WO1999037688A1 - Polymeres greffes obtenus par microsuspension et leur procede de production - Google Patents

Polymeres greffes obtenus par microsuspension et leur procede de production Download PDF

Info

Publication number
WO1999037688A1
WO1999037688A1 PCT/EP1999/000392 EP9900392W WO9937688A1 WO 1999037688 A1 WO1999037688 A1 WO 1999037688A1 EP 9900392 W EP9900392 W EP 9900392W WO 9937688 A1 WO9937688 A1 WO 9937688A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
weight
graft
polymer
microsuspension
Prior art date
Application number
PCT/EP1999/000392
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mckee
Heiner GÖRRISSEN
Michael Fischer
Walter Kastenhuber
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1999037688A1 publication Critical patent/WO1999037688A1/fr

Links

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
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated ethers
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • 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
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
    • C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
    • 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
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/02—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of vinyl esters with monocarboxylic acids
    • 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

Definitions

  • the invention relates to microsuspension (graft) polymers, processes for their preparation, their use and molding compositions containing them.
  • Emulsion polymerization has long been used to produce small-particle polymer particles. It is a heterogeneous reaction process in which unsaturated monomers or monomer solutions are emulsified in a continuous phase, usually water, with the aid of an emulsifier system and polymerized with initiators which form free radicals. A colloidal dispersion of the polymer or the polymer solution, a so-called latex, is obtained as the product.
  • the emulsifier system forms micelles into which the at least partially water-soluble monomers from the emulsified monomer droplets migrate through the water phase. With the help of initiators contained in the water phase, the polymerization is triggered in the micelles.
  • the monomers used must have a certain water solubility in order to be able to migrate from the monomer droplets through the aqueous phase into the micelles.
  • Examples of monomers that can be used are styrene, butadiene, acrylic acid, vinyl chloride, acrylonitrile and others. A corresponding procedure is described in Encyclopedia of Polymer Science and Engineering, Volume 6, page 1 (1986), John Wiley & Sons, New York.
  • the object of the present invention is to provide a process for the production of particulate polymers of sparingly or not water-soluble monomers which avoids the disadvantages of the known processes.
  • the object is achieved according to the invention by a rubber-elastic microsuspension polymer AI with an average particle diameter of 0.08 to 100 ⁇ m from components All to A13, the total weight of which is 100% by weight, all: 1 to 100% by weight of monomers a water solubility of less than
  • al2 0 to 99% by weight of further copolymerizable monomers as component A12.
  • al3 0 to 10% by weight of crosslinking monomers as component A13.
  • microsuspension graft polymer A from al: 1 to 99.9% by weight of a graft core, as defined above, as component AI, a2: 0.1 to 99% by weight of at least one graft shell from an organic Polymer as component A2. - 3 -
  • microsuspension polymerization is described, for example, in DE-A-44 43 886.
  • the (graft) polymers according to the invention are preferably obtained as follows:
  • the liquid monomer or liquid monomer mixture which is to be polymerized to give the particulate (core) polymer is mixed with water and a protective colloid.
  • the (preferably water-insoluble) polymerization initiator is either counteracted either now or only after the monomers have been dispersed. - 4 -
  • a dispersion of tiny monomer droplets in water is produced from the heterogeneous mixture by intensive stirring at high speed with strong shear. Intensive mixers of any type are suitable for this.
  • the desired particle size can be determined, for example, by taking light micrographs and counting the number of particles which have a specific diameter.
  • the polymerization is started by heating the dispersion.
  • the reaction with moderate stirring, during which the droplets are no longer broken up, is continued until the conversion, based on the amount of monomers originally used, is above 50%, preferably above 85%.
  • the reaction can be terminated at this stage. If a microsuspension polymer consisting of only one core is desired, the reaction can be terminated at this stage. If a microsuspension graft polymer is desired, the reaction with the monomers from which the corresponding shells are to be made is continued in a manner known per se. The grafting can also be started when the polymerization conversion of the core monomers is still incomplete and above 50%, preferably above 85%. In this case, the shell and core form a more fluid transition compared to the sharper demarcation of core and shell polymer in the event that the core monomers are initially completely converted.
