CN105131309A - Polymer/synthetic Laponite composite colloid dispersing agent and preparation method thereof - Google Patents
Polymer/synthetic Laponite composite colloid dispersing agent and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polymer/synthetic Laponite nano composite colloid particle dispersing agent and a preparation method thereof and solves the problem of complicated conventional preparation method process of polymer/Laponite nano composite colloid particles and the problem about complicated modification of Laponite. According to the method, monomers and a Laponite aqueous dispersing agent are mixed firstly, and a pre-emulsion is obtained; then an initiator solution is added to the obtained pre-emulsion for a reaction, and the polymer/synthetic Laponite nano composite colloid particle dispersing agent is obtained, wherein the initiator is a water-soluble anionic initiator. With the method, a water-soluble azo anionic initiator is applied to Pickering emulsion polymerization, and long-chain side groups have a stabilizing function on colloid particles and enhance the acting force of a Laponite lamella layer and the colloid particles, so that an emulsion still has excellent stability and the smaller dispersing degree under the condition that any emulsifier or macromolecular co-monomer is not added.
Description
Technical field
The invention belongs to high molecular nanometer composite emulsion example dispersion liquid field, nano combined latex particle dispersion liquid of lithium silicate magnesium being specifically related to a kind of polymkeric substance/synthetic and preparation method thereof.
Background technology
Letex polymerization is widely used in the fields such as coating, makeup, food, medicine.Traditional letex polymerization needs to add tensio-active agent with stabilized emulsion system, however tensio-active agent add some performance that membership affects emulsion, the such as water resistance etc. of film forming properties, film.Tensio-active agent has certain toxicity in addition, and the application therefore in biological medicine food etc. is restricted.The letex polymerization stable with solids and Pickering letex polymerization containing tensio-active agent, do not avoid the shortcoming of conventional emulsion polymerizations, are with a wide range of applications.
Because solid nanoparticles is in the self-assembly of interface in Pickering letex polymerization, many Nano-grade latex composite particless with novel texture and property can be synthesized.In recent years along with the development of nano-solid particle technology of preparing and going deep into of Interface Study, and the demand that nano composite material is growing, Pickering emulsion polymerization technology is more and more active.In numerous solid nanoparticles, flaky silicic acid salt material is because of its cheapness, stable performance, add the thermal characteristics and mechanical property etc. that obviously can improve material and obtain the favor of investigator on a small quantity, and the lithium silicate magnesium (Laponite) of synthetic has good rheological property and film forming properties and receives much concern in various flaky silicic acid salt material.Although have some investigators to use the nano combined emulsion particle of the method for Pickering letex polymerization synthetic polymer/Laponite (Negrete-HerreraetalPolymer/Laponitecompositecolloidsthro ughemulsionpolymerization:Influenceoftheclaymodification levelonparticlemorphology.Macromolecules2006 at present, 39 (26), 9177-9184), but the modifying process that generally can relate to Laponite complexity, sometimes the absorption adding macromolecular stabilizer agent or the common monomer promotion Laponite of macromole and latex particle is needed, and tensio-active agent can be added with stable emulsion, sometimes two-step approach can also be related to or seed emulsion polymerization carrys out the nano combined latex particle of synthetic polymer/Laponite, the condition of this complexity limits its application in industrial production.
Summary of the invention
The object of the invention is to solve existing polymkeric substance/Laponite nano combined latex particle preparation method's complex process or Laponite being carried out to the problem of complicated modification, and nano combined latex particle dispersion liquid of a kind of lithium silicate magnesium of polymkeric substance/synthetic and preparation method thereof is provided.
First the present invention provides the preparation method of the nano combined latex particle dispersion liquid of a kind of lithium silicate magnesium of polymkeric substance/synthetic, and the method comprises:
Step one: obtain Laponite aqueous dispersions by soluble in water for Laponite powder, by monomer and the mixing of Laponite aqueous dispersions, obtains pre-emulsion;
Step 2: be dissolved in by initiator in the NaOH aqueous solution or deionized water, obtain initiator solution, then adds initiator solution in the pre-emulsion that step one obtains and reacts, obtain the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic; Described initiator is water-soluble azo anionoid initiator.
