EP2010581A1 - Use of carboxyl-functional polyvinyl acetates for producing bmc parts - Google Patents

Use of carboxyl-functional polyvinyl acetates for producing bmc parts

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Publication number
EP2010581A1
EP2010581A1 EP07728208A EP07728208A EP2010581A1 EP 2010581 A1 EP2010581 A1 EP 2010581A1 EP 07728208 A EP07728208 A EP 07728208A EP 07728208 A EP07728208 A EP 07728208A EP 2010581 A1 EP2010581 A1 EP 2010581A1
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EP
European Patent Office
Prior art keywords
weight
parts
carboxyl
polyvinyl acetate
solid
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EP07728208A
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German (de)
French (fr)
Inventor
René GRÄWE
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Wacker Chemie AG
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Wacker Chemie AG
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Publication of EP2010581A1 publication Critical patent/EP2010581A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/06—Unsaturated polyesters
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate

Definitions

  • the invention relates to the use of carboxyl-functional polyvinyl acetate solid resins for the production of BMC moldings.
  • Unsaturated polyester resin compositions are frequently used in the production of sheet-like plastic parts. These polyester resins are reaction products of a dicarboxylic acid or a dicarboxylic acid anhydride with a polyol. Such polyester resin compositions also contain a monomer having ethylenically unsaturated groups, generally styrene. Styrene is added to the polyester resin composition to dissolve the polyester and to ensure that the polyester composition is a flowable mass. To reinforce the plastic parts obtained with the polyester resin composition, the polyester resin compositions still contain fiber materials such as glass fiber, carbon fiber or corresponding fiber mats.
  • the low-profile additive reduces shrinkage during curing, reduces residual stresses, reduces micro-cracking and facilitates compliance with manufacturing tolerances.
  • the low-profile additives are thermoplastics such as polystyrene, polymethyl methacrylate and in particular polyvinyl acetate. Polyvinyl acetates having up to 1% by weight of carboxyl-functional comonomer units are also used. At higher levels of carboxyl functional comonomer units, shrinkage reduction is unsatisfactory.
  • Two methods for the production of thermoset moldings from FRP composites are BMC technology (BuIk Molding Compound) and SMC technology (Sheet Molding Compound).
  • a pasty mass of styrenic polyester resin solution, low profile additive, crosslinking catalyst, filler, mold release agent and optionally other additives is prepared, which is applied to a polyamide film. Subsequently, fiberglass is sprinkled on this layer, and finally applied another layer of the pasty mass. This sheet sandwich is then peeled from the film, cut into pieces and pressed using pressure and temperature to form parts.
  • the constituents of the compound, the styrenic polyester resin solution, the low profile additive, the crosslinking catalyst, filler, mold release agent and optionally other additives are mixed to a pasty mass, then admixed with glass fiber, and then using pressure and temperature the molded part manufactured.
  • Acrylic acid copolymers in formulations with thickening agents is also described in DE-OS 2104575.
  • the invention relates to the use of carboxyl-functional polyvinyl acetate solid resins as an additive in formulations without thickening agents for molding compositions for the production of BMC molded parts.
  • Suitable comonomers having carboxyl groups for the preparation of carboxyl-functional polyvinyl acetate solid resins are simply ethylenically unsaturated mono- and dicarboxylic acids. Preference is given to acrylic acid, methacrylic acid, fumaric acid, crotonic acid. Particularly preferred is crotonic acid.
  • the proportion of comonomer units having carboxyl groups in the polyvinyl acetate solid resin is from 0.5 to 10% by weight, preferably greater than 1% by weight up to 10% by weight, particularly preferably from 3 to 10% by weight. , in each case based on the total weight of the solid polyvinyl acetate resin.
  • the preparation of the carboxyl-functional polyvinyl acetate solid resins is carried out in a known manner by the mass, suspension, or preferably solution polymerization process.
  • Suitable solvents are, for example, monohydric, aliphatic alcohols having 1 to 6 C atoms, preferably methanol, ethanol, propanol, isopropanol. Particularly preferred are ethanol and isopropanol.
  • the reaction is generally carried out under Ruckfluß discipline, generally at a polymerisation sation level of 40 0 C to 140 0 C, carried out to the
  • the initiators used are organic peroxides or azo compounds. Suitable examples include diacyl peroxides such as dilauroyl peroxide, peroxo esters such as t-butyl peroxypivalate or t-butyl peroxo-2-ethylhexanoate, or peroxodicarbonates such as ethyl peroxodicarbonate.
  • the amount of initiator is generally from 0.01 to 5.0 wt .-%, based on the monomers.
  • the initiators can both be submitted and metered. It has proven useful to submit part of the required amount of initiator and to dose the remainder continuously during the reaction.
  • the adjustment of the molecular weight can be carried out in a manner known to the skilled worker by polymerization in the presence of molecular weight regulators.
  • Suitable regulators are, for example, alcohols such as ethanol or isopropanol, aldehydes such as acetaldehyde or propionaldehyde, silane-containing regulators such as mercaptosilanes, for example 3-mercaptopropyltrimethoxysilane.
  • the polymers can be prepared by a batch process, all components of the polymerization mixture being initially charged in the reactor, or by a seim batch process, with one or more components being initially introduced and the remainder being metered in, or a continuous one Polymerization are carried out, wherein the components are added during the polymerization.
  • the dosages may optionally be carried out separately (spatially and temporally).
  • a typical formulation for unsaturated polyester resin compositions for molding compositions for the BMC technique contains 60 to 70 parts by weight of unsaturated polyester resin (as a 50 to 75% solution in styrene), 30 to 40 parts by weight of low-profile additives (as a 30 to 50% solution in styrene) such as polyvinyl acetate or polymethyl methacrylate, 0.5 to 2 parts by weight of initiator such as t-butyl perbenzoate, 150 to 200 parts by weight of filler such as calcium carbonate, 25 to 30 wt.
  • unsaturated polyester resin as a 50 to 75% solution in styrene
  • low-profile additives as polyvinyl acetate or polymethyl methacrylate
  • initiator such as t-butyl perbenzoate
  • filler such as calcium carbonate
  • Parts of glass fiber 0.5 to 3 parts by weight of mold release agents such as zinc stearate, and optionally other additives, such as pigments, flame retardant additives.
  • the formulations contain no thickening agents Tel such as basic metal compounds, such as oxides or hydroxides of metals of the 1st to 3rd main group of the PSE.
  • Additive preferably based on polyvinyl acetate or polymethyl methacrylate, wholly or partly replaced by carboxyl-functional polyvinyl acetate.
  • the carbo- xylated polyvinyl acetate solid resin in an amount of 10 to 100 wt .-%, preferably 50 to 80 wt .-%, each based on the weight of low-profile additive in the recipe used. It is expedient to use this additive in a styrenic solution.
  • Polyvinyl acetate solid resin with 5% by weight crotonic acid units and a weight-average molecular weight Mw 67,500.
  • Polyvinyl acetate solid resin containing 5% by weight crotonic acid units and having a weight average molecular weight M w 116750.
  • the table or the graph shows that, when the filler is admixed with the homopolymers, an extreme increase in viscosity occurs, whereas in the case of copolymers of comparable molecular weight, the increase in viscosity in the case of filler additions is very moderate.

Abstract

The invention relates to the use of carboxyl-functional polyvinyl acetate solid resins as additives in formulations without thickeners for producing BMC parts.

Description

Verwendung von carboxylfunktionellen Polyvinylacetaten zur Herstellung von BMC-FormteilenUse of carboxyl-functional polyvinyl acetates for the production of BMC moldings
Die Erfindung betrifft die Verwendung von carboxylfunktionel- len Polyvinylacetat-Festharzen zur Herstellung von BMC- Formteilen .The invention relates to the use of carboxyl-functional polyvinyl acetate solid resins for the production of BMC moldings.
Bei der Herstellung von flächigen Kunststoffteilen werden häufig ungesättigte Polyesterharz-Zusammensetzungen (UP-Harze) eingesetzt. Diese Polyesterharze sind Reaktionsprodukte einer Dicarbonsäure oder eines Dicarbonsäureanhydrids mit einem Po- lyol. Derartige Polyesterharz-Zusammmensetzungen enthalten auch ein Monomeres mit ethylenisch ungesättigten Gruppen, im allgemeinen Styrol. Styrol wird der Polyesterharz-Zusammen- setzung zugegeben um den Polyester zu lösen und sicherzustellen, dass die Polyesterzusammensetzung eine fließbare Masse ist. Zur Verstärkung der mit der Polyesterharz-Zusammensetzung erhaltenen Kunststoffteile enthalten die Polyesterharz-Zusammensetzungen noch Fasermaterialien wie Glasfaser, Carbonfaser oder entsprechende Fasermatten.Unsaturated polyester resin compositions (UP resins) are frequently used in the production of sheet-like plastic parts. These polyester resins are reaction products of a dicarboxylic acid or a dicarboxylic acid anhydride with a polyol. Such polyester resin compositions also contain a monomer having ethylenically unsaturated groups, generally styrene. Styrene is added to the polyester resin composition to dissolve the polyester and to ensure that the polyester composition is a flowable mass. To reinforce the plastic parts obtained with the polyester resin composition, the polyester resin compositions still contain fiber materials such as glass fiber, carbon fiber or corresponding fiber mats.
Problematisch bei der Verarbeitung solcher Polyesterharz- Zusammensetzungen (Fiber Reinforced Plastic composites = FPR composites) ist der Volumenschwund während der Wärmehärtung des Polyesterharzes. Zur Reduzierung des Schrumpfs bei derThe problem with the processing of such polyester resin compositions (Fiber Reinforced Plastic Composites = FPR composites) is the volume shrinkage during the heat curing of the polyester resin. To reduce the shrinkage in the
Aushärtung des Polyesterharzes werden diesem daher sogenannte Low-Profile-Additive zugegeben. Das Low-Profile-Additiv reduziert das Schrumpfen beim Aushärten, baut Eigenspannungen ab, verringert Mikrorissbildung, und erleichtert die Einhaltung von Fertigungstoleranzen. Bei den Low-Profile-Additiven handelt es sich um Thermoplaste wie Polystyrol, Polymethylmethac- rylat und insbesondere Polyvinylacetat . Es werden auch Polyvi- nylacetate mit bis zu 1 Gew.-% carboxylfunktionellen Comonome- reinheiten, eingesetzt. Bei höherem Gehalt an carboxylfunktio- nellen Comonomereinheiten ist die Schrumpfreduzierung nicht zufriedenstellend. Zwei Verfahren zur Herstellung von duroplastischen Formkörpern aus FRP-Composites sind die BMC-Technik (BuIk Molding Compound) und die SMC-Technik (Sheet Molding Compound) . Bei dem SMC-Verfahren wird eine pastöse Masse aus styrolischer Polyes- terharz-Lösung, Low Profile Additiv, Vernetzungskatalysator, Füllstoff, Formtrennmittel sowie gegebenenfalls weiteren Zusatzstoffen hergestellt, welche auf einen Polyamidfilm aufgetragen wird. Anschließend wird Glasfaser auf diese Schicht aufgestreut, und schließlich eine weitere Schicht der pastösen Masse aufgetragen. Dieses flächige Sandwich wird dann von der Folie abgezogen, in Stücke geschnitten und unter Anwendung von Druck und Temperatur zu Formteilen verpresst.Curing of the polyester resin therefore this so-called low-profile additives are added. The low-profile additive reduces shrinkage during curing, reduces residual stresses, reduces micro-cracking and facilitates compliance with manufacturing tolerances. The low-profile additives are thermoplastics such as polystyrene, polymethyl methacrylate and in particular polyvinyl acetate. Polyvinyl acetates having up to 1% by weight of carboxyl-functional comonomer units are also used. At higher levels of carboxyl functional comonomer units, shrinkage reduction is unsatisfactory. Two methods for the production of thermoset moldings from FRP composites are BMC technology (BuIk Molding Compound) and SMC technology (Sheet Molding Compound). In the SMC process, a pasty mass of styrenic polyester resin solution, low profile additive, crosslinking catalyst, filler, mold release agent and optionally other additives is prepared, which is applied to a polyamide film. Subsequently, fiberglass is sprinkled on this layer, and finally applied another layer of the pasty mass. This sheet sandwich is then peeled from the film, cut into pieces and pressed using pressure and temperature to form parts.
Bei dem BMC-Verfahren werden die Bestandteile des Compounds, die styrolische Polyesterharz-Lösung, das Low Profile Additive, der Vernetzungskatalysator, Füllstoff, Formtrennmittel sowie gegebenenfalls weitere Zusatzstoffe zu einer pastösen Masse vermischt, danach Glasfaser zugemischt, und anschließend unter Anwendung von Druck und Temperatur das Formteil herge- stellt.In the BMC process, the constituents of the compound, the styrenic polyester resin solution, the low profile additive, the crosslinking catalyst, filler, mold release agent and optionally other additives are mixed to a pasty mass, then admixed with glass fiber, and then using pressure and temperature the molded part manufactured.
Für das BMC-Verfahren werden derzeit nicht funktionalisierte Polyvinylacetat-Festharze als Low-Profile-Additive eingesetzt. Nachteilig ist dabei, dass die Zugabe von Füllstoffen, welche die Rezeptur verbilligen, begrenzt wird durch die relativ hohe Eigenviskosität von styrolischen Polyvinylacetat-Lösungen . Für das SMC-Verfahren ist aus der EP 501176 Al bekannt, dass das Eindicken von härtbaren Polyesterharz-Formmassen durch Zusatz von Säuregruppen enthaltenden thermoplastischen Vinylpolymeren beschleunigt werden kann. Die Verwendung Vinylacetat-For the BMC process currently non-functionalized solid polyvinyl acetate resins are used as low-profile additives. The disadvantage here is that the addition of fillers which reduce the cost of the formulation is limited by the relatively high intrinsic viscosity of styrenic polyvinyl acetate solutions. For the SMC process it is known from EP 501176 A1 that thickening of curable polyester resin molding compositions can be accelerated by addition of thermoplastic vinyl polymers containing acid groups. The use of vinyl acetate
Acrylsäure-Copolymerisaten in Rezepturen mit Eindickmitteln ist auch in der DE-OS 2104575 beschrieben.Acrylic acid copolymers in formulations with thickening agents is also described in DE-OS 2104575.
Es bestand daher die Aufgabe, einen Weg zu finden, welcher die Einarbeitung größerer Füllstoffmengen in die Rezeptur von Formmassen für das BMC-Verfahren ermöglicht. Überraschenderweise wurde gefunden, dass mit carboxylfunktio- nellen Polyvinylacetat-Festharzen, bei gleichem Molekulargewicht, styrolische Losungen mit wesentlich geringerer Eigen- viskositat resultieren, was die Einarbeitung höherer FuIl- stoffmengen ermöglicht.It was therefore an object to find a way that allows the incorporation of larger amounts of filler in the formulation of molding compositions for the BMC process. Surprisingly, it has been found that carboxyl-functional polyvinyl acetate solid resins, with the same molecular weight, result in styrenic solutions with significantly lower intrinsic viscosity, which makes it possible to incorporate higher amounts of fuel.
Gegenstand der Erfindung ist die Verwendung von carboxylfunk- tionellen Polyvinylacetat-Festharzen als Additiv in Formulierungen ohne Eindickmittel für Formmassen zur Herstellung von BMC-Formteilen.The invention relates to the use of carboxyl-functional polyvinyl acetate solid resins as an additive in formulations without thickening agents for molding compositions for the production of BMC molded parts.
Geeignete Comonomere mit Carboxyl-Gruppen für die Herstellung von carboxylfunktionellen Polyvinylacetat-Festharzen sind einfach ethylenisch ungesättigte Mono- und Dicarbonsauren . Bevor- zugt werden Acrylsaure, Methacrylsaure, Fumarsaure, Crotonsau- re . Besonders bevorzugt ist Crotonsaure. Der Anteil an Comono- mereinheiten mit Carboxyl-Gruppen im Polyvinylacetat-Festharz betragt 0,5 bis 10 Gew.-%, vorzugsweise großer als 1 Gew.-% bis zu 10 Gew.-%, besonders bevorzugt 3 bis 10 Gew.-%, jeweils bezogen auf das Gesamtgewicht des Polyvinylacetat-Festharzes .Suitable comonomers having carboxyl groups for the preparation of carboxyl-functional polyvinyl acetate solid resins are simply ethylenically unsaturated mono- and dicarboxylic acids. Preference is given to acrylic acid, methacrylic acid, fumaric acid, crotonic acid. Particularly preferred is crotonic acid. The proportion of comonomer units having carboxyl groups in the polyvinyl acetate solid resin is from 0.5 to 10% by weight, preferably greater than 1% by weight up to 10% by weight, particularly preferably from 3 to 10% by weight. , in each case based on the total weight of the solid polyvinyl acetate resin.
Die Herstellung der carboxylfunktionellen Polyvinylacetat- Festharze erfolgt in bekannter Weise nach dem Masse-, Suspen- sions-, oder vorzugsweise Losungspolymerisations-Verfahren . Geeignete Losungsmittel sind beispielsweise einwertige, ali- phatische Alkohole mit 1 bis 6 C-Atomen, vorzugsweise Methanol, Ethanol, Propanol, Isopropanol. Besonders bevorzugt werden Ethanol und Isopropanol. Die Reaktion wird im allgemeinen unter Ruckflußbedingungen, im allgemeinen bei einer Polymeri- sationstemperatur von 400C bis 1400C, durchgeführt, um dieThe preparation of the carboxyl-functional polyvinyl acetate solid resins is carried out in a known manner by the mass, suspension, or preferably solution polymerization process. Suitable solvents are, for example, monohydric, aliphatic alcohols having 1 to 6 C atoms, preferably methanol, ethanol, propanol, isopropanol. Particularly preferred are ethanol and isopropanol. The reaction is generally carried out under Ruckflußbedingungen, generally at a polymerisation sation level of 40 0 C to 140 0 C, carried out to the
Siedekuhlung zur Abfuhrung der Reaktionswarme zu nutzen. Dies kann bei Normaldruck als auch unter leichtem Überdruck erfolgen .Siedekuhlung to dissipate the heat of reaction to use. This can be done at atmospheric pressure as well as under slight overpressure.
Als Inititatoren werden organische Peroxide oder Azoverbindun- gen verwendet. Geeignet sind beispielsweise Diacylperoxide wie Dilauroylperoxid, Peroxoester wie t-Butylperoxopivalat oder t- Butylperoxo-2-ethylhexanoat, oder Peroxodicarbonate wie Di- ethylperoxodicarbonat . Die Initiatormenge beträgt im allgemeinen von 0,01 bis 5,0 Gew.-%, bezogen auf die Monomeren. Die Initiatoren können sowohl vorgelegt als auch dosiert werden. Dabei hat es sich bewährt, einen Teil der benötigten Initia- tormenge vorzulegen und den Rest kontinuierlich während der Reaktion zu dosieren.The initiators used are organic peroxides or azo compounds. Suitable examples include diacyl peroxides such as dilauroyl peroxide, peroxo esters such as t-butyl peroxypivalate or t-butyl peroxo-2-ethylhexanoate, or peroxodicarbonates such as ethyl peroxodicarbonate. The amount of initiator is generally from 0.01 to 5.0 wt .-%, based on the monomers. The initiators can both be submitted and metered. It has proven useful to submit part of the required amount of initiator and to dose the remainder continuously during the reaction.
Die Einstellung des Molekulargewichts kann in dem Fachmann bekannter Weise durch Polymerisation in Gegenwart von Molekular- gewichtsreglern erfolgen. Geeignete Regler sind beispielsweise Alkohole wie Ethanol oder Isopropanol, Aldehyde wie Acetalde- hyd oder Propionaldehyd, silanhaltige Regler wie Mercaptosila- ne, beispielsweise 3-Mercaptopropyltrimethoxysilan .The adjustment of the molecular weight can be carried out in a manner known to the skilled worker by polymerization in the presence of molecular weight regulators. Suitable regulators are, for example, alcohols such as ethanol or isopropanol, aldehydes such as acetaldehyde or propionaldehyde, silane-containing regulators such as mercaptosilanes, for example 3-mercaptopropyltrimethoxysilane.
Zur Herstellung der Polymerisate kann nach einem Batchverfah- ren gearbeitet werden, wobei alle Komponenten des Polymerisationsansatzes im Reaktor vorgelegt werden, oder nach einem Se- mi-Batchverfahren, wobei einzelne oder mehrere Komponenten vorgelegt werden und der Rest zudosiert wird, oder eine konti- nuierliche Polymerisation durchgeführt werden, wobei die Komponenten während der Polymerisation zudosiert werden. Die Dosierungen können gegebenenfalls separat (räumlich und zeitlich) durchgeführt werden.The polymers can be prepared by a batch process, all components of the polymerization mixture being initially charged in the reactor, or by a seim batch process, with one or more components being initially introduced and the remainder being metered in, or a continuous one Polymerization are carried out, wherein the components are added during the polymerization. The dosages may optionally be carried out separately (spatially and temporally).
Die Formulierungen von FRP-Composites für die BMC-TechnikThe formulations of FRP composites for the BMC technique
(BuIk Molding Compound) sind dem Fachmann bekannt. Eine typische Formulierung für ungesättigte Polyesterharz-Zusammensetzungen für Formmassen für die BMC-Technik enthält 60 bis 70 Gew. -Teile ungesättigtes Polyesterharz (als 50 bis 75 %-ige Lösung in Styrol), 30 bis 40 Gew. -Teile Low-Profile-Additive (als 30 bis 50 %-ige Lösung in Styrol) wie Polyvinylacetat o- der Polymethylmethacrylat, 0,5 bis 2 Gew. -Teile Initiator wie t-Butylperbenzoat, 150 bis 200 Gew. -Teile Füllstoff wie Calciumcarbonat, 25 bis 30 Gew. -Teile Glasfaser, 0,5 bis 3 Gew. Teile Formtrennmittel wie Zinkstearat, sowie gegebenenfalls weitere Zusatzstoffe, beispielsweise Pigmente, flammhemmende Zusätze. Die Formulierungen enthalten keine Eindickmit- tel wie basische Metallverbindungen, beispielsweise Oxide oder Hydroxide von Metallen der 1. bis 3. Hauptgruppe des PSE.(BuIk Molding Compound) are known in the art. A typical formulation for unsaturated polyester resin compositions for molding compositions for the BMC technique contains 60 to 70 parts by weight of unsaturated polyester resin (as a 50 to 75% solution in styrene), 30 to 40 parts by weight of low-profile additives (as a 30 to 50% solution in styrene) such as polyvinyl acetate or polymethyl methacrylate, 0.5 to 2 parts by weight of initiator such as t-butyl perbenzoate, 150 to 200 parts by weight of filler such as calcium carbonate, 25 to 30 wt. Parts of glass fiber, 0.5 to 3 parts by weight of mold release agents such as zinc stearate, and optionally other additives, such as pigments, flame retardant additives. The formulations contain no thickening agents Tel such as basic metal compounds, such as oxides or hydroxides of metals of the 1st to 3rd main group of the PSE.
Bei der erfindungsgemäßen Verwendung wird das Low-Profile-In the use according to the invention, the low-profile
Additiv, bevorzugt auf der Basis von Polyvinylacetat oder Po- lymethylmethacrylat, ganz oder teilweise mit carboxylfunktio- nellem Polyvinylacetat ersetzt. Im allgemeinen wird das carbo- xylierte Polyvinylacetat-Festharz in einer Menge von 10 bis 100 Gew.-%, vorzugsweise 50 bis 80 Gew.-%, jeweils bezogen auf die Gewichtsmenge an Low-Profile-Additiv in der Rezeptur, eingesetzt. Es ist dabei zweckmäßig dieses Additiv in styroli- scher Lösung einzusetzen.Additive, preferably based on polyvinyl acetate or polymethyl methacrylate, wholly or partly replaced by carboxyl-functional polyvinyl acetate. In general, the carbo- xylated polyvinyl acetate solid resin in an amount of 10 to 100 wt .-%, preferably 50 to 80 wt .-%, each based on the weight of low-profile additive in the recipe used. It is expedient to use this additive in a styrenic solution.
Die nachfolgenden Beispiele dienen zur weiteren Erläuterung der Erfindung:The following examples serve to further illustrate the invention:
Es wurden die Viskositäten von Festharzlösungen in Styrol mit und ohne Füllstoff für verschiedene Festharze ermittelt:The viscosities of solid resin solutions in styrene with and without filler for various solid resins were determined:
Copol :Copol:
Polyvinylacetat-Festharz mit 5 Gew.-% Crotonsäure-Einheiten und einem gewichtsmittleren Molekulargewicht Mw = 67500. Homol : Polyvinylacetat-Festharz mit gewichtsmittlerem Molekulargewicht Mw = 69000. Homo2 :Polyvinyl acetate solid resin with 5% by weight crotonic acid units and a weight-average molecular weight Mw = 67,500. Homol: Polyvinyl acetate solid resin having a weight-average molecular weight Mw = 69,000. Homo2:
Polyvinylacetat-Festharz mit gewichtsmittlerem Molekulargewicht Mw = 116600. Copo2:Polyvinyl acetate solid resin with weight-average molecular weight Mw = 116600. Copo2:
Polyvinylacetat-Festharz mit 5 Gew.-% Crotonsäure-Einheiten und einem gewichtsmittleren Molekulargewicht Mw = 116750. Copo3 : Polyvinylacetat-Festharz mit 5 Gew.-% Crotonsäure-Einheiten und einem gewichtsmittleren Molekulargewicht Mw = 137000.Polyvinyl acetate solid resin containing 5% by weight crotonic acid units and having a weight average molecular weight M w = 116750. Copo 3: solid polyvinyl acetate resin containing 5% by weight crotonic acid units and having a weight average molecular weight Mw = 137,000.
Es wurden jeweils eine 40 Gew.-%-ige Lösung der aufgelisteten Polymere in Styrol hergestellt, und die Viskosität der Lösun- gen jeweils bei 23°C mit einem Brookfield-Messgerät ermittelt. Die Messergebnisse sind in der nachfolgenden Tabelle und in dem nachfolgenden Graphen als V in ST (Viskosität in Styrol) in mPas angegeben.In each case, a 40% strength by weight solution of the listed polymers in styrene was prepared, and the viscosity of the solvents was determined. each determined at 23 ° C with a Brookfield meter. The measurement results are given in the following table and in the following graph as V in ST (viscosity in styrene) in mPas.
Anschließend wurden jeweils 200 Gew. -Teile der styrolischen Polymerlösungen mit 300 Gew. -Teilen Calciumcarbonat (Omyacarb 5GU) vermischt und und die Viskosität der Dispersionen jeweils bei 23°C mit einem Brookfield-Messgerät ermittelt. Die Messergebnisse sind in der nachfolgenden Tabelle und in dem nachfolgenden Graphen als V in ST+F (Viskosität in Styrol mit Füllstoff) in mPas angegeben.200 parts by weight of the styrenic polymer solutions were subsequently mixed with 300 parts by weight of calcium carbonate (omyacarb 5GU) and the viscosity of the dispersions was determined in each case at 23 ° C. using a Brookfield measuring instrument. The measurement results are given in the following table and in the following graph as V in ST + F (viscosity in styrene with filler) in mPas.
Die Tabelle bzw. der Graph zeigt, dass bei Zumischung von Füllstoff zu den Homopolymerisaten ein extremer Viskositätsanstieg erfolgt, während bei den Copolymerisaten vergleichbaren Molekulargewichts der Viskositätsanstieg bei Füllstoffzugäbe sehr moderat ausfällt.The table or the graph shows that, when the filler is admixed with the homopolymers, an extreme increase in viscosity occurs, whereas in the case of copolymers of comparable molecular weight, the increase in viscosity in the case of filler additions is very moderate.
Copol Homol Homo2 Copo2 Copo3Copol Homol Homo2 Copo2 Copo3
V in ST [mPas] 1030 1230 2310 3090 3700V in ST [mPas] 1030 1230 2310 3090 3700
V in ST+F [mPas] 9850 67400 71200 19000 32200 V in ST + F [mPas] 9850 67400 71200 19000 32200

Claims

Patentansprüche : Claims:
1. Verwendung von carboxylfunktionellen Polyvinylacetat- Festharzen als Additiv in Formulierungen ohne Eindickmit- tel zur Herstellung von BMC-Formteilen .1. Use of carboxyl-functional polyvinyl acetate solid resins as an additive in formulations without thickening agent for the production of BMC molded parts.
2. Verwendung nach Anspruch 1, wobei carboxylfunktionelle Po- lyvinylacetat-Festharze mit Comonomereinheiten, welche sich von einfach ethylenisch ungesättigten Mono- oder Di- carbonsäuren ableiten, eingesetzt werden.2. Use according to claim 1, wherein carboxyl-functional polyvinyl acetate solid resins having comonomer units which are derived from monoethylenically unsaturated monocarboxylic or dicarboxylic acids are used.
3. Verwendung nach Anspruch 1 oder 2, wobei der Anteil an Comonomereinheiten mit Carboxyl-Gruppen im Polyvinylacetat- Festharz 0,5 bis 10 Gew.-%, bezogen auf das Gesamtgewicht des Polyvinylacetat-Festharzes, beträgt.3. Use according to claim 1 or 2, wherein the proportion of comonomer units having carboxyl groups in the solid polyvinyl acetate resin is 0.5 to 10 wt .-%, based on the total weight of the solid polyvinyl acetate resin.
4. Verwendung nach Anspruch 1 bis 3, wobei die Formulierung 60 bis 70 Gew. -Teile ungesättigtes Polyesterharz (als 50 bis 75 %-ige Lösung in Styrol) , 30 bis 40 Gew. -Teile Low- Profile-Additive (als 30 bis 50 %-ige Lösung in Styrol) , 0,5 bis 2 Gew. -Teile Initiator, 150 bis 200 Gew. -Teile Füllstoff, 25 bis 30 Gew. -Teile Glasfaser, 0,5 bis 3 Gew. Teile Formtrennmittel, sowie gegebenenfalls weitere Zusatzstoffe, enthält.4. Use according to claim 1 to 3, wherein the formulation 60 to 70 parts by weight of unsaturated polyester resin (as a 50 to 75% solution in styrene), 30 to 40 parts by weight Low-profile additives (than 30 bis 50% solution in styrene), 0.5 to 2 parts by weight of initiator, 150 to 200 parts by weight of filler, 25 to 30 parts by weight of glass fiber, 0.5 to 3 parts by weight of mold release agent, and optionally other additives.
5. Verwendung nach Anspruch 4, wobei 10 bis 100 Gew.-%, bezogen auf die Gewichtsmenge an Low-Profile-Additiv in der Rezeptur, durch das carboxylfunktionelle Polyvinylacetat- Festharz ersetzt werden.5. Use according to claim 4, wherein 10 to 100 wt .-%, based on the weight amount of low-profile additive in the recipe, are replaced by the carboxyl-functional polyvinyl acetate solid resin.
6. Verwendung nach Anspruch 4, wobei 50 bis 80 Gew.-%, bezogen auf die Gewichtsmenge an Low-Profile-Additiv in der Rezeptur, durch das carboxylfunktionelle Polyvinylacetat- Festharz ersetzt werden. 6. Use according to claim 4, wherein 50 to 80 wt .-%, based on the weight amount of low-profile additive in the formulation, are replaced by the carboxyl-functional polyvinyl acetate solid resin.
EP07728208A 2006-04-27 2007-04-18 Use of carboxyl-functional polyvinyl acetates for producing bmc parts Withdrawn EP2010581A1 (en)

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DE102006019686A DE102006019686A1 (en) 2006-04-27 2006-04-27 Use of carboxyl functional polyvinyl acetate solid resin as an additive in formulation for the production of bulk molding compound-molded parts
PCT/EP2007/053746 WO2007125035A1 (en) 2006-04-27 2007-04-18 Use of carboxyl-functional polyvinyl acetates for producing bmc parts

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DE102008054482A1 (en) 2008-12-10 2010-06-17 Wacker Chemie Ag Graft copolymers and their use as low-profile additives
DE102009001498A1 (en) 2009-03-11 2010-09-16 Wacker Chemie Ag Use of vinyl ester copolymers as low-profile additives (LPA)
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DE102010028952A1 (en) 2010-05-12 2011-11-17 Wacker Chemie Ag Low-profile additives based on renewable raw materials
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