WO2006053711A1 - Matieres a mouler tenaces a base de polymeres de styrene, ces matieres contenant une charge - Google Patents

Matieres a mouler tenaces a base de polymeres de styrene, ces matieres contenant une charge Download PDF

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Publication number
WO2006053711A1
WO2006053711A1 PCT/EP2005/012232 EP2005012232W WO2006053711A1 WO 2006053711 A1 WO2006053711 A1 WO 2006053711A1 EP 2005012232 W EP2005012232 W EP 2005012232W WO 2006053711 A1 WO2006053711 A1 WO 2006053711A1
Authority
WO
WIPO (PCT)
Prior art keywords
styrene
butadiene
component
mixture according
mixture
Prior art date
Application number
PCT/EP2005/012232
Other languages
German (de)
English (en)
Inventor
Graham Edmund Mc Kee
Hans-Jürgen RENNER
Daniel Wagner
Chris Dearmitt
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
Priority claimed from DE200410055539 external-priority patent/DE102004055539A1/de
Priority claimed from DE200510046818 external-priority patent/DE102005046818A1/de
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO2006053711A1 publication Critical patent/WO2006053711A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates

Definitions

  • the invention relates to a mixture containing
  • thermoplastic styrene-acrylonitrile copolymers with graft rubbers based on polybutadiene or acrylic esters are known to the person skilled in the art as ABS or ASA. To change the property profile, these are also processed into blends with other thermoplastic polymers, in particular polycarbonate (PC) or polyamide (PA).
  • PC polycarbonate
  • PA polyamide
  • WO 00/36010 describes thermoplastic molding compositions of ABS or ASA polymers which are mixed with elastomeric styrene-butadiene block copolymers to improve their flowability and at the same time have good mold release properties.
  • WO 03/11964 describes thermoplastic molding compositions of impact polystyrene and an elastomeric styrene-butadiene block copolymer having improved stress cracking resistance.
  • WO 99/46330 discloses mixtures of elastomeric and rigid styrene-butadiene block copolymers with polystyrene.
  • Styrene-butadiene block copolymers with random copolymer blocks and a low 1,2-vinyl content are known from WO 97/40079 and WO 00/58380.
  • Fillers can be incorporated into thermoplastic molding compositions based on styrene polymers to change the physical properties. Often fillers, in particular fibrous fillers are used to increase the stiffness of the moldings. Furthermore, fillers and pigments are used to change the color, gloss or electrical conductivity of the molding compositions. As a rule, the toughness and stress cracking resistance of the molding composition decreases.
  • the object of the present invention was to remedy the aforementioned disadvantages and to find filler-containing molding compositions based on styrene polymers, which in particular have a high degree of toughness even with thin molded parts. Furthermore, the molding compositions should have a matte surface.
  • the mixture contains
  • thermoplastic elastomer based on styrene S-TPE
  • Suitable styropolymers are the polymers known as acrylonitrile-butadiene-styrene polymer (ABS) or acrylonitrile-styrene-acrylic ester polymer (ASA). They usually consist of a styrene-acrylonitrile copolymer matrix (SAN) having an average molecular weight Mw in the range from 40,000 to 250,000 g / mol and a graft rubber.
  • the SAN matrix can be obtained in a known manner by bulk, solution suspension, precipitation or emulsion polymerization.
  • the graft rubber usually consists of a graft core of a polydiene or acrylic ester, to which a graft shell of styrene and acrylonitrile and / or methyl methacrylate is applied.
  • Toughened polystyrene can be prepared by mass or solution polymerization of styrene in the presence of polybutadiene or styrene
  • Butadiene block copolymers are obtained. This results in a matrix of polystyrene with trapped rubber particles that can form different morphologies, eg. Capsule particles, salami particles or cellulosic particles, and may have different average particle sizes.
  • Suitable styrene-butadiene block copolymers which consist of at least two polystyrene blocks S and at least one styrene-butadiene copolymer block S / B are, for example, star-branched block copolymers, as described in EP-A 0654488.
  • block copolymers having at least two hard blocks S 1 and S 2 of vinylaromatic monomers having at least one intervening statis ⁇ soft block B / S of vinyl aromatic monomers and diene, wherein the proportion of hard blocks over 40 wt .-%, based on the total Block copolymer is and the 1, 2-vinyl content in soft block B / S is below 20%, as described in WO 00/58380.
  • thermoplastic elastomers S-TPE
  • the S-TPE preferably has an elongation at break of more than 300%, particularly preferably more than 500%, in particular more than 600%, measured to ISO 527, and is present in an amount in the range from 40 to 95% by weight. , preferably 60 to 80 wt .-%, based on the stretch film, mixed.
  • Particularly preferred are mixed as TPE-S is a linear or star-shaped styrene-butadiene block copolymer with external polystyrene blocks S and, between these, styrene-butadiene copolymer blocks with a random styrene / butadiene distribution (S / B) random, or with a styrene gradient NDOM
  • the total butadiene content is preferably in the range from 15 to 50% by weight, more preferably in the range from 25 to 40% by weight, the total styrene content is preferably in the range from 50 to 85% by weight, particularly preferably in the range of 60 to 75% by weight.
  • the styrene-butadiene block (S / B) consists of 30 to 75% by weight of styrene and 25 to 70% by weight of butadiene.
  • a block (S / B) particularly preferably has a butadiene content of 35 to 70% by weight and a styrene content of 30 to 65% by weight.
