EP1263820A1 - Procede pour produire des matieres plastiques resistant aux chocs - Google Patents

Procede pour produire des matieres plastiques resistant aux chocs

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Publication number
EP1263820A1
EP1263820A1 EP01902358A EP01902358A EP1263820A1 EP 1263820 A1 EP1263820 A1 EP 1263820A1 EP 01902358 A EP01902358 A EP 01902358A EP 01902358 A EP01902358 A EP 01902358A EP 1263820 A1 EP1263820 A1 EP 1263820A1
Authority
EP
European Patent Office
Prior art keywords
mixture
rubber
dispersion
monomer
weight
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Withdrawn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
EP01902358A
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mc Kee
Hermann Gausepohl
Norbert Niessner
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1263820A1 publication Critical patent/EP1263820A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • 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

Definitions

  • the invention relates to a ner process for producing impact-resistant plastics based on crosslinked rubber particles, and to an impact-resistant plastic obtainable with the ner process.
  • Impact-resistant plastics show an increased load capacity against mechanical influences, which they have for many applications, e.g. B. make it particularly suitable for everyday items. These special properties are achieved through the structure of these plastics, in which domains of elastomers, e.g. B. rubbers, are embedded in a matrix of thermoplastics.
  • the multiphase nature and thus also the domain structure of such impact-resistant plastics is based on their construction from various polymer components which are not or only partially miscible with one another.
  • Their impact strength results from an increased energy absorption during the deformation up to the break. The energy is used to form micro-voids or to initiate sliding processes of the matrix polymer chains.
  • the multi-phase is therefore a necessary prerequisite for achieving high impact strength.
  • the two chemically different polymer components form a dispersion which shows little phase separation during processing and which does not tend to homogenize or form a macromolecular solution when exposed to more intense temperatures;
  • the most effective coupling at the interfaces of the elastomer particles is achieved by graft copolymerization.
  • the procedure is generally such that a rubber is placed on which a copolymer is then grafted on by polymerization with a monomer mixture.
  • DE-A 29 10 168 discloses stable, flowable dispersions of rubbers in the form of discrete particles with an average diameter of 100-3000 nm in organic liquids which, as rubber, crosslink 1-20% by weight (based on the total dispersion) Diene rubber contains 0 - 20 wt .-% water in the form of a water-in-oil emulsion. As a continuous organic phase, they contain 99-66% by weight of C 10 alkyl acrylates or alkyl (meth) acrylates, methyl methacrylate, ethyl acrylate or n-hexyl acrylate.
  • they can also be a mixture of 85-50% by weight of styrene or methylstyrene and 15-50% by weight of acrylonitrile, methacrylonitrile or C 6 -C 6 alkyl acrylates or alkyl (meth) acrylates, methyl methacrylate, ethyl acrylate as the liquid phase , contain n-hexyl acrylate.
  • the continuous organic phase is a mixture of 85 - 50 wt .-% - C 10 alkyl acrylate or alkyl (meth) acrylate, or 15 - 50 wt .- proposed% acrylonitrile, methacrylonitrile or styrene.
  • the continuous organic phase can optionally contain up to 60% by weight of a liquid hydrocarbon.
  • the diene rubbers are generally highly cross-linked. They contain at least 50% by weight, preferably more than 70% by weight, of gel.
  • the rubbers are generally in the form of aqueous rubber dispersions obtained by emulsion polymerization, as latices.
  • rubbers they preferably contain homopolymers of conjugated dienes having 4 to 8 carbon atoms, such as butadiene, isoprene, chloroprene or their copolymers, with up to 40% by weight, preferably up to 10% by weight, of a vinyl compound, such as acrylonitrile, methacrylonitrile , Styrene, ⁇ -methylstyrene, halostyrenes, - C 4 -alkylstyrenes, - C -alkylstyrenes, - C 6 alkyl acrylates and methacrylates, acrylic acid, methacrylic acid, vinylsulfonic acid, allylsulfonic acid, alkylene glycol diacrylates and methacrylates and diphenylbenzene.
  • a vinyl compound such as acrylonitrile, methacrylonitrile , Styrene, ⁇ -methylstyrene, halostyrenes, - C 4 -alkyls
  • Aqueous emulsions of crosslinked, rubber-like diene polymers are dispersed in certain organic liquids, so that the diene polymers are dispersed as swollen particles.
  • the water of the original emulsion is also dispersed in the organic liquid as a water-in-oil emulsion. If necessary, the water can be removed by selectively breaking the water-in-oil emulsion and separating the water. For most applications of the organic rubber dispersions, however, it is not necessary to separate the water. However, it must be dispersed in a stable manner and must not separate out as a separate phase.
  • DE-A 44 40 676 describes a process for the production of rubber molding compounds and rubber-modified molding compounds prepared by the process.
  • a mixture which contains at least one alkyl acrylate or methacrylate, a first monomer having two or more double bonds and optionally a second monomer or more is polymerized to give a rubber, preferably with free radicals.
