CN104610239A - Preparation method for composite terminated waterborne epoxy resin curing agent - Google Patents
Preparation method for composite terminated waterborne epoxy resin curing agent Download PDFInfo
- Publication number
- CN104610239A CN104610239A CN201510031632.9A CN201510031632A CN104610239A CN 104610239 A CN104610239 A CN 104610239A CN 201510031632 A CN201510031632 A CN 201510031632A CN 104610239 A CN104610239 A CN 104610239A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- epoxy resin
- reaction
- consumption
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- 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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
Abstract
The invention discloses a preparation method for a benzoxazine intermediate containing a maleimide biphenyl diphenol structure. The preparation method comprises the following steps: (1) producing a synthesis reaction 1, namely adding an aldehyde compound and a solvent into a reaction container and mixing uniformly under the normal pressure at a normal temperature, adding an amine compound into the container while stirring, and reacting for at least 10 hours at 0-100 DEG C under the normal pressure; after reacting, pouring reaction liquor into washing liquor for washing, filtering, collecting solid matters, and drying at 30-100 DEG C to obtain an intermediate containing a triazine structure; (2) producing a synthesis reaction 2, namely adding the solid matters (triazine), the aldehyde compound, biphenyl diphenol and 1,4-dioxane into the reaction container in sequence, mixing uniformly, heating to 110 DEG C, performing reflux reaction for 30 hours to obtain reaction liquor containing earthy yellow deposits, pouring the obtained reaction liquor into de-ionized water, fully stirring, depositing, performing suction filtration, washing with the de-ionized water and ethanol for multiple times, and drying in a drying oven to obtain an earthy yellow powdery solid target product.
Description
Technical field:
The invention belongs to the preparation field of epoxy curing agent, particularly a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent.
Background technology:
Epoxypaint has that hardness is high, wear resistance good, sticking power is high and the feature such as chemical resistance is excellent, is widely used in field of coating.In recent years, along with improving constantly of people's environmental consciousness, many countries have promulgated the environmental regulation of restriction volatile organic solvent (VOC) in succession, and the Water-borne modification of coating becomes the important trend of paint development.The Water-borne modification technology of epoxy resin is mainly divided into emulsion process and the large class of salt forming method two both at home and abroad at present.Emulsion process refer to epoxy resin direct emulsification, need not the self-emulsifying of additional emulsifying agent or aqueous epoxy curing agent emulsification.And salify rule becomes to be rich in acid or be rich in the resin of alkali, then neutralize with the alkali of small molecules quality or acid.Aqueous epoxy curing agent emulsion epoxy resin is most important Water-borne modification technology, and it can overcome the shortcoming of other water-borne modification methods.
In epoxy curing agent, amine curing agent kind is many, consumption is large, purposes is wide, but general amine curing agent at normal temperatures large, the toxicity of volatility large, solidify fast, proportioning too sternly, even absorbing carbon dioxide reduce effect.And aqueous epoxy curing agent is through traditional amine curing agent modification and obtains, which overcome the shortcoming of unmodified amine curing agent, do not affect the process based prediction model of film, and be solvent with water, VOC content meets environmental requirement.
Aqueous epoxy curing agent is divided into I type aqueous epoxy curing agent and the large class of II type aqueous epoxy curing agent two.For I type water-borne epoxy systems, require that the existing solidification function of solidifying agent has emulsification function again.The I type aqueous epoxy curing agent succeeded in developing the earliest is Casmide 360 and the modified product Casmide 362 thereof of Thomas Swan company.In early days, adopt amidation polyamines to be used as the solidifying agent of I type water-borne epoxy systems, although it can make liquid epoxies emulsification, the performance after solidification is not good, water tolerance and chemical resistant properties poor, need to the performance after its in addition solidification of modification guarantee close to solvent epoxy varnish coating.Because the working life of the epoxy-resin systems of polyamide-based solidifying agent emulsification is shorter, the film snappiness of solidification is poor, impact property is poor, the shortcoming that film is partially crisp, modified polyamide-based solidifying agent performance is still not satisfactory, therefore, for the solidifying agent mainly polyamine-epoxy affixture of I type water-borne epoxy systems.
