CN1497025A - Polymer nanoparticle preparation material and its use as cement sealant - Google Patents
Polymer nanoparticle preparation material and its use as cement sealant Download PDFInfo
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- CN1497025A CN1497025A CNA031326927A CN03132692A CN1497025A CN 1497025 A CN1497025 A CN 1497025A CN A031326927 A CNA031326927 A CN A031326927A CN 03132692 A CN03132692 A CN 03132692A CN 1497025 A CN1497025 A CN 1497025A
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Abstract
A coating composition for inhibiting the penetration of water through a cementitious material comprising polymeric nanoparticles having a mean particle diameter of from 1 to 50nm is disclosed. The polymeric nanoparticles may be combined with latex binders or silicon containing polymers to provide a coating which seals the very small pores within the cementitious infrastructure.
Description
The present invention relates to coating, especially for the coating of coating cement material such as cement, breeze block etc.
Anti-sealing migration permeate water mud material (no matter whether these materials and building structure is still relevant with horizontal plane such as road, walkway, floor, airport runways) has become architect and slip-stick artist's major objective, because at first use is these materials.Because of its high porous internal structure, water can permeate masonry part, concrete and other cement matrix of buildings.Water can destroy base material, especially when freezing, and its corrodible steel strongthener of imbedding.In addition, the motion of water turnover buildings masonry part can extract salt and at the ugly salt stain of its surface deposition.For reducing these problems, a lot of mineral substrates seal with solvent base or aqueous-based polymers.
Solvent-based sealant thinks and deeper infiltrates in the hole, and their to get rid of water very good.Yet there is the danger that impairs one's health and catch fire in solvent (total formulation 50% to 80%).The water-based latex sealing agent is safer usually, but that its particle can not infiltrate is dark like that, because to compare the latex particle size quite big with the cement hole of smaller szie.Think that the more little infiltration of particle size is good more.
A kind of possible solution is provided by WO 99/01522, this patent disclosure use the polymer beads of 1-60nm.These fine particles prepare by the mode that amine and aliphatic carboxylic acid reaction generate ammonium salt.These polymer beads then combine the fundamental component of the formulation that is configured for being coated with cement matrix with linking agent.Yet,, basic cpd is added in the formulation for prevent that crosslinking reaction took place before coating is applied to substrate surface.This basic cpd is organic or inorganic amine such as ammonia, dimethylamine or diethylamine.After being applied to substrate surface, the basic cpd volatilization makes crosslinking reaction carry out then.
The problem of this method is before coating is suitably solidified on substrate surface very deleterious material is volatilized from coating.This is must be with the result that is not suitable for of the compound treatment of this patent disclosure.
Therefore, need a kind of particulate coating formulation that contains, this particle very micropodia does not meanwhile need with an organic solvent or can not discharge poisonous cross-linked inhibitor to fill the minimum hole in the inner cement structures and to form the coated substrates of enough resistant to water penetration.Polymer nano granules formulation for coating material of the present invention can be realized these purposes.
The present invention includes polymer nano granules (" PNP ").Each PNP has the median size of 1 to 50 nanometer (" nm "), and at least a polyenoid by 1 to 100wt% belongs to unsaturated monomer and forms.Each PNP particle diameter is more preferably 1 to 30nm, and most preferably 1 to 10nm.
In second embodiment of the present invention, PNP described herein can with conventional latex cement sealing cement, as available from Rohm and Haas, Phila, the CS-400 compounding of PA.
The 3rd embodiment of the present invention comprises PNP and conventional silicon-containing polymer cement seal agent combination.
Crosslinked PNP of the present invention can form by polymerization technique well known by persons skilled in the art.These technologies comprise polycondensation, cationoid polymerisation, ring-opening metathesis polymerization, anionoid polymerization and radical polymerization.Most preferred technology is the radical addition polymerization of free radical polymerizable monomer and at least a cross-linking monomer.
Following writing a Chinese character in simplified form used herein except as otherwise noted, otherwise will have following implication: C=℃; μ m=micron; The UV=ultraviolet ray; The revolution of rpm=per minute; The nm=nanometer; The J=joule; The cc=cubic centimetre; The g=gram; The wt%=weight percent; The L=liter; The mL=milliliter; The MIAK=methyl isoamyl ketone; The MIBK=methyl iso-butyl ketone (MIBK); PMA=gathers (methyl acrylate); The CyHMA=cyclohexyl methacrylate; EG=ethylene glycol; The DPG=dipropylene glycol; DEA=diethylene glycol monoethyl ether acetic ester; The BzA=benzyl acrylate; The BzMA=benzyl methacrylate; MAPS=MATS=methacrylic acid (trimethoxysilyl) propyl diester; PETTA=four/nitrilotriacetic pentaerythritol ester; PPG4000DMA=dimethacrylate polypropylene glycol 4000 esters; DPEPA=five vinylformic acid dipentaerythritol ester; TMSMA=methacrylic acid trimethyl silyl ester; Two (trimethylsiloxane group) methyl-monosilanes of MOPTSOMS=methacryloxypropyl; MOPMDMOS=3-methacryloxypropyl methyl dimethoxysilane; TAT=triallyl-1,3,5-triazines-2,4, and 6-(1H, 3H, 5H)-triketone; The IBOMA=isobornyl methacrylate; The PGMEA=propylene glycol monomethyl ether; PEGMEMA475=gathers (Ethylene Glycol Methyl ether) methacrylic ester Mw=475; EUG=oxymethoxyallylbenzene (4-allyl group-2-methoxyphenol); With PGDMA=dimethyl allene acid propylene glycol ester.