  • the rubber formed is dissolved in a third monomer or more to form a second mixture, optionally with the addition of a solvent, or swollen.
  • the rubber is either water-free during its production or, for example in the case of production by emulsion polymerization, is first dried after removal of the water.
  • the second mixture formed after dissolving or swelling is polymerized to give the rubber-modified molding compound.
  • the first monomers are alkyl methacrylate, butanediol diacrylate, divinylbenzene, triallyl cyanurate and dihydrodicyclopentadienyl acrylate, the latter being preferred.
  • a disadvantage of the process according to DE-A 4440676 is that the rubber must first be freed of water when it is produced by emulsion polymerization. To do this the corresponding work steps are required, which makes the process more time-consuming and also involves higher costs.
  • DE-A 24 00 659 describes a process for the production of rubber-modified resins.
  • an alkadiene rubber is dispersed, which is grafted with monovinylidene aromatic monomers and alkyl nitrile monomers.
  • the grafting required for sufficient force transmission between the polymer matrix and rubber is therefore carried out in a separate step.
  • the object of the invention is therefore to provide a method for producing impact-resistant plastics and an impact-resistant plastic obtainable by this method.
  • This object is achieved with a method for producing an impact-resistant plastic based on crosslinked rubber particles, wherein
  • an aqueous dispersion or suspension of particles of a crosslinked rubber is produced from a first monomer mixture which has a proportion of conjugated diene compounds of less than 50 % By weight, preferably less than 5% by weight, in particular less than 2% by weight,
  • the dispersion or suspension is optionally precipitated to obtain an aqueous rubber particle mixture with a water content of at least 5% by weight
  • a rubber in particle form is produced, onto which at least one further monomer is grafted in a further step (c).
  • the backbone of the resulting graft polymer is formed by the rubber, and the graft pastes are formed from the at least one further monomer. Because there is no 100% grafting, part of the rubber remains ungrafted and a chain polymer is simultaneously formed from the at least one further polymer, so that three types of molecules are present in the molding composition. Since the rubber is not dried before being added to the at least one further monomer, the production of the impact-resistant plastic is simplified. The water is added together with the rubber particles to the second mixture, which contains at least one further monomer.
  • the water introduced into the reaction mixture in this way can be used advantageously in various ways.
  • the water can prevent the rubber particles from swelling, a gel forming and the reaction mixture becoming very viscous. Rather, the reaction mixture maintains the state of an easily mobile liquid. This makes it easier to pump around or during the polymerization of the at least one further monomer can be stirred without difficulty, as a result of which the heat generated during the reaction can be dissipated more easily.
  • the water can also be used directly to cool the reaction by evaporating it during the polymerization. At the same time, oxygen is removed from the reaction system, resulting in a better color of the end product.
  • the rubber dispersion or the aqueous rubber particle mixture can be added to the second mixture in step (c) in various ways.
  • the dispersion can be added directly to the mixture. If different monomers are provided in the second mixture, it is also possible, however, to initially introduce one of the monomers, then to add the rubber suspension or the aqueous rubber particle mixture and then to add the further monomers to the monomer mixture. This is e.g. B. useful if the further monomer of the second mixture is more volatile than water and the water should be separated before the polymerization of the second mixture. In this case, a less volatile monomer of the second mixture is initially introduced. Then the aqueous rubber dispersion is added and the water is separated off, for example by distillation.
  • step (d) The more volatile monomers can then be added in order to then polymerize the monomer mixture in step (d).
  • part of the monomer mixture may be initially introduced, then for the rubber dispersion to be added, and, if appropriate, for the remaining monomer mixture to be added after the water has been removed.
  • the aqueous suspension of the rubber particles can be coagulated in step (b) to reduce the water content.
  • the dispersion of the rubber particles thus obtained generally has a water content of 5-60% by weight. A water content of less than 5% by weight no longer enables the advantages described above.
  • the water content of the coagulated rubber suspension can be reduced to the desired water content with the aid of pressure, centrifugation or drying.
  • the coagulation of the rubber particles can also be carried out after adding the rubber suspension to the second mixture.
  • the polymerization of the at least one monomer of the second mixture can take place immediately after the addition of the rubber dispersion.