Preferably, described monomer is selected from one or more in vinylbenzene, n-butyl acrylate, lauryl ester, Hydroxyethyl acrylate, methacrylic acid, acrylic or methacrylic acid methyl esters.
Preferably, described Laponite powder and the mass ratio of monomer are (0.001-0.5): 1.
Preferably, described Laponite powder is LaponiteXLS or LaponiteRD.
Preferably, the massfraction of described Laponite aqueous dispersions is 1%-15%.
Preferably, described water-soluble azo anionoid initiator is ammonium persulphate, Potassium Persulphate or azo dinitrile valeric acid.
Preferably, described temperature of reaction is 65-85 DEG C, and the reaction times is 4-7h.
The nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that the present invention also provides above-mentioned preparation method to obtain.
Beneficial effect of the present invention
First the present invention provides the preparation method of the nano combined latex particle dispersion liquid of a kind of lithium silicate magnesium of polymkeric substance/synthetic, the method first obtains Laponite aqueous dispersions by soluble in water for Laponite powder, by monomer and the mixing of Laponite aqueous dispersions, obtain pre-emulsion; Then initiator is dissolved in the NaOH aqueous solution or deionized water, obtains initiator solution, initiator solution is added in the pre-emulsion obtained and reacts, obtain the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic; Described initiator is water-soluble anionic initiator.Compare with prior art, preparation method of the present invention does not add any emulsifying agent and macromole monomer altogether, water-soluble azo anionoid initiator is used in Pickering letex polymerization by the method, the side base of long-chain plays stabilization to latex particle, and Laponite lamella and latex particle reactive force can be made to strengthen, make do not add any emulsifying agent and macromole altogether in monomer situation emulsion still there is excellent stability and less dispersity, and preparation method is simple, cost is low.
The nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that the present invention also provides above-mentioned preparation method to obtain, this dispersion liquid has satisfactory stability, less dispersity, just has the good transparency, excellent mechanical property and thermal stability after this latex particle dispersion liquid drying and forming-film.
Accompanying drawing explanation
Fig. 1 is high resolution transmission electron microscopy (TEM) figure of the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that embodiment 6 obtains;
Fig. 2 is high resolution transmission electron microscopy (TEM) figure of the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that embodiment 9 obtains;
Fig. 3 is the grain size distribution of the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that embodiment 5-7 obtains.
Embodiment
First the present invention provides the preparation method of the nano combined latex particle dispersion liquid of a kind of lithium silicate magnesium of polymkeric substance/synthetic, and the method comprises:
Step one: obtain Laponite aqueous dispersions by soluble in water for Laponite powder, by monomer and the mixing of Laponite aqueous dispersions, obtains pre-emulsion;
Step 2: be dissolved in by initiator in the NaOH aqueous solution or deionized water, obtain initiator solution, then adds initiator solution in the pre-emulsion that step one obtains and reacts, obtain the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic; Described initiator is water-soluble azo anionoid initiator.
According to the present invention, first Laponite powder is dissolved in deionized water and dissolves, preferably dissolve under the condition of magnetic agitation, described churning time is preferably 1-2h, obtain Laponite aqueous dispersions, the massfraction of described Laponite aqueous dispersions is preferably 1%-15%, then by monomer and the mixing of Laponite aqueous dispersions, monomer is preferably first put into reaction unit by described mixing, then Laponite aqueous dispersions and deionized water is added, carry out mechanical stirring, described mixing speed is preferably 800-1200rpm, churning time is preferably 15-30min, make monomer and Laponite aqueous dispersions fully mixed, after rapid stirring terminates, adjust rotating speed stir, described rotating speed is preferably 300-4000rpm, churning time is preferably 10-20min, obtained pre-emulsion, described Laponite powder is preferably LaponiteXLS or LaponiteRD, described monomer is preferably selected from one or more in vinylbenzene, n-butyl acrylate, lauryl ester, Hydroxyethyl acrylate, methacrylic acid, acrylic or methacrylic acid methyl esters, be more preferably vinylbenzene or vinylbenzene and n-butyl acrylate mixture, in described mixture, the mol ratio of vinylbenzene and n-butyl acrylate is preferably 1:1, described Laponite powder and the mass ratio of monomer are preferably (0.001-0.5): 1, are more preferably (0.005-0.3): 1.
According to the present invention, initiator is dissolved in the NaOH aqueous solution or deionized water, described initiator and the mol ratio of NaOH are preferably 1:(2-2.5), obtain initiator solution, be then slowly added drop-wise in pre-emulsion obtained above by initiator solution and react, described temperature of reaction is preferably 65-85 DEG C, be more preferably 75-80 DEG C, reaction times is preferably 4-7h, is more preferably 5-6h, obtains the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic; Described initiator is water-soluble azo anionoid initiator, be preferably ammonium persulphate (APS), Potassium Persulphate (KPS) or azo dinitrile valeric acid (ACVA), be more preferably azo dinitrile valeric acid, initiator molar mass is preferably the 0.3%-1.0% of monomer molar quality.The present invention is owing to being used in Pickering letex polymerization by water-soluble azo anionoid initiator, the side base of long-chain plays stabilization to latex particle, and Laponite lamella and latex particle reactive force can be made to strengthen, make do not add any emulsifying agent and macromole altogether in monomer situation emulsion still there is excellent stability.
The nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that the present invention also provides above-mentioned preparation method to obtain.
Below in conjunction with specific embodiment, the present invention will be further described in detail, and the raw material related in embodiment is commercially available.
Embodiment 1
2.5gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 7h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 173nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 1 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.059.
Embodiment 2
2.5gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.228g (1mmol) initiator A PS, be dissolved in 5mL deionized water, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 7h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 139nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 2 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.057.
Embodiment 3
2.5gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.270g (1mmol) initiator KPS, be dissolved in 5mL deionized water, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 7h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 144nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 3 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.062.
Embodiment 4
2.5gLaponiteRD powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 7h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 189nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 4 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.095.
Embodiment 5
0.125LaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 5h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 182nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 5 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.008.
Embodiment 6
3.75gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 5h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 183nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 6 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.016.
Fig. 1 is high resolution transmission electron microscopy (TEM) figure of the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that embodiment 6 obtains, as can be seen from Figure 1, latex balloon is spherical, even particle size distribution, and Laponite lamella is adsorbed on the surface of latex balloon.
Embodiment 7
7.5gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 7h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 153nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 7 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.119.
Fig. 3 is the grain size distribution of the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that embodiment 5-7 obtains, as can be seen from Figure 3, particle diameter is unimodal distribution and dispersity is less, but increases to some extent along with the increase particle dispersion degree of nanoparticle content.
Embodiment 8
2.5gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 11.2gSt, 13.8gBA (mol ratio 1:1) adds in four-hole boiling flask, at this moment the temperature of water-bath is made to rise to 60 DEG C, open nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 80 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 4h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 403nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 1 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.279.
Embodiment 9
3.75gLaponiteXLS powder is configured to the aqueous dispersions of massfraction 15%, to be poured in four-hole boiling flask and to add 82.5g deionized water, the total mass of the deionized water in system is made to be 130g, taking 25gSt adds in four-hole boiling flask, at this moment makes the temperature of water-bath rise to 60 DEG C, opens nitrogen protection device, churned mechanically rotating speed is set to 1000rpm, rapid stirring 20min, after rapid stirring completes, reduction rotating speed stablizes 10min to 350rpm, obtains pre-emulsion;
Take 0.280g (1mmol) initiator A CVA, be dissolved in the NaOH aqueous solution of 5mL0.4mmol/L, obtain initiator solution, by water-bath temperature to 75 DEG C, then in above-mentioned four-hole boiling flask, dropwise initiator solution is added, terminate reaction after reaction 5h, carry out the emulsion obtained to filter the nano combined latex particle dispersion liquid of the lithium silicate magnesium namely obtaining polymkeric substance/synthetic.
It is 204nm that the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic embodiment 9 obtained records diameter by Zetasizer, and polydispersity index PDI is 0.010.
Fig. 2 is high resolution transmission electron microscopy (TEM) figure of the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that embodiment 9 obtains, as can be seen from Figure 2, latex balloon is spherical, even particle size distribution, and Laponite lamella is adsorbed on the surface of latex balloon.
Claims (8)
1. a preparation method for the nano combined latex particle dispersion liquid of the lithium silicate magnesium of polymkeric substance/synthetic, it is characterized in that, the method comprises:
Step one: obtain Laponite aqueous dispersions by soluble in water for Laponite powder, by monomer and the mixing of Laponite aqueous dispersions, obtains pre-emulsion;
Step 2: be dissolved in by initiator in the NaOH aqueous solution or deionized water, obtain initiator solution, then adds initiator solution in the pre-emulsion that step one obtains and reacts, obtain the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic; Described initiator is water-soluble azo anionoid initiator.
2. the preparation method of the nano combined latex particle dispersion liquid of lithium silicate magnesium of a kind of polymkeric substance/synthetic according to claim 1, it is characterized in that, described monomer is selected from one or more in vinylbenzene, n-butyl acrylate, lauryl ester, Hydroxyethyl acrylate, methacrylic acid, acrylic or methacrylic acid methyl esters.
3. the preparation method of the nano combined latex particle dispersion liquid of lithium silicate magnesium of a kind of polymkeric substance/synthetic according to claim 1, is characterized in that, described Laponite powder and the mass ratio of monomer are (0.001-0.5): 1.
4. the preparation method of the nano combined latex particle dispersion liquid of lithium silicate magnesium of a kind of polymkeric substance/synthetic according to claim 1, it is characterized in that, described Laponite powder is LaponiteXLS or LaponiteRD.
5. the preparation method of the nano combined latex particle dispersion liquid of lithium silicate magnesium of a kind of polymkeric substance/synthetic according to claim 1, is characterized in that, the massfraction of described Laponite aqueous dispersions is 1%-15%.
6. the preparation method of the nano combined latex particle dispersion liquid of lithium silicate magnesium of a kind of polymkeric substance/synthetic according to claim 1, it is characterized in that, described water-soluble azo anionoid initiator is ammonium persulphate, Potassium Persulphate or azo dinitrile valeric acid.
7. the preparation method of the nano combined latex particle dispersion liquid of lithium silicate magnesium of a kind of polymkeric substance/synthetic according to claim 1, it is characterized in that, described temperature of reaction is 65-85 DEG C, and the reaction times is 4-7h.
8. the nano combined latex particle dispersion liquid of lithium silicate magnesium of polymkeric substance/synthetic that obtains of any one preparation method of claim 1-7.
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| CN106866870A (en) * | 2017-03-02 | 2017-06-20 | 郑州轻工业学院 | A kind of pH response composite microgels based on Laponite RD and preparation method thereof |
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| CN107325224A (en) * | 2017-08-08 | 2017-11-07 | 芜湖通全科技有限公司 | A kind of preparation method of asphalt paint modification emulsion |
| CN107880207A (en) * | 2017-11-21 | 2018-04-06 | 四川大学 | Novel aqueous acroleic acid resin/lithium soap soil composite leather coating agent prepared by a kind of Pickering emulsion polymerization technologies |
| CN107880853A (en) * | 2017-12-08 | 2018-04-06 | 中国科学院长春应用化学研究所 | Nano combined phase transformation latex particle dispersion liquid of polyacrylic acid long-chain alkyl groupses/lithium metasilicate magnesium and preparation method and application |
| CN110065950A (en) * | 2019-05-06 | 2019-07-30 | 中国海洋大学 | The preparation method of transparent soft clay based on lithium metasilicate magnesium and its resulting soft clay |
| CN110527006A (en) * | 2019-09-09 | 2019-12-03 | 青岛科技大学 | A kind of heat-insulation composite material and its preparation method and application for coping with fire scenario |
| CN117701054A (en) * | 2023-12-13 | 2024-03-15 | 雅图高新材料股份有限公司 | Blending water for water paint and preparation method thereof |
| CN117701054B (en) * | 2023-12-13 | 2024-06-11 | 雅图高新材料股份有限公司 | Blending water for water paint and preparation method thereof |
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