EP1084187A1 - Thermoplastic molding material exhibiting a high puncturing resistance and a good antistatic behavior - Google Patents

Thermoplastic molding material exhibiting a high puncturing resistance and a good antistatic behavior

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Publication number
EP1084187A1
EP1084187A1 EP99913275A EP99913275A EP1084187A1 EP 1084187 A1 EP1084187 A1 EP 1084187A1 EP 99913275 A EP99913275 A EP 99913275A EP 99913275 A EP99913275 A EP 99913275A EP 1084187 A1 EP1084187 A1 EP 1084187A1
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EP
European Patent Office
Prior art keywords
component
weight
acrylonitrile
proportion
styrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP99913275A
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German (de)
French (fr)
Inventor
Peter Barghoorn
Peter Ittemann
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Priority claimed from DE1998117993 external-priority patent/DE19817993A1/en
Application filed by BASF SE filed Critical BASF SE
Publication of EP1084187A1 publication Critical patent/EP1084187A1/en
Withdrawn legal-status Critical Current

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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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • Thermoplastic molding compound with high puncture resistance and good antistatic behavior is thermoplastic molding compound with high puncture resistance and good antistatic behavior
  • the equipment increases the internal lubrication of the molding compounds, which improves the processing range in the Injection molding leads.
  • the molecular weight of the block Y can be 1200 to 3650, the proportion of ethylene oxide units being 10 to 30% by weight.
  • EP-A-0 125 801 it is known to provide polymer blends of polycarbonate and impact-resistant styrene / acrylonitrile copolymer to improve the processing range with the aforementioned three-block copolymers of the formula X-Y-X.
  • the molecular weight of the polypropylene oxide block Y can be, for example, 1200, 2250 or 3600.
  • the proportion of ethylene oxide is 10 or 40% by weight.
  • the object of the present invention is to provide impact-resistant copolymers of styrene and / or x-methylstyrene with acrylonitrile which have increased puncture resistance and at the same time have good antistatic behavior.
  • the object is achieved by a molding compound composed of the components Abis C and optionally D,
  • a hard component composed of one or more copolymers of styrene and / or ⁇ -methylstyrene with acrylonitrile, the proportion of acrylonitrile being 10 to 50% by weight, as component A,
  • b 5 to 70% by weight of at least one graft copolymer B.
  • bl 10 to 90% by weight of at least one rubber-elastic particulate graft base with a glass transition temperature below 0 ° C. as component B1 and
  • b2 10 to 90% by weight of at least one graft pad from a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile, the The proportion of acrylonitrile is 10 to 50% by weight, as component B2,
  • c 0.1 to 10% by weight of at least one three-block copolymer of the formula X-Y-X with a central block Y composed of propylene oxide units with an average molecular weight in the range from 2,000 to 4,000 and terminal
  • d 0 to 10% by weight, based on the total weight of components A to C, of further customary auxiliaries and fillers as component D.
  • Molding compositions suitable for finishing with components A, B and D are described, for example, in DE-A-29 01 576 and in particular in DE-A-197 28 629, which is older and not prepublished.
  • the component of acrylonitrile in component A is preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight, in particular 18.5 to 36% by weight.
  • component B the proportion of component B1 is preferably 20 to 80% by weight, particularly preferably 25 to 75% by weight, the proportion of component B2 is preferably 20 to 80% by weight, particularly preferably 25 to 75% by weight %.
  • the proportion of acrylonitrile in component B2 is preferably 15 to 40% by weight, particularly preferably 15 to 35% by weight.
  • the average molecular weight of block Y is from
  • Propylene oxide units preferably 2200 to 3800, particularly preferably 2300 to 53500, in particular approximately 2300, approximately 2750 or approximately 3250, each +/- 10%.
  • the average proportion of the terminal blocks X composed of ethylene oxide units, based on component C, is preferably 3 to 28
  • % By weight, particularly preferably 8 to 24% by weight, in particular approximately 8 to 14 or approximately 18 to 24% by weight.
  • Component A preferably has a viscosity number VZ (determined according to DIN 15 53726 at 25 ° C., 0.5% by weight in dimethylformamide) of 50 to 120 ml / g, particularly preferably 52 to 110 ml / g and in particular 55 to 105 ml / g on. It is particularly preferably a styrene acrylonitrile copolymer. Such copolymers are obtained in a known manner by bulk, solution, suspension, precipitation or emulsion polymerization, bulk and solution polymerization being preferred. Details of these processes are described, for example, in the plastics handbook, edited by R. Vieweg and G Daumiller, volume V "Polystyrol", Carl-Hanser-Verlag Kunststoff 1969, page 118 ff.
  • VZ viscosity number
  • Component B is a graft copolymer with a rubber-elastic particulate graft base with a glass transition temperature below 0 ° C.
  • the graft base can be selected from all known suitable chewing-elastic polymers. It is preferably ABS (acrylonitrile / butadiene / styrene), ASA (acrylonitrile / styrene / alkyl acrylate), EPDM, Siloxane or other rubbers.
  • Component B1 is preferably at least one (co) polymer
  • bll 60 to 100 wt .-%, preferably 70 to 100 wt .-% of at least one conjugated diene, C ⁇ - ⁇ o-alkyl acrylate or mixtures thereof as
  • Component B1 different monoethylenically unsaturated monomers as component B 12 and b1: 0 to 10% by weight, preferably 0 to 6% by weight, of at least one crosslinking monomer as component B13.
  • conjugated dienes B1 in particular butadiene, isoprene, chloroprene or mixtures thereof as well as the Ci-io-alkyl acrylates listed below and mixtures thereof come into consideration.
  • component B12 may contain monomers which vary the mechanical and thermal properties of the core within a certain range.
  • monoethylenically unsaturated comonomers are styrene, substituted styrenes, acrylonitrile, methacrylonitrile, acrylic acid,
  • Methacrylic acid dicarboxylic acids such as maleic acid and fumaric acid and their
  • Anhydrides such as maleic anhydride, nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole,
  • Acrylic acid and methacrylic acid such as phenyl acrylate, phenyl methacrylate, Benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate, N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexylmaleimide, unsaturated ethers such as vinyl methyl ether and mixtures thereof.
  • N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexylmaleimide
  • unsaturated ethers such as vinyl methyl ether and mixtures thereof.
  • Styrene, ⁇ -methylstyrene, n-butyl acrylate, methyl methacrylate or mixtures thereof are preferably used as component B12, in particular styrene and n-butyl acrylate or mixtures thereof, especially styrene.
  • component B12 in particular styrene and n-butyl acrylate or mixtures thereof, especially styrene.
  • the proportion of component B1 is preferably 70 to 99.9, particularly preferably 90 to 99% by weight and the proportion of component B12 0.1 to 30, particularly preferably 1 to 10% by weight.
  • Butadiene / styrene and n-butyl acrylate styrene copolymers in the stated amount range are particularly preferred.
  • crosslinking monomers of component B13 are divinyl compounds such as divinylbenzene, diallyl compounds such as diallyl maleate, allyl esters of acrylic and methacrylic acid, dihydrodicyclopentadienyl acrylate (DCPA), divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl deseller and divinyl alcohol and butane-1,4-diols.
  • the graft B2 is preferably a styrene / acrylonitrile copolymer.
  • the graft copolymers B are usually prepared by the emulsion polymerization process. Polymerization is generally carried out at a temperature of 20 to 100, preferably 30 to 80 ° C. Common emulsifiers are often used, for example alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or resin soaps. The alkali metal salts, in particular the sodium or potassium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms, are preferably used. As a rule, the emulsifiers are used in amounts of 0.5 to 5% by weight, in particular 0.5 to 3% by weight, based on the monomers used in the preparation of the graft base.
  • Sufficient water is preferably used to prepare the dispersion so that the finished dispersion has a solids content of 20 to 50% by weight. Usually a water / monomer ratio of 2: 1 to 0.7: 1 is used.
  • radical formers which decompose at the selected reaction temperature are suitable for starting the polymerization reaction, that is to say both those which decompose thermally on their own and those which do so in the presence of a redox system.
  • Free radical formers for example peroxides such as preferably peroxosulfates (for example sodium or potassium persulfate) and azo compounds such as azodiisobutyronitrile are preferably suitable as polymerization initiators.
  • redox systems in particular those based on hydroperoxides such as cumene hydroperoxide, can also be used.
  • the polymerization initiators are used in an amount of 0.1 to 1% by weight, based on the graft base monomers.
  • the radical formers and also the emulsifiers are added to the reaction batch, for example discontinuously as a total amount at the beginning of the reaction, or divided into several portions, batchwise at the beginning and at one or more later times, or continuously during a certain time interval.
  • the continuous addition can also take place along a gradient, e.g. can be ascending or descending, linear or exponential, or also stepwise (stair function).
  • Molecular weight regulators such as ethylhexylthioglycolate, n- or t- Use dodecyl mercaptan or other mercaptans, terpinols and dimeric methylstyrene or other compounds suitable for regulating the molecular weight.
  • the molecular weight regulators are added batchwise or continuously to the reaction mixture, as was described above for the radical formers and emulsifiers.
  • buffer substances such as Na 2 HPO 4 / NaH 2 PO 4 , sodium hydrogen carbonate or buffer based on citric acid / citrate can also be used. Regulators and buffer substances are used in the usual quantities, so that further details are not necessary.
  • the graft base can also be produced by polymerizing the monomers B1 in the presence of a finely divided latex (so-called “seed latex mode of operation" of the polymerization).
  • This latex is introduced and can consist of monomers forming rubber-elastic polymers, or also of other monomers, as already mentioned.
  • Suitable seed latices consist, for example, of polybutadiene or polystyrene.
  • the graft base B1 can be produced in the so-called feed process.
  • a certain proportion of the monomers is introduced and the polymerization is started, after which the remainder of the monomers (“feed fraction”) B1 are added as feed during the polymerization.
  • feed fraction the remainder of the monomers
  • the feed parameters shape of the gradient, amount, duration, etc.
  • the statements made regarding the addition of the radical start or emulsifier also apply here analogously.
  • Graft polymers with several "soft” and “hard” shells are also suitable.
  • the precise polymerization conditions, in particular the type, quantity and dosage of will emulsifier and of the other polymerization auxiliaries preferably selected so that the latex of the graft polymer B obtained has a mean particle size, defined by the d 5 o of the particle size, from 80 to 800 microns, preferably 80 to 600 nm and particularly preferably 85 to 400 nm.
  • the reaction conditions are coordinated with one another in such a way that the polymer particles have a bimodal particle size distribution, that is to say a size distribution with two more or less pronounced maxima.
  • the bimodal particle size distribution is preferably achieved by a (partial) agglomeration of the polymer particles. This can be done, for example, as follows: The monomers which form the core are polymerized up to a conversion of usually at least 90%, preferably greater than 95%, based on the monomers used. This turnover is usually reached after 4 to 20 hours.
  • the rubber latex obtained has an average particle size d 50 of at most 200 nm and a narrow particle size distribution (almost monodisperse system).
  • the rubber latex is agglomerated. This is usually done by adding a dispersion of an acrylic ester polymer.
  • a copolymer of 96% ethyl acrylate and 4% methacrylamide is particularly preferred.
  • the agglomerating dispersion can optionally also contain several of the acrylic ester polymers mentioned.
  • the concentration of the acrylic ester polymers in the dispersion used for agglomeration should generally be between 3 and 40% by weight.
  • 0.2 to 20, preferably 1 to 5 parts by weight of the agglomeration dispersion per 100 parts of the rubber latex, in each case calculated on solids, are used.
  • the agglomeration is carried out by adding the agglomerating dispersion to the rubber.
  • the rate of addition is normally not critical, generally it takes about 1 to 30 minutes at a temperature between 20 and 90 ° C, preferably between 30 and 75 ° C.
