WO2019020156A1 - Hydrophobic and cold water-soluble vinyl alcohol copolymers - Google Patents

Hydrophobic and cold water-soluble vinyl alcohol copolymers Download PDF

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Publication number
WO2019020156A1
WO2019020156A1 PCT/EP2017/068589 EP2017068589W WO2019020156A1 WO 2019020156 A1 WO2019020156 A1 WO 2019020156A1 EP 2017068589 W EP2017068589 W EP 2017068589W WO 2019020156 A1 WO2019020156 A1 WO 2019020156A1
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vinyl alcohol
mol
alcohol copolymers
vinyl
monomer units
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PCT/EP2017/068589
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German (de)
French (fr)
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Abdulmajid Hashemzadeh
Udo EISLEBEN
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Wacker Chemie Ag
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Priority to PCT/EP2017/068589 priority Critical patent/WO2019020156A1/en
Publication of WO2019020156A1 publication Critical patent/WO2019020156A1/en

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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
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to vinyl alcohol copolymers and processes for their preparation and their use.
  • Polymers stabilized with protective colloids are mainly used in the form of their aqueous dispersions or water-redispersible polymer powders (dispersion powders) in many applications, for example as coating agents or adhesives, for a wide variety of substrates, for example as cementitious tile adhesives.
  • Dispersion powders are polymer powders which are obtainable by spray-drying the corresponding aqueous polymer dispersions.
  • Water-redispersible polymer powders are generally obtained by drying the corresponding aqueous polymer dispersions in the presence of a drying aid (generally a protective colloid) and, if appropriate, antiblocking agents and, if appropriate, further additives.
  • the drying process prevents the polymer particles from irreversibly sticking because the polymer particles are enveloped by the protective colloid particles.
  • this protective colloid matrix which dissolves again when the polymer powder is dispersed in water, causes the polymer particles to be present again with the particle size of the starting dispersion in the aqueous redispersion (TIZ fraberichte, 1985, Vol. 109 (9), 698).
  • protective colloids generally polyvinyl alcohols are used, for example in the process which in the
  • WO 2013/017491 AI is described.
  • the use of polyvinyl alcohol is desirable because, in comparison to systems which are stabilized by low molecular weight compounds (emulsifiers), it itself contributes to the strength (for example adhesion values in the tile adhesive).
  • emulsifiers low molecular weight compounds
  • problems can arise in the production and use of polyvinyl alcohol. polymerized polymers occur, in particular if the polyvinyl alcohol has a higher degree of saponification.
  • EP 1020493 A1 describes the use of a partially acetalized, water-soluble polyvinyl alcohol as a drying aid in the preparation of a water-redispersible polymer powder by spray-drying the corresponding polymer dispersion.
  • WO 2012/159848 Al fully hydrolyzed vinyl acetate
  • Isopropenyl acetate copolymers are used as a protective colloid for stabilizing an aqueous polymer dispersion and as a drying aid for drying an aqueous polymer dispersion.
  • EP 477900 A2 describes disperse powder compositions with polyvinyl alcohol, which still contain fully hydrolyzed vinyl acetate-1-methylvinyl acetate copolymers in order to improve the properties of building materials modified therewith.
  • Fully hydrolyzed or partially hydrolyzed copolymers of vinyl acetate and 1-alkylvinyl esters are known from EP 1180528 B1, which optionally also contain monomer units derived from vinyl esters of alpha-branched carboxylic acids.
  • WO 99/16794 Al describes the preparation of stabilized with protective colloid, aqueous polymer dispersions, being used as protective colloids teilverseifte copolymers of vinyl acetate and vinyl esters of alpha-branched carboxylic acids having 9 to 11 carbon atoms.
  • EP 1400557 Al describes the use of a vinyl alcohol copolymer with 1 to 12 mol% of ethylene units as a drying aid in the production of dispersion powders.
  • EP 1420033 B1 uses partially hydrolysed vinyl acetate-ethylene copolymers as a protective colloid in the preparation of a copolymer dispersion and as a drying aid in the spray-drying of aqueous polymer dispersions.
  • WO 2010/091766 A1 a copolymer of 11 mol% vinyl sulfonate, 45 mol%, is used in Example 3. Vinyl acetate, 33 mol% VeovalO and 11 mol% of vinyl alcohol used as a dispersant in a pigment preparation.
  • the object of the invention was to provide vinyl alcohol copolymers which have a hydrophobic character and which, even at a high degree of hydrolysis (degree of saponification), still have good storage stability (viscosity stability) and good solubility in water.
  • the invention provides vinyl alcohol copolymers with a) from 80 to 99 mol%, preferably from 85 to 97 mol% of vinyl alcohol monomer units,
  • Preferred vinyl esters of unbranched or branched alkylcarboxylic acids having 3 to 18 carbon atoms are vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate and vinyl esters of ⁇ -branched monocarboxylic acids having 5 to 13 carbon atoms, for example, vinyl pivalate, VeoVa9 R , VeoVal0 R or VeoVall R (trade name Hexion).
  • Particularly preferred are the vinyl esters of ⁇ -branched monocarboxylic acids having 9 to 10 carbon atoms (VeoVa9 R and VeoVal0 R ).
  • suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and its anhydride, monoesters of fumaric acid or maleic acid, such as the ethyl and isopropyl esters or unsaturated fatty acids having 7 to 25
  • Carbon atoms as well as the salts of said carboxylic acids. Preference is given to acrylic and methacrylic acid, maleic acid (anhydride) and crotonic acid, and the salts of the carboxylic acids mentioned.
  • R 4 is Ci- to C 4 alkylene, and the salts of said acids.
  • Suitable monomers with quaternary ammonium groups as monomers c) are diallyldimethylammonium chloride (DADMAC), diallyl diethylammonium chloride (DADEAC), (3-methacryloxy) ropyltrimethylammonium chloride (MPTAC), (3-methacryloxy) ethyltrimethylammonium chloride (METAC), (3 Methacrylamido) ropyltrimethylammonium chloride (MAPTAC).
  • DADMAC diallyldimethylammonium chloride
  • DADEAC diallyl diethylammonium chloride
  • MPTAC (3-methacryloxy) ropyltrimethylammonium chloride
  • METAC (3-methacryloxy) ethyltrimethylammonium chloride
  • MATAC 3 Methacrylamido) ropyltrimethylammonium chloride
  • Suitable monomers having a phosphoric acid radical are vinylphosphonic acid and dimethyl vinylphosphonate, phosphoalkylmethacrylates such as phosphoethyl methacrylate and phosphopropyl methacrylate.
  • the most preferred monomers c) are vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof.
  • reactive monomers from the group of ethylenically unsaturated monomers with alkoxysilane group or epoxy group or amine group or amide group can be copolymerized.
  • the vinyl alcohol copolymers can be prepared in a known manner by means of radical polymerization of vinyl acetate with the comonomers mentioned below b) and c) and subsequent hydrolysis of the resulting vinyl acetate copolymers.
  • Suitable solvents are, for example, methanol, ethanol, propanol, isopropanol and an ethanol-isopropanol mixture.
  • the polymerization is carried out under reflux at a temperature of 35 ° C to 100 ° C.
  • the radical initiation takes place by adding common initiators.
