CN105482079B - A kind of nonionic waterborne epoxy curing agent and preparation method thereof - Google Patents
A kind of nonionic waterborne epoxy curing agent and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of nonionic waterborne epoxy curing agent and preparation method thereof, the curing agent contains the methoxy poly (ethylene glycol) nonionic functional segments for being grafted on curing agent side chain, is synthesized with the following raw material, each raw material dosage percentage：Diisocyanate 2~5%, methoxy poly (ethylene glycol) 8~12%, bisphenol A type epoxy resin 19~30%, mono-epoxy compounds 7~13%, polyamine 10~17%, surplus are deionized water, and the methoxy poly (ethylene glycol) molecular weight is 500~800.The curing agent VOC of the present invention is extremely low, there is preferable dispersiveness to face, filler, the component A prepared with the curing agent has preferable stability, coating is configured to aqueous epoxy resins, extensive use can be carried out in industrial antisepsis field, floor field etc., there is excellent flexibility, anticorrosive property, chemical-resistant.Preparation method is easy to operation, simple process, meets environmental requirement.
Description
Technical field
The present invention relates to a kind of nonionic waterborne epoxy curing agent and preparation method thereof.
Background technology
Epoxy resin is led due to its unique chemical constitution and excellent mechanical property, the more and more extensive adhesive that is applied to
Domain and terrace, anticorrosive paint field, especially obtain extensive concern and application in paint field.With the attention of environmental protection ideas, ring
Guarantor's regulation is increasingly severe, and waterborne epoxy coatings arises at the historic moment, and user is more and more harsh to its solvent limitation, to film
More and more higher can be required.Waterborne epoxy coatings system forms its film forming matter by aqueous epoxy resins and aqueous epoxy curing agent,
The design feature of aqueous epoxy curing agent, solvent, film performance, TOVC (VOC) to coating rise
Key effect.
Existing aqueous epoxy curing agent is generally divided into ionic and nonionic, a handful of curing agent be cation-
Nonionic.Ionic curing agent is that had in resin using forming waterborne dispersions in organic acid and by the way of tertiary amine
Suitable data proves that organic acid suppresses have negative work to the face of curing agent, filler dispersion stabilization, film anticorrosion corrosion energy, flash rusting
With；Nonionic curing agent is that non-ionic polyethers segment is introduced in curing agent, is allowed to Water-borne modification.Generally, nonionic chain
Section be by block, chain extension access curing agent in, make curing agent Water-borne modification, but easily cause curing agent viscosity increase, it is necessary to compared with
Multi-solvent is diluted to reduce viscosity.Also there are some curing agent using excess polyhydric amine and epoxy resin or the epoxy containing polyether segment
Resin chain extension, then by being evaporated under reduced pressure, solvent is removed with unnecessary amine to ensure the low solvent and ordered structure of curing agent spy
Point, but preparation technology is complicated, steams solvent and is not readily separated with unnecessary amine and recycle, and causes wastage of material and environmental pollution.
The content of the invention
The present invention first purpose be：A kind of nonionic waterborne epoxy curing agent is provided, it is introduced in a manner of being grafted
Appropriate methoxy poly (ethylene glycol) non-ionic hydrophilic segment, avoid existing with block fashion introducing non-ionic hydrophilic segment institute
The foregoing shortcomings brought.
Realizing the technical scheme of first purpose of the invention is：A kind of nonionic waterborne epoxy curing agent, its feature exist
In it contains the methoxy poly (ethylene glycol) nonionic functional segments for being grafted on curing agent side chain, is synthesized with the following raw material, each raw material
Dosage percentage：2~5 parts of diisocyanate, methoxy poly (ethylene glycol) 8~12%, bisphenol A type epoxy resin 19~
30%, mono-epoxy compounds 7~13%, polyamine 10~17%, surplus is deionized water, the methoxy poly (ethylene glycol) molecule
Measure as 500~800.
In above-mentioned nonionic waterborne epoxy curing agent, the diisocyanate is toluene di-isocyanate(TDI), isophorone
One or both of diisocyanate.