  • the rubber latex can also be agglomerated by other agglomerating agents such as acetic anhydride. Agglomeration by pressure or freezing (pressure or freeze agglomeration) is also possible. The methods mentioned are known to the person skilled in the art.
  • the rubber particles Under the conditions mentioned, only a part of the rubber particles is agglomerated, so that a bimodal distribution is produced. After agglomeration there are generally more than 50, preferably between 75 and 95% of the particles (number distribution) in the non-agglomerated state.
  • the partially agglomerated rubber latex obtained is relatively stable, so that it can be easily stored and transported without coagulation occurring.
  • the graft B2 can be produced under the same conditions as the preparation of the graft base B1, the B2 being able to be produced in one or more process steps. For example, at In a two-stage grafting process, polymerize styrene or ⁇ -methylstyrene alone and then styrene and acrylonitrile in two successive steps. This two-stage grafting (first styrene, then styrene / acrylonitrile) is a preferred embodiment. Further details on the preparation of the graft polymers B are described in DE-A 12 60 135 and 31 49 358 and EP-A-0 735 063.
  • graft polymerization on the graft base B1 again in an aqueous emulsion. It can be carried out in the same system as the polymerization of the graft base, and further emulsifier and initiator can be added. These need not be identical to the emulsifiers or initiators used to prepare the graft base B1. For example, it may be expedient to use a persulfate as the initiator for the preparation of the graft base B1, but to use a redox initiator system for the polymerization of the graft shell B2. For the rest, what has been said for the preparation of the graft base B1 applies to the choice of emulsifier, initiator and polymerization auxiliaries.
  • the monomer mixture to be grafted on can be added to the reaction mixture all at once, batchwise in several stages or, preferably, continuously during the polymerization.
  • the three-block copolymers of the formula XYX used according to the invention can be prepared in a manner known per se (N. Schönfeldt, surface-active ethylene oxide adducts, scientific publishing company mbH Stuttgart, 1976, page 53 ff) by polymerization, initially producing a medium-sized polypropylene oxide block Y. one end of each block Ethylene oxide units is attached.
  • the molecular weights given above are generally the average molecular weights (number average M n , for example determined from the OH number according to DIN 53240).
  • Preferred three-block copolymers and their preparation are also described in EP-A-0 125 801 and EP-A-0 018 591.
  • auxiliaries and fillers can be used as component D.
  • Such substances are, for example, lubricants or mold release agents, waxes, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers or reinforcing agents or antistatic agents, and also other additives or mixtures thereof.
  • Suitable lubricants and mold release agents are e.g. Stearic acids, stearyl alcohol, stearic acid esters or amides as well as silicone oils, montan waxes and waxes based on polyethylene and polypropylene.
  • Pigments are, for example, titanium dioxide, phthalocyanines, ultramarine blue, iron oxides or carbon black, as well as the entire class of organic pigments.
  • Dyes are to be understood as all dyes which can be used for the transparent, semi-transparent or non-transparent decolorization of polymers, in particular those which are suitable for coloring styrene copolymers. Dyes of this type are known to the person skilled in the art.
  • Flame retardants which can be used are, for example, the halogen-containing or phosphorus-containing compounds known to the person skilled in the art, magnesium hydroxide and other customary compounds or mixtures thereof. Likewise red phosphorus suitable.
  • Suitable antioxidants are, in particular, sterically hindered mononuclear or multinuclear phenolic antioxidants, which can be substituted in various ways and can also be bridged via substituents. In addition to monomers, this also includes oligomeric compounds, which can be made up of several phenolic base bodies. Hydroquinones and hydroquinone analogs and substituted compounds are also suitable, as are antioxidants based on tocopherols and their derivatives. Mixtures of different antioxidants can also be used. In principle, all commercially available compounds or compounds suitable for styrene copolymers can be used, such as Topanol® or Irganox®.
  • Suitable light stabilizers are e.g. various substituted resorcinols, salicylates, benzotriazoles, benzophenones, HALS (hindered amine light stabilizers), such as those e.g. are commercially available as Tinuvin.
  • fibrous or powdered fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, cut glass, glass balls and WoUastonit, particularly preferably glass fibers. If glass fibers are used, they can be equipped with a size and an adhesion promoter for better compatibility with the blend components. The glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings).
  • Carbon black, amorphous silica, magnesia are suitable as particulate fillers.
  • sium carbonate (chalk) powdered quartz, mica, mica, bentonite, talc, feldspar or in particular calcium silicates such as WoUastonit and kaolin.
  • the molding compositions are preferably produced by producing the individual components A to C and, if appropriate, D separately and then mixing the components.
  • Suitable processes for producing the molding compositions are described, for example, in EP-A-0 135 801, EP-B-0 018 591 and in particular DE-A-197 28 628.
  • the molding compositions according to the invention can be used for the production of moldings, fibers or films. Such processes for the production of moldings, fibers or films are listed in the specified publications.
  • 43120 g of the monomer mixture specified in Table 1 are in the presence of 432 g of tert-dodecyl mercaptan (TDM), 311 g of potassium salt of C 2 -C 2 o-fatty acids, 82 g of potassium persulfate, 147 g of sodium hydrogen carbonate and 58400 g of water at 65 ° C polymerized to a polybutadiene latex.
  • TDM tert-dodecyl mercaptan
  • 311 g of potassium salt of C 2 -C 2 o-fatty acids 311 g of potassium salt of C 2 -C 2 o-fatty acids
  • 82 g of potassium persulfate 147 g of sodium hydrogen carbonate
  • 58400 g of water at 65 ° C polymerized to a polybutadiene latex.
  • the procedure was as described in EP-A-0 062 901, Example 1, page 9, line 20 - page 10, line 6. The conversion was 95% or
  • n-butyl acrylate polymer is used as the graft base B1
  • the procedure is as in EP-A-0 735 063, Examples VI, V2, 14 V and 15 V.
  • the graft polymer dispersion obtained with a bimodal particle size distribution had an average particle size d 50 of 150 to 350 nm and a d 90 value of 400 to 600 nm. A first maximum of the particle size distribution was in the range of 50 to 150 nm, a second maximum in the range of 200 to 600 nm.
  • the dispersion obtained was mixed with an aqueous dispersion of an antioxidant and then coagulated by adding a magnesium sulfate solution.
  • the coagulated rubber was centrifuged off from the dispersion water and washed with water. A rubber with about 30% by weight of adhering or enclosed residual water was obtained.
  • thermoplastic polymers A were prepared by the process of continuous solution polymerization, as described in the plastics handbook, ed. R. Vieweg and G Daumiller, volume V "Polystyrol", Carl-Hanser-Verlag Kunststoff 1969, pp 122-124 .
  • Table 3 summarizes the compositions and properties.
  • the graft rubber B containing residual water was dried with warm air in a vacuum and mixed intimately with the further component A in an extruder, type ZSK 30 from Werner and Pfleiderer, at 250 ° C. and 250 min ⁇ 1 with a throughput of 10 kg h.
  • the molding compound was extruded and the molten polymer mixture was subjected to rapid cooling by introducing it into a 30 ° C water bath.
  • the solidified molding compound was granulated. 4. Measurements taken
  • Swelling index of the graft base B1 A film was produced from the aqueous dispersion of the graft base by evaporating the water. 0.2 g of this film was mixed with 50 g of toluene. After 24 hours the toluene was aspirated from the swollen sample and the sample weighed out. After drying the sample in vacuo at 110 ° C. for 16 hours, it was weighed out again. The following were calculated:
  • the average particle size d is the weight average of the particle size, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972) pages 782 to 796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the dio value indicates the particle diameter in which 10% by weight of all particles have a smaller and 90% by weight a larger diameter. Conversely, for the d9o-value that 90 wt .-% of all particles have a smaller, and 10 wt .-% have a larger diameter than the diameter which corresponds to the d 9 o value.
  • Viscosity number VZ it was determined according to DIN 53726 on a 0.5% by weight solution of the polymer in dimethylformamide.
  • test specimens were produced from the granules of the molding compounds, namely standard small bars (see DIN 53453), shoulder bars, round disks with a diameter of 60 mm and 2 mm or rectangular disks with a thickness of 2 mm .
  • the melt temperature was 250 ° C. in each case and the mold temperature in each case 60 ° C., unless stated otherwise.
  • Vicat The heat resistance according to Vicat was determined on pressed platelets according to ISO 306 / B with a load of 50 N and a heating rate of 50 K / h.
  • the penetration work aD was determined according to ISO 6603-2 on round disks or rectangular disks 40 x 40 mm by the plastic test at 23 ° C, whereby the test specimens were produced at 250 melting temperature.
  • Dust chamber test The dust is whirled up in a dust chamber for 10 seconds. Coarse dirt is blown off and the formation of stamen is assessed visually.

Abstract

The inventive molding material contains components A to C and optionally D; a: 20 to 94 wt. % of a hard component comprised of one or more copolymers of styrene and/or alpha -methyl styrene with acrylonitrile, whereby the proportion of acrylonitrile is equal to 10 to 50 wt. %, as component A; b: 5 to 70 wt. % of a graft copolymer B comprised of b1: 10 to 90 wt. % of at least one rubber elastic, particle-shaped graft base having a glass transition temperature of less than 0 DEG C, as component B1, and b2: 10 to 90 wt. % of at least one graft coating comprised of a copolymer of styrene and/or alpha -methyl styrene with acrylonitrile, whereby the proportion of acrylonitrile is equal to 10 to 50 wt. %, as component B2; c: 0.1 to 10 wt. % of at least one triple-block copolymer of formula X-Y-X having a centrally located block Y comprised of propylene oxide units with an average molecular weight ranging from 2,000 to 4,000 and terminal blocks X comprised of ethylene oxide units whose average proportion in the triple-block copolymer is equal to 2 to 35 wt. %, as component C, whereby the total weight of components A to C amounts to 100 wt. %; d: 0 to 10 wt. %, with regard to the total weight of components A to C, of additional, common auxiliary agents and fillers as component D.

Description

Thermoplastische Formmasse mit hoher Durchstoßfestigkeit und gutem antistatischem Verhalten Thermoplastic molding compound with high puncture resistance and good antistatic behavior
Die Erfindung betrifft thermoplastische Formmassen mit hoher Durchstoßfestigkeit und gutem antistatischem Verhalten. Bei den Formmassen handelt es sich um schlagzähmodifizierte Copolymerisate von Styrol und/oder α-Methylstyrol mit Acrylnitril.The invention relates to thermoplastic molding compositions with high puncture resistance and good antistatic behavior. The molding compositions are impact-modified copolymers of styrene and / or α-methylstyrene with acrylonitrile.
Schlagzähmodifizierte Styrol/ Acrylnitril-Copolymerisate werden bei einer Vielzahl von Anwendungen eingesetzt. Bevorzugt werden sie zur Herstellung von Formkö ern verwendet, die gute mechanische Eigenschaften aufweisen sollen. Oft ist es notwendig, derartige Formkörper antistatisch auszurüsten. Die Ausrüstung erfolgt in der Regel durch Zusatz eines Antistatikums zu den Formmassen. Um eine ausreichende Anwendungsbreite der Formmassen zu gewährleisten, ist es wünschenswert, die Formmasse für einen breiten Bereich an Ber- arbeitungsbedingungen anzupassen.Impact-modified styrene / acrylonitrile copolymers are used in a large number of applications. They are preferably used for the production of molded articles which are said to have good mechanical properties. It is often necessary to provide such molded articles with antistatic properties. The finishing is usually done by adding an antistatic to the molding compounds. In order to ensure a sufficient range of use of the molding compositions, it is desirable to adapt the molding composition to a wide range of processing conditions.