  • multi-shell polymers can be obtained. This can also depend on the particle size desired. Processes for the preparation of multi-shell graft copolymers are described, for example, in EP-A-0 548 762. If the graft cores are relatively small and it is desired to introduce a larger amount of the core polymer into the particles, multi-shell graft copolymers can also be produced in which one of the shells is built up from the core monomers. - 5 -
  • the monomers are generally dispersed at a temperature of 0 to 100 ° C., preferably at about room temperature. As a rule, 0.2 to 10 kg of water are used per kg of monomers.
  • the protective colloids suitable for stabilizing the dispersion are water-soluble polymers which coat the monomer droplets and the polymer particles formed therefrom and in this way protect against coagulation.
  • Protective colloids are cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose, poly-N-vinyl pyrrolidone, polyvinyl alcohol and polyethylene oxide, anionic polymers such as polyacrylic acid and cationic polymers such as poly-N-vinyl imidazole.
  • the amount of these protective colloids is preferably 0.1 to 5% by weight, based on the total mass of the monomers of the core.
  • low molecular weight surface-active compounds for example of the anionic or cationic soap type, can also be used.
  • Such compounds, which are usually used for emulsion polymerizations are described, for example, in "Emulsion Polymerization and Emulsion Polymers", published by P.A. Lovell and M. El-Aasser, John Wiley & Sons, Chichester (1997), pages 224 to 227.
  • Free radical initiators are suitable as polymerization initiators, in particular those which are soluble in the monomers and which preferably have a half-life of 10 hours when the temperature is between 25 and 150 ° C.
  • Such initiators are described, for example, in the AKZO "Initiators for Polymer Production" product catalog.
  • peroxides such as lauryl peroxide, peroxosulfates, tert-butyl perpivalate and azo compounds such as azodiisobutyronitrile are suitable.
  • oil-soluble radical formers preferably dilauryl peroxide, benzoyl peroxide and 2,2'-azo-bis-isobutyronitrile
  • Initiators such as hydrogen peroxide, potassium, ammonium and sodium peroxide are used, in particular if smaller particles of less than 1.0 ⁇ m are also to be obtained.
  • initiators can be used to produce the graft core and the graft shells.
  • the amount of initiators is generally 0.1 to 2.5% by weight, based on the amount of monomers.
  • reaction mixture preferably contains buffer substances, such as Na 2 HPO 4 / NaH 2 PO 4 or Na citrate / citric acid, in order to set an essentially constant pH.
  • buffer substances such as Na 2 HPO 4 / NaH 2 PO 4 or Na citrate / citric acid
  • molecular weight regulators such as ethylhexyl thioglycolate or decenyl mercaptan, are generally added during the polymerization, in particular of the monomers which make up the shells.
  • the temperature in the polymerization of the monomers of the core is generally 25 to 150 ° C., preferably 50 to 120 ° C.
  • the shells are generally grafted onto the core at a temperature of 25 to 150 ° C., preferably 50 to 120 ° C.
  • the lower limit values of these ranges correspond to the decomposition temperatures of the polymerization initiators used in each case.
  • the microsuspension polymer AI has an average particle diameter of 0.08 to 100 ⁇ m, preferably 0.2 to 50 ⁇ m, particularly preferably 0.3 to 30 ⁇ m.
  • the particle size can be determined using different methods. For example, it is determined by light scattering. The light scattering method, as available from Leeds & Northrop, North Wales, PA, is preferred. It can also be used with devices from Particle Data, Elmhurst, Illinois, USA, for example with the ELZONE * 280PC system.
  • Component AI contains 1 to 100% by weight, preferably 3 to 100% by weight, particularly preferably 5 to 100% by weight of monomers with a water solubility of less than 0.01% at 23 ° C., preferably less than 0.007%, particularly preferably less than 0.005% as component All.
  • the figures are% by weight and relate to the amount of water.
  • component AI are preferably C ⁇ Q-alkyl methOacrylate, C ⁇ - Aralkyl (meth) acrylate, C ⁇ o-Ary me ⁇ acrylate,. 2 o-alkaryl (meth) acrylate, ⁇ -olefins with 2 to 20 C atoms, polyisobutylenes with 3 to 50 isobutene units and optionally a terminal vinyl or vinylidene group, polypropylenes with a terminal vinyl or vinylidene group with 3 to 100 propylene units, oligohexene , Oligooctadecen, C ⁇ 40 -alkyl vinyl ether, mono- or diesters of maleic acid or fumaric acid with Cg ⁇ -alkanols, vinyl esters of saturated C 1M0 -carboxylic acids or mixtures thereof.
  • Monomers whose water solubility is not above the water solubility of n-octyl acrylate are particularly preferably used.
  • C 8 are particularly preferred.
  • ⁇ - Aralkyl net acrylate C ⁇ o- aryl (meth) acrylate, C 7 . 2 o-alkaryl (meth) acrylate, ⁇ -olefins with 6-20 C atoms, polyisobutylenes with 5-30 isobutene units and possibly a terminal vinyl or vinylidene group, polypropylenes with a terminal vinyl vinylidene group with 7-30 propylene units, C 10.24 -Alkyl vinyl ether and vinyl esters of saturated C 10 . 24 carboxylic acids.
  • the monomers of component All can be polymerized without comonomers or copolymerized with monomers of components A12 and A13.
  • monomers of components A12 and A13 For example, 0 to 99% by weight, preferably 0 to 97% by weight, particularly preferably 0 to 95% by weight, of further copolymerizable monomers - 8th -
