WO2001046317A1 - Matieres moulables thermoplastiques transparentes, resistant aux chocs - Google Patents

Matieres moulables thermoplastiques transparentes, resistant aux chocs Download PDF

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Publication number
WO2001046317A1
WO2001046317A1 PCT/EP2000/012516 EP0012516W WO0146317A1 WO 2001046317 A1 WO2001046317 A1 WO 2001046317A1 EP 0012516 W EP0012516 W EP 0012516W WO 0146317 A1 WO0146317 A1 WO 0146317A1
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Prior art keywords
weight
graft
transparent
component
impact
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PCT/EP2000/012516
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German (de)
English (en)
Inventor
Graham Edmund Mckee
Axel Gottschalk
Christian Schade
Rainer Neumann
Claudia Messinger
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Basf Aktiengesellschaft
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Publication of WO2001046317A1 publication Critical patent/WO2001046317A1/fr

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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
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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

Definitions

  • the invention relates to transparent, impact-resistant thermoplastic molding compositions made from a hard methyl methacrylate polymer (A), a hard styrene / acrylonitrile polymer (B), a soft graft copolymer (C) from graft branches or graft shell (s), containing alkyl (meth ) acrylates and optionally vinyl aromatic compounds and crosslinking monomers, and a rubber as the graft copolymer backbone, which has a bimodal particle size distribution, and optionally conventional additives (D), the difference between the refractive index of component C) and that of the mixture of components A) and B ) and optionally D) is less than 0.01.
  • A hard methyl methacrylate polymer
  • B hard styrene / acrylonitrile polymer
  • C soft graft copolymer
  • s graft branches or graft shell
  • s containing alkyl (meth ) acrylates and optionally vinyl aromatic compounds and cross
  • the invention further relates to a process for the production of these molding compositions and their use for the production of films, fibers and moldings.
  • the connection relates to fibers, films and molded parts, essentially containing the molding compositions according to the invention, and their use for the production of devices in medical technology or medical diagnostics.
  • thermoplastic molding compositions based on methyl methacrylate and styrene / acrylonitrile copolymers are already known to the person skilled in the art.
  • the molding compositions described in DE-AS 20 45 742 however, have a styrene / acrylonitrile copolymer, the composition of which ensures the transparency of the molded parts only at low processing temperatures.
  • it is regularly desirable to work at higher temperatures since in this way the mechanical properties of the molded parts obtained are improved and mold filling during injection molding can be achieved more easily.
  • DE-OS 28 28 517 discloses transparent molding compositions consisting of a mixture of polymethyl ethacrylate and styrene / acrylonitrile copolymers as a hard component and a soft component based on polybutadiene or a styrene / butadiene copolymer rubber, which with styrene and acrylonitrile in a certain , well-defined composition is grafted.
  • these molding compositions can also be processed at higher temperatures without having to accept any loss in transparency, they always show a certain yellowing and have one unpleasant smell, which precludes use in the packaging sector from the outset.
  • EP-A 062 223 provides that graft copolymer polymers with a polybutadiene or styrene / butadiene block copolymer backbone and grafted-on side branches made of (meth) acrylic acid star and optionally vinylaromatic compounds are used as the soft component are.
  • the molding compositions obtained according to EP-A 062 223 still leave something to be desired in terms of improved mechanical properties. Because given the transparency, the molding compounds should also because of their simple, precise and permanent laser markability (see also EP-A 0 764 189) a very wide range of applications not only in the packaging sector but also in other areas, e.g. for medical technology products, as long as improved product properties can be set, especially with regard to toughness values.
  • the present invention was therefore based on the object of providing transparent thermoplastic molding compositions which are distinguished by very good mechanical properties, in particular high toughness values, do not tend to yellow, are odorless and show good transparency.
  • thermoplastic molding compositions which contain a mixture of
  • thermoplastic molding compositions Furthermore, a process for the production of transparent, impact-resistant thermoplastic molding compositions and their use for the production of moldings, fibers and films have been found.
  • films, fibers and moldings as well as their use for the production of packaging material or for the production of devices in medical technology or medical diagnostics were found.
  • a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate with up to 10% by weight of an alkyl acrylate with 1 to 8 carbon atoms in the alkyl radical, preferably methyl or butyl acrylate, are used as hard component A).
