CN1354760A - Waterborne thickeners and dispersants haivng improved chemical resistance - Google Patents

Waterborne thickeners and dispersants haivng improved chemical resistance Download PDF

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Publication number
CN1354760A
CN1354760A CN00808616A CN00808616A CN1354760A CN 1354760 A CN1354760 A CN 1354760A CN 00808616 A CN00808616 A CN 00808616A CN 00808616 A CN00808616 A CN 00808616A CN 1354760 A CN1354760 A CN 1354760A
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monomer
polymkeric substance
weight
acid
big
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G·A·范狄赞德
K·R·欧勒森
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • 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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Improved dispersants and thickeners for use with latex polymers are disclosed which are polymerized from monomers having crosslinking functionality or elevated levels of macromonomers, or both. Latex polymers suitable for use with the thickeners and dispersants of the present invention can be prepared by a two stage polymerization of a first stage polymer and a second stage polymer wherein a monomer having crosslinking functionality is included in the first stage polymer, the second stage polymer, or both.

Description

Improved water base thickening material of chemical-resistant and dispersion agent
Invention field
The present invention relates to have the latex polymer of bridging property functional group, this latex polymer for example is suitable in the latex paint composition and makes thickening material and dispersion agent.
Background of invention
Latex paint normally is coated on the matrix and the dry successive film that forms, and plays the effect of decorating and protecting matrix.This coating often is to be coated on the interior wall or exterior wall surface of buildings, and this moment, coating was abundant flowable fluid, form successive and film, and dry at ambient temperature.
It is latex polymer that latex paint contains organic polymer binder usually, and pigment and various paint additive.In exsiccant was filmed, polymer binder played the effect of pigment tackiness agent, and exsiccant was filmed bond on the matrix.Pigment can be organic or inorganic, except that playing weather resistance and hardness effect, pigment also light tight and painted on work, although some coating contains seldom or do not contain lighttight pigment, such coating is known as varnish.The production of coating comprises the preparation polymer binder, mixes each component, ground pigment in dispersion medium, and be diluted to commercial standards.
General latex paint is used very extensive, because the discharging of their volatile organic compounds is low, and is easier to cleaning than solvent-based coating.Yet compare with the solvent-based coating system, typical latex paint lacks the chemical-resistant that solvent-based coating provided.
Typically, the crosslinked chemical-resistant that improves coating of polymer coating, and cohesive strength, wear resistance and exterior durability.Make a kind of common mode of crosslinked polymer be, make the outside cross-linking agent reaction of the reactive polymer that contains functional group and polyfunctionality.Outside cross-linking agent can with reactive polymer pre-mixing (so-called one canned system) together, perhaps can be before application it be mixed immediately with reactive polymer (so-called two-pack system).Because simple and be easy to handle, common one canned system is desired.
The bridging property functional groups is gone in the latex, make in one-step polymerization thing and two-stage polymerization objects system, carry out crosslinked.For example USP 5326843 discloses a kind of like this latex, wherein adds Hydroxyethyl acrylate in polymerisable monomer component, to give the one-step polymerization objects system with reactive functional groups.Hydroxy functional group can form cured film with aminoplastics and polyisocyanates reaction.Crosslinkable latex for example also is disclosed among WO 95/29963, WO 95/29944 (two step latex) and the USP 4144212,4522962 and 5414041 (a step latex).
Except giving binder polymer with the bridging property functional group, also need the latex paint composition is further improved, these improvement can provide improved performance, for example chemical-resistant.
Summary of the invention
The present invention relates to have and improve for example thickening material and the dispersion agent used of the water-based paint of chemical-resistant of performance.Have now found that to have thickening material or dispersion agent that bridging property functional group or big monomer content improve by use some in coating composition, perhaps these two can make and has for example latex paint composition of chemical-resistant of splendid performance.Randomly, also can use latex adhesive with crosslinked group.Can regulate the crosslinked group that is present in thickening material or the dispersion agent or the big monomer content of raising, so that the desired properties optimization of coating composition.More specifically,, can design, make its chemical-resistant, erosion resistance, wet fastness and/or the cementability of actual substrate with raising to the latex paint composition by changing crosslinked group content or the big monomer content on thickening material or the dispersion agent.Latex paint composition of the present invention for example can be self-vulcanizing, curing oven or radiation curing.
The invention provides applicable to for example polymkeric substance of compositions such as building coating, industry and car paint, sealing agent, tackiness agent, paper-coating composition, printing ink and varnish.Detailed Description Of The Invention
According to the present invention, be suitable for the latex polymer of making tackiness agent and comprise the polymkeric substance that those are obtained by one or more suitable monomer polymerizations.Typically, tackiness agent is by one or more copolymerizable single ethylenically unsaturated monomers, obtains as vinyl monomer and acrylic monomer polymerization.
Be applicable to that vinyl monomer of the present invention comprises any compound that vinyl-functional is the unsaturated part of alkene that has, except having the compound of acrylic functional group, for example vinylformic acid, methacrylic acid, these sour esters, vinyl cyanide and acrylamide.Preferably, vinyl monomer is selected from vinyl ester, vinyl-arene, vinyl fat hydrocarbon, vinyl alkyl ethers and composition thereof.
Suitable vinyl monomer comprises vinyl ester, for example propionate, vinyl laurate, new vinyl acetate acid, n-nonanoic acid vinyl acetate, capric acid vinyl acetate, vinyl neodecanoate, vinyl butyrate, vinyl benzoate, sec.-propyl vinyl-acetic ester and similar vinyl ester; Vinyl-arene, for example vinylbenzene, vinyl toluene and similar low alkyl group vinylbenzene, chlorostyrene, Vinyl toluene, vinyl naphthalene and Vinylstyrene; Vinyl fat hydrocarbon monomer, for example vinylchlorid, vinylidene chloride and alpha-olefin, for example ethene, propylene, iso-butylene, and conjugated diene, for example 1,3-divinyl, methyl-2-divinyl, 1,3-pentadiene, 2,3-dimethylbutadiene, isoprene, cyclohexadiene, cyclopentadiene and Dicyclopentadiene (DCPD); And vinyl alkyl ethers, for example methylvinylether, isopropyl-ethylene base ether, n-butyl vinyl ether and IVE.
Be applicable to that acrylic monomer of the present invention comprises any compound with acrylic-functional.Preferred acrylic monomer is selected from aromatic derivative, acrylamide and the vinyl cyanide of alkyl acrylate, alkyl methacrylate, vinylformic acid and methacrylic acid and vinylformic acid and methacrylic acid.Typically, the alkyl ester in each molecule of alkyl acrylate and alkyl methacrylate monomer (being also referred to as " acrylic or methacrylic acid alkyl ester " here) partly contains has an appointment 1～12, preferred about 1～5 carbon atom.