  • component A12 can be used as component A12.
  • These can be comonomers polymerizable with the emulsion polymerization (free radical).
  • .g-alkyl meth acrylates preferably n-butyl acrylate and / or 2-ethylhexyl acrylate, can be used.
  • Styrene, ⁇ -methylstyrene, acrylonitrile and methacrylonitrile can also be used.
  • Other suitable comonomers are described in Ulimann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pages 1-30, Verlag Chemie, Weinheim.
  • crosslinking monomers can be used as component A13.
  • this are bifunctional and polyfunctional comonomers such as butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers, bifunctional alcohols such as ethylene glycol or butane-l, 4-diol, diesters of acrylic acid and methacrylic acid with the bifunctionalelles Alcohols, 1,4-divinylbenzene and triallyl cyanurate.
  • the acrylic ester of tricyclodecenyl alcohol is particularly preferred
  • the microsuspension graft polymers A of this type are from 1 to 99.9% by weight, preferably 10 to 99.5% by weight, particularly preferably 40 to 99% by weight, one as above described graft core as component AI and 0.1 to 99% by weight, preferably 0.5 to 90% by weight, particularly preferably 1 to 60% by weight, of at least one graft shell composed of a polymer as component A2.
  • Component A2 may in particular be styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid ester or mixtures thereof.
  • the outermost shell preferably corresponds to the matrix polymer or is compatible or partially compatible with it.
  • a very low degree of grafting is predominantly reactive groups that can react with the polymer matrix, for example. Examples are (meth) acrylic acid and glycidyl (meth) acrylate, which can react with polyamides, for example.
  • the particulate graft polymers according to the invention serve mainly as additives to brittle, thermoplastic, macromolecular base materials (polymer matrix).
  • the invention also relates to a molding composition of this type comprising components A to D, the total weight of which gives 100% by weight, a: 1 to 85% by weight, preferably 2 to 80% by weight, of at least one microsuspension graft polymer described above as component A, b: 15 to 99% by weight, preferably 20 to 98% by weight, of a polymer matrix, for example Polyamide, polyester, polyoxymethylene or preferably a polymer made from styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid esters or mixtures thereof as component B, c: 0 to 50% by weight, preferably 0 to 40% by weight, fibrous or particulate fillers or mixtures thereof as component C, and d: 0 to 40% by weight, preferably 0 to 30%
  • component A By adding component A, the impact strength of the molding composition is improved. On the other hand, caused by diffuse reflection (scattering) of the light on the large particles, molding compounds with reduced surface gloss and correspondingly matt molded parts are obtained.
  • the rubber-elastic particles are incorporated into the melt of matrix B, so that the molding composition formed is composed of thermoplastic matrix B and the graft polymer particles dispersed therein.
  • the rule is that the outermost shell and the matrix material B are compatible or partially compatible with one another. In many cases this means - 10 -
  • outer graft shell is made of the same or similar material as the base polymer.
  • the technically most important base polymers are homopolymers of styrene, methyl acrylate, (C M alkyl) methacrylates and acrylonitrile, copolymers of these monomers and other comonomers such as methacrylonitrile, ie these monomers and monomer mixtures are suitable depending on the structure of base polymer B. to build up the outer graft shell.
  • the outer shell is to be relatively hard, intermediate shells made of a less hard material can be recommended.
  • the first hard grafting shell can be followed by a shell made of soft material, for example the core material, which can often further improve the properties of the thermoplastic molding compositions produced from the matrix B and the graft polymer particles A and the moldings produced therefrom.
  • the relationships between the nature of both components in the molding compositions and the material properties correspond, moreover, to those known for the base material and graft polymers which are prepared by emulsion polymerization.
  • base materials B other than those mentioned, e.g. Polyesters, polyamides, polyvinyl chloride, polycarbonates and polyoxymethylene. In these cases, compatible and partially compatible graft shells can be easily determined through a few preliminary tests.
  • Compatibility is understood as miscibility at the molecular level.
  • One polymer is considered to be compatible with another if the molecules of both polymers are statistically distributed in the solid state, i.e. if the concentration of a polymer along any vector neither increases nor decreases. Conversely, it is considered incompatible if two phases are formed in the solid state, which are separated from one another by a sharp phase boundary. Along a vector intersecting the phase interface, the concentration of one polymer suddenly increases from zero to 100% and that of the other from 100% to zero. - 11 -
