Classifications

• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
  • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
  • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
  • C08F291/02—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to elastomers
• • 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

Definitions

• the invention relates to particulate emulsion polymers, graft copolymers thereof and molding compositions containing them which have improved impact strength.
• the invention also relates to a process for the preparation of the emulsion polymers and graft copolymers and to the use of the graft copolymers and thermoplastic molding compositions.
• thermoplastic molding compositions such as acrylonitrile-butadiene-styrene (ABS) copolymers and acrylate-styrene-acrylonitrile (ASA) copolymers are used in a large number of applications because of their advantageous mechanical properties.
• ABS acrylonitrile-butadiene-styrene
• ASA acrylate-styrene-acrylonitrile
• a rubber latex is generally first produced, which, for example, can be incorporated into a polymer matrix after grafting.
• Chewable indices which are obtained in the homopolymerization or mixed polymerization of butadiene, often have particle diameters of the order of 50 to 150 nm. ABS polymers which are produced with such rubbers often have a relatively low toughness. For this reason, attempts are made to produce and use chewing indexes with larger particles.
• the small-sized rubber latex used is therefore preferably used in agglomerated form in order to achieve improved mechanical properties.
• DE-A-24 27 960 relates to a ner process for the production of impact-resistant thermoplastic molding compositions based on rubber-like polymers.
• the rubber latex obtained is at least partially agglomerated by adding an agglomerating agent based on an acrylic ester polymer dispersion. It is then grafted with styrene, acrylonitrile and / or methyl methacrylate, and the graft rubber obtained is introduced into a polymer matrix.
• the object of the present invention is to provide particulate emulsion polymers and graft copolymers and thermoplastic molding compositions obtainable therefrom which have improved notched impact strength compared to known molding compositions.
• they should have an advantageous combination of mechanical properties such as toughness, penetration work, flowability and surface gloss.
• a l l 70 to 100% by weight of butadiene or at least one C 1-8 alkyl ester of acrylic acid or mixtures thereof as component AI 1,
• a l3 0 to 30% by weight of further copolymerizable monomers as component AI 3,
• the graft copolymers are preferably incorporated into thermoplastic molding compositions.
• thermoplastic molding composition comprising, based on the amount of components A and B and, if appropriate, C and / or D, which gives a total of 100% by weight,
• component A a: 10 to 90% by weight of a graft copolymer as defined above as component A,
• c 0 to 80% by weight of polycarbonates, polyamides, polyesters, polyether ketones,
• d 0 to 50 wt .-% fibrous or particulate fillers or their
• thermoplastic molding compositions with improved mechanical properties, in particular with increased impact strength are obtained if the graft copolymers used for their preparation have a polymodal particle size distribution in which less than 40% by weight, preferably in each particle size interval of 50 nm in width less than 37.5% by weight, more preferably less than 35% by weight, particularly preferably less than 32.5% by weight, in particular less than 30% by weight of the particles.
• the mean particle diameter relates to the weight. In particular, it is the d 5 o of the cumulative mass distribution by means of an ultracentrifuge is determined.
• the particle size distribution is also preferably determined using an ultracentrifuge, as explained in more detail below.
• thermoplastic molding compositions It has been found according to the invention that such a broad particle size distribution leads to the advantageous thermoplastic molding compositions.
• the integral is generally plotted over the mass or weight as a function of the particle size. If one chooses an arbitrary interval of the particle size with a width of 50 nm, then according to the invention the increase in weight or mass in the integral is less than 40% by weight, preferably less than 37.5% by weight, more preferably less than 35% by weight .-%, particularly preferably less than 32.5 wt .-%, in particular less than 30 wt .-%.
• the particle sizes in an agglomerated latex are usually in the range of up to 1,000 nm. As a rule, therefore, the interval of 50 nm is within this particle size range of up to 1,000 nm. According to the invention, the above condition is for a particle size window of 50 nm in width to fulfill.
