EP1045871A1 - Polymerisat greffe en micro-suspension et son procede de fabrication - Google Patents

Polymerisat greffe en micro-suspension et son procede de fabrication

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Publication number
EP1045871A1
EP1045871A1 EP99906161A EP99906161A EP1045871A1 EP 1045871 A1 EP1045871 A1 EP 1045871A1 EP 99906161 A EP99906161 A EP 99906161A EP 99906161 A EP99906161 A EP 99906161A EP 1045871 A1 EP1045871 A1 EP 1045871A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
polymer
microsuspension
graft
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Withdrawn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
EP99906161A
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mc Kee
Norbert Mosbach
Heiner GÖRRISSEN
Michael Fischer
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 EP1045871A1 publication Critical patent/EP1045871A1/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Withdrawn legal-status Critical Current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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Definitions

  • the invention relates to microsuspension graft polymers, processes for their preparation, their use and molding compositions containing them.
  • Polymer blends often contain rubber-elastic graft copolymers which are said to give the polymer blends increased toughness. They can also serve as matting agents in the polymer blends.
  • the graft copolymers can be prepared by the emulsion, suspension or microsuspension process.
  • emulsion polymerization In emulsion polymerization, a heterogeneous reaction process, unsaturated monomers or monomer solutions are emulsified in a continuous phase, usually water, using an emulsifier system and polymerized with initiators which form free radicals. During the reaction, the emulsifier system forms micelles into which the at least partially water-soluble monomers from the emulsified monomer droplets migrate through the water phase.
  • a corresponding method is described in the Encyclopedia of Polymer Science and Engineering, Volume 6, page 1 (1986), John Wiley and Sons, New York.
  • microsuspension polymerization a liquid monomer mixture in water is distributed into very fine droplets using a protective colloid under strong shear.
  • the droplets are polymerized with a polymerization initiator which is soluble in the droplets, and the small polymer particles obtained can subsequently be grafted.
  • a corresponding one The method is described in DE-A-44 43 886.
  • the graft copolymers described have a core to shell weight ratio of 60:40.
  • microsuspension graft polymers do not have sufficient mattness and hardness in all applications.
  • the object of the present invention is to provide microsuspension polymers which avoid the disadvantages of the known graft polymers and in particular show reduced light reflection, good dyeability and improved mechanical properties.
  • microsuspension polymers composed of a graft core and a graft shell, in which the proportion of the graft shell is 45% by weight or more, based on the graft polymer, show reduced light reflection and advantageous mechanical properties, in particular advantageous hardness.
  • Component AI preferably 25 to 55 wt .-%, particularly preferably 30 to 50 wt .-%.
  • the proportion of component B1 is preferably 45 to 75% by weight, particularly preferably 50 to 70% by weight.
  • microsuspension polymers A according to the invention show the above advantages in particular in comparison to microsuspension polymers which are composed of the same basic building blocks and in which the proportion of the graft shell is 40% by weight.
  • the molding compositions according to the invention with the same rubber component (preferably polybutyl acrylate) content, a clearer matting effect can be observed with reduced scattering and an improvement in the mechanical properties.
  • the lower scatter improves the colorability of the molding compositions containing the microsuspension polymers according to the invention.
  • microsuspension polymerization is described, for example, in DE-A-4443 886.
  • a method for producing the above microsuspension graft polymer is preferred
  • 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 also added now 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. Intensive mixers of any type are suitable for this.
  • the desired particle size can be determined, for example, for diameters greater than 1 ⁇ m by taking light microscopic images 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 with the monomers from which the corresponding shells are to be produced is then 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%.
  • 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.
  • the monomers are generally dispersed at a temperature of 0 to 100 ° C., preferably at about room temperature. As a rule, 0.4 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.
  • 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-vinylimidazole 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.
  • 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 lauroyl peroxide, peroxosulfates, tert-butyl perpivalate and azo compounds such as azodiisobutyronitrile are suitable.
  • oil-soluble radical formers preferably dilauroyl peroxide, benzoyl peroxide and 2,2'-azo-bis-isobutyronitrile
  • water-soluble initiators such as hydrogen peroxide, potassium, ammonium and sodium peroxide and persulfates, can also be used, especially if smaller particles of less than 1.0 ⁇ m should 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 HPO 4 / NaH 2 PO or Na citrate / citric acid, in order to set an essentially constant pH.
  • buffer substances such as Na HPO 4 / NaH 2 PO or Na citrate / citric acid
  • molecular weight regulators such as ethylhexylthioglycolate or dodecyl mercaptan are generally added during the polymerization, in particular of the monomers that make up the shells.
  • the temperature in the polymerization of the monomers of the core is generally 25 to 150 ° C., preferably 45 to 120 ° C.
  • the shells are generally grafted onto the core at a temperature of 25 to 150 ° C., preferably 45 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 preferably has a glass transition temperature of below 0 ° C, particularly preferably of below minus 10 ° C. Any suitable rubber-elastic polymers can be used.
  • Component AI is preferably composed of components All to A13, the total weight of which is 100% by weight,
  • the proportion of component All is preferably 60 to 100% by weight, particularly preferably 80 to 100% by weight.
  • the proportion of component AI 2 is preferably 0 to 8% by weight, particularly preferably 0.1 to 6% by weight.
  • the proportion of component AI 3 is preferably 0 to 35% by weight, particularly preferably 0 to 15% by weight.
  • Component All is preferably a C 8 alkyl acrylate, particularly preferably n-butyl acrylate and / or 2-ethylhexyl acrylate. 0 to 50% by weight of component All can also be replaced by one or more of the following monomers Al 3: styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, C9-40-alkyl (meth) acrylate, C-Mo-aralky ⁇ met acrylate, C6-40-aryl (meth) acrylate, C ⁇ o-alkaryl nettyacrylate, ⁇ -olefins with 2 to 20 C atoms, polyisobutylenes with 3 to 50 isobutene units and optionally terminal vinyl or vinylidene group, polypropylenes with terminal vinyl - Or vinylidene group with 3 to 100 propylene units, oligohexene, oligooctadecene, C o-
