CN102702419A - Preparation method of montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion - Google Patents
Preparation method of montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion Download PDFInfo
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Abstract
The invention discloses a preparation method of a montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion. The preparation method of the montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion comprises the following steps: dispersing sodium-based montmorillonite, an emulsifying agent and a buffering agent into water; stirring to obtain a sodium-based montmorillonite suspension; adding a core monomer mixture and an initiating agent solution into the sodium-based montmorillonite suspension, and preserving heat for 0.5 hours to obtain a seed emulsion; dripping the remaining core monomer mixture into the seed emulsion, and preserving heat for 1 hour to obtain a deep blue core emulsion; and adding the initiating agent solution and a shell monomer mixture into core emulsion, preserving heat for 2 hours and regulating pH value to obtain the opalescent bluish montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion. The prepared montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion is good in water resistance and heat resistance of a coating, adjustable in gloss of a latex film, free of organic solvent, environment-friendly, relatively high in solid content (32 to 45%), relatively small in particle size, bluish, high in stability (storage stability is more than six months) and good in a film-forming property at room temperature.
Description
Technical field
The present invention relates to acrylate hybrid core-shell emulsion polymerization technical field, be specifically related to a kind of preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion.
Background technology
The polyacrylate(s) emulsion film has characteristics such as strength of coating height, cohesiveness are good, good weatherability; And through rational second-order transition temperature design; Can design the film forming emulsion of air dry under normal temperature condition, thereby be widely used in industrial circles such as building inside and outside wall coating, wood lacquer, leather adhesive.But simultaneously, the polyacrylate(s) emulsion also has some shortcomings, and most of polyacrylic ester resinoids belong to thermoplastic resin on the one hand; On its linear molecule, lack cross-linking set; Be difficult to form three-dimensional netted crosslinked filming, thereby at high temperature be prone to return sticking, lack flexibility again during low temperature; The polar group of esters of acrylic acid influences the water tolerance of acrylic polymer on the other hand.
To the shortcoming of above-mentioned polyacrylate emulsion, people have developed organosilicon, organic fluorine modified acrylic ester resin on the one hand, through copolymerization or physical blending organosilicon, organic fluorine are introduced in the polymkeric substance and are improved the water tolerance and the resistance toheat of filming.
Patent CN 101781390A has described a kind of preparation method of used for building exterior wall nucleocapsid high-silicon silicone acrylic emulsion; The preparation earlier of this method contains the organosilicon oligopolymer emulsion of unsaturated double-bond; Then with acrylic ester monomer copolymerization organosilicon crylic acid latex, this emulsion film has good water tolerance and contamination resistance.
Patent CN102199241A has introduced a kind of aqueous fluorine-containing preparing acrylate emulsion method, and research shows that the propenoate latex film water-intake rate after a small amount of vinylformic acid ten trifluoro monooctyl ester modifications significantly reduces.
Patent CN 1594381A utilizes the monomer swell ptfe micropowder, and the water tolerance for preparing the latex film that polytetrafluoroethylmodified modified acrylic ester emulsion processes is better, has reduced production cost.
On the other hand, the easy high temperature that solves linear vinyl resin through crosslinking technological returns sticking shortcoming.
Patent CN101092470A has described the preparation method of a kind of highly filled crosslinked polystyrene-propenoate (little) letex polymerization; The outstanding advantage of this method is in polymerization process, to introduce the diacetone-acryloamide(DAA) functional monomer; After adding contains the monomer of diazanyl in the emulsion of preparing; The latex film thermotolerance of preparation improves, and the easy high temperature that has overcome acrylic polymer to a certain extent returns sticking shortcoming.
The organic and inorganic composite emulsion is a kind of advanced composite material that occurs in recent years; It utilizes physics, chemical process that inorganic materials and organic polymer are combined with each other under certain condition; The good characteristics that had both kept the traditional polymer emulsion; Have the advantage of inorganic materials again concurrently, become one of research focus of present emulsion polymerization field.Wherein polynite is widely used in preparation organic-inorganic hybrid nanometer matrix material with its abundant raw material, cheap and special laminate structure.
Mostly the polynite of using in the letex polymerization at present is the modification of process quaternary ammonium salt, improves monomeric intercalation effect with this.Exist a shortcoming to be because hydrophobicity is strong through quaternary ammonium salt-modified polynite, difficult being dispersed in the water.
Patent CN1143868C has reported that a kind of in-situ emulsion polymerization prepares the method for polyacrylic ester/clay nanocomposites; This method utilizes the swelling property of polynite in water to prepare dispersiveness hybridisation emulsion preferably, the process of having avoided loaded down with trivial details sodium-based montmorillonite to organise.
Combine the report of organic inorganic hybridization technology preparation montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion also fewer at present.
Summary of the invention
, high temperature relatively poor to existing polyacrylic ester latex film water tolerance returns sticking and the relatively poor defective of resistance toheat; Primary and foremost purpose of the present invention is to provide a kind of preparation method with montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of network interpenetrating structure, and the cost of this method is lower.
Another object of the present invention is to provide the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion that obtains by method for preparing with network interpenetrating structure; This emulsion can room temperature film-forming; The glossiness of latex film can be regulated, and water tolerance, the thermotolerance of latex film significantly improve.
A purpose more of the present invention is to provide above-mentioned purposes with montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of network interpenetrating structure.
The object of the invention is realized through following technical proposals:
A kind of preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion may further comprise the steps:
(1) preparation of sodium-based montmorillonite suspension-s
Get the sodium-based montmorillonite of 0.43-1.35%, the emulsifying agent of 0.72-0.90% and the buffer reagent of 0.24-0.30% and be dispersed in the water of 48-60%, stir 24-72h, obtain sodium-based montmorillonite suspension-s:
(2) preparation of seed emulsion
Add the nuclear monomer mixture of 1.5-2.2% in the sodium-based montmorillonite suspension-s, heat temperature raising adds the initiator solution of 2.4-3.0% again to 70-85 ℃, and the system of treating occurs when light blue, and insulation 0.5h obtains seed emulsion;
(3) preparation of nuclear emulsion
Drip the nuclear monomer mixture of 13.6-20.0% in the seed emulsion, drip off in the 1.5-2h, 70-85 ℃ of insulation 1h obtains navy blue nuclear emulsion;
(4) preparation of core-shell emulsion
Toward examining the initiator solution that adds 2.4-3.0% in the emulsion; Drip the shell monomer mixture of 15-22%, drip off in the 2-3h; The initiator solution that adds 1.2-1.5% again, insulation 2h is cooled to 50 ℃ then, regulates the pH value to 6-8, filters, and obtains the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light;
The per-cent of step (1)-(4) described per-cent imvite modified acrylate hybrid core-shell emulsion raw material total mass for each composition accounts for;
The loading capacity of the said sodium-based montmorillonite of step (1) is 90-120mmol/100g;
The described emulsifying agent of step (1) by anionic emulsifier and nonionic emulsifying agent by mass ratio (3-0.33): 1 forms;
Described anionic emulsifier is dodecyl phenenyl sulfate or sodium lauryl sulphate;
Described nonionic emulsifying agent is a TX10, preferred polyoxyethylene nonylphenol or polyoxyethylene octylphenol ether;
The described buffer reagent of step (1) is more than one in sodium hydrogencarbonate, Sodium phosphate, dibasic or the SODIUM PHOSPHATE, MONOBASIC;
Contain the linking agent that massfraction is 0.1-3.0% in the described nuclear monomer mixture in step (2) and (3);
Also comprise soft monomer and hard monomer in the described nuclear monomer mixture in step (2) and (3), the mass ratio of soft monomer and hard monomer is (3: 7)-(1: 9), preferred 3: 7;
Contain the linking agent that massfraction is 1-3% in the described shell monomer mixture of step (4);
Also comprise soft monomer and hard monomer in the described shell monomer mixture of step (4), the mass ratio of soft monomer and hard monomer is (9: 1)-(7: 3), preferred 7: 3;
Described soft monomer is a kind of in ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer or the ethyl acrylate;
Described hard monomer is a kind of in TEB 3K, vinylbenzene, Jia Jibingxisuanyizhi or the 2-hydroxyethyl methacrylate;
The massfraction of initiator is 4% in step (2) and (4) described initiator solution;
Described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or the ammonium persulphate;
Described linking agent is a kind of in TGM 1, dimethacrylate triglycol ester or the diethyleneglycol dimethacrylate(DEGDMA);
The described filtration of step (4) was 200 purpose filter clothes.
The montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion that is obtained by method for preparing can be used for interior external rendering, also can be used as woodenware and the plastics coating base-material with coating.
The present invention has following advantage and effect with respect to prior art:
(1) preparation method of the present invention is simple, has avoided the process that organises of polynite, and the dispersion of sodium-based montmorillonite in emulsion is better.
(2) core-shell emulsion of the present invention's preparation has the strong and stronger characteristics of shell hydrophobicity of nuclear wetting ability, and is good by the water-resistance property of coating and the resistance toheat of this emulsion preparation.
(3) the preparation method of the present invention glossiness that can regulate latex film through the content of regulating inorganic clay (being polynite).
(4) emulsion of the present invention preparation does not contain organic solvent, and is environmentally friendly, and solid content higher (32-45%), emulsion particle diameter are less, emulsion blueing light, good stability (package stability is greater than more than half a year), room temperature film-forming performance are good.
Description of drawings
Fig. 1 is the infrared spectrum of sodium-based montmorillonite and the embodiment 2 prepared core-shell emulsions that obtain.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
Embodiment 1
A kind of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is prepared by following method:
(1) obtains sodium-based montmorillonite suspension-s with stirring 24h in 0.3 gram sodium-based montmorillonite (loading capacity 90mmol/100g), 0.45 gram SDS, 0.15 gram OP-10,0.2 gram sodium hydrogencarbonate adding, the 40 gram water.
(2) in the four-hole reaction flask of reflux exchanger, mechanical stirrer, nitrogen conduit, constant pressure funnel is housed; Add sodium-based montmorillonite suspension-s, the nuclear monomer mixture (0.7g TEB 3K+0.3g Bing Xisuandingzhi+0.01g TGM 1) of step (1), stir, when being warming up to 70 ℃; Add 2 gram potassium persulfate solutions (massfraction 4%); The system of treating occurs when light blue, insulation half hour, obtains seed emulsion.
(3) preparation of nuclear emulsion: in the seed emulsion of step (2), drip nuclear monomer mixture (6.3g TEB 3K+2.7g Bing Xisuandingzhi+0.09g TGM 1) continuously; 1.5h in drip off; 70 ℃ of insulation 1h obtain navy blue nuclear emulsion;
(4) preparation of core-shell emulsion: in the nuclear emulsion of step (3), add 2 gram potassium persulfate solutions (massfraction 4%), drip shell monomer mixture (3g TEB 3K+7g Bing Xisuandingzhi+0.1g TGM 1) continuously, dripping of control shell monomer is fast; Drip off in the 2h; Add 1 gram potassium persulfate solution (massfraction 4%), insulation 2h, stopped reaction; When being cooled to 50 ℃; Regulate the pH value to 7-8, cross 200 purpose filter clothes, obtain the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light.
Embodiment 2
A kind of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is prepared by following method:
(1) obtains sodium-based montmorillonite suspension-s with stirring 48h in 0.6 gram sodium-based montmorillonite (loading capacity 90mmol/100g), 0.4 gram SDS, 0.2 gram OP-10,0.2 gram sodium hydrogencarbonate adding, the 40 gram water.