  • the proportion of the polystyrene blocks S is preferably in the range of 5 to 40 wt .-%, in particular in the range of 25 to 35 wt .-%, based on the total Blockcopoly ⁇ mer.
  • the proportion of the copolymer blocks S / B is preferably in the range of 60 to 95 wt .-%, in particular in the range of 65 to 75 wt .-%.
  • linear styrene-butadiene block copolymers of the general structure S- (S / B) -S with one or more, lying between the two S blocks, a static styrene / butadiene distribution having blocks (S / B) ra ⁇ do m - such block copolymers are of medium by anionic polymerization in a nonpolar Amsterdams ⁇ with addition of a polar cosolvent or a potassium salt obtainable, for example as described in WO 95/35335 and WO 97/40079.
  • the vinyl content is understood to be the relative proportion of 1,2-linkages of the diene units, based on the sum of the 1,2-, 1,4-cis and 1,4-trans linkages.
  • the 1,2-vinyl content in the styrene-butadiene copolymer block (S / B) is preferably below 20%, in particular in the range from 10 to 18%, particularly preferably in the range from 12 to 16%.
  • Suitable inorganic fillers are, for example, titanium dioxide, talc, chalk, kaolin, carbon black, aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz powder, aerosil, alumina, wollastonite or colored pigments
  • the mixtures may also contain conventional dispersing aids, such as low molecular weight waxes, for.
  • B polyethylene waxes or stearates, such as magnesium or calcium stearate.
  • the mixture according to the invention can be carried out by mixing methods known per se, for example by adding component C to a melt of components A and B. It is expedient to use extruders, for. b. Single-screw or twin-screw extruders or other conventional plasticizing devices, such as Brabender mills or Banbury mixers.
  • the fillers are preferably used in so-called masterbatches.
  • FIG. 1 shows the electron micrograph of an ultrathin section of an inventive mixture of impact polystyrene (HIPS) (component A)) and styroflex (component B)), which contains 20% by weight of CaCO 3 (component C)).
  • HIPS impact polystyrene
  • component B styroflex
  • Kau ⁇ chuk particles (2) and CaCO 3 (3) are embedded in the polystyrene matrix (1).
  • the component B) can be seen in cross-section as threads (4) with an average length / diameter ratio of> 5, preferably> 10, particularly preferably> 15.
  • the mixture according to the invention may comprise further thermoplastic polymers, such as polyolefins, for example homo- or copolymers of ethylene or propylene, mono- or copolymers of acrylates, for example methyl methacrylate or polyphenylene ether.
  • polyolefins for example homo- or copolymers of ethylene or propylene
  • mono- or copolymers of acrylates for example methyl methacrylate or polyphenylene ether.
  • the mixtures according to the invention can be processed into foam strands or sheets.
  • a chemical or physical blowing agent for example an inorganic gas such as nitrogen or carbon dioxide
  • thermoplastic molding compositions are distinguished by the fact that the addition of relatively high amounts of inorganic fillers compensates for the drop in mechanical properties in the thermoplastic molding composition by component B) or even increases the toughness. Furthermore, the thermoplastic molding compositions are less sensitive to foreign polymers and impurities since component B) has good compatibility with various thermoplastic polymers, in particular with various styrene polymers and polyolefins.
  • the mixtures according to the invention can be processed by extrusion, injection molding, vacuum or glass molding or foaming to form sheets or moldings. They have a very matt surface and can also be processed into thin-walled molded parts, such as yogurt cups.
  • the mixtures according to the invention have a high resistance to stress cracking, in particular in contact with oils and fats. They are therefore suitable for the production of molded parts for refrigerators, e.g. for refrigerator interior trim.
  • Styroflex® 2G66 thermoplastic elastomer based on styrene
  • butadiene block copolymers with statistical S / B middle block of BASF Aktiengesellschaft are butadiene block copolymers with statistical S / B middle block of BASF Aktiengesellschaft.
  • SB2 Styrolux 3G55 (star-branched styrene-butadiene block copolymer of 25 wt% butadiene and 25 wt% styrene).
  • CaCO 3 Carbitol 110 S, Imerys Company, Cornwall, England with a mean
  • Particle size of 2 microns and a coating of stearic acid Particle size of 2 microns and a coating of stearic acid.
  • CaCO 3 -batch 60% by weight batch of calcium carbonate (Carbital 110S), prepared by melt extrusion with PS 495F on a ZSK 30 extruder.
  • TiO 2 batch 60% by weight of TiO 2 and 40% by weight of standard polystyrene 158K (BASF AG)
  • the notched impact strength was measured according to ISO 179-2 / 1 EA (F).
  • the biaxial toughness was measured in the puncture test on 2.1 mm or 1.05 mm thick platelets in accordance with ISO 6603-2 / 40/20 / C.
  • Table 2 shows the gloss values which were determined at a measuring angle of 60 ° in accordance with DIN 67530 with a microgloss reflector (BYK-Gardener GmbH, Geretsried) on the beakers).
  • the elongation at break determined on the basis of the "flexural strip method" described in ISO 4599.
  • the injection molded tensile test bars were stretched over bending templates with the radius 170 mm and a) 50 minutes in an autoclave at 300 mbar Exposed to pressure of a cyclopentane atmosphere (CP) or b) coated the surface under tension with a mixture of olive oil / oleic acid (1: 1), stored for 24 h and then measured in the tensile test according to ISO 527.
  • CP cyclopentane atmosphere
  • ISO 527 As reference Tensile test bars measured without media (air).

