CN104558528A - Phosphorus-containing polyamine self-emulsifying epoxy resin curing agent, and preparation method and use thereof - Google Patents
Phosphorus-containing polyamine self-emulsifying epoxy resin curing agent, and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a phosphorus-containing polyamine self-emulsifying epoxy resin curing agent. The method comprises the following steps: firstly adding polyamine, aromatic aldehyde or aromatic ketone and DOPO to a four-necked flask, taking absolute ethyl alcohol as a solvent, taking triethylamine as a catalyst, stirring, heating up and performing a reflux reaction, cooling to room temperature, pouring a reaction liquid to deionized water, precipitating out, carrying out suction filtration, washing with water, re-crystallizing a crude product, and drying to obtain a phosphorus-containing polyamine epoxy resin curing agent; then preparing a non-ionic waterborne epoxy self-emulsifying agent; and finally, preparing the phosphorus-containing polyamine self-emulsifying epoxy resin curing agent with DOPO as a side group by using the phosphorus-containing polyamine epoxy resin curing agent and the non-ionic waterborne epoxy self-emulsifying agent. The phosphorus-containing polyamine self-emulsifying epoxy resin curing agent with DOPO as the side group, prepared by the method provided by the invention, has flame retardant, heat resistant and self-emulsifying functions to meet the preparation needs of a fire-retardant and heat-resistant waterborne epoxy paint base material.
Description
Technical field
The present invention relates to a kind of Phosphorous Containing Polyamines epoxy curing agent and preparation method thereof and purposes, especially a kind of side base is Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of DOPO and preparation method thereof and purposes.
Background technology
Epoxy resin is used widely in coating, building, electronics etc. because of the electricity of tool excellence, mechanical property and chemical resistance, but, the limiting oxygen index(LOI) (LOI) of most epoxide resin material is all lower than 22%, easy firing in atmosphere, this makes them in use there is great potential safety hazard, limits its range of application, therefore, preparation thermal characteristics is excellent, and the epoxy resin that fire retardancy is high becomes research emphasis.
Improve ethoxyline resin antiflaming performance to have and add fire retardant type and reactive flame retardant two kinds of modes outward, add fire retardant type outward and exist and matrix poor compatibility, flame-retardant additive migration and the problem such as the thermostability that causes and flame retardant resistance deterioration.
Organic phosphorus flame retardant by generate high dehydrated polyphosphoric acid and make the carbonization of oxygen-bearing organic matter rapid dehydration formed have three-dimensional dense structure sticky, not easily volatile carbon compound be covered in by combustion thing surface, thus reduce the generation of flammable effusion thing, hinder oxygen to the diffusion of reaction zone, play few cigarette, environmental protection that few toxicity, corrosive gases generate completely cuts off fire retarding effect.
In the middle of phosphorus flame retardant, the luxuriant and rich with fragrance compounds 9 of phosphine, assorted-10-phospho hetero phenanthrene-10-oxide compound (DOPO) of 10-dihydro-9-oxy and derivative thereof, because having unique molecular structure and good reactivity worth (the P-H reactive hydrogen in its structure, be very easy to form new compound with electron deficiency carbon (as double bond, carbonyl or epoxy group(ing) etc.)), be preparation feedback type phosphorus-containing flame-retardant epoxy resin preferred material.Reaction-type flame-retarding epoxy resin is divided into also to be had flame-retardant modified two aspects of solidifying agent ethoxyline resin antiflaming modification.DOPO can directly and epoxy resin prepolymer react obtained phosphorus-containing flame-retardant epoxy resin, Wang etc. are with a series of phosphorous epoxy resin of DOPO and bisphenol A diglycidyl ether (DGEBA) Reactive Synthesis.TGA research shows, the thermostability of cured article reduces with the increase of phosphorus content, but still is better than other phosphorous polymer, and carbon left increases thereupon.But the introducing of DOPO makes epoxide group reduce, because this reducing cross-linking density and the rigidity of resin, moreover adopt DOPO to carry out modification to commercialization epoxy resin, its ring texture steric effect makes it react increase, and cost is relatively high.
DOPO is incorporated in conventional epoxy polyamine curing agent, both the P factor by increasing realizes flame retardant properties, heat and the mechanical property of epoxy material is increased again by the rigidity phenyl ring on it, and, introduced by DOPO in polyamine curing agent, steric hindrance is little, while can being introduced into easily, the resin after solidification is made to have excellent flame retardant resistance, thermostability and higher Tg, and less to the Effect on Mechanical Properties of resin.
Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent, by epoxy self-emulsifying function, can realize the Water-borne modification of epoxy easily, again by reducing emulsifying agent or not using emulsifying agent to improve the over-all properties of epoxy emulsion.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part and a kind of preparation method that side base is the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of DOPO that contains is provided; Another object of the present invention is to provide a kind of adopts described method to prepare, and has fire-retardant, heat-resisting and self-emulsifying function concurrently, can meet the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of fire protection flame retarding hot water resistance epoxy coating preparation needs; Another object of the present invention is to provide a kind of described Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent preparing the application in epoxy frie retardant coating.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent, said method comprising the steps of:
(1) preparation of Phosphorous Containing Polyamines epoxy curing agent: in the four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, adds polyamines, aromatic aldehyde or aromatic ketone, DOPO, adds that solvent made by dehydrated alcohol, catalyzer made by triethylamine, stir, be warming up to 80 DEG C of back flow reaction 12h, be cooled to room temperature, reaction solution is poured in deionized water, there is Precipitation, suction filtration, washing, carries out recrystallization to thick product, drying, obtains Phosphorous Containing Polyamines epoxy curing agent;
(2) preparation of non-ion aqueous epoxy self-emulsifier: in the four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add polyamines and propylene glycol monomethyl ether, with constant pressure funnel, the mixing solutions being dissolved with chainextender diglycidylether and propylene glycol monomethyl ether is added wherein under stirring, 5h is reacted under 45 ~ 90 DEG C of steady temperatures, then the propylene glycol monomethyl ether solution of bifunctional epoxy resin is added, reaction 3h, obtains non-ion aqueous epoxy self-emulsifier;
(3) preparation of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent: in the four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add the Phosphorous Containing Polyamines epoxy curing agent that step (1) obtains, the non-ion aqueous epoxy self-emulsifier that step (2) obtains is added under stirring, at 70 DEG C, react 3 ~ 5h, obtain the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that side base is DOPO.
The mixed solution of ethanol and water can be adopted to carry out recrystallization to thick product in step described above (1), the product after recrystallization can at 60 DEG C of vacuum-drying 12h.In step described above (3), the add-on of Phosphorous Containing Polyamines epoxy curing agent and non-ion aqueous epoxy self-emulsifier there is no particular restriction, and those skilled in the art can according to the content proportioning of practical situation and the Phosphorous Containing Polyamines epoxy curing agent needing suitable selection to add and non-ion aqueous epoxy self-emulsifier.
As the preferred implementation of the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, in described step (1), the mol ratio of polyamines, aromatic aldehyde or aromatic ketone, DOPO is 1:2:2.
As the preferred implementation of the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, polyamines in described step (1) and step (2) is quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, hexanediamine, Ursol D or 4,4 '-benzidine.
As the preferred implementation of the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, the aromatic aldehyde in described step (1) or aromatic ketone are phenyl aldehyde, substituted benzaldehyde, benzophenone, substituted benzene ketone or 4,4 '-diphenyl-dimethanal.
As the preferred implementation of the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, the DOPO in described step (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or derivatives thereof.
As the preferred implementation of the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, the chainextender diglycidylether in described step (2) is ethylene glycol diglycidylether, propylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, polyethyleneglycol diglycidylether, diethylene glycol diglycidyl glyceryl ether, diethylene glycol diglycidyl ether, Diethylene Glycol glycidyl ether or polyether glycol diglycidylether.
Meanwhile, present invention also offers the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent adopting method described above to prepare, it is containing DOPO side base.
In addition, present invention also offers Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent described above and prepare the application in epoxy frie retardant coating, for realizing this object, the technical scheme that the present invention takes is: the application in epoxy frie retardant coating prepared by a kind of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent described above, comprises the following steps:
Epoxy resin and Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent being imported to join paints in cup, add water, stir into uniform epoxy emulsion, the solid content of described epoxy emulsion is more than 50%, described epoxy emulsion is directly carried out painting film preparation fire protection coating, or using described epoxy emulsion as base-material, add other auxiliary agent, prepare epoxy frie retardant coating.
As Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention in the preferred implementation preparing the application in epoxy frie retardant coating, with the mol ratio of epoxy group(ing) and ammonia hydrogen for 1:1 adds described epoxy resin and Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent.
As Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention in the preferred implementation preparing the application in epoxy frie retardant coating, described epoxy resin is that (trade mark is E-51 to bisphenol A type epoxy resin, E-44, E-55, E-56, E-54, E-56D, E-52D, E-53D, E-48D, E-35 or E-20), (trade mark is 672 to the strain of glycidyl ester type epoxy tree, 731, 771, 712, CY183 or NGA), (trade mark is 6458 to bisphenol f type epoxy resin, 6445, 6420, YDF-170, YDF-2001, YDF-8170, CYDF-170 or CYDF-180), (trade mark is 669 to diglycidyl ether type epoxy resin, 664-2, 664-3, 668, 63 or 696) Resorcinol type epoxy (trade mark literary composition 680 or J-80).
The present invention compared with prior art, has following advantage and effect:
(1) quasi-Mannich reaction is adopted to be incorporated in traditional epoxy polyamine solidifying agent by DOPO that is phosphorous and the certain resistance toheat of tool, introduce the polyamines chain with surface active function more wherein, thus preparation contains N, P and the epoxy polyamine curing agent of the certain resistance toheat of tool;
(2) the epoxy polyamine curing agent prepared by has fire-retardant, heat-resisting, self-emulsifying triple functions concurrently, prepares epoxy coating with this solidifying agent, can realize self-emulsifying and the Water-borne modification of epoxy resin easily, can give again coating certain fire retardant performance;
(3) by DOPO and derivative thereof, functional modification is carried out to polyamine curing agent, the phosphorous factor is introduced in solidifying agent, and then preparation feedback type flame retardant coating, avoid outer poor compatibility of adding the such as fire retardant and matrix that type phosphorus fire retardant brings, the defects such as fire retardant migration, thus ensure good and lasting flame retardant effect, ensure long-term stability and the homogeneity of flame retardant effect, therefore, the preparation of this process has the water-base epoxy polyamine curing agent of anti-flaming function and corresponding epoxy flame retardant coating base-material thereof, the process of fire protection flame retarding coating is simple, with low cost, be suitable for the suitability for industrialized production of frie retardant coating.
Embodiment
For better the object, technical solutions and advantages of the present invention being described, below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
A kind of embodiment of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent described in the present embodiment adopts following methods to be prepared from:
(1) preparation of Phosphorous Containing Polyamines epoxy curing agent: nitrogen access equipment is being housed, reflux condensing tube, in 500 ml four-hole boiling flasks of thermometer and mechanical stirrer, add 0.05 mol triethylene tetramine, 0.1 mol phenyl aldehyde and 0.1 mol DOPO, add 150 ml dehydrated alcohols and make solvent, catalyzer made by 0.6 g triethylamine, stir, be warming up to 80 DEG C of back flow reaction 12 h, be cooled to room temperature, reaction solution is poured in deionized water, namely a large amount of Precipitation is had, suction filtration, wash three times, with ethanol: water mixed liquid carries out recrystallization to thick product, 60 DEG C of vacuum-drying 12 h, obtain Phosphorous Containing Polyamines epoxy curing agent,
(2) preparation of non-ion aqueous epoxy self-emulsifier: in the 500 ml four-hole boiling flasks that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add stearylamine and solvent propylene glycol methyl ether, with constant pressure funnel, the mixing solutions of polyoxyethylene glycol bisglycidyl ether-400 and propylene glycol monomethyl ether is added wherein under stirring, stirring reaction 5 h under 70 DEG C of steady temperatures, then the propylene glycol monomethyl ether solution of bisphenol A epoxide resin E-51 is added, react 3 h at 50 DEG C, obtain non-ion aqueous epoxy self-emulsifier;
(3) preparation of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent: in the 500 ml four-hole boiling flasks that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add the Phosphorous Containing Polyamines epoxy curing agent that step (1) obtains, the non-ion aqueous epoxy self-emulsifier that step (2) obtains is added under stirring, half an hour finishes, react 3 h under maintaining 70 DEG C of temperature, obtain the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that side base is DOPO.
