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WO2008141952A1 - Polymères complexes de chlorure de vinyle siliconés - Google Patents

Polymères complexes de chlorure de vinyle siliconés Download PDF

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Publication number
WO2008141952A1
WO2008141952A1 PCT/EP2008/055732 EP2008055732W WO2008141952A1 WO 2008141952 A1 WO2008141952 A1 WO 2008141952A1 EP 2008055732 W EP2008055732 W EP 2008055732W WO 2008141952 A1 WO2008141952 A1 WO 2008141952A1
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Prior art keywords
vinyl chloride
chloride copolymers
weight
vinyl
copolymers according
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PCT/EP2008/055732
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German (de)
English (en)
Inventor
Thomas Köhler
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Wacker Chemie AG
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Wacker Chemie AG
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Classifications

    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • 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
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the invention relates to siliconized vinyl chloride copolymers, processes for their preparation, and their use in particular in paint resin compositions.
  • WO 07/025847 A1 discloses a process in which vinyl chloride and vinyl acetate are copolymerized in aqueous suspension in the presence of a vinyl chloride-vinyl acetate mixed polymer which is soluble in ethyl acetate in order to improve solubility.
  • the object was to provide a vinyl chloride copolymer which has improved solubility at room temperature in organic solvents such as ketones or esters. This problem was solved by means of siliconization of the vinyl chloride polymers.
  • organopolymers are modified with silicones in such a way that the organomonomers are polymerized in the presence of a silicone to give silicone organocopolymers, thus providing a more stable attachment of the silicone building block in the finished coating enable. This is particularly important if you want to use the products in food-grade applications and avoid migration from the coating.
  • compositions which contain 0.1 to 20 wt.% Of a silicone organocopolymer, which by free radical polymerization of a mixture containing 1 to 50 wt.% Of one or more silicones with or is available without polymerizable groups. Siliconized vinyl chloride copolymers are not described therein.
  • EP 1354900 A1 a mixture of low molecular weight polysiloxane (n ⁇ 30) having a terminal polymerizable group and of relatively high molecular weight polysiloxane (n> 55) having one or two terminal polymerizable groups in the presence of ethylenic is used to prepare extrudable, low migration silicone organocopolymers polymerized unsaturated monomers.
  • EP 0131911 A1 discloses vinyl chloride copolymers, grafted copolymers or blends of different polymers or copolymers, the polymers or copolymers comprising vinyl chloride units and / or organosilicon units, such as organosilane, polymerizable organopolysiloxane or nonpolymerizable organopolysiloxane units, and, optionally, units of further ethylenically unsaturated monomers, such as acrylic acid esters.
  • organosilicon units such as organosilane, polymerizable organopolysiloxane or nonpolymerizable organopolysiloxane units
  • units of further ethylenically unsaturated monomers such as acrylic acid esters.
  • EP 0131911 A1 only discloses that the polymers or copolymers described therein are insoluble in organic solvents.
  • WO 05/087827 A1 discloses a process for preparing silicone-containing copolymers of ethylenically unsaturated organomonomer and 5 to 50% by weight of silicone macromer in the form of their aqueous polymer dispersions or water-redispersible polymer powders, wherein the polymerization in the presence of water-soluble initiator and oil-soluble initiator to reduce the amount of migratable free silicone.
  • JP-A 61-061825 discloses heat-shrinkable casting resins based on vinyl chloride copolymers which contain from 1 to 50% by weight of polymerizable unsaturated silicone components and which can be prepared by suspension polymerization, wherein the elasticity is introduced by the silicone part.
  • the invention provides vinyl chloride copolymers obtainable by free-radically initiated polymerization of a mixture comprising a) from 50 to 99.99% by weight of vinyl chloride, b) from 1 to 50% by weight of one or more monomers from the group consisting of vinyl esters and methacrylates, c ) 0.01 to ⁇ 5% by weight of one or more copolymerizable silicones, and d) 0 to 10% by weight of one or more further comonomers copolymerizable with a), b) and c) from the group comprising epoxide functional comonomers, acrylic esters, ethylenically unsaturated monocarboxylic and dicarboxylic acids and their anhydrides, and also dialkyl esters of ethylenically unsaturated dicarboxylic acids, the data being added in% by weight to 100% by weight and based on the total weight of the vinyl chloride Copolymers are obtained.
  • the siliconized vinyl chloride copolymers contain from 55 to 90% by weight of vinyl chloride, more preferably from 60 to 85% by weight of vinyl chloride.