Suitable acrylic monomer comprises for example methyl acrylate and methyl methacrylate, ethyl propenoate and Jia Jibingxisuanyizhi, butyl acrylate and butyl methacrylate, propyl acrylate and propyl methacrylate, 2-EHA and methacrylic acid 2-ethylhexyl, cyclohexyl acrylate and cyclohexyl methacrylate, decyl acrylate and decyl-octyl methacrylate, isodecyl acrylate and isodecyl methacrylate, benzyl acrylate and benzyl methacrylate, isobornyl acrylate and isobornyl methacrylate, vinylformic acid peopentyl ester and methacrylic acid peopentyl ester, methacrylic acid 1-adamantyl (adamatyl) ester, and butyl for example, phenyl and cresylglycidylether and vinylformic acid and methacrylic acid, acrylic acid hydroxy alkyl ester and hydroxyalkyl methacrylate be vinylformic acid and hydroxyethyl methylacrylate and hydroxypropyl acrylate for example, the various reaction product of amino acrylates and amino methyl acrylate.The suitable acid or the monomer of anhydride-functional comprise vinylformic acid, methacrylic acid, ethylacrylic acid, α-Lv Daibingxisuan, Ba Dousuan, citraconic acid, methylfumaric acid, methylene-succinic acid, toxilic acid, fumaric acid, 3-acrylamido-3 Methylbutanoic acid, acrylic anhydride, methacrylic anhydride, the ethyl propylene acid anhydrides, crotonic anhydride, citraconic anhydride, the methylfumaric acid acid anhydride, itaconic anhydride, maleic anhydride, fumaric acid anhydride, right-the vinylbenzene carboxylic acid, right-styrene sulfonic acid, vinyl sulfonic acid, methacrylic acid 2-sulphur ethyl ester, methacrylic acid 3-sulphur propyl ester, vinylformic acid 3-sulphur propyl ester, 2-acrylamido-2-methyl propane sulfonic acids etc. comprise their mixture.
Except above-mentioned concrete monomer, one of ordinary skill in the art would recognize that, available other monomer replaces specifically described monomer or to wherein adding other monomer in the preparation of tackiness agent (and following dispersion agent and thickening material), allyl monomer or give the monomer of wet bonding for example is as methacryloyl amido ethyl ethylidene-urea.Relating to other monomeric other particular content that these are applicable to copolymerization in the present invention, is known to those skilled in the art.These other monomeric consumption depends on concrete monomer and their specific functions, and those skilled in the art can determine their consumption.
Randomly, binder polymer of the present invention can have bridging property functional group.In this one side content of the present invention, be used to make at least a monomer of tackiness agent polymeric for containing the ethylenically unsaturated monomer of " potential crosslinked " or " back is crosslinked " ability, here used " potential crosslinked " or " back crosslinked " ability be meant, monomer has further the ability of reacting with for example linking agent after initial formation polymkeric substance for some time.Crosslinked activation can be undertaken by applying energy, is for example undertaken by heating or radiation.Can also cause reacting pH value, oxygen level or other variation etc. of generation by change, come the crosslinked of activated polymer with drying.Realize that the crosslinked concrete grammar of binder polymer is unimportant for the present invention.Producing crosslinked various chemical processes in latex is being known in the art.
In film process, carry out crosslinked monomeric example and comprise the monomer that contains carbonyl, for example propenal, methacrolein, diacetone-acryloamide(DAA), diacetone Methacrylamide and etheric acid vinyl acetate.For example when aqueous polymer emulsions also contained the linking agent of suitable add-on, it is crosslinked that these monomers form the back.Linking agent can be the crosslinked compound of any promotion binder polymer, comprises polymkeric substance, no matter whether it is dissolved in the aqueous phase of latex composition.Concrete linking agent is unimportant for the present invention.Shi Yi such compound is the aliphatic series of 2～20 carbon atoms and two hydrazides and three hydrazides of aromatic dicarboxylic acid especially.These examples for compounds are oxalic acid two hydrazides, adipic dihydrazide and sebacic dihydrazide.
Another can produce the crosslinked monomer in back and for example be methacrylic acid 2-acetoacetoxy groups ethyl ester (being used in combination separately or with other compound such as oxalic dialdehyde).
Other is suitable for the crosslinked monomer in back and contains the compound of hydrolyzable organosilicon key for those.The example is methacryloxy-propyl trimethoxy silicane and vinyltrimethoxy silane.Other suitable monomer for example is disclosed in DE-A 4341260.If the dispersive polymer particle has carboxyl, it is crosslinked then can also to carry out the back by the metal-salt (for example Mg, Ca, Zn or Zr salt) that adding has a polyvalent cation.
The monomer that contains epoxy group(ing), hydroxyl and/or N-hydroxyalkyl, for example glycidyl acrylate, N hydroxymethyl acrylamide and-Methacrylamide, and the α of dibasic alcohol and about 3～6 carbon atoms, the monobasic ester of β-monoethylenically unsaturated carboxylic acid, for example the hydroxyl ethyl ester of vinylformic acid and methacrylic acid, hydroxyl n-propyl ester or hydroxyl n-butyl are crosslinked after they are suitable for too.
Typically, based on the gross weight of polymkeric substance, binder polymer of the present invention contains 0.5～10 weight % that has an appointment, at least a monomer with bridging property functional group of preferred about 1～6 weight %.Preferably, based on the gross weight of binder polymer (the monomeric gross weight that promptly is used for the polymerization the first step polymkeric substance and the second step polymkeric substance), binder polymer contains less than about 25 weight %, is more preferably less than about 20 weight %, most preferably less than the monomer with bridging property functional group of about 15 weight %.
Typically, the particle diameter of binder polymer is about 0.1～1.0 micron, preferred about 0.2～0.4 micron, and more preferably from about 0.25～0.3 micron.Typically, the Tg of tackiness agent of the present invention is-60～100 ℃ approximately, preferred-30～70 ℃ approximately, more preferably from about-15～60 ℃.Terminology used here Tg is meant the second-order transition temperature of polymkeric substance.The determination techniques of glass transition temperature of polymer is known for a person skilled in the art.A kind of determination techniques so for example is a dsc.A kind of method of useful especially estimation glass transition temperature of polymer is provided by Fox,
1/Tg (polymkeric substance)=x 1/ Tg 1+ x 2/ Tg 2+ x 3/ Tg 3+ ... + x n/ Tg n(1) x wherein iBe the weight fraction of component i in multipolymer, Tg iSecond-order transition temperature for component i homopolymer.The second-order transition temperature of homopolymer can find in as " polymer handbook " in any data that openly can get.For example, the homopolymer glass transition temperature of typical monomers is: vinyl acetate=-32 ℃, butyl acrylate=-54 ℃, vinyl neodecanoate=-3 ℃, 2-EHA=-65 ℃.
Typically, with the composition of 40～60 weight % solid contents, use brookfield's viscometer, it is about 20～3000 using No. 2 rotors, the viscosity of the tackiness agent of the present invention that records under 60 rev/mins rotating speed, preferred about 50～1500 centipoises (" cP ").Typically, the molecular weight of tackiness agent of the present invention is about 5 * 10 4～10 7, preferred about 200000～1000000g/gmol.Unless add explanation in addition, terminology used here " molecular weight " is meant number-average molecular weight (" Mn ").The technology that changes molecular weight is known, comprises and for example uses polyfunctional monomer and chain-transfer agent.The technology of measuring the number-average molecular weight of latex polymer is known for a person skilled in the art.A kind of technology so for example is a gel permeation chromatography.Under the situation of two-stage polymerization thing, unless add explanation in addition, molecular weight refers to the molecular weight after the first step polymkeric substance and the polymkeric substance difference polymerization of second step.
