CN102643378A - Emulsifier-free vinyl acetate-maleic anhydride copolymer emulsion and preparation and application thereof - Google Patents
Emulsifier-free vinyl acetate-maleic anhydride copolymer emulsion and preparation and application thereof Download PDFInfo
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Abstract
The invention provides emulsifier-free vinyl acetate-maleic anhydride copolymer emulsion, which utilizes vinyl acetate, maleic anhydride, butyl acrylate and methacrylonitrile beta-hydroxyethyl acrylate as comonomers, utilizes potassium sulfate or ammonium persulfate as an initiator, utilizes sodium bicarbonate as a neutralizer and utilizes deionized water as solvent, and is prepared by emulsifier-free emulsion polymerization. Interior wall humidity-conditioning paint which is prepared by compounding and grinding the emulsifier-free vinyl acetate copolymer emulsion serving as a film former and pigments and fillers including palygorskite, bentonite and the like has excellent water absorption, water-retaining property, water resistance, permeability and anti-frost and anti-condensation performance, can be used for painting indoor walls of buildings, and has a humidity conditioning function.
Description
Technical field
The invention belongs to technical field of macromolecules, relate to a kind of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and preparation thereof; The present invention also relates to this no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion simultaneously as the application of film forming matter in preparation interior wall humidity controlling coating.
Background technology
Humidity controlling coating is the functional paint with suction, moisture releasing characteristic, can on the surface of coated article, form have protection, the filming of decoration, humidity conditioning function.In general, they all are made up of film forming matter, porous/layer color stuffing and auxiliary agent, can brush construction and the dry film forming of ability on the coated article surface.The water sensitive breathing coating is different from general humidity controlling coating; Compare with present humidity controlling coating and must have stronger water-absorbent, water-retentivity and water-alkali resistance property; Can form on the coated article surface and integrate filming of functions such as protection, decoration, damping, water-permeable and air permeable; Promptly the response of water is wanted fast, the performance of raising/reduction humidity will be got well, and has to keep the metastable ability of indoor air humidity within a certain period of time; Coating for a long time can not foaming under dampness, shedding, distortion (Kang Yuli, Wu Yuting, Song Leilei etc." development of compound humidity controlling coating and experimental study ", coatings industry, 2007,37 (8): 26 ~ 29).
Emulsifier-free emulsion polymerization is the monodisperse polymer micro-sphere of preparation surface cleaning and the effective ways that improve the emulsion film performance.Owing to do not add emulsifying agent (not adding conventional small-molecular emulsifier more precisely) in the emulsifier-free emulsion polymerization or only add small amounts of emulsifiers (less than its micelle-forming concentration), to introduce the water-soluble monomer copolymerization usually or adopt reactive surfactant, macromole emulsifying agent etc.Xing Changmin (Xing Changmin; Yang Wantai; Maleic anhydride/vinyl acetate emulsifier-free emulsion polymerization prepares the surface reaction monodisperse polymer micro-sphere. the academic free paper session of national polymer in 2005) with maleic anhydride (MALEIC ANHYDRIDE; Maleic anhydride is commonly called as maleic anhydride, writes a Chinese character in simplified form MA.) in specific organic solvent, carry out copolymerization with two kinds of monomers of vinyl-acetic ester (VAc), can obtain a kind of stabilized emulsion system of copolymer microsphere of new chemical composition easily.The stability of this system derives from the interaction of functional group that copolymer microsphere itself contains and specific medium molecule.(D. mren such as mren; A.Boztu; E. Ylmaz; H. B. Zengin. Viscometric investigation of compatibilization of the poly (vinyl chloride)/poly (ethylene-co-vinyl acetate) blends by terpolymer of maleic anhydride – styrene – vinyl acetate Original Research Article. Journal of Molecular Structure; 2008,891 (1-3): 329 – 332.) synthesized maleic anhydride-styrene-vinyl acetate terpolymer, measured the lyotropy of this multipolymer with viscosimetry.Carja etc. as with the new hybrid material, have done the LDH-copolymer-maleic anhydride and have studied (G to the performance of this kind material
.Carja, G. C. Chitanu B, Y. Kameshima, H. Chiriac, K. Okada. LDH – maleic anhydride copolymers as new hybrid materials and their textural organisation