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un mélange contenant A) 35 à 95 % en poids d'un polymère de styrène choisi parmi un polymère d'acrylonitrile-butadiène-styrène (ABS), un polymère d'acrylonitrile-styrène-acrylester (ASA), du polystyrène standard ou du polystyrène choc (PSC) ou des mélanges de ceux-ci, B) 1 à 10 % en poids d'un copolymère séquencé de styrène-butadiène composé d'au moins deux séquences de polystyrène S et d'au moins une séquence de copolymère de styrène-butadiène S/B et C) 4 à 55 % en poids d'une charge inorganique, la somme des composants A), B) et C) représentant 100 % en poids. L'invention concerne également un procédé de production de ce mélange et l'utilisation dudit mélange pour produire des fibres, des films, des corps façonnés et des produits alvéolaires.
PCT/EP2005/012232 2004-11-17 2005-11-15 Matieres a mouler tenaces a base de polymeres de styrene, ces matieres contenant une charge WO2006053711A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102004055539.7 2004-11-17
DE200410055539 DE102004055539A1 (de) 2004-11-17 2004-11-17 Masterbatch auf Basis von Styrol-Butadien-Blockcopolymeren
DE200510046818 DE102005046818A1 (de) 2005-09-29 2005-09-29 Zähe, Füllstoff-haltige Formmassen auf Basis von Styrolpolymeren
DE102005046818.7 2005-09-29

Publications (1)

Publication Number Publication Date
WO2006053711A1 true WO2006053711A1 (fr) 2006-05-26

