CN109354655A - A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent - Google Patents
A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent Download PDFInfo
- Publication number
- CN109354655A CN109354655A CN201811335431.8A CN201811335431A CN109354655A CN 109354655 A CN109354655 A CN 109354655A CN 201811335431 A CN201811335431 A CN 201811335431A CN 109354655 A CN109354655 A CN 109354655A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- curing agent
- parts
- aqueous epoxy
- cationic
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08G59/5006—Amines aliphatic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention relates to a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent, contain hydrophilic quaternary ammonium salt cationic and nonionic long-chain Water-borne modification group in molecular structure；Polyhydric aliphatic amine is located at the branched positional of the curing agent, can play curing reaction with epoxy resin.Contain duplicate hydrophilic quaternary ammonium salt cationic, nonionic long-chain Water-borne modification group in the molecular structure of curing agent of the present invention；The polyhydric aliphatic amine of curing reaction can be played with epoxy resin, with self-emulsifying, the polyhydric aliphatic amine structure crosslink density that reacts it with epoxy resin is higher simultaneously, surface drying faster, it is set to have the fast feature of curing rate, the epoxy resin after the present invention solidifies has the advantages that hardness is high, toughness is sufficient.
Description
Technical field
The present invention relates to a kind of aqueous epoxy curing agent more particularly to a kind of cationic self-emulsification aqueous epoxy resin are fast
Solid agent, belongs to environmental technology field.
Background technique
Epoxy resin structural contains epoxy group, hydroxyl and ehter bond isoreactivity group, have many excellent electrical insulation capabilities,
Physical mechanical property, corrosion resistance and adhesive property, it penetrates into each side of people's life in direct or indirect mode
Face, in economic high-tech area, such as aerospace, anticorrosive paint, construction material, industry ground slab coating.Epoxy coating
It is generally divided into solvent epoxy varnish and aqueous epoxy resins.With the development of world economy and science and technology, the environmental consciousness of people
It is increasingly enhanced.Solvent epoxy varnish volatile organic solvent in production and work progress, causes sternly human ecological environment
Heavily contaminated endangers human health, limits development and its application.
Compared with solvent based coating, waterborne epoxy coatings can be washed with water using safe, VOC content is low and smell is small
Outstanding advantages of.Therefore, water-base epoxy self-emulsifying aqueous epoxy hardener is both a kind of curing agent and epoxy for essence
The emulsifier of resin, technical characterstic are to improve its amphipathic property, make up to balanced polarities curing agent by being modified.
After epoxy resin, curing agent, water mix by stirring, stable dispersion heterogeneous structure is formed.Existing waterborne curing agent exists dry
Dry speed is slow, the disadvantage low to epoxy resin emulsifying power.
Chinese patent CN201410828589.4 provides a kind of system of acid amide type self-emulsifying aqueous epoxy resin curing agent
Preparation Method, the synthesis of synthesis, self-emulsifying aqueous epoxy resin curing agent including amide groups polyamines long-chain and etc..The preparation side
Contain hydrophilic amide groups polyamines in its molecular structure of acid amide type self-emulsifying aqueous epoxy resin curing agent made from method simultaneously
Backbone and lipophilic bisphenol a resin structure are free of long polyether chains and organic acid；Amide groups polyamines backbone to paint
Film has the performances such as good flexibility, resistance to acid and alkali, improves the water resistance of paint film without long polyether chains and organic acid and opens up
The wide application field of aqueous epoxy resins；Meanwhile polyamines structure makes paint film crosslink density high, has very high pencil hard
Degree.Due to the amide structure of the curing agent, the shortcomings that there are slow drying speeds.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the present invention is intended to provide a kind of cationic self-emulsified aqueous epoxy tree
Rouge quick-drying curing agent.
A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent, which is characterized in that contain in its molecular structure
Hydrophilic quaternary ammonium salt cationic and nonionic long-chain Water-borne modification group；Polyhydric aliphatic amine is located at the branch position of the curing agent
Set, can with epoxy resin rise curing reaction, and the crosslink density reacted with epoxy resin is higher, surface drying faster.
