CA1162340A - Polyurethane prepolymer amine salt emulsifier for emulsion polymerization processes - Google Patents
Polyurethane prepolymer amine salt emulsifier for emulsion polymerization processesInfo
- Publication number
- CA1162340A CA1162340A CA000368247A CA368247A CA1162340A CA 1162340 A CA1162340 A CA 1162340A CA 000368247 A CA000368247 A CA 000368247A CA 368247 A CA368247 A CA 368247A CA 1162340 A CA1162340 A CA 1162340A
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- Prior art keywords
- amine
- component
- prepolymer
- acid
- reacting
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/28—Emulsion polymerisation with the aid of emulsifying agents cationic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Aqueous polymer latexes are prepared in an emulsion polymerization process wherein a polyurethane prepolymer amine salt is used to replace conven-tional emulsifiers or surfactants. Latices produced by this process eliminate the effects of the residues in the finished product left by conventional emulsifiers since the polyurethane prepolymer amine salt upon curing becomes part of the cured latex.
Description
~6234Q
BACKGROUND OF TH~ INVENTION
Emulsion polymerization probably had its origin in the observations by early scientists of natural latexes or saps exuded by many plants. The most important of these is without a doubt, natural Tubber latex. Natural rubber is a milklike collodial dispersion in water of polyisoprene particles protected from coagulation by natural proteins and emulsifiers. The earliest reference to emulsion polymerization is made in German patent DRP 250690 in 1909. Work on emulsion polymerization continued in Germany through World War I with relatively little progress being made in the technical development. Industrial development of emulsion polymerization appears to have started toward the end of the 1920's. In German Patent DRP 558,890 ~1927) there is described the polymerization of butadiene to a synthetic latex using soaps as emulsifiers and hydrogen peroxide as the initiator.
The first significant breakthrough in the industrial development of emulsion polymerization occurred in 1938 when it was shown that polymerization occurs in the aqueous phase and not in the monomer droplets. Understanding the mechanism of the emulsion polymerization widened knowledge so that predictions and improvements of the techniques could be made.
The advantages of emulsion polymerization over other methods such as bulk or solution polymerization are as follows:
~ 1) An emulsion polymerized product, i.e. the latex itself, is in an ideal form for use in paints and surface coatings, adhesives, paper coating and impregnation, leather treatment, textile treatment, dipping and latex foam rubber.
BACKGROUND OF TH~ INVENTION
Emulsion polymerization probably had its origin in the observations by early scientists of natural latexes or saps exuded by many plants. The most important of these is without a doubt, natural Tubber latex. Natural rubber is a milklike collodial dispersion in water of polyisoprene particles protected from coagulation by natural proteins and emulsifiers. The earliest reference to emulsion polymerization is made in German patent DRP 250690 in 1909. Work on emulsion polymerization continued in Germany through World War I with relatively little progress being made in the technical development. Industrial development of emulsion polymerization appears to have started toward the end of the 1920's. In German Patent DRP 558,890 ~1927) there is described the polymerization of butadiene to a synthetic latex using soaps as emulsifiers and hydrogen peroxide as the initiator.
The first significant breakthrough in the industrial development of emulsion polymerization occurred in 1938 when it was shown that polymerization occurs in the aqueous phase and not in the monomer droplets. Understanding the mechanism of the emulsion polymerization widened knowledge so that predictions and improvements of the techniques could be made.
The advantages of emulsion polymerization over other methods such as bulk or solution polymerization are as follows:
~ 1) An emulsion polymerized product, i.e. the latex itself, is in an ideal form for use in paints and surface coatings, adhesives, paper coating and impregnation, leather treatment, textile treatment, dipping and latex foam rubber.
(2) Control of the initiator, propagation, chain transfer, and termination reaction is easy and, in most cases, at a relatively low polymeri-zation temperature. -.~!C~
~6234~
~6234~
(3) Emulsion polymerization lends itself to easy continuous process operation .
~ 4) ~ligh rates of polymerization can be obtained simultaneously with high degrees of polymerization.
(5) In contrasts to solutions of polymers, the viscosity of a latex is independent of the molecular weight of the polymer it contains. Thus high polymer concentrations can be obtained at low viscosity.
(6) Emulsion polymerization uses water as tne inexpensive solvent eliminating solvent recovery problems and fire risk factors.
(7) When a solid product is required work up of the polymer presents no problems since the latex is simply coagulated in an appropriate manner and the coagulated crumb washed with water of other aqueous solutions, pressed and dried.
It has been said that the choice of an emulsifier is probably the most important single factor in an emulsion polymerization recipe. First, the emulsifier must produce a stable emulsion between the monomer and water phases and later a stable latex. Second, it must not interfere adversely with the initiation system or the propagation of the reaction. Third, since the emulsifier residues will remain in the product recovered after polymerization it must impart no adverse properties to the product.
Numerous synthetic emulsifiers have been studied for their efficiency in emulsion polymerization. ~ccording to the nature of the hydrophilic groups, surface active agents can be divided into four classes: (a) anionic, (b) cationic, (c) amphoteric, and (d) nonionic. Each of these main groups can be further subdivided chemically according to the hydrophilic group (e.g.
carboxylic acids, sulfates, sulfonates) and according to the hydrophobic group (e.g. alkyl, alkylaryl, alkylamide, alkylester). Thus the choice from the o number of possible permutations and combinations is very wide.
Illustrative of suitable surfactants commonly employed in emulsion polymerization processes of the prior art are the anionic surfactants such as potassium caprylate, potassium myristate, potassium palmitate, potassium stearate, potassium oleate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, potassium dehydroabietate, sodium rosinate, alkyl sodium sulfosuccinate esters and the like; cationic surfactants such as the long chain quaternary amine salts; and nonionic surfactants such as ethylene oxide condensates of oleyl alcohol, cetyl alcohol, lauryl alcohol etc., ethylene oxide condensates of linoleic acid, lauric acid, ricinoleic acid, caproic acid, etc., block copolymer of ethylene oxide and propylene oxide and the ethylene oxide condensates of octyl phenol or nonyl phenol.
The role of the emulsifier in emulsion polymerization is threefold:
(a) an increased amount of the monomer is taken into the water phase owing to solubilization in the micelles; (b) the nonsolubilized monomer is emulsified into fine stable droplets; and (c) the latex particles created are protected against coagulation during and after the polymerization.
It is known that different emulsifiers have molar concentrations below which no micelle formation occurs. This is the critical micelle concen-tration, i.e., cmc. In most cases no polymerization of significance occurs below the critical micelle concentration (cmc). As the concentration of the emulsifier is lowered, the number of latex particles formed is decreased. It is known that emulsifier residue left in the latex system can leave the latex with undesirable properties, i.e., the latex may lose some of its stability.
It has been recognized that an emulsifier should bring three basic properties to a latex system. These properties are (a) good solubility at the polymerization temperature, (b) good solubilizing power, and (c) imparting good stability to the latex. Further, the emulsifier must not interfere with the initiation or the propagation of the polymerization reactions.
The variety of initiator systems in emulsion polymerization processes is no less than the variety of emulsifiers described. All systems used commercially are based on the liberation of an active free radical. These active free radicals are produced by either of two means la) thermal decomposi-tion of a compound into free radicals or (b) interaction of chemical agents to produce free radicals.
The most commonly used initiators are those compounds containing a peroxide bond, i.e., -0-0-. The organic peroxides can be regarded as being derived from hydrogen peroxide by replacement of hydrogens by organic groups.
Some specific organic peroxide initiators are diisopropyl peroxycarbon-ate, caprylyl peroxide, lauroyl peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, cumene peroxide and tert-butyl peroxybenzoate. Compounds that release peroxydi-sulfate ions may also be used as an initiator.
Hydrogen peroxide-iron systems can be used as the initiators for the polymerization of certain monomers, e.g. methyl methacrylate and acrylonitrile while the organic hydroperoxides are preferred for the less polar monomers such as styrene and butadiene. For the manufacture of "cold" SBR recipes containing p-methane hydroperoxide, pinone hydroperoxide, or diiosopropylbenzene hydro-peroxide are most frequently encountered.
In addition emulsifiers and initiators, certain materials may be added to the emulsion polymerization reaction mixture to retard or inhibit the pro-pagation reaction. Any substances which will trap free radicals and either destroy them, prevent them from getting to the locus of polymerization, or ~1 ~4l~
produce by transfer another free radical which is not active as a polymerizationinitiators or inhibitors may be used. Some substances may act as both retarder and an inhibitor. Some commonly used substances are diethylhydroxylamine, hydroquinone, methylether of hydroquinone, p-aminophenol, water soluble dithio-carbamates, etc.
The Invention This application claims a process and the latices produced thereby where the conventional surface active agents and/or emulsifiers are replaced by a polyurethane prepolymer amine salt. This polyurethane prepolymer amine salt eliminates the effects of the residues in the finished product by the emulsifier remaining therein since the salt upon curing of the latex becomes a part of the cured latex.
The no~el polyurethane prepolymer amine salt when used in emulsion polymerization systems has been found to act as a particle initiator and thus can be substituted for seed latex used in preparing latex compositions where a high degree of uniformity in particle size is required (for example see United States Patent 3,397,165). It has been found that the novel polyurethane pre-polymer amine salt when used in an emulsion polymerization system acts as a stabilizing medium for the latex system.
In the process of this invention latex initiation is performed in accordance with the procedures known in the art. The aqueous reaction medium is charged to the reaction zone and the monomer or monomers to be polymerized are thereafter fed continuously to the aqueous medium in the reaction zone together with a catalyst and, if desired, surfactants, buffer, etc. By the term "aqueous reaction medium" is meant water plus any o~her constituents, e.g.
catalyst, surfactants, buffer, etc. which are present in the reaction zone in which the polymerization of this process is carried out. The temperature of 34~
initiation varies depending on the type of monomers used and the amount and type of catalyst used, and those skilled in the art will know the correct initiation temperature for any given system. Typically, when polymerizing lower alkyl acrylate or methacrylate monomers, e.g. methyl methacrylate, N-butyl acrylate, etc., it is preferred to initiate polymerization at a temperature of from about 40 to about 84C depending on the catalyst employed.