  • the rubber particles are first swollen in the monomers of the second mixture, preferably for more than 5 minutes, and then the monomers of the second mixture are polymerized.
  • the properties of the impact-resistant plastic can also be influenced by first polymerizing at least one monomer of the second mixture and adding the rubber dispersion only after partial polymerization has taken place. The remaining monomers of the second mixture are then polymerized to form a graft shell on the rubber particles.
  • the reaction can also be carried out in such a way that the monomers of the second mixture are first polymerized in bulk in the presence of the rubber particles. After the reaction has partly proceeded, water is added and the reaction is brought to an end in suspension. This is of advantage if the reaction mixture becomes too viscous during bulk polymerization to enable controlled processing.
  • the monomers which can be used for the second mixture are not subject to any restrictions, except that they must be capable of free-radical polymerization.
  • the second mixture contains at least one monomer which is selected from the group formed by styrene, acrylonitrile and methyl methacrylate.
  • the first monomer mixture contains at least one monomer which is selected from the Group formed by ethylhexyl acrylate, butyl acrylate, dimethylsiloxane, ethylene and ⁇ -olefins with 3 to 20 carbon atoms.
  • the second mixture can also contain at least one further polymer which is preferably compatible or partially compatible with the polymer obtained from the second monomer mixture.
  • Compatibility is understood to mean that there is no phase separation between the at least one further polymer and the polymer obtained from the second mixture.
  • the further polymer can be produced, for example, by partially polymerizing the second monomer mixture, then adding the rubber dispersion to the partially polymerized monomer mixture and then completing the polymerization of the second mixture.
  • the further polymer preferably has a glass transition temperature T g of more than 0 ° C., preferably more than 20 ° C., particularly preferably more than 50 ° C.
  • the rubber preferably has a glass transition temperature of less than 0 ° C., preferably less than -10 ° C., particularly preferably less than -20 ° C., the glass temperature being determined by means of SDC in accordance with ASTM 3418.
  • the rubber therefore has the required softness.
  • the glass transition temperature can be adjusted either by using an acrylate or methacrylate, the polymer of which has the desired glass transition temperature, or by using a mixture of acrylate or methacrylates, which have different lengths of the side chains. This setting of the glass temperature is based on the fact that the glass temperature of acrylate and methacrylate polymers initially decreases with increasing length of the side chain, then passes through a minimum and finally increases again.
  • the minimum is a side chain of about 7 carbon atoms for polyacrylates and for 10 for polymethacrylates.
  • the rubber particles may have a hard core made of a copolymer, which preferably has a glass transition temperature of more than 0 ° C, particularly preferably more than 10 ° C, in particular more than 20 ° C.
  • This hard core can consist of polystyrene, for example.
  • the hard core preferably has a refractive index of more than 1.53, preferably more than 1.56, in particular more than 1.57.
  • Impact-resistant plastics that contain small rubber particles are usually opaque. It is very difficult to color them. Due to the hard core, the refractive index of the rubber particles can be matched to the surrounding polymer matrix, which reduces light scattering. This balance is achieved particularly well with a hard core that contains styrene or a styrene derivative. These polymers show a particularly high refractive index.
  • the rubber particles in the polymer matrix preferably have a size of less than 10 ⁇ m, preferably less than 5 ⁇ m, in particular less than 4 ⁇ m.
  • the particle size relates to the size of the rubber particles in the end product.
  • the rubber particles preferably have a swelling index between 2 and 100, preferably 3 and 70, in particular 5 and 60.
  • the source index is determined in the following way. A film is cast with the dispersion of the grafted, crosslinked rubber particles and the water is evaporated at 23 ° C. The film is then dried at 50 ° C. and reduced pressure. Approximately 0.5 g of the film is swollen in a solvent such as tetrahydrofuran or dimethylformamide for 24 hours. The polymer gel is then separated from the solvent not incorporated into the gel by centrifugation. The gel is weighed, then dried and weighed again. The swelling index (QI) is calculated using the following equation:
  • a solvent can be added to the second monomer mixture, in an amount, based on the weight of the second mixture, of up to 80% by weight, preferably up to 60% by weight, in particular up to 20% by weight.
  • Suitable solvents are, for example, toluene, ethylbenzene, dimethylformamide, acetone etc.
  • the polymerization of the second mixture is particularly advantageously carried out without the presence of a solvent.
  • the addition of solvent is advantageous if the viscosity of the second mixture increases too much during the polymerization.
  • the second mixture contains a protective colloid.
  • a suitable protective colloid is, for example, polyvinyl alcohols.