  • Suitable comonomers b) are one or more ethylenically unsaturated monomers from the group comprising vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 18 carbon atoms or methacrylic acid esters of unbranched or branched alcohols having 1 to 18 carbon atoms.
  • Preferred vinyl esters 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 C-C-branched monocarboxylic acids having 9 to 13 carbon atoms, for example VeoVa9 or VeoValO (trade names of Company Hexion).
  • vinyl acetate Most preferred is vinyl acetate.
  • the siliconized vinyl chloride copolymers which contain as comonomer units b) those which are derived from vinyl esters can also be saponified so that comonomer units b) as well as vinyl ester units also contain vinyl alcohol units. Preferably, it is saponified such that up to 10% by weight of vinyl alcohol units in the copolymer, based on the total weight of the siliconized vinyl chloride copolymer.
  • Suitable comonomers b) from the group of methacrylic esters are esters of unbranched or branched alcohols having 1 to 15 C atoms.
  • Preferred methacrylic acid esters are methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate. Particularly preferred is methyl methacrylate.
  • Suitable comonomers b) are also hydroxyalkyl
  • (meth) acrylates having C 1 to C 4 -alkyl radicals, preferably hydroxyethyl acrylate and hydroxypropyl acrylate.
  • the vinyl chloride copolymers contain 10 to 50 wt .-% of comonomers b), more preferably, the vinyl chloride copolymers contain 15 to 40 wt .-% of comonomers b).
  • Suitable copolymerizable silicones c) are diorganopolysiloxanes having at least 5 diorganosiloxane units and one or two polymerisable groups. Suitable polymerizable groups are ethylenically unsaturated groups. The copolymerizable groups can be arranged in the chain or terminal.
  • n number of diorganosiloxane units
  • copolymerizable silicones c) diorganopolysiloxanes having the general formula (SiR2 ⁇ ) n SiR3- a R 1 a, where R is the same or different, and a monohydric term, optionally substituted alkyl, alkenyl or alkoxy group each having 1 to 18 carbon atoms, or an optionally substituted aryl radical, , R 1 represents a polymerisable group, a is the same or different and 0 or 1, wherein at least one a is 1, and n is an integer of 5 to 2,000.
  • radicals R are methyl, ethyl, n-propyl, iso-propyl, 1-n-butyl, 2-n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • -Pentyl radical hexyl radicals such as the n-hexyl radical, heptyl radicals such as the n-heptyl radical, octyl radicals such as the n-octyl radical and iso-octyl radicals such as the 2, 2, 4-trimethylpentyl radical, nonyl radicals such as the n-nonyl radical, decyl radicals such as n -De- cylrest, dodecyl radicals such as the n-dodecyl radical, and octadecyl radicals such as the n-octadecyl radical, alkenyl radicals, such as the vinyl and the allyl radical; Cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl radicals, aryl radicals such as the phenyl, naphthy
  • the radical R is a monovalent hydrocarbon radical having 1 to 18 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl , Hexyl and phenyl radical, with the methyl to propyl radical and the phenyl radical being particularly preferred.
  • Preferred alkoxy radicals R are those having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy and n-butoxy radicals, which may optionally be substituted by oxyalkylene radicals, such as oxyethylene or oxymethylene radicals. Particularly preferred are the methoxy and ethoxy. If appropriate, the radicals R mentioned can also be substituted, for example with halogen, mercapto groups, epoxy-functional groups, carboxyl groups, keto groups, enamine groups, amino groups, aminoethylamino groups, isocyanate groups, aryloxy groups, alkoxysilyl groups and hydroxyl groups.
  • Suitable polymerizable groups R 1 are alkenyl radicals having 2 to 8 C atoms.
  • Examples of such polymerizable groups are the vinyl, allyl, butenyl, as well as acryloxyalkyl and methacryloxyalkyl group, wherein the alkyl radicals 1 to 4 carbon atoms contain. Preference is given to the vinyl group, acryloxymethyl, methacryloxymethyl, 3-acryloxypropyl and 3-methacryloxypropyl group.
  • Preferred copolymerizable silicones are c) OC, CO-di-vinyl-polydimethylsiloxanes, CC, G) -di- (3-acryloxypropyl) -poly-dimethylsiloxanes, OC, G) -di- (3-methacryloxypropyl) -polydimethylsiloxanes , CC, G) -di (acryloxymethyl) -polydimethylsiloxanes, CC-monovinyl-polydimethylsiloxanes, CC-mono- (3-acryloxypropyl) -polydimethylsiloxanes, ⁇ -mono- (3-methacryloxypropyl) -polydimethylsiloxanes, CC- Mono (acryloxymethyl) -polydimethylsiloxanes, CC-mono- (methacryloxymethyl) -polydimethylsiloxanes.
  • the preparation of the copolymerizable silicone c) is known in the art, it can, for example, by ring-opening
  • Suitable epoxide-functional comonomers d) are, for example, methyl glycidyl acrylate, methyl glycidyl methacrylate, allyl glycidyl ether, allyl phenol glycidyl ether, glycidyl acrylate, glycidyl methacrylate. Preference is given to glycidyl methacrylate (GMA).
  • Examples of acrylic acid esters suitable as comonomer component d) are esters of unbranched or branched alcohols having 1 to 18 C atoms, in particular having 1 to 15 C atoms.
  • Acrylic acid esters are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate. Particularly preferred are methyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate.