Binder polymer of the present invention can contain hydrophobic group.Above-mentioned ethylenically unsaturated monomer for example can carry out polymerization to introduce hydrophobic group with one or more polymerisable big monomers.These big monomers contain hydrophobic parts and can with the alkoxylate part of other monomer polymerization.USP 4703080 discloses the hydrophobic adhesive resin, and the content with this patent is incorporated herein by reference here.Preferred big monomer is the urethanes monomer, and it comprises that monohydroxy tensio-active agent and monoene belong to the reaction product of unsaturated isocyanate.These big monomers are known for a person skilled in the art.
In the content, binder polymer contains sour functional emulsoid in one aspect of the invention.Be applicable to that concrete acid functional monomer of the present invention comprises, for example vinylformic acid, methacrylic acid and toxilic acid.
Gross weight based on polymkeric substance, a kind of preferred vinyl acrylate adhesive resin contains the vinyl fatty ester of 40～60 weight %, the methyl methacrylate of about 30～50 weight %, the methacrylic acid of the diacetone-acryloamide(DAA) of about 0.5～10 weight % and about 0.5～5 weight %.
Gross weight based on polymkeric substance, a kind of preferred acryloid cement resin contains the butyl acrylate of 20～35 weight % that have an appointment, the methyl methacrylate of 40～65 weight %, the diacetone-acryloamide(DAA) of about 0.5～10 weight %, the vinyl cyanide of the methacrylic acid of about 0.5～5 weight % and about 5～10 weight %.
In a preferred version of the present invention, tackiness agent is the two-stage polymerization thing that contains the first step polymkeric substance and the second step polymkeric substance.
The first step polymkeric substance is by randomly having in the presence of the bridging property monomer, the monomer mixture letex polymerization is made, and wherein monomer mixture comprises with the monomer of at least a carboxylic acid of multiple comonomer reaction or anhydride-functional or can give the monomer of the first step polymkeric substance alkali susceptibility.
The amount that is present in acid in the first step letex polymerization or anhydride functional group has determined the solubleness of the first step when adding alkali.Chemical property and the sequence of monomer in polymkeric substance according to molecular weight, acid or the anhydride monomers of the hydrophobicity of comonomer, polymkeric substance distribute, and the minimum that needs acid or anhydride functional group is with dissolve polymer.Based on the total monomer weight that adds in the first step reaction, the acid or the monomeric preferred weight of anhydride-functional that are present in the first step polymerization are at least about 2 weight %, preferably at least 3 weight %, more preferably from about 5 weight % to 50 weight %; Further more preferably from about 8～30 weight %, most preferably from about 10～20 weight %.
The illustrative example that is applicable to the first step polymeric comonomer is for example vinylbenzene of methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, decyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, hydroxyethyl methylacrylate, Rocryl 410, vinylbenzene, replacement such as other C of alpha-methyl styrene, vinyl cyanide, vinyl acetate and vinylformic acid and methacrylic acid 1～C 12Alkyl ester or hydroxy alkyl ester, 2 ethyl hexanoic acid vinyl acetate, propionate, vinyl neodecanoate, new n-nonanoic acid vinyl acetate, a kind of vinyl acetate that the alkanecarboxylic acid (commodity) (versatic acid) of side chain arranged, new vinyl acetate acid etc., and/or their mixture.
The first step polymkeric substance can be various molecular weight.Can control molecular weight by adding suitable chain-transfer agent well known in the art.The example of suitable chain-transfer agent comprises for example alkyl sulfhydryl, as octyl mercaptan and decyl mercaptan, and mercaptoacetate such as ethyl thioglycolate and 2-ethylhexyl mercaptoacetate, and mercaptopropionic acid ester such as the different monooctyl ester of thiohydracrylic acid.In a preferred embodiment, chain-transfer agent can be selected from thiohydracrylic acid 2-ethylhexyl, the different monooctyl ester of thiohydracrylic acid or its mixture.Typically, the Mn of the first step polymkeric substance is 50000～1000000g/gmol.Preferably, the Mn of the first step polymkeric substance is at least 50000, more preferably about 50000～100000g/gmol.
Of the present invention one preferred aspect in, when the first step polymerization finishes, in the first step alkali polymer soluble, add neutralizing agent or alkali, with swelling, be partly dissolved or dissolve polymer basically.Suitable alkali comprises other the IA and the oxyhydroxide of IIA family etc. of ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and all.2-methyl ethylene imine is also effective to the neutralization of the first step alkali soluble polymer, and it can give the final product wet bonding simultaneously.
Based on the equivalent of the acid in the alkali soluble polymer, typically, in the alkali soluble polymer, add 0.01～1.5 normal alkali, with swelling, be partly dissolved or dissolve the alkali soluble polymer basically, make to form stable dispersion medium concerning the second step polymerization.
In one aspect of the invention, the first step latex polymer can store with the form of its preparation, for used with post neutralization.In another aspect of this invention, the first step polymkeric substance can be neutralized, and is used as the dispersion medium of other latex polymer, comprises the second step emulsion polymerization process of the present invention.
By with the medium of the first step polymkeric substance, find that final product has improved film forming properties, chemical-resistant and other characteristic as the second step letex polymerization of alkali insoluble monomer.
Be applicable to that the second step polymeric monomer is preferably the alkali insoluble monomer, i.e. those essentially no carboxylic acids or anhydride functional group's monomer for example has the monomer of vinylformic acid, vinylbenzene, vinyl or versatic functional group.Terminology used here " essentially no " is meant, based on the gross weight of polymkeric substance, less than about 10 weight %, preferably less than about 5 weight %, is more preferably less than about 2 weight %.
Second optional components that goes on foot in the polymerization that can be included in the alkali insoluble polymer comprises for example other monomer, as monomer, linking agent, chain-transfer agent and other component well known in the art of vinyl ester, acid and/or anhydride-functional.If use suitable chain-transfer agent or linking agent, Mn can be 500～500000, and is perhaps bigger to unlimited.Randomly, also can in the second step polymerization, be incorporated into bridging property functional group, so that final latex product has cross-linking properties; Yet condition is, be attached in the first step polymkeric substance or the second step polymkeric substance at least a.
Desired properties and the acid content in each step according to final latex composition join the required ratio of carrying out the second step monomer polymerization in the first step polymeric media and have covered wide range.For example, [for example 10 parts/100 parts resins when using the material of height carboxylation more, the first step that promptly contains the first step resin of 20% methacrylic acid added for second step (" p.h.r ")], the amount that joins the first step polymkeric substance in the second step polymerization can be less, perhaps when using the material of lower carboxylation [20p.h.r. that for example contains the first step resin of 10% methacrylic acid], the amount that joins the first step polymkeric substance in the second step polymerization can be bigger.Optimum range comprises about 1: 99 to 99: 1.The part by weight of the preferred second step monomer addition is about 5: 95 to 95: 5, most preferably from about 10: 80 to 80: 10.
Tackiness agent of the present invention for example can be used for building coating, industry and car paint, sealing agent, tackiness agent, paper-coating composition, printing ink and varnish etc.
In coating proportioning, can use the alkali insoluble polymer that is dispersed in the first step neutral polymkeric substance based on solid weight, its amount ranges is about 5～90 weight % of coating proportioning gross weight.Found to have good chemical-resistant, high-luster and improved anti-anti-caking with the coating proportioning of these specific polymers preparations.Except that tackiness agent of the present invention, coating proportioning also can contain additive commonly used, as pigment, filler, dispersion agent, wetting agent, coalescing agent, rheology modifier (being also referred to as " thickening material "), dry delayed-action activator, sterilant, defoamer etc.Detailed in being used for the concrete components selection and the consumption of formulation for coating material, be known for a person skilled in the art.