Aus FR-B-1 239 902 sind Polymerharze bekannt, die antielektrostatisch ausgerüstet sind. Unter anderem können Formmassen, die Polystyrol-, Polyacrylnitril- und Polybutadieneinheiten aufweisen, mit Dreiblockcopolymeren der Formel X-Y-X ausgerüstet werden, wobei Y einen Polypropylenoxidblock mit einem Molekulargewicht von 1000 bis 1800 bedeutet und X jeweils Polyethylenoxidblöcke bedeuten, wobei der Anteil an Polyethylenoxid 20 bis 80% beträgt. Aus EP-B 0 018 591 ist es bekannt, Styrol/Acrylnitril-Copolymere, die keine Kautschukkomponente enthalten, mit den vorgenannten Dreiblockcopolymeren der Formel X-Y-X auszurüsten. Durch die Ausrüstung wird die Innenschmierung der Formmassen erhöht, was zu einer Verbesserung der Verarbeitungsbreite im Spritzguß führt. Im Dreiblockcopolymer kann das Molekulargewicht des Blocks Y 1200 bis 3650 betragen, wobei der Anteil an Ethylenoxideinheiten 10 bis 30 Gew.- % beträgt.From FR-B-1 239 902 polymer resins are known which are equipped with an anti-electrostatic treatment. Among other things, molding compositions which have polystyrene, polyacrylonitrile and polybutadiene units can be equipped with triblock copolymers of the formula XYX, where Y is a polypropylene oxide block with a molecular weight of 1000 to 1800 and X is in each case polyethylene oxide blocks, the proportion of polyethylene oxide being 20 to 80% is. From EP-B 0 018 591 it is known to provide styrene / acrylonitrile copolymers which contain no rubber component with the aforementioned three-block copolymers of the formula XYX. The equipment increases the internal lubrication of the molding compounds, which improves the processing range in the Injection molding leads. In the three-block copolymer, the molecular weight of the block Y can be 1200 to 3650, the proportion of ethylene oxide units being 10 to 30% by weight.
Aus EP-A-0 125 801 ist es bekannt, Polymerblends aus Polycarbonat und schlagzäh ausgerüstetem Styrol/Acrylnitril-Copolymerisat zur Verbesserung der Verarbeitungsbreite mit den vorgenannten Dreiblockcopolymeren der Formel X-Y-X auszurüsten. Dabei kann das Molekulargewicht des Polypropylenoxidblocks Y beispielsweise 1200, 2250 oder 3600 betragen. Der Anteil an Ethylenoxid beträgt dabei 10 oder 40 Gew.-%.From EP-A-0 125 801 it is known to provide polymer blends of polycarbonate and impact-resistant styrene / acrylonitrile copolymer to improve the processing range with the aforementioned three-block copolymers of the formula X-Y-X. The molecular weight of the polypropylene oxide block Y can be, for example, 1200, 2250 or 3600. The proportion of ethylene oxide is 10 or 40% by weight.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von schagzäh ausgerüsteten Copolymerisaten von Styrol und/oder x-Methylstyrol mit Acrylnitril, die eine erhöhte Durchstoßfestigkeit bei gleichzeitig gutem antistatischem Verhalten aufweisen.The object of the present invention is to provide impact-resistant copolymers of styrene and / or x-methylstyrene with acrylonitrile which have increased puncture resistance and at the same time have good antistatic behavior.
Die Aufgabe wird erfmdungsgemäß gelöst durch eine Formmasse aus den Komponenten Abis C und gegebenenfalls D,According to the invention, the object is achieved by a molding compound composed of the components Abis C and optionally D,
a: 20 bis 94 Gew.-% einer Hartkomponente aus einem oder mehreren Copolymerisaten von Styrol und/oder α-Methylstyrol mit Acrylnitril, wobei der Anteil an Acrylnitril 10 bis 50 Gew.-% beträgt, als Komponente A,a: 20 to 94% by weight of a hard component composed of one or more copolymers of styrene and / or α-methylstyrene with acrylonitrile, the proportion of acrylonitrile being 10 to 50% by weight, as component A,
b: 5 bis 70 Gew.-% mindestens eines Propfcopolymerisats B ausb: 5 to 70% by weight of at least one graft copolymer B.
bl: 10 bis 90 Gew.-% mindestens einer kautschukelastischen teilchen- förmigen Pfropfgrundlage mit einer Glasübergangstemperatur unter 0°C als Komponente Bl undbl: 10 to 90% by weight of at least one rubber-elastic particulate graft base with a glass transition temperature below 0 ° C. as component B1 and
b2: 10 bis 90 Gew.-% mindestens einer Pfropfauflage aus einem Copo- lymerisat von Styrol und/oder α-Methylstyrol mit Acrylnitril, wobei der Anteil an Acrylnitril 10 bis 50 Gew.-% beträgt, als Komponente B2,b2: 10 to 90% by weight of at least one graft pad from a copolymer of styrene and / or α-methylstyrene with acrylonitrile, the The proportion of acrylonitrile is 10 to 50% by weight, as component B2,
c: 0,1 bis 10 Gew.-% mindestens eines Dreiblockcopolymers der Formel X-Y-X mit einem mittelständigen Block Y aus Propylenoxideinheiten mit einem mittleren Molekulargewicht im Bereich von 2.000 bis 4.000 und endständigenc: 0.1 to 10% by weight of at least one three-block copolymer of the formula X-Y-X with a central block Y composed of propylene oxide units with an average molecular weight in the range from 2,000 to 4,000 and terminal
Blocks X aus Ethylenoxideinheiten, deren mittlerer Anteil im Dreiblockcopolymer 2 bis 35 Gew.-% beträgt, als Komponente C,Blocks X of ethylene oxide units, the average proportion of which in the three-block copolymer is 2 to 35% by weight, as component C,
wobei das Gesamtgewicht der Komponenten Abis C 100 Gew.-% ergibt,the total weight of the components Abis C being 100% by weight,
d: 0 bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten A bis C, weiterer üblicher Hilfs- und Füllstoffe als Komponente D.d: 0 to 10% by weight, based on the total weight of components A to C, of further customary auxiliaries and fillers as component D.
Zur Ausrüstung geeignete Formmassen mit den Komponenten A, B und D sind dabei beispielsweise in der DE-A-29 01 576 und insbesondere in der prioritätsälteren, nicht vorveröffentlichten DE-A-197 28 629 beschrieben.Molding compositions suitable for finishing with components A, B and D are described, for example, in DE-A-29 01 576 and in particular in DE-A-197 28 629, which is older and not prepublished.
In den erfindungsgemäßen Formmassen beträgt der Anteil der Komponente A vorzugsweise 40 bis 84,9 Gew.-%, besonders bevorzugt 55 bis 79,7 Gew.-%. Der Anteil der Komponente B beträgt vorzugsweise 15 bis 50 Gew.-%, besonders bevorzugt 20 bis 40 Gew.-%. Der Anteil der Komponente C beträgt vorzugsweise 0,1 bis 5 Gew.-%, besonders bevorzugt 0,3 bis 2 Gew.-%. Der Anteil der Komponente D beträgt vorzugsweise 0 bis 5 Gew.-%, besonders bevorzugt 0 bis 3 Gew.-%.The proportion of component A in the molding compositions according to the invention is preferably 40 to 84.9% by weight, particularly preferably 55 to 79.7% by weight. The proportion of component B is preferably 15 to 50% by weight, particularly preferably 20 to 40% by weight. The proportion of component C is preferably 0.1 to 5% by weight, particularly preferably 0.3 to 2% by weight. The proportion of component D is preferably 0 to 5% by weight, particularly preferably 0 to 3% by weight.
In Komponente A beträgt der Anteil an Acrylnitril vorzugsweise 10 bis 50 Gew.-%, besonders bevorzugt 15 bis 40 Gew.-%, insbesondere 18,5 bis 36 Gew.-%.The component of acrylonitrile in component A is preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight, in particular 18.5 to 36% by weight.
In Komponente B beträgt der Anteil der Komponente Bl vorzugsweise 20 bis 80 Gew.-%, besonders bevorzugt 25 bis 75 Gew.-%, der Anteil der Komponente B2 vorzugsweise 20 bis 80 Gew.-%, besonders bevorzugt 25 bis 75 Gew.-%. Dabei beträgt der Anteil an Acrylnitril in Komponente B2 vorzugsweise 15 bis 40 Gew.-%, besonders bevorzugt 15 bis 35 Gew.-%.In component B the proportion of component B1 is preferably 20 to 80% by weight, particularly preferably 25 to 75% by weight, the proportion of component B2 is preferably 20 to 80% by weight, particularly preferably 25 to 75% by weight %. there The proportion of acrylonitrile in component B2 is preferably 15 to 40% by weight, particularly preferably 15 to 35% by weight.
In Komponente C beträgt das mittlere Molekulargewicht des Blocks Y ausIn component C, the average molecular weight of block Y is from
Propylenoxideinheiten vorzugsweise 2200 bis 3800, besonders bevorzugt 2300 bis 5 3500, insbesondere etwa 2300, etwa 2750 oder etwa 3250, jeweils +/- 10%. Der mittlere Anteil der endständigen Blocks X aus Ethylenoxideinheiten beträgt, bezogen auf die Komponente C, vorzugsweise 3 bis 28Propylene oxide units preferably 2200 to 3800, particularly preferably 2300 to 53500, in particular approximately 2300, approximately 2750 or approximately 3250, each +/- 10%. The average proportion of the terminal blocks X composed of ethylene oxide units, based on component C, is preferably 3 to 28
Gew.-%, besonders bevorzugt 8 bis 24 Gew.-%, insbesondere etwa 8 bis 14 oder etwa l8 bis 24 Gew.-%. 0% By weight, particularly preferably 8 to 24% by weight, in particular approximately 8 to 14 or approximately 18 to 24% by weight. 0
Komponente AComponent A
Komponente A weist vorzugsweise eine Viskositätszahl VZ (ermittelt nach DIN 15 53726 bei 25°C, 0,5 Gew.-% in Dimethylformamid) von 50 bis 120 ml/g, besonders bevorzugt 52 bis 110 ml/g und insbesondere 55 bis 105 ml/g auf. Besonders bevorzugt handelt es sich um ein Styro Acrylnitril-Copolymerisat. Derartige Copolymerisate erhält man in bekannter Weise durch Masse-, Lösungs-, Suspensions-, Fällungs- oder Emulsionspolymerisation, wobei Masse- und 20 Lösungspolymerisation bevorzugt sind. Einzelheiten dieser Verfahren sind beispielsweise im Kunststoffhandbuch, Herausgeber R. Vieweg und G Daumiller, Band V "Polystyrol", Carl-Hanser- Verlag München 1969, Seite 118 ff. beschrieben.Component A preferably has a viscosity number VZ (determined according to DIN 15 53726 at 25 ° C., 0.5% by weight in dimethylformamide) of 50 to 120 ml / g, particularly preferably 52 to 110 ml / g and in particular 55 to 105 ml / g on. It is particularly preferably a styrene acrylonitrile copolymer. Such copolymers are obtained in a known manner by bulk, solution, suspension, precipitation or emulsion polymerization, bulk and solution polymerization being preferred. Details of these processes are described, for example, in the plastics handbook, edited by R. Vieweg and G Daumiller, volume V "Polystyrol", Carl-Hanser-Verlag Munich 1969, page 118 ff.
25 Komponente B25 component B
Komponente B ist ein Pfropfcopolymerisat mit einer kautschukelastischen teilchenförmigen Pfropfgrundlage mit einer Glasübergangstemperatur unter 0°C. Dabei kann die Pfropfgrundlage aus allen bekannten geeigneten kau- 30 tschukelastischen Polymeren ausgewählt sein. Vorzugsweise handelt es sich um ABS (Acrylnitril/Butadien/Styrol)-, ASA (Acrylnitril/Styrol/Alkylacrylat)-, EPDM-, Siloxan- oder andere Kautschuke.Component B is a graft copolymer with a rubber-elastic particulate graft base with a glass transition temperature below 0 ° C. The graft base can be selected from all known suitable chewing-elastic polymers. It is preferably ABS (acrylonitrile / butadiene / styrene), ASA (acrylonitrile / styrene / alkyl acrylate), EPDM, Siloxane or other rubbers.
