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WO1999037690A1 - Procede pour produire des polymeres particulaires - Google Patents

Procede pour produire des polymeres particulaires Download PDF

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Publication number
WO1999037690A1
WO1999037690A1 PCT/EP1999/000393 EP9900393W WO9937690A1 WO 1999037690 A1 WO1999037690 A1 WO 1999037690A1 EP 9900393 W EP9900393 W EP 9900393W WO 9937690 A1 WO9937690 A1 WO 9937690A1
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Prior art keywords
weight
polymer
component
polymers
monomers
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.)
Ceased
Application number
PCT/EP1999/000393
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German (de)
English (en)
Inventor
Graham Edmund Mckee
Heiner GÖRRISSEN
Jürgen Koch
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BASF SE
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BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP99907397A priority Critical patent/EP1045865A1/fr
Publication of WO1999037690A1 publication Critical patent/WO1999037690A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Definitions

  • the invention relates to a process for the production of particulate polymers, such polymers and their use for the production of small-sized polymer particles which can be, for example, rubber-elastic and can be used as a rubber component in polymer blends.
  • the polymer particles can be produced by the microsuspension process.
  • a liquid monomer or liquid monomer mixture which is to be polymerized to the particulate polymer is mixed with water and a protective colloid.
  • the preferably water-insoluble polymerization initiator is added at this point in time or only after the monomers have been dispersed, if appropriate also after the dispersion has been heated.
  • a dispersion of tiny monomer droplets in water is produced from the heterogeneous mixture by intensive stirring at high speed with strong shear or by using ultrasound. Intensive mixers of any type, high-pressure homogenizers and ultrasound are used for this.
  • the polymerization is carried out by heating the dispersion and continued with moderate stirring, during which the droplets are no longer divided, until a desired conversion is achieved.
  • Core-shell polymer particles can be obtained by adding different monomers at different times.
  • the protective colloids used to stabilize the dispersion are generally water-soluble polymers which coat the monomer droplets and the polymer particles formed therefrom and in this way protect them from coagulation.
  • the production of particulate microsuspension polymers is described, for example, in DE-A-44 43 886.
  • DE-A-44 43 886 states that low molecular weight surface-active compounds such as anionic or cationic soaps cannot be added in microsuspension polymerization.
  • microsuspension polymers do not have a sufficiently small particle size for all applications.
  • dispersions obtained are often difficult to coagulate.
  • the object of the present invention is to provide a process for the production of particulate polymers with a small particle size, the polymers being easy to coagulate.
  • the object is achieved according to the invention by a process for the production of rubber-elastic particulate polymers by (1) dispersing all: 85 to 100% by weight of ethylenically unsaturated monomers whose homopolymers are rubber-elastic as components All, al2: 0 to 15% by weight % crosslinking monomers as component A12, in water using a protective colloid and an emulsifier 3
  • a dispersion with an average particle diameter of 0.08 to 8 ⁇ m (2) polymerization of the droplets with a, preferably hydrophobic radical, polymerization initiator and optionally (3) graft polymerization of the mixture obtained in step (2) in the presence of ethylenically unsaturated monomers.
  • the particulate polymers according to the invention can advantageously be mixed with thermoplastic polymers, the following properties resulting: -
  • the surface gloss, depending on the spraying conditions, can be set slightly between high-gloss and matt
  • the molded body shows fewer flow lines and streaks on the surface
  • the foam body shows a higher one Toughness, even in the cold, especially a combination of high biaxial and uniaxial toughness - the molding compounds are easier to color
  • the particulate polymers obtained in the process according to the invention can be precipitated or coagulated. If a microsuspension polymer is prepared without the addition of a soap, then no precipitation or coagulation of the microsuspension dispersions can be achieved by adding conventional precipitants, such as those used for the precipitation of polymers prepared by the emulsion process. This means that, for example, when microsuspension polymers are incorporated into thermoplastics, the microsuspension polymer must be spray-dried or pumped directly into the polymer melt (see EP-A-0 125 483). In both processing methods, auxiliaries remain in the microsuspension polymer and can lead to premature aging and discoloration of the products. The procedures are also expensive.
  • the (graft) polymers according to the invention are preferably obtained as follows:
  • the liquid monomer or monomer mixture which is to be polymerized to give the (core) polymer is mixed with water, a protective colloid and a
  • the polymerization initiator is either also now or only after dispersing the monomer or monomers or after
  • Preparing monomer droplets in water Intensive mixers of any type and ultrasound are suitable for this.
  • the desired particle size within the range according to the invention can be determined, for example, by taking light microscopic images and by counting the number of particles which have a specific diameter.
  • the polymerization is started by heating the dispersion.
