CN1285629C - Compound containing silicate for polymer and composition prepared with the compound - Google Patents
Compound containing silicate for polymer and composition prepared with the compound Download PDFInfo
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- CN1285629C CN1285629C CN 02126371 CN02126371A CN1285629C CN 1285629 C CN1285629 C CN 1285629C CN 02126371 CN02126371 CN 02126371 CN 02126371 A CN02126371 A CN 02126371A CN 1285629 C CN1285629 C CN 1285629C
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Abstract
A polymer compound having a silicon ester moiety is provided. The silicon ester moiety is located at one end of the polymer compound. The polymer compound contains as polymerized units ethylenically unsaturated monomer and at least one functional group that is pendant to the polymer backbone of the polymer compound. The polymer compound is useful for modifying the surface properties of inorganic substrates. Also provided are a method of preparing the polymer compound and an inorganic substrate that has been treated with the polymer compound.
Description
The polymer compound of the siliceous ester moiety of relate generally to of the present invention.Especially the polymer compound that contains the estersil part group that is positioned at polymer compound one end.In addition, this polymer compound also contains the functional group that is suspended on the polymer compound main chain.This polymer compound is used to handle the inorganic matrix surface to improve surface property or inorganic surfaces functional group is provided as coupling agent.The present invention also provides a kind of method for preparing polymer compound.
Silane coupling agent is widely used in the performance of improving the material contain inorganic substance and organic substance interface, as is coated to the polymeric coating of metal or metal oxide surface, or has inorganic pigment granules and be scattered in wherein polymeric coating.Handle inorganic surfaces with silane coupling agent and improved interfacial adhesion between inorganic materials and the organic materials, for example cause coating and metal oxide surface better bonding or improved the consistency of inorganic particle in the polymkeric substance.Silane coupling agent is characterised in that and contains the hydrolyzable silylation that is connected with organic group.The reaction of hydrolyzable silylation, thus covalent linkage formed with the surface of inorganic substance, organic group is connected with inorganic substance, so has improved the surface property of inorganic substance.The organic group that connects typically provides the improved consistency with organic materials (as polymkeric substance).Silane coupling agent is used to improve the surface property of inorganic particle, thereby is provided in the plastics better dispersed.
For example United States Patent (USP) 4061503 discloses the polyethers that replaces with silicon compound as the coupling agent treatment titanium dioxide granule.The polyethers that this silicon compound replaces contains be connected with polyalkylene oxide groups hydrolyzable silica-based.This patent disclosure the titanium dioxide handled of the polyethers that replaces with silicon compound have the consistency or the dispersiveness of improvement in plastics or resin system inside.Yet, do not have to disclose polyethers and plastics or the resin system formation covalent linkage that this silicon compound replaces.
Coupling agent is required, and it can provide the covalent linkage between inorganic materials and organic materials interface.With compare based on the mixture of more weak interaction of molecules, the formation of covalent linkage make to form and to have the mixture that improves performance between inorganic-organic interface, as the consistency that is produced by dispersion force or hydrogen bond.
In the present invention, polymer compound with reactive group is provided, be used for forming covalent linkage between inorganic matrix and at least one functional group, it can react with second kind of matrix (as the polymkeric substance with complementary functional groups), thereby forms covalent linkage with second kind of matrix.This polymer compound has the organic polymer component, and described organic polymer component is prepared by ethylenically unsaturated monomers, and it has at least one and is suspended on functional group on the organic polymer component main chain.This polymer compound is used to improve the surface property of inorganic materials, as the water dispersible that provides inorganic particle to improve, and it also is used to form composite particles, this composite particles contain by the polymer beads of covalent bonding around inorganic particle.Compare with the coating of routine, in coating, be used in particular for providing with the composite particles of polymer compound of the present invention preparation having improved opacifying property coating.
According to a first aspect of the invention, provide a kind of polymer compound that contains organic polymer component and semiremote pawl group, wherein the organic polymer component has as the ethylenically unsaturated monomers of polymerized unit and has at least one functional pendant groups; And semiremote pawl group has estersil part and form the sulphur atom of bonding with the organic polymer component.
A second aspect of the present invention provides a kind of method for preparing polymer compound, and comprising following step: preparation contains at least a reaction mixture that has the ethylenically unsaturated monomers of functional group and have the mercaptan compound of estersil part; Make the reaction mixture polymerization, form polymer compound; Wherein this polymer compound contains organic polymer component and semiremote pawl group, and described organic polymer component contains the ethylenically unsaturated monomers as the band functional group of polymerized unit; And described semiremote pawl group is formed by mercaptan compound, and it has the sulphur atom that forms bonding with the organic polymer component.
A third aspect of the present invention provides a kind of surface-treated inorganic matrix, and this inorganic matrix comprises the inorganic matrix with surface; With the residue of the polymer compound that contains organic polymer component and semiremote pawl group, described organic polymer component has as the ethylenically unsaturated monomers of polymerized unit and has at least one functional pendant groups; And described semiremote pawl group has the silanol that forms the sulphur atom of bonding and at least one and the reaction of inorganic matrix surface formation covalent linkage with the organic polymer component.
Term as used herein " (methyl) acrylate " is meant acrylate or methacrylic ester, and term " (methyl) vinylformic acid " is meant acrylic or methacrylic acid.
Covalent linkage be between two atoms by sharing the key that at least one pair of electronics forms, it gets rid of ionic linkage clearly, by absorbing key that (comprising chemical absorption and physical absorption) form, Van der Waals key or the key by dispersion force formation.