Vorzugsweise ist Komponente Bl mindestens ein (Co)polymerisat ausComponent B1 is preferably at least one (co) polymer
bll: 60 bis 100 Gew.-%, vorzugsweise 70 bis 100 Gew.-% mindestens eines konjugierten Diens, Cι-ιo-Alkylacrylats oder Gemischen davon alsbll: 60 to 100 wt .-%, preferably 70 to 100 wt .-% of at least one conjugated diene, Cι-ιo-alkyl acrylate or mixtures thereof as
Komponente Bll, bl2: 0 bis 30 Gew.-%, vorzugsweise 0 bis 25 Gew.-% mindestens eines vonComponent B1, bl2: 0 to 30% by weight, preferably 0 to 25% by weight, of at least one of
Komponente Bll verschiedenen monoethylenisch ungesättigten Monomeren als Komponente B 12 und bl3: 0 bis 10 Gew.-%, vorzugsweise 0 bis 6 Gew.-% mindestens eines vernetzenden Monomeren als Komponente B13.Component B1 different monoethylenically unsaturated monomers as component B 12 and b1: 0 to 10% by weight, preferably 0 to 6% by weight, of at least one crosslinking monomer as component B13.
Als konjugierte Diene Bll kommen insbesondere Butadien, Isopren, Chloropren oder Gemische davon wie auch die nachstehend aufgeführten Ci-io-Alkylacrylate und Gemische davon in Betracht. Bevorzugt verwendet man Butadien oder Isopren oder deren Gemische, speziell Butadien oder n-Butylacrylat.As conjugated dienes B1, in particular butadiene, isoprene, chloroprene or mixtures thereof as well as the Ci-io-alkyl acrylates listed below and mixtures thereof come into consideration. Butadiene or isoprene or mixtures thereof, especially butadiene or n-butyl acrylate, are preferably used.
Gegebenenfalls können als Komponente B12 Monomere enthalten sein, die die mechanischen und thermischen Eigenschaften des Kerns in einem gewissen Bereich variieren. Als Beispiele derartiger monoethylenisch ungesättigter Comonomere können Styrol, substituierte Styrole, Acrylnitril, Methacrylnitril, Acrylsäure,Optionally, component B12 may contain monomers which vary the mechanical and thermal properties of the core within a certain range. Examples of such monoethylenically unsaturated comonomers are styrene, substituted styrenes, acrylonitrile, methacrylonitrile, acrylic acid,
Methacrylsäure, Dicarbonsäuren wie Maleinsäure und Fumarsäure sowie derenMethacrylic acid, dicarboxylic acids such as maleic acid and fumaric acid and their
Anhydride wie Maleinsäureanhydrid, Stickstoff-funktionelle Monomere wie Dimethylaminoethylacrylat, Diethylaminoethylacrylat, Vinylimidazol,Anhydrides such as maleic anhydride, nitrogen-functional monomers such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, vinylimidazole,
Vinylpyrrolidon, Vinylcaprolactam, Vinylcarbazol, Vinylanilin, Acryl- amid, Cι-ιo-Alkylester der Acrylsäure wie Methylacrylat, Ethylacrylat, n-Vinyl pyrrolidone, vinyl caprolactam, vinyl carbazole, vinyl aniline, acrylic amide, Cι-ιo-alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-
Propylacrylat, i-Propylacrylat, n-Butylacrylat, Isobutylacrylat, sec.Butylacrylat, tert.-Propyl acrylate, i-propyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert.-
Butylacrylat, Ethylhexylacrylat, die entsprechenden C1-10-Alkylester der Methacrylsäure sowie Hydroxyethylacrylat, aromatische und araliphatische Ester derButyl acrylate, ethylhexyl acrylate, the corresponding C 1-10 alkyl esters of methacrylic acid and hydroxyethyl acrylate, aromatic and araliphatic esters of
Acrylsäure und Methacrylsäure wie Phenylacrylat, Phenylmethacrylat, Benzylacrylat, Benzylmethacrylat, 2-Phenylethylacrylat, 2-Phenylethylmethacrylat, 2-Phenoxyethylacrylat sowie 2-Phenoxyethylmethacrylat, N-substituierte Maleinimide wie N-Methyl-, N-Phenyl- und N-Cyclohexylmaleinimid, ungesättigte Ether wie Vinylmethylether sowie Gemische davon genannt werden.Acrylic acid and methacrylic acid such as phenyl acrylate, phenyl methacrylate, Benzyl acrylate, benzyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, 2-phenoxyethyl acrylate and 2-phenoxyethyl methacrylate, N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexylmaleimide, unsaturated ethers such as vinyl methyl ether and mixtures thereof.
Bevorzugt werden Styrol, α-Methylstyrol, n-Butylacrylat, Methylmethacrylat oder deren Gemische als Komponente B12 eingesetzt, insbesondere Styrol und n- Butylacrylat oder deren Gemische, speziell Styrol. Sofern eine Komponente B12, jedoch keine Komponente B13 eingesetzt wird, beträgt der Anteil der Komponente Bll vorzugsweise 70 bis 99,9, besonders bevorzugt 90 bis 99 Gew.-% und der Anteil der Komponente B12 0,1 bis 30, besonders bevorzugt 1 bis 10 Gew.-%. Besonders bevorzugt sind Butadien/Styrol-und n-Butylacrylat Styrol-Copolymere in dem angegebenen Mengenbereich.Styrene, α-methylstyrene, n-butyl acrylate, methyl methacrylate or mixtures thereof are preferably used as component B12, in particular styrene and n-butyl acrylate or mixtures thereof, especially styrene. If a component B12 but no component B13 is used, the proportion of component B1 is preferably 70 to 99.9, particularly preferably 90 to 99% by weight and the proportion of component B12 0.1 to 30, particularly preferably 1 to 10% by weight. Butadiene / styrene and n-butyl acrylate styrene copolymers in the stated amount range are particularly preferred.
Beispiele für vernetzende Monomere der Komponente B13 sind Divinylver- bindungen wie Divinylbenzol, Diallylverbindungen wie Diallylmaleat, Allyl- ester der Acryl- und Methacrylsäure, Dihydrodicyclopentadienylacrylat (DCPA), Divinylester von Dicarbonsäuren wie der Bernsteinsäure und Adipinsäure, Diallyl- und Divinylether bifunktioneller Alkohole wie des Ethylenglykols und Butan- 1,4- diols.Examples of crosslinking monomers of component B13 are divinyl compounds such as divinylbenzene, diallyl compounds such as diallyl maleate, allyl esters of acrylic and methacrylic acid, dihydrodicyclopentadienyl acrylate (DCPA), divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl deseller and divinyl alcohol and butane-1,4-diols.
Die Pfropfauflage B2 ist vorzugsweise ein Styrol/ Acrylnitril-Copolymerisat.The graft B2 is preferably a styrene / acrylonitrile copolymer.
Üblicherweise werden die Pfropfcopolymerisate B nach dem Verfahren der Emulsionspolymerisation hergestellt. Dabei polymerisiert man in der Regel bei einer Temperatur von 20 bis 100, bevorzugt 30 bis 80°C. Häufig werden übliche Emulgatoren mitverwendet, beispielsweise Alkalimetallsalze von Alkyl- oder Alkylarylsulfonsäuren, Alkylsulfate, Fettalkoholsulfonate, Salze höherer Fettsäuren mit 10 bis 30 Kohlenstoffatomen, Sulfosuccinate, Ethersulfonate oder Harzseifen. Vorzugsweise verwendet man die Alkalimetallsalze, insbesondere die Natrium- oder Kaliumsalze von Alkylsulfonaten oder Fettsäuren mit 10 bis 18 Kohlenstoffatomen. In der Regel werden die Emulgatoren in Mengen von 0,5 bis 5 Gew.-%, insbesondere von 0,5 bis 3 Gew.-%, bezogen auf die bei der Herstellung der Pfropfgrundlage eingesetzten Monomere, eingesetzt.The graft copolymers B are usually prepared by the emulsion polymerization process. Polymerization is generally carried out at a temperature of 20 to 100, preferably 30 to 80 ° C. Common emulsifiers are often used, for example alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms, sulfosuccinates, ether sulfonates or resin soaps. The alkali metal salts, in particular the sodium or potassium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms, are preferably used. As a rule, the emulsifiers are used in amounts of 0.5 to 5% by weight, in particular 0.5 to 3% by weight, based on the monomers used in the preparation of the graft base.
Vorzugsweise verwendet man zur Herstellung der Dispersion soviel Wasser, daß die fertige Dispersion einen Feststoffgehalt von 20 bis 50 Gew.-% aufweist. Üblicherweise wird bei einem Wasser/Monomeren- Verhältnis von 2:1 bis 0,7:1 gearbeitet.Sufficient water is preferably used to prepare the dispersion so that the finished dispersion has a solids content of 20 to 50% by weight. Usually a water / monomer ratio of 2: 1 to 0.7: 1 is used.
Zum Starten der Polymerisationsreaktion sind alle Radikalbildner geeignet, die bei der gewählten Reaktionstemperatur zerfallen, also sowohl solche, die allein thermisch zerfallen, als auch solche, die dies in Gegenwart eines Redox-Systems tun. Als Polymerisationsinitiatoren kommen vorzugsweise Radikalbildner, beispielsweise Peroxide wie bevorzugt Peroxosulfate (etwa Natrium- oder Kaliumpersulfat) und Azoverbindungen wie Azodiisobutyronitril in Betracht. Es können jedoch auch Redox-Systeme, insbesondere solche auf Basis von Hydroperoxiden wie Cumolhydroperoxid, eingesetzt werden.All radical formers which decompose at the selected reaction temperature are suitable for starting the polymerization reaction, that is to say both those which decompose thermally on their own and those which do so in the presence of a redox system. Free radical formers, for example peroxides such as preferably peroxosulfates (for example sodium or potassium persulfate) and azo compounds such as azodiisobutyronitrile are preferably suitable as polymerization initiators. However, redox systems, in particular those based on hydroperoxides such as cumene hydroperoxide, can also be used.
In der Regel werden die Polymerisationsinitiatoren in einer Menge von 0,1 bis 1 Gew.-%, bezogen auf die Pfropfgrundlage-Monomeren, eingesetzt.As a rule, the polymerization initiators are used in an amount of 0.1 to 1% by weight, based on the graft base monomers.
Die Radikalbildner und auch die Emulgatoren werden dem Reaktionsansatz beispielsweise diskontinuierlich als Gesamtmenge zu Beginn der Reaktion, oder aufgeteilt in mehrere Portionen absatzweise zu Beginn und zu einem oder mehreren späteren Zeitpunkten zugefügt, oder kontinuierlich während eines bestimmten Zeitintervalls zugefügt. Die kontinuierliche Zugabe kann auch entlang eines Gradienten erfolgen, der z.B. auf- oder absteigend, linear oder exponentiell, oder auch stufenweise (Treppenfunktion) sein kann.The radical formers and also the emulsifiers are added to the reaction batch, for example discontinuously as a total amount at the beginning of the reaction, or divided into several portions, batchwise at the beginning and at one or more later times, or continuously during a certain time interval. The continuous addition can also take place along a gradient, e.g. can be ascending or descending, linear or exponential, or also stepwise (stair function).