  • suitable comonomer component d) ethylenically unsaturated mono- and di-carboxylic acids and their anhydrides are acrylic acid, methacrylic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, maleic anhydride.
  • comonomers d) are the mono- and dialkyl esters of dicarboxylic acids with C 1 - to C 6 -alkyl groups, for example ethyl fumarate and dibutyl maleate.
  • the epoxide-functional comonomers d) are preferably copolymerized in an amount of 0.01 to 5.0% by weight, particularly preferably 0.1 to 0.5% by weight.
  • the acrylic esters or the alkyl esters of ethylenically unsaturated dicarboxylic acids are preferably copolymerized in an amount of from 0.1 to 10.0% by weight, particularly preferably from 2 to 9% by weight.
  • the free-radically initiated polymerization can be carried out by means of solution polymerization, suspension polymerization and emulsion polymerization.
  • the suspension polymerization and the emulsion polymerization are preferred.
  • the polymerization temperature is generally from 20 0 C to 80 0 C.
  • the initiation of the polymerization can be carried out with the customary water-soluble or monomer-soluble initiators or redox initiator combinations.
  • water-soluble initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid.
  • Examples of monomer-soluble initiators are dicetyl peroxydi- carbonate, dicyclohexyl peroxydicarbonate, dibenzoyl peroxide, di- lauryl peroxide and tert. Butyl peroxypivalate.
  • the initiators mentioned are generally used in an amount of 0.01 to 1.0 wt .-%, preferably 0.1 to 0.5 wt .-%, each based on the total weight of
  • organic solvents such as Ci- to C 5 -alkanols such as methanol, ethanol or isopropanol, Ci- to C 5 alkyl esters of Ci- to C 5 -carboxylic acids such as methyl acetate tat, ethyl acetate or ketones such as acetone and methyl ethyl ketone used.
  • emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
  • anionic surfactants such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol
  • Suitable protective colloids are, for example, partially hydrolyzed and fully hydrolyzed polyvinyl alcohols, celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives.
  • the surface-active substances are used in an amount of from 0.01 to 5% by weight, based on the total weight of the comonomers.
  • regulating substances can be used during the polymerization. If regulators are used, they are usually used in amounts of from 0.02 to 10.0% by weight, based on the monomers to be polymerized, and are metered in separately or else premixed with reaction components. Examples of such substances are halogenated alkanes and halogenated alkenes such as carbon tetrachloride, chloroform, methyl chloride, trichlorethylene and aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde and isobutyraldehyde.
  • polymerization is carried out in the presence of propionaldehyde.
  • Propionaldehyde has over other regulators such as trichlorethylene the advantage that with smaller amounts already a regulatory effect is achieved. It is therefore preferably, depending on the desired molecular weight, in an amount of 0.02 to 5 wt .-%, based on monomer added.
  • the monomers can be added in total or be introduced in portions and the remainder be added after the initiation of the polymerization.
  • the dosages can be carried out separately (spatially and temporally) or the components to be metered can be metered in all or in part pre-emulsified.
  • the optionally epoxy-containing vinyl monomers as a whole are metered in continuously or more preferably continuously.
  • residual monomer removal can be postpolymerized using known methods, for example by postpolymerization initiated with the redox catalyst.
  • Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and optionally by passing or passing inert inert gases, such as air, nitrogen or steam.
  • ком ⁇ онент during or after the polymerization, from 0.001 to 0.1% by weight of one or more carboxylic acids from the group comprising aliphatic and alicyclic, saturated and unsaturated dicarboxylic acids having 1 to 10 carbon atoms and aliphatic and alicyclic, saturated and unsaturated hydroxy-mono-, hydroxy-di-, hydroxy-tri-carboxylic acids having 3 to 10 carbon atoms and 1 to 4 hydroxy groups are added.
  • the addition preferably takes place after completion of the monomer metering and before, during or after the removal of residual monomer.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and also maleic acid and fumaric acid.
  • Particularly preferred are the hydroxycarboxylic acids mentioned, for example tartronic acid, malic acid, tartaric acid, citric acid, iso-citric acid, ascorbic acid, iso-ascorbic acid.
  • ascorbic acid and iso-ascorbic acid are preferred, in particular combinations of ascorbic acid or iso-ascorbic acid with citric acid.
  • the amount of (iso) ascorbic acid and citric acid is preferably in each case from 0.005 to 0.05 wt .-%, each based on the total weight of the monomers.
  • the siliconized vinyl chloride copolymer obtained according to this process can be isolated by conventional methods by precipitation, filtration and subsequent drying
  • the siliconized vinyl chloride copolymers are suitable, for example, as binders for paints, especially in heat seal coatings, for example for aluminum coating. They are characterized by their excellent solubility in all common solvents for paints. It should be emphasized that the products not only dissolve in the frequently used as solvent ketones, but even at room temperature (23 ° C) are also readily soluble in vinyl chloride-vinyl acetate copolymers critical solvents such as aliphatic esters without heating.