According to parts by weight, the cationic self-emulsification aqueous epoxy resin quick-drying curing agent takes free radical polymerization
Method, comprising the following steps:
(1) under logical nitrogen and condition of ice bath, 10-12 part two preparation of polyhydric aliphatic amine monomers: is added into reaction unit
The vinyl monomer that hydroxyl replaces, is then added dropwise 4-8 parts of sulfonic acids, reaction process dropwise into reaction kettle under stirring condition
By the sour gas discharged in alkaline drying tube absorbing reaction, whole process temperature is no more than 5 DEG C, after 30min is added dropwise
Continue insulation reaction 2-5h, discharging must may replace alkene, ice bath is spare；10-12 parts of more second are added under condition of ice bath in a kettle
Alkenyl polyamine compound, stirring, being then added dropwise 10-12 parts dropwise into reaction kettle under stirring condition may replace alkene, and 1h is dripped
Continue to stir insulation reaction 2-3h after finishing, whole process temperature is no more than 5 DEG C, obtains polynary aliphatic amine monomer crude product, be with water
Salt in solvent extraction polyhydric aliphatic amine monomers crude product repeats after extracting upper layer 3-5 times, upper layer after moisture is distilled off,
Obtain polyhydric aliphatic amine monomers；
(2) low-temperature catalyzed free radical polymerization: by 6-8 parts of cationic monomers, 4-6 parts of branched chain type aqueous monomers, 8-15 parts of steps
Suddenly the polyhydric aliphatic amine monomers in (1), stir evenly under room temperature in mixing arrangement, and it is spare to obtain dropping liquid a；0.5-1 parts are drawn
Hair agent is dissolved in 10 parts of hydrotropic solvents, and it is spare to obtain dropping liquid b；Under logical condition of nitrogen gas, 15-25 parts of hydrotropic solvents are added to reaction
In device, it is heated to 50-60 DEG C, dropping liquid a, dropping liquid b is at the uniform velocity added dropwise into reactor from different dropwise adding tanks respectively, the two is same
When be added dropwise in 3-4h, 0.05-0.1 part initiators 2-3h that keeps the temperature that the reaction was continued is added after being added dropwise, is cooled to room temperature
Cationic self-emulsification aqueous epoxy resin quick-drying curing agent.
The vinyl monomer that the dihydroxy replaces be 3,4- dihydroxy -1- butylene, cis- 1,4- dihydroxy -2- butylene,
At least one of trans- 1,4- dihydroxy -2- butylene, 2,3- dihydroxy -1- butylene.
The sulfonic acid is p-methyl benzenesulfonic acid, paratoluensulfonyl chloride, chlorosulfonic acid, benzene sulfonyl chloride, adjacent tosyl
At least one of chlorine, o-toluene sulfonic acid.
The alkaline drying tube be calcium hydroxide drying tube, quick lime drying tube, in sodium hydroxide drying tube at least
It is a kind of.
More vinyl polyamine compounds are isophorone diamine, front three basic ring diamine, ethylenediamine, divinyl
At least one of base triamine, triethylene tetraamine, tetraethylenepentamine
The cationic monomer be N, N, N- trimethylallylammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac,
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, chlorination N, N, N- trimethyl-(1- (4- ethenylphenyl)) first ammonium, acryloyl-oxy
EthyMmethylammonium bromide, methylacryoyloxyethyl trimethylammonium bromide, chlorination N- methyl -2- vinylpyridine, chlorination N- first
At least one of base -4-vinylpridine.
The branched chain type aqueous monomers are methacrylic acid macrogol ester, polyalkylene glycol acrylate ester, allyl are poly-
Ethylene glycol, methacrylic polyethylene glycol, relative molecular weight 600-1200.
The initiator is hydrogen peroxide, dibenzoyl peroxide, perbenzoic acid, azodiisobutyronitrile, azo two
At least one of different heptonitrile.
