EP1330494A1 - Matieres de moulage a resistance au froid amelioree - Google Patents

Matieres de moulage a resistance au froid amelioree

Info

Publication number
EP1330494A1
EP1330494A1 EP01992741A EP01992741A EP1330494A1 EP 1330494 A1 EP1330494 A1 EP 1330494A1 EP 01992741 A EP01992741 A EP 01992741A EP 01992741 A EP01992741 A EP 01992741A EP 1330494 A1 EP1330494 A1 EP 1330494A1
Authority
EP
European Patent Office
Prior art keywords
weight
impact
pmma
shell
molding composition
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Withdrawn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
EP01992741A
Other languages
German (de)
English (en)
Inventor
Klaus Schultes
Michael Wicker
Werner Höss
Klaus Albrecht
Hans-Jürgen Kress
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.)
Roehm GmbH Darmstadt
Original Assignee
Roehm GmbH Darmstadt
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 Roehm GmbH Darmstadt filed Critical Roehm GmbH Darmstadt
Publication of EP1330494A1 publication Critical patent/EP1330494A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08L51/003—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 macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft 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
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08L51/08—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—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 macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes

Definitions

  • the invention relates to impact-resistant polymethacrylate molding compositions (PMMA molding compositions) with improved low-temperature impact strength.
  • PMMA molding materials use core / shell (K / S) or core / shell / shell (K / S1 / S2) particles (particle size 100-1000 nm) as impact modifiers, which are usually via emulsion polymerization getting produced.
  • the core consists of an elastomeric phase - in K / S1 / S2 particles, the elastomeric phase is generally the shell that has been grafted onto the core (S1).
  • suspension polymers can also be used.
  • the elastomeric phase grafted with MMA is relatively finely distributed in the beads (matrix material - e.g. PMMA).
  • the elastomeric phase usually consists of cross-linked copolymer, which is largely produced with the help of butyl acrylate.
  • an elastomeric phase e.g. Polybutadiene used.
  • K / S and K / S1 / S2 particles are described in the literature.
  • the KS particles are grafted silicone particles - MMA, styrene and acrylonitrile are used as grafting monomers.
  • a specialty are K / S particles in which the core consists of a silicone and acrylic rubber mixture (no grafting) (inter alia EP 430 134).
  • K / S1 / S2 particles are described, inter alia, in DE 3 617 267, DE 3 720475, DE 3 801 537, DE 3 822 667, DE 3 839 587, DE 4 040 986, DE 4 342 048 and EP 433 906.
  • the core of the K / S1 / S2 particles in DE 3 720 475 consists of a vinyl rubber, S1 of silicone rubber and S2 of various copolymers.
  • the graft copolymers produced are used as impact modifiers for certain plastics (often PC, SAN, polystyrene) or polymer blends.
  • EP 430 134 Here, a core consisting of a silicone rubber and an acrylic rubber (these looped rubbers are produced by swelling and subsequent polymerization of acrylate derivatives in the silicone latex) is grafted with vinyl monomers.
  • the material for impact modification of molding compositions is also described - however, only polycarbonate (PC) and / or polyester molding compositions are mentioned here.
  • No. 4,690,986 Here an impact-resistant molding compound (sz) is claimed which is produced on the basis of a graft copolymer (via emulsion polymerization).
  • the graft copolymer is a K / S product.
  • the core consists of a crosslinking agent (siloxane with methacrylate group connected via several CH2 groups) and tetrafunctional silane as a crosslinking agent. Both the molding compound (sz) itself and the manufacturing process for this are described.
  • JP 612,135,462 Here a molding composition (sz) is claimed which is produced on the basis of a graft copolymer (via emulsion polymerization).
  • the graft copolymer consists of siloxane grafted with vinyl monomers.
  • EP 308 198 Here a molding compound made of PMMI and grafted polysiloxane is claimed.
  • the grafted polysiloxane is produced by grafting monomers and at least one "graft crosslinking agent".
  • the graft crosslinking agent is the crosslinking agent (siloxane with methacrylate group connected via several CH 2 groups) in US Pat. No. 4,690,986.
  • the tetrafunctional silane is also mentioned as a crosslinking agent in the subclaims.
  • EP 332 188 Here a graft copolymer similar to that used in EP 430134 is used to modify FM.
