CN102532401A - Elastic emulation and preparation method thereof - Google Patents
Elastic emulation and preparation method thereof Download PDFInfo
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- CN102532401A CN102532401A CN2011104407988A CN201110440798A CN102532401A CN 102532401 A CN102532401 A CN 102532401A CN 2011104407988 A CN2011104407988 A CN 2011104407988A CN 201110440798 A CN201110440798 A CN 201110440798A CN 102532401 A CN102532401 A CN 102532401A
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- elastic emulsion
- deionized water
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- emulsion
- monomer
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000004945 emulsification Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 8
- 239000004816 latex Substances 0.000 claims description 8
- 229920000126 latex Polymers 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- -1 organosilicon Substances 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 230000002902 bimodal effect Effects 0.000 claims description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000011109 contamination Methods 0.000 abstract description 2
- 239000003002 pH adjusting agent Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002449 FKM Polymers 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical class CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to elastic emulation, which is formed by polymerizing hard monomers, soft monomers, functional monomers, composite emulsifiers, organic silicon, initiators, pH modifiers and deionized water. A preparation method of the elastic emulation is further provided. The elastic emulation has high elasticity, better anti-contamination performance, lower film-forming temperature and better waterproof performance and is capable of being widely used in the preparation processing of building coatings such as outer wall systems and waterproof coating systems, particularly application systems where emulation has elasticity and film-forming temperature is lower.
Description
Technical field
The present invention relates to trade sales coating and use emulsion, relate in particular to a kind of elastic emulsion and preparation method thereof.
Background technology
Along with improving constantly of science and technology development and trade sales coating performance, emulsion is as a kind of requisite component, at many polymkeric substance breast coating; Sticker, flocculation agent, viton; During the production of impact-resistant copolymerized thing etc. is synthetic, become a very important part.And give itself to have many good characteristics, make it in the historical progress of last 100 years, gradually changed into a foundation stone in the chemical industry.And at this wherein, the cinnamic acrylic ester emulsion is because the monomeric species of its raw material is various, and range of product is many and have good integrated application performance, makes that its development in this field is relatively rapider always.
Self-evident, the application of cinnamic acrylic ester emulsion in building trade also is more and more important, and the continuous enhancing of Along with people's environmental consciousness, and water milk type coating has become important developing direction of coatings industry.
How to improve the performance of Water-borne Coatings Emulsion, defective such as one of them key factor is exactly the problem of emulsion, and traditional emulsion exists film-forming temperature higher, and water tolerance is bad, and big limitations its application in water milk type coating.
Summary of the invention
The object of the invention provides a kind of elastic emulsion to the problems referred to above exactly, has fundamentally overcome because the defective of the Water-borne Coatings Emulsion aspect of performance that the emulsion factor is caused.
Another object of the present invention is to provide a kind of method for preparing elastic emulsion of the present invention.
The technical scheme that the present invention is adopted in order to reach the goal is:
A kind of elastic emulsion of the present invention is formed by following polymerizable raw material:
Hard monomer, soft monomer, functional monomer, compound emulsifying agent, organosilicon, initiator, pH regulator agent and deionized water;
Wherein, said hard monomer is at least a in vinylbenzene and the TEB 3K;
Said soft monomer is at least a in Bing Xisuandingzhi, ethyl propenoate and the Isooctyl acrylate monomer;
Said functional monomer is at least a in vinylformic acid, methylacrylic acid, Hydroxyethyl acrylate and the Rocryl 400;
Said compound emulsifying agent be phenolic ether sulphate and TX10 by weight 5.2: 0.8 composite making;
Said organosilicon is that METHYL TRICHLORO SILANE and dichloromethyl phenylsilane are by 7.5: 3.5 composite making of mass ratio;
Said initiator is a persulphate;
Said pH regulator agent is the pH regulator agent of hierarchy of control pH value for 5-9.
Above-mentioned a kind of elastic emulsion, wherein, said hard monomer is that vinylbenzene and TEB 3K are by 3.2: 4.8 composite making of mass ratio.
Above-mentioned a kind of elastic emulsion, wherein, the latex micella particle diameter of said elastic emulsion is 80～140 nanometers; And latex particle size presents bimodal distribution in the size distribution analysis; Wherein, latex micella particle diameter be 100 nanometers account for total amount 5-15%, and between the 80-120 nanosection, present normal distribution; Latex micella particle diameter be 130 nanometers account for total amount 70-75%, and between the 120-140 nanosection, present normal distribution.
Above-mentioned a kind of elastic emulsion, wherein, said raw materials in part by weight is following:
Above-mentioned raw materials is the commercially available prod.
The present invention also provides a kind of preparation method of elastic emulsion, may further comprise the steps:
A. earlier with quantitative compound emulsifying agent and deionized water, join in the polymerization reaction kettle, stir and intensification;
B. in the preparatory emulsification still with quantitative deionized water, compound emulsifying agent, hard monomer adding, stir and obtain pre-emulsion after 30 minutes, weighing 16% weight ratio wherein is subsequent use as rebasing seed reaction solution;
C. the temperature with polymerization reaction kettle is raised to 85-90 ℃; Drop into the rebasing seed reaction solution for preparing among the step B, add rebasing initiator for reaction 30-45 minute again, continue to add deionized water toward polymerization reaction kettle; Slowly cool the temperature to 65 ℃, and the control controlled temperature is at 65-70 ℃;
D. polymerization reaction kettle was vacuumized 4 hours, be warming up to 75 ℃ of residue pre-emulsions that step B is prepared again, from preparatory emulsification still, drop in the polymerization reaction kettle, drip initiator with second constant speed simultaneously with first constant speed;
When E. question response drops to 1.5 hours; Suspend and drip pre-emulsion and initiator; In preparatory emulsification still, add quantitative soft monomer and functional monomer, add organosilicon simultaneously, stir and obtain mixed reaction solution after 55 minutes; With the 3rd constant speed, drip mixed reaction solution and initiator simultaneously toward polymerization reaction kettle;
F. after dripping end, polymerization reaction kettle 85-90 ℃ of insulation 0.5-1 hour, is cooled to 40 ℃,, regulate the pH value at 5-9 with the pH regulator agent, regulate solid content at 25%-60% with deionized water, filter discharging with 100 order filter bags.
The preparation method of above-mentioned a kind of elastic emulsion; Wherein, Preparatory emulsification still described in the step B is for opening curved blade type, and the number of blade is 5 leaves, and its diameter is 0.66 with preparatory emulsification still diameter ratio; Its blade diameter is 4.2 with the ratio of depth of blade, and the mixing speed of emulsification still is controlled at 850-880 rev/min in advance.
The preparation method of above-mentioned a kind of elastic emulsion, wherein, the deionized water specific conductivity described in steps A, B, the C is controlled at 0.1 μ s/cm-1 μ s/cm.
The preparation method of above-mentioned a kind of elastic emulsion, wherein, the vacuum tightness that vacuumizes described in the rapid D remains on the 280-300 mmhg, and said first constant speed is 50～80 milliliters of PMs, and said second constant speed is 3～5 milliliters of PMs.
The preparation method of above-mentioned a kind of elastic emulsion, wherein, said the 3rd constant speed of step e is 250～300 milliliters of PMs.
The preparation method of above-mentioned a kind of elastic emulsion, wherein, the pH regulator agent is ammoniacal liquor, wherein NH in the step F
3Content be controlled at 5-8%, said deionized water specific conductivity is controlled at 350 μ s/cm～380 μ s/cm.
Formulation selection of the present invention the proportioning of suitable soft, hard monomer, used negatively charged ion and nonionic emulsifying agent and mixed, and passed through hud polymerization; The gradient dropwise reaction makes, thereby has guaranteed that cinnamic acrylic ester emulsion of the present invention has higher elasticity, contamination resistance preferably; Lower film-forming temperature; And water tolerance preferably, can be widely used in the preparation process of trade sales coating, such as external wall system; The waterproof paint system especially needs emulsion to have in the lower application system of elasticity and film-forming temperature.
Embodiment
Below through specific embodiment the present invention is carried out a step and sets forth, but should not limit the present invention by any way.
Embodiment:
A. earlier with the compound emulsifying agent of 1.5 weight parts and the deionized water of 15 weight parts, join in the polymerization reaction kettle, stir and intensification;
B. with the deionized water of 25 weight parts; 0.5 the compound emulsifying agent of weight part; The hard monomer of 37 weight parts (vinylbenzene and 15 parts by weight of methylmethacrylate that comprise 22 weight parts) adds in the preparatory emulsification still; Stir and obtain pre-emulsion after 30 minutes, weighing 10 weight parts wherein are subsequent use as rebasing seed reaction solution;
C. the temperature with the steps A polymerization reaction kettle is raised to 85-90 ℃; Drop into the rebasing seed reaction solution of 10 weight parts for preparing among the step B; Add the rebasing initiator of 1 weight part (persulphate) reaction 30-45 minute again; Continue to add 5 parts by weight of deionized water toward polymerization reaction kettle, slowly cool the temperature to 65 ℃, and the control controlled temperature is at 65-70 ℃;
D. polymerization reaction kettle was vacuumized 4 hours; Be warming up to 75 ℃ of residue 52.5 weight part pre-emulsions that step B is obtained again; First constant speed from preparatory emulsification still (60 milliliters of PMs) drops in the polymerization reaction kettle, drips the initiator (persulphate) of 2 weight parts simultaneously with second constant speed (60 milliliters of PMs);
When E. question response drops to 1.5 hours; Suspend and drip pre-emulsion and initiator; In preparatory emulsification still, add 38 parts by weight of acrylic butyl esters and 20 parts by weight of acrylic, add the organosilicon of 1 weight part simultaneously, stir and prepare mixed reaction solution after 55 minutes; With the 3rd constant speed (250 milliliters of PMs), continue to drip the initiator (persulphate) of mixed reaction solution and 1 weight part simultaneously;
F. after treating that mixed reaction solution all dropwises in the preparatory emulsification still; Stop to drip, polymerization reaction kettle 85-90 ℃ of insulation 0.5-1 hour, is cooled to 40 ℃; As required; With in the ammoniacal liquor of 2 weight parts and behind the pH, regulate solid content at 25%-60% with deionized water, filter discharging with 100 order filter bags.
The elastic emulsion that this embodiment prepares, its each item performance is following: the oyster white aqueous dispersion, not stratified, there is not deposition, no skinning is uniform state after the stirring; Viscosity: 200 ± 50mpa.s; PH value: 7 ± 1; Solid content: 45%.
Above embodiment only supplies to explain the present invention's usefulness; But not limitation of the present invention; The technician in relevant technologies field under the situation that does not break away from the spirit and scope of the present invention, can also make various conversion or modification; Therefore all technical schemes that are equal to also should belong to category of the present invention, should be limited each claim.
Claims (10)
1. an elastic emulsion is characterized in that, is to be formed by following polymerizable raw material:
Hard monomer, soft monomer, functional monomer, compound emulsifying agent, organosilicon, initiator, pH regulator agent and deionized water;
Wherein, said hard monomer is at least a in vinylbenzene and the TEB 3K;
Said soft monomer is at least a in Bing Xisuandingzhi, ethyl propenoate and the Isooctyl acrylate monomer;
Said functional monomer is at least a in vinylformic acid, methylacrylic acid, Hydroxyethyl acrylate and the Rocryl 400;
Said compound emulsifying agent be phenolic ether sulphate and TX10 by weight 5.2: 0.8 composite making;
Said organosilicon is that METHYL TRICHLORO SILANE and dichloromethyl phenylsilane are by 7.5: 3.5 composite making of mass ratio;
Said initiator is a persulphate;
Said pH regulator agent is the pH regulator agent of hierarchy of control pH value for 5-9.
2. a kind of elastic emulsion as claimed in claim 1 is characterized in that, said hard monomer is that vinylbenzene and TEB 3K are by 3.2: 4.8 composite making of mass ratio.
3. a kind of elastic emulsion as claimed in claim 1; It is characterized in that; The latex micella particle diameter of said elastic emulsion is 80～140 nanometers, and latex particle size presents bimodal distribution in the size distribution analysis, wherein; Latex micella particle diameter be 100 nanometers account for total amount 5-15%, and between the 80-120 nanosection, present normal distribution; Latex micella particle diameter be 130 nanometers account for total amount 70-75%, and between the 120-140 nanosection, present normal distribution.
4. a kind of elastic emulsion as claimed in claim 1 is characterized in that, said raw materials in part by weight is following:
5. the preparation method of an elastic emulsion as claimed in claim 1 is characterized in that, may further comprise the steps:
A. earlier with quantitative compound emulsifying agent and deionized water, join in the polymerization reaction kettle, stir and intensification;
B. in the preparatory emulsification still with quantitative deionized water, compound emulsifying agent, hard monomer adding, stir and obtain pre-emulsion after 30 minutes, weighing 16% weight ratio wherein is subsequent use as rebasing seed reaction solution;
C. the temperature with polymerization reaction kettle is raised to 85-90 ℃; Drop into the rebasing seed reaction solution for preparing among the step B, add rebasing initiator for reaction 30-45 minute again, continue to add deionized water toward polymerization reaction kettle; Slowly cool the temperature to 65 ℃, and the control controlled temperature is at 65-70 ℃;
D. polymerization reaction kettle was vacuumized 4 hours, be warming up to 75 ℃ of residue pre-emulsions that step B is prepared again, from preparatory emulsification still, drop in the polymerization reaction kettle, drip initiator with second constant speed simultaneously with first constant speed;
When E. question response drops to 1.5 hours; Suspend and drip pre-emulsion and initiator; In preparatory emulsification still, add quantitative soft monomer and functional monomer, add organosilicon simultaneously, stir and obtain mixed reaction solution after 55 minutes; With the 3rd constant speed, drip mixed reaction solution and initiator simultaneously toward polymerization reaction kettle;
F. after dripping end, polymerization reaction kettle 85-90 ℃ of insulation 0.5-1 hour, is cooled to 40 ℃,, regulate the pH value at 5-9 with the pH regulator agent, regulate solid content at 25%-60% with deionized water, filter discharging with 100 order filter bags.
6. the preparation method of a kind of elastic emulsion as claimed in claim 5; It is characterized in that; Preparatory emulsification still described in the step B is for opening curved blade type, and the number of blade is 5 leaves, and its diameter is 0.66 with preparatory emulsification still diameter ratio; Its blade diameter is 4.2 with the ratio of depth of blade, and the mixing speed of emulsification still is controlled at 850-880 rev/min in advance.
7. the preparation method of a kind of elastic emulsion as claimed in claim 5 is characterized in that, the deionized water specific conductivity described in steps A, B, the C is controlled at 0.1 μ s/cm-1 μ s/cm.
8. the preparation method of a kind of elastic emulsion as claimed in claim 5; It is characterized in that; The vacuum tightness that vacuumizes described in the step D remains on the 280-300 mmhg, and said first constant speed is 50～80 milliliters of PMs, and said second constant speed is 3～5 milliliters of PMs.
9. the preparation method of a kind of elastic emulsion as claimed in claim 5 is characterized in that, said the 3rd constant speed of step e is 250～300 milliliters of PMs.
10. the preparation method of a kind of elastic emulsion as claimed in claim 5 is characterized in that, the pH regulator agent is ammoniacal liquor, wherein NH in the step F
3Content be controlled at 5-8%, said deionized water specific conductivity is controlled at 350 μ s/cm～380 μ s/cm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110440798.8A CN102532401B (en) | 2011-12-23 | 2011-12-23 | Elastic emulation and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110440798.8A CN102532401B (en) | 2011-12-23 | 2011-12-23 | Elastic emulation and preparation method thereof |
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| CN102532401A true CN102532401A (en) | 2012-07-04 |
| CN102532401B CN102532401B (en) | 2014-01-08 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483893A (en) * | 2013-08-23 | 2014-01-01 | 无锡市金盛助剂厂 | Waterproof paint and preparation method thereof |
| CN105175600A (en) * | 2015-10-13 | 2015-12-23 | 三棵树涂料股份有限公司 | Core-shell-type styrene-acrylic emulsion with dual-gradient structures contained in shell layers and preparing method thereof |
| CN105754031A (en) * | 2014-12-16 | 2016-07-13 | 浙江新力化工有限公司 | Acrylic acid waterproof emulsion with high low-temperature resistance and preparation method thereof |
| CN106010047A (en) * | 2016-07-12 | 2016-10-12 | 固安金盾时代建筑防水材料有限公司 | Base-layer treating agent for waterproof roll material and production method thereof |
| CN106278041A (en) * | 2016-08-15 | 2017-01-04 | 山东天汇防水材料有限公司 | A kind of super-hydrophobic JS water-repellent paint and preparation method thereof |
| CN106348675A (en) * | 2016-08-15 | 2017-01-25 | 山东天汇防水材料有限公司 | Waterproof cement-based coating and preparation method thereof |
| CN106590293A (en) * | 2016-12-17 | 2017-04-26 | 吴德炳 | Preparation method of weather-resistant external wall coating |
| CN106905810A (en) * | 2017-03-23 | 2017-06-30 | 北京东方雨虹防水技术股份有限公司 | A kind of preparation method of water-based elastic paint emulsion, water-based elastic paint emulsion and coating |
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| CN111648133A (en) * | 2020-06-02 | 2020-09-11 | 北京建筑材料科学研究总院有限公司 | Alkali-resistant flame-retardant waterproof air-permeable agent and film for building with ultra-low energy consumption and preparation method thereof |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483893A (en) * | 2013-08-23 | 2014-01-01 | 无锡市金盛助剂厂 | Waterproof paint and preparation method thereof |
| CN105754031A (en) * | 2014-12-16 | 2016-07-13 | 浙江新力化工有限公司 | Acrylic acid waterproof emulsion with high low-temperature resistance and preparation method thereof |
| CN105175600A (en) * | 2015-10-13 | 2015-12-23 | 三棵树涂料股份有限公司 | Core-shell-type styrene-acrylic emulsion with dual-gradient structures contained in shell layers and preparing method thereof |
| CN106010047A (en) * | 2016-07-12 | 2016-10-12 | 固安金盾时代建筑防水材料有限公司 | Base-layer treating agent for waterproof roll material and production method thereof |
| CN106278041B (en) * | 2016-08-15 | 2018-12-18 | 山东天汇防水股份有限公司 | A kind of super-hydrophobic JS water-repellent paint and preparation method thereof |
| CN106348675A (en) * | 2016-08-15 | 2017-01-25 | 山东天汇防水材料有限公司 | Waterproof cement-based coating and preparation method thereof |
| CN106278041A (en) * | 2016-08-15 | 2017-01-04 | 山东天汇防水材料有限公司 | A kind of super-hydrophobic JS water-repellent paint and preparation method thereof |
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Denomination of invention: Elastic emulsion and preparation method thereof Effective date of registration: 20220222 Granted publication date: 20140108 Pledgee: Shanghai Rural Commercial Bank Co.,Ltd. Jinshan sub branch Pledgor: SHANGHAI MORFANT NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2022310000034 |
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