  • the siliconized vinyl chloride copolymers are also suitable for use as a primer, as an adhesive, as a binder in printing inks and as a coating agent.
  • a copolymer was obtained with 62% by weight of vinyl chloride, 20% by weight of silicone, 17% by weight of vinyl acetate and 1% by weight of fumaric acid.
  • Comparative Example 3 Analogously to the procedure of Comparative Example 1, a copolymer of 77% by weight of vinyl chloride, 5% by weight of silicone fraction, 17% by weight of vinyl acetate, 1% by weight of fumaric acid was prepared. A 20 wt .-% solution of the copolymer in ethyl acetate showed after heating to 50 0 C many undissolved particles and a milky, quale appearance.
  • Example 11 Analogously to the procedure of Comparative Example 5, a copolymer of 81.9% by weight of vinyl chloride, 0.1% by weight of silicone fraction, 17% by weight of vinyl acetate, 1% by weight of fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed even after heating to 50 0 C no turbidity and remained homogeneous after 2 days.
  • a 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 0 C and remained homogeneous after 2 days.
  • Example 12 Analogously to the procedure of Example 12, a copolymer of 81.5 wt .-% vinyl chloride, 0.5 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 0 C and remained homogeneous after 2 days.
  • Example 14 Analogously to the procedure of Example 12, a copolymer of 81.75 wt .-% vinyl chloride, 0.25 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 0 C and remained homogeneous after 2 days.
  • Example 12 Analogously to the procedure of Example 12, a copolymer of 81.9 wt .-% vinyl chloride, 0.1 wt .-% silicone content, 17 wt .-% vinyl acetate, 1 wt .-% fumaric acid was prepared. A 20 wt .-% - solution of the copolymer in methyl ethyl ketone or ethyl acetate showed no turbidity even after heating to 50 0 C and remained homogeneous after 2 days.
  • the polymers prepared in Examples and Comparative Examples were evaluated for their solubility in various solvents as well as the clarity and consistency of the solution as follows.
  • MEK methyl ethyl ketone
  • EtAc ethyl acetate
  • the solvent was placed in a 250 ml glass bottle and the material to be dissolved was added slowly (within approximately 30 seconds) with rapid stirring (stirrer disk of 35 mm diameter and 1000 rpm) that a solution with 20 wt .-% solids content was obtained.
  • Another property of the vinyl chloride copolymers modified by the copolymerization with the copolymerizable silicones is the surface friction of vinyl chloride-polymer coated surfaces which overlay the surface of the vinyl chloride copolymers Sliding friction coefficients (GRK, kinematic value, force in motion) and static friction coefficients (HRK, static value, force from standstill) are described.
  • the sample was dissolved in ethyl acetate at 20% strength by weight and applied to soft aluminum foil with a 24 ⁇ m spiral doctor blade. Subsequently, the sample was dried at 150 ° C. for 10 seconds.
  • the contact angle for the evaluation of surface properties such as e.g. hydrophobicity.
  • the measurement of the static contact angle was carried out with the method of the lying drop with the contact angle measuring device DSA10 from. Krüss / Hamburg.
  • a drop of liquid (in this case water) of a certain volume was applied to the sample by means of a syringe (sessile drop).
  • a digital image analysis of the drop was performed by video camera.
  • Table 2 shows the coefficient of sliding friction (GRK), the static friction coefficient (HRK) and the contact angle of coatings which were produced with the VC copolymers of the corresponding (comparative) examples.
  • the contact angle which is accessible by the use of the comparative example 16, this is about 80 °.
  • the contact angle can be increased and thus the hydrophobicity of the surface can be permanently increased. It turns out that even with the use of 1% by weight of copolymerizable silicone, a maximum level is achieved which corresponds to the usual of siliconized surfaces.
  • the GRK and HRK lowered and reaches ⁇ be already in use of 0.25 wt .-% of silicone copolymerizable an approximate minimum. By further increasing the amount of copolymerizable silicone used, the GRK and HRK can no longer be significantly reduced.
  • the tested site was examined to determine whether and how much the film has come off the substrate and adheres to the adhesive tape ®.
  • the test was carried out in several places under the same condition.
  • the rating is in grades from 1 to 4, with 1 being the best and 4 being the worst rating:
  • the method described here is used to determine the blocking point of adjacent coatings above a certain temperature.
  • Block point the sealing jaws are heated to 30 0 C. If the sample does not block, the determination is repeated, increasing the temperature in 5 ° C increments. After loading, the sealed piece of foil is cut off with scissors and smoothed by hand. By pulling apart the sample placed against each other, the sticking, sticking or total blocking of the sample is visually evaluated. To assess the blocking point, the temperature at which the specimens adhere to one another is given in 0 C.

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Abstract

L'invention concerne des polymères complexes de chlorure de vinyle obtenus par polymérisation initiée par voie radicalaire d'un mélange contenant a) 50 à 99,99 % en masse de chlorure de vinyle, b) 1 à 50 % en masse d'un ou de plusieurs monomères du groupe des esters vinyliques et des esters de l'acide méthacrylique,10 c) 0,01 à < 5 % en masse d'une ou de plusieurs silicones copolymérisables et d) 0 à 10 % en masse d'un ou de plusieurs autres comonomères copolymérisables avec a), b) et c) du groupe comprenant des comonomères à fonction époxyde, des esters acryliques, des acides monocarboxyliques et dicarboxyliques éthyléniquement insaturés ainsi que leurs anhydrides, ainsi que des alkylesters d'acides dicarboxyliques éthyléniquement insaturés, les pourcentages en masse s'ajoutant pour former un total de 100 % en masse et se rapportant chacun à la masse totale des polymères complexes de chlorure de vinyle.
PCT/EP2008/055732 2007-05-23 2008-05-09 Polymères complexes de chlorure de vinyle siliconés Ceased WO2008141952A1 (fr)

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DE102007023933.7 2007-05-23
DE200710023933 DE102007023933A1 (de) 2007-05-23 2007-05-23 Siliconisierte Vinylchlorid-Mischpolymerisate

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Citations (3)

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Publication number Priority date Publication date Assignee Title
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JPS6162548A (ja) * 1984-09-04 1986-03-31 Shin Etsu Chem Co Ltd 包装材料用塩化ビニル系樹脂組成物
JPS61118451A (ja) * 1984-11-13 1986-06-05 Shin Etsu Chem Co Ltd 架橋性塩化ビニル系樹脂組成物

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