WO2001016230A1 - Thermoplastische formmassen auf basis bestimmter pfropfkautschukkomponenten - Google Patents
Thermoplastische formmassen auf basis bestimmter pfropfkautschukkomponenten Download PDFInfo
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- WO2001016230A1 WO2001016230A1 PCT/EP2000/008123 EP0008123W WO0116230A1 WO 2001016230 A1 WO2001016230 A1 WO 2001016230A1 EP 0008123 W EP0008123 W EP 0008123W WO 0116230 A1 WO0116230 A1 WO 0116230A1
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- 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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- C08F2/00—Processes of polymerisation
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- C08F2/22—Emulsion polymerisation
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- 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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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- 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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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
Definitions
- the invention relates to thermoplastic molding compositions of the ABS type or of the ABS blend type, comprising improved graft rubber components which are obtained by emulsion polymerization using special initiator systems and compliance with defined reaction conditions.
- ABS-type molding compounds are made of two-phase plastics
- thermoplastic copolymer in particular of styrene and acrylonitrile, in which the styrene can be replaced in whole or in part by ⁇ -methylstyrene or methyl methacrylate; this copolymer, also known as SAN resin or matrix resin, forms the outer phase;
- graft polymer which has been prepared by grafting one or more of the monomers mentioned under I onto butadiene homo- or copolymer (“graft base”).
- This graft polymer (“elastomer phase” or “graft rubber”) forms the disperse
- plastic mixtures can also contain other polymer components such as Aromatic polycarbonate resins, polyester carbonate resins, polyester resins or polyamide resins contain, whereby so-called ABS blend systems are obtained.
- Graft rubbers produced using redox initiator systems have proven particularly useful as impact modifiers (see, for example, EP 482 451 and the literature cited therein), good toughness generally being achieved.
- the disadvantage is that top surface gloss, elongation at break and thermoplastic flowability are often not sufficient or are subject to strong fluctuations.
- graft rubbers produced by redox initiation tend to an increased content of unreacted monomers, which is due to the addition of
- Metal ions e.g. Fe ions
- Fe ions can be reduced in the reaction mixture, but this leads to losses in other properties (e.g. thermal stability, color of the polymer).
- the invention relates to thermoplastic molding compositions of the ABS type or of the ABS blend type, containing
- A) at least one by radical emulsion polymerization of resin-forming vinyl monomers, preferably of compounds of the formulas (I) and (II) described below, particularly preferably of styrene and / or acrylonitrile, styrene and / or acrylonitrile being replaced in whole or in part can be obtained by ⁇ -methylstyrene, methyl methacrylate or N-phenylmaleimide, in the presence of rubber in latex form with a glass transition temperature ⁇ 0 ° C using an initiator combination of a persulfate compound and a redox initiator system and obtained elastic-thermoplastic graft polymer and B) at least one copolymer of styrene and acrylonitrile, it being possible for styrene and / or acrylonitrile to be replaced in whole or in part by ⁇ -methylstyrene or methyl methacrylate or N-phenylmaleimide and, if appropriate
- the per-sulfate compound in amounts of 0.05 to 1.5% by weight, preferably 0.08 to 1.2% by weight and particularly preferably 0.1 to 1, 0% by weight (based in each case on the monomers metered in up to the point in time at which the redox initiator is added) is added after a monomer addition of 1 to 50% by weight, preferably 2.5 to 40% by weight, particularly preferably 5 to 30% by weight and very particularly preferably 7.5 to 25% by weight (based in each case on the total amount of monomers) of the redox initiator components in amounts of 0.1 to 2.5% by weight, preferably 0.2 to 2 % By weight and particularly preferably from 0.5 to 1.5% by weight (based in each case on the monomers metered in from the time of the redox initiator addition) are added.
- Suitable rubbers for producing the elastic-thermoplastic graft polymers according to the invention are in principle all rubber-like polymers in emulsion form with a glass transition temperature below 0 ° C.
