C8)-Alkylester (wie z.B. Methylmethacrylat, n-Butylacrylat, t-Butylacrylat) und/oder ungesättigte Carbonsäuren (wie Maleinsäure) und/oder Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren (beispielsweiseDl 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) alkyl esters such as eg methyl methacrylate, ethyl methacrylate), 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
Maleinsäureanhydrid und N-Phenyl-Maleinimid).Maleic anhydride and N-phenyl-maleimide).
Die (Co)Polymerisate D sind harzartig, thermoplastisch und kautschukfrei.The (co) polymers D are resinous, thermoplastic and rubber-free.
Besonders bevorzugt ist das Copolymerisat aus D.l Styrol und D.2 Acrylnitril.The copolymer of D.l styrene and D.2 acrylonitrile is particularly preferred.
Die (Co)Polymerisate gemäß D sind bekannt und lassen sich durch radikalische Polymerisation, insbesondere durch Emulsions-, Suspensions-, Lösungs- oder Massepolymerisation herstellen. Die (Co)Polymerisate besitzen vorzugsweise Molekular- gewichte Mw (Gewichtsmittel, ermittelt durch Lichtstreuung oder Sedimentation) zwischen 15 000 und 200 000.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.
Komponente EComponent E
Die erfindungsgemäßen Polymerblends können übliche Additive, wie Flarnm- schutzmittel, Anti-Dripping-Mittel, feinstteilige anorganische Verbindungen, Gleit- und Entformungsmittel, Nukleierungsmittel, Antistatika, Stabilisatoren, Füll- und Verstärkungsstoffe sowie Farbstoffe und Pigmente enthalten.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 reinforcing materials, and also dyes and pigments.
Die erfindungsgemäßen Polymerblends können im allgemeinen 0.01 bis 20 Gew.-%, bezogen auf die Gesamt-Formmasse, Flammschutzmittel enthalten. Beispielhaft werden als Flammschutzmittel organische Halogenverbindungen wie Decabrombis- phenylether, Tetrabrombisphenol, anorganische Halogenverbindungen wie Ammoniumbromid, Stickstoffverbindungen, wie Melamin, Melaminformaldehyd- Harze, anorganische Hydroxidverbindungen wie Mg-Alhydroxid, anorganischeThe polymer blends according to the invention can generally contain 0.01 to 20% by weight, based on the total molding composition, of flame retardants. Examples of 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
Verbindungen wie Aluminiumoxide, Titandioxide, Antimonoxide, Barium-meta-
borat, Hydroxoantimonat, Zirkonoxid, Zirkonhydroxid, Molybdänoxid, Arnmonium- molybdat, Zinnborat, Ammom'umborat, Barium-metaborat und Zinnoxid sowie Siloxanverbindungen genannt.Compounds such as aluminum oxides, titanium dioxides, antimony oxides, barium meta borate, molybdate hydroxoantimonate, zirconium oxide, zirconium oxide, molybdenum oxide, Arnmonium-, Ammom 'umborat tin borate, barium metaborate and tin oxide as well as siloxane compounds called.
Als Flammschutzverbindungen können ferner Phosphorverbindungen, wie sie in derAs flame retardant compounds, phosphorus compounds such as those in the
EP-A-363 608, EP-A-345 522 oder EP-A-640 655 beschrieben sind, eingesetzt werden.EP-A-363 608, EP-A-345 522 or EP-A-640 655 are used.
Die einsetzbaren anorganischen Verbindungen umfassen Verbindungen eines oder mehrerer Metalle der 1. bis 5. Hauptgruppe und der 1. bis 8. Nebengruppe desThe inorganic compounds which can be used include compounds of one or more metals of the 1st to 5th main group and the 1st to 8th subgroup of
Periodensystems, bevorzugt der 2. bis 5. Hauptgruppe und der 4. bis 8. Nebengruppe, besonders bevorzugt der 3. bis 5. Hauptgruppe und der 4. bis 8. Nebengrappe mit den Elementen Sauerstoff, Schwefel, Bor, Phosphor, Kohlenstoff, Stickstoff, Wasserstoff und/oder Silicium.Periodic table, preferably the 2nd to 5th main group and the 4th to 8th subgroup, particularly preferably the 3rd to 5th main group and the 4th to 8th subgroup with the elements oxygen, sulfur, boron, phosphorus, carbon, nitrogen , Hydrogen and / or silicon.