  • the proportion of these copolymers based on methyl methacrylate is regularly at least 60% by weight, preferably more than 80% by weight and in particular above 90% by weight.
  • the incorporation of alkyl acrylates into the methyl methacrylate polymer improves the flowability and the thermal stability of component A) and thus also that of the molding compositions according to the invention.
  • Component A) advantageously has an average molecular weight M w > 50,000 g / mol, preferably> 75,000 g / mol and particularly preferably> 100,000 g / mol.
  • alkyl acrylates in principle include those having 1 to 8 carbon atoms in the alkyl radical.
  • C ⁇ ⁇ to Cs alkyl esters of acrylic acid examples are: ethyl, propyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and 2-ethylhexyl acrylate and mixtures of the compounds mentioned, in particular but methyl, ethyl, n-butyl, 2-ethylhexyl acrylate or mixtures of the latter compounds, with methyl acrylate being particularly preferred.
  • the methyl methacrylate polymers with an alkyl acrylate content of 0.5 to 7.0% by weight have sufficient heat resistance.
  • homopolymers and copolymers according to component A) having an average molecular weight M w in the range from 50,000 to 300,000 g / mol, determined by light scattering in chloroform, are suitable as blend components for the molding compositions according to the invention.
  • Methyl methacrylate copolymers according to component A) can be prepared by bulk, solution or bead polymerization using generally known methods (see, for example, synthetic Stoff-Handbuch, Volume XI, "Polymethacrylate”, Vieweg / Esser, Carl-Hanser-Verlag, 1975), but are also commercially available as such.
  • the hard component B) of the molding composition according to the invention is a copolymer of 78 to 88% by weight of a vinylaromatic monomer and 22 to 12% by weight of acrylonitrile. Outside of these composition ranges, cloudy processing parts with weld lines are obtained at processing temperatures above 240 ° C. Styrene is preferably used as the vinyl aromatic monomer; Blend component B) is then a so-called SA copolyme risate.
  • the copolymers B) those are particularly preferred which have a viscosity number, determined in a 0.5% strength solution in dimethylformamide, in the range from 30 to 250, preferably in the range from 50 to 150 and particularly preferably in the range from 60 to 120 ,
  • the copolymers can be prepared by known processes, for example by bulk, solution, suspension or emulsion polymerization. Copolymers produced in solution are preferably used, a preferred process being described in British Pat. No. 1,472,195.
  • the copolymers B) advantageously have weight-average molecular weights, determined by light scattering in dimethylformamide, in the range from 60,000 to 300,000 g / mol.
  • the vinylaromatic monomer component of the copolymer B) can be used not only on styrene, but also on styrene which is monosubstituted to trisubstituted with C 1 -C 8 -alkyl radicals, such as p-methylstyrene or p-butylstyrene and? -Methylstyrene. Styrene is preferably used.
  • methacrylonitrile or mixtures of acrylonitrile and methacrylonitrile are also suitable as vinyl cyanide component of the copolymers B).
  • Acrylonitrile is preferred.
  • the soft component C) of the molding composition according to the invention is a graft copolymer with a rubber with a glass transition temperature below 0 ° C. as the graft base or graft core.
  • Polybutadiene, polyisoprene, copolymers of butadiene and isoprene or copolymers of butadiene and / or isoprene with styrene or an in position or preferably at the core with one (or at the core also with several) alkyl group (s) are used as the graft base or core. , preferably methyl, substituted styrene with up to 12 carbon atoms in question.
  • the graft base or the graft core of the graft copolymer preferably has a glass transition temperature of ?? 0 ° C., particularly preferably ?? - 20 ° C and especially ?? - 30 ° C.
  • the rubbers used accordingly have elastomeric properties.
  • a measure of this elastomeric property is the glass transition temperature according to KH Illers and H. Breuer, Kolloid-Zeitschrift 1961, 176, p.110.
  • the elastomeric graft base is produced in a customary manner by emulsion polymerization, as described, for example, in the Encyclopaedia of Polymercience and Engineering, 1985, Vol. 1, pp. 401ff.
  • the graft shells are then grafted on in a likewise known manner and the graft copolymers obtained are spray dried.