- Diene rubbers i.e. Homopolymers of conjugated dienes with 4 to 8
- C atoms such as butadiene, isoprene, chloroprene or their copolymers with up to 60% by weight, preferably up to 30% by weight, of a vinyl monomer, for example acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, halostyrenes, C1-C4- Alkylstyrenes, Cj-Cg-alkyl acrylates, Ci-Cg-alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene;
- a vinyl monomer for example acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, halostyrenes, C1-C4- Alkylstyrenes, Cj-Cg-alkyl acrylates, Ci-Cg-alkyl methacrylates, alkylene glycol diacrylates, al
- Acrylate rubbers i.e. Homopolymers and copolymers of C 1 -C 8 alkyl acrylates, e.g. Homopolymers of ethyl acrylate, butyl acrylate or copolymers with up to 40% by weight, preferably not more than 10% by weight, of mono-vinyl monomers, e.g. Styrene, acrylonitrile, vinyl butyl ether, acrylic acid (ester), methacrylic acid (ester), vinyl sulfonic acid.
- Those acrylate rubber homopolymers or copolymers which contain 0.01 to 8% by weight of divinyl or polyvinyl compounds and / or N-methylolacrylamide or N-
- methylol methacrylamide or other compounds which act as crosslinkers e.g. Divinylbenzene, triallyl cyanurate.
- Polybutadiene rubbers SBR rubbers with up to 30% by weight of copolymerized styrene and acrylate rubbers are preferred, especially those which contain a core
- Latices with average particle diameters d5Q of 0.05 to 2.0 ⁇ m, preferably 0.08 to 1.0 ⁇ m and particularly preferably 0.1 to 0.5 ⁇ m are suitable for the preparation of the graft polymers according to the invention.
- the gel contents of the rubbers used can be varied within wide limits, preferably between 30 and 95% by weight (determination by the wire cage method in toluene (cf. Houben-Weyl, Methods of Organic Chemistry, Macromolecular Substances, Part 1, p. 307 (1961), Thieme Verlag Stuttgart)).
- the rubber latex (a) preferably has a particle size distribution range from 30 to 100 nm, particularly preferably from 40 to 80 nm, the rubber latex (b) from 50 to 500 nm, particularly preferably from 100 to 400 nm (measured in each case as d 0 -d, o value from the integral particle size distribution).
- the mixtures contain the rubber latices (a) and (b) preferably in a ratio of 90:10 to 10:90, particularly preferably 60:40 to 30:70 (in each case based on the respective solids content of the latices).
- the mean particle diameters are determined by means of an ultracentrifuge (cf. W. Scholtan, H. Lange: Kolloid-Z. U Z. Polymer 250, pp. 782-796 (1972).
- the rubber latices used can be produced by emulsion polymerization, the required reaction conditions, auxiliary substances and working techniques are known in principle.
- anionic emulsifiers such as alkyl sulfates, acyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturated fatty acids (for example oleic acid, stearic acid) and alkaline disproportionated or hydrogenated abietic or tall oil acid can be used as emulsifiers; emulsifiers with a carboxyl group (for example salts of C 10 -C 1 fatty acids, disproportionated abietic acid).
- rubber polymer latices can also be produced by emulsifying finished rubber polymers in aqueous media (cf. Japanese patent application 55 125 102).
- Suitable graft monomers which are polymerized in the presence of the rubbery polymers present in emulsion form are virtually all compounds which can be polymerized in emulsion to give thermoplastic resins, e.g. Vinylaromatics of the formula (I) or compounds of the formula (II) or mixtures thereof,
- Rl is hydrogen or methyl
- R ⁇ is hydrogen, halogen or alkyl having 1 to 4 carbon atoms in the ortho-meta or para position
- R ⁇ is hydrogen or methyl
- X represents CN, R 4 OOC or R 5 R 6 NOC,
- R4 is hydrogen or alkyl of 1 to 4 carbon atoms
- R5 and R6 independently of one another are hydrogen, phenyl or alkyl having 1 to 4 carbon atoms.
- Examples of compounds of the formula (I) are styrene, ⁇ -methylstyrene, p-methylstyrene and vinyltoluene.
- Compounds of formula (II) are acrylonitrile and methyl methacrylate.
- Other monomers suitable in principle are e.g. Vinyl acetate and N-phenylmaleimide.