  • common initiators are percarbons such as cyclohexyl peroxydicarbonate, peresters such as t-butyl per neodecanoate or t-butyl peroxypivalate, peroxide initiators such as t-butyl hydroperoxide, diacyl peroxides such as dilauroyl peroxide, and azo initiators such as azobisisobutyronitrile (AIBN), 2,2 "azobis (AIBN).
  • AIBN azobisisobutyronitrile
  • AIBN 2,2 "azobis (AIBN).
  • the monomers can be initially introduced in total, be metered in in their entirety, or be charged in portions, and the remainder added after the initiation of the polymerization.
  • the initiator is preferably initially introduced and the remaining portion each to Siert.
  • the adjustment of the molecular weight can be carried out in a manner known to the skilled worker by polymerization in the presence of molecular weight regulators.
  • the saponification (transesterification, hydrolysis) of the vinyl acetate copolymer takes place in a manner known per se, for example by the kneader process or in a stirred tank, preferably in the alkaline phase with the addition of base.
  • the vinyl acetate copolymer is in alcoholic solution with monohydric aliphatic alcohols having 1 to 4 carbon atoms or mixtures thereof as a solvent. Particularly preferred are methanol and an ethanol / isopropanol mixture.
  • the content of vinyl acetate copolymer in the solution is 20 to 85 wt .-%, preferably 30 to 80 wt .-%.
  • alkaline catalysts are, for example, the hydroxides, alkoxides and carbonates of alkali or alkaline earth metals. Preference is given to sodium hydroxide.
  • the alkaline catalysts are preferably used in alcoholic solution. Most preferred is a methanolic solution of NaOH.
  • the amounts of alkaline catalyst used are generally 0.2 to 20.0 wt .-%, based on the vinyl acetate copolymer.
  • the hydrolysis is generally carried out at temperatures of 40 ° C to 90 ° C, preferably 50 ° C to 85 ° C, generally in a stirred tank. By adding the catalyst solution, saponification is initiated. Upon reaching the desired degree of hydrolysis, the hydrolysis is stopped. Preferably, the ester formed in the transesterification is distilled off during the Versei- tion reaction. In the preferred alkaline-catalyzed hydrolysis, the termination takes place by addition of acidic reagents, such as carboxylic acids or mineral acids, preferably acetic acid.
  • the solvent is distilled off, for example by means of steam stripping and the vinyl alcohol copolymer dissolved in water.
  • the vinyl alcohol Copolymer can also be separated by precipitation or drying of the liquid phase and isolated as a solid.
  • the vinyl alcohol copolymers according to the invention are suitable as protective colloids, dispersants, drying aids and for use in coating compositions, preferably for paper coating in paper coating formulations. Also preferred is their use as a protective colloid in the preparation of aqueous polymer dispersions and their use as a drying aid in drying, in particular spray drying, of aqueous polymer dispersions.
  • Vinyl ester of versatic acid R 10 (VeoVa R 10) 177 g
  • An initiator solution of 125 g of PPV in 1880 g of methanol was added within 240 minutes.
  • a monomer mixture 1 with 999 g of VeoVa R 10 and 18661 g of vinyl acetate was metered in with a metering time of 180 minutes.
  • the monomer solution 2, 1319 g of a 25% aqueous solution of vinyl sulfonate was metered in with a metering time of 195 minutes.
  • the reactor was locked, the pressure in the reactor increased to 0.2 bar and post-polymerized at 100 ° C for one hour. Thereafter, the polymer solution was cooled to 30 ° C and diluted with methanol to a 31 wt .-% solution. The polymer solution was coated without stirring with 38440 g of methanol and then a mixture of 775 g of methanol and 657 g of 46% sodium hydroxide solution was added and stirred. After two hours, the solution was neutralized with 342 g of acetic acid (99.8%). Subsequently, methanol and by-products were removed by steam stripping. After stripping, the vinyl alcohol copolymer was taken up in water and diluted to a 20% by weight solution.
  • Example 2 the procedure was as in Example 1, with the difference that the monomers vinyl acetate (VAc), VeoVa 10 and vinyl sulfonate (VS) in the monomer mixture 1 and the monomer solution 2 in such Quantities were added so that in each case the total amounts indicated in Table 1 were obtained.
  • the monomer c) used was DADMAC (diallyldimethylammonium chloride) and in example 6 as monomer c) AMPS (2-acrylamido-2-methylpropanesulfonic acid) instead of vinylsulfonate.
  • no vinylsulfonic acid was used. Table 1:
  • Viscosity Stability Testing The 20% by Weight Aqueous Solutions of the Vinyl Alcohol
  • Copolymers of Examples 1, 2, 3 and 5 and Comparative Example 4 were each stored for 1 day (ld) and 14 days (14d) at 23 ° C. After these storage times, the Brookfield viscosity was determined in each case. The determination of the Brookfield viscosities of the aqueous solutions was carried out with a
  • Table 2 shows in each case the composition of the vinyl alcohol copolymers from the examples and the comparative example. The proportions in the copolymer are in each case given in mol% and were determined by means of 1H NMR spectroscopy and elemental analysis (sulfur or nitrogen). Table 2:
  • VK Viscosity
  • the vinyl alcohol copolymers of the examples according to the invention show a very good viscosity stability over the entire period of 14 days. Testing the Redispersibility of the Films of the Vinyl Alcohol Copolymers
  • the vinyl alcohol copolymers were stabilized with an aqueous polyvinyl alcohol-stabilized (polyvinyl alcohol: Höppler viscosity 5 mPa.s, degree of hydrolysis 88 mol%) ethylene-vinyl acetate copolymer dispersion having a glass transition temperature Tg of -7 ° C and a solids content of 53 wt .-%, in an amount of 10 wt.%, Based on the total dry weight, blended.
  • polyvinyl alcohol-stabilized polyvinyl alcohol: Höppler viscosity 5 mPa.s, degree of hydrolysis 88 mol
  • ethylene-vinyl acetate copolymer dispersion having a glass transition temperature Tg of -7 ° C and a solids content of 53 wt .-%, in an amount of 10 wt.%, Based on the total dry weight, blended.
  • 0.2 mm thick films were produced from the mixtures on glass plates and these were dried at room temperature for 24 hours and then dried at 105 ° C. for 15 minutes.
  • a drop of water was applied at room temperature with a pipette to a homogeneous point of the film to be tested, and rubbed after 60 seconds exposure time of the water droplets with the fingertip at the same point until the glass plate at this Was film-free, the film fell into pieces of film or was completely preserved.
  • the redispersibility of the polymer films was evaluated by the following evaluation scheme:
  • Grade 1 Film can be readily redispersed by light rubbing or redispersed already on its own;
  • Grade 3 Film can only be redispersed by vigorous rubbing to form pieces of film

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Abstract

The invention relates to vinyl alcohol copolymerisates with a) 80 to 99 mol.% of vinyl alcohol monomer units, b) 0.5 to 10 mol.% of monomer units which are derived from vinyl esters of unbranched or branched alkyl carboxylic acids with 3 to 18 C atoms, c) 0.5 to 10 mol.% of monomer units which are derived from ethylenically unsaturated monomers with one or more functional groups selected from the group comprising a carboxylic acid group, a sulfonic acid group, a quaternized amin group, a phosphoric acid group, and the salts thereof, and d) 0 to 5 mol.% of vinyl acetate monomer units, wherein the specifications in mol.% add up to 100 mol.% in each case.