  • Graft copolymers with an elastic graft core or graft base and with one or more graft shells can be used for toughening, graft copolymers with a three-shell structure being regularly preferred.
  • double-skinned graft copolymers, such as in EP-B 0 062 223, under suitable graft copolymers C) provided that they are present in the molding compositions according to the invention in a bimodal particle size distribution.
  • alkyl esters of methacrylic acid especially the C- * . - to C ⁇ -alkyl esters such as methyl methacrylate, ethyl methacrylate, n-, i-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate , n-octyl methacrylate or 2-ethylhexyl methacrylate and mixtures of these monomers in question, with methyl methacrylate being particularly preferred.
  • alkyl to Ca alkyl esters can also be used in a corresponding manner as alkyl esters of acrylic acid.
  • Crosslinking monomers essentially include di- or polyfunctional comonomers, with particular preference being given to alkylene glycol dimethacrylates such as ethylene, propylene and butylene glycol dimethacrylate and likewise allyl methacrylate, methacrylate of glycerol, trimethylpropane or pentaerythritol and to vinylbenzenes such as di- or trivivolbenzene.
  • the proportion of bimodal component C) with a smaller average particle size has an average particle size in the range from 0.03 to 0.1 ⁇ m, preferably from 0.04 to 0.08 ⁇ m and particularly preferably from 0.045 to 0.07 ⁇ m.
  • the proportion of component C) with a larger average particle diameter has such particles with average particle sizes in the range from 0.125 to 0.225 ⁇ m, preferably from 0.140 to 0.200 ⁇ m and particularly preferably from 0.15 to 0.190 ⁇ m.
  • the bimodal component C) preferably contains less than 15% by weight and in particular less than 10% by weight of particles with an average particle size in the range from 0.1 to 0.125 ⁇ m.
  • Component (CI) is preferably present, based on the total weight of component C), in proportions in the range from 3 to 30, preferably from 5 to 20 and particularly preferably from 9 to 17% by weight.
  • the proportion of component (C-II) in the graft copolymer C) is preferably 70 to 97, preferably 80 to 95 and particularly preferably 83 to 91% by weight.
  • the mean particle size and the particle size distribution are determined via the integral mass distribution.
  • the mean particle sizes are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymers, 1972, 250, 782-796.
  • 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 mean particle diameter which is also referred to as the dso value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the dso value.
  • the particles then have a larger diameter than the dso value.
  • the d ⁇ o and dgo values resulting from the integral mass distribution are used.
  • the d ⁇ o ⁇ or dgo ⁇ er the integral mass distribution is defined according to the dso value with the difference that they are based on 10 to 90 wt .-% of the particles. The quotient
  • the transparent, impact-resistant thermoplastic molding composition according to the invention consists of a mixture of A) 15 to 70% by weight and particularly preferably from 20 to 40% by weight of a methyl methacrylate polymer composed of 90 to 100% by weight of methyl methacrylate and 10 to 0% by weight of an alkyl acrylate having 1 to 8 carbon atoms in the alkyl radical,
  • a graft copolymer with a bimodal particle size distribution containing 50 to 80% by weight, based on the graft copolymer, of an elastomeric graft base (Ci) with a glass transition temperature of less than -20 ° C., consisting essentially of 60 to 90% by weight of butadiene and / or isoprene and 10 to 40% by weight of styrene and / or alkylstyrene with up to 12 carbon atoms in the alkyl part, and 20 to 50% by weight of a hard graft shell (C)) essentially consisting of 40 to 100 wt .-% of one or more methacrylic acid esters of -C ⁇ to Cs-alkanols (C ⁇ )), 0 to
  • the transparent impact-resistant molding composition contains a mixture of
  • a graft copolymer with a bimodal particle size distribution comprising, based on the graft copolymer, 40 to 80% by weight of a graft base (Ci)) essentially, consisting of 65 to 90% by weight of butadiene or isoprene and 10 to 35% by weight of styrene, 10 to 30% by weight of a first graft shell (C 3 )), essentially consisting of 30 to 95% by weight , in particular 30 to 60 wt .-% styrene (C 31 )) and 5 to 70 wt .-% of a C - * .- to Cg alkyl ester of (meth) acrylic acid (C32)) and 0 to 2% by weight of a crosslinking monomer (C 33 )) and 10 to 30 *% by weight of a second graft shell (C 4 )), consisting essentially of 70 to 100%
  • blend components A) and B) and the graft copolymer C) always add up to 100% by weight in the abovementioned lists.