Conventional I type aqueous epoxy curing agent is all that polyamine curing agent is carried out chain extension, grafting, salify mostly, in the molecule introduce nonpolar group because of, become the aqueous dispersible curing agent with close epoxy molecule structure, it carries out emulsification as cationic emulsifier to epoxy resin simultaneously, can be made into stable emulsion after two component mixing.The more modified polyamine solidifying agent of current use is epoxy-polyamines affixture, the preparation method that epoxide modified polyamine curing agent is conventional is generally divided into two kinds: 1) adopt polyethylene polyamine and monocycle oxygen or polyepoxy compound addition, the primary amine hydrogen of about 60% is closed, then with bisphenol-A epoxy addition with it, reach suitable hydrophilic-lipophilic balance, again with formaldehyde reaction further by primary amine hydrogen methylolation, the epoxy systems of this solidifying agent solidification has good gloss, hardness and chemical-resistant; 2) when polyamines is excessive with bisphenol-A epoxy addition, then close primary amine hydrogen with aliphatic monocyclic oxygen or aromatic monocyclic oxygen compound, with water or water-miscible organic solvent dilution after synthesis, the affixture of gained is settled solution, finally, in affixture acetic acid and part amine hydrogen.As Shimp etc. adopts low molecule quality loop epoxy resins and polyethylene polyamine reaction to generate polyamine-epoxy affixture, again through mono-epoxy compounds by its end-blocking, and with in acetic acid and the secondary amine of part, to regulate the HLB of solidifying agent and to reduce the reactive behavior of solidifying agent, extend solidifying agent working life.Afterwards, developed the I type waterborne curing agent technology that some are new, and do not need to adopt organic acid salify.As Stark etc. adopts epoxy resin and excessive m-xylene diamine to react to generate and hold epoxy amine additives, then react with end carboxyl Aethoxy Sklerol and generate amide-amine, then obtain I type aqueous epoxy curing agent through end-blocking.
For II type aqueous epoxy curing agent, because the epoxy resin in II type aqueous epoxy resin systems is made into emulsion in advance, do not need aqueous epoxy curing agent to carry out emulsification to epoxy resin again, thus only need have the function of linking agent.The modification of II type aqueous epoxy curing agent and I type aqueous epoxy curing agent has similarity, as polyamide resin and acetic acid, phosphoric acid or hydrochloric acid reaction obtain ammonium salt, then obtains modified polyamide solidifying agent the auxiliary lower water-soluble of alcohol ether solvent.The II type aqueous epoxy curing agent of current use mainly adopts the aliphatic amide or glycidyl ether and epoxy resin that are embedded with hydrophilic polyoxyethylene segment or the obtained epoxy-amine class solidifying agent of polyethylene polyamine reaction, or to react with dimeracid and generate polyamide-based solidifying agent, it utilize the wetting ability of polyoxyethylene segment to make solidifying agent can be stable is scattered in water, and adopt epoxy resin can improve the consistency of solidifying agent and epoxy resin as chainextender.
As Klein etc. adopts polyoxyethylene diglycidylether and bisphenol A epoxide resin to be obtained by reacting epoxy resin from dispersion, then react with polypropyleneoxide diamine and isophorone diamine and generate epoxy-amine class solidifying agent.Klein etc. adopt bisphenol A epoxide resin, polyoxyethylene diglycidylether and bisphenol-a reaction to obtain epoxy resin dispersion, then generate with polyethylene polyamine reaction and hold amido epoxy-amide adduct, obtain II type aqueous epoxy curing agent finally by end-blocking.