  • solubility parameter as a quantitative measure is e.g. the Polymer Handbook, ed. J. Brandrup and E.H. Immergut, 3rd edition, Wiley, New York 1989, pp. VII / 519-V ⁇ / 550.
  • the graft polymers according to the invention are generally used in amounts of 1 to 85, preferably 2 to 80,% by weight, based on the amount of their mixture with the base polymer. Shaped bodies made from such mixtures are highly light-scattering and therefore particularly matt to opaque.
  • concentrations of 2 to 10% by weight of the graft polymers are recommended. There with these - 12 -
  • the particles according to the invention achieve a matting effect, often without impairing mechanical properties, as can be observed with conventional matting agents such as chalk or silica gel.
  • the protective colloids used in the production of the core polymers have, because of their higher molecular mass and greater space filling of the molecules, much less effort than the low molecular weight emulsifiers to migrate to the surface of the plastic. High molecular protective colloids are therefore far less likely to exude from a molded part.
  • the molding compositions modified with the particles according to the invention and the moldings produced therefrom have the advantages of improved printability and so-called anti-blocking properties, ie the surfaces of the moldings “roughened” by the particles do not adhere to one another.
  • This effect due to adhesion is known, for example, from plastic films.
  • Films containing particles according to the invention and layered on top of one another in a stack can be separated from one another without any problems, in contrast to films which do not contain such particles. - 13 -
  • the molding compositions can contain fibrous or particulate fillers or mixtures thereof as component C.
  • fibrous or particulate fillers or mixtures thereof are carbon fibers or glass fibers, for example made of E, A or C glass. They can preferably be equipped with a size and an adhesion promoter.
  • Other fillers or reinforcing materials are glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite.
  • the molding compositions can also contain additives of all kinds as component D.
  • additives of all kinds as component D for example, Lubricants and mold release agents, pigments, flame retardants, dyes, stabilizers and antistatic agents, all of which are added in the usual amounts.
  • the molding compositions according to the invention can be prepared by mixing processes known per se, e.g. by incorporating the particulate graft polymer into the base material at temperatures above the melting point of the base material, in particular at temperatures of 150 to 350 ° C. in conventional mixing devices. Films, fibers and moldings with reduced surface gloss (mattness) and high impact strength can be produced from the molding compositions according to the invention.
  • the polymer components do not separate in the films, fibers and moldings.
  • the particle size distribution was determined using an Elzone ® 28.0PC device from Particle
  • the D (50) value is the value at which 50 volume percent of the particles are larger and 50 volume percent of the particles are smaller than this value.
  • the following batch was stirred under nitrogen with a Dispermat at 7000 rpm for 20 minutes.
  • the Dispermat came from VMA-Getzmann GmbH, D-51580 Reichshof and was provided with a 5cm tooth lock washer. This process was repeated and the two emulsions obtained were mixed.
  • step (a) To the finished and stable dispersion from step (a) came 1714.6 g of water, followed by 151.4 g of a 10% strength Mowiol 8-88 solution in water, 1135.8 g of styrene and 378.6 g of acrylonitrile, where the monomers were added as a feed of 120 minutes. After a reaction time of 150 minutes, the mixture was cooled. The amount of coagulum was 1 g (moist).
  • the average particle size was 2.4 ⁇ m.
  • Example 1 was repeated, but instead of 540.2 g of lauryl acrylate, 540.2 g became
  • the amount of coagulum was 10 g (moist).
  • the average particle size was 2.3 ⁇ m.
  • Example 1 was repeated, but in addition 27.5 g of a 40% solution of the potassium salt of a C 12 were used in the emulsification step. lg -paraffin sulfonic acid in water (emulsifier K30) used per emulsifier.
  • the amount of coagulum was 1 g and the mean particle size was 0.52 ⁇ m.
  • Example 3 was repeated, but stearyl acrylate was used instead of lauryl acrylate.
  • the amount of coagulum was 3 g and the mean particle size was 0.52 ⁇ m.
  • Example 4 was repeated, but instead of 540.2 g butyl acrylate and 540.2 g stearyl acrylate, 110.3 g butyl acrylate and 992.3 g stearyl acrylate were used.
  • the amount of coagulum was 1 g and the mean particle size was 0.77 ⁇ m.
  • Example 5 was repeated, but lauryl acrylate was used instead of stearyl acrylate.
  • the amount of coagulum was 2 g.
  • Example 4 was repeated, but instead of 540.2 g of butyl acrylate and 540.2 g of stearyl acrylate, 1080.5 g of lauryl acrylate were used. The amount of coagulum was 1 g.
  • Paraffin sulfonic acid in water 1.1 g potassium persulfate - 17 -
  • the batch was polymerized for 60 minutes.
  • stage 1 There was coagulation during the preparation of stage 1. The batch coagulated completely during grafting.
  • Example 8 was repeated, but with stearyl acrylate instead of lauryl acrylate.
  • stage 1 There was coagulation during the preparation of stage 1. The batch coagulated completely during grafting.