The hydrotropic solvent is at least one of ethyl alcohol, ethylene glycol monobutyl ether, glycol monoethyl ether.
Compared with the existing technology, the present invention has the following advantages that or the utility model has the advantages that (1) present invention passes through dihydroxy substitution
The substitution reaction of vinyl monomer has synthesized polyhydric aliphatic amine monomers, and the monomer amine value is higher；(2) the polyhydric aliphatic amine described in
Response type catalyst of the monomer as free radical polymerization reduces the temperature of polymerization reaction while participating in polymerizeing as monomer
Degree；(3) contain duplicate hydrophilic quaternary ammonium salt cationic, nonionic long-chain water in the molecular structure of quick-drying curing agent of the present invention
Property group；The polyhydric aliphatic amine that curing reaction can be played with epoxy resin has self-emulsifying, while polyhydric aliphatic amine structure
The crosslink density for reacting it with epoxy resin is higher, surface drying faster makes it have the fast feature of curing rate, solid through the present invention
Epoxy resin after change has the advantages that hardness is high, toughness is sufficient.
Specific embodiment
Below with reference to embodiment to a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent of the invention do into
The description of one step.It is understood that specific embodiment described herein is used only for explaining related invention, rather than to the hair
Bright restriction.
Embodiment 1
A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent contains hydrophilic quaternary ammonium salt sun in molecule
Ion and nonionic long-chain Water-borne modification group；The polyhydric aliphatic amine that curing reaction can be played with epoxy resin is located at the curing agent
Branched positional, the crosslink density reacted with epoxy resin is higher, surface drying faster.
According to parts by weight, the radical polymerization of the cationic self-emulsification aqueous epoxy resin quick-drying curing agent
The following steps are included:
(1) under logical nitrogen and condition of ice bath, 12 parts of 3,4- bis- preparation of polyhydric aliphatic amine monomers: are added into reaction unit
Hydroxyl-1-butene, is then added dropwise 8 parts of paratoluensulfonyl chlorides dropwise into reaction kettle under stirring condition, reaction process passes through hydrogen-oxygen
Change the sour gas discharged in calcium drying tube absorbing reaction, whole process temperature is no more than 5 DEG C, and 30min continues after being added dropwise
Insulation reaction 5h, discharging, must may replace alkene, ice bath is spare；12 parts of isophorone diamine are added under condition of ice bath in a kettle,
Stirring, being then added dropwise 12 parts under stirring condition dropwise into reaction kettle may replace alkene, and 1h continues stirring heat preservation after being added dropwise anti-
3h is answered, whole process temperature is no more than 5 DEG C, obtains polynary aliphatic amine monomer crude product, takes water as a solvent extraction polyhydric aliphatic amine list
Salt in body crude product repeats after extracting upper layer 5 times, and upper layer obtains polyhydric aliphatic amine monomers after moisture is distilled off.
(2) low-temperature catalyzed free radical polymerization: by 6 parts of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chlorides, 4 parts of poly- second of acrylic acid
Polyhydric aliphatic amine monomers in diol ester, 8 parts of steps (1), stir evenly under room temperature in mixing arrangement, it is spare to obtain dropping liquid a；
0.5 part of dibenzoyl peroxide is dissolved in 10 parts of glycol monoethyl ethers, it is spare to obtain dropping liquid b；Under logical condition of nitrogen gas, by 15 parts
Glycol monoethyl ether is added in reactor, is heated to 50 DEG C, and drop is at the uniform velocity added dropwise into reactor from different dropwise adding tanks respectively
Liquid feeding a, dropping liquid b, the two are added dropwise in 3h simultaneously, and 0.05 part of dibenzoyl peroxide heat preservation is added after being added dropwise and continues
2h is reacted, cationic self-emulsification aqueous epoxy resin quick-drying curing agent is cooled to room temperature to obtain.