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WO (1) WO2006053711A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1772490A1 (fr) * 2005-09-29 2007-04-11 Basf Aktiengesellschaft Pièces moulées à base de polymères de styrène et de matières de charge inorganiques
WO2009004018A1 (fr) * 2007-07-03 2009-01-08 Basf Se Composition de moulage thermoplastique à partir de polymères abs et de polymères sbs
CN113861615A (zh) * 2021-10-25 2021-12-31 浙江远景体育用品有限公司 一种铝塑合金摩托车头盔材料及制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023823A1 (fr) * 1995-02-02 1996-08-08 Basf Aktiengesellschaft Feuille souple et transparente a base d'un polymerisat de styrene, en particulier pour l'emballage de produits alimentaires, et son procede de production
US5760134A (en) * 1995-10-02 1998-06-02 Basf Aktiengesellschaft Thermoplastic molding materials
WO1999046330A1 (fr) * 1998-03-10 1999-09-16 Basf Aktiengesellschaft Melanges polymeres constitues de polymeres de styrene
WO2000036010A1 (fr) * 1998-12-16 2000-06-22 Basf Aktiengesellschaft Matieres moulables thermoplastiques
WO2000066662A1 (fr) * 1999-05-03 2000-11-09 Basf Aktiengesellschaft Composition elastomere thermoplastique
US6177517B1 (en) * 1994-12-27 2001-01-23 Basf Aktiengesellschaft Thermoplastic molding masses based on graft copolymers and block polymers
WO2003011964A1 (fr) * 2001-07-27 2003-02-13 Basf Aktiengesellschaft Polystyrol resilient, brillant, resistant aux fissures par contrainte
WO2003057779A1 (fr) * 2002-01-07 2003-07-17 Denki Kagaku Kogyo Kabushiki Kaisha Composition de resine electroconductrice
WO2005075561A1 (fr) * 2004-02-09 2005-08-18 Basf Aktiengesellschaft Matieres moulables constituees de polymeres de styrene a surface mate

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6177517B1 (en) * 1994-12-27 2001-01-23 Basf Aktiengesellschaft Thermoplastic molding masses based on graft copolymers and block polymers
WO1996023823A1 (fr) * 1995-02-02 1996-08-08 Basf Aktiengesellschaft Feuille souple et transparente a base d'un polymerisat de styrene, en particulier pour l'emballage de produits alimentaires, et son procede de production
US5760134A (en) * 1995-10-02 1998-06-02 Basf Aktiengesellschaft Thermoplastic molding materials
WO1999046330A1 (fr) * 1998-03-10 1999-09-16 Basf Aktiengesellschaft Melanges polymeres constitues de polymeres de styrene
WO2000036010A1 (fr) * 1998-12-16 2000-06-22 Basf Aktiengesellschaft Matieres moulables thermoplastiques
WO2000066662A1 (fr) * 1999-05-03 2000-11-09 Basf Aktiengesellschaft Composition elastomere thermoplastique
WO2003011964A1 (fr) * 2001-07-27 2003-02-13 Basf Aktiengesellschaft Polystyrol resilient, brillant, resistant aux fissures par contrainte
WO2003057779A1 (fr) * 2002-01-07 2003-07-17 Denki Kagaku Kogyo Kabushiki Kaisha Composition de resine electroconductrice
WO2005075561A1 (fr) * 2004-02-09 2005-08-18 Basf Aktiengesellschaft Matieres moulables constituees de polymeres de styrene a surface mate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1772490A1 (fr) * 2005-09-29 2007-04-11 Basf Aktiengesellschaft Pièces moulées à base de polymères de styrène et de matières de charge inorganiques
WO2009004018A1 (fr) * 2007-07-03 2009-01-08 Basf Se Composition de moulage thermoplastique à partir de polymères abs et de polymères sbs
KR101546401B1 (ko) 2007-07-03 2015-08-21 스티롤루션 유럽 게엠베하 Ａｂｓ-중합체 및 ｓｂｓ-중합체로부터의 열가소성 성형 조성물
CN113861615A (zh) * 2021-10-25 2021-12-31 浙江远景体育用品有限公司 一种铝塑合金摩托车头盔材料及制备方法
CN113861615B (zh) * 2021-10-25 2022-10-11 浙江远景体育用品股份有限公司 一种铝塑合金摩托车头盔材料及制备方法

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