- Preferred monomers are mixtures of styrene and acrylonitrile, ⁇ -methylstyrene and acrylonitrile, of styrene, acrylonitrile and methyl methacrylate and combinations of these monomer mixtures with N-phenylmaleimide.
- Preferred graft polymers A) according to the invention are those which by graft polymerization of styrene and acrylonitrile in a weight ratio of 90:10 to 50:50, preferably 80:20 to 65:35 (styrene can be replaced in whole or in part by ⁇ - Methylstyrene or methyl methacrylate) in the presence of such amounts Rubber, preferably polybutadiene, are obtained to give graft polymers with rubber contents of 20 to 80% by weight, preferably 30 to 75% by weight and particularly preferably 35 to 70% by weight.
- the inventive graft polymers A) are prepared in such a way that at least one persulfate compound is added to the rubber latex or the rubber latex mixture at the beginning of the grafting reaction.
- Suitable persulfate compounds are, for example and preferably, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, particularly preferred
- Persulfate compound is potassium peroxodisulfate.
- the persulfate compound is used in amounts of 0.05 to 1.5% by weight, preferably 0.08 to 1.2% by weight and particularly preferably 0.1 to 1.0% by weight (in each case based on the monomers metered in before or from the starting point of the persulfate compound addition).
- a redox initiator system is added by weight (based in each case on the total amount of monomers).
- Suitable redox initiator systems generally consist of an organic oxidizing agent and a reducing agent, with heavy metal ions preferably also being present in the reaction medium.
- Organic oxidizing agents suitable according to the invention are, for example and preferably, di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert-butyl hydroperoxide, p-menthane hydroperoxide or mixtures thereof cumene hydroperoxide and tert-butyl hydroperoxide are preferred.
- H 2 O 2 can also be used.
- Reducing agents which can be used according to the invention are preferably water-soluble compounds having a reducing action, preferably selected from the group consisting of the salts of sulfinic acid, salts of sulfurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium bisulfite, ascorbic acid and their salts, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacid Sugar (e.g. glucose or dextrose), iron (II) salts such as Iron (II) sulfate, tin (II) salts such as e.g. Tin (II) chloride, titanium (III) salts such as titanium (III) sulfate.
- a reducing action preferably selected from the group consisting of the salts of sulfinic acid, salts of sulfurous acid, sodium dithionite, sodium sulfite, sodium hyposulfite, sodium bisulfite, ascorbic acid
- Particularly preferred reducing agents are dextrose, ascorbic acid (salts) or sodium formaldehyde sulfoxylate (Rongalit C).
- the amount of redox initiator component is distributed among oxidizing and reducing agents as follows:
- the amount of oxidizing agent used is generally 0.05 to 2.0% by weight, preferably 0.1 to 1.5% by weight and particularly preferably 0.2 to 1.2% by weight.
- the amount of reducing agent is generally 0.05 to 1.5% by weight, preferably 0.08 to 1.2% by weight and particularly preferably 0.1 to 1.0% by weight.
- both the persulfate compound and the redox initiator components are used in the form of aqueous solutions, aqueous emulsions, aqueous suspensions or other aqueous dispersions.
- the remaining monomers are then metered in and the polymerization is completed.
- the invention further relates to a process for producing graft rubbers by emulsion polymerization using an initiator combination of a persulfate compound and a redox system, where i) the graft monomers are metered into the rubber latex,
- the persulfate compound in amounts of 0.05 to 1.5 wt .-% (based on the up to the time of
- the redox initiator components are added in amounts of 0.1 to 2.5% by weight (based on the monomers metered in from the time the persulfate compound is added).
- the reaction temperature in the production of the graft rubbers A) according to the invention can be varied within wide limits. It is generally 25 ° C to 160 ° C, preferably 40 ° C to 90 ° C; the temperature at the beginning of the monomer metering very particularly preferably differs from the temperature at the end of the monomer metering zone by at most 20 ° C., preferably at most 10 ° C. and particularly preferably at most 5 ° C.
- molecular weight regulators can be used in the graft polymerization, preferably in amounts of 0.05 to 2% by weight, particularly preferably in amounts of 0.1 to 1% by weight (in each case based on the total amount of monomer).
