EP1472297A2 - Copolymerisats greffes de caoutchouc de silicone a structure noyau-enveloppe, matiere de moulage a resilience modifiee et corps moules et procede de production correspondant - Google Patents

Copolymerisats greffes de caoutchouc de silicone a structure noyau-enveloppe, matiere de moulage a resilience modifiee et corps moules et procede de production correspondant

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Publication number
EP1472297A2
EP1472297A2 EP03701507A EP03701507A EP1472297A2 EP 1472297 A2 EP1472297 A2 EP 1472297A2 EP 03701507 A EP03701507 A EP 03701507A EP 03701507 A EP03701507 A EP 03701507A EP 1472297 A2 EP1472297 A2 EP 1472297A2
Authority
EP
European Patent Office
Prior art keywords
silicone rubber
graft copolymers
weight
rubber graft
shell
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.)
Withdrawn
Application number
EP03701507A
Other languages
German (de)
English (en)
Inventor
Klaus Schultes
Reiner Müller
Werner Höss
Klaus Albrecht
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1472297A2 publication Critical patent/EP1472297A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • 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
    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2989—Microcapsule with solid core [includes liposome]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • Silicone rubber graft copolymers with a core-shell structure Silicone rubber graft copolymers with a core-shell structure, impact-modified molding compounds and moldings, and processes for their production
  • the present invention relates to silicone rubber graft copolymers with a core-shell structure and to impact-resistant molding compositions and moldings obtainable therefrom, and to processes for their production
  • Shaped bodies are required for various applications, which must have excellent impact strength even in the cold.
  • this includes components for refrigerators, pipes and automobiles that can be exposed to the cold.
  • silicone rubber graft copolymers that have a core-shell structure
  • K / S have been used to improve the impact strength.
  • such modifiers also have a structure that comprises two shells (K / S1 / S2).
  • EP 430 134 discloses the production of modifiers to improve the impact strength of molding compositions.
  • a core consisting of a silicone rubber and an acrylic rubber is grafted with vinyl monomers.
  • the material is also used for the impact modification of molding compounds - however, only polycarbonate (PC) and / or polyester molding compounds are mentioned here.
  • the document US 4,690,986 represents an impact-resistant molding composition which is produced on the basis of a graft copolymer (via emulsion polymerization).
  • the graft copolymer is a K / S product.
  • the core consists of a crosslinking agent (siloxane with methacrylate group connected via several CH 2 groups) and tetrafunctional silane as a crosslinking agent. Both the molding compound and a manufacturing process are described.
  • JP 612,135,462 describes a molding composition which is produced on the basis of a graft copolymer (via emulsion polymerization).
  • the graft copolymer consists of siloxane grafted with vinyl monomers.
  • EP 308 198 discloses a molding compound made of PMMI and grafted polysiloxane.
  • the grafted polysiloxane is produced by grafting monomers and at least one "graft crosslinking agent".
  • the graft crosslinking agent is the crosslinking agent described in US Pat. No. 4,690,986 (siloxane with methacrylate group connected via several CH groups).
  • the tetrafunctional silane is also mentioned as a crosslinking agent in the subclaims.
  • EP 332 188 describes graft copolymers which are similar to those described in EP 430134. These graft copolymers are used to modify
  • Molding compounds used.
  • particles are grafted with styrene and these are used to modify a polyether / polysulfone blend.
  • DE 43 42 ' 048 discloses graft copolymers with a K / S1 / S2 structure.
  • a silicone rubber acts as the core, Sl is predominantly made of acrylates (min. 70%) and for the production of the shell S2 z.
  • B. monomer mixtures are used which contain 50-100% methyl methacrylate.
  • Impact-resistant molding compositions based on the graft copolymers described are also shown in the subclaims, the polymer for the matrix also being very broad here.
  • a molding composition which consists of 20-80% conventional polymers and 80-20% graft copolymers is shown in DE 3839287.
