EP1049732A1 - Procede de fabrication de polymerisats (greffes) en microsuspension ayant l'elasticite du caoutchouc - Google Patents

Procede de fabrication de polymerisats (greffes) en microsuspension ayant l'elasticite du caoutchouc

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Publication number
EP1049732A1
EP1049732A1 EP99902551A EP99902551A EP1049732A1 EP 1049732 A1 EP1049732 A1 EP 1049732A1 EP 99902551 A EP99902551 A EP 99902551A EP 99902551 A EP99902551 A EP 99902551A EP 1049732 A1 EP1049732 A1 EP 1049732A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
graft
polymer
polymers
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Withdrawn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
EP99902551A
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mc Kee
Heiner GÖRRISSEN
Jürgen Koch
Walter Kastenhuber
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
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Filing date
Publication date
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Publication of EP1049732A1 publication Critical patent/EP1049732A1/fr
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms

Definitions

  • the invention relates to processes for producing rubber-elastic microsuspension (piTOpf) polymers, such polymers and molding compositions thereof.
  • piTOpf rubber-elastic microsuspension
  • microsuspension polymerization process as described, for example, in DE-A-44 43 886 and EP-A-0 716 101, makes rubber elastic
  • Polymer particles in particular graft copolymers, with a particle size of less than 50 ⁇ m are accessible.
  • Such graft copolymers are often used for the impact-resistant finishing of polymer molding compositions, for example based on styrene and acrylonitrile.
  • such graft copolymers are also used in these molding compositions in order to obtain a matt surface.
  • DE-A-44 43 886 relates to particulate rubber-elastic graft polymers which are suitable for improving the quality of macromolecular base materials and consist of a plug core with an average particle diameter of 1 to 100 ⁇ m and one or more shells.
  • the graft polymers simultaneously increase the impact resistance of non-elastic polymers and act as matting agents.
  • EP-A-0 716 101 describes thermoplastic molding compositions composed of a matrix copolymer, particulate graft copolymers with an average particle diameter of 0.03 to 1 ⁇ m and particulate crosslinked copolymers with an average particle diameter of 0.05 to 50 ⁇ m.
  • the molding compositions constructed in this way are impact modified and matted. - 2 -
  • graft rubber-elastic microsuspension
  • the object is achieved according to the invention by a process for the production of rubber-elastic microsuspension (graft) polymers
  • Total weight is 100% by weight
  • al3 0.1 to 50% by weight of aliphatic hydrocarbon polymers with a glass transition temperature of below 0 ° C. as component A13,
  • microsuspension (graft) polymers thus obtained and molding compositions containing them, and their use in fibers, foils and foam bodies.
  • the ethylenically unsaturated monomers used as component All in process step (1) are preferably present in an amount of 55 to 99% by weight, in particular 60 to 98% by weight.
  • All monomers that can be polymerized with free radicals can be used.
  • monomers can be used whose
  • Homopolymers are rubber. Elastic.
  • the term “rubber-elastic” here preferably means those polymers whose glass transition temperature is below room temperature (25 ° C.), preferably below 0 ° C., particularly preferably below -10 ° C.
  • Examples of such monomers are C 6 -, preferably C S - alkyl (meth) acrylates, in particular n-butyl acrylate and / or ethylhexyl acrylate,
  • Methyl methacrylate, ethyl acrylate, styrene, acrylonitrile, butadiene and isoprene which can be substituted, derivatives of (meth) acrylic acid such as epoxy and
  • Alkyl acrylates especially n-butyl acrylate and ethylhexyl acrylate. Further monomers which can additionally be used as components are found in Ullman's Encyclopedia of Technical Chemistry, 4th Edition, Volume 19, pages 1 to 30 (Verlag Chemie,
  • crosslinking agents 0 to 20% by weight, preferably 0 to 15% by weight, in particular 0 to 10% by weight, of crosslinking agents can be used as component A12 in the monomer dispersion
  • Monomers are present.
  • examples of such monomers are bifunctional or polyfunctional comonomers such as 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.
  • bifunctional or polyfunctional comonomers such as 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
  • Acrylic acid esters of tricyclodecenyl alcohol (dihydrodicyclopentadienyl acrylate) and the allyl esters of acrylic acid and methacrylic acid.
  • Component A13 contains 0.1 to 50% by weight, preferably 1 to 45% by weight, in particular 2 to 40% by weight, of aliphatic hydrocarbon polymers with a
  • Glass transition temperature of below 0 ° C, preferably below -10 ° C before.
  • Polymers are preferably aliphatic C 2 . 10 -, preferably C 3 . 5 - hydrocarbons used. Examples are polybutenes, poly dienes such as polybutadiene, polyisoprene, ethylene polymers and ethylene copolymers with. Others
  • Olefins such as C 3 - 32 - preferably C 3 .
