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EP0000590B1 - Aqueous dispersions of vinyl chloride copolymers, process for producing them and their use - Google Patents

Aqueous dispersions of vinyl chloride copolymers, process for producing them and their use Download PDF

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Publication number
EP0000590B1
EP0000590B1 EP78100561A EP78100561A EP0000590B1 EP 0000590 B1 EP0000590 B1 EP 0000590B1 EP 78100561 A EP78100561 A EP 78100561A EP 78100561 A EP78100561 A EP 78100561A EP 0000590 B1 EP0000590 B1 EP 0000590B1
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EP
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Prior art keywords
weight
vinyl chloride
dispersion
percent
polymerization
Prior art date
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EP78100561A
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German (de)
French (fr)
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EP0000590A1 (en
Inventor
Herbert Dr. Eck
Christof Dr. Kemenater
Manfred Hannebaum
Wilhelm Kaiser
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Wacker Chemie AG
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Wacker Chemie AG
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Classifications

    • 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
    • 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
    • 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 aqueous copolymer dispersions with high proportions of vinyl chloride units in polymers which contain only polyvinyl alcohol as protective colloid, their preparation and their use.
  • Aqueous copolymer dispersions containing vinyl chloride, vinyl acetate and ethylene units are known from DE - A - 21 19 549 and 22 52 285.
  • the protective colloid / emulsifier system In order to achieve stable dispersions, it has always been necessary to take special measures with regard to the protective colloid / emulsifier system. Furthermore, it was often essential to maintain critical amounts of ionic or non-ionic emulsifiers.
  • These special colloid stabilization systems consisting of emulsifiers, protective colloids and auxiliary monomers can not only be reproducibly complied with under relatively complicated technical conditions, but sometimes also have a disadvantageous effect on various uses of the dispersions, for example in adhesives or concrete admixtures.
  • Adhesives containing auxiliary monomers or emulsifiers generally have lower water resistance.
  • the polymerization or copolymerization must under no circumstances be carried out until the monomers, vinyl chloride or vinyl acetate have been largely consumed.
  • FR-A-23 24 655 proposes dispersions of ethylene-vinyl ester-vinyl chloride-methacrylic ester copolymers which, particularly because of their specific composition, are said to give films of high saponification and weather resistance.
  • Emulsifiers and optionally monomers with strongly polar groups must also be used in the preparation of these copolymer dispersions, since otherwise, particularly when protective colloid is used alone, strongly rheopexic, strongly settling copolymer dispersions are formed, which result in sticky, cloudy spreads.
  • the object of the invention was to find copolymer dispersions which without auxiliary monomers, i. H. without monomers with strongly polar groups, e.g. of carboxylic acid, sulfonic acid, carbonamide groups or emulsifiers are to be polymerized economically to stable dispersions.
  • auxiliary monomers i. H. without monomers with strongly polar groups, e.g. of carboxylic acid, sulfonic acid, carbonamide groups or emulsifiers are to be polymerized economically to stable dispersions.
  • dispersions e.g. B. in some adhesives and paints
  • copolymer dispersions with compositions of 60 to 80 percent by weight vinyl chloride units, 8 to 20 percent by weight vinyl acetate units and 10 to 25 percent by weight ethylene units and 0.5 to 5 percent by weight of units of olefinically unsaturated N- To strive for methylolamides.
  • N-methylolacrylamide N-methylol methacrylamide
  • N-methylolallyl carbamate N-methylolallyl ether
  • Mannich bases N-methylol ester of N-methylolacrylamide
  • N-methylol methacrylamide or N-methyl olallyl carbamate examples of olefinically unsaturated N-methylolamides.
  • the dispersions are produced in heated and coolable stirred autoclaves.
  • the required amount of polyvinyl alcohol 2 to 15 percent by weight, preferably 4.5 to 12 percent by weight, based on the dispersion, with saponification numbers between 20 and 240 and 300 to 2000 monomer units in the polymer molecule, dissolved in water, is initially introduced.
  • One type of polyvinyl alcohol can be used alone, but also mixtures of different polyvinyl alcohols.
  • the polymerization is generally carried out with redox catalyst amounts between 0.01 and 3 percent by weight. In general, the entire required amount of the oxidizing catalyst portion, or its main amount, is initially charged and the polymerization is controlled by metering in the reducing agent.
  • the reducing agent can also be introduced in a known manner and the reaction with the oxidizing agent can be controlled.
  • 0.01-0.5 percent by weight, preferably 0.03-0.3 percent by weight, of reducing agent and 0.01-2 percent by weight, preferably 0.03-0.8 percent by weight, of oxidizing agent are required, the ratio of oxidizing agent depending on the process to reducing agent is 0.15 to 6.
  • the oxidizing component of the catalyst are ammonium or potassium persulfate, hydrogen peroxide and t-butyl hydroperoxide.
  • reducing agent component examples include sodium sulfite, sodium metabisulfite, zinc or sodium formaldehyde sulfoxylate.
  • H / noble metal sol catalysts are suitable as activators with the simultaneous use of small amounts of heavy metal salts. Suitable redox catalyst systems are described, inter alia, in "Fundamental Principles of Polymerization", GF D'Alelio, John Wiley & Sons Inc., New York 1952 on pages 333 ff.
  • the polyvinyl alcohol can be wholly or only partially, i.e. for example, half.
  • the monomer concentration of the liquid monomers during the monomer metering should not fall below 5 percent by weight and not exceed 20 percent by weight.
  • the ethylene pressure used varies between 20 and 150 bar, depending on the amount of ethylene to be installed.
  • the preferred pressure range is 35 to 100 bar.
  • the pressure required is strongly dependent on the viscosity and the stirring effect in the polymerization batch. The lower the viscosity and the better the material circulation in the autoclave, the less ethylene pressure is required to incorporate the desired amount of ethylene into the resin, naturally taking into account the copolymerization and solubility parameters.
  • the polymerization temperature is 10 to 85 ° C, preferably 20 to 50 ° C.
  • the remaining vinyl chloride and vinyl acetate and the 0.5 to 5 percent by weight of the olefinic unsaturated N-methylolamides, the methylol group of which may also be etherified are fed to the reaction vessel, the ethylene pressure being kept constant.
  • the reaction time depends, for example, on the heat dissipation, i.e. the stirring and cooling system, and the desired monomer concentration during the polymerization and the catalyst system.
  • the polymerization is complete when there is no longer any noticeable heat development and the vinyl acetate monomer concentration has preferably dropped below 1.5 percent by weight.
  • the polymerization is generally complete after 10 to 20 hours.
  • the reaction mixture is then polymerized by adding additional catalyst and by heating until the vinyl acetate content is below 0.5 percent by weight.
  • This generally requires catalyst amounts of 0.005-0.1 percent by weight, preferably 0.0 1 -0.04 percent by weight, based on the dispersion of the oxidizing agent and the reducing agent.
  • the dispersions according to the invention can be used in a variety of ways. They show pigment stability and are ideal as binders in emulsion paints. The relatively good flame resistance, the high binding capacity and the high saponification resistance enable the dispersions to be used as binders in hydraulically setting building materials, and they also show high adhesive strength and water resistance when used in adhesives. In combination with trivalent acid hydrolyzing metafl salts, there are favorable pot lives and water resistance. The same applies in connection with strong protonic acids, e.g. Phosphoric acid, sulfuric acid and sulfonic acids, hydrochloric acid.
  • strong protonic acids e.g. Phosphoric acid, sulfuric acid and sulfonic acids, hydrochloric acid.
  • the hardener additives are added to the dispersion in the form of their concentrated aqueous solution, in the case of salts (20 to 70% by weight), in the case of protonic acids (10 to 50% by weight) in amounts of 2 to 10% by volume.
  • the adhesive strength after long cold water storage or long boiling water storage (storage sequence No. 9 of the standard B4 / 9) is assessed according to the highest stress classes of this standard.
  • Another important parameter that describes the use properties of dispersion adhesives in combination with inorganic salts is the pot life. This should be longer than a week for use in certain adhesive application units. These conditions are sometimes exceeded considerably by the adhesives used in combination with hardener additives.
  • emulsifiers When using the dispersion according to the invention as a binder in hydraulically setting building materials and in paints, it is customary to add emulsifiers to the dispersions in amounts of 0.05 to 1.5 percent by weight.
  • Suitable nonionic emulsifiers include aliphatic ethers of polyoxyethylene, e.g. Polyoxyethylene lauryl ether, oleyl ether and alkylaryl ether, polyoxyethylene octylphenyl ether, nonylphenyl ether.
  • esters and amides such as polyoxyethylene laurate, oleate, isonate, N-polyoxyethylene lauramide, are suitable.
  • Block polymers of ethylene and propylene oxide can also be used. It is also often advantageous to use defoamers in amounts of 0.05 to 0.3 percent by weight of the active substance.
  • acidic salts or strong protonic acids are added, like both adhesives. This results in a waterproof coating.
  • acidic salts are, for example, trivalent metal salts of the main and subgroup of the periodic system of the elements with strong protonic acids.
  • Preferred hardeners in this connection are acidic phosphates, phosphoric acid, aluminum nitrate and chromium (III) nitrate. This paint off Dispersion and hardener have favorable pot lives and have a corrosion-inhibiting effect on iron with excellent adhesion.
  • the hardeners for salts are added to the dispersion in the form of their concentrated aqueous solution or the protonic acids in semi-concentrated form in amounts of 2 to 8 percent by weight.
  • An inorganic, setting material such as hydraulic cement, Portland cement, natural cement (Roman cement) or alumina cement is used as the mortar binder.
  • Excess cement additives such as gypsum, gypsum mortar, calcium phosphate, lime or other such calcium-containing binders, magnesium oxychloride, magnesite or other magnesium-containing or oxysalt compositions or other similar setting inorganic substances, such as are used as binders for unmodified concrete and mortar compositions, can optionally be added .
  • Sand, stones, concrete, crushed stone, gravel, granite, carborundum, aluminum oxide, emery, marble quarry, sawdust, slag, asbestos, mica, talc, flint stones or artificial products such as e.g. powdered ceramic materials used.
  • the latex coating compositions can e.g. (Capped) polyisocyanates, water-condensable urea formaldehyde or thermosetting melamine formaldehyde resins are added.
  • Pigments such as clays, aluminum silicates, calcium carbonate, magnesium carbonate, mica, talc, diatomaceous earth or titanium oxide, zinc phosphates, zinc chromates, iron oxide, chromium oxide can also be added.
  • alkaline-reacting and carbonate-containing products can only be added if no acidic hardeners are added.
  • paints are suitable as protective or decorative coatings for metal, wood or mineral surfaces, for example.
  • Fillers are also occasionally added when the dispersions are used in waterproof adhesives.
  • Light spar, heavy spar and other mineral substances are mentioned which do not react alkaline and do not contain a carbonate group.
  • protective colloids in particular polyvinyl alcohol, are added subsequently.
  • Preservatives, dyes, plasticizers, film-forming aids and thickeners may be mentioned as further possible additives.
  • plasticizers are butyl diglycol acetate, acetylrizinol butyl ester, diesters of oxalic acid, succinic acid, adipic acid, phthalic acid with aliphatic, branched or unbranched alcohols with 2-16 carbon atoms, such as e.g.
  • Organic solvents in the form of aromatic hydrocarbons or aliphatic hydrocarbons can also be added.
  • the dispersion obtained has a solids content of 51.8 percent by weight, a viscosity, measured in the Epprecht rheometer stage C 111 of 5900 m Pa.s and a minimum film formation temperature of 20 ° C.
  • the dispersion is frost, pigment and shear stable and has good strength values.
  • the tear strength of the film was approximately 12.5 N / mm 2 with an elongation at break of approximately 350%.
  • the defoamer consists of 94 percent by weight dimethylsiloxane with a viscosity above 20 centistokes at 25 ° C, 6 percent by weight silicon dioxide in finely divided form. With a plastic / cement factor of 0.05 and a water / cement factor of 0.48, the following values are determined:
  • Example 1 Each 275 g of a polyvinyl alcohol with a saponification number around 70 and viscosities of 13 or 6 m Pa.s are dissolved together with the catalyst in water as in Example 1. With the same process conditions as in Example 1, only with the difference that a solution of 50 g of N-methylolacrylamide in 100 cc of water / methanol (1: 1) is metered in simultaneously with the vinyl chloride - vinyl acetate metering.
  • Dispersion is obtained with a solids content of 51.7 percent by weight, a viscosity (rheometer level C 111) of 4930 m Pa.s and a minimum film-forming temperature of 15 ° C. It is frost, pigment and shear stable and has good strength values.
  • the test according to DIN 68603 as an adhesive with the addition of chromium (III) nitrate (the amount mentioned in Example 1) showed Lgf. No. 9 4.1 N / mm 2
  • the dispersion produced in this way is resistant to frost, pigment and shear, has a solids content of 53.2 percent by weight and a viscosity measured in the Epprecht rheometer (stage C 111) of 11,700 m Pa.s.
  • Aluminum nitrate (5 percent by weight of a 70% aqueous solution. The concentration information seeded: 70% generally calculated on the brine containing 9 water of crystallization).
  • polyvinyl alcohol with a saponification number of 20 is used.
  • the Höppler viscosity of the polyvinyl alcohols used is 13 or 5 m Pa.s.
  • the reaction is controlled by adding formaldehyde sodium sulfoxylate.
  • the polymerization is complete after 14 hours, the product is adjusted to pH 7 with ammonia, let down, post-polymerized and degassed.
  • the dispersion obtained has a solids content of 52.5, a viscosity (Rheometer C 111) of 2500 m Pa.s and a minimum film-forming temperature of 20 ° C. It is resistant to shear, pigment and frost and, when uncured, has a tensile strength of 18 N / mm 2 with an elongation at break of approx. 290%.
  • Chromium nitrate
  • the polymerization is carried out very analogously to Example 3, but a polyvinyl alcohol with a saponification number of 200 was used.
  • the solids content of the dispersion is 52.9 percent by weight, the viscosity (Rheometer C 111) 7300 m Pa.s and the minimum film formation temperature 25 ° C.
  • the pigment and poorly stable dispersion has a K value of 63.
  • N-methylolacrylamide 210 g
  • the solids content of the dispersion is 54.1 percent by weight, the viscosity (Rheometer C 111) 750 m Pa.s and the minimum film formation temperature 18 ° C. It is frost, pigment and shear stable.
  • the solids content of the dispersion is 53.1 percent by weight, the viscosity (rheometer C III) 2800 m Pa.s and the minimum film formation temperature 14 ° C. It is frost, pigment and shear stable.
  • the solids content of the dispersion is 53.9 percent by weight, the viscosity (Rheometer C 111) is 3400 m Pa.s and the minimum film formation temperature is 16 ° C.
  • the polymerization is carried out analogously to Example 5, but instead of 175 g of N-methylolacrylamide, 175 g of N-methylolallyl carbamate are copolymerized.
  • the product has a solids content of 51.4 percent by weight, a viscosity (Rheometer C 111) of 2100 m Pa.s and a minimum film formation temperature of 19 ° C. It is frost, pigment and shear stable.