  • the impact-resistant plastics obtainable with the process according to the invention show very advantageous properties.
  • the invention therefore also relates to an impact-resistant plastic, as can be obtained with the method according to the invention.
  • the impact-resistant plastic obtainable with the process according to the invention can also be mixed with at least one additional polymer
  • Poly (ether) sulfones are polypropylene, polyethylene, polytetrafluoroethylene (PTFE) and polystyrene acrylonitrile. To be favoured
  • PPE Polyphenylene ether
  • syndiotactic polystyrene syndiotactic polystyrene
  • the polymer produced by polymerizing the second monomer mixture consists of more than 15% by weight
  • Acrylonitrile and / or methyl methacrylate are polycarbonates, polyesters, Polyamides and copolymers of acrylonitrile and / or methyl methacrylate are preferred.
  • the impact-resistant plastics can also contain additives such as lubricants and mold release agents, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers and reinforcing agents and antistatic agents in the amounts customary for these agents.
  • additives such as lubricants and mold release agents, pigments, dyes, flame retardants, antioxidants, light stabilizers, fibrous and powdery fillers and reinforcing agents and antistatic agents in the amounts customary for these agents.
  • Styrene, acrylonitrile, butyl acrylate and dihydrodicyclopentadienyl acrylate were obtained from BASF AG and prepared without further purification.
  • t-Dodecyl mercaptan was purchased from Bayer AG;
  • Benzoyl peroxide was purchased from Akzo Nobel Chemicals GmbH;
  • Moviol ® 8-88 is a polyvinyl alcohol with a degree of hydrolysis of 88 mol% and a viscosity as a 4% solution in water at 20 ° C of 8 mPa / s, measured according to DIN 53015, and is sold by the former Hoechst AG.
  • Moviol ® 4-88 corresponds to Moviol ® 8-88 with the difference that the viscosity of a 4% solution in water at 20 ° C is 4 mPa / s.
  • the emulsifier K30 is the sodium salt of a C 12 - Ci6 paraffin sulfonic acid and is sold by Bayer AG.
  • Tetrasodium diphosphate was purchased from Merck KGaA.
  • a polybutyl acrylate dihydrodicyclopentadienyl acrylate dispersion (98: 2) was prepared by emulsion polymerization.
  • To prepare a seed latex 16 g of butyl acrylate and 0.4 g of tricyclodecenyl acrylate in 150 g of water with the addition of 1 g of the sodium salt of a C12-C18 paraffin sulfonic acid, 0.3 g of potassium persulfate, 0.3 g of sodium hydrogen carbonate and
  • the solids content was 41.1% and the particle size was 0.080 mm (monodisperse).
  • Ultra-Turax ® stirrer stirred at 7500 rpm for 3 minutes and then into one 6-liter steel kettle transferred, which was equipped with a stirrer and a thermometer, which acted as a baffle.
  • the reaction mixture was heated to 86 ° C with nitrogen and stirring at 150 rpm. After 20 minutes at 86 ° C, a conversion of 14.1% was reached. There were 0.92 g of dicumyl peroxide and 15.2 g of Luviskol ® K90, 6.09 g of Ertivinol ® 30/93 and
  • the reaction mixture was cooled and the solids content was separated off by filtration over Calico ® .
  • the polymer was dried at 80 ° C. under reduced pressure. Small standard sticks were produced from the dried material at a melting temperature of 240 ° C. by injection molding.
  • the reaction mixture was cooled and the solids were separated off by filtration through Calico R and dried at 80 ° C. under reduced pressure.
  • the dried polymer material was used at a melting temperature of 240 ° C. and a mold temperature of 60 ° C.
  • the rubber dispersion was prepared analogously to Example 2 (a).
  • Example 2 (b) Analogously to Example 2 (b), 690 g of styrene, 230 g of acrylonitrile and 1.5 g of t-dodecyl mercaptan were added to 207.8 g of the rubber dispersion. The mixture was swollen at room temperature for 3 hours and then 1.3 g of benzoyl peroxide and 1.33 g of tert-butyl perpivalate were added. The reaction mixture was transferred to a 6 liter steel kettle and as in
  • Example 2 (b) a solution of 15.2 g Luviskol ® K90, 6.09 g Ertivinol ® 30/93 and 2.03 g Na 4 P 2 O 7 in 2030 g water was added. The mixture was converted into a suspension by increasing the stirrer speed and polymerized at 60 ° C. After 2 hours a further 1.23 g of tert-butyl perpivalate were added and the reaction mixture for 12 hours at 60 ° C and for polymerized for a further 5 hours at 86 ° C. The reaction mixture was worked up analogously to Example 2 (b).
  • the rubber dispersion was prepared analogously to Example 2 (a).
  • Example 2 (b) There were 0.81 g of dicumyl peroxide as well as analogous to Example 2 (b), a solution of 15.2 Luviskol ® K90, 6.09 g Ertivinol ® 30/93 and 2.03 g NA PO 7 in 2030 g water was added. The reaction mixture was polymerized and worked up as in Example 2 (b).
  • the rubber dispersion was prepared analogously to Example 2 (a), but no K 30 emulsifier was added.
  • the solids content the dispersion was 38.8%.
  • the mean particle size (D 50) was determined by Fraunhofer laser diffraction to be 1.21 ⁇ m.
  • the mixture was then heated to 60 ° C. and stirred under nitrogen (150 rpm). After 180 minutes, a conversion of 22.2% was reached, whereupon the reaction mixture was increased by increasing the stirrer speed and adding 0.97 g of dicumyl peroxide and a solution of 19.5 g of Luviskol ® K90, 5.85 g of Ertivinol ® 30/93 and 1.95 g Na 4 P 2 O 7 in 1950 g