• the ratio O ⁇ / O n of the weight average d 5 o to the number average d 5 o of the particle size is ⁇ 5, particularly preferably ⁇ 4, in particular ⁇ 3.
• the weight average d of the particle size is determined by means of an analytical ultracentrifuge, the number average of Particle size, also using an analytical ultracentrifuge, compare W. Scholtan, 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 d t o value indicates the particle diameter at which 10% by weight of all particles have a smaller and 90% by weight a larger diameter. Conversely, for the dgo value indicates 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 integral, plotted against the particle size is preferably a monotonically increasing function. This means that there is no plateau in the course of the function from 0 to 100% by weight, but a steadily increasing curve.
• the graft copolymers according to the invention can be prepared by
• 500 nm preferably 130 to 450 nm, in particular 130 to 400 nm
• the production of the particulate emulsion polymers or graft copolymers can generally be carried out by a process as described in DE-A-24 27 960.
• a rubber latex is produced in the basic level.
• This base rubber preferably has a glass transition temperature of less than -20 ° C, particularly preferably less than -30 ° C.
• a mixture of monomers is used
• a l l 70 to 100% by weight, preferably 80 to 100% by weight of butadiene or at least one .s-alkyl ester of acrylic acid or mixtures thereof, as component AI 1,
• butadiene, n-butyl acrylate and / or ethylhexyl acrylate are preferably used as component All.
• crosslinking monomers can be used as component A 12.
• Polyfunctional crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate,
• DCPA Dicyclopentadienyl acrylate
• Further copolymerizable monomers AI 3 are preferably monomers which are also contained in the matrix polymer of the molding composition.
• Examples are vinyl aromatic monomers such as styrene, styrene derivatives of the general formula
• R 1 and R 2 represent hydrogen or d- to C 8 -alkyl
• N-substituted maleimides such as N-methyl, N-phenyl and N-cyclohexyl maleimide
• aromatic and araliphatic esters of acrylic acid and methacrylic acid such as
• unsaturated ethers such as vinyl methyl ether, and mixtures thereof.
• Preferred examples are MMA, styrene, acrylonitrile, MA, glycidyl (meth) acrylate, acrylamide, methacrylamide, imides or vinyl ethers, as well as methylstyrene and methacrylonitrile.
• Al 3 styrene is preferably used as component in an amount of 0 to 30% by weight, preferably 0 to 20% by weight, preferably 5 to 15% by weight if present.
• the monomer mixture is emulsified in water in the presence of emulsifiers, for example alkali metal salts of alkyl or alkylaryl sulfonates, alkyl sulfates, fatty alcohol sulfonates or fatty acids with 10 to 30 carbon atoms.
• emulsifiers for example alkali metal salts of alkyl or alkylaryl sulfonates, alkyl sulfates, fatty alcohol sulfonates or fatty acids with 10 to 30 carbon atoms.
• Sodium salts of alkyl sulfonates or fatty acids with 12 to 18 carbon atoms are preferably used.
• the emulsifiers are used in amounts of 0.3 to 5, particularly preferably 0.35 to 2.0% by weight, based on the monomers.
• the usual buffer salts such as sodium bicarbonate, citrate buffer and systems such as sodium pyrophosphate can be used.
• the polymerization is preferably carried out at temperatures from 30 to 90 ° C. in the presence of customary initiators.
• customary initiators are persulfates or organic peroxides.
• molecular weight regulators such as mercaptans or terpinols can optionally be added.
• the solids content in the aqueous dispersion after the polymerization is preferably 25 to 50% by weight, particularly preferably 30 to 45% by weight.
• the particle size obtained after the polymerization is generally below 150 nm.
• the rubber latex obtained in the first step is agglomerated. This is preferably done by adding a dispersion of an acrylic ester polymer, as described, for example, in DE-A-24 27 960. Copolymers of ethyl acrylate and methacrylamide in which the proportion of methacrylamide is 0.1 to 20% by weight are particularly preferably used.