  • particles are grafted with styrene and these are used to modify a polyether / polysulfone blend.
  • DE 4 342 048 Here a graft copolymer is claimed as K / S1 / S2 particles.
  • a silicone rubber acts as the core - S1 is predominantly made of acrylates (min. 70%) - the monomers for S2 are very broad (e.g. 50-100% methyl methacrylate).
  • Sz - FM are also described in the subclaims based on the claimed graft copolymer - the polymer for the matrix is also very broad here.
  • an FM which consists of 20-80% of conventional polymers and 80-20% of graft copolymers.
  • the graft copolymer consists of K / S1 / S2 particles, the core being composed of silicone rubber and S1 of acrylate rubber.
  • S2 is produced by redox polymerization (emulsion) of various monomers. As an example, only a sz-modified SAN molding compound is listed.
  • WO 99/41315 Here, a dispersion is claimed which contains a mixture of particles consisting of vinyl copolymers and consisting of PMMA-coated silicone rubber. This dispersion can be used, among other things, as an impact modifier.
  • Impact-resistant molding compounds based on PMMA are manufactured on a large scale. Increased impact strength of the molding compounds is achieved by using so-called impact modifiers. These modifiers are compounded into the corresponding PMMA standard molding compounds. With the help of the usual modifiers, which contain butyl acrylate rubber as an elastomeric phase, acceptable impact strengths down to -10 ° C in PMMA FM are achieved. In order to achieve acceptable impact strengths at even lower temperatures, another rubber (with a lower glass transition temperature (T g ) than butyl acrylate rubber) must be used as the elastomeric phase.
  • T g glass transition temperature
  • z. B polybutadiene as an elastomeric phase.
  • a modifier should now be found which achieves an acceptable impact strength of the PMMA molding compounds or the PMMA / SAN blends at lower temperatures ( ⁇ - 10 ° C) and the weather resistance of the molding compound or blend in comparison to those with modifiers based on polybutadiene PMMA molding compounds or PMMA / SAN blends is improved.
  • melt viscosity, strand expansion, heat distortion temperature or Vicat softening temperature of the corresponding molding compounds must not suffer from the use of the new modifiers.
  • EP 492 376 claims a graft copolymer (and also the process for producing this graft copolymer), which consists of K / S or K / S1 / S2 particles.
  • the core and the optional intermediate shell are made of silicone rubber and are more precisely defined - the outer shell is made by emulsion polymerization of various monomers (without any other emulsifier).
  • the particle size is limited to 10-300 nm - the polydispersity index is a maximum of 0.2.
  • the graft copolymer claimed is, inter alia, mixed with PMMA and the KSZ measured at 23 ° C.
  • EP 492 376 describes the preparation of the silicone graft copolymers and describes their use for impact modification of polyvinyl chloride (PVC), PMMA, polystyrene (PS) and styrene-acrylonitrile copolymer (SAN).
  • PVC polyvinyl chloride
  • PS polystyrene
  • SAN styrene-acrylonitrile copolymer
  • the notched impact strength of PMMA blends was only determined at 23 ° C Celsius, and there are no indications as to their usability or even special effects at lower temperatures.
  • the compositions of the individual examples are documented in Appendix 1.
  • Precipitated emulsion polymer consisting of silicone elastomer particles with
  • PMMA sleeve The material is largely free of emulsifiers. Production described in EP 492 376). Particle size approx. 100 nm, monomodal distribution.
  • Acrylic rubber modifier from Röhm Composition: core: copolymer of methyl methacrylate (95.7% by weight), ethyl acrylate
  • the production of the modifier is based on the method as disclosed in DE 33 00 526. Testing the molding compounds
  • Test specimens were produced from the mixed molding compositions.
  • the molding compounds and the corresponding test specimens were tested using the following methods:
  • Vicat softening temperature Determination of the Vicat (16h / 80 ° C): softening temperature test standard ISO 306 (method B50): (1994)
  • HDT (16h / 80 ° C A 1.8MPa): determination of the dimensional stability temperature, test standard: ISO 75 (Sept. 1993)
  • the notched impact strength of the individual molding compositions is at the same level at 23 ° C. - at -20 ° C. the notched impact strength is significantly higher (better) for the molding compositions mixed with silicone modifier.
  • melt viscosity, strand expansion, dimensional stability temperature or Vicat softening temperature remain at the same level in all the molding compositions compared.