  • the graft copolymer has a K / SI / S2 structure, the core being made of silicone rubber and SI made of acrylate rubber.
  • S2 is produced by redox polymerization (emulsion) of various monomers. As an example, only an impact modified SAN molding compound is listed.
  • EP 492 376 describes graft copolymers which have a K / S or K / S1 / S2 structure.
  • the core and the optional intermediate shell are made of silicone rubber and are more precisely defined - the outer shell is made by emulsion polymerization of various monomers. It is particularly problematic that the addition of large amounts of additives can lead to a deterioration in the mechanical properties of the plastics, so that the total amounts that can be added are very limited.
  • the invention was based on the object of providing modifiers which lead to a significant improvement in the impact strength of molding compositions over a wide temperature range.
  • Claim 17 a solution to the underlying problem.
  • Molding compounds equipped with graft copolymers show very good behavior at low temperatures. Very good impact strength values are achieved in particular at temperatures below 0 ° C.
  • Silicone rubber graft copolymers of the present invention can be produced inexpensively.
  • Moldings obtained from the molding compositions according to the present teaching show an excellent modulus of elasticity.
  • special embodiments show a modulus of elasticity according to ISO 527-2 of at least 1500, preferably at least 1600, particularly preferably at least 1700 MPa.
  • moldings according to the invention are very heat-resistant and weather-resistant.
  • the core a) of the silicone rubber graft copolymer according to the invention comprises organosilicon polymer which has the general formula
  • the radicals R are preferably alkyl radicals, such as the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. - Butyl, amyl, hexyl radical; Alkenyl residues like that
  • Hydrocarbon radicals such as the chloromethyl, 3-chloropropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl and 5, 5, 5, 4, 4, 3, 3-heptafluoropentyl radical, and the chlorophenyl radical;
  • Mercaptoalkyl radicals such as the 2-mercaptoethyl and 3-mercaptopropyl radical
  • Cyanoalkyl radicals such as the 2-cyanoethyl and 3-cyanopropyl radicals
  • Aminoalkyl radicals such as the 3-aminopropyl radical
  • Acyloxyalkyl radicals such as the 3-acryloxypropyl and 3-methacryloxypropyl radical
  • Hydroxyalkyl radicals such as the hydroxypropyl radical.
  • radicals methyl, ethyl, propyl, phenyl, ethenyl, 3-methacryloxypropyl and 3-mercaptopropyl are particularly preferred, preferably less than 30 mol% of the radicals in the siloxane polymer being ethenyl, 3-methacryloxypropyl or 3-mercaptopropyl groups.
  • the vinyl groups of the core c) according to the invention can be obtained, inter alia, by using organic silicon compounds which have ethenyl, propenyl, butenyl, pentenyl, hexenyl and / or allyl radicals.
  • the content of vinyl groups of the core a) before the grafting is in particular in the range from 0.5 to 10 mol%, preferably 1 to 6 mol% and particularly preferably 2 to 3 mol%.
  • Mol% is understood as the molar proportion of the starting compounds containing vinyl groups, which arithmetically have a vinyl group, in all monomeric organic compounds Silicon compounds that are used to produce the core a).
  • the vinyl groups are distributed inhomogeneously in the silicone core, the proportion in the outer region of the silicone core being higher than in the region of the center of gravity.
  • Preferably 85%, particularly preferably 90% of all vinyl groups are in the outer shell of the silicone core.
  • Vinyl esters such as vinyl acetate
  • Styrene substituted styrenes with an alkyl substituent in the side chain, such as. B. ⁇ -methylstyrene and ⁇ -ethylstyrene, substituted styrenes with an alkyl substituent on the ring, such as vinyltoluene and p-methylstyrene, halogenated styrenes, such as, for example, monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; Heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4-vinylpyridine, 2, 3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3-vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-l-viny
  • Hydroxylalkyl (meth) acrylates such as 3-hydroxypropy1 (meth) acrylate
  • These monomers can be used individually or as a mixture. Mixtures which contain methacrylates and acrylic acid esters are particularly preferred. These mixtures can be the other monomers comprise, which are copolymerizable with these (meth) acrylates. These monomers are also mentioned previously.