Embodiment 2
A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent contains hydrophilic quaternary ammonium salt sun in molecule
Ion and nonionic long-chain Water-borne modification group；The polyhydric aliphatic amine that curing reaction can be played with epoxy resin is located at the curing agent
Branched positional, the crosslink density reacted with epoxy resin is higher, surface drying faster.
According to parts by weight, the radical polymerization of the cationic self-emulsification aqueous epoxy resin quick-drying curing agent
The following steps are included:
(1) under logical nitrogen and condition of ice bath, 10 parts of 2,3- bis- preparation of polyhydric aliphatic amine monomers: are added into reaction unit
Hydroxyl-1-butene, is then added dropwise 4 parts of chlorosulfonic acids dropwise into reaction kettle under stirring condition, reaction process is dry by sodium hydroxide
The sour gas discharged in dry pipe absorbing reaction, whole process temperature are no more than 5 DEG C, and it is anti-that subsequent continuation of insurance temperature is added dropwise in 30min
2h is answered, discharges, alkene must be may replace, ice bath is spare；10 parts of tetraethylenepentamines are added under condition of ice bath in a kettle, stir,
Then being added dropwise 10 parts under stirring condition dropwise into reaction kettle may replace alkene, and 1h continues to stir insulation reaction 2h after being added dropwise,
Whole process temperature is no more than 5 DEG C, obtains polynary aliphatic amine monomer crude product, takes water as a solvent extraction polyhydric aliphatic amine monomers and slightly produces
Salt in object repeats after extracting upper layer 3 times, and upper layer obtains polyhydric aliphatic amine monomers after moisture is distilled off.
(2) low-temperature catalyzed free radical polymerization: by 7 parts of N, N, N- trimethylallylammonium chloride, 5 parts of poly- second of methacrylic
Polyhydric aliphatic amine monomers in glycol (relative molecular weight 1200), 12 parts of steps (1) stir under room temperature in mixing arrangement
It is even, it is spare to obtain dropping liquid a；0.8 part of azobisisoheptonitrile is dissolved in 10 parts of ethylene glycol monobutyl ethers, it is spare to obtain dropping liquid b；Logical nitrogen
Under the conditions of gas, 19 parts of ethylene glycol monobutyl ethers are added in reactor, are heated to 56 DEG C, respectively from different dropwise adding tanks to reaction
Dropping liquid a, dropping liquid b are at the uniform velocity added dropwise in device, the two is added dropwise in 3.5h simultaneously, and 0.07 part of azo two is added after being added dropwise
Different heptonitrile heat preservation the reaction was continued 2.6h, is cooled to room temperature to obtain cationic self-emulsification aqueous epoxy resin quick-drying curing agent.
Embodiment 3
A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent contains hydrophilic quaternary ammonium salt sun in molecule
Ion and nonionic long-chain Water-borne modification group；The polyhydric aliphatic amine that curing reaction can be played with epoxy resin is located at the curing agent
Branched positional, the crosslink density reacted with epoxy resin is higher, surface drying faster.
According to parts by weight, the radical polymerization of the cationic self-emulsification aqueous epoxy resin quick-drying curing agent
The following steps are included:
(1) preparation of polyhydric aliphatic amine monomers: under logical nitrogen and condition of ice bath, into reaction unit, 10.5 parts of addition is trans-
Isosorbide-5-Nitrae-dihydroxy -2- butylene, is then added dropwise 5 parts of p-methyl benzenesulfonic acid dropwise into reaction kettle under stirring condition, reaction process passes through
The sour gas discharged in quick lime drying tube absorbing reaction, whole process temperature are no more than 5 DEG C, and 30min is added dropwise subsequent
Continuous insulation reaction 4h, discharging must may replace alkene, ice bath is spare；11 parts of front three basic rings are added under condition of ice bath in a kettle
Diamine, stirring, being then added dropwise 10.5 parts under stirring condition dropwise into reaction kettle may replace alkene, and 1h continues to stir after being added dropwise
Insulation reaction 2.5h is mixed, whole process temperature is no more than 5 DEG C, obtains polynary aliphatic amine monomer crude product, and it is more to take water as a solvent extraction
Salt in first aliphatic amine monomer crude product repeats after extracting upper layer 4 times, and upper layer obtains polyhydric aliphatic after moisture is distilled off
Amine monomers.