Any reactor, properly equipped, can be used in the carrying out of emulsion polymerization reactions. The different types of reactors and their suitability for emulsion polyerization are well known to those skilled in the art. Typically, a stirred tank with means for controlling temperature and pressure, means for providing a continuous feed of the monomer, catalyst, surfactant, buffer, etc., means for continuously withdrawing a portion of the tank's contents, and, where desired, means for providing an inert atmosphere (e.g. N2) above the reactants, is suitably employed as the reactor.
The emulsion polymerizable monomers which are useful in the process of our invention are any of the monomers having at least one olefinically unsaturated group of the formula C=C
which are known to those skilled in the art to undergo addition polymerization under the conditions of emulsion polymerization in an aqueous medium. These monomers are so well known to those skilled in the art as to require no further elaboration herein. Nonetheless, one can mention as illustrative thereof, unsaturated compounds such as ethylene, propylene, l-butene, 2-butene, isobutyl-ene, l-pentene, 2-methyl-2-butene, l-hexene, 4-methyl-1-pentene, 3,3-dimethyl-l-butene, 2,4,4-trimethyl-1-pentene, 6-ethyl-1-hexene, l-heptene, l-octene, l-decene, l-dodecene, allene, butadiene, isoprene, chloroprene, l,5-hexadiene, 1~34~
1,3,5-hextriene, divinylacetylene, cyclopentadiene, dicyclopentadiene, norbornene, norbornadiene, methylnorbornene, cyclohexene, styrene, alpha-chlorostyrene, alphamethylstyrene, allylbenzene, phenylacetylene, l-phenyl-l, 3-butadiene vinylnaphthalene, 4-methylstyrene, 2,4-dimethylstyrene, 3-ethylstyrene, 2,4-diethylstyrene, 2-methoxystyrene, 4~methoxy-3-methylstyrene, 4-chlorostyrene, 3,4-dimethyl-alpha-methylstyrene, 3-bromo-4-methyl-alpha-methylstyrene, 2,5-dichlorostyrene, 4-fluorostyrene, 3-iodostyrene, 4-cyanostyrene, 4-vinylbenzoic acid, 4-acetoxystyrene, 4-vinyl benzyl alcohol, 3-hydroxystyrene, 1,4-dihyroxy-styrene, 3-hydroxystyrene 1,4-dihydroxystyrene, 3-nitrostyrene, 2-aminostyrene,
~ 4) ~ligh rates of polymerization can be obtained simultaneously with high degrees of polymerization.
(5) In contrasts to solutions of polymers, the viscosity of a latex is independent of the molecular weight of the polymer it contains. Thus high polymer concentrations can be obtained at low viscosity.
(6) Emulsion polymerization uses water as tne inexpensive solvent eliminating solvent recovery problems and fire risk factors.
(7) When a solid product is required work up of the polymer presents no problems since the latex is simply coagulated in an appropriate manner and the coagulated crumb washed with water of other aqueous solutions, pressed and dried.
It has been said that the choice of an emulsifier is probably the most important single factor in an emulsion polymerization recipe. First, the emulsifier must produce a stable emulsion between the monomer and water phases and later a stable latex. Second, it must not interfere adversely with the initiation system or the propagation of the reaction. Third, since the emulsifier residues will remain in the product recovered after polymerization it must impart no adverse properties to the product.
Numerous synthetic emulsifiers have been studied for their efficiency in emulsion polymerization. ~ccording to the nature of the hydrophilic groups, surface active agents can be divided into four classes: (a) anionic, (b) cationic, (c) amphoteric, and (d) nonionic. Each of these main groups can be further subdivided chemically according to the hydrophilic group (e.g.
carboxylic acids, sulfates, sulfonates) and according to the hydrophobic group (e.g. alkyl, alkylaryl, alkylamide, alkylester). Thus the choice from the o number of possible permutations and combinations is very wide.
Illustrative of suitable surfactants commonly employed in emulsion polymerization processes of the prior art are the anionic surfactants such as potassium caprylate, potassium myristate, potassium palmitate, potassium stearate, potassium oleate, sodium decyl sulfonate, sodium dodecyl sulfonate, sodium tetradecyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, potassium dehydroabietate, sodium rosinate, alkyl sodium sulfosuccinate esters and the like; cationic surfactants such as the long chain quaternary amine salts; and nonionic surfactants such as ethylene oxide condensates of oleyl alcohol, cetyl alcohol, lauryl alcohol etc., ethylene oxide condensates of linoleic acid, lauric acid, ricinoleic acid, caproic acid, etc., block copolymer of ethylene oxide and propylene oxide and the ethylene oxide condensates of octyl phenol or nonyl phenol.
The role of the emulsifier in emulsion polymerization is threefold:
(a) an increased amount of the monomer is taken into the water phase owing to solubilization in the micelles; (b) the nonsolubilized monomer is emulsified into fine stable droplets; and (c) the latex particles created are protected against coagulation during and after the polymerization.
It is known that different emulsifiers have molar concentrations below which no micelle formation occurs. This is the critical micelle concen-tration, i.e., cmc. In most cases no polymerization of significance occurs below the critical micelle concentration (cmc). As the concentration of the emulsifier is lowered, the number of latex particles formed is decreased. It is known that emulsifier residue left in the latex system can leave the latex with undesirable properties, i.e., the latex may lose some of its stability.
It has been recognized that an emulsifier should bring three basic properties to a latex system. These properties are (a) good solubility at the polymerization temperature, (b) good solubilizing power, and (c) imparting good stability to the latex. Further, the emulsifier must not interfere with the initiation or the propagation of the polymerization reactions.
The variety of initiator systems in emulsion polymerization processes is no less than the variety of emulsifiers described. All systems used commercially are based on the liberation of an active free radical. These active free radicals are produced by either of two means la) thermal decomposi-tion of a compound into free radicals or (b) interaction of chemical agents to produce free radicals.
The most commonly used initiators are those compounds containing a peroxide bond, i.e., -0-0-. The organic peroxides can be regarded as being derived from hydrogen peroxide by replacement of hydrogens by organic groups.
Some specific organic peroxide initiators are diisopropyl peroxycarbon-ate, caprylyl peroxide, lauroyl peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, cumene peroxide and tert-butyl peroxybenzoate. Compounds that release peroxydi-sulfate ions may also be used as an initiator.
Hydrogen peroxide-iron systems can be used as the initiators for the polymerization of certain monomers, e.g. methyl methacrylate and acrylonitrile while the organic hydroperoxides are preferred for the less polar monomers such as styrene and butadiene. For the manufacture of "cold" SBR recipes containing p-methane hydroperoxide, pinone hydroperoxide, or diiosopropylbenzene hydro-peroxide are most frequently encountered.
In addition emulsifiers and initiators, certain materials may be added to the emulsion polymerization reaction mixture to retard or inhibit the pro-pagation reaction. Any substances which will trap free radicals and either destroy them, prevent them from getting to the locus of polymerization, or ~1 ~4l~
produce by transfer another free radical which is not active as a polymerizationinitiators or inhibitors may be used. Some substances may act as both retarder and an inhibitor. Some commonly used substances are diethylhydroxylamine, hydroquinone, methylether of hydroquinone, p-aminophenol, water soluble dithio-carbamates, etc.
The Invention This application claims a process and the latices produced thereby where the conventional surface active agents and/or emulsifiers are replaced by a polyurethane prepolymer amine salt. This polyurethane prepolymer amine salt eliminates the effects of the residues in the finished product by the emulsifier remaining therein since the salt upon curing of the latex becomes a part of the cured latex.
The no~el polyurethane prepolymer amine salt when used in emulsion polymerization systems has been found to act as a particle initiator and thus can be substituted for seed latex used in preparing latex compositions where a high degree of uniformity in particle size is required (for example see United States Patent 3,397,165). It has been found that the novel polyurethane pre-polymer amine salt when used in an emulsion polymerization system acts as a stabilizing medium for the latex system.
In the process of this invention latex initiation is performed in accordance with the procedures known in the art. The aqueous reaction medium is charged to the reaction zone and the monomer or monomers to be polymerized are thereafter fed continuously to the aqueous medium in the reaction zone together with a catalyst and, if desired, surfactants, buffer, etc. By the term "aqueous reaction medium" is meant water plus any o~her constituents, e.g.
catalyst, surfactants, buffer, etc. which are present in the reaction zone in which the polymerization of this process is carried out. The temperature of 34~
initiation varies depending on the type of monomers used and the amount and type of catalyst used, and those skilled in the art will know the correct initiation temperature for any given system. Typically, when polymerizing lower alkyl acrylate or methacrylate monomers, e.g. methyl methacrylate, N-butyl acrylate, etc., it is preferred to initiate polymerization at a temperature of from about 40 to about 84C depending on the catalyst employed.
Any reactor, properly equipped, can be used in the carrying out of emulsion polymerization reactions. The different types of reactors and their suitability for emulsion polyerization are well known to those skilled in the art. Typically, a stirred tank with means for controlling temperature and pressure, means for providing a continuous feed of the monomer, catalyst, surfactant, buffer, etc., means for continuously withdrawing a portion of the tank's contents, and, where desired, means for providing an inert atmosphere (e.g. N2) above the reactants, is suitably employed as the reactor.
The emulsion polymerizable monomers which are useful in the process of our invention are any of the monomers having at least one olefinically unsaturated group of the formula C=C
which are known to those skilled in the art to undergo addition polymerization under the conditions of emulsion polymerization in an aqueous medium. These monomers are so well known to those skilled in the art as to require no further elaboration herein. Nonetheless, one can mention as illustrative thereof, unsaturated compounds such as ethylene, propylene, l-butene, 2-butene, isobutyl-ene, l-pentene, 2-methyl-2-butene, l-hexene, 4-methyl-1-pentene, 3,3-dimethyl-l-butene, 2,4,4-trimethyl-1-pentene, 6-ethyl-1-hexene, l-heptene, l-octene, l-decene, l-dodecene, allene, butadiene, isoprene, chloroprene, l,5-hexadiene, 1~34~
1,3,5-hextriene, divinylacetylene, cyclopentadiene, dicyclopentadiene, norbornene, norbornadiene, methylnorbornene, cyclohexene, styrene, alpha-chlorostyrene, alphamethylstyrene, allylbenzene, phenylacetylene, l-phenyl-l, 3-butadiene vinylnaphthalene, 4-methylstyrene, 2,4-dimethylstyrene, 3-ethylstyrene, 2,4-diethylstyrene, 2-methoxystyrene, 4~methoxy-3-methylstyrene, 4-chlorostyrene, 3,4-dimethyl-alpha-methylstyrene, 3-bromo-4-methyl-alpha-methylstyrene, 2,5-dichlorostyrene, 4-fluorostyrene, 3-iodostyrene, 4-cyanostyrene, 4-vinylbenzoic acid, 4-acetoxystyrene, 4-vinyl benzyl alcohol, 3-hydroxystyrene, 1,4-dihyroxy-styrene, 3-hydroxystyrene 1,4-dihydroxystyrene, 3-nitrostyrene, 2-aminostyrene,
4-N,N-dimethylaminostyrene, 4-phenylstyrene, 4-chloro-1-vinylnaphthalene, acrylic acid, methacrylic acid, acrolein, methacrolein, acrylonitrile~ meth-acrylonitrile, acrylate, methacrylamide methyl acrylate, methyl methacrylate, norbornenyl acrylate, norbornyl diacrylate, 2-hydroxyethyl acrylate, 2-phenoxy-ethyl acrylate, trimethoxysilyloxypropyl acrylate, dicyclopentenyl acrylate, cyclohexyl acrylate, 2-tolyloxyethyl acrylate, N,N-dimethylacrylamide, isopropyl methacrylate, ethyl acrylate, methyl alpha-chloroacrylate, betadimethylamino-ethyl methacrylate, N-methyl methacrylamide, ethyl methacrylate, 2-ethylhexyl acrylate, neopentyl glycol diacrylate, cyclohexyl methacrylate, beta-bromoethyl methacrylate, benzyl methacrylate, phenol methacrylate, neopentyl methacrylate, butyl methacrylate, chloroacrylic acid, methyl chloroacrylic acid, hexyl acrylate, dodecyl acrylate, 3-methyl l-butyl acrylate, 2-ethoxyethyl acrylate, phenyl acrylate, butoxyethoxyethyl acrylate, 2-methoxyethyl acrylate, isodecyl acrylate, pentaerythritol triacrylate, methoxy poly (ethyleneoxy) acrylate, tridecoxy : poly (ethyleneoxy) acrylate, chloroacrylonitrile, dichloroisopropyl acrylate, ethacrylonitrile, N-phenyl acrylamide, N,N-diethylacrylamide, N-cyclohexyl acrylamide, vinyl chloride, vinylidene chloride, vinylidene cyanide, vinyl fluoride, vinylidene fluoride, trichlorethene, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl butyral, vinyl propionate, vinyl chloro-acetate, isopropenyl acetate, vinyl formate, vinyl methoxyacetate, vinyl caproate, vinyl oleate, vinyl adipate, methyl vinyl ketone, methyl isopropenyl ketone, vinyl phenyl ketone, methyl alpha-chlorovinyl ketone, ethyl vinyl ketone, divinyl ketone, allylidene diacetate, methyl vinyl ether, 2-methoxy-ethyl vinyl ether, 2-chloroethyl vinyl ether, methoxyethoxy ethyl vinyl ether, hydroxyethyl vinyl ether, aminoethyl vinyl ether, alpha-methylvinyl methyl ether, divinyl ether, divinyl ether of ethylene glycol or diethylene glycol or triethanolamine, cyclohexyl vinyl ether, benzyl vinyl etherJ phenethyl vinyl ether, cresyl vinyl etherJ hydroxyphenyl vinyl etherJ chlorophenyl vinyl etherJ
napthyl, vinyl ether, dimethyl maleate, diethyl maleate, di-(2-ethylhexyl) maleate, maleic anhydride, dimethyl fumarate, dipropyl fumarate, diamyl fumarate, vinyl ethyl sulfide, divinyl sulfide, vinyl p-tolyl sulfide, divinyl sulfone, vinyl ethyl sulfoneJ vinyl ethyl sulfoxideJ vinyl sulfonic acidJ
sodium vinyl sulfonate, vinyl sulfonamide, vinyl benzamide, vinyl pyridineJ
N-vinyl pyrollidoneJ N-vinyl carbazole, N-(vinyl benzyl)-pyrrolidiene, N-(vinyl benzyl) piperidine, l-vinyl pyrene, 2-isopropenyl furanJ 2-vinyl dibenzofuran, 2-methyl-5-vinyl-pyridineJ 3-isopropenyl pyridineJ vinyl piperidineJ 2-vinyl quinoline, 2-vinyl benzoxazoleJ 4-methyl-5-vinyl-thiazoleJ vinyl thiopheneJ
2-isopropenyl thiopheneJ indeneJ coumaraone, l-chloroethyl vinyl sulfide, vinyl 2-ethoxyethyl sulfideJ vinyl phenyl sulfideJ vinyl 2-naphthyl sulfideJ allyl mercaptans, divinyl sulfoxide, vinyl phenyl sulfoxide, vinyl chlorophenyl sulfoxide, methyl vinyl sulfonate, vinyl sulfoanilide, and the like.
The catalysts, buffers, and any other constituents which can be employed in the emulsion polymerization reaction mixture in the process of this invention are the same as those which can be employed in the known emulsion polymerization processes of the prior art. The particular choice of the materialsJ other than the emulsifierJ to be employed does not constitute the il~234~
invention and is a matter of routinism in the art of emulsion po]ymerization.
The catalyst employed is typically a free radical initiator or a redox catalyst. One can mention, as merely illustrative of suitable catalysts which can be employed, free radical initiators such as hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-bis(hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, azo-bis-isobutylonitrile, ammonium persulfate, sodium persulfate, potassium persulfate, sodium perphosphate,potassium perphosphate isopropyl peroxycarbonate, etc; and redox catalyst systems such as sodium persulate-sodium formaldehyde sulfoxylate, cumene hydro-peroxide-sodium mètabisulfite, hydrogen peroxide-ascorbic acid, sulfur dioxide-ammonium persulphate, etc.
The catalysts are employed in the usual catalytically effective concentration which are known to those skilled in the art of emulsion polymerization.
The novel polyurethane polymer amine salt emulsifier is the subject of Canadian Application Serial No. 350,885 filed on April 29, 1980.
The polyurethane polymer amine salt consists essentially of the reaction product of an NCO-terminated prepolymer blocked with an oxime reacted with an amine and then further reacted with an acid whereby infinitely water dilutable waterborne polyurethane polymer amine salts are obtained.
As used throughout this application the term "waterborne"
will indicate the state or condition of the amine salts of the ~1~234~
amine reaction product with the oxime blocked isocyanate prepolymers in an aqueous medium. It is not always apparent whether the polyurethane polymers in water is a microscopically - 9a -,~
34~
heterogenous mixture of two or more finely divided phases, i.e., liquid in liquid, and thus a dispersion or whether the polyurethane polymers are partially or wholly dissolved in the aqueous base and thus a solution.
We have observed the polyurethane polymers in water where the resulting product appears to be optically clear indicating a homogenous solution. In this situations we believe that the individual molecules of polyurethane polymers are not bound together. On the other hand we have also observed polyurethane polymers in water where the resulting product is cloudy indicating a dispersion.
Thus when used in this application the term "waterborne" will mean the novel amine salts in an aqueous system and may be either a homogenous solution, a dispersion or any combination thereof.
In order to provide a satisfactory end product having adequate film forming characteristics it has been recognized that branched reactants must be included in the preparation of the waterborne polyurethane in order to get the necessary cross-linking to produce a three dimensional polymeric structure upon curing. Therefore it is understood throughout the following description that either the polyol, the polyfunctional amine, the prepolymer, a portion of each or any combination thereof shall have a reactive functionality greater than two.
The novel polyurethane polymer amine salt is made in four basic steps.
First, a polyol is reacted with a polyisocyanate to prepare an NCO-terminated prepolymer. The prepolymer is blocked with an oxime in the second step. Third, the oxide blocked NCO-terminated prepolymer is reacted with one or more selected polyfunctional amines as hereinafter described. The amine reaction product is reacted with an acid. We found that in order to obtain a product with useful properties that a reactant having functionality greater than 2 should be used in the first and/or third steps. Thus functionality of the NCO-prepolymer plus functionality of the polyfunctional amine will be at least four or greater.
It has been found that the reaction product of the polyfunctional amines with the oxime blocked NC0-terminated prepolymer tends to increase in viscosity with time until a complete gelation/setting up of the product occurs.
Thus in another aspect of this invention it has unexpectantly been discovered that the gelation time and viscosity of the waterborne polyurethane polymer dispersion can be controlled and/or adjusted by the addition of a secondary amine to the reaction product.
The isocyanate capped polyoxyalkylene polyol, NC0-terminated prepolymer or urethane prepolymer useful in the invention are prepared by reacting polyoxy-alkylene polyol with an excess of polyisocyanate, e.g., toluene diisocyanate.
The polyol should have a molecular weight of from about 200 to about 200,000 and preferably from about 600 to about 6,000. The hydroxyl functionality following reaction is from 2 to about 8. When the isocyanate functionality of the polyol and the corresponding isocyanate functionality of the prepolymer is two the functionality of the step 3 amine reactant must be greater than two.
When the isocyanate functionality of the prepolymer is greater than two the functionality of the amine reactant in step 3 may be as little as two.
The preferred isocyanate capped or NC0-terminated prepolymer consists of a mixture of (1) an isocyanate capped hydrophilic polyoxyethylene diol, said diol having an ethylene oxide content of at least 40 mole percent; and (2) an isocyanate capped polyol having a hydroxy functionality in the range 3 to 8 prior to capping; said isocyanate capped polyol being present in an amount in the range 2.9 to 50~ by weight of (1) and (2).
