CN101157751B - Aqueous epoxy resin and preparation method and method for preparing varnish by using aqueous epoxy resin - Google Patents
Aqueous epoxy resin and preparation method and method for preparing varnish by using aqueous epoxy resin Download PDFInfo
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- CN101157751B CN101157751B CN200710018757A CN200710018757A CN101157751B CN 101157751 B CN101157751 B CN 101157751B CN 200710018757 A CN200710018757 A CN 200710018757A CN 200710018757 A CN200710018757 A CN 200710018757A CN 101157751 B CN101157751 B CN 101157751B
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Abstract
The present invention provides a modified waterborne epoxy resin by using 2, 2-bis (hydroxymethyl) propionic acid and diisocyanate and a preparation method thereof, the resin is prepared by reaction and synthesis at 50 to 65 DEG C after the mixing of 100 parts of epoxy resin, 10 to 12 parts of 2, 2-bis (hydroxymethyl) propionic acid, 15 to 17 parts of toluene diisocyanate and 50 to 60 parts of cosolvent according to the weight parts. The present invention also provides the preparation method of preparing emulsion varnish by the waterborne epoxy resin, the waterborne epoxy resin is neutralized by using the alkaline aqueous solution and is prepared into the stable waterborne epoxy emulsion with the solid content of 50 to 60 percent by emulsifying, and the curing agent is added, so the present invention can be used as the environment-friendly varnish. The waterborne epoxy resin which is prepared by the present invention has the technical characteristics of fine particles, high emulsion stability and high hardness of the cured products, etc., so the present invention can be widely applied to the coatings, adhesives, fine chemical additives and other fields.
Description
Technical field
The present invention relates to a kind of aqueous epoxy resins and preparation method thereof and prepare the method for varnish with this aqueous epoxy resins.
Background technology
Resins, epoxy is to contain two or more epoxy group(ing) in the molecule, and forms the general name of the compound of three-dimensional cross-linked netted cured article in the presence of suitable chemical reagent.Owing to contain unique epoxy group(ing) and alkyl, ehter bond isoreactivity group and polar group in its molecular structure, thereby have good physical and mechanical property, mechanical property, electrical insulation capability, chemical resistance and an adhesiveproperties, be widely used as the aspect such as casting, moulding material, tackiness agent, laminating material, matrices of composite material of coating and plastic packaging, electronic material, be penetrated into all respects from the daily living article to the high-technology field with the form of direct or indirect use.But Resins, epoxy commonly used is insoluble in water, only is dissolved in organic solvents such as aromatic hydrocarbons, ketone and alcohols, and therefore the application of traditional Resins, epoxy is accompanied by the use of organic solvent mostly.And organic solvent not only price is more expensive, and have volatility, environment is polluted, this shortcoming makes the application of conventional solvent type Resins, epoxy be subjected to very big restriction.Along with urgent and strict to requirement on environmental protection order benefit, do not contain volatile organic compound (Noc), or the organic compound of low volatility (voc), or do not contain the research direction that the system that is harmful to air pollutant (HAP) has become type material.Water-borne modification of epoxy resins research has become the focus of domestic and international research.
At present, the method for preparing the aqueous epoxy resin system mainly contains 3 kinds: (one) direct method, and promptly mechanical process grinds Resins, epoxy with ball mill, colloidal mill, homogenizer etc., adds emulsifier aqueous solution then, by mechanical stirring particle is scattered in the water again; (2) phase reversion method promptly becomes oil-in-water state with polymkeric substance from the water-in-oil state-transition by phase reversion; (3) self-emulsification claims chemical method again, is about to the water-based group and introduces in the Resins, epoxy molecular skeleton, makes its possess hydrophilic property, thereby can disperse in water.Preceding two kinds of methods are simple to operate, but the particle diameter that makes is bigger, and curing performance is bad.Though and the chemic modified method preparation process is many, the particle diameter that makes is less, and the microemulsion good stability has more practical significance.At present, introduce aqueous substance by chemic modified method and comprise and introduce contraposition methyl hydroxybenzoate or contraposition benzaminic acid etc., but can open epoxide group, therefore the good character of retaining ring epoxy resins itself owing to introduce polar group.