Term " (methyl) acrylic acid or the like " comprises vinylformic acid and methacrylic, and term " (methyl) acrylate " comprises acrylate and methacrylic ester.In addition, term " (methyl) acrylamide " is meant acrylamide and Methacrylamide." alkyl " comprises straight chain, side chain and cyclic alkyl.
Here Ding Yi all scopes are to comprise end value and capable of being combined.
Aqueous composition of the present invention comprises the aqueous dispersion of polymer particles of median size 1 to 50 nanometer (nm), and these particles comprise that at least a polyenoid as polymerized unit belongs to unsaturated monomer and the unsaturated water-soluble monomer of at least a olefinic.Term used herein " dispersion " be meant the physical condition that comprises at least two kinds of out of phase materials, wherein first be distributed in mutually second mutually in, second is continuum mutually." moisture " is meant by water-bearing media weight, contains the medium of 50 to 100wt% water.
Here the polymer beads that is called polymer nano granules (" PNP ") is an addition polymer, and its at least a polyenoid that contains as polymer unit belongs to unsaturated monomer and the unsaturated water-soluble monomer of at least a olefinic.Can be used for suitable polyenoid of the present invention and belong to unsaturated monomer and comprise two-, three-, four-or more senior multifunctional ethylenically unsaturated monomer, as Vinylstyrene, trivinylbenzene, divinyl toluene, the divinyl pyridine, the divinyl naphthalene, divinyl dimethylbenzene, two (methyl) vinylformic acid glycol ester, trimethylolpropane tris (methyl) acrylate, diethylene glycol divinyl ether, the trivinyl hexanaphthene, (methyl) vinylformic acid allyl ester, two (methyl) vinylformic acid glycol ether ester, two (methyl) vinylformic acid propylene glycol ester, 2,2-dimethylpropane-1,3-two (methyl) acrylate, two (methyl) vinylformic acid 1, the 3-butanediol ester, two (methyl) vinylformic acid 1, the 4-butanediol ester, two (methyl) vinylformic acid 1,6-hexylene glycol ester, two (methyl) vinylformic acid tripropylene glycol ester, two (methyl) vinylformic acid triethyleneglycol ester, two (methyl) vinylformic acid Tetraglycol 99 ester, two (methyl) polyalkylene glycol acrylate ester is as two (methyl) polyalkylene glycol acrylate 200 esters and two (methyl) polyalkylene glycol acrylate, 600 esters, two (methyl) vinylformic acid ethoxylation dihydroxyphenyl propane ester, two (methyl) vinylformic acid polytetramethylene glycol ester, three (methyl) vinylformic acid pentaerythritol ester, triethoxy three (methyl) vinylformic acid trihydroxymethylpropanyl ester, glyceryl propoxy-three (methyl) acrylate, four (methyl) vinylformic acid pentaerythritol ester, monohydroxy five (methyl) vinylformic acid dipentaerythritol ester, divinyl silane, trivinyl silane, dimethyl divinyl silane, the divinyl methyl-monosilane, methyl trivinyl silane, phenylbenzene divinyl silane, the divinyl phenyl silane, the trivinyl phenyl silane, the divinyl aminomethyl phenyl silane, tetrem thiazolinyl silane, dimethyl vinyl sily oxide, poly-(ethylene methacrylic radical siloxane), poly-(vinyl hydrogen siloxane), poly-(phenyl vinyl siloxanes) and its mixture.Term " (methyl) acrylic acid or the like " comprises vinylformic acid and methacrylic, and term " (methyl) acrylate " comprises acrylate and methacrylic ester.In addition, term " (methyl) acrylamide " is meant acrylamide and Methacrylamide." alkyl " comprises straight chain, side chain and cyclic alkyl.
Typically, PNP contains at least that at least a polymeric polyenoid of 1wt% belongs to unsaturated monomer, by PNP weight.Up to and the polymeric polyenoid that comprises 99.5wt% belong to unsaturated monomer (by the weight of PNP) and be effective in the particle of the present invention.The amount that the polymeric polyenoid belongs to unsaturated monomer is preferably 1 to 80%, more preferably 1 to 60%, and 1 to 25% (weight) most preferably is by the weight of PNP.
PNP also comprises at least a water-soluble monomer as polymerized unit." water-soluble monomer " refers under 25 ℃ of temperature the 7wt% at least of the solubleness in water here, preferred 9wt% at least, the most preferably monomer of 12wt% at least.Monomeric dissolubility data can be at for example " Polymer Handbook " (SecondEdition, J.Brandrup, E.H.Immergut, Editors, John Wiley ﹠amp; Sons is NewYork) with " Merk Index " (Eleventh Edition, Merck﹠amp; Co.Inc., Rahway, New Jersey) in find.The example of water-soluble monomer comprises unsaturated ion monomer of olefinic and the unsaturated water-soluble nonionic monomer of olefinic.Typically, the amount of polymeric water-soluble monomer is 0.5wt% at least, based on the weight of PNP.Up to and comprise that the polymeric water-soluble monomer (by the weight of PNP) of 99wt% can be effective in the particle of the present invention.
Here the unsaturated ion monomer of olefinic that is called " ion monomer " is the monomer that can disperse to have in the water-bearing media of PNP ionic charge therein.Suitable ion monomer for example comprises acidiferous monomer, contains alkali monomer, ampholytic monomer; The monomer and other monomer that can form ion monomer subsequently that contain quaternary nitrogen are as forming those monomers of ion monomer by acid-alkali reaction neutralization.Suitable acid groups comprises carboxylic acid group and strong acid, as phosphoric acid and sulfur acid.Suitable base groups comprises amine.The monomeric amount of polymerization plasma is preferably 0.5 to 99wt%, and more preferably 1 to 50wt%, and further more preferably 2 to 40wt%, most preferably 3 to 25wt%, by the weight of PNP.