Ferner kann man Molekulargewichtsregler wie Ethylhexylthioglycolat, n- oder t- Dodecylmercaptan oder andere Mercaptane, Terpinole und dimeres Methylstyrol oder andere zur Regelung des Molekulargewichts geeignete Verbindungen mitverwenden. Die Molekulargewichtsregler werden dem Reaktionsansatz diskontinuierlich oder kontinuierlich zugefügt, wie dies für die Radikalbildner und Emulgatoren zuvor beschrieben wurde.Molecular weight regulators such as ethylhexylthioglycolate, n- or t- Use dodecyl mercaptan or other mercaptans, terpinols and dimeric methylstyrene or other compounds suitable for regulating the molecular weight. The molecular weight regulators are added batchwise or continuously to the reaction mixture, as was described above for the radical formers and emulsifiers.
Zur Einhaltung eines konstant bleibenden pH-Wertes, der vorzugsweise bei 6 bis 9 liegt, kann man Puffersubstanzen wie Na2HPO4/NaH2PO4, Natrium- hydrogencarbonat oder Puffer auf Basis Citronensäure/Citrat, mitverwenden. Regler und Puffersubstanzen werden in den üblichen Mengen eingesetzt, so daß sich nähere Angaben hierzu erübrigen.To maintain a constant pH, which is preferably 6 to 9, buffer substances such as Na 2 HPO 4 / NaH 2 PO 4 , sodium hydrogen carbonate or buffer based on citric acid / citrate can also be used. Regulators and buffer substances are used in the usual quantities, so that further details are not necessary.
Man kann die Pfropfgrundlage in einer besonderen Ausfuhrungsform auch durch Polymerisation der Monomeren Bl in Gegenwart eines feinteiligen Latex herstellen (sog. "Saatlatex-Fahrweise" der Polymerisation). Dieser Latex wird vorgelegt und kann aus kautschukelastische Polymere bildenden Monomeren, oder auch aus anderen Monomeren, wie sie bereits genannt wurden, bestehen. Geeignete Saatlatices bestehen beispielsweise aus Polybutadien oder Polystyrol.In a special embodiment, the graft base can also be produced by polymerizing the monomers B1 in the presence of a finely divided latex (so-called "seed latex mode of operation" of the polymerization). This latex is introduced and can consist of monomers forming rubber-elastic polymers, or also of other monomers, as already mentioned. Suitable seed latices consist, for example, of polybutadiene or polystyrene.
In einer anderen bevorzugten Ausführungsform kann man die Pfropfgrundlage Bl im sogenannten Zulaufverfahren herstellen. Bei diesem Verfahren wird ein bestimmter Anteil der Monomeren vorgelegt und die Polymerisation gestartet, wonach man den Rest der Monomeren ("Zulaufanteil") Bl als Zulauf während der Polymerisation zufügt. Die Zulaufparameter (Gestalt des Gradienten, Menge, Dauer, etc.) hängen von den anderen Polymerisationsbedingungen ab. Sinngemäß gelten auch hier die zur Zugabeweise des Radikalstartes bzw. Emulgators gemachten Ausführungen.In another preferred embodiment, the graft base B1 can be produced in the so-called feed process. In this process, a certain proportion of the monomers is introduced and the polymerization is started, after which the remainder of the monomers (“feed fraction”) B1 are added as feed during the polymerization. The feed parameters (shape of the gradient, amount, duration, etc.) depend on the other polymerization conditions. The statements made regarding the addition of the radical start or emulsifier also apply here analogously.
Weiterhin eigenen sich auch Pfropfpolymerisate mit mehreren "weichen" und "harten" Schalen. Die genauen Polymerisationsbedingungen, insbesondere Art, Menge und Dosierung des Emulgators und der anderen Polymerisationshilfsstoffe werden bevorzugt so gewählt, daß der erhaltene Latex des Pfropfpolymerisates B eine mittlere Teilchengröße, definiert durch den d5o-Wert der Teilchengrößenverteilung, von 80 bis 800 um, bevorzugt 80 bis 600 nm und besonders bevorzugt 85 bis 400 nm aufweist.Graft polymers with several "soft" and "hard" shells are also suitable. The precise polymerization conditions, in particular the type, quantity and dosage of will emulsifier and of the other polymerization auxiliaries preferably selected so that the latex of the graft polymer B obtained has a mean particle size, defined by the d 5 o of the particle size, from 80 to 800 microns, preferably 80 to 600 nm and particularly preferably 85 to 400 nm.
Gemäß einer Ausfuhrungsform der Erfindung stimmt man die Reaktionsbedingungen so aufeinander ab, daß die Polymerisat-Teilchen eine bimodale Teilchengrößenverteilung aufweisen, also eine Größenverteilung mit zwei mehr oder weniger ausgeprägten Maxima.According to one embodiment of the invention, the reaction conditions are coordinated with one another in such a way that the polymer particles have a bimodal particle size distribution, that is to say a size distribution with two more or less pronounced maxima.
Bevorzugt wird die bimodale Teilchengrößenverteilung durch eine (teilweise) Agglomeration der Polymerteilchen erzielt. Dazu kann beispielsweise wie folgt vorgegangen werden: Man polymerisiert die Monomeren, welche den Kern aufbauen, bis zu einem Umsatz von üblicherweise mindestens 90, bevorzugt größer 95 %, bezogen auf die eingesetzten Monomeren. Dieser Umsatz ist in der Regel nach 4 bis 20 Stunden erreicht. Der erhaltene Kautschuklatex hat eine mittlere Teilchengröße d50 von maximal 200 nm und eine enge Teilchengrößenverteilung (nahezu monodisperses System).The bimodal particle size distribution is preferably achieved by a (partial) agglomeration of the polymer particles. This can be done, for example, as follows: The monomers which form the core are polymerized up to a conversion of usually at least 90%, preferably greater than 95%, based on the monomers used. This turnover is usually reached after 4 to 20 hours. The rubber latex obtained has an average particle size d 50 of at most 200 nm and a narrow particle size distribution (almost monodisperse system).
In der zweiten Stufe wird der Kautschuklatex agglomeriert. Dies geschieht in der Regel durch Zugabe einer Dispersion eines Acrylesterpoiymerisates. Vorzugsweise werden Dispersionen von Copolymerisaten von (Cι-C4-Alkyl)estern der Acrylsäure, vorzugsweise von Ethylacrylat, mit 0,1 bis 10 Gew.-% polare Polymerisate bildenden Monomeren, wie Acrylsäure, Methacrylsäure, Acrylamid oder Methacrylamid, N-Methylolmethacrylarnid oder N- Vinylpyrrolidon, eingesetzt. Besonders bevorzugt ist ein Copolymerisat aus 96 % Ethylacrylat und 4 % Methacrylamid. Die Agglomerierdispersion kann gegebenenfalls auch mehrere der genannten Acrylesterpolymerisate enthalten. Die Konzentration der Acrylesterpolymerisate in der zur Agglomeration verwendeten Dispersion soll im allgemeinen zwischen 3 und 40 Gew.-% liegen. Bei der Agglomeration werden 0,2 bis 20, vorzugsweise 1 bis 5 Gew.-Teile der Agglomerierdispersion auf 100 Teile des Kautschuklatex, jeweils berechnet auf Feststoffe, eingesetzt. Die Agglomeration wird durch Zugabe der Agglomerierdispersion zum Kautschuk durchgeführt. Die Geschwindigkeit der Zugabe ist normalerweise nicht kritisch, im allgemeinen dauert sie etwa 1 bis 30 Minuten bei einer Temperatur zwischen 20 und 90°C, vorzugsweise zwischen 30 und 75°C.In the second stage, the rubber latex is agglomerated. This is usually done by adding a dispersion of an acrylic ester polymer. Dispersions of copolymers of (C 1 -C 4 -alkyl) esters of acrylic acid, preferably of ethyl acrylate, with 0.1 to 10% by weight of monomers forming polar polymers, such as acrylic acid, methacrylic acid, acrylamide or methacrylamide, N-methylol methacrylamide or N-vinyl pyrrolidone used. A copolymer of 96% ethyl acrylate and 4% methacrylamide is particularly preferred. The agglomerating dispersion can optionally also contain several of the acrylic ester polymers mentioned. The concentration of the acrylic ester polymers in the dispersion used for agglomeration should generally be between 3 and 40% by weight. In the agglomeration, 0.2 to 20, preferably 1 to 5 parts by weight of the agglomeration dispersion per 100 parts of the rubber latex, in each case calculated on solids, are used. The agglomeration is carried out by adding the agglomerating dispersion to the rubber. The rate of addition is normally not critical, generally it takes about 1 to 30 minutes at a temperature between 20 and 90 ° C, preferably between 30 and 75 ° C.
Außer mittels einer Acrylesterpolymerisat-Dispersion kann der Kautschuklatex auch durch andere Agglomeriermittel wie Essigsäureanhydrid agglomeriert werden. Auch eine Agglomeration durch Druck oder Einfrieren (Druck- bzw. Gefrieragglomeration) ist möglich. Die genannten Methoden sind dem Fachmann bekannt.In addition to an acrylic polymer dispersion, the rubber latex can also be agglomerated by other agglomerating agents such as acetic anhydride. Agglomeration by pressure or freezing (pressure or freeze agglomeration) is also possible. The methods mentioned are known to the person skilled in the art.
Unter den genannten Bedingungen wird nur ein Teil der Kautschukteilchen agglomeriert, so daß eine bimodale Verteilung entsteht. Dabei liegen nach der Agglomeration im allgemeinen mehr als 50, vorzugsweise zwischen 75 und 95 % der Teilchen (Zahlen-Verteilung) im nicht agglomerierten Zustand vor. Der erhaltene teilagglomerierte Kautschuklatex ist verhältnismäßig stabil, so daß er ohne weiteres gelagert und transportiert werden kann, ohne daß Koagulation eintritt.Under the conditions mentioned, only a part of the rubber particles is agglomerated, so that a bimodal distribution is produced. After agglomeration there are generally more than 50, preferably between 75 and 95% of the particles (number distribution) in the non-agglomerated state. The partially agglomerated rubber latex obtained is relatively stable, so that it can be easily stored and transported without coagulation occurring.
Um eine bimodale Teilchengrößenverteilung des Pfropfpolymerisates B zu erzielen, ist es auch möglich, zwei verschiedene Pfropfpolymerisate B' und B", die sich in ihrer mittleren Teilchengröße unterscheiden, getrennt voneinander in üblicher Weise herzustellen und die Pfropfpolymerisate B' und B" im gewünschten Mengenverhältnis zusammenzugeben.In order to achieve a bimodal particle size distribution of the graft polymer B, it is also possible to prepare two different graft polymers B 'and B ", which differ in their average particle size, separately from one another in the customary manner and to combine the graft polymers B' and B" in the desired quantitative ratio .
Die Herstellung der Pfropfauflage B2 kann unter den gleichen Bedingungen wie die Herstellung der Pfropfgrundlage Bl erfolgen, wobei man die Auflage B2 in einem oder mehreren Verfahrensschritten herstellen kann. Beispielsweise kann man bei einer zweistufigen Pfropfung zunächst Styrol bzw. α-Methylstyrol alleine und danach Styrol und Acrylnitril in zwei aufeinander folgenden Schritten polymerisieren. Diese zweistufige Pfropfung (zunächst Styrol, dann Styrol/ Acrylnitril) ist eine bevorzugte Ausführungsform. Weitere Einzelheiten zur Herstellung der Pfropfpolymerisate B sind in den DE-A 12 60 135 und 31 49 358 sowie EP-A-0 735 063 beschrieben.The graft B2 can be produced under the same conditions as the preparation of the graft base B1, the B2 being able to be produced in one or more process steps. For example, at In a two-stage grafting process, polymerize styrene or α-methylstyrene alone and then styrene and acrylonitrile in two successive steps. This two-stage grafting (first styrene, then styrene / acrylonitrile) is a preferred embodiment. Further details on the preparation of the graft polymers B are described in DE-A 12 60 135 and 31 49 358 and EP-A-0 735 063.
Es ist vorteilhaft, die Pfropfpolymerisation auf die Pfropfgrundlage Bl wiederum in wäßriger Emulsion durchzuführen. Sie kann im gleichen System wie die Polymerisation der Pfropfgrundlage vorgenommen werden, wobei weiter Emulgator und Initiator zugegeben werden kann. Diese müssen mit den zur Herstellung der Pfropfgrundlage Bl verwendeten Emulgatoren bzw. Initiatoren nicht identisch sein. So kann es z.B. zweckmäßig sein, als Initiator für die Herstellung der Pfropfgrundlage Bl ein Persulfat zu verwenden, zur Polymerisation der Pfropfhülle B2 jedoch ein Redoxinitiatorsystem einzusetzen. Im übrigen gilt für die Wahl von Emulgator, Initiator und Polymerisationshilfsstoffen das bei der Herstellung der Pfropfgrundlage Bl Gesagte. Das aufzupfropfende Monomerengemisch kann dem Reaktionsgemisch auf einmal, absatzweise in mehreren Stufen oder vorzugsweise kontinuierlich während der Polymerisation zugegeben werden.It is advantageous to carry out the graft polymerization on the graft base B1 again in an aqueous emulsion. It can be carried out in the same system as the polymerization of the graft base, and further emulsifier and initiator can be added. These need not be identical to the emulsifiers or initiators used to prepare the graft base B1. For example, it may be expedient to use a persulfate as the initiator for the preparation of the graft base B1, but to use a redox initiator system for the polymerization of the graft shell B2. For the rest, what has been said for the preparation of the graft base B1 applies to the choice of emulsifier, initiator and polymerization auxiliaries. The monomer mixture to be grafted on can be added to the reaction mixture all at once, batchwise in several stages or, preferably, continuously during the polymerization.
Soweit bei der Pfropfung der Pfropfgrundlage Bl nicht gepfropfte Polymere aus den Monomeren B2 entstehen, werden die Mengen, die in der Regel unter 10 Gew.-% von B2 liegen, der Masse der Komponente B zugeordnet.If, when the graft base B1 is grafted, non-grafted polymers are formed from the monomers B2, the amounts which are generally below 10% by weight of B2 are assigned to the mass of component B.
Komponente CComponent C
Die Herstellung der erfindungsgemäß eingesetzten Dreiblockcopolymere der Formel X-Y-X kann in an sich bekannter Weise (N. Schönfeldt, grenzflächenaktive Ethylenoxid-Addukte, wissenschaftliche Verlagsgesellschaft mbH Stuttgart, 1976, Seite 53 ff) durch Polymerisation erfolgen, wobei zunächst ein mittelständiger Polypropylenoxidblock Y hergestellt wird, an dessen beiden Enden je ein Block aus Ethylenoxideinheiten angelagert wird. Bei dem vorstehend angegebenen Molekulargewichten handelt es sich in der Regel um die mittleren Molekulargewichte (Zahlenmittel Mn, beispielsweise bestimmt aus der OH-Zahl nach DIN 53240).The three-block copolymers of the formula XYX used according to the invention can be prepared in a manner known per se (N. Schönfeldt, surface-active ethylene oxide adducts, scientific publishing company mbH Stuttgart, 1976, page 53 ff) by polymerization, initially producing a medium-sized polypropylene oxide block Y. one end of each block Ethylene oxide units is attached. The molecular weights given above are generally the average molecular weights (number average M n , for example determined from the OH number according to DIN 53240).
Bevorzugte Dreiblockcopolymere und deren Herstellung sind auch in EP-A-0 125 801 und EP-A-0 018 591 beschrieben.Preferred three-block copolymers and their preparation are also described in EP-A-0 125 801 and EP-A-0 018 591.
Komponente DComponent D
Als Komponente D können weitere übliche Hilfs- und Füllstoffe eingesetzt werden. Derartige Stoffe sind beispielsweise Gleit- oder Entformungsmittel, Wachse, Pigmente, Farbstoffe, Flammschutzmittel, Antioxidantien, Stabilisatoren gegen Lichteinwirkung, faser- und pulverformige Füll- oder Verstärkungsmittel oder Antistatika, sowie andere Zusatzstoffe, oder deren Mischungen.Further conventional auxiliaries and fillers can be used as component D. Such substances are, for example, lubricants or mold release agents, waxes, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers or reinforcing agents or antistatic agents, and also other additives or mixtures thereof.
Geeignete Gleit- und Entformungsmittel sind z.B. Stearinsäuren, Stearylalkohol, Stearinsäureester oder -amide sowie Siliconöle, Montanwachse und Wachse auf Basis von Polyethylen und Polypropylen.Suitable lubricants and mold release agents are e.g. Stearic acids, stearyl alcohol, stearic acid esters or amides as well as silicone oils, montan waxes and waxes based on polyethylene and polypropylene.
Pigmente sind beispielsweise Titandioxid, Phthalocyanine, Ultramarinblau, Eisenoxide oder Ruß, sowie die gesamte Klasse der organischen Pigmente.Pigments are, for example, titanium dioxide, phthalocyanines, ultramarine blue, iron oxides or carbon black, as well as the entire class of organic pigments.
Unter Farbstoffen sind alle Farbstoffe zu verstehen, die zur transparenten, halbtransparenten oder nichttransparenten Entfärbung von Polymeren verwendet werden können, insbesondere solche, die zur Einfärbung von Styrolcopolymeren geeignet sind. Derartige Farbstoffe sind dem Fachmann bekannt.Dyes are to be understood as all dyes which can be used for the transparent, semi-transparent or non-transparent decolorization of polymers, in particular those which are suitable for coloring styrene copolymers. Dyes of this type are known to the person skilled in the art.
Als Flammschutzmittel können z.B. die dem Fachmann bekannten halogenhaltigen oder phosphorhaltigen Verbindungen, Magnesiumhydroxid, sowie andere gebräuchliche Verbindungen oder deren Mischungen verwendet werden. Ebenso ist roter Phosphor geeignet.Flame retardants which can be used are, for example, the halogen-containing or phosphorus-containing compounds known to the person skilled in the art, magnesium hydroxide and other customary compounds or mixtures thereof. Likewise red phosphorus suitable.
Geeignete Antioxidantien sind insbesondere sterisch gehinderte einkernige oder mehrkernige phenolische Antioxidantien, die auf verschiedene Weise substituiert und auch über Substituenten verbrückt sein können. Hierzu zählen neben monomeren auch oligomere Verbindungen, die aus mehreren phenolischen Grundkörpern aufgebaut sein können. Ferner kommen Hydrochinone und Hydrochinonanaloge und substituierte Verbindungen in Betracht, ebenso Antioxidantien auf Basis von Tocopherolen und deren Derivaten. Auch Mischungen verschiedener Antioxidantien können verwendet werden. Prinzipiell können alle handelsüblichen oder für Styrolcopolymere geeigneten Verbindungen eingesetzt werden, etwa Topanol® oder Irganox®.Suitable antioxidants are, in particular, sterically hindered mononuclear or multinuclear phenolic antioxidants, which can be substituted in various ways and can also be bridged via substituents. In addition to monomers, this also includes oligomeric compounds, which can be made up of several phenolic base bodies. Hydroquinones and hydroquinone analogs and substituted compounds are also suitable, as are antioxidants based on tocopherols and their derivatives. Mixtures of different antioxidants can also be used. In principle, all commercially available compounds or compounds suitable for styrene copolymers can be used, such as Topanol® or Irganox®.
Zusammen mit den zuvor beispielhaft genannten phenolischen Antioxidantien können sogenannte Costabilisatoren mitverwendet werden, insbesondere phosphor- oder schwefelhaltige Costabilisatoren. Solche P- oder S-haltigen Costabilisatoren sind dem Fachmann bekannt und handelsüblich.So-called costabilizers, in particular phosphorus or sulfur-containing costabilizers, can also be used together with the phenolic antioxidants mentioned above by way of example. Such P- or S-containing costabilizers are known to the person skilled in the art and are commercially available.
Geeignete Stabilisatoren gegen Lichteinwirkung sind z.B. verschiedene substituierte Resorcine, Salicylate, Benzotriazole, Benzophenone, HALS (Hindered Amine Light Stabilizers), wie sie z.B. als Tinuvin kommerziell erhältlich sind.Suitable light stabilizers are e.g. various substituted resorcinols, salicylates, benzotriazoles, benzophenones, HALS (hindered amine light stabilizers), such as those e.g. are commercially available as Tinuvin.
Als Beispiele für faserförmige bzw. pulverformige Füllstoffe seien Kohlenstoffoder Glasfasern in Form von Glasgeweben, Glasmatten oder Glasseidenrovings, Schnittglas, Glaskugeln sowie WoUastonit genannt, besonders bevorzugt Glasfasern. Bei der Verwendung von Glasfasern können diese zur besseren Verträglichkeit mit den Blendkomponenten mit einer Schlichte und einem Haftvermittler ausgerüstet sein. Die Einarbeitung der Glasfasern kann sowohl in Form von Kurzglasfasern als auch in Form von Endlossträngen (Rovings) erfolgen.Examples of fibrous or powdered fillers are carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, cut glass, glass balls and WoUastonit, particularly preferably glass fibers. If glass fibers are used, they can be equipped with a size and an adhesion promoter for better compatibility with the blend components. The glass fibers can be incorporated both in the form of short glass fibers and in the form of endless strands (rovings).
Als teilchenförmige Füllstoffe eignen sich Ruß, amorphe Kieselsäure, Magne- siumcarbonat (Kreide), gepulverter Quarz, Glimmer, Mica, Bentonite, Talkum, Feldspat oder insbesondere Calciumsilikate wie WoUastonit und Kaolin.Carbon black, amorphous silica, magnesia are suitable as particulate fillers. sium carbonate (chalk), powdered quartz, mica, mica, bentonite, talc, feldspar or in particular calcium silicates such as WoUastonit and kaolin.
Die einzelnen Zusatzstoffe werden in den jeweils üblichen Mengen verwendet, so daß sich nähere Angaben hierzu erübrigen.The individual additives are used in the usual amounts, so that further details are unnecessary.
Herstellung der FormmassenProduction of molding compounds
Die Herstellung der Formmassen erfolgt vorzugsweise durch separates Herstellen der einzelnen Komponenten A bis C und gegebenenfalls D und nachfolgendes Vermischen der Komponenten.The molding compositions are preferably produced by producing the individual components A to C and, if appropriate, D separately and then mixing the components.
Geeignete Verfahren zur Herstellung der Formmassen sind beispielsweise in EP-A-0 135 801, EP-B-0 018 591 und insbesondere DE-A-197 28 628 beschrieben.Suitable processes for producing the molding compositions are described, for example, in EP-A-0 135 801, EP-B-0 018 591 and in particular DE-A-197 28 628.
Die erfindungsgemäßen Formmassen können zur Herstellung von Formkörpern, Fasern oder Folien verwendet werden. Derartige Verfahren zur Herstellung von Formkörpern, Fasern oder Folien sind in den angegebenen Druckschriften aufgeführt.The molding compositions according to the invention can be used for the production of moldings, fibers or films. Such processes for the production of moldings, fibers or films are listed in the specified publications.
Die Erfindung wird nachstehend anhand von Beispielen näher erläutert. The invention is explained in more detail below with the aid of examples.
BeispieleExamples
1. Herstellung des Pfropfpolymerisates B1. Preparation of the graft polymer B
1.1. Herstellung der Pf ropf grundlage B 11.1. Preparation of the graft base B 1
43120 g der in Tabelle 1 angegebenen Monomerenmischung werden in Gegenwart von 432 g tert.-Dodecylmercaptan (TDM), 311 g Kaliumsalz von Cι2-C2o- Fettsäuren, 82 g Kaliumpersulfat, 147 g Natriumhydrogencarbonat und 58400 g Wasser bei 65°C zu einem Polybutadienlatex polymerisiert. Im einzelnen wurde verfahren wie in der EP-A-0 062 901, Bsp. 1, S. 9, Z. 20 - S. 10, Z. 6 beschrieben. Der Umsatz betrug 95 % oder darüber. Die mittlere Teilchengröße d50 des Latex betrug 80 bis 120 nm.43120 g of the monomer mixture specified in Table 1 are in the presence of 432 g of tert-dodecyl mercaptan (TDM), 311 g of potassium salt of C 2 -C 2 o-fatty acids, 82 g of potassium persulfate, 147 g of sodium hydrogen carbonate and 58400 g of water at 65 ° C polymerized to a polybutadiene latex. In detail, the procedure was as described in EP-A-0 062 901, Example 1, page 9, line 20 - page 10, line 6. The conversion was 95% or more. The average particle size d 50 of the latex was 80 to 120 nm.
Zur Agglomeration des Latex wurden 35000 g des erhaltenen Latex bei 65°C durch Zugabe von 2700 g einer Dispersion (Feststoffgehalt 10 Gew.-%) aus 96 Gew.-% Ethylacrylat und 4 Gew.-% Methacrylsäureamid agglomeriert (partielle Agglomeration).To agglomerate the latex, 35000 g of the latex obtained were agglomerated at 65 ° C. by adding 2700 g of a dispersion (solids content 10% by weight) composed of 96% by weight of ethyl acrylate and 4% by weight of methacrylic acid amide (partial agglomeration).
Bei Verwendung eines n-Butylacrylat-Polymers als Pfropfgrundlage Bl wird wie in EP-A-0 735 063, Beispielen VI, V2, 14 V und 15 V vorgegangen.If an n-butyl acrylate polymer is used as the graft base B1, the procedure is as in EP-A-0 735 063, Examples VI, V2, 14 V and 15 V.
1.2. Herstellung der Pfropfauflage B21.2. Production of the graft B2
Dem agglomerierten Latex wurden 9000 g Wasser, 130 g Kaliumsalz von G2-C20- Fettsäuren und 17 g Kaliumperoxodisulfat zugefügt. Anschließend wurden die in Tabelle 2 angegebenen Monomerenmischungen bei 75°C innerhalb von 4 Stunden unter Rühren zugefügt. Der Umsatz, bezogen auf die Pfropfmonomeren, war nahezu quantitativ. Die erhaltene Pfropfpolymerisat-Dispersion mit bimodaler Teilchengrößenverteilung wies eine mittlere Teilchengröße d50 von 150 bis 350 nm und einen d9o-Wert von 400 bis 600 nm auf. Ein erstes Maximum der Teilchengrößenverteilung lag im Bereich 50 bis 150 nm, ein zweites Maximum im Bereich 200 bis 600 nm.9000 g of water, 130 g of potassium salt of G2-C20 fatty acids and 17 g of potassium peroxodisulfate were added to the agglomerated latex. The monomer mixtures given in Table 2 were then added at 75 ° C. over the course of 4 hours with stirring. The turnover, based on the graft monomers, was almost quantitative. The graft polymer dispersion obtained with a bimodal particle size distribution had an average particle size d 50 of 150 to 350 nm and a d 90 value of 400 to 600 nm. A first maximum of the particle size distribution was in the range of 50 to 150 nm, a second maximum in the range of 200 to 600 nm.
Die erhaltene Dispersion wurde mit einer wässrigen Dispersion eines Anti- oxidans versetzt und anschließend durch Zugabe einer Magnesiumsulfatlösung koaguliert. Der koagulierte Kautschuk wurde vom Dispersionswasser abzentrifugiert und mit Wasser gewaschen. Man erhielt einen Kautschuk mit ca. 30 Gew.-% anhaftendem bzw. eingeschlossenem Restwasser.The dispersion obtained was mixed with an aqueous dispersion of an antioxidant and then coagulated by adding a magnesium sulfate solution. The coagulated rubber was centrifuged off from the dispersion water and washed with water. A rubber with about 30% by weight of adhering or enclosed residual water was obtained.
Tabelle 1: Pfropfgrundlage BlTable 1: Graft base Bl
K2 wurde gemäß DE-A-31 49 358 erhalten.K2 was obtained according to DE-A-31 49 358.
Tabelle 2: Pfropf aufläge B2 und fertiges Pfropfpolymerisat BTable 2: Graft pads B2 and finished graft polymer B
2. Herstellung der Polymerisate A 2. Preparation of the polymers A
Die thermoplastischen Polymerisate A wurden nach dem Verfahren der kontinuierlichen Lösungspolymerisation hergestellt, wie es im Kunststoff- Handbuch, Hrg. R. Vieweg und G Daumiller, Band V "Polystyrol", Carl-Hanser- Verlag München 1969, S 122 - 124, beschrieben ist. Tabelle 3 faßt die Zusammensetzungen und Eigenschaften zusammen.The thermoplastic polymers A were prepared by the process of continuous solution polymerization, as described in the plastics handbook, ed. R. Vieweg and G Daumiller, volume V "Polystyrol", Carl-Hanser-Verlag Munich 1969, pp 122-124 . Table 3 summarizes the compositions and properties.
Tabelle 3: KomponentenTable 3: Components
3. Herstellung der Abmischungen aus Komponenten A und B3. Production of the blends from components A and B
Abmischung nach vorheriger Trocknung des Pfropfkautschuks BMixing after drying the graft rubber B
Der Restwasser enthaltende Pfropfkautschuk B wurde mit Warmluft im Vakuum getrocknet und mit der weiteren Komponente A in einem Extruder, Typ ZSK 30 von Werner und Pfleiderer, bei 250°C und 250 min-1 bei einem Durchsatz von 10 kg h innig vermischt. Die Formmasse wurde extrudiert und die schmelzflüssige Polymermischung wurde einer schnellen Abkühlung unterworfen, in dem sie in ein Wasserbad von 30°C eingeleitet wurde. Die erstarrte Formmasse wurde granuliert. 4. Durchgeführte MessungenThe graft rubber B containing residual water was dried with warm air in a vacuum and mixed intimately with the further component A in an extruder, type ZSK 30 from Werner and Pfleiderer, at 250 ° C. and 250 min −1 with a throughput of 10 kg h. The molding compound was extruded and the molten polymer mixture was subjected to rapid cooling by introducing it into a 30 ° C water bath. The solidified molding compound was granulated. 4. Measurements taken
Quellungsindex der Pfropfgrundlage Bl: Aus der wässrigen Dispersion der Pfropfgrundlage wurde durch Verdampfen des Wassers ein Film hergestellt. 0,2 g dieses Films wurden mit 50 g Toluol versetzt. Nach 24 Stunden wurde das Toluol von der aufgequollenen Probe abgesaugt und die Probe ausgewogen. Nach 16 Stunden Trocknen der Probe im Vakuum bei 110°C wurde erneut ausgewogen. Es wurden berechnet:Swelling index of the graft base B1: A film was produced from the aqueous dispersion of the graft base by evaporating the water. 0.2 g of this film was mixed with 50 g of toluene. After 24 hours the toluene was aspirated from the swollen sample and the sample weighed out. After drying the sample in vacuo at 110 ° C. for 16 hours, it was weighed out again. The following were calculated:
έ _Λ_--kA∞, ΛI Masse der aufgequollenen, abgesaugten Probeέ _ Λ _-- kA∞ , ΛI Mass of the swollen, aspirated sample
Masse der im Vakuum getrockneten ProbeMass of the sample dried in a vacuum
Masse der im Vakuum getrockneten ProbeMass of the sample dried in a vacuum
Seigehalt = .100 %Content of = = 100%
Einwaage der Probe vor der QuellungWeigh the sample before swelling
Teilchengrößen des Kautschuklatex:Particle sizes of the rubber latex:
Bei der Angabe der mittleren Teilchengröße d handelt es sich um das Gewichtsmittel der Teilchengröße, wie sie mittels einer analytischen Ultrazentrifuge entsprechend der Methode von W. Scholtan und H. Lange, Kolloid-Z. und Z.-Polymere 250 (1972) Seiten 782 bis 796, bestimmt wurden. Die Ultrazentrifugenmessung liefert die integrale Massenverteilung des Teilchendurchmessers einer Probe. Hieraus läßt sich entnehmen, wieviel Gewichtsprozent der Teilchen einen Durchmesser gleich oder kleiner einer bestimmten Größe haben.The average particle size d is the weight average of the particle size, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972) pages 782 to 796. The ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
Der dio-Wert gibt denjenigen Teilchendurchmesser an, bei dem 10 Gew.-% aller Teilchen einen kleineren und 90 Gew.-% einen größeren Durchmesser haben. Umgekehrt gilt für den d9o-Wert, daß 90 Gew.-% aller Teilchen einen kleineren und 10 Gew.-% einen größeren Durchmesser haben als derjenige Durchmesser, der dem d9o-Wert entspricht. Der gewichtsmittlere Teilchendurchmesser d5o bzw. vo lumenmittlere Teilchendurchmesser D50 gibt denjenigen Teilchendurchmesser an, bei dem 50 Gew.-% bzw. Vol.-% aller Teilchen einen größeren und 50 Gew.-% bzw. Völ.-% einen kleineren Teilchendurchmesser aufweisen, dio-, d50- und d9o- Wert charakterisieren die Breite Q der Teilchengrößenverteilung, wobei Q = (d9o- dι0)/dso. Je kleiner Q ist, desto enger ist die Verteilung.The dio value indicates the particle diameter in which 10% by weight of all particles have a smaller and 90% by weight a larger diameter. Conversely, for the d9o-value that 90 wt .-% of all particles have a smaller, and 10 wt .-% have a larger diameter than the diameter which corresponds to the d 9 o value. The weight average particle diameter d 5 o or Volume average particle diameter D 50 indicates the particle diameter at which 50% by weight or vol.% of all particles have a larger and 50% by weight or vol.% has a smaller particle diameter, dio-, d 50 - and d 9 o value characterize the width Q of the particle size distribution, where Q = (d9o-dι 0 ) / dso. The smaller Q is, the narrower the distribution.
Viskositätszahl VZ: sie wurde ermittelt nach DIN 53726 an einer 0,5 Gew.-%igen Lösung des Polymerisates in Dimethylformamid.Viscosity number VZ: it was determined according to DIN 53726 on a 0.5% by weight solution of the polymer in dimethylformamide.
Für die Bestimmung der folgenden mechanischen und Antistatik-Werte wurden aus dem Granulat der Formmassen durch Spritzguß Probekörper hergestellt, und zwar Norm-Kleinstäbe (siehe DIN 53453), Schulterstäbe, Rundscheiben von 60 mm Durchmesser und 2 mm Dicke bzw. Rechteckscheiben von 2 mm Dicke. Die Schmelzetemperatur betrug jeweils 250°C und die Formtemperatur jeweils 60°C, sofern nicht anders angegeben.For the determination of the following mechanical and antistatic values, test specimens were produced from the granules of the molding compounds, namely standard small bars (see DIN 53453), shoulder bars, round disks with a diameter of 60 mm and 2 mm or rectangular disks with a thickness of 2 mm . The melt temperature was 250 ° C. in each case and the mold temperature in each case 60 ° C., unless stated otherwise.
Vicat: die Wärmeformbeständigkeit nach Vicat wurde an Preßplättchen nach ISO 306/B mit einer Belastung von 50 N und einer Aufheizrate von 50 K/h bestimmt.Vicat: The heat resistance according to Vicat was determined on pressed platelets according to ISO 306 / B with a load of 50 N and a heating rate of 50 K / h.
ao: die Durchstoßarbeit aD wurde nach ISO 6603-2 an Rundscheiben oder Rechteckscheiben 40 x 40 mm durch den Plastechontest bei 23 °C bestimmt, wobei die Probekörper bei 250 Schmelztemperatur hergestellt wurden. ao: The penetration work aD was determined according to ISO 6603-2 on round disks or rectangular disks 40 x 40 mm by the plastic test at 23 ° C, whereby the test specimens were produced at 250 melting temperature.
Antistatisches Verhalten:Antistatic behavior:
1.) Staubkammerprüfung: In einer Staubkammer wird 10 sec lang der Staub aufgewirbelt. Grob anhängender Schmutz wird abgeblasen und die Staub- blumenbildung visuell beurteilt.1.) Dust chamber test: The dust is whirled up in a dust chamber for 10 seconds. Coarse dirt is blown off and the formation of stamen is assessed visually.
2.) an Rundscheiben (60 mm Durchmesser, 2mm Dicke) nach der Corona- Methode (in Anlehnung an DIN VDE 0303 T.3). E (15) ist vorhandene Restladung nach 15 min als Maß für die Wirksamkeit des Antistatikums.2.) on round disks (60 mm diameter, 2mm thickness) according to the Corona method (based on DIN VDE 0303 T.3). E (15) is the remaining charge after 15 min as a measure of the effectiveness of the antistatic.
Beispiel VI (Vergleich)Example VI (comparison)
Ein Gemisch aus 66 Gew.-% Komponente Aa und 34 Gew.-% Komponente Ba wurde bei 250°C extrudiert (ZSK 30, Werner & Pfeiderer), die Wärmeformbeständigkeit wurde bestimmt und das antistatische Verhalten in der Staubkammer geprüft. Die Ergebnisse sind in Tabelle 4 aufgeführt.A mixture of 66% by weight of component Aa and 34% by weight of component Ba was extruded at 250 ° C. (ZSK 30, Werner & Pfeiderer), the heat resistance was determined and the antistatic behavior in the dust chamber was checked. The results are shown in Table 4.
Beispiele V2 bis V8, 9, 10Examples V2 to V8, 9, 10
Ein Gemisch aus 66 Gew.-% Komponente Aa und 34 Gew.-% Komponente Ba wurde bei 250°C mit den in Tabelle 4 angegebenen Antistatika extrudiert (ZSK 30, Werner & Pfeiderer), die Wärmeformbeständigkeit wurde bestimmt und antistatische Verhalten in der Staubkammer geprüft. Die Ergebnisse sind in Tabelle 4 aufgeführt. Beispiel Vll (Vergleich)A mixture of 66% by weight of component Aa and 34% by weight of component Ba was extruded at 250 ° C. with the antistatic agents given in Table 4 (ZSK 30, Werner & Pfeiderer), the heat resistance was determined and antistatic behavior in the dust chamber checked. The results are shown in Table 4. Example Vll (comparison)
Ein Gemisch aus 71 Gew.-% Komponente Ab und 29 Gew.-% Komponente Ba wurde bei 250°C (ZSK 30, Werner & Pfeiderer) extrudiert, die Wärme- formbeständigkeit wurde bestimmt und antistatische Verhalten im Corona Test geprüft. Außerdem wurde das Durchstoßverhalten getestet. Die Ergebnisse sind in Tabelle 5 aufgeführt.A mixture of 71% by weight of component Ab and 29% by weight of component Ba was extruded at 250 ° C. (ZSK 30, Werner & Pfeiderer), the heat resistance was determined and antistatic behavior was tested in the corona test. The puncture behavior was also tested. The results are shown in Table 5.
Beispiele V12, 13 bis 15Examples V12, 13 to 15
Ein Gemisch aus 71 Gew.-% Komponente Ab und 29 Gew.-% Komponente Ba wurde bei 250°C mit den in Tabelle 5 angegebenen Antistatika extrudiert (ZSK 30, Werner & Pfeiderer), die Wärmeformbeständigkeit wurde bestimmt und antistatische Verhalten im Corona Test geprüft. Außerdem wurde das Durchstoßverhalten getestet. Die Ergebnisse sind in Tabelle 5 aufgeführt.A mixture of 71% by weight of component Ab and 29% by weight of component Ba was extruded at 250 ° C. with the antistatic agents given in Table 5 (ZSK 30, Werner & Pfeiderer), the heat resistance was determined and antistatic behavior in the Corona test checked. The puncture behavior was also tested. The results are shown in Table 5.
Wie aus den Beispielen zu ersehen ist, sind weder Ethylenoxid- noch Propylenoxid- Homopolymere wirksam. Nur EO/PO-Dreiblockcopolymere mit einem PO-Block von 2000 bis 4000 und einem EO-Anteil unter 30 Gew.-% sind wirksam als Antistatikum und Verbesserer der Mechanik.As can be seen from the examples, neither ethylene oxide nor propylene oxide homopolymers are effective. Only EO / PO three-block copolymers with a PO block from 2000 to 4000 and an EO content below 30% by weight are effective as an antistatic and an improvement in mechanics.
Beispiele V16, 17, 18Examples V16, 17, 18
Ein Gemisch aus 71 Gew.-% Ac und 29 Gew.-% Bc wurde bei 250°C mit den in Tabelle 6 angegebenen Antistatika extrudiert, und das antistatische Verhalten wurde im Staubkammertest bestimmt. Außerdem wurde das Durchstoßverhalten gestestet. Tabelle 4A mixture of 71% by weight Ac and 29% by weight Bc was extruded at 250 ° C with the antistatic agents shown in Table 6, and the antistatic behavior was determined in the dust chamber test. The puncture behavior was also tested. Table 4
Tabelle 6Table 6

Claims

Patentansprüc Patent claims
1. Fόrmmass1. Dimension
a: 20 bi von 10 bia: 20 bi from 10 bi
b: 5 bisb: 5 to
bl:bl:
b2:b2:
c: 0,1 einem mittelständigen Block Y aus Propylenoxideinheiten mit einem mittleren Molekulargewicht im Bereich von 2.000 bis 4.000 und endständigen Blocks X aus Eth lenoxideinheiten deren mittlerer Anteil im Dreiblockco ol mer 2 bis c: 0.1 a medium-sized block Y from propylene oxide units with an average molecular weight in the range from 2,000 to 4,000 and terminal blocks X from ethylene oxide units whose average proportion in the Dreiblockco ol mer 2 bis
2. Formmasse nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente A ein Styrol/ Acrylnitril-Copolymerisat ist.2. Molding composition according to claim 1, characterized in that component A is a styrene / acrylonitrile copolymer.
3. Formmasse nach Anspruch 2, dadurch gekennzeichnet, daß der Anteil an Acrylnitril in Komponente A 10 bis 50 Gew.-% beträgt.3. Molding composition according to claim 2, characterized in that the proportion of acrylonitrile in component A is 10 to 50 wt .-%.
4. Formmasse nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Komponente Bl mindestens ein (Co)polymerisat ist aus bll: 60 bis 100 Gew.-% mindestens eines konjugierten Diens, Ci-iö-Alkylacrylats oder4. Molding composition according to one of claims 1 to 3, characterized in that the component B1 is at least one (co) polymer from B1: 60 to 100% by weight of at least one conjugated diene, Ci-iö-alkyl acrylate or
Gemischen davon als Komponente Bll, bl2: 0 bis 30 Gew.-% mindestens eines von Komponente Bll verschiedenen monoethylenisch ungesättigten Monomeren als Komponente B12 und bl3: 0 bis 10 Gew.-% mindestens eines vernetzenden Monomeren als Komponente B13.Mixtures thereof as component B1, B12: 0 to 30% by weight of at least one monoethylenically unsaturated monomer different from component B1 as component B12 and B13: 0 to 10% by weight of at least one crosslinking monomer as component B13.
5. Formmasse nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß in Komponente C das mittlere Molekulargewicht des Blocks Y 2.200 bis 3.400 und der mittlere Anteil an Blocks X im Dreiblockcopolymer 5 bis 25 Gew.-% beträgt.5. Molding composition according to one of claims 1 to 4, characterized in that in component C the average molecular weight of block Y is 2,200 to 3,400 and the average proportion of blocks X in the three-block copolymer is 5 to 25% by weight.
6. Verfahren zur Herstellung einer Formmasse nach einem der Ansprüche 1 bis 5 durch separate Herstellung der einzelnen Komponenten A bis C und gegebenenfalls D und nachfolgendes Vermischen der Komponenten.6. A method for producing a molding composition according to any one of claims 1 to 5 by separate production of the individual components A to C and optionally D and subsequent mixing of the components.
7. Verwendung von Formmassen nach einem der Ansprüche 1 bis 5 zur Herstellung von Formkö ern, Fasern oder Folien.7. Use of molding compositions according to one of claims 1 to 5 for the production of molded articles, fibers or films.
8. Formkörper, Fasern oder Folien aus einer Formmasse nach einem der Ansprüche 1 bis 5.8. Moldings, fibers or films made from a molding composition according to one of claims 1 to 5.
9. Verwendung von Dreiblockcopolymeren der Formel X-Y-X mit einem mittelständigen Block Y aus Propylenoxideinheiten mit einem mittleren Molekulargewicht im Bereich von 2.000 bis 4.000 und endständigen Blocks X aus Ethylenoxidemheiten, deren mittlerer Anteil im Dreiblockcopolymer 2 bis 28 Gew-% beträgt, zur Erhöhung der Durchstoßfestigkeit von schlagzähmodifizierten Copolymerisaten von Styrol und/oder ä-Methylstyrol mit Acrylnitril bei gleichzeitig gutem antistatischem Verhalten. 9. Use of three-block copolymers of the formula XYX with a medium-sized one Block Y from propylene oxide units with an average molecular weight in the range from 2,000 to 4,000 and terminal blocks X from ethylene oxide units, the average proportion of which in the three-block copolymer is 2 to 28% by weight, to increase the puncture resistance of impact-modified copolymers of styrene and / or α-methylstyrene Acrylonitrile with good antistatic behavior.
EP99913275A 1998-03-31 1999-03-18 Thermoplastic molding material exhibiting a high puncturing resistance and a good antistatic behavior Withdrawn EP1084187A1 (en)

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DE19814423 1998-03-31
DE19814423 1998-03-31
DE1998117993 DE19817993A1 (en) 1998-04-22 1998-04-22 Improving puncture resistance of impact-modified styrene/acrylonitrile copolymers while imparting good antistatic properties
DE19817993 1998-04-22
PCT/EP1999/001810 WO1999050348A1 (en) 1998-03-31 1999-03-18 Thermoplastic molding material exhibiting a high puncturing resistance and a good antistatic behavior

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DE19906066A1 (en) 1999-02-12 2000-08-17 Basf Ag Thermoplastic molding compounds
DE19906040A1 (en) * 1999-02-12 2000-08-17 Basf Ag Thermoplastic molding compounds
DE10026858A1 (en) * 2000-05-31 2001-12-06 Basf Ag Stabilized thermoplastic molding compounds
DE10145775A1 (en) * 2001-09-17 2003-04-03 Bayer Ag ABS compositions with improved combinations of properties
JP4699031B2 (en) * 2005-01-13 2011-06-08 日東電工株式会社 Adhesive products and substrates for adhesive products
US8545953B2 (en) * 2007-02-28 2013-10-01 Styrolution GmbH Hollow polystyrene body obtained by injection stretch blow moulding
CN102585422B (en) * 2012-01-03 2014-08-06 江苏南亚电缆集团有限公司 Anti-static ABS (Acrylonitrile Butadiene Stryrene) material and preparation method thereof
KR102214221B1 (en) * 2014-01-28 2021-02-08 이네오스 스티롤루션 그룹 게엠베하 Thermoplastic molding compounds with optimized flowability-toughness ratio
KR101984068B1 (en) 2015-08-31 2019-09-03 주식회사 엘지화학 Thermoplastic resin and thermoplastic resin composition comprising the same
WO2017082661A1 (en) 2015-11-11 2017-05-18 (주) 엘지화학 Thermoplastic resin composition and molded article comprising same
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