Though m-xylene diamine is aromatic amine, have again the character of aliphatic amide when it participates in solidification, therefore some II type aqueous epoxy curing agents are also the modified products of m-xylene diamine.As MIT's m-xylene diamine and epoxy chloropropane generate epoxy-amide adduct under sodium hydroxide effect, as aqueous epoxy curing agent (commercial disignation G-328), there is excellent performance.Then, G-328 and di-carboxylic acid are obtained by reacting polyamidoamines solidifying agent by Mitsubishi.Also have and adopt aliphatic cyclic amine modified product as aqueous epoxy curing agent.Generate end ring oxygen compound as aliphatic amide and epoxy resin react by Vincent etc., then react obtained solidifying agent with a kind of aliphatic cyclic amine (PACM).
Ciba company have studied a kind of novel I I type aqueous epoxy curing agent, SA solidifying agent is a kind of water miscible epoxy-amide adduct, and highly active solidifying agent is a kind of soluble epoxide-amine additives of modification, regulated the reactive behavior of solidifying agent by the proportioning of the two.It does not need to adopt agglomerated solvent for solids epoxy dispersion, can obtain the epoxy coating of O-VOC.And traditional II type water-borne epoxy systems needs to add agglomerated solvent with the Tg reducing resin is beneficial to the coalescent of resin particle, this has brought volatile organic solvent into.And this novel I I type aqueous epoxy curing agent solves this problem.
Aqueous epoxy coating had both had the good chemical-resistant of solvent epoxy coatings, tack, Physical Mechanical, electric insulating quality, had again the features such as low stain, easy construction, low price.Since developing aqueous epoxy coating technology abroad to 20 century 70s, aqueous epoxy coating is widely used.And as the matching used aqueous epoxy curing agent of water-borne epoxy systems, its process based prediction model of character on film has vital impact.Abroad, the research for aqueous epoxy curing agent is more, also has some industrialized products, but expensive.At home, the research of aqueous epoxy curing agent is less, rarely has ripe product.Therefore, develop the aqueous epoxy curing agent with independent intellectual property right Coating Industry in Our Country is significant.
In sum, Chinese scholars has carried out large quantifier elimination to the preparation of aqueous epoxy curing agent, but has not yet to see containing the synthesis of compound end-blocking aqueous epoxy resin curing agent of maleimide and any report of application and patent.Any report and the patent of this novel material and other resin modified products is not seen yet.Therefore the successful research and development of this product, will expand the production application field of conventional epoxies solidifying agent, promote further developing of this industry.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, this kind of method technique be simple, environmental protection, and range of reaction temperature is wide, and reaction conditions is gentle, is conducive to suitability for industrialized production.
The preparation method of a kind of compound end-blocking aqueous epoxy resin curing agent of the present invention, processing step is as follows successively:
(1) by aminated compounds, phase-transfer catalyst, with after appropriate organic solvent dissolution, under the condition of nitrogen protection, is warming up to 65 DEG C, then drips epoxy chloropropane, after dripping, is cooled to 55 DEG C of reactions 2 ~ 8 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid alkali, being then warming up to 50 DEG C and carrying out ring-closure reaction 1 ~ 6 hour.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by appropriate ethyl acetate, after repeatedly washing, steams removing ethyl acetate namely obtain target product in 45 DEG C of backspins with deionized water---a kind of compound end-blocking aqueous epoxy resin curing agent.
In the method for the invention, aminated compounds described in step (1) is N-(4-aminophenyl) maleimide, phase-transfer catalyst is the one in benzyltriethylammoinium chloride or tetrabutylammonium chloride, organic solvent is a kind of in dehydrated alcohol, propyl alcohol or their mixture, the mol ratio of aminated compounds and epoxy chloropropane is 1: 2.5 ~ 1: 3, phase-transfer catalyst consumption is 1% (mass ratio) of epoxy chloropropane consumption, and the consumption of organic solvent is 10 ~ 12 times (quality) of epoxy chloropropane consumption.
In the method for the invention, the solid alkali described in step (2) is the one in sodium hydroxide or potassium hydroxide, and its consumption is 2 ~ 2.5 times (amount of substances) of aminated compounds consumption.
In the method for the invention, the consumption of the ethyl acetate described in step (3) is 10 ~ 14 times of consumption of organic solvent in step (1), and deionized water wash number of times is 3 ~ 4 times.
In the method for the invention, the target product described in step (3)---a kind of structure of compound end-blocking aqueous epoxy resin curing agent is:
The structure of aminated compounds N-(4-aminophenyl) maleimide is:
Reaction equation of the present invention is as follows:
Embodiment
Embodiment 1
In the present embodiment, a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, its processing step is as follows successively:
(1) by N-(4-aminophenyl) maleimide 20.2g; phase-transfer catalyst benzyltriethylammoinium chloride 0.25g is with after 300ml anhydrous alcohol solution; under the condition of nitrogen protection; be warming up to 65 DEG C; then epoxy chloropropane 24.9g is dripped; after dripping, be cooled to 55 DEG C of reactions 5 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid sodium hydroxide 8.6g, being then warming up to 50 DEG C and carrying out ring-closure reaction 3 hours.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by 3000ml ethyl acetate, after deionized water wash 3 times, target product---a kind of compound end-blocking aqueous epoxy resin curing agent, the product yield 45% that namely removing ethyl acetate obtains viscous brown shape is steamed in 45 DEG C of backspins.
Embodiment 2
In the present embodiment, a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, its processing step is as follows successively:
(1) by N-(4-aminophenyl) maleimide 20.2g; after phase-transfer catalyst tetrabutylammonium chloride 0.25g dissolves with 300ml propyl alcohol; under the condition of nitrogen protection; be warming up to 65 DEG C; then epoxy chloropropane 24.9g is dripped; after dripping, be cooled to 55 DEG C of reactions 4 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid sodium hydroxide 8.6g, being then warming up to 50 DEG C and carrying out ring-closure reaction 4 hours.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by 4200ml ethyl acetate, after deionized water wash 3 times, target product---a kind of compound end-blocking aqueous epoxy resin curing agent, the product yield 52% that namely removing ethyl acetate obtains viscous brown shape is steamed in 45 DEG C of backspins.
Embodiment 3
In the present embodiment, a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, its processing step is as follows successively:
(1) by N-(4-aminophenyl) maleimide 20.2g; phase-transfer catalyst benzyltriethylammoinium chloride 0.25g is with after 360ml anhydrous alcohol solution; under the condition of nitrogen protection; be warming up to 65 DEG C; then epoxy chloropropane 29.9g is dripped; after dripping, be cooled to 55 DEG C of reactions 6 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid potassium hydroxide 8.6g, being then warming up to 50 DEG C and carrying out ring-closure reaction 2 hours.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by 3000ml ethyl acetate, after deionized water wash 3 times, target product---a kind of compound end-blocking aqueous epoxy resin curing agent, the product yield 56% that namely removing ethyl acetate obtains viscous brown shape is steamed in 45 DEG C of backspins.
Embodiment 4
In the present embodiment, a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, its processing step is as follows successively:
(1) by N-(4-aminophenyl) maleimide 20.2g; phase-transfer catalyst benzyltriethylammoinium chloride 0.25g is with after 360ml anhydrous alcohol solution; under the condition of nitrogen protection; be warming up to 65 DEG C; then epoxy chloropropane 29.9g is dripped; after dripping, be cooled to 55 DEG C of reactions 7 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid sodium hydroxide 10.75g, being then warming up to 50 DEG C and carrying out ring-closure reaction 4 hours.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by 4200ml ethyl acetate, after deionized water wash 3 times, target product---a kind of compound end-blocking aqueous epoxy resin curing agent, the product yield 52% that namely removing ethyl acetate obtains viscous brown shape is steamed in 45 DEG C of backspins.
Embodiment 5
In the present embodiment, a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, its processing step is as follows successively:
(1) by N-(4-aminophenyl) maleimide 20.2g; phase-transfer catalyst tetrabutylammonium chloride 0.25g is with after 300ml anhydrous alcohol solution; under the condition of nitrogen protection; be warming up to 65 DEG C; then epoxy chloropropane 29.9g is dripped; after dripping, be cooled to 55 DEG C of reactions 3 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid potassium hydroxide 8.6g, being then warming up to 50 DEG C and carrying out ring-closure reaction 5 hours.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by 3000ml ethyl acetate, after deionized water wash 3 times, target product---a kind of compound end-blocking aqueous epoxy resin curing agent, the product yield 48% that namely removing ethyl acetate obtains viscous brown shape is steamed in 45 DEG C of backspins.
Embodiment 6
In the present embodiment, a kind of preparation method of compound end-blocking aqueous epoxy resin curing agent, its processing step is as follows successively:
(1) by N-(4-aminophenyl) maleimide 20.2g; after phase-transfer catalyst benzyltriethylammoinium chloride 0.25g dissolves with 360ml propyl alcohol; under the condition of nitrogen protection; be warming up to 65 DEG C; then epoxy chloropropane 24.9g is dripped; after dripping, be cooled to 55 DEG C of reactions 6 hours.
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid sodium hydroxide 10.75g, being then warming up to 50 DEG C and carrying out ring-closure reaction 2 hours.
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by 4200ml ethyl acetate, after deionized water wash 3 times, target product---a kind of compound end-blocking aqueous epoxy resin curing agent, the product yield 51% that namely removing ethyl acetate obtains viscous brown shape is steamed in 45 DEG C of backspins.
Claims (4)
1. a preparation method for compound end-blocking aqueous epoxy resin curing agent, is characterized in that processing step is as follows successively:
(1) by aminated compounds, phase-transfer catalyst, with after appropriate organic solvent dissolution, under the condition of nitrogen protection, is warming up to 65 DEG C, then drips epoxy chloropropane, after dripping, is cooled to 55 DEG C of reactions 2 ~ 8 hours;
(2) reaction system be cooled to 30 ~ 40 DEG C and add solid alkali, being then warming up to 50 DEG C and carrying out ring-closure reaction 1 ~ 6 hour;
(3) after reaction terminates, be cooled to room temperature, suction filtration, filtrate extracts by appropriate ethyl acetate, after repeatedly washing, steams removing ethyl acetate namely obtain target product in 45 DEG C of backspins with deionized water---a kind of compound end-blocking aqueous epoxy resin curing agent.
2. the preparation method of a kind of compound end-blocking aqueous epoxy resin curing agent according to claim 1, it is characterized in that the aminated compounds described in step (1) is N-(4-aminophenyl) maleimide, phase-transfer catalyst is the one in benzyltriethylammoinium chloride or tetrabutylammonium chloride, organic solvent is dehydrated alcohol, a kind of in propyl alcohol or their mixture, the mol ratio of aminated compounds and epoxy chloropropane is 1: 2.5 ~ 1: 3, phase-transfer catalyst consumption is 1% (mass ratio) of epoxy chloropropane consumption, the consumption of organic solvent is 10 ~ 12 times (quality) of epoxy chloropropane consumption.
3. the preparation method of a kind of compound end-blocking aqueous epoxy resin curing agent according to claim 1, it is characterized in that the solid alkali described in step (2) is the one in sodium hydroxide or potassium hydroxide, its consumption is 2 ~ 2.5 times (amount of substances) of aminated compounds consumption.
4. the preparation method of a kind of compound end-blocking aqueous epoxy resin curing agent according to claim 1, it is characterized in that the consumption of the ethyl acetate described in step (3) is 10 ~ 14 times of consumption of organic solvent in step (1), deionized water wash number of times is 3 ~ 4 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510031632.9A CN104610239A (en) | 2015-01-22 | 2015-01-22 | Preparation method for composite terminated waterborne epoxy resin curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510031632.9A CN104610239A (en) | 2015-01-22 | 2015-01-22 | Preparation method for composite terminated waterborne epoxy resin curing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104610239A true CN104610239A (en) | 2015-05-13 |
Family
ID=53144919
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510031632.9A Pending CN104610239A (en) | 2015-01-22 | 2015-01-22 | Preparation method for composite terminated waterborne epoxy resin curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104610239A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661936A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Preparation method of water-based epoxy curing agent |
| CN114956663A (en) * | 2022-06-28 | 2022-08-30 | 常州绿玛特建筑科技有限公司 | Remoldable and formable epoxy mortar and preparation method thereof |
-
2015
- 2015-01-22 CN CN201510031632.9A patent/CN104610239A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661936A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Preparation method of water-based epoxy curing agent |
| CN112661936B (en) * | 2019-10-16 | 2023-10-13 | 中国石油化工股份有限公司 | Preparation method of water-based epoxy curing agent |
| CN114956663A (en) * | 2022-06-28 | 2022-08-30 | 常州绿玛特建筑科技有限公司 | Remoldable and formable epoxy mortar and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106987194B (en) | Nonionic waterborne epoxy resin emulsion, nonionic waterborne epoxy curing agent, preparation methods of nonionic waterborne epoxy resin emulsion and nonionic waterborne epoxy curing agent and waterborne epoxy resin varnish | |
| CN105440232B (en) | A kind of preparation technology of water-soluble methyl-etherified melamine resin | |
| CN103739828B (en) | A kind of preparation method of the high-temperature-resistant epoxy resin solidifying agent based on cardanol | |
| CN105175687B (en) | The preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent | |
| CN110066383A (en) | A kind of aqueous epoxy curing agent of ionic and its preparation method and application | |
| CN102190800A (en) | Preparation method of nonionic waterborne epoxy curing agent | |
| CN101134806A (en) | Method for preparing aqueous epoxy resin hardener | |
| CN104262589A (en) | Nonionic self-emulsifying water-based epoxy curing agent with Gemini surfactant structure and preparation method thereof | |
| CN101402720A (en) | Process for producing cold curing watersoluble solidifying agent of epoxy resin | |
| CN103224611A (en) | Modified alicyclic amine curing agent and preparation method thereof | |
| CN104610239A (en) | Preparation method for composite terminated waterborne epoxy resin curing agent | |
| CN106554482B (en) | A kind of preparation method of the star-like aqueous epoxy curing agent of high-performance | |
| CN108358749A (en) | A kind of production method of propargyl alcohol | |
| CN103554442A (en) | Cardanol derivative curing agent and preparation method thereof | |
| CN107446115B (en) | Preparation method of nano modified bisphenol A epoxy resin | |
| CN107759754B (en) | The method for preparing glycolylurea formaldehyde resin using 4-Hydroxyphenyl hydantoin production waste residue | |
| CN105330822A (en) | Water-borne epoxy resin curing agent | |
| CN108929618B (en) | Paint suitable for decorative coating and preparation method thereof | |
| CN104725361B (en) | A kind of preparation method of hindered amine light stabilizer 3346 | |
| CN105585683A (en) | Method for preparing melamine formaldehyde resin flocculating agent | |
| CN105949958A (en) | Waterborne epoxy modified polyamine curing agent and waterborne epoxy anti-corrosion primer coating | |
| CN104693338A (en) | Acrylic hyperdispersing agent and preparation method thereof | |
| CN108373533A (en) | A kind of preparation method of self-emulsifying aqueous epoxy hardener | |
| CN113861802A (en) | Liquid water-based epoxy resin, preparation method and application thereof, composition, coating product and preparation method thereof | |
| CN102382229B (en) | Preparation method of chlorinated polyether resin with core-shell structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150513 |
|
| WD01 | Invention patent application deemed withdrawn after publication |