In above-mentioned nonionic waterborne epoxy curing agent, the mono-epoxy compounds is butyl glycidyl ether, phenyl contracting
One or both of water glycerin ether, o-tolyl glycidol ether, octyl glycidyl ether, benzyl glycidyl ether.
In above-mentioned nonionic waterborne epoxy curing agent, the polyamine is one in triethylene tetramine and TEPA
Kind or two kinds.
Above-mentioned nonionic waterborne epoxy curing agent, it is characterised in that the epoxide number of the bisphenol A type epoxy resin is
0.18~0.51.
Second object of the present invention is：A kind of easy to operation, simple process is provided, meets the nonionic of environmental requirement
The preparation method of aqueous epoxy curing agent.
Realizing the technical scheme of second purpose of the invention is：A kind of system of above-mentioned nonionic waterborne epoxy curing agent
Preparation Method, it is characterised in that prepare raw material by above-mentioned each raw material dosage, preservation is stand-by, then divides three steps to synthesize, specific behaviour
Make as follows：
1. prepare the semiclosed thing A of isocyanates
Diisocyanate is added in reaction vessel, 45~80 DEG C is warming up to and the poly- second two of methoxyl group is added dropwise in this temperature
Alcohol, time for adding are 2~4h, are added dropwise, and after 50~80 DEG C are incubated 2h, measure-NCO content no longer reduces, that is, are made different
The semiclosed thing A of cyanate, above operation are carried out under agitation；
2. prepare intermediate product B
Bisphenol A type epoxy resin is added in reaction vessel, 50~100 DEG C is warming up to, in 1.5~4h 1. step is made
Isocyanates semiclosed thing A points more parts, add at equal intervals in reaction vessel, temperature all adds at 50~100 DEG C around here
Afterwards, then between 50 DEG C~110 DEG C progressively heat up and be incubated, amount to 4~6h, measure-NCO content, until-NCO content ﹤
During 0.3wt%, terminate reaction, intermediate product B is made, above operation is carried out under agitation；
3. prepare nonionic waterborne epoxy curing agent
Polyamine is added in reaction vessel, 45~80 DEG C is warming up to and mono-epoxy compounds, 2~4h is added dropwise in this temperature
Inside be added dropwise, 2~4h be incubated at 50~80 DEG C, then, at 50 ± 2 DEG C, by step 2. obtained intermediate product B points more parts,
Add at equal intervals in reaction vessel, after all being added in 1.5~4h, then progressively heat up and be incubated between 45~90 DEG C, always
4~6h is counted, adds deionized water, nonionic waterborne epoxy curing agent is made, above operation is carried out under agitation.
In the preparation method of above-mentioned nonionic waterborne epoxy curing agent, the step 2. in, step is 1. obtained
After the semiclosed thing A of isocyanates is all added, then at 60 ± 2 DEG C 2h are incubated, are warming up to 80 ± 2 DEG C of insulation 2h afterwards, then heat up
To 100 ± 2 DEG C of insulation 2h, measure-NCO content terminates reaction, intermediate product B is made until during-NCO content ﹤ 0.3wt%, with
Upper operation is carried out under agitation.
In the preparation method of above-mentioned nonionic waterborne epoxy curing agent, the step 3. in, step is 2. obtained
After intermediate product B is added, then at 50 ± 2 DEG C 2h are incubated, are warming up to 70 ± 2 DEG C of insulation 2h afterwards, then are warming up to 80 ± 2 DEG C of insulations
After 2h, deionized water is added, nonionic waterborne epoxy curing agent is made, above operation is carried out under agitation.
