CN109384907A - A kind of preparation method of aqueous epoxy curing agent - Google Patents
A kind of preparation method of aqueous epoxy curing agent Download PDFInfo
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- CN109384907A CN109384907A CN201811382433.2A CN201811382433A CN109384907A CN 109384907 A CN109384907 A CN 109384907A CN 201811382433 A CN201811382433 A CN 201811382433A CN 109384907 A CN109384907 A CN 109384907A
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- curing agent
- epoxy
- epoxy resin
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4064—Curing agents not provided for by the groups C08G59/42 - C08G59/66 sulfur containing compounds
Abstract
The present invention provides a kind of preparation methods of aqueous epoxy curing agent, to solve the problems, such as water-borne modification of epoxy resin, simple process, function admirable.The technical solution adopted by the present invention is that: synthesizing a kind of both ends by the ratio that epoxy resin E51 and the only polyetheramine with a primary amine are 2:1 in molar ratio first is epoxy group and the not only not only oleophylic containing epoxy segment but also containing polyethylene segment but also hydrophilic emulsifier, the emulsifier is a kind of reactive emulsifier with epoxy-reactive group, can be used as modified epoxy.Then grafted amine curing agent is removed with the emulsifier, by the active hydrogen reaction of epoxy group and amine curing agent on emulsifier, the hydrophilic and oleophilic structure of emulsifier is introduced into the molecular structure of amine curing agent.Finally the primary amine at both ends is blocked to get aqueous epoxy curing agent, curing agent is allowed to have the function of emulsion epoxy resin, not having to additional emulsifier can emulsion epoxy resin well.
Description
Technical field
The present invention relates to a kind of preparation methods of aqueous epoxy curing agent.Prepared aqueous epoxy curing agent technique letter
Dan ﹑ function admirable.
Background technique
The compound of epoxy group in molecular structure containing two or more is referred to as epoxy resin.According to composition
The difference of epoxy molecule skeleton can be divided into aliphatic epoxy resin, cycloaliphatic epoxy resin, aromatic epoxy resin etc..
The epoxy resin of solid epoxy resin and liquid can be divided into again according to the existence of epoxy resin at room temperature.Asphalt mixtures modified by epoxy resin
Rouge cannot make its macromolecular particle aggregation film forming, i.e. not any use of epoxy resin itself by the volatilization of decentralized medium.
Epoxy resin could only form a film under the action of curing agent, with the generation of chemical reaction in its film forming procedure, belong to double
Component System.Epoxy resin is mainly to pass through epoxy group on its strand or hydroxyl is gone with curing agent appropriate in item appropriate
Curing reaction film forming occurs under part, film forming matter has tridimensional network, has many excellent performances, such as its chemically-resistant
Corrosivity is very good, and electrical insulating property is very good, and adhesive force is also very good etc., these excellent performances make epoxy resin extensive
It is a kind of very important thermosetting resin applied to the every aspect of life.Common epoxy resin is dissolved only in organic solvent
And it is not soluble in water, the organic solvent for capableing of fine dissolved epoxy has alcohols, alcohol ethers, ketone and aromatic hydrocarbons etc..However
The volatility of organic solvent is usually quite greatly, and after solvent epoxy coatings film forming, the organic solvent in system will be whole
It evaporate into air and causes serious environmental pollution, greatly influence people's health.Moreover, the price of organic solvent compared with
It is expensive, cause the greatly wasting of resources.Enhancing with people to the pay attention to day by day and concept of health of environmental protection, therefore develop
It takes water as a solvent or the aqueous epoxy resins of decentralized medium is more and more paid attention to.
Mainly there are five systems for water-borne epoxy systems.
I type aqueous epoxy resin systems are the liquid-state epoxy resins by aqueous epoxy curing agent and low relative molecular mass
Composition.The liquid-state epoxy resin of low relative molecular mass includes bisphenol A type epoxy resin and the bisphenol F type epoxy tree of liquid
The mixture of the bisphenol A type epoxy resin and bisphenol f type epoxy resin of rouge and liquid.Outer plus emulsification is not required in this kind of system
Agent carrys out emulsion epoxy resin, because aqueous epoxy curing agent is both emulsifier and curing agent for epoxy resin.It is aqueous
The synthesis of epoxy hardener is to remove the amido with polyethylene polyamine by its epoxy group using epoxy molecule chain as skeleton structure
Reaction becomes amphiphilic compound, to introduce hydrophilic segment so as to emulsify the low molecular weight epoxy of liquid well
Resin.The advantages of I type aqueous epoxy resin systems is can be made into not solvent-laden waterborne epoxy coatings, meets environmental protection, and apply
The hardness of film increases also very fast.The disadvantage is that the surface drying time of film is long, the extension at any time of the viscosity of system and become larger, be applicable in
Phase is short, only 2 ~ 4h, and rheological property is also unstable within its working life.