Description

Hydrophobe und kaltwasserlösliche Vinylalkohol -Copolymere  Hydrophobic and cold water soluble vinyl alcohol copolymers
Die Erfindung betrifft Vinylalkohol-Copolymere sowie Verfahren zu deren Herstellung und deren Verwendung. The invention relates to vinyl alcohol copolymers and processes for their preparation and their use.
Mit Schutzkolloiden stabilisierte Polymerisate werden vor allem in Form deren wässriger Dispersionen oder in Wasser redisper- gierbaren Polymerpulver (Dispersionspulver) in vielerlei Anwendungen, beispielsweise als Beschichtungsmittel oder Klebemit- tel, für die unterschiedlichsten Substrate, beispielsweise als zementäre Fliesenkleber, eingesetzt. Dispersionspulver sind Polymerpulver, welche durch Sprühtrocknung der entsprechenden wässrigen Polymerdispersionen zugänglich sind. In Wasser redis- pergierbare Polymerpulver werden im Allgemeinen durch Trocknung der entsprechenden wässrigen Polymerdispersionen, in Gegenwart von einer Trocknungshilfe (im Allgemeinen ein Schutzkolloid) und gegebenenfalls von Antiblockmittel und gegebenenfalls weiteren Additiven erhalten. Aufgrund des Schutzkolloidanteils wird zum einen beim Trocknungsvorgang verhindert, dass die Po- lymerteilchen irreversibel verkleben, da die Polymerteilchen von den Schutzkolloid-Teilchen umhüllt werden. Zum anderen bewirkt diese Schutzkolloid-Matrix, welche sich beim Dispergieren des Polymerpulvers in Wasser wieder auflöst, dass die Polymerpartikel wieder mit der Partikelgröße der Ausgangsdispersion in der wässrigen Redispersion vorliegen (TIZ-Fachberichte , 1985, Vol . 109 (9) , 698) . Polymers stabilized with protective colloids are mainly used in the form of their aqueous dispersions or water-redispersible polymer powders (dispersion powders) in many applications, for example as coating agents or adhesives, for a wide variety of substrates, for example as cementitious tile adhesives. Dispersion powders are polymer powders which are obtainable by spray-drying the corresponding aqueous polymer dispersions. Water-redispersible polymer powders are generally obtained by drying the corresponding aqueous polymer dispersions in the presence of a drying aid (generally a protective colloid) and, if appropriate, antiblocking agents and, if appropriate, further additives. On account of the protective colloid content, on the one hand the drying process prevents the polymer particles from irreversibly sticking because the polymer particles are enveloped by the protective colloid particles. On the other hand, this protective colloid matrix, which dissolves again when the polymer powder is dispersed in water, causes the polymer particles to be present again with the particle size of the starting dispersion in the aqueous redispersion (TIZ Fachberichte, 1985, Vol. 109 (9), 698).
Als Schutzkolloide werden in der Regel Polyvinylalkohole eingesetzt, beispielsweise in dem Verfahren, welches in der As protective colloids generally polyvinyl alcohols are used, for example in the process which in the
WO 2013/017491 AI beschrieben ist. Der Einsatz von Polyvinyl- alkohol ist erstrebenswert, weil dieser im Vergleich zu Systemen, die durch niedermolekulare Verbindungen (Emulgatoren) stabilisiert sind, selbst zur Festigkeit (beispielsweise Haftzugswerte im Fliesenkleber) beiträgt. Probleme können aber bei der Herstellung und bei der Anwendung von mit Polyvinylalkohol sta- bilisierten Polymerisaten auftreten, insbesondere wenn der Po- lyvinylalkohol einen höheren Verseifungsgrad aufweist. WO 2013/017491 AI is described. The use of polyvinyl alcohol is desirable because, in comparison to systems which are stabilized by low molecular weight compounds (emulsifiers), it itself contributes to the strength (for example adhesion values in the tile adhesive). However, problems can arise in the production and use of polyvinyl alcohol. polymerized polymers occur, in particular if the polyvinyl alcohol has a higher degree of saponification.
Zur Überwindung dieser Nachteile werden im Stand der Technik Alternativen zu Polyvinylalkohol vorgeschlagen. Die EP 1020493 AI beschreibt die Verwendung eines teilacetalisierten, wasserlöslichen Polyvinylalkohols als Trocknungshilfe bei der Herstellung eines in Wasser redispergierbaren Polymerpulvers mittels Sprühtrocknung der entsprechenden Polymerdispersion. In der WO 2012/159848 AI werden vollverseifte Vinylacetat-To overcome these disadvantages, alternatives to polyvinyl alcohol are proposed in the prior art. EP 1020493 A1 describes the use of a partially acetalized, water-soluble polyvinyl alcohol as a drying aid in the preparation of a water-redispersible polymer powder by spray-drying the corresponding polymer dispersion. In WO 2012/159848 Al fully hydrolyzed vinyl acetate
Isopropenylacetat-Copolymerisate als Schutzkolloid zur Stabilisierung einer wässrigen Polymerdispersion und als Trocknungs- hilfe zur Trocknung einer wässrigen Polymerdispersion verwendet. Die EP 477900 A2 beschreibt Dispersionspulver- Zusammensetzungen mit Polyvinylalkohol, welche zur Verbesserung der Eigenschaften von damit modifizierten Baustoffen noch vollverseifte Vinylacetat-l-Methylvinylacetat-Copolymerisate enthalten. Aus der EP 1180528 Bl sind vollverseifte oder teilverseifte Mischpolymerisate von Vinylacetat und 1-Alkylvinylester bekannt, welche gegebenenfalls noch Monomereinheiten enthalten, welche sich von Vinylestern von alpha-verzweigten Carbonsäuren ableiten. Die WO 99/16794 AI beschreibt die Herstellung von mit Schutzkolloid stabilisierten, wässrigen Polymerdispersionen, wobei als Schutzkolloide teilverseifte Copolymerisate von Vi- nylacetat und Vinylester von alpha-verzweigten Carbonsäuren mit 9 bis 11 C-Atomen eingesetzt werden. Die EP 1400557 AI beschreibt die Verwendung eines Vinylalkohol-Copolymerisats mit 1 bis 12 Mol-% Ethyleneinheiten als Trocknungshilfe bei der Herstellung von Dispersionspulvern. In der EP 1420033 Bl werden teilverseifte Vinylacetat-Ethylen-Copolymerisate als Schutzkolloid bei der Herstellung einer Copolymerdispersion und als Trocknungshilfe bei der Sprühtrocknung von wässrigen Polymerdispersionen eingesetzt. In der WO 2010/091766 AI wird in Beispiel 3 ein Copolymerisat aus 11 Mol-% Vinylsulfonat , 45 Mol-% Vinylacetat, 33 Mol-% VeovalO und 11 Mol-% Vinylalkohol als Dispergiermittel in einer Pigmentzubereitung eingesetzt. Isopropenyl acetate copolymers are used as a protective colloid for stabilizing an aqueous polymer dispersion and as a drying aid for drying an aqueous polymer dispersion. EP 477900 A2 describes disperse powder compositions with polyvinyl alcohol, which still contain fully hydrolyzed vinyl acetate-1-methylvinyl acetate copolymers in order to improve the properties of building materials modified therewith. Fully hydrolyzed or partially hydrolyzed copolymers of vinyl acetate and 1-alkylvinyl esters are known from EP 1180528 B1, which optionally also contain monomer units derived from vinyl esters of alpha-branched carboxylic acids. WO 99/16794 Al describes the preparation of stabilized with protective colloid, aqueous polymer dispersions, being used as protective colloids teilverseifte copolymers of vinyl acetate and vinyl esters of alpha-branched carboxylic acids having 9 to 11 carbon atoms. EP 1400557 Al describes the use of a vinyl alcohol copolymer with 1 to 12 mol% of ethylene units as a drying aid in the production of dispersion powders. EP 1420033 B1 uses partially hydrolysed vinyl acetate-ethylene copolymers as a protective colloid in the preparation of a copolymer dispersion and as a drying aid in the spray-drying of aqueous polymer dispersions. In WO 2010/091766 A1, a copolymer of 11 mol% vinyl sulfonate, 45 mol%, is used in Example 3. Vinyl acetate, 33 mol% VeovalO and 11 mol% of vinyl alcohol used as a dispersant in a pigment preparation.
