WO2010006967A1 - Utilisation de résines solides d’ester polyvinylique comme modifiant choc pour des plastiques thermodurcissables - Google Patents

Utilisation de résines solides d’ester polyvinylique comme modifiant choc pour des plastiques thermodurcissables Download PDF

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WO2010006967A1
WO2010006967A1 PCT/EP2009/058645 EP2009058645W WO2010006967A1 WO 2010006967 A1 WO2010006967 A1 WO 2010006967A1 EP 2009058645 W EP2009058645 W EP 2009058645W WO 2010006967 A1 WO2010006967 A1 WO 2010006967A1
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resins
vinyl
polyvinyl ester
group
solid
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PCT/EP2009/058645
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German (de)
English (en)
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Michael Tobias Zarka
René GRÄWE
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Wacker Chemie Ag
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Priority to EP09780294A priority Critical patent/EP2303938A1/fr
Publication of WO2010006967A1 publication Critical patent/WO2010006967A1/fr

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    • 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
    • C08F218/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—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 acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers

Definitions

  • thermosets Use of polyvinyl ester solid resins as impact modifiers for thermosets
  • the invention relates to the use of polyvinyl ester solid resins as Schlagzahmodifizierer for thermosets, Schlagkahmodi fizierer containing reaction resin compositions and the impact-modified thermosets available therefrom.
  • Thermosets are closely meshed plastics which can be obtained by irreversible and covalent crosslinking of reaction resins.
  • Duroplastics are characterized by high chemical and thermal resistance due to their high crosslinking density.
  • Reaction resins are according to DIN 16945: 1989-03 liquid or flowable resins which can cure on their own or with reactants, such as hardener or accelerator, by polymerization or polyaddition without splitting volatile components to thermosets.
  • Technically important reaction resins include unsaturated polyester resins (UP resins), vinyl ester resins (VE resins), methyl methacrylate resins and epoxy resins (EP).
  • Impact resistance is a measure of the resistance of a material to breakage when it is impacted, for example, by impact or impact. The impact resistance is measured as energy required to break per surface.
  • impact resins are usually added to reaction resins so that impact-modified thermosetting plastics are obtained after curing.
  • Examples of common impact modifiers are rubbery additives such as graft copolymers having a core-shell structure containing an elastomeric siloxane or organopolymer core and a polymer shell grafted thereon.
  • the cores are usually highly cross-linked and elastic and have particular character.
  • the elastomeric Kern is able to absorb and dissipate the energy introduced by impact stress.
  • the grafted-on polymer shell ensures compatibilization and compatibility of the impact modifier with the individual constituents of the reaction resin compositions and thus counteracts phase separation.
  • No. 4,918,132 describes core-shell polymers for impact modification of thermoplastic polyester resins.
  • the core-shell polymers were obtained by graft copolymerization of organic vinyl monomers onto crosslinked cores, which are composites of organosilicon compounds and ethylenically unsaturated organic monomers.
  • EP-A 537014 describes impact-modified polycarbonates containing particles with a polysiloxane / organopolymer core and an organopolymer shell.
  • WO-A 02/36682 and WO-A 02/36683 teach thermoplastic molding compositions of polymethylmethacrylate (PMMA) having improved low-temperature impact strength.
  • PMMA polymethylmethacrylate
  • silicone elastomers are used which carry a PMMA shell.
  • thermosets such as unsaturated polyesters
  • GB 2284816 and US 3652722 also recommend core-shell polymers.
  • a disadvantage of the core-shell polymers is their elaborate and generally multi-step synthesis.
  • the preparation of the core-shell polymers is generally carried out in a heterogeneous, aqueous phase, wherein a residual moisture usually remains in the polymerization product.
  • the residual moisture can lead to a hydrolytic degradation of the polymer chains during the processing of impact modifiers with the reaction resins, such as, for example, unsaturated polyester resins, and thus cause a deterioration of the mechanical properties of thermosetting plastics obtainable therefrom.
  • thermosets using nitroxyl-terminated reactive methacrylate macroinitiators, which are described in US Pat
  • reaction resins crosslink, they are incorporated into the resulting polymeric network.
  • a disadvantage of these systems is the expensive synthesis of the macroinitiators.
  • the process is limited to vinyl aromatic-containing reaction resins and thus not widely applicable.
  • an increase in impact strength at low temperatures not possible because this Schlagzahmodifizierer are required with very low glass transition temperatures and on the other hand gangigen Po Iy (meth) acrylates glass transition temperatures of major equal -60 0 C have.
  • thermosetting plastics which do not have the abovementioned disadvantages and with which thermosets having improved impact strengths become accessible.
  • the object has been achieved by using polyvinyl ester solid resins as Schlagzahmodifizierer based on one or more vinyl esters of short-chain acids and one or more monomers from the group comprising vinyl esters of long-chain acids and polymerizable silicones.