Beispiele für solche Verbindungen sind Oxide, Hydroxide, wasserhaltige Oxide, Sulfate, Sulfite, Sulfide, Carbonate, Carbide, Nitrate, Nitrite, Nitride, Borate, Silikate, Phosphate, Hydride, Phosphite oder Phosphonate. Hierzu zählen beispielsweise TiN, TiO2, SnO2, WC, ZnO, Al2O3, AIO(OH), ZrO2, Sb2O3, SiO2, Eisenoxide, NaSO4, BaSO4, Vanadiumoxide, Zinkborat, Silicate wie AI-Silikate,Examples of such compounds are oxides, hydroxides, water-containing oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates. 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 4 , BaSO 4 , vanadium oxides, zinc borate, silicates such as Al-silicates,
Mg-Silikate, ein, zwei, dreidimensionale Silikate, Mischungen und dotierte Verbindungen sind ebenfalls verwendbar. Des weiteren können diese nanoskaligen Partikel mit organischen Molekülen oberflächenmodifiziert sein, um eine bessere Verträglichkeit mit den Polymeren zu erzielen. Auf diese Weise lassen sich hydrophobe oder hydrophile Oberflächen erzeugen.Mg silicates, one, two, three-dimensional silicates, mixtures and doped compounds can also be used. Furthermore, these 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.
Die durchschnittlichen Teilchendurchmesser sind kleiner gleich 200 um, bevorzugt kleiner gleich 150 nm, insbesondere 1 bis 100 nm.
Teilchengröße und Teilchendurchmesser bedeutet immer den mittleren Teilchendurchmesser d50, ermittelt durch Ulfrazentrifügenmessungen nach W.Scholtan et al. Kolloid-Z. und Z. Polymere 250 (1972), S.782 bis 796.The average particle diameters are less than or equal to 200 μm, preferably less than or equal to 150 nm, in particular 1 to 100 nm. Particle size and particle diameter always mean the average particle diameter d 50 , determined by Ulfrazentrifügen measurements according to W. Scholtan et al. Colloid-Z. and Z. Polymers 250 (1972), pp.782 to 796.
Die anorganischen Verbindungen können als Pulver, Pasten, Sole, Dispersionen oderThe inorganic compounds can be in the form of powders, pastes, brine, dispersions or
Suspensionen vorliegen. Durch Ausfällen können aus Dispersionen, Solen oder Suspensionen Pulver erhalten werden.Suspensions are present. Precipitation can be used to obtain powders from dispersions, brines or suspensions.
Die Pulver können nach üblichen Verfahren in die thermoplastischen Kunststoffe eingearbeitet werden, beispielsweise durch direktes Kneten oder Extrudieren derThe powders can be incorporated into the thermoplastic materials by customary methods, for example by direct kneading or extrusion of the
Bestandteile der Formmasse und den feinstteiligen anorganischen Pulvern. Bevorzugte Verfahren stellen die Herstellung eines Masterbatch, z.B. in Flammschutzadditiven, anderen Additiven, Monomeren, Lösungsmitteln, in Komponente A oder die Cofällung von Dispersionen der Komponenten B oder C mit Dispersionen, Suspensionen, Pasten oder Solen der feinstteiligen anorganischen Materialien dar.Components of the molding compound 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 very finely divided inorganic materials.