Der Erfindung lag die Aufgabe zugrunde Vinylalkohol-Copolymeri- sate zur Verfügung zu stellen, welche hydrophoben Charakter aufweisen und auch bei hohem Hydrolysegrad (Verseifungsgrad) noch gute Lagerstabilität (Viskositätsstabilität) und gute Löslichkeit in Wasser aufweisen. Gegenstand der Erfindung sind Vinylalkohol-Copolymerisate mit a) 80 bis 99 Mol-%, vorzugsweise 85 bis 97 Mol-% Vinylalkohol- Monomereinheiten, The object of the invention was to provide vinyl alcohol copolymers which have a hydrophobic character and which, even at a high degree of hydrolysis (degree of saponification), still have good storage stability (viscosity stability) and good solubility in water. The invention provides vinyl alcohol copolymers with a) from 80 to 99 mol%, preferably from 85 to 97 mol% of vinyl alcohol monomer units,
b) 0,5 bis 10 Mol-%, vorzugsweise 1 bis 8 Mol-% Monomereinheiten, welche sich von Vinylestern von unverzweigten oder ver- zweigten Alkylcarbonsäuren mit 3 bis 18 C-Atomen ableiten, c) 0,5 bis 10 Mol-% vorzugsweise 1 bis 8 Mol-% Monomereinheiten, welche sich von ethylenisch ungesättigten Monomeren mit einer oder mehreren funktionellen Gruppen, ausgewählt aus der Gruppe umfassend Carbonsäure-Rest , Sulfonsäure-Rest , quaterni- sierter Amin-Rest, Phosphorsäure-Rest, sowie deren Salze, ableiten, und b) from 0.5 to 10 mol%, preferably from 1 to 8 mol%, of monomer units derived from vinyl esters of unbranched or branched alkylcarboxylic acids having 3 to 18 carbon atoms, c) from 0.5 to 10 mol% preferably 1 to 8 mol% of monomer units derived from ethylenically unsaturated monomers having one or more functional groups selected from the group consisting of carboxylic acid radical, sulfonic acid radical, quaternized amine radical, phosphoric acid radical, and salts thereof, derive, and
d) 0 bis 5 Mol-% vorzugsweise 1 bis 4 Mol-% Vinylacetat- Monomereinheiten, d) 0 to 5 mol%, preferably 1 to 4 mol% of vinyl acetate monomer units,
wobei sich die Angaben in Mol-% jeweils auf 100 Mol-% the data in mol% being in each case 100 mol%
aufaddieren. add up.
Als Vinylester von unverzweigten oder verzweigten Alkylcarbonsäuren mit 3 bis 18 C-Atomen bevorzugt sind Vinylpropionat , Vi- nylbutyrat, Vinyl-2-ethylhexanoat , Vinyllaurat, 1-Methylvinyl- acetat und Vinylester von α-verzweigten Monocarbonsauren mit 5 bis 13 C-Atomen, beispielsweise Vinylpivalat , VeoVa9R, VeoVal0R oder VeoVallR (Handelsnamen der Firma Hexion) . Besonders bevorzugt sind die Vinylester von α-verzweigten Monocarbonsauren mit 9 bis 10 C-Atomen (VeoVa9R und VeoVal0R) . Als Monomere c) geeignete ethylenisch ungesättigte Carbonsäuren sind beispielsweise Acrylsäure, Methacrylsäure , Crotonsäure, Itaconsäure, Fumarsäure, Maleinsäure und deren Anhydrid, Mono- ester der Fumarsäure oder der Maleinsäure, wie die Ethyl- und Isopropylester oder ungesättigte Fettsäuren mit 7 bis 25 Preferred vinyl esters of unbranched or branched alkylcarboxylic acids having 3 to 18 carbon atoms are vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate and vinyl esters of α-branched monocarboxylic acids having 5 to 13 carbon atoms, for example, vinyl pivalate, VeoVa9 R , VeoVal0 R or VeoVall R (trade name Hexion). Particularly preferred are the vinyl esters of α-branched monocarboxylic acids having 9 to 10 carbon atoms (VeoVa9 R and VeoVal0 R ). As monomers c) suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid and its anhydride, monoesters of fumaric acid or maleic acid, such as the ethyl and isopropyl esters or unsaturated fatty acids having 7 to 25
Kohlenstoffatomen, sowie die Salze der genannten Carbonsäuren. Bevorzugt sind die Acryl- und Methacrylsäure, Maleinsäure (anhy- drid) und Crotonsäure, sowie die Salze der genannten Carbonsäuren .  Carbon atoms, as well as the salts of said carboxylic acids. Preference is given to acrylic and methacrylic acid, maleic acid (anhydride) and crotonic acid, and the salts of the carboxylic acids mentioned.
Als Monomere c) geeignete Monomere mit Sulfonsäure-Gruppe sind Vinylsulfonsäure , Styrolsulfonsäure , Allylsulfonsäure , Methal- lylsulfonsäure , p-Methallyloxyphenylsulfonsäure , und Sulfonsäu- ren der allgemeinen Formel CH2=CR1-CO-X-CR2R3-R4-S03H, wobei X = O oder NH, und R1, R2, R3 gleich oder verschieden sind und dieMonomers c) suitable monomers with sulfonic acid group are vinylsulfonic acid, styrenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, p-Methallyloxyphenylsulfonsäure, and sulfonic acids of the general formula CH 2 = CR 1 -CO-X-CR 2 R 3 -R 4 - S0 3 H, where X = O or NH, and R 1 , R 2 , R 3 are identical or different and the
Bedeutung H und Ci- bis C3-Alkyl haben, und R4 Ci- bis C4-Alkylen ist, sowie die Salze der genannten Säuren. Bevorzugt werden Vinylsulfonsäure , Sulfopropyl (meth) acrylat , 2 -Acrylamido- 2 -Meth- ylpropansulfonsäure und Methallylsulfonsäure , l-Allyloxy-2-Hy- droxy- Sulfonsäure, Acrylsäure- (3 -sulfopropyl) -Ester, Methacrylsäure- (3 -sulfopropyl) -Ester, Itaconsäure-bis- (3 -sulfopropyl) - Ester, sowie die Salze der genannten Säuren. Meaning H and Ci to C 3 alkyl, and R 4 is Ci- to C 4 alkylene, and the salts of said acids. Preference is given to vinylsulfonic acid, sulfopropyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid and methallylsulfonic acid, 1-allyloxy-2-hydroxy-sulfonic acid, acrylic acid (3-sulfopropyl) ester, methacrylic acid (3-sulfopropyl ) Ester, itaconic acid bis (3-sulfopropyl) - esters, and the salts of said acids.