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  • Medicinal Chemistry (AREA)
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  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Description

Die Erfindung bezieht sich auf wäßrige Copolymerdispersionen mit hohen Anteilen an Vinylchlorideinheiten in Polymeren, die lediglich Polyvinylalkohol als Schutzkolloid enthalten, deren Herstellung und deren Verwendung.The invention relates to aqueous copolymer dispersions with high proportions of vinyl chloride units in polymers which contain only polyvinyl alcohol as protective colloid, their preparation and their use.

Wäßrige Copolymerdispersionen, die Vinylchlorid-, Vinlacetat- und Äthyleneinheiten enthalten, sind aus DE - A - 21 19 549 und 22 52 285 bekannt. Zur Erzielung stabiler Dispersionen war es bisher stets notwendig, besondere Maßnahmen hinsichtlich des Schutzkolloid/Emulgatorsystems zu ergreifen. Weiterhin war es oft unabdingbar, kritische Mengen ionischer oder auch nicht-ionischer Emulgatoren einzuhalten. Diese speziellen Kolloidstabilisierungssysteme aus Emulgatoren, Schutzkolloiden und Hilfsmonomeren sind nicht nur unter relativ komplizierten technischen Bedingungen reproduzierbar einzuhalten, sondern wirken sich manchmal auch bei verschiedenen Verwendungszwecken der Dispersionen, wie beispielsweise in Klebstoffen oder Betonzusatzmitteln, nachteilig aus. Hilfsmonomere- bzw. emulgatorhaltige Klebstoffe haben im allgemeinen geringere Wasserfestigkeiten. Ältere veröffentlichte Anmeldungen, wie beispielsweise die deutsche Patentanmeldung F 15- 300 IV b/39c, beschreiben die Herstellung thermostabiler Polymerisate oder Mischpolymerisate von Vinylchlorid. Allerdings wird dort als erfindungsspezifisch herausgestellt, daß die Polymerisation bzw. Copolymerisation auf keinen Fall bis zum weitgehenden Verbrauch der Monomeren, Vinylchlorid bzw. Vinylacetat geführt werden darf.Aqueous copolymer dispersions containing vinyl chloride, vinyl acetate and ethylene units are known from DE - A - 21 19 549 and 22 52 285. In order to achieve stable dispersions, it has always been necessary to take special measures with regard to the protective colloid / emulsifier system. Furthermore, it was often essential to maintain critical amounts of ionic or non-ionic emulsifiers. These special colloid stabilization systems consisting of emulsifiers, protective colloids and auxiliary monomers can not only be reproducibly complied with under relatively complicated technical conditions, but sometimes also have a disadvantageous effect on various uses of the dispersions, for example in adhesives or concrete admixtures. Adhesives containing auxiliary monomers or emulsifiers generally have lower water resistance. Older published applications, such as the German patent application F 15-300 IV b / 39c, describe the production of thermostable polymers or copolymers of vinyl chloride. However, it is emphasized as specific to the invention that the polymerization or copolymerization must under no circumstances be carried out until the monomers, vinyl chloride or vinyl acetate have been largely consumed.