  • the monomers which form the shell polymerize with one another radically more rapidly than with the double bonds in the silicone rubber particles.
  • Copolymerization parameters include in, for example, B. Vollmert, Grundriß der Molecular Chemie, Volume I, Structural Principles Polymer Synthesis I [Polymerization], E. Vollmert-Verlag Düsseldorf 1988, p.114 and following. Since the parameters for the double bonds in the silicone particles are not accessible, the parameters of the monomers belonging to them can be considered.
  • the copolymerization parameters can either be determined, calculated using the corresponding e, Q values or looked up in the literature (see, for example, the sources cited above).
  • the monomers that form the shell polymerize with one another at least twice as fast as with the double bonds in the silicone rubber particles.
  • the ratio of acrylic acid ester to methacrylate can vary widely.
  • the weight ratio of acrylic acid ester to methacrylate of the mixture for producing the shell c) is in the range from 50:50 to 1:99, particularly preferably in the range from 10:90 to 2:98 and very particularly preferably in the range from 5:95 to 3:97 without any limitation.
  • the ratio of the weight of core a) and shell b) to the weight of the shell c) of the silicone rubber graft copolymers is preferably in the range from 90:10 to 20:80, in particular from 80:20 to 30:70 and particularly preferably from 70: 30 to 55:65, without any limitation.
  • the particle size can be measured with a
  • Coulter N4 can be measured in water at room temperature (23 ° C). This determination device becomes different with corresponding reference latices
  • Particle size the particle size of which is determined by ultracentrifuge measurements, is checked.
  • the particle size accordingly relates to one determined according to the previously mentioned method
  • the polysiloxane graft base can be produced by the emulsion polymerization process.
  • the radical R ' stands for alkyl radicals with 1 to 6 carbon atoms, aryl radicals or substituted hydrocarbon radicals, methyl, ethyl and propyl radicals are preferred.
  • the remainder R has the meaning previously defined.
  • Acids can be used as such or, if appropriate, in a mixture with their salts. If anionic emulsifiers are used, it is advantageous to use those whose aliphatic substituents contain at least 8 carbon atoms. Aliphatic substituted benzenesulfonic acids are preferred as anionic emulsifiers. If cationic emulsifiers are used, it is advantageous to use halides.
  • the amount of emulsifier to be used is from 0.5 to 20.0% by weight, preferably 1.0 to 3.0% by weight, in each case based on the amount of organosilicon compounds used.
  • the silane or the silane mixture is added in doses.
  • the emulsion polymerization is carried out at a temperature of 30 to 90 ° C, preferably 60 to 85 ° C. According to a preferred aspect of the present invention, the core a) is produced at normal pressure.
  • the pH of the polymerization mixture can fluctuate over a wide range. This value is preferably in the range from 1 to 4, particularly preferably from 2 to 3.
  • the residence time in the reactor is generally between 30 and 60 minutes, without this being intended to impose a restriction.
  • the stability of the emulsion In the case of batchwise preparation of the graft base, it is advantageous for the stability of the emulsion to be stirred for a further 0.5 to 5.0 hours after the end of the metering.
  • the alcohol released during the hydrolysis especially in the case of a high proportion of silane of the general formula RSi (OR ') 3 , can be removed by distillation in accordance with a preferred embodiment.
  • Examples of silanes of the general formula R 2 Si (OR ') 2 are dimethyldiethoxysilane or dimethyldimethoxysilane.
  • silanes of the general formula RSi (OR ') 3 are methyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and methacryloxypropyltrimethoxysilane.
  • silanes of the general formula Si (OR ') are tetramethoxysilane or tetraethoxysilane.
  • the graft base is grafted with the organosilicon shell polymer b) before the ethylenically unsaturated monomers are grafted on.