Als Monomere c) geeignete Monomere mit quarternären Ammonium- gruppen sind Diallyldimethylammoniumchlorid (DADMAC) , Diallyl- diethylammoniumchlorid (DADEAC) , (3 -Methacryloxy) ropyltri- methylammoniumchlorid (MPTAC) , ( 3 -Methacryloxy) ethyltrimethyl- ammoniumchlorid (METAC) , (3 -Methacrylamido) ropyltrimethyl- ammoniumchlorid (MAPTAC) . Suitable monomers with quaternary ammonium groups as monomers c) are diallyldimethylammonium chloride (DADMAC), diallyl diethylammonium chloride (DADEAC), (3-methacryloxy) ropyltrimethylammonium chloride (MPTAC), (3-methacryloxy) ethyltrimethylammonium chloride (METAC), (3 Methacrylamido) ropyltrimethylammonium chloride (MAPTAC).
Geeignete Monomere mit Phosphorsäurerest sind Vinylphosphonsäu- re und Vinylphosphonsäuredimethylester , Phosphoalkylmethacryla- te wie Phosphoethylmethacrylat und Phosphopropylmethacrylat. Am meisten bevorzugt werden als Monomere c) Vinylsulfonsäure , 2-Acrylamido-2-methylpropansulfonsäure, und deren Salze. Suitable monomers having a phosphoric acid radical are vinylphosphonic acid and dimethyl vinylphosphonate, phosphoalkylmethacrylates such as phosphoethyl methacrylate and phosphopropyl methacrylate. The most preferred monomers c) are vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and salts thereof.
Optional können noch bis zu 5 Mol-% reaktive Monomere aus der Gruppe der ethylenisch ungesättigten Monomere mit Alkoxysilan- gruppe oder Epoxygruppe oder Amingruppe oder Amidgruppe copoly merisiert werden. Bevorzugt werden Vinyltriethoxysilan, Vinyl- tris (2 -methoxyethoxy) silan, Vinyltriacetoxysilan, 3-Methacryl- oxypropyltrimethoxysilan, Glycidylmethacrylat , Diaceton-acryl- amid, N-Vinylformamid und Vinylamin. Optionally, up to 5 mol% of reactive monomers from the group of ethylenically unsaturated monomers with alkoxysilane group or epoxy group or amine group or amide group can be copolymerized. Preference is given to vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, glycidyl methacrylate, diacetone-acrylamide, N-vinylformamide and vinylamine.
Die Vinylalkohol-Copolymerisate können in bekannter Weise mittels radikalischer Polymerisation von Vinylacetat mit den unte b) und c) genannten Comonomeren und anschließender Hydrolyse der dabei erhaltenen Vinylacetat -Copolymerisate hergestellt werden. Vorzugsweise durch Substanzpolymerisation, Emulsionspo lymerisation, Suspensionspolymerisation oder besonders bevorzugt durch Polymerisation in organischen Lösungsmitteln, am meisten bevorzugt in alkoholischer Lösung mit einwertigen, aliphatischen Alkoholen mit 1 bis 4 C-Atomen oder deren Gemischen als Lösungsmittel. Geeignete Lösungsmittel sind beispielsweise Methanol, Ethanol, Propanol, Isopropanol sowie ein Ethanol-Isopropanol-Gemisch. Die Polymerisation wird unter Rückfluss bei einer Temperatur von 35°C bis 100°C durchgeführt Die radikalische Initiierung erfolgt mittels Zugabe gängiger Initiatoren. Beispiele für gängige Initiatoren sind Percarbona te wie Cyclohexylperoxydicarbonat , Perester wie t-Butylper- neodecanoat oder t-Butylperoxypivalat , Peroxid-Initiatoren wie t-Butylhydroperoxid, Diacylperoxide wie Dilauroylperoxid, und Azoinitiatoren wie Azobisisobutyronitril (AIBN) , 2,2"-Azobis- (4 -methoxy- 2 , 4 -dimethylvaleronitril) . Die Monomere können insgesamt vorgelegt werden, insgesamt zudosiert werden oder in An teilen vorgelegt werden, und der Rest nach der Initiierung der Polymerisation zudosiert werden. Der Initiator wird vorzugswei se teilweise vorgelegt und der restliche Anteil jeweils zudo- siert. Die Einstellung des Molekulargewichts kann in dem Fachmann bekannter Weise durch Polymerisation in Gegenwart von Molekulargewichtsreglern erfolgen. Die Verseifung (Umesterung, Hydrolyse) des Vinylacetat-Copoly- merisats erfolgt in an sich bekannter Weise, zum Beispiel nach dem Kneterverfahren oder im Rührkessel, vorzugsweise im Alkalischen unter Zugabe von Base. Vorzugsweise liegt das Vinyl- acetat-Copolymerisat in alkoholischer Lösung mit einwertigen, aliphatischen Alkoholen mit 1 bis 4 C-Atomen oder deren Gemischen als Lösungsmittel vor. Besonders bevorzugt werden Methanol und ein Ethanol/lsopropanol-Gemisch . Der Gehalt an Vinyl- acetat-Copolymerisat in der Lösung beträgt 20 bis 85 Gew.-%, vorzugsweise 30 bis 80 Gew.-%. Zur Initiierung der Hydrolyse werden bevorzugt alkalische Katalysatoren eingesetzt. Dies sind beispielsweise die Hydroxide, Alkoholate und Carbonate von Alkali- oder Erdalkalimetallen. Bevorzugt wird Natriumhydroxid. Die alkalischen Katalysatoren werden vorzugsweise in alkoholischer Lösung eingesetzt. Am meisten bevorzugt ist eine methano- lische Lösung von NaOH. Die eingesetzten Mengen an alkalischem Katalysator betragen im Allgemeinen 0,2 bis 20,0 Gew.-%, bezogen auf das Vinylacetat-Copolymerisat . Die Hydrolyse wird im Allgemeinen bei Temperaturen von 40°C bis 90 °C, vorzugsweise 50°C bis 85°C, im Allgemeinen in einem Rührkessel durchgeführt. Durch Zugabe der Katalysatorlösung wird die Verseifung initiiert. Bei Erreichen des gewünschten Hydrolysegrades wird die Hydrolyse abgebrochen. Vorzugsweise wird während der Versei- fungsreaktion der bei der Umesterung gebildete Ester abdestilliert. Bei der bevorzugten alkalisch katalysierten Hydrolyse erfolgt der Abbruch durch Zugabe von sauren Reagentien, wie Carbonsäuren oder Mineralsäuren, vorzugsweise Essigsäure. The vinyl alcohol copolymers can be prepared in a known manner by means of radical polymerization of vinyl acetate with the comonomers mentioned below b) and c) and subsequent hydrolysis of the resulting vinyl acetate copolymers. Preferably by bulk polymerization, Emulsionspo polymerization, suspension polymerization or more preferably by polymerization in organic solvents, most preferably in alcoholic solution with monohydric, aliphatic alcohols having 1 to 4 carbon atoms or mixtures thereof as a solvent. Suitable solvents are, for example, methanol, ethanol, propanol, isopropanol and an ethanol-isopropanol mixture. The polymerization is carried out under reflux at a temperature of 35 ° C to 100 ° C. The radical initiation takes place by adding common initiators. Examples of common initiators are percarbons such as cyclohexyl peroxydicarbonate, peresters such as t-butyl per neodecanoate or t-butyl peroxypivalate, peroxide initiators such as t-butyl hydroperoxide, diacyl peroxides such as dilauroyl peroxide, and azo initiators such as azobisisobutyronitrile (AIBN), 2,2 "azobis (AIBN). 