  • Polyvinyl ester solid resins have hitherto been used, for example, as coating agents, water repellents or as additives for paints, cosmetics or building chemical products, as described in WO-A 03/085035 for copolymers based on vinyl esters and polymerizable silicones.
  • vinyl esters a) are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl-2-ethylhexanoate, 1-methylvylate, vinyl pivalate and VeoVa9® (Resolution). Preference is given to vinyl acetate.
  • At least 20% by weight, particularly preferably at least 30% by weight and most preferably from 40 to 80% by weight, of monomers a), based on the total weight of the monomers for preparing the polyvinyl ester solid resins, are preferably used polyvinyl acetate solid resins.
  • Vmylester of group b) examples include Vmyllaurat and Vmylester of ⁇ -branched Monocarbonsauren with 10 or 11 C-atoms, such as VeoValO® or VeoVall® (Resolution). Particularly preferred is methyl laurate.
  • the solid polyvinyl ester resins For the preparation of the solid polyvinyl ester resins, it is preferred to use up to 80% by weight and more preferably up to 65% by weight of vinyl ester of group b), based on the total weight of the monomers for preparing the polyvinyl esters. Solid resins. When vinyl esters of group b) are used, these vinyl esters most preferably used 10 to 45 wt .-%, based on the total weight of the monomers for the preparation of the solid polyvinyl ester resins.
  • the silicones of group b) are examples of radicals R is methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert.
  • radical R is a monovalent hydrocarbon radical
  • Preferred alkoxy radicals R are those having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy and n-butoxy radicals, which may optionally be substituted by oxyalkylene radicals, such as oxyethylene or oxymethylene radicals. Particularly preferred are the methoxy and ethoxy.
  • the cited alkyl radicals and alkoxy radicals R may optionally also be substituted, for example with halogen, mercapto groups, epoxy-functional groups, carboxy groups, keto groups, enamine groups, amino groups, aminoethylamino groups, isocyanate groups, aryloxy groups, alkoxysilyl groups and hydroxyl groups.
  • Suitable polymerizable groups R 1 are alkenyl radicals having 2 to 8 C atoms.
  • Examples of such polymerizable groups are the vinyl, allyl, butenyl, and acryloxyalkyl and methacryloxyalkyl group, wherein the alkyl radicals contain 1 to 4 carbon atoms.
  • Preferred silicones of group b) are linear or branched polydialkylsiloxanes having a chain length of 10 to 1000, preferably 20 to 500 SiR 2 O units.
  • ⁇ , ⁇ -divinyl-polydimethylsiloxanes ⁇ , ⁇ -di- (3-acryloxypropyl) polydimethylsiloxanes, ⁇ , ⁇ -di- (3-methacryloxypropyl) polydimethylsiloxanes.
  • the silicones which are only monosubstituted with unsaturated groups are ⁇ -monovinyl-polydimethylsiloxanes, ⁇ -mono- (3-acryloxypropyl) -polydimethylsiloxanes, ⁇ -mono- (acryloxymethyl) -polydimethylsiloxanes, ⁇ -mono- (3-methacryloxypropyl) -
  • Polydimethylsiloxanes are preferred.
  • the monofunctional polydimethylsiloxanes contain an alkyl or alkoxy radical, preferably a methyl or butyl radical, at the other end of the chain.
  • the vinyl groups are preferably at the chain end.
  • examples of such mixtures are silicones of the solvent-free Dehesive ® -6 series (branched) or Dehesive ® - 9-row (unbranched) from Wacker Chemie AG.
  • the proportion of non-functional polydialkylsiloxanes is up to 15% by weight, preferably up to 5% by weight; the proportion of monofunctional polydialkylsiloxanes up to 50% by weight; and the proportion of difunctional polydialkylsiloxanes at least 50 wt .-%, preferably at least 60 wt .-%, each based on the total weight of the silicone c).
  • silicone of group b) are ⁇ , ⁇ -divinyl-polydimethylsiloxanes, or a binary mixture of ⁇ , ⁇ -divinyl-polydimethylsiloxanes with ⁇ -monovinyl-polydimethylsiloxanes, or a ternary mixture of ⁇ , ⁇ -divinyl-polydimethylsiloxanes, ⁇ -monovinyl-polydimethylsiloxanes with unfunctionalized polydimethysiloxane.
  • the silicones of group b) are preferably up to 70 wt .-%, more preferably from 1 to 70 wt .-%, most preferably from 10 to 70 wt .-% and most preferably 25 to 55 wt .-%, based on the total weight of the monomers for the preparation of the solid polyvinyl ester resins.
  • polyvinyl ester solid resins for example acrylic acid esters or methacrylic esters of unbranched or unbranched branched alcohols having 1 to 15 carbon atoms, olefins, vinyl ethers or vinyl halides.
  • methacrylic esters or acrylic acid esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate,
  • Butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate.
  • olefins examples include ethene, propene, 1-alkylethenes and polyunsaturated alkenes, such as 1,3-butadiene and isoprene. Preference is given to ethene and 1,3-butadiene.
  • a preferred vinyl ether is methyl vinyl ether.
  • a preferred vinyl halide is vinyl chloride.
  • one or more further monomers d) can be used, such as, for example, ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, crotonic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitrites, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid, such as the diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or salts thereof, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid.
  • ethylenically unsaturated mono- and dicarboxylic acids preferably acrylic acid, crotonic acid, methacrylic acid, fumaric acid and maleic acid
  • post-crosslinking comonomers for example acrylamidoglycolic acid (AGA), methyl acrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers such as isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and of N-methylolallyl carbamate.