The suitable carboxylic acid monomer that contains comprises the carboxylic acid monomer, as (methyl) vinylformic acid, acryloxy propionic and Ba Dousuan; Dicarboxylic acid monomer such as methylene-succinic acid, toxilic acid, fumaric acid and citraconic acid; For the monomer of dicarboxylic acid half ester as containing a carboxylic acid functional and a C
1-6The monomer of ester.Preferred vinylformic acid and methacrylic acid.Suitable strong acid monomer comprises the sulfuric acid monomer, as 2-acrylamido-2-methyl propane sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, (methyl) sulfoethyl acrylate, (methyl) vinylformic acid sulfopropyl ester, 2-acrylamido-2-methylpropane-sulfinic acid, vinylbenzene-sulfinic acid and vinyl-sulfinic acid; With phosphorus acid monomer such as 2-phospho ethyl (methyl) acrylate, vinyl phosphoric acid and vinyl phosphorous acid.Other acid mono comprises the big monomer that contains terminal unsaturation acid, and is as US5, disclosed in 710,227.Phosphorus acid monomer suits, because they can provide the improvement cohesive force to some base material (as metal).
The suitable alkali monomer that contains comprises the monomer with amine functional group, comprise (methyl) vinylformic acid N, N-dimethylaminoethyl ester, (methyl) vinylformic acid N, N-diethyllaminoethyl ester, (methyl) vinylformic acid N-tertiary butyl amino-ethyl ester, N, N-dimethylamino-propyl (methyl) acryloyl is by, p-aminophenyl ethene, N, N-dicyclohexyl allyl amine, allyl amine, diallyl amine, DMAA, N-ethyl DMAA, crot(on)yl amine and N-ethyl-methyl allyl amine; Monomer with pyridine functional groups comprises 2-vinyl pyridine and 4-vinylpridine; Monomer such as vinyl piperidines with piperidines functional group; Have the monomer of imidazoles functional group, comprise vinyl imidazole.The alkali monomer that contains that other is suitable comprises (methacrylic) oxazolidinyl ethyl ester, vinyl benzyl amine, ethenylphenyl amine, replacement diallyl amine, (methyl) vinylformic acid 2-morpholine ethyl ester, methacrylamidopropyltrimethyl trimethyl ammonium chloride, diallyldimethylammonium chloride, 2-trimethylammonium ethyl-methyl vinylformic acid ammonium chloride etc.
Suitable ampholytic monomer comprises sulfonic acid N-vinyl imidazole inner salt and N, N-diformazan-N-(3-methacrylamido third)-N-(3-sulfo group propyl group) ammonium trimethyl-glycine.
Wherein the suitable functional monomer that forms acid or alkali subsequently of functional group comprises that the monomer that contains epoxy-functional is as (methyl) glycidyl acrylate and allyl glycidyl ether; Acid anhydrides such as maleic anhydride; Ester such as methyl acrylate; And halogenide.Suitable Halogen functional monomer comprises aromatic vinyl halogenide and (methyl) vinylformic acid alkylhalide group ester.Suitable aromatic vinyl halogenide comprises vinyl chloride and vinyl benzyl bromine.Other suitable functional monomer comprises chlorallylene, allyl bromide 98 and (methyl) acrylate chloride.Suitable (methyl) vinylformic acid alkylhalide group ester comprises (methyl) vinylformic acid chloromethyl ester.Wherein the suitable functional monomer that forms the non-ionic water-soluble group subsequently of functional group comprises vinyl-acetic ester.The PNP that is hydrolyzed to of polymeric vinyl-acetic ester provides hydroxyl.
The polyenoid that is similarly water-soluble monomer belongs to unsaturated monomer and also is used to prepare PNP.In these embodiments, the present invention is categorized as polyenoid with these monomers and belongs to unsaturated monomer and water-soluble monomer.The example that water-soluble polyenoid belongs to unsaturated monomer is phospho two (a methacrylic acid ethyl ester).
The unsaturated water-soluble nonionic monomer of olefinic is called " water-soluble nonionic monomer " here.The monomeric example of water-soluble nonionic comprises that (methyl) acrylic acid hydroxy alkyl ester is as (methyl) hydroxyethyl acrylate and (methyl) vinylformic acid hydroxypropyl ester; (methyl) acrylic acid poly-(alkylene oxide) ester such as poly-(oxyethane) 20 esters of methacrylic acid and poly-(propylene oxide) 150 esters of vinylformic acid; Acrylamide and Methacrylamide.The monomeric amount of polymeric water-soluble nonionic is preferably 0.5 to 99wt%, and more preferably 20 to 90wt%, and further more preferably 30 to 80wt%, most preferably 40 to 70wt%, by the weight of PNP.When PNP comprises as the ion monomer of polymerized unit and non-ionic water-soluble monomer, the polymerization non-ionic water-soluble monomer of preferred low amount.
PNP randomly comprises as one or more of polymerized unit and does not belong to the 3rd monomer that polyenoid belongs to unsaturated monomer and do not belong to water-soluble monomer.The 3rd suitable monomer comprises (methyl) vinylformic acid C
1-C
24Alkyl ester is as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) Ethyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) vinylformic acid pentadecyl ester, (methyl) vinylformic acid cetyl ester, (methyl) vinylformic acid stearyl and (methyl) vinylformic acid nonadecyl ester and its mixture.Other the 3rd suitable monomer comprises vinyl-acetic ester; Branched paraffin carboxylic acid's vinyl acetate (vinyl versatate) vinyl acetate; Diisobutylene; The monomer such as N-(ethylidene urea groups ethyl)-4-valeramide, N-(ethylidene urea groups ethyl)-10-undecanoic amide, fumaric acid butyl ethylidene urea groups ethyl ester, fumaric acid methyl ethylidene urea groups ethyl ester, fumaric acid benzyl N-(ethylidene urea groups ethyl) ester and toxilic acid benzyl N-(the ethylidene urea groups ethyl) ester that contain urea groups; Vi-ny l aromatic monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, p-methylstyrene, vinyl xylene, ethyl vinyl benzene, vinyl naphthalene, vinyl-dimethyl benzene and Nonylphenoxy propenyl polyethoxylated alcohols.Vi-ny l aromatic monomers also comprises its corresponding counterpart that replaces, and as halide derivative, promptly contains one or more halogen groups such as fluorine, chlorine, bromine; With nitro, cyano group, (C
1-C
10) alkoxyl group, halogen (C
1-C
10) alkyl, (C
1-C
10) alkoxyl group, carboxyl etc.
PNP has 1 to 50nm, and preferred 1 to 40nm, and more preferably 1 to 30nm, and more preferably 1 to 25nm, further more preferably 1 to 20nm, and 1 to 10nm mean diameter most preferably.PNP generally has 1.5nm at least, the preferred average particulate diameter of 2nm at least.A kind of method of measuring the particle size (median size) of PNP is to use standard dynamic light scattering technology, wherein related function is converted into the hydromeehanics size with LaPlace conversion method such as CONTIN.
Usually, comprise the PNP that belongs to unsaturated monomer as the polyenoid that is lower than 10wt% of polymerized unit, have glass transition temp-90 to 170 ℃ (belonging to the non-existent composition of unsaturated monomer), by synthetic determine with dsc method for the polymeric polyenoid.Contain the PNP that polyenoid as the 50wt% at least of polymerized unit belongs to unsaturated monomer and be considered to have at least 50 ℃ glass transition temp.
PNP of the present invention generally has " apparent weight-average molecular weight " 5,000 to 1,000,000, and is preferred 10,000 to 500,000, and more preferably 15,000 to 100,000." performance weight-average molecular weight " used herein reflection PNP particulate size is used the standard gel chromatography, for example uses 40 ℃ THF solvent, 3 Plgel
TMChromatographic column (Polymer Labs, Amherst, MA), 100 dusts (10nm), 10
3Dust (100nm), 10
4Dust (1 micron), 30cm is long, 7.8mm ID, 1ml/min, 100 μ l volume injected are with Polymer Labs CALIBRE
TMSoftware, proofread and correct with the polystyrene standard sample of narrowly distributing.
This PNP randomly has makes PNP be scattered in suitable hydrophilic characteristics in the water-bearing media.Characterizing the hydrophilic a kind of method of PNP is to calculate the Hansch parameter.The Hansch parameter is calculated with the group contribution method.The monomeric unit that forms polymkeric substance is designated as the hydrophobicity contribution, and calculates the relative hydrophobicity of polymkeric substance based on monomeric weight in average in the polymkeric substance.Hansch and Fujita, J.Amer.Chem.Soc., 86,1616-1626 (1964); H.Kubinyi, Methods and Principles ofMedicinal Chemistry, Volume l, people such as R.Mannhold, Eds., VCH, Weinheim (1963); C.Hansch and A.Leo, Substitutent Constants for CorrelationAnalysis in Chemistry and Biology, Wiley, New YorK (1979); And C.Hansch, P.Maloney, T.Fujita and R.Muir, Nature, 194.178-180 (1962).
Several monomeric hydrophobicity contribution margins are listed in table 1.
Table 1
The monomeric hydrophobic contribution
Ethyl propenoate 2.11
Butyl acrylate 3.19
2-EHA 5.22
Vinylbenzene 4.29
Methyl methacrylate 1.89
Jia Jibingxisuanyizhi 2.43
Butyl methacrylate 3.51
Isobornyl methacrylate 5.0
Divinyl 4.0
Vinylformic acid-2.52
Methacrylic acid-2.2
Maleic anhydride-3.5
Preferred PNP has Hansch parameter-2.5 to 4, perhaps-1 to 3.
This PNP is optional to comprise other functional group, and it provides by the monomer that polymerization contains those groups or its precursor group.The optional ionic group by PNP of functional group is connected with PNP with the suitable compound reaction.For example, make it contain the wetting ability side group carboxy-containing acid group's PNP modification by hydroxy-acid group and suitable alcohol such as the reaction of end capped polyalkylene oxide.In addition, functional group is fixed on the PNP by non-free radical reaction, but thus contain this group and and the modified compound of the complementarity reactive group of PNP covalent bonding between form ion or covalent linkage, as US5, instruction in 270,380.
But the complementarity reactive group in PNP and the modified compound provides ion or covalent bonding.Additional ionic bonding comprises that soda acid interacts and the ion pair bonding of electronegative and positively charged atom.But the covalent bonding by the complementarity reactive group comprises, for example (a) acetylacetic ester-aldehyde; (b) acetylacetic ester-amine; (c) amine-aldehyde; (d) amine-acid anhydrides; (e) amine-isocyanic ester; (f) amine-epoxy; (g) aldehyde-hydrazides; (i) acid-epoxy; (j) acid-carbodiimide; (k) acid-chloromethyl ester; (j) acid-chloromethyl amine; (m) acid-acid anhydrides; (n) acid-aziridine; (o) epoxy-mercaptan; (p) isocyanic ester-alcohol.But first or second reactive group of each centering or be present among the PNP, or be present in the modified compound.
The appropriate method that preparation contains the aqueous composition that is dispersed in the PNP in the water-bearing media may further comprise the steps: preparation contains the non-aqueous PNP dispersion of the PNP that is dispersed at least a solvent; With non-aqueous PNP dispersion is mixed with water-bearing media.Here " non-water (property) " is meant and comprises 0 to the medium that is lower than 50wt% water (by the weight of non-aqueous media).The aqueous composition that will comprise PNP with before water-bearing media mixes, during or randomly partially or completely neutralization afterwards, described PNP comprises the ion monomer as polymerized unit.
The suitable polymeric method that is used to prepare non-aqueous PNP dispersion is that at least a polyenoid belongs to unsaturated monomer, at least a water-soluble monomer and at least a the 3rd optional monomeric free radical solution polymerization.Here " solution polymerization " is meant the radical addition polymerization in the suitable solvent of polymkeric substance.Here " suitable solvent of polymkeric substance " is meant that linear random (being total to) polymkeric substance that has with the substantially similar polymeric monomeric unit of PNP dissolves in solvent.The other method of selecting suitable solvent or solvent mixture is to use the solubility parameter analysis.According to these class methods, the solubility parameter of the suitability of solvent by PNP and solvent (as Van Krevelen parameter δ d, δ p, δ h and δ v) basically coupling determine.For example, referring to, people such as Van Krevelen,
Properties of Polymer.Their Estimation and Correlation with Chemical Structure, Elsevier ScientificPublishing Co., 1976; People such as Olabisi,
Polymer-Polymer Miscibility, Academic Press, NY, 1979; People such as Coleman,
Specific Interactions and The Miscibility of Polymer Blends, Technomic, 1991; And A.F.M.Barton,
CRC Handbook of Solubility Parameters and Other Cohesion Parameters, 2
NdEd., CRC Press, 1991. δ d are dispersed interactional measuring, and δ p is measuring of polar interaction, and δ h is measuring of interaction of hydrogen bond, and δ v measures for dispersed and polar interaction.This solubility parameter also can be calculated by for example group contribution method, or by for example determination of experimental method known in the art.Preferred solvent has the 5 (J/cms of δ v parameter in polymkeric substance δ v parameter
3)
1/2, preferred 1 (J/cm
3)
1/2In.The polymeric suitable solvent comprises organic solvent, as hydro carbons, and paraffinic, halohydrocarbon, is fluoridized and brominated hydrocarbon at chlorination; Aromatic hydrocarbons; Ether; Ketone; Ester; Alcohol; With its mixture.Specially suitable solvent, the composition that depends on PNP comprises dodecane, mesitylene, dimethylbenzene, diphenyl ether, gamma-butyrolactone, ethyl acetate, ethyl lactate, propylene glycol monomethyl ether, caprolactone, 2-heptanone, methyl iso-butyl ketone (MIBK), acetone, methyl ethyl ketone, diisobutyl ketone, propylene glycol monomethyl ether, alkyl alcohol such as Virahol, decyl alcohol and the trimethyl carbinol; And supercritical co.
Non-aqueous PNP dispersion is by at first will preparing in solvent or solvent mixture and a part of monomer adding reaction vessel.The monomer material is made up of monomer, initiator and chain-transfer agent usually.Kick off temperature is generally 55 ℃ to 125 ℃, although by using suitable low temperature known in the art or high-temperature initiator, lower or higher initiator temperature is possible.When subsequently feed intake (heel charge) when reaching the temperature that is enough to initiated polymerization, the surplus of monomer material or monomer material is added in the reactor.The monomeric charge time is generally 15 minutes to 4 hours, although can imagine the shorter and longer time.During monomer addition, it is constant that temperature of reaction generally keeps, although can change temperature of reaction.After finishing monomer mixture charge, the other initiator in solvent can be added in the reaction and/or with reaction mixture and keep for some time.
Control PNP particle size and distribution realize by following one or more methods: selective solvent, select initiator, total solid content, amount of initiator, the type of polyfunctional monomer and amount, the type of ion monomer and amount, the type of chain-transfer agent and amount and reaction conditions.
The initiator that can be used for radical polymerization of the present invention comprises, for example one or more in peroxy esters, alkyl hydroperoxide, dialkyl peroxide, azo initiator, persulphate, the redox initiator etc.The amount of the radical initiator that uses is generally 0.05 to 10wt%, by the total monomer amount.Chain-transfer agent randomly is used to control the extent of polymerization that can be used for PNP of the present invention.Suitable chain-transfer agent for example comprises: alkyl sulfhydryl such as lauryl mercaptan; Aromatic hydrocarbons such as toluene with active hydrogen; With alkyl halide such as bromine trichloroethane.
In a kind of method of preparation aqueous composition of the present invention, the monomeric at least a portion of the polymerization plasma of PNP is neutralized with at least a neutralization reagent, to be formed up to the non-aqueous PNP dispersion of small part neutral.The polymerization plasma monomeric unit of PNP can neutralize by multiple mode.When the polymerization plasma monomeric unit was acidity, neutralization reagent was generally alkali.And when the polymerization plasma monomeric unit was alkalescence, neutralization reagent was generally acid.Suitable alkali comprises inorganic and organic bases.Suitable mineral alkali comprises FR oxyhydroxide, carbonate, supercarbonate and the acetate bases of basic metal or alkaline-earth metal.Suitable organic bases comprises ammonia, primary/second month in a season/tertiary amine, diamines and triamine.Preferred alkaline neutralization reagent comprises sodium hydroxide and ammonium hydroxide.Suitable acid comprises carboxylic acid such as acetate; Dicarboxylic acid; (2) carboxylic acid/alcohol acid; Aromatic acid such as phenylformic acid; With various other acid as boric acid, carbonic acid, citric acid, acid iodide, nitrous acid, nitric acid, Periodic acid, phosphoric acid, phosphorous acid, sulfuric acid, sulfurous acid and spirit of salt.The alkali of the above-mentioned type and acid are not thought restricted.
The amount of the required neutralization reagent of the non-aqueous PNP dispersion that neutralizes is generally determined with respect to the molar weight of the polymerization plasma monomeric unit of PNP by neutralization reagent.Under the situation that is not subjected to the particular theory restriction, for the amount (being feeding quantity) of stablizing the required polymerization plasma monomeric unit of PNP (promptly keeping particle size between the transition phase from non-water to water-bearing media) will change with PNP composition and performance variation, it is believed that the hydrophobic performance, Tg, crosslinking degree of PNP and be important variable from the counter ion type of neutralization reagent.For stable aqueous PNP dispersion (wherein the flocculation of PNP is reduced to minimum) is provided, the polymerization plasma monomeric unit is preferably at least 20%, more preferably at least 50%, and further more preferably at least 80%, most preferably at least 90% be neutralized.
In and PNP also can carry out according to variety of way.In one approach, non-water PNP dispersion is under agitation added in the solution that contains neutralization reagent.Preferably neutralization reagent is added when stirring non-aqueous PNP dispersion with the aqueous solution form, to provide to the non-aqueous PNP dispersion of small part neutral.
Contain in a kind of method of aqueous composition of dispersive PNP in preparation, the non-water PNP of near small part neutral dispersion combines with water-bearing media.The optional neutralization reagent that is used for PNP that comprises of water-bearing media, in the case, non-water PNP dispersion can neutralize and combine with water-bearing media simultaneously.Water-bearing media randomly comprises tensio-active agent, and it can change the stability of PNP, or changes other performance such as its surface tension of gained PNP water dispersion.
The order of this part neutral non-water PNP dispersion of blending and water-bearing media is unimportant.Be suitable for blended the whole bag of tricks and unit describe in The Chemical Engineer ' s Handbook, 5thEdition Perry and Chilton, Eds., McGraw-Hill, Ch.21,1973.Usually,, simultaneously the non-water PNP of part neutral dispersion is joined in the water-bearing media,, reduce to the flocculation of PNP minimum thus to guarantee solvent and water-bearing media thorough mixing with the water-bearing media continuously stirring.
The suitable weight percentage of PNP in aqueous composition by the gross weight of aqueous composition, is generally 1 to 90wt%, and more general 2 to 75wt%, and further more general 4 to 65wt%, and further more general 8 to 55wt%, and the most general 10 to 45wt%.
Do not need to use tensio-active agent although prepare aqueous composition of the present invention, and general non-water PNP dispersion goes up surfactant-free substantially, randomly comprise tensio-active agent.When having tensio-active agent, its amount generally is lower than 3wt%, more generally is lower than 2wt%, more generally is lower than 1wt%, further generally is lower than 0.5wt%, further generally is lower than 0.2wt%, by the gross weight of PNP.
Aqueous composition is randomly handled to remove at least a portion solvent and optional water, improved the solid content of PNP thus.Make the appropriate method of PNP enrichment comprise distillating method, as forming the azeotrope of water and suitable solvent; Evaporating solvent or water; By lyophilize or the dry aqueous composition of spray-dired mode; Solvent extraction technology; And ultrafiltration technology.Preferably will be at least 25wt%, more preferably 50wt% at least, further more preferably at least 75wt% and most preferably the water used in solvent of 100wt% exchange.Removing desolvates preferably carries out under the condition that as far as possible reduces the unstable effect of PNP (i.e. flocculation).
In other method, aqueous composition of the present invention is prepared by a method comprising the following steps: preparation comprises the non-water PNP dispersion of the PNP that is dispersed at least a solvent, and this solvent both had been the suitable solvent of PNP, and was perhaps miscible with water again; Non-water PNP dispersion is combined with water-bearing media.Be suitable for containing acrylic acid PNP and comprise Virahol and ether alcohol (for example ethylene glycol monobutyl ether and carbiphene) with the example of the perhaps miscible this suitable solvent of water.In this method, do not need to add neutralization reagent when PNP combines with water and make particle have stability.
Other embodiments of aqueous composition of the present invention have the PNP content of wide region.The PNP weight fraction is generally 0.1 to 99wt%, and more general 1 to 90wt%, and further more general 2 to 75wt%, and further more general 5 to 50wt%, and is the most general 10 to 40wt%, by the weight of aqueous composition.
Provide the following examples and further specify all respects of the present invention.
Embodiment 1. preparation cross-linked polymer nano particles
The 500mL reactor is loaded onto thermopair, temperature regulator, sweeping gas inlet, had water cooling reflux exchanger, agitator and feed hopper that sweeping gas exports.In feed hopper, drop into 201.60g by 18.00g methyl methacrylate (purity 100%), 2.00g dimethacrylate glycol ether ester (purity 100%), 1.60g tert-pentyl peroxide pivalate at 75% solution and 180.00g diisobutyl ketone (" the DIBK ") monomer mixture formed of mineral turpentine (mineralspirits) in (Luperox-554-M-75).The reactor that will contain 180.00gDIBK is then used nitrogen wash 30 minutes, and then heating is so that the material in the reactor is heated to 75 ℃.When the material in the reactor reaches 75 ℃, the monomer mixture in the feed hopper was evenly dropped in the reactor in 90 minutes.After monomer mixture charge finishes 30 minutes, central first of aliquots containig (chaser aliquot) also appended by the tert-pentyl peroxide pivalate of 0.06g 75% solution and two of forming of 2.00gDIBK in mineral turpentine (Luperox-554-M-75) in interpolations-interval 30 minutes.After second interpolation of appending aliquots containig finishes, the material in the anti-device is kept 2.5 hours down to finish reaction at 80 ℃.By using the heptane precipitate and separate, filtration is collected and is dry under vacuum, obtains white powder with resulting polymers.This material is dissolved in the propylene glycol monomethyl ether once more.So to have particle size distribution be 0.8 to 5.0nm to the nano particle that forms and on average be of a size of 1.4nm (by the dynamic laser scattering method), and molecular weight is about 22,642g/mol and number-average molecular weight are about 14,601g/mol, Mw/Mn 1.6 (the measuring by GPC) that distribute.
Embodiment 2. prepares cross-linked polymer nano particle AAEM/ALMA multipolymer by the semi-batch emulsion polymerization.
Mixture by 28%w/w solid Texapon Special (" ALS "), 12.4g acetoacetoxyethyl methacrylate (" AAEM ") and the 1.78g allyl methacrylate (" ALMA ") of 17g deionized water, 8.85g prepares monomer emulsion.Then by the 28%w/w solid ALS of 600g deionized water, 15.0g and the 0.15g ammonium persulphate in the 1mL deionized water (" APS ") preparation feedback still material.With the reactor material with being heated to 90 ℃ under the nitrogen purge.1 semi-simple precursor emulsion is added in the reactor material under stirring with 200rpm.After 20 minutes, add the residual monomer emulsion.The still temperature is descended maintenance 30 minutes at 90 ℃, is cooled to 55 ℃, add solution and 0.010g sodium hydrosulfite 90min formaldehyde (" SSF ") the solution in 1mL deionized water of 0.02g tertbutyl peroxide (" t-BHP ") in the 1mL deionized water then respectively.Reaction is cooled to envrionment temperature and emulsion is passed through the filtration of 400 and 100 mesh sieves respectively.
Sample is separated from water by lyophilize, produce the frangible free flowing powder of white thus.With the gained white powder with a large amount of second distillations and deionized water wash to remove the most surfaces promoting agent.
The AAEM/ALMA multipolymer of the preparation of embodiment 3. cross-linked polymer nano particles-by discontinuous emulsion polymerization method preparation.
28%w/w solid ALS, 12.4gAAFM and the mixture of 1.78gALMA in bottle by 17g deionized water, 8.85g prepare monomer emulsion.Then by the 28%w/w solid ALS of 600g deionized water, 15.0g and the 0.15gAPS preparation feedback still material in the 1mL deionized water.With the reactor material with being heated to 90 ℃ under the nitrogen purging.Monomer emulsion is all being joined in the reactor material with the 200rpm stirring next time.After 30 minutes, the reaction flask temperature is cooled to 75 ℃, adds the solution of t-BHP in the 1mL deionized water of 0.02g then.To react and further be cooled to 55 ℃, and add the solution of 0.010gSSF in the 2mL deionized water.Reaction is cooled to envrionment temperature and emulsion is passed through the filtration of 400 and 100 mesh sieves respectively.
Embodiment 4. is equipped with the cross-linked polymer nano particle by progressively addition polymerization legal system.
28%w/w solid ALS, 68g ethyl acetate (" EA "), 17g methyl methacrylate (" MMA "), 12.5g Vinylstyrene (" DVB ") and 5g methacrylic acid (" MAA ") preparation monomer emulsion by 100g water, 1.60g.To comprise the 28%w/w solid ALS of 445g water, 22.2g and the reactor material of 0.37gAPS and in nitrogen atmosphere, be heated to 85 ℃.Monomer emulsion was added in the reactor in 90 minutes.To be reflected at 85 ℃ behind reinforced the end and keep 30 minutes, be cooled to 65 ℃ then.After the cooling, add 1.33g10% ferric sulfate (FeSO
4).After 1 minute, add the t-BHP of 0.2g70%, add 0.10g100% saccharosonic acid (" IAA ") after 2 minutes and will react maintenance 15 minutes.Add second by identical order and in the identical time and append the material system.Reaction is cooled to envrionment temperature and emulsion is passed through the filtration of 400 mesh sieves.
5: embodiment: the masonry part that immerses buildings
Employed PNP is made up of the 40MMA/45EHA/10TMPTA/5MAA by 68.2% solids concn in diethylene glycol monobutyl ether on the whole.By being prepared as follows material solution:
PNP 119g
Water 148g
Ammoniacal liquor 3g calculates 30% solid.
Brookfield viscosity 60,600 centipoises (rotating shaft 4, rotating speed 6rpm)
A. the sealing agent that is used for fibrocement
1.?Rhoplex?CS-4000?156g
Water 133g
Ethylene glycol butyl ether 11.3g calculates 25% solid
1.b. will A.1 further be diluted to 10% solid.
2.Rhoximat PR-3500 is diluted to 10% solid
3. the material solution with PNP further is diluted to 10% solid
4.Paraloid B-66,10% solid in dimethylbenzene.
The square at medium density fiber cement edge (siding) (is reached 15 second time in 10 * 10cm) the immersion coating, takes out and jolting, wipe unnecessary coating with paper handkerchief then.After dry 1 day, with cross-sectional area 13.8cm
2The band measuring graduates along the edge epoxy bond.The further curing of Resins, epoxy after 1 day, is filled to the 25ml scale with this graduated cylinder, 24 hours observing water quantity fall off rates.
The ml of the water that passes through and time relation
Coating solid 8 hours 24 hours
No coating--9.5 28
1 25％ 2.6 5.6
1.b. 10％ 4.5 13.5
2 10％ 3.3 11.0
3 10％ 3.7 7.7
4 10％ 1.0 2.5
For 10% solid aqueous-based polymers (1.b, 2,3), base material does not have the appearance facial mask of polymkeric substance, and its outward appearance does not change with uncoated comparing.Wherein, PNP of the present invention (3) draining after 24 hours is the most effective.By using higher solids latex (1) or can realizing bigger draining by use solvent based polyalcohol (4).Latter two forms distinguishable band gloss film on the fibrocement surface.
B. concrete sealing agent
Prescription 5:
Water 44.29
Ethylene glycol butyl ether 3.75
FC-120 wetting agent 0.04
SE-21 defoamer 0.05
Ammonium hydroxide, 28% to pH8
CS-4000 (4% solid) 51.87
6: will fill a prescription then 5 with the material solution of PNP by 90/10 weight ratio blending (being diluted to 20% solid).
The sealing agent is brushed on the concrete shearing coherent mass (shear bond block) dry 1 hour then.Drip 1 and to put on this surface and observe into pearl and the infiltration situation.
Coating 5. original observed are to water Cheng Zhu.Water droplet is to become bead form continual and steady 1 hour after applying water.
Coating 6. original observed are to water Cheng Zhu.Water droplet penetrated coating and is deep into slightly in the concrete substrate piece after 1 hour.
C. the gloss sealing agent on the concrete
Prepare the fresh concrete base material by 300 part of 45 order sand, 100 parts of Portland cements and 44 parts of water.Preparation pie piece (10cm) also solidified 7 days in the chamber of humidity.Coating then.
7.Paraloid B-66,25% solid in dimethylbenzene.
8.PNP material solution be diluted to 20% solid (with B.6 identical)
Coating is brushed on base material with about 1 mil thick, and dry 24 hours.
Gloss=the 1.2/8.5 of coating 7. under 20 °/60 °.The globule keeps pearl to reach 90 minutes when applying.By Taber abrasion (CS-10F wheel and 250g counter weight), 200 very little fragmentations of circulation rear film.
Gloss=the 3.4/18.5 of coating 8. under 20 °/60 °.The globule flattens and made coating wetting after 11-12 minute when applying.By Taber abrasion (CS-10F wheel and 250g counter weight), by film fragmentation (poorer) medium after 200 circulations than #7.
Solvent-based coating is generally expected that to have the higher gloss of film that forms than from polymer beads.Therefore, the high gloss of coating #8 is astonishing.
Claims (6)
1. coating composition that is used to seal cement surface comprises the polymer nano granules with median size of 1 to 50nm, and each polymer nano granules comprises that 1 to 99.5wt% at least a polyenoid belongs to unsaturated monomer.
2. the composition of claim 1, wherein diameter is 1 to 30nm.
3. the composition of claim 2, wherein diameter is 1 to 10nm.
4. the composition of claim 1 also comprises latex type cement seal binding agent.
5. the composition of claim 1 also comprises the agent of silicon-containing polymer cement seal.
6. a method that suppresses water permeate water mud material comprises that the coating composition with claim 1 is applied on the cement material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US41459402P | 2002-09-30 | 2002-09-30 | |
| US60/414,594 | 2002-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1497025A true CN1497025A (en) | 2004-05-19 |
Family
ID=34272324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031326927A Pending CN1497025A (en) | 2002-09-30 | 2003-06-13 | Polymer nanoparticle preparation material and its use as cement sealant |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264665A (en) * | 2008-12-22 | 2011-11-30 | 瓦克化学股份公司 | Hydraulicity sealing composition |
| CN103936915A (en) * | 2014-04-25 | 2014-07-23 | 上海正欧实业有限公司 | Organosilicone concrete antiseptic penetrating agent and preparation method thereof |
| US8957137B2 (en) | 2008-12-22 | 2015-02-17 | Wacker Chemie Ag | Acid-resistant, hydraulically setting masses |
-
2003
- 2003-06-13 CN CNA031326927A patent/CN1497025A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264665A (en) * | 2008-12-22 | 2011-11-30 | 瓦克化学股份公司 | Hydraulicity sealing composition |
| US8722772B2 (en) | 2008-12-22 | 2014-05-13 | Wacker Chemie Ag | Hydraulically setting sealing composition |
| US8957137B2 (en) | 2008-12-22 | 2015-02-17 | Wacker Chemie Ag | Acid-resistant, hydraulically setting masses |
| CN102264665B (en) * | 2008-12-22 | 2016-10-19 | 瓦克化学股份公司 | Hydraulicity sealing composition |
| CN103936915A (en) * | 2014-04-25 | 2014-07-23 | 上海正欧实业有限公司 | Organosilicone concrete antiseptic penetrating agent and preparation method thereof |
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