According to the present invention, the dispersion agent with bridging property functional group is provided and/or has had the thickening material of bridging property functional group.
Can use any suitable dispersion agent according to the present invention.Be applicable to preferably that the polymer dispersant with bridging property functional group of the present invention comprises unsaturated carboxylic acid monomer, the monoene that is different from the carboxylic acid monomer belongs to unsaturated monomer, contain hydrophobic part and can and have the monomeric reaction product of potential crosslinked functional group with the big monomer of the alkoxylate part of other monomer polymerization.
Typically, be applicable to that the unsaturated carboxylic acid monomer of preparation dispersion agent is α, β-monoethylenically unsaturated carboxylic acid.Preferred carboxylic acid monomer is selected from vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, toxilic acid and composition thereof.Particularly preferably be methacrylic acid.Typically, based on the gross weight of polymkeric substance, carboxylic acid monomer's concentration is about 20～70 weight %, preferred about 20～50 weight %, more preferably from about 35～45 weight %.When for example sodium hydroxide reacted with alkali, the monomeric amount of optimization acid was enough to provide the dissolved polymers structure and its viscosity is increased.
According to the present invention, the monoene that is different from the carboxylic acid monomer belongs to unsaturated monomer and preferably contains ethyl group.More preferably, this monomer is an acrylate.Most preferably, this monomer is an ethyl propenoate.Typically, based on the gross weight of polymkeric substance, the amount that the monoene that is different from carboxylic acid belongs to unsaturated monomer is about 5～70 weight %, preferred about 10～50 weight %.Randomly, dispersion agent can contain or not contain big monomer.When not using big monomer, for example it can be waited the ethyl propenoate of weight percent to replace.
Be applicable to the preparation dispersion agent of the present invention big monomer contain hydrophobic part and can with the alkoxylate part of other monomer polymerization.Terminology used here " big monomer " is meant the polymerisable monomer of the reaction product that contains two or more compounds.This big monomer comprises for example any alkoxylate such as ethoxylation or propenoxylated monomer, and this monomer has the unsaturated part of olefinic and by hydrophobic aliphatic chain end-blocking.The example of undersaturated polymerizable moiety comprises part, methacryloyl, maleoyl, clothing health acyl group, crotonyl, unsaturated urethane part, half ester maleoyl, half ester clothing health acyl group, the CH that contains vinyl 2=CHCH 2The methacryloyl amido of-O-, methacryloyl amido and replacement.The example of hydrophobic part comprise per molecule have the linearity of at least one carbon atom, preferred about 1～30 carbon atom or branching, saturated or undersaturated alkyl, alkaryl be alkylaryl or arylalkyl or aryl.
Preferred big monomer is to contain the urethanes monomer that monohydroxy tensio-active agent and monoene belong to the reaction product of unsaturated isocyanate.Preferably, the urethanes monomer be monohydroxy nonionogenic tenside and the monoene urethane reaction product that belongs to unsaturated monoisocyanates, nonionic urethanes monomer, wherein monoene belongs to unsaturated monoisocyanates and preferably lacks ester group, α for example, alpha-alpha-dimethyl--pseudoallyl benzyl isocyanate ester.The monohydroxy nonionogenic tenside itself is known, and is generally for example hydrophobic substance of ethoxylation of alkoxylate, and they contain the oxidation ethylidene part of adduction, so that the hydrophilic parts of molecule to be provided.These hydrophobic substances are generally fatty alcohol or alkylphenol, and wherein carbochain contains at least one carbon atom, and preferred about 1～30 carbon atom is to provide the hydrophobic part of tensio-active agent.The example of these tensio-active agents is the ethylene oxide adduct of dodecanol or octyl group or nonylphenol, and they are that commodity can get, and for every mole of hydrophobic part, and they contain about 5～150, preferred 25～60 moles oxyethane.Other hydrophobicity surrogate for example is disclosed in those composite hydrophobic materials described in the USP 5488180 that 1996.1.30 authorizes, and also is applicable to the present invention.
Be applicable to that it can be any isocyanic ester that can effectively form requisite carbamate key company that the monomeric monoene of preparation urethanes belongs to unsaturated isocyanate.Preferably, isocyanic ester is that monoene belongs to unsaturated monoisocyanates.Can use any copolymerizable unsaturated part, as acrylate and the unsaturated part of methacrylic ester.The unsaturated part of the allyl group that provides by vinyl carbinol also can be provided.Being preferably these compounds of hydroxyl-functional derivative form, is to pass through C 2～C 4Monoepoxide forms hydroxy ester as oxyethane, propylene oxide or butylene oxide ring and acrylic or methacrylic acid-respons and obtains, and these compounds that obtain preferably react with equimolar amount and organic diisocyanate such as tolylene diisocyanate or isophorone diisocyanate.It is styryl derivative that preferred monoene belongs to monoisocyanates, as α, and alpha-alpha-dimethyl--pseudoallyl benzyl isocyanate ester, and this unsaturated monoisocyanates lacks ester group, so its formation lacks the carbamate of this group.Typically, the amount that monoene belongs to unsaturated isocyanate is about 0.1-2.0 with respect to being used for preparing big monomeric monohydroxy tensio-active agent (based on mol ratio): 1, and preferred about 1.0: 1.0.
Be applicable to that big monomer of the present invention also can be represented by following general formula:
Figure A0080861600141
Wherein: R 1Monovalence residue for replacement or unsubstituted hydrophobic compound;
Each R 2Can be identical or different, for replacing or unsubstituted divalent hydrocarbon residue base;
R 3For replacing or unsubstituted divalent hydrocarbon residue base;
R 4, R 5And R 6Can be identical or different, be hydrogen or replacement or unsubstituted monovalence hydrocarbon residue;
Z is 0～150.
Illustrative R 1Substituting group comprises that for example simple or compound contains the hydrophobic grouping of 1～30 carbon atom, as alkyl, aryl, aralkyl, alkaryl and cycloalkyl.
Illustrative R 3Substituting group comprises for example organic residue of ether, ester, carbamate, acid amides, urea, acid anhydrides etc., comprises their mixture.R 3Substituting group can be described as " connection portion " between the unsaturated part of tensio-active agent that has hydrophobic part or pure and mild big monomeric compound usually.
The alkylidene oxide part that is included in the big monomeric compound can be homopolymer or the block or the random copolymers of straight or branched epoxy alkane.Also can use mixture such as the oxyethane and the propylene oxide of epoxy alkane.Other detailed relevant these big monomeric preparations are known for a person skilled in the art, and for example are disclosed among the USP 4514552,4801671,5292828,5292843 and 5294693, are introduced into as a reference here.
Typically, based on the gross weight of polymer dispersant, big monomeric amount is about 0～60 weight %, preferred about 0.5～50 weight %, more preferably from about 5～40 weight %.Typically, big monomeric molecular weight is about 400～8000g/gmol.
Typically, use down brookfield's viscometers at 20 ℃, 60 rev/mins down with the compositions of No. 2 rotor mensuration 20～50 weight % solid contents, the result of the present invention not in the viscosity of the dispersion agent of form be about 5～1500cP.Typically, the molecular weight of dispersion agent of the present invention is about 10 3～10 6, preferred about 5000～20000g/gmol.Typically, the particle diameter of dispersion agent is about 0.05～1.0 micron, preferred about 0.1～0.4 micron, and more preferably from about 0.1～0.3 micron.Typically, the Tg of dispersion agent of the present invention is about 0～90 ℃, preferred about 5～60 ℃, and more preferably from about 15～35 ℃.