  • alkyl ethers such as isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrylamide and of N-methylolallyl carbamate.
  • epoxide-functional ethylenically unsaturated comonomers such as glycidyl methacrylate and glycidyl acrylate.
  • ethylenically unsaturated monomers having hydroxyl or CO groups for example methacrylic acid and acrylic acid hydroxyalkyl esters such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate, and also compounds such as diacetone acrylamide and acetoacetoxyethyl acrylate or methacrylate.
  • copolymerizable ethylenically unsaturated silanes for example vinylsilanes such as vinyltrimethoxysilane or vinyltriethoxysilane or (meth) acrylsilanes, for example GENIOSIL® GF-31 (methacryloxypropyltrimethoxysilane), XL-33 (methacryloxymethyltrimethoxysilane), XL-32 (methacryloxymethyldimethylmethoxysilane ), XL-34 (methacryloxymethylmethyldimethoxysilane) and XL-36 (methacryloxymethyltriethoxysilane) (each trade name of Wacker Chemie).
  • vinylsilanes such as vinyltrimethoxysilane or vinyltriethoxysilane or (meth) acrylsilanes
  • GENIOSIL® GF-31 methacryloxypropyltrimethoxysilane
  • XL-33 methacryloxymethyltrimethoxy
  • polyvinyl ester solid resins containing as monomer units a) vinyl acetate and as silicone units of group b) ⁇ , ⁇ -divinyl-polydimethylsiloxane or a binary mixture of ⁇ , ⁇ -divinyl-polydimethylsiloxane with ⁇ -monovinyl-polydimethylsiloxane or a ternary mixture of ⁇ , ⁇ -divinyl Polydimethylsiloxane, ⁇ -monovinyl Pol ⁇ dimethylsiloxan with unfunctionalized polydimethysiloxane included.
  • the solid polyvinyl ester resins containing one or more vinyl ester units of group b) have a molecular weight Mw of preferably from 10,000 to 350,000 g / mol, more preferably from 70,000 to 350,000 g / mol.
  • the glass transition temperatures Tg of the solid polyvinyl ester resins containing one or more vinyl esters units of group b) are preferably from -20 to 50 0 C, particularly preferably -10 to 40 0 C and most preferably -5 ° to 20 ° C.
  • the solid polyvinyl ester resins containing one or more silicone units of group b) preferably have a molecular weight Mw of 20,000 to 130,000 g / mol.
  • the glass transition temperatures Tg of the solid polyvinyl ester resins containing one or more silicone moieties of group b) are preferably from -140 to 50 0 C, more preferably -130 to 40 ° C, and most preferably -130 to 3O 0 C.
  • two glass transition temperatures Tg may also occur, wherein a glass transition temperature Tg preferably occurs between -140 0 C to -100 ° C and the other glass transition temperature Tg preferably between -20 to 40 0 C, more preferably -10 to 30 0 C, and most preferably -5 to 2O 0 C.
  • Two glass transition temperatures Tg occur in particular when the each covalently linked, but per se non-contractual silicone and vinyl ester Partially segregate units and form silicone or vinyl ester domains (microphase separation).
  • the polyvinyl ester solid resins are prepared by means of free-radical-initiated bulk or solution polymerization processes of the ethylenically unsaturated monomers in the presence of radical initiators.
  • the polymerization products can also be present in the form of a dispersion during the polymerization.
  • the solution polymerization is preferred.
  • Suitable organic solvents are, for example, alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol or 1-propanol, ketones, such as acetone or methyl ethyl ketone, esters, such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate or Methoxypropyl acetate, or aromatic hydrocarbons having 6 to 15 carbon atoms, such as xylene.
  • alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n-propanol or 1-propanol
  • ketones such as acetone or methyl ethyl ketone
  • esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate or Methoxypropyl acetate
  • aromatic hydrocarbons having 6 to 15 carbon atoms, such as xylene.
  • mixtures of several organic solvents such as, for example, isopropanol / ethyl acetate or methoxypropyl acetate / isopropanol mixtures.
  • the content of water is preferably ⁇ _ 10 wt .-%, more preferably ⁇ . 1 wt .-% and most preferably ⁇ 0.01 wt .-%, each based on the total mass of the organic solvent used.
  • the polymerization is preferably carried out at temperatures of 0 0 C to 150 0 C, preferably from 20 0 C to 13O 0 C, more preferably from 30 ° C to 120 ° C.
  • the polymerization can be carried out batchwise or continuously, with the introduction of all or individual constituents of the reaction mixture, with partial introduction and subsequent addition of individual constituents of the reaction mixture or after the metering process without presentation.
  • initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, t-butyl hydroperoxide, potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, t-butyl peroxobenzoate, isopropylbenzene monohydroperoxide and azobisisobutyronitrile.
  • the initiators mentioned are preferably used in amounts of from 0.01 to 4.0% by weight, based on the total weight of the monomers used, for the preparation of the organosilicone copolymers.
  • Suitable reducing agents are sulfites and bisulfites of monovalent cations, for example sodium sulfite, the derivatives of sulfoxylic acid, such as zinc or alkali metal formaldehyde sulfoxylates, for example sodium hydroxymethanesulfinate and ascorbic acid.
  • the amount of reducing agent is preferably 0.15 to 3% by weight of the monomers used for the preparation of the organosilicone copolymers.
  • a metal compound which is soluble in the polymerization medium and whose metal component is redox-active under the polymerization conditions for example based on iron or vanadium
  • Particularly preferred initiators are t-butyl peroxypivalate, and t-butyl peroxobenzoate, and the peroxide / reducing agent combinations ammonium persulfate / sodium hydroxymethanesulfinate and potassium persulfate / sodium hydroxymethanesulfinate.