Polymer compound of the present invention comprises polymer chain (being called " organic polymer component " herein) and the group that is connected with an end of this organic polymer component (being called " semiremote pawl group " herein).This semiremote pawl group has at least one estersil part.Polymer compound is characterised in that following general formula:
A-L-S-Q
Wherein Q is the organic polymer component, and A-L-S is a semiremote pawl group, and A is the estersil part, and L is that linking group and S are sulphur atoms.In the presence of water, the estersil partial reaction forms at least one silanol.This silanol can form covalent linkage with inorganic surfaces (as metal and metal oxide surface) reaction and with inorganic surfaces, thereby the polymer compound of reaction is bonded on the inorganic surfaces.The polymer compound of reaction is connected with inorganic surfaces, the feasible surface property that has improved inorganic surfaces.
Described semiremote pawl group contains linking group and at least one estersil part.This semiremote pawl group also contains sulphur atom, and sulphur atom provides bonding between linking group and organic polymer component end.Linking group contains at least one carbon atom and it divalent group typically, and it is oxygen or carbon with the silicon atom bonding of estersil part.Preferred linking group is the carbon with the silicon atom bonding of estersil part.Suitable linking group comprise alkenyl as:
-CH
2-
-CH
2-CH
2-
-CH
2CH
2CH
2-
-CH(CH
3)CH
2-
With aryl as:
-CH
2-C
6H
4-CH
2CH
2-
To form under the employed condition of silanol, the bonding between linking group and the estersil part is stable to hydrolysis in fact in hydrolysis estersil part.Semiremote pawl group contains one or more estersil parts.The semiremote pawl group that preferably has an estersil part.
Described estersil partly has the Sauerstoffatom that forms bonding between Siliciumatom and organic group, and it is characterised in that following general formula:
(R
1O)
n(R
2)
3-nSi-is R wherein
1And R
2Be to contain the organic group of at least one carbon atom and the integer that n is 1-3.R
1Example comprise that alkyl (as methyl, ethyl and propyl group), acyloxy are (as H
3CC (O)-and H
3CH
2C (O)-).Select R independently
1Organic group and R
2Organic group.For example, suitable estersil comprises that partly mixed ester is (as (CH
3O) (C
2H
5O)
2Si-and (CH
3O) (C
2H
5O) (CH
3) Si-) and the blended monoesters (as (CH
3O) (C
2H
5) (CH
3) Si-and (CH
3O) (C
6H
5CH
2) (CH
3) Si-).That suitable estersil partly comprises is single-, two-and three esters (as single-, two-and trialkoxysilane groups; Single-, two-and three acyloxy silane groups and single-, two-and three aryloxy silane groups).Preferred silicon three esters.In the presence of moisture, the estersil group is hydrolyzed, and forms silanol.Silicon diester and silicon three esters carry out part or all of hydrolysis, form one or more silanols, and wherein each silanol can form covalent linkage with inorganic surfaces.Hydrolysis degree depends on various factors, comprising the size of hydrolysising condition such as pH and ester group.Preferred estersil group is the alkoxysilane groups with 1-3 carbon atom.More preferably methyl esters and ethyl ester.
Described semiremote pawl examples of groups comprises:
(CH
3O)
3Si-CH
2CH
2CH
2-S-，
(CH
3CH
2O)
3Si-CH
2CH
2CH
2-S-，
(CH
3CH
2O)
2(CH
3)Si-CH
2-S-，
(CH
3O)
2(CH
3)Si-CH
2CH
2CH
2-S-，
(CH
3C (O) O)
3Si-CH
2CH
2CH
2-S-and
(CH
3O)(CH
3)
2Si-C
6H
4-CH
2-S-。
Described organic polymer component is a kind of polymer chain, and this polymer chain is characterised in that and contains as the ethylenically unsaturated monomers of polymerized unit and have at least one functional group that is suspended on the main polymer chain.Prepare polymer compound by at least a addition polymerization with ethylenically unsaturated monomers (being called " first monomer " herein) of functional group or functional group's precursor.Cause forming homopolymer by containing the polymer compound that only one type the first monomeric reaction mixture polymerization obtains.Perhaps the polymer compound that is obtained by the reaction mixture polymerization that contains two kinds of first different monomeric reaction mixtures or the monomer outside first monomer and first monomer (being called " second monomer " herein) causes forming multipolymer.Multipolymer also comprises and containing as first monomer of polymerized unit, second polymer of monomers different with two or more, and contains two kinds of first different monomers, second polymer of monomers different with one or more kinds.The arrangement of polymerization single polymerization monomer in multipolymer comprises the polymkeric substance of the random ordering of monomeric unit of reaction, and the polymkeric substance of non-random ordering (as segmented copolymer).In one embodiment, first monomer that has functional group's precursor group by polymerization at first prepares polymer compound.After the polymerization, change into functional pendant groups, obtain polymer compound by making precursor group.The example of precursor group is an alkyl group, and it is hydrolyzed the formation acid groups subsequently.
Described organic polymer component contains at least one and two or more different functional groups randomly, and this functional group is suspended on the main chain of polymer chain.The example of suitable functional group comprises carboxylic acid, acid anhydrides, alcohol, mercaptan, aldehyde, amine (as primary, the second month in a season and tertiary amine), acid amides, epoxide, thiorane, aziridine, halogen (as bromine and chlorine), isocyanic ester, carbodiimide, lsothiocyanates and etheric acid group.Other suitable functional group comprises phosphorated acid, and it is meant the group with POH part, and wherein the hydrogen atom among the POH is ionizable.Also be included in the term " phosphorated acid " is these sour salt.Example comprises by the ester of phospho acid, phosphonic acids, phosphoric acid, burnt phospho acid, tetra-sodium, its part and the group of salt formation thereof.In addition, other suitable functional group comprises the acid of sulfur-bearing, and it is meant the group with SOH part, and wherein the hydrogen atom among the SOH is ionizable.Also be included in the term " acid of sulfur-bearing " is these sour salt.Example comprises the group that is formed by sulfuric acid and sulfonic acid (sulphorous acid).Get rid of alkyl group clearly as functional group.
