US20060025551A1 - Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin - Google Patents

Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin Download PDF

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Publication number
US20060025551A1
US20060025551A1 US11/219,903 US21990305A US2006025551A1 US 20060025551 A1 US20060025551 A1 US 20060025551A1 US 21990305 A US21990305 A US 21990305A US 2006025551 A1 US2006025551 A1 US 2006025551A1
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weight
vinyl
acid
comonomers
polymerization
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US11/219,903
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Stephan Kaiser
Karl Weber
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Wacker Chemie AG
Westlake Vinnolit GmbH and Co KG
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Wacker Polymer Systems GmbH and Co KG
Vinnolit GmbH and Co KG
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Assigned to WACKER POLYMER SYSTEMS GMBH & CO. KG, VINNOLIT GMBH & CO. KG reassignment WACKER POLYMER SYSTEMS GMBH & CO. KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WEBER, KARL, KAISER, STEPHAN
Publication of US20060025551A1 publication Critical patent/US20060025551A1/en
Assigned to WACKER CHEMIE AG reassignment WACKER CHEMIE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WACKER POLYMER SYSTEMS GMBH & CO. KG
Priority to US12/584,101 priority Critical patent/US7888429B2/en
Abandoned legal-status Critical Current

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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
    • C08F214/00—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 a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride

Definitions

  • the invention relates to a process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymer solid resins and to the use thereof, in particular in coating resin compositions.
  • Vinyl chloride copolymers containing epoxy groups are used as binders in coatings. Their use in heat-seal coatings, for example, for aluminum coating, should be singled out.
  • Epoxy-containing vinyl chloride-vinyl acetate copolymers are well established but are obtainable only as solutions, for example in toluene and/or methyl ethyl ketone. For the user, this has the disadvantage that the choice of the solvent in which the coating resin is applied is greatly limited, for example to the solvent in which the coating resin is offered, or to solvents compatible therewith.
  • an object of the invention is to provide epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resins. This and other objects are achieved by a process in which vinyl chloride is copolymerized with epoxy group-containing comonomers and vinyl ester comonomers in the presence of aldehyde molecular weight regulators.
  • the invention relates to a process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resins obtainable by means of aqueous, free radical polymerization of a mixture comprising
  • Suitable epoxide-containing vinyl monomers b) are, for example, methylglycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether, allylphenol glycidyl ether and glycidyl methacrylate.
  • Glycidyl methacrylate (GMA) is preferred.
  • Preferred vinyl ester monomers c) are those of carboxylic acids having 1 to 12 carbon atoms.
  • Vinyl acetate is most preferred.
  • Preferably from 5 to 15% by weight of the vinyl ester monomers c), in particular vinyl acetate, are copolymerized.
  • Suitable further copolymerizable comonomers d) include one or more ethylenically unsaturated monomers from the group of acrylates or methacrylates of branched or straight-chain alcohols or diols having 1 to 18 carbon atoms, and ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof.
  • Preferred monomers from the group consisting of acrylates or methacrylates are esters of straight-chain or branched alcohols having 1 to 15 carbon atoms.
  • Particularly preferred methacrylates or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate and 2-ethylhexyl acrylate.
  • Methyl acrylate, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate are most preferred.
  • Suitable ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof are acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid and maleic anhydride.
  • the free radical polymerization is effected by means of suspension polymerization.
  • the polymerization temperature is in general from 20° C. to 80° C.
  • the initiation of the polymerization can be effected with the customary water-soluble or monomer-soluble initiators or redox initiator combinations.
  • water-soluble initiators are the sodium, potassium and ammonium salts of peroxoydisulfuric acid.
  • monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide and tert-butyl peroxypivalate.
  • the initiators are used in general in an amount of from 0.01 to 1.0% by weight, preferably from 0.1 to 0.5% by weight, based in each case on the total weight of the monomers.
  • polymerization is effected in water in the presence of surface-active substances such as protective colloids and/or emulsifiers.
  • Suitable protective colloids are, for example, partly hydrolyzed polyvinyl alcohols and cellulose ethers.
  • Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants such as alkylsulfates having a chain length of from 8 to 18 carbon atoms, alkane- or alkylarylsulfonates having from 8 to 18 carbon atoms, ester and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkylpolylglycol ethers or alkylarylpolyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
  • anionic surfactants such as alkylsulfates having a chain length of from 8 to 18 carbon atoms, alkane- or alkylarylsulfonates having from 8 to 18 carbon atoms, ester and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as al
  • 0.001 to 0.1% by weight preferably from 0.005 to 0.05% by weight of ascorbic acid and/or isoascorbic acid, based in each case on the total weight of the comonomers, are optionally added during or after the polymerization.
  • Ascorbic acid is preferably used. The addition is preferably effected after the end of the monomer metering and before, during or after the removal of residual monomers.
  • citric acid is also added in addition to ascorbic acid and/or isoascorbic acid is most preferred.
  • the amount of citric acid is from 0.001 to 0.1% by weight, preferably from 0.005 to 0.05% by weight, based in each case on the total weight of the comonomers.
  • regulating substances are used during the polymerization.
  • the regulators are used in amounts of from 0.02 to 10.0% by weight, based on the monomers to be polymerized, and are metered separately or in a form premixed with reaction components.
  • Suitable regulators are aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
  • Polymerization is preferably effected in the presence of propionaldehyde.
  • propionaldehyde Compared with other regulators such as, for example, trichloroethylene, propionaldehyde has the advantage that a regulating effect is achieved even with small amounts. It is therefore preferably added in an amount of from 0.02 to 5% by weight, based on the monomer, depending on the desired molecular weight.
  • the monomers can be metered in together or can be initially introduced in portions and the remainder metered in after initiation of the polymerization.
  • the meterings can be carried out separately (with respect to space and time), or some or all of the components to be metered can be metered in preemulsified form.
  • postpolymerization can be effected for removing residual monomers with the use of known methods, for example by postpolymerization initiated by a redox catalyst.
  • Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing inert entraining gases such as air, nitrogen or steam, through or over the reaction mixture.
  • the epoxy-modified vinyl chloride-vinyl ester copolymers can be isolated from the aqueous dispersion in the form of solid resin by means of customary methods, by precipitation, filtration and subsequent drying, or by means of decanting and subsequent drying.
  • the drying can be effected in a manner known to those skilled in the art, for example in a tumble drier, in a flow tube, in a fluidized bed, or in a cyclone drier.
  • the epoxy-modified vinyl chloride-vinyl ester copolymers are distinguished by high blocking resistance up to 180° C., and by high chemical resistance to solvents, acids and bases.
  • the epoxy-modified vinyl chloride-vinyl ester copolymers in the form of their solid resins are suitable, for example, as adhesives, in particular for the adhesive bonding of security features in banknotes or plastic cards, and as binders for coatings, for example for aluminum coatings.
  • a copolymer comprising 82% by weight of vinyl chloride, 9% by weight of vinyl acetate and 9% by weight of glycidyl methacrylate was prepared by the suspension polymerization process, the comonomers having been completely initially introduced before initiation of the polymerization. After the end of the polymerization, the batch was let down to atmospheric pressure, and 0.05% by weight of ascorbic acid was added. Thereafter, demonomerization was effected and the copolymer was filtered, washed and dried. A white, flowable powder was obtained.
  • a copolymer was prepared from 82% by weight of vinyl chloride, 9% by weight of vinyl acetate and 9% by weight of glycidyl methacrylate by the emulsion polymerization process. At the end of the reaction, the mixture was let down to atmospheric pressure and 0.02% by weight of ascorbic acid and 0.0025% by weight of citric acid, based in each case on the total weight of the comonomers and in each case as a 10% strength aqueous solution, were added to the batch. Thereafter, demonomerization was effected and the copolymer was precipitated, filtered, washed and dried. A white, flowable powder was obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

A process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymers in the form of the solid resins involves aqueous, free radical polymerization of a mixture comprising a) from 50 to 90% by weight of vinyl chloride, b) from 5 to 25% by weight of epoxide-containing vinyl monomers and c) from 5 to 25% by weight of one or more vinyl esters of straight-chain or branched alkylcarboxylic acids having 1 to 18 carbon atoms, d) from 0 to 40% by weight of further comonomers copolymerizable with a), b) and c), the data in % by weight summing to 100% by weight, and subsequent drying of the aqueous dispersions obtained thereby, polymerization being effected by means of suspension polymerization in the presence of aldehyde regulators.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation of PCT/EP2004/002213, filed Mar. 4, 2004.
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The invention relates to a process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymer solid resins and to the use thereof, in particular in coating resin compositions.
  • 2. Background Art
  • Vinyl chloride copolymers containing epoxy groups are used as binders in coatings. Their use in heat-seal coatings, for example, for aluminum coating, should be singled out. Epoxy-containing vinyl chloride-vinyl acetate copolymers are well established but are obtainable only as solutions, for example in toluene and/or methyl ethyl ketone. For the user, this has the disadvantage that the choice of the solvent in which the coating resin is applied is greatly limited, for example to the solvent in which the coating resin is offered, or to solvents compatible therewith.
    • SUMMARY OF THE INVENTION
  • Against this background, an object of the invention is to provide epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resins. This and other objects are achieved by a process in which vinyl chloride is copolymerized with epoxy group-containing comonomers and vinyl ester comonomers in the presence of aldehyde molecular weight regulators.
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)
  • The invention relates to a process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resins obtainable by means of aqueous, free radical polymerization of a mixture comprising
      • a) from 50 to 90% by weight of vinyl chloride,
      • b) from 5 to 25% by weight of epoxide-containing vinyl monomers and
      • c) from 5 to 25% by weight of one or more vinyl esters of straight-chain or branched alkylcarboxylic acids having from 1 to 18 carbon atoms,
      • d) from 0 to 40% by weight of further comonomers copolymerizable with a), b) and c), the weight percentages totaling 100% by weight,
        and subsequent drying of the aqueous dispersions obtained thereby, characterized in that polymerization is effected by means of suspension polymerization in the presence of regulators selected from the group consisting of the aldehydes.
  • Preferably from 70 to 90% by weight, more preferably from 75 to 85% by weight of vinyl chloride is copolymerized.
  • Suitable epoxide-containing vinyl monomers b) are, for example, methylglycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether, allylphenol glycidyl ether and glycidyl methacrylate. Glycidyl methacrylate (GMA) is preferred. Preferably from 5 to 15% by weight, more preferably from 8 to 15% by weight of epoxide-containing vinyl monomers b), in particular glycidyl methacrylate, are copolymerized.
  • Preferred vinyl ester monomers c) are those of carboxylic acids having 1 to 12 carbon atoms. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having 9 to 13 carbon atoms, for example VeoVa9R or VeoVa10R (trade names of Shell) are particularly preferred. Vinyl acetate is most preferred. Preferably from 5 to 15% by weight of the vinyl ester monomers c), in particular vinyl acetate, are copolymerized.
  • Suitable further copolymerizable comonomers d) include one or more ethylenically unsaturated monomers from the group of acrylates or methacrylates of branched or straight-chain alcohols or diols having 1 to 18 carbon atoms, and ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof.
  • Preferred monomers from the group consisting of acrylates or methacrylates are esters of straight-chain or branched alcohols having 1 to 15 carbon atoms. Particularly preferred methacrylates or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate and 2-ethylhexyl acrylate. Methyl acrylate, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and 2-ethylhexyl acrylate are most preferred.
  • Examples of suitable ethylenically unsaturated mono- and dicarboxylic acids and anhydrides thereof are acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid and maleic anhydride.
  • The free radical polymerization is effected by means of suspension polymerization. The polymerization temperature is in general from 20° C. to 80° C. The initiation of the polymerization can be effected with the customary water-soluble or monomer-soluble initiators or redox initiator combinations. Examples of water-soluble initiators are the sodium, potassium and ammonium salts of peroxoydisulfuric acid. Examples of monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide and tert-butyl peroxypivalate. The initiators are used in general in an amount of from 0.01 to 1.0% by weight, preferably from 0.1 to 0.5% by weight, based in each case on the total weight of the monomers.
  • In the suspension polymerization, polymerization is effected in water in the presence of surface-active substances such as protective colloids and/or emulsifiers. Suitable protective colloids are, for example, partly hydrolyzed polyvinyl alcohols and cellulose ethers. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants such as alkylsulfates having a chain length of from 8 to 18 carbon atoms, alkane- or alkylarylsulfonates having from 8 to 18 carbon atoms, ester and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkylpolylglycol ethers or alkylarylpolyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
  • For improving the thermal stability of the solid resins, from 0.001 to 0.1% by weight, preferably from 0.005 to 0.05% by weight of ascorbic acid and/or isoascorbic acid, based in each case on the total weight of the comonomers, are optionally added during or after the polymerization. Ascorbic acid is preferably used. The addition is preferably effected after the end of the monomer metering and before, during or after the removal of residual monomers. An embodiment in which citric acid is also added in addition to ascorbic acid and/or isoascorbic acid is most preferred. The amount of citric acid is from 0.001 to 0.1% by weight, preferably from 0.005 to 0.05% by weight, based in each case on the total weight of the comonomers.
  • For controlling the molecular weight, regulating substances are used during the polymerization. The regulators are used in amounts of from 0.02 to 10.0% by weight, based on the monomers to be polymerized, and are metered separately or in a form premixed with reaction components. Suitable regulators are aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
  • Polymerization is preferably effected in the presence of propionaldehyde. Compared with other regulators such as, for example, trichloroethylene, propionaldehyde has the advantage that a regulating effect is achieved even with small amounts. It is therefore preferably added in an amount of from 0.02 to 5% by weight, based on the monomer, depending on the desired molecular weight.
  • The monomers can be metered in together or can be initially introduced in portions and the remainder metered in after initiation of the polymerization. The meterings can be carried out separately (with respect to space and time), or some or all of the components to be metered can be metered in preemulsified form. After the end of the polymerization, postpolymerization can be effected for removing residual monomers with the use of known methods, for example by postpolymerization initiated by a redox catalyst. Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing inert entraining gases such as air, nitrogen or steam, through or over the reaction mixture.
  • The epoxy-modified vinyl chloride-vinyl ester copolymers can be isolated from the aqueous dispersion in the form of solid resin by means of customary methods, by precipitation, filtration and subsequent drying, or by means of decanting and subsequent drying. The drying can be effected in a manner known to those skilled in the art, for example in a tumble drier, in a flow tube, in a fluidized bed, or in a cyclone drier.
  • The epoxy-modified vinyl chloride-vinyl ester copolymers are distinguished by high blocking resistance up to 180° C., and by high chemical resistance to solvents, acids and bases.
  • The epoxy-modified vinyl chloride-vinyl ester copolymers in the form of their solid resins are suitable, for example, as adhesives, in particular for the adhesive bonding of security features in banknotes or plastic cards, and as binders for coatings, for example for aluminum coatings.
  • The following examples serve for further explanation of the invention:
    • EXAMPLE 1
  • A copolymer comprising 82% by weight of vinyl chloride, 9% by weight of vinyl acetate and 9% by weight of glycidyl methacrylate was prepared by the suspension polymerization process, the comonomers having been completely initially introduced before initiation of the polymerization. After the end of the polymerization, the batch was let down to atmospheric pressure, and 0.05% by weight of ascorbic acid was added. Thereafter, demonomerization was effected and the copolymer was filtered, washed and dried. A white, flowable powder was obtained.
    • EXAMPLE 2
  • A copolymer was prepared from 82% by weight of vinyl chloride, 9% by weight of vinyl acetate and 9% by weight of glycidyl methacrylate by the emulsion polymerization process. At the end of the reaction, the mixture was let down to atmospheric pressure and 0.02% by weight of ascorbic acid and 0.0025% by weight of citric acid, based in each case on the total weight of the comonomers and in each case as a 10% strength aqueous solution, were added to the batch. Thereafter, demonomerization was effected and the copolymer was precipitated, filtered, washed and dried. A white, flowable powder was obtained.
    • EXAMPLE 3
  • The procedure was analogous to example 2, with the difference that polymerization was effected in the presence of 2% by weight of propionaldehyde, based on total monomer. A 20% strength by weight solution of the copolymer in methyl ethyl ketone had a lower solution viscosity than the product from example 3 and remained completely colorless even after a storage time of one week at 60° C.
  • While embodiments of the invention have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.

Claims (11)

1. A process for the preparation of epoxy-modified vinyl chloride-vinyl ester copolymers in the form of solid resin, comprising free radically polymerizing a mixture comprising
a) from 50 to 90 percent by weight of vinyl chloride,
b) from 5 to 25 percent by weight of one or more epoxide-containing vinyl monomers and
c) from 5 to 25 percent by weight of one or more vinyl esters of straight-chain or branched alkylcarboxylic acids having from 1 to 18 carbon atoms,
d) from 0 to 40 percent by weight of further comonomers copolymerizable with a), b) and c), the percents by weight of a), b), c), and d) totalling 100% by weight,
and subsequently drying an aqueous dispersion obtained thereby, wherein said polymerizing is effected by means of suspension polymerization in the presence of one or more aldehyde regulators.
2. The process of claim 1, wherein from 5 to 15% by weight of epoxide-containing vinyl monomers are polymerized.
3. The process of claim 1, whererin one or more epoxide-containing vinyl monomers selected from the group consisting of methyl glycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether, allylphenol glycidyl ether and glycidyl methacrylate are copolymerized as comonomers b).
4. The process of claim 1, wherein one or more vinyl esters selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having 9 to 13 carbon atoms, are copolymerized as comonomers c), optionally in combination with one or more comonomers selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid, maleic acid and maleic anhydride.
5. The process of claim 1, wherein from 0.001 to 0.1% by weight of ascorbic acid and/or isoascorbic acid, based on the total weight of the comonomers, are added during or after the polymerization, and optionally from 0.001 to 0.1% by weight of citric acid, based on the total weight of the comonomers, is also added in addition to the ascorbic acid and/or isoascorbic acid.
6. The process of claim 5 wherein citric acid is added.
7. The process of claim 1, wherein polymerization takes place in the presence of from 0.02 to 10% by weight, based on the monomers to be polymerized, of regulators.
8. The process of claim 1, wherein polymerization is effected in the presence of propionaldehyde.
9. A coating binder, comprising the product produced by the process of claim 1.
10. A process for adhesive bonding, comprising applying an adhesive comprising the product produced by the process of claim 1 to at least one substrate to be bonded to a second substrate, and contacting said substrates together.
11. The process of claim 19, wherein one of said substrates comprises a security feature.
US11/219,903 2003-03-06 2005-09-06 Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin Abandoned US20060025551A1 (en)

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DE10309857A DE10309857A1 (en) 2003-03-06 2003-03-06 Epoxy-modified vinyl chloride-vinyl ester copolymer solid resins
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PCT/EP2004/002213 WO2004078806A1 (en) 2003-03-06 2004-03-04 Epoxy-modified vinyl chloride-vinyl ester copolymer solid resin

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100256287A1 (en) * 2007-12-03 2010-10-07 Wacker Chemie Ag Radically cross-linkable polymer compositions containing epoxy-functional copolymers
US8952096B2 (en) 2008-12-10 2015-02-10 Wacker Chemie Ag Graft copolymers and use thereof as low-profile additives

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005041593A1 (en) * 2005-09-01 2007-03-08 Wacker Polymer Systems Gmbh & Co. Kg Process for the preparation of vinyl chloride-vinyl acetate copolymers in the form of their solid resins
JP5729286B2 (en) * 2010-12-24 2015-06-03 日信化学工業株式会社 Vinyl chloride resin, method for producing the same, and ink
CN103396750B (en) * 2013-07-16 2015-12-02 江苏斯德瑞克化工有限公司 The preparation of water-based glue paste and metal/polypropylene composite material making method
KR102357574B1 (en) * 2017-08-07 2022-02-08 와커 헤미 아게 Copolymers of vinyl chloride, vinyl acetate and long chain vinyl esters
CN107955108B (en) * 2017-10-26 2019-10-25 无锡洪汇新材料科技股份有限公司 A kind of preparation method of epoxy-modified vinyl chloride acrylate copolymer emulsion
CN109134736A (en) * 2018-06-21 2019-01-04 安徽大学 A kind of anticorrosive paint aqueous polyvinylidene dichloroethylene-acrylic ester copolymer latex and preparation method thereof
CN114478893B (en) * 2021-12-29 2024-03-26 石河子大学 Hydrophilic vinyl chloride copolymer resin and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2993034A (en) * 1955-06-02 1961-07-18 Swern Daniel Copolymers of vinyl chloride and vinyl epoxystearate
US4345056A (en) * 1976-07-02 1982-08-17 Wacker-Chemie Gmbh Process for suspension polymerization of vinyl chloride employing mixed protective colloids
US4693934A (en) * 1984-06-08 1987-09-15 Tdk Corporation Magnetic recording medium for image recording
US4707411A (en) * 1984-05-11 1987-11-17 Nippon Zeon Co., Ltd. Magnetic paint for magnetic recording media
US4900777A (en) * 1981-10-06 1990-02-13 Wacker-Chemie Gmbh Process for the manufacture of aqueous copolymer dispersions and their use
US4970127A (en) * 1986-10-20 1990-11-13 Union Carbide Chemicals And Plastics Company Inc. Novel vinyl chloride resins and compositions incorporating such resins