  • This shell b) is also produced by the emulsion polymerization process.
  • the radicals R and R ' have the meanings already mentioned.
  • no further emulsifier is added since the in the Amount of emulsifier present for the stabilization is generally sufficient.
  • the polymerization for grafting on the shell b) is carried out at a temperature of 15 to 90 ° C. and preferably 60 to 85 ° C. This is usually done at normal pressure.
  • the pH of the polymerization mixture is from 1 to 4, preferably from 2 to 3.
  • This reaction step can also be carried out either continuously or batchwise.
  • the residence times in the reactor with continuous display, or the subsequent stirring times in the reactor with discontinuous display depend on the amount of silanes or siloxanes metered in and are preferably from 2 to 6 hours. It is most convenient that
  • Siloxane elastomer sols should be at most 25% by weight, both without and with organosilicon shell polymer b), since otherwise a high increase in viscosity makes further processing of the brine as a graft base difficult. From such brines Coagulation available polysiloxanes show elastomeric properties.
  • a simple method for characterizing the elasticity is to determine the swelling factor analogously to the method specified in US Pat. No. 4,775,712. The swelling factor should have a value> 3.
  • the aforementioned ethylenically unsaturated monomers are grafted onto the polysiloxane graft base, preferably grafted with the organosilicon shell polymer b).
  • the organic monomers are metered in in an amount which is preferably 5 to 95% by weight, particularly preferably 30 to 70% by weight, in each case based on the total weight of the graft copolymer.
  • the grafting is preferably carried out by the emulsion polymerization process in the presence of water-soluble or monomer-soluble
  • Suitable radical initiators are water-soluble peroxo compounds, organic peroxides, hydroperoxides or azo compounds.
  • the polymerization of the shell is particularly preferably initiated, for example, with K 2 S 2 0s, KHS0 5 , NaHS0 5 and butyl hydroperoxide.
  • the radical initiators are mixed with a reduction component, so that the polymerization can be carried out at a lower temperature.
  • the shell c) has organic polymers which are prepared by radical polymerization at a temperature of at most 65 ° C., the initiator being added to the reaction vessel in at least two portions, an addition being necessary to start the polymerization and a further addition at least 2 minutes, preferably at least 10 minutes and particularly preferably at least 20 minutes after the start of the polymerization.
  • After the start of the polymerization refers to the time at which radical formation takes place in the presence of monomers in an amount that permits polymerization. This point in time depends on the initiator system chosen and the temperature, and inhibitors may also have to be considered.
  • the initiator is added to the reaction vessel in three, in particular four and preferably five or more, portions, the addition taking place after at least 2 minutes, preferably at least 10 minutes and particularly preferably at least 20 minutes.
  • the initiator is particularly preferably added continuously to the reaction vessel over a period of at least one hour.
  • continuous means that small amounts are added to the reaction vessel over the entire period, the rate of addition being able to vary.
  • the monomers are likewise added to the reaction vessel batchwise or continuously over a period of at least one hour.
  • both the monomers and the initiator are added to the reaction mixture over a period of at least two hours.
  • the preparation of a mixture comprising monomers and initiator is useful. This mixture is then added to the reaction vessel, preferably over a period of at least one hour, preferably two hours.
  • the concentration of initiator in the reaction vessel is kept less than or equal to 0.05% by weight, preferably less than or equal to 0.03% by weight, based on the entire reaction mixture.
  • Oxidation and reduction components are preferably used in an amount of 0.01 to 4% by weight, preferably 0.02 to 2% by weight, based on the amount of monomer, over the entire course of the reaction.
  • the graft copolymers can be isolated from the emulsion by known processes.
  • organosilicon shell b) imparts an improved phase connection of the organopolymer shell c) to the organosilicon graft base.