- Suitable molecular weight regulators are, for example, n-dodecyl mercaptan, t-decodyl mercaptan, dimeric ⁇ -methylstyrene, terpinolene and mixture combinations of these compounds.
- the above-mentioned compounds can be used as emulsifiers in the graft polymerization reaction.
- the graft rubber latex A) is worked up by known methods, for example by spray drying or by adding salts and / or acids, washing the precipitated products and drying the powder.
- the vinyl resins B) used are preferably copolymers of styrene and acrylonitrile in a weight ratio of 90:10 to 50:50, it being possible for styrene and / or acrylonitrile to be replaced in whole or in part by ⁇ -methylstyrene and / or methyl methacrylate; optionally up to 30% by weight (based on vinyl resin) of another monomer from the series of maleic anhydride, maleimide, N- (cyclo) -alkylmaleimide, N- (alkyl) -phenylmaleimide can also be used.
- the weight average molecular weights (M w ) of these resins can be varied within wide limits, preferably they are between approximately 40,000 and 200,000, particularly preferably between 50,000 and 150,000.
- the proportion of the elastic-thermoplastic graft polymer (A) in the molding compositions according to the invention can be varied within wide limits; it is preferably 1 to 80% by weight, particularly preferably 5 to 50% by weight.
- the necessary or appropriate additives for example antioxidants, UV stabilizers, peroxide destroyers, antistatic agents, lubricants, mold release agents, flame retardants, fillers or reinforcing materials (glass fibers, carbon fibers, etc.) can be added to the molding compositions according to the invention during production, processing, further processing and final shaping. ) and colorants.
- the final shaping can be carried out on commercially available processing units and includes, for example, injection molding processing, sheet extrusion with, if appropriate, subsequent hot shaping, cold shaping, extrusion of tubes and profiles or calendar processing.
- ABS-type molding compositions according to the invention can be mixed with other polymers (component C).
- Suitable blend partners are selected, for example, from at least one polymer, selected from the group consisting of polycarbonates, polyesters, polyester carbonates and polyamides.
- thermoplastic polycarbonates and polyester carbonates are known (see, for example, DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396, DE-OS 3 077 934), e.g. can be produced by reacting diphenols of the formulas (III) and / or (IV)
- R 'and R ⁇ independently of one another represent hydrogen, methyl or halogen, in particular hydrogen, methyl, chlorine or bromine,
- R ⁇ and RIO independently of one another hydrogen, halogen preferably chlorine or
- Ci-Cg-alkyl preferably methyl, ethyl, Cs-Cg-cycloalkyl, preferably cyclohexyl, Cg-Ci o-aryl, preferably phenyl, or C7-C12-aralkyl, preferably phenyl-Ci-C4-alkyl, especially benzyl mean
- n is an integer from 4 to 7, preferably 4 or 5
- n 0 or 1
- Rl 1 and Rl2 can be selected individually for each X and are independently hydrogen or C 1 -C 6 -alkyl and
- carbonic acid halides preferably phosgene
- aromatic dicarboxylic acid dihalides preferably benzenedicarboxylic acid dihalides
- Phase boundary polycondensation or with phosgene by polycondensation in a homogeneous phase (the so-called pyridine process), the molecular weight being able to be adjusted in a known manner by an appropriate amount of known chain terminators.
- Suitable diphenols of the formulas (III) and (TV) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) ) -2-methylbutane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2- Bis (4-hydroxy-3,5-dibromophenyl) propane, l, l-bis (4-hydroxyphenyl) cyclohexane, l, l-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis (4-hy- droxyphenyl) -3,3,5,5-tetramethylcyclohexane or 1, 1-bis (4
- Preferred diphenols of the formula (III) are 2,2-bis (4-hydroxyphenyl) propane and l, l-bis (4-hydroxyphenyl) cyclohexane, the preferred phenol of the formula (IV) is 1,1-
- Mixtures of diphenols can also be used.
- Suitable chain terminators are e.g. Phenol, p-tert-butylphenol, long-chain alkylphenols such as 4- (1,3-tetramethylbutyl) phenol according to DE-OS 2 842 005, monoalkylphenols, dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-OS 3 506 472, such as p-nonylphenol, 2,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethylheptyl) phenol and 4th - (3,5-Dimethylheptyl) phenol.
- the amount of chain terminators required is generally 0.5 to
- the suitable polycarbonates or polyester carbonates can be linear or branched; branched products are preferably by the incorporation of 0.05 to 2.0 mol%, based on the sum of the diphenols used, of three - or more than three-functional compounds, e.g. those with three or more than three phenolic OH groups.
- the suitable polycarbonates or polyester carbonates can contain aromatically bound halogen, preferably bromine and / or chlorine; they are preferably halogen-free.
- thermoplastic polyesters are preferably polyalkylene terephthalates, ie reaction products made from aromatic dicarboxylic acids or their reactive derivatives (eg dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or arylaliphatic diols and mixtures of such reaction products.
- Preferred polyalkylene terephthalates can be prepared from terephthalic acids (or their reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Volume VIII, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973).
- 80 to 100 preferably 90 to 100 mol% of the dicarboxylic acid residues, terephthalic acid residues and 80 to 100, preferably 90 to 100 mol% of the diol residues are 1,4-ethylene glycol and / or butanediol residues.
- the preferred polyalkylene terephthalates can contain, in addition to ethylene glycol or butanediol 1,4, residues from 0 to 20 mol% of residues of other aliphatic diols with 3 to 12 C atoms or cycloaliphatic diols with 6 to 12 C atoms, e.g. Residues of 1,3-propanediol, 2-ethylpropane-1,3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 3-methylpentanediol, 3 and -1,6 , 2-
- the polyalkylene terephthalates can be branched by incorporating relatively small amounts of trihydric or tetravalent alcohols or trihydric or tetravalent carboxylic acids, as are described in DE-OS 1 900270 and US Pat. No. 3,692,744.
- preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol. It is advisable not to use more than 1 mol% of the branching agent, based on the acid component.
- polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example its dialkyl ester) and ethylene glycol and / or 1,4-butanediol and mixtures of these polyalkylene terephthalates.
- Preferred polyalkylene terephthalates are also copolyesters which are made from at least two of the alcohol components mentioned above: particularly preferred copolyesters are poly (ethylene glycol butanediol 1,4) terephthalates.
- the preferably suitable polyalkylene terephthalates generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, each measured in Phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° 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, mixtures 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-xylylene diamine and / or hexamethylene diamine and / or 2,2,4-trimethylhexamethylene diamine and / or 2,2,4-trimethylhexamethylene diamine and / or isophorone diamine and the composition of which is known in principle.
- polyamides which are wholly or partly prepared from lactams with 7- 12 C 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.
- diamines such as ethylenediamine, hexamethylenediamine, decamethylenediamine, 2,2,4- and / or 2,4,4-trimethylhexamethylenediamine, 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 acid, adipic acid, azelaic acid, decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and
- Copolymers which are obtained by polycondensation of several monomers are also suitable, furthermore 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, 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'-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.
- 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.
- At least one polymer selected from the group of polycarbonates, polyesters, polyester carbonates and polyamides is additionally used, its amount is up to 500 parts by weight, preferably up to 400 parts by weight and particularly preferably up to 300 parts by weight (each based on 100 parts by weight of A + B).
- a polybutadiene latex mixture 58.5 parts by weight (calculated as a solid) of a polybutadiene latex mixture (50% with an average particle diameter d 50 of 423 nm and a gel content of 82% by weight and 50% with an average particle diameter d 50 of 288 nm and a gel content of 56% by weight, both produced by radical polymerization) are brought to a solids content of about 20% by weight with water, after which the mixture is heated to 75 ° C. Then 0.1 part by weight of potassium peroxodisulfate (dissolved in water) is added and 6.225 parts by weight of a monomer mixture of 73% by weight of styrene and 27% by weight of acrylonitrile are metered in uniformly at 75 ° C. in the course of 30 minutes.
- a polybutadiene latex mixture 50% with an average particle diameter d 50 of 423 nm and a gel content of 82% by weight and 50% with an average particle diameter d 50 of 288
- 1.72 parts by weight (calculated as solid) of the sodium salt of a resin acid mixture (Dresinate 731, Abieta Chemie GmbH, Gersthofen, dissolved in alkaline water) are metered in over 4 h.
