CN102532404A - High-water-resistance acrylate emulsion and preparation method thereof - Google Patents
High-water-resistance acrylate emulsion and preparation method thereof Download PDFInfo
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- CN102532404A CN102532404A CN201110457958XA CN201110457958A CN102532404A CN 102532404 A CN102532404 A CN 102532404A CN 201110457958X A CN201110457958X A CN 201110457958XA CN 201110457958 A CN201110457958 A CN 201110457958A CN 102532404 A CN102532404 A CN 102532404A
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- 239000000839 emulsion Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 6
- 238000004945 emulsification Methods 0.000 title claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 33
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003973 paint Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 150000001282 organosilanes Chemical class 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- -1 acrylic ester Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 239000012874 anionic emulsifier Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 2
- BJBSSZXHNOQYAI-UHFFFAOYSA-N [Na].C(CC)S(=O)(=O)O.C(C(=C)C)(=O)OCCO Chemical compound [Na].C(CC)S(=O)(=O)O.C(C(=C)C)(=O)OCCO BJBSSZXHNOQYAI-UHFFFAOYSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract 1
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 150000002605 large molecules Chemical group 0.000 abstract 1
- 239000004816 latex Substances 0.000 abstract 1
- 229920000126 latex Polymers 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a high-water-resistance acrylate emulsion. The emulsion comprises the following raw materials in percentage by weight: 20%-25% of styrene, 15%-20% of butyl acrylate, 3%-5% of methyl methacrylate, 1%-3% of acrylic acid, 1%-2% of organic silicon monomer, 1%-2% of mixed emulsifying agent, 0.5% of sodium bicarbonate, 0.5% of initiator and the balance of water. According to the invention, in the emulsion polymerization process, a reaction type emulsifying agent is adopted to carry out a polymerization reaction, and the emulsifying agent is polymerized to a large molecule chain in the polymerization process, thereby reducing the transfer of the emulsifying agent in a paint film, reducing the water adsorption rate of the paint film and improving water resistance; through adopting a nucleus-shell polymerization process, a shell polymerization part is subjected to copolymerization modification with organic silicon, so that a hydrophobic structure is formed on the surface of a latex particle, thereby improving the water resistance after film formation finally; and through the synergistic effect of the two methods, the water resistance of the prepared emulsion is greatly improved and the prepared emulsion can be widely applied to production and preparation of paints for inner and outer walls.
Description
Technical field
The present invention relates to the synthetic field of macromolecular material, be specially a kind of enhanced water resistance acrylic ester emulsion that is mainly used in trade sales coating, the present invention also comprises this preparing acrylate emulsion method.
Background technology
Trade sales coating is very fast with the acrylic emulsion development in recent years, and is along with aqueous architectural coating obtains increasing application in life, also increasingly high to the acrylic emulsion performance demands.Process the problem that trade sales coating generally can face the water resistance difference by ordinary method synthetic acrylic emulsion, this is because emulsion can be applied to stronger emulsifying agent of some wetting abilities and hydrophilic monomer in the preparation process.These hydrophilic component can show very strong water-absorbent at coating surface; More particularly at the inner small-molecular emulsifier of paint film; Can absorbing moisture again with after water contacts, cause phenomenons such as paint film occurs turning white, bubbles even comes off along with the time moves to the surface.Therefore, how improving the water resistance behind the emulsion film forming, be not only the important topic in the synthetic field of coating emulsion, is a research direction of current emulsion polymerization technology.
Summary of the invention
Technical problem to be solved by this invention provides a kind of enhanced water resistance acrylic ester emulsion and preparation method thereof, the water tolerance after the raising coating emulsion film forming.
Technical problem of the present invention adopts following technical proposals to solve:
A kind of enhanced water resistance acrylate paint emulsion is characterized in that being prepared from following raw material and proportioning:
Vinylbenzene: 20%～25%, Bing Xisuandingzhi: 15%～20%, TEB 3K 3%～5%, vinylformic acid 1%～3%, an organosilane monomer 1%～2%, blending emulsifiers 1%～2%, sodium hydrogencarbonate 0.5%, initiator 0.5%, surplus is a water.
Described initiator is ammonium persulphate or Sodium Persulfate.
Described an organosilane monomer is γ-An Bingjisanyiyangjiguiwan (KH550) or γ-An Bingjisanjiayangjiguiwan (KH551).
The quality proportioning of each emulsifying agent is in the described blending emulsifiers: nonionic emulsifying agent: anionic emulsifier: reactive emulsifier=1:2:1～2.
Described anionic emulsifier is sodium lauryl sulphate (K12); Said nonionic emulsifying agent is OP-10; Said reactive emulsifier is: allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) or hydroxyethyl methacrylate propyl sulfonic acid sodium (HMPS).
Preparation technology's flow process of aforesaid propylene acid esters coating emulsion is following:
(1) 10% of water inventory with the initiator dissolving during usefulness was filled a prescription, and processed initiator solution, subsequent use;
(2) will fill a prescription in the blending emulsifiers total amount 60% with prescription in water inventory 40%, whole sodium hydrogencarbonate, and vinylformic acid, Bing Xisuandingzhi; Vinylbenzene, the methyl methacrylate polymerization monomer carries out high speed dispersion, the preparation pre-emulsion; Pre-emulsion is divided into A, two parts of B, the A:B weight ratio is 2:1; In B, adding an organosilane monomer mixes
(3) will fill a prescription in the blending emulsifiers total amount 40%; 50% of water inventory drops into reaction kettle in the prescription; Be warmed up to 80-85 ℃; Slowly add pre-emulsion A that configures and 6/10 of the initiator solution that configures, drip pre-emulsion B and 3/10 of the initiator solution that configures then, all pre-emulsions added at 3-3.5 hour;
(4) add 1/10 of the initiator solution that configures after, keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate emulsion viscosity, pack discharging at 90 ℃.
Major technique characteristics of the present invention are following:
1, in the process of letex polymerization, adopt the emulsifying agent of response type to carry out polyreaction, emulsifying agent participates in being aggregated on the macromolecular chain in polymerization process, has reduced the migration of emulsifying agent in paint film, has reduced the water-intake rate of paint film, has improved water tolerance.
2, through adopting the technology of nuclear-shell polymerization, adopt organosilicon to carry out modification by copolymerization, make the emulsion particle surface form a kind of hydrophobic structure, improved the water tolerance after the final film forming at the shell polymeric part.
Through the synergy of these two kinds of methods, can make the water tolerance behind the prepared emulsion film forming obtain very big raising, can be widely used in the production preparation of coating for internal and external wall.
Embodiment
Embodiment 1
Vinylbenzene 20g, Bing Xisuandingzhi 20g, TEB 3K 5g, vinylformic acid 1g, an organosilane monomer KH550 1g, blending emulsifiers 2g (op-10 0.4g, K12 0.8g, AHPS 0.8g), sodium hydrogencarbonate 0.5g, ammonium persulphate 0.5g, deionized water 50g.
(1) 0.5g ammonium persulphate and 5g water are mixed with initiator solution.（5mL）
(2) in the 200mL four-hole bottle, blending emulsifiers and 20g water, the 0.5g sodium hydrogencarbonate of 1.2g mixed; Add polymerization single polymerization monomers such as vinylformic acid 3g, Bing Xisuandingzhi 20g, vinylbenzene 20g, TEB 3K 5g then and carry out high speed dispersion; Preparation monomer pre-emulsion; Pre-emulsion is divided into A, and two parts of B (the A:B weight ratio is 2:1) add an organosilane monomer KH550 1g and mix in B.
(3) with the 0.8g blending emulsifiers; The water of 25g drops in the 200mL four-hole bottle; Be warmed up to 80-85 ℃, successively slowly drip pre-emulsion A and the pre-emulsion B that configures, drip initiator solution 4.5mL (always 90% of amount of initiator) simultaneously and carry out polyreaction; Whole process maintains the temperature at 80-85 ℃, and pre-emulsion and initiator all added about about 3-3.5 hour.
(4) add initiator solution 0.5mL (total amount of initiator 10%), keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate the emulsion pH value to 7-8, filter, pack with ammoniacal liquor at 90 ℃.
Embodiment 2
Vinylbenzene: 25g, Bing Xisuandingzhi: 15g, TEB 3K 3g, vinylformic acid 3g, an organosilane monomer KH551 2g, blending emulsifiers 1g (op-10 0.2g, K12 0.4g, HMPS 0.4g), sodium hydrogencarbonate 0.5g, Sodium Persulfate 0.5g, deionized water 50g.
Reaction process is following:
(1) 0.5g ammonium persulphate and 5g water are mixed with initiator solution (5mL).
(2) in the 200mL four-hole bottle, blending emulsifiers and 20g water, the 0.5g sodium hydrogencarbonate of 0.8g mixed, add the vinylformic acid of formula ratio then, Bing Xisuandingzhi; Vinylbenzene; Polymerization single polymerization monomers such as TEB 3K carry out high speed dispersion, and preparation monomer pre-emulsion is divided into A with pre-emulsion; Two parts of B (the A:B weight ratio is 2:1) add 1g KH-550 and mix in B.
(3) with the 1.2g blending emulsifiers; The water of 25g drops in the 200mL four-hole bottle; Be warmed up to 80-85 ℃, successively slowly drip pre-emulsion A and the pre-emulsion B that configures, drip initiator solution 4.32mL (always 90% of amount of initiator) simultaneously and carry out polyreaction; Whole process maintains the temperature at 80-85 ℃, and pre-emulsion and initiator all added about about 3-3.5 hour.
(4) add initiator 0.5mL (total amount of initiator 10%), keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate the emulsion pH value to 7-8, filter, pack with ammoniacal liquor at 90 ℃.
The above is merely and the present invention relates to the part instance; Other relate to instance because length is limit the present invention; Can not list one by one; In every case according to know-why of the present invention above instance is done equivalent modifications or proportioning variation in prescription given to this invention and technology, all within protection scope of the present invention.
Claims (6)
1. enhanced water resistance acrylate paint emulsion is characterized in that being prepared from following raw material and proportioning:
Vinylbenzene: 20%～25%, Bing Xisuandingzhi: 15%～20%, TEB 3K 3%～5%, vinylformic acid 1%～3%, an organosilane monomer 1%～2%, blending emulsifiers 1%～2%, sodium hydrogencarbonate 0.5%, initiator 0.5%, surplus is a water.
2. a kind of high water-resisting type acrylic ester emulsion according to claim 1 is characterized in that described initiator is ammonium persulphate or Sodium Persulfate.
3. a kind of high water-resisting type acrylic ester emulsion according to claim 1 is characterized in that described an organosilane monomer is γ-An Bingjisanyiyangjiguiwan (KH550) or γ-An Bingjisanjiayangjiguiwan (KH551).
4. a kind of high water-resisting type acrylic ester emulsion according to claim 1 is characterized in that the quality proportioning of each emulsifying agent in the described blending emulsifiers is: nonionic emulsifying agent: anionic emulsifier: reactive emulsifier=1:2:1～2.
5. according to claim 1 or 4 described a kind of enhanced water resistance acrylic ester emulsions, it is characterized in that described anionic emulsifier is sodium lauryl sulphate (K12); Said nonionic emulsifying agent is OP-10; Said reactive emulsifier is: allyloxy hydroxypropyl azochlorosulfonate acid sodium (AHPS) or hydroxyethyl methacrylate propyl sulfonic acid sodium (HMPS).
6. the described a kind of enhanced water resistance preparing acrylate emulsion method of claim 1 is characterized in that by following prepared:
(1) 10% of water inventory with the initiator dissolving during usefulness was filled a prescription, and processed initiator solution, subsequent use;
(2) will fill a prescription in the blending emulsifiers total amount 60% with prescription in water inventory 40%, whole sodium hydrogencarbonate, and vinylformic acid, Bing Xisuandingzhi; Vinylbenzene, the methyl methacrylate polymerization monomer carries out high speed dispersion, the preparation pre-emulsion; Pre-emulsion is divided into A; Two parts of B, the A:B weight ratio is 2:1, in B, adds an organosilane monomer and mixes;
(3) will fill a prescription in the blending emulsifiers total amount 40%; 50% of water inventory drops into reaction kettle in the prescription; Be warmed up to 80-85 ℃; Slowly add pre-emulsion A that configures and 6/10 of the initiator solution that configures, drip pre-emulsion B and 3/10 of the initiator solution that configures then, all pre-emulsions added at 3-3.5 hour;
(4) add 1/10 of the initiator solution that configures after, keep temperature of reaction, react 1 hour, be cooled to below 40 ℃, regulate emulsion viscosity, pack discharging at 90 ℃.
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| CN201110457958XA CN102532404B (en) | 2011-12-31 | 2011-12-31 | High-water-resistance acrylate emulsion and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964502A (en) * | 2012-11-06 | 2013-03-13 | 海南必凯水性涂料有限公司 | Water-resistant high-gloss water-based styrene-acrylic emulsion and preparation method thereof |
| CN103193924A (en) * | 2013-04-03 | 2013-07-10 | 衡水新光化工有限责任公司 | Phase-control film-formation styrene-acrylate painting emulsion and preparation method thereof |
| CN104193874A (en) * | 2014-08-27 | 2014-12-10 | 颐中（青岛）实业有限公司 | Modified styrene-acrylic emulsion with high glass transition temperature and low film formation temperature |
| CN104693340A (en) * | 2013-12-06 | 2015-06-10 | 上海展辰涂料有限公司 | Carpentry paint emulsion with core-shell structure and preparation method thereof |
| CN105348973A (en) * | 2015-11-24 | 2016-02-24 | 三棵树涂料股份有限公司 | Exterior wall coating containing silicone acrylic emulsion with core-shell structure and preparation method thereof |
| CN105601799A (en) * | 2016-01-05 | 2016-05-25 | 广州中国科学院工业技术研究院 | Core/shell type organosilicone-modified acrylate emulsion and preparation method and application thereof |
| CN106065044A (en) * | 2016-07-28 | 2016-11-02 | 苏州合志电子有限公司 | A kind of preparation method of woodcare paint styrene-acrylic emulsion |
| CN107082851A (en) * | 2017-05-25 | 2017-08-22 | 广东工业大学 | A kind of preparation method of water repellent type acrylic acid ester emulsion |
| CN104311739B (en) * | 2014-11-14 | 2017-11-24 | 杭州蓝励新材料有限公司 | Organic-silicon-modified styrene-butadiene latex and preparation method thereof |
| CN110857370A (en) * | 2018-08-24 | 2020-03-03 | 佛山朗能建材科技有限公司 | Hydrophobic elastic waterproof coating and preparation method thereof |
| CN111171215A (en) * | 2020-02-25 | 2020-05-19 | 北京汉莫克化学技术有限公司 | A kind of environment-friendly agricultural dispersant and preparation method thereof |
| CN111793401A (en) * | 2020-07-09 | 2020-10-20 | 西卡(上海)管理有限公司 | Waterproof coating and preparation method thereof |
| CN112194750A (en) * | 2019-07-08 | 2021-01-08 | 安徽米兰士装饰材料有限公司 | A kind of preparation method of environment-friendly acrylic emulsion transparent waterproof glue |
| CN114479595A (en) * | 2021-07-13 | 2022-05-13 | 江苏膜可光学材料有限公司 | Novel water-based environment-friendly paint for enhancing surface adhesive performance of packaging box and process flow |
| CN117659793A (en) * | 2023-12-05 | 2024-03-08 | 临沂大学 | A one-component waterproof coating based on fluorosilicone polyacrylate emulsion and its preparation method and application |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964502A (en) * | 2012-11-06 | 2013-03-13 | 海南必凯水性涂料有限公司 | Water-resistant high-gloss water-based styrene-acrylic emulsion and preparation method thereof |
| CN103193924A (en) * | 2013-04-03 | 2013-07-10 | 衡水新光化工有限责任公司 | Phase-control film-formation styrene-acrylate painting emulsion and preparation method thereof |
| CN103193924B (en) * | 2013-04-03 | 2016-01-20 | 衡水新光化工有限责任公司 | Phased film forming styrene-acrylic coating emulsion and preparation method |
| CN104693340A (en) * | 2013-12-06 | 2015-06-10 | 上海展辰涂料有限公司 | Carpentry paint emulsion with core-shell structure and preparation method thereof |
| CN104193874A (en) * | 2014-08-27 | 2014-12-10 | 颐中（青岛）实业有限公司 | Modified styrene-acrylic emulsion with high glass transition temperature and low film formation temperature |
| CN104193874B (en) * | 2014-08-27 | 2016-09-14 | 颐中（青岛）实业有限公司 | A kind of high glass transition temperature low film formation temperature modifying cinepazid emulsion |
| CN104311739B (en) * | 2014-11-14 | 2017-11-24 | 杭州蓝励新材料有限公司 | Organic-silicon-modified styrene-butadiene latex and preparation method thereof |
| CN105348973A (en) * | 2015-11-24 | 2016-02-24 | 三棵树涂料股份有限公司 | Exterior wall coating containing silicone acrylic emulsion with core-shell structure and preparation method thereof |
| CN105348973B (en) * | 2015-11-24 | 2017-08-15 | 三棵树涂料股份有限公司 | Silicon-acrylic lates outer wall coatings containing core shell structure and preparation method thereof |
| CN105601799A (en) * | 2016-01-05 | 2016-05-25 | 广州中国科学院工业技术研究院 | Core/shell type organosilicone-modified acrylate emulsion and preparation method and application thereof |
| CN106065044A (en) * | 2016-07-28 | 2016-11-02 | 苏州合志电子有限公司 | A kind of preparation method of woodcare paint styrene-acrylic emulsion |
| CN107082851A (en) * | 2017-05-25 | 2017-08-22 | 广东工业大学 | A kind of preparation method of water repellent type acrylic acid ester emulsion |
| CN110857370A (en) * | 2018-08-24 | 2020-03-03 | 佛山朗能建材科技有限公司 | Hydrophobic elastic waterproof coating and preparation method thereof |
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