The polyoxyethylene diol is the reaction product of alkylene oxides of which at least ~0 mole percent is ethylene oxide with an initiator such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol 1~23~1~
or mixtures thereof. Preferably the molecular weight of the diol is between abo~t 400 to about 6,000.
Examples of suitable polyols (to be capped with polyisocyanates) include: (A) essentially linear polyols formed for example by reaction of ethylene oxide with ethylene glycol as an initiator. Mixtures of ethylene oxide with other alkylene oxide can be employed so long as the mole percent of ethylene oxide is at least 40 percent. Where the linear polyethers are mixtures of ethylene oxide with e.g., propylene oxide, the polymer can be either random or a block copolymer. A second class of polyol (B) includes those with a hydroxy functionality of 3 or more. Such polyols are commonly formed by react-ing alkylene oxides with a polyfunctional initiator such as trimethylolpropane, pentaerythritol, etc. In forming the polyol B, the alkylene oxide used can be ethylene oxide or mixtures of ethylene oxide with other alkylene oxides as described above. Useful polyols can be further exemplified by (C) linear branched polyfunctional polyols as exemplified in A and B above together with an initiator or crosslinker. A specific example of C is a mixture of polyethyl-ene glycol (m.w. about 1,000) with trimethylolpropane, trimethylolethane or glycerine. This mixture can be subsequently reacted with excess polyisocyanate to provide a prepolymer useful in the invention. Alternatively the linear or branched polyols, (e.g., polyethylene glycol) can be reacted separately with excess polyisocyanate. The initiator, e.g., trimethylolpropane, can also be separately reacted with polyisocyanate. Subsequently the two capped materials can be combined to form the prepolymer.
Polyoxyalkylene polyol is terminated or capped by reaction with a polyisocyanate. The reaction may be carried out in an inert moisture-free atmosphere such as under a nitrogen blanket, at atmospheric pressure at a temperature in the range of from about 0C to about 120C for a period of time 11~23~0 of about 20 hours depending upon the temperature and degree of agitation. This reaction may be effected also under atmospheric conditions provided the product is not exposed to excess moisture.
Capping of the polyoxyalkylene polyol may be effected using stoichio-metric amounts of reactants. Desirably, however, an excess of isocyanate is used to insure complete capping of the polyol. Thus, the ratio of isocyanate groups to the hydroxyl groups used is between about 2 to about ~ isocyanate to hydroxyl, and preferably about 2 to about 2.5 isocyanate to hydroxyl molar ratio.
To obtain the maximum strength, solvent resistance, heat resistance and the like, the isocyanate capped polyoxyalkylene polyol reaction products are formulated in such a manner as to give crosslinked polymer network.
Any ketoxime is ef~ective among these being acetone oxime, butanone oxime, cyclohexanone oxime, and the like. An oxime based on a relatively volatile ketone is believed to be preferred. The most preferred oxime is butanone oxime, also commonly known as methyl ethyl ketoxime. Mixtures of oximes may be used, but there is no known merit in so doing. The proportions of oxime utilized may range from about 0.7 to about 1.2 equivalents of the isocyanate groups present. A more preferred range is 1.05 to 1.15 equivalents.
To prepare the blocked prepolymer, the oxime and prepolymer are simply admixed at temperatures of from 50 to 70C for from about 1/2 to 1-1/2 hours.
A solvent is not generally necessary although materials such as butyl cellosolve acetate can be employed. Other appropriate solvents include materials which are not reactive with either the oxime or urethane groups. Based on the moles of reactive oxime and NCO groups involved, the NOH/NCO molar ratio should be from about 0.7 to about 1.2 and preferably from about 1.05 to about 1.15. Generally it is most effective to use sufficient oxime to completely react with the NCO
11~23~3~
groups .
In preparing the blocked prepolymer the oxime selected to provide a product that will undergo curing reactions in a reasonable time at a reasonable temperature. The curing temperature is influenced by materials such as sub-strates and catalysts so that in curing the waterborne polyurethane dispersion temperatures outside the range of 140-180C can be employed. Curing temperatures of at least 120C have proved convenient in view of the curing times which must be employed. Lower temperatures result in longer cure times unless a catalyst is employed. Numerous oximes and catalysts which can be employed are described in: Petersen, Liebigs Ann. Chem., 562 tl949), p. 215; Wicks, Progress in Organic Coatings, 3 (1975), pp. 73-99; and Hill et al, Journal of Paint Tech., 43 (1971) p. 55. Oximes having the above unblocking temperatures are liquid materials at temperatures of about 80C, and the condensation products with urethane prepolymers are miscible with water or can be dispersed in water with the aid of surfactants. Generally the oximes are aliphatic cyclic, straight-chain or branched materials containing 2-8 (preferably 3-6) carbons.
The oxime blocked NCO-terminated prepolymer is reacted with an amine that is capable of causing the polymer to cure at a low temperature. Many of the amines usable within the scope of Applicants' invention are well known in the art and are referred to as polyfunctional amines. Specific examples of amines include, but are not limited to, ethylenediamine 1,3 propane-diamine, diethylenetriamine, triethylenetetramine, iminobispropylamine, tetraethylene-pentamine, methyliminobispropylamine, 2t2-aminoethylamine)-ethanol and the polyoxypropyleneamines manufactured by Jefferson Chemical Company, Inc. and ~ n~R ~
sold under the trade m moc JEFFAMINE D-400, D-2000 and T-403. The polyoxy-propyleneamines are aliphatic polyether primary di- and tri-functional amines derived from propylene oxide adducts of diols and triols.
34C~
As can be observed from the amines listed some of the amines can be represented by general formulae NH2R'-NH'2 and HO-R NH2 where R' is a C2C6 group .
We have found in our experimental work that polyfunctional amines with a functionality of at least 2 primary amine end groups are the preferred amines in getting adequate curing of the polyurethane polymer subsequently produced.
Some of the polyfunctional amines may be represented by the formula H2N- (CnH2n- 1 ) Z~CnH2n NH2 where z is an integer from 1 to 4, n is an integer larger than 1 and R is hydro gen, an alkyl group of 1 to 4 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms.
The polyoxypropyleneamines may be represented by the formula N}12CH~CH3)CH2~ CH2CH(CH3 ~x NH2 where x is greater than 2, and by the formula CH2 { CH2-cH-(cH ~ NH2 CH3CH2 C -CH2{CH2-CH- (CH~NH2 ~H2 { CH -CH-(CH ~ NH2 where x+y+z is about 5.3. The molecular weights of these polyoxypropylene amines range from 200 to 2000 or larger with the preferred polyoxypropyleneamines having molecular weights of about 400 to 2000.
The amount of polyfunctional amine added to the oxime blocked NC0-terminated prepolymer should be in the range of 0.6 to 1.5 equivalents with thepreferable range between 0.9 to 1.1 equivalents based on the total equivalents of all the isocyanate groups present in the NC0-terminated prepolymer.
Where the isocyanate functionality of the NC0-terminated prepolymer is two, a polyfunctional amine having a functionality of greater than two is required in order to provide a satisfactory cross-linked product. When the isocyanate functionality of the NC0-terminated prepolymer is greater than two, the polyfunctional amine functionality may be as little as two. It is to be understood from this that in the same reactive sys~em that the functionality of the NC0-terminated prepolymer and the amine or polyoxypropyleneamines will have a total functionality of greater than four.
The reaction between the oxime blocked prepolymer and the polyfunc-tionalamine is controlled by adding an acid or a mixture of acid and water prior to the completion of the reaction. Failure to control the amine-oxime blocked prepolymer reaction at the proper time may result in an amine reaction product too viscous for the purposes of this invention. Thus the proper portions of the blocked prepolymer and polyfunctional amine are placed in a reaction vessel and reacted under controlled conditions of heating and stirring. With experience we have been able to determine the state of the reaction by observing the increase in viscosity. With proper equipment such as temperature controlled mixing head devices the reaction times can be rapid at elevated temperatures.
For example reaction times can be as short as about 3 minutes at about 95C, 4 minutes at about 80C, etc. Preferred reaction times are from about one-half hour to about one hour with temperatures between about 40 and 60C. Sufficient acid or water-acid mixture is stirred into the amine reaction product to lower the pH value to about 5 or below.
The cationically stabilized waterborne polyurethane polymers are prepared by dispersing the amine reaction product in water in the presence of sufficient acid to provide a pH of from about 5 or below. In preparing the waterborne polymers the acid can be added directly to the amine reaction product and admixed therewith followed by dilution with water. This is the preferred 3~0 method. However, it is also possible to first add the acid to the water followed by dispersion of the amine reaction product in the water. Other addi-tives such as surfactants, ultraviolet absorbers, stabilizers, pigments, etc., may be formulated into the waterborne polyurethane polymers as required.
It has been found that if the pH is not controlled within the broad range set forth above, settling problems are encountered and/or portions of the amine reaction product reacts with the water to form a crust. While the pH
value range is to be considered we have found that from about 1 to 10 parts or more of acid may be used for each 100 parts of amine reaction product. A more preferred range is from about 4 to 8 parts acic per 100 parts amine reaction product. ~hese waterborne polymers have been found to be stable for periods of several months at ambient temperatures, e.g., 20C, and also exhibit excellent resistance to freeze-thaw cycles.
While any organic or inorganic acid will form the amine salt and per-form the function of controlling the pH value, the acids which we have used in-clude glacial acetic acid, acrylic acid, citric acid, ethylenediaminetetraacetic (fiDTA) acid, formic acid~glycine (aminoacetic acid), hydrochloric acid, lactic acid (alpha-hydroxypropionic acid), orthophosphoric acid ~H3P04), phosphorous acid (H3P03), sulfamic acid, sulfuric acid, tartaric acid (dihydroxysuccinic acid), paratoluenesulfonic acid and mixtures thereof.