  • the transparent molding composition according to the invention contains
  • the copolymer a vinyl aromatic monomer, preferably styrene, and
  • the graft copolymer, a first graft shell obtainable by polymerizing a monomer mixture consisting of 30 to 60% by weight, preferably 40 to 50% by weight, of a vinylaromatic monomer, preferably styrene, 40 to 60% by weight, preferably of 40 to 55 wt .-%, a Ci bis
  • wt .-% preferably from 0 to 1.2 wt .-% of a crosslinking monomer and 10 to 30% by weight, preferably from 10 to 25% by weight, based on the graft copolymer, of a second graft shell, obtainable by polymerizing a monomer mixture consisting of 70 to 98% by weight, preferably from 75 to 92% by weight %, a C ⁇ ⁇ to Cs alkyl ester of methacrylic acid and
  • the latter embodiment is particularly preferred when the quantitative ratio of the first graft shell to the second graft shell is in the range from 2: 1 to 1: 2, the refractive index of the first graft shell is greater than the refractive index of the second graft shell and the refractive index of the overall graft shell is smaller than the refractive index of the core, the amount of the difference between the refractive index of the graft copolymer and that of the impact-modified matrix being less than or equal to 0.01, preferably less than or equal to 0.05.
  • the quantitative ratio of intermediate shell to outer shell is preferably in the range from 2: 1 to 1: 2.
  • the two graft shells are produced in the presence of the core by methods known from the literature, in particular by emulsion polymerization (cf. Encyclopedia of Polymer, Science and Engineering, 1985, Vol. 1, p. 401 ff).
  • the seed procedure Due to the so-called seed procedure used, no new particles are formed in the production of the two graft shells.
  • the seed procedure enables the number and type of particles in both grafting stages to be determined by the amount and type of emulsifier used.
  • the emulsion polymerization is usually triggered by polymerization initiators.
  • Ionic and non-ionogenic emulsifiers can be used in emulsion polymerization.
  • Suitable emulsifiers are, for example, dioctyl sodium sulfosuccinate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylphenoxypolyethylene sulfonates and salts of long-chain carboxylic and sulfonic acids.
  • suitable nonionic emulsifiers are fatty alcohol polyglycol ethers, alkylaryl polyglycol ethers, fatty acid monoethanolamides and ethoxylated fatty acid amides and amines.
  • the total amount of emulsifier is preferably 0.05 to 5% by weight.
  • Polymerization initiators which can be used are ammonium and alkali peroxodisulfates such as potassium peroxodisulfate and initiator combination systems such as sodium persulfate, sodium hydrosulfite, potassium persulfate, sodium formaldehyde sulfoxylate and potassium peroxodisulfate, sodium di-thionite-iron-II-sulfate, the polymerization temperature being active and in the case of the thermo-nium-n-sulfate Alkali peroxodisulfates at 50 to 100 ° C and in the initiator combinations, which are effective as redox systems, may be less, for example in the range from 20 to 50 ° C.
  • the total amount of initiator is preferably between 0.02 and 1.0% by weight, based on the finished emulsion polymer.
  • polymerization regulators can also be used.
  • the following are used as polymerization regulators: Alkyl mercaptans such as n- or tert-dodecyl mercaptan.
  • the polymerization regulators are usually used in an amount of 0.01 to 1.0% by weight, based on the particular stage.
  • the emulsion graft copolymer to be used according to the invention is prepared in such a way that an aqueous mixture consisting of monomers, emulsifier, initiator, regulator and a buffer system is placed in a reactor inertized with nitrogen, rendered inert with stirring and brought to the polymerization temperature.
  • Monomers, emulsifiers, initiators and regulators can also be supplied completely or partially as feed to the aqueous receiver.
  • the graft shells are produced by emulsion polymerization with the addition of the monomers in the presence of the core already formed.
  • the emulsion graft copolymer is isolated from the latex obtained in a known manner by spray drying or precipitation, filtration and subsequent drying.