The solution have the advantages that：
1st, the nonionic waterborne epoxy curing agent of technical solution of the present invention be using methoxy poly (ethylene glycol) as it is non-from
Sub- hydroaropic substance and curing agent side chain is grafted on, therefore had the following advantages that：
1. the hydroaropic substance usage amount of curing agent of the present invention is reduced compared with block fashion, and does not influence the water-based of curing agent
Change, simultaneously because reduce the usage amount of nonionic hydrophilic substance, therefore use the coating of curing agent of the present invention preparation, its film it is resistance to
Water-based, antiseptic property is improved；
2. curing agent of the present invention as non-ionic hydrophilic material and is grafted on curing agent side using methoxy poly (ethylene glycol)
Chain, make the viscosity of curing agent lower, realize higher solids content, and without organic solvent diluting in building-up process, significantly
VOC is reduced, meets environmental requirement increasingly strict at present, avoids and is caused with block fashion introducing non-ionic hydrophilic segment
Shortcomings caused by curing agent viscosity is larger；
3. the polyamine dosage of curing agent of the present invention is appropriate, excess amine is not used, therefore without molten by being evaporated under reduced pressure removing
Agent and unnecessary amine, the solvent that it also avoid steaming are not readily separated with unnecessary amine and recycled, and cause wastage of material and environmental pollution
The shortcomings that.
2nd, because the curing agent of the present invention is nonionic, it is therefore not necessary to which organic acid neutralizes, be advantageous to strengthen curing agent
Scattered face, the stability of filler, be advantageous to suppress the flash rusting phenomenon of water paint on metal base, be advantageous to the long-acting of film
Anticorrosion.
3rd, the preparation method of nonionic waterborne epoxy curing agent provided by the invention, curing agent can be made in building-up process
It is middle to obtain lower viscosity, without organic solvent diluting in building-up process, without by being evaporated under reduced pressure organic solvent or excess
Polyamine realizes the Diamond Search of curing agent, makes preparation technology easier, and can reduce production cost.
Embodiment
The present invention is described further with reference to embodiments, but is not limited to this.
Embodiment and comparative example raw materials are unless otherwise indicated commercially available industrial goods, can be purchased by commercial channel
.
During nonionic waterborne epoxy curing agent synthesis of the present invention, each raw material dosage percentage is as follows：Two is different
Cyanate 2~5%, methoxy poly (ethylene glycol) 8~12%, bisphenol A type epoxy resin 19~30%, mono-epoxy compounds 7~
13%, polyamine 10~17%, surplus is deionized water.
Embodiment 1 prepares nonionic waterborne epoxy curing agent
(1) raw material is prepared
Each raw material is weighed by the dosage of table 1, it is stand-by；
Table 1
(2) preparation method
Three steps are divided to synthesize, concrete operations are as follows：
1. prepare the semiclosed thing A of isocyanates
IPDI is added in reaction vessel, 50 ± 2 DEG C is warming up to and methoxyl group is added dropwise in this temperature
Polyethylene glycol, time for adding 4h, is added dropwise, and is to slowly warm up to 80 ± 2 DEG C in 1h, after being incubated 2h, determine every half an hour-
NCO content, until-NCO content declines in 5.1wt% or so and no longer, that is, the semiclosed thing A of isocyanates, above operation is made
Carry out under agitation；
2. prepare intermediate product B
Bisphenol A type epoxy resin E-44 is added in reaction vessel, is warming up to 60 ± 2 DEG C, by step 1. obtained isocyanide
Semiclosed thing A of acid esters etc. points 4 parts, interval 30min is added once, and temperature treats the semiclosed thing A of isocyanates at 60 ± 2 DEG C around here
All add after, then 60 ± 2 DEG C be incubated 2h, be warming up to afterwards 80 ± 2 DEG C insulation 2h, then be warming up to 100 ± 2 DEG C insulation 2h,
Measure-NCO content, until during-NCO content ﹤ 0.3wt%, terminate reaction, intermediate product B is made, the above operates under agitation
Carry out；
3. prepare nonionic waterborne epoxy curing agent
TEPA is added in reaction vessel, 50 ± 2 DEG C is warming up to, butyl glycidyl is added dropwise at this temperature
Ether, 2h are added dropwise, and are warming up to 70 ± 2 DEG C, are incubated 4h, are cooled to 50 ± 2 DEG C afterwards, by step 2. obtained intermediate product B
4 parts of decile, interval 30min are added once, and during which temperature is at 50 ± 2 DEG C, until intermediate product B is all added, then at 50 ± 2 DEG C
Be incubated 2h, be warming up to afterwards 70 ± 2 DEG C insulation 2h, then be warming up to 80 ± 2 DEG C insulation 2h after, add deionized water, be made it is non-from
Subtype aqueous epoxy curing agent, above operation are carried out under agitation.