(2) low-temperature catalyzed free radical polymerization: by 8 parts of chlorination N- methyl -4-vinylpridines, 6 parts of poly- second of methacrylic
Polyhydric aliphatic amine monomers in glycol (relative molecular weight 800), 15 parts of steps (1) stir under room temperature in mixing arrangement
It is even, it is spare to obtain dropping liquid a；1 part of hydrogen peroxide is dissolved in 10 parts of ethyl alcohol, it is spare to obtain dropping liquid b；Under logical condition of nitrogen gas, by 25 parts
Ethyl alcohol is added in reactor, is heated to 60 DEG C, and dropping liquid a, drop is at the uniform velocity added dropwise into reactor from different dropwise adding tanks respectively
Liquid feeding b, the two are added dropwise in 4h simultaneously, are added the heat preservation of 0.1 part of hydrogen peroxide after being added dropwise the reaction was continued 3h, be cooled to room temperature
Obtain cationic self-emulsification aqueous epoxy resin quick-drying curing agent.
Certain brand aqueous epoxy curing agent (comparative example) is bought on the market, respectively by the embodiment 1-3 of 20 parts by weight, right
Ratio is added in 35 parts of water, is denoted as No. 1, No. 2, No. 3, No. 4 respectively, and 25 parts of commercially available rings are added after being uniformly dispersed thereto respectively
Uniformly, 0.4 part of aqueous organic silicon modified by polyether levelling agent, dispersion is then added in oxygen resin E-51, high speed dispersion emulsification thereto
It is uniform that epoxide terrace paint, physical property are shown in Table 1；Roller coating will be taken out after 1-4 epoxide terrace paint in cement plate surface, pass through brush
3 times to No. 1-4 coating thickness are 50 microns ± 5 microns, and rear test performance such as the following table 2 is fully cured in film:
Table 1: the performance table for the epoxide terrace paint that embodiment and comparative example are prepared
Table 2: the paint film property table for the epoxide terrace paint that embodiment and comparative example are prepared
Although the present invention has been explained in detail and has referred to embodiment, for those of ordinary skill in the art, show
Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.
Claims (10)
1. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent, which is characterized in that contain parent in its molecular structure
Aqueous quaternary ammonium salt cationic and nonionic long-chain Water-borne modification group, polyhydric aliphatic amine are located at the branched positional of the curing agent,
Curing reaction can be played with epoxy resin.
2. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 1, which is characterized in that
According to parts by weight, radical polymerization is taken in preparation, comprising the following steps:
(1) under logical nitrogen and condition of ice bath, 10-12 parts of dihydroxy the preparation of polyhydric aliphatic amine monomers: are added into reaction unit
Substituted vinyl monomer, is then added dropwise 4-8 parts of sulfonic acids dropwise into reaction kettle under stirring condition, reaction process passes through
The sour gas discharged in alkaline drying tube absorbing reaction, whole process temperature are no more than 5 DEG C, and 30min continues after being added dropwise
Insulation reaction 2-5h, discharging, must may replace alkene, ice bath is spare；10-12 parts of more vinyl are added under condition of ice bath in a kettle
Polyamine compounds, stirring, being then added dropwise 10-12 parts dropwise into reaction kettle under stirring condition may replace alkene, after 1h is added dropwise
Continue to stir insulation reaction 2-3h, whole process temperature is no more than 5 DEG C, obtains polynary aliphatic amine monomer crude product, take water as a solvent
The salt in polyhydric aliphatic amine monomers crude product is extracted, is repeated after extracting upper layer 3-5 times, upper layer obtains after moisture is distilled off
Polyhydric aliphatic amine monomers；
(2) low-temperature catalyzed free radical polymerization: by 6-8 parts of cationic monomers, 4-6 parts of branched chain type aqueous monomers, 8-15 parts of steps (1)
In polyhydric aliphatic amine monomers, stirred evenly under room temperature in mixing arrangement, it is spare to obtain dropping liquid a；0.5-1 parts of initiators are molten
In 10 parts of hydrotropic solvents, it is spare to obtain dropping liquid b；Under logical condition of nitrogen gas, 15-25 parts of hydrotropic solvents are added in reactor,
It is heated to 50-60 DEG C, dropping liquid a, dropping liquid b is at the uniform velocity added dropwise into reactor from different dropwise adding tanks respectively, the two exists simultaneously
3-4h is added dropwise, and 0.05-0.1 part initiators 2-3h that keeps the temperature that the reaction was continued is added after being added dropwise, be cooled to room temperature it is positive from
Subtype self-emulsification aqueous epoxy resin quick-drying curing agent.
3. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
The vinyl monomer that the dihydroxy replaces is 3,4- dihydroxy -1- butylene, cis- 1,4- dihydroxy -2- butylene, trans- 1,4-
At least one of dihydroxy -2- butylene, 2,3- dihydroxy -1- butylene.
4. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
The sulfonic acid is p-methyl benzenesulfonic acid, paratoluensulfonyl chloride, chlorosulfonic acid, benzene sulfonyl chloride, o-toluenesulfonyl chloride, adjacent toluene
At least one of sulfonic acid.
5. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
The alkaline drying tube is at least one of calcium hydroxide drying tube, quick lime drying tube, sodium hydroxide drying tube.
6. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
More vinyl polyamine compounds be isophorone diamine, front three basic ring diamine, ethylenediamine, diethylene triamine,
At least one of triethylene tetraamine, tetraethylenepentamine.
7. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
The cationic monomer is N, N, N- trimethylallylammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, metering system
Acyloxyethyl trimethyl ammonium chloride, chlorination N, N, N- trimethyl-(1- (4- ethenylphenyl)) first ammonium, acrylyl oxy-ethyl front three
Base ammonium bromide, methylacryoyloxyethyl trimethylammonium bromide, chlorination N- methyl -2- vinylpyridine, chlorination N- methyl -4- ethylene
At least one of yl pyridines.
8. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
The branched chain type aqueous monomers are methacrylic acid macrogol ester, polyalkylene glycol acrylate ester, allyl polyglycol, first
Base allyl polyglycol.
9. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, which is characterized in that
The initiator is hydrogen peroxide, in dibenzoyl peroxide, perbenzoic acid, azodiisobutyronitrile, azobisisoheptonitrile
At least one.
10. a kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent according to claim 2, feature exist
In the hydrotropic solvent is at least one of ethyl alcohol, ethylene glycol monobutyl ether, glycol monoethyl ether.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011304205.0A CN112300344A (en) | 2018-11-10 | 2018-11-10 | Preparation method of water-based quick-drying epoxy floor paint |
| CN202011304164.5A CN112480790A (en) | 2018-11-10 | 2018-11-10 | Epoxy floor paint with high hardness and sufficient toughness and application thereof |
| CN202011304217.3A CN112409549A (en) | 2018-11-10 | 2018-11-10 | Cationic water-based epoxy resin high-efficiency emulsifier |
| CN202011309019.6A CN112321801A (en) | 2018-11-10 | 2018-11-10 | Preparation method of cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
| CN202011304232.8A CN112409576A (en) | 2018-11-10 | 2018-11-10 | Water-based epoxy resin coating |
| CN201811335431.8A CN109354655B (en) | 2018-11-10 | 2018-11-10 | Cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811335431.8A CN109354655B (en) | 2018-11-10 | 2018-11-10 | Cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
Related Child Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011304205.0A Division CN112300344A (en) | 2018-11-10 | 2018-11-10 | Preparation method of water-based quick-drying epoxy floor paint |
| CN202011309019.6A Division CN112321801A (en) | 2018-11-10 | 2018-11-10 | Preparation method of cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
| CN202011304164.5A Division CN112480790A (en) | 2018-11-10 | 2018-11-10 | Epoxy floor paint with high hardness and sufficient toughness and application thereof |
| CN202011304217.3A Division CN112409549A (en) | 2018-11-10 | 2018-11-10 | Cationic water-based epoxy resin high-efficiency emulsifier |
