EP2217660A1 - Compositions de polymères aptes à la polymérisation radicalaire et contenant des copolymères à fonctionnalité époxy - Google Patents

Compositions de polymères aptes à la polymérisation radicalaire et contenant des copolymères à fonctionnalité époxy

Info

Publication number
EP2217660A1
EP2217660A1 EP08858142A EP08858142A EP2217660A1 EP 2217660 A1 EP2217660 A1 EP 2217660A1 EP 08858142 A EP08858142 A EP 08858142A EP 08858142 A EP08858142 A EP 08858142A EP 2217660 A1 EP2217660 A1 EP 2217660A1
Authority
EP
European Patent Office
Prior art keywords
epoxy
functional
monomers
polymer compositions
radically crosslinkable
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Withdrawn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
EP08858142A
Other languages
German (de)
English (en)
Inventor
Thomas Köhler
René GRÄWE
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.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
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 Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP2217660A1 publication Critical patent/EP2217660A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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

Definitions

  • EP-A 0075765 recommends free-radically crosslinkable polymer compositions for the production of composite components, which contain, as LPA polymers based on vinyl acetate or alkyl acrylates and additionally ethylenically unsaturated fatty acid esters, through which the formation of composite components with as smooth as possible less corrugated surfaces is favored.
  • US Pat. No. 4,525,498 discloses radically crosslinkable polymer compositions comprising unsaturated polyester resin, vinyl acetate-based or alkyl acrylate-based LPA and saturated, epoxy group-bearing, low molecular weight compounds by which the shrinkage-reducing effect of the LPA during curing increased the composition and the surface properties of the composite components can be improved.
  • a significant increase in the mechanical properties of the composite components did not cause the addition of epoxide group-bearing, low molecular weight compounds. In addition, low molecular weight compounds tend to migrate and are easily released from the composite components.
  • epoxy-functional copolymers based on vinyl acetate and one or more monomers b), such as in particular glycidyl methacrylate, and optionally vinyl laurate, acrylic acid or crotonic acid in the abovementioned amounts.
  • the epoxy-functional copolymers preferably contain the epoxy-functional monomer units in random distribution, i. the epoxy-functional copolymers are preferably not grafted with epoxy-functional monomers or compounds.
  • Suitable reactive monomers are the monomers which are suitable, preferably or particularly preferred, which are also suitable, preferred or particularly preferred for the polymerization for the preparation of the epoxy-functional copolymers.
  • Very particularly preferred reactive monomers are styrene, methyl methacrylate, methyl acrylate and butyl acrylate. The most preferred reactive monomer is styrene.
  • Suitable polyols preferably have 2 to 20 and more preferably 2 to 10 carbon atoms. Polyols preferably carry 2 to 3, more preferably 2 alcohol groups. Examples of suitable polyols are ethylene glycol, diethylene glycol,
  • the unsaturated polyester resins have molecular weights Mw of preferably 500 to 10,000 g / mol, more preferably 500 to 6,000 g / mol, and most preferably 1,000 to 6,000 g / mol.
  • Vinyl ester resins are reaction products which are formed by polyadditions or esterification reactions of phenol derivatives and ethylenically unsaturated mono- or dicarboxylic acids or dicarboxylic anhydrides having 3 to 20 carbon atoms, such as, for example, acrylic acids or methacrylic acids.
  • Preferred phenol derivatives are bisphenol A and phenol novolac.
  • the preparation of the vinyl ester resins is known to the person skilled in the art.
  • Suitable initiators are, for example, t-butyl perbenzoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, dibenzoyl peroxide, t-amyl peroxypivalate, di (2-ethylhexyl) peroxydicarbonate, 1,1-bis (t-butyl peroxy ) -3, 3, 5-trimethylcyclohexane, di (4-t-butylcyclohexyl) peroxydicarbonate, azobisisobutyronitrile.
  • the solutions of the radically crosslinkable polymers in reactive monomer and the epoxy-functional copolymers and optionally the further components such as the initiator, filler, mold release agent or other polymers, low-profile additives or additives are mixed to form a pasty mass, Thereafter, if appropriate, glass fiber is admixed, and then the resulting free-radically crosslinkable polymer compositions are cured using pressure and temperature to form the composite component. For example, reflectors for car headlights are produced with this technology.
  • a radically crosslinkable polymer composition in the form of a pasty mass of a solution of free-radically crosslinkable polymers in reactive monomer and the epoxy-functional Copolymer and optionally the other components such as initiator, filler, mold release agents, other polymers, low-profile additives or additives produced and applied to a polyamide film.
  • glass fiber is sprinkled onto this layer, then optionally a further layer of the pasty mass is applied and finally covered with a further polyamide film.
  • This sheet sandwich is then peeled from the film, cut into pieces and pressed using compression and temperature to composite components.
  • Composite components made by this technique are used, for example, as tailgates of automobiles.
  • GMA glycidyl methacrylate; the indication in Gew. -% refers to the total weight of the copolymer.
  • Mw molecular weight M w (weight average) determined by means of SEC "Si ze exclusion chromatography", polystyrene standard, THF; 6O 0 C.
  • BF flexural strength: determined according to DIN EN I SO 14125. The flexural strength of the composite components was determined on the basis of the test specimens according to EN ISO 14125. The test results for the various specimens are listed in Table 2.

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)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des compositions de polymères aptes à la polymérisation radicalaire, contenant un ou plusieurs polymères aptes à la polymérisation radicalaire, un ou plusieurs monomères éthyléniquement insaturés (monomères réactifs), éventuellement des initiateurs, des charges et d'autres additifs. L'invention est caractérisée en ce que ces compositions comportent en outre un ou plusieurs copolymères d'ester de vinyle à fonctionnalité époxy sans halogénure vinylique (copolymères à fonctionnalité époxy).
EP08858142A 2007-12-03 2008-12-01 Compositions de polymères aptes à la polymérisation radicalaire et contenant des copolymères à fonctionnalité époxy Withdrawn EP2217660A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007055692A DE102007055692A1 (de) 2007-12-03 2007-12-03 Radikalisch vernetzbare Polymerisat-Zusammensetzungen enthaltend Epoxy-funktionelle Copolymere
PCT/EP2008/066531 WO2009071508A1 (fr) 2007-12-03 2008-12-01 Compositions de polymères aptes à la polymérisation radicalaire et contenant des copolymères à fonctionnalité époxy

Publications (1)

Publication Number Publication Date
EP2217660A1 true EP2217660A1 (fr) 2010-08-18

Family

ID=40336469

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08858142A Withdrawn EP2217660A1 (fr) 2007-12-03 2008-12-01 Compositions de polymères aptes à la polymérisation radicalaire et contenant des copolymères à fonctionnalité époxy

Country Status (6)

Country Link
US (1) US20100256287A1 (fr)
EP (1) EP2217660A1 (fr)
CN (1) CN101883823A (fr)
CA (1) CA2704889C (fr)
DE (1) DE102007055692A1 (fr)
WO (1) WO2009071508A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008054482A1 (de) * 2008-12-10 2010-06-17 Wacker Chemie Ag Pfropfcopolymere und deren Verwendung als Low-Profile-Additive
CN111154370B (zh) * 2020-01-15 2021-06-08 华东理工大学 一种抗菌丙烯酸酯涂料及其制备方法与应用
CN113930060A (zh) * 2021-10-25 2022-01-14 河北多凯复合材料有限公司 一种新型高性能防静电阻燃复合材料及其制备方法

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US3437514A (en) * 1967-08-02 1969-04-08 Ford Motor Co Radiation crosslinking of alpha-beta unsaturated paint binder resin
US3574157A (en) * 1969-02-03 1971-04-06 Fred Markus Coating composition of epoxy resins,polyester resins,and vinyl monomers
US3718714A (en) 1970-09-16 1973-02-27 Union Carbide Corp Unsaturated polyester compositions
US3689309A (en) * 1970-12-21 1972-09-05 Ford Motor Co Epoxy-vinyl copolymer and graded-rubber paint and process
US4284736A (en) 1971-01-18 1981-08-18 Union Carbide Corporation Unsaturated polyester compositions
US3997627A (en) * 1973-08-29 1976-12-14 Mitsubishi Rayon Co., Ltd. Polyester molding compositions containing hydroxy containing vinyl monomers and coated molded articles thereof
US4341877A (en) * 1980-06-04 1982-07-27 Ppg Industries, Inc. Sizing composition and sized glass fibers and process
US4525498A (en) 1980-10-16 1985-06-25 Union Carbide Corporation Polyester fiber reinforced molding compounds
CA1196118A (fr) 1981-09-11 1985-10-29 Kenneth E. Atkins Compositions ameliorees de polyester a mouler
US4448941A (en) * 1981-12-07 1984-05-15 Ford Motor Company Resin binder for fiber composite materials
US4473618A (en) * 1983-05-13 1984-09-25 Owens-Corning Fiberglas Corporation Chrome-free sizing composition containing titanium acetyl acetonate for glass fiber gun roving
US6329475B1 (en) * 1992-08-12 2001-12-11 The Dow Chemical Company Curable epoxy vinylester composition having a low peak exotherm during cure
AU7845594A (en) * 1993-09-28 1995-04-18 Cambridge Industries, Inc. Additives to improve surface characteristics of unsaturated polyester molding composition
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US5712036A (en) * 1996-05-08 1998-01-27 N.V. Owens-Corning S.A. High solubility size compositon for fibers
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DE10054162A1 (de) * 2000-11-02 2002-05-16 Wacker Polymer Systems Gmbh Verfahren zur Herstellung von Holzpressplatten
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DE102007055694A1 (de) * 2007-12-03 2009-06-04 Wacker Chemie Ag Vernetzbare Vinylester-Copolymerisate und deren Verwendung als Low-Profile-Additive

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See references of WO2009071508A1 *

Also Published As

Publication number Publication date
CA2704889C (fr) 2012-09-11
CN101883823A (zh) 2010-11-10
US20100256287A1 (en) 2010-10-07
WO2009071508A1 (fr) 2009-06-11
DE102007055692A1 (de) 2009-06-04
CA2704889A1 (fr) 2009-06-11

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