II type aqueous epoxy resin systems are by the solid epoxy resin of aqueous epoxy curing agent and high relative molecular mass
Lotion composition.Epoxy resin is not soluble in water, is dissolved only in solvent, it is therefore necessary to which hydrophilic segment is introduced in its strand to be obtained
To stable aqueous epoxy emulsion, the solid epoxy resin lotion of the high relative molecular mass of the overwhelming majority used in reality is all
It is basic raw material with the liquid-state epoxy resin of low relative molecular mass.Polyoxyethylene segments or polypropylene oxide chain will be contained
The hydrophilic segments such as section are introduced into epoxy molecule chain, then add water dispersion under the action of cosolvent such as gylcol ether to obtain the final product
Stable aqueous epoxy emulsion, this method have the presence of solvent, will increase environmental protection pressure.
III type aqueous epoxy resin systems are the liquid-state epoxy resins by aqueous epoxy curing agent and low relative molecular mass
Lotion composition, the liquid-state epoxy resin lotion of low molecular weight is usually to pass through phase inversion technique under conditions of adding emulsifier outside
To prepare.Additional emulsifier gives film bring defect, and emulsifier molecules can be precipitated in the surface of film.
IV type aqueous epoxy resin systems by polyurethane-modified epoxy hardener with aqueous epoxy emulsion by forming
's.The synthetic route that modified epoxy resin curing agent is removed with polyurethane is first to use the isocyanate group and polyether polyol of polyurethane
Hydroxyl react, hydrophilic segment is introduced into the strand of polyurethane, obtains polyurethane prepolymer, then by itself and epoxy
Resin carries out graft reaction, is then neutralized into salt with triethylamine, and water is added to carry out chain extending reaction.This method complex process, it is at high cost, and
And the problems such as being handled not environmentally there are waste.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of aqueous epoxy curing agent, to solve existing epoxy resin water
Property is there are working life is short, and rheological property is unstable within the scope of working life, and not environmentally, complex process, at high cost, performance difference etc. is asked
Topic.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is that: first by epoxy resin E51 and only have
The polyetheramine for having a primary amine be in molar ratio the ratio of 2:1 synthesize a kind of both ends be epoxy group and not only containing epoxy segment but also
Not only oleophylic containing polyethylene segment but also hydrophilic emulsifier, the emulsifier are a kind of response type creams with epoxy-reactive group
Agent can be used as modified epoxy.Then grafted amine curing agent is removed with the emulsifier, passes through the ring on emulsifier
The hydrophilic and oleophilic structure of emulsifier is introduced into the molecule knot of amine curing agent by the active hydrogen reaction of oxygen groups and amine curing agent
In structure.The function for allowing curing agent that there is emulsion epoxy resin to get aqueous epoxy curing agent is finally blocked to the primary amine at both ends
Can, not having to additional emulsifier can emulsion epoxy resin well.
A kind of the step of preparation method of aqueous epoxy resin curing agent, is as follows:
Step 1: the preparation of reactive emulsifier, is added 10~15 parts of (" part " indicates mass fraction, similarly hereinafter) rings in a kettle
Oxygen resin E51 and 30~45 parts of polyetheramine M2070, starts stirring, and temperature controls at 90~100 DEG C, reacts a few hours, pass through survey
Epoxide number determines reaction end.
Step 2: putting into 30~40 parts of amine curing agent m-xylene diamines in a kettle, heat temperature raising, temperature rises to 50
℃；
Step 3: starting that 20~30 parts of emulsifiers are added dropwise into reaction kettle, 5~10 parts of Sodium Allyl Sulfonate, 3~5 part third are added dropwise
Olefin(e) acid -2- acrylamide-2-methyl propane sulfonic copolymer (AA/AMPS), temperature are controlled at 50~70 DEG C；
Step 4: emulsifier starts to keep the temperature after being added dropwise, temperature is controlled at 50~70 DEG C；
Step 5: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.