  • I0 olefins and with dienes such as butadiene, isoprene, hexadiene, octadiene, norbornene and dicyclopentadiene as well as styrenes.
  • Polybutene which is a butene / isobutene copolymer, is particularly preferably used.
  • the molecular weight M n of the polymer of component A13 is generally 250 to 750,000, preferably 250 to 400,000, particularly preferably 250 to 250,000.
  • the liquid mixture of the components All to AI 3, which is to be polymerized to the (core) polymer, is mixed with water and a protective colloid.
  • the polymerization initiator is either added at this point in time or only after the monomers have been dispersed, or also after the dispersion has been heated.
  • the heterogeneous mixture becomes sheared by intensive stirring or a dispersion of minute monomer droplets in water is produced by ultrasound at high speed.
  • Intensive mixers of any type, high-pressure homogenizers and ultrasonic devices are suitable for this.
  • the desired particle size within the defined range can be determined, for example, by taking light microscopic images and counting the number of particles which have a specific diameter.
  • M-in starts the polymerization by heating the dispersion.
  • the reaction which is then carried out with moderate stirring, during which the droplets are no longer divided, is continued until the conversion, based on the monomers, is above 50%, particularly preferably above 85%. If no subsequent grafting is carried out, polymerization is carried out until the end of the reaction.
  • the reaction in stage 3 is continued in the presence of ethylenically unsaturated monomers to build up the polymer shell in a manner known per se.
  • the grafting can also begin when the polymerization conversion of the core monomers is still incomplete and is above 50%, preferably above 85%. In this case, the graft 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.
  • the graft polymer can have one or more shells. Different shells can have different compositions, the outermost shell should have the same or a similar composition as a matrix polymer into which the graft polymers are to be introduced.
  • the dispersion of the monomers is usually at a temperature from 0 to
  • the proportion of all A12 and A13 in the mixture to be emulsified is 5 to 85% by weight, preferably 10 to 80% by weight, particularly preferably 10 to 70% by weight.
  • 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 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.
  • the amount of these protective colloids is preferably 0.1 to 5% by weight, based on the total mass of the monomers.
  • low molecular weight surface-active compounds for example of the anionic or cationic soap type, can also be present. In this case, smaller polymer particles are obtained. Examples of such soaps are sodium, potassium or ammonium salts of sulfonic acids and C ⁇ o- 30 C for 10 - 30 - fatty acids.
  • Free radical formers are suitable as polymerization initiators, in particular those which are soluble in the monomers and which preferably have a half-life of 10
  • Suitable peroxides such as dilauroyl peroxide, peroxosulfates, tert-butyl perpivalate 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.
  • reaction mixture can contain buffer substances such as NaH 2 PO 4 or Na
  • molecular weight regulators are generally used in the polymerization, in particular of the monomers which form graft shells - 7 -
  • the polymerization temperature of the monomers for the production 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 polymer particles obtained in step (1) preferably have a medium one
  • the monomers used for grafting in step (3) are preferably selected from styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid esters or mixtures thereof.
  • the invention also relates to an M-crosuspension (graft) polymer which can be prepared by the process described above.
  • This microsuspension (graft) polymer is suitable for the production of molding compounds or for the treatment of leather, textiles or paper.
  • a corresponding molding composition according to the invention contains components A to D, the total weight of which is 100% by weight
  • a polymer matrix for example of polyamide, polyester, polyoxymethylene, preferably a polymer of styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid 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
  • component D 0 to 30% by weight of further additives as component D.
  • Preferred quantitative ranges are 1 to 75% by weight for component A, 25 to 99% by weight for component B, 0 to 40% by weight for component C and 0 to 25% by weight for component D. Quantities from 2 to 70 are particularly preferred
  • component A 30 to 98% by weight for component B, 0 to 30% by weight for component C and 0 to 20% by weight for component D.
  • the particulate graft polymers according to the invention serve mainly as additives to brittle thermoplastic macromolecular base materials
  • graft polymers of component B. On the one hand, this improves their impact strength, on the other hand, due to diffuse reflection (scattering) of the light on the large particles, molding compositions with reduced surface gloss and correspondingly matt molded parts are obtained. Furthermore, the addition of the graft polymers means that the molding composition is not colored, or is colored only very slightly, yellow.