The curing agent solids content is 60.3wt%, and amine hydrogen equivalent=228 ± 10 (are counted) in the form of supply.
Embodiment 2 prepares nonionic waterborne epoxy curing agent
(1) raw material is prepared
Each raw material is weighed by the dosage of table 2, it is stand-by；
Table 2
| Component | Material name and specification | Dosage, g (wt%) |
| Diisocyanate | IPDI | 222(3.16) |
| Methoxy poly (ethylene glycol) | Molecular weight 560~640 | 600(8.53) |
| Bisphenol A type epoxy resin | E-44 | 1363.5(19.38) |
| Polyamine | TEPA | 1135.8(16.14) |
| Mono-epoxy compounds | Phenyl glycidyl ether | 900(12.79) |
| Deionized water | 2814.2(40) | |
| It is total | 7035.5(100) |
(2) preparation method
Three steps are divided to synthesize, concrete operations are as follows：
1. prepare the semiclosed thing A of isocyanates and 2. prepare intermediate product B method it is identical with embodiment 1；
3. prepare nonionic waterborne epoxy curing agent
TEPA is added in reaction vessel, 50 ± 2 DEG C is warming up to, phenyl glycidyl is added dropwise at this temperature
Ether, 2h are added dropwise, and are warming up to 70 ± 2 DEG C, are incubated 4h, are cooled to 50 ± 2 DEG C afterwards, by step 2. obtained intermediate product B
4 parts of decile, interval 30min are added once, and during which temperature is at 50 ± 2 DEG C, until intermediate product B is all added, then at 50 ± 2 DEG C
Be incubated 2h, be warming up to afterwards 70 ± 2 DEG C insulation 2h, then be warming up to 80 ± 2 DEG C insulation 2h after, add deionized water, be made it is non-from
Subtype aqueous epoxy curing agent, above operation are carried out under agitation.
The curing agent solids content is 60.5wt%, and amine hydrogen equivalent=235 ± 10 (are counted) in the form of supply.
Embodiment 3 prepares nonionic waterborne epoxy curing agent
(1) raw material is prepared
Each raw material is weighed by the dosage of table 3, it is stand-by；
Table 3
| Component | Material name and specification | Dosage, g (wt%) |
| Diisocyanate | IPDI | 222(3.45) |
| Methoxy poly (ethylene glycol) | Molecular weight 560~640 | 600(9.31) |
| Bisphenol A type epoxy resin | E-44 | 1363.5(21.16) |
| Polyamine | Triethylene tetramine | 900(13.97) |
| Mono-epoxy compounds | Butyl glycidyl ether | 780(12.11) |
| Deionized water | 2577.2(40) | |
| It is total | 6442.7(100) |
(2) preparation method
Three steps are divided to synthesize, concrete operations are as follows：
1. prepare the semiclosed thing A of isocyanates and 2. prepare intermediate product B method it is identical with embodiment 1；
3. prepare nonionic waterborne epoxy curing agent
Triethylene tetramine is added in reaction vessel, 50 ± 2 DEG C is warming up to, butyl glycidyl is added dropwise at this temperature
Ether, 2h is added dropwise, after dripping, is warming up to 70 ± 2 DEG C, be incubated 4h, be cooled to 50 ± 2 DEG C afterwards, by step 2. obtained centre
Product B etc. points 4 parts, interval 30min is added once, and during which temperature is at 50 ± 2 DEG C, until intermediate product B is all added, then 50
± 2 DEG C insulation 2h, be warming up to afterwards 70 ± 2 DEG C insulation 2h, then be warming up to 80 ± 2 DEG C insulation 2h after, add deionized water, be made
Nonionic waterborne epoxy curing agent, above operation are carried out under agitation.