  • Additional monomers are C 7 - 2 o-aralkyl (meth) acrylate, C. 6 2 o-aryl (meth) acrylate, C7-20-alkaryl (meth) acrylate, ⁇ -olefins with 6-20 C atoms, polyisobutylenes with 5-30 isobutene units and possibly terminal vinyl or vinylidene group, polypropylenes with terminal Vinyl or vinylidene group with 7-30 propylene units, C ⁇ o-2 4 -alkyl vinyl ether and vinyl esters of saturated C10- 2 -carboxylic acids.
  • crosslinking monomers can be used as component Al 2.
  • crosslinking monomers include 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, diesters of acrylic acid and methacrylic acid with the bifunctional alcohols such as ethylene glycol or butane-1,4-diol, 1,4 - divinylbenzene and triallyl cyanurate.
  • the acrylic ester of tricyclodecenyl alcohol (dihydrodicyclopentadienyl acrylate) and allyl esters of acrylic acid and methacrylic acid are particularly preferably used.
  • Component B1 is in particular styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, (meth) acrylic acid ester or mixtures thereof. If the microsuspension graft polymers are to be incorporated into matrix polymers, the outer shell and the matrix polymer are preferably compatible or partially compatible.
  • 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 is 100% by weight,
  • a 0.5 to 80% by weight, preferably 1 to 60% by weight, preferably 1 to 50% by weight, of at least one microsuspension graft polymer described above as component A, a ': 0 to 79.5% by weight. %, preferably 0 to 59% by weight of an ASA, ABS or AES polymer of component A ', b: 20 to 99.5% by weight, preferably 40 to 99% by weight, of a polymer matrix, for example polyamide, polyester, polyoxymethylene, polycarbonates, polysulfone, polyether sulfone or preferably polymers 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
  • component C Fillers or their mixtures as component C, and d: 0 to 50% by weight, preferably 0 to 40% by weight, of further additives as component D.
  • 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 the matrix B, so that the molding material formed from the thermoplastic matrix
  • base polymers compatible, the rule is that their outer graft shell is partially compatible or compatible with the base polymer and preferably consists of the same or as similar a material as the base polymer.
  • the technically most important base polymers are homopolymers of styrene, methyl acrylate, (C-alkyl methacrylates and acrylonitrile, copolymers of these monomers and other comonomers such as methacrylonitrile, ie these monomers and monomer mixtures are suitable for building up the external ones, depending on the structure of base polymer B. Graft bowl.
  • 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 produced from the matrix B and the graft polymer particles A and the molding bodies produced therefrom can often 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, 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.
  • a vector intersecting the phase interface suddenly increases the concentration of one polymer 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 edition, Wiley, New York 199, p. VH / 519-VII / 550.
  • the graft polymers (A) according to the invention are generally used in amounts of 0.5 to 80, preferably 1 to 60, particularly preferably 1 to 50% by weight, based on the amount of their mixture with the base polymer Shaped bodies from such mixtures are very light-friendly and therefore particularly matt to - 12 -
  • concentrations of 0.5 to 10% by weight of the graft polymers A are recommended. Since at these low concentrations only a relatively small increase in impact strength would be achieved, conventional, Use very fine-particle rubber-elastic modifiers in the usual amounts for this, minus the amount of the graft polymer according to the invention used as a matting agent.
  • 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 larger 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 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 molded articles with reduced surface gloss (mattness) and high impact strength can be produced from the molding compositions according to the invention. No separation of the polymer components occurs in the films, fibers and molded bodies.
  • the particle size distribution of the microsuspension polymer was determined using an Elzone® 280PC device from Particle Data, Elmhurst Illinois, USA.
  • the particle size of the emulsion polymer was measured using an ultracentrifuge.
  • 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. This approach was made twice.
  • the Dispermat came from VMA-Getzmann GmbH, D-51580 Reichshof and was provided with a 5 cm tooth lock washer.
  • the weight ratio of graft shell (polystyrene / acrylonitrile, SAN) to graft core (polymer of n-butyl acrylate and dihydrodicyclopentadienyl acrylate, PBA + DCPA) was 40:60.
  • the D 5 was o-value of the particle size distribution of 2.5 in.
  • Example 1 was repeated, but the ratio of graft shell to graft core was 50:50.
  • Example 1 was repeated, but the ratio of graft shell to graft core was 60:40.
  • Example 1 was repeated, but the ratio of graft shell to graft core was 70:30. - 16 -
  • Rubber-elastic graft polymer (core cross-linked polybutyl acrylate, shell styrene-acrylonitrile copolymer), weight-average particle diameter approx. 90 nm.
  • the completion of the monomer addition was left to react for an hour.
  • the resulting latex had a solids content of 40% and a weight-average particle size d 5 o of 76 nm.
  • the polymer dispersion containing the polymer from f2, was coagulated by adding a magnesium sulfate solution and mixed with the styrene / acrylonitrile copolymer fl in an extruder type ZSK 30 from Werner and Pfleiderer.
  • the blends contained 50% by weight of component fl (PSAN) and 50% by weight of component f2 (emulsion graft rubber).
  • the ASA molding compound was melted together with further polystyrene-acrylonitrile copolymer (al) in a ZSK 30 extruder from Werner and Pfleiderer (260 ° C.).
  • the polymer suspensions from experiments 1 to 4 were pumped into this polymer melt and the water was drawn off along the extruder.
  • the finished mixture was discharged from the extruder as a polymer strand and granulated.
  • the amount of polybutyl acrylate from the micro-suspension polymer and emulsion polymer in the blends was kept constant at 28.8% by weight and 18.0% by weight.
  • Example shell core% by weight ASA% by weight PSAN MS polymer light reflection% (1) scattering (2)% by weight from experiment £ 2 ⁇
  • Example shell core% by weight ASA% by weight PSAN% by weight MS light reflection% A at 23 ° C kJ / - AKLbie 23 ° C kJ / - test number polymer 0) m ⁇ 2 280/60 ° C m ⁇ 2 280/60 ° C (4) f2 fl from experiment (3)
  • the sample plates were measured both over a white and a black background using a VIS spectrophotometer (Ultrascan from Hunter). Using a computer program based on the Kubelka-Munk theory (based on DIN 53234), the specific scatter at the wavelengths between 400 and 700 nm was calculated from these measurements.
  • a product that can be colored very well has minimal scatter.
  • AKL Punch impact strength measured on standard small bars at 23 ° C according to DIN 53753-L-3-3.0 (edition 4/81). The standard small bars were injection molded at a polymer melt temperature of 280 ° C and a mold temperature of 60 ° C.