Primary amine is blocked step 6: 10~15 parts of phenyl glycidyl ethers are added dropwise in a kettle, temperature control exists
50~70 DEG C；
Step 7: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end；
Step 8: 5 parts of polyetheramine D400 are added in a kettle to get aqueous epoxy curing agent.
Preferably, the temperature of the step 3 is controlled at 55 DEG C；
Preferably, the temperature of the step 6 is controlled at 67 DEG C.
Raw material of the present invention is easy to get, simple process, low in cost, gained curing agent are had excellent performance, industrialization easy to accomplish.Benefit
Preparing aqueous epoxy curing agent with the method for the present invention not only has the function of emulsion epoxy resin, moreover it is possible to emulsive oily asphalt mixtures modified by epoxy resin
Rouge.Also, the aqueous epoxy curing agent adds water dispersion that the aqueous latex of epoxy hardener that solid content is 50% is made.Acrylic acid -2-
The addition of acrylamide-2-methyl propane sulfonic copolymer can promote film comprehensive performance, while make resulting product in water
It is uniformly dispersed.Have many advantages, such as that good insulation preformance and adhesive force and hardness are high using rear obtained film.Storage stability is excellent
It is good, placed under room temperature 1 year it is not stratified, freeze-thaw stability is excellent, and low temperature is not demulsified, and curing performance is excellent.
The polyetheramine M2070 that the present invention uses is that molecular weight is about 2000 to contain only a primary amino group i.e. two active hydrogens
The polyetheramine of atom, manufacturer have Yangzhou morningization and Hensel to step, and raw material is easy to get, and price is suitable.
Specific embodiment
Combined with specific embodiments below, implementation method of the invention is described in further details.
Embodiment one
The synthesis of aqueous epoxy curing agent:
Step 1: the preparation of reactive emulsifier, is added 10 parts of (" part " indicates mass fraction, similarly hereinafter) asphalt mixtures modified by epoxy resin in a kettle
The rouge E51 and 30 parts of U.S. polyetheramine M2070(graceful polyethers M-2070 of Hensel), stirring is started, temperature is controlled at 90~100 DEG C, instead
A few hours are answered, determine reaction end by surveying epoxide number；
Step 2: putting into 30 parts of amine curing agent hexamethylene diamines in a kettle, heat temperature raising, temperature rises to 50 DEG C；
Step 3: starting 20 parts of the dropwise reaction type emulsifier into reaction kettle, 8 parts of Sodium Allyl Sulfonate, 3 parts of acrylic acid-being added dropwise
2- acrylamide-2-methyl propane sulfonic copolymer (AA/AMPS), temperature are controlled at 55 DEG C；
Step 4: starting to keep the temperature after being added dropwise, temperature is controlled at 62 DEG C；
Step 5: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.
Primary amine is blocked step 6: 10 parts of allyl glycidyl ethers are added dropwise in a kettle, temperature is controlled 67
℃；
Step 7: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.Reaction end is determined by infrared spectroscopy, is reaction end after the characteristic peak of epoxy group disappears；
Step 8: 5 parts of polyetheramine D400 are added in a kettle to get aqueous epoxy curing agent.
After the aqueous latex of epoxy hardener that solid content is 50% is made in gained aqueous epoxy curing agent, centrifugal pump 3000r/
The revolving speed of min turn 30min without precipitating, without layering, mechanical stability is excellent, and freeze-thaw stability is excellent, and room temperature 1 year is without broken
Cream, no layering.
Cure test:
20 parts of epoxy resin and 10 parts of aqueous epoxy resins are weighed, are stirred evenly, with aqueous epoxy curing agent emulsion epoxy resin
After E51, additional 10 parts of deionized waters carry out high speed dispersion to get water-borne epoxy systems.This water-borne epoxy systems is used into film
Stick is uniformly applied to tinplate sheet surface, and after 100 DEG C of solidification 30min, appearance of film is smooth uniform, colorless and transparent, and pencil is hard
5H is spent, impact resistant strength 50cm, 7 grades of flexibility, adhesion 1 grade, water resistance is excellent, and chemical resistance is excellent, and curing agent performance is excellent
It is good, it is all satisfied national standard.
