CN101845114A - Preparation method of fluorinated acrylate microemulsion - Google Patents
Preparation method of fluorinated acrylate microemulsion Download PDFInfo
- Publication number
- CN101845114A CN101845114A CN 201010185728 CN201010185728A CN101845114A CN 101845114 A CN101845114 A CN 101845114A CN 201010185728 CN201010185728 CN 201010185728 CN 201010185728 A CN201010185728 A CN 201010185728A CN 101845114 A CN101845114 A CN 101845114A
- Authority
- CN
- China
- Prior art keywords
- fluorinated acrylate
- methyl
- monomer
- ester
- consumption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a method for preparing fluorinated acrylate microemulsion, which comprises the following steps: using first part of deionized water for mixing anionic emulsifier, nonionic emulsifier and crosslinking agent into solution, adding the rest deionized water, fluorinated acrylate monomer and acrylate monomer into a polymeric kettle, feeding with nitrogen and replacing and pre-emulsifying for 0.5h at 60DEG C; and firstly adding a t reducer, and then adding oxidant and copper sulfate solution simultaneously, keeping the water bath temperature to be 70DEG C, and carrying out the reaction for 5 to 8h. Because the special the catalyst copper sulfate is added into a redox initiator system and the reaction temperature is strictly controlled in a polymerization process, the preparation method of fluorinated acrylate microemulsion obtains 20 to 30nm of fluorinated acrylate microemulsion within 5 to 8h by one-step feeding without adding any comonomer, the operation is simple and the stability of the obtained latex is good.
Description
Technical field
The present invention relates to a kind of fluorine-containing ester microemulsion preparation method.
Background technology
Microemulsion is a kind of isotropic, transparent or semitransparent dispersion system on stable on the thermodynamics, the optics, its particle diameter is less than 100nm, and the miniemulsion particle diameter is 100~400nm, the ordinary emulsion particle diameter generally in the hundreds of nanometer to thousands of nanometers. median size increases and is twice, and minimum film-forming temperature raises 2.8 ℃.Particle diameter is big more, and the compactness of its latex film and smoothness are also poor more.And the particle diameter of microemulsion is less than order of magnitude of ordinary emulsion, and its volume is with regard to little three orders of magnitude, and this makes the minimum film-forming temperature of microemulsion reduce, and effectively population increases greatly, thereby microemulsion has better perviousness and affinity.
The micro-emulsion polymerization reaction mostly is radical polymerization greatly, preparating mechanism is based on the micella mechanism of nucleation, and homogeneous nucleation is also deposited, and system inside all exists a large amount of micellas in whole polymerization process, under very high transformation efficiency, still can produce new polymer particle, show the feature of continuous nucleation.In the conventional synthetic method, be not to add comonomer etc. in polymerization process, adopt the special surface promoting agent exactly, cost is higher, complex operation, and also emulsion property is relatively poor.
Fluorinated acrylate monomer has low surface energy and surface tension, and the acrylic ester monomer copolymerization of easy and structural similitude, on the polyacrylic ester polymer side chain, introduce perfluoroalkyl, can obtain waterproof, antifouling, grease proofing, fluorinated acrylate polymer with good solvent resistance.Fluorine-containing ester microemulsion latex particle size is very little, has fabulous wettability, levelling property and rheological, can with the conventional emulsions physical blending, realize 2 kinds of emulsion property complementations, the surface property of modified acroleic acid esters polymer is played a very important role.By adding this fluorine-containing ester microemulsion, can significantly reduce the viscosity of blending emulsion, improve the water tolerance of glued membrane, solvent resistance, glued membrane has the high transparency, can be used as the protection varnish of metallic substance.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the fluorine-containing ester microemulsion, in polymerization process, do not add comonomer, and reaction monomers once feeds intake, need not to add, adopt [copper sulfate/Potassium Persulphate-Sulfothiorine] catalysis-redox initiation system, just can make the fluorine-containing ester microemulsion that particle diameter is 25nm in 5-8 hour.