• the concentration of the acrylic ester polymers in the agglomerating dispersion is preferably 3 to 40% by weight, particularly preferably 5 to 20% by weight.
• the particle size is preferably approximately in the range of the particle size of the latex to be agglomerated.
• the ratio of the average particle size of the agglomerating latex to the average particle size of the substrate latex is preferably 0.2 to 2, particularly preferably 0.5 to 1.5.
• the agglomeration is preferably carried out at a temperature of 20 to 120 ° C, particularly preferably 30 to 100 ° C.
• the agglomerating latex is preferably added in such a way that 1 to 1/100 of the total amount of the agglomerating latex to be added is introduced per minute.
• the agglomeration time is preferably 1 minute to 2 hours, particularly preferably 10 to 60 minutes.
• the amount of the agglomerating latex, based on the latex to be agglomerated, is preferably 0.1 to 20, preferably 0.5 to 10, in particular 1 to 5% by weight, based on fatty substances.
• the agglomeration can improve the space-time yield and cycle time of the polymerization process.
• the (partially) agglomerated latex obtained is grafted to produce the graft copolymers according to the invention.
• the proportion of the graft shell in the graft copolymer is preferably 10 to 90% by weight.
• the graft shell or graft is preferably composed of 65 to 83% by weight of styrene or a (meth) acrylic acid ester, in particular styrene as component A 21 and 17 to 35% by weight of acrylonitrile.
• the grafting can be carried out with the addition of any regulator and initiator.
• any regulator and initiator for example, peroxide or redox initiators can be used.
• the grafting is also described in DE-A-24 27 960.
• the graft copolymers according to the invention are preferably mixed with at least one matrix polymer and, if appropriate, further ingredients to produce thermoplastic molding compositions. These are described below:
• Component B is an amorphous polymer.
• SAN styrene-acrylonitrile
• AMSAN ⁇ -methylstyrene-acrylonitrile
• SMSAN styrene-maleic acid (anhydride) -acrylonitrile polymers
• Component B is preferably a copolymer of
• bl 60-100% by weight, preferably 65-80% by weight, units of a vinylaromatic monomer, preferably styrene, a substituted styrene or a (meth) acrylic acid ester or mixtures thereof, in particular styrene and / or ⁇ -methylstyrene as component B 1,
• b2 0 to 40% by weight, preferably 20-35% by weight, of units of an ethylenically unsaturated monomer, preferably acrylonitrile or methacrylonitrile or methyl methacrylate (MMA), in particular acrylonitrile as component B2.
• an ethylenically unsaturated monomer preferably acrylonitrile or methacrylonitrile or methyl methacrylate (MMA), in particular acrylonitrile as component B2.
• it is composed of 60-99% by weight of vinyl aromatic monomers and 1-40% by weight of at least one of the other specified monomers.
• Component B is preferably an amorphous polymer, as described above as graft A2.
• component B is a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile used.
• the acrylonitrile content in these copolymers of component B is 0-40% by weight, preferably 20-35% by weight, based on the total weight of component B.
• Component B also includes those formed in the graft copolymerization to prepare component A. free, non-grafted styrene / acrylonitrile copolymers.
• component B has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately prepared component B.
• This additional, separately produced component B can preferably be a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer.
• These copolymers can be used individually or as a mixture for component B, so that the additional, separately prepared component B of the molding compositions used according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer and a methylstyrene / acrylonitrile copolymer can act.
• component B of the molding compositions used according to the invention consists of a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer
• the acrylonitrile content of the two copolymers should preferably not be more than 10% by weight, preferably not more than 5% by weight, based on the total weight of the copolymer. differ from each other.
• Component B preferably has a viscosity number of 40 to 150, preferably 50 to 120, in particular 60 to 100. The viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
• Components A and B and optionally C, D can be mixed in any desired manner by all known methods. If components A and B have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together and to work up the polymer mixture. Preferably, however, components A and B are mixed by extruding, kneading or rolling the components together, e.g. B. at 180 - 400 ° C, wherein the components, if necessary, have previously been isolated from the solution obtained in the polymerization or aqueous dispersion.