Embodiment two
The synthesis of aqueous epoxy curing agent:
Step 1: the preparation of reactive emulsifier, is added 12 parts of (" part " indicates mass fraction, similarly hereinafter) asphalt mixtures modified by epoxy resin in a kettle
Rouge E51 and 35 parts of polyetheramine M2070 starts stirring, and temperature is controlled at 90~100 DEG C, reacts a few hours, true by surveying epoxide number
Determine reaction end.
Step 2: putting into 35 parts of amine curing agent hexamethylene diamines in a kettle, heat temperature raising, temperature rises to 50 DEG C；
Step 3: starting that 30 parts of emulsifiers are added dropwise into reaction kettle, 6 parts of Sodium Allyl Sulfonate, 5 parts of acrylic acid -2- propylene are added dropwise
Amide -2- methyl propane sulfonic acid copolymer (AA/AMPS), temperature are controlled at 55 DEG C；
Step 4: emulsifier starts to keep the temperature after being added dropwise, temperature is controlled at 60 DEG C；
Step 5: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.
Primary amine is blocked step 6: 13 parts of allyl glycidyl ethers are added dropwise in a kettle, temperature is controlled 50
~70 DEG C；
Step 7: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.Reaction end is determined by infrared spectroscopy, is reaction end after the characteristic peak of epoxy group disappears；
Step 8: 8 parts of polyetheramines 400 are added in a kettle to get aqueous epoxy curing agent.
After the aqueous latex of epoxy hardener that solid content is 50% is made in gained aqueous epoxy curing agent, centrifugal pump 3000r/
The revolving speed of min turn 30min without precipitating, without layering, mechanical stability is excellent, and freeze-thaw stability is excellent, and room temperature 1 year is without broken
Cream, no layering.
Cure test:
20 parts of epoxy resin and 10 parts of aqueous epoxy resins are weighed, are stirred evenly, with aqueous epoxy curing agent emulsion epoxy resin
After E51, additional 10 parts of deionized waters carry out high speed dispersion to get water-borne epoxy systems.This water-borne epoxy systems is used into film
Stick is uniformly applied to tinplate sheet surface, and after 100 DEG C of solidification 30min, appearance of film is smooth uniform, colorless and transparent, and pencil is hard
4H is spent, impact resistant strength 50cm, 7 grades of flexibility, adhesion 1 grade, water resistance is excellent, and chemical resistance is excellent, and curing agent performance is excellent
It is good, it is all satisfied national standard.
Combined with specific embodiments below, implementation method of the invention is described in further details.
Embodiment three
The synthesis of aqueous epoxy curing agent:
Step 1: the preparation of reactive emulsifier, is added 15 parts of (" part " indicates mass fraction, similarly hereinafter) asphalt mixtures modified by epoxy resin in a kettle
Rouge E51 and 40 parts of polyetheramine M2070 starts stirring, and temperature is controlled at 90~100 DEG C, reacts a few hours, true by surveying epoxide number
Determine reaction end.
Step 2: putting into 40 parts of amine curing agent hexamethylene diamines in a kettle, heat temperature raising, temperature rises to 50 DEG C；
Step 3: starting that 25 parts of emulsifiers are added dropwise into reaction kettle, 10 parts of Sodium Allyl Sulfonate, 5 parts of acrylic acid -2- propylene are added dropwise
Amide -2- methyl propane sulfonic acid copolymer (AA/AMPS), temperature are controlled at 68 DEG C；
Step 4: emulsifier starts to keep the temperature after being added dropwise, temperature is controlled at 53 DEG C；
Step 5: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.
Primary amine is blocked step 6: 15 parts of allyl glycidyl ethers are added dropwise in a kettle, temperature is controlled 50
~70 DEG C；
Step 7: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end.Reaction end is determined by infrared spectroscopy, is reaction end after the characteristic peak of epoxy group disappears；
Step 8: 10 parts of polyetheramines 400 are added in a kettle to get aqueous epoxy curing agent.
After the aqueous latex of epoxy hardener that solid content is 50% is made in gained aqueous epoxy curing agent, centrifugal pump 3000r/
The revolving speed of min turn 30min without precipitating, without layering, mechanical stability is excellent, and freeze-thaw stability is excellent, and room temperature 1 year is without broken
Cream, no layering.