4-methoxy-2,4-dimethylvaleronitrile.) The monomers can be initially introduced in total, be metered in in their entirety, or be charged in portions, and the remainder added after the initiation of the polymerization.The initiator is preferably initially introduced and the remaining portion each to Siert. The adjustment of the molecular weight can be carried out in a manner known to the skilled worker by polymerization in the presence of molecular weight regulators. The saponification (transesterification, hydrolysis) of the vinyl acetate copolymer takes place in a manner known per se, for example by the kneader process or in a stirred tank, preferably in the alkaline phase with the addition of base. Preferably, the vinyl acetate copolymer is in alcoholic solution with monohydric aliphatic alcohols having 1 to 4 carbon atoms or mixtures thereof as a solvent. Particularly preferred are methanol and an ethanol / isopropanol mixture. The content of vinyl acetate copolymer in the solution is 20 to 85 wt .-%, preferably 30 to 80 wt .-%. To initiate the hydrolysis, preference is given to using alkaline catalysts. These are, for example, the hydroxides, alkoxides and carbonates of alkali or alkaline earth metals. Preference is given to sodium hydroxide. The alkaline catalysts are preferably used in alcoholic solution. Most preferred is a methanolic solution of NaOH. The amounts of alkaline catalyst used are generally 0.2 to 20.0 wt .-%, based on the vinyl acetate copolymer. The hydrolysis is generally carried out at temperatures of 40 ° C to 90 ° C, preferably 50 ° C to 85 ° C, generally in a stirred tank. By adding the catalyst solution, saponification is initiated. Upon reaching the desired degree of hydrolysis, the hydrolysis is stopped. Preferably, the ester formed in the transesterification is distilled off during the Versei- tion reaction. In the preferred alkaline-catalyzed hydrolysis, the termination takes place by addition of acidic reagents, such as carboxylic acids or mineral acids, preferably acetic acid.
Nach Beendigung der Verseifungsreaktion wird das Lösungsmittel abdestilliert, beispielsweise mittels Dampfstrippen und das Vi- nylalkohol-Copolymerisat in Wasser gelöst. Das Vinylalkohol- Copolymerisat kann auch durch Fällung oder Trocknung von der flüssigen Phase abgetrennt werden und als Feststoff isoliert werden . After completion of the saponification reaction, the solvent is distilled off, for example by means of steam stripping and the vinyl alcohol copolymer dissolved in water. The vinyl alcohol Copolymer can also be separated by precipitation or drying of the liquid phase and isolated as a solid.
Die erfindungsgemäßen Vinylalkohol-Copolymerisate eignen sich als Schutzkolloide, Dispergiermittel, Trocknungshilfe und zur Verwendung in Beschichtungsmitteln, vorzugsweise zur Papierbe- schichtung in Papierstrichformulierungen. Bevorzugt wird auch deren Verwendung als Schutzkolloid bei der Herstellung von wässrigen Polymerdispersionen und deren Verwendung als Trocknungshilfe bei der Trocknung, insbesondere der Sprühtrocknung, von wässrigen Polymerdispersionen. The vinyl alcohol copolymers according to the invention are suitable as protective colloids, dispersants, drying aids and for use in coating compositions, preferably for paper coating in paper coating formulations. Also preferred is their use as a protective colloid in the preparation of aqueous polymer dispersions and their use as a drying aid in drying, in particular spray drying, of aqueous polymer dispersions.
Die nachfolgenden Beispiele dienen der weiteren Erläuterung der Erfindung : The following examples serve to further explain the invention:
Herstellung der Vinylalkohol-Copolymerisate: Beispiel 1 : Preparation of the Vinyl Alcohol Copolymers: Example 1
In einem 70 -Liter-Reaktor mit Rührer und Kühler wurden folgende Stoffe vorgelegt: The following substances were placed in a 70 liter reactor with stirrer and condenser:
Methanol 12660 g t-Butyl-Peroxypivalat (PPV, 75 %-ige Lösung) 31 gMethanol 12660 g t-butyl peroxypivalate (PPV, 75% solution) 31 g
Vinylester der VersaticsäureR10 (VeoVaR10) 177 gVinyl ester of versatic acid R 10 (VeoVa R 10) 177 g
Vinylacetat 3290 gVinyl acetate 3290 g
Vinylsulfonat (25 %-ige Lösung) 233 g Vinyl sulfonate (25% solution) 233 g
Beim Rühren unter Stickstoffatmosphare wurde die Lösung auf 60 °C aufgeheizt und 30 Minuten polymerisiert . Danach wurden folgende Stoffe zudosiert: While stirring under nitrogen atmosphere, the solution was heated to 60 ° C and polymerized for 30 minutes. Thereafter, the following substances were added:
Eine Initiatorlösung von 125 g PPV in 1880 g Methanol wurde innerhalb 240 Minuten zudosiert. Eine Monomermischung 1 mit 999 g VeoVaR10 und 18661 g Vinylacetat wurde mit einer Dosierzeit von 180 Minuten zudosiert. An initiator solution of 125 g of PPV in 1880 g of methanol was added within 240 minutes. A monomer mixture 1 with 999 g of VeoVa R 10 and 18661 g of vinyl acetate was metered in with a metering time of 180 minutes.
Die Monomerlösung 2, 1319 g einer 25 %-igen, wässrigen Lösung von Vinylsulfonat wurde mit einer Dosierzeit von 195 Minuten zudo- siert. The monomer solution 2, 1319 g of a 25% aqueous solution of vinyl sulfonate was metered in with a metering time of 195 minutes.
Nach Dosierende wurde der Reaktor verriegelt, der Druck im Reaktor auf 0,2 bar erhöht und bei 100°C eine Stunde nachpolymeri- siert. Danach wurde die Polymerlösung auf 30°C abgekühlt und mit Methanol auf eine 31 Gew.-%-ige Lösung verdünnt. Die Polymerlösung wurde ohne Rühren mit 38440 g Methanol überschichtet und danach eine Mischung aus 775 g Methanol und 657 g 46 %-iger Natronlauge zugegeben und gerührt. Nach zwei Stunden wurde die Lösung mit 342 g Essigsäure (99,8 %-ig) neutralisiert. Anschließend wur- den Methanol und die Nebenprodukte mittels Dampfstrippen entfernt. Nach dem Strippen wurde das Vinylalkohol-Copolymerisat in Wasser aufgenommen und auf eine 20 Gew.-%-ige Lösung verdünnt. After metering, the reactor was locked, the pressure in the reactor increased to 0.2 bar and post-polymerized at 100 ° C for one hour. Thereafter, the polymer solution was cooled to 30 ° C and diluted with methanol to a 31 wt .-% solution. The polymer solution was coated without stirring with 38440 g of methanol and then a mixture of 775 g of methanol and 657 g of 46% sodium hydroxide solution was added and stirred. After two hours, the solution was neutralized with 342 g of acetic acid (99.8%). Subsequently, methanol and by-products were removed by steam stripping. After stripping, the vinyl alcohol copolymer was taken up in water and diluted to a 20% by weight solution.
Bei den Beispielen 2, 3, 5 und 6 sowie dem Vergleichsbeispiel 4 wurde wie in Beispiel 1 vorgegangen, mit dem Unterschied, dass die Monomeren Vinylacetat (VAc) , VeoVa 10 und Vinylsulfonat (VS) in der Monomermischung 1 und der Monomerlösung 2 in solchen Mengen zugegeben wurden, dass jeweils die in der Tabelle 1 angegebenen Gesamtmengen erhalten wurden. Bei Beispiel 5 wurde als Mono- mer c) DADMAC (Diallyldimethylammoniumchlorid) und bei Beispiel 6 als Monomer c) AMPS (2-Acrylamido-2-methylpropansulfonsäure) statt Vinylsulfonat verwendet. In dem Vergleichsbeispiel 4 wurde keine Vinylsulfonsäure verwendet. Tabelle 1: In Examples 2, 3, 5 and 6 and Comparative Example 4, the procedure was as in Example 1, with the difference that the monomers vinyl acetate (VAc), VeoVa 10 and vinyl sulfonate (VS) in the monomer mixture 1 and the monomer solution 2 in such Quantities were added so that in each case the total amounts indicated in Table 1 were obtained. In example 5, the monomer c) used was DADMAC (diallyldimethylammonium chloride) and in example 6 as monomer c) AMPS (2-acrylamido-2-methylpropanesulfonic acid) instead of vinylsulfonate. In Comparative Example 4, no vinylsulfonic acid was used. Table 1:
Zugabemengen für die Monomere in Vorlage und Dosierung  Addition levels for the monomers in template and dosage
Figure imgf000010_0001
Figure imgf000010_0001
* DADMAC = Diallyldimethylammoniumchlorid  * DADMAC = diallyldimethylammonium chloride
**AMPS = 2-Acrylamido-2-methylpropansulfonsäure  ** AMPS = 2-acrylamido-2-methylpropanesulfonic acid
Testung der Viskositätsstabilität: Die 20 Gew.-%-igen, wässrigen Lösungen der Vinylalkohol-Viscosity Stability Testing: The 20% by Weight Aqueous Solutions of the Vinyl Alcohol
Copolymerisate aus den Beispielen 1, 2, 3 und 5 sowie dem Vergleichsbeispiel 4 wurden jeweils 1 Tag (ld) bzw. 14 Tage (14d) bei 23 °C gelagert. Nach diesen Lagerzeiten wurde jeweils die Brookfield-Viskosität bestimmt. Die Bestimmung der Brookfield- Viskositäten der wässrigen Lösungen erfolgte mit einem Copolymers of Examples 1, 2, 3 and 5 and Comparative Example 4 were each stored for 1 day (ld) and 14 days (14d) at 23 ° C. After these storage times, the Brookfield viscosity was determined in each case. The determination of the Brookfield viscosities of the aqueous solutions was carried out with a
Brookfieldviskosimeter bei 23 °C, unter Verwendung von Spindel 4 bei 20 Umdrehungen pro Minute. Die Brookfield-Viskosität wurde in mPas angegeben. In Tabelle 2 ist jeweils die Zusammensetzung der Vinylalkohol- Coolymerisate aus den Beispielen und dem Vergleichsbeispiel angegeben. Die Anteile im Copolymerisat sind jeweils in Mol-% angegeben und wurden mittels 1H NMR Spektroskopie und Elementaranalyse (Schwefel bzw. Stickstoff) ermittelt. Tabelle 2 : Brookfield viscometer at 23 ° C, using spindle 4 at 20 revolutions per minute. Brookfield viscosity was reported in mPas. Table 2 shows in each case the composition of the vinyl alcohol copolymers from the examples and the comparative example. The proportions in the copolymer are in each case given in mol% and were determined by means of 1H NMR spectroscopy and elemental analysis (sulfur or nitrogen). Table 2:
Figure imgf000011_0001
Figure imgf000011_0001
* VK = Viskosität Im Unterschied zu dem Vinylalkohol-Copolymerisat von Vergleichsbeispiel 4 zeigen die Vinylalkohol-Copolymerisate aus den erfindungsgemäßen Beispiele über den gesamten Zeitraum von 14 Tagen eine sehr gute Viskositätsstabilität. Testung der Redispergierbarkeit der Filme der Vinylalkohol- Copolymerisate :  * VK = Viscosity In contrast to the vinyl alcohol copolymer of Comparative Example 4, the vinyl alcohol copolymers of the examples according to the invention show a very good viscosity stability over the entire period of 14 days. Testing the Redispersibility of the Films of the Vinyl Alcohol Copolymers
Zur Testung der Redispergierbarkeit der Vinylalkohol- Copolymerisate wurden diese mit einer wässrigen Polyvinylalko- hol-stabilisierten ( Polyvinylalkohol : Höppler-Viskosität 5 mPa-s, Hydrolysegrad 88 Mol-%) Ethylen-Vinylacetat-Copolymer- dispersion mit einer Glasübergangstemperatur Tg von -7°C und einem Feststoffgehalt von 53 Gew.-%, in einer Menge von 10 Gew.%, bezogen auf das Gesamttrockengewicht, abgemischt. To test the redispersibility of the vinyl alcohol copolymers, they were stabilized with an aqueous polyvinyl alcohol-stabilized (polyvinyl alcohol: Höppler viscosity 5 mPa.s, degree of hydrolysis 88 mol%) ethylene-vinyl acetate copolymer dispersion having a glass transition temperature Tg of -7 ° C and a solids content of 53 wt .-%, in an amount of 10 wt.%, Based on the total dry weight, blended.
Aus den Mischungen wurden auf Glasplatten jeweils 0,2 mm dicke Filme hergestellt und diese bei Raumtemperatur 24 Stunden getrocknet und anschließend 15 Minuten bei 105°C getrocknet. Zur Überprüfung der Redispergierbarkeit wurde bei Raumtemperatur mit einer Pipette jeweils ein Wassertropfen auf eine homogene Stelle des zu prüfenden Filmes aufgebracht, und nach 60 Sekunden Einwirkzeit der Wassertropfen mit der Fingerkuppe so lange an der gleichen Stelle verrieben, bis die Glasplatte an dieser Stelle filmfrei war, der Film in Filmstücke zerfiel oder vollständig erhalten blieb. 0.2 mm thick films were produced from the mixtures on glass plates and these were dried at room temperature for 24 hours and then dried at 105 ° C. for 15 minutes. To check the redispersibility, a drop of water was applied at room temperature with a pipette to a homogeneous point of the film to be tested, and rubbed after 60 seconds exposure time of the water droplets with the fingertip at the same point until the glass plate at this Was film-free, the film fell into pieces of film or was completely preserved.