• the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and as moist crumbs are mixed with component B, the complete drying of the graft copolymers then taking place during the mixing.
• the masses contain, in addition to components A and B, additional components C and / or D, and, if appropriate, further additives, as described below.
• the polymers of component C of the molding composition are preferably selected from at least one polymer made from polycarbonates, partially crystalline polyamides, partially aromatic copolyamides, polyesters, polyether ketones, polyoxyalkylenes and polyarylene sulfides. Polymer mixtures can also be used.
• Partially crystalline, preferably linear, polyamides such as polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-6,12 and partially crystalline copolyamides based on these components are suitable as component C of the molding composition according to the invention.
• partially crystalline polyamides can be used, the acid component of which consists entirely or partially of adipic acid and / or terephthalic acid and / or isophthalic acid and / or suberic acid and / or sebacic acid and / or azelaic acid and / or dodecanedicarboxylic acid and / or a cyclohexanedicarboxylic acid, and the like
• Diamine component wholly or partly in particular consists of m- and / or p-xylylenediamine and / or hexamethylenediamine and / or 2,2,4- and / or 2,4,4-trimemylhexamemylenediamine and / or isophoronediamine
• polyester preferably aromatic-aliphatic polyester
• polyalkylene terephthalates e.g. based on ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol and 1,4-bis-hydroxymethylcyclohexane, as well as polyalkylene naphthalates.
• Aromatic polyether ketones can also be used as component C, as described, for example, in patent specifications GB 1 078 234, US Pat. No. 4,010,147, EP-A-0 135 938, EP-A-0 292 211, EP-A-0 275 035, EP-A-0 270 998, EP-A-0 165 406, and in the publication by CK Sham et. al., Polymer 29/6, 1016-1020 (1988).
• polyoxyalkylenes e.g. Polyoxymethylene and oxymethylene polymers are used.
• suitable components C are the polyarylene sulfides, especially the polyphenylene sulfide.
• Suitable polycarbonates C are known per se. They preferably have a molecular weight (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polyslyrole standards) in the range from 10,000 to 60,000 g / mol. They can be obtained, for example, in accordance with the processes of DE-B-1 300 266 by interfacial polycondensation or in accordance with the process of DE-A-1 495 730 by reacting diphenyl carbonate with bisphenols.
• Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as also hereinafter - referred to as bisphenol A.
• aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4'- Dihydroxydiphenyl sulfite, 4,4'-dihydroxydiphenylmethane, l, l-di- (4-hydroxyphenyl) ethane, 4,4-dihydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, in particular l, l-bis (4-hydroxyphenyl) -3.3 , 5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
• 2,2-di (4-hydroxyphenyl) pentane 2,6-dihydroxynaphthalene
• Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
• Copolycarbonates according to US Pat. No. 3,737,409 can also be used; of particular interest are copolycarbonates based on bisphenol A and di- (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by a high heat resistance. It is also possible to use mixtures of different polycarbonates.
• the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. The relative solution viscosities of the polycarbonates used preferably differ by no more than 0.05, in particular no more than 0.04.
• the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts of 0-50% by weight, preferably 10-40% by weight, based in each case on the total molding composition.
• the addition of polycarbonates leads, among other things, to higher thermal stability and improved crack resistance of the molding compositions.
• component D contain preferred thermoplastic molding compositions of 0 - 50 wt .-%, preferably 0 - 40 wt .-%, in particular 0-30 wt .-% of fibrous or teilchenfb '-shaped fillers or mixtures thereof, in each case based on the total Foimmasse. These are preferably commercially available products.
• Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the total molding composition.
• the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers (staples) with a length of 1-10 ⁇ m, preferably 3-6 ⁇ m, can be used.
• fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
• metal flakes e.g. aluminum flakes from Transmet Corp.
• metal powder e.g. aluminum flakes from Transmet Corp.
• metal fibers e.g. nickel-coated glass fibers
• metal-coated fillers e.g. nickel-coated glass fibers
• other additives that shield electromagnetic waves are mixed into the molding compositions according to the invention.
• Aluminum flakes K 102 from Transmet
• EMI electro-magnetic interference
• the masses can be mixed with additional carbon fibers, carbon black, in particular conductivity carbon black, or nickel-coated carbon fibers.
• the molding compositions according to the invention may also contain other additives which are typical and customary for polycarbonates, SAN polymers and graft copolymers or mixtures thereof.
• additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers for improving the thermostability, for increasing the stability to light, for increasing the resistance to hydrolysis and the resistance to chemicals, agents against heat decomposition and in particular the lubricants / lubricants for the production of moldings or moldings are appropriate.
• additives can be metered in at any stage of the production process, but preferably at an early point in time, in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
• Suitable stabilizers are the usual hindered phenols, but also vitamin E or analogue compounds, as well as butylated condensation products of p-cresol and dicyclopentadiene, e.g. B. Wingstay ® from Goodyear.
• HALS stabilizers Hindered Amine Light Stabilizers
• benzophenones such as Tinuvin ® 770 (HALS absorber, bis (2,2,6,6- tetramethyl-4-piperidyl) sebazate) or Tinuvin ® P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol), Topanol ® ).
• Tinuvin ® such as Tinuvin ® 770 (HALS absorber, bis (2,2,6,6- tetramethyl-4-piperidyl) sebazate) or Tinuvin ® P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol
• Topanol ® Tinuvin ®
• Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters, amide wax (bisstearylamide), polyolefin waxes or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12-30 carbon atoms.
• the amounts of these additives range from 0.05 to 5% by weight.
• Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives, the usual amounts being 0.001-5% by weight.
• Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
• Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01-5% by weight, based on the total molding composition.
• the molding compounds can be processed into moldings, semi-finished products and foils.
• thermoplastic molding compositions used in accordance with the known methods of thermoplastic processing.
• the production can be carried out by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
• polybutadiene Emulsion The polybutadiene latex is produced as described in Example 1.1, page 12 (graft base) of DE-A 19728 629.
• 227 parts of the polybutadiene latex are diluted with 11 parts of water and heated to 65 ° C.
• 20 parts of an aqueous dispersion of an ethyl acrylate copolymer are added, which contains 96% by weight of ethyl acrylate and 4% by weight of methacrylamide.
• the solids content of this dispersion is 10% by weight, based on the dispersion.
• the polybutadiene latex thus obtained is heated to 75 ° C. and 9.5 parts of a 10% strength by weight potassium stearate solution are added. 0.12 part of potassium peroxodisulfate and 10 parts of a mixture of styrene and acrylonitrile are added. The weight ratio of styrene to acrylonitrile in this mixture is 8: 2. 15 minutes after the start of the grafting reaction, a mixture of 41 parts of styrene and 10 parts of acrylonitrile is metered in within 3 hours. After the end of the feed, 0.12 part of potassium peroxide sulfate is again added and polymerization is continued at 80 ° C. for 90 minutes.
• the particle size distribution obtained after agglomeration and grafting is shown in FIG. 1.
• the particle diameter D in nm is plotted on the X axis, and the percentage by weight of the particles on the Y axis is plotted as x [m].
• the resulting graft polymer is precipitated in a magnesium sulfate solution at 95 ° C. and suction filtered.
• the moist graft rubber is worked into an SAN matrix using an extruder, which contained 24% acrylonitrile and 76% styrene.
• the grafted polybutadiene is mixed with the SAN matrix in a weight ratio of 3: 7.
• the particle size distributions in FIG. 1 correspond to Examples 1, 2 and 3 from top to bottom.
• Test specimens were produced from the granules by injection molding.

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