WO2009119255A1 - Polymère de chlorure de vinyle - Google Patents

Polymère de chlorure de vinyle Download PDF

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Publication number
WO2009119255A1
WO2009119255A1 PCT/JP2009/053866 JP2009053866W WO2009119255A1 WO 2009119255 A1 WO2009119255 A1 WO 2009119255A1 JP 2009053866 W JP2009053866 W JP 2009053866W WO 2009119255 A1 WO2009119255 A1 WO 2009119255A1
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Prior art keywords
vinyl chloride
weight
parts
group
chloride polymer
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PCT/JP2009/053866
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English (en)
Japanese (ja)
Inventor
晴久 増田
晶彦 上田
一郎 谷井
征彦 一花
Original Assignee
ダイキン工業株式会社
日信化学工業株式会社
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Application filed by ダイキン工業株式会社, 日信化学工業株式会社 filed Critical ダイキン工業株式会社
Priority to CN200980111033.0A priority Critical patent/CN101981069B/zh
Priority to JP2010505482A priority patent/JPWO2009119255A1/ja
Publication of WO2009119255A1 publication Critical patent/WO2009119255A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—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 a halogen; Compositions of derivatives of such polymers
    • C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on 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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a vinyl chloride polymer and a vinyl chloride resin composition comprising the vinyl chloride polymer and a vinyl chloride resin.
  • the vinyl chloride polymer and the vinyl chloride resin composition are excellent in water and oil repellency.
  • Vinyl chloride resin is excellent in properties such as flame retardancy, mechanical properties, weather resistance, water resistance, and scratch resistance, and it is possible to adjust flexibility in a wide range by blending a plasticizer. It is used in a wide range of applications, such as films, sheets, miscellaneous goods, artificial leather, wire coverings, wallpaper, building materials, molded products such as pipes, and base resins for inks and paints.
  • vinyl chloride resin does not have sufficient water and oil repellency, and when used for the above-mentioned purposes, it may be difficult to remove moisture and oil, especially when used outdoors. Therefore, the improvement is demanded.
  • Patent Document 1 Japanese Patent Laid-Open No. 9-143326
  • An object of the present invention is to improve the water / oil repellency of a vinyl chloride resin. Another object of the present invention is to improve stain resistance and friction resistance.
  • the present invention relates to a vinyl chloride copolymer comprising 100 parts by weight of a structural unit (A-1) derived from vinyl chloride and 1 to 20 parts by weight of a structural unit (A-2) derived from a fluorine-containing acrylate ester. (A) is provided.
  • the present invention also provides a vinyl chloride resin composition comprising (A) 0.2 to 20 parts by weight of a vinyl chloride polymer and (B) 100 parts by weight of a vinyl chloride resin.
  • the water / oil repellency of the vinyl chloride resin can be improved. Further, when the vinyl chloride polymer and the vinyl chloride resin composition are used as molding materials, stain resistance can be imparted without degrading moldability, and the vinyl chloride polymer can be used as an ink. Alternatively, when used as a coating, abrasion resistance can be imparted without deteriorating color developability.
  • the structural unit (A-1) is derived from vinyl chloride.
  • the structural unit (A-2) is derived from a fluorine-containing acrylate ester.
  • the fluorine-containing acrylate ester has the formula (I): (Wherein X is a hydrogen atom, methyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, CFX 1 X 2 (where X 1 and X 2 are a hydrogen atom, fluorine atom, chlorine atom, bromine atom) Or an iodine atom), a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 —
  • the Rf group is preferably a perfluoroalkyl group or a perfluoroalkenyl group.
  • the Rf group has from 1 to 21, in particular from 1 to 6, in particular 4 or 6, carbon atoms.
  • Examples of Rf groups are -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).
  • Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group having 6 to 10 carbon atoms or a cyclic aliphatic group, a —CH 2 CH 2 N (R 1 ) SO 2 — group (where R 1 is the number of carbon atoms 1 to 4 alkyl groups) or —CH 2 CH (OY 1 ) CH 2 — group (where Y 1 is a hydrogen atom or an acetyl group).
  • the aliphatic group is preferably an alkylene group (particularly having 1 to 4 carbon atoms, such as 1 or 2).
  • the aromatic group and the cycloaliphatic group may be either substituted or unsubstituted.
  • fluorine-containing monomer is as follows.