  • the reaction is carried out with moderate stirring, during which the droplets are no longer divided, and is continued until the conversion, based on the monomers, is above 50%, particularly preferably above 85%.
  • the reaction with the monomers to produce the graft shell can be continued in a manner known per se.
  • the grafting can also begin when the polymerization conversion of the core monomer 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 monomer is initially completely converted.
  • the graft polymer can have one or more graft shells. If the particles are in a matrix, e.g. a thermoplastic polymer, incorporated, it is advantageous if the outermost graft shell is compatible or partially compatible with the matrix.
  • a matrix e.g. a thermoplastic polymer
  • the core monomers are generally dispersed at a temperature of 0 to 100 ° C., preferably at room temperature.
  • the weight ratio of monomer to water is 1:99 to 85:15, preferably 15:85 to 80:20, particularly preferably 20:80 to 70:30.
  • 0.5 to 10 kg of water are used per kg of the monomers.
  • the protective colloids suitable for stabilizing the dispersion are generally water-soluble polymers which coat the monomer droplets and the polymer particles formed therefrom and in this way protect them from coagulation.
  • Suitable 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. Further suitable protective colloids are described in "Emulsion Polymerization and Emulsion Polymers", edited by P. Lovell and M. El-Aasser, Verlag Wiley and Sons 1997, page 226.
  • the amount of these protective colloids is preferably 0.1 to 5% by weight, particularly preferably 0.2 to 4% by weight, based on the total mass of the core monomers.
  • the additional emulsifier used is used in an amount of 0.005 to * 10% by weight.
  • the emulsifier is preferably cationic or anionic, in particular cationic or anionic soaps can be used become. These are described, for example, in "Encyclopedia of Polymer Science and Technology", J. Wiley and Sons (1966), Volume 5, pages 816 to 818, and in the preceding book “Emulsion Polymerization and Emulsion Polymers” on page 224. Examples are alkali metal salts of organic carboxylic acids with s chain lengths of 8 to 30 carbon atoms, preferably 12 to 18 carbon atoms. These are commonly referred to as soaps. As a rule, they are used as sodium, potassium or ammonium salts. In addition, alkyl sulfates and alkyl or alkylarylsulfonates can be used as anionic emulsifiers.
  • Suitable cationic emulsifiers are salts of amines or diamines, quaternary ammonium salts, and salts of long-chain substituted cyclic amines, such as pyridine, morpholine, piperidine. Quaternary ammonium salts of trialkylamines are used in particular.
  • the alkyl radicals therein preferably have 1 to 20 carbon atoms. 5
  • Free radical formers are suitable as polymerization initiators, in particular those which are soluble in the monomers and preferably have a half-life of 10 hours if the temperature is between 25 and 150 ° C.
  • peroxides such as dilauroyl peroxide, peroxosulfates, teit-butyl perpivalate 0 and azo compounds such as azodiisobutyronitrile are suitable.
  • Various 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.
  • Suitable initiators are described in the Akzo product catalog "Initiators for Polymer Production".
  • Water-soluble initiators are, for example, hydrogen peroxide, potassium, ammonium and sodium peroxide or persulfate.
  • reaction mixture can preferably contain buffer substances such as Na 2 HPO 4 / NaH 2 PO 4 or Na citrate / citric acid in order to set a substantially constant pH.
  • molecular weight regulators such as ethylhexylthioglycolate or dodecyl mercaptan are generally added in the polymerization, in particular of the monomers which form the graft shells.
  • the polymerization temperature of the monomers for the (core) polymer is generally 25 to 150 ° C, preferably 50 to 120 ° C.
  • the shells are grafted onto the core in general at 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.
  • crosslinking monomers can be used as component A12.
  • Such bifunctional or polyfunctional comonomers are, for example, butadiene and isoprene, divinyl esters of dicarboxylic acids such as succinic acid and adipic acid, diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol and butane-1,4-diol, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols mentioned, 1,4-divinylbenzene and triallyl cyanurate.
  • the acrylic acid ester of tricyclodecenyl alcohol (dihdrodicyclopentadienyl acrylate) and the AUyl esters of acrylic acid and methacrylic acid are particularly preferred.
  • crosslinkers are also described in Ullmann's Encyclopedia of Technical Chemistry, 4th edition, volume 19, pages 1-30.
  • the polymer particles are used as impact modifiers for thermoplastics, they preferably have a glass transition temperature of less than 0 ° C., particularly preferably less than -10 ° C.
  • the particle size of the polymer droplets obtained in stage (2) is 0.08 to 8 ⁇ m, preferably 0.1 to 4 ⁇ m, in particular 0.15 to 2.0 ⁇ m.
  • the mean particle diameter corresponds to the D 50 value, according to which 50% by weight of all particles have a smaller and 50% by weight a larger diameter.
  • the D 10 and Dgo values are often specified, which are defined accordingly.
  • the polymer particles can have a homogeneous structure or consist of a core and one or more shells.
  • the particulate polymers produced according to the invention can be incorporated into a large number of thermoplastic molding compositions.
  • the molding compositions show good mechanical properties, in particular good toughness, and the surface gloss can be varied within wide limits.
  • Molding compositions according to the invention contain components A to D, the total weight of which is 100% by weight,
  • a 0.1 to 80% by weight of at least one particulate polymer as described above as component A, b: 20 to 99.9% by weight of a polymer matrix, for example polyamide,