The first suitable monomer comprises isocyanate-monomer (as pseudoallyl benzyl isocyanate ester between methacrylic acid ethyl isocyanate and dimethyl); acetoacetyl monomer (as (methyl) vinylformic acid acetoacetyl ethyl ester); aldehyde monomer (as propenal and Methylacrylaldehyde); amine monomers is (as (methyl) vinylformic acid tertiary butyl aminoethyl ester; (methyl) vinylformic acid aminopropyl ester; (methyl) vinylformic acid dimethylaminoethyl ester; (methyl) vinylformic acid ammonia butyl ester; (methyl) vinylformic acid aminoethyl ester); amide monomer (as (methyl) acrylamide) and (methyl) vinylformic acid oxazolidinyl ethyl ester; epoxy monomer (as (methyl) glycidyl acrylate); the monomer of hydroxyl is (as (methyl) acrylic acid hydroxy alkyl ester; comprising (methyl) vinylformic acid 2-hydroxyethyl ester and (methyl) vinylformic acid 3-hydroxyethyl ester); halogenated monomer (as (methyl) vinylformic acid 2-bromo-ethyl ester and (methyl) vinylformic acid bromopropyl ester); halogenated methyl vinylbenzene; the carboxylic acid monomer is (as (methyl) vinylformic acid; methylene-succinic acid; toxilic acid); the monomer that has phosphorated acid is (as (methyl) vinylformic acid phospho ethyl ester; vinyl phosphonate; allyl group phosphoric acid; 2-acrylamido-2-methylpropane phosphonic acids; α-phosphono vinylbenzene; 2-methacrylamido-2-methylpropane phosphonic acids; and salt) and the monomer of acid that has a sulfur-bearing (as vinyl sulfonic acid; methallylsulfonic acid; styrene sulfonic acid; N-(2-sulfo group-1,1-dimethyl ethyl) acrylamide; 2-acrylamido-2-methyl propane sulfonic acid; and salt).
A large amount of ethylenically unsaturated monomers is suitable as the second optional monomer, comprising vinylbenzene, divinyl, alpha-methyl styrene, Vinyl toluene, vinyl naphthalene, ethene, propylene, vinyl-acetic ester, vinyl branched paraffin carboxylic acid ester (verstate), vinylchlorid, vinylidene chloride, vinyl cyanide, methacrylonitrile, (methyl) acrylic acid various C
1-C
40Alkyl ester ((methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid dodecyl ester, (methyl) vinylformic acid ring pentyl ester, (methyl) lauryl acrylate and (methyl) octadecyl acrylate), other (methyl) acrylate is (as (methyl) isobornyl acrylate, (methyl) vinylformic acid benzyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-phenyl chlorocarbonate and (methyl) vinylformic acid 1-naphthyl ester, and (methyl) alkyl acrylate oxyalkyl ester is as (methyl) vinylformic acid alcoxyl ethyl ester).
The polymerization degree of organic polymer component is at least 3, and preferably at least 10, more preferably at least 25.The OK range of the polymerization degree is 3-1000, is preferably 10-250, more preferably 25-100.The polymerization degree of polymer compound is a mean polymerisation degree, and wherein by being used to make polymer compound polymeric first monomer and the second monomeric mole number to calculate mean polymerisation degree divided by the mole number of mercaptan compound, described mercaptan compound contains the estersil part.
In the presence of mercaptan compound with at least one estersil part, make the ethylenically unsaturated monomers polymerization, thus the preparation polymer compound.This mercaptan compound serves as chain-transfer agent and influences the polymerization degree of organic polymer component.The organic polymer component of gained has the mercaptan compound of the reaction that connects on an end of its polymer chain.The organic polymer component that the mercaptan compound formation semiremote pawl group of reaction and polymer chain form polymer compound of the present invention.
The suitable mercaptan compound of preparation polymer compound has following general formula:
(R
1O)
n(R
2)
3-nSi-R
3-SH is R wherein
1And R
2Be the organic group that contains at least one carbon atom, R
3Be that the divalent organic group alkylidene group of 1-20 carbon (as contain) and n are the round valuess of 1-3.Suitable mercaptan compound includes, but are not limited to 3-mercapto propyl group methyl dimethoxysilane, thiopurine methyltransferase methyldiethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyl trimethoxysilane.
For preparing polymer compound by the mercaptan compound, at least a first monomer and the randomly at least a second monomeric reaction mixture that contain with at least one estersil part, various polymerization techniques are suitable.The water yield in the reaction mixture is sufficiently low, the feasible hydrolysis of estersil part or the crosslinking reaction between the estersil part of not taking place in fact.Suitable polymerization technique comprises non-aqueous solution polymerization, non-aqueous emulsion polymerization and mass polymerization.Typically, with intermittently, semicontinuous, continuous processing or it is in conjunction with carrying out these polymerization techniques.
The selection process for preparing polymer compound of the present invention is to use organic solvent (as ethanol, butylacetate, Virahol, toluene, dimethylbenzene, methyl iso-butyl ketone (MIBK), 2,2,4-trimethylammonium-1,3-pentanediol isobutyrate, methyl amylketone, butyl glycol ether, Diethylene Glycol butyl ether, propylene glycol methyl ether acetate and dipropylene glycol monomethyl ether) solution polymerization.