Als Füll- und Verstärkungsmaterialien kommen z.B. Glasfasern, gegebenenfalls geschnitten oder gemahlen, Glasperlen, Glaskugeln, blättchenförmiges Verstärkungsmaterial, wie Kaolin, Talk, Glimmer, Silicate, Quarz, Talkum, Titandioxid, Wollastonit, Mika, Kohlefasern oder deren Mischung in Betracht. Vorzugsweise werden als Verstärkungsmaterial geschnittene oder gemahlene Glasfasern eingesetzt. Bevorzugte Füllstoffe, die auch verstärkend wirken können sind Glaskugeln, Glimmer, Silikate, Quarz, Talkum, Titandioxid, Wollastonit.As filling and reinforcing materials come e.g. Glass fibers, optionally cut or ground, glass beads, glass balls, flake-like reinforcing material, such as kaolin, talc, mica, silicates, quartz, talc, titanium dioxide, wollastonite, 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.
Die Polymerblends der vorliegenden Erfindung können zur Herstellung von Formkörpern jeder Art verwendet werden. Insbesondere können Formkörper durch Spritz- guss hergestellt werden. Beispiele für herstellbare Formkörper sind: Gehäuseteile jeder Art, z.B. für Haushaltsgeräte, wie Saftpressen, Kaffeemaschinen, Mixer, für Büromaschinen, wie Computer, Drucker, Monitore oder Abdeckplatten für den Bau- sektor und Teile für den Kfz-Sektor.
Gegenstand der vorliegenden Erfindung ist ebenfalls die Verwendung der erfindungsgemäßen Polymerblends zur Herstellung von Formteilen sowie die Formteile selbst.The polymer blends of the present invention can be used to produce moldings of any kind. In particular, moldings can be produced by injection molding. Examples of moldings that can be produced are: housing parts of all kinds, for example for household appliances, such as juicers, coffee machines, mixers, for office machines, such as computers, printers, monitors or cover plates for the construction sector and parts for the motor vehicle sector. The present invention also relates to the use of the polymer blends according to the invention for the production of moldings and to the moldings themselves.
Besonders geeignet sind die Polymerblends zur Herstellung von Formteilen an die besonders hohe Ansprüche hinsichtlich der Reißdehnung und Zugfestigkeit gestellt werden.The polymer blends are particularly suitable for the production of molded parts which have particularly high demands with regard to elongation at break and tensile strength.
Im folgenden wird die Erfindung anhand einiger Beispiele näher erläutert:
The invention is explained in more detail below with the aid of a few examples:
BeispieleExamples
1. Eingesetzte Komponenten1. Components used
A Polyamid (DURETHAN B30 der Fa. Bayer AG, Leverkusen,A polyamide (DURETHAN B30 from Bayer AG, Leverkusen,
Deutschland)Germany)
Bl Pfropφolymerisat von 40 Gew.-Teilen eines Copolymerisats aus Styrol und Acrylnitril im Verhältnis von 73:27 auf 60Bl graft polymer of 40 parts by weight of a copolymer of styrene and acrylonitrile in a ratio of 73:27 to 60
Gew.-Teile teilchenförmig vernetzten Polybutadienkautschuk (mittlerer Teilchendurchmesser d50=0,28 μm), hergestellt durch Emulsionspolymerisation B2 Masse ABSParts by weight of particulate crosslinked polybutadiene rubber (average particle diameter d 50 = 0.28 μm), produced by emulsion polymerization B2 mass ABS
(1) Magnum 3504 = Masse-ABS-Polymerisat der DOW Chemical Company Midland, Michigan USA (2) Lustran LTD, der Fa. Bayer AG(1) Magnum 3504 = bulk ABS polymer from DOW Chemical Company Midland, Michigan USA (2) Lustran LTD, from Bayer AG
B3 Schlagzähes Polystyrol (Polystyrol 495F, BASF AG,B3 impact-resistant polystyrene (polystyrene 495F, BASF AG,
Ludwigshafen, Deutschland Cl Verträglichkeitsvermittler: Terpolymer von Styrol und Acrylnitril (2.1:1 Gew.-Verhältnis enthaltend 1 Mol-% Maleinsäure- anhydridLudwigshafen, Germany Cl compatibility agent: Terpolymer of styrene and acrylonitrile (2.1: 1 weight ratio containing 1 mol% maleic anhydride