When needs bridging property functional group, typically,, be applicable to that the dispersion agent of latex composition of the present invention should contain 0.5～50 weight %, at least a monomer of preferred 20～35 weight % with bridging property functional group based on the gross weight of polymer dispersant.
Can use the soluble thickening material of any suitable alkali according to the present invention.The suitable soluble thickening material of alkali for example is disclosed in USP 4514552,4722962,5292828 and 5292843, is introduced into as a reference here.The preferred soluble thickening material of alkali contains the water miscible liquid reaction product of following substances, and these materials are unsaturated carboxylic acid monomer such as methacrylic acid; The monoene that is different from the carboxylic acid monomer belongs to unsaturated monomer such as ethyl propenoate; Contain hydrophobic part and can with the big monomer of the alkoxylate of other monomer polymerization part.Randomly, thickening material can contain or not contain big monomer.When not using big monomer, for example available ethyl propenoate of weight percent that waits replaces it.When needs bridging property functional group, also can in reaction, introduce aforesaid monomer with bridging property functional group.The monoene that be used for thickening material polymeric unsaturated carboxylic acid monomer, is different from the carboxylic acid monomer belong to unsaturated monomer and big monomer and cross-linking monomer can comprise as above to binder polymer and dispersion agent described those.Usually, big monomer is the urethanes monomer, and it is the urethanes reaction product that monohydroxy tensio-active agent and monoene belong to unsaturated monoisocyanates.Typically, the monohydroxy tensio-active agent comprises ethoxylation or propenoxylated fatty alcohol or alkylphenol.
Of the present invention one preferred aspect in, use for example above-mentionedly to prepare thickening material for those used monomers of preferred dispersing agent.Typically, based on the gross weight of polymkeric substance, big monomeric amount is about 1～20 weight %, preferred about 5～15 weight %.
Typically, use down brookfield's viscometers at 20 ℃, 60 rev/mins down with the compositions of No. 2 rotor mensuration 20～50 weight % solid contents, the result of the present invention not in the viscosity of the thickening material of form be about 5～1500cP.Typically, the molecular weight of thickening material of the present invention is about 10 4～10 7, preferred about 20000～200000g/gmol.Typically, the particle diameter of thickening material is about 0.05～1.0 micron, preferred about 0.1～0.4 micron, and more preferably from about 0.1～0.3 micron.Typically, the Tg of thickening material of the present invention is about 0～90 ℃, preferred about 5～60 ℃, and more preferably from about 15～55 ℃.
When needs bridging property functional group, typically,, be applicable to that the thickening material of latex composition of the present invention contains 0.5～35 weight % that has an appointment, at least a monomer of preferred 1～5 weight % with bridging property functional group based on the gross weight of thickening material polymkeric substance.
In another aspect of this invention, dispersion agent or thickening material at least a do not have bridging property functional group.The substitute is, big monomeric content is preferably in above-mentioned preferable range.More detailed those skilled about suitable dispersion agent and thickening material is known.
Typically, tackiness agent of the present invention, dispersion agent and thickening material are colloidal form, i.e. aqueous dispersion, or solution form, and they can pass through emulsion polymerization prepared in the presence of chain-transfer agent and initiator.The preparation of latex composition is known in this area.Any known radical polymerization technique that is used to form polymkeric substance, for example emulsion, solution, suspension or mass polymerization technology all can be used among the present invention.These methods comprise a feeding method, nucleocapsid method and the counter-rotating nucleocapsid method that for example generates uniform or structural particle.About method of emulsion polymerization and condition are known for a person skilled in the art in more detail.Yet typically, be aggregated under about 35～90 ℃ and in water-bearing media, carry out.Pressure is unimportant, and it depends on used monomeric character, can be determined by those skilled in the art.
Preferably have chain-transfer agent in polymerization process, based on total monomer content, its concentration is about 0.01～5 weight %, preferred about 0.1～2 weight %.Can use water-insoluble and water-soluble chain transfer agent.The illustrative example that is essentially water miscible chain-transfer agent is alkyl and aryl mercaptan, as butanethiol, Thiovanic acid, mercaptoethanol, 3-Mercapto-1 and 2-methyl-2-propylmercaptan.The illustrative example that is essentially water-insoluble chain-transfer agent comprises for example uncle's lauryl mercaptan, thiophenol, four thiohydracrylic acid pentaerythritol esters, octyl-decyl mercaptan, tetradecyl mercaptan and 2-ethylhexyl-3-mercaptopropionic acid ester.
When carrying out letex polymerization, preferably use its concentration to be enough to the initiator (this area is also referred to as catalyzer) of catalytic polymerization.Typically, based on the monomer weight that adds, the variation range of this concentration is about 0.01～3 weight %.Yet preferred initiator concentration is for adding monomeric 0.05～2 weight %, most preferably from about 0.1～1 weight % approximately.Used in any case concrete concentration will depend on the monomer mixture that specifically reacts and used concrete initiator, and its detailed content is known for a person skilled in the art.The illustrative example of suitable initiator comprises hydrogen peroxide, peracetic acid, tertbutyl peroxide, di-tert-butyl hydrogen peroxide, dibenzoyl peroxide, the benzoyl hydrogen peroxide, peroxidation 2, the 4-dichloro-benzoyl, 2,5-dimethyl-2,5-two (hydrogen peroxide) hexane, peroxybenzoic acid, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, t-butyl peroxy-acetate, dilauroyl peroxide, dioctanoyl peroxide, the peroxidation distearyl, dibenzoyl peroxide, di-isopropyl peroxydicarbonate, peroxy dicarbonate didecyl ester, peroxy dicarbonate dicicosyl ester, the peroxybenzoic acid di tert butyl carbonate, 2,2 '-azo two-2, the 4-methyl pentane nitrile, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, peroxophosphoric acid sodium, Diisopropyl azodicarboxylate, and any other known initiator.The same redox-catalyst system in addition that is suitable for is as Sodium Persulfate-sodium sulfoxylate formaldehyde, isopropyl benzene hydroperoxide-sodium metabisulfite, hydrogen peroxide-xitix and other known redox system.And as known to those skilled in the art, if need, the metal ion that can add trace is as the promotor of improving rate of polymerization.
Be applicable to that the concrete tensio-active agent that carries out polyreaction has no importance for the present invention.Exemplary surfactants comprises anion surfactant, as the sodium salt of sodium lauryl sulphate, tridecyl ether sodium sulfate, sulfo-succinic acid diester and alkyl aryl polyether sulphonate; And nonionogenic tenside, as the ethylene oxide condensate and the propylene glycol adducts of alkyl aryl polyether alcohol, propylene oxide.Can use reactive surfactant, promptly those can with the tensio-active agent of other monomer polymerization that is used for preparing polymkeric substance.