The following specific examples are illustrative but not limitative of our invention, it being understood that similar improved results are obtain-able with other combinations of different composition specified above. All such variations which do not depart from the basic concept of the invention and composition disclosed above are intended to come within the scope of the amended claims.
Preparation of Polyurethane Prepolymer Amine Salt -A preferred isocyanate terminated polyol prepolymer is prepared by mixing a hydrophilic polyoxyethylene diol having an ethylene oxide content of at least 40 mole percent with a polyol having a hydroxyl functionality in the range 3 to 8, said polyol being present in the admixture in an amount in the range 1.0 to 20% by weight, reacting with the mixture at a temperature in the range 0 to 120C an amount of a diisocyanate equal to 1.8 - 1.9 NCO to OH
equivalents for a time sufficient ~o cap substantially all the hydroxyl groups of the admixture, adding additional diisocyanate to provide 0.1 - 0.3 equivalents of NCO per initial equivalent of OH in excess of the theoretical amount necessary to react with the hydroxyl groups.
To 100 grams of the NCO terminated polyol prepolymer at 24C in a stainless steel vessel is added 22 grams of butanone oxime with stirring. The reaction of the oxime with the isocyanate is exothermic and the temperature went to 60C. A hot water bath is used to control the temperature between 80-90C for twenty minutes.
After twenty minutes and the temperature at 90C, 12 grams of diethyl-enetriamine is added with stirring. The reaction with the amine is also exothermic which accelerates chain extension.
The viscogity continues to increase and after ten minutes at 90-95C, 7.1 grams of glacial acetic acid and 7.1 grams of o-phosphoric acid dissolved in 100 grams of deionized water is slowly added to control the viscosity. After all the acid/water mixture is in, the material is cooled and packaged. Water may be added to achieve the desired % non volatiles (%N.V) and viscosity.
Typical physical properties of the emulsifier prepared are:
1~23`4~?
% N.V 52.0 pH 4.5-6.9 Viscosity (Brookfield LVF) 600-1000 cps Appearance clear, straw colored solution To a two liter resin kettle fitted with a condenser, thermometer, graduated addition funnel, stirrer, and a nitrogen source was added 327.5 g.
of demeneralized water, 2.0 g of isoascorbic acid, and 687.5 g (196.6 grams nonvolatiles) of cationic polyurethane prepolymer amine salt @ 24% nonvolatiles.
The mixture was stirred and heated to 40C, under a nitrogen blanket.
At 40C, 100 g of a monomer mixture of 240.0 g of methylmethacrylate, 120.0 g of butylacrylate, 40.0 g of acrylonitrile and 8.0 g of acrylic acid was added to the kettle with stirring. To the material in the resin kettle was charged 4 cc of 30% hydrogen peroxide. The heat of reaction caused the tempera-ture to go from 41C to 47C in three minutes. The remaining monomer mixture was charged at a rate to maintain a temperature of 55-60C in the resin kettle without auxiliary heating. Discrete shots of 30% H202 were added at 2 cc levels during the monomer mixture addition. The total monomer mixture addition time was 39 minutes. When the last of the monomer mixture was charged, the temperature was 57C.
Eight minutes after the final monomer mixture addition and at a temperature of 54C, 0.1 g of isoascorbic acid dissolved in 10 cc demineralized water and 1.0 g of tertiary butylhydroperoxide were added to reduce the free monomer.
The two liter resin kettle (after packaging latex) had no solid build-up at all and required only a water rinse. The resulting latex had 39.6% Total Solids, a pH value of 4.3, a surface tension of 43.2 dynes/cm and a Brookfield - lg -46~
LVF #1 @ 60 viscosity of 53.4 centipoises.
REACTANT % WET
vinylidene chloride 67 640 butyl acrylate 15.0 144 glacial acetic acid 2 16 polyurethane prepolymer amine 17 400 salt @ 40% solids ascorbic acid .2 2 hydrogen peroxide 1.0 10 demineralized water - 800 To a 2 liter resin kettle fitted with a thermometer, stirrer and addition funnel was added 800 g. water, 400 g. polyurethane prepolymer amine salt at 40% solids, and 2 g. ascorbic acid. This mixture was heated to 36C under a nitrogen purge.
To the above was added 200 cc of a mixture consisting of 640 g.
vinylidene chloride, 144 g. butyl acrylate, and 16 g. glacial acetic acid followed by the addition of 2 cc of 20% hydrogen peroxide. The heat or reaction raised the temperature to 46C. The remainder of the monomer was added in 100 cc increments along with 1-2 cc shots of hydrogen peroxide to maintain a tem-perature range of 45-50C. After the last of the monomer was added, a 2 cc parting shot of hydrogen peroxide was added and the batch was allowed to cook to reach maximum conversion. The latex had the following properties:
Total Solids 39.0%
Conversion 81.6%
Surface Tension 52.8 dynes/cm pH Value 4.0 Examples 3 through 12 below illustrate emulsion polymerization using the poly-urethane prepolymer amine salt as emulsifier with various monomer combinations.
The procedure used in Examples 3-12 was that described in Example 2. All ingredients are indicated in weight percent.
234~) Example 3-Weight %
vinylidene chloride 32 styrene 33 acrylic acid 2 Example 4:
Weight %
vinylidene chloride 56 methylacrylate 5 acrylic acid 2 Example 5:
Weight %
methylmethacrylate 6 butylacrylate 13 methylacrylate 37 acrylic acid 6 Examples 6, 7, 8:
Weight %
methylmethacrylate 49 42 39 butyl acrylate 25 21 20 acrylonitrile 8 7 6 acrylic acid 2 2 2 Examples 9,_10:
Weight %
vinylidene chloride 33 28 styrene 33 28 butyl acrylate 16 14 acrylic acid 2 2 ~1~2~5 Example 11:
Weight %
methylmethacrylate 71 Example 12:
Weight %
12_1 12-2 methylmethacrylate 42 37 butylacrylate 21 18 acrylonitrile 7 6 acrylic acid 2 2 The te~ns and expressions which have beem employed are used as terms of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.
,,
napthyl, vinyl ether, dimethyl maleate, diethyl maleate, di-(2-ethylhexyl) maleate, maleic anhydride, dimethyl fumarate, dipropyl fumarate, diamyl fumarate, vinyl ethyl sulfide, divinyl sulfide, vinyl p-tolyl sulfide, divinyl sulfone, vinyl ethyl sulfoneJ vinyl ethyl sulfoxideJ vinyl sulfonic acidJ
sodium vinyl sulfonate, vinyl sulfonamide, vinyl benzamide, vinyl pyridineJ
N-vinyl pyrollidoneJ N-vinyl carbazole, N-(vinyl benzyl)-pyrrolidiene, N-(vinyl benzyl) piperidine, l-vinyl pyrene, 2-isopropenyl furanJ 2-vinyl dibenzofuran, 2-methyl-5-vinyl-pyridineJ 3-isopropenyl pyridineJ vinyl piperidineJ 2-vinyl quinoline, 2-vinyl benzoxazoleJ 4-methyl-5-vinyl-thiazoleJ vinyl thiopheneJ
2-isopropenyl thiopheneJ indeneJ coumaraone, l-chloroethyl vinyl sulfide, vinyl 2-ethoxyethyl sulfideJ vinyl phenyl sulfideJ vinyl 2-naphthyl sulfideJ allyl mercaptans, divinyl sulfoxide, vinyl phenyl sulfoxide, vinyl chlorophenyl sulfoxide, methyl vinyl sulfonate, vinyl sulfoanilide, and the like.
The catalysts, buffers, and any other constituents which can be employed in the emulsion polymerization reaction mixture in the process of this invention are the same as those which can be employed in the known emulsion polymerization processes of the prior art. The particular choice of the materialsJ other than the emulsifierJ to be employed does not constitute the il~234~
invention and is a matter of routinism in the art of emulsion po]ymerization.
The catalyst employed is typically a free radical initiator or a redox catalyst. One can mention, as merely illustrative of suitable catalysts which can be employed, free radical initiators such as hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-bis(hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, azo-bis-isobutylonitrile, ammonium persulfate, sodium persulfate, potassium persulfate, sodium perphosphate,potassium perphosphate isopropyl peroxycarbonate, etc; and redox catalyst systems such as sodium persulate-sodium formaldehyde sulfoxylate, cumene hydro-peroxide-sodium mètabisulfite, hydrogen peroxide-ascorbic acid, sulfur dioxide-ammonium persulphate, etc.
The catalysts are employed in the usual catalytically effective concentration which are known to those skilled in the art of emulsion polymerization.
The novel polyurethane polymer amine salt emulsifier is the subject of Canadian Application Serial No. 350,885 filed on April 29, 1980.
The polyurethane polymer amine salt consists essentially of the reaction product of an NCO-terminated prepolymer blocked with an oxime reacted with an amine and then further reacted with an acid whereby infinitely water dilutable waterborne polyurethane polymer amine salts are obtained.
As used throughout this application the term "waterborne"
will indicate the state or condition of the amine salts of the ~1~234~
amine reaction product with the oxime blocked isocyanate prepolymers in an aqueous medium. It is not always apparent whether the polyurethane polymers in water is a microscopically - 9a -,~
34~
heterogenous mixture of two or more finely divided phases, i.e., liquid in liquid, and thus a dispersion or whether the polyurethane polymers are partially or wholly dissolved in the aqueous base and thus a solution.
We have observed the polyurethane polymers in water where the resulting product appears to be optically clear indicating a homogenous solution. In this situations we believe that the individual molecules of polyurethane polymers are not bound together. On the other hand we have also observed polyurethane polymers in water where the resulting product is cloudy indicating a dispersion.
Thus when used in this application the term "waterborne" will mean the novel amine salts in an aqueous system and may be either a homogenous solution, a dispersion or any combination thereof.
In order to provide a satisfactory end product having adequate film forming characteristics it has been recognized that branched reactants must be included in the preparation of the waterborne polyurethane in order to get the necessary cross-linking to produce a three dimensional polymeric structure upon curing. Therefore it is understood throughout the following description that either the polyol, the polyfunctional amine, the prepolymer, a portion of each or any combination thereof shall have a reactive functionality greater than two.
