CN102199240A - Preparation method of styrene-acrylate copolymer emulsion used in antirust paint - Google Patents
Preparation method of styrene-acrylate copolymer emulsion used in antirust paint Download PDFInfo
- Publication number
- CN102199240A CN102199240A CN 201110064224 CN201110064224A CN102199240A CN 102199240 A CN102199240 A CN 102199240A CN 201110064224 CN201110064224 CN 201110064224 CN 201110064224 A CN201110064224 A CN 201110064224A CN 102199240 A CN102199240 A CN 102199240A
- Authority
- CN
- China
- Prior art keywords
- component
- deionized water
- emulsion
- total amount
- acrylic ester
- 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.)
- Pending
Links
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a novel method for preparing a styrene-acrylate copolymer emulsion used in antirust primer paint. The method comprises steps that: (1) phosphate ester functional monomers are subject to a polymerization reaction; two hydroxyl groups of each phosphate ester group are subject to a chelation reaction on the metal surface, such that a dense phosphate ester (salt) protective film is formed on the metal surface, and water molecules and other salt ions are prevented from contacting the metal; the introduced phosphate ester group assists in improving the adhesion of painted coatings on metal surfaces, and in improving the antirust capacity of the painted coatings; (2) diacetone acrylamide (DAAM) and adipic dihydrazide (ADH) form a cross-linking system of the antirust emulsion; hydrazine groups in hydrazino-(NH2-NH2) and ketone groups in the DAAM (C=O) are subject to a dehydration condensation reaction, wherein the ketone groups are copolymerized on the copolymer; through outer cross-linking, a emulsion film with a three-dimensional reticular structure is obtained; (3) an emulsifying system is formed by combining a reactive anion emulsifier and a non-ion emulsifier, such that problems of emulsion deposition and gelling are solved. With the method provided by the invention, an aqueous emulsion with a high solid content is prepared, and water resistance and weathering resistance of the antirust paint is improved.
Description
Technical field
The invention belongs to field of polymer material preparing technology, the preparation method of a kind of rust proof paint with interpolymer latex of polystyrene and acrylic ester is provided especially.
Background technology
The financial loss that the whole world causes because of metallic corrosion every year is about 7000～10,000 hundred million dollars, is 6 times that natural disasteies such as earthquake, floods, typhoon cause the financial loss summation approximately, accounts for 2%～4% of various countries' gross national product (GDP).Be to reduce the loss that is caused because of corrosion, people have taked many measures for many years, but still effective, most economical up to now with protective system, use the most general.
Acrylic ester polymer (PA) is a saturated structures because of its main chain, so be that the coating of filmogen has excellent anti-outdoor aging with the acrylate copolymer, protects the light tint retention, is the polymkeric substance of cost performance optimum in all kinds of coating filmogens.The Water-borne modification of acrylate copolymer class rust proof paint is the difficult problem of coating industry always, and Water-borne modification is the inevitable development trend of rust proof paint.But Water-borne modification must solve following key issue: how (1) solves because of the sudden strain of a muscle rust of the introducing appearance of water, dodges the erosion problem; (2) how solve compactness, the water tolerance problem of the glued membrane of base-material acrylate copolymer from molecular designing, the design of emulsion particle form; (3) how to make the very low but problem that glued membrane hardness and compactness are better filmed behind the film forming curing cross-linked of Tg.
Chinese patent CN101250365 select for use contain bound phosphate groups acrylate monomer PAM100, PAM200 in the presence of water soluble starter in 70 ℃～90 ℃ with the acrylic ester monomer copolymerization, obtain can suppressing to dodge the antirust emulsion of rust.Though there are shortcomings such as the latex film degree of crosslinking is not enough, the salt water resistance performance is poor, PAM series phosphate ester monomer price height in the anti-rust excellent performance that dodges of its emulsion, is difficult to widely popularize on market.
Summary of the invention
The object of the present invention is to provide the preparation method of the rust proof paint of the simple excellent property of a kind of technology with the base-material emulsion.Problems such as sudden strain of a muscle rust, the paint film compactness that this method occurs when being used for rust proof paint at the water-based benzene emulsion is poor, salt water resistance performance difference, from monomer, emulsifying agent and molecular designing, with acrylic ester monomer, vinylbenzene etc. is main monomer, phosphoric acid ester function monomer APE-2005 and normal temperature crosslinked monomer DAAM are function monomer, become rusty, do all excellent waterborne anti-rust lacquer interpolymer latex of polystyrene and acrylic ester of wet sticking power in the hope of making anti-the sudden strain of a muscle in the presence of reactive emulsifier.
This patent is composite as emulsification system with response type anionic emulsifier and nonylphenol class nonionic emulsifying agent.The response type anionic emulsifier is usually by reactive double bond and the tensio-active agent that the anion sulfoacid group is formed, can improve bad phenomenon such as slagging scorification such as emulsion, coating, precipitation, gel, and help the water-based emulsion of high solids content to prepare, improve performances such as water tolerance, sticking power, weathering resistance.The nonylphenol class nonionic emulsifying agent improves the salt tolerance of emulsion.Common anionic emulsifier emulsifying capacity height, polymerization velocity is fast, the latex particle size of preparation is less, but salt stability is not as nonionic emulsifying agent, the purpose of selective reaction type anionic emulsifier is to reduce the migration of free emulsifying agent when film forming to produce phenomenon of phase separation, further improves compactness, the water tolerance of film.Selecting nonionic emulsifier simultaneously is the salt stability that improves emulsion, and insensitive to the variation of pH value.Therefore the compatibility of the two is all having good embodiment aspect polymerization behavior, the water tolerance.
The phosphate ester monomer (APE-2005) that this patent uses is that phosphoric acid and hydroxyethyl methylacrylate esterification obtain, and its monoester content is 80%, and dibasic acid esters content contains a spot of phosphoric acid 17%.It is similar to phosphoric acid to the metallic surface mechanism of action; be that two hydroxyls of bound phosphate groups and metallic surface chelatropic reaction takes place form fine and close phosphoric acid ester (salt) protective membrane in the metallic surface; form fine and close screen layer; prevent water molecules and other salt ions and metallic contact, have tangible antirust ability.In multipolymer, introduce the phosphoric acid ester functional group simultaneously and also improved the sticking power of filming, further increase the antirust ability of filming with the metallic surface.
This patent selects diacetone-acryloamide(DAA) (DAAM) and adipic dihydrazide (ADH) to form the cross-linking system of antirust benzene emulsion.Diazanyl (NH in the adipic dihydrazide
2-NH
2) and be copolymerized between the ketone carbonyl (C=O) in the diacetone-acryloamide(DAA) on the acrylic ester polymer dehydration condensation takes place, make the polymkeric substance of original linear structure become the latex film of tridimensional network by external crosslinking.
Concrete processing step is as follows:
A. emulsifying agent is dissolved in deionized water, mix the back and add initiator, wherein the emulsifying agent consumption is (20%～30%) of total amount, and the deionized water consumption is (40%～45%) of total amount, initiator amount is total amount (65%～70%), is made as component 1.
B. designing solid content is 40%～50%, second-order transition temperature (Tg) is 20 ℃～30 ℃, add deionized water, open and stir, begin to drip St (35%～40%), acrylate monomer (50%～60%), methacrylic acid (1%～3%), phosphoric acid ester function monomer (0%～5%) stirring and emulsifying 1h behind the adding emulsifying agent (1.0%～3.0%).Wherein the monomer consumption is total amount (95%～100%), and deionized water is (25%～30%) of total amount, and the emulsifying agent consumption is (70%～80%) of total amount, is made as component 2.
C. will remain initiator and be dissolved in deionized water, wherein initiator amount is (30%～35%) of total amount, and the deionized water consumption is (20%～25%) of total amount, is made as component 3.
D. DAAM (0%～5%) is dissolved in small amount of deionized water, is made as component 4.
The ADH (0%～2.5%) that e. will be equal to DAAM 50% mass ratio is dissolved in deionized water, is made as component 5.
F. the component 1 rebasing liquid that step a is obtained is put into reactor and is stirred, N
2Under the protection, water-bath is rapidly heated to 80 ℃～83 ℃, treats temperature-stable after 80 ℃, begins to drip component 2 that is obtained by step b and the component 3 that is obtained by step c, and the dropping time is controlled at 3.5h to 4.0h, begins to drip component 4 when dropping to half the time.The pH value of system changes in the observation process, suitably adds sodium bicarbonate aqueous solution, keeps the pH value between 3～5.
G. with being cooled to below 40 ℃ behind the above-mentioned emulsion insulation 1h that makes, add component 5, being neutralized to the pH value with ammoniacal liquor is 7～8, filters discharging and makes the antirust benzene emulsion of using.
2. according to right 1 described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester, it is characterized in that: described in steps percentage composition is mass percent.
3. according to the described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester of right 1, it is characterized in that: initiator can be for as ammonium persulphate (APS), Potassium Persulphate over cure acids such as (KPS).
4. according to the described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester of right 1, it is characterized in that: among the step b proportioning of anionic emulsifier and nonionic emulsifier can be 3: 1～1: 3; The response type anionic emulsifier can be for allyl ether series sulfonate, as COPS-1, and NRS-10 etc.; Nonionic emulsifying agent can be alkylphenol polyoxyethylene, as NP series etc.
5. according to right 1 described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester, it is characterized in that: the described acrylic ester monomer of step b can be for as ethyl propenoate (EA), methyl methacrylate (MMA), n-butyl acrylate materials such as (BA); The phosphoric acid ester function monomer is that phosphoric acid and hydroxyethyl methylacrylate esterification obtain, and its monoester content is 80%, and dibasic acid esters content contains a spot of phosphoric acid 17%.
The invention has the advantages that: owing to select the compound scheme of response type anionic emulsifier and nonionic emulsifying agent for use, the stability of emulsion polymerization excellence that makes, emulsion particle diameter is less, paint film density height, water-tolerant; Adopt the technology of phosphoric acid ester function monomer, vinylbenzene, acrylic ester monomer copolymerization, guarantee on the one hand the cheap of the popularity of raw material sources and cost, the more important thing is to have solved the sudden strain of a muscle rust problem that occurs when water-borne coatings is used for metal base, also further improve the dried wet sticking power of paint film on metal base; The adipic dihydrazide (ADH) of sneaking in diacetone-acryloamide(DAA) that polymerization is advanced in the macromolecular chain (DAAM) and the emulsion is formed antirust cross-linking system with benzene emulsion, guarantee on the one hand just crosslinking reaction can take place at normal temperatures, avoid some paint solidification need toast the energy consumption issues of bringing, in addition, this cross-linking system can obtain the degree of crosslinking more than 90%, paint film compactness height, water tolerance is significantly increased.
Project is enumerated
Embodiment
Embodiment 1
Steps A: take by weighing 0.72g COPS-1,0.30g CO-897 and 0.80gAPS respectively and be dissolved in the 60.00g deionized water, be made as component 1; Take by weighing 2.88g COPS-1 and 1.16g CO-897 is dissolved in the 40.00g deionized water, splash into 72.00g BA, 72.00g St, 25.20g MMA, 3.60g MAA, 3.60g APE-2005 phosphoric acid ester function monomer after stirring respectively, high-speed stirring 1h, obtain the oyster white pre-emulsion, be made as component 2; Take by weighing 0.40g APS and be dissolved in the 35.00g deionized water, be made as component 3; Take by weighing 3.60g DAAM and be dissolved in the 5.00g deionized water, be made as component 4; Take by weighing 1.80gADH and be dissolved in the 18.00g deionized water, be made as component 5.
Step B: component 1 is placed at N
2In the 1000mL four-hole boiling flask under protection, the quick agitation condition; be rapidly heated to 80 ℃～83 ℃ by water-bath; treat temperature-stable (10min～15min) after 80 ℃; adopt the semi-continuous emulsion polymerizing method; component 2 and component 3 are added drop-wise in the above-mentioned system, and the time of dropping always is about 4h, (a half that wherein is about total amount at the dropping monomer; begin to drip component 4), be incubated 1h then.
Step C: above-mentioned emulsion is cooled to below 40 ℃, is neutralized to pH 7～8 with ammoniacal liquor, disposable adding component 5 stirs the discharging of 30min after-filtration, obtains the waterborne anti-rust benzene emulsion.
Measure emulsion according to GB/T 1725-2007, the cohesion rate is 0.30%; By the sticking power of GB/T 1720-1979 (1989) with the method mensuration emulsion glued membrane of drawing a circle, it does wet sticking power is 2 grades; The hardness of measuring emulsion film by GB/T 6739-2006 is 4H; 100 ℃ of dryings in IR bake again after the emulsion room temperature 7d film forming are measured its degree of crosslinking and are about 80%; Measure the salt water resistance performance of filming by GB/T 10834-2008, the result shows behind the saline soak 280h bubble and slight iron mold.Rust appears dodging within 10min.
Embodiment 2
Steps A: take by weighing 1.08g COPS-1,0.43g CO-897 and 0.80gAPS respectively and be dissolved in the 60.00g deionized water, be made as component 1; Take by weighing 4.32g COPS-1 and 1.73g CO-897 is dissolved in the 40.00g deionized water, splash into 72.00g BA, 70.20g St, 25.20g MMA, 3.60g MAA, 3.60g APE-2005 phosphoric acid ester function monomer after stirring respectively, high-speed stirring 1h, obtain the oyster white pre-emulsion, be made as component 2; Take by weighing 0.40g APS and be dissolved in the 35.00g deionized water, be made as component 3; Take by weighing 5.40g DAAM and be dissolved in the 5.00g deionized water, be made as component 4; Take by weighing 2.70gADH and be dissolved in the 27.00g deionized water, be made as component 5.
Other steps are shown in embodiment 1.
Measure emulsion according to GB/T 1725-2007, the cohesion rate is 0.20%; By the sticking power of GB/T 1720-1979 (1989) with the method mensuration emulsion glued membrane of drawing a circle, it does wet sticking power is 2 grades; The hardness of measuring emulsion film by GB/T 6739-2006 is 4H; 100 ℃ of dryings in IR bake again after the emulsion room temperature 7d film forming are measured its degree of crosslinking and are about 90%; Measure the salt water resistance performance of filming by GB/T 10834-2008, the result shows behind the saline soak 400h bubble and slight iron mold.
Embodiment 3
Steps A: take by weighing 1.08g COPS-1,0.43g CO-897 and 0.80gAPS respectively and be dissolved in the 60.00g deionized water, be made as component 1; Take by weighing 4.32g COPS-1 and 1.73g CO-897 is dissolved in the 40.00g deionized water, splash into 70.20g BA, 70.20g St, 23.40g MMA, 3.60g MAA, 7.20g APE-2005 phosphoric acid ester function monomer after stirring respectively, high-speed stirring 1h, obtain the oyster white pre-emulsion, be made as component 2; Take by weighing 0.40g APS and be dissolved in the 35.00g deionized water, be made as component 3; Take by weighing 5.40g DAAM and be dissolved in the 5.00g deionized water, be made as component 4; Take by weighing 2.70gADH and be dissolved in the 27.00g deionized water, be made as component 5.
Other steps are shown in embodiment 1.
Measure emulsion according to GB/T 1725-2007, the cohesion rate is 0.52%; By the sticking power of GB/T 1720-1979 (1989) with the method mensuration emulsion glued membrane of drawing a circle, it does wet sticking power is 1 grade; The hardness of measuring emulsion film by GB/T 6739-2006 is 3H; 100 ℃ of dryings in IR bake again after the emulsion room temperature 7d film forming are measured its degree of crosslinking and are about 90%; Measure the salt water resistance performance of filming by GB/T 10834-2008, the result shows behind the saline soak 400h bubble and slight iron mold; Not having the rust of sudden strain of a muscle phenomenon occurs.
Embodiment 4
Steps A: take by weighing 1.08g COPS-1,0.43g CO-897 and 0.80gAPS respectively and be dissolved in the 60.00g deionized water, be made as component 1; Take by weighing 4.32g COPS-1 and 1.73g CO-897 is dissolved in the 40.00g deionized water, splash into 69.30g BA, 69.30g St, 23.40g MMA, 3.60g MAA, 9.00g APE-2005 phosphoric acid ester function monomer after stirring respectively, high-speed stirring 1h, obtain the oyster white pre-emulsion, be made as component 2; Take by weighing 0.40g APS and be dissolved in the 35.00g deionized water, be made as component 3; Take by weighing 5.40g DAAM and be dissolved in the 5.00g deionized water, be made as component 4; Take by weighing 2.70gADH and be dissolved in the 27.00g deionized water, be made as component 5.
Other steps are shown in embodiment 1.
Measure emulsion according to GB/T 1725-2007, the cohesion rate is 0.80%; By the sticking power of GB/T 1720-1979 (1989) with the method mensuration emulsion glued membrane of drawing a circle, it does wet sticking power is 1 grade; The hardness of measuring emulsion film by GB/T 6739-2006 is 3H; 100 ℃ of dryings in IR bake again after the emulsion room temperature 7d film forming are measured its degree of crosslinking and are about 90%; Measure the salt water resistance performance of filming by GB/T 10834-2008, the result shows behind the saline soak 380h bubble and slight iron mold; Not having the rust of sudden strain of a muscle phenomenon occurs.
Embodiment 5
Steps A: take by weighing 1.08g COPS-1,0.43g CO-897 and 0.80gAPS respectively and be dissolved in the 60.00g deionized water, be made as component 1; Take by weighing 4.32g COPS-1 and 1.73g CO-897 is dissolved in the 40.00g deionized water, splash into 69.30g BA, 69.30g St, 25.20g MMA, 3.60g MAA, 7.20g APE-2005 phosphoric acid ester function monomer after stirring respectively, high-speed stirring 1h, obtain the oyster white pre-emulsion, be made as component 2; Take by weighing 0.40g APS and be dissolved in the 35.00g deionized water, be made as component 3; Take by weighing 5.40g DAAM and be dissolved in the 5.00g deionized water, be made as component 4; Take by weighing 2.70gADH and be dissolved in the 27.00g deionized water, be made as component 5.
Other steps are shown in embodiment 1.
Measure emulsion according to GB/T 1725-2007, the cohesion rate is 0.54%; By the sticking power of GB/T 1720-1979 (1989) with the method mensuration emulsion glued membrane of drawing a circle, it does wet sticking power is 1 grade; The hardness of measuring emulsion film by GB/T 6739-2006 is 3H; 100 ℃ of dryings in IR bake again after the emulsion room temperature 7d film forming are measured its degree of crosslinking and are about 90%; Measure the salt water resistance performance of filming by GB/T 10834-2008, the result shows behind the saline soak 480h bubble and slight iron mold; Not having the rust of sudden strain of a muscle phenomenon occurs.
Claims (5)
1. a rust proof paint is with the method for interpolymer latex of polystyrene and acrylic ester, and its preparation process is:
A. emulsifying agent is dissolved in deionized water, mix the back and add initiator, wherein the emulsifying agent consumption is (20%～30%) of total amount, and the deionized water consumption is (40%～45%) of total amount, initiator amount is total amount (65%～70%), is made as component 1.
B. designing solid content is 40%～50%, second-order transition temperature (Tg) is 20 ℃～30 ℃, add deionized water, open and stir, begin to drip St (35%～40%), acrylate monomer (50%～60%), methacrylic acid (1%～3%), phosphoric acid ester function monomer (0%～5%) stirring and emulsifying 1h behind the adding emulsifying agent (1.0%～3.0%).Wherein the monomer consumption is total amount (95%～100%), and deionized water is (25%～30%) of total amount, and the emulsifying agent consumption is (70%～80%) of total amount, is made as component 2.
C. will remain initiator and be dissolved in deionized water, wherein initiator amount is (30%～35%) of total amount, and the deionized water consumption is (20%～25%) of total amount, is made as component 3.
D. DAAM (0%～5%) is dissolved in small amount of deionized water, is made as component 4.
The ADH (0%～2.5%) that e. will be equal to the DAAM50% mass ratio is dissolved in deionized water, is made as component 5.
F. the component 1 rebasing liquid that step a is obtained is put into reactor and is stirred, N
2Under the protection, water-bath is rapidly heated to 80 ℃～83 ℃, treats temperature-stable after 80 ℃, begins to drip component 2 that is obtained by step b and the component 3 that is obtained by step c, and the dropping time is controlled at 3.5h to 4.0h, begins to drip component 4 when dropping to half the time.The pH value of system changes in the observation process, suitably adds sodium bicarbonate aqueous solution, keeps the pH value between 3～5.
G. with being cooled to below 40 ℃ behind the above-mentioned emulsion insulation 1h that makes, add component 5, being neutralized to the pH value with ammoniacal liquor is 7～8, filters discharging and makes the rust proof paint interpolymer latex of polystyrene and acrylic ester.
2. according to right 1 described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester, it is characterized in that: described in steps percentage composition is mass percent.
3. according to the described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester of right 1, it is characterized in that: initiator can be for as ammonium persulphate (APS), Potassium Persulphate over cure acids such as (KPS).
4. according to the described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester of right 1, it is characterized in that: among the step a proportioning of response type anionic emulsifier and nonionic emulsifier can be 3: 1～1: 3; The response type anionic emulsifier can be for allyl ether series sulfonate, as COPS-1, and NRS-10 etc.; Nonionic emulsifying agent can be alkylphenol polyoxyethylene, as NP series etc.
5. according to right 1 described a kind of method for preparing rust proof paint with interpolymer latex of polystyrene and acrylic ester, it is characterized in that: the described acrylic ester monomer of step b can be for as ethyl propenoate (EA), methyl methacrylate (MMA), n-butyl acrylate materials such as (BA); The phosphoric acid ester function monomer is that phosphoric acid and hydroxyethyl methylacrylate esterification obtain, and contains monoesters and dibasic acid esters and a spot of phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110064224 CN102199240A (en) | 2011-03-17 | 2011-03-17 | Preparation method of styrene-acrylate copolymer emulsion used in antirust paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110064224 CN102199240A (en) | 2011-03-17 | 2011-03-17 | Preparation method of styrene-acrylate copolymer emulsion used in antirust paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102199240A true CN102199240A (en) | 2011-09-28 |
Family
ID=44660253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110064224 Pending CN102199240A (en) | 2011-03-17 | 2011-03-17 | Preparation method of styrene-acrylate copolymer emulsion used in antirust paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102199240A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432743A (en) * | 2011-11-25 | 2012-05-02 | 常州光辉化工有限公司 | Polymer emulsion for waterborne metal anticorrosive coating and preparation method of polymer emulsion |
| CN103319645A (en) * | 2013-05-31 | 2013-09-25 | 南京洁雅新材料有限公司 | Water-based metallic protective agent and productive technology thereof |
| CN103555109A (en) * | 2013-11-11 | 2014-02-05 | 山东乐化漆业股份有限公司 | Water-based antirust paint and preparation method thereof |
| CN103833888A (en) * | 2013-09-22 | 2014-06-04 | 西安佳龙油漆新技术发展有限公司 | Preparation method of aqueous fluorine-modified phosphorus-containing acrylate emulsion |
| CN104892816A (en) * | 2015-05-13 | 2015-09-09 | 衡水新光化工有限责任公司 | In-situ nano hybridization styrene-acrylic emulsion and rust-resisting paint using the emulsion as base material |
| CN105273117A (en) * | 2015-10-17 | 2016-01-27 | 佛山市顺德区巴德富实业有限公司 | Styrene-acrylic emulsion with flash rust prevention function and preparation method of styrene-acrylic emulsion |
| CN105294906A (en) * | 2014-06-18 | 2016-02-03 | 上海丰野表面处理剂有限公司 | Water-based acrylic emulsion used for antimicrobial and corrosion resistant primer and antimicrobial and corrosion resistant primer |
| CN105440862A (en) * | 2015-12-02 | 2016-03-30 | 铜陵市肆得科技有限责任公司 | Modified waste plastic added anticorrosive coating for pump valve |
| CN105440867A (en) * | 2015-12-02 | 2016-03-30 | 铜陵市肆得科技有限责任公司 | Anti-corrosive pump valve acrylic coating with anti-oxidation and antistatic effects |
| CN105462421A (en) * | 2015-12-02 | 2016-04-06 | 铜陵市肆得科技有限责任公司 | Water-borne acrylic coating having high combination property and applied to pump valve |
| CN105482598A (en) * | 2015-12-02 | 2016-04-13 | 铜陵市肆得科技有限责任公司 | New waterproof self-drying acrylic anti-rust paint |
| CN105505085A (en) * | 2015-12-02 | 2016-04-20 | 铜陵市肆得科技有限责任公司 | Novel rusted and anti-rust water-based acrylic coating for pump valves |
| CN105693938A (en) * | 2014-11-28 | 2016-06-22 | 合众（佛山）化工有限公司 | Preparation method of imidized SMA modified cationic styrene-acrylic emulsion |
| CN106565893A (en) * | 2016-10-21 | 2017-04-19 | 中山市巴德富化工科技有限公司 | Water-based styrene-acrylic emulsion for primer and topcoat integrated metallic paint and preparation method of water-based styrene-acrylic emulsion |
| CN106589213A (en) * | 2016-12-15 | 2017-04-26 | 佛山海特化工科技有限公司 | Self-crosslinkingacrylic emulsion for water-based metallic paint and preparation method thereof |
| CN107434837A (en) * | 2017-09-08 | 2017-12-05 | 江门市制漆厂有限公司 | A kind of priming paint acrylic resin and preparation method thereof |
| CN108641029A (en) * | 2018-04-19 | 2018-10-12 | 常州顺斯康复合新材料有限公司 | A kind of metal protection water-and acrylate is from dry nanoemulsions and preparation method thereof |
| CN109111815A (en) * | 2018-08-14 | 2019-01-01 | 江苏欣特蓝水性纳米科技有限公司 | A kind of PVC water-and acrylate nano coating lotion |
| CN110642974A (en) * | 2019-09-17 | 2020-01-03 | 湖北工业大学 | Preparation method of polar small monomer modified sulfonic benzene ring core-shell emulsion polymer |
| CN111234078A (en) * | 2019-05-22 | 2020-06-05 | 五邑大学 | Antirust acrylate emulsion and preparation method thereof |
| CN111356707A (en) * | 2017-11-22 | 2020-06-30 | 阿科玛法国公司 | Emulsion polymer compositions and their use in low odor water resistant coatings |
| CN112239518A (en) * | 2020-10-10 | 2021-01-19 | 湘江涂料科技有限公司 | Acrylic acid copolymer emulsion for improving early water resistance and glossiness of coating and application thereof |
| CN112409531A (en) * | 2020-10-19 | 2021-02-26 | 惠州市惠阳区嘉泰涂料有限公司 | Water-based acrylic emulsion and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0013836A1 (en) * | 1978-12-29 | 1980-08-06 | Rohm And Haas Company | Compositions containing acrylic emulsion copolymers and their use as thickeners |
| EP0816404A2 (en) * | 1996-06-28 | 1998-01-07 | Dow Corning Toray Silicone Company, Limited | Methods for preparing silicone-modified vinyl polymers |
| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN101787097A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Preparation method of water-soluble solid styrene-acrylic resin |
-
2011
- 2011-03-17 CN CN 201110064224 patent/CN102199240A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0013836A1 (en) * | 1978-12-29 | 1980-08-06 | Rohm And Haas Company | Compositions containing acrylic emulsion copolymers and their use as thickeners |
| EP0816404A2 (en) * | 1996-06-28 | 1998-01-07 | Dow Corning Toray Silicone Company, Limited | Methods for preparing silicone-modified vinyl polymers |
| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN101787097A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Preparation method of water-soluble solid styrene-acrylic resin |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432743B (en) * | 2011-11-25 | 2014-03-05 | 常州光辉化工有限公司 | Polymer emulsion for waterborne metal anticorrosive coating and preparation method of polymer emulsion |
| CN102432743A (en) * | 2011-11-25 | 2012-05-02 | 常州光辉化工有限公司 | Polymer emulsion for waterborne metal anticorrosive coating and preparation method of polymer emulsion |
| CN103319645A (en) * | 2013-05-31 | 2013-09-25 | 南京洁雅新材料有限公司 | Water-based metallic protective agent and productive technology thereof |
| CN103319645B (en) * | 2013-05-31 | 2016-08-10 | 南京洁雅新材料有限公司 | A kind of part aqueous metal protection agent and production technology thereof |
| CN103833888A (en) * | 2013-09-22 | 2014-06-04 | 西安佳龙油漆新技术发展有限公司 | Preparation method of aqueous fluorine-modified phosphorus-containing acrylate emulsion |
| CN103555109A (en) * | 2013-11-11 | 2014-02-05 | 山东乐化漆业股份有限公司 | Water-based antirust paint and preparation method thereof |
| CN103555109B (en) * | 2013-11-11 | 2016-01-06 | 山东乐化漆业股份有限公司 | A kind of aqueous antirust paint and preparation method thereof |
| CN105294906A (en) * | 2014-06-18 | 2016-02-03 | 上海丰野表面处理剂有限公司 | Water-based acrylic emulsion used for antimicrobial and corrosion resistant primer and antimicrobial and corrosion resistant primer |
| CN105693938A (en) * | 2014-11-28 | 2016-06-22 | 合众（佛山）化工有限公司 | Preparation method of imidized SMA modified cationic styrene-acrylic emulsion |
| CN105693938B (en) * | 2014-11-28 | 2018-06-26 | 合众（佛山）化工有限公司 | A kind of preparation method of imidizate SMA modified cation styrene-acrylic emulsions |
| CN104892816A (en) * | 2015-05-13 | 2015-09-09 | 衡水新光化工有限责任公司 | In-situ nano hybridization styrene-acrylic emulsion and rust-resisting paint using the emulsion as base material |
| CN105273117A (en) * | 2015-10-17 | 2016-01-27 | 佛山市顺德区巴德富实业有限公司 | Styrene-acrylic emulsion with flash rust prevention function and preparation method of styrene-acrylic emulsion |
| CN105505085A (en) * | 2015-12-02 | 2016-04-20 | 铜陵市肆得科技有限责任公司 | Novel rusted and anti-rust water-based acrylic coating for pump valves |
| CN105462421A (en) * | 2015-12-02 | 2016-04-06 | 铜陵市肆得科技有限责任公司 | Water-borne acrylic coating having high combination property and applied to pump valve |
| CN105440867A (en) * | 2015-12-02 | 2016-03-30 | 铜陵市肆得科技有限责任公司 | Anti-corrosive pump valve acrylic coating with anti-oxidation and antistatic effects |
| CN105482598A (en) * | 2015-12-02 | 2016-04-13 | 铜陵市肆得科技有限责任公司 | New waterproof self-drying acrylic anti-rust paint |
| CN105440862A (en) * | 2015-12-02 | 2016-03-30 | 铜陵市肆得科技有限责任公司 | Modified waste plastic added anticorrosive coating for pump valve |
| CN106565893B (en) * | 2016-10-21 | 2019-02-05 | 成都巴德富科技有限公司 | A kind of bottom surface unification metallic paint waterborne styrene-acrylic emulsion and preparation method thereof |
| CN106565893A (en) * | 2016-10-21 | 2017-04-19 | 中山市巴德富化工科技有限公司 | Water-based styrene-acrylic emulsion for primer and topcoat integrated metallic paint and preparation method of water-based styrene-acrylic emulsion |
| CN106589213A (en) * | 2016-12-15 | 2017-04-26 | 佛山海特化工科技有限公司 | Self-crosslinkingacrylic emulsion for water-based metallic paint and preparation method thereof |
| CN106589213B (en) * | 2016-12-15 | 2019-05-03 | 广东海特高新材料有限公司 | A kind of aqueous metallic paint self-crosslinking acrylic lotion and preparation method thereof |
| CN107434837B (en) * | 2017-09-08 | 2019-10-29 | 江门市制漆厂有限公司 | A kind of priming paint acrylic resin and preparation method thereof |
| CN107434837A (en) * | 2017-09-08 | 2017-12-05 | 江门市制漆厂有限公司 | A kind of priming paint acrylic resin and preparation method thereof |
| CN111356707A (en) * | 2017-11-22 | 2020-06-30 | 阿科玛法国公司 | Emulsion polymer compositions and their use in low odor water resistant coatings |
| CN108641029A (en) * | 2018-04-19 | 2018-10-12 | 常州顺斯康复合新材料有限公司 | A kind of metal protection water-and acrylate is from dry nanoemulsions and preparation method thereof |
| CN109111815A (en) * | 2018-08-14 | 2019-01-01 | 江苏欣特蓝水性纳米科技有限公司 | A kind of PVC water-and acrylate nano coating lotion |
| CN111234078A (en) * | 2019-05-22 | 2020-06-05 | 五邑大学 | Antirust acrylate emulsion and preparation method thereof |
| CN110642974A (en) * | 2019-09-17 | 2020-01-03 | 湖北工业大学 | Preparation method of polar small monomer modified sulfonic benzene ring core-shell emulsion polymer |
| CN112239518A (en) * | 2020-10-10 | 2021-01-19 | 湘江涂料科技有限公司 | Acrylic acid copolymer emulsion for improving early water resistance and glossiness of coating and application thereof |
| CN112239518B (en) * | 2020-10-10 | 2023-11-21 | 湘江涂料科技有限公司 | Acrylic copolymer emulsion for improving early water resistance and glossiness of coating and application thereof |
| CN112409531A (en) * | 2020-10-19 | 2021-02-26 | 惠州市惠阳区嘉泰涂料有限公司 | Water-based acrylic emulsion and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102199240A (en) | Preparation method of styrene-acrylate copolymer emulsion used in antirust paint | |
| CN101429267B (en) | Preparation and uses of epoxy/acrylic acid hybridisation emulsion | |
| CN102115517B (en) | Preparation method for anti-rust soap-free acrylate emulsion | |
| CN101585899B (en) | Cationic modified epoxy resin emulsion and preparation method and application thereof | |
| CN101597355B (en) | Water-based room temperature crosslinking acrylic acid emulsion and preparation method thereof | |
| DE50010894D1 (en) | Aqueous coating agent, process for its preparation and its use | |
| CN102127271A (en) | Water-based epoxy modified phosphorus-containing styrene-acrylic antirust emulsion and synthesis method thereof | |
| CN102838712A (en) | Preparation method of hydroxyl-terminated aqueous core shell emulsion for anticorrosive paint | |
| CN112409877A (en) | Preparation method of flame-retardant water-based core-shell acrylate resin coating | |
| CN101283041B (en) | Aqueous dispersion | |
| CN103059212A (en) | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof | |
| CN102807643B (en) | Emulsifying agent for emulsion polymerization and preparation method thereof | |
| CN102532403A (en) | Shell-structure acrylic emulsion for dispersible glue powder and preparation method of shell-structure acrylic emulsion | |
| CN103833888A (en) | Preparation method of aqueous fluorine-modified phosphorus-containing acrylate emulsion | |
| CN110591006A (en) | Preparation method of high-temperature-resistant film-forming styrene-acrylic emulsion for paper printing | |
| CN108359047A (en) | A kind of waterborne acrylic paint and preparation method thereof that graphene is modified | |
| CN104045173A (en) | Novel non-phosphorus quadripolymer scale inhibitor and preparation method thereof | |
| CN101967213A (en) | Preparation method of carboxyl-contained polyacrylic ester with low molecular weight | |
| CN102241798A (en) | Manufacture method of synthetic resin from waste polystyrene foamed plastic | |
| CN105693944A (en) | Preparation method of high-temperature-resistant modified styrene acrylic emulsion | |
| CN101445574B (en) | Core-shell polymer emulsion for manufacturing re-dispersible latex powder, and preparation method thereof | |
| CN114276637A (en) | Composite dispersing agent for grinding nano calcium carbonate and preparation method thereof | |
| CN102002125B (en) | Acrylic resin emulsion for fingerprint-resistant paint and preparation method thereof | |
| CN104098767A (en) | Preparation method of polyaniline-epoxy graft modified acrylic ester compound | |
| CN109897132A (en) | A kind of acrylic acid ester emulsion and preparation method thereof with flame retarding function |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110928 |