The curing agent solids content is 60.5wt%, and amine hydrogen equivalent=268 ± 10 (are counted) in the form of supply.
Embodiment 4 prepares nonionic waterborne epoxy curing agent
(1) raw material is prepared
Each raw material is weighed by the dosage of table 4, it is stand-by；
Table 4
| Component | Material name and specification | Dosage, g (wt%) |
| Diisocyanate | IPDI | 222(4.14) |
| Methoxy poly (ethylene glycol) | Molecular weight 560~640 | 600(11.18) |
| Bisphenol A type epoxy resin | 901 | 1440(26.83) |
| Polyamine | TEPA | 567.9(10.58) |
| Mono-epoxy compounds | Butyl glycidyl ether | 390(7.27) |
| Deionized water | 2147(40) | |
| It is total | 5366.9(100) |
(2) preparation method
Three steps are divided to synthesize, concrete operations are as follows：
1. the method for preparing the semiclosed thing A of isocyanates is identical with embodiment 1；
2. prepare intermediate product B
Bisphenol A type epoxy resin 901 is added in reaction vessel, is warming up to 90 ± 2 DEG C, by step 1. obtained isocyanic acid
Semiclosed thing A of ester etc. points 8 parts, interval 30min is added once, and temperature treats that the semiclosed thing A of isocyanates is complete at 90 ± 2 DEG C around here
Portion add after, then 90 ± 2 DEG C be incubated 2h, be warming up to afterwards 100 ± 2 DEG C insulation 2h, measure-NCO content, until-NCO content
During ﹤ 0.3wt%, terminate reaction, intermediate product B is made, above operation is carried out under agitation；
3. prepare nonionic waterborne epoxy curing agent
TEPA is added in reaction vessel, 50 ± 2 DEG C is warming up to, butyl glycidyl is added dropwise at this temperature
Ether, 2h is added dropwise, after dripping, is warming up to 70 ± 2 DEG C, be incubated 4h, be cooled to 50 ± 2 DEG C afterwards, by step 2. obtained centre
Product B etc. points 4 parts, interval 30min is added once, and during which temperature is at 50 ± 2 DEG C, until intermediate product B is all added, then
50 ± 2 DEG C insulation 2h, be warming up to afterwards 70 ± 2 DEG C insulation 2h, then be warming up to 80 ± 2 DEG C insulation 2h after, add deionized water, system
Nonionic waterborne epoxy curing agent is obtained, above operation is carried out under agitation.
The curing agent solids content is 60.6wt%, and amine hydrogen equivalent=358 ± 10 (are counted) in the form of supply.
Embodiment 5 prepares nonionic waterborne epoxy curing agent
(1) raw material is prepared
Each raw material is weighed by the dosage of table 5, it is stand-by；
Table 5
| Component | Material name and specification | Dosage, g (wt%) |
| Diisocyanate | Toluene di-isocyanate(TDI) | 174(2.58) |
| Methoxy poly (ethylene glycol) | Molecular weight 560~640 | 600(8.88) |
| Bisphenol A type epoxy resin | E-44 | 1363.5(20.18) |
| Polyamine | TEPA | 1135.8(16.81) |
| Mono-epoxy compounds | Butyl glycidyl ether | 780(11.55) |
| Deionized water | 2702(40) | |
| It is total | 6755.3(100) |
(2) preparation method
Three steps are divided to synthesize, concrete operations are as follows：
1. prepare the semiclosed thing A of isocyanates
Toluene di-isocyanate(TDI) is added in reaction vessel, is warming up to 50 ± 2 DEG C, and the poly- second of methoxyl group is added dropwise in this temperature
Glycol, 4h is added dropwise, is added dropwise, is to slowly warm up to 80 ± 2 DEG C in 1h, after being incubated 2h, every half an hour measure-NCO content, directly
Extremely-NCO content declines in 5.43wt% or so and no longer, that is, the semiclosed thing A of isocyanates is made, and the above operates under agitation
Carry out；
2. prepare intermediate product B
Bisphenol A type epoxy resin E-44 is added in reaction vessel, is warming up to 60 ± 2 DEG C, by step 1. obtained isocyanide
Semiclosed thing A of acid esters etc. points 4 parts, interval 30min is added once, is incubated around here at 60 ± 2 DEG C, is treated the semiclosed thing A of isocyanates