Landscapes

  • 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)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne une matière de moulage aux propriétés de résilience, qui se caractérise en ce qu'elle est particulièrement résiliente à de basses températures (-20 °C, -40°C). Cette résistance aux basses températures est rendue possible par l'utilisation d'un élastomère silicone.
EP01992741A 2000-10-31 2001-10-22 Matieres de moulage a resistance au froid amelioree Withdrawn EP1330494A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10054053A DE10054053A1 (de) 2000-10-31 2000-10-31 PMMA-Formmassen mit verbesserter Kälteschlagzähigkeit
DE10054053 2000-10-31
PCT/EP2001/012173 WO2002036683A1 (fr) 2000-10-31 2001-10-22 Matieres de moulage a resistance au froid amelioree

Publications (1)

Publication Number Publication Date
EP1330494A1 true EP1330494A1 (fr) 2003-07-30

Family

ID=7661734

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01992741A Withdrawn EP1330494A1 (fr) 2000-10-31 2001-10-22 Matieres de moulage a resistance au froid amelioree

Country Status (7)

Country Link
US (1) US6906142B2 (fr)
EP (1) EP1330494A1 (fr)
JP (1) JP2004513203A (fr)
AU (1) AU2002221714A1 (fr)
CA (1) CA2427432A1 (fr)
DE (1) DE10054053A1 (fr)
WO (1) WO2002036683A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10203565C1 (de) * 2002-01-29 2003-07-10 Roehm Gmbh Verfahren zur Herstellung eines schlagzähen Polymethylmethacrylat- Formkörpers und Verwendung des so hergestellten Kunststoffformkörpers
DE10204890A1 (de) * 2002-02-06 2003-08-14 Roehm Gmbh Schlagzähe Formmasse und Formkörper
DE10236240A1 (de) * 2002-02-06 2003-08-14 Roehm Gmbh Silicon-Pfropfcopolymerisate mit Kern-Hülle-Struktur, schlagzähmodifizierte Formmassen und Formkörper sowie Verfahren zu deren Herstellung
DE10349144A1 (de) * 2003-10-17 2005-05-12 Roehm Gmbh Polymermischung für mattierte Spritzgußteile
DE102008001825A1 (de) 2008-05-16 2009-11-19 Wacker Chemie Ag Verwendung von Organosilicon-Copolymeren als Schlagzähmodifizierer
DE102009020937A1 (de) * 2009-05-12 2010-11-18 Bayer Materialscience Ag Kälte schlagzähe Coextrusionsfolien
US8288494B2 (en) * 2009-12-31 2012-10-16 Cheil Industries Inc. Transparent thermoplastic resin composition with improved impact strength and melt flow index
CN103421265B (zh) * 2013-04-26 2014-12-10 彭朕财 透明pmma增韧剂
KR20150047991A (ko) * 2013-10-25 2015-05-06 제일모직주식회사 착색성 및 기계적 물성이 우수한 열가소성 수지 조성물
TWI515253B (zh) * 2013-12-02 2016-01-01 奇美實業股份有限公司 聚甲基丙烯酸酯組成物及用於保護光學元件之保護膜
KR101993516B1 (ko) * 2017-05-12 2019-06-26 롯데첨단소재(주) 착색성 및 기계적 물성이 우수한 열가소성 수지 조성물
CN109265614B (zh) * 2018-06-23 2021-08-24 深圳市宝聚合新材料技术应用有限公司 超韧pmma树脂及其制备方法、应用

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Publication number Priority date Publication date Assignee Title
JP2608439B2 (ja) * 1988-01-25 1997-05-07 三菱レイヨン株式会社 耐衝撃性樹脂組成物
DE69311463T2 (de) * 1992-02-06 1998-02-05 Mitsubishi Rayon Co Pfropfpolymerteilchen, herstellung davon, und diese enthaltende zusammensetzung
DE4233386A1 (de) * 1992-10-05 1994-04-07 Basf Ag Transparente Formmasse
DE4239436A1 (de) * 1992-11-24 1994-05-26 Basf Ag Transparente Formmasse
DE19544563A1 (de) * 1995-11-30 1997-06-05 Roehm Gmbh Farb- und witterungsstabile Schlagzäh-Formmassen auf Basis Polymethylmethacrylat und Verfahren zu ihrer Herstellung
JP4124863B2 (ja) * 1997-08-01 2008-07-23 三菱レイヨン株式会社 熱可塑性樹脂組成物
DE19914605A1 (de) * 1999-03-30 2000-10-05 Roehm Gmbh Polyalkylmethacrylat-Plastisole mit verbesserten Fließeigenschaften

Non-Patent Citations (1)

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Title
See references of WO0236683A1 *

Also Published As

Publication number Publication date
DE10054053A1 (de) 2002-05-29
CA2427432A1 (fr) 2003-04-30
JP2004513203A (ja) 2004-04-30
WO2002036683A1 (fr) 2002-05-10
US6906142B2 (en) 2005-06-14
AU2002221714A1 (en) 2002-05-15
US20040039083A1 (en) 2004-02-26

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