Landscapes

  • 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)

Abstract

L'invention concerne un polymère A' obtenu par microsuspension, possédant l'élasticité du caoutchouc et présentant un diamètre moyen de particules compris entre 0,08 à 100 νm. Ce polymère est constitué des composants A11 à A13 dont le poids total est égal à 100 % en poids, a11 représentant 1 à 100 % en poids de monomères présentant une solubilité dans l'eau inférieure à 0,01 % à 23 °C, en tant que composant A11; a12 représentant 0 à 99 % en poids d'autres monomères copolymérisables, en tant que composant A12; a13 représentant 0 à 10 % en poids de monomères réticulants en tant que composant A13.
PCT/EP1999/000392 1998-01-21 1999-01-21 Polymeres greffes obtenus par microsuspension et leur procede de production WO1999037688A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19802093.7 1998-01-21
DE1998102093 DE19802093A1 (de) 1998-01-21 1998-01-21 Mikrosuspensions(pfropf)polymerisate und Verfahren zu ihrer Herstellung

Publications (1)

Publication Number Publication Date
WO1999037688A1 true WO1999037688A1 (fr) 1999-07-29

Family

ID=7855213

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/000392 WO1999037688A1 (fr) 1998-01-21 1999-01-21 Polymeres greffes obtenus par microsuspension et leur procede de production

Country Status (2)