  • the molding compositions are suitable for the production of fibers, films or moldings.
  • 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 outermost shell of the particles is compatible or partially compatible with the polymer of matrix B.
  • the outer graft shell can consist of the same or as similar a material as the base polymer.
  • 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, as a result of which the properties of the thermoplastic molding compositions prepared from B and the graft polymer particles A and the moldings produced therefrom can often be further improved.
  • the relationships between the nature of the two components in the molding compositions and the material properties correspond, moreover, to those known for the base material and graft polymers, which are characterized by
  • Emulsion polymerization can be produced.
  • base materials B other than those mentioned, for example polyesters, polyamides, polyvinyl chloride, polycarbonates and polyoxymethylene.
  • compatible and partially compatible graft shells can be identified by some
  • 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 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.
  • partially compatible polymers are the pairs of polymethyl methacrylate / copolymer from styrene and acrylonitrile, polymethyl methacrylate / polyvinyl chloride and polyvinyl chloride / copolymer from styrene and acrylonitrile, and the three-phase system polycarbonate / polybutadiene / copolymer from styrene and acrylonitrile.
  • solubility parameter as a quantitative measure is, for example, the Polymer Handbook, ed. J. Brandrup and EH Immergut, 3rd edition, Wiley, New York 1989, pp. VII / 519-VII / 550 refer to.
  • the graft polymers according to the invention are generally used in amounts of 0.1 to 80, preferably 1 to 75, particularly preferably 2 to 70, especially 3 to 45% 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. Since only a relatively small increase in impact strength would result at these low concentrations, conventional, fine-particle rubber-elastic modifiers can be used in the usual amounts for this, minus the amount of the graft polymer according to the invention used as a matting agent.
  • opaque polymers which already contain modifying agents which make impact resistant, for example styrene modified with polybutadiene, - 11 -
  • ABS Acrylonitrile copolymer
  • ASA styrene-acrylonitrile copolymer
  • AES styrene-acrylonitrile copolymer
  • EPDM ethylene-propylene-diene polymer
  • 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 moldings produced therefrom have the advantages of improved printability and so-called antiblocking properties, ie the surfaces of the moldings “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.
  • Preferred fibrous or particulate fillers of component C are
  • Carbon fibers or glass fibers such as E, A or C glass fibers are used. These can be equipped with a size and with an adhesion promoter. Glass beads, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can also be added as fillers or reinforcing materials.
  • the molding compositions can also contain additives of all kinds as component D. - 12 -
  • lubricants and mold release agents examples include lubricants and mold release agents, pigments, anti-hammers, dyes, stabilizers and antistatic agents, all of which are added in the usual amounts.
  • the molding compositions according to the invention can be prepared according to known methods
  • Mixing processes are carried out, for example, 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. From the molding compositions according to the invention, films, fibers and moldings with reduced
  • Indopol ® L-65 and Indopol ® Hl 00 and H300 are isobutylene-butene copolymers from Amoco.
  • the products have the following molecular weights Mn, measured by gel permeation chromatography (see Bulletin 12-23, "Amoco Polybutenes,
  • the D (50) value is given for the following tests.
  • 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 was from VMA-Getzmann GmbH, D-51580 Reichshof and provided with a 5 cm tooth lock washer.
  • the monomers were added as a feed of 150 minutes. After that was
  • Example 1 was repeated, but with Indopol ® H 300 instead of Indopol ® L-65.
  • the D (50) value was 2.4 ⁇ m. 14 -
  • Example 1 was repeated, but without the indopole polymer.
  • the graft polymers of Examples 1, 2 and V3 were incorporated into a polymer matrix (48 parts by weight of graft polymer and 52 parts by weight of polymer matrix) made of poly (styrene and acrylonitrile) of 67:33.
  • the copolymer had a viscosity number of 80 ml / g, determined according to DIN 53726 at 25 ° C., 0.5% by weight in dimemylformamide.
  • the blends were produced by introducing the rubber dispersion into the copolymer.
  • the impact strength according to DIN 53453 at 23 ° C and the color and surface properties of standard small bars were then assessed visually. The results are shown in the table.
  • V3 11 more yellow than 1 and 2 half matt

