CN102408513B - Preparation method of phosphate modified acrylate emulsion - Google Patents
Preparation method of phosphate modified acrylate emulsion Download PDFInfo
- Publication number
- CN102408513B CN102408513B CN 201110309888 CN201110309888A CN102408513B CN 102408513 B CN102408513 B CN 102408513B CN 201110309888 CN201110309888 CN 201110309888 CN 201110309888 A CN201110309888 A CN 201110309888A CN 102408513 B CN102408513 B CN 102408513B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- polymerization
- phosphate
- ester
- preparation
- 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.)
- Active
Links
Images
Abstract
The invention relates to a preparation method of phosphate modified acrylate emulsion. The preparation method not only has relatively low cost, but also can effectively improve the flame retardation property of polyacrylate emulsion. The preparation method of phosphate modified acrylate emulsion comprises the following steps of: (1) primary polymerization: pre-emulsifying 10-20 parts of methyl methacrylate, 2-3 parts of methacrylic acid, 1-2 parts of acrylonitrile and 10-15 parts of styrene, then performing primary emulsion polymerization, and adjusting the pH value to obtain the primary polymerized emulsion; and (2) secondary polymerization: pre-emulsifying 30-45 parts of hydroxyl methacrylate substance, then adding the pre-emulsified product and 5-10 parts of phosphate monomer into the primary polymerized solution, and performing secondary emulsion polymerization to obtain the phosphate modified acrylate emulsion with a core-shell structure, wherein the phosphate monomer is trichloroethyl phosphate, trichloropropyl phosphate or n-ethyl phosphate; the molecular weight of polymer in the obtained phosphate modified acrylate emulsion is 2000-3000; and the particle size is 0.2-0.6 mu m.
Description
Technical field
The present invention relates to a kind of preparation method of phosphate modified acrylic ester emulsion.
Background technology
Acrylic ester emulsion is because its excellent water resistance, agglutinating value(of coal), film-forming properties, weathering resistance and guarantor's light are protected the advantages such as look and mechanical property, be widely used and be emulsion paint, in textile fabric, leather, paper, glass fibre sleeve and external wall, be widely used, but because it belongs to organic substance, it is inflammable to meet fire after the film forming, produce thick smoke and the in a large number generation of objectionable impuritiess, affected its range of application, therefore it is carried out the flame retardant resistance modification and be very important.
The unsaturated monomer of introducing the phosphoric acid group in acrylic ester emulsion carries out modification by copolymerization, can improve the flame retardant properties of emulsion.But the unsaturated monomer of this phosphoric acid group needs special preparation, and expensive.
Summary of the invention
The invention provides a kind of preparation method of phosphate modified acrylic ester emulsion, not only cost is lower, but and the flame retardant properties of Effective Raise polyacrylate dispersion.
The preparation method of described phosphate modified acrylic ester emulsion is:
(1) polymerization
To carry out a letex polymerization after 10-20 part methyl methacrylate, 2-3 part methacrylic acid, 1-2 part vinyl cyanide and the 10-15 part vinylbenzene pre-emulsification, obtain the polymerized emulsion that the pH value is 5-6 after adjusting the pH value, wherein polymericular weight is 2000-4000, and particle diameter is the 0.2-1 micron;
(2) after polymerization
After 30-45 part hydroxyethyl methacrylate Ester pre-emulsification, and 5-10 part phosphate ester monomer adds in polymerized emulsion together, carries out the secondary letex polymerization, obtains the phosphate modified acrylic ester emulsion of nucleocapsid structure,
Above-mentioned umber is mass fraction, and described phosphate ester monomer is trichloroethyl phosphate, trichlorine propyl phosphate or the positive ethyl ester of phosphoric acid, and the molecular weight of polymkeric substance is 2000-3000 in the phosphate modified acrylic ester emulsion of gained, and particle diameter is the 0.2-0.6 micron.
The nucleocapsid structure of phosphate modified acrylic ester emulsion can be confirmed by transmission electron microscope (hereinafter to be referred as the TEM) testing method of routine.
Preferably, use altogether emulsifying agent 2-5 part in a described polymerization and the after polymerization process, initiator 0.3-0.6 part, chain-transfer agent 2-4 part.
As preferred version, described phosphate modified acrylic ester emulsion obtains through the core-shell emulsion polymerization method with the raw material that following quality group becomes: methyl methacrylate 10-20%, methacrylic acid 2-3%, hydroxyethyl methacrylate Ester 30-45%, vinyl cyanide 1-2%, vinylbenzene 10-15%, phosphoric acid ester material 5-10%, emulsifying agent 2-5%, initiator 0.3-0.6%, chain-transfer agent 2-4%, buffered soln 3-5%, surplus is water, and wherein, described initiator is FeSO
47H
2The mass ratio of O, tertbutyl peroxide and rongalite is (0.5-1): (0.5-1): mixture (0.3-0.5), and the step of core-shell emulsion polymerization is as follows:
(1) polymerization
1.1 polymerized emulsion of pre-emulsification: with the 20-35% of water inventory, the emulsifying agent of 20-30% and all methyl methacrylate, vinylbenzene, methacrylic acid, vinyl cyanide, chain-transfer agent mixing prepare one time the polymerization pre-emulsion;
A 1.2 polymerization: the 35-50% that adds water inventory is added in the four-hole bottle, and one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds the FeSO of 40-60%
47H
2O drips the 50-70% tertbutyl peroxide is dissolved in the solution that forms in the 2-5% water, and then drips rongalite and be dissolved in the solution that forms in the 2-5% water, and reaction adds buffered soln again and obtains polymerized emulsion one time after finishing;
(2) after polymerization
2.1 pre-emulsification after polymerization emulsion: the 20-30% of water inventory, remaining emulsifying agent and hydroxyethyl methacrylate Ester are mixed, and preparation after polymerization pre-emulsion cools off stand-by;
2.2 after polymerization process: a polymerized emulsion is heated to 80 ℃, drips after polymerization pre-emulsion, phosphate ester monomer and remaining tertbutyl peroxide and be dissolved in the solution that forms in the 3-8% water, 3～4h dropwises, and then adds remaining FeSO
47H
2React under the O, heat-retaining condition.
The hydroxyethyl methacrylate Ester is preferably hydroxyethyl methylacrylate or hydroxyethyl methacrylate monooctyl ester.
Described emulsifying agent is preferably polyoxyethylene nonylphenol ether vitriol or allyl polyethenoxy ether derivative vitriol, and polyoxyethylene nonylphenol ether vitriol preferred molecular weight is 600-700.
Described chain-transfer agent is preferably Dodecyl Mercaptan.
It is 50% ammonia soln that described buffered soln is preferably massfraction.Buffered soln can disposable whole addings when a polymerization, also can add in two batches when a polymerization and after polymerization, as long as guarantee that the pH value of polymerized emulsion makes it to stablize.
The present invention introduces the phosphoric acid ester with flame retardant properties in the acrylic ester emulsion building-up process, transesterification reaction by comonomer vinylformic acid hydroxyl Ester and phosphoric acid ester, make phosphate group and multipolymer form covalent bonds, it is high that acrylic ester emulsion after the modification has possessed flame retarding efficiency, little and the eco-friendly characteristics of corrodibility, effectively reduced the heat decomposition temperature of acrylic ester emulsion, improved its thermal stability, simultaneously, the vertical combustion experimental result of the phosphate modified acrylic ester emulsion after the film forming shows, belong to flameless combustion behind the emulsion film forming after the modification, and extinguish behind the 2s combustion time, smokelessly, without dropping, and good mechanical property and adhesive property in the situation that thermostability improves greatly, have been guaranteed.This invention has guaranteed the expansion of acrylic ester emulsion range of application, and has guaranteed at application safeties in particular cases such as high temperature, fire, and environmental protection is had important contribution.The phosphoric acid ester material that the present invention uses is common material, need not to prepare especially function monomer, and price is far below the unsaturated monomer of phosphoric acid group, so product cost is lower.
Description of drawings
Fig. 1 is synthetic emulsion DSC curve: b (product of embodiment 2) after a, the modification before the modification.We can find out in the DSC curve, and we can find out from a curve, and 82.3 ℃ of endotherm(ic)peaks of locating are the endotherm(ic)peaks of sloughing planar water; 327.4 ℃ locate as sloughing the corresponding endotherm(ic)peak of organic substance decomposing in water of constitution and the acrylic ester emulsion; By contrast a, the b curve finds that the corresponding peak of b curve and a all to the high temperature direction migration has occured, and illustrates that the adding of phosphoric acid ester can delay organic heat decomposition temperature effectively, improves the thermal stability of emulsion;
Fig. 2 is the infrared spectrogram of Comparative Examples 1 (the front emulsion of modification) and embodiment 1 (phosphate modified rear emulsion).Among the figure, 3300cm
-1Absorption peak be-stretching vibration of OH 2950cm
-1Bimodal then be the stretching vibration of alkyl-CH, 1730cm
-1Stretching vibration for-C=O.1530-1590cm
-1Between multiplet be the association peak of phenyl ring, 1100cm
-1Stretching vibration for-C-O.As can be seen from Figure, existence owing to vinylformic acid hydroxyl ester in the Comparative Examples 1 gained acrylic ester emulsion has the strongest-OH vibration peak, and embodiment 1 is phosphate modified owing to having added, and-OH weakens at the peak, the basic disappearance advantageously proved the formation of phosphoric acid ester-acrylate compound thing structure.
Embodiment
In following examples, the emulsion property testing method is as follows:
1) film-forming properties
Carry out polymer cement waterproof paint according to following proportioning and film, coating thickness 1.5mm ± 0.2mm, maintenance under the standard conditions after the demoulding (curing condition: 23 ± 2 ℃ of temperature, humidity 60 ± 5%) 168h observe and are coated with membrane stage:
| Starting material | Weight (g) |
| Emulsion | 100 |
| Water | 145 |
| FOAMASTER TMThe NXZ defoamer | 0.5 |
| Silicate cement P.O.42.5 | 100 |
| Talcum powder 800 orders | 80 |
2) thermostability behind the emulsion film forming
Take by weighing 10g emulsion film forming in the tetrafluoroethylene mould, 50 ℃ of dryings 4 hours, carry out the DSC test, reference standard: GB/T19466.3-2004 plastics dsc (DSC) third part: the mensuration of temperature and enthalpy of melting and crystallization, and reference standard GB/T2408-1996 " Plastics Combustion method for testing performance Using Horizontal Bridgman Method and normal beam technique " carries out combustionproperty test, record heat decomposition temperature, combustion case and combustion time.
3) coating watertightness, cohesive strength, tensile property test
Reference standard: JC/T894-2001 " polymer cement waterproof paint " is according among the B 1) proportioning test.
Comparative Examples 1,
The component prescription is composed as follows:
Testing sequence: (1) monomer pre-emulsification: with 40% of water inventory, 50% polyoxyethylene nonylphenol ether vitriol, Sodium dodecylbenzene sulfonate emulsifying agent and whole ammonia soln join in the flask, drip methyl methacrylate, hydroxyethyl methylacrylate, vinylbenzene carries out the monomer pre-emulsification, time for adding 50min, temperature 40-50 ℃, stirring velocity 450-480r/min.
(2) letex polymerization: get 10% of above-mentioned pre-emulsification monomer and join in the remaining water, add simultaneously 80 ℃ of stirrings of remaining emulsifying agent, add 10% ammonium persulphate in this emulsion and stir 30min, emulsion presents light blue fluorescence, continue to drip remaining pre-emulsification monomer and initiator, time is controlled at 3-4h, and temperature is 75-80 ℃, obtains the emulsion of milky white colour band blue-fluorescence.
Comparative Examples 2,
The component prescription is composed as follows:
Testing sequence: (1) monomer pre-emulsification: with 40% of water inventory, 50% polyoxyethylene nonylphenol ether vitriol, Sodium dodecylbenzene sulfonate emulsifying agent and whole ammonia soln join in the flask, drip methyl methacrylate, hydroxyethyl methylacrylate, vinylbenzene carries out the monomer pre-emulsification, time for adding 50min, temperature 40-50 ℃, stirring velocity 450-480r/min.
(2) letex polymerization: get 10% of above-mentioned pre-emulsification monomer and join in the remaining water, add simultaneously 80 ℃ of stirrings of remaining emulsifying agent, add 10% ammonium persulphate in this emulsion and stir 30min, emulsion presents light blue fluorescence, continue to drip remaining pre-emulsification monomer and initiator, in dripping residue pre-emulsification monomer process, drip simultaneously the positive ethyl ester monomer of phosphoric acid, the front 30min that drips, emulsion, along with the emulsion viscosity that increases that drips the positive ethyl ester of phosphoric acid increases, there is gel seize phenomenon, the failure of an experiment to occur even occur.
The component prescription is composed as follows:
Synthesis step is as follows:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all methyl methacrylate, vinylbenzene, methacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of lower high-speed stirring prepare one time the polymerization pre-emulsion, cool off stand-by;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add again 50% massfraction and be 50% ammonia soln.The molecular weight 2000 of a polymerized emulsion, 0.2 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and hydroxyethyl methylacrylate be added in the four-hole boiling flask, 50 ℃ of lower high-speed stirring, preparation after polymerization pre-emulsion cools off stand-by;
The after polymerization process: a polymerized emulsion is heated to 80 ℃, drips after polymerization pre-emulsion, the positive ethyl ester monomer of phosphoric acid and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and then adds remaining FeSO
47H
2O, insulation 1h.
Show that by the scattering of light result emulsion molecular weight is 2800, particle diameter is 0.3 micron.
The emulsion property test result is as follows:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, without bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.85 | 307 | 1.13 | 0.3MPa 30min is |
| Embodiment | ||||
| 1 | 2.02 | 298 | 1.15 | 0.3MPa 30min is waterproof |
Embodiment 2,
The component prescription is composed as follows:
Synthesis step is as follows:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all methyl methacrylate, vinylbenzene, methacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of lower high-speed stirring prepare one time the polymerization pre-emulsion, cool off stand-by;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add again 50% massfraction and be 50% ammonia soln.The molecular weight 2200 of a polymerized emulsion, 0.2 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and hydroxyethyl methylacrylate class material be added in the four-hole boiling flask, 50 ℃ of lower high-speed stirring, preparation after polymerization pre-emulsion cools off stand-by;
The after polymerization process: a polymerized emulsion is heated to 80 ℃, drips after polymerization pre-emulsion, trichloroethyl phosphate and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and then adds remaining FeSO
47H
2O, insulation 1h.
Show that by the scattering of light result emulsion molecular weight is 3000, particle diameter is 0.3 micron.
The emulsion property test result:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, without bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.68 | 300 | 1.12 | 0.3MPa 30min is waterproof |
| Embodiment 2 | 1.81 | 287 | 1.15 | 0.3MPa 30min is waterproof |
Embodiment 3,
The component prescription is composed as follows:
Synthesis step is as follows:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all methyl methacrylate, vinylbenzene, methacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of lower high-speed stirring prepare one time the polymerization pre-emulsion, cool off stand-by;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add again 50% massfraction and be 50% ammonia soln.The molecular weight 3000 of a polymerized emulsion, 0.4 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and hydroxyethyl methacrylate monooctyl ester class material be added in the four-hole boiling flask, 50 ℃ of lower high-speed stirring, preparation after polymerization pre-emulsion cools off stand-by;
The after polymerization process: a polymerized emulsion is heated to 80 ℃, drips after polymerization pre-emulsion, trichlorine propyl phosphate and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and then adds remaining FeSO
47H
2O, insulation 1h.
Show that by the scattering of light result emulsion molecular weight is 4000, particle diameter is 0.4 micron.
The emulsion property test result is as follows:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, without bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.96 | 321 | 1.13 | 0.3MPa 30min is waterproof |
| Embodiment 3 | 2.12 | 308 | 1.15 | 0.3MPa 30min is waterproof |
Embodiment 4,
The component prescription is composed as follows:
Synthesis step is as follows:
(1) polymerization
With 20%, 30% emulsifying agent of water inventory and all methyl methacrylate, vinylbenzene, methacrylic acid, vinyl cyanide, Dodecyl Mercaptan join in the four-hole boiling flask, 50 ℃ of lower high-speed stirring prepare one time the polymerization pre-emulsion, cool off stand-by;
A polymerization process: add water inventory 50% in four-hole bottle, one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds 40%FeSO
47H
2O drips 70% tertbutyl peroxide is dissolved in the solution that forms in 2% water, and then drips rongalite and be dissolved in the solution that forms in 5% water, reaction 30min.Add again 50% massfraction and be 50% ammonia soln.The molecular weight 2600 of a polymerized emulsion, 0.3 micron of particle diameter.
(2) after polymerization
With water inventory 20%, remaining emulsifying agent and hydroxyethyl methacrylate monooctyl ester class material be added in the four-hole boiling flask, 50 ℃ of lower high-speed stirring, preparation after polymerization pre-emulsion cools off stand-by;
The after polymerization process: a polymerized emulsion is heated to 80 ℃, drips after polymerization pre-emulsion, trichloroethyl phosphate and remaining tertbutyl peroxide and be dissolved in the solution that forms in 3% water, 3.5h dropwises, and then adds remaining FeSO
47H
2O, insulation 1h.
Show that by the scattering of light result emulsion molecular weight is 3000, particle diameter is 0.3 micron.
The emulsion property test result:
1) film-forming properties
Specimen surface after maintenance is uniform and smooth, without bubble, hollowing, pinprick and orange peel phenomenon.
2) thermostability behind the emulsion film forming
3) coating watertightness, cohesive strength, tensile property test
| Sample | Tensile strength/MPa | Elongation at break/% | Cohesive strength/MPa | Watertightness |
| Comparative Examples 1 | 1.76 | 300 | 1.10 | 0.3MPa 30min is waterproof |
| Embodiment 4 | 1.98 | 286 | 1.13 | 0.3MPa 30min is waterproof |
Through the TEM test, Comparative Examples 1 and the resulting emulsion of embodiment 1-4 are complete form of spherical particles, and the inside and outside bright-dark degree of particle is different, and the outer layer depth of internal color can be inferred as the nucleocapsid structure with sphere.
Claims (6)
1. the preparation method of a phosphate modified acrylic ester emulsion is characterized in that,
(1) polymerization
To carry out a letex polymerization after 10-20 part methyl methacrylate, 2-3 part methacrylic acid, 1-2 part vinyl cyanide and the 10-15 part vinylbenzene pre-emulsification, obtain the polymerized emulsion that the pH value is 5-6 after adjusting the pH value, wherein polymericular weight is 2000-3000, and particle diameter is the 0.2-0.4 micron;
(2) after polymerization
After 30-45 part hydroxyethyl methacrylate Ester pre-emulsification, and 5-10 part phosphate ester monomer adds in polymerized emulsion together, carries out the secondary letex polymerization, obtains the phosphate modified acrylic ester emulsion of nucleocapsid structure,
Above-mentioned umber is mass fraction, described phosphate ester monomer is trichloroethyl phosphate, trichlorine propyl phosphate, described hydroxyethyl methacrylate Ester is hydroxyethyl methylacrylate or hydroxyethyl methacrylate monooctyl ester, the molecular weight of polymkeric substance is 2000-4000 in the phosphate modified acrylic ester emulsion of gained, and particle diameter is the 0.2-0.6 micron.
2. the preparation method of phosphate modified acrylic ester emulsion as claimed in claim 1 is characterized in that, uses altogether emulsifying agent 2-5 part in a described polymerization and the after polymerization process, initiator 0.3-0.6 part, chain-transfer agent 2-4 part.
3. the preparation method of a phosphate modified acrylic ester emulsion is characterized in that, the raw material that becomes with following quality group obtains through the core-shell emulsion polymerization method: methyl methacrylate 10-20%, methacrylic acid 2-3%, hydroxyethyl methacrylate Ester 30-45%, vinyl cyanide 1-2%, vinylbenzene 10-15%, phosphoric acid ester material 5-10%, emulsifying agent 2-5%, initiator 0.3-0.6%, chain-transfer agent 2-4%, buffered soln 3-5%, surplus is water, wherein, described initiator is FeSO
47H
2The mass ratio of O, tertbutyl peroxide and rongalite is (0.5-1): (0.5-1): mixture (0.3-0.5), described hydroxyethyl methacrylate Ester is hydroxyethyl methylacrylate or hydroxyethyl methacrylate monooctyl ester, and the step of core-shell emulsion polymerization is as follows:
(1) polymerization
1.1 polymerized emulsion of pre-emulsification: with the 20-35% of water inventory, the emulsifying agent of 20-30% and all methyl methacrylate, vinylbenzene, methacrylic acid, vinyl cyanide, chain-transfer agent mixing prepare one time the polymerization pre-emulsion;
A 1.2 polymerization: the 35-50% that adds water inventory is added in the four-hole bottle, and one time the polymerization pre-emulsion also joins in the four-hole bottle, is heated to 60 ℃, adds the FeSO of 40-60%
47H
2O drips the 50-70% tertbutyl peroxide is dissolved in the solution that forms in the 2-5% water, and then drips rongalite and be dissolved in the solution that forms in the 2-5% water, and reaction adds buffered soln again and obtains polymerized emulsion one time after finishing;
(2) after polymerization
2.1 pre-emulsification after polymerization emulsion: the 20-30% of water inventory, remaining emulsifying agent and hydroxyethyl methacrylate Ester are mixed, and preparation after polymerization pre-emulsion cools off stand-by;
2.2 after polymerization process: a polymerized emulsion is heated to 80 ℃, drips after polymerization pre-emulsion, phosphate ester monomer and remaining tertbutyl peroxide and be dissolved in the solution that forms in the 3-8% water, 3 ~ 4h dropwises, and then adds remaining FeSO
47H
2React under the O, heat-retaining condition.
4. the preparation method of phosphate modified acrylic ester emulsion as claimed in claim 2 or claim 3 is characterized in that described emulsifying agent is polyoxyethylene nonylphenol ether vitriol or allyl polyethenoxy ether derivative vitriol.
5. the preparation method of phosphate modified acrylic ester emulsion as claimed in claim 2 or claim 3 is characterized in that described chain-transfer agent is Dodecyl Mercaptan.
6. the preparation method of phosphate modified acrylic ester emulsion as claimed in claim 3 is characterized in that, described buffered soln is that massfraction is the ammonia soln of 30-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110309888 CN102408513B (en) | 2011-10-13 | 2011-10-13 | Preparation method of phosphate modified acrylate emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110309888 CN102408513B (en) | 2011-10-13 | 2011-10-13 | Preparation method of phosphate modified acrylate emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408513A CN102408513A (en) | 2012-04-11 |
| CN102408513B true CN102408513B (en) | 2013-03-13 |
Family
ID=45910895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110309888 Active CN102408513B (en) | 2011-10-13 | 2011-10-13 | Preparation method of phosphate modified acrylate emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408513B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964514B (en) * | 2012-11-23 | 2015-04-01 | 陕西科技大学 | Preparation method of polyacrylate emulsion containing silicon, fluorine and phosphate group |
| CN104098736B (en) * | 2013-04-07 | 2016-08-03 | 广东多正化工科技有限公司 | Hybrid silicon-containing modified acrylate emulsion and application thereof and preparation method |
| CN103897184B (en) * | 2014-04-16 | 2016-04-27 | 扬州大学 | A kind of preparation method of polyaniline-polyacrylic acid ester complexes |
| CN105111876B (en) * | 2014-07-27 | 2017-06-13 | 河北晨阳工贸集团有限公司 | Building, the preparation method of the core-shell type aqueous acrylic resin coating of furniture |
| CN104311725A (en) * | 2014-10-17 | 2015-01-28 | 上海应用技术学院 | Flame retardant polyacrylate emulsion and preparation method thereof |
| CN104497051A (en) * | 2014-12-20 | 2015-04-08 | 王树礼 | Method for preparing reactive type halogen-free flame retardant for coating |
| CN106478880B (en) * | 2016-10-16 | 2018-06-19 | 韶关市连邦环保新材料股份有限公司 | A kind of polyacrylate resin and preparation method thereof |
| CN106497286A (en) * | 2016-10-26 | 2017-03-15 | 中国人民解放军空军勤务学院 | A kind of metal anti-corrosive paint |
| CN108250877B (en) * | 2017-12-19 | 2020-07-17 | 吉力水性新材料科技（珠海）有限公司 | Phosphate modified acrylic water-based industrial coating |
| CN109749560B (en) * | 2019-01-25 | 2021-06-18 | 西安天亿胶粘材料有限公司 | High-heat-resistant resin for thermal transfer coating and preparation method thereof |
| CN111116781B (en) * | 2020-01-13 | 2022-10-11 | 上海大学 | Acrylic thermoplastic resin for halogen-free flame-retardant glass fiber reinforced composite material and preparation method thereof |
| CN114672211A (en) * | 2022-05-12 | 2022-06-28 | 甘肃公航旅永新材料科技有限公司 | Easily-cleaned high-solid highway guardrail coating with wet rust and preparation method thereof |
| CN116355479A (en) * | 2023-03-16 | 2023-06-30 | 深圳市鸿合创新信息技术有限责任公司 | Water-based paint, preparation method thereof and engineering plastic |
| CN117106346B (en) * | 2023-08-24 | 2024-03-12 | 科顺防水科技股份有限公司 | Waterproof coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250365A (en) * | 2008-03-28 | 2008-08-27 | 江苏荣昌化工有限公司 | Method for manufacturing acrylic ester emulsion containing phosphate group for antiseptic paint |
| CN101775101A (en) * | 2010-02-05 | 2010-07-14 | 广东工业大学 | Organic silicon / hydroxyl phosphate composite modified water emulsion acrylic resin and preparation method and application thereof |
-
2011
- 2011-10-13 CN CN 201110309888 patent/CN102408513B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250365A (en) * | 2008-03-28 | 2008-08-27 | 江苏荣昌化工有限公司 | Method for manufacturing acrylic ester emulsion containing phosphate group for antiseptic paint |
| CN101775101A (en) * | 2010-02-05 | 2010-07-14 | 广东工业大学 | Organic silicon / hydroxyl phosphate composite modified water emulsion acrylic resin and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408513A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408513B (en) | Preparation method of phosphate modified acrylate emulsion | |
| CN101580680B (en) | Crosslinkable polyethylene hot-melt adhesive composition and preparation method and application thereof | |
| CN104277172A (en) | Water-based waterproof acrylate emulsion and preparation method thereof | |
| CN102408853A (en) | Water-based body flame-resistant acrylate adhesive and preparation method thereof | |
| CN101448884A (en) | Expandable polyethylene resin particle and method for production thereof | |
| CN101982477A (en) | Acrylic emulsion capable of simultaneously modifying two silane coupling agents and preparation method thereof | |
| CN109054570B (en) | Environment-friendly high-strength elastic coating and preparation method thereof | |
| CN102964514A (en) | Preparation method of polyacrylate emulsion containing silicon, fluorine and phosphate group | |
| CN102492085A (en) | Organosilicon-modified styrene-acrylic architectural waterproof latex and preparation method thereof | |
| CN101781390A (en) | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall | |
| CN102190971A (en) | Preparation method of combined phosphorus type flame-retardant acrylic ester pressure-sensitive adhesive | |
| CN101092470A (en) | Method for preparing microemulsion with high solid content of crosslinked polystyrene and acrylic (ester) | |
| CN104031514B (en) | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of flame retardant resistance | |
| CN102533186A (en) | Adhesive for alkali resistant acrylate glass fiber mesh cloth shaping, and preparation method thereof | |
| CN104262530A (en) | Unmodified silica sol/polystyrene-acrylate nano core-shell emulsion and preparation method thereof | |
| CN105367697A (en) | Silicone acrylic emulsion having core-shell structure and preparation method thereof | |
| CN105418824A (en) | Reaction-activity-controllable acrylate emulsion and preparation method thereof | |
| CN103059212A (en) | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof | |
| CN105802421A (en) | Damping fireproof coating and preparing method thereof | |
| CN109796554B (en) | Elastic emulsion for zero-titanium system and preparation method thereof | |
| CN103554334A (en) | Internal plasticizing monomer-modified acrylate/inorganic nano composite emulsion and preparation method thereof | |
| CN105778595A (en) | Fire retardant coating for buildings | |
| CN102391800A (en) | Water-based flame-retardant acrylate pressure sensitive adhesive and preparation method thereof | |
| CN105062291B (en) | A kind of preparation method of fireproof coating | |
| CN105693944A (en) | Preparation method of high-temperature-resistant modified styrene acrylic emulsion |
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 | ||
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: JIANGSU SUBOTE NEW MATERIAL CO., LTD. JAINGSU ACADEMY OF BUILDING RESEARCH CO., LTD. Effective date: 20140514 Owner name: JIANGSU SUBOTE NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: BOTE NEW MATERIAL CO., LTD., JIANGSU Effective date: 20140514 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140514 Address after: 211103, No. 59 West Wan An Road, Jiangning District, Jiangsu, Nanjing Patentee after: Jiangsu Subute New Materials Co., Ltd. Address before: 211103, No. 59 West Wan An Road, Jiangning District, Jiangsu, Nanjing Patentee before: Jiangsu Bote New Materials Co., Ltd. Patentee before: Jiangsu Subute New Materials Co., Ltd. Patentee before: Jiangsu Provincial Architectural Science Institute Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 210008 No. 12, Beijing West Road, Gulou District, Nanjing City, Jiangsu Province Patentee after: Jiangsu Subute New Materials Co., Ltd. Address before: No. 59, Wan An West Road, Jiangning District, Nanjing, Jiangsu Patentee before: Jiangsu Subute New Materials Co., Ltd. |