Embodiment 2
A kind of embodiment of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent described in the present embodiment adopts following methods to be prepared from:
(1) preparation of Phosphorous Containing Polyamines epoxy curing agent: nitrogen access equipment is being housed, reflux condensing tube, in 500 ml four-hole boiling flasks of thermometer and mechanical stirrer, add 0.05 mol quadrol, 0.1 mol benzophenone and 0.1 mol DOPO, add 150 ml dehydrated alcohols and make solvent, catalyzer made by 0.6 g triethylamine, stir, be warming up to 80 DEG C of back flow reaction 12 h, be cooled to room temperature, reaction solution is poured in deionized water, namely a large amount of Precipitation is had, suction filtration, wash three times, with ethanol: water mixed liquid carries out recrystallization to thick product, 60 DEG C of vacuum-drying 12h, obtain Phosphorous Containing Polyamines epoxy curing agent,
(2) preparation of non-ion aqueous epoxy self-emulsifier: in the 500 ml four-hole boiling flasks that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add stearylamine and solvent propylene glycol methyl ether, with constant pressure funnel, the mixing solutions of ethylene glycol bis glycidyl ether and propylene glycol monomethyl ether is added wherein under stirring, stirring reaction 5h at 70 DEG C, then the propylene glycol monomethyl ether solution of epoxy resin E-44 is added, react 3 h at 50 DEG C, obtain non-ion aqueous epoxy self-emulsifier;
(3) preparation of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent: in the 500ml four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add the Phosphorous Containing Polyamines epoxy curing agent that step (1) obtains, the non-ion aqueous epoxy self-emulsifier that step (2) obtains is added under stirring, half an hour finishes, react 5h under maintaining 70 DEG C of temperature, obtain the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that side base is DOPO.
Embodiment 3
A kind of embodiment of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent described in the present embodiment adopts following methods to be prepared from:
(1) preparation of Phosphorous Containing Polyamines epoxy curing agent: nitrogen access equipment is being housed, reflux condensing tube, in 500 ml four-hole boiling flasks of thermometer and mechanical stirrer, add 0.05 mol tetraethylene pentamine, 0.1 mol is to tolyl aldehyde and 0.1 mol DOPO, add 150 ml dehydrated alcohols and make solvent, catalyzer made by 0.6 g triethylamine, stir, be warming up to 80 DEG C of back flow reaction 12 h, be cooled to room temperature, reaction solution is poured in deionized water, namely a large amount of Precipitation is had, suction filtration, wash three times, with ethanol: water mixed liquid carries out recrystallization to thick product, 60 DEG C of vacuum-drying 12 h, obtain Phosphorous Containing Polyamines epoxy curing agent,
(2) non-ion aqueous epoxy self-emulsifier preparation: in the 500 ml four-hole boiling flasks that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add eicosyl amine and solvent propylene glycol methyl ether, with constant pressure funnel, the mixing solutions of butyleneglycol bisglycidyl ether and propylene glycol monomethyl ether is added wherein under stirring, stirring reaction 5 h at 70 DEG C, then the propylene glycol monomethyl ether solution of epoxy resin E-44 is added, react 3 h at 50 DEG C, obtain non-ion aqueous epoxy self-emulsifier;
(3) preparation of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent: in the 500 ml four-hole boiling flasks that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add the Phosphorous Containing Polyamines epoxy curing agent that step (1) obtains, the non-ion aqueous epoxy self-emulsifier that step (2) obtains is added under stirring, half an hour finishes, react 3 h under maintaining 70 DEG C of temperature, obtain the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that side base is DOPO.
Embodiment 4
A kind of embodiment of the application in epoxy frie retardant coating prepared by Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, comprises the following steps:
At 50 DEG C, the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that 10 g bisphenol epoxy E-51 and 5 g embodiments 1 prepare is poured into and joins paint cup, deionized water is added at the temperature of 50 ~ 60 DEG C, high-speed stirring, to there is uniform epoxy emulsion, makes its solid content more than 50%, obtains frie retardant coating base-material used, add other auxiliary agent wherein, as pigment, defoamer, filler etc., preparation becomes the epoxy frie retardant coating met needed for unlike material surface.
Embodiment 5
A kind of embodiment of the application in epoxy frie retardant coating prepared by Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, comprises the following steps:
At 50 DEG C, the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that 10 g bisphenol epoxy E-51 and 5 g embodiments 2 prepare is poured into and joins paint cup, deionized water is added at the temperature of 50 ~ 60 DEG C, high-speed stirring, to there is uniform epoxy emulsion, makes its solid content more than 50%, obtains frie retardant coating base-material used, add other auxiliary agent wherein, as pigment, defoamer, filler etc., preparation becomes the epoxy frie retardant coating met needed for unlike material surface.