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53104684A (en) * 1977-02-24 1978-09-12 Shin Etsu Chem Co Ltd Preparation of vinyl chloride polymer
DE3041887A1 (en) * 1980-11-06 1982-06-09 Henkel KGaA, 4000 Düsseldorf STABILIZER COMBINATION FOR THERMOPLASTIC, IN PARTICULAR POLYMERISATES BASED ON VINYL CHLORIDE, AND METHOD FOR THERMOFORMING THESE POLYMERISATES
BR8705574A (en) * 1986-10-20 1988-05-24 Union Carbide Corp VINYL CHLORIDE COPOLIMER SUITABLE TO BE USED AS A BINDING RESIN FOR PARTICULAR MATERIAL; AND MAGNETIC RECORDING MEDIA
DE3829711A1 (en) * 1988-09-01 1990-03-22 Basf Ag POLYMER DISPERSIONS AND SOLUTIONS CONTAINING VINYL CHLORIDE-GLYCIDYL METHACRYLATE COPOLYMERISATE, METHOD FOR THE PRODUCTION AND THEIR USE FOR THE PRODUCTION OF BINDERS ON THE LACQUER SECTOR AND POWDER
NO166189C (en) * 1989-02-08 1991-06-12 Norsk Hydro As CIRCULATED THERMOSTABLE POLYMER AND MANUFACTURING THEREOF.
JPH0386744A (en) * 1989-08-30 1991-04-11 Sekisui Chem Co Ltd Vinyl chloride copolymer-derived glass laminate interlayer composition and glass laminate interlayer
JP2849931B2 (en) * 1989-11-20 1999-01-27 日本ゼオン株式会社 Method for producing vinyl chloride polymer for paste
JPH0489810A (en) * 1990-08-03 1992-03-24 Shin Etsu Chem Co Ltd Preparation of vinyl chloride polymer having low degree of polymerization
DE4124819A1 (en) * 1991-07-26 1993-01-28 Basf Ag AQUEOUS POLYMER DISPERSIONS
JPH07278209A (en) * 1994-04-12 1995-10-24 Sekisui Chem Co Ltd Production of vinyl chloride polymer
JPH082154A (en) * 1994-06-17 1996-01-09 Tokin Corp Magnetic stripe card and production thereof
US5641845A (en) * 1995-08-11 1997-06-24 Libbey-Owens-Ford Co. Copolymers of vinyl chloride, allyl glycidyl ether, and a vinyl ester and method of making the same
JPH10168104A (en) * 1996-12-10 1998-06-23 Mitsubishi Chem Corp Polymerization of vinyl chloride monomer
JP3445457B2 (en) * 1996-12-25 2003-09-08 タキロン株式会社 Flame retardant vinyl chloride resin molding
DE19733156A1 (en) * 1997-07-31 1999-02-04 Wacker Chemie Gmbh Crosslinkable powder composition redispersible in water
JPH11140256A (en) * 1997-11-04 1999-05-25 Tosoh Corp Spherical vinyl chloride-based blended resin for paste processing, production thereof and vinyl chloride resin composition for paste processing containing the same
WO1999050356A1 (en) * 1998-03-31 1999-10-07 Daicel Chemical Industries, Ltd. Thermoplastic resin composition, water-based composition, heat-sensitive pressure-sensitive adhesive, and heat-sensitive sheet
JP2001139698A (en) * 1999-11-17 2001-05-22 Shin Etsu Chem Co Ltd Polyvinyl chloride resin hard molded article for outdoor building material
JP3967173B2 (en) * 2001-05-09 2007-08-29 株式会社クレハ Polyvinylidene chloride resin composition and method for producing the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2993034A (en) * 1955-06-02 1961-07-18 Swern Daniel Copolymers of vinyl chloride and vinyl epoxystearate
US4345056A (en) * 1976-07-02 1982-08-17 Wacker-Chemie Gmbh Process for suspension polymerization of vinyl chloride employing mixed protective colloids
US4900777A (en) * 1981-10-06 1990-02-13 Wacker-Chemie Gmbh Process for the manufacture of aqueous copolymer dispersions and their use
US4707411A (en) * 1984-05-11 1987-11-17 Nippon Zeon Co., Ltd. Magnetic paint for magnetic recording media
US4693934A (en) * 1984-06-08 1987-09-15 Tdk Corporation Magnetic recording medium for image recording
US4970127A (en) * 1986-10-20 1990-11-13 Union Carbide Chemicals And Plastics Company Inc. Novel vinyl chloride resins and compositions incorporating such resins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100256287A1 (en) * 2007-12-03 2010-10-07 Wacker Chemie Ag Radically cross-linkable polymer compositions containing epoxy-functional copolymers
US8952096B2 (en) 2008-12-10 2015-02-10 Wacker Chemie Ag Graft copolymers and use thereof as low-profile additives

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