Fluorine-containing ester microemulsion of the present invention is a raw material with fluorinated acrylate monomer and acrylic ester monomer, at water soluble oxidized reduction initiating system, metallic salt catalyzer, carry out letex polymerization under the effect of anionic emulsifier, nonionic emulsifier, linking agent and form.Suitable fluorinated acrylate monomer of the present invention is that (methyl) perfluoroalkyl acrylate, (methyl) vinylformic acid contain the fluorine-containing alkyl ester of heteroatoms, (methyl) vinylformic acid perfluoroalkyl carboxylic acid amide esters, (methyl) vinylformic acid perfluoroalkyl sulphonamide ester.Suitable acrylic ester monomer of the present invention is (methyl) alkyl-acrylates, (methyl) acrylic acid hydroxy alkyl ester, (methyl) vinylformic acid amido ethyl ester etc.Oxygenant in the water soluble oxidized reduction initiating system comprises Potassium Persulphate, ammonium persulphate, reductive agent comprises Sulfothiorine, S-WAT, composite ratio (mass ratio) is 5: 4, and its total consumption is 5~9 parts (the present invention serves as to calculate benchmark with total monomer consumption 100 weight parts all except that particularly pointing out).Suitable anionic emulsifier is alkyl-sulphate or alkylsulfonate, and alkyl-sulphate commonly used has sodium lauryl sulphate, potassium octadecyl sulfate etc.; Alkylsulfonate commonly used has Sodium dodecylbenzene sulfonate, sodium laurylsulfonate etc.Suitable nonionic emulsifier is poly-lauryl alcohol oxyethane, polypropylene glycol oxyethane, polyethylene oxide Sorbitol Powder mono fatty acid ester, alkylphenol polyoxyethylene.The composite ratio (mass ratio) of anionic emulsifier and nonionic emulsifying agent is 4: 1, and its consumption is 8~10 parts.It is considered herein that in the emulsion polymerization systems an amount of metallic salt catalyzer of adding can quicken the generating rate of free radical, nucleation period is shortened, the polymerization initial stage, a large amount of solubilising micellas changed emulsion particle into, thereby obtain the very thin microemulsion of particle diameter, the metallic salt catalyzer of selecting for use is a copper sulfate, and its consumption is 0.02~0.04 part.The present invention adopts linking agent to improve the physical strength of polymeric film, and available linking agent has Viscoat 295 (TMPTA), N hydroxymethyl acrylamide (NMA), Ethylene glycol dimethacrylate (EGDMA), and its consumption is 12 parts.The consumption of deionized water is 10~15 times of total monomer consumption in the emulsion polymerization systems of the present invention.At first various auxiliary agents are mixed with solution with the part deionized water, remaining deionized water and mix monomer are joined in the polymeric kettle, logical nitrogen is replaced, and behind pre-emulsification 0.5h under 60 ℃, adds Sulfothiorine earlier, again Potassium Persulphate and micro-copper sulfate solution are added simultaneously, keep bath temperature at 70 ℃, react after 5-8 hour, transformation efficiency reaches 93-98%, cooling discharge, can obtain particle diameter is the fluorine-containing ester microemulsion of 20-30nm.
The present invention is owing to added special catalyst sulfuric acid copper in redox initiation system, and in polymerization process strict control reaction temperature, therefore need not add under the situation of comonomer, adopt and once feed intake, in 5-8 hour, promptly obtained the fluorine-containing ester microemulsion of 20-30nm, simple to operate and the gained latex stability is good.
NDJ-1 type Rotary Viscosimeter is measured emulsion viscosity.Condition determination is as follows: temperature is 25 ℃ during mensuration; Use No. 1 rotor; Rotating speed is 60r/min, sees GB/T1723-1993
The emulsion package stability
Measure the emulsion package stability according to GB6753.3-86.
Freeze-thaw stability
Measure the emulsion freeze-thaw stability according to GB/T 9268-1988.
The latex film after tackiness
Measure the paint film after tackiness according to GB/T 1762-1989.
The paint film resistance to medium
Measure the medium-resistance of filming according to GB/274-1988
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention, should understand, these embodiment only are used to the present invention is described and are not used in and limit the scope of the invention, should understand in addition, after the content of having read the present invention's instruction, those skilled in the art can make various changes or modification to the present invention, and these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment one
In the prescription, trifluoroethyl methacrylate can also be vinylformic acid perfluoroalkyl analog derivatives such as methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters
Methyl methacrylate can also be acrylic acid alkyl ester derivatives such as butyl acrylate.
According to above prescription, water is joined in the withstand voltage polymeric kettle, add monomer trifluoroethyl methacrylate and methyl methacrylate, compound emulsifying agent.Replace three times with nitrogen, open and stir, temperature is risen to 60 ℃, behind the pre-emulsification 0.5h, add Sulfothiorine earlier, again Potassium Persulphate and copper sulfate solution are added simultaneously.System moment was become translucent light blue by oyster white, and temperature rises rapidly, keeps bath temperature at 70 ℃, calculated a monomer conversion every two hours.After the polyreaction 8 hours, transformation efficiency reaches 97%, cooling discharge, and just can obtain particle diameter is the fluorine-containing ester microemulsion of 22.7nm.
Table 1 emulsion and film performance
Table 1 is a perfluoroalkyl methacrylate, and the alkyl methacrylate mass ratio is gained emulsion and a film performance after the copolymerization in 1: 4.As can be seen from Table 1, poly-fluorine-containing acrylic ester microemulsion has excellent water tolerance energy and solvent resistance, and emulsion viscosity is lower, and after tackiness reaches 1 grade, and elongation at break is very low, the latex film hardening.Have good physicals and lower surface energy by filming of this microemulsion preparation, can be used for providing top coat with outstanding waterproof/antifouling property.
Embodiment two
In the prescription, trifluoroethyl methacrylate can also be vinylformic acid perfluoroalkyl analog derivatives such as methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters
Methyl methacrylate can also be butyl acrylate, waits the acrylic acid alkyl ester derivative
According to above prescription, water is joined in the withstand voltage polymeric kettle, add monomer trifluoroethyl methacrylate and methyl methacrylate, compound emulsifying agent.Replace three times with nitrogen, open and stir, temperature is risen to 60 ℃, behind the pre-emulsification 0.5h, add Sulfothiorine earlier, again Potassium Persulphate and copper sulfate solution are added simultaneously.System moment was become translucent light blue by oyster white, and temperature rises rapidly, keeps bath temperature at 70 ℃, calculated a monomer conversion every two hours.After the polyreaction 8 hours, transformation efficiency reaches 96%, cooling discharge, and just can obtain particle diameter is the fluorine-containing ester microemulsion of 27.7nm.
Table 2 emulsion and film performance
Table 2 is a perfluoroalkyl methacrylate, and the alkyl methacrylate mass ratio is gained emulsion and a film performance after the copolymerization in 2: 3.As can be seen from Table 2, poly-fluorine-containing acrylic ester microemulsion has excellent water tolerance energy and solvent resistance, and emulsion viscosity is lower, and after tackiness reaches 1 grade, and elongation at break is very low, the latex film hardening.Have good physicals and lower surface energy by filming of this microemulsion preparation, can be used for providing top coat with outstanding waterproof/antifouling property.
Embodiment three
In the prescription, trifluoroethyl methacrylate can also be vinylformic acid perfluoroalkyl analog derivatives such as methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters
Methyl methacrylate can also be butyl acrylate, waits the acrylic acid alkyl ester derivative
According to above prescription, water is joined in the withstand voltage polymeric kettle, add monomer trifluoroethyl methacrylate and methyl methacrylate, compound emulsifying agent.Replace three times with nitrogen, open and stir, temperature is risen to 60 ℃, behind the pre-emulsification 0.5h, add Sulfothiorine earlier, again Potassium Persulphate and copper sulfate solution are added simultaneously.System moment was become translucent light blue by oyster white, and temperature rises rapidly, keeps bath temperature at 70 ℃, calculated a monomer conversion every two hours.After the polyreaction 8 hours, transformation efficiency reaches 98%, cooling discharge, and just can obtain particle diameter is the fluorine-containing ester microemulsion of 28.2nm.
Table 3 emulsion and film performance
Table 3 is a perfluoroalkyl methacrylate, and the alkyl methacrylate mass ratio is gained emulsion and a film performance after the copolymerization in 1: 1.As can be seen from Table 3, poly-fluorine-containing acrylic ester microemulsion has excellent water tolerance energy and solvent resistance, and emulsion viscosity is lower, and after tackiness reaches 1 grade, and elongation at break is very low, the latex film hardening.Have good physicals and lower surface energy by filming of this microemulsion preparation, can be used for providing top coat with outstanding waterproof/antifouling property.
Embodiment four
In the prescription, trifluoroethyl methacrylate can also be vinylformic acid perfluoroalkyl analog derivatives such as methacrylic acid hexafluoro butyl ester, methacrylic acid ten difluoro heptyl esters.
Methyl methacrylate can also be acrylic acid alkyl ester derivatives such as butyl acrylate.