Embodiment 6
A kind of embodiment of the application in epoxy frie retardant coating prepared by Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention, comprises the following steps:
At 50 DEG C, the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that 10 g bisphenol epoxy E-51 and 5 g embodiments 3 prepare is poured into and joins paint cup, deionized water is added at the temperature of 50 ~ 60 DEG C, high-speed stirring, to there is uniform epoxy emulsion, makes its solid content more than 50%, obtains frie retardant coating base-material used, add other auxiliary agent wherein, as pigment, defoamer, filler etc., preparation becomes the epoxy frie retardant coating met needed for unlike material surface.
Embodiment 7
The thermotolerance of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention and flame retardant resistance test
Adopt the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent for preparing of embodiment 1,2,3 as tested object respectively, the solidifying agent that comparative example adopts is triethylene tetramine.
Test Sample Preparation Procedure is: get bisphenol A type epoxy resin 2 g, add solidifying agent 0.45 g being dissolved in 2 ml acetone, at 40 DEG C, vacuum drains acetone, imports in silicon rubber mould, and 40 DEG C solidify 24 hours, then at 150 DEG C of solidification 4 h, obtains test sample.
The Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent being adopted by solidifying agent in above-mentioned preparation process embodiment 1,2,3 to prepare respectively and the triethylene tetramine of comparative example, obtain the test sample of embodiment 1,2,3 and comparative example.
Distinguish the limiting oxygen index(LOI) of the test sample of testing example 1,2,3 and comparative example according to GB/T 2406.1-2008, result is as shown in table 1.
Table 1 thermotolerance and flame retardancy test results
As seen from Table 1, Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention has good thermotolerance and flame retardant resistance.
Embodiment 8
The stability test of the epoxy frie retardant coating adopting Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention to prepare
Adopt the epoxy frie retardant coating for preparing of embodiment 4,5,6 as tested object respectively, testing method is respectively: with centrifugal precipitation mechanism through centrifugal 30 min of 2500 r/min, observes whether occur breakdown of emulsion and layering; Epoxy frie retardant coating is placed 3 months at 40 DEG C of thermostat containers, observes whether occur breakdown of emulsion and layering; By epoxy frie retardant coating at-20 ~ 25 DEG C of circulating freezing resistance 72 h, observe whether occur breakdown of emulsion and layering.Test result is in table 2.
The stability test structure of table 2 epoxy frie retardant coating base-material
As seen from Table 2, the epoxy frie retardant coating that Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent of the present invention prepares has good stability.
Finally to should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a preparation method for Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent, is characterized in that, comprises the following steps:
(1) preparation of Phosphorous Containing Polyamines epoxy curing agent: in the four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, adds polyamines, aromatic aldehyde or aromatic ketone, DOPO, adds dehydrated alcohol and makes solvent, catalyzer made by triethylamine, stirs, is warming up to 80 DEG C of back flow reaction 12h, be cooled to room temperature, reaction solution is poured in deionized water, has Precipitation, suction filtration, washing, recrystallization is carried out to thick product, dry, obtain Phosphorous Containing Polyamines epoxy curing agent;
(2) preparation of non-ion aqueous epoxy self-emulsifier: in the four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add polyamines and propylene glycol monomethyl ether, with constant pressure funnel, the mixing solutions being dissolved with chainextender diglycidylether and propylene glycol monomethyl ether is added wherein under stirring, 3 ~ 5h is reacted under 45 ~ 90 DEG C of steady temperatures, then the propylene glycol monomethyl ether solution of bifunctional epoxy resin is added, reaction 3h, obtains non-ion aqueous epoxy self-emulsifier;
(3) preparation of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent: in the four-hole boiling flask that nitrogen access equipment, reflux condensing tube, thermometer and mechanical stirrer are housed, add the Phosphorous Containing Polyamines epoxy curing agent that step (1) obtains, the non-ion aqueous epoxy self-emulsifier that step (2) obtains is added under stirring, at 70 DEG C, react 5h, obtain the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that side base is DOPO.
2. the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent as claimed in claim 1, is characterized in that, in described step (1), the mol ratio of polyamines, aromatic aldehyde or aromatic ketone, DOPO is 1:2:2.
3. the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent as claimed in claim 1, it is characterized in that, polyamines in described step (1) and step (2) is quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, hexanediamine, Ursol D or 4,4 '-benzidine.
4. the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent as claimed in claim 1, it is characterized in that, aromatic aldehyde in described step (1) or aromatic ketone are phenyl aldehyde, substituted benzaldehyde, benzophenone, substituted benzene ketone or 4,4 '-diphenyl-dimethanal.