  • 2 OCOCH CH 2 Rf-SO 2 N (C 2 H 5)
  • Rf represents a linear or branched fluoroalkyl group having 1 to 21 carbon atoms or a fluoroalkenyl group having 1 to 21 carbon atoms.
  • the vinyl chloride polymer may further contain a structural unit (A-3) derived from a saturated fatty acid vinyl ester.
  • Saturated fatty acids are generally monocarboxylic acids.
  • the saturated fatty acid may have 1 to 30 carbon atoms, for example 1 to 20 carbon atoms.
  • Specific examples of the saturated fatty acid vinyl ester are vinyl acetate, monochloro vinyl acetate, vinyl propionate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate and the like.
  • the vinyl chloride polymer may further contain one or more structural units (A-4) derived from an active hydrogen group-containing vinyl ester.
  • the active hydrogen group is a group containing an active hydrogen atom and reacts with isocyanate, epoxy, and the like. Examples of the active hydrogen group include a hydroxyl group, a carboxyl group, and an amino group. In the active hydrogen group-containing vinyl ester, the number of active hydrogen groups may be 1 to 5, for example 1 to 3, in particular 1.
  • Examples of the hydroxyl group-containing vinyl ester include 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-1 methylethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, ( Examples include 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,4-cyclohexanedimethanol monoacrylate, N-methylolacrylamide and the like.
  • carboxyl group-containing vinyl ester examples include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxypropyl hexahydrophthalic acid, 2 -Acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid and the like.
  • amino group-containing vinyl ester examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
  • (Meth) acrylic acid is a generic term for acrylic acid and methacrylic acid.
  • the vinyl chloride polymer may contain a structural unit (A-5) other than the structural unit (A-1) to the structural unit (A-4).
  • Specific examples of the monomer for deriving the other structural unit (A-5) include styrene, ⁇ -methylstyrene, acrylonitrile, ethylene, propylene, isobutylene, butadiene, glycidyl (meth) acrylate, allyl glycidyl ether, and hydroxyethyl.
  • the structural unit (A-2) is 1 to 20 parts by weight, for example 2 to 15 parts by weight, particularly 3 to 10 parts by weight, and the structural unit (A-3) is 50 parts by weight or less, for example 1 to 40 parts by weight. Especially 5-30 parts by weight, The structural unit (A-4) is 30 parts by weight or less, for example, 1 to 20 parts by weight, particularly 2 to 15 parts by weight, The structural unit (A-5) is preferably 10 parts by weight or less, for example, 5 parts by weight or less, particularly 0.1 to 5 parts by weight.
  • the number average molecular weight of the vinyl chloride polymer is preferably in the range of 5,000 to 500,000, particularly 10,000 to 100,000.
  • the number average molecular weight is measured by gel permeation chromatography (GPC) after dissolving a vinyl chloride polymer in tetrahydrofuran (THF) (in terms of styrene).
  • the vinyl chloride polymer in the present invention can be produced by any ordinary polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • the polymerization method that can be used include emulsion polymerization and suspension polymerization. Suspension polymerization is particularly preferred.
  • the vinyl chloride polymer is preferably produced by copolymerization by suspension polymerization of vinyl chloride monomer and fluorine-containing acrylate ester monomer, or suspension polymerization of vinyl chloride monomer, fluorine-containing acrylate ester monomer and vinyl acetate monomer. .
  • the fluorine-containing acrylate ester monomer may be charged together with the vinyl chloride monomer, or at the time when 50% to 70% (for example, 50% or 60%) of the total polymerization reaction time has elapsed during the polymerization or the latter stage of the polymerization. , In a batch).
  • the vinyl chloride polymer of the present invention can be produced by general solution polymerization, precipitation polymerization, suspension polymerization, emulsion polymerization and the like by radical polymerization.
  • Polymerization initiators used in the production include persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, hydrogen peroxide; diisopropyl peroxydicarbonate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroper Organic peroxide initiators such as oxide and dibutyl peroxide; nitrogen-containing initiators such as azobisisobutyronitrile and azobisisovaleronitrile are exemplified, and these may be used alone or as required Polymerization can be carried out by a conventional method using these in combination with a reducing agent such as acidic sodium sulfite, Rongalite, L-ascorbic acid, saccharides and amines.
  • a reducing agent such
  • solvents include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and butyl acetate.
  • solvents in the case of precipitation polymerization include methanol, ethanol, Examples include alcohols such as isopropanol; hydrocarbons such as hexane and pentane.
