EP0000590B1 - Wässrige Vinylchlorid-Copolymerdispersionen, deren Herstellung und Verwendung - Google Patents

Wässrige Vinylchlorid-Copolymerdispersionen, deren Herstellung und Verwendung 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
European Patent Office
Prior art keywords
weight
vinyl chloride
dispersion
percent
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP78100561A
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German (de)
English (en)
French (fr)
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EP0000590A1 (de
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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Paints Or Removers (AREA)
EP78100561A 1977-08-01 1978-08-01 Wässrige Vinylchlorid-Copolymerdispersionen, deren Herstellung und Verwendung Expired EP0000590B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772734656 DE2734656A1 (de) 1977-08-01 1977-08-01 Waessrige vinylchlorid-copolymerdispersionen, deren herstellung und verwendung
DE2734656 1977-08-01

Publications (2)

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EP0000590A1 EP0000590A1 (de) 1979-02-07
EP0000590B1 true EP0000590B1 (de) 1981-10-14

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EP78100561A Expired EP0000590B1 (de) 1977-08-01 1978-08-01 Wässrige Vinylchlorid-Copolymerdispersionen, deren Herstellung und Verwendung

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US (1) US4189415A (enrdf_load_stackoverflow)
EP (1) EP0000590B1 (enrdf_load_stackoverflow)
JP (2) JPS5426892A (enrdf_load_stackoverflow)
AT (1) AT363685B (enrdf_load_stackoverflow)
CH (1) CH636891A5 (enrdf_load_stackoverflow)
DE (2) DE2734656A1 (enrdf_load_stackoverflow)
IT (1) IT1106621B (enrdf_load_stackoverflow)
SE (1) SE440084B (enrdf_load_stackoverflow)

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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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 (de) * 1981-04-15 1982-11-11 Hoechst Ag, 6000 Frankfurt Waessrige polyvinylester-dispersion, verfahren zu ihrer herstellung und ihre verwendung
JPS5855355A (ja) 1981-09-22 1983-04-01 住友化学工業株式会社 改質されたセメント組成物
JPS59120669A (ja) * 1982-12-28 1984-07-12 Asahi Chem Ind Co Ltd 耐スパ−ク性の高周波接着剤
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
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
US4735986A (en) * 1985-08-02 1988-04-05 Air Products And Chemicals, Inc. Vinyl acetate/ethylene copolymer emulsions useful as carpet adhesives
JPS6320308A (ja) * 1986-07-14 1988-01-28 Hoechst Gosei Kk 保護コロイド系アクリルハイドロゾルの製造方法
JPH0755851B2 (ja) * 1987-02-20 1995-06-14 宇部興産株式会社 高強度セメント硬化体及びその製造方法
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 (it) * 1989-06-15 1992-06-18 Francesco Carlin Procedimento per la produzione in emulsione acquosa di miscele di alcoli polivinilici e prodotti cosi' ottenuti.
CA2077086A1 (en) * 1990-12-27 1992-06-28 Chia-Chen Lo 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 (ja) * 1992-04-10 2004-08-04 住友化学工業株式会社 接着剤
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 (ko) * 2016-06-21 2019-09-23 주식회사 엘지화학 염화비닐계 중합체의 제조방법
CN114350189B (zh) * 2021-12-21 2023-03-24 云南正邦科技有限公司 一种适用于低温高湿环境的防水涂料

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US3830761A (en) * 1971-10-26 1974-08-20 Air Prod & Chem Vinyl chloride-ethylene-vinyl acetate resin binders
DE2309368C3 (de) * 1973-02-24 1984-09-27 Bayer Ag, 5090 Leverkusen Kontinuierliches Verfahren zur Herstellung von Copolymerisat-Dispersionen
JPS5058131A (enrdf_load_stackoverflow) * 1973-09-14 1975-05-20
DE2527915A1 (de) * 1974-06-26 1976-01-08 Union Carbide Corp Vinylchlorid-vinylacetat-aethylen- terpolymerisat
DE2456576C3 (de) * 1974-11-29 1983-03-10 Wacker-Chemie GmbH, 8000 München Verfahren zur kontinuierlichen Herstellung von Äthylen-Vinylacetat-Copolymerdispersionen
DE2541934A1 (de) * 1975-09-19 1977-03-24 Wacker Chemie Gmbh Verseifungsfeste copolymerdispersionen

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

Also Published As

Publication number Publication date
JPS6154811B2 (enrdf_load_stackoverflow) 1986-11-25
JPS5426892A (en) 1979-02-28
AT363685B (de) 1981-08-25
JPS5611937A (en) 1981-02-05
IT7850519A0 (it) 1978-07-28
CH636891A5 (de) 1983-06-30
US4189415A (en) 1980-02-19
SE440084B (sv) 1985-07-15
EP0000590A1 (de) 1979-02-07
DE2734656A1 (de) 1979-02-22
IT1106621B (it) 1985-11-11
DE2861160D1 (en) 1981-12-24
JPS5915350B2 (ja) 1984-04-09
SE7808280L (sv) 1979-02-02
ATA556078A (de) 1981-01-15

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