  • the isolation of the polyvinyl ester solid resins from the solvent after polymerization can be carried out by removing the solvent by means of distillation, by precipitation and filtration of the solid polyvinyl ester resins by addition of a non-solvent, by decantation or by a combination of these methods.
  • the solid polyvinyl ester resins are generally in the form of a solid or of a high viscosity oil in isolated form.
  • the solid polyvinyl ester resins are optically transparent.
  • the invention further provides reaction resin compositions comprising one or more impact modifiers, one or more reaction resins, optionally one or more reactive monomers, optionally one or more Other additives and optionally one or more additives, characterized in that the impact modifier is at least one polyvinyl ester solid resin according to the invention.
  • Suitable reaction resins are, for example, unsaturated polyester resins (UP), vinyl ester resins (VE), diallyl phthalate resins (DAP), methacrylate resins and epoxy resins. Unsaturated polyester resins (UP) or vinyl ester resins (VE) are preferred. Most preferred are vinyl ester resins (VE). Curing of the reaction resins gives thermosets.
  • the unsaturated polyester resins are reaction products of one or more dicarboxylic acids or one or more dicarboxylic acid anhydrides with one or more polyols.
  • the preparation of the unsaturated polyester resins is known to the person skilled in the art.
  • the dicarboxylic acids or dicarboxylic acid anhydrides preferably have 2 to 20, more preferably 4 to 20 and most preferably 4 to 10 carbon atoms.
  • the unsaturated polyester resins contain at least one ethylenically unsaturated dicarboxylic acid or at least one ethylenically unsaturated dicarboxylic acid anhydride.
  • Preferred ethylenically unsaturated dicarboxylic acids or dicarboxylic acid anhydrides are maleic acid, maleic anhydride, fumaric acid, methylmaleic acid and itaconic acid. Particularly preferred are maleic acid, Malemsaurean- hydride and fumaric acid.
  • saturated dicarboxylic acids or anhydrides can be used.
  • Suitable saturated acids or dicarboxylic acid anhydrides are, for example, orthophthalic acid, isophthalic acid, phthalic anhydride, terephthalic acid, hexahydrophthalic acid, adipic acid, succinic acid and isophthalic acid.
  • 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.
  • Suitable polyols are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerol and 1,1,1-trimethylolpropane.
  • 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.
  • Vinylester resins are reaction products which are formed by polyadditions or esterification reactions of phenol derivatives and ethylenically unsaturated mono- or dicarboxylic acids or dicarboxylic acid 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 reactive monomers are the same monomers a), c) or vinyl nyl esters of group b), preferably or particularly preferably, which are also correspondingly listed for the polymerization for the preparation of the polyvinyl ester solid resins.
  • Very particularly preferred reactive monomers are styrene, methyl methacrylate, methyl acrylate and butyl acrylate. The most preferred reactive monomer is styrene.
  • polyfunctional ethylenically unsaturated monomers include acrylate derivatives, which are commonly used in UV-curing systems.
  • polyfunctional ethylenically unsaturated monomers are (meth) acrylic acid anhydride, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol 400- (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, glycerol 1,3-di (meth)
  • additives are hard, such as initiators, or accelerators.
  • Suitable initiators are, for example, the initiators listed above for the free-radically initiated polymerization for the preparation of the polyvinyl ester solid resins.
  • suitable additives are fibrous reinforcing materials, in particular glass fibers, carbon fibers, manmade fibers, such as polyester or polyamide, natural fibers, such as cotton or cellulose; Glass beads; mineral fillers, such as calcium carbonate, dolomite, aluminum hydroxide, kaolin, barium sulfate; Dyes, such as pigments; stabilizers; Flame retardants and other other polymers are used.
  • fibrous reinforcing materials in particular glass fibers, carbon fibers, manmade fibers, such as polyester or polyamide, natural fibers, such as cotton or cellulose; Glass beads; mineral fillers, such as calcium carbonate, dolomite, aluminum hydroxide, kaolin, barium sulfate; Dyes, such as pigments; stabilizers; Flame retardants and other other polymers are used.
  • Particularly preferred additives are fibrous Verstarkungsstoffe.
  • Most preferred additives are glass fibers.
  • reaction resin compositions according to the invention are obtainable by adding the impact modifiers, comprising at least one solid polyvinyl ester resin, and optionally the reactive monomers and / or optionally the additives and / or optionally the additives, simultaneously or spatially or temporally separated to the reaction resins, usually resulting in reaction resin compositions in the form of solutions or dispersions.
  • the mixing of the individual constituents of the reaction resin compositions can be carried out using the usual devices known to the person skilled in the art, such as, for example, reactors, Ruhr kettles or mixers, and centrifuges, such as flugeler, anchor or blade extruders.
  • the reaction resin compositions preferably contain from 0.25 to 25% by weight, more preferably from 0.5 to 10% by weight, on most preferably 1 to 5% by weight of solid polyvinyl ester resins; preferably 10 to 99.75 wt.%, more preferably 20 to 95 wt.%, most preferably 30 to 80 wt.% of reaction resins; 0 to 10 wt .-%, in particular 0 to 6 wt .-% additives; and 0 to 89.75% by weight, especially 5 to 80% by weight of additives; where the data in wt .-% on the total mass of the respective reaction resin composition refers and adds up to 100 wt.% Total.