All add after, then 60 ± 2 DEG C be incubated 2h, be warming up to afterwards 80 ± 2 DEG C insulation 2h, then be warming up to 100 ± 2 DEG C insulation 2h
Afterwards, measure-NCO content, until during-NCO content ﹤ 0.3wt%, terminate reaction, obtain intermediate product B, above operation is being stirred
Mix lower progress；
3. prepare nonionic waterborne epoxy curing agent
TEPA is added in reaction vessel, 50 ± 2 DEG C is warming up to, butyl glycidyl is added dropwise at such a temperature
Ether, 2h is added dropwise, after dripping, is warming up to 70 ± 2 DEG C, be incubated 4h, be cooled to 50 ± 2 DEG C afterwards, by step 2. obtained centre
Product B etc. points 4 parts, interval 30min is added once, and during which temperature is at 50 ± 2 DEG C, until intermediate product B is all added, then 50
± 2 DEG C insulation 2h, be warming up to afterwards 70 ± 2 DEG C insulation 2h, then be warming up to 80 ± 2 DEG C insulation 2h after, add deionized water, be made
Nonionic waterborne epoxy curing agent, above operation are carried out under agitation.
The curing agent solids content is 60.2wt%, and amine hydrogen equivalent=225 ± 10 (are counted) in the form of supply.
Embodiment 6 prepares bi-component aqueous epoxy coating and detects its coating property
(1) formulation for coating material
Using nonionic waterborne epoxy curing agent made from embodiment 3 as prepare coating curing agent, with pigment, fill out
Material, auxiliary agent, deionized water composition component A；Using commercially available epoxy emulsion as B component, specific formula is shown in Table 6.
Table 6
(2) Paint preparation technology
In material-compound tank, 1., 2., 3., 4. the raw material of table 6 is put into successively under stirring, scattered at a high speed (30~
40HZ) 5~10min, then 5., 6., 7., 8., 9., 10. the raw material of table 6 is sequentially added under stirring, disperse (30 at a high speed
~40HZ) 5~10min, then fineness≤35 μm are ground to through being sanded, stop stirring, filtering and discharging, adjustment solids content to 59 ±
2wt%, component A is made.
Obtained component A is well mixed with B component by the dosage of table 6, adds deionized water adjustment viscosity (applying -4 glasss)
It is standby to 25~30s, as bi-component aqueous epoxy iron oxide red coating.
(3) prepared by test board
Bi-component aqueous epoxy iron oxide red coating obtained above is sprayed on the cold-rolled steel sheet polished, at room temperature from dry
7 days, thickness of dry film was controlled at 30~40 μm.
(4) the above-mentioned model film performance of coatings industry concerned countries standard detection is pressed, testing result is listed in the table below 7.
Table 7
Embodiment 7 prepares the bi-component aqueous epoxy iron oxide red coating of comparative example 1 and 2 and detects its coating property
The formulation for coating material of comparative example 1 and 2 is formulated essentially identical with embodiment 6, and difference is, the curing agent of comparative example 1
Ionic aqueous epoxy curing agent is neutralized for commercially available acid, solids content is 60 ± 2wt%；The curing agent of comparative example 2 is commercially available embedding
Section nonionic waterborne epoxy curing agent, solids content is 50 ± 2wt%.
Test sample plate is prepared as described in Example 6 and carries out correlated performance detection, the results are shown in Table 8.
Table 8
As can be seen from Table 8, compared with curing agent used in comparative example 1 and 2, the nonionic made from technical solution of the present invention
The component A for the bi-component aqueous epoxy iron oxide red coating that type aqueous epoxy curing agent is prepared, its VOC content is extremely low, and iron oxide red slurry is stable
Property is excellent；The Corrosion Protections such as film is water-fast, acid and alkali-resistance, resistance to neutral salt spray are good, have an obvious technique effect, and market prospects are wide
It is wealthy.