  • polyvinyl alcohol polymers such as polyvinyl alcohol and polyvinyl acetate partial saponified products; cellulose derivatives such as methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose; polyvinyl pyrrolidone, polyacrylamide, malee
  • synthetic polymers such as acid-styrene copolymers and maleic acid-methyl vinyl ether copolymers
  • natural polymers such as starch and gelatin.
  • anionic emulsifiers such as alkyl or alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, alkyl allyl sulfosuccinate; polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxy Nonionic emulsifiers such as ethylene carboxylic acid esters are exemplified.
  • the monomers, polymerization initiators, suspension stabilizers, emulsifiers and the like shown above may be added to the polymerization system at the start of the polymerization, or may be added in portions during the polymerization. it can.
  • particles are agglomerated by adding an aqueous solution of an inorganic salt such as sodium chloride, calcium chloride, or sodium sulfate or adding a water-soluble organic solvent according to a known salting-out method after polymerization. Filter, wash and dry.
  • the vinyl chloride resin is generally a hard vinyl chloride resin or a soft vinyl chloride resin.
  • the addition amount of the vinyl chloride polymer is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
  • the vinyl chloride resin composition uses, for example, a vinyl chloride polymer solid (for example, powder or pellets) and a vinyl chloride resin solid (for example, powder or pellets), and the vinyl chloride polymer under heating.
  • a vinyl chloride polymer solid for example, powder or pellets
  • a vinyl chloride resin solid for example, powder or pellets
  • the vinyl chloride polymer under heating.
  • it can be produced by melt-mixing a vinyl chloride resin with a kneading apparatus such as a twin-screw extruder under a temperature condition in the range of 150 to 200 ° C.
  • the vinyl chloride polymer and the vinyl chloride resin composition can be used as molded articles such as films, sheets, miscellaneous goods, artificial leather, electric wire coverings, wallpaper, building materials, pipes and the like. Furthermore, the vinyl chloride polymer can be used as an additive for ink, coating or paint.
  • the vinyl chloride polymer containing the structural unit (A-4) is mixed with an isocyanate group-containing compound, whereby the strength of the dry film is increased by crosslinking of the active hydrogen group and the isocyanate group, and the solvent resistance is excellent. .
  • This mixture can be used as a coating or paint film.
  • the isocyanate group-containing compound used in the present invention is a compound having two or more (for example, 2 to 6) isocyanate groups in the molecule.
  • the amount used is preferably set so that the isocyanate group is 1 mol or more, for example, 1.02 to 2 mol, particularly 1.1 to 1.5 mol, per mol of the active hydrogen group.
  • 0.5 mol or more of the isocyanate group-containing compound is preferable with respect to 1 mol of the active hydrogen group.
  • the isocyanate group-containing compound may be diisocyanate, triisocyanate and the like.
  • isocyanate group-containing compounds include aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, xylylene diisocyanate; phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, diphenyl Aromatic polyisocyanates such as ethane diisocyanate, ditolylene diisocyanate, and triphenylmethane triisocyanate can be mentioned.
  • urethane-modified products carbodiimide-modified products, biuret-modified products, isocyanurate-modified products, and the like may be used.
  • the isocyanate group-containing compound may be used alone or in combination of two or more.
  • a methyl ethyl ketone solution (concentration: 3% by weight) of the vinyl chloride polymer produced in Examples and Comparative Examples is prepared and applied on a glass plate so as to have a film thickness of 0.3 ⁇ m.
  • the film was naturally dried at 25 ° C. for 12 hours and then heated at 80 ° C. for 30 minutes to obtain a vinyl chloride polymer film.
  • 1 ⁇ l of water was dropped and the contact angle was determined.
  • the vinyl chloride polymer compositions produced in the examples and comparative examples were compression-molded under a condition of 200 ° C. and 3 MPa using a heat press machine to produce a sheet having a thickness of 0.5 mm. On this sheet, 1 ⁇ l of water was dropped and the contact angle was determined.
  • a methyl ethyl ketone solution (concentration: 3% by weight) of the vinyl chloride polymer produced in Examples and Comparative Examples is prepared and applied on a glass plate so as to have a film thickness of 0.3 ⁇ m.
  • the film was naturally dried at 25 ° C. for 12 hours and then heated at 80 ° C. for 30 minutes to obtain a vinyl chloride polymer film.