  • thermosetting plastics obtained by curing inventive reaction resin compositions.
  • the curing of the reaction resin compositions is preferably carried out at temperatures of ⁇ 20 0 C, more preferably from 20 to 200 0 C and most preferably from 20 to 165 0 C.
  • the curing of the reaction resin compositions in the presence of one or several initiators by free-radically initiated polymerization.
  • curing at the particular temperature may also be carried out using pressures of ⁇ 1 mbar, more preferably from 1 to 200,000 mbar, and most preferably from 1,000 to 200,000 mbar.
  • thermosets can be produced by the usual methods, such as, for example, by hand lamination, fiber spraying, winding processes, Sheet Molding Compound Technology (SMC), Bulk Molding Compound Technology (BMC), Resin Transfer Molding (RTM), Resin Injection Molding (RTM). RIM).
  • SMC Sheet Molding Compound Technology
  • BMC Bulk Molding Compound Technology
  • RTM Resin Transfer Molding
  • RTM Resin Injection Molding
  • RIM Resin Injection Molding
  • the impact-modified thermosets have high impact strengths and high impact strengths. Since the polyvinyl ester solid resins according to the invention can also have very low glass transition temperatures Tg, it is also possible according to the invention to obtain thermosets which have high impact strengths at very low temperatures.
  • the novel reaction resin compositions or the impact-modified thermosets according to the invention are also available with very low or no residual water content, so that hydrolytic degradation can be prevented.
  • the polyvinyl ester solid resins particularly preferred as impact modifiers based on vinyl esters a) and silicones as monomer b) (silicone organocopolymers) have a microphase-separated structure.
  • the silicone domains are embedded therein in a continuous polyvinyl ester matrix, wherein the diameter of the silicone domains is preferably below the wavelength range of visible light, which leads to an optical transparency of the silicone organocopolymers.
  • the diameter of the silicone domains is preferably ⁇ 400 nm, more preferably from 10 to 300 nm, and most preferably from 10 to 200 nm.
  • the vinyl ester units a) of the solid polyvinyl ester resins ensure very good compatibility with the other components of the reaction resin compositions.
  • the monomers c) or the monomers d) for example, the polarity of the solid polyvinyl ester resins can be varied and their compatibility with a wide variety of reaction resins can be improved.
  • PDMS mixture Mixture of three polydimethylsiloxanes each having a chain length of about 100 dimethylsiloxane units and containing 5% by weight of unfunctionalized polydimethylsiloxane, 20% by weight of ⁇ ⁇ Monovinyl polydimethylsiloxane and 75 wt .-% ⁇ , ⁇ -divinyl-polydimethylsiloxane contains.
  • TPEH t-butyl peroxy-2-ethylhexanoate
  • PDMS mixture 700 g of isopropanol, and 2.5 g of t-butyl peroxy-2-ethylhexanoate (TBPEH) submitted. Under reflux, a further 250 g of vinyl acetate were added during 4 hours. The mixture was then stirred under reflux for 2 h. Then the solvent and volatiles were removed by distillation, first under normal pressure, then under vacuum.
  • TPEH t-butyl peroxy-2-ethylhexanoate
  • Atlac-E-Coat 65 vinyl ester resin Atlac-E-Coat 65 (styrenic solution, trade name of DSM);
  • Accelerator NL-49 P (trade name of Akzo Nobel).
  • Trigonox 239 (peroxide, initiator, trade name of Akzo Nobel).
  • the amount of styrene specified here was added in addition to the amount of styrene already present in A or B, respectively.
  • an impact modifier in the respective solution of the vinyl ester resin A or B in styrene was optionally dissolved in styrene in an overhead shaker as indicated in Table 2.
  • the accelerator NL 49 P and the initiator Trigonox 239 were added to the respective reaction resin composition only immediately before they were cured and briefly stirred in with a glass rod.
  • thermosets without glass fibers
  • the respective reaction resin composition was poured into a Teflon mold and 24 h at room temperature, for 24 hours at 6O 0 C and then (4 mm 1 cm, thickness length 8 cm, width) cured for 3 h at 9O 0 C to a test piece.
  • thermoset resins modified according to the invention have improved strength both in the case of glass fiber reinforcement (Examples 15 to 21) and without glass fiber reinforcement (Examples 8 to 14) over corresponding non-impact modified thermosets (Comparative Examples 5, 6) , 9 and 10 respectively) have significantly higher impact strengths.
  • thermosets With conventional impact modifiers based on core-shell polymers, in the case of non-glass-fiber-reinforced thermosets, similar impact strengths can be achieved as with impact-modified thermosets according to the invention (Table 3: Examples 11-14 and Comparative Examples 7 and 8).
  • the impact modifiers according to the invention are obtainable by simple free-radical copolymerization of monomers and consequently with less effort than core-shell polymers.
  • thermosets which are particularly relevant in practice, even lower impact strengths are achieved with conventional core-shell polymers as impact modifiers (Table 4: Comparative Examples 11 and 12) than in corresponding thermosets without the use of impact modifiers (Table 4: Comparative Examples 9 and 12) 10).
  • impact-modified glass fiber-reinforced thermosets according to the invention (Table 4: Examples 15 and 21) have a higher impact strength than the non-impact modified systems of Comparative Examples 9 and 10.

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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L’invention concerne l’utilisation de résines solides d’ester polyvinylique comme modifiant choc pour des plastiques thermodurcissables, caractérisée en ce que les résines solides d’ester polyvinylique peuvent être obtenues par polymérisation en solution ou en masse amorcée de manière radicalaire de a) un ou plusieurs esters vinyliques d’acides monocarboxyliques linéaires ou ramifiés avec 1 à 9 atomes de carbone, et b) un ou plusieurs monomères polymérisables choisis dans le groupe comprenant de l’ester vinylique d’acides monocarboxyliques linéaires ou ramifiés de 10 à 18 atomes de carbone et des silicones de la formule générale R1 aR3-aSiO (SiR2O)nSiR3-aR1 a, R étant identique ou différent, et représentant un reste alkyle ou alkoxy monovalent, éventuellement substitué, avec chaque fois 1 à 18 atomes de carbone, R1 représentant un groupe polymérisable, a étant 0 ou 1, et au moins un reste R1 étant présent dans chaque molécule, et n = 10 à 1000.
PCT/EP2009/058645 2008-07-18 2009-07-08 Utilisation de résines solides d’ester polyvinylique comme modifiant choc pour des plastiques thermodurcissables WO2010006967A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09780294A EP2303938A1 (fr) 2008-07-18 2009-07-08 Utilisation de résines solides d'ester polyvinylique comme modifiant choc pour des plastiques thermodurcissables