  • Poly (meth) acrylates are known in the art. These polymers are generally obtained by radical polymerization of mixtures which
  • Preferred poly (meth) acrylates are obtainable by polymerizing mixtures which have at least 20% by weight, in particular at least 60% by weight and particularly preferably at least 80% by weight, based on the total weight of the monomers to be polymerized, of methyl methacrylate ,
  • the poly (meth) acrylate molding compositions may contain further polymers in order to modify the properties.
  • these polymers include polyacrylonitriles, polystyrenes, polyethers, polyesters, polycarbonates and polyvinyl chlorides. These polymers can be used individually or as a mixture, and copolymers which can be derived from the abovementioned polymers can also be added to the molding compositions. These include, in particular, styrene-acrylonitrile polymers (SAN), which are preferably added to the molding compositions in an amount of up to 45% by weight.
  • SAN styrene-acrylonitrile polymers
  • Such particularly preferred molding compositions are available under the trade name PLEXIGLAS® from Rhausen ⁇ GmbH & Co. KG commercially available.
  • Such acrylate rubber modifiers are known per se. These are copolymers which have a core-shell structure, the core and the shell having a high proportion of the (meth) acrylates described above.
  • Preferred acrylate rubber modifiers have a structure with two shells, which differ in their composition.
  • Particularly preferred acrylate rubber modifiers have the following structure, among others:
  • Core polymer with a methyl methacrylate content of at least 90% by weight, based on the weight of the core.
  • Shell 1 polymer with a butyl acrylate content of at least 80% by weight, based on the weight of the first shell.
  • Shell 2 polymer with a methyl methacrylate content of at least 90% by weight, based on the weight of the second shell.
  • a preferred acrylate rubber modifier can have the following structure:
  • the ratio of core to shell (s) of the acrylate rubber modifiers can vary within wide ranges.
  • the weight ratio core to shell K / S is preferably in the range from 20:80 to 80:20, preferably from 30:70 to 70:30 to modifiers with one shell or the ratio of core to shell 1 to shell 2 K / S1 / S2 in the range from 10:80:10 to 40:20:40, particularly preferably from 20:60:20 to 30:40:30 for modifiers with two shells.
  • the particle size of the acrylate rubber modifiers is usually in the range from 50 to 1000 nm, preferably 100 to 500 nm and particularly preferably from 150 to 450 nm, without any intention that this should impose a restriction.
  • the weight ratio of silicone rubber graft copolymer is increased Acrylate rubber modifiers in the range from 1:10 to 10: 1, preferably from 4: 6 to 6: 4.
  • Special molding compounds consist of fl) 20 to 95% by weight of (meth) acrylate polymers, f2) 0 to 45% by weight of styrene-acrylonitrile polymers, f3) 5 to 60% by weight of silicone rubber graft copolymers f4) 0 to 60 %
  • impact modifier based on acrylate rubber, in each case based on the weight of the components fl to f4, and customary additives and additives.
  • the molding compositions can contain customary additives of all kinds. These include antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, dyes, flow improvers, fillers, light stabilizers and organic phosphorus compounds such as phosphites or phosphonates, pigments, weathering protection agents and plasticizers.
  • Shaped articles which have excellent notched impact strength values can be obtained from the molding compositions described above by known processes, such as, for example, injection molding or extrusion.
  • shaped bodies obtained in this way can contain a Vicat
  • Softening temperature according to ISO 306 (B50) of at least 85, preferably at least 90 and particularly preferably at least 95 ° C, a notched impact strength KSZ (Izod 180 / leA, 1.8 MPa) according to ISO 180 of at least 3.0 kJ / m 2 at - 20 ° C and at least 2.5 kJ / m 2 at -40 ° C, an elastic modulus according to ISO 527-2 of at least 1500, preferably at least 1600, particularly preferably at least 1700 MPa.
  • the molding composition according to the invention is particularly suitable for the production of mirror housings, spoilers of vehicles, pipes, covers or components for refrigerators.
  • Silicone rubber dispersion without casing c were produced based on the examples described in EP-0 492 376 on pages 5-7.