Summary of the invention
The primary problem that solves of the present invention provides a kind of 2, aqueous epoxy resins of 2-dimethylol propionic acid and tolylene diisocyanate modification and preparation method thereof, secondly, the preparation method of the good water-base epoxy varnish of a kind of solidified nature is provided by resulting aqueous epoxy resins.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of aqueous epoxy resins, structure are the compound that following general formula is represented:
Concrete structure can be as shown in the formula the expression compound:
n＝0.4。
A kind of above-mentioned 2, the preparation method of water-dilutable epoxide resin of 2-dimethylol propionic acid and tolylene diisocyanate modification, comprise the steps: according to the mass fraction: 100 parts of Resins, epoxy, 2, reacted 4-6 hour down at 50-65 ℃ after 2-dimethylol propionic acid 10-12 part, tolylene diisocyanate 15-17 part, acetone 10-30 part are mixed, obtain the aqueous epoxy resins of modification.Related chemical equation is as follows:
In the such scheme, described Resins, epoxy is bisphenol A type epoxy resin, and its oxirane value is 0.51-0.18mol/100g.
The above-mentioned aqueous epoxy resins of a kind of usefulness prepares the method for varnish, may further comprise the steps:
A. prepare aqueous epoxy emulsion earlier, according to the mass fraction,,, make the aqueous epoxy emulsion that solid content is 40%-60% then with its emulsification with the neutralization earlier of 100 parts of aqueous epoxy resins, alkaline aqueous solution 65-85 part; Described alkaline aqueous solution is a sodium hydroxide, yellow soda ash or triethylamine aqueous solution a kind of, and concentration is 3-8wt%;
B. according to the mass fraction, get the epoxy resin latex of 100 parts of step a, add 10-30 part solidifying agent, be stirred well to and mix, application was carried out in slaking in 5 minutes; Described solidifying agent is the long-chain fat amine of diethylenetriamine, urea, polymeric amide, NX-2003[water-based group] a kind of.
Aqueous epoxy resins provided by the invention is because its reaction is by introducing hydrophilic radical on the Resins, epoxy side chain, not opening epoxide group, so can be good at the character of retaining ring epoxy resins itself; Prepared aqueous epoxy resin emulsion varnish has good curing performance.
Table 1 has been listed hardness and the sticking power that the present invention adopts varnish behind the corresponding solidifying agent.
Table 1
Solidified aqueous epoxy resins varnish in the table 1, the oxirane value that records by hydrochloric acid-acetone method is 0.18mol/100g; Condition of cure is ambient cure, 25 ℃ of temperature, 5 hours set times; Hardness adopts standard GB6739-86; Sticking power adopts standard GB9286-88.
As shown in Table 1, diethylenetriamine, urea, polymeric amide, long-chain fat amine NX-2003 that contains the water-based group etc. all can be used as the solidifying agent of this aqueous epoxy resins varnish, so aqueous epoxy resins has the stronger adaptability of technology, has fully shown technique effect of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described in further details.
Embodiment 1
The preparation of aqueous epoxy resins: in the there-necked flask that stirring and temperature regulating device are housed, add 10 grams 2, the 2-dimethylol propionic acid, 30 gram acetone, 17 gram tolylene diisocyanates, 100 restrain epoxy resin E-44s, are heated to 60 ℃, and reaction stopped in 5 hours under this temperature.
With the aqueous epoxy resins 100g that makes, with aqueous sodium hydroxide solution 65g (wherein sodium hydroxide 2g) neutralization, again with agitator with its emulsification, high-speed stirring 20 minutes, rotating speed is 1000 rev/mins, makes solid content and be 60% stabilized aqueous epoxy emulsion.
Viscosity: 2300mp.s
Epoxy equivalent (weight): 0.17mol/100g
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The preparation of water-base epoxy varnish: get the 10g modified epoxy resin emulsion, be cured with 1 gram diethylenetriamine, be stirred well to and mix, application was carried out in slaking in 5 minutes, and condition of cure is normal temperature (25 ℃ of temperature, 3 hours set time).The performance test of the water-base epoxy varnish of present embodiment is as shown in table 2:
Table 2
| Hardness (GB6739-86) | Sticking power (GB9286-88) | Water tolerance | 5％H 2SO 4 | 5％N aOH |
| 6H | 2 | Paint film slightly whitened in 5 days | 5 days: non-foaming, do not peel off | 2 days: non-foaming, do not peel off |
Embodiment 2
The preparation of aqueous epoxy resins: in the there-necked flask that stirring and temperature regulating device are housed, add 12 grams 2, the 2-dimethylol propionic acid, 20 gram acetone, 17 gram tolylene diisocyanates, 100 restrain epoxy resin E-44s, are heated to 50 ℃, and reaction stopped in 6 hours under this temperature.
With the aqueous epoxy resins 100g that makes, with aqueous sodium hydroxide solution 75g (wherein sodium hydroxide 2.5g) neutralization, again with agitator with its emulsification, high-speed stirring 20 minutes, rotating speed is 1000 rev/mins, makes solid content and be 55% stabilized aqueous epoxy emulsion.
Viscosity: 2400mp.s
Epoxy equivalent (weight): 0.19mol/100g
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The preparation of water-base epoxy varnish: get the 10g modified epoxy resin emulsion, be cured with 2 gram polymeric amide, be stirred well to and mix, application was carried out in slaking in 5 minutes, and condition of cure is normal temperature (25 ℃ of temperature, 3 hours set time).The performance test of the water-base epoxy varnish of present embodiment is as shown in table 3:
Table 3
| Hardness (GB6739-86) | Sticking power (GB9286-88) | Water tolerance | 5％H 2SO 4 | 5％N aOH |
| 5H | 2 | Paint film slightly whitened in 5 days | 5 days: non-foaming, do not peel off | 3 days: non-foaming, do not peel off |
Embodiment 3
The preparation of aqueous epoxy resins: in the there-necked flask that stirring and temperature regulating device are housed, add 12 grams 2, the 2-dimethylol propionic acid, 10 gram acetone, 15 gram tolylene diisocyanates, 100 restrain epoxy resin E-44s, are heated to 55 ℃, and reaction stopped in 5 hours under this temperature.
With the aqueous epoxy resins 100g that makes, with aqueous sodium hydroxide solution 85g (wherein sodium hydroxide 3g) neutralization, again with agitator with its emulsification, high-speed stirring 20 minutes, rotating speed is 1000 rev/mins, makes solid content and be 50% stabilized aqueous epoxy emulsion.
Viscosity: 2700mp.s
Epoxy equivalent (weight): 0.19mol/100g
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The preparation of water-base epoxy varnish: get the 10g modified epoxy resin emulsion, be cured with 2 gram urea, be stirred well to and mix, application was carried out in slaking in 5 minutes, and condition of cure is normal temperature (25 ℃ of temperature, 3 hours set time).The performance test of the water-base epoxy varnish of present embodiment is as shown in table 4:
Table 4
| Hardness (GB6739-86) | Sticking power (GB9286-88) | Water tolerance | 5％H 2SO 4 | 5％N aOH |
| 6H | 1 | Paint film slightly whitened in 5 days | 5 days non-foaming, do not peel off | 3 days non-foaming, do not peel off |
Embodiment 4
The preparation of aqueous epoxy resins: in the there-necked flask that stirring and temperature regulating device are housed, add 12 grams 2, the 2-dimethylol propionic acid, 30 gram acetone, 17 gram tolylene diisocyanates, 100 restrain epoxy resin E-44s, are heated to 50 ℃, and reaction stopped in 5 hours under this temperature.
With the aqueous epoxy resins 100g that makes, with aqueous sodium carbonate 65g (wherein yellow soda ash 5g) neutralization, again with agitator with its emulsification, high-speed stirring 20 minutes, rotating speed is 1000 rev/mins, makes solid content and be 60% stabilized aqueous epoxy emulsion.
Viscosity: 2000mp.s
Epoxy equivalent (weight): 0.19mol/100g
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The preparation of water-base epoxy varnish: get the 10g modified epoxy resin emulsion, be cured with 3 gram NX-2003, be stirred well to and mix, application was carried out in slaking in 5 minutes, and condition of cure is normal temperature (25 ℃ of temperature, 3 hours set time).The performance test of the water-base epoxy varnish of present embodiment is as shown in table 5:
Table 5
| Hardness (GB6739-86) | Sticking power (GB9286-88) | Water tolerance | 5％H 2SO 4 | 5％N aOH |
| 5H | 2 | Paint film slightly whitened in 5 days | 5 days non-foaming, do not peel off | 2 days non-foaming, do not peel off |
Embodiment 5
The preparation of aqueous epoxy resins: in the there-necked flask that stirring and temperature regulating device are housed, add 11 grams 2, the 2-dimethylol propionic acid, 30 gram acetone, 17 gram tolylene diisocyanates, 100 restrain epoxy resin E-44s, are heated to 65 ℃, and reaction stopped in 4 hours under this temperature.
With the aqueous epoxy resins 100g that makes, with triethylamine aqueous solution 65g (wherein triethylamine 5.5g) neutralization, again with agitator with its emulsification, high-speed stirring 20 minutes, rotating speed is 1000 rev/mins, makes solid content and be 60% stabilized aqueous epoxy emulsion.
Viscosity: 2000mp.s
Epoxy equivalent (weight): 0.19mol/100g
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The preparation of water-base epoxy varnish: get the 10g modified epoxy resin emulsion, be cured with 2 gram NX-2003, be stirred well to and mix, application was carried out in slaking in 5 minutes, and condition of cure is normal temperature (25 ℃ of temperature, 3 hours set time).The performance test of the water-base epoxy varnish of present embodiment is as shown in table 6:
Table 6
| Hardness (GB6739-86) | Sticking power (GB9286-88) | Water tolerance | 5％H 2SO 4 | 5％N aOH |
| 6H | 2 | Paint film slightly whitened in 5 days | 5 days non-foaming, do not peel off | 2 days non-foaming, do not peel off |
Embodiment 6
The preparation of aqueous epoxy resins: in the there-necked flask that stirring and temperature regulating device are housed, add 12 grams 2, the 2-dimethylol propionic acid, 30 gram acetone, 16 gram tolylene diisocyanates, 100 restrain epoxy resin E-44s, are heated to 50 ℃, and reaction stopped in 5 hours under this temperature.
With the aqueous epoxy resins 100g that makes, with triethylamine aqueous solution 65g (wherein triethylamine 5.5g) neutralization, again with agitator with its emulsification, high-speed stirring 20 minutes, rotating speed is 1000 rev/mins, makes solid content and be 60% stabilized aqueous epoxy emulsion.
Viscosity: 2000mp.s
Epoxy equivalent (weight): 0.19mol/100g
The stability of epoxy resin latex: centrifugal stability: 2000 rev/mins, 30 minutes not stratified.
The preparation of water-base epoxy varnish: get the 10g modified epoxy resin emulsion, be cured with 1 gram NX-2003, be stirred well to and mix, application was carried out in slaking in 5 minutes, and condition of cure is normal temperature (25 ℃ of temperature, 3 hours set time).The performance test of the water-base epoxy varnish of present embodiment is as shown in table 7:
Table 7
| Hardness (GB6739-86) | Sticking power (GB9286-88) | Water tolerance | 5％H 2SO 4 | 5％N aOH |
| 6H | 1 | Paint film slightly whitened in 5 days | 5 days non-foaming, do not peel off | 3 days non-foaming, do not peel off |
Claims (3)
1. an aqueous epoxy resins is characterized in that, the compound that structure such as following general formula are represented:
2. described preparation method of water-dilutable epoxide resin of claim 1, it is characterized in that, comprise the steps: according to the mass fraction: 100 parts of Resins, epoxy, 2, reacted 4-6 hour down at 50-65 ℃ after 2-dimethylol propionic acid 10-12 part, tolylene diisocyanate 15-17 part, acetone 10-30 part are mixed, obtain aqueous epoxy resins; Described Resins, epoxy is bisphenol A type epoxy resin, and the equation of reaction is as follows:
3. one kind prepares the method for varnish with the described aqueous epoxy resins of claim 1, may further comprise the steps:
A. prepare aqueous epoxy emulsion earlier, according to the mass fraction,,, make the aqueous epoxy emulsion that solid content is 40%-60% then with its emulsification with the neutralization earlier of 100 parts of aqueous epoxy resins, alkaline aqueous solution 65-85 part; Described alkaline aqueous solution is a sodium hydroxide, yellow soda ash or triethylamine aqueous solution a kind of, and concentration is 3-8wt%;
B. according to the mass fraction, get the epoxy resin latex of 100 parts of step a, add 10-30 part solidifying agent, be stirred well to and mix, application was carried out in slaking in 5 minutes; Described solidifying agent is a kind of of diethylenetriamine, urea, polymeric amide, NX-2003.
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| CN101550226B (en) * | 2009-05-06 | 2011-04-27 | 上海电动工具研究所 | Method for preparing water soluble epoxy insulated resin in alkaline medium |
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| CN104072784A (en) * | 2014-07-10 | 2014-10-01 | 南通河海大学海洋与近海工程研究院 | Surface treatment method for improving compatibility of polyaniline and epoxy resin |
| CN104861772B (en) * | 2015-04-21 | 2017-09-15 | 江苏兴文包装有限公司 | Aqueous epoxy resins base link stuff, water-based ink and its preparation method and application |
| CN106243912A (en) * | 2016-07-06 | 2016-12-21 | 韩立 | A kind of aqueous epoxide resin paint and preparation method thereof |
| CN110828104A (en) * | 2019-10-23 | 2020-02-21 | 上海太朔材料技术有限公司 | Moulded inductor made of aqueous epoxy resin and manufacturing process thereof |
| CN111100530A (en) * | 2019-12-09 | 2020-05-05 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Water-emulsion epoxy insulating impregnating varnish and preparation method thereof |
| CN110885421B (en) * | 2019-12-13 | 2021-11-12 | 中国林业科学研究院林产化学工业研究所 | High-compatibility organosilicon modified epoxy resin polyol aqueous dispersion and preparation method thereof |
| CN112480850A (en) * | 2020-12-19 | 2021-03-12 | 重庆禄成建筑工程有限公司 | Environment-friendly high-strength adhesive |
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