- the latex After a one-hour post-reaction time at 85 ° C, the latex is cooled to 23 ° C; the residual monomers are then determined by gas chromatography using the head space analysis technique (see, for example, B. Kolb in “Gas Chromatography in Images", Wiley-VCH, Weinheim, 1999, and the literature cited therein):
- the graft latex is then coagulated with a magnesium sulfate / acetic acid mixture after the addition of about 1 part by weight of a phenolic antioxidant and, after washing with water, the resulting powder is dried at 70.degree.
- Example 2 (comparison)
- Example 1 is repeated, with 0.039 part by weight of t-butyl hydroperoxide and 0.033 part by weight of sodium ascorbate being added after heating the polybutadiene latex mixture to 75 ° C., and then 41.5 parts by weight of a monomer mixture of 73 in parallel over the course of 4 hours %
- styrene and 27% by weight of acrylonitrile 0.221 part by weight of t-butyl hydroperoxide and 0.187 part by weight of sodium ascorbate are uniformly metered in.
- the emulsifier is added and further treatment is carried out analogously to Example 1.
- Example 1 is repeated, with 6.225 before the addition of the potassium peroxodisulfate
- Redox initiator, metering in of emulsifier and further treatment are carried out analogously to Example 1.
- Example 3 is repeated, with no potassium persulfate being added to the mixture of polybutadiene latex mixture and 6.225 parts by weight of monomer mixture and the redox initiator components described in Example 2 being added as described in Example 2.
- the emulsifier is added and further treatment is carried out analogously to Example 1.
- the notched impact strength is determined according to method ISO 1801 A on bars measuring 80 x 10 x 4 mm at room temperature and at -40 ° C.
- the elongation at break DR is determined as part of the determination of the tensile modulus of elasticity according to method ISO 527 on F 3 shoulder bars.
- the melt flowability MVR is determined according to method DIN 53 753 at 260 ° C (5 kg load).
- the surface gloss was assessed visually as follows:
- the molding compositions according to the invention have improved flow properties and better gloss properties.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/069,862 US6716916B1 (en) | 1999-09-01 | 2000-08-21 | Thermoplastic molding materials based on particular graft rubber constituents |
DE50011703T DE50011703D1 (de) | 1999-09-01 | 2000-08-21 | Thermoplastische formmassen auf basis bestimmter pfropfkautschukkomponenten |
JP2001520781A JP2003508572A (ja) | 1999-09-01 | 2000-08-21 | 特定のグラフトゴム成分に基く熱可塑性成形用組成物 |
MXPA02002201A MXPA02002201A (es) | 1999-09-01 | 2000-08-21 | Masas de moldeo termoplasticas basadas en determinados componentes de caucho injertado. |
CA002386703A CA2386703A1 (en) | 1999-09-01 | 2000-08-21 | Thermoplastic molding compositions based on certain graft rubber components |
EP00960497A EP1214375B1 (de) | 1999-09-01 | 2000-08-21 | Thermoplastische formmassen auf basis bestimmter pfropfkautschukkomponenten |
AU72783/00A AU7278300A (en) | 1999-09-01 | 2000-08-21 | Thermoplastic molding materials based on particular graft rubber constituents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19941491.2 | 1999-09-01 | ||
DE19941491A DE19941491A1 (de) | 1999-09-01 | 1999-09-01 | Thermoplastische Formmassen auf Basis bestimmter Pfropfkautschukkomponenten |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001016230A1 true WO2001016230A1 (de) | 2001-03-08 |