According to above prescription, water is joined in the withstand voltage polymeric kettle, add monomer trifluoroethyl methacrylate and methyl methacrylate, compound emulsifying agent.Replace three times with nitrogen, open and stir, temperature is risen to 60 ℃, behind the pre-emulsification 0.5h, add Sulfothiorine earlier, again Potassium Persulphate and copper sulfate solution are added simultaneously.System moment was become translucent light blue by oyster white, and temperature rises rapidly, keeps bath temperature at 70 ℃, calculated a monomer conversion every two hours.After the polyreaction 8 hours, transformation efficiency reaches 97%, cooling discharge, and just can obtain particle diameter is the fluorine-containing ester microemulsion of 30.6nm.
Table 4 emulsion and film performance
Table 4 is a perfluoroalkyl methacrylate, and the alkyl methacrylate mass ratio is gained emulsion and a film performance after the copolymerization in 7: 3.As can be seen from Table 4, poly-fluorine-containing acrylic ester microemulsion has excellent water tolerance energy and solvent resistance, and it is big that emulsion viscosity becomes, after tackiness is 2 grades, can find that emulsion and film performance descend to some extent, but it is water-fast, solvent resistance is still stronger, can be used as the waterproof antifouling coating.
Embodiment five
According to above prescription, water is joined in the withstand voltage polymeric kettle, add monomer methacrylic acid hexafluoro butyl ester and butyl acrylate, compound emulsifying agent is replaced three times with nitrogen, opens and stirs, temperature is risen to 60 ℃, behind the pre-emulsification 0.5h, add Sulfothiorine earlier, again Potassium Persulphate and copper sulfate solution are added simultaneously.System moment was become translucent light blue by oyster white, and temperature rises rapidly, keeps bath temperature at 70 ℃, calculated a monomer conversion every two hours.After the polyreaction 8 hours, transformation efficiency reaches 95%, cooling discharge, and just can obtain particle diameter is the fluorine-containing ester microemulsion of 32.5nm.
Table 5 emulsion and film performance
Table 5 is a Perfluorocaprylic Acid methacryloyl amido ethyl ester, and vinylformic acid amido ethyl ester mass ratio is gained emulsion and a film performance after the copolymerization in 1: 1.As can be seen from Table 5, poly-fluorine-containing acrylic ester microemulsion has excellent water tolerance energy and solvent resistance, and emulsion viscosity is lower, and after tackiness reaches 1 grade, and elongation at break is very low, the latex film hardening.Have good physicals and lower surface energy by filming of this microemulsion preparation, can be used for providing top coat with outstanding waterproof/antifouling property.
Claims (1)
1. fluorinated acrylate preparation of microemulsion method is characterized in that step is as follows:
With fluorinated acrylate monomer and acrylic ester monomer is raw material, at water soluble oxidized reduction initiating system, metallic salt catalyst sulfuric acid copper, carries out letex polymerization under the effect of anionic emulsifier, nonionic emulsifier and linking agent;
Described fluorinated acrylate monomer is that (methyl) perfluoroalkyl acrylate, (methyl) vinylformic acid contain the fluorine-containing alkyl ester of heteroatoms, (methyl) vinylformic acid perfluoroalkyl carboxylic acid amide esters or (methyl) vinylformic acid perfluoroalkyl sulphonamide ester; Described acrylic ester monomer is (methyl) alkyl-acrylates, (methyl) acrylic acid hydroxy alkyl ester or (methyl) vinylformic acid amido ethyl ester; Oxygenant in the water soluble oxidized reduction initiating system is Potassium Persulphate or ammonium persulphate, reductive agent is Sulfothiorine or S-WAT, oxygenant and reductive agent mass ratio are 5: 4, with fluorinated acrylate monomer and total consumption 100 mass parts of acrylic ester monomer serves as to calculate benchmark, below mentioning consumption all is as benchmark, and the total consumption of water soluble oxidized reduction initiating system is 5~9 parts; Described anionic emulsifier is alkyl-sulphate or alkylsulfonate, and described nonionic emulsifier is poly-lauryl alcohol oxyethane, polypropylene glycol oxyethane, polyethylene oxide Sorbitol Powder mono fatty acid ester, alkylphenol polyoxyethylene; The mass ratio of anionic emulsifier and nonionic emulsifying agent is 4: 1, and total consumption of ionic emulsifying agent and nonionic emulsifying agent is 8~10 parts; The copper sulfate consumption is 0.02~0.04 part; Linking agent has Viscoat 295, N hydroxymethyl acrylamide or Ethylene glycol dimethacrylate, and dosage of crosslinking agent is 12 parts; The consumption of deionized water is fluorinated acrylate monomer and acrylic ester monomer consumption 10~15 times;
At first anionic emulsifier, nonionic emulsifier and linking agent are mixed with solution with the part deionized water, remaining deionized water, fluorinated acrylate monomer and acrylic ester monomer are joined in the polymeric kettle, logical nitrogen is replaced, behind pre-emulsification 0.5h under 60 ℃, add reductive agent earlier, again oxygenant and copper sulfate solution are added simultaneously, keep bath temperature, reacted 5-8 hour at 70 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010101857288A CN101845114B (en) | 2010-05-28 | 2010-05-28 | Preparation method of fluorinated acrylate microemulsion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010101857288A CN101845114B (en) | 2010-05-28 | 2010-05-28 | Preparation method of fluorinated acrylate microemulsion |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101845114A true CN101845114A (en) | 2010-09-29 |
CN101845114B CN101845114B (en) | 2012-07-18 |
Family
ID=42769943
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010101857288A Expired - Fee Related CN101845114B (en) | 2010-05-28 | 2010-05-28 | Preparation method of fluorinated acrylate microemulsion |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101845114B (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060952A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Styrene-acrylate emulsion with hydrophobic oleophylic fluorine-silicon-modified nuclear shell structure and preparation method thereof |
CN102585086A (en) * | 2012-03-05 | 2012-07-18 | 陕西科技大学 | Preparation method of fluorine-containing polyacrylate soap-free emulsion |
CN103507371A (en) * | 2012-06-20 | 2014-01-15 | 苏州金海薄膜科技发展有限公司 | Scratch-resistant stain-repellent screen protection film |
CN103694779A (en) * | 2013-12-14 | 2014-04-02 | 衢州市中通化工有限公司 | Mixed wax for printing oil and preparation method for mixed wax |
CN104193878A (en) * | 2014-07-23 | 2014-12-10 | 合肥德美畜牧技术有限公司 | Preparation method of NMA (N-methylol acrylamide) modified fluorinated acrylate emulsion |
CN105793303A (en) * | 2013-12-04 | 2016-07-20 | 诺华股份有限公司 | Soft hydrophobic acrylic materials |
CN105884976A (en) * | 2014-12-26 | 2016-08-24 | 成都美保康新材料有限公司 | Water-borne wood paint resin used outdoors and preparation method thereof |
CN108239220A (en) * | 2018-02-08 | 2018-07-03 | 上海昱邦化工科技有限公司 | A kind of aqueous acrylic emulsion and preparation method thereof |
CN108997623A (en) * | 2018-08-11 | 2018-12-14 | 界首市梦佳怡家居有限公司 | A kind of preparation method of resistant latex bed mattress |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1337415A (en) * | 2001-08-31 | 2002-02-27 | 清华大学 | Prepn prolcess of polyvinylidene difluoride modified polyacrylate emulsion |
CN1800224A (en) * | 2005-08-15 | 2006-07-12 | 高明 | Fluorocarbon elastomer latex and its preparation method |
-
2010
- 2010-05-28 CN CN2010101857288A patent/CN101845114B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1337415A (en) * | 2001-08-31 | 2002-02-27 | 清华大学 | Prepn prolcess of polyvinylidene difluoride modified polyacrylate emulsion |
CN1800224A (en) * | 2005-08-15 | 2006-07-12 | 高明 | Fluorocarbon elastomer latex and its preparation method |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102060952B (en) * | 2010-10-29 | 2013-02-13 | 华南理工大学 | Styrene-acrylate emulsion with hydrophobic oleophylic fluorine-silicon-modified nuclear shell structure and preparation method thereof |
CN102060952A (en) * | 2010-10-29 | 2011-05-18 | 华南理工大学 | Styrene-acrylate emulsion with hydrophobic oleophylic fluorine-silicon-modified nuclear shell structure and preparation method thereof |
CN102585086A (en) * | 2012-03-05 | 2012-07-18 | 陕西科技大学 | Preparation method of fluorine-containing polyacrylate soap-free emulsion |
CN102585086B (en) * | 2012-03-05 | 2014-07-30 | 陕西科技大学 | Preparation method of fluorine-containing polyacrylate soap-free emulsion |
CN103507371A (en) * | 2012-06-20 | 2014-01-15 | 苏州金海薄膜科技发展有限公司 | Scratch-resistant stain-repellent screen protection film |
US10722612B2 (en) | 2013-12-04 | 2020-07-28 | Alcon Inc. | Soft hydrophobic acrylic materials |
CN105793303A (en) * | 2013-12-04 | 2016-07-20 | 诺华股份有限公司 | Soft hydrophobic acrylic materials |
CN103694779A (en) * | 2013-12-14 | 2014-04-02 | 衢州市中通化工有限公司 | Mixed wax for printing oil and preparation method for mixed wax |
CN103694779B (en) * | 2013-12-14 | 2015-07-01 | 衢州市中通化工有限公司 | Preparation method for mixed wax for printing oil |
CN104193878A (en) * | 2014-07-23 | 2014-12-10 | 合肥德美畜牧技术有限公司 | Preparation method of NMA (N-methylol acrylamide) modified fluorinated acrylate emulsion |
CN105884976A (en) * | 2014-12-26 | 2016-08-24 | 成都美保康新材料有限公司 | Water-borne wood paint resin used outdoors and preparation method thereof |
CN108239220A (en) * | 2018-02-08 | 2018-07-03 | 上海昱邦化工科技有限公司 | A kind of aqueous acrylic emulsion and preparation method thereof |
CN108239220B (en) * | 2018-02-08 | 2021-08-27 | 上海昱邦化工科技有限公司 | Water-based acrylic emulsion and preparation method thereof |
CN108997623A (en) * | 2018-08-11 | 2018-12-14 | 界首市梦佳怡家居有限公司 | A kind of preparation method of resistant latex bed mattress |
Also Published As
Publication number | Publication date |
---|---|
CN101845114B (en) | 2012-07-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101845114B (en) | Preparation method of fluorinated acrylate microemulsion | |
CN104530302B (en) | A kind of Ludox/polyacrylate dispersion of high silicon content and preparation method thereof | |
CN103864982A (en) | Preparation method of fluorinated acrylate emulsion | |
CN102702419B (en) | Preparation method of montmorillonite-modified crosslinked acrylate-hybridized core-shell emulsion | |
CN101585894B (en) | Preparation method of vinyl acetate-acrylate copolymerization emulsion | |
CN102532403B (en) | Shell-structure acrylic emulsion for dispersible glue powder and preparation method of shell-structure acrylic emulsion | |
CN101838371A (en) | Method for preparing high-solid-content and low-viscosity core-shell structure styrene-acrylic emulsion | |
CN102850479B (en) | Preparation method of cationic styrene-acrylic microemulsion | |
CN101724116A (en) | Polymer emulsion and preparation method thereof | |
CN101560278B (en) | Methyl methacrylate-styrene copolymer containing fluoro-acrylate and preparation method thereof | |
CN104628923A (en) | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by oil-soluble initiator | |
CN102585086A (en) | Preparation method of fluorine-containing polyacrylate soap-free emulsion | |
CN100404567C (en) | Preparation process of non organic solvent type fluorine-containing soapless emulsion | |
CN102911540A (en) | Hydrophobic MMA (Methl Methacrylate) resin floor coating and preparation method thereof | |
CN104262530A (en) | Unmodified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method thereof | |
CN106749860A (en) | The preparation method of nano-cellulose/fluorine-contaninig polyacrylate complex emulsions | |
CN103059212A (en) | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof | |
CN105418826A (en) | Preparation of self-emulsifying perfluoropolyether monomer and application of self-emulsifying perfluoropolyether monomer in synthesis of fluorine-containing miniemulsion | |
CN107602769A (en) | A kind of method of synthesis MBS resins | |
CN104628924A (en) | Method for preparing aggregation-induced emission type polymer fluorescent nanoparticle through mini-emulsion polymerization initiated by water-soluble initiator | |
CN103570886A (en) | Organic silicon modified fluorinated acrylate polymer and preparation method thereof | |
CN106632791B (en) | One kind resisting fresh cement accumulation of salt in the surface soil priming paint styrene-acrylic emulsion and preparation method thereof | |
CN102504087A (en) | Preparation method for silicic acrylic ester soap-free emulsion stabilized by protective colloid | |
CN106366238A (en) | Fluorine and nano-particle modified ethylene-propylene antibacterial emulsion | |
CN102199258B (en) | Polyether modified silicon acrylic flexible resin and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120718 Termination date: 20150528 |
|
EXPY | Termination of patent right or utility model |