  • Graft copolymers have a particle size of 67 nm in radius, which is determined with a Coulter N4 device.
  • the particles have a core / shell ratio (K / S) of 60/40.
  • the dispersion is frozen at -20 ° C and thawed after 2 days.
  • the solid is then filtered off and dried at 60 ° C.
  • the strand expansion was determined in accordance with DIN 54811 (1984).
  • the softening temperature is in accordance with DIN ISO 306 (Aug. 1994); Mini Vicat system (16h / 80 ° C) determined.
  • the Izod impact strength is measured in accordance with ISO 180 (1993).
  • the modulus of elasticity is determined according to ISO 527-2. The data thus obtained are set out in Table 1.
  • Example 1 was essentially repeated. However, a mixture of 3 g of sodium persulfate in 50 g of water was used as the initiator, the use of acetic acid and iron (II) sulfate being dispensed with. Furthermore, the temperature of the Reactor set to 80 ° C, after the end of the feed, the temperature is maintained at 80 ° C for 240 minutes.
  • the particles have a core / shell ratio (K / S) of 60/40.
  • Example 1 is essentially repeated, but using a mixture of 761.3 g of methyl methacrylate and 31.7 g of ethyl acrylate as a monomer instead of pure methyl methacrylate.
  • Example 1 According to Example 1, 22.5 g of the particles thus obtained were incorporated in 77.5 g of polymethyl methacrylate molding composition. The values thus obtained are also listed in Table 1. Table 1

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne des copolymérisats greffés de caoutchouc de silicone à structure noyau-enveloppe présentant au moins un noyau a) en polymère silicium organique, correspondant à la formule (R2Si02/2)x.(RSi03/2)y.(Si04/2)z, x = entre 0 et 99,5 % en mole, y = entre 0,5 et 100 % en mole, z = entre 0 et 50 % en mole, R désigne des restes alkyle ou alkényle identiques ou différents ayant entre 1 et 6 atomes de C, des restes aryle ou des restes hydrocarbures substitués, ainsi qu'au moins une enveloppe c) en polymère organique. Lesdits copolymérisats greffés de caoutchouc de silicone s'obtiennent par : production de l'enveloppe organique c) par polymérisation par voie radicalaire, à une température maximale de 65 °C et par adjonction de l'initiateur en au moins deux portions à la cuve de réaction. Une autre adjonction intervient au moins 2 minutes après le début de la polymérisation.
EP03701507A 2002-02-06 2003-01-14 Copolymerisats greffes de caoutchouc de silicone a structure noyau-enveloppe, matiere de moulage a resilience modifiee et corps moules et procede de production correspondant Withdrawn EP1472297A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10206518 2002-02-06
DE10206518 2002-02-06
DE10236240 2002-08-07
DE10236240A DE10236240A1 (de) 2002-02-06 2002-08-07 Silicon-Pfropfcopolymerisate mit Kern-Hülle-Struktur, schlagzähmodifizierte Formmassen und Formkörper sowie Verfahren zu deren Herstellung
PCT/EP2003/000267 WO2003066695A2 (fr) 2002-02-06 2003-01-14 Copolymerisats greffes de caoutchouc de silicone a structure noyau-enveloppe, matiere de moulage a resilience modifiee et corps moules et procede de production correspondant

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AU (1) AU2003202558A1 (fr)
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WO2003066695A2 (fr) 2003-08-14
AU2003202558A1 (en) 2003-09-02
KR20040099271A (ko) 2004-11-26
DE10236240A1 (de) 2003-08-14
US20080305335A1 (en) 2008-12-11
KR100854939B1 (ko) 2008-08-29
JP2005517058A (ja) 2005-06-09
US20050124761A1 (en) 2005-06-09
AU2003202558A8 (en) 2003-09-02
CA2471332A1 (fr) 2003-08-14
MXPA04007629A (es) 2004-11-10

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