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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)

Abstract

L'invention concerne un procédé pour produire une matière plastique résistant aux chocs, à base de particules de caoutchouc réticulé, ledit procédé consistant à : (a) produire une dispersion ou une suspension aqueuse de particules d'un caoutchouc réticulé à partir d'un premier mélange de monomères présentant < 50 % en poids, de préférence < 5 % en poids, idéalement < 2 % en poids de composés diène conjugués ; (b) précipiter la dispersion ou la suspension, éventuellement avec obtention d'un mélange de particules de caoutchouc aqueux, présentant une teneur en eau d'au moins 5 % en poids ; (c) ajouter la suspension ou la dispersion de particules du caoutchouc ou le mélange de particules de caoutchouc aqueux à un deuxième mélange qui contient au moins un autre monomère ; et (d) polymériser les monomères du deuxième mélange. L'invention concerne également une matière plastique résistant aux chocs obtenue selon ledit procédé.
EP01902358A 2000-01-27 2001-01-26 Procede pour produire des matieres plastiques resistant aux chocs Withdrawn EP1263820A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10003508A DE10003508A1 (de) 2000-01-27 2000-01-27 Verfahren zur Herstellung schlagzäher Kunststoffe
DE10003508 2000-01-27
PCT/EP2001/000895 WO2001055232A1 (fr) 2000-01-27 2001-01-26 Procede pour produire des matieres plastiques resistant aux chocs

Publications (1)

Publication Number Publication Date
EP1263820A1 true EP1263820A1 (fr) 2002-12-11

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EP01902358A Withdrawn EP1263820A1 (fr) 2000-01-27 2001-01-26 Procede pour produire des matieres plastiques resistant aux chocs

Country Status (6)

Country Link
US (1) US20030018127A1 (fr)
EP (1) EP1263820A1 (fr)
KR (1) KR20020068410A (fr)
AU (1) AU2001230211A1 (fr)
DE (1) DE10003508A1 (fr)
WO (1) WO2001055232A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080080606A (ko) * 2005-12-12 2008-09-04 카네카 코포레이션 중합체 입자 및 그 제조 방법, 그리고 그 중합체 입자를함유하는 수지 조성물, 및 성형체

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5230996B2 (fr) * 1972-05-15 1977-08-11
IL47035A (en) * 1974-07-01 1978-04-30 Stauffer Chemical Co Process for the preparation of interpolymer particles containing an acrylic elastomer and vinyl chloride
DE3839588A1 (de) * 1988-11-24 1990-05-31 Bayer Ag Polymerblendsysteme mit guter alterungsbestaendigkeit
US5380785A (en) * 1993-04-05 1995-01-10 The Goodyear Tire & Rubber Company Rubbery polymer
DE69626361T2 (de) * 1995-10-27 2004-02-12 Atofina Chemicals, Inc. Schlagzähmodifikator vom Kern/Schale-Typ für thermoplastische Polymere

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0155232A1 *

Also Published As

Publication number Publication date
WO2001055232A1 (fr) 2001-08-02
KR20020068410A (ko) 2002-08-27
AU2001230211A1 (en) 2001-08-07
DE10003508A1 (de) 2001-08-02
US20030018127A1 (en) 2003-01-23

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