C2 Styrol-Isopropylen-2-Oxazolin-Copolymer mit einem Gewichtsmittel Mw von ca. 15.2 x 104 kg/mol gemessen mittels GPC auf Polystyrol-Standard geeicht (Epocros® RPS-1005 der Fa. Nippon Shokubai Co. Ltd., Japan). D Styrol/ Acrylnitril-Copolymerisat mit einem Styrol/ Acrylnitril-C2 styrene-isopropylene-2-oxazoline random copolymer having a weight average M w of about 15.2 x 10 4 kg / mol measured by GPC on polystyrene standard calibrated (Epocros ® RPS-1005 of Fa. Nippon Shokubai Co. Ltd., Japan ). D styrene / acrylonitrile copolymer with a styrene / acrylonitrile
Verhältnis von 72:28 und einer Grenzviskosität von 0,75 dl/g (Messung in Dimethylformamid bei 20°C) F Additive
2. Herstellung der PolymerblendsRatio of 72:28 and an intrinsic viscosity of 0.75 dl / g (measurement in dimethylformamide at 20 ° C) F additives 2. Production of the polymer blends
Die erfindungsgemäßen Polymerblends werden hergestellt, indem man die jeweiligen Bestandteile in bekannter Weise vermischt und bei Temperaturen von 200 bis 300°C in üblichen Aggregaten, wie Innenknetern, Extrudern und Doppelwellenschnecken schmelzcompoundiert oder schmelzextrudiert, wobei die fluorierten Polyolefine vorzugsweise in Form der bereits erwähnten koagulierten Mischung eingesetzt werden.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.
Die Vermischung der einzelnen Bestandteile kann in bekannter Weise sowohl sukzessiv als auch simultan erfolgen, und zwar sowohl bei etwa 20°C (Raumtemperatur) als auch bei erhöhter Temperatur.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.
Masse- ABS bzw. Mischung aus Masse- und Emulsions-ABS sowie HLPSBulk ABS or mixture of bulk and emulsion ABS as well as HLPS
Tabelle 1Table 1
4. Mit HLPS 4. With HLPS
Die Bestimmung der Wärmeformbeständigkeit nach Vicat B erfolgt gemäßThe Vicat B heat resistance is determined in accordance with
DIN 53 460 (ISO 306) an Stäben der Abmessung 80 x 10 x 4 mm.DIN 53 460 (ISO 306) on rods measuring 80 x 10 x 4 mm.
HDT A wurde bestimmt bei 1,8 MPa gem. ISO 75HDT A was determined at 1.8 MPa. ISO 75
Die Schmelzvolumenrate wurde bestimmt nach ISO 527The melt volume rate was determined according to ISO 527
Die Bewitterung wurde bestimmt gem. SAE J 1885 Gerät Uerit: Xe WO ll Spühzyklus: 102=18 Lichtzeit: 1000 h Bestrahlungsenergie: 1260 KJ/m2 Bestrahlung: 144.9 MJ/m2 The weathering was determined according to SAE J 1885 device Uerit: Xe WO ll spray cycle: 102 = 18 light time: 1000 h radiation energy: 1260 KJ / m 2 radiation: 144.9 MJ / m 2
Der E-Modul wurde bestimmt gemäß DIN 53 457/ISO 527 Die Reißdehnung wurde bestimmt nach ISO 527
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
Claims
1. Polymerblends enthaltend1. Containing polymer blends
A) Polyamid,A) polyamide,
B) mittels Masse-, Lösungs- oder Masse-Suspensions-Polymerisations- verfahrens hergestelltes Pfropφolymerisat von,B) graft polymer prepared by means of bulk, solution or bulk suspension polymerization process,
B.l 50-99 Gew.-% eines oder mehrerer Vinylmonomere auf,B.l 50-99 wt .-% of one or more vinyl monomers,
B.2 50-1 Gew.-% einer oder mehrerer Pfropfgrundlagen mit einer Glasumwandlungstemperatur < 10°C,B.2 50-1% by weight of one or more graft bases with a glass transition temperature <10 ° C,
oder schlagzähem Polystyrol,or impact-resistant polystyrene,
C) mindestens einen Verträglichkeitsvermittler enthaltend mindestens ein thermoplastisches Polymer mit polaren Gruppen und gegebenenfallsC) at least one compatibilizer containing at least one thermoplastic polymer with polar groups and optionally
D) mindestens ein Vinyl(co)polymerisat.D) at least one vinyl (co) polymer.