Family
ID=7920316
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/008123 WO2001016230A1 (de) | 1999-09-01 | 2000-08-21 | Thermoplastische formmassen auf basis bestimmter pfropfkautschukkomponenten |
Country Status (14)
Country | Link |
---|---|
US (1) | US6716916B1 (de) |
EP (1) | EP1214375B1 (de) |
JP (1) | JP2003508572A (de) |
KR (1) | KR100675230B1 (de) |
CN (1) | CN1142979C (de) |
AR (1) | AR028484A1 (de) |
AU (1) | AU7278300A (de) |
CA (1) | CA2386703A1 (de) |
DE (2) | DE19941491A1 (de) |
ES (1) | ES2248111T3 (de) |
MX (1) | MXPA02002201A (de) |
RU (1) | RU2002108177A (de) |
TW (1) | TW562833B (de) |
WO (1) | WO2001016230A1 (de) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005071013A1 (de) * | 2004-01-27 | 2005-08-04 | Basf Aktiengesellschaft | Thermoplastische formmassen auf basis von styrolcopolymeren und polyamiden |
US7186778B2 (en) * | 2000-12-05 | 2007-03-06 | Bayer Aktiengesellschaft | Thermoplastic molding compositions |
US7790805B2 (en) * | 2002-11-29 | 2010-09-07 | Bayer Materialscience Ag | Impact-modified blends |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8969476B2 (en) * | 2002-06-21 | 2015-03-03 | Sabic Global Technologies B.V. | Impact-modified compositions |
US20040225034A1 (en) * | 2003-05-09 | 2004-11-11 | General Electric Company | Impact-modified compositions and method |
DE102007035462A1 (de) | 2007-07-28 | 2009-01-29 | Lanxess Deutschland Gmbh | Verfahren zur Herstellung von Pfropfkautschuken |
RU2010147711A (ru) * | 2008-04-24 | 2012-05-27 | Байер МатириальСайенс АГ (DE) | Поликарбонатные композиции с модифицированной ударной вязкостью, высокой устойчивостью к гидролизу и светлой натуральной окраской |
DE102009015039A1 (de) * | 2009-03-26 | 2010-09-30 | Bayer Materialscience Ag | Schlagzähmodifizierte Polycarbonat-Zusammensetzungen zur Herstellung metallisierter Formkörper mit homogenem Oberflächenglanz |
KR101063227B1 (ko) * | 2009-10-12 | 2011-09-07 | 현대자동차주식회사 | 나일론-4 복합재료 조성물 |
EP2657258A1 (de) * | 2012-04-23 | 2013-10-30 | Bayer MaterialScience AG | Verfahren zur Herstellung von ABS-Zusammensetzungen mit verbesserter Oberfläche nach Wärme-Feucht-Lagerung |
KR102232439B1 (ko) * | 2017-06-22 | 2021-03-25 | 주식회사 엘지화학 | 공중합체 조성물, 이의 제조방법 및 이를 포함하는 열가소성 수지 조성물 |
WO2024028309A1 (de) * | 2022-08-04 | 2024-02-08 | Ineos Styrolution Group Gmbh | Thermoplastische abs-formmassen mit einer guten eigenschaftskombination von verarbeitbarkeit und oberflächenqualität |
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GB1255797A (en) * | 1967-12-12 | 1971-12-01 | Japan Synthetic Rubber Co Ltd | Method for producing a heat resistant graft copolymer |
EP0051336A1 (de) * | 1980-10-31 | 1982-05-12 | Stamicarbon B.V. | Polymerzusammensetzung |
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WO2000004067A1 (de) * | 1998-07-15 | 2000-01-27 | Bayer Aktiengesellschaft | Thermoplastische formmassen auf basis hochwirksamer pfropfkautschukkomponenten |
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US4151128A (en) * | 1968-07-30 | 1979-04-24 | Mobil Oil Corporation | Graft copolymers by suspension process following emulsion |
DE2420358B2 (de) | 1974-04-26 | 1980-02-07 | Bayer Ag, 5090 Leverkusen | Formmassen |
DE2724360C3 (de) | 1977-05-28 | 1988-03-24 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von thermoplastischen Formmassen auf Basis von Vinylpolymerisaten |