5. the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent as claimed in claim 1, it is characterized in that, the DOPO in described step (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or derivatives thereof.
6. the preparation method of Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent as claimed in claim 1, it is characterized in that, the chainextender diglycidylether in described step (2) is ethylene glycol diglycidylether, propylene glycol diglycidylether, butanediol diglycidyl ether, hexanediol diglycidyl ether, polyethyleneglycol diglycidylether, diethylene glycol diglycidyl glyceryl ether, diethylene glycol diglycidyl ether, Diethylene Glycol glycidyl ether or polyether glycol diglycidylether.
7. adopt the Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent that described method as arbitrary in claim 1-6 obtains, it contains DOPO side base.
8. Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent, preparing the application in epoxy frie retardant coating, is characterized in that as claimed in claim 7, comprises the following steps:
Epoxy resin and Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent being imported to join paints in cup, add water, stir into uniform epoxy emulsion, the solid content of described epoxy emulsion is more than 50%, described epoxy emulsion is directly carried out painting film preparation fire protection coating, or using described epoxy emulsion as base-material, add other auxiliary agent, prepare epoxy frie retardant coating.
9. apply as claimed in claim 8, it is characterized in that, with the mol ratio of epoxy group(ing) and ammonia hydrogen for 1:1 adds described epoxy resin and Phosphorous Containing Polyamines self-emulsifying epoxy resin solidifying agent.
10. apply as claimed in claim 8, it is characterized in that, described epoxy resin is bisphenol A type epoxy resin, glycidyl ester type epoxy resin, bisphenol f type epoxy resin, diglycidyl ether type epoxy resin or Resorcinol type epoxy.
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| CN105622923A (en) * | 2016-01-04 | 2016-06-01 | 中南民族大学 | TGIC/DOPO/fluorinated acrylate modified water-borne phosphorus-containing fluorine-containing epoxy curing agent and preparation method therefor |
| CN105885754A (en) * | 2016-05-03 | 2016-08-24 | 上海大学 | Low-temperature type flame retardant epoxy resin adhesive and preparation method thereof |
| CN110078899A (en) * | 2019-05-28 | 2019-08-02 | 长春顺风新材料有限公司 | A kind of preparation method of novel aqueous epoxy curing agent |
| CN113698610A (en) * | 2021-09-29 | 2021-11-26 | 武汉工程大学 | Hyperbranched phosphorus-silicon-containing aliphatic amine flame-retardant curing agent, preparation method thereof and application thereof in fireproof coating |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
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| CN105622923A (en) * | 2016-01-04 | 2016-06-01 | 中南民族大学 | TGIC/DOPO/fluorinated acrylate modified water-borne phosphorus-containing fluorine-containing epoxy curing agent and preparation method therefor |
| CN105622923B (en) * | 2016-01-04 | 2018-01-16 | 中南民族大学 | Phosphorous fluorine-containing epoxy hardener of TGIC/DOPO/ fluorinated acrylate modified water-solubles and preparation method thereof |
| CN105885754A (en) * | 2016-05-03 | 2016-08-24 | 上海大学 | Low-temperature type flame retardant epoxy resin adhesive and preparation method thereof |
| CN105885754B (en) * | 2016-05-03 | 2019-10-11 | 上海大学 | Low form fire retarding epoxide resin adhesive and preparation method thereof |
| CN110078899A (en) * | 2019-05-28 | 2019-08-02 | 长春顺风新材料有限公司 | A kind of preparation method of novel aqueous epoxy curing agent |
| CN110078899B (en) * | 2019-05-28 | 2021-06-04 | 长春顺风新材料有限公司 | Preparation method of water-based epoxy resin curing agent |
| CN113698610A (en) * | 2021-09-29 | 2021-11-26 | 武汉工程大学 | Hyperbranched phosphorus-silicon-containing aliphatic amine flame-retardant curing agent, preparation method thereof and application thereof in fireproof coating |
| CN113698610B (en) * | 2021-09-29 | 2022-05-10 | 武汉工程大学 | Hyperbranched phosphorus-silicon-containing aliphatic amine flame-retardant curing agent, preparation method thereof and application thereof in fireproof coating |
| CN113956750A (en) * | 2021-11-12 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Benzoxazine/epoxy resin composite flame-retardant anticorrosive coating and preparation method thereof |
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