(2) in the four-hole reaction flask of reflux exchanger, mechanical stirrer, nitrogen conduit, constant pressure funnel is housed, add the sodium-based montmorillonite suspension-s of step (1), nuclear monomer mixture (0.7g TEB 3K+0.3g Bing Xisuandingzhi+0.01g TGM 1); Stir; When being warming up to 75 ℃, add 2 gram Sodium Persulfate solution (massfraction 4%), the system of treating occurs when light blue; Be incubated half hour, obtain seed emulsion.
(3) preparation of nuclear emulsion: in the seed emulsion of step (2), drip nuclear monomer mixture (6.3g TEB 3K+2.7g Bing Xisuandingzhi+0.09g TGM 1) continuously; 1.5h in drip off; 75 ℃ of insulation 1h obtain navy blue nuclear emulsion;
(4) preparation of core-shell emulsion: in the nuclear emulsion of step (3), add 2 gram Sodium Persulfate solution (massfraction 4%), drip shell monomer mixture (3g TEB 3K+7g Bing Xisuandingzhi+0.1g TGM 1) continuously, dripping of control shell monomer is fast; Drip off in the 2h; Add 1 gram Sodium Persulfate solution (massfraction 4%), insulation 2h, stopped reaction; When being cooled to 50 ℃; Regulate the pH value to 7-8, cross 200 purpose filter clothes, obtain the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light.
Embodiment 3
A kind of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is prepared by following method:
(1) obtains sodium-based montmorillonite suspension-s with stirring 72h in 0.9 gram sodium-based montmorillonite (loading capacity 90mmol/100g), 0.15 gram SDS, 0.45 gram OP-10,0.2 gram sodium hydrogencarbonate adding, the 40 gram water.
(2) in the four-hole reaction flask of reflux exchanger, mechanical stirrer, nitrogen conduit, constant pressure funnel is housed, add the sodium-based montmorillonite suspension-s of step (1), nuclear monomer mixture (0.7g TEB 3K+0.3g Bing Xisuandingzhi+0.01g TGM 1); Stir; When being warming up to 80 ℃, add 2 gram ammonium persulfate solutions (massfraction 4%), the system of treating occurs when light blue; Be incubated half hour, obtain seed emulsion.
(3) preparation of nuclear emulsion: in the seed emulsion of step (2), drip nuclear monomer mixture (6.3 gram TEB 3Ks+2.7 gram Bing Xisuandingzhi+0.09g TGM 1s) continuously; 1.5h in drip off; 80 ℃ of insulation 1h obtain navy blue nuclear emulsion;
(4) preparation of core-shell emulsion: in the nuclear emulsion of step (3), add 2 gram ammonium persulfate solutions (massfraction 4%), drip shell monomer mixture (3g TEB 3K+7g Bing Xisuandingzhi+0.1g TGM 1) continuously, dripping of control shell monomer is fast; Drip off in the 2h; Add 1 gram ammonium persulfate solution (massfraction 4%), insulation 2h, stopped reaction; When being cooled to 50 ℃; Regulate the pH value to 7-8, cross 200 purpose filter clothes, obtain the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light.
Embodiment 4
A kind of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is prepared by following method:
(1) obtains sodium-based montmorillonite suspension-s with stirring 24h in 0.3 gram sodium-based montmorillonite (loading capacity 90mmol/100g), 0.45 gram SDS, 0.15 gram OP-10,0.2 gram sodium hydrogencarbonate adding, the 40 gram water.
(2) in the four-hole reaction flask of reflux exchanger, mechanical stirrer, nitrogen conduit, constant pressure funnel is housed, add the sodium-based montmorillonite suspension-s of step (1), nuclear monomer mixture (0.84g TEB 3K+0.36g Bing Xisuandingzhi+0.024g TGM 1); Stir; When being warming up to 75 ℃, add 2 gram potassium persulfate solutions (massfraction 4%), the system of treating occurs when light blue; Be incubated half hour, obtain seed emulsion.
(3) preparation of nuclear emulsion: in the seed emulsion of step (2), drip nuclear monomer mixture (7.56g TEB 3K+3.24g Bing Xisuandingzhi+0.216g TGM 1) continuously; Drip off in the 2h; 75 ℃ of insulation 1h obtain navy blue nuclear emulsion;
(4) preparation of core-shell emulsion: in the nuclear emulsion of step (3), add 2 gram potassium persulfate solutions (massfraction 4%), drip shell monomer mixture (3.6g TEB 3K+8.4g Bing Xisuandingzhi+0.24g TGM 1) continuously, dripping of control shell monomer is fast; 2.5h in drip off; Add 1 gram potassium persulfate solution (massfraction 4%), insulation 2h, stopped reaction; When being cooled to 50 ℃; Regulate the pH value to 7-8, cross 200 purpose filter clothes, obtain the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light.
Embodiment 5
A kind of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is prepared by following method:
(1) obtains sodium-based montmorillonite suspension-s with stirring 48h in 0.9 gram sodium-based montmorillonite (loading capacity 90mmol/100g), 0.15 gram SDS, 0.45 gram OP-10,0.2 gram sodium hydrogencarbonate adding, the 40 gram water.
(2) in the four-hole reaction flask of reflux exchanger, mechanical stirrer, nitrogen conduit, constant pressure funnel is housed, add the sodium-based montmorillonite suspension-s of step (1), nuclear monomer mixture (0.84g TEB 3K+0.36g Bing Xisuandingzhi+0.036g TGM 1); Stir; When being warming up to 75 ℃, add 2 gram Sodium Persulfate solution (massfraction 4%), the system of treating occurs when light blue; Be incubated half hour, obtain seed emulsion.
(3) preparation of nuclear emulsion: in the seed emulsion of step (2), drip nuclear monomer mixture (7.56g TEB 3K+3.24g Bing Xisuandingzhi+0.324g TGM 1) continuously; Drip off in the 2h; 75 ℃ of insulation 1h obtain navy blue nuclear emulsion;
(4) preparation of core-shell emulsion: in the nuclear emulsion of step (3), add 2 gram Sodium Persulfate solution (massfraction 4%), drip shell monomer mixture (3.6g TEB 3K+8.4g Bing Xisuandingzhi+0.36g TGM 1) continuously, dripping of control shell monomer is fast; 2.5h in drip off; Add 1 gram Sodium Persulfate solution (massfraction 4%), insulation 2h, stopped reaction; When being cooled to 50 ℃; Regulate the pH value to 7-8, cross 200 purpose filter clothes, obtain the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light.
Embodiment 6
A kind of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is prepared by following method:
(1) obtains sodium-based montmorillonite suspension-s with stirring 48h in 0.6 gram sodium-based montmorillonite (loading capacity 90mmol/100g), 0.4 gram SDS, 0.2 gram OP-10,0.2 gram sodium hydrogencarbonate adding, the 40 gram water.
(2) in the four-hole reaction flask of reflux exchanger, mechanical stirrer, nitrogen conduit, constant pressure funnel is housed, add the sodium-based montmorillonite suspension-s of step (1), nuclear monomer mixture (1.26g TEB 3K+0.54g Bing Xisuandingzhi+0.036g TGM 1); Stir; When being warming up to 75 ℃, add 2 gram ammonium persulfate solutions (massfraction 4%), the system of treating occurs when light blue; Be incubated half hour, obtain seed emulsion.
(3) preparation of nuclear emulsion: in the seed emulsion of step (2), drip nuclear monomer mixture (11.34g TEB 3K+4.86g Bing Xisuandingzhi+0.324g TGM 1) continuously; Drip off in the 2h; 75 ℃ of insulation 1h obtain navy blue nuclear emulsion;
(4) preparation of core-shell emulsion: in the nuclear emulsion of step (3), add 2 gram ammonium persulfate solutions (massfraction 4%), drip shell monomer mixture (5.4g TEB 3K+12.6g Bing Xisuandingzhi+0.36g methacrylic acid glycol ester) continuously, dripping of control shell monomer is fast; Drip off in the 3h; Add 1 gram ammonium persulfate solution (massfraction 4%), insulation 2h, stopped reaction; When being cooled to 50 ℃; Regulate the pH value to 7-8, cross 200 purpose filter clothes, obtain the montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion of oyster white blueing light.
The resulting performance of products test of embodiment 1-6
Testing method:
1) IR Characterization: get the 2-5g emulsion, with the calcium chloride solution breakdown of emulsion of 5-10% (massfraction), with the distilled water wash polymkeric substance for several times, filtering drying adopts the method for pressing potassium bromide troche to obtain infrared spectrum.Figure-1 is the infrared spectrum of embodiment-2 sample and sodium-based montmorillonite.
2) package stability: whether emulsion, observing at set intervals has deposition to separate out if at room temperature being deposited, and it is long more to separate out the used time of deposition, and package stability is good more.
3) mensuration of glossiness: the glossiness of measuring latex film with 60 ° of angles of GZ-II vancometer.
4) mensuration of water-intake rate: taking by weighing length and width is that 2cm * 2cm, quality are m
1Latex film, immerse in the deionized water, take out behind the 24h and blot surface-moisture with filter paper, weighing is designated as m
2, water-intake rate can be used computes:
Water-intake rate (%)=[(m
2-m
1)/m
1] * 100%
5) stable on heating mensuration: thermogravimetric analysis (NETZSCH TG 209F3), nitrogen atmosphere, 10 ℃/min of temperature rise rate is with the thermotolerance of 5% weightless temperature sign latex film.
The result is shown in Fig. 1 and table 1.
Among Fig. 1,3400-3600cm
-1Absorption peak be the hydroxyl stretching vibration peak of sodium-based montmorillonite, 1050cm
-1The absorption peak at place is the Si-O-Si stretching vibration peak of polynite, 1100cm
-1The absorption peak at place is the C-O-C stretching vibration peak, 2950cm
-1And 2870cm
-1The absorption peak at place is-CH
2-stretching vibration peak, 1735cm
-1Stretching vibration peak for the two keys of carbon oxygen in the ester group; The core-shell emulsion of embodiment 2 is at 1600cm
-1Near do not have tangible absorption peak, show that monomer polymerization is complete.The result of Fig. 1 shows, contains two kinds of staples of polyacrylic ester and polynite in the latex film matrix material.
Table 1
Can find out by table 1; The core-shell emulsion package stability of the inventive method preparation is relatively good; Latex film water tolerance and thermotolerance that polyacrylate emulsion after imvite modified prepares are all improved significantly; And along with polynite content improves, the glossiness of latex film has a trend that reduces and rise, and just means also that the amount that can select a suitable polynite prepares that a kind of glossiness is low, water tolerance and the good polyacrylate emulsion of resistance toheat.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is characterized in that may further comprise the steps:
(1) preparation of sodium-based montmorillonite suspension-s
Get the sodium-based montmorillonite of 0.43-1.35%, the emulsifying agent of 0.72-0.90% and the buffer reagent of 0.24-0.30% and be dispersed in the water of 48-60%, stir 24-72h, obtain sodium-based montmorillonite suspension-s:
(2) preparation of seed emulsion
Add the nuclear monomer mixture of 1.5-2.2% in the sodium-based montmorillonite suspension-s, heat temperature raising adds the initiator solution of 2.4-3.0% again to 70-85 ℃, and the system of treating occurs when light blue, and insulation 0.5h obtains seed emulsion;
(3) preparation of nuclear emulsion
Drip the nuclear monomer mixture of 13.6-20.0% in the seed emulsion, drip off in the 1.5-2h, 70-85 ℃ of insulation 1h obtains examining emulsion;
(4) preparation of core-shell emulsion
Toward examining the initiator solution that adds 2.4-3.0% in the emulsion; Drip the shell monomer mixture of 15-22%, drip off in the 2-3h; The initiator solution that adds 1.2-1.5% again, insulation 2h is cooled to 50 ℃ then, regulates the pH value to 6-8, filters, and obtains montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion;
Step (1)-(4) described per-cent accounts for the per-cent of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion raw material total mass for each composition;
Contain the linking agent that massfraction is 0.1-3.0% in the described nuclear monomer mixture in step (2) and (3);
Also comprise soft monomer and hard monomer in the described nuclear monomer mixture in step (2) and (3), the mass ratio of soft monomer and hard monomer is (3: 7)-(1: 9);
Contain the linking agent that massfraction is 1-3% in the described shell monomer mixture of step (4);
Also comprise soft monomer and hard monomer in the described shell monomer mixture of step (4), the mass ratio of soft monomer and hard monomer is (9: 1)-(7: 3);
Described linking agent is a kind of in TGM 1, dimethacrylate triglycol ester or the diethyleneglycol dimethacrylate(DEGDMA);
Described soft monomer is a kind of in ethyl propenoate, Bing Xisuandingzhi, Isooctyl acrylate monomer or the ethyl acrylate;
Described hard monomer is a kind of in TEB 3K, vinylbenzene, Jia Jibingxisuanyizhi or the 2-hydroxyethyl methacrylate.
2. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 1 is characterized in that:
The described emulsifying agent of step (1) by anionic emulsifier and nonionic emulsifying agent by mass ratio (3-0.33): 1 forms;
Described anionic emulsifier is dodecyl phenenyl sulfate or sodium lauryl sulphate;
Described nonionic emulsifying agent is a TX10.
3. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 2 is characterized in that: described nonionic emulsifying agent is polyoxyethylene nonylphenol or polyoxyethylene octylphenol ether.
4. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 1 is characterized in that: the described buffer reagent of step (1) is more than one in sodium hydrogencarbonate, Sodium phosphate, dibasic or the SODIUM PHOSPHATE, MONOBASIC.
5. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 1 is characterized in that: in the described nuclear monomer mixture in step (2) and (3), the mass ratio of soft monomer and hard monomer is 3: 7.
6. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 1 is characterized in that: in the described shell monomer mixture of step (4), the mass ratio of soft monomer and hard monomer is 7: 3.
7. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 1 is characterized in that:
The massfraction of initiator is 4% in step (2) and (4) described initiator solution;
Described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or the ammonium persulphate.
8. the preparation method of montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion according to claim 1 is characterized in that: the loading capacity of the said sodium-based montmorillonite of step (1) is 90-120mmol/100g.
9. a montmorillonite, modified crosslinking agent acrylate hybrid core-shell emulsion is characterized in that: be to be prepared by each described method of claim 1-8.
The described montmorillonite, modified crosslinking agent acrylate hybrid of claim 9 core-shell emulsion at interior external rendering, woodenware and plastics coating with the application in the coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951781A (en) * | 2014-05-15 | 2014-07-30 | 中国建筑材料科学研究总院 | Preparation method of efficient molecular sieve desiccant with core-shell nanostructure |
| CN103980412A (en) * | 2014-05-15 | 2014-08-13 | 中国建筑材料科学研究总院 | Method for preparing high-efficiency molecular sieve desiccant with nanometer core-shell structure |
| CN104387521A (en) * | 2014-11-27 | 2015-03-04 | 武汉工程大学 | Preparation method for compounding and modifying acrylate core-shell emulsion through montmorillonite and methacrylic acid |
| CN104530890A (en) * | 2014-11-27 | 2015-04-22 | 武汉工程大学 | Water-based acrylate fireproof coating and preparation method thereof |
| CN105017912A (en) * | 2015-07-29 | 2015-11-04 | 苏州荣昌复合材料有限公司 | Acrylic emulsion coat |
| CN105111606A (en) * | 2015-09-18 | 2015-12-02 | 肇庆学院 | Polymer/clay nanometer composite material of core-shell structure and preparing method thereof |
| CN105713475A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Cement-based concrete waterproof protective coating and preparation method thereof |
| CN105713474A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Organic montmorillonoid modified elastic paint for protecting concrete surface and preparation method thereof |
| WO2019108175A1 (en) * | 2017-11-29 | 2019-06-06 | Celanese International Corporation | Biocide- and ammonia-free polymer dispersions |
| CN114018855A (en) * | 2021-10-22 | 2022-02-08 | 哈尔滨工程大学 | Preparation method of infrared test sample of low-glass-transition-temperature water-based polymer emulsion |
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| CN102206395A (en) * | 2011-03-31 | 2011-10-05 | 广东工业大学 | Preparation method and application of nano-montmorillonite/polyacrylate composite material |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206395A (en) * | 2011-03-31 | 2011-10-05 | 广东工业大学 | Preparation method and application of nano-montmorillonite/polyacrylate composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103951781A (en) * | 2014-05-15 | 2014-07-30 | 中国建筑材料科学研究总院 | Preparation method of efficient molecular sieve desiccant with core-shell nanostructure |
| CN103980412A (en) * | 2014-05-15 | 2014-08-13 | 中国建筑材料科学研究总院 | Method for preparing high-efficiency molecular sieve desiccant with nanometer core-shell structure |
| CN103951781B (en) * | 2014-05-15 | 2016-05-25 | 中国建筑材料科学研究总院 | A kind of preparation method of nano core-shell structure efficient molecular sieve drier |
| CN104530890A (en) * | 2014-11-27 | 2015-04-22 | 武汉工程大学 | Water-based acrylate fireproof coating and preparation method thereof |
| CN104387521A (en) * | 2014-11-27 | 2015-03-04 | 武汉工程大学 | Preparation method for compounding and modifying acrylate core-shell emulsion through montmorillonite and methacrylic acid |
| CN105017912A (en) * | 2015-07-29 | 2015-11-04 | 苏州荣昌复合材料有限公司 | Acrylic emulsion coat |
| CN105111606A (en) * | 2015-09-18 | 2015-12-02 | 肇庆学院 | Polymer/clay nanometer composite material of core-shell structure and preparing method thereof |
| CN105713475A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Cement-based concrete waterproof protective coating and preparation method thereof |
| CN105713474A (en) * | 2015-12-11 | 2016-06-29 | 江苏苏博特新材料股份有限公司 | Organic montmorillonoid modified elastic paint for protecting concrete surface and preparation method thereof |
| CN105713475B (en) * | 2015-12-11 | 2018-01-23 | 江苏苏博特新材料股份有限公司 | A kind of cement-base concrete waterproof protective coating and preparation method thereof |
| CN105713474B (en) * | 2015-12-11 | 2018-05-11 | 江苏苏博特新材料股份有限公司 | A kind of organic imvite modified elastic coating for being used as concrete surface protection and preparation method thereof |
| WO2019108175A1 (en) * | 2017-11-29 | 2019-06-06 | Celanese International Corporation | Biocide- and ammonia-free polymer dispersions |
| US11608441B2 (en) | 2017-11-29 | 2023-03-21 | Celanese International Corporation | Biocide- and ammonia-free polymer dispersions |
| CN114018855A (en) * | 2021-10-22 | 2022-02-08 | 哈尔滨工程大学 | Preparation method of infrared test sample of low-glass-transition-temperature water-based polymer emulsion |
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