Claims (8)
1. a kind of nonionic waterborne epoxy curing agent, it is characterised in that it, which contains, is grafted on the methoxyl group of curing agent side chain and gathers
Ethylene glycol nonionic functional segments, are synthesized with the following raw material, each raw material dosage percentage：Diisocyanate 2~
5%, methoxy poly (ethylene glycol) 8~12%, bisphenol A type epoxy resin 19~30%, mono-epoxy compounds 7~13%, polyamine
10~17%, surplus is deionized water, and the methoxy poly (ethylene glycol) molecular weight is 500~800；
Described nonionic waterborne epoxy curing agent, it is characterised in that it is that point three steps synthesize, and step is as follows：
1. prepare the semiclosed thing A of isocyanates
Diisocyanate is added in reaction vessel, is warming up to 45~80 DEG C, and methoxy poly (ethylene glycol), drop is added dropwise in this temperature
It is 2~4h between added-time, after 50~80 DEG C are incubated 2h, the semiclosed thing A of isocyanates is made；
2. prepare intermediate product B
Bisphenol A type epoxy resin is added in reaction vessel, is warming up to 50~100 DEG C, in 1.5~4h, isocyanates half is sealed
A points more parts of thing is closed, adds in reaction vessel reacted at equal intervals, progressively heats up and is incubated between 50 DEG C~110 DEG C, 4~
After 6h, intermediate product B is made；
3. prepare nonionic waterborne epoxy curing agent
Polyamine is added in reaction vessel, is warming up to 45~80 DEG C, mono-epoxy compounds is added dropwise in 2~4h polyamine is entered
Row end-blocking, after the completion of end-blocking, 2~4h are incubated at 50~80 DEG C, at a temperature of 50 ± 2 DEG C, by B points more parts of intermediate product, etc. between
Every add block after product in, reacted, progressively heated up between 45~90 DEG C and be incubated 4~6h, be eventually adding from
Sub- water, is made nonionic waterborne epoxy curing agent, and above operation is carried out under agitation.
2. nonionic waterborne epoxy curing agent according to claim 1, it is characterised in that the diisocyanate is first
One or both of phenylene diisocyanate, IPDI.
3. nonionic waterborne epoxy curing agent according to claim 1, it is characterised in that the mono-epoxy compounds is
Butyl glycidyl ether, phenyl glycidyl ether, o-tolyl glycidol ether, octyl glycidyl ether, benzyl glycidol
One or both of ether.
4. nonionic waterborne epoxy curing agent according to claim 1, it is characterised in that the polyamine is triethylene
One or both of tetramine and TEPA.
5. nonionic waterborne epoxy curing agent according to claim 1, it is characterised in that the bisphenol type epoxy tree
The epoxide number of fat is 0.18~0.51.
6. the preparation method of the nonionic waterborne epoxy curing agent described in a kind of claim 1, it is characterised in that will by right
Each raw material dosage described in 1 is asked to prepare raw material, preservation is stand-by, then divides three steps to synthesize, and concrete operations are as follows：
1. prepare the semiclosed thing A of isocyanates
Diisocyanate is added in reaction vessel, 45~80 DEG C is warming up to and methoxy poly (ethylene glycol), drop is added dropwise in this temperature
It is 2~4h between added-time, is added dropwise, after 50~80 DEG C are incubated 2h, measure-NCO content no longer reduces, that is, isocyanates is made
Semiclosed thing A, above operation are carried out under agitation；
2. prepare intermediate product B
Bisphenol A type epoxy resin is added in reaction vessel, is warming up to 50~100 DEG C, 1.5~4h is interior 1. obtained different by step
Semiclosed thing A points more parts of cyanate, adding at equal intervals in reaction vessel, temperature is at 50~100 DEG C around here, after all adding, then
Progressively heat up and be incubated between 50 DEG C~110 DEG C, amount to 4~6h, measure-NCO content, until-NCO content ﹤ 0.3wt%
When, terminate reaction, intermediate product B is made, above operation is carried out under agitation；
3. prepare nonionic waterborne epoxy curing agent
Polyamine is added in reaction vessel, 45~80 DEG C is warming up to and mono-epoxy compounds is added dropwise in this temperature, dripped in 2~4h
Add complete, 2~4h be incubated at 50~80 DEG C, then, at 50 ± 2 DEG C, by step 2. obtained intermediate product B points more parts, etc. between
Every adding in reaction vessel, after all being added in 1.5~4h, then progressively heat up and be incubated between 45~90 DEG C, total 4~
6h, deionized water is added, nonionic waterborne epoxy curing agent is made, above operation is carried out under agitation.