[J]. Applied Clay Science, 2008,41 (3-4): 107 – 112.).Li Xiu waits (Li Xiuqing, Song Yongqiang, Li Chunping, Liu Peng clearly.Synthetic and the performance study [J] of styrene-maleic anhydride copolymer. Inner Mongol University of Technology's journal. 2006; 25 (3): 215-220) discover that vinylbenzene (St)-maleic anhydride (MA) multipolymer is a kind of novel high polymer material with excellent heat resistance, rigidity and dimensional stability, be widely used in the field such as emulsifying agent, textile auxiliary agent, printing-ink, matrix material, curing agent for epoxy resin of properties-correcting agent, the agricultural chemicals of latex coating, water conditioner, tackiness agent.Wang Liyong (Wang Liyong; Appoint Tianrui. synthetic [J] of vinylformic acid/maleic anhydride High hydrophilous resin. process engineering journal, 2005,5 (2): 162-165.); It is raw material with vinylformic acid (AA), acrylate and maleic anhydride (MA) that research is arranged; Ammonium persulphate (APS) is an initiator, and N,N methylene bis acrylamide (MBA) and glycerine are linking agent; Adopt water solution polymerization process to synthesize a kind of novel High hydrophilous resin and investigated the influence of dosage of crosslinking agent, initiator amount and maleic anhydride ammonification degree the High hydrophilous resin water absorbing properties; And optimized condition through orthogonal experiment, and find that the consumption of maleic anhydride in High hydrophilous resin can reach 15%, replace the acrylic amide synthesizing super absorbent resin can reduce the production cost of High hydrophilous resin greatly with maleic anhydride.
Chinese patent ZL200810187001, ZL200810187002, ZL200810187003 and CN101906189A disclose amphipathic PEMULEN TR2 emulsion and potato starch graft emulsion respectively; And it is applied to water sensitive breathing coating and function humidity controlling coating respectively; Although they have water-absorbent and damping performance preferably, still there is certain defective aspect the wetting ability of coating and the abrasion resistance.
The emulsion-type humidity controlling coating is the present the hottest type of research, and this is that physical and chemical performance is good because resin can be with the form stable dispersion of latex in water, safety and environmental protection, and cost is low.At present, using emulsions such as pure third, phenylpropyl alcohol, silicon third, vinyl acetate, can prepare the emulsion-type humidity controlling coating with addition of the porous layer color stuffing again, is the main body of humidity controlling coating.But also there is following problem in the humidity controlling coating with ordinary emulsion is processed: at first, ordinary emulsion (like phenylpropyl alcohol, pure third, silicon third, aqueous polyvinyl acetate emulsion etc.) still belongs to hydrophobic resin, and water-intake rate is little usually, and water-absorbent is poor.Its two, though traditional humidity controlling coating also uses the porous color stuffing, supporting with it is hydrophobic resin; Behind the coating drying and forming-film; The most duct of color stuffing, space and surface are stopped up or embedding by hydrophobic resin, so whole coating shows as stronger hydrophobicity, are a kind of " water blocking layers "; The damping effect can only lean on that a spot of polar group combines to play a role with water in a small amount of exposed porous color stuffing that does not wrap and the resin, so the damping performance greatly reduces.This hydrophobic resin cooperates the humidity controlling coating that makes only to have certain moisture absorption but not water-absorbent with wetting ability perforated color stuffing, the damping DeGrain, and water tolerance reduces much than common interior wall coating.
Summary of the invention
The objective of the invention is provides a kind of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion to the problem that exists in the prior art.
Another object of the present invention provides a kind of preparation method who does not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion;
A further object of the invention is that film forming matter is used to prepare the interior wall humidity controlling coating with no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion exactly.
(1) no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
1, the preparation of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
The present invention does not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion; Be to be comonomer with vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methacrylic beta-hydroxy ethyl ester; With vitriolate of tartar or ammonium persulphate is initiator; With the sodium hydrogencarbonate is neutralizing agent, is solvent with the deionized water, adopts emulsifier-free emulsion polymerization and gets.Its concrete proportioning raw materials and preparation method are following:
Proportioning raw materials: in weight part
10 ~ 40 parts of vinyl-acetic esters, 1 ~ 10 part of maleic anhydride, 1 ~ 30 part of Bing Xisuandingzhi, 1 ~ 10 part of methacrylic beta-hydroxy ethyl ester, 1 ~ 3 part of initiator, 1 ~ 15 part of neutralizing agent, 70 ~ 100 parts of deionized waters.
Preparation technology: in reactor drum, add earlier deionized water, neutralizing agent, 1/3 ~ 1/2 initiator, be warming up to 40 ~ 95 ℃, fully stir it is fully dissolved; Add vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methacrylic beta-hydroxy ethyl ester and residue initiator again,, obtain copolymer emulsion 40 ~ 95 ℃ of following isothermal reactions 1 ~ 6 hour; Be cooled to 25 ~ 65 ℃, the use mass concentration is 5 ~ 25% ammoniacal liquor adjust pH=7 ~ 10, filters, and promptly getting does not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion.
Said neutralizing agent sodium hydrogencarbonate is joined the aqueous solution that can process mass concentration 2 ~ 10% and is added, and also can directly add by its intrinsic form.
The aqueous solution that said initiator can be mixed with mass concentration 1 ~ 5% adds, and also can directly add by its intrinsic form.
2, the performance test of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
2.1 fundamental property: table 1 is the fundamental property index of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion.The result of table 1 shows that the no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion of the present invention's preparation has reached trade sales coating and used the emulsion standard.
Table 1: no soap vinyl acetate copolymer emulsion fundamental property index
2.2 the mensuration of cohesion rate: after polyreaction is accomplished; Filter emulsion with 100 mesh filter screens, collect on the filter screen, reactor wall and the condensation prod that stirs, rinse out the emulsion of stick on top with tap water; In baking oven, dry to constant weight then, the percentage that the weight of condensation prod accounts for amount of monomer is the cohesion rate.
Cohesion rate=condensation prod weight/monomer total amount * 100%;
Test result: 0.5% of cohesion rate≤monomer total amount.
2.3 the mensuration of solids content and transformation efficiency: press GB1725-79 solids coatings assay method.Petridish with dried and clean baked 30 minutes in 105 ± 2 ℃ of baking ovens earlier.Moisture eliminator is put in taking-up, be cooled to room temperature after, weigh.With the sampling of ground drop bottle, take by weighing 1.5 ~ 2 gram samples (perchloropolyvinyl paint sampling 2 ~ 2.5 grams, acrylic paint and solids content are lower than 15% lacquer class sampling 4 ~ 5 grams) with the decrement method; Place the petridish of having weighed, make sample spread bottom equably in container, be put in adjusted then and be to temperature bake 8 hours in 80 ℃ the air blast constant temperature oven after; After taking-up is put into moisture eliminator and is cooled to room temperature; Weigh, and then put into baking oven and baked 30 minutes, take out put into moisture eliminator and be cooled to room temperature after; Weigh, the weight difference of weighing for twice to front and back is not more than (all weighings are accurate to 0.01 gram) till 0.01 gram.Solids content % (X) is calculated as follows:
Solids content X=W1-W/G * 100 (1)
Transformation efficiency=X * (W1-W)/Wn * 100% (2)
In the formula: W---container weight (g)
W1---bake back sample and container weight (g)
G---sample weight (g)
Wn---monomer total amount (g).
Measure the result: the present invention's preparation no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion solids content is 15 ~ 43%, transformation efficiency is 70 ~ 95%.
2.4 the mensuration of particle diameter:
Detection method: at 25 ℃, 90 ° of scattering angle are measured under the condition of weaker concn (< 0.01 %) with Zetasizer particle diameter appearance.
Detected result: the no soap vinyl-acetic ester-copolymer-maleic anhydride particle size of emulsion of the present invention's preparation is 130 ~ 256nm.
2.5 do not have the paint film property of soap vinyl-acetic ester-copolymer-maleic anhydride emulsion: take out a small amount of emulsion from container; Measure viscosity, particle diameter, the solid performance of grading; Then with the emulsion brushing on the sheet glass and galvanized iron sheet of cleaning, press the preparation of the general preparation method of GB/1727-92 paint film and detect model, specified standards condition held 2d in GB/9278-88; Drying and forming-film, it is as shown in table 2 to measure the paint film fundamental property.Can find out that from table 2 the present invention does not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion paint film and has sticking power and water-absorbent preferably.
Table 2 detects for the fundamental property of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion paint film
(2) indoor humidity controlling coating
1, the preparation of indoor humidity controlling coating: the indoor humidity controlling coating of the present invention is as main film forming matter with no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion; With polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment is that color stuffing is prepared from, and its concrete proportioning raw materials and preparation technology are following:
Raw material: 20 ~ 60 parts of no soap vinyl-acetic esters-copolymer-maleic anhydride emulsion; 1 ~ 30 part of polygorskite, 1 ~ 30 part of wilkinite, 2 ~ 50 parts in zeyssatite, 1 ~ 30 part of polynite, 5 ~ 35 parts of talcum powder, 1 ~ 30 part of white titanium pigment; 0.03 ~ 0.3 part of linking agent, 60 ~ 260 parts of deionized waters.
Preparation technology: earlier polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment are mixed the back and mix well with deionized water; To wherein adding no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and linking agent; Be ground to fineness after mixing below 80 μ m; Filter, check, pack, promptly getting does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating.
Said linking agent is a diacetone-acryloamide(DAA)
In actual production, also can add antiseptic-germicide, toughener, skimmer or the like as required, also can add pigment.
2, the performance test of indoor humidity controlling coating
2.1 fundamental property test
Table 3 is the film performance test result of the interior wall humidity controlling coating of the present invention's preparation.The test result of table 3 shows: the breathing coating of the present invention's preparation; Can not only reach the domestic emulsion-type interior wall coating standard of generally using; And on water-absorbent, time of drying and alkali resistance project, far be more than present GB; Can substitute existing emulsion-type interior wall coating fully, when solving indoor damping problem, have important use value and realistic meaning.
Table 3: the film performance test result of interior wall humidity controlling coating
2.2 damping performance test
A) moisturization: the coating for preparing is painted on the sheet glass, and drying and forming-film.Write down initial AT and humidity in the artificial airtight weather damping case that volume is 42L earlier, put into the damping case to the model after the some saturated suctions of having weighed then, regularly measure the variation of humiture in the case, make humidification curve (see figure 1).
B) wet performance falls: the coating for preparing is painted on the sheet glass, and drying and forming-film.Atmospheric moisture in the artificial airtight weather damping case that first water ware is 42L with volume transfers to 85 ~ 100%; And stable for some time; The record start humiture is put into case to some dry models of having weighed then, regularly measures the variation of humiture in the case; Make and fall wet graphic representation, result such as Fig. 1.
Can know by Fig. 1, the water ware can with artificial damping case in 4h by relative humidity 30% humidification to 50%, humidification to 60% in 12h.With the humidity controlling coating plate of water ware homalographic can be with artificial damping case at 2 h by relative humidity 30% humidification to 75%, humidification to 90% in 6h.When being that 90% damping case octal is opened with relative humidity, the window that is equivalent to the room is opened and is removed wetly, can see among the figure when about 1h; The relative humidity of damping case reduces to 45% by 90%; Be coated with flitch as for wherein the time when what will dry to constant weight, when about 1h, the humidity in the case just reduces to 45% by 90%; And both humidity of damping case all when about 8h, reduce to 20%.Humidity controlling coating by no soap vinyl acetate copolymer emulsion preparation has certain damping performance.
2.3 water-intake rate is measured
The sheet glass of getting ready is accurately weighed, and the coating film forming matter with preparation is painted on the sheet glass then, weighs, and at room temperature under 100 ℃, dries to constant weight behind the drying and forming-film; Taking-up is weighed, and then immerses in 25 ± 1 ℃ the deionized water and regularly take out, and blots film coated surface moisture with filter paper rapidly; Weigh immediately, and then put into water and soak, so repeat; Quality until last coated plate no longer changes, and makes the coating water-intake rate to time curve, and is as shown in Figure 2.
The result of Fig. 2 shows: water-intake rate reaches 50% when 10min, when 0.5h, has reached 100% and behind 1h, reach 200%, reaches as high as 252%, and visible this humidity controlling coating film forming matter has stronger water-absorbent.
In sum, the relative prior art of the present invention has the following advantages:
1, no soap vinyl-acetic ester of the present invention-copolymer-maleic anhydride emulsion; Be to be that comonomer is polymerized, because maleic anhydride is the wetting ability polar group, after introducing maleic anhydride on the high polymer main chain with vinyl-acetic ester (VAc), maleic anhydride (MA), Bing Xisuandingzhi (BA), methacrylic beta-hydroxy ethyl ester (HEMA); Strengthened the interaction between polymer and the water; Can increase the water absorbing properties of resin, thereby copolymer emulsion improving the water absorbing properties of resin on than the basis of strong adhesive force, be the indoor humidity controlling coating that film forming matter prepares with it; The protection decoration function can be played, the novel humidity controlling coating of indoor humidity can be regulated again automatically.When higher or coating was met water when ambient moisture, the coating suction reduced indoor relative humidity; When humidity is low, again the water that sucks is discharged, improve indoor humidity, so repeatedly, regulate atmospheric moisture.
2, not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion be hydrophilic polymer in the present invention; Contain a large amount of hydrophilic radicals (like carboxyl, hydroxyl, carbonyl etc.); And with porous, multilayer fillers such as wilkinite, zeyssatite, polygorskites is skeleton; Specific surface area that porous, multilayer filler are huge and pore volume provide necessary expansion space for this copolymer emulsion suction back volumetric expansion again, thereby make the humidity controlling coating that obtains have damping performance preferably.
3, the present invention is that the humidity controlling coating that solvent is processed does not contain organic solvent and emulsifying agent with water; On the basis that guarantees above-mentioned good damping performance and over-all properties, overcome the shortcoming of traditional humidity controlling coating, in production and construction process; More inexpensive environmental protection, and practice thrift petroleum resources.
Description of drawings
Fig. 1 does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating coating damping The performance test results (test condition: 25 ℃ of room temperatures) for the present invention;
C-I: humidity controlling coating coating humidification curve of the present invention; B-I: the humidification curve of blank test;
C-D: wet curve falls in humidity controlling coating coating of the present invention; B-D: blank test wet curve falls;
Fig. 2 is the water-intake rate of humidity controlling coating coating of the present invention.
Embodiment
Be described further through the preparation and the performance of specific embodiment below copolymer emulsion of the present invention and humidity controlling coating thereof.
(1) preparation of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
Proportioning raw materials: in weight part
10 parts of vinyl-acetic esters, 1 part of maleic anhydride, 10 parts of Bing Xisuandingzhis, 3 parts of methacrylic beta-hydroxy ethyl esters, 1 part of initiator, 1 part of neutralizing agent, 70 parts of deionized waters.
Preparation technology: in the four-hole boiling flask that electric mixer, TM, prolong and tap funnel are housed, add deionized water, neutralizing agent NaHCO
3The aqueous solution (1%wt) of the aqueous solution (3%wt) and 1/3 part of initiator potassium persulfate, heat temperature raising to 60 ℃ following a stirring fully dissolved it; Drip monomer vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methylacrylic acid-β hydroxypropyl acrylate and remaining initiator (dripping off in about 6 hours) then,, obtain copolymer emulsion 60 ℃ of reactions 2 hours; Be cooled to 25 ℃ then, the use mass concentration is 8% ammoniacal liquor accent pH=10, and 100 mesh sieves filter, encapsulation, and numbering, promptly obtaining modification does not have soap vinyl acetate copolymer emulsion.
(2) performance index of copolymer emulsion:
Fundamental property: see table 1.
Cohesion rate: 0.5% of≤monomer total amount;
Solids content: 37.8%;
Transformation efficiency: 79%;
Emulsion particle diameter: 149nm.
(3) preparation of humidity controlling coating
Proportioning raw materials: in weight part
20 parts of no soap vinyl-acetic esters-copolymer-maleic anhydride emulsion, 5 parts of polygorskites, 5 parts of wilkinites, 50 parts in zeyssatite, 1 part of polynite, 12 parts of talcum powder, 10 parts of white titanium pigments, 0.1 part of linking agent diacetone-acryloamide(DAA), 60 parts of deionized waters;
Preparation technology: earlier polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment are mixed the back and mix well with deionized water; To wherein adding no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and linking agent; Be ground to fineness after mixing below 80 μ m; Filter, check, pack, promptly getting does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating.
(4) performance test of humidity controlling coating
Fundamental property: see table 3;
Damping performance: see Fig. 1;
Water absorbing properties: water-intake rate is 249%.
(1) preparation of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
Proportioning raw materials: in weight part
40 parts of vinyl-acetic esters, 10 parts of maleic anhydrides, 1 part of Bing Xisuandingzhi, 5 parts of methacrylic beta-hydroxy ethyl esters, 3 parts of initiators, 5 parts of neutralizing agents, 90 parts of deionized waters.
Preparation technology: in the four-hole boiling flask that electric mixer, TM, prolong and tap funnel are housed, add deionized water, add neutralizing agent NaHCO
3The aqueous solution (1%wt) of the aqueous solution (3%wt) and 1 part of initiator potassium persulfate, heat temperature raising to 60 ℃ following a stirring fully dissolved it; Drip monomer vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methylacrylic acid-β hydroxypropyl acrylate and remaining initiator (dripping off in about 6 hours) then,, obtain copolymer emulsion 95 ℃ of reactions 1 hour; Be cooled to 35 ℃ then, the use mass concentration is 2 ~ 25% ammoniacal liquor accent pH=10, and 100 mesh sieves filter, encapsulation, and numbering, promptly obtaining modification does not have soap vinyl acetate copolymer emulsion.
(2) performance index of copolymer emulsion:
Fundamental property: see table 1.
Cohesion rate: 0.5% of≤monomer total amount;
Solids content: 39%;
Transformation efficiency: 76%;
Emulsion particle diameter: 179nm.
(3) preparation of humidity controlling coating
Proportioning raw materials: in weight part
60 parts of no soap vinyl-acetic esters-copolymer-maleic anhydride emulsion, 30 parts of polygorskites, 1 part of wilkinite, 2 parts in zeyssatite, 30 parts of polynites, 10 parts of talcum powder, 20 parts of white titanium pigments, 0.03 part of linking agent diacetone-acryloamide(DAA), 260 parts of deionized waters;
Preparation technology: earlier polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment are mixed the back and mix well with deionized water; To wherein adding no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and linking agent; Be ground to fineness after mixing below 80 μ m; Filter, check, pack, promptly getting does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating.
(4) performance test of humidity controlling coating
Fundamental property: see table 3;
Damping performance: see Fig. 1;
Water absorbing properties: water-intake rate is 253%.
(1) preparation of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
Proportioning raw materials: in weight part
20 parts of vinyl-acetic esters, 3 parts of maleic anhydrides, 30 parts of Bing Xisuandingzhis, 10 parts of methacrylic beta-hydroxy ethyl esters, 2 parts of initiators, 15 parts of neutralizing agents, 100 parts of deionized waters.
Preparation technology: in the four-hole boiling flask that electric mixer, TM, prolong and tap funnel are housed, add deionized water, add neutralizing agent NaHCO
3The aqueous solution (1%wt) of the aqueous solution (3%wt) and 1 part of initiator potassium persulfate, heat temperature raising to 60 ℃ following a stirring fully dissolved it; Drip monomer vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methylacrylic acid-β hydroxypropyl acrylate and remaining initiator (dripping off in about 6 hours) then,, obtain copolymer emulsion 60 ℃ of reactions 2 hours; Be cooled to 25 ℃ then, the use mass concentration is 2 ~ 25% ammoniacal liquor accent pH=9, and 100 mesh sieves filter, encapsulation, and numbering, promptly obtaining modification does not have soap vinyl acetate copolymer emulsion.
(2) performance index of copolymer emulsion:
Fundamental property: see table 1.
Cohesion rate: 0.1% of≤monomer total amount;
Solids content: 43%;
Transformation efficiency exists: 90%;
Emulsion particle diameter: 130nm.
(3) preparation of humidity controlling coating
Proportioning raw materials: in weight part
50 parts of no soap vinyl-acetic esters-copolymer-maleic anhydride emulsion, polygorskite 1,30 parts of wilkinites, 10 parts in zeyssatite, 10 parts of polynites, 5 parts of talcum powder, 30 parts of white titanium pigments, 0.3 part of linking agent diacetone-acryloamide(DAA), 200 parts of deionized waters.
Preparation technology: earlier polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment are mixed the back deionized water and mix well; To wherein adding no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and linking agent; Be ground to fineness after mixing below 80 μ m; Filter, check, pack, promptly getting does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating.
(4) performance test of humidity controlling coating
Fundamental property: see table 3;
Damping performance: see Fig. 1;
Water absorbing properties: water-intake rate is 198%.
(1) preparation of no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion
Proportioning raw materials: in weight part
30 parts of vinyl-acetic esters, 5 parts of maleic anhydrides, 20 parts of Bing Xisuandingzhis, 5 parts of methacrylic beta-hydroxy ethyl esters, 2 parts of initiators, 3 parts of neutralizing agents, 80 parts of deionized waters.
Preparation technology: in the four-hole boiling flask that electric mixer, TM, prolong and tap funnel are housed, add deionized water, add neutralizing agent NaHCO
3The aqueous solution (1%wt) of the aqueous solution (3%wt) and 1 part of initiator potassium persulfate, heat temperature raising to 70 ℃ following a stirring fully dissolved it; Drip monomer vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methylacrylic acid-β hydroxypropyl acrylate and remaining initiator (dripping off in about 6 hours) then,, obtain copolymer emulsion 70 ℃ of reactions 3 hours; Be cooled to 40 ℃ then, the use mass concentration is 2 ~ 25% ammoniacal liquor accent pH=8, and 100 mesh sieves filter, encapsulation, and numbering, promptly obtaining modification does not have soap vinyl acetate copolymer emulsion.
(2) performance index of copolymer emulsion
Fundamental property: see table 1.
Cohesion rate: 0.4% of≤monomer total amount;
Solids content: 36.5%;
Transformation efficiency exists: 80%;
Emulsion particle diameter: 256nm.
(3) preparation of humidity controlling coating
Proportioning raw materials: in weight part
30 parts of no soap vinyl-acetic esters-copolymer-maleic anhydride emulsion, 10 parts of polygorskites, 10 parts of wilkinites, 20 parts in zeyssatite, 20 parts of polynites, 35 parts of talcum powder, 1 part of white titanium pigment, 0.2 part of linking agent diacetone-acryloamide(DAA), 150 parts of deionized waters.
Preparation technology: earlier polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment are mixed the back and mix well with deionized water; To wherein adding no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and linking agent; Be ground to fineness after mixing below 80 μ m; Filter, check, pack, promptly getting does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating.
(4) performance test of humidity controlling coating
Fundamental property: see table 3;
Damping performance: see Fig. 1;
Water absorbing properties: water-intake rate is 239%.
Claims (10)
1. there is not soap vinyl-acetic ester-copolymer-maleic anhydride emulsion; Be to be comonomer with vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methacrylic beta-hydroxy ethyl ester; With vitriolate of tartar or ammonium persulphate is initiator; With the sodium hydrogencarbonate is neutralizing agent, is solvent with the deionized water, adopts emulsifier-free emulsion polymerization and gets.
2. do not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion according to claim 1, it is characterized in that: said each raw material carries out proportioning by following weight part:
10 ~ 40 parts of vinyl-acetic esters, 1 ~ 10 part of maleic anhydride, 1 ~ 30 part of Bing Xisuandingzhi, 1 ~ 10 part of methacrylic beta-hydroxy ethyl ester, 1 ~ 3 part of initiator, 1 ~ 15 part of neutralizing agent, 70 ~ 100 parts of deionized waters.
3. the preparation method who does not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion according to claim 1 is in reactor drum, to add earlier deionized water, neutralizing agent, 1/3 ~ 1/2 initiator, is warming up to 40 ~ 95 ℃, fully stirs it is fully dissolved; Add vinyl-acetic ester, maleic anhydride, Bing Xisuandingzhi, methacrylic beta-hydroxy ethyl ester and residue initiator,, obtain copolymer emulsion 40 ~ 95 ℃ of following isothermal reactions 1 ~ 6 hour; Be cooled to 25 ~ 65 ℃, with ammoniacal liquor adjust pH=7 ~ 10, filter, promptly getting does not have soap vinyl-acetic ester-copolymer-maleic anhydride emulsion.
4. like the preparation method of the said no soap vinyl-acetic ester of claim 3-copolymer-maleic anhydride emulsion, it is characterized in that: said each raw material carries out proportioning by following weight part:
10 ~ 40 parts of vinyl-acetic esters, 1 ~ 10 part of maleic anhydride, 1 ~ 30 part of Bing Xisuandingzhi, 1 ~ 10 part of methacrylic beta-hydroxy ethyl ester, 1 ~ 3 part of initiator, 1 ~ 15 part of neutralizing agent, 70 ~ 100 parts of deionized waters.
5. like the preparation method of claim 3 or 4 said no soap vinyl-acetic ester-copolymer-maleic anhydride emulsions, it is characterized in that: said neutralizing agent sodium hydrogencarbonate is mixed with the aqueous solution of mass concentration 2 ~ 10%.
6. like the preparation method of claim 3 or 4 said no soap vinyl-acetic ester-copolymer-maleic anhydride emulsions, it is characterized in that: said initiator is mixed with the aqueous solution of mass concentration 1 ~ 5%.
7. like the preparation method of claim 3 or 4 said no soap vinyl-acetic ester-copolymer-maleic anhydride emulsions, it is characterized in that: the mass concentration of said ammoniacal liquor is 5 ~ 25%.
8. there is not soap vinyl-acetic ester-copolymer-maleic anhydride emulsion according to claim 1 as the application of film forming matter in preparation interior wall humidity controlling coating.
Like the said no soap vinyl-acetic ester of claim 8-copolymer-maleic anhydride emulsion as the application of film forming matter in preparation interior wall humidity controlling coating, it is characterized in that: be that raw material and prepared by following weight part forms:
Raw material: 20 ~ 60 parts of no soap vinyl-acetic esters-copolymer-maleic anhydride emulsion; 1 ~ 30 part of polygorskite, 1 ~ 30 part of wilkinite, 2 ~ 50 parts in zeyssatite, 1 ~ 30 part of polynite, 5 ~ 35 parts of talcum powder, 1 ~ 30 part of white titanium pigment; 0.03 ~ 0.3 part of linking agent, 60 ~ 260 parts of deionized waters;
Preparation technology: earlier polygorskite, wilkinite, zeyssatite, polynite, talcum powder, white titanium pigment are mixed the back and mix well with deionized water; To wherein adding no soap vinyl-acetic ester-copolymer-maleic anhydride emulsion and linking agent; Be ground to fineness after mixing below 80 μ m; Filter, check, pack, promptly getting does not have soap vinyl acetate copolymer emulsion-based humidity controlling coating.
Like the said no soap vinyl-acetic ester of claim 9-copolymer-maleic anhydride emulsion as the application of film forming matter in preparation interior wall humidity controlling coating, it is characterized in that: said linking agent is a diacetone-acryloamide(DAA).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231825A (en) * | 2014-09-19 | 2014-12-24 | 苏州云舒新材料科技有限公司 | Building interior wall latex and preparation method thereof |
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| CN1618826A (en) * | 2003-11-19 | 2005-05-25 | 北京化工大学 | Method of copolymerization of maleic anhydride and vinyl acetate |
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| JPS6185420A (en) * | 1984-10-04 | 1986-05-01 | Idemitsu Petrochem Co Ltd | Three-component copolymer |
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| XING CHANGMIN ET AL.: "Stabilizer-Free Dispersion Copolymerization of Maleic Anhydride and Vinyl Acetate. I. Effects of Principal Factors on Microspheres", 《JOURNAL OF POLYMER SCIENECE PART A: POLYMER CHEMISTRY》, vol. 43, no. 17, 11 July 2005 (2005-07-11), pages 3760 - 3770 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231825A (en) * | 2014-09-19 | 2014-12-24 | 苏州云舒新材料科技有限公司 | Building interior wall latex and preparation method thereof |
| CN104231825B (en) * | 2014-09-19 | 2016-05-25 | 苏州云舒新材料科技有限公司 | A kind of inner wall of building latex and preparation method thereof |
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