Cure test:
20 parts of epoxy resin and 10 parts of aqueous epoxy resins are weighed, are stirred evenly, with aqueous epoxy curing agent emulsion epoxy resin
After E51, additional 10 parts of deionized waters carry out high speed dispersion to get water-borne epoxy systems.This water-borne epoxy systems is used into film
Stick is uniformly applied to tinplate sheet surface, and after 100 DEG C of solidification 30min, appearance of film is smooth uniform, colorless and transparent, and pencil is hard
4H is spent, impact resistant strength 50cm, 7 grades of flexibility, adhesion 1 grade, water resistance is excellent, and chemical resistance is excellent, and curing agent performance is excellent
It is good, it is all satisfied national standard.
Claims (3)
1. a kind of preparation method of aqueous epoxy resin curing agent, it is characterized in that steps are as follows for the preparation method:
Step 1: the preparation of reactive emulsifier, is added 10~15 mass parts epoxy resin E51 and 30~45 parts in a kettle
Polyetheramine M2070 starts stirring, and temperature is controlled at 90~100 DEG C, reacts a few hours, determines reaction end by surveying epoxide number；
Step 2: putting into 30~40 mass parts amine curing agent hexamethylene diamines in a kettle, heat temperature raising, temperature rises to 50 DEG C；
Step 3: starting that 20~30 parts of emulsifiers are added dropwise into reaction kettle, 5~10 parts of Sodium Allyl Sulfonate, 3~5 part third are added dropwise
Olefin(e) acid -2- acrylamide-2-methyl propane sulfonic copolymer, temperature are controlled at 50~70 DEG C；
Step 4: emulsifier starts to keep the temperature after being added dropwise, temperature is controlled at 50~70 DEG C；
Step 5: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end；
Primary amine is blocked step 6: 10~15 parts of allyl glycidyl ethers are added dropwise in a kettle, temperature is controlled 50
~70 DEG C；
Step 7: starting to sample after heat preservation 1h, reaction end is determined by infrared spectroscopy, after the characteristic peak of epoxy group disappears
As reaction end；
Reaction end is determined by infrared spectroscopy, is reaction end after the characteristic peak of epoxy group disappears；
Step 8: 5~10 parts of polyetheramines 400 are added in a kettle to get aqueous epoxy curing agent.
2. the preparation method of a kind of aqueous epoxy resin curing agent according to claim 1, it is characterized in that the step 3
Temperature control at 55 DEG C.
3. the preparation method of a kind of aqueous epoxy resin curing agent according to claim 1, it is characterized in that the step 6
Temperature control at 67 DEG C.
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| CN201811382433.2A CN109384907A (en) | 2018-11-20 | 2018-11-20 | A kind of preparation method of aqueous epoxy curing agent |
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| CN201811382433.2A CN109384907A (en) | 2018-11-20 | 2018-11-20 | A kind of preparation method of aqueous epoxy curing agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020211092A1 (en) * | 2019-04-18 | 2020-10-22 | 万华化学集团股份有限公司 | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof |
| CN113493638A (en) * | 2021-07-20 | 2021-10-12 | 湖北工业大学 | Method for modifying wet basal plane of aluminum sulfate cement by using hydrophilic micromolecule epoxy composite resin |
| CN113583172A (en) * | 2021-07-27 | 2021-11-02 | 湖北工业大学 | Long-chain polyether amine hydrophilic low-molecular-weight polymer and preparation method thereof |
| CN113874414A (en) * | 2019-05-23 | 2021-12-31 | 巴斯夫涂料有限公司 | Aqueous resin dispersion and aqueous coating composition containing the same |
-
2018
- 2018-11-20 CN CN201811382433.2A patent/CN109384907A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020211092A1 (en) * | 2019-04-18 | 2020-10-22 | 万华化学集团股份有限公司 | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof |
| US11597796B2 (en) | 2019-04-18 | 2023-03-07 | Wanhua Chemical Group Co., Ltd. | Ionic aqueous epoxy curing agent, preparation method therefor and use thereof |
| CN113874414A (en) * | 2019-05-23 | 2021-12-31 | 巴斯夫涂料有限公司 | Aqueous resin dispersion and aqueous coating composition containing the same |
| CN113493638A (en) * | 2021-07-20 | 2021-10-12 | 湖北工业大学 | Method for modifying wet basal plane of aluminum sulfate cement by using hydrophilic micromolecule epoxy composite resin |
| CN113583172A (en) * | 2021-07-27 | 2021-11-02 | 湖北工业大学 | Long-chain polyether amine hydrophilic low-molecular-weight polymer and preparation method thereof |
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