  • Precipitation can be, for example, aqueous solutions of inorganic salts such as sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride, aqueous solutions of salts of formic acid such as magnesium formate, calcium formate and zinc formate, aqueous solutions of inorganic acids such as sulfuric and phosphoric acid as well as aqueous ammoniacal and amine solutions and others aqueous alkaline solutions, such as sodium and potassium hydroxide can be used.
  • inorganic salts such as sodium chloride, sodium sulfate, magnesium sulfate and calcium chloride
  • salts of formic acid such as magnesium formate, calcium formate and zinc formate
  • aqueous solutions of inorganic acids such as sulfuric and phosphoric acid
  • Drying can be carried out, for example, by freeze, spray, fluidized bed and circulating air drying.
  • EP-B 0 062 223 apply to the production of transparent, impact-modified matrix materials containing at least two blend components A) and B), which can be used as a basis for the molding compositions according to the invention.
  • component C In order to obtain the bimodal particle size distribution of component C), there are basically different ways to proceed. On the one hand, it is possible to combine the latices of components (C-I) and (C-II) obtained separately using emulsion graft copolymerization before the precipitation step using inorganic salts. It is also possible to combine separately prepared graft bases with different average particle sizes and to subject them to a common grafting reaction. Furthermore, it is also possible to produce components (C-I) and (C-II) separately and to mix them only after their precipitation, filtration and drying. This mixing can take place both before addition to the other components which form the molding composition according to the invention and only when all the components forming the molding composition according to the invention are combined.
  • bimodal particle size distributions can be obtained by means of agglomeration during or after the polymerization of the graft particles of component C) (see also DE-OS 2 427 960 and Angewandte Makromolekulare Chemie, 1968 (2), pages 1 to 25). Finally, bimodal particle size distributions can also be generated in situ according to EP-A 081 083, EP-A 0 129 699 or EP-A 0 568 831.
  • the molding compositions according to the invention can also contain up to 20% by weight of conventional additives, preference being given to using only those additives which are transparent Do not or only slightly affect the molding compound.
  • additives are styrene / maleic anhydride co- Polymers, dyes, stabilizers, lubricants and / or antistatic agents.
  • 2, 6-disubstituted phenols or organic phosphites are suitable as stabilizers.
  • Mixtures of at least one 2,6-disubstituted phenol and at least one organic phosphite are preferred. These mixtures are described in detail in WO 98/45365 (there as component C), to which reference is hereby expressly made.
  • 2,6-disubstituted phenols which have a quaternary C atom in the 2- and / or 6-position which is linked directly to the aromatic ring.
  • the t-butyl and the 1 '-methylcyclohexyl group are suitable as such substituents.
  • Suitable 2,6-diphenols are, for example, 2,6-di-t-butyl-4-methylphenol, 1,6-triethylene glycol bis- [3- (3,5-di- (1,1-dimethylethyl) -4-hydroxyphenyl) propionic acid] ester, butylated reaction products of p-cresol and dicyclopentadiene, for example according to CAS Reg.-No.
  • the 2, 6-diphenols listed can be used alone or in a mixture. They are used preferably in amounts of 0.02 to 5, particularly preferably from 0.05 to 1 and in particular in amounts of 0.1 to 0.5% by weight, based on the total weight of the polymer mixture.
  • Preferred organic phosphites are triisooctylphosphite, triisodecylphosphite, trilaurylphosph.it, diisooctylphenylphosph.it, diisodecylphenylphosphite, dilaurylphenylphosphite, isooctyldiphenylphosphite, diphenyldistophosphate, bisphenityldiphosphite, diphenyllaurylthritol, diphenyl bisphenylphosphite, diphenyl bisphenylphosphite
  • the organic phosphites listed are preferably used in amounts of 0.02 to 5, particularly preferably 0.05 to 1 and in particular in amounts of 0.1 to 0.5% by weight, based on the total weight of the polymer mixture.
  • Mixing of blend components A), B) and the graft copolymer (s) C) * s ⁇ .ie if desired, the additives D) usually takes place in the melt at temperatures in the range of 200 to 280 ° C. This is achieved, for example, by melt extrusion. It is also possible to mix solutions or suspensions of the components and then to remove the solvent or suspension medium.
  • thermoplastic molding compositions can be produced from the thermoplastic molding compositions according to the invention, moldings being accessible primarily by injection molding or by molding.