The novel polyurethane polymer amine salt is made in four basic steps.
First, a polyol is reacted with a polyisocyanate to prepare an NCO-terminated prepolymer. The prepolymer is blocked with an oxime in the second step. Third, the oxide blocked NCO-terminated prepolymer is reacted with one or more selected polyfunctional amines as hereinafter described. The amine reaction product is reacted with an acid. We found that in order to obtain a product with useful properties that a reactant having functionality greater than 2 should be used in the first and/or third steps. Thus functionality of the NCO-prepolymer plus functionality of the polyfunctional amine will be at least four or greater.
It has been found that the reaction product of the polyfunctional amines with the oxime blocked NC0-terminated prepolymer tends to increase in viscosity with time until a complete gelation/setting up of the product occurs.
Thus in another aspect of this invention it has unexpectantly been discovered that the gelation time and viscosity of the waterborne polyurethane polymer dispersion can be controlled and/or adjusted by the addition of a secondary amine to the reaction product.
The isocyanate capped polyoxyalkylene polyol, NC0-terminated prepolymer or urethane prepolymer useful in the invention are prepared by reacting polyoxy-alkylene polyol with an excess of polyisocyanate, e.g., toluene diisocyanate.
The polyol should have a molecular weight of from about 200 to about 200,000 and preferably from about 600 to about 6,000. The hydroxyl functionality following reaction is from 2 to about 8. When the isocyanate functionality of the polyol and the corresponding isocyanate functionality of the prepolymer is two the functionality of the step 3 amine reactant must be greater than two.
When the isocyanate functionality of the prepolymer is greater than two the functionality of the amine reactant in step 3 may be as little as two.
The preferred isocyanate capped or NC0-terminated prepolymer consists of a mixture of (1) an isocyanate capped hydrophilic polyoxyethylene diol, said diol having an ethylene oxide content of at least 40 mole percent; and (2) an isocyanate capped polyol having a hydroxy functionality in the range 3 to 8 prior to capping; said isocyanate capped polyol being present in an amount in the range 2.9 to 50~ by weight of (1) and (2).
The polyoxyethylene diol is the reaction product of alkylene oxides of which at least ~0 mole percent is ethylene oxide with an initiator such as ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol 1~23~1~
or mixtures thereof. Preferably the molecular weight of the diol is between abo~t 400 to about 6,000.
Examples of suitable polyols (to be capped with polyisocyanates) include: (A) essentially linear polyols formed for example by reaction of ethylene oxide with ethylene glycol as an initiator. Mixtures of ethylene oxide with other alkylene oxide can be employed so long as the mole percent of ethylene oxide is at least 40 percent. Where the linear polyethers are mixtures of ethylene oxide with e.g., propylene oxide, the polymer can be either random or a block copolymer. A second class of polyol (B) includes those with a hydroxy functionality of 3 or more. Such polyols are commonly formed by react-ing alkylene oxides with a polyfunctional initiator such as trimethylolpropane, pentaerythritol, etc. In forming the polyol B, the alkylene oxide used can be ethylene oxide or mixtures of ethylene oxide with other alkylene oxides as described above. Useful polyols can be further exemplified by (C) linear branched polyfunctional polyols as exemplified in A and B above together with an initiator or crosslinker. A specific example of C is a mixture of polyethyl-ene glycol (m.w. about 1,000) with trimethylolpropane, trimethylolethane or glycerine. This mixture can be subsequently reacted with excess polyisocyanate to provide a prepolymer useful in the invention. Alternatively the linear or branched polyols, (e.g., polyethylene glycol) can be reacted separately with excess polyisocyanate. The initiator, e.g., trimethylolpropane, can also be separately reacted with polyisocyanate. Subsequently the two capped materials can be combined to form the prepolymer.
Polyoxyalkylene polyol is terminated or capped by reaction with a polyisocyanate. The reaction may be carried out in an inert moisture-free atmosphere such as under a nitrogen blanket, at atmospheric pressure at a temperature in the range of from about 0C to about 120C for a period of time 11~23~0 of about 20 hours depending upon the temperature and degree of agitation. This reaction may be effected also under atmospheric conditions provided the product is not exposed to excess moisture.
Capping of the polyoxyalkylene polyol may be effected using stoichio-metric amounts of reactants. Desirably, however, an excess of isocyanate is used to insure complete capping of the polyol. Thus, the ratio of isocyanate groups to the hydroxyl groups used is between about 2 to about ~ isocyanate to hydroxyl, and preferably about 2 to about 2.5 isocyanate to hydroxyl molar ratio.
To obtain the maximum strength, solvent resistance, heat resistance and the like, the isocyanate capped polyoxyalkylene polyol reaction products are formulated in such a manner as to give crosslinked polymer network.
Any ketoxime is ef~ective among these being acetone oxime, butanone oxime, cyclohexanone oxime, and the like. An oxime based on a relatively volatile ketone is believed to be preferred. The most preferred oxime is butanone oxime, also commonly known as methyl ethyl ketoxime. Mixtures of oximes may be used, but there is no known merit in so doing. The proportions of oxime utilized may range from about 0.7 to about 1.2 equivalents of the isocyanate groups present. A more preferred range is 1.05 to 1.15 equivalents.
To prepare the blocked prepolymer, the oxime and prepolymer are simply admixed at temperatures of from 50 to 70C for from about 1/2 to 1-1/2 hours.
A solvent is not generally necessary although materials such as butyl cellosolve acetate can be employed. Other appropriate solvents include materials which are not reactive with either the oxime or urethane groups. Based on the moles of reactive oxime and NCO groups involved, the NOH/NCO molar ratio should be from about 0.7 to about 1.2 and preferably from about 1.05 to about 1.15. Generally it is most effective to use sufficient oxime to completely react with the NCO
11~23~3~
groups .
In preparing the blocked prepolymer the oxime selected to provide a product that will undergo curing reactions in a reasonable time at a reasonable temperature. The curing temperature is influenced by materials such as sub-strates and catalysts so that in curing the waterborne polyurethane dispersion temperatures outside the range of 140-180C can be employed. Curing temperatures of at least 120C have proved convenient in view of the curing times which must be employed. Lower temperatures result in longer cure times unless a catalyst is employed. Numerous oximes and catalysts which can be employed are described in: Petersen, Liebigs Ann. Chem., 562 tl949), p. 215; Wicks, Progress in Organic Coatings, 3 (1975), pp. 73-99; and Hill et al, Journal of Paint Tech., 43 (1971) p. 55. Oximes having the above unblocking temperatures are liquid materials at temperatures of about 80C, and the condensation products with urethane prepolymers are miscible with water or can be dispersed in water with the aid of surfactants. Generally the oximes are aliphatic cyclic, straight-chain or branched materials containing 2-8 (preferably 3-6) carbons.
The oxime blocked NCO-terminated prepolymer is reacted with an amine that is capable of causing the polymer to cure at a low temperature. Many of the amines usable within the scope of Applicants' invention are well known in the art and are referred to as polyfunctional amines. Specific examples of amines include, but are not limited to, ethylenediamine 1,3 propane-diamine, diethylenetriamine, triethylenetetramine, iminobispropylamine, tetraethylene-pentamine, methyliminobispropylamine, 2t2-aminoethylamine)-ethanol and the polyoxypropyleneamines manufactured by Jefferson Chemical Company, Inc. and ~ n~R ~
sold under the trade m moc JEFFAMINE D-400, D-2000 and T-403. The polyoxy-propyleneamines are aliphatic polyether primary di- and tri-functional amines derived from propylene oxide adducts of diols and triols.
34C~
As can be observed from the amines listed some of the amines can be represented by general formulae NH2R'-NH'2 and HO-R NH2 where R' is a C2C6 group .
We have found in our experimental work that polyfunctional amines with a functionality of at least 2 primary amine end groups are the preferred amines in getting adequate curing of the polyurethane polymer subsequently produced.
Some of the polyfunctional amines may be represented by the formula H2N- (CnH2n- 1 ) Z~CnH2n NH2 where z is an integer from 1 to 4, n is an integer larger than 1 and R is hydro gen, an alkyl group of 1 to 4 carbon atoms, or a hydroxyalkyl group of 1 to 4 carbon atoms.
The polyoxypropyleneamines may be represented by the formula N}12CH~CH3)CH2~ CH2CH(CH3 ~x NH2 where x is greater than 2, and by the formula CH2 { CH2-cH-(cH ~ NH2 CH3CH2 C -CH2{CH2-CH- (CH~NH2 ~H2 { CH -CH-(CH ~ NH2 where x+y+z is about 5.3. The molecular weights of these polyoxypropylene amines range from 200 to 2000 or larger with the preferred polyoxypropyleneamines having molecular weights of about 400 to 2000.
The amount of polyfunctional amine added to the oxime blocked NC0-terminated prepolymer should be in the range of 0.6 to 1.5 equivalents with thepreferable range between 0.9 to 1.1 equivalents based on the total equivalents of all the isocyanate groups present in the NC0-terminated prepolymer.
Where the isocyanate functionality of the NC0-terminated prepolymer is two, a polyfunctional amine having a functionality of greater than two is required in order to provide a satisfactory cross-linked product. When the isocyanate functionality of the NC0-terminated prepolymer is greater than two, the polyfunctional amine functionality may be as little as two. It is to be understood from this that in the same reactive sys~em that the functionality of the NC0-terminated prepolymer and the amine or polyoxypropyleneamines will have a total functionality of greater than four.
The reaction between the oxime blocked prepolymer and the polyfunc-tionalamine is controlled by adding an acid or a mixture of acid and water prior to the completion of the reaction. Failure to control the amine-oxime blocked prepolymer reaction at the proper time may result in an amine reaction product too viscous for the purposes of this invention. Thus the proper portions of the blocked prepolymer and polyfunctional amine are placed in a reaction vessel and reacted under controlled conditions of heating and stirring. With experience we have been able to determine the state of the reaction by observing the increase in viscosity. With proper equipment such as temperature controlled mixing head devices the reaction times can be rapid at elevated temperatures.
For example reaction times can be as short as about 3 minutes at about 95C, 4 minutes at about 80C, etc. Preferred reaction times are from about one-half hour to about one hour with temperatures between about 40 and 60C. Sufficient acid or water-acid mixture is stirred into the amine reaction product to lower the pH value to about 5 or below.
The cationically stabilized waterborne polyurethane polymers are prepared by dispersing the amine reaction product in water in the presence of sufficient acid to provide a pH of from about 5 or below. In preparing the waterborne polymers the acid can be added directly to the amine reaction product and admixed therewith followed by dilution with water. This is the preferred 3~0 method. However, it is also possible to first add the acid to the water followed by dispersion of the amine reaction product in the water. Other addi-tives such as surfactants, ultraviolet absorbers, stabilizers, pigments, etc., may be formulated into the waterborne polyurethane polymers as required.
It has been found that if the pH is not controlled within the broad range set forth above, settling problems are encountered and/or portions of the amine reaction product reacts with the water to form a crust. While the pH
value range is to be considered we have found that from about 1 to 10 parts or more of acid may be used for each 100 parts of amine reaction product. A more preferred range is from about 4 to 8 parts acic per 100 parts amine reaction product. ~hese waterborne polymers have been found to be stable for periods of several months at ambient temperatures, e.g., 20C, and also exhibit excellent resistance to freeze-thaw cycles.
While any organic or inorganic acid will form the amine salt and per-form the function of controlling the pH value, the acids which we have used in-clude glacial acetic acid, acrylic acid, citric acid, ethylenediaminetetraacetic (fiDTA) acid, formic acid~glycine (aminoacetic acid), hydrochloric acid, lactic acid (alpha-hydroxypropionic acid), orthophosphoric acid ~H3P04), phosphorous acid (H3P03), sulfamic acid, sulfuric acid, tartaric acid (dihydroxysuccinic acid), paratoluenesulfonic acid and mixtures thereof.
The following specific examples are illustrative but not limitative of our invention, it being understood that similar improved results are obtain-able with other combinations of different composition specified above. All such variations which do not depart from the basic concept of the invention and composition disclosed above are intended to come within the scope of the amended claims.
Preparation of Polyurethane Prepolymer Amine Salt -A preferred isocyanate terminated polyol prepolymer is prepared by mixing a hydrophilic polyoxyethylene diol having an ethylene oxide content of at least 40 mole percent with a polyol having a hydroxyl functionality in the range 3 to 8, said polyol being present in the admixture in an amount in the range 1.0 to 20% by weight, reacting with the mixture at a temperature in the range 0 to 120C an amount of a diisocyanate equal to 1.8 - 1.9 NCO to OH
equivalents for a time sufficient ~o cap substantially all the hydroxyl groups of the admixture, adding additional diisocyanate to provide 0.1 - 0.3 equivalents of NCO per initial equivalent of OH in excess of the theoretical amount necessary to react with the hydroxyl groups.
To 100 grams of the NCO terminated polyol prepolymer at 24C in a stainless steel vessel is added 22 grams of butanone oxime with stirring. The reaction of the oxime with the isocyanate is exothermic and the temperature went to 60C. A hot water bath is used to control the temperature between 80-90C for twenty minutes.
After twenty minutes and the temperature at 90C, 12 grams of diethyl-enetriamine is added with stirring. The reaction with the amine is also exothermic which accelerates chain extension.
The viscogity continues to increase and after ten minutes at 90-95C, 7.1 grams of glacial acetic acid and 7.1 grams of o-phosphoric acid dissolved in 100 grams of deionized water is slowly added to control the viscosity. After all the acid/water mixture is in, the material is cooled and packaged. Water may be added to achieve the desired % non volatiles (%N.V) and viscosity.
Typical physical properties of the emulsifier prepared are:
1~23`4~?
% N.V 52.0 pH 4.5-6.9 Viscosity (Brookfield LVF) 600-1000 cps Appearance clear, straw colored solution To a two liter resin kettle fitted with a condenser, thermometer, graduated addition funnel, stirrer, and a nitrogen source was added 327.5 g.
of demeneralized water, 2.0 g of isoascorbic acid, and 687.5 g (196.6 grams nonvolatiles) of cationic polyurethane prepolymer amine salt @ 24% nonvolatiles.
The mixture was stirred and heated to 40C, under a nitrogen blanket.
At 40C, 100 g of a monomer mixture of 240.0 g of methylmethacrylate, 120.0 g of butylacrylate, 40.0 g of acrylonitrile and 8.0 g of acrylic acid was added to the kettle with stirring. To the material in the resin kettle was charged 4 cc of 30% hydrogen peroxide. The heat of reaction caused the tempera-ture to go from 41C to 47C in three minutes. The remaining monomer mixture was charged at a rate to maintain a temperature of 55-60C in the resin kettle without auxiliary heating. Discrete shots of 30% H202 were added at 2 cc levels during the monomer mixture addition. The total monomer mixture addition time was 39 minutes. When the last of the monomer mixture was charged, the temperature was 57C.
Eight minutes after the final monomer mixture addition and at a temperature of 54C, 0.1 g of isoascorbic acid dissolved in 10 cc demineralized water and 1.0 g of tertiary butylhydroperoxide were added to reduce the free monomer.
The two liter resin kettle (after packaging latex) had no solid build-up at all and required only a water rinse. The resulting latex had 39.6% Total Solids, a pH value of 4.3, a surface tension of 43.2 dynes/cm and a Brookfield - lg -46~
LVF #1 @ 60 viscosity of 53.4 centipoises.
REACTANT % WET
vinylidene chloride 67 640 butyl acrylate 15.0 144 glacial acetic acid 2 16 polyurethane prepolymer amine 17 400 salt @ 40% solids ascorbic acid .2 2 hydrogen peroxide 1.0 10 demineralized water - 800 To a 2 liter resin kettle fitted with a thermometer, stirrer and addition funnel was added 800 g. water, 400 g. polyurethane prepolymer amine salt at 40% solids, and 2 g. ascorbic acid. This mixture was heated to 36C under a nitrogen purge.
To the above was added 200 cc of a mixture consisting of 640 g.
vinylidene chloride, 144 g. butyl acrylate, and 16 g. glacial acetic acid followed by the addition of 2 cc of 20% hydrogen peroxide. The heat or reaction raised the temperature to 46C. The remainder of the monomer was added in 100 cc increments along with 1-2 cc shots of hydrogen peroxide to maintain a tem-perature range of 45-50C. After the last of the monomer was added, a 2 cc parting shot of hydrogen peroxide was added and the batch was allowed to cook to reach maximum conversion. The latex had the following properties:
Total Solids 39.0%
Conversion 81.6%
Surface Tension 52.8 dynes/cm pH Value 4.0 Examples 3 through 12 below illustrate emulsion polymerization using the poly-urethane prepolymer amine salt as emulsifier with various monomer combinations.
The procedure used in Examples 3-12 was that described in Example 2. All ingredients are indicated in weight percent.
234~) Example 3-Weight %
vinylidene chloride 32 styrene 33 acrylic acid 2 Example 4:
Weight %
vinylidene chloride 56 methylacrylate 5 acrylic acid 2 Example 5:
Weight %
methylmethacrylate 6 butylacrylate 13 methylacrylate 37 acrylic acid 6 Examples 6, 7, 8:
Weight %
methylmethacrylate 49 42 39 butyl acrylate 25 21 20 acrylonitrile 8 7 6 acrylic acid 2 2 2 Examples 9,_10:
Weight %
vinylidene chloride 33 28 styrene 33 28 butyl acrylate 16 14 acrylic acid 2 2 ~1~2~5 Example 11:
Weight %
methylmethacrylate 71 Example 12:
Weight %
12_1 12-2 methylmethacrylate 42 37 butylacrylate 21 18 acrylonitrile 7 6 acrylic acid 2 2 The te~ns and expressions which have beem employed are used as terms of description and not of limitation, and there is no intention, in the use of such terms and expressions, of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed.
,,
Claims (27)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for producing latexes by aqueous emulsion polymerization of one or more polymerizable monomers the improvement wherein the polymerization is carried out in the presence of polyurethane prepolymer amine salt emulsifier, said emulsifier prepared by reacting a first component comprising an isocyanate capped hydrophilic polyol having a reaction functionality of two or greater with a second component comprising a ketoxime to form an oxime blocked prepolymer, reacting a third component comprising a polyfunctional amine having a function-ality of two or greater with said oxime blocked prepolymer to form an amine reaction product, reacting a fourth component comprising an acid with said amine reaction product whereby an infinitely water dilutable polyurethane polymer amine salt is formed and diluting said polyurethane polymer amine with water.
2. The process of Claim 1 wherein the polymerizable monomer is selected from the group consisting of lower alkyl acrylate, lower alkyl methacrylate, acrylonitrile, acrylic acid, vinyldiene chloride, styrene and mixtures thereof.
3. The process of Claim 1 wherein said second component is butanone oxime.
4. The process of Claim 3 wherein said third component is selected from the group consisting of diethylenetriamine, triethylenetetramine, iminobispropyl-amine, tetraethylenepentamine, methyliminobispropylamine, 2(2-aminoethylamine)-ethanol, ethylenediamine, 1,3-propanediamine, polyoxypropyleneamine, and mixtures thereof.
5. The process of Claim 4 wherein said fourth component is selected from the group of acids consisting of acetic, acrylic, citric, ethylenediamine-tetraacetic, formic, glycine, lactic, o-phosphoric, phosphorous, p-toluene-sulfonic, sulfamic, tartaric, hydrochloride and mixtures thereof.
6. The process of claim 3 wherein said third component is a mixture of diethylenetriamine and an amine selected from the group consisting of diethylamine, dibutylamine and dihexylamine.
7. The process of claim 6 wherein said fourth component is selected from aqueous acetic acid, aqueous o-phosphoric acid and mixtures thereof.
8. The process of claim 4 wherein a viscosity controlling agent selected from the group consisting of diethylamine, dibutyl-amine and dihexylamine is included in said third component.
9. The process of claim 8 wherein the fourth component is an aqueous mixture of glacial acetic and phosphoric acids.
10. An emulsion composition prepared by emulsion polymerization of a polymerizable vinyl monomer in the presence of an emulsifier characterized in that the emulsifier is a waterborne composition consisting essentially of the sequential reaction products of (a) a first component comprising isocyanate capped hydrophilic polyether polyol prepolymer having a reactive functionality of at least two, said prepolymer consisting of a mixture of (1) from about 2.9 to about 50% by weight of said mixture of an isocyanate capped polyol having a hydroxyl functionality in the range of 3 to 8 prior to capping; and (2) from about 97.1 to about 50% by weight of said mixture of an isocyanate capped hydrophilic polyoxyethylene diol, said diol having an ethylene oxide content of at least 40 mole percent, with (b) a second component comprising a ketoxime whereby an oxime blocked prepolymer is formed, reacting said oxime blocked prepolymer with (c) a third component comprising a polyfunctional amine whereby an amine reaction product is formed, and reacting said amine reaction product with (d) a fourth component comprising an aqueous acid to form a water-borne emulsifier composition.
11. The composition of Claim 10 wherein said second component is butanone oxime.
12. The composition of Claim 11 wherein said third component is selected from the group consisting of diethylenetriamine, triethylenetetramine, iminobis-propylamine, tetraethylenepentamine, methyliminobispropylamine, 2(2-aminoethyl-amine)-ethanol, ethylenediamine, 1,3-propenediamine, polyoxypropyleneamine, and mixtures thereof.
13. The composition of Claim 12 wherein said fourth component is selected from the group of acids consisting of acetic, acrylic, citric, ethylenediamine-tetraacetic, formic, glycine, lactic, o-phosphoric, phosphorous, p-toluene-sulfonic, sulfamic, tartaric, hydrochloric and mixtures thereof.
14. The composition of Claim 11 wherein said third component is a mixture of diethylenetriamine and an amine selected from the group consisting of di-ethylamine, dibutylamine and dihexylamine.
15. The composition of Claim 14 wherein said fourth component is selected from aqueous acetic acid, aqueous o-phosphoric acid and mixtures thereof.
16. The composition of Claim 13 wherein the vinyl monomer is selected from the group consisting of lower alkyl acrylate, lower alkyl methacrylate, acrylonitrile, acrylic acid, vinyldiene chloride, styrene and mixtures thereof.
17. The composition of Claim 12 wherein a viscosity controlling agent selected from the group consisting of diethylamine, dibutylamine and dihexyl-amine is included in said third component.
18. The method of Claim 17 wherein the fourth component is an aqueous mixture of glacial acetic and phosphoric acids.
19. In an emulsion polymerization procedure for forming vinylidene chloride homopolymer or copolymers by heating a monomer charge containing vinyl-idene chloride in the presence of a water soluble initiator and an emulsifier to a latex containing particles of said polymers, the improvement which comprises using as an emulsifier composition consisting essentially of a waterborne polyurethane prepolymer polymer amine salt wherein said salt is formed by reacting from about 0.7 to about 1.2 equivalents of, based on prepolymer NCO
groups, a ketoxime with a polyurethane prepolymer having free NCO groups to form an oxime blocked prepolymer, said prepolymer consists of a mixture of from about 2.9 to about 50% by weight of said mixture of an isocyanate capped polyol having a hydroxyl functionality in the range of 3 to 8 prior to capping; and from about 97.1 to about 50% by weight of said mixture of an isocyanate capped hydrophilic polyoxyethylene diol, said diol having an ethylene oxide content of at least 40 mole percent, reacting said blocked prepolymer with from about 0.6 to about 1.5 equivalents of, based on prepolymer NCO groups, a polyfunctional amine to form an amine reaction product, reacting said amine reaction product with from about 1 to about 10 parts of an acid per 100 parts of said amine reaction product to form an amine salt and diluting said amine salt with water to be less than 60% total non-volatiles content.
groups, a ketoxime with a polyurethane prepolymer having free NCO groups to form an oxime blocked prepolymer, said prepolymer consists of a mixture of from about 2.9 to about 50% by weight of said mixture of an isocyanate capped polyol having a hydroxyl functionality in the range of 3 to 8 prior to capping; and from about 97.1 to about 50% by weight of said mixture of an isocyanate capped hydrophilic polyoxyethylene diol, said diol having an ethylene oxide content of at least 40 mole percent, reacting said blocked prepolymer with from about 0.6 to about 1.5 equivalents of, based on prepolymer NCO groups, a polyfunctional amine to form an amine reaction product, reacting said amine reaction product with from about 1 to about 10 parts of an acid per 100 parts of said amine reaction product to form an amine salt and diluting said amine salt with water to be less than 60% total non-volatiles content.
20. The method of Claim l9 wherein said ketoxime is butanone oxime, said polyfunctional amine is diethylenetriamine and said acid is glacial acetic.
21. The method of Claim 19 wherein the polyfunctional amine is an aliphatic/
polyoxypropyleneamine having a molecular weight of about 230.
polyoxypropyleneamine having a molecular weight of about 230.
22. The method of Claim 19 wherein the polyfunctional amine is Where x+y+z is about 5.3 and having a molecular weight of about 400.
23. The method of Claim 19 wherein said polyfunctional amine is selected from the group consisting of diethylenetriamine, triethylenetetramine, iminobis-propylamine, tetraethylenepentamine, methyliminobispropylamine, 2(2-aminoethyl-amine) ethanol, ethylenediamine, 1,3-propanediamine, polyoxypropyleneamine, and mixtures thereof.
24. The method of Claim 19 wherein said acid is selected from the group of acids consisting of acetic, acrylic, citric, ethylenediaminetetraacetic, formic, glycine, lactic, o-phosphoric, phosphorous, p-toluenesulfonic, sulfamic, tartaric, hydrochloric and mixtures thereof.
25. The method of Claim 23 wherein said polyfunctional amine is diethylene-triamine in admixture with an amine selected from the group consisting of diethylamine, dibutylamine and dihexylamine.
26. The method of Claim 25 wherein said acid is selected from aqueous acetic acid, aqueous o-phosphoric acid and mixtures thereof.
27. An emulsifier comprising a waterborne polyurethane prepolymer amine salt obtained by (1) admixing a hydrophilic polyoxyethylene diol having an ethylene oxide content of at least 40 mole percent with a polyol having a hydroxyl functionality in the range 3 to 8, said polyol being present in the admixture in an amount in the range 1.0 to 20% by weight, reacting with the admixture at a temperature in the range 0 to 120°C, an amount of diisocyanate equal to 1.8 -1.9 NCO equivalents for a time sufficient to cap substantially all the hydroxyl groups of the admixture and thereafter adding additional diisocyanate to provide 0.1 - 0.3 equivalents of NCO per initial equivalent of OH in excess of the theoretical amount necessary to react with the hydroxyl groups to form an NCO-terminated prepolymer;
(2) reacting said NCO-terminated prepolymer with from about 1.05 to about 1.15 equivalents of butanone oxime to form a butanone oxime blocked pre-polymer;
(3) reacting said butanone oxime block prepolymer with from about 0.9 to about 1.1 equivalents of diethylenetriamine to form an amine reaction product; and (4) reacting said amine reaction product with water containing from about 4 to about 8 parts of a mixture of acetic and phosphoric acids per 100 parts of said amine reaction product such that the resulting waterborne composi-tion contains from about 20 to about 50% by weight non-volatiles.
(2) reacting said NCO-terminated prepolymer with from about 1.05 to about 1.15 equivalents of butanone oxime to form a butanone oxime blocked pre-polymer;
(3) reacting said butanone oxime block prepolymer with from about 0.9 to about 1.1 equivalents of diethylenetriamine to form an amine reaction product; and (4) reacting said amine reaction product with water containing from about 4 to about 8 parts of a mixture of acetic and phosphoric acids per 100 parts of said amine reaction product such that the resulting waterborne composi-tion contains from about 20 to about 50% by weight non-volatiles.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11579080A | 1980-01-28 | 1980-01-28 | |
| US115,790 | 1980-01-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1162340A true CA1162340A (en) | 1984-02-14 |
Family
ID=22363403
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000368247A Expired CA1162340A (en) | 1980-01-28 | 1981-01-09 | Polyurethane prepolymer amine salt emulsifier for emulsion polymerization processes |
Country Status (6)
| Country | Link |
|---|---|
| CA (1) | CA1162340A (en) |
| DE (1) | DE3102039A1 (en) |
| FR (1) | FR2474511A1 (en) |
| GB (1) | GB2068391A (en) |
| IT (1) | IT1170655B (en) |
| SE (1) | SE8100308L (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4446439A1 (en) * | 1994-12-23 | 1996-06-27 | Hoechst Ag | Polymer dispersions based on a cationic polyurethane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1085454A (en) * | 1964-11-06 | 1967-10-04 | Du Pont | Compositions for the formation of polyether-urethane/polyurea copolymers |
-
1981
- 1981-01-09 CA CA000368247A patent/CA1162340A/en not_active Expired
- 1981-01-20 SE SE8100308A patent/SE8100308L/en not_active Application Discontinuation
- 1981-01-22 DE DE19813102039 patent/DE3102039A1/en not_active Withdrawn
- 1981-01-27 FR FR8101497A patent/FR2474511A1/en not_active Withdrawn
- 1981-01-27 IT IT47641/81A patent/IT1170655B/en active
- 1981-01-28 GB GB8102602A patent/GB2068391A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| DE3102039A1 (en) | 1981-12-17 |
| SE8100308L (en) | 1981-07-29 |
| GB2068391A (en) | 1981-08-12 |
| IT8147641A0 (en) | 1981-01-27 |
| IT8147641A1 (en) | 1982-07-27 |
| IT1170655B (en) | 1987-06-03 |
| FR2474511A1 (en) | 1981-07-31 |
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