In the preparation of two step latex polymers, following is that the generality of the preparation emulsion polymerization that is dispersed in the alkali insoluble polymer in the dissolved alkali soluble polymer is basically described.In a typical reaction, in the presence of chain-transfer agent and initiator, in the reactor that carries out letex polymerization, add acrylic or methacrylic acid, acrylate or methacrylic ester and/or styrene monomer, have the monomer of bridging property functional group and the mixture of other optional components.Typically, use tensio-active agent or emulsifying agent and in water-bearing media, carry out polymerization.The variation of temperature scope can be about 35～90 ℃ or higher; Preferred temperature is about 70～85 ℃.Pressure is unimportant and depend on used monomeric character, and gaseous monomer needs superatmospheric pressure usually.When finishing the first step monomer addition, reaction is maintained under the temperature of reaction content until residual monomer less than about 5000ppmw, add required neutralizing agent then, until the first step polymkeric substance by swelling, be partly dissolved or dissolving basically.Under said temperature, in the first step polymeric media, add the second step monomer then, comprise that optional components is as having the monomer of bridging property functional group.When second step, monomer addition finished, reactor to be kept under temperature of reaction about 1 hour, cooling is also collected latex product.Randomly, can further neutralize to latex this moment.
Can use other the known additive that is generally used in the emulsion polymerization, for example linking agent, rheology modifier, dispersing auxiliary, emulsifying agent, photosensitizers, tinting material, sterilant, mould inhibitor etc.But also can add other functional monomer, as contain those monomers of wet bonding functional group.About the further detailed content of these additives and functional monomer is known for a person skilled in the art.
Typically, based on the weight of tackiness agent, dispersion agent, thickening material and water, contain the polymeric reaction product of tackiness agent of the present invention, dispersion agent or thickening material, its solids content is that polymer content is about 15～65 weight %, preferred about 20～65 weight %, more preferably from about 25～60 weight %.
Embodiment
Following embodiment plays illustrative purpose, and is not to be meant to limit appended scope.Except that given here specific embodiment, the given embodiment of patent application series No.60/138086 that submits in 1999.6.8 also incorporates the application into as a reference.Embodiment M1 prepares big monomer with less hydrophobic substance
To one being furnished with thermometer, heating jacket, thermoswitch, agitator, nitrogen gatherer, comprising in 1 liter of glass reactor of condenser of Dean-Stark collector, adding nonylphenol is 40 mole ethoxylate 930g of less hydrophobic substance.Be blown at nitrogen and down the content in the reactor be heated to 110 ℃ and kept 2 hours, remove the moisture of trace simultaneously and be collected in (usually less than 1g) in the Dean-Stark collector.Then the content in the reactor is cooled to 80 ℃, replaces the Dean-Stark collector with condenser, and turn off nitrogen, be blown into air 15 minutes.Be blown into continuously under the conditions of air, sequentially in reactor, add 0.02g methoxyl group-quinhydrones inhibitor, 0.50g dibutyl tin dilaurate catalyzer and 99.7g α, alpha-alpha-dimethyl--pseudoallyl benzyl isocyanate ester (m-TMI, CYTEC, Stamford, the product of CT).The quick heat release of initial period makes temperature of reaction raise about 8 ℃, and keeping content after this is 80 ℃, keeps 2 hours again.Then product is cooled to room temperature.Final product is the wax that outward appearance is white in color, and the content of its remaining isocyanate is 0.5%, and has kept 98% the unsaturated part of initial olefinic (hereinafter referred to as " big monomer M 1 ").
Embodiment M2 prepares big monomer with bigger hydrophobic substance
Basically prepare big monomer according to embodiment M1, different is replaces nonylphenol (less hydrophobic substance) with 40 mole ethoxylates of dinonyl phenol (bigger hydrophobic substance), and the amount of conditioned reaction thing is to keep 1: 1 mol ratio (hereinafter referred to as " big monomer M 2 ").
Synthesizing of embodiment A styrene acrylic polymers
In one 2 liters monomer barrel, add 245g water, 4.0g TRITONTM GR-9M tensio-active agent (Union Carbide Corporation, Danbury, CT), 120g vinylbenzene, 17g methyl methacrylate (Aldrich), 48g methacrylic acid (Aldrich), 30g 2-EHA and 25g diacetone-acryloamide(DAA) (" DAAM "), the preparation monomer mixture.In another monomer barrel of 2 liters, add 250g water, 6.0g TRITON TMGR-9M, 100g diacetone-acryloamide(DAA), 543g methyl methacrylate (Aldrich) and 365g 2-EHA prepare second monomer mixture.3 liters of chuck resin flask with being furnished with four blade stainless steel machinery agitators, Claisen pipe connecting, Friedrichs water condenser, nitrogen gatherer, bubble trap, thermometer and monomer addition inlet add 609g water and 8gGR-9M (Union Carbide).
Preparation initial oxidation agent solution in an other container, it is by dissolving 3g ammonium persulphate preparation in 24g water.Prepare delayed oxidizer solution equally in another container, it is by dissolving 6g ammonium persulphate preparation in 140g water.Be blown under the nitrogen, by making reactor be heated to 80 ℃ through reactor jacket circulating temperature control water.After the reinforced temperature of reactor reaches 80 ℃, in reactor, add the initial oxidation agent solution.After 2 minutes, " the Teflon pipe by the FMI pump, was sent into the monomer material through 40 minutes in the clockwise reactor, and temperature of reaction remains on 79～81 ℃ simultaneously under continuously stirring, to use 1/8.After monomer addition is finished, make to be reflected at and proceed 15 minutes under 80 ℃.The solution of ammonium hydroxide that in product, adds 20g 30 weight %.Through after 15 minutes, in reactor, added second monomer mixture again, add delayed oxidizer solution simultaneously through 2 hours.With product maintain 80 ℃ 1 hour.The solution of ammonium hydroxide that in products therefrom, adds 20g 15 weight % again.Then product is cooled to room temperature.The solid content of gained is that the pH value of 48% latex is 8, is measured by Microtrac particle size analyzer (Leeds-Northrop), and its volume average particle size is 93 nanometers (" nm ").Based on the molar weight of diacetone-acryloamide(DAA), in the refrigerative product, add the adipic dihydrazide of 0.75 times of molar weight.
Embodiment B prepares crosslinkable thickening material
The TRITON that in one bottle, adds ethyl propenoate (" EA "), methacrylic acid (" MAA "), the big monomer M 2 of DAAM, 13g 75% TMThe solution of GR-9M tensio-active agent and 3g distill deionized water, and disperse content wherein to prepare monomer mixture (300g) by thermal agitation.Add EA, MAA, DAAM and big monomer M 1 according to the given amount of following table 1.
The catalyst feed mixture that preparation is made up of 0.53g Sodium Persulfate and 52.47g water in another container.To immerse water bath with thermostatic control and be furnished with four blade stainless steel machinery agitators, Claisen pipe connecting, water condenser, nitrogen gatherer, bubble trap, thermometer and monomer and 2 liters of resin flask of the reinforced inlet of catalyzer in, add 1.20g sodium vinyl sulfonate and 658.5g water.Monomer mixture is joined in 1 liter of monomer addition graduated cylinder, and catalyst solution is joined in the reinforced graduated cylinder of 125 milliliters of catalyzer.Be blown under the nitrogen, reactor is being heated to 70 ℃, in reactor, adding 33 milliliters of monomer mixtures and 3 milliliters of catalyst feed mixtures then.Reactor is heated to 80 ℃ subsequently.After making monomer reaction form the seed product in 20 minutes, 76～82 ℃ of temperature of reaction, under the continuously stirring, " Teflon manages; by the FMI pump, the speed with 1.94 ml/min and 0.27 ml/min adds monomer and catalyst feed mixture in reactor respectively to use 1/8.Reaction was carried out 1 hour again, and cooled product is also filtered with 200 purpose nylon cloths afterwards.From reactor and filter cloth, collect coagulum.Product is the low viscosity latex of solid content about 40%, and its pH value is about 2.5.