Typically, in the preparation polymer compound, use polymerization starter.Suitable polymerization starter is included in thermolysis under the polymerization temperature, produces the initiator of free radical.The example that produces the initiator of free radical comprises that persulphate is (as ammonium persulphate or basic metal (potassium, sodium or lithium)), azo-compound is (as 2,2 '-azo two (isopropyl cyanide), 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 1-tertiary butyl azo cyanocyclohexanoic alkane), hydroperoxide (as t-butyl hydroperoxide and cumene hydroperoxide), superoxide is (as benzoyl peroxide, decanoyl peroxide (capryl), di-t-butyl peroxide, 3,3 '-two (tert-butyl hydroperoxide) ethyl butyrate, 3,3 '-two (t-amyl peroxy) ethyl butyrate, t-amyl peroxy-2-ethylhexanoate and t-butylperoxy pivarate), cross ester (t-butyl peroxy-acetate, cross terephthaldehyde's tert-butyl acrylate and t-butylperoxyl benzoate), and peroxocarbonate (as two (1-cyano group-1-methylethyl) peroxy dicarbonate) and peroxophosphoric acid ester.Typically use polymerization starter separately or use polymerization starter with the oxidation component form of redox system, described redox system also comprises reduction components such as xitix, toxilic acid, oxyacetic acid (glycolic acid), oxalic acid, lactic acid, Thiovanic acid or alkali metal sulfite, more particularly be hydrosulphite, hyposulfite (hyposulfite) or metabisulphite, as sodium bisulfite, inferior potassium sulfite and inclined to one side Potassium hydrogen sulfite or formaldehyde sodium sulfoxylate).Initiator comprises 0.001wt%-5wt% with the appropriate amount of the reduction components of choosing wantonly, based on the weight for the treatment of ethylenically unsaturated monomers in the polymeric monomer mixture.Perhaps use promotor (as the muriate and the vitriol of cobalt, iron, nickel or copper) slightly.The example of redox-catalyst system comprises t-butyl hydroperoxide/formaldehyde sodium sulfoxylate/Fe (II), and ammonium persulphate/sodium bisulfite (sodium bisulfite)/sodium bisulfite (sodium hydrosulfite)/Fe (11).Polymerization temperature is included as 20 ℃ to about 120 ℃ temperature.
Described polymer compound is used to improve the surface property of inorganic matrix.In this application, polymer compound and inorganic matrix reaction, thus the polymer compound of reaction is connected with the surface of inorganic matrix, so improve the surface composition of inorganic matrix.Preparation surface-treated inorganic matrix method comprises randomly makes polymer compound contact with the surface of inorganic matrix in the presence of acid or alkali.The estersil partial reaction, and form covalent linkage between inorganic matrix, thus an end of the polymer compound of reaction is connected with inorganic matrix.The reaction of estersil part typically takes place in the presence of moisture, and this can cause the hydrolysis of estersil and form one or more silanol.This silanol can be reacted with inorganic matrix, and forms the bonding that usefulness-M-O-Si-structure is represented, wherein M is the atoms metal in the inorganic matrix.Suitable atoms metal includes, but are not limited to titanium, aluminium, zirconium, silicon, zinc, chromium, tin, iron and lead.Think silanol can with from the teeth outwards or in the inorganic matrix reaction with atoms metal of near surface, perhaps can with from the teeth outwards or in the inorganic matrix reaction with oxide skin of near surface.Preferably with inorganic matrix reaction with titanium dioxide, silicon-dioxide, zinc oxide film.Randomly use the dry processed inorganic matrix of heat or make it dry.
Perhaps, described polymer compound with prehydrolysis before inorganic matrix contacts.In this method, polymer compound contacts with moisture and in estersil part partially or completely after the hydrolysis, the polymer compound of this prehydrolysis contacts with inorganic matrix.
The time cycle that the reaction of described polymer compound and inorganic matrix is finished can change on a large scale, and this depends on many factors, comprising surface area, temperature and the optional PH that contains water of the concentration of polymer compound and water, inorganic matrix.The typical time cycle is that the several seconds is to a couple of days. the technology such as silicon nucleus magnetic resonance and infrared spectra is applicable to the level of response of monitoring polymer compound and inorganic matrix.
Described surface-treated inorganic matrix has the polymer compound residue with inorganic matrix surface covalent bonding, and wherein the surface-treated inorganic matrix forms by polymer compound and inorganic matrix reaction.This polymer compound residue has the silanol (it can form bonding with inorganic matrix) of at least one reaction, and also has at least one functional pendant groups.The surface-treated inorganic matrix is used for preparing material (as the dry polymer coating on the metallic surface) with inorganic organic interface and the polymeric matrix (as pigment, filler and the extender particle of dried paint) that contains inorganic particle.Polymer compound of the present invention also is used to handle glass (comprising glass fibre), thereby better bonding with organic phase (as polymkeric substance) is provided.
Suitable inorganic matrix be characterised in that have can and the silanol reacted surface and make and inorganic matrix between form covalent linkage.Suitable inorganic matrix comprises having the matrix that homogeneous forms and have two-phase or the matrix of the heterogeneous composition of heterogenetic (seal nuclear/shell inorganic particle, the dipole inorganic particle of the nuclear/shell inorganic particle of nuclear, more than nuclear fully or not exclusively and have the inorganic particle in a plurality of single-phase zones on other phase surface as shell) more.Inorganic particle (as titanium dioxide granule) can have silicon-dioxide, aluminum oxide or zirconic single coating or laminated coating.For example, be applicable to that the titanium dioxide granule in the paint typically has the coating of silicon-dioxide and the coating of aluminum oxide.Suitable inorganic matrix has the surface of containing metal, metal oxide, sulfide, salt, nonmetal, nonmetal sulfide and nonmetal oxide.The surface of inorganic matrix comprises the self-faced and the surface-treated surface of inorganic matrix, and wherein surface treatment is provided for forming the suitable surface of covalent linkage.Form covalent linkage with the lip-deep atom of inorganic matrix, wherein the inorganic matrix surface comprises any optional coating or surface treatment.In the presence of water, the surface of inorganic matrix can have hydroxyl.
In one embodiment, contact the preparation mixture with the second kind of material that has complementary functional groups by making the surface-treated inorganic matrix that has functional pendant groups.The reaction of functional pendant groups and complementary functional groups provides the mixture that has covalent linkage between inorganic matrix and second kind of material.This covalent linkage provides has the interface of improving resistance to be separated (for example because of being separated that heating produces).Also provide improve between the material bonding at the covalent linkage that forms between inorganic matrix and the organic substrate.Be suitable for comprising with the functional pendant groups of complementary functional groups reaction, for example isocyanic ester or isothiocyanate group (they can be selected from alcohol, amine, the complementary functional groups reaction of urea or acid anhydrides), aldehyde radical (they can react with the complementary functional groups that is selected from acetoacetyl or amine), acetoacetyl (they can react with the complementary functional groups that is selected from aldehyde or amine), epoxide, thiorane or '-aziridino (they can be selected from alcohol, carboxylic acid, acid anhydrides, the complementary functional groups reaction of amine or mercaptan), the carbon diimino (they can be selected from carboxylic acid, alcohol, the complementary functional groups reaction of amine and mercaptan), halogenated alkane or benzyl halide base (they can react with the complementary functional groups that is selected from amine and carboxylic acid), amine or mercaptan (they can be selected from epoxide, aziridine, thiorane, acetoacetyl, isocyanic ester, the reaction of the complementary functional groups of lsothiocyanates and carbodiimide) and carboxylic acid (they can be selected from epoxide, aziridine, the complementary functional groups reaction of thiorane and carbodiimide).
Randomly in the reaction of carrying out in the presence of the catalyzer between functional pendant groups and the suitable complementary functional groups.For example, tertiary amine and pink salt are the suitable catalyst of reacting as between the isocyanate groups of functional pendant groups and the alcohol as complementary functional groups.Conventional analytical technology (as infrared spectra, NMR (Nuclear Magnetic Resonance) spectrum and ultraviolet-visible spectrum) is suitable for measuring the level of response between functional pendant groups and the complementary functional groups.
In one embodiment, use polymer compound of the present invention to prepare composite particles.Composite particles have by a plurality of secondary granules around single centrophyten.This centrophyten is an inorganic particle, and this secondary granule is a polymer beads.In this embodiment, use polymer compound to prepare composite particles, wherein the surperficial covalent bonding of polymer beads and inorganic particle.Polymer beads is connected by the key that is formed by polymer compound indirectly with inorganic particle.This key has a kind of covalent linkage that forms with inorganic particle and the second kind of covalent linkage that forms with polymer beads.These composite particles are used in painted coating composition (as paint), so that provide the opacifying property of enhancing degree to the exsiccant coating.Perhaps use these composite particles and prepare dry coating, this dry coating has required covering degree, but requires content of titanium dioxide to be lower than conventional dry coating.Use the composite particles of polymer compound of the present invention preparation also be used for providing inorganic particle (as pigment, filler and extender) at polymeric matrix improved dispersiveness and with the consistency of polymeric matrix.
The suitable shape of the inorganic particle that the preparation composite particles is used comprises sphere (as spherical, oblate spheroid shape, long ball shape and irregular spherical), cube (as cubes and rhombus), sheet (comprising plain film, recessed and lug) and irregularly shaped.In coating composition, it is 10 nanometers (nm) to 10 microns median size that spherical inorganic particle generally has, and is preferably 100nm-2 μ m, more preferably 200nm-500nm.Aspheric inorganic particle generally has the overall dimension less than 10 microns, preferably less than 1 micron be more preferably less than 500nm.
The example of inorganic particle comprises filler particles, extender particle and granules of pigments.Suitable inorganic particle comprises Zinc oxide particles, antimony oxide particle, barium oxide particle, calcium sulfate particle, zirconia particles, alumina particle, chrome oxide particle, ferric oxide particles, magnesium oxide particle, particles of lead oxide, zns particle, lithopone, titanium dioxide, clay particle (as kaolin and laminated clay particle), silica dioxide granule (as silicon oxide), talc particle and mica particles.Preferably, inorganic particle is to comprise the titanium dioxide of rutile and anatase octahedrite and more preferably, and inorganic particle is a rutile titanium dioxide.
In one embodiment, polymer compound is the hydrophilic polymeric compounds, and it is used for the modified inorganic particles surface, thereby provides inorganic particle bigger wetting ability.The surface more easily is dispersed in the water-bearing media with the compound modified inorganic particle of hydrophilic polymer.For example, these inorganic particles can be dispersed under the condition of not using high shear mixing in the water, and this method typically is used to prepare the aqueous dispersion of pigment, often are called slurry or transfer rare pigment.Inorganic particle with the hydrophilic polymer compound treatment of this embodiment can be dispersed in the water-bearing media under the situation of using low shear-mixed (as manual stirring).In addition, contain the trend reduction that the surface is precipitated out from water-bearing media with the aqueous dispersion of the inorganic particle of hydrophilic polymer modification, thereby the shelf life of improved stability of aqueous pigment dispersions and prolongation is provided.The inorganic particle that is used as the hydrophilic polymer compound treatment that has acidic group or anhydride group of functional group can be dispersed in the pK that pH is close to or higher than acidic group or passes through the acid of anhydride group hydrolysis formation
aUnder water-bearing media in, preferably than this pK
aHigh at least one the pH unit of value.Disperseing suitable pH value with the inorganic particle of the hydrophilic polymer compound treatment that has acidic group is to be at least 4 pH value, preferably is at least 6, more preferably is at least 7.And have amine or amido group inorganic particle as the hydrophilic polymer compound treatment of functional group can be dispersed in pH near or than the pK of amine or acid amides
aIn the low water-bearing media, preferably than this pK
aLow at least one the pH unit of value.Disperseing the employed suitable pH value of inorganic particle with the hydrophilic polymer compound treatment that has amine or amido group is to be less than or equal to 8 pH value, preferably be less than or equal to 7 be more preferably less than or equal 6.Can be dispersed in the water-bearing media that pH is 1-14 with having the inorganic particle of hydroxyl as the hydrophilic polymer compound treatment of functional group.
The hydrophilic polymer examples for compounds comprises:
(CH
3O)
3Si-C
2H
4-S-[gathers (2-hydroxyethyl methacrylate); DP=75]
(C
2H
5O)
2(CH
3) Si-C
3H
6-S-[gathers (vinylformic acid); DP=55]
(CH
3)
2(CH
3) Si-CH
2-S-[gathers (acrylamide); DP=92]
In above-mentioned example, the composition of organic polymer component is with term " poly-(monomeric title) " expression, its representative in the organic polymer component as the contained monomer of polymerized unit.The polymerization degree of organic polymer component represented in term " DP ".The organic polymer component of hydrophilic polymeric compounds is multipolymer typically.
The hydrophilic polymeric compounds also is suitable for use as the sizing agent of glass fibre, so that processed glass fibre is dispersed in the water better.
Following embodiment has set forth the compositions and methods of the invention.These embodiment will help those skilled in the art to understand the present invention, yet the present invention in no case should be limited to this.
Embodiment 1-prepares polymer compound
Embodiment 1.1-contains the polymer compound of side group aldehyde and alcohol functional group
By at first in the 250ml round-bottomed flask of being furnished with reflux exchanger, magnetic stirrer, thermopair and nitrogen inlet tube, adding 75.0g butylacetate, preparation polymer compound.With the content of nitrogen purging flask, and be heated to 88 ℃.Then in flask, be added in the 0.05g Vazo in the 2.5g butylacetate
TM67 initiators (Vazo is E.I.Dupont de Nemours and Co., Wilmington, the trade mark of DE).In 30 minutes time period, in flask, dropwise add the monomer mixture of the 3-mercaptopropyl trimethoxysilane (MPTMS) that contains 25g butylacetate, 12.5g methyl methacrylate (MMA), 12.5g methacrylic acid hydroxyl ethyl ester (HEMA) and 0.77g.The time period that the content of flask was left standstill 15 minutes, be warmed up to 95 ℃ and under 95 ℃, keep time period of 40 minutes then.Then, add the 55.5g anhydrous dimethyl sulphoxide then, then add 4.85g DIC and the 1.11g pyridine-hydrochloric acid that is dissolved in the 5g dimethyl sulfoxide (DMSO) the content cool to room temperature of flask.The time period that the content of flask was left standstill 72 hours.Form white precipitate and be removed by filtration.Residual mixture contains the polymer compound of 9.8wt% solid embodiment 1.1.Embodiment 1.1 is the polymer compounds with semiremote pawl group, and wherein semiremote pawl group contains Trimethoxy silane part and the organic polymer component that has side group aldehyde radical and alcohol radical.The average composition of embodiment 1.1 is to contain following unitary polymer compound as reaction: MMA
24.5HEMA
19.4HEAMA
6.1MPTMS
1, wherein the acrylic acid 2-hydroxyl of HEAMA represent methylidene acetaldehyde ester and subscript are represented the mole number of each reaction material.The MPTMS of reaction is a semiremote pawl group.
Embodiment 1.2-contains the polymer compound of side group acetoacetyl functional group and side group hydroxy functional group
By at first in the 500ml round-bottomed flask of being furnished with reflux exchanger, magnetic stirrer, thermopair and nitrogen inlet tube, adding 140g dehydrated alcohol, the polymer compound of preparation embodiment 1.2.With the content of nitrogen purging flask and be heated to 76 ℃.Then in flask, add the 0.225g Vazo that is included in the 3g dehydrated alcohol
TMThe solution of 67 initiators.In 30 minutes time period, to flask, dropwise add the monomer mixture that contains 10g methacrylic acid acetoacetyl ethyl ester (AAEM), 80g Hydroxyethyl Acrylate (HEA) and 9g (3-mercapto propyl group) Trimethoxy silane (MPTMS) from dropping funnel.Heat release raises the temperature to 80 ℃.With 5g dehydrated alcohol rinsing dropping funnel, subsequently it is joined in the flask.Reaction mixture maintains under 75-80 ℃ the temperature, and stirs 1 hour time period.Then make the content cool to room temperature of flask.Flask contains the polymer compound solution of the embodiment 1.2 of 40wt% solid content.The average composition of embodiment 1.2 is to contain following unitary polymer compound as reaction: AAEM
1HEA
15MPTMS
1The MPTMS of reaction is a semiremote pawl group.
Embodiment 1.3-contains the polymer compound of side group acetoacetyl functional group, side group carboxylic acid group functional group and side group hydroxy functional group
Except monomer mixture contains 10g methacrylic acid acetoacetyl ethyl ester (AAEM), 70g Hydroxyethyl Acrylate (HEA), 10g methacrylic acid (MAA) and 9g (3-mercapto propyl group) Trimethoxy silane (MPTMS), prepare the polymer compound of embodiment 1.3 according to the step of embodiment 1.2.The average composition of embodiment 1.3 is to contain following unitary polymer compound as reaction: AAEM
1HEA
13.1MAA
2.5MPTMS
1The MPTMS of reaction is a semiremote pawl group.
Embodiment 1.4-contains the polymer compound of side group acetoacetyl functional group, side group phosphorated acid (phosphorusacid) functional group and side group hydroxy functional group
Except monomer mixture contains 10g methacrylic acid acetoacetyl ethyl ester (AAEM), 70g Hydroxyethyl Acrylate (HEA), 12g methacrylic acid 2-phospho ethyl ester (PEM), 2g methacrylic acid (MAA) and 9g (3-mercapto propyl group) Trimethoxy silane (MPTMS), prepare the polymer compound of embodiment 1.4 according to the step of embodiment 1.2.The average composition of embodiment 1.4 is to contain following unitary polymer compound as reaction: AAEM
1HEA
13.1PEM1MAA
0.5MPTMS
1The MPTMS of reaction is a semiremote pawl group.
Embodiment 1.5-contains the polymer compound of side group acetoacetyl functional group and side group hydroxy functional group
Except monomer mixture contains 20g methacrylic acid acetoacetyl ethyl ester (AAEM), 4g Hydroxyethyl Acrylate (HEA), 66g methacrylic acid macrogol ester (molecular weight=360) (PEGMA) and 9g (the 3-mercapto propyl group) Trimethoxy silane (MPTMS), prepare the polymer compound of embodiment 1.5 according to the step of embodiment 1.2.The average composition of embodiment 1.5 is to contain following unitary polymer compound as reaction: AAEM
2HEA
0.7PEGMA
4MPTMS
1The MPTMS of reaction is a semiremote pawl group.
The titanium dioxide that embodiment 2-preparation is handled with polymer compound
Embodiment 2.1-contains the aqueous dispersion of the titanium dioxide that the polymer compound of useful embodiment 1.1 handles
Preparation surface-treated titanium dioxide granule, this particle aldehyde with the connection functional group.
In the grinding tube, place the mixture of 95g ethanol and 5g water.Then the grinding tube is placed in Premier mill (Premier Mill) decollator of being furnished with rotary knife.Under mixing, in the grinding tube, add the TiPure of 400g
TMR-706 titanium dioxide (TiPure is E.I.DuPont deNemours and Company, Wilmington, the trade mark of DE).With 2000rpm grinding mixture 20 minutes, with the dispersed titanium dioxide particle.Next the polymer compound solution that adds 80g embodiment 1.1 then adds 3 hydrochloric acid.Grinding mixture is 5 minutes in addition.Reduce grinding rate to gentle agitation, and stirred the mixture 25 minutes.Mixture is transferred in the plastic tank, and the second alcohol and water is at room temperature evaporated, the titanium dioxide granule that provides the surface to handle with the polymer compound residue of embodiment 1.1.Surface-treated titanium dioxide is functionalized with aldehyde radical.
By at first in the grinding tube, adding 104.6g water, 6.14g Tamol
TM731 dispersion agents (Tamol is Rohm and Haas Company, Philadelphia, the trade mark of PA), 6.94g Colloid
TM643 dispersion agents (Colloid is the trade mark of Allied Colloids Limited Company) and 1.14g sodium hydroxide (50wt% solution), preparation contains the aqueous dispersion of the surface-treated titanium dioxide granule of embodiment 2.1.Use is furnished with the Premier mill decollator of rotary knife, mixes the content in the grinding tube, then adds the surface-treated titanium dioxide granule of 384g embodiment 2.1.With 2000rpm grinding mixture 20 minutes, provide the aqueous dispersion of the surface-treated titanium dioxide granule that contains embodiment 2.1.
Embodiment 2.2-contains the aqueous dispersion of the titanium dioxide that the polymer compound of useful embodiment 1.2 handles
Preparation surface-treated titanium dioxide granule, this particle acetoacetyl with the connection functional group and the hydroxy functional group that is connected.
In the grinding tube, place the mixture of 200g ethanol and 10g deionized water.Then the grinding tube is placed in the decollator of being furnished with rotary knife.Under mixing, in the grinding tube, add 400g TiPure
TMR-706 titanium dioxide.Grinding mixture 20 minutes is with the dispersed titanium dioxide particle.Next add 3g ammonium hydroxide, then add the polymer compound of 50g embodiment 1.2.Grinding mixture is 30 minutes in addition.Make at room temperature dry 3 days time period of mixture, then 70 ℃ down dry 1 hour to remove any residual ethanol or water.Machinery crushing and screening gained powder obtain fines.By using decollator, the 407g fines is dispersed in the 106g deionized water preparation aqueous dispersion.The aqueous dispersion of embodiment 2.2 contains 79.3wt% solid surface-treated titanium dioxide.
Embodiment 3-prepares composite particles
Embodiment 3.1-is by the composite particles of the prepared in reaction of functional titanium dioxide granule of aldehyde and the functional polymer beads of acetoacetyl
By making the surface-treated titanium dioxide granule reaction of functional polymer beads of acetoacetyl and the embodiment 2.1 that has aldehyde functional group, preparation composite particles.By dropwise and under mixing to the Rhoshield of 51.44g
TMAdd the aqueous dispersion that 46.83g contains the surface-treated titanium dioxide granule of embodiment 2.1 in 3188 polymeric dispersions (Rhoshield is the trade mark of Rohm and HaasCompany), the preparation composite particles.Rhoshield
TM3188 polymkeric substance have provided the functional dispersion of polymer particle of 40wt% solid acetoacetyl and it has the average particulate diameter of 120nm.The mixture of gained is placed on the cylinder at least 12 hours time period.The composite particle dispersions of embodiment 3.1 has the solid content of 56.6wt%.Composite particles contains 63wt% titanium dioxide granule and 37wt% polymer beads.
Embodiment 3.2-is by the composite particles of the prepared in reaction of functional titanium dioxide granule of acetoacetyl and the functional polymer beads of aldehyde
By making the surface-treated titanium dioxide granule reaction of functional polymer beads of aldehyde and the embodiment 2.1 that has acetoacetyl functional group, preparation composite particles.
Preparation contains the monomer of aldehyde
By to 1 of the 4-hydroxy benzaldehyde that in the flask under the nitrogen atmosphere, adds 7.9g, 10g methacrylic acid 2-ethyl isocyanate, 17.8g, 4-two alkane and 1 dibutyltin dilaurate, preparation feedback mixture.The content of mixing flask 2 days keeps nitrogen atmosphere simultaneously.What gained solution contained that 50wt% has a following structure contains aldehyde monomer (ACM):
CH
2＝C(CH
3)C(O)-C
2H
2-NH-C(O)O-C
6H
4C(O)H
Wherein aldehyde radical is positioned at the 4-position of aryl.
The functional polymer beads of preparation aldehyde
By in the reaction flask that contains nitrogen atmosphere, adding 119.3g deionized water and 2.4g tensio-active agent-A (lauryl (oxyethane)
4Sodium sulfate), preparation contains the aqueous dispersion of the functional polymer beads of aldehyde.The content of flask is heated to 85 ℃.Next the mixture that adds 1.5g deionized water, 0.12g tensio-active agent-A, 2.7g butyl acrylate and 2.7g methyl methacrylate then adds the mixture that contains the 0.3g Sodium Persulfate that is dissolved in the 2.5g deionized water.The content of stirred flask 10 minutes.In 15 minutes time period, in flask, add and contain the monomer emulsion that 32.3g butyl acrylate (BA), 32.7g methyl methacrylate (MMA), 1g vinylformic acid (AA) and 6.12g contain aldehyde monomer (ACM).The content of flask is remained on 85 ℃ of following time periods of 15 minutes.Then be added in the solution of the 0.1g Sodium Persulfate in the 1g water.The temperature of the content to 50 ℃ of cooling flask then adds 2g ammonium hydroxide.Make the content cool to room temperature of flask.The gained aqueous dispersion contains the polymer beads of 100nm median size and has the solid content of 35.8wt%.The average composition of polymer beads is 45.3BA/45.3MMA/7.9ACM/1.3AA, based on the monomeric weight of reaction.
By making the surface-treated titanium dioxide granule reaction of functional polymer beads of aldehyde and embodiment 2.2, preparation has the composite particles of aldehyde functional group.
Claims (10)
1. polymer compound, it comprises:
A) organic polymer component, it comprises as the alkene chain type unsaturated monomer of polymerized unit and has at least one functional pendant groups; With
B) semiremote pawl group, it has:
I) estersil part and
Ii) form the sulphur atom of bonding with described organic polymer component;
Described polymer compound has formula A-L-S-Q, and wherein Q is described organic polymer component, and A-L-S is described semiremote pawl group, and A is described estersil part, and L is a linking group, and S is a sulphur atom.
2. polymer compound as claimed in claim 1, wherein said at least one functional pendant groups is selected from acid, alcohol, aldehyde, amine, acid amides, epoxy, halogen, acetoacetyl, lsothiocyanates and the isocyanic ester of carboxylic acid, acid anhydrides, phosphorated acid, sulfur-bearing.
3. polymer compound as claimed in claim 1, wherein said organic polymer component have and are at least 10 the polymerization degree.
4. method for preparing the described polymer compound of claim 1, it comprises the steps:
A) preparation comprises the reaction mixture of at least a ethylenically unsaturated monomers with functional group and the mercaptan compound with estersil part;
B) make described reaction mixture polymerization, form described polymer compound.
5. surface-treated inorganic matrix, it comprises:
A) has surperficial inorganic matrix; With
B) polymer compound residue, this polymer compound are the described polymer compounds of claim 1.
6. surface-treated inorganic matrix as claimed in claim 5, wherein said inorganic matrix is selected from titanium dioxide, silicon-dioxide, zinc oxide, titanium, aluminium, zirconium, silicon, zinc, chromium, tin, iron and lead.
7. surface-treated inorganic matrix as claimed in claim 5, wherein said functional group is selected from acid, alcohol, aldehyde, amine, acid amides, epoxy, halogen, acetoacetyl, lsothiocyanates and the isocyanic ester of carboxylic acid, acid anhydrides, phosphorated acid, sulfur-bearing.
8. surface-treated inorganic matrix as claimed in claim 5, wherein said inorganic matrix are to exist with the particle form of mean diameter less than 10 microns.
9. surface-treated inorganic matrix as claimed in claim 8, the polymerization degree of wherein said organic polymer component is at least 25; Be selected from alcohol, carboxylic acid, amine and acid amides with described functional group.
10. surface-treated inorganic matrix as claimed in claim 9; Wherein said inorganic matrix is selected from silicon-dioxide, titanium dioxide and zinc oxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US30692901P | 2001-07-20 | 2001-07-20 | |
| US60/306,929 | 2001-07-20 | ||
| US60/386,730 | 2002-06-10 |
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