Die FR-A-23 24 655 schlägt Dispersionen aus Äthylen-Vinylester-Vinylchlorid-Methacrylester-Copolymerisaten vor, die insbesondere aufgrund ihrer spezifischen Zusammensetzung Filme hoher Verseifungs- und Wetterbeständigkeit ergeben sollen.FR-A-23 24 655 proposes dispersions of ethylene-vinyl ester-vinyl chloride-methacrylic ester copolymers which, particularly because of their specific composition, are said to give films of high saponification and weather resistance.

Auch bei der Herstellung dieser Copolymerisatdispersionen müssen Emulgatoren und gegebenenfalls Monomere mit stark polaren Gruppen verwendet werden, da andernfalls, insbesondere bei alleiniger Verwendung von Schutzkolloid, stark rheopexe, sich stark absetzende Copolymer- dispersionen entstehen, die stippige, trübe Aufstriche ergeben.Emulsifiers and optionally monomers with strongly polar groups must also be used in the preparation of these copolymer dispersions, since otherwise, particularly when protective colloid is used alone, strongly rheopexic, strongly settling copolymer dispersions are formed, which result in sticky, cloudy spreads.

Aufgabe der Erfindung war es, Copolymerdispersionen zu finden, die ohne Hilfsmonomere, d. h. ohne Monomeren mit stark polaren Gruppen, wie z.B. von Carboxyl-, Sulfonsäure, Carbonamidgruppen bzw. Emulgatoren in wirtschaftlicher Weise zu stabilen Dispersionen zu polymerisieren sind.The object of the invention was to find copolymer dispersions which without auxiliary monomers, i. H. without monomers with strongly polar groups, e.g. of carboxylic acid, sulfonic acid, carbonamide groups or emulsifiers are to be polymerized economically to stable dispersions.

Gegenstand der Erfindung sind wäßrige Vinylchlorid-Copolymer-dispersionen mit Feststoffgehalten zwischen 30 und 70 Gewichtsprozent, enthaltend Copolymere aus

  • 50-85 Gewichtsprozent Vinylchlorideinheiten
  • 5-35 Gewichtsprozent Vinylacetateinheiten und
  • 5-30 Gewichtsprozent Äthyleneinheiten,

die dadurch gekennzeichnet sind, daß die Dispersion Schutzkolloid
  • 2-15 Gewichtsprozent eines oder mehrerer Polyvinylalkohole, bezogen auf die Dispersion, mit Verseifungszahlen zwischen 20 und 240 und Polymerisationsgraden zwischen 300 und 200 enthält und daß die Copolymeren in Abwesenheit von Emulgatoren und Monomeren mit stark polaren Gruppen hergestellt worden sind.
The invention relates to aqueous vinyl chloride copolymer dispersions with solids contents between 30 and 70 percent by weight, containing copolymers
  • 50-85 weight percent vinyl chloride units
  • 5-35 weight percent vinyl acetate units and
  • 5-30 weight percent ethylene units,

which are characterized in that the dispersion protective colloid
  • Contains 2-15 percent by weight of one or more polyvinyl alcohols, based on the dispersion, with saponification numbers between 20 and 240 and degrees of polymerization between 300 and 200 and that the copolymers have been prepared in the absence of emulsifiers and monomers with strongly polar groups.

Für bestimmte Verwendungswecke der Dispersionen, z. B. in manchen Klebstoffen und Anstrichmitteln, ist es vorteilhaft, zusätzlich 0,5 bis 5 Gewichtsprozent Einheiten olefinisch ungesättigter N-Methylolamide einzupolymerisieren.For certain uses of the dispersions, e.g. B. in some adhesives and paints, it is advantageous to additionally polymerize 0.5 to 5 weight percent units of olefinically unsaturated N-methylolamides.

Die genannten Harzzusammensetzungen stellen Grenzbereiche dar, in manchen Fällen mag es von Vorteil sein, Copolymerdispersionen mit Zusammensetzungen von 60 bis 80 Gewichtsprozent Vinylchlorideinheiten, 8 bis 20 Gewichtsprozent Vinylacetateinheiten und 10 bis 25 Gewichtsprozent Äthyleneinheiten und 0,5 bis 5 Gewichtsprozent an Einheiten olefinisch ungesättigter N-Methylolamide anzustreben.The resin compositions mentioned represent limit ranges, in some cases it may be advantageous to use copolymer dispersions with compositions of 60 to 80 percent by weight vinyl chloride units, 8 to 20 percent by weight vinyl acetate units and 10 to 25 percent by weight ethylene units and 0.5 to 5 percent by weight of units of olefinically unsaturated N- To strive for methylolamides.

Olefinisch ungesättigte N-Methylolamide sind beispielsweise N-Methylolacrylamid; N-Methylolmethacrylamid; N-Methylolallylcarbamat; N-Methylolallyläther, Mannich-Basen, N-Methylolester von N-Methylolacrylamid; N-Methylolmethacrylamid oder N-Methylolallylcarbamat.Examples of olefinically unsaturated N-methylolamides are N-methylolacrylamide; N-methylol methacrylamide; N-methylolallyl carbamate; N-methylolallyl ether, Mannich bases, N-methylol ester of N-methylolacrylamide; N-methylol methacrylamide or N-methyl olallyl carbamate.

Die Dispersionen werden in beheiz- und kühlbaren Rührautoklaven hergestellt. Dazu wird die erforderliche Polyvinylalkoholmenge, 2 bis 15 Gewichtsprozent, vorzugsweise 4,5 bis 12 Gewichtsprozent, bezogen auf die Dispersion, mit Verseifungszahlen zwischen 20 und 240 und 300 bis 2000 Monomereinheiten im Polymermolekül, gelöst in Wasser, vorgelegt. Dabei kann eine Polyvinylalkoholtype allein, aber auch Gemische verschiedener Polyvinylalkohole zur Anwendung kommen. Die Polymerisation wird Imallgemeinem mit Redoxkatalysatormengen zwischen 0,01 und 3 Gewichtsprozent durchgeführt. Im allgemeinen legt man die gesamte benötigte Menge des oxidierend wirkenden Katalysatoranteils, bzw. dessen Hauptmenge, vor und steuert die Polymerisation durch Zudosierung des Reduktionsmittels. Es kann jedoch auch in bekannter Weise das Reduktionsmittel vorgelegt werden und die Reaktion mit dem Oxidationsmittel gesteuert werden. Schließlich ist auch die Steuerung der Polymerisation durch gleichzeitiges Zudosieren beider Komponenten möliche. Man benötigt 0,01-0,5 Gewichtsprozent, vorzugsweise 0,03-0,3 Gewichtsprozent an Reduktionsmittel und 0,01-2 Gewichtsprozent, vorzugsweise 0,03-0,8 Gewichtsprozent an Oxidationsmittel, wobei je nach Verfahren das Verhältnis von Oxidationsmittel zu Reduktionsmittel 0,15 bis 6 beträgt. Beispiele für die oxidierend wirkende Komponente des Katalysators sind Ammonium- oder Kaliumpersulfat, Wasserstoffperoxid und t-Butylhydroperoxid. Beispiele für die Reduktionsmittelkomponente sind Natriumsulfit, Natriummetabisulfit, Zink- oder Natriumformaldehydsulfoxylat. Ebenso eignen sich H,/Edelmetallsolkatalysatoren unter gleichzeitiger Verwendung geringer Mengen von Schwermetallsalzen als Aktivatoren. Geeignete Redoxkatalysatorsysteme sind u.a. in "Fundamental Principles of Polymerization", G.F. D'Alelio, John Wiley & Sons Inc., New York 1952 auf den Seiten 333 ff beschrieben.The dispersions are produced in heated and coolable stirred autoclaves. For this, the required amount of polyvinyl alcohol, 2 to 15 percent by weight, preferably 4.5 to 12 percent by weight, based on the dispersion, with saponification numbers between 20 and 240 and 300 to 2000 monomer units in the polymer molecule, dissolved in water, is initially introduced. One type of polyvinyl alcohol can be used alone, but also mixtures of different polyvinyl alcohols. The polymerization is generally carried out with redox catalyst amounts between 0.01 and 3 percent by weight. In general, the entire required amount of the oxidizing catalyst portion, or its main amount, is initially charged and the polymerization is controlled by metering in the reducing agent. However, the reducing agent can also be introduced in a known manner and the reaction with the oxidizing agent can be controlled. Finally, it is also possible to control the polymerization by metering in both components at the same time. 0.01-0.5 percent by weight, preferably 0.03-0.3 percent by weight, of reducing agent and 0.01-2 percent by weight, preferably 0.03-0.8 percent by weight, of oxidizing agent are required, the ratio of oxidizing agent depending on the process to reducing agent is 0.15 to 6. Examples for the oxidizing component of the catalyst are ammonium or potassium persulfate, hydrogen peroxide and t-butyl hydroperoxide. Examples of the reducing agent component are sodium sulfite, sodium metabisulfite, zinc or sodium formaldehyde sulfoxylate. Likewise, H / noble metal sol catalysts are suitable as activators with the simultaneous use of small amounts of heavy metal salts. Suitable redox catalyst systems are described, inter alia, in "Fundamental Principles of Polymerization", GF D'Alelio, John Wiley & Sons Inc., New York 1952 on pages 333 ff.

Vor Polymerisationsbeginn werden gewöhnlich 10 bis 20 Gewichtsprozent der Gesamtmenge Vinylchlorid und Vinylacetat in die Polyvinylalkohollösung eindosiert und der Polymerisationsansatz mit Äthylen gesättigt. Dabei wird der Polymerisationsansatz gerührt. Der Polyvinylalkohol kann ganz oder nur teilweise, d.h. beispielsweise zur Hälfte, vorgelegt werden. Die Monomerkonzentration der flüssigen Monomeren sill während der Monomerdosierung 5 Gewichtsprozent nicht unter- und 20 Gewichtsprozent nicht überschreiten.Before the start of polymerization, 10 to 20 percent by weight of the total amount of vinyl chloride and vinyl acetate are usually metered into the polyvinyl alcohol solution and the polymerization batch is saturated with ethylene. The polymerization batch is stirred. The polyvinyl alcohol can be wholly or only partially, i.e. for example, half. The monomer concentration of the liquid monomers during the monomer metering should not fall below 5 percent by weight and not exceed 20 percent by weight.

Der angewandte Äthylendruck schwankt, je nach der Äthylenmenge, die eingebaut werden soll, zwischen 20 und 150 bar. Der vorzugsweise benutzte Druckbereich ist 35 bis 100 bar. Der erforderliche Druck ist stark von der Viskosität und dem Rühreffekt im Polymerisationsansatz abhängig. Je niedriger die Viskosität und je besser die Stoffumwälzung im Autoklaven ist, desto weniger Athylendruck ist zum Einbau der gewünschten Menge Äthylen is das Harz, natürlich unter Berücksichtigung der Copolymerisations- und Löslichkeitsparameter, erforderlich.The ethylene pressure used varies between 20 and 150 bar, depending on the amount of ethylene to be installed. The preferred pressure range is 35 to 100 bar. The pressure required is strongly dependent on the viscosity and the stirring effect in the polymerization batch. The lower the viscosity and the better the material circulation in the autoclave, the less ethylene pressure is required to incorporate the desired amount of ethylene into the resin, naturally taking into account the copolymerization and solubility parameters.

Die Polymerisationstemperatur beträgt 10 bis 85°C, vorzugsweise 20 bis 50°C. Im Verlauf der Reaktion wird das restliche Vinylchlorid und Vinylacetat sowie die 0,5 bis 5 Gewichtsprozent der olefinischen ungesättigten N-Methylolamide, deren Methylolgruppe auch veräthert sein kann, dem Reaktionsgefäß zugeführt, wobei der Äthylendruck konstant gehalten wird.The polymerization temperature is 10 to 85 ° C, preferably 20 to 50 ° C. In the course of the reaction, the remaining vinyl chloride and vinyl acetate and the 0.5 to 5 percent by weight of the olefinic unsaturated N-methylolamides, the methylol group of which may also be etherified, are fed to the reaction vessel, the ethylene pressure being kept constant.

Die Reaktionsdauer hängt beispielsweise von der Wärmeabführung, d.h. dem Rühr- und Kühlsystem, und der gewünschten Monomerkonzentration während der Polymerisation sowie dem Katalysatorsystem ab. Im allgemeinen ist die Polymerisation beendet, wenn keine merkliche Wärmeentwicklung mehr feststellbar ist und die Vinylacetatmonomerkonzentration vorzugsweise unter 1,5 Gewichtsprozent abgesunken ist.The reaction time depends, for example, on the heat dissipation, i.e. the stirring and cooling system, and the desired monomer concentration during the polymerization and the catalyst system. In general, the polymerization is complete when there is no longer any noticeable heat development and the vinyl acetate monomer concentration has preferably dropped below 1.5 percent by weight.

Nach 10 bis 20 Stunden ist die Polymerisation Im allgemeinen beendet. Danach wird das Reaktionsgemisch durch Zugabe von zusätzlichem Katalysator und durch Erwärmen nachpolymerisiert bis der Vinylacetatgehalt unter 0,5 Gewichtsprozent liegt. Dazu sind im allgemeinen Katalysatormengen von 0,005-0,1 Gewichtsprozent, vorzugsweise 0,0 1 -0,04 Gewichtsprozent, bezogen auf die Dispersion des Oxidationsmittels und des Reduktionsmittels, notwendig.The polymerization is generally complete after 10 to 20 hours. The reaction mixture is then polymerized by adding additional catalyst and by heating until the vinyl acetate content is below 0.5 percent by weight. This generally requires catalyst amounts of 0.005-0.1 percent by weight, preferably 0.0 1 -0.04 percent by weight, based on the dispersion of the oxidizing agent and the reducing agent.

Die erfindungsgemaßen Dispersionen können vielseitig verwendet werden. Sie zeigen Pigmentstabilität und eignen sich hervorragend als Bindemittel in Dispersionsfarben. Die verhältnismäßig gute Flammfestigkeit, das hohe Bindevermögen und die hohe Verseifungsfestigkeit ermöglichen den Einsatz der Dispersionen als Bindemittel in hydraulisch abbindenden Baustoffen, außerdem zeigen sie hohe Klebefestigkeit und Wasserfestigkeiten bei der Verwendung in Klebemitteln. In Verbindung mit dreiwertigen sauer hydrolysierenden Metaflsalzen ergeben sich günstige Topfzeiten und Wasserfestigkeiten. Das gleiche gilt auch in Verbindung mit starken Protonsäuren, wie z.B. Phosphorsäure,, Schwefelsäure und Sulfonsäuren, Salzsäure. Die Härterzusätze werden bei Salzen in Form ihrer konzentrierten wäßrigen Lösung, bei Salzen (20 bis 70 Gew.-%ig), bei Protonsäuren (10 bis 50 Gew.-%ig) in Mengen von 2 bis 10 Volumenprozent zur Dispersion gegeben.The dispersions according to the invention can be used in a variety of ways. They show pigment stability and are ideal as binders in emulsion paints. The relatively good flame resistance, the high binding capacity and the high saponification resistance enable the dispersions to be used as binders in hydraulically setting building materials, and they also show high adhesive strength and water resistance when used in adhesives. In combination with trivalent acid hydrolyzing metafl salts, there are favorable pot lives and water resistance. The same applies in connection with strong protonic acids, e.g. Phosphoric acid, sulfuric acid and sulfonic acids, hydrochloric acid. In the case of salts, the hardener additives are added to the dispersion in the form of their concentrated aqueous solution, in the case of salts (20 to 70% by weight), in the case of protonic acids (10 to 50% by weight) in amounts of 2 to 10% by volume.

Die Eigenschaften der Dispersionen bei der Verwendung in Holzverklebungen unter Zusatz von dreiwertigen anorganischen Salzen, wie beispielsweise Chromnitrat bzw. Aluminiumnitrat, wurden entsprechend der DIN 68603 geprüft. Nach dem höchsten Beanspruchungsklassen dieser Norm wird die Klebfestigkeit nach längerer Kaltwasserlagerung bzw. längerer Kochendwasserlagerung (Lagerungsfolge Nr. 9 der Norm = B4/9) beurteilt. Eine weitere wichtige Größe, die die Verwendungseigenschaften von Dispersionsklebstoffen in Kombination mit anorganischen Salzen beschreibt, ist die Topfzeit. Diese soll für den Einsatz in bestimmten Klebstoffauftragsaggregaten länger als eine Woche sein. Diese Bedingungen werden von den in Kombination mit Härterzusätzen verwendeten Klebstoffen teilweise sogar erheblich überschritten.The properties of the dispersions when used in wood bonds with the addition of trivalent inorganic salts, such as chromium nitrate or aluminum nitrate, were tested in accordance with DIN 68603. The adhesive strength after long cold water storage or long boiling water storage (storage sequence No. 9 of the standard = B4 / 9) is assessed according to the highest stress classes of this standard. Another important parameter that describes the use properties of dispersion adhesives in combination with inorganic salts is the pot life. This should be longer than a week for use in certain adhesive application units. These conditions are sometimes exceeded considerably by the adhesives used in combination with hardener additives.

Bei der Anwendung der erfindungsgemäßen Dispersion als Bindemittel in hydraulisch abbindenden Baustoffen und in Anstrichmitteln ist es üblich, Emulgatoren in Mengen von 0,05 bis 1,5 Gewichtsprozent den Dispersionen beizumischen. Geeignete nichtionische Emulgatoren sind u.a. aliphatische Äther von Polyoxyäthylen, wie z.B. Polyoxyäthylenlauryläther, -oleyläther und -alkylaryläther, Polyoxyäthylenoctylphenyläther, -nonylphenyläther. Außerdem eignen sich Ester und Amide, wie beispielsweise Polyoxyäthylen-laurat, -oleat, -isononat, N-Polyoxyäthylenlauramid. Auch Blockpolymere des Äthylen- und Propylenoxids können mitverwendet werden. Ebenso ist es häufig vorteilhaft, Entschäumer in Mengen von 0,05 bis 0,3 Gewichtsprozent der Wirksubstanz mitzuverwenden.When using the dispersion according to the invention as a binder in hydraulically setting building materials and in paints, it is customary to add emulsifiers to the dispersions in amounts of 0.05 to 1.5 percent by weight. Suitable nonionic emulsifiers include aliphatic ethers of polyoxyethylene, e.g. Polyoxyethylene lauryl ether, oleyl ether and alkylaryl ether, polyoxyethylene octylphenyl ether, nonylphenyl ether. In addition, esters and amides, such as polyoxyethylene laurate, oleate, isonate, N-polyoxyethylene lauramide, are suitable. Block polymers of ethylene and propylene oxide can also be used. It is also often advantageous to use defoamers in amounts of 0.05 to 0.3 percent by weight of the active substance.

Bei Verwendung der Dispersionen als Anstrichmittel werden wie beiden Klebstoffen saure Salze oder auch starke Protonsäuren zugesetzt. Dadurch resultiert ein wasserfester Anstrich. Solch saure Salze sind beispielsweise dreiwertige Metallsalze der Haupt- und Nebengruppe des periodischen Systems der Elemente mit starken Protonsäuren. Bevorzugte Härter in diesem Zusammenhang sind saure Phosphate, Phosphorsäure, Aluminiumnitrat und Chrom(III)nitrat. Diese Anstrichmittel aus Dispersion und Härter weisen günstige Topfzeiten auf und wirken z.B. auf Eisen korrosionshemmend bei ausgezeichneter Haftung. Auch hier werden die Härter bei Salzen in Form ihrer konzentrierten wäßrigen Lösung bzw. die Protonsäuren in halbkonzentrierter Form in Mengen von 2 bis 8 Gewichtsprozent zur Dispersion gegeben.When using the dispersions as paints, acidic salts or strong protonic acids are added, like both adhesives. This results in a waterproof coating. Such acidic salts are, for example, trivalent metal salts of the main and subgroup of the periodic system of the elements with strong protonic acids. Preferred hardeners in this connection are acidic phosphates, phosphoric acid, aluminum nitrate and chromium (III) nitrate. This paint off Dispersion and hardener have favorable pot lives and have a corrosion-inhibiting effect on iron with excellent adhesion. Here too, the hardeners for salts are added to the dispersion in the form of their concentrated aqueous solution or the protonic acids in semi-concentrated form in amounts of 2 to 8 percent by weight.

Als Mörtelbindemittel wir ein anorganisch, abbindendes Material wie hydraulischer Zement, Portlandzement, Naturzement (Romanzement) oder Tonerdezement verwendet. Überliche Zementzusätze wie Gips, Gipsmörtel, Calciumphosphat, Kalk oder andere derartige calciumhaltige Bindemittel, Magnesiumoxychlorid, Magnesit oder andere magnesiumhaltige oder Oxysalzmassen oder andere ähnliche abbindende anorganische Substanzen, wie sie als Bindemittel für nicht-modifizierte Beton- und Mörtelmassen verwendet werden, können gegebenenfalls zugesetzt werden. Als übliche Zuschlagsmaterialien werden Sand, Steine, Beton, Schotter, Kies, Granit, Carborundum, Aluminiumoxid, Schmirgel, Marmorbruch, Sägespäne, Schlacke, Asbest, Glimmer, Talkum, Flintsteine oder Kunstprodukte wie z.B. gepulverte Keramikmaterialien eingesetzt.An inorganic, setting material such as hydraulic cement, Portland cement, natural cement (Roman cement) or alumina cement is used as the mortar binder. Excess cement additives such as gypsum, gypsum mortar, calcium phosphate, lime or other such calcium-containing binders, magnesium oxychloride, magnesite or other magnesium-containing or oxysalt compositions or other similar setting inorganic substances, such as are used as binders for unmodified concrete and mortar compositions, can optionally be added . Sand, stones, concrete, crushed stone, gravel, granite, carborundum, aluminum oxide, emery, marble quarry, sawdust, slag, asbestos, mica, talc, flint stones or artificial products such as e.g. powdered ceramic materials used.

Bei der Verwendung der Dispersionen in Anstrichsmitteln kann den Latexüberzugsmassen z.B. (verkappte) Polyisocyanate, wasserkondensierbare Harnstofformaldehyde- oder wärmehärtbare Melaminformaldehydharze zugesetzt werden. Ebenso können Pigmente wie beispielsweise Tone, Aluminiumsilicate, Calciumcarbonat, Magnesiumcarbonat, Glimmer, Talkum, Diatomeenerde oder Titanoxid, Zinkphosphate, Zinkchromate, Eisenoxid, Chromoxid zugesetzt werden. Dabei können alkalisch reagierende und carbonathaltige Produkte selbstverständlich nur zugeschlagen werden, wenn keine sauren Härter zugesetzt werden. Viele andere, dem Fachman bekannte Verarbeitungshilfsstoffe wie Verdickungsmittel, Koaleszenzhilfsmittel, Füllstoffe und Verstärkungsmittel, Weichmacher, Verlaufmittel und Streckmittel, Antioxidantien und Stabilisatoren, Fungizide können ebenso mitverwendet werden. Die Anstrichmittel eignen sich als Schutz- oder Dekorationsüberzüge von beispielsweise Metall, Holz oder mineralischen Oberflächen.When using the dispersions in paints, the latex coating compositions can e.g. (Capped) polyisocyanates, water-condensable urea formaldehyde or thermosetting melamine formaldehyde resins are added. Pigments such as clays, aluminum silicates, calcium carbonate, magnesium carbonate, mica, talc, diatomaceous earth or titanium oxide, zinc phosphates, zinc chromates, iron oxide, chromium oxide can also be added. Of course, alkaline-reacting and carbonate-containing products can only be added if no acidic hardeners are added. Many other processing aids known to those skilled in the art, such as thickeners, coalescing aids, fillers and reinforcing agents, plasticizers, leveling agents and extenders, antioxidants and stabilizers, and fungicides can also be used. The paints are suitable as protective or decorative coatings for metal, wood or mineral surfaces, for example.

Auch bei der Verwendung der Dispersionen in wasserfesten Klebstoffen werden gelegentlich Füllstoffe zugegeben. Genannt seien Leichtspat, Schwerspat und andere mineralische Stoffe, die nicht alkalisch reagieren und keine Carbonatgruppe enthalten. In gewissen Fällen werden Schutzkolloide, insbesondere Polyvinylalkohol nachträglich zugegeben. Als weitere mögliche Zusatzstoffe seien Konservierungsmittel, Farbstoffe, Weichmacher, Verfilmungshilfsmittel und Verdickungsmittel erwähnt. Als Weichmacher seien beispielsweise Butyldiglycolacetat, Acetylrizinolbutylester, Diester der Oxalsäure, Bernsteinsäure, Adipinsäure, Phthalsäure mit aliphatischen, verzweigten oder unverzweigten Alkoholen mit 2-16 Kohlenstoffatomen, wie z.B. Oxalsäuredibutylester, Bernsteinsäuredibutylester, Diisobutylphthalat, Dioctylphthalat, Diisotridecylphthalat sowie Glykole, wie z.B. Äthylenglykol, Hexamethylenglykol, ferner Benzylalkohol und Ester-Alkoholgemische, Diphenoxyphenylformal. Ebenso können organische Lösungsmittel in Form von aromatischen Kohlenwasserstoffen bzw. aliphatischen Kohlenwasserstoffen zugesetzt werden.Fillers are also occasionally added when the dispersions are used in waterproof adhesives. Light spar, heavy spar and other mineral substances are mentioned which do not react alkaline and do not contain a carbonate group. In certain cases, protective colloids, in particular polyvinyl alcohol, are added subsequently. Preservatives, dyes, plasticizers, film-forming aids and thickeners may be mentioned as further possible additives. Examples of plasticizers are butyl diglycol acetate, acetylrizinol butyl ester, diesters of oxalic acid, succinic acid, adipic acid, phthalic acid with aliphatic, branched or unbranched alcohols with 2-16 carbon atoms, such as e.g. Oxalic acid dibutyl ester, succinic acid dibutyl ester, diisobutyl phthalate, dioctyl phthalate, diisotridecyl phthalate and glycols, such as e.g. Ethylene glycol, hexamethylene glycol, also benzyl alcohol and ester-alcohol mixtures, diphenoxyphenyl formal. Organic solvents in the form of aromatic hydrocarbons or aliphatic hydrocarbons can also be added.

Beispiel 1example 1

400 g Polyvinylalkohol mit der Verseifungszahl 60 und einer Höpplerviskosität von 13 m Pa.s (einer 4 Gew.-%igen wäßrigen Lösung bei 20°C) werden zusammen mit 40 g Kaliumpersulfat in 2,4 I Wasser gelöst. Unter Rühren und bei einer Polymerisationstemperatur von 30°C wird eine Mischung von 4,2 kg Vinylchlorid und 0,8 kg Vinylacetat kontinuierlich zudosiert. Während der gesamten Polymerisationszeit wird der Äthylendruck bei 50 bar konstant gehalten. Die Polymerisation wurde durch Zugabe von einer 1 %igen Natriumformaldehydsulfoxylatlösung gestartet und durch weiteren Zusatz von Reduktionsmittel gesteuert. Insgesamt war der Verbrauch an Reduktionsmittel der genannten Konzentration 770 g (7,7 g Reduktionsmittel 100 %ig). Nach 15 Stunden war die Polymerisation beendet. In der Nachpolymerisationsphase wurden erneut.

Figure imgb0001
400 g of polyvinyl alcohol with a saponification number of 60 and a Höppler viscosity of 13 m Pa.s (a 4% by weight aqueous solution at 20 ° C.) are dissolved in 2.4 l of water together with 40 g of potassium persulfate. A mixture of 4.2 kg of vinyl chloride and 0.8 kg of vinyl acetate is metered in continuously with stirring and at a polymerization temperature of 30 ° C. The ethylene pressure is kept constant at 50 bar during the entire polymerization time. The polymerization was started by adding a 1% sodium formaldehyde sulfoxylate solution and controlled by further addition of reducing agent. In total, the consumption of reducing agent of the concentration mentioned was 770 g (7.7 g of reducing agent 100%). The polymerization was complete after 15 hours. In the post-polymerization phase were again.
Figure imgb0001

Die erhaltene Dispersion hat einen Feststoffgehalt von 51,8 Gewichtsprozent, eine Viskosität, gemessen im Epprecht Rheometer Stufe C 111 von 5900 m Pa.s und eine Mindestfilmbildungstemperatur von 20°C. Die Dispersion ist frost-, pigment- und scherstabil und hat gute Festigkeitswerte. Nach Zugabe von 2 Gewichtsprozent Butyldiglycolacetat zur Dispersion betrug die Reißfestigkeit des Filmes ca. 12,5 N/mm2 bei einer Bruchdehnung von ca. 350%. Die Prüfung von Holzverklebungen mit einem Gemisch der Dispersion mit 5 Gewichtsprozent einer 40 Gew.-%igen, hergestellt aus 70 Gewichtsteilen des kristallwasserhaltigen (9 H20)-Salzes in 30 Gewichtsteilen Wasser, wäßrigen Lösung von Chrom(III)nitrat ergab nach der DIN 68603 die folgenden Klebfestigkeiten:

Figure imgb0002
The dispersion obtained has a solids content of 51.8 percent by weight, a viscosity, measured in the Epprecht rheometer stage C 111 of 5900 m Pa.s and a minimum film formation temperature of 20 ° C. The dispersion is frost, pigment and shear stable and has good strength values. After adding 2 percent by weight of butyl diglycol acetate to the dispersion, the tear strength of the film was approximately 12.5 N / mm 2 with an elongation at break of approximately 350%. The examination of wood bonds with a mixture of the dispersion with 5 percent by weight of a 40 wt .-%, made from 70 parts by weight of the water (9 H 2 0) salt in 30 parts by weight of water, aqueous solution of chromium (III) nitrate showed that DIN 68603 the following adhesive strengths:
Figure imgb0002

Bei der Verwendung der Dispersion als Betonzusatzmittel unter Mitverwendung eines üblichen Entschäumers in einer Menge von 0,1 Gewichtsprozent, bezogen auf die Dispersion, ergeben sich die in der Tabelle aufgeführten Werte. Der Entschäumer besteht aus 94 Gewichtsprozent Dimethylsiloxan mit einer Viscosität über 20 Centistokes bei 25°C, 6 Gewichtsprozent Siliciumdioxid in feinverteilter Form. Bei einem Kunststoff/Zementfaktor von 0,05 und einem Wasser/Zementfaktor von 0,48 werden die folgenden Werte ermittelt:

Figure imgb0003
When the dispersion is used as a concrete additive using a conventional defoamer in an amount of 0.1 percent by weight, based on the dispersion, the values listed in the table are obtained. The defoamer consists of 94 percent by weight dimethylsiloxane with a viscosity above 20 centistokes at 25 ° C, 6 percent by weight silicon dioxide in finely divided form. With a plastic / cement factor of 0.05 and a water / cement factor of 0.48, the following values are determined:
Figure imgb0003

Beispiel 2Example 2

Je 275 g eines Polyvinylalkohols mit einer Verseifungszahl um 70 und Viskositäten von 13 bzw. 6 m Pa.s werden zusammen mit dem Katalysator wie in Beispiel 1 im Wasser gelöst. Bei gleichen Verfahrensbedingungen wie in Beispiel 1, lediglich mit dem Unterschied, daß gleichzeitig mit der Vinylchlorid - Vinylacetatdosierung eine Lösung von 50 g N-Methylolacrylamid in 100 ccm Wasser/Methanol (1:1) zudosiert werden.Each 275 g of a polyvinyl alcohol with a saponification number around 70 and viscosities of 13 or 6 m Pa.s are dissolved together with the catalyst in water as in Example 1. With the same process conditions as in Example 1, only with the difference that a solution of 50 g of N-methylolacrylamide in 100 cc of water / methanol (1: 1) is metered in simultaneously with the vinyl chloride - vinyl acetate metering.

Man erhält Dispersion mit einem Feststoffgehalt von 51,7 Gewichtsprozent, einer Viskosität (Rheometer Stufe C 111) von 4930 m Pa.s und einer Mindestfilmbildungstemperatur von 15°C. Sie ist frost-, pigment- und scherstabil und hat gute Festigkeitswerte. die Prüfung nach DIN 68603 als Klebstoff unter Zusatz von Chrom(III)nitrat (der in Beispiel 1 genannten Menge) ergab
Lgf. Nr. 9 4,1 N/mm2 Dispersion is obtained with a solids content of 51.7 percent by weight, a viscosity (rheometer level C 111) of 4930 m Pa.s and a minimum film-forming temperature of 15 ° C. It is frost, pigment and shear stable and has good strength values. the test according to DIN 68603 as an adhesive with the addition of chromium (III) nitrate (the amount mentioned in Example 1) showed
Lgf. No. 9 4.1 N / mm 2

Beispiel 3Example 3

Bei Verfahrensbedingungen wie in Beispiel 2, jedoch unter Verwendung der doppelten Menge N-Methylolacrylamid und 440 g einer Mischung von Polyvinylalkohol mit einer Verseifungszahl von 140. 140 g davon weisen eine Höpplerviskosität von 13 und 300 g von 5 m Pa.s. auf.Under process conditions as in Example 2, but using twice the amount of N-methylolacrylamide and 440 g of a mixture of polyvinyl alcohol with a saponification number of 140. 140 g thereof have a Höppler viscosity of 13 and 300 g of 5 m Pa.s. on.

Die so hergestellte Dispersion ist frost-, pigment- und scherstabil, hat einen Festgehalt von 53,2 Gewichtsprozent und eine Viskosität gemessen im Epprecht Rheometer (Stufe C 111) von 11700 m Pa.s.The dispersion produced in this way is resistant to frost, pigment and shear, has a solids content of 53.2 percent by weight and a viscosity measured in the Epprecht rheometer (stage C 111) of 11,700 m Pa.s.

Folgende Werte wurden bei der Prüfung der Klebfestigkeit nach DIN 68603 erhalten. Bei Zusatz von Chromnitrat (5 Gewichtsprozent der Dispersion einer 70 %igen wäßrigen Lösung)

Figure imgb0004
The following values were obtained when testing the adhesive strength according to DIN 68603. With the addition of chromium nitrate (5% by weight of the dispersion of a 70% aqueous solution)
Figure imgb0004

Aluminiumnitrat (5 Gewichtsprozent einer 70 %igen wäßrigen Lösung. Die Konzentrationsangabe besaat: 70 %ia berechnet auf das kristallwasserhaltiae Sole mit 9 Kristallwasser).

Figure imgb0005
Aluminum nitrate (5 percent by weight of a 70% aqueous solution. The concentration information seeded: 70% generally calculated on the brine containing 9 water of crystallization).
Figure imgb0005

Beispiel 4Example 4

Bei sonst gleicher Verfahrensweise wie in Beispiel 3 wird unter Verwendung von Polyvinylalkohol mit einer Verseifungszahl von 20 gearbeitet. Die Höpplerviskositäten der eingesetzten Polyvinylalkohole ist 13 bzw. 5 m Pa.s.If the procedure is otherwise the same as in Example 3, polyvinyl alcohol with a saponification number of 20 is used. The Höppler viscosity of the polyvinyl alcohols used is 13 or 5 m Pa.s.

Die Prüfung der Klebfestigkeit nach DIN 68603 ergab unter Verwendung von Chrom(III)nitrat (in der in Beispiel 1 qenannten Menqe)

Figure imgb0006
The test of the adhesive strength according to DIN 68603 showed using chromium (III) nitrate (in the menqe named in Example 1)
Figure imgb0006

Beispiel 5Example 5

440 g eines Polyvinylalkohols mit einer Verseifungszahl von 140 und einer Höpplerviskosität von 5 m Pa.s werden zusammen mit 40 g Kaliumpersulfat in Wasser gelöst und auf ca. 37°C erwämt. Nun werden eine Mischung von 4,2 kg Vinylchlorid und 0,8 kg Vinylacetat innerhalb 5 Stunden kontinuierlich eindosiert. Während dieser Zeit werden der Äthylendruck auf 50 bar gehalten und 175 g N-Methylolacrylamid in wäßrig/methanolischer Lösung eindosiert.440 g of a polyvinyl alcohol with a saponification number of 140 and a Höppler viscosity of 5 m Pa.s are dissolved together with 40 g of potassium persulfate in water and heated to approx. 37 ° C. Now a mixture of 4.2 kg of vinyl chloride and 0.8 kg of vinyl acetate are continuous within 5 hours dosed. During this time, the ethylene pressure is kept at 50 bar and 175 g of N-methylolacrylamide are metered into an aqueous / methanolic solution.

Die Reaktion wird durch Zugabe von Formaldehydnatriumsulfoxylat gesteuert. Nach 14 Stunden ist die Polymerisation abgeschlossen, das Produkt wird mit Ammoniak auf pH 7 eingestellt, entspannt, nachpolymerisiert und entgast.The reaction is controlled by adding formaldehyde sodium sulfoxylate. The polymerization is complete after 14 hours, the product is adjusted to pH 7 with ammonia, let down, post-polymerized and degassed.

Die erhaltene Dispersion hat einen Festgehalt von 52,5, eine Viskosität (Rheometer C 111) von 2500 m Pa.s und eine Mindestfilmbildungstemperatur von 20°C. Sie ist scher-, pigment- und froststabil und weist im unvermetzten Zustand eine Reißfestigkeit von 18 N/mm2 bei einer Bruchdehnung von ca. 290% auf.The dispersion obtained has a solids content of 52.5, a viscosity (Rheometer C 111) of 2500 m Pa.s and a minimum film-forming temperature of 20 ° C. It is resistant to shear, pigment and frost and, when uncured, has a tensile strength of 18 N / mm 2 with an elongation at break of approx. 290%.

Die Prüfung nach DIN 68603 ergibt bei Verwendung von Chromnitrat

Figure imgb0007
Aluminiumnitrat:

  • Lgf. Nr. 9 4,8 N/mm2
The test according to DIN 68603 shows when using chromium nitrate
Figure imgb0007
 Aluminum nitrate:
  • Lgf. No. 9 4.8 N / mm 2

Ein nachträgliche Zugabe von 1 Gewichtsprozent Polyvinylalkohol auf Dispersion verändert diese Werte unwesentlich.A subsequent addition of 1 percent by weight of polyvinyl alcohol on dispersion changes these values insignificantly.

Chromnitrat:

Figure imgb0008
Chromium nitrate:
Figure imgb0008

Aluminiumnitrat:

  • Lgf. Nr. 9 4,9 N/mm2
Aluminum nitrate:
  • Lgf. No. 9 4.9 N / mm 2

Die Topfzeit beträgt über 20 Tage.

  • 5% 25 Gew.-%iger Phosphorsäure:
    • Lgf. Nr. 9 4,5 N/mm 2
    • Topfzeit: über
    • 14 Tage
  • 5% 25 Gew.-%iger Schwefelsäure:
    • Lgf. Nr. 9 4,0 N/mm2
    • Topfzeit: über
    • 14 Tage
The pot life is over 20 days.
  • 5% 25% by weight phosphoric acid:
    • Lgf. No. 9 4.5 N / m m 2
    • Pot life: about
    • 14 days
  • 5% 25% by weight sulfuric acid:
    • Lgf. No. 9 4.0 N / mm 2
    • Pot life: about
    • 14 days

Beispiel 6Example 6

Die Durchführung der Polymerisation geschieht ganz analog von Beispiel 3, jedoch wurde ein Polyvinylalkohol mit der Verseifungszahl 200 eingesetzt.The polymerization is carried out very analogously to Example 3, but a polyvinyl alcohol with a saponification number of 200 was used.

Der Festgehalt der Dispersion beträgt 52,9 Gewichtsprozent, die Viskosität (Rheometer C 111) 7300 m Pa.s und die Mindestfilmbildungstemperatur 25°C. Die pigment- und schwerstabile Dispersion hat einen K-Wert von 63.The solids content of the dispersion is 52.9 percent by weight, the viscosity (Rheometer C 111) 7300 m Pa.s and the minimum film formation temperature 25 ° C. The pigment and poorly stable dispersion has a K value of 63.

Die Prüfung nach DIN 68603 ergab bei Zusatz von Chromnitrat (in der Beispiel 1 genannten Menge)

Figure imgb0009
The test according to DIN 68603 resulted in the addition of chromium nitrate (amount mentioned in example 1)
Figure imgb0009

Aluminiumnitrat:Aluminum nitrate: (Menge wie in Beispiel 3)(Amount as in example 3)

Figure imgb0010
Figure imgb0010

Beispiel 7Example 7

Im Vergleich zum Versuch 5 werden folgende Änderungen durchgeführt:

  • 1) Reaktionstemperatur: 30°C
The following changes are made compared to experiment 5:
  • 1) Reaction temperature: 30 ° C

) N-Methylolacrylamid: 210 g) N-methylolacrylamide: 210 g

Der Festgehalt der Dispersion beträgt 54,1 Gewichtsprozent, die Viskosität (Rheometer C 111) 750 m Pa.s und die Mindestfilmbildungstemperatur 18°C. Sie ist frost-, pigment- und scherstabil.The solids content of the dispersion is 54.1 percent by weight, the viscosity (Rheometer C 111) 750 m Pa.s and the minimum film formation temperature 18 ° C. It is frost, pigment and shear stable.

Die Prüfung nach DIN 68603 ergab mitThe test according to DIN 68603 resulted in

hromnitratchromium nitrate

Figure imgb0011
Figure imgb0011

AluminiumnitratAluminum nitrate

Figure imgb0012
Figure imgb0012

Beispiel 8Example 8

Im Vergleich zu Beispiel 5 werden folgende Änderungen durchgeführt:

  • 1) Reaktionstemperatur: 40-45°C
  • 2) N-Methylolacrylamid: 230 g (4 Gewichtsprozent)
The following changes are made compared to example 5:
  • 1) Reaction temperature: 40-45 ° C
  • 2) N-methylolacrylamide: 230 g (4 percent by weight)

Der Festgehalt der Dispersion beträgt 53,1 Gewichtsprozent, die Viskosität (Rheometer C III) 2800 m Pa.s und die Mindestfilmbildungstemperatur 14°C. Sie ist frost-, pigment- und scherstabil.The solids content of the dispersion is 53.1 percent by weight, the viscosity (rheometer C III) 2800 m Pa.s and the minimum film formation temperature 14 ° C. It is frost, pigment and shear stable.

Die Prüfung nach DIN 68603 ergab mit Chromnitrat:

Figure imgb0013
The test according to DIN 68603 showed with chromium nitrate:
Figure imgb0013

Beispiel 9/10Example 9/10

Ein Ersatz imn Beispiel 8 von N-Methylolcarylamid durch die entsprechenden Methoxy- bzw. Isobutoxyäther erbrachte keine signifikante Änderung der Dispersionseigenschaften.Replacing N-methylolcarylamide in Example 8 with the corresponding methoxy or isobutoxy ether did not result in a significant change in the dispersion properties.

Beispiel 11 1Example 11 1

Im Vergleich zu Beispiel 5 wurder folgende Änderung durchgeführt:

  • 1) Reaktionstemperatur 40°C
  • 2) N-Methylolacrylamid 420 g
Compared to example 5, the following change was made:
  • 1) reaction temperature 40 ° C
  • 2) N-methylol acrylamide 420 g

Der Festgehalt der Dispersion beträgt 53,9 Gewichtsprozent, die Viskosität (Rheometer C 111) 3400 m Pa.s und die Mindestfilmbildungstemperatur 16°C.The solids content of the dispersion is 53.9 percent by weight, the viscosity (Rheometer C 111) is 3400 m Pa.s and the minimum film formation temperature is 16 ° C.

Die Prüfung nach DIN 68603 ergab mit Aluminiumnitratzusatz:

Figure imgb0014
The test according to DIN 68603 with aluminum nitrate added:
Figure imgb0014

Beispiel 12Example 12

Die Durchführung der Polymerisation geschieht analog Beispiel 5, jedoch werden statt 175 g N-Methylolacrylamid 175 g N-Methylolallylcarbamat einpolymerisiert.The polymerization is carried out analogously to Example 5, but instead of 175 g of N-methylolacrylamide, 175 g of N-methylolallyl carbamate are copolymerized.

Das Produkt weist einen Festgehalt von 51,4 Gewichtsprozent, eine Viskosität (Rheometer C 111) von 2100 m Pa.s und eine Mindestfilmbildungstemperatur von 19°C auf. Sie ist frost-, pigment- und scherstabil.The product has a solids content of 51.4 percent by weight, a viscosity (Rheometer C 111) of 2100 m Pa.s and a minimum film formation temperature of 19 ° C. It is frost, pigment and shear stable.

Die Prüfung nach DIN 68603 ergibt bei Zusatz von Chromnitrat:

Figure imgb0015
The test according to DIN 68603 results in the addition of chromium nitrate:
Figure imgb0015

Aluminiumnitrat:Aluminum nitrate:

Figure imgb0016
Figure imgb0016

Claims (6)

1. Aqueous vinyl chloride copolymer dispersions having solids contents of between 30 and 70% by weight, containing copolymers comprising
50―85% by weight of vinyl chloride units,
5-35% by weight of vinyl acetate units, and
5-30% by weight of ethylene units,

characterized in that said dispersion further contains 2 to 15% by weight, based on the dispersion, of one or more polyvinyl alcohols having a saponification number of between 20 and 240 and a polymerization degree of between 300 and 2000, and that said copolymers were manufactured in the absence of emulsifiers and monomers having highly polar groups.
2. Aqueous vinyl chloride copolymer dispersions according to claim 1, characterized in that 0.5 to 5% by weight of units of olefinically unsaturated N-methylolamides are additionally copolymerized.
3. Process for the production of vinyl choride copolymer dispersions according to claim 1 by polymerization in an aqueous medium at temperatures of between +10 and +85°C using 0.01 to 3% by weight of redox catalyst systems while stirring, and by post-polymerization with the addition of a further 0.005 to 0.1% by weight of the respective components of the redox catalyst system, characterized in that, calculated on the total solids content of the dispersion,
50-85% by weight of vinyl chloride,
5-35% by weight of vinyl acetate and, optionally,
0.5-5% by weight of an olefinically unsaturated N-methylolamide are polymerized at a constant ethylene pressure of between 20 and 150 bar in the presence of 2 to 15% by weight of one or more polyvinyl alcohols having a saponification number of between 20 and 240 and a polymerization degree of between 300 and 2000 in the absence of emulsifiers and monomers having highly polar groups, at monomer concentrations of the liquid monomers during metering in of the monomers of between 5 and 20% by weight.
4. Use of the dispersions according to claims 1 to 2 as binders in hydraulically setting building materials.
5. Use of the dispersions according to claims 1 to 2 in combination with acidic hardener additives in adhesives.
6. Use of the dispersions according to claims 1 to 2 in combination with aluminium nitrate, chromium nitrate, acidic phosphates or phosphoric acid as hardener additives in coating agents.
EP78100561A 1977-08-01 1978-08-01 Aqueous dispersions of vinyl chloride copolymers, process for producing them and their use Expired EP0000590B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984000369A1 (en) 1982-07-20 1984-02-02 Wacker Chemie Gmbh Method for the preparation of polymer dispersions and utilization thereof

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4319012A (en) * 1979-08-23 1982-03-09 The B. F. Goodrich Company Suspension polymerization process for making vinyl resins for use in plastisol
JPS5728106A (en) * 1980-07-25 1982-02-15 Nippon Oil & Fats Co Ltd Organic peroxide emulsified in water
DE3115163A1 (en) * 1981-04-15 1982-11-11 Hoechst Ag, 6000 Frankfurt AQUEOUS POLYVINYL ESTER DISPERSION, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
JPS5855355A (en) 1981-09-22 1983-04-01 住友化学工業株式会社 Reformed cement composition
JPS59120669A (en) * 1982-12-28 1984-07-12 Asahi Chem Ind Co Ltd Spark-resistant high-frequency adhesive
EP0136717A3 (en) * 1983-10-06 1986-09-03 Air Products And Chemicals, Inc. Polyvinyl alcohol-vinyl acetate-ethylene interpolymers having oxygen barrier properties
US4714731A (en) * 1984-01-20 1987-12-22 Air Products And Chemicals, Inc. Metal container coating compositions comprising stable emulsions of water resistant polyvinyl alcohol-stabilized vinyl chloride-ethylene copolymers
US4673702A (en) * 1984-01-20 1987-06-16 Air Products And Chemicals, Inc. Stable emulsions of water resistant polyvinyl alcohol-stabilized vinyl chloride-ethylene copolymers
US4536012A (en) * 1984-05-15 1985-08-20 H. B. Fuller Company Book binding process
US4678829A (en) * 1984-06-20 1987-07-07 Air Products And Chemicals, Inc. Metal container coating compositions comprising stable emulsions of water resistant polyvinyl alcohol-stabilized vinyl chloride-ethylene copolymers
US4716192A (en) * 1985-06-20 1987-12-29 Air Products And Chemicals, Inc. Stable emulsions of water resistant polyvinyl alcohol-stabilized vinyl chloride-ethylene copolymers
US4735986A (en) * 1985-08-02 1988-04-05 Air Products And Chemicals, Inc. Vinyl acetate/ethylene copolymer emulsions useful as carpet adhesives
US4921898A (en) * 1985-08-02 1990-05-01 Air Products And Chemicals, Inc. Vinyl acetate-ethylene copolymer emulsions prepared in the presence of a stabilizing system of a low molecular weight polyvinyl alcohol and a surfactant
JPS6320308A (en) * 1986-07-14 1988-01-28 Hoechst Gosei Kk Production of protective colloid system acryl hydrosol
JPH0755851B2 (en) * 1987-02-20 1995-06-14 宇部興産株式会社 High-strength cement hardened body and method for producing the same
US4767816A (en) * 1987-06-24 1988-08-30 Air Products And Chemicals, Inc. Polyvinyl alcohol-stabilized vinyl chloride-ethylene-hydroxyethyl acrylate copolymer emulsions having enhanced water and solvent resistant properties
US5416181A (en) * 1989-02-10 1995-05-16 Penford Products Company Reinforced films made from water soluble polymers
US4999239A (en) * 1989-03-20 1991-03-12 Air Products And Chemicals, Inc. Ethylene-vinyl chloride copolymer emulsions containing tetramethylol glycoluril for use as binder compositions
US5092953A (en) * 1989-03-21 1992-03-03 Air Products And Chemicals, Inc. Aqueous vinyl chloride-ethylene copolymer/polyisocyanate adhesive compositions for wood composites
IT1235098B (en) * 1989-06-15 1992-06-18 Francesco Carlin PROCEDURE FOR THE PRODUCTION IN WATER EMULSION OF MIXTURES OF POLYVINYL ALCOHOLS AND PRODUCTS SO OBTAINED.
EP0519044A1 (en) * 1990-12-27 1992-12-23 Union Carbide Chemicals & Plastics Technology Corporation Poly(vinyl chloride) copolymer laminating adhesives
US5244695A (en) * 1992-03-17 1993-09-14 Air Products And Chemicals, Inc. Aqueous binder saturants used in a process for making nonwoven filters
JP3550159B2 (en) * 1992-04-10 2004-08-04 住友化学工業株式会社 adhesive
US5387638A (en) * 1992-09-07 1995-02-07 Kuraray Co., Ltd. Emulsion composition
US6436865B1 (en) * 2000-11-13 2002-08-20 Multibond Inc. Liquid catalyst for crosslinking with an amino resin
KR102024141B1 (en) * 2016-06-21 2019-09-23 주식회사 엘지화학 Method for preparing vinyl chloride polymer
CN114350189B (en) * 2021-12-21 2023-03-24 云南正邦科技有限公司 Waterproof coating suitable for low-temperature high-humidity environment

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL297480A (en) * 1962-09-04
NL135976C (en) * 1967-05-05
US3501440A (en) * 1968-04-16 1970-03-17 Nippon Carbide Kogyo Kk Process for preparing vinyl chloride/ethylene copolymers
US3639326A (en) * 1968-05-20 1972-02-01 Allied Chem Vinyl terpolymer compositions
US3816363A (en) * 1968-05-27 1974-06-11 Lanza Ltd Saponification resistant,aqueous synthetic resin dispersion
US3660332A (en) * 1969-09-05 1972-05-02 Nippon Carbide Kogyo Kk Process for preparing granular graft copolymers
US3830761A (en) * 1971-10-26 1974-08-20 Air Prod & Chem Vinyl chloride-ethylene-vinyl acetate resin binders
DE2309368C3 (en) * 1973-02-24 1984-09-27 Bayer Ag, 5090 Leverkusen Continuous process for the production of copolymer dispersions
JPS5058131A (en) * 1973-09-14 1975-05-20
DE2527915A1 (en) * 1974-06-26 1976-01-08 Union Carbide Corp VINYL CHLORIDE-VINYL ACETATE-AETHYLENE TERPOLYMERISATE
DE2456576C3 (en) * 1974-11-29 1983-03-10 Wacker-Chemie GmbH, 8000 München Process for the continuous production of ethylene-vinyl acetate copolymer dispersions
DE2541934A1 (en) * 1975-09-19 1977-03-24 Wacker Chemie Gmbh SOAP RESISTANT COPOLYMER DISPERSIONS

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1984000369A1 (en) 1982-07-20 1984-02-02 Wacker Chemie Gmbh Method for the preparation of polymer dispersions and utilization thereof

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