Table 1 has been listed the method according to Embodiment B, with the various thickening materials of listed monomer preparation.Each component provides with the weight percentage based on total polymer weight.
Table 1
Embodiment M2 MAA EA DAAM tensio-active agent
B1??????????15????????40?????????35????????10?????????Rhodafac?RE-610
B2??????????5?????????40?????????45????????10?????????Rhodafac?RE-610
B3??????????15????????40?????????40????????5??????????Rhodafac?RE-610
B4??????????5?????????40?????????50????????5??????????Rhodafac?RE-610
B5??????????5?????????40?????????50????????5??????????Triton?GR-9M
B6??????????5?????????40?????????45????????10?????????Triton?GR-9M
B7??????????15????????40?????????35????????10?????????Triton?GR-9M
B8??????????15????????40?????????40????????5??????????Triton?GR-9M
Embodiment C prepares noncrosslinking thickening material
The TRITON that in one bottle, adds ethyl propenoate (" EA "), methacrylic acid (" MAA "), big monomer M 2,13g 75% TMThe solution of GR-9M tensio-active agent and 3g distillation deionized water, and by thermal agitation dispersion content wherein, preparation monomer mixture (300g).Add EA, MAA and big monomer M 1 according to being similar to the given amount of above-mentioned table 1.
The catalyst feed mixture that preparation is made up of 0.53g Sodium Persulfate and 52.47g water in another container.To immerse water bath with thermostatic control and be furnished with four blade stainless steel machinery agitators, Claisen pipe connecting, water condenser, nitrogen gatherer, bubble trap, thermometer and monomer and 2 liters of resin flask of the reinforced inlet of catalyzer in, add 1.20g sodium vinyl sulfonate and 658.5g water.Monomer mixture is joined in 1 liter of monomer addition graduated cylinder, and catalyst solution is joined in the reinforced graduated cylinder of 125 milliliters of catalyzer.Be blown under the nitrogen, reactor is being heated to 70 ℃, in reactor, adding 33 milliliters of monomer mixtures and 3 milliliters of catalyst feed mixtures then.Reactor is heated to 80 ℃ subsequently.After making monomer reaction form the seed product in 20 minutes, 76～82 ℃ of temperature of reaction, under the continuously stirring, " Teflon manages; by the FMI pump, the speed with 1.94 ml/min and 0.27 ml/min adds monomer and catalyst feed mixture in reactor respectively to use 1/8.Reaction was carried out 1 hour again, and cooled product is also filtered with 200 purpose nylon cloths afterwards.From reactor and filter cloth, collect coagulum.Product is the low viscosity latex of solid content about 40%, and its pH value is about 2.5.
Embodiment D prepares crosslinkable dispersion agent
The TRITON that in one bottle, adds ethyl propenoate (" EA "), methacrylic acid (" MAA "), the big monomer M 1 of DAAM, 13g 75% TMThe solution of GR-9M tensio-active agent and 3g distillation deionized water, and by thermal agitation dispersion content wherein, preparation monomer mixture (300g) adds EA, MAA, DAAM and big monomer M 1 according to the given amount of following table 2.
The catalyst feed mixture that preparation is made up of 0.53g Sodium Persulfate and 52.47g water in another container.To immerse water bath with thermostatic control and be furnished with four blade stainless steel machinery agitators, Claisen pipe connecting, water condenser, nitrogen gatherer, bubble trap, thermometer and monomer and 2 liters of resin flask of the reinforced inlet of catalyzer in, add 1.20g sodium vinyl sulfonate and 658.5g water.Monomer mixture is joined in 1 liter of monomer addition graduated cylinder, and catalyst solution is joined in the reinforced graduated cylinder of 125 milliliters of catalyzer.Be blown under the nitrogen, reactor is being heated to 70 ℃, in reactor, adding 33 milliliters of monomer mixtures and 3 milliliters of catalyst feed mixtures subsequently.Reactor is heated to 80 ℃ subsequently.After making monomer reaction form the seed product in 20 minutes, 76～82 ℃ of temperature of reaction, under the continuously stirring, " Teflon manages; by the FMI pump, the speed with 1.94 ml/min and 0.27 ml/min adds monomer and catalyst feed mixture in reactor respectively to use 1/8.Reaction was carried out 1 hour again, and cooled product is also filtered with 200 purpose nylon cloths afterwards.From reactor and filter cloth, collect coagulum.Product is the low viscosity latex of solid content about 25%.Product being neutralized to its pH value subsequently is about 9.0.
Table 2 has been listed the method according to embodiment D, with the various dispersion agents of listed monomer preparation.Each component provides with the weight percentage based on total polymer weight.
Table 2
Embodiment M1 MAA EA DAAM tensio-active agent
D1??????????0??????????17.5????????82.5???????0????????????Triton?GR-9M
D2??????????0??????????17.5????????62.5???????20???????????Triton?GR-9M
D3??????????0??????????17.5????????47.5???????35???????????Triton?GR-9M
D4??????????20?????????17.5????????62.5???????0????????????Triton?GR-9M
D5??????????20?????????17.5????????42.5???????20???????????Triton?GR-9M
D6??????????20?????????17.5????????27.5???????35???????????Triton?GR-9M
D7??????????40?????????17.5????????42.5???????0????????????Triton?GR-9M
D8??????????40?????????17.5????????22.5???????20???????????Triton?GR-9M
D9??????????40?????????17.5????????7.5????????35???????????Triton?GR-9M
Embodiment E prepares noncrosslinking dispersion agent
The TRITON that in one bottle, adds ethyl propenoate (" EA "), methacrylic acid (" MAA "), big monomer M 1,13g 75% TMThe solution of GR-9M tensio-active agent and 3g distillation deionized water, and by thermal agitation dispersion content wherein, preparation monomer mixture (300g).Add EA, MAA and big monomer M 1 according to being similar to the given amount of above-mentioned table 2.
The catalyst feed mixture that preparation is made up of 0.53g Sodium Persulfate and 52.47g water in another container.To immerse water bath with thermostatic control and be furnished with four blade stainless steel machinery agitators, Claisen pipe connecting, water condenser, nitrogen gatherer, bubble trap, thermometer and monomer and 2 liters of resin flask of the reinforced inlet of catalyzer in, add 1.20g sodium vinyl sulfonate and 658.5g water.Monomer mixture is joined in 1 liter of monomer addition graduated cylinder, and catalyst solution is joined in the reinforced graduated cylinder of 125 milliliters of catalyzer.Be blown under the nitrogen, reactor is being heated to 70 ℃, in reactor, adding 33 milliliters of monomer mixtures and 3 milliliters of catalyst feed mixtures subsequently.Reactor is heated to 80 ℃ subsequently.After making monomer reaction form the seed product in 20 minutes, 76～82 ℃ of temperature of reaction, under the continuously stirring, " Teflon manages; by the FMI pump, the speed with 1.94 ml/min and 0.27 ml/min adds monomer and catalyst feed mixture in reactor respectively to use 1/8.Reaction was carried out 1 hour again, and cooled product is also filtered with 200 purpose nylon cloths afterwards.From reactor and filter cloth, collect coagulum.Product is the low viscosity latex of solid content about 25%.Product being neutralized to its pH value subsequently is about 9.0.