JPH0742384B2 (ja) * | 1987-04-21 | 1995-05-10 | 日本合成ゴム株式会社 | 熱可塑性樹脂組成物 |
DE4033806A1 (de) | 1990-10-24 | 1992-04-30 | Bayer Ag | Lichtalterungsbestaendige polycarbonat-formmassen |
JP3332302B2 (ja) * | 1995-03-16 | 2002-10-07 | 電気化学工業株式会社 | 熱可塑性樹脂組成物 |
DE19520286A1 (de) * | 1995-06-02 | 1996-12-05 | Bayer Ag | ABS-Formmassen mit verbesserten Eigenschaften |
-
1999
- 1999-09-01 DE DE19941491A patent/DE19941491A1/de not_active Withdrawn
-
2000
- 2000-08-21 CN CNB008153051A patent/CN1142979C/zh not_active Expired - Fee Related
- 2000-08-21 RU RU2002108177/04A patent/RU2002108177A/ru not_active Application Discontinuation
- 2000-08-21 DE DE50011703T patent/DE50011703D1/de not_active Expired - Lifetime
- 2000-08-21 EP EP00960497A patent/EP1214375B1/de not_active Expired - Lifetime
- 2000-08-21 CA CA002386703A patent/CA2386703A1/en not_active Abandoned
- 2000-08-21 JP JP2001520781A patent/JP2003508572A/ja active Pending
- 2000-08-21 AU AU72783/00A patent/AU7278300A/en not_active Abandoned
- 2000-08-21 KR KR1020027002694A patent/KR100675230B1/ko not_active IP Right Cessation
- 2000-08-21 WO PCT/EP2000/008123 patent/WO2001016230A1/de active IP Right Grant
- 2000-08-21 ES ES00960497T patent/ES2248111T3/es not_active Expired - Lifetime
- 2000-08-21 MX MXPA02002201A patent/MXPA02002201A/es active IP Right Grant
- 2000-08-21 US US10/069,862 patent/US6716916B1/en not_active Expired - Fee Related
- 2000-08-30 TW TW089117557A patent/TW562833B/zh not_active IP Right Cessation
- 2000-08-30 AR ARP000104522A patent/AR028484A1/es not_active Application Discontinuation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US3542905A (en) * | 1967-08-11 | 1970-11-24 | Japan Synthetic Rubber Co Ltd | Process for preparing heat resistant graft copolymers |
GB1255797A (en) * | 1967-12-12 | 1971-12-01 | Japan Synthetic Rubber Co Ltd | Method for producing a heat resistant graft copolymer |
EP0051336A1 (de) * | 1980-10-31 | 1982-05-12 | Stamicarbon B.V. | Polymerzusammensetzung |
US5700852A (en) * | 1994-04-06 | 1997-12-23 | Japan Synthetic Rubber Co., Ltd. | Paper coating composition |
WO2000004067A1 (de) * | 1998-07-15 | 2000-01-27 | Bayer Aktiengesellschaft | Thermoplastische formmassen auf basis hochwirksamer pfropfkautschukkomponenten |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7186778B2 (en) * | 2000-12-05 | 2007-03-06 | Bayer Aktiengesellschaft | Thermoplastic molding compositions |
US7790805B2 (en) * | 2002-11-29 | 2010-09-07 | Bayer Materialscience Ag | Impact-modified blends |
WO2005071013A1 (de) * | 2004-01-27 | 2005-08-04 | Basf Aktiengesellschaft | Thermoplastische formmassen auf basis von styrolcopolymeren und polyamiden |
KR101197943B1 (ko) | 2004-01-27 | 2012-11-05 | 바스프 에스이 | 스티롤 공중합체 및 폴리아미드로부터 제조된 열가소성성형물 |
Also Published As
Publication number | Publication date |
---|---|
KR100675230B1 (ko) | 2007-01-29 |
CN1142979C (zh) | 2004-03-24 |
CA2386703A1 (en) | 2001-03-08 |
EP1214375B1 (de) | 2005-11-23 |
KR20020027603A (ko) | 2002-04-13 |
ES2248111T3 (es) | 2006-03-16 |
US6716916B1 (en) | 2004-04-06 |
DE19941491A1 (de) | 2001-03-15 |
TW562833B (en) | 2003-11-21 |
AR028484A1 (es) | 2003-05-14 |
AU7278300A (en) | 2001-03-26 |
JP2003508572A (ja) | 2003-03-04 |
DE50011703D1 (de) | 2005-12-29 |
CN1387552A (zh) | 2002-12-25 |
EP1214375A1 (de) | 2002-06-19 |
MXPA02002201A (es) | 2002-11-07 |
RU2002108177A (ru) | 2003-11-10 |
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