CN1858076A - Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method - Google Patents
Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method Download PDFInfo
- Publication number
- CN1858076A CN1858076A CN 200610050461 CN200610050461A CN1858076A CN 1858076 A CN1858076 A CN 1858076A CN 200610050461 CN200610050461 CN 200610050461 CN 200610050461 A CN200610050461 A CN 200610050461A CN 1858076 A CN1858076 A CN 1858076A
- Authority
- CN
- China
- Prior art keywords
- phase solution
- group
- monomer
- organic silicon
- methyl
- 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
Abstract
The present invention discloses fine emulsion polymerizing process to prepare organosilicon modified acrylate copolymer emulsion. The process includes the following steps: 1) dissolving emulsifier in 0.01-10 weight portions in water of 50-400 weight portions to form water phase solution; 2) mixing two or more kinds of vinyl monomers in 10-200 weight portions and organosilicon monomer in 1-30 weight portions to form oil phase solution; 3) mixing the water phase solution and the oil phase solution, and crushing in a high shearing field for 2-30 min to form fine emulsion; and 4) transferring the fine emulsion into a reactor, heating to 40-160 deg.c and adding initiator in 0.05-10 weight portions to initiate polymerization for 2-18 hr, and cooling slowly to room temperature before discharging. The process is simple, efficient and environment friendly, and may have organosilicon introduced in relatively high content.
Description
Technical field
The present invention relates to a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion.
Background technology
Because polysiloxane has characteristics such as bond energy is big, molecule is submissive, surface energy is low, uvioresistant performance is good, the silicone-modified polyacrylate water-borne coatings, be expected to become the environment-friendly type building exterior coating of a kind of high-weatherability and contamination resistance, but also can be used for the aspects such as outer layer coating, softening agent and water repellent finishing agent of tackiness agent, paper coating, woodwork coating, textile fibres.
By molecular designing, the silicone-modified polyacrylate emulsion of self-crosslinkable after the preparation film forming, thus the content of organic volatile branch (VOC) in the minimizing water-borne coatings prescription also comes into one's own.Simply organopolysiloxane and polyacrylate dispersion are carried out physical blending and prepare the silicone-modified polyacrylate water-borne coatings, coating performance does not improve.This mainly is because two kinds of isolating causes of interlaminar resin generation macroface.Thereby in the acrylate monomer letex polymerization, directly organo-siloxane is grafted on the polyacrylate backbone, form the main method that poly-(acrylate-organo-siloxane) becomes the high performance organo-silicon modified polyacrylate dispersion of preparation.
In the conventional emulsion polymerization process, oil phase substance needs to move to emulsion particle from monomer droplet by water, can not directly organopolysiloxane be grafted on the polyacrylate backbone.Thereby in letex polymerization, must use small molecules organo-siloxane monomer.When acrylate monomer carried out free-radical emulsion polymerization, organo-siloxane generation hydrolysis-condensation reaction generated organopolysiloxane, is grafted on the polyacrylate backbone simultaneously.Thereby organo-siloxane needs to be easy to take place just be difficult to avoid with water contact premature hydrolysis condensation from monomer droplet to the emulsion particle migration by water in letex polymerization, generate condensation product, not only make the emulsion unstability, and difficult control multipolymer is formed, film-forming properties is also bad, and this is the main difficult point of emulsion polymerization prepared organic silicon modified propenoic ester copolymer.
Mini-emulsion polymerization is a kind of New Emulsion polymerization process that grows up the seventies in 20th century.Be different from conventional emulsion polymerization, mini-emulsion polymerization is based on the monomer droplet mechanism of nucleation.The fine drop of monomer droplet about by pre-dispersed one-tenth 50 ~ 500nm, these drops will directly be caught the free radical that water produces and be become polymer particle.Monomer droplet can be regarded as nano-reactor, monomer directly carries out polymerization therein, by the migration of water to latex particle, this has shown great advantage to the organosilane monomer of having avoided easy premature hydrolysis condensation for the letex polymerization of organosilane monomer from monomer droplet.At present mini-emulsion polymerization be used for organosilicon-modified acrylate report also seldom.
The monomer modified acrylate of vinyl organosilicon is to utilize the vinyl group on its molecule to carry out free-radical polymerized with (methyl) acrylate monomer.But in film process, because the chain length of organosilicon side chain is shorter, in case after being bonded on the acrylate backbone, will be by other side chains " covering ", also be difficult to stretch, move to coating surface easily by acrylate resin molecule " embedding ", thereby influenced organic-silicon-modified effect, therefore must increase the length of siliceous side chain from the angle of molecular designing.Such as using vinyl organosilicon monomers (coupling organosilicon) such as vinyltrimethoxy silane, vinyltriethoxysilane at first to form the active grafting site of siloxanes with the acrylate monomer copolymerization, non-vinylsiloxane carries out grafting, cross-linking modified by these active grafting sites again.Like this, on the one hand, the siloxane-acrylate copolymer molecule that makes is pectination, after the film forming, and siliceous side chain tensible and align on film surface and form crosslinking structure, thus significantly improve the surface property of film; On the other hand, by graft reaction, under the prerequisite that does not change organosilicon content, replaced the higher vinyl silicon monomer of partial valence with the lower siloxanes of valency, thereby greatly reduced production cost.
This patent utilizes the characteristics of mini-emulsion polymerization droplet nucleation mechanism, is raw material with commercial organosilicon, it is grafted on the main polymer chain at acrylate polymerization processes by molecular designing, prepares high performance organo-silicon modified polyacrylate dispersion with this.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion.
The step of method is as follows:
1) with 0.01～10 part emulsifying agent, be dissolved in 50～400 parts of water, form aqueous phase solution;
2) organosilane monomer with 10～200 parts of two or more vinyl monomers or many vinyl polymerizations monomer, 1～30 part of weight mixes, and forms oil-phase solution;
3) aqueous phase solution and oil-phase solution is mixed, pulverize 2～30 minutes formation miniemulsions through high shear field;
4) miniemulsion is moved into reactor, be warming up to 40～160 ℃, add 0.05～10 part of initiator, initiated polymerization, polymerization is after 2～18 hours, slowly cools to discharging after the room temperature.
Described step 2) adds 0.01～10 part assistant for emulsifying agent and form oil-phase solution.
The present invention utilizes the mini-emulsion polymerization technology, and the thought of binding molecule design has been selected suitable organosilane monomer for use, has prepared the good organic silicon modified propenoic ester copolymer emulsion of stable performance.One big innovation of this patent is the method that has adopted mini-emulsion polymerization, and combine the thought of molecular designing, by the migration of water to latex particle, this has shown great advantage to the organosilane monomer that the New Emulsion polymerization process that grow up this seventies in 20th century can be avoided easy premature hydrolysis condensation for the letex polymerization of organosilane monomer from monomer droplet; And the thought of molecular designing not only can reduce cost, and can make the organosilicon of adding can neatly move the surface that is arranged in polymeric film, play maximum modified effect, make polymeric film show hydrophobicity, contamination resistance, thereby reduce organosilyl consumption.The advantage of mini-emulsion polymerization also has: (1) system stability is high, helps industrial enforcement; (2) particle diameter of product latex reaches 50～500 nanometers; (3) polymerization efficiency height is produced and is easy to control etc.; (4) be dispersion medium with water, heat-transfer effect is good, and is environmentally friendly.Innovative point of the present invention is not only to have adopted this New Emulsion polymerization process of mini-emulsion polymerization, but also combines the thinking of molecular designing, for the further industrialization of organic silicon modified acrylic ester aqueous system has proposed a kind of novelty, high-efficiency method.
Embodiment
The chemical structure of general formula of used organosilane monomer is respectively (I), (II) and (III) among the present invention:
R
1-Si-(R
2)
3 (I)
R wherein
1Group is: vinyl, (methyl) acryloyl-oxy methyl, (methyl) acrylyl oxy-ethyl, (methyl) acryloyl-oxy propyl group, (methyl) acryloyl-oxy sec.-propyl or (methyl) acryloyl-oxy C
1-C
10Alkyl, R
2Group is: C
1-C
8Alkoxyl group, acetoxyl or hydroxyl,
(R
3)
n-Si-(R
4)
4-n (II)
R wherein
3Group is: H, C
1-C
16Alkyl, C
5-C
10Aryl, C
5-C
6Cycloalkyl, R
4Group is: C
1-C
8Alkoxyl group, acetoxyl or hydroxyl, R
5Group is: H, C
1-C
16Alkyl, C
5-C
10Aryl, C
5-C
6Cycloalkyl, R
6Group is: C1-C8 alkoxyl group, acetoxyl, hydroxyl, epoxy group(ing) or oxyethylene group, n are 0,2 or 3; M is the integer between 1 to 999,
The content of organosilicon (I) is the 0.1%-30% of vinyl main monomer amount, and organosilicon (II) and content (III) are the 0.1%-30% of vinyl main monomer amount;
Described vinyl monomer is: vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene, vinyl pyrrolidone or N hydroxymethyl acrylamide.
Multi-vinyl monomer is: Vinylstyrene, Ethylene glycol dimethacrylate, allyl methyl vinylformic acid, ethylene glycol diacrylate, diacrylate butanediol ester, tetramethylene dimethacrylate, dimethacrylate DOPCP, hexanodioic acid dimethacrylate, dimethacrylate triglycol, dimethacrylate Tetraglycol 99, TriMethylolPropane(TMP), tetramethylolmethane tetramethyl-vinylformic acid or Vinylstyrene.
Emulsifying agent is: one or more mixtures of sodium lauryl sulphate, cetyl trimethylammonium bromide, soil matrix phenol polyethenoxy ether, OP series, MS-1, Span, tween or Sodium dodecylbenzene sulfonate, addition are 0.01～10% of amount of monomer.
Initiator is persulphate, hydrogen peroxide and derivative thereof, NP-O2 or N, N, and N, N-Tetramethyl Ethylene Diamine, addition are 0.05～10% of amount of monomer.
The high shear field effect is provided by ultrasonic grinding instrument, high-pressure homogenizer or super gravity field generating unit.
Assistant for emulsifying agent is: C
18-C
24Pure and mild C
16-C
24Alkane, consumption are 0.01～10 part.The affiliation that adds of assistant for emulsifying agent increases the VOC content of system, also can make the degradation of polymeric film simultaneously, such as sticking power and oil repellency etc.Under certain condition, can not add assistant for emulsifying agent, the organosilicon of employed high hydrophobicity can play the effect of similar assistant for emulsifying agent among the present invention, delay and stop monomer from the migration (Ostwald ripening) of small droplets to big drop, thereby obtain the less monomer droplet of stable particle diameter, can obtain the desired film properties of wanting simultaneously.
Embodiment 1:
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) restrain vinylbenzene, 10 with 10 and restrain butyl acrylates, 0.3 gram vinyltriethoxysilane, 1 gram methyltrimethoxy silane, 1 gram dimethyldimethoxysil,ne mixing stirring, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Embodiment 2:
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) 10 gram vinyl toluenes, 10 are restrained butyl acrylates, 0.3 and restrain vinyltriethoxysilane, 1 gram methyltrimethoxy silane, 1 gram dimethyldimethoxysil,ne, 0.4 gram n-Hexadecane mixing stirring, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Embodiment 3:
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) 10 gram vinyl toluenes, 10 are restrained butyl acrylates, 0.3 and restrain gamma-methyl allyl acyloxypropyl trimethoxysilane, 1 gram methyltrimethoxy silane, 1 gram dimethyldimethoxysil,ne, 0.4 gram stearyl alcohol mixing stirring, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Comparing embodiment 1: do not add organosilicon
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) 10 gram vinylbenzene, 10 gram butyl acrylates, 0.4 gram n-Hexadecane are mixed stirring, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Comparing embodiment 2: organosilicon content increases
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) restrain vinylbenzene, 10 with 10 and restrain butyl acrylates, 0.6 gram vinyltriethoxysilane, 2 gram methyltrimethoxy silanes, 2 gram dimethyldimethoxysil,ne mixing stirrings, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Comparing embodiment 3: organosilicon content increases
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) restrain vinylbenzene, 10 with 10 and restrain butyl acrylates, 0.9 gram vinyltriethoxysilane, 3 gram methyltrimethoxy silanes, 3 gram dimethyldimethoxysil,ne mixing stirrings, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Embodiment 4
1) 0.4 gram sodium lauryl sulphate and 0.4 gram OP-10 are dissolved in the 75 gram water, form aqueous phase solution;
2) 5 gram vinylbenzene, 5 gram methyl methacrylates, 10 are restrained butyl acrylates, 0.3 and restrain gamma-methyl allyl acyloxypropyl trimethoxysilane, 1 gram methyltrimethoxy silane, 1 gram dimethyldimethoxysil,ne, 0.4 gram n-Hexadecane mixing stirring, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Embodiment 5:
1) 0.8 gram sodium lauryl sulphate is dissolved in the 75 gram water, forms aqueous phase solution;
2) 10 gram vinyl toluenes, 10 are restrained butyl acrylates, 0.3 and restrain gamma-methyl allyl acyloxypropyl trimethoxysilane, 1 gram methyltrimethoxy silane, 1 gram dimethyldimethoxysil,ne, 0.4 gram n-Hexadecane mixing stirring, form oil-phase solution;
3) above-mentioned aqueous phase solution and oil-phase solution is mixed, magnetic agitation is 10 minutes in the ice-water bath, and (amplitude 70%, and 600W) ultrasonication is 15 minutes, forms miniemulsion to give birth to KS-600Sonifier with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, feed 60 ℃ of hot water baths, the aqueous solution (0.15 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, behind the polyase 13 hour, slowly cool to discharging after the room temperature.
Emulsion property and copolymer coated performance
| Embodiment | Median size (nm) | Contact angle (degree) | Water-intake rate (%) | Package stability |
| 1 | 76.5 | 95.9 | 8.52 | Good |
| 2 | 70.4 | 103.2 | 6.36 | Good |
| 3 | 70.9 | 105.5 | 6.79 | Good |
| Comparing embodiment 1 | 80.9 | 73.9 | 13.97 | Good |
| Comparing embodiment 2 | 74.3 | 104.6 | 6.96 | Good |
| Comparing embodiment 3 | 74.8 | 104.7 | 6.54 | Good |
| 4 | 72.3 | 105.7 | 5.39 | Good |
| 5 | 73.4 | 104.8 | 6.14 | Good |
Particle diameter and distribution are measured with Zetasizer3000 HAS Zeta potential nanometer laser particle size analyzer (Britain Malvern); Contact angle is to measure liquid with OCA 20 video optics contact angle instruments (German Dataphysics company) with water, and measuring temperature is 25 ℃; The water-intake rate of film: drying at room temperature 2 days, be cut into 20nm * 20nm * 1nm small pieces, place 60 ℃ of vacuum-dryings 24 hours, soak in the distilled water, regularly take out, filter paper is washed dried surface-moisture, weighs and calculates water-intake rate; Package stability: GB6753.3-86.
Claims (6)
1. method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion is characterized in that the step of method is as follows:
1) with 0.01～10 part emulsifying agent, be dissolved in 50～400 parts of water, form aqueous phase solution;
2) organosilane monomer with 10～200 parts of two or more vinyl monomers or many vinyl polymerizations monomer, 1～30 part of weight mixes, and forms oil-phase solution;
3) aqueous phase solution and oil-phase solution is mixed, pulverize 2～30 minutes formation miniemulsions through high shear field;
4) miniemulsion is moved into reactor, be warming up to 40～160 ℃, add 0.05～10 part of initiator, initiated polymerization, polymerization is after 2～18 hours, slowly cools to discharging after the room temperature.
2. a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion according to claim 1 is characterized in that, described miniemulsion is that the monomer droplet of 50～300nm is scattered in the water and forms for dripping the footpath.
3. a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion according to claim 1 is characterized in that described step 2) assistant for emulsifying agent that adds 0.01～10 part forms oil-phase solution.
4. a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion according to claim 1 is characterized in that, the chemical structure of general formula of described organosilane monomer is respectively (I), (II) and (III):
R
1-Si-(R
2)
3 (I)
R wherein
1Group is: vinyl, (methyl) acryloyl-oxy methyl, (methyl) acrylyl oxy-ethyl, (methyl) acryloyl-oxy propyl group, (methyl) acryloyl-oxy sec.-propyl or (methyl) acryloyl-oxy C
1-C
10Alkyl, R
2Group is: C
1-C
8Alkoxyl group, acetoxyl or hydroxyl,
(R
3)
n-Si-(R
4)
4-n (II)
R wherein
3Group is: H, C
1-C
16Alkyl, C
5-C
10Aryl, C
5-C
6Cycloalkyl, R
4Group is: C
1-C
8Alkoxyl group, acetoxyl or hydroxyl, R
5Group is: H, C
1-C
16Alkyl, C
5-C
10Aryl, C
5-C
6Cycloalkyl, R
6Group is: C1-C8 alkoxyl group, acetoxyl, hydroxyl, epoxy group(ing) or oxyethylene group, n are 0,2 or 3; M is the integer between 1 to 999,
The content of organosilicon (I) is the 0.1%-30% of vinyl main monomer amount, and organosilicon (II) and content (III) are the 0.1%-30% of vinyl main monomer amount.
5. a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion according to claim 1, it is characterized in that described vinyl monomer is: vinylformic acid, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, Hydroxyethyl acrylate, vinylbenzene or vinyl toluene.
6. a kind of method of utilizing fine emulsion polymerization to prepare the organic silicon modified propenoic ester copolymer emulsion according to claim 1, it is characterized in that, described emulsifying agent is: one or more mixtures of sodium lauryl sulphate, soil matrix phenol polyethenoxy ether, OP series or Sodium dodecylbenzene sulfonate, addition are 0.01～10% of amount of monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100504615A CN100348627C (en) | 2006-04-21 | 2006-04-21 | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100504615A CN100348627C (en) | 2006-04-21 | 2006-04-21 | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1858076A true CN1858076A (en) | 2006-11-08 |
| CN100348627C CN100348627C (en) | 2007-11-14 |
Family
ID=37297036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100504615A Expired - Fee Related CN100348627C (en) | 2006-04-21 | 2006-04-21 | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100348627C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560592C (en) * | 2006-12-13 | 2009-11-18 | 中国科学院广州化学研究所 | A kind of siliceous (methyl) acrylate monomer and multipolymer thereof and their preparation method |
| CN101386663B (en) * | 2008-10-30 | 2010-10-06 | 上海三瑞高分子材料有限公司 | Multifunctional acrylic ester emulsion |
| CN101575398B (en) * | 2009-06-05 | 2011-04-20 | 天津碧海蓝天水性高分子材料有限公司 | Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves |
| CN101638451B (en) * | 2008-08-01 | 2012-05-09 | 上海富臣化工有限公司 | Nano polyacrylate emulsion for water-based wood coating and method for preparing same |
| CN102464784A (en) * | 2010-11-19 | 2012-05-23 | 北京佳盛世纪科技有限公司 | Synthesis method of organic silicon modified acrylate copolymer |
| CN101293941B (en) * | 2007-04-24 | 2013-05-29 | 关西涂料株式会社 | Production method of pigment-dispersing resin |
| CN105218762A (en) * | 2015-10-28 | 2016-01-06 | 广州中国科学院工业技术研究院 | Novel organosilicon water repllents and preparation method thereof |
| CN106916263A (en) * | 2017-02-08 | 2017-07-04 | 佛山沛涂科技有限公司 | A kind of method of organic-silicon-modified automobile coating water-based acrylic resin |
| CN117468268A (en) * | 2023-12-27 | 2024-01-30 | 湖南大道新材料有限公司 | Water-blocking paper bag and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI425083B (en) * | 2011-12-08 | 2014-02-01 | Taiwan Textile Res Inst | Method for fabricating emulsion |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594380A (en) * | 2004-07-09 | 2005-03-16 | 中山大学 | Process for preparing silicon acrylic latex |
-
2006
- 2006-04-21 CN CNB2006100504615A patent/CN100348627C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100560592C (en) * | 2006-12-13 | 2009-11-18 | 中国科学院广州化学研究所 | A kind of siliceous (methyl) acrylate monomer and multipolymer thereof and their preparation method |
| CN101293941B (en) * | 2007-04-24 | 2013-05-29 | 关西涂料株式会社 | Production method of pigment-dispersing resin |
| CN101638451B (en) * | 2008-08-01 | 2012-05-09 | 上海富臣化工有限公司 | Nano polyacrylate emulsion for water-based wood coating and method for preparing same |
| CN101386663B (en) * | 2008-10-30 | 2010-10-06 | 上海三瑞高分子材料有限公司 | Multifunctional acrylic ester emulsion |
| CN101575398B (en) * | 2009-06-05 | 2011-04-20 | 天津碧海蓝天水性高分子材料有限公司 | Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves |
| CN102464784A (en) * | 2010-11-19 | 2012-05-23 | 北京佳盛世纪科技有限公司 | Synthesis method of organic silicon modified acrylate copolymer |
| CN105218762A (en) * | 2015-10-28 | 2016-01-06 | 广州中国科学院工业技术研究院 | Novel organosilicon water repllents and preparation method thereof |
| CN106916263A (en) * | 2017-02-08 | 2017-07-04 | 佛山沛涂科技有限公司 | A kind of method of organic-silicon-modified automobile coating water-based acrylic resin |
| CN117468268A (en) * | 2023-12-27 | 2024-01-30 | 湖南大道新材料有限公司 | Water-blocking paper bag and preparation method and application thereof |
| CN117468268B (en) * | 2023-12-27 | 2024-03-22 | 湖南大道新材料有限公司 | Water-blocking paper bag and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100348627C (en) | 2007-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1858076A (en) | Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method | |
| CN1274756C (en) | Nano silicon dioxide/acrylate composite emulsion and process for preparing same | |
| CN101024751B (en) | Coating material containing POSS acrylate copolymer and preparing method | |
| Bao et al. | Recent advances in the modification of polyacrylate latexes | |
| JP2009542827A5 (en) | ||
| CN102007187B (en) | Anorganic nanoparticles and polymer composites created with same | |
| CN102731734B (en) | Method for grafting polymer on nano-grade SiO2 surface | |
| CN109666111A (en) | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion | |
| CN1304436C (en) | Process for preparing reaction functional macromolecule/Al2O3 nano composite particles | |
| Zhu et al. | Effects of length and organic modification of attapulgite nanorods on attapulgite/polystyrene nanocomposite via in-situ radical bulk polymerization | |
| CN102241866A (en) | Transparent acrylic acid silicone resin nano composite material and preparation method thereof | |
| CN1385447A (en) | Organic silicon-acrylate nano emulsion | |
| CN1757668A (en) | High molecule/calcium carbonate nanometer particles, functional particles and prepn. method thereof | |
| CN1517373A (en) | Composition of elastic organic silicon phenylpropyl resin emulsion for paint and its preparation method | |
| CN108329686B (en) | Preparation method of high-performance nylon nano composite material | |
| CN106632875A (en) | Inorganic nanoparticle-modified fluorinated acrylate hydrophobic emulsion and preparation method thereof | |
| CN1253492C (en) | Preparation of carboxy silicon oil emulsion | |
| CN111825860B (en) | Graphene/silicon dioxide double-hybrid wall material modified polystyrene microsphere and preparation method thereof | |
| CN1560094A (en) | Nano macromolecule microball of epoxy function type cross-linked nucleocapsid structure and preparation process thereof | |
| CN101058625A (en) | Composite latex of organic silicon resin and acrylic ester polymers, and preparation method thereof | |
| CN1244602C (en) | High performance silicon emulsion and its preparation | |
| CN102007153B (en) | Polymerisable substance with connected nanoparticles | |
| CN114213568B (en) | Light conversion microsphere, preparation method and application | |
| CN111825926A (en) | Organic/inorganic hybrid three-component Janus particle and preparation method thereof | |
| CN1218969C (en) | Composite nano epoxy functional polymer/SiO2 particle and its prepn process |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Beijing Eastern Acrylic Chemical Technology Co., Ltd. Assignor: Zhejiang University Contract fulfillment period: 2009.4.30 to 2014.4.29 contract change Contract record no.: 2009990000611 Denomination of invention: Method for preparing organic silicon modified propenoic ester copolymer emusion by fine emulsion polymerizing method Granted publication date: 20071114 License type: Exclusive license Record date: 2009.6.4 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.4.30 TO 2014.4.29; CHANGE OF CONTRACT Name of requester: BEIJING DONGFANG YAKELI CHEMICAL SCIENCE CO., LTD. Effective date: 20090604 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071114 Termination date: 20140421 |