  • the thermoplastic molding compositions can also be pressed, calendered, extruded or vacuum molded.
  • thermoplastic molding compositions according to the invention are notable in particular for very good impact strength with very good optical properties. They are transparent or almost transparent, continue to have a very low proportion of scattered light and show no noticeable yellowing even when stored under heat. Injection molded parts show no weld line markings and are characterized by high transparency and a high surface gloss.
  • a prerequisite for the transparency of the molding compositions according to the invention is that the difference between the refractive index of the soft component C) and that of the mixture of the two hard components A) and B) and optionally the additives D) is less than 0.01.
  • the refractive index of the mixture of the hard components results from the linear combination of the refractive indices of the individual components with their weight fractions.
  • the refractive index of the hard component is adjusted by a suitable choice of the ratios of the components A): B).
  • the molding compositions according to the invention or the films, fibers and moldings obtainable therefrom are particularly suitable as packaging material for luxury foods or foodstuffs and for devices in medical technology or medical diagnosis.
  • the refractive index n 25 o was determined using an Abbe refractometer according to the method for measuring the refractive index for solid bodies (see Ullmann's Encyclopedia of Industrial Chemistry, Volume 2/1, p. 486, edited by W. Foerst; Urban and Schwarzenberg, Kunststoff -Berlin, 1961).
  • the impact strength was determined in accordance with the ISO 179 / leA specification.
  • the transparency or haze of the moldings obtained was determined in accordance with ASTM D-1003 and the yellow index in accordance with ASTM D-1925-67.
  • C-I graft copolymer with a graft core made from butadiene and styrene (76:24) (50%), a first graft shell made from styrene
  • n 25 D 1,540, average particle diameter 0.05 ⁇ m;
  • C-II composition as C-I; average particle size 0.175 ⁇ m.
  • the glass transition temperature of the graft bases of (C-I) and (C-II) was below -20 ° C.
  • the above components were mixed and melt extruded at 250 ° C.
  • the granules obtained were sprayed off at a melt temperature of 250 ° C. to form 2 mm thick round disks.
  • the yellow index was measured in accordance with ASTM D-1925.
  • the yellow index is based on color measures that are calculated from the transmission spectrum in accordance with ASTM D-1925.
  • the light type D65 and the large field normal observer are used as a basis.
  • the following table shows the respective compositions of the mixtures, the yellowness index, the transparency, the haze and the impact strength.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matières moulables thermoplastiques transparentes, résistant aux chocs, contenant un mélange comprenant : un polymère de méthylméthacrylate (A) ; un copolymère de monomères aromatiques vinyliques et d'acrylonitrile (B) ; un copolymère greffé à répartition granulométrique bimodale (C), comprenant un noyau de greffe élastomère et une ou plusieurs enveloppes de greffe, contenant un ester d'acide (méth)acrylique et éventuellement des monomères aromatiques vinyliques et/ou des monomères réticulants ; ainsi qu'éventuellement des additifs (D), la somme des pourcentages en poids de A), B) et C) étant égale à 100, et la différence entre l'indice de réfraction du composant C) et celui du mélange des composants A) et B) ainsi qu'éventuellement D) étant inférieure à 0,01.
PCT/EP2000/012516 1999-12-20 2000-12-11 Matieres moulables thermoplastiques transparentes, resistant aux chocs WO2001046317A1 (fr)

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DE1999161894 DE19961894A1 (de) 1999-12-20 1999-12-20 Transparente, schlagzähe thermoplastische Formmassen
DE19961894.1 1999-12-20

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WO2020126722A1 (fr) 2018-12-19 2020-06-25 Röhm Gmbh Composition acrylique présentant une résistance accrue aux alcools, aux huiles et aux graisses
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DE102004006193A1 (de) * 2004-02-06 2005-08-25 Basf Ag Thermoplastische Formmassen mit verbesserten mechanischen und optischen Eigenschaften
CN101296960B (zh) * 2005-10-28 2011-12-07 阿科玛法国公司 具有抗冲改性剂粒度的双峰分布的抗冲改性丙烯酸类材料
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WO2023285593A1 (fr) 2021-07-16 2023-01-19 Röhm Gmbh Composition polymère acrylique transparente présentant une résistance accrue aux alcools et aux graisses

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