Die Redispergierbarkeit der Polymerfilme wurde mit folgendem Bewertungsschema beurteilt: The redispersibility of the polymer films was evaluated by the following evaluation scheme:
Note 1: Film lässt sich durch leichtes Reiben sofort redisper- gieren oder redispergiert bereits selbständig; Grade 1: Film can be readily redispersed by light rubbing or redispersed already on its own;
Note 2: Film lässt sich durch Reiben redispergieren, wenig re- dispergierbare Filmstücke möglich;  Note 2: Film can be redispersed by rubbing; less re-dispersible film pieces possible;
Note 3: Film lässt sich nur durch kräftiges Reiben unter Bildung von Filmstücken redispergieren;  Grade 3: Film can only be redispersed by vigorous rubbing to form pieces of film;
Note 4 : Film lässt sich auch durch längeres kräftiges Reiben nicht redispergieren, sondern zerfällt in Filmstücke.  Note 4: Film can not be redispersed by prolonged vigorous rubbing, but decays into pieces of film.
Die Ergebnisse sind in Tabelle 3 zusammengefasst .· The results are summarized in Table 3.
Tabelle 3 Table 3
Figure imgf000012_0001
Figure imgf000012_0001
Die Testergebnisse zur Redispergierbarkeit zeigen, dass mit den Abmischungen mit den erfindungsgemäßen Vinylalkohol- Copolymerisaten eine hervorragende Redispergierbarkeit erhalten wird. The redispersibility test results show that the blends with the vinyl alcohol copolymers according to the invention give excellent redispersibility.

Claims

Patentansprüche claims
1. Vinylalkohol-Copolymerisate mit 1. Vinyl alcohol copolymers with
a) 80 bis 99 Mol-% Vinylalkohol-Monomereinheiten,  a) 80 to 99 mol% of vinyl alcohol monomer units,
b) 0,5 bis 10 Mol-% Monomereinheiten, welche sich von Vi- nylestern von unverzweigten oder verzweigten Alkylcarbon- säuren mit 3 bis 18 C-Atomen ableiten,  b) from 0.5 to 10 mol% of monomer units which are derived from vinyl esters of unbranched or branched alkylcarboxylic acids having 3 to 18 carbon atoms,
c) 0,5 bis 10 Mol-% Monomereinheiten, welche sich von ethy- lenisch ungesättigten Monomeren mit einer oder mehreren funktionellen Gruppen ausgewählt aus der Gruppe umfassend Carbonsäure-Rest , Sulfonsäure-Rest , quaternisierter Amin- Rest, Phosphorsäure-Rest , sowie deren Salze, ableiten, und d) 0 bis 5 Mol-% Vinylacetat-Monomereinheiten,  c) 0.5 to 10 mol% of monomer units which are selected from ethylenically unsaturated monomers having one or more functional groups selected from the group consisting of carboxylic acid radical, sulfonic acid radical, quaternized amine radical, phosphoric acid radical, and the like Salts, and d) 0 to 5 mol% of vinyl acetate monomer units,
wobei sich die Angaben in Mol-% jeweils auf 100 Mol-% aufaddieren .  wherein the data in mol% in each case add up to 100 mol%.
2. Vinylalkohol-Copolymerisate nach Anspruch 1, dadurch gekennzeichnet, dass als Monomereinheiten b) solche enthalten sind, welche sich von einem Vinylester von a-verzweigten Monocarbonsäuren mit 9 bis 10 C-Atomen ableiten. 2. Vinyl alcohol copolymers according to claim 1, characterized in that the monomer units b) are those which are derived from a vinyl ester of a-branched monocarboxylic acids having 9 to 10 carbon atoms.
3. Vinylalkohol-Copolymerisate nach Anspruch 1 oder 2, 3. vinyl alcohol copolymers according to claim 1 or 2,
dadurch gekennzeichnet, dass als Monomereinheiten c) solche enthalten sind, welche sich von Vinylsulfonsäure , 2-Acryl- amido-2 -methylpropansulfonsäure , und deren Salzen ableiten.  characterized in that the monomer units c) are those which are derived from vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their salts.
4. Vinylalkohol-Copolymerisate nach Anspruch 1 bis 3 dadurch gekennzeichnet, dass d) 1 bis 4 Mol-% Vinylacetat- Monomereinheiten enthalten sind. 4. vinyl alcohol copolymers according to claim 1 to 3, characterized in that d) 1 to 4 mol% of vinyl acetate monomer units are included.
5. Verfahren zur Herstellung von Vinylalkohol -Copolymerisaten nach Anspruch 1 bis 4 mittels radikalischer Polymerisation von Vinylacetat mit den unter b) und c) genannten Comonome- ren und anschließender Hydrolyse der dabei erhaltenen Vinylacetat - Copolymerisate . Verfahren zur Herstellung von Vinylalkohol-Copolymerisaten nach Anspruch 5, dadurch gekennzeichnet, dass die dabei er haltenen Vinylalkohol-Copolymerisate in Wasser gelöst werden . 5. A process for preparing vinyl alcohol copolymers according to claim 1 to 4 by means of free-radical polymerization of vinyl acetate with the comonomers mentioned under b) and c) and subsequent hydrolysis of the resulting vinyl acetate copolymers. A process for the preparation of vinyl alcohol copolymers according to claim 5, characterized in that the case he held vinyl alcohol copolymers are dissolved in water.
Verfahren zur Herstellung von Vinylalkohol-Copolymerisaten nach Anspruch 5, dadurch gekennzeichnet, dass die dabei er haltenen Vinylalkohol-Copolymerisate mittels Fällung oder Trocknung als Feststoff hergestellt werden. A process for the preparation of vinyl alcohol copolymers according to claim 5, characterized in that the case he held vinyl alcohol copolymers are prepared by precipitation or drying as a solid.
Verwendung der Vinylalkohol-Copolymerisate nach Anspruch 1 bis 4 als Schutzkolloid, als Dispergiermittel, als Trocknungshilfe oder in Beschichtungsmitteln, vorzugsweise zur Papierbeschichtung in Papierstrichformulierungen. Use of the vinyl alcohol copolymers of claims 1 to 4 as a protective colloid, as a dispersant, as a drying aid or in coating compositions, preferably for paper coating in paper coating formulations.
Verwendung der Vinylalkohol-Copolymerisate nach Anspruch 1 bis 4 als Schutzkolloid bei der Herstellung von wässrigen Polymerdispersionen . 10. Verwendung der Vinylalkohol-Copolymerisate nach Anspruch 1 bis 4 als Trocknungshilfe bei der Trocknung von wässrigen Polymerdispersionen . Use of the vinyl alcohol copolymers according to Claims 1 to 4 as protective colloid in the preparation of aqueous polymer dispersions. 10. Use of the vinyl alcohol copolymers according to claim 1 to 4 as a drying aid in the drying of aqueous polymer dispersions.
PCT/EP2017/068589 2017-07-24 2017-07-24 Hydrophobic and cold water-soluble vinyl alcohol copolymers WO2019020156A1 (en)

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