| CN202011304232.8A Division CN112409576A (en) | 2018-11-10 | 2018-11-10 | Water-based epoxy resin coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109354655A true CN109354655A (en) | 2019-02-19 |
| CN109354655B CN109354655B (en) | 2020-12-22 |
Family
ID=65344783
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011309019.6A Withdrawn CN112321801A (en) | 2018-11-10 | 2018-11-10 | Preparation method of cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
| CN201811335431.8A Active CN109354655B (en) | 2018-11-10 | 2018-11-10 | Cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
| CN202011304205.0A Withdrawn CN112300344A (en) | 2018-11-10 | 2018-11-10 | Preparation method of water-based quick-drying epoxy floor paint |
| CN202011304164.5A Withdrawn CN112480790A (en) | 2018-11-10 | 2018-11-10 | Epoxy floor paint with high hardness and sufficient toughness and application thereof |
| CN202011304232.8A Withdrawn CN112409576A (en) | 2018-11-10 | 2018-11-10 | Water-based epoxy resin coating |
| CN202011304217.3A Withdrawn CN112409549A (en) | 2018-11-10 | 2018-11-10 | Cationic water-based epoxy resin high-efficiency emulsifier |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011309019.6A Withdrawn CN112321801A (en) | 2018-11-10 | 2018-11-10 | Preparation method of cationic self-emulsifying water-based epoxy resin quick-drying curing agent |
Family Applications After (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011304205.0A Withdrawn CN112300344A (en) | 2018-11-10 | 2018-11-10 | Preparation method of water-based quick-drying epoxy floor paint |
| CN202011304164.5A Withdrawn CN112480790A (en) | 2018-11-10 | 2018-11-10 | Epoxy floor paint with high hardness and sufficient toughness and application thereof |
| CN202011304232.8A Withdrawn CN112409576A (en) | 2018-11-10 | 2018-11-10 | Water-based epoxy resin coating |
| CN202011304217.3A Withdrawn CN112409549A (en) | 2018-11-10 | 2018-11-10 | Cationic water-based epoxy resin high-efficiency emulsifier |
Country Status (1)
| Country | Link |
|---|---|
| CN (6) | CN112321801A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605892B (en) * | 2022-03-22 | 2022-12-23 | 厦门双瑞船舶涂料有限公司 | Organosilicon quaternary ammonium salt modified epoxy anticorrosive paint and preparation method thereof |
| CN114989695B (en) * | 2022-04-21 | 2023-02-10 | 宁波宣威彩色世界涂料有限公司 | Water-based environment-friendly odor-free quick-drying floor paint |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070142572A1 (en) * | 2005-12-16 | 2007-06-21 | Shun Ogawa | Curing agent composition for epoxy resins and epoxy resin composition |
| CN103421140A (en) * | 2013-07-23 | 2013-12-04 | 中蓝晨光化工研究设计院有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
| CN107177031A (en) * | 2017-04-17 | 2017-09-19 | 烟台大学 | A kind of GMA modified amine curing agent and resist sagging coating |
-
2018
- 2018-11-10 CN CN202011309019.6A patent/CN112321801A/en not_active Withdrawn
- 2018-11-10 CN CN201811335431.8A patent/CN109354655B/en active Active
- 2018-11-10 CN CN202011304205.0A patent/CN112300344A/en not_active Withdrawn
- 2018-11-10 CN CN202011304164.5A patent/CN112480790A/en not_active Withdrawn
- 2018-11-10 CN CN202011304232.8A patent/CN112409576A/en not_active Withdrawn
- 2018-11-10 CN CN202011304217.3A patent/CN112409549A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070142572A1 (en) * | 2005-12-16 | 2007-06-21 | Shun Ogawa | Curing agent composition for epoxy resins and epoxy resin composition |
| CN103421140A (en) * | 2013-07-23 | 2013-12-04 | 中蓝晨光化工研究设计院有限公司 | Epoxy resin curing agent and preparation method thereof |
| CN104558529A (en) * | 2014-12-26 | 2015-04-29 | 江苏苏博特新材料股份有限公司 | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent |
| CN107177031A (en) * | 2017-04-17 | 2017-09-19 | 烟台大学 | A kind of GMA modified amine curing agent and resist sagging coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112409549A (en) | 2021-02-26 |
| CN112321801A (en) | 2021-02-05 |
| CN109354655B (en) | 2020-12-22 |
| CN112480790A (en) | 2021-03-12 |
| CN112300344A (en) | 2021-02-02 |
| CN112409576A (en) | 2021-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101921373B (en) | Acrylic modified epoxy resin emulsion and preparation method thereof | |
| CN100586979C (en) | Preparation method of acrylic acid-epoxy resin modified aqueous polyurethane | |
| CN107573474B (en) | Silicone-modified waterborne polyurethane-acrylic resin emulsion and preparation method thereof | |
| CN108329438B (en) | High-acid-resistance water-based epoxy dispersion and preparation method thereof | |
| CN100387653C (en) | Monocomponent self-cross-linking epoxy acrylic acid composite emulsion , its preparation method and uses | |
| CN108864412A (en) | High-solid low-viscosity epoxy curing agent for waterborne epoxy self-leveling terrace and preparation method thereof | |
| CN102199389B (en) | Self-crosslinking acrylic resin leather finishing agent and preparation method thereof | |
| KR20120099600A (en) | Epoxy resin imbibed polymer particles | |
| CN104262589A (en) | Nonionic self-emulsifying water-based epoxy curing agent with Gemini surfactant structure and preparation method thereof | |
| CN102408853A (en) | Water-based body flame-resistant acrylate adhesive and preparation method thereof | |
| CN1891772B (en) | Epoxy resin emulsion for water-based coating, and its preparing method | |
| CN106833238A (en) | A kind of Weak solvent ink absorption coating emulsion-type film forming matter and preparation method thereof | |
| CN1908023A (en) | Acrylic acid bulk hybridization emulsion composition | |
| CN101161742A (en) | Bicomponent automobile cathode electrophoresis paint and preparation method thereof | |
| CN1239492A (en) | Dithiocarbonate compsn. | |
| CN109354655A (en) | A kind of cationic self-emulsification aqueous epoxy resin quick-drying curing agent | |
| CN101864025A (en) | Preparation method of polyacrylate microgel emulsion and application thereof | |
| CN105439852B (en) | A kind of synthetic method of the single-ended ether-ether series compound of polyalkylene glycol acrylate | |
| CN103467672A (en) | Water-based organic silicon-modified epoxy resin and preparation method thereof | |
| CN110511356A (en) | A kind of silicon oil modified aqueous epoxy curing agent of epoxy and phenyl and preparation method thereof | |
| CN1594427A (en) | Process for preparing water soluble epoxy resin grouting agent | |
| CN1139643C (en) | Flexible coatings with low surface tack and surface tension | |
| CN109468020A (en) | A kind of water-base epoxy surface lacquer and its preparation method and application suitable for electrical equipment | |
| CN109942742A (en) | A kind of water dispersion glass coated polymeric and preparation method thereof | |
| CN113861802A (en) | Liquid water-based epoxy resin, preparation method and application thereof, composition, coating product and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20201202 Address after: 511300 Xian Cun Zhen Shang Jing Cun Da Tang tou, Zengcheng District, Guangzhou City, Guangdong Province Applicant after: Guangzhou Yuda Electronic Technology Co., Ltd Address before: 410219 No. 653, Group 11, Baishazhou Village, Baishazhou Street, Wangcheng District, Changsha City, Hunan Province Applicant before: Liu Peng |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |