CN103145955A - Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof - Google Patents
Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN103145955A CN103145955A CN2013100412628A CN201310041262A CN103145955A CN 103145955 A CN103145955 A CN 103145955A CN 2013100412628 A CN2013100412628 A CN 2013100412628A CN 201310041262 A CN201310041262 A CN 201310041262A CN 103145955 A CN103145955 A CN 103145955A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- curing agent
- preparation
- water
- cardanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention discloses a non-ionic self-emulsifying epoxy resin curing agent and a preparation method thereof. The method comprises that polyethylene glycol and epoxy resin of low molecular weight are adopted to pre-prepare a water-based chain segment under the function of a catalytic agent, the water-based segment is reacted with a mannich base which is prepared from cardanol, formaldehyde and polymine, and at the same time, organosilicone is added to conduct partial end blocking, compatibility of a system on an inorganic component is increased, and the non-ionic cashew phenol amine epoxy curing agent with the self-emulsifying capacity is obtained. The natural cardanol and the polyethylene glycol in the main raw materials of the curing agent have no adverse effect on environment. The prepared curing agent integrates the advantages of non-ionic emulsion and cashew phenol amine.
Description
Technical field
The present invention relates to a kind of nonionic self-emulsifying epoxy resin curing agent and preparation method thereof.
Background technology
The mechanical property that epoxy resin product is excellent with it and chemical resistance are widely used in life and industrial circle, epoxy curing agent is the product for epoxy cure, to curable epoxy resin, material impact can be arranged, wherein can be for room temperature curing epoxy be mainly amine curing agent.Along with the rules that social environmental consciousness raising and many countries have issued stricter restriction volatile organic solvent, the Water-borne modification product becomes trend already.Cardanol itself is a kind of byproduct in a kind of cashew nut processing industry, originates natural, biodegradable, meets Sustainable development.The commercialized development of cardanol is mainly the preparation of modified phenolic resins, also be applied to the Mannich base preparation, excellent product performance after the Mannich base cured epoxy resin made, but be oil product, Chinese patent CN02116454.1, Chinese patent CN201210106159.2, Chinese patent CN200810033592.1 has proposed the preparation method of cashew pnenolic aldehyde amine, all there is following deficiency in these patents: the solidifying agent viscosity obtained is larger, for oil product, construction inconvenience, instrument cleans difficulty, if clean with organic solvent, must endanger healthy generation of constructor, at wet substrate surface, as wet concrete surface, can not finely sprawl and come, may cause various problem of appearance after solidifying, performance also must descend, therefore range of application is restricted, can not with the water-based material compound use, as can not be directly be used for modified portland cement.
Aqueous epoxy curing agent is to the addition of polyamine chain extension mostly by epoxy resin, then with obtaining with salify in acid, waterborne curing agent for ionic, wherein as Chinese patent CN200910063839.9, proposed with epoxy resin to the polyamine addition after with in organic acid and salify make the ionic waterborne curing agent.Chinese patent CN200910052238.8 is that the Mannich base to making carries out salify and makes ionic Mannich waterborne curing agent, it is both ionic Water-borne modification product, they have requirement to pH in its use procedure, and quite responsive, in formula, layering likely occurs after mixing in the composition different from other, compatibleness is bad, and owing to having, acid is residual has the erosion of sudden strain of a muscle effect to metal base.Therefore, the application of the combination of formula and coating all is restricted.Similarly also have Chinese patent CN200810153095.5, Chinese patent CN200810042955.8 etc., all there is above-mentioned same problem in these ionic waterborne curing agents.
Chinese patent CN200710026284.1 has proposed to prepare non-ion aqueous solidifying agent with polyether glycol diglycidylether and aromatic series or fat polyamine, its thinking connects the non-ionic water segment by epoxy addition amine exactly, but the product water tolerance obtained and resistance to chemical reagents have larger decline with respect to the epoxy addition amine hardener that does not carry out the Water-borne modification modification, Chinese patent CN201010142715.2 proposed with Aethoxy Sklerol with react and obtain non-ion aqueous solidifying agent with aliphatic amide or aromatic amine under solvent after epoxy resin reacts, it is actually still nonionic modified with carrying out after epoxy resin addition chain extension aliphatic amide or aromatic amine, just the addition chain extension of amine with connect non-ionic segments and carry out in a step, so the solidifying agent product that Chinese patent CN200710026284.1 and CN201010142715.2 obtain is same type.Obtain nonionic modified addition amine hardener, with respect to the addition amine hardener, its water tolerance and resistance to chemical reagents can obviously descend.And, according in these two patent descriptions, seeing that this products production, reaction time consumption are relatively long, more than 10h, operation steps is many substantially.Similar nonionic modified addition amine hardener also has Chinese patent CN201110377636.4, and it has used more organic solvent as acetone and butanone in preparation process, has not only improved cost, also be unfavorable for the direct labor health.
Summary of the invention
The object of the invention is to, for prior art deficiency and vacancy, provides a kind of nonionic self-emulsifying epoxy resin curing agent and preparation method thereof.In the method, do not use in organic acid and salify, the reaction conditions gentleness, take natural raw material cardanol, and the proportioning by raw material changes easy control performance, and in preparation process, not with an organic solvent, product and epoxy resin compatibility and water dispersible are good.
A kind of nonionic self-emulsifying epoxy resin curing agent provided by the invention includes following structural formula:
Wherein, R is C
15h
31, C
15h
29, C
15h
27, C
15h
25; 44≤n≤181.
The preparation method of a kind of nonionic self-emulsifying epoxy resin curing agent provided by the invention, concrete steps are as follows:
(1) by cardanol: formaldehyde: the mol ratio of aminated compounds is 1:1～2:1～2, first add cardanol and amine chemicals to stir under 70～80 ℃, then splash into the formaldehyde solution of 37wt%, in 30～60min, drip off, be warmed up to 90～100 ℃ again, react 2～4h, Warm Wash is washed away unreacted formaldehyde and aminated compounds, last decompression dehydration, obtain the cashew pnenolic aldehyde amine compound;
(2) with polyoxyethylene glycol and low-molecular-weight epoxy resin 1:1～2 in molar ratio, join reactor, be warmed up to 60～90 ℃ of lower meltings and be uniformly mixed, gradation slowly adds catalyzer, every 20min, add once, 0.1～1wt% that the total consumption of catalyzer is system, make water-based segment performed polymer after reacting 40～180min;
(3) by the water-based segment performed polymer made, cashew pnenolic aldehyde amine compound and organosilicon add reactor, water-based segment performed polymer consumption is 5～25wt%, 0～3wt% that the organosilicon consumption is the cashew pnenolic aldehyde amine compound, be warming up to 70～100 ℃ of reaction 1～2h, then be cooled to 50～60 ℃, under stirring, splash into deionized water, drip off rear continuation and stir 30min, obtain the nonionic self-emulsifying epoxy resin curing agent.
In described step (1), aminated compounds be diethylenetriamine, triethylene tetramine, polyethylene polyamine, m-xylene diamine, isophorone diamine, mphenylenediamine or the Meng alkane diamines.
In described step (2), polyoxyethylene glycol is:
, 44≤n≤181.
In described step (2), low-molecular-weight epoxy resin is Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin or the cycloaliphatic epoxides that epoxy equivalent (weight) is less than 250.
In described step (2), catalyzer is boron trifluoride diethyl etherate, triphenylphosphine, iron trichloride, aluminum chloride, tindichloride or tin tetrachloride.
In described step (3), organosilicon is γ-glycidyl ether oxypropyl trimethyl silane or γ-aminopropyl triethoxysilane.
With respect to prior art, the present invention has following beneficial effect:
(1) however the present invention has taken a day cheap cardanol is raw material.
(2) by introducing the cardanol structure of natural long-chain in Mannich reaction, make solidifying agent retain the character of Mannich base, have the characteristics of aliphatic amide and polymeric amide concurrently simultaneously, the solidifying agent obtained is water-fast, chemical-resistant resistance, the mechanical property excellence, again by nonionic modified, make the outstanding oiliness solidifying agent characteristic of this performance farthest be incorporated in water-based system, be about to the cashew pnenolic aldehyde amine Water-borne modification of oiliness, and the product obtained and epoxy resin compatibility be the while stably dispersing well, insensitive to the pH in formula, and its range of application is greatly enlarged.Add organosilicon to carry out the sticking power that modification is conducive to improve cured film and inorganic substrate, the consistency of inorganic materials in raising system and formula, improve the overall performance of filming after film forming.
(3) the prepared solidifying agent of the present invention is not containing organic solvent.
(4) step mainly contains three steps, and Preparation equipment is simple, and technique is simple, and the reaction conditions gentleness is with short production cycle.
The accompanying drawing explanation
The infrared spectrogram that Fig. 1 is the prepared cashew pnenolic aldehyde amine compound of embodiment 1.
The prepolymer infrared spectrogram that Fig. 2 is the prepared polyoxyethylene glycol of embodiment 1 and epoxy resin.
Fig. 3 is polyethylene glycol 6000, Macrogol 4000, and Macrogol 2000 and Racemic glycidol ether type epoxy E51 1:2 in molar ratio react the GPC spectrogram of the water-based segment of preparation, and its molecular weight is corresponding spectral line a, b, c respectively.
The infrared spectrogram that Fig. 4 is the prepared solidifying agent of embodiment 1.
Fig. 5 is the prepared solidifying agent of embodiment 1
1the H-NMR spectrogram.
Fig. 6 is the prepared solidifying agent of embodiment 1
13the C-NMR spectrogram.
The size distribution figure that Fig. 7 is the prepared curing agent emulsion of embodiment 1.
The 1H-NMR spectrogram that Fig. 8 is the prepared solidifying agent of embodiment 2.
Embodiment
In order better to understand the present invention, below in conjunction with embodiment, the present invention is described in further detail, but the scope of protection of present invention is not limited to the scope that embodiment means.
embodiment 1
The m-xylene diamine of 100g cardanol and 58.93g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 32.43g of 37wt% under stirring, 30min dropwises, after being warmed up to 100 ℃ of reaction 3h, warm water washs, standing branch vibration layer, then, under 70 ℃, the 30min that dewaters reduces pressure under-0.095MPa vacuum tightness, obtain maroon liquid, the amine value is 256mgKOH/g, and viscosity is 1765mPas, is down to room temperature stand-by.
The epoxy resin E51 of 100g polyethylene glycol 6000 and 13.06g is joined in the 250ml flask of belt stirrer, be warmed up to 90 ℃, under stirring, divide and add catalyzer boron trifluoride diethyl etherate 0.27g altogether for 6 times, every minor tick 20min, reaction 120min, obtain white waxy solid.
Extracting waste waxy solid 15g and above-mentioned maroon liquid 85g drop in the there-necked flask of 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, then be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the white powder curing agent emulsion of solid content 50%.
Centrifugal 30min under 3000rpm is not stratified for this emulsion, median size 670nm, viscosity 344mPas, amine value 203mKOH/g, after solidifying with the epoxy equivalent (weight) water-based bisphenol A type epoxy resin (solid content is 70%) that is 250～280, pencil hardness is 3H, sticking power is 0 grade, shock-resistance is 35kgcm, be greater than 4 hours working life, surface drying time<3h, do solid work<30h, filming after solidifying is yellowish transparent, glossiness is good, filming respectively after completion of cure filmed intact in the NaOH solution of the HCl solution of 3.5% NaCl solution and 3.5% and 3.5% after dipping 168h.
The product that Fig. 5 in accompanying drawing is embodiment 1
1the spectrogram of H-NMR, can see that in figure chemical shift δ=7～8 are for the hydrogen on benzene ring hydrogen and phenolic hydroxyl group, δ=5.2～6.3 places are the hydrogen on the unsaturated double-bond on the cardanol side chain, δ=4.1～4.5 are the hydrogen on the methylene radical between bridge joint phenyl ring and amido, the sharp-pointed strong peak at δ=4 places is the hydrogen on methylene radical in polyoxyethylene glycol, three peaks at δ=2.3～3.3 places are the hydrogen on the methylene radical be connected with two keys or phenyl ring on the cardanol side chain, the peak at δ=2 and 0.4 place is the hydrogen on amido, the peak at δ=1.7 places is the hydrogen on the methylene radical on the cardanol side chain, the peak at δ=1.2～1.3 places is the hydrogen on cardanol side chain terminal methyl.To knowing the general situation of the hydrogen on each group in the integration at each peak, the hydrocarbon quantity of cardanol side chain is about 27 H, hydrogen on two nitrogen is about 2.4 H, and the hydrogen connected on the methylene radical between phenyl ring and amido has 6, and the hydrogen on phenyl ring and phenolic hydroxyl group has 8.Above-mentioned right
1the chemical shift of H-NMR spectrogram, the analysis of integration information and the solidifying agent structure proposed in claim are consistent.
The product that Fig. 6 in accompanying drawing is embodiment 1
13the spectrogram of C-NMR, peak δ in figure=14～36 places are the carbon on the cardanol side chain, peak δ=47 are the carbon that is connected the methylene radical of phenyl ring and amine with 52 places, peak δ=53 are the carbon of the methylene radical of connection cardanol and amido, peak δ=71 places are the carbon in the ethyl in repeating segment in polyoxyethylene glycol, the solvent peak that δ=77～78 are deuterochloroform, the peak of between δ=113～158 is the peak that the carbon in two keys forms, and comprises the carbon on unsaturated double-bond on carbon on phenyl ring and cardanol side chain.From
13the information obtained in the C-NMR spectrum is consistent with the solidifying agent chemical structure of mentioning in claim.
embodiment 2
The isophorone diamine of 90g cardanol and 66.3g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 26.76g of 37wt% under stirring, 30min dropwises, after being warmed up to 100 ℃ of reaction 3h, warm water washs, standing branch vibration layer, then, under 70 ℃, the 30min that dewaters reduces pressure under-0.095MPa vacuum tightness, obtain maroon liquid, the amine value is 295mgKOH/g, and viscosity is 2256mPas, is down to room temperature stand-by.
The epoxy resin E51 of 100g polyethylene glycol 6000 and 13.06g is joined in the 250ml flask of belt stirrer, be warmed up to 90 ℃, under stirring, divide and add catalyzer boron trifluoride diethyl etherate 0.27g altogether for 6 times, every minor tick 20min, reaction 120min, obtain white waxy solid.
The γ of extracting waste waxy solid 20g and above-mentioned maroon liquid 80g and 3g-glycidyl ether oxypropyl trimethyl silane drops in the there-necked flask of 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, then be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the white powder curing agent emulsion of solid content 50%.
Centrifugal 30min under 3000rpm is not stratified for this emulsion, median size 1459nm, viscosity 380mPas, amine value 199mKOH/g, after solidifying with the epoxy equivalent (weight) water-based bisphenol A type epoxy resin (solid content is 70%) that is 250～280, pencil hardness is 3H, sticking power is 2 grades, shock-resistance is 50kgcm, surface drying time<3h, do solid work<30h, and filming after completion of cure filmed respectively intact in 3.5% NaCl solution after dipping 168h, film and turn white after dipping 100h in 3.5% HCl solution, in 3.5% NaOH solution, after dipping 168h, film and turn white.
Fig. 8 in accompanying drawing is embodiment 2 products
1the spectrogram of H-NMR, can see that in figure chemical shift δ=6.8～7.6 are for the hydrogen on benzene ring hydrogen and phenolic hydroxyl group, δ=5.3～6.5 places are the hydrogen on the unsaturated double-bond on the cardanol side chain, δ=4.1～4.5 are the hydrogen on the methylene radical between bridge joint phenyl ring and amido, the sharp-pointed strong peak at δ=4 places is the hydrogen on methylene radical in polyoxyethylene glycol, and the unimodal of δ=3.5～3.6 places is on γ-glycidyl ether oxypropyl trimethyl silane
the hydrogen peak, the peak at δ=2.35～3.33 places is hydrogen on the methylene radical be connected with two keys or phenyl ring on the cardanol side chain and methylene radical on the isophorone diamine be connected with amido, hydrogen on methyne, the peak at δ=2.2 places be γ-glycidyl ether oxypropyl trimethyl silane with the amine ring-opening reaction after hydrogen on the hydroxyl that forms, show that γ-glycidyl ether oxypropyl trimethyl silane has connected, the peak at δ=2 places is the hydrogen on amido, the peak at δ=1.7～1.2 places is the cardanol side chain, hydrogen on the methylene radical that isophorone diamine and γ-glycidyl ether oxypropyl trimethyl silane top is divided.To Fig. 8
1the information that the chemical shift of H-NMR spectrogram, the analysis of integration information obtain is consistent with the solidifying agent structure proposed in claim.
embodiment 3
The triethylene tetramine of 100g cardanol and 63.27g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 32.43g of 37wt% under stirring, 30min dropwises, after being warmed up to 100 ℃ of reaction 2h, warm water washs, standing branch vibration layer, then, under 70 ℃, the 30min that dewaters reduces pressure under-0.095MPa vacuum tightness, obtain maroon liquid, the amine value is 268mgKOH/g, and viscosity is 1605mPas, is down to room temperature stand-by.
The epoxy resin E51 of 100g polyethylene glycol 6000 and 13.06g is joined in the 250ml flask of belt stirrer, be warmed up to 90 ℃, under stirring, divide and add catalyzer boron trifluoride diethyl etherate 0.27g altogether for 6 times, every minor tick 20min, reaction 120min, obtain white waxy solid.
Extracting waste waxy solid 8g and above-mentioned maroon liquid 92g drop in the there-necked flask of 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the white powder curing agent emulsion of solid content 50%.
Centrifugal 30min under 3000rpm is not stratified for this emulsion, median size 714nm, viscosity 843mPas, amine value 236mKOH/g, after solidifying with the epoxy equivalent (weight) water-based bisphenol A type epoxy resin (solid content is 70%) that is 250～280, pencil hardness is 3H, sticking power is 0 grade, and shock-resistance is 40kgcm, surface drying time<2.5h, do solid work<30h, filming respectively after completion of cure filmed intact in the NaOH solution of the HCl solution of 3.5% NaCl solution and 3.5% and 3.5% after dipping 168h.
embodiment 4
The diethylenetriamine of 100g cardanol and 48.10g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 32.43g of 37wt% under stirring, 30min dropwises, after being warmed up to 100 ℃ of reaction 2h, warm water washs, standing branch vibration layer, then, under 70 ℃, the 30min that dewaters reduces pressure under-0.095MPa vacuum tightness, obtain maroon liquid, the amine value is 247mgKOH/g, and viscosity is 930mPas, is down to room temperature stand-by.
The epoxy resin E51 of 100g polyethylene glycol 6000 and 13.06g is joined in the 250ml flask of belt stirrer, be warmed up to 90 ℃, under stirring, divide and add catalyzer boron trifluoride diethyl etherate 0.27g altogether for 6 times, every minor tick 20min, reaction 120min, obtain white waxy solid.
The γ-aminopropyl triethoxysilane of extracting waste waxy solid 10g and above-mentioned maroon liquid 90g and 3g drops in the there-necked flask of 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the white powder curing agent emulsion of solid content 50%.
Centrifugal 30min under 3000rpm is not stratified for this emulsion, median size 1194nm, viscosity 124mPas, amine value 208mKOH/g, after solidifying with the epoxy equivalent (weight) water-based bisphenol A type epoxy resin (solid content is 70%) that is 250～280, pencil hardness is 2～3H, sticking power is 0 grade, shock-resistance is 45kgcm, surface drying time<2.6h, do solid work<30h, filming respectively after completion of cure filmed intact in the NaOH solution of the HCl solution of 3.5% NaCl solution and 3.5% and 3.5% after dipping 168h.
embodiment 5
The m-xylene diamine of 100g cardanol and 90.66g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 54.06g of 37%wt under stirring, 30min dropwises, be warmed up to 100 ℃ of reaction 3h, then, under 70 ℃, the 30min that dewaters reduces pressure under-0.095MPa vacuum tightness, obtain maroon liquid, be down to room temperature stand-by.
The terephthalic acid diglycidyl ester of 100g PEG 8000 and 6.95g is joined in the 250ml flask of belt stirrer, be warmed up to 90 ℃, under stirring, the catalyzer boron trifluoride diethyl etherate is 0.01g altogether, and reaction 40min, obtain white waxy solid.The γ of extracting waste waxy solid 20g and above-mentioned maroon liquid 80g and 3g-glycidyl ether oxypropyl trimethyl silane drops in the there-necked flask of 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the curing agent emulsion of solid content 50%.
embodiment 6
The isophorone diamine of 90g cardanol and 60g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 28.62g of 37wt% under stirring, 30min dropwises, and is warmed up to warm water washing after 100 ℃ of reaction 3h, standing branch vibration layer, then under 70 ℃, under-0.095MPa vacuum tightness, the decompression 30min that dewaters, obtain maroon liquid, is down to room temperature stand-by.
The bicyclopentadiene dioxide of 100g Macrogol 2000 and 17g is joined in the 250ml flask of belt stirrer, be warmed up to 60 ℃, under stirring, divide and add catalyzer boron trifluoride diethyl etherate 0.36g altogether for 5 times, every minor tick 20min, reaction 104min, obtain the shape material.Get in the there-necked flask of wax 20g and above-mentioned maroon liquid 80g input 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, then be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the white powder curing agent emulsion of solid content 50%.
embodiment 7
The triethylene tetramine of 100g cardanol and 60g is added in the 250ml there-necked flask that agitator, reflux condensing tube and constant pressure funnel are housed, be heated to 70 ℃, be added dropwise to the formaldehyde solution 33.32g of 37wt% under stirring, 30min dropwises, and is warmed up to warm water washing after 100 ℃ of reaction 2h, standing branch vibration layer, then under 70 ℃, under-0.095MPa vacuum tightness, the decompression 30min that dewaters, obtain maroon liquid, is down to room temperature stand-by.
The bicyclopentadiene dioxide of 100g Macrogol 4000 and 8.21g is joined in the 250ml flask of belt stirrer, be warmed up to 90 ℃, under stirring, divide and add catalyzer triphenylphosphine 0.50g altogether for 5 times, every minor tick 20min, until product can complete water-soluble waxy substance.Get in the there-necked flask of wax 20g and above-mentioned maroon liquid 80g input 250ml belt stirrer, condensing reflux pipe, be stirred and heated to 70 ℃, maintain 60min, be cooled to 60 ℃, drip deionized water 100g, 30min drips, then high-speed stirring 30min, cooling discharge, obtain the white powder curing agent emulsion of solid content 50%.
Claims (7)
1. a nonionic self-emulsifying epoxy resin curing agent is characterized in that including following structural formula:
Wherein, R is C
15h
31, C
15h
29, C
15h
27or C
15h
25; 44≤n≤181.
2. the preparation method of the described solidifying agent of claim 1 is characterized in that concrete steps are as follows:
(1) according to cardanol: formaldehyde: the mol ratio of aminated compounds is 1:1～2:1～2, first add cardanol and amine chemicals, under 70～80 ℃, stir, then splash into the formaldehyde solution of 37wt%, drip off in 30～60min, then be warmed up to 90～100 ℃, reaction 2～4h, Warm Wash is washed away unreacted formaldehyde and aminated compounds, and last decompression dehydration, obtain the cashew pnenolic aldehyde amine compound;
(2) with polyoxyethylene glycol and low-molecular-weight epoxy resin 1:1～2 in molar ratio, join reactor, be warmed up to 60～90 ℃ of lower meltings and be uniformly mixed, gradation slowly adds catalyzer, every 20min, add once, 0.1～1wt% that the total consumption of catalyzer is system, make water-based segment performed polymer after reacting 40～180min;
(3) by the water-based segment performed polymer made, cashew pnenolic aldehyde amine compound and organosilicon add reactor, water-based segment performed polymer consumption is 5～25wt%, 0～3wt% that the organosilicon consumption is the cashew pnenolic aldehyde amine compound, be warming up to 70～100 ℃ of reaction 1～2h, then be cooled to 50～60 ℃, under stirring, splash into deionized water, drip off rear continuation and stir 30min, obtain the nonionic self-emulsifying epoxy resin curing agent.
3. preparation method according to claim 2 is characterized in that: in described step (1), aminated compounds be diethylenetriamine, triethylene tetramine, polyethylene polyamine, m-xylene diamine, isophorone diamine, mphenylenediamine or the Meng alkane diamines.
4. preparation method according to claim 2, it is characterized in that: in described step (2), polyoxyethylene glycol is:
, 44≤n≤181.
5. preparation method according to claim 2, it is characterized in that: in described step (2), low-molecular-weight epoxy resin is Racemic glycidol ether type epoxy, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin or the cycloaliphatic epoxides that epoxy equivalent (weight) is less than 250.
6. preparation method according to claim 2, it is characterized in that: in described step (2), catalyzer is boron trifluoride diethyl etherate, triphenylphosphine, iron trichloride, aluminum chloride, tindichloride or tin tetrachloride.
7. preparation method according to claim 2, it is characterized in that: in described step (3), organosilicon is γ-glycidyl ether oxypropyl trimethyl silane or γ-aminopropyl triethoxysilane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100412628A CN103145955A (en) | 2013-02-04 | 2013-02-04 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100412628A CN103145955A (en) | 2013-02-04 | 2013-02-04 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103145955A true CN103145955A (en) | 2013-06-12 |
Family
ID=48544307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100412628A Pending CN103145955A (en) | 2013-02-04 | 2013-02-04 | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103145955A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262589A (en) * | 2014-09-05 | 2015-01-07 | 广州秀珀化工股份有限公司 | Nonionic self-emulsifying water-based epoxy curing agent with Gemini surfactant structure and preparation method thereof |
| CN104725604A (en) * | 2014-12-23 | 2015-06-24 | 上海美东生物材料股份有限公司 | Waterborne curing agent and preparation method thereof |
| CN106220803A (en) * | 2016-08-24 | 2016-12-14 | 泰州精英化成医药科技有限公司 | A kind of polymerization of phenolic aldehyde ammonia polymer resin |
| CN106397780A (en) * | 2016-09-13 | 2017-02-15 | 安徽大学 | Preparation method of functional epoxy resin curing agent |
| CN107759755A (en) * | 2017-10-26 | 2018-03-06 | 湖北绿色家园材料技术股份有限公司 | Using the low cost of chemical industry leftover bits and pieces preparation, environment-friendly type stone material dry suspending adhesive curing agent |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | A kind of modified by cardanol aqueous epoxy curing agent and preparation method thereof |
| CN110938209A (en) * | 2019-12-17 | 2020-03-31 | 岳阳中展科技有限公司 | Preparation method and application of cardanol-based waterborne epoxy resin curing agent |
| CN111171309A (en) * | 2020-02-19 | 2020-05-19 | 中科院广州化灌工程有限公司 | Reactive emulsifier, water-based epoxy resin emulsion, preparation and application |
| CN111876763A (en) * | 2020-07-16 | 2020-11-03 | 武汉迪赛环保新材料股份有限公司 | Chromium-free surface treatment liquid for zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN112646163A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method of cardanol polyether polyol with high pentane intersolubility |
| CN113061233A (en) * | 2021-03-05 | 2021-07-02 | 卡德莱化工(珠海)有限公司 | Waterborne emulsion epoxy curing agent and preparation method and application thereof |
| CN113072686A (en) * | 2021-05-06 | 2021-07-06 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
| CN113214814A (en) * | 2021-04-13 | 2021-08-06 | 广州大学 | Low-temperature curing high-strength precoated sand material and preparation method thereof |
| CN109734922B (en) * | 2018-12-27 | 2021-09-17 | 常熟耐素生物材料科技有限公司 | Nonionic reactive epoxy resin emulsifier and preparation method thereof |
| CN114249881A (en) * | 2021-12-06 | 2022-03-29 | 浙江万盛股份有限公司 | Non-solvent cardanol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof |
| CN116694194A (en) * | 2023-06-05 | 2023-09-05 | 浙江天女集团制漆有限公司 | Water-based epoxy resin heat-conducting insulating coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333286A (en) * | 2007-06-26 | 2008-12-31 | 上海经天新材料科技有限公司 | Amine epoxy curing agent modified by cardanol |
| CN101899141A (en) * | 2009-05-31 | 2010-12-01 | 上海美东生物材料有限公司 | Self-emulsifying water borne epoxy resin curing agent and preparation method thereof |
| CN102190800A (en) * | 2010-03-06 | 2011-09-21 | 中国石油化工集团公司 | Preparation method of nonionic waterborne epoxy curing agent |
-
2013
- 2013-02-04 CN CN2013100412628A patent/CN103145955A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333286A (en) * | 2007-06-26 | 2008-12-31 | 上海经天新材料科技有限公司 | Amine epoxy curing agent modified by cardanol |
| CN101899141A (en) * | 2009-05-31 | 2010-12-01 | 上海美东生物材料有限公司 | Self-emulsifying water borne epoxy resin curing agent and preparation method thereof |
| CN102190800A (en) * | 2010-03-06 | 2011-09-21 | 中国石油化工集团公司 | Preparation method of nonionic waterborne epoxy curing agent |
Non-Patent Citations (1)
| Title |
|---|
| 段颖等: "新型非离子型水性环氧固化剂的制备", 《涂料工业》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262589A (en) * | 2014-09-05 | 2015-01-07 | 广州秀珀化工股份有限公司 | Nonionic self-emulsifying water-based epoxy curing agent with Gemini surfactant structure and preparation method thereof |
| CN104725604A (en) * | 2014-12-23 | 2015-06-24 | 上海美东生物材料股份有限公司 | Waterborne curing agent and preparation method thereof |
| CN106220803A (en) * | 2016-08-24 | 2016-12-14 | 泰州精英化成医药科技有限公司 | A kind of polymerization of phenolic aldehyde ammonia polymer resin |
| CN106397780B (en) * | 2016-09-13 | 2019-05-21 | 安徽大学 | A kind of preparation method of functional epoxy resin curing agent |
| CN106397780A (en) * | 2016-09-13 | 2017-02-15 | 安徽大学 | Preparation method of functional epoxy resin curing agent |
| CN107759755A (en) * | 2017-10-26 | 2018-03-06 | 湖北绿色家园材料技术股份有限公司 | Using the low cost of chemical industry leftover bits and pieces preparation, environment-friendly type stone material dry suspending adhesive curing agent |
| CN109517141B (en) * | 2018-10-11 | 2021-01-01 | 安徽大学 | Cardanol modified waterborne epoxy curing agent and preparation method thereof |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | A kind of modified by cardanol aqueous epoxy curing agent and preparation method thereof |
| CN109734922B (en) * | 2018-12-27 | 2021-09-17 | 常熟耐素生物材料科技有限公司 | Nonionic reactive epoxy resin emulsifier and preparation method thereof |
| CN110938209A (en) * | 2019-12-17 | 2020-03-31 | 岳阳中展科技有限公司 | Preparation method and application of cardanol-based waterborne epoxy resin curing agent |
| CN111171309A (en) * | 2020-02-19 | 2020-05-19 | 中科院广州化灌工程有限公司 | Reactive emulsifier, water-based epoxy resin emulsion, preparation and application |
| CN111876763A (en) * | 2020-07-16 | 2020-11-03 | 武汉迪赛环保新材料股份有限公司 | Chromium-free surface treatment liquid for zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN112646163A (en) * | 2020-12-14 | 2021-04-13 | 山东一诺威新材料有限公司 | Preparation method of cardanol polyether polyol with high pentane intersolubility |
| CN113061233A (en) * | 2021-03-05 | 2021-07-02 | 卡德莱化工(珠海)有限公司 | Waterborne emulsion epoxy curing agent and preparation method and application thereof |
| CN113214814A (en) * | 2021-04-13 | 2021-08-06 | 广州大学 | Low-temperature curing high-strength precoated sand material and preparation method thereof |
| CN113072686A (en) * | 2021-05-06 | 2021-07-06 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
| CN113072686B (en) * | 2021-05-06 | 2022-11-11 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
| CN114249881A (en) * | 2021-12-06 | 2022-03-29 | 浙江万盛股份有限公司 | Non-solvent cardanol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof |
| CN114249881B (en) * | 2021-12-06 | 2023-09-26 | 浙江万盛股份有限公司 | Solvent-free cashew phenol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof |
| CN116694194A (en) * | 2023-06-05 | 2023-09-05 | 浙江天女集团制漆有限公司 | Water-based epoxy resin heat-conducting insulating coating and preparation method thereof |
| CN116694194B (en) * | 2023-06-05 | 2024-02-02 | 浙江天女集团制漆有限公司 | Water-based epoxy resin heat-conducting insulating coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103145955A (en) | Non-ionic self-emulsifying epoxy resin curing agent and preparation method thereof | |
| CN105315437B (en) | A kind of self-emulsifying aqueous epoxy hardener of nonionic and preparation method thereof | |
| CN101885832B (en) | Preparation and application of latent nonionic self-emulsifying epoxy curing agent | |
| CN106987194A (en) | A kind of non-ion aqueous epoxy resin latex and nonionic waterborne epoxy curing agent and its preparation method and aqueous epoxy resins varnish | |
| CN102250321B (en) | Quick-drying room temperature curing waterborne epoxy resin curing agent and preparation method thereof | |
| CN103554439B (en) | A kind of preparation method of low smell epoxy hardener | |
| CN105175687B (en) | The preparation method of Diamond Search high-flexibility aqueous epoxy resin curing agent | |
| CN102516502B (en) | Preparation method of novel Mannich water-based epoxy curing agent | |
| CN105504296B (en) | A kind of nonionic waterborne epoxy curing agent and preparation method thereof | |
| CN103435779A (en) | Preparation method of polyamino organic silicon curing agent, epoxy corrosion resistant protective paint using curing agent and preparation method thereof | |
| CN104558529A (en) | Preparation method of amide self-emulsifying water-borne epoxy resin curing agent | |
| CN107189084A (en) | The aqueous epoxy emulsion prepared by the emulsifying agent of the functional group of bis-epoxy containing isocyanates | |
| CN103130982A (en) | Composite method and solidifying method of fluorine-containing high temperature resisting organosilicon epoxy resin | |
| CN104403618B (en) | Cold curing high-strength halogen-free is from fire self-extinguishing type epoxy casting body and preparation method thereof | |
| CN108070093A (en) | A kind of preparation method of aqueous epoxy resin emulsion | |
| CN108611036A (en) | A kind of preparation method of cardanol glycidyl ether modified epoxy adhesive | |
| CN105754451B (en) | Fry starch of konjak epoxy resin and preparation method thereof and the coating with its preparation | |
| CN102358686A (en) | Aqueous epoxy cement mortar | |
| CN104877111A (en) | Fluorine-containing epoxy curing agent capable of normal-temperature curing, and preparation and application thereof | |
| CN103804691B (en) | The preparation method of toughness reinforcing high-temperature-resistant silicon resin | |
| CN108250899A (en) | A kind of air drying type room temperature-cured aqueous epoxy water-repellent paint and its preparation method and application | |
| CN107163242A (en) | The response type epoxy emulsifying agent prepared using monoisocyanates polyoxyethylene monomethyl ether | |
| CN106750187A (en) | A kind of heavy corrosion protection epoxy powder high tenacity phenols curing agent and preparation method and application | |
| CN106752723A (en) | A kind of water-base epoxy antiseptic varnish and preparation method thereof | |
| CN106117519B (en) | The preparation method of the low peculiar smell Diamond Search aqueous epoxy curing agent of environment-friendly type |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130612 |