In following formulation for coating material, use above-mentioned tackiness agent, thickening material and dispersion agent.Except that polymkeric substance described here, also can contain other additive commonly used in the coating proportioning, as pigment, filler, wetting agent, coalescing agent, sterilant and defoamer etc.
Embodiment F prepares latex paint
Under stirring at low speed, add following component and prepare the pigment grind thing: the dispersion agent of the ammonia soln of 54.96g water, 5.92g 28% and 2.76g embodiment D9 by order in HSD type grinding plant.When improving stirring, add 200.8g TiPure R-706 TiO 2 pigment (DuPont) lentamente.About 1 hour of grinding mixture is perhaps until the fine grainding thing that obtains 8 Hegman.Reduce and stir and adding 25.6g ethylene glycol and 1.8g BYK 035 defoamer.
By adding 10.32g water in a mixing tank, and under agitation in mixing tank, add the thickening material of 0.25g Embodiment B 5 and the ammonia soln of 0.05g 28%, preparation thickening material pre-composition.
Stir down by in the abrasive material mixture, adding the adhesive resin of 568.72g embodiment A, preparation coating.Stir this mixture after about 30 minutes, be sequentially added into following component: 21.64g Exxate 1000 (a kind of agglomerated solvent, Exxon), 5.44g ArcosolveDPNB (dipropylene glycol n-butyl ether, Arco Chemicals) and 11.64g Exxate 900 (acetate oxo ester in the ninth of the ten Heavenly Stems, Exxon).Under agitation add the thickening material pre-composition then.Add 2.6gFlash X-150 rust inhibitor (flash rust inhibitor) then (Halox), add subsequently 1.48g Surfynol 104BC defoamer (Air Products) and 1.48g Byk 307 (wetting agent, BYK-Chemie).Add 2.76g dispersion agent D9 then.Compo is diluted to required application viscosity with 54.57g water with it then until evenly.
Embodiment G prepares coating
Under stirring at low speed, add following component and prepare the pigment grind thing: the dispersion agent of the ammonia soln of 54.96g water, 5.92g 28% and 2.55g embodiment D5 by order in HSD type grinding plant.When improving stirring, add 200.8g TiPure R-706 TiO 2 pigment (DuPont) lentamente.About 1 hour of grinding mixture is perhaps until the fine grainding thing that obtains 8 Hegman.Reduce and stir and adding 25.6g ethylene glycol and 1.8g BYK 035 defoamer.
By adding 10.32g water in a mixing tank, and under agitation in mixing tank, add the thickening material of 0.25g Embodiment B 5 and the ammonia soln of 0.05g 28%, preparation thickening material pre-composition.
Stir down by in the abrasive material mixture, adding the adhesive resin of 581.48g embodiment A, preparation coating.Stir this mixture after about 30 minutes, be sequentially added into following component: 21.64g Texanol (Eastman Chemicals), 5.44g Arcosolve DPNB (dipropylene glycol n-butyl ether, Arco Chemicals) and 12.73g Exxate 900 (acetate oxo ester in the ninth of the ten Heavenly Stems, Exxon).Under agitation add the thickening material pre-composition then.Add 2.6g Flash X-150 rust inhibitor then, add subsequently 1.48g Surfynol 104BC defoamer (Air Products) and 1.48g Byk 307 (wetting agent, BYK-Chemie).Add 2.76g dispersion agent D9 then.Compo is diluted to required application viscosity with 45.5g water with it then until evenly.
Basically the method according to embodiment F and G prepares coating.Use the quality of the coating that following standard evaluation obtains by coating.
The baking oven baking
The performance test methods test
Gloss 20o
The MEK wiping is until exposing matrix
Salt fog ASTM B117 100 hours
According to the method described above coating is tested, and in following table 3, provided the result.
Table 3
The coating test result
Dispersion agent Gloss, 20o The MEK wiping Salt fog 100 hours
????D1 ????26 ????95 ????10.5
????D2 ????29 ????103 ????14.25
????D3 ????33 ????110 ????18
????D4 ????36 ????164 ????17
????D5 ????39 ????170 ????20.75
????D6 ????43 ????177 ????21
????D7 ????40 ????230 ????15
????D8 ????49 ????238 ????22
????D9 ????53 ????246 ????21.75
Although by a plurality of concrete schemes the present invention is described, under the prerequisite of the spirit and scope of the present invention that do not deviate from the claims proposition, can make other change to it.

Claims (11)

1. one kind by the polymkeric substance that comprises that following monomer polymerization obtains:
(i) unsaturated carboxylic acid monomer;
The monoene that (ii) is different from the carboxylic acid monomer belongs to unsaturated monomer; And
(iii) contain hydrophobic parts and the big monomer that can belong to the alkoxylate part of polymerization of unsaturated monomers with carboxylic acid monomer and monoene;
It is characterized in that based on the gross weight of polymkeric substance, described monomer also contains at least a monomer with bridging property functional group of 0.5～50 weight % that has an appointment.
2. the polymkeric substance of claim 1, wherein said monomer with bridging property functional group comprises the monomer that contains carbonyl.
3. the polymkeric substance of claim 2, wherein said monomer is selected from propenal, methacrolein, diacetone-acryloamide(DAA), diacetone Methacrylamide and etheric acid vinyl acetate.
4. the polymkeric substance of claim 1, wherein based on the gross weight of polymkeric substance, the monomeric amount with bridging property functional group is about 5～50 weight %.
5. the polymkeric substance of claim 1, its number-average molecular weight is about 5000～20000g/gmol.
6. the polymkeric substance of claim 1, its number-average molecular weight is about 20000～200000g/gmol.
7. the polymkeric substance of claim 1, wherein based on the gross weight of polymkeric substance, big monomeric amount is about 5～50 weight %.
8. the polymkeric substance of claim 1, wherein based on the gross weight of polymkeric substance, big monomeric amount is about 1～20 weight %.
9. one kind by the polymkeric substance that comprises that following monomer polymerization obtains:
(i) unsaturated carboxylic acid monomer;
The monoene that (ii) is different from the carboxylic acid monomer belongs to unsaturated monomer; And
(iv) contain hydrophobic parts and the big monomer that can belong to the alkoxylate part of polymerization of unsaturated monomers with carboxylic acid monomer and monoene;
It is characterized in that based on the gross weight of polymkeric substance, described big monomeric amount is about 0.5～50 weight %.
10. the polymkeric substance of claim 1, wherein based on the gross weight of polymkeric substance, big monomeric amount is about 5～40 weight %.
11. the polymkeric substance of claim 9, wherein big monomeric hydrophobic parts contains 1～30 carbon atom.
CN00808616A 1999-06-08 2000-06-08 Waterborne thickeners and dispersants haivng improved chemical resistance Pending CN1354760A (en)

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US6646058B1 (en) * 2001-02-21 2003-11-11 The Sherwin-Williams Company Water-borne paint composition having improved hiding and scrub-resistance
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US9790374B2 (en) 2010-06-04 2017-10-17 Columbia Insurance Company Aqueous cross-linking compositions and methods
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CN102224175B (en) * 2008-11-21 2013-11-06 赫尔克里士公司 Non-hydrocarbyl hydrophobically modified polycarboxylic polymers

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