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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

Le polymérisat A en micro-suspension est constitué par a1: 10 à 25 % en poids d'un noyau de greffage formé d'un polymère ayant l'élasticité du caoutchouc, de diamètre moyen de particules compris entre 0,08 et 100 mu m, en tant que composant A1, et b1: 45 à 90 % en poids d'au moins une enveloppe de greffage formée d'un polymère organique, en tant que composant B1.
EP99906161A 1998-01-21 1999-01-19 Polymerisat greffe en micro-suspension et son procede de fabrication Withdrawn EP1045871A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1998102110 DE19802110A1 (de) 1998-01-21 1998-01-21 Mikrosuspensionspfropfpolymerisate und Verfahren zu ihrer Herstellung
DE19802110 1998-01-21
PCT/EP1999/000307 WO1999037699A1 (fr) 1998-01-21 1999-01-19 Polymerisat greffe en micro-suspension et son procede de fabrication

Publications (1)

Publication Number Publication Date
EP1045871A1 true EP1045871A1 (fr) 2000-10-25

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Application Number Title Priority Date Filing Date
EP99906161A Withdrawn EP1045871A1 (fr) 1998-01-21 1999-01-19 Polymerisat greffe en micro-suspension et son procede de fabrication

Country Status (3)

Country Link
EP (1) EP1045871A1 (fr)
DE (1) DE19802110A1 (fr)
WO (1) WO1999037699A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2350862T3 (es) * 2000-03-24 2011-01-27 Cray Valley S.A. Composiciones para el tratamiento de cuero que contienen dispersiones acuosas de polímeros filmógenos en ausencia de disolvente orgánico.
WO2014146970A1 (fr) 2013-03-19 2014-09-25 Styrolution Group Gmbh Matières moulables mattes résistant aux intempéries pour procédé d'extrusion
KR102256898B1 (ko) 2014-04-02 2021-05-31 이네오스 스티롤루션 그룹 게엠베하 개선된 기계적 특성을 지닌 열가소성 성형 조성물의 제조 방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1526148A (fr) * 1967-04-10 1968-05-24 Ugine Kuhlmann Compositions thermoplastiques de moulage résistant au choc et au vieillissement
DE4443886A1 (de) * 1994-12-09 1996-06-13 Basf Ag Kautschukelastische Pfropfpolymerisate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9937699A1 *

Also Published As

Publication number Publication date
DE19802110A1 (de) 1999-07-22
WO1999037699A1 (fr) 1999-07-29

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