Applications Claiming Priority (2)

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DE102008040551.5 2008-07-18
DE102008040551A DE102008040551B3 (de) 2008-07-18 2008-07-18 Verwendung von Polyvinylester-Festharzen als Schlagzähmodifizierer für Duroplasten

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WO2010006967A1 true WO2010006967A1 (fr) 2010-01-21

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PCT/EP2009/058645 WO2010006967A1 (fr) 2008-07-18 2009-07-08 Utilisation de résines solides d’ester polyvinylique comme modifiant choc pour des plastiques thermodurcissables

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EP (1) EP2303938A1 (fr)
DE (1) DE102008040551B3 (fr)
WO (1) WO2010006967A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006037272A1 (de) * 2006-08-09 2008-02-14 Wacker Chemie Ag Hochfeststoffhaltige Lösungen von Silikonorganocopolymeren mit hohem Silikongehalt und hohem Feststoffgehalt und Verfahren zu deren Herstellung und deren Verwendung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2617547C (fr) * 2005-08-02 2013-10-08 Arkema Inc. Procedes pour produire des polymeres aromatiques de vinyle au moyen de macro-initiateurs (meth)acryliques

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006037272A1 (de) * 2006-08-09 2008-02-14 Wacker Chemie Ag Hochfeststoffhaltige Lösungen von Silikonorganocopolymeren mit hohem Silikongehalt und hohem Feststoffgehalt und Verfahren zu deren Herstellung und deren Verwendung

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DE102008040551B3 (de) 2010-02-11
EP2303938A1 (fr) 2011-04-06

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