Country Link
DE (1) DE19802093A1 (fr)
WO (1) WO1999037688A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005021335A1 (de) * 2005-05-04 2006-11-09 Röhm Gmbh Verfahren zur Herstellung von Perlpolymerisaten mit einer mittleren Teilchengröße im Bereich von 1 µm bis 40 µm sowie Perlpolymerisat aufweisende Formmassen und Formkörper

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849480A (en) * 1985-10-23 1989-07-18 E. I. Du Pont De Nemours And Company Crosslinked polymer microparticle
WO1992000719A1 (fr) * 1990-07-09 1992-01-23 Dowbrands Inc. Composition de maquillage
EP0708145A1 (fr) * 1994-10-20 1996-04-24 Basf Aktiengesellschaft Masses de moulage thermoplastiques
DE4443886A1 (de) * 1994-12-09 1996-06-13 Basf Ag Kautschukelastische Pfropfpolymerisate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4849480A (en) * 1985-10-23 1989-07-18 E. I. Du Pont De Nemours And Company Crosslinked polymer microparticle
WO1992000719A1 (fr) * 1990-07-09 1992-01-23 Dowbrands Inc. Composition de maquillage
EP0708145A1 (fr) * 1994-10-20 1996-04-24 Basf Aktiengesellschaft Masses de moulage thermoplastiques
DE4443886A1 (de) * 1994-12-09 1996-06-13 Basf Ag Kautschukelastische Pfropfpolymerisate

Also Published As

Publication number Publication date
DE19802093A1 (de) 1999-07-22

Similar Documents

Publication Publication Date Title
DE3686057T2 (de) Verfahren zur herstellung von polymerteilchen, diese polymerteilchen und ihre verwendung.
EP0113924B1 (fr) Agent de modification de la résistance à l'impact
DE69115546T2 (de) Herstellung von Polymerteilchen
DE68907521T2 (de) Mehrstufige opazifierende Polymerpartikel mit absorbierter nichtpolymerisierbarer Säure.
DE69633916T2 (de) Verbundmaterial und daraus hergestellte formteile
DE2249023C3 (de) Thermoplastische Formmassen
EP0796287B1 (fr) Procede pour la preparation des polymeres greffes caoutchouteux
DE2432994A1 (de) Pfropfpolymere und ihre verwendung zur verbesserung der schlagfestigkeit von vinylchlorid-homo- oder copolymeren
EP0033365B1 (fr) Procédé de préparation de masses à mouler résistant au choc
DE3723274A1 (de) Sequenz-erzeugte polymerteilchen, waessrige dispersionen von sequenz-erzeugten polymerteilchen, verfahren zur herstellung von sequenz-erzeugten polymerteilchen und verwendung von sequenz-erzeugten polymerteilchen
DE3886833T2 (de) Verfahren zur Herstellung von Pfropfharzzusammensetzungen.
EP1049737B1 (fr) Procede de precipitation de polymerisats en microsuspension
DE2511799A1 (de) Verfahren zur herstellung eines vinylpfropfmischpolymerharzes
DE3885546T2 (de) Verfahren zur Herstellung eines schlagfesten thermoplastischen Harzes.
EP0094525B1 (fr) Caoutchouc greffé pour la modification de masses à mouler thermoplastiques
WO1999037688A1 (fr) Polymeres greffes obtenus par microsuspension et leur procede de production
WO1999037699A1 (fr) Polymerisat greffe en micro-suspension et son procede de fabrication
EP1049732A1 (fr) Procede de fabrication de polymerisats (greffes) en microsuspension ayant l'elasticite du caoutchouc
DE1570855C3 (de) Verfahren zur Herstellung eines Pfropfmischpolymerisats
EP0124700B1 (fr) Masses transparentes de chlorure de polyvinyle
WO1999037690A1 (fr) Procede pour produire des polymeres particulaires
EP1045864A1 (fr) Polymere obtenu par microsuspension renfermant des groupes acide
DE1950622A1 (de) Verbessertes ABS-Harz und Verfahren zu seiner Herstellung
AT226436B (de) Verfahren zur Herstellung von heterogen aufgebauten Mischpolymerisaten
DE3104409A1 (de) Schlagzaehe thermoplastische formmassen

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP KR MX US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: KR

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA