CN109306033A - A kind of epoxy acrylate composite emulsion and its preparation method and application - Google Patents
A kind of epoxy acrylate composite emulsion and its preparation method and application Download PDFInfo
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- CN109306033A CN109306033A CN201811153042.3A CN201811153042A CN109306033A CN 109306033 A CN109306033 A CN 109306033A CN 201811153042 A CN201811153042 A CN 201811153042A CN 109306033 A CN109306033 A CN 109306033A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
本发明提供了一种环氧丙烯酸酯复合乳液及其制备方法和应用，属于水性涂料技术领域。本发明提供的环氧丙烯酸酯复合乳液由包括以下质量份数的原料制备得到：乙烯基类单体20～30份；环氧树脂10～25份；磷酸酯乳化剂1.5～3份；甲基丙烯酸十八烷基酯0.5～1份；引发剂0.2～0.5份；缓冲剂0.2～0.5份；水50～80份。本发明提供的环氧丙烯酸酯复合乳液采用细乳液聚合工艺，使复合乳液中环氧树脂含量较高，增强涂层的附着力和防腐性能，另外，磷酸酯乳化剂不仅可以乳化稳定单体，且在成膜过程中可与金属离子发生络合作用，形成一层致密的磷酸盐保护膜，从而克服了传统乳化剂对乳液涂层性能的影响。The invention provides an epoxy acrylate composite emulsion and a preparation method and application thereof, belonging to the technical field of water-based coatings. The epoxy acrylate composite emulsion provided by the present invention is prepared from the following raw materials in parts by mass: 20-30 parts of vinyl monomers; 10-25 parts of epoxy resin; 1.5-3 parts of phosphate emulsifier; 0.5-1 part of octadecyl acrylate; 0.2-0.5 part of initiator; 0.2-0.5 part of buffer; 50-80 parts of water. The epoxy acrylate composite emulsion provided by the invention adopts a mini-emulsion polymerization process, so that the epoxy resin content in the composite emulsion is higher, and the adhesion and anti-corrosion performance of the coating are enhanced. In addition, the phosphate emulsifier can not only emulsify and stabilize the monomer, And in the process of film formation, it can complex with metal ions to form a dense phosphate protective film, thereby overcoming the influence of traditional emulsifiers on the performance of emulsion coatings.
Description
Technical field
The present invention relates to technical field of aqueous paint, in particular to a kind of Epoxy-Acrylate Hybrid Emulsion and its preparation side
Method and application.
Background technique
Water paint has a vast market development prospect based on its compatibility and protectiveness to environment.Currently, exploitation
The water paint of application mainly includes with waterborne acrylic paint, aqueous epoxy resins, waterborne polyurethane resin etc. and its changing
Property polymer be base-material coating variety.However, single variety water paint can't be with solvent based coating in certain performances
It contends with, to limit its popularization and application, therefore researchs and develops Compound waterborne coating, by the mutual supplement with each other's advantages between resin,
The integrated application performance for improving coating material, is the important directions of water paint future development.
Epoxy resin and acrylic resin are all important one of synthetic resin.Epoxy resin has unique epoxy
Base, hydroxyl, ehter bond isoreactivity group have excellent adhesive force, impermeability and chemical-resistant, but its coating after curing of coating
More crisp, ultra-violet resistance and outdoor weathe resistance are poor.And acrylate has good weatherability, protects light colour retention, so
And its coating is also easy to produce hot sticky cold crisp phenomenon.Therefore, above two resin is organically combined, by between each component
Have complementary advantages to improve the overall performance of coating, becomes the main hot spot that scholars study.
Currently, the preparation method of Epoxy-Acrylate Hybrid Emulsion has physical blending process, esterification process and emulsion graft copolymerization
Method.Physical blending process is to mix epoxy resin and emulsifier, is diluted with water to obtain epoxy emulsion, then by epoxy resin latex with
It is mixed containing the acrylic resin of carboxyl and tertiary amine, epoxy acrylate compound aqueous dispersion system, such as United States Patent (USP) is prepared
US4,247,439 etc..Between this method preparation process is simple, but there are storage stability differences component the problems such as poor compatibility.Ester
Change method has main steps that first is that mixed solvent carries out semi-loop reaction with n-butanol and propylene glycol monomethyl ether, then by poly- with acrylic acid
It closes object progress esterification and obtains soluble epoxide acrylate, such as Chinese patent CN102432773A, CN102042738A, beauty
State's patent US4,247,439, US2,068,967 etc..Although the technique can improve compatibility between the two resin, these chemistry
Reaction carries out in organic solvent, and organic solvent is inflammable and explosive, to production and construction band inconvenience.In addition, epoxy group
Consumption, influence the final crosslink density of coating.Emulsion graft copolymerization method is the skeleton that hydrophilic radical is introduced into epoxy resin
In, then using double bond as reflecting point, using semi-continuous seed emulsion polymerization method, copolymerization, synthesis are carried out with other monomers
Waterborne epoxy acrylate-grafted composite emulsion, such as Chinese patent CN102964536A, United States Patent (USP) US4,212,781, US4,
578,888 etc..This method grafting rate is lower, and reaction controllability is poor, due to the hydrophobicity of epoxy resin, the multiple emulsion of preparation
Middle epoxy content is lower.Separately there is Chinese patent CN105732881A to report a kind of acrylate composite emulsion, by epoxy resin
It is dissolved in vinyl monomer, by high pressure homogenizer, high-shear homogenizing machine, emulsification grinder, lobed rotor pump, recirculation type cream
After change machine, vacuum homogeneous emulsifying machine emulsification, causes thin polymerization reaction, obtain waterborne epoxy acrylate multiple emulsion.The technique
Although ensure that most of epoxy group is retained in lotion, the presence of conventional emulsifier and assistant for emulsifying agent was forming a film
Cheng Zhonghui dissociates to coating surface, causes film adhesive reduction, poor water resistance, coating whiting, antiseptic property difference etc., influences to apply
Layer performance.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of Epoxy-Acrylate Hybrid Emulsion and preparation method thereof and answering
With Epoxy-Acrylate Hybrid Emulsion provided by the invention can not only improve the content of epoxy resin, also overcome traditional cream
Influence of the agent to emulsion coating performance.
The present invention provides a kind of Epoxy-Acrylate Hybrid Emulsions, are prepared by the raw material for including following mass fraction
It arrives:
Preferably, the vinyl monomer is styrene, methyl methacrylate, butyl acrylate, methacrylic acid
Two or more mixture in butyl ester and isooctyl methacrylate.
Preferably, the epoxy resin is in bisphenol A-type E-42 epoxy resin, E-44 epoxy resin and E-51 epoxy resin
It is one or more.
Preferably, the phosphate emulsifier is alkyl acrylate phosphate and/or siloxanes phosphate.
Preferably, the initiator is potassium peroxydisulfate or ammonium persulfate.
Preferably, the buffer is that phosphoric acid hydrogen is received or phosphoric acid hydrogen two is received.
The present invention also provides the preparation methods of above-mentioned Epoxy-Acrylate Hybrid Emulsion, including following preparation step:
1) the phosphate emulsifier of the mass fraction is mixed with 40~60 parts of water, obtains emulsifier aqueous solution；By institute
The water mixing for stating the initiator, buffer and remainder of mass fraction, obtains initiator solution；By the mass fraction
Epoxy resin, octadecyl methacrylate and vinyl monomer mixing, obtain monomer mixed solution；
2) monomer mixed solution in the step 1) is mixed with emulsifier aqueous solution, successively stirring and ultrasonication are thin
Change, obtains miniemulsion；
3) miniemulsion that the initiator solution in the step 1) is added dropwise in the step 2) is mixed and is polymerize
Reaction, obtains Epoxy-Acrylate Hybrid Emulsion.
Preferably, the rate stirred in the step 2) is 700~900r/min.
Preferably, ultrasonication described in the step 2) refinement frequency be ultrasound stop within 5 seconds 5 seconds, power be 650~
950W, total sonication time are 15~20min.
Preferably, the temperature of polymerization reaction is 75~85 DEG C in the step 3), time of the polymerization reaction is 4~
6h。
The present invention also provides the preparations that above-mentioned Epoxy-Acrylate Hybrid Emulsion is used for metallic paint.
Advantageous effects: the present invention provides a kind of Epoxy-Acrylate Hybrid Emulsion, epoxy third provided by the invention
Olefin(e) acid ester composite emulsion is by including that the raw material of following mass fraction is prepared: vinyl monomer 20~30；Part epoxy resin
15~25 parts；1.5~3 parts of phosphate emulsifier；0.5~1 part of octadecyl methacrylate；0.2~0.5 part of initiator；
0.2~0.5 part of buffer；50~80 parts of water.It can be improved asphalt mixtures modified by epoxy resin in Epoxy-Acrylate Hybrid Emulsion provided by the invention
The content of rouge improves the adhesive force and antiseptic property of coating, in addition, emulsifier used in multiple emulsion is phosphate emulsifier, it should
Emulsifier not only can be with stable emulsifying monomer, but also multiple emulsion of the invention is prepared metallic paint and is used for metal surface, phosphoric acid
With metal ion complexing can occur for ester emulsifier in film forming procedure, form one layer of fine and close phosphate coating, thus
Overcome influence of the conventional emulsifier to emulsion coating performance.In addition the first of Epoxy-Acrylate Hybrid Emulsion provided by the invention
Base octadecyl acrylate can play the role of assistant for emulsifying agent, make the monomer emulsions obtained by refinement in the course of the polymerization process
It keeps stablizing.
The present invention also provides the preparation method of Epoxy-Acrylate Hybrid Emulsion, the present invention is by the phosphorus of the mass fraction
Acid esters emulsifier is mixed with 40~60 parts of water, obtains emulsifier aqueous solution；By the initiator of the mass fraction, buffer and remain
The water mixing of remaining part point, obtains initiator solution；By the epoxy resin of the mass fraction, octadecyl methacrylate
It is mixed with vinyl monomer, obtains monomer mixed solution；The monomer mixed solution is mixed with emulsifier aqueous solution, is successively stirred
It is refined with ultrasonication, obtains miniemulsion；The initiator solution and the miniemulsion are mixed and carry out polymerization reaction, is obtained
Epoxy-Acrylate Hybrid Emulsion.The method that the present invention uses mini-emulsion polymerization, does not require migration of the monomer in water phase, directly
Cause polymerization in monomer droplet, the content of epoxy resin in multiple emulsion can not only be improved, also retain most ring
Oxygen groups guarantee degree of cross linking when film forming；And almost all of monomer droplet causes polymerization simultaneously, and obtained latex particle is flat
Equal partial size is small, and particle diameter distribution is uniform.
Specific embodiment
The present invention provides a kind of Epoxy-Acrylate Hybrid Emulsions, are prepared by the raw material for including following mass fraction
It arrives:
In the present invention, according to parts by weight, the raw material for preparing the Epoxy-Acrylate Hybrid Emulsion includes vinyl
20~30 parts of class monomer, more preferably 25 parts.In the present invention, the vinyl monomer is preferably styrene, metering system
Two or more mixture in sour methyl esters, butyl acrylate, butyl methacrylate and isooctyl methacrylate.
The present invention is not particularly limited the amount ratio of the mixture medium vinyl monomer, is mixed with arbitrary proportion.
In the present invention, on the basis of the parts by weight of the vinyl monomer, the epoxy acrylate Composite Milk
The raw material of liquid includes 15~25 parts of epoxy resin, more preferably 18~20 parts；In the present invention, the epoxy resin is bisphenol-A
One of type E-42 epoxy resin, E-44 epoxy resin and E-51 epoxy resin are a variety of.
In the present invention, on the basis of the parts by weight of the vinyl monomer, the epoxy acrylate Composite Milk
1.5~3 parts of the phosphoric acid ester emulsifier of liquid；In the present invention, the phosphate emulsifier is preferably alkyl acrylic
Ester phosphate and/or siloxanes phosphate；In the present invention, when the phosphate emulsifier be alkyl acrylate phosphate and
When siloxanes phosphate, the present invention is not particularly limited the mass ratio of alkyl acrylate phosphate and siloxanes phosphate,
It is mixed with arbitrary proportion.In the present invention, the phosphate emulsifier not only can with stable emulsifying vinyl monomer, but also
Complexing occurs with metal ion in film forming procedure, one layer of fine and close phosphate coating is formed, to overcome tradition
Influence of the emulsifier to emulsion coating performance.
In the present invention, on the basis of the parts by weight of the vinyl monomer, the epoxy acrylate Composite Milk
The raw material of liquid includes 0.5~1 part of octadecyl methacrylate.In the present invention, the octadecyl methacrylate
It can play the role of assistant for emulsifying agent, the monomer emulsions obtained by fine crankshaft is made to keep stable in the course of the polymerization process.
In the present invention, on the basis of the parts by weight of the vinyl monomer, the epoxy acrylate Composite Milk
The raw material of liquid includes 0.2~0.5 part of initiator, more preferably 0.3~0.4 part；In the present invention, the initiator is preferably sulphur
Sour potassium and/or ammonium persulfate.
In the present invention, on the basis of the parts by weight of the vinyl monomer, the epoxy acrylate Composite Milk
The raw material of liquid includes 0.2~0.5 part of buffer；In the present invention, the buffer is preferably that phosphoric acid hydrogen is received and/or phosphoric acid hydrogen two
It receives.
The present invention also provides the preparation methods of above-mentioned Epoxy-Acrylate Hybrid Emulsion, including following preparation step:
1) the phosphate emulsifier of the mass fraction is mixed with 40~60 parts of water, obtains emulsifier aqueous solution；By institute
The water mixing for stating the initiator, buffer and remainder of mass fraction, obtains initiator solution；By the mass fraction
Epoxy resin, octadecyl methacrylate and vinyl monomer mixing, obtain monomer mixed solution；
2) monomer mixed solution in the step 1) is mixed with emulsifier aqueous solution, successively stirring and ultrasonication are thin
Change, obtains miniemulsion；
3) miniemulsion that the initiator solution in the step 1) is added dropwise in the step 2) is mixed and is polymerize
Reaction, obtains Epoxy-Acrylate Hybrid Emulsion.
The present invention mixes the phosphate emulsifier of the mass fraction with 40~60 parts of water, obtains emulsifier aqueous solution；
The water of the initiator of the mass fraction, buffer and remainder is mixed, initiator solution is obtained；By the mass parts
Several epoxy resin, octadecyl methacrylate and vinyl monomer mixing, obtains monomer mixed solution.The present invention is to institute
The method for stating mixing is not particularly limited, and selects those skilled in the art known ground mixed method.
After obtaining emulsifier aqueous solution, initiator solution and monomer mixed solution, the present invention is by monomer mixed solution and emulsifies
The mixing of agent aqueous solution, successively stirring and ultrasonication refinement, obtain miniemulsion.
In the present invention, the rate of the stirring is preferably 700~900r/min, more preferably 750~850r/min,
Most preferably 800r/min.
In the present invention, the frequency of the ultrasonication refinement is preferably that ultrasound is stopped 5 seconds for 5 seconds；The ultrasonication refinement
Power be preferably 650~950W, more preferably 700~900W, most preferably 800~850W；The ultrasonication refinement
Time is preferably 15~20min.Present invention preferably uses ultrasonic cell disruptors to carry out ultrasonication refinement.The present invention passes through
The partial size of Fine by Ultrasonic reduction miniemulsion.
In the present invention, the concrete mode that the monomer mixed solution is mixed with emulsifier aqueous solution preferably mixes monomer
Drop is added in emulsifier aqueous solution.In the present invention, the time for adding is preferably 5~10min.
After obtaining miniemulsion, the initiator solution and the miniemulsion are mixed and carry out polymerization reaction by the present invention, are obtained
To Epoxy-Acrylate Hybrid Emulsion.
In the present invention, the temperature of the polymerization reaction is preferably 75~85 DEG C, and more preferably 80 DEG C；The polymerization reaction
Time be preferably 4~6h, more preferably 5~5.5h.In the present invention, almost in all monomers in the slender lotion
Drop causes polymerization simultaneously, therefore obtained latex particle average grain diameter is small, and particle diameter distribution is uniform.
In the present invention, the initiator solution and the method for miniemulsion mixing are preferably by initiator solution
It is added drop-wise in miniemulsion.In the present invention, the time for adding is 2.0~3.0h.
In the present invention, the polymerization reaction preferably carries out under anaerobic.The present invention preferably passes through nitrogen and provides nothing
Oxygen environment.
In the present invention, after the polymerization reaction, include successively also heat preservation, be cooled to room temperature and filter.
In the present invention, the time of the heat preservation is preferably 2.0~3.0h, more preferably 2.5h.
The present invention is not particularly limited the method for filtering, selects method well known to those skilled in the art.
The present invention also provides the preparations that above-mentioned Epoxy-Acrylate Hybrid Emulsion is used for metallic paint.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
1) by mass parts) in terms of part, 50 parts of deionized waters are taken, by 2 parts of phosphates (alkyl acrylate phosphate) emulsifier
It is dissolved in and emulsifier aqueous solution is wherein made；0.4 part of potassium peroxydisulfate and 0.4 disodium hydrogen phosphate are dissolved in 10 parts of water, initiation is made
Agent aqueous solution；Successively take 10 parts of E-44 epoxy resin, 2 parts of octadecyl methacrylates, 18 parts of methyl methacrylates, 12
Part butyl acrylate, is made monomer mixed solution after mixing.
2) monomer mixed solution prepared by step 1) is added dropwise in the emulsifier aqueous solution prepared in step 1), with 700r/
After the rate stirring 30min of min, (600W ultrasound 20min) then is refined with ultrasonic cell disruptor, forms stable thin cream
Liquid.
3) miniemulsion prepared in step 2) is added at one time in four-hole bottle, leads to nitrogen displacement, is warming up to 75 DEG C, so
A dropping step 1 afterwards) in initiator solution, react 3h after, keep the temperature 2h, be down to room temperature, filtering and discharging obtains epoxy acrylic
Ester composite emulsion.
Embodiment 2
Be added in embodiment 1 10 parts of E-44 epoxy resin are replaced with into 15 parts of E-44, other are same as Example 1.
Embodiment 3
Be added in embodiment 1 10 parts of E-44 epoxy resin are replaced with into 20 parts of E-44, other are same as Example 1.
Embodiment 4
Be added in embodiment 1 10 parts of E-44 epoxy resin are replaced with into 25 parts of E-44, other are same as Example 1.
Embodiment 5
Be added in embodiment 12 parts of phosphate emulsifiers are replaced with into 1.5 parts of phosphate emulsifiers, other and embodiment 1
It is identical.
Embodiment 6
Be added in embodiment 12 parts of phosphate emulsifiers are replaced with into 1 part of phosphate emulsifier, other and 1 phase of embodiment
Together.
Comparative example 1
Be added in embodiment 12 parts of phosphate emulsifiers are replaced with into 0.5 part of nonylphenol polyoxyethylene ether and 1.5 parts of alkene
Propoxyl group nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate emulsifier, other are same as Example 1.
By epoxy acrylate Composite Milk prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4 and comparative example 1
Liquid passes through the corrosion-resistant of polarization curve test evaluation coating by national standard test film water absorption rate, partial size and particle diameter distribution
Performance, treated, and data see the table below:
The spreading property of Epoxy-Acrylate Hybrid Emulsion obtained in 1 Examples 1 to 6 of table and comparative example 1
E in tablecorrFor corrosion potential；IcorrFor corrosion current；RpFor polarization resistance；PE% is protection efficiency
The method of the present embodiment 1 substitutes the nonylphenol polyoxyethylene ether of Compositional type using phosphate emulsifier as shown in Table 1
With allyloxy nonyl phenol propyl alcohol polyoxyethylene ether ammonium sulfate emulsifier, prepared waterborne epoxy acrylate multiple emulsion is applied
Layer corrosion electric current density small an order of magnitude, the protection efficiency of coating are increased to 93.5% from 70.4%, have preferable anti-
Rotten performance.And with the increase of epoxy resin content, the corrosion potential of coating is stepped up, corrosion electric current density gradually under
Drop, illustrates coating antiseptic performance enhancement.The waterborne epoxy acrylate multiple emulsion partial size of Examples 1 to 4 preparation, particle diameter distribution
Comparative example is significantly lower than with the water absorption rate of film.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
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| CN110982377A (en) * | 2019-12-02 | 2020-04-10 | 株洲飞鹿高新材料技术股份有限公司 | Water-based epoxy coating for rail transit interior decoration and preparation method thereof |
| CN111378081A (en) * | 2020-03-31 | 2020-07-07 | 陕西立高涂料有限公司 | Preparation method of fluorosilicone modified epoxy resin emulsion for anticorrosive paint |
| CN116876221A (en) * | 2023-07-04 | 2023-10-13 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110982377A (en) * | 2019-12-02 | 2020-04-10 | 株洲飞鹿高新材料技术股份有限公司 | Water-based epoxy coating for rail transit interior decoration and preparation method thereof |
| CN110982377B (en) * | 2019-12-02 | 2021-08-03 | 株洲飞鹿高新材料技术股份有限公司 | Water-based epoxy coating for rail transit interior decoration and preparation method thereof |
| CN111378081A (en) * | 2020-03-31 | 2020-07-07 | 陕西立高涂料有限公司 | Preparation method of fluorosilicone modified epoxy resin emulsion for anticorrosive paint |
| CN111378081B (en) * | 2020-03-31 | 2023-11-14 | 陕西立高涂料有限公司 | Preparation method of fluorine-silicon modified epoxy resin emulsion for anticorrosive paint |
| CN116876221A (en) * | 2023-07-04 | 2023-10-13 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
| CN116876221B (en) * | 2023-07-04 | 2024-03-08 | 广东创新精细化工实业有限公司 | Fluorine-free waterproof agent, preparation method thereof and application thereof in fabric |
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Application publication date: 20190205 |