2. Polymerblends nach Anspruch 1, dadurch gekennzeichnet, dass sie 10 - 98 Gew.-Teile Polyamid,2. polymer blends according to claim 1, characterized in that they have 10 - 98 parts by weight of polyamide,
0,5 - 80 Gew.-Teile eines Gemisches der Komponenten B und gegebenenfalls D und0.5-80 parts by weight of a mixture of components B and optionally D and
0,5 - 50 Gew.-Teile der Komponente C enthalten.Contain 0.5 - 50 parts by weight of component C.
3. Polymerblends nach Anspruch 1, dadurch gekennzeichnet, dass sie 15 - 70 Gew.-Teile Polyamid, 10 - 70 Gew.-Teile eines Gemisches der Komponenten B und gegebenenfalls D und3. polymer blends according to claim 1, characterized in that they contain 15-70 parts by weight of polyamide, 10 - 70 parts by weight of a mixture of components B and optionally D and
1 - 30 Gew.-Teile der Komponente C enthalten.Contain 1 to 30 parts by weight of component C.
4. Polymerblends nach Anspruch 1, dadurch gekennzeichnet, dass sie 20 - 60 Gew.-Teile Polyamid,4. polymer blends according to claim 1, characterized in that they contain 20-60 parts by weight of polyamide,
20 - 65 Gew.-Teile eines Gemisches der Komponenten B und gegebenenfalls D und 2 - 10 Gew.-Teile der Komponente C enthalten.Contain 20-65 parts by weight of a mixture of components B and optionally D and 2-10 parts by weight of component C.
5. Polymerblends gemäß einem der vorhergehenden Ansprüche, wobei Vinyl- monomere B.l Gemische sind aus5. Polymer blends according to one of the preceding claims, wherein vinyl monomers B.l mixtures are made of
B.l.l Styrol, α-Methylstyrol, halogen- oder alkylkernsubstituierte Styrole und/oder (Met^Acrylsäure- -Cs-alkylester undB.l.l styrene, α-methylstyrene, halogen- or alkyl nucleus-substituted styrenes and / or (Met ^ acrylic acid -Cs alkyl ester and
B.l.2 ungesättigte Nitrile, (Meth)Acrylsäure-Cι-C8-alkylester und/oder Derivate ungesättigter Carbonsäuren.Bl2 unsaturated nitriles, (meth) acrylic acid -CC 8 alkyl esters and / or derivatives of unsaturated carboxylic acids.
6. Polymerblends nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass Komponente C wenigstens ein vinylaromatisches Monomer (C.l) ausgewählt aus der Gruppe C2-C12-Alkyl(meth)acrylate, Methacryl- nitrile und Acrylnitrile sowie α, ß-ungesättigte Komponenten enthaltend Dicarbonsäureanhydride (C.2) enthält.6. Polymer blends according to one of the preceding claims, characterized in that component C at least one vinyl aromatic monomer (Cl) selected from the group C 2 -C 12 alkyl (meth) acrylates, methacrylonitriles and acrylonitriles and α, β-unsaturated components containing dicarboxylic anhydrides (C.2).
7. Polymerblends nach einem der vorhergehenden Ansprüche, wobei Komponente D Vinyl(co)polymerisate von mindestens einem Monomer aus der Gruppe der Vinylaromaten, Vinylcyaniden, (Meth)Acrylsäure-(C1-C8)-alkyl- ester, ungesättigte Carbonsäuren sowie Derivate ungesättigter Carbonsäure sind.7. Polymer blends according to one of the preceding claims, wherein component D vinyl (co) polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides, (meth) acrylic acid (C 1 -C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acid.