  • Polyester polyoxymethylene, polycarbonate, polysulfone, polyether sulfone or preferably a polymer of styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic esters or mixtures thereof as component B, c: 0 to 50% by weight of fibrous or particulate fillers or their mixtures as component C and d: 0 up to 30% by weight of further additives as component D.
  • the amount of component A is preferably 1 to 75% by weight, in particular 2 to 70% by weight.
  • the amount of component B is preferably 25 to 99% by weight, in particular 30 to 98% by weight.
  • the amount of component C is preferably 0 to 40% by weight, in particular 0 to 30% by weight.
  • the amount of component D is preferably 0 to 25% by weight, in particular 0 to 20% by weight.
  • the polymer particles are incorporated into the melt of matrix B, so that the molding compound formed is built up from thermoplastic matrix B and the (graft) polymer particles dispersed therein.
  • the outermost shell of the particles is preferably compatible or partially compatible with the polymer matrix B, or it reacts with the polymer matrix B.
  • aryl acid or glycidyl methacrylate can be built into the particle, which react with functional groups of the matrix.
  • the technically most important base polymers are mentioned above. Homopolymers of styrene, methyl acrylate, (C ⁇ 4 -alkyl) methacrylates and acrylonitrile, copolymers of these monomers and other comonomers such as methacrylonitrile are preferred. Depending on the structure of the base polymer B, these monomers and monomer mixtures are also suitable for building the outer graft shell.
  • Recommend intermediate shells made of a less hard material can be attached to the first hard grafting shell
  • Graft polymer particles A produced thermoplastic molding compositions and the moldings produced therefrom often can be further improved.
  • 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 as preferred, 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.
  • it is considered to be incompatible if two phases are formed in the solid state, which are separated from one another by a sharp phase boundary. Along a vector that intersects the phase interface, the concentration of one polymer suddenly increases from zero to 100% and that of the other from 100% to zero.
  • solubility parameter as a quantitative measure is e.g. the Polymer Handbook, ed. J. Brandrup and E.H. Immergut, 3rd ed., Wüey, New York 1989, pp. VII / 519- VII / 550.
  • the graft polymers according to the invention are generally used in amounts of 1 to 60, preferably 2 to 45,% by weight, based on the amount of their mixture with the base polymer. Shaped bodies made from such mixtures can be highly light-scattering and therefore particularly matt to opaque.
  • concentrations of 2 to 10% by weight of the graft polymers are recommended. Since only a relatively small increase in impact strength would result at these low concentrations, conventional, very finely divided rubber-elastic modifiers can be used in the usual amounts for this, minus the amount of the graft polymer used as matting agent.
  • opaque polymers can also be used as impact-resistant
  • EPDM EPDM modified styrene-acrylonitrile copolymer
  • AES graft polymers
  • the particles according to the invention achieve a matting effect without noticeably 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 molded parts produced therefrom have the advantages of improved printability and so-called anti-blocking properties, i.e. the surfaces of the molded parts "roughened” by the particles do not adhere to one another.
  • This effect which is 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.
  • the molding compositions can contain fibrous and particulate fillers as component C.
  • examples are reinforcing agents such as carbon fibers and glass fibers, in particular E, A and C glass fibers. These can be equipped with a size and an adhesion promoter.
  • Other suitable 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 for example, Lubricants and mold release agents, pigments, and the like.
  • 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 particle size distribution was determined using a Microtac UPA 150 laser scattered light device, manufacturer Leeds & Northrup.
  • the D (10), D (50) and D (90) values are given for the following experiments.
  • the D (50) value is the value at which 50% by volume of the particles are larger and 50% by volume of the particles are smaller than this value.
  • the D (10) and D (90) values are defined accordingly.
  • the following batch was stirred under nitrogen with a Dispermat at 7000 rpm for 20 minutes.
  • the Dispermat was from VMA-Getzmann GmbH, D-51580 Reichshof, and provided with a 5 cm tooth lock washer.
  • Example 2 was repeated, but in the first stage only 12.5 g of this solution 10 were used instead of 25 g of a 40% solution of the emulsifier K30 in water.
  • Example 4 was repeated, but in the first stage, instead of 50 g 16
  • Example 4 was repeated, but in the first stage, instead of 50 g of a 40% solution of the emulsifier K30 in water, only 2.5 g of this solution were used.
  • polymers from the examples were incorporated into polymer styrene / acrylonitrile as polymer B. This was, as usual, in the extruder (ZSK 30 from Werner and
  • Polymer B hard thermoplastic copolymer, type 65% styrene + 35% acrylonitrile, viscosity number according to DIN 53 726: 80 ml / g (0.5% in dimethylformamide at 23 ° C).
  • PSAN polystyrene / acrylonitrile
  • AK impact strength, measured according to DIN 53453 at 23 ° C on standard small rods (50 x 6 x 4 mm) with milled notch.
  • the standard small rods were injection molded at a polymer melt temperature of 280 ° C and a mold temperature of 60 ° C.
  • Example V7 polymer does not fail
  • Example V8 polymer does not fail

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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)

Abstract

L'invention concerne un procédé pour produire des polymères particulaires présentant l'élasticité du caoutchouc. Ce procédé consiste (1) à mettre en dispersion a11: 85 à 100 % en poids de monomères éthyléniquement insaturés dont les homopolymères présentent l'élasticité du caoutchouc, en tant que composant A11, et a12: 0 à 15 % en poids de monomères réticulants en tant que composant A12, dans l'eau, au moyen d'un colloïde protecteur et d'un émulsifiant pour former une dispersion présentant un diamètre moyen de particules compris entre 0,08 et 8 mu m, (2) à polymériser les gouttelettes avec un initiateur de polymérisation radicalaire, et éventuellement (3) à effectuer une polymérisation avec greffage du mélange obtenu à l'étape (2) en présence de monomères éthyléniquement insaturés.
PCT/EP1999/000393 1998-01-21 1999-01-21 Procede pour produire des polymeres particulaires Ceased WO1999037690A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99907397A EP1045865A1 (fr) 1998-01-21 1999-01-21 Procede pour produire des polymeres particulaires

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19802128.3 1998-01-21
DE19802128A DE19802128A1 (de) 1998-01-21 1998-01-21 Verfahren zur Herstellung von teilchenförmigem Polymerisaten

Publications (1)

Publication Number Publication Date
WO1999037690A1 true WO1999037690A1 (fr) 1999-07-29

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/000393 Ceased WO1999037690A1 (fr) 1998-01-21 1999-01-21 Procede pour produire des polymeres particulaires

Country Status (3)

Country Link
EP (1) EP1045865A1 (fr)
DE (1) DE19802128A1 (fr)
WO (1) WO1999037690A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992000335A1 (fr) * 1990-06-29 1992-01-09 Vinamul Limited Polymerisation d'emulsion
DE4443886A1 (de) * 1994-12-09 1996-06-13 Basf Ag Kautschukelastische Pfropfpolymerisate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992000335A1 (fr) * 1990-06-29 1992-01-09 Vinamul Limited Polymerisation d'emulsion
DE4443886A1 (de) * 1994-12-09 1996-06-13 Basf Ag Kautschukelastische Pfropfpolymerisate

Also Published As

Publication number Publication date
DE19802128A1 (de) 1999-07-22
EP1045865A1 (fr) 2000-10-25

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