  • On the vinyl chloride polymer film 1.7 ⁇ l of n-hexadecane was dropped, and the contact angle was determined.
  • the vinyl chloride polymer compositions produced in the examples and comparative examples were compression-molded under a condition of 200 ° C.
  • the composition of the copolymer was 3.3 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
  • Synthesis example 2 A copolymer was synthesized in the same manner as in Synthesis Example 1 except that C6F13MA monomer was changed to 120 parts by weight and vinyl chloride was changed to 1080 parts by weight. The composition of the copolymer was 11.9 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
  • Synthesis example 3 A copolymer was synthesized in the same manner as in Synthesis Example 1 except that C6F13MA monomer was changed to 180 parts by weight and vinyl chloride was changed to 1020 parts by weight. The composition of the copolymer was 19 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
  • Synthesis example 4 In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen replacement, 560 parts by weight of deionized water, 460 parts by weight of methanol, 366 parts by weight of vinyl chloride, 175 parts by weight of vinyl acetate, 36 monomers of C6F13MA monomer 1 part by weight, 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose are added, and the temperature is raised to 70 ° C. while stirring to initiate the polymerization reaction. Further, 623 parts by weight of vinyl chloride is continuously added over 5 hours. And reacted.
  • the composition of the copolymer was 3.9 parts by weight of C6F13MA monomer and 16.7 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
  • Synthesis example 5 In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen substitution, 560 parts by weight of deionized water, 460 parts by weight of methanol, 297 parts by weight of vinyl chloride, 360 parts by weight of vinyl acetate, 36 parts by weight of C6F13MA monomer , 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose were added, the temperature was raised to 70 ° C. while stirring to start the polymerization reaction, and 507 parts by weight of vinyl chloride was continuously added over 5 hours. Reacted.
  • the composition of the copolymer was 4.8 parts by weight of C6F13MA monomer and 42.4 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
  • Synthesis Example 6 A copolymer was synthesized in the same manner as in Synthesis Example 4 except that the amount of C6F13MA monomer was 160 parts by weight, initial charge of vinyl chloride was 310 parts by weight, additional vinyl chloride was 600 parts by weight, and vinyl acetate was 130 parts by weight. .
  • the composition of the copolymer was 18.9 parts by weight of C6F13MA monomer and 13.5 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
  • Synthesis example 7 A copolymer was synthesized in the same manner as in Synthesis Example 1, except that 360 parts by weight of the C6F13MA monomer and 840 parts by weight of vinyl chloride were used. The composition of the copolymer was 46.1 parts by weight of C6F13MA monomer with respect to 100 parts by weight of vinyl chloride.
  • Synthesis example 8 In a polymerization vessel equipped with a stirrer, thermometer and nitrogen gas inlet, after nitrogen substitution, 560 parts by weight of deionized water, 460 parts by weight of methanol, 253 parts by weight of vinyl chloride, 480 parts by weight of vinyl acetate, 36 parts by weight of C6F13MA monomer , 3 parts by weight of benzoyl peroxide and 1 part by weight of hydroxypropyl methylcellulose were added, the temperature was raised to 70 ° C. while stirring, the polymerization reaction was started, and 431 parts by weight of vinyl chloride was continuously added over 5 hours. Reacted.
  • the composition of the copolymer was 5.7 parts by weight of C6F13MA monomer and 66.4 parts by weight of vinyl acetate with respect to 100 parts by weight of vinyl chloride.
  • Synthesis Example 9 A copolymer was synthesized in the same manner as in Synthesis Example 4 except that 60 parts by weight of 2-hydroxypropyl acrylate was added and 306 parts by weight of the initially charged vinyl chloride was changed.
  • the composition of the copolymer was 4.2 parts by weight of C6F13MA monomer, 17.8 parts by weight of vinyl acetate, and 6.9 parts by weight of 2-hydroxypropyl acrylate with respect to 100 parts by weight of vinyl chloride.
  • Synthesis Example 10 A copolymer was prepared in the same manner as in Synthesis Example 4 except that 96 parts by weight of 2-hydroxypropyl acrylate and 24 parts by weight of 2-hydroxy-1-methylethyl acrylate were added, and 246 parts by weight of the initially charged vinyl chloride was changed to 246 parts by weight. Synthesized. The composition of the copolymer was 4.5 parts by weight of C6F13MA monomer, 19.1 parts by weight of vinyl acetate, 11.8 parts by weight of 2-hydroxypropyl acrylate, 3 parts by weight of 2-hydroxy-1-methylethyl acrylate, relative to 100 parts by weight of vinyl chloride. Was part.