Abstract

La fabrication de polymérisats (greffés) en microsuspension ayant l'élasticité du caoutchouc s'effectue comme suit: (1) dispersion dans l'eau, avec emploi d'un colloïde protecteur en une dispersion de particules de diamètre moyen 0,08 à 100 νm, d'un mélange de composants A11 à A13, formant un total de 100 % en poids, avec a11: 30 à 99,9 % en poids de monomères éthyléniquement insaturés, comme composant A11, a12: 0 à 20 en poids de monomères réticulés, comme composant A12, a13: 0,1 à 50 % en poids d'un polymère hydrocarbure aliphatique de température de transition vitreuse inférieure à 0 °C, comme composant A13, (2) polymérisation des gouttelettes par un initiateur de polymérisation radicalaire et, éventuellement, polymérisation par greffage du mélange obtenu au stade (2), en présence de monomères éthyléniquement insaturés.
EP99902551A 1998-01-21 1999-01-19 Procede de fabrication de polymerisats (greffes) en microsuspension ayant l'elasticite du caoutchouc Withdrawn EP1049732A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19802094 1998-01-21
DE1998102094 DE19802094A1 (de) 1998-01-21 1998-01-21 Verfahren zur Herstellung von kautschukelastischen Mikrosuspensions(propf)polymerisaten
PCT/EP1999/000305 WO1999037700A1 (fr) 1998-01-21 1999-01-19 Procede de fabrication de polymerisats (greffes) en microsuspension ayant l'elasticite du caoutchouc

Publications (1)

Publication Number Publication Date
EP1049732A1 true EP1049732A1 (fr) 2000-11-08

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EP99902551A Withdrawn EP1049732A1 (fr) 1998-01-21 1999-01-19 Procede de fabrication de polymerisats (greffes) en microsuspension ayant l'elasticite du caoutchouc

Country Status (3)

Country Link
EP (1) EP1049732A1 (fr)
DE (1) DE19802094A1 (fr)
WO (1) WO1999037700A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10027860A1 (de) 2000-06-06 2001-12-13 Basf Ag Verfahren zur Herstellung von als Lacke verwendbaren Mikrosuspensionspolymerisaten
US20100249325A1 (en) * 2006-01-19 2010-09-30 Basf Se Polymer powder with high rubber content and production thereof
WO2017198593A1 (fr) * 2016-05-20 2017-11-23 Ineos Styrolution Group Gmbh Masses moulées de copolymère d'ester acrylique - styrène - acrylonitrile ayant une proportion optimisée de monomères résiduels

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
DE69207902T2 (de) * 1991-03-25 1996-06-20 Exxon Chemical Patents Inc Pfropfpolymere aus isomonoolefin und alkylstyrol
DE4443886A1 (de) * 1994-12-09 1996-06-13 Basf Ag Kautschukelastische Pfropfpolymerisate
EP0810240A1 (fr) * 1996-05-31 1997-12-03 Elf Atochem S.A. Latex à base de copolymères du chlorure de vinyle de structure particulière, son procédé de fabrication et ses applications
DE19702733A1 (de) * 1997-01-27 1998-07-30 Basf Ag Thermoplastische Formmassen mit hoher Zähigkeit
DE19715821A1 (de) * 1997-04-16 1998-10-22 Basf Ag Thermoplastische Formmasse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9937700A1 *

Also Published As

Publication number Publication date
DE19802094A1 (de) 1999-07-22
WO1999037700A1 (fr) 1999-07-29

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