8. Polymerblends gemäß der vorhergehenden Ansprüche, enthaltend wenigstens ein Additiv ausgewählt aus der Gruppe der Gleit- und Entformungsmittel,8. polymer blends according to the preceding claims, containing at least one additive selected from the group of lubricants and mold release agents,
Nukleiermittel, Antistatika, Stabilisatoren, Farbstoffe und Pigmente.Nucleating agents, antistatic agents, stabilizers, dyes and pigments.
9. Polymerblends gemäß einem der vorhergehenden Ansprüche enthaltend ein Flammschutzmittel.9. polymer blends according to any one of the preceding claims containing a flame retardant.
10. Verwendung der Polymerblends nach einem vorhergehenden Ansprüche zur Herstellung von Formkörpern.10. Use of the polymer blends according to one of the preceding claims for the production of moldings.
11. Formkörper erhältlich aus Polymerblends nach einem der Ansprüche 1 bis 9.11. Moldings obtainable from polymer blends according to one of claims 1 to 9.
12. Gehäuseteile, Abdeckplatten und Teile für den Kfz-Sektor, erhältlich aus Polymerblends nach einem der Ansprüche 1 bis 9. 12. Housing parts, cover plates and parts for the motor vehicle sector, available from polymer blends according to one of claims 1 to 9.
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2000124933 DE10024933A1 (en) | 2000-05-19 | 2000-05-19 | Polymer blends with good tensile strength and elongation contain a polyamide together with graft copolymers (e.g., ABS) or high-impact polystyrene and a polar group-containing compatibilizer |
DE10024933 | 2000-05-19 | ||
DE2000124935 DE10024935A1 (en) | 2000-05-19 | 2000-05-19 | Polyamide blends useful for making weathering-resistant shaped products include a graft copolymer based on a silicone, ethylene-propylene, ethylene-propylene-diene or acrylate rubber |
DE10024935 | 2000-05-19 | ||
DE2001109225 DE10109225A1 (en) | 2001-02-26 | 2001-02-26 | Impact-resistant polyamide composition, useful for making moldings, includes graft and vinyl copolymers, compatibility improver and anisotropic inorganic solid |
DE10109225 | 2001-02-26 | ||
PCT/EP2001/005140 WO2001090246A1 (en) | 2000-05-19 | 2001-05-07 | Polymer blends containing polyamide and rubber modified polymers produced by a mass polymerisation method |
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EP1287075A1 true EP1287075A1 (en) | 2003-03-05 |
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EP01931688A Withdrawn EP1287074A1 (en) | 2000-05-19 | 2001-05-07 | Weather-resistant polymer blends |
EP01933938A Withdrawn EP1287075A1 (en) | 2000-05-19 | 2001-05-07 | Polymer blends containing polyamide and rubber modified polymers produced by a mass polymerisation method |
EP01927943A Withdrawn EP1287067A1 (en) | 2000-05-19 | 2001-05-07 | Impact-resistant modified polymer compositions |
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EP01931688A Withdrawn EP1287074A1 (en) | 2000-05-19 | 2001-05-07 | Weather-resistant polymer blends |
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EP01927943A Withdrawn EP1287067A1 (en) | 2000-05-19 | 2001-05-07 | Impact-resistant modified polymer compositions |
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EP (3) | EP1287074A1 (en) |
JP (3) | JP2003534432A (en) |
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DE10231001A1 (en) * | 2002-07-09 | 2004-02-12 | Volkswagen Ag | Tool made of plastic |
DE10233170A1 (en) * | 2002-07-22 | 2004-02-12 | Bayer Ag | Polymer blends based on polyamide |
DE10254877A1 (en) * | 2002-11-25 | 2004-06-03 | Bayer Ag | Impact-modified polyamide composition useful for making shaped products, especially automobile bodywork parts, contains electrically conductive carbon particles and a graft copolymer |
JP2006507402A (en) * | 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 | Polymer composition with improved impact resistance |
DE10310693A1 (en) * | 2003-03-12 | 2004-09-23 | Bayer Ag | Impact-modified polymer compositions |
WO2005040281A1 (en) * | 2003-10-10 | 2005-05-06 | Basf Aktiengesellschaft | Thermoplastic molding compositions |
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