  • TK-800 Shin-Etsu Chemical vinyl chloride resin MB-8: Sekisui Plastics acrylic resin SC-208: ADEKA Ca / Zn stabilizer RUP-14: ADEKA Ba / Zn stabilizer AC-186: ADEKA Ba / Zn stabilizer TOTM: Tri-2-ethylhexyl tolmellitate (Asahi Denka Kogyo) Hiwax 220P: Polyethylene lubricant manufactured by Mitsui Petrochemical Industries EW-100: RIKEN vitamin ester ester lubricant NS-400: Calcium carbonate from Nitto Flour Industries SP-703: Chisso-containing organophosphate compound manufactured by Shikoku Kasei
  • Examples 13 to 16 Using the compound composition shown in Table 4, using a twin screw extruder with a diameter of 30 mm, each material was stirred and mixed under the conditions of a cylinder temperature of 180 ° C. and a screw rotation speed of 200 rpm, and a vinyl chloride resin composition was prepared. Obtained. Using the resin composition, extrusion molding was performed with a 20 mm diameter short-axis extruder (screw CR3.0, rotation speed: 60 rpm) equipped with a T-die mold to produce a sheet having a thickness of 1.5 mm. Various characteristics were evaluated. The results are shown in the table below.
  • the vinyl chloride polymer and the vinyl chloride resin composition can be used as molded articles such as films, sheets, miscellaneous goods, artificial leather, electric wire coverings, wallpaper, building materials, pipes and the like. Furthermore, the vinyl chloride polymer can be used as an additive for ink, coating or paint.

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

L’invention concerne un polymère de chlorure de vinyle, comprenant 100 parties en poids d’une unité constituante (A-1), dérivée du chlorure de vinyle, et 1 à 20 parties en poids d’une unité constituante (A-2), dérivée d’un ester acrylate fluoré. L’invention concerne également une composition de résine de chlorure de vinyle, comprenant (A) 0,2 à 20 parties en poids du polymère de chlorure de vinyle et (B) 100 parties en poids d’une résine de chlorure de vinyle. Le polymère de chlorure de vinyle peut comprendre en outre 50 parties en poids ou moins d’une unité constituante (A-3) dérivée d’un ester vinylique d’acide gras saturé. De plus, le polymère de chlorure de vinyle peut comprendre en outre 30 parties en poids ou moins d’une unité constituante (A-4) dérivée d’un ester vinylique contenant un groupe à hydrogène actif. Il devient possible d’améliorer les propriétés hydrofuges/oléofuges d’une résine de chlorure de vinyle.
PCT/JP2009/053866 2008-03-28 2009-03-02 Polymère de chlorure de vinyle WO2009119255A1 (fr)

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CN200980111033.0A CN101981069B (zh) 2008-03-28 2009-03-02 氯乙烯类聚合物
JP2010505482A JPWO2009119255A1 (ja) 2008-03-28 2009-03-02 塩化ビニル系重合体

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709874A (zh) * 2014-01-14 2014-04-09 钱计兴 氟树脂改性聚氯乙烯清料及含有该清料的底漆及面漆
KR20150040878A (ko) * 2012-08-01 2015-04-15 아사히 가라스 가부시키가이샤 발수발유제 조성물 및 물품
KR20170008477A (ko) * 2015-07-14 2017-01-24 주식회사 엘지화학 염화비닐계 수지 조성물, 이의 제조방법 및 이로부터 제조된 염화비닐계 수지 성형품
KR20170008480A (ko) * 2015-07-14 2017-01-24 주식회사 엘지화학 염화비닐계 수지 조성물, 이의 제조방법 및 이로부터 제조된 염화비닐계 수지 성형품

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CN103709874A (zh) * 2014-01-14 2014-04-09 钱计兴 氟树脂改性聚氯乙烯清料及含有该清料的底漆及面漆
KR20170008477A (ko) * 2015-07-14 2017-01-24 주식회사 엘지화학 염화비닐계 수지 조성물, 이의 제조방법 및 이로부터 제조된 염화비닐계 수지 성형품
KR20170008480A (ko) * 2015-07-14 2017-01-24 주식회사 엘지화학 염화비닐계 수지 조성물, 이의 제조방법 및 이로부터 제조된 염화비닐계 수지 성형품
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