EP2010581A1 - Utilisation de polyacétates de vinyle à fonction carboxyle pour produire des pièces bmc - Google Patents

Utilisation de polyacétates de vinyle à fonction carboxyle pour produire des pièces bmc

Info

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
Authority
EP
European Patent Office
Prior art keywords
weight
parts
carboxyl
polyvinyl acetate
solid
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Withdrawn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
EP07728208A
Other languages
German (de)
English (en)
Inventor
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 EP2010581A1 publication Critical patent/EP2010581A1/fr
Withdrawn legal-status Critical Current

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne l'utilisation de résines solides de polyacétate de vinyle à fonction carboxyle comme additif dans des formulations sans épaississant pour produire des pièces BMC.
EP07728208A 2006-04-27 2007-04-18 Utilisation de polyacétates de vinyle à fonction carboxyle pour produire des pièces bmc Withdrawn EP2010581A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006019686A DE102006019686A1 (de) 2006-04-27 2006-04-27 Verwendung von carboxylfunktionellen Polyvinylacetaten zur Herstellung von BMC-Formteilen
PCT/EP2007/053746 WO2007125035A1 (fr) 2006-04-27 2007-04-18 Utilisation de polyacétates de vinyle à fonction carboxyle pour produire des pièces bmc

Publications (1)

Publication Number Publication Date
EP2010581A1 true EP2010581A1 (fr) 2009-01-07

Family

ID=38171288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07728208A Withdrawn EP2010581A1 (fr) 2006-04-27 2007-04-18 Utilisation de polyacétates de vinyle à fonction carboxyle pour produire des pièces bmc

Country Status (6)

Country Link
US (1) US20090182090A1 (fr)
EP (1) EP2010581A1 (fr)
JP (1) JP2009534508A (fr)
CN (1) CN101432323A (fr)
DE (1) DE102006019686A1 (fr)
WO (1) WO2007125035A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007047837A1 (de) 2007-11-21 2009-05-28 Wacker Chemie Ag Herstellung von Lösungen von Vinylpolymeren in reaktiven Monomeren
DE102007055692A1 (de) 2007-12-03 2009-06-04 Wacker Chemie Ag Radikalisch vernetzbare Polymerisat-Zusammensetzungen enthaltend Epoxy-funktionelle Copolymere
DE102008054482A1 (de) 2008-12-10 2010-06-17 Wacker Chemie Ag Pfropfcopolymere und deren Verwendung als Low-Profile-Additive
DE102009001498A1 (de) 2009-03-11 2010-09-16 Wacker Chemie Ag Verwendung von Vinylester-Copolymeren als Low-Profile-Additive (LPA)
DE102009001818A1 (de) 2009-03-24 2010-09-30 Wacker Chemie Ag Verwendung von Schutzkolloid-stabilisierten Polymerisaten als Low-Profile-Additive (LPA)
DE102010028952A1 (de) 2010-05-12 2011-11-17 Wacker Chemie Ag Low-Profile-Additive auf Basis nachwachsender Rohstoffe
DE102012200735A1 (de) 2012-01-19 2013-07-25 Wacker Chemie Ag Verwendung von funktionalisierten Polymerisaten als Low-Profile-Additive (LPA)
CN110337425B (zh) 2017-03-03 2023-03-14 瓦克化学股份公司 乙酸乙烯酯共聚物在冷固化体系中作为减缩添加剂的用途
CN107603095A (zh) * 2017-09-18 2018-01-19 张家港九力新材料科技有限公司 一种可常温使用的低收缩剂及其制备方法
WO2020228953A1 (fr) 2019-05-15 2020-11-19 Wacker Chemie Ag Utilisation de copolymères d'acétate de vinyle en tant qu'additif de faible retrait

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4626570A (en) * 1984-06-29 1986-12-02 Union Carbide Corporation Low shrinking thermosetting polyester resin compositions and a process for the preparation thereof
DE3617514A1 (de) * 1986-05-24 1987-11-26 Bayer Ag Verfahren zur herstellung schrumpfarmer formkoerper auf polyesterbasis
DE4106341A1 (de) * 1991-02-28 1992-09-03 Basf Ag Eingedickte haertbare formmasse aus ungesaettigten polyesterharzen
DE19532872A1 (de) * 1995-09-06 1997-03-13 Menzolit Fibron Gmbh Eingefärbte Dekor-Partikel in glasfaserverstärkten Duroplasten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007125035A1 *

Also Published As

Publication number Publication date
DE102006019686A1 (de) 2007-10-31
JP2009534508A (ja) 2009-09-24
CN101432323A (zh) 2009-05-13
US20090182090A1 (en) 2009-07-16
WO2007125035A1 (fr) 2007-11-08

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