7. the preparation method of nonionic waterborne epoxy curing agent according to claim 6, it is characterised in that in the step
Suddenly 2. in, by step after 1. the semiclosed thing A of obtained isocyanates is all added, then at 60 ± 2 DEG C be incubated 2h, be warming up to afterwards
80 ± 2 DEG C insulation 2h, then be warming up to 100 ± 2 DEG C insulation 2h, measure-NCO content until-NCO content ﹤ 0.3wt% when, terminate
Reaction, is made intermediate product B, and above operation is carried out under agitation.
8. the preparation method of nonionic waterborne epoxy curing agent according to claim 6, it is characterised in that in the step
Suddenly 3. in, by step after 2. obtained intermediate product B is added, then at 50 ± 2 DEG C be incubated 2h, be warming up to 70 ± 2 DEG C of insulations afterwards
2h, then after being warming up to 80 ± 2 DEG C of insulation 2h, add deionized water, nonionic waterborne epoxy curing agent is made, above operation is equal
Carry out under agitation.
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| CN107840940B (en) * | 2017-10-25 | 2020-02-07 | 中南林业科技大学 | Preparation method of curing agent for epoxy powder coating |
| CN110229310B (en) * | 2019-07-16 | 2020-07-07 | 上海骁鹏新材料科技有限公司 | Curing agent for modified waterborne epoxy resin and preparation method thereof |
| CN110591048B (en) * | 2019-09-23 | 2021-07-30 | 安徽大学 | Preparation method of fluorine-containing waterborne epoxy curing agent |
| CN111087607B (en) * | 2019-12-09 | 2022-12-06 | 湖南柯盛新材料有限公司 | Preparation method and application of self-emulsifying accelerant for epoxy colored sand |
| CN114686069B (en) * | 2020-12-28 | 2023-03-31 | 中海油常州涂料化工研究院有限公司 | Polyacrylate resin modified waterborne epoxy emulsion and preparation method thereof |
| CN114853973A (en) * | 2021-06-18 | 2022-08-05 | 宜兴市华夏化工材料有限公司 | High-solid-content low-VOC hydrophilic modified epoxy resin and preparation method thereof |
| CN114806317B (en) * | 2022-03-17 | 2023-05-26 | 安徽欣苗新材料科技有限公司 | Container floor water-based asphalt paint and processing method thereof |
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| CN101824133B (en) * | 2010-04-28 | 2011-12-07 | 天津大学 | Preparation method for waterborne polyurethane modified epoxy resin curing agent |
| CN101838386A (en) * | 2010-05-26 | 2010-09-22 | 天津大学 | Method for preparing waterborne polyurethane taken as waterborne epoxy hardener |
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Address after: China CNOOC Building No. 25 Beijing 100010 Dongcheng District Chaoyangmen North Street, room 1414 Co-patentee after: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Co-patentee after: CNOOC CHANGZHOU EP COATING Co.,Ltd. Address before: China CNOOC Building No. 25 Beijing 100010 Dongcheng District Chaoyangmen North Street, room 1414 Co-patentee before: CNOOC CHANGZHOU PAINT CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Co-patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Co-patentee before: CNOOC CHANGZHOU EP COATING Co.,Ltd. |
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