CN111499882A - Non-ionic water-based epoxy resin emulsion and preparation method thereof - Google Patents
Non-ionic water-based epoxy resin emulsion and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
The invention belongs to the technical field of epoxy resin, and particularly relates to a non-ionic water-based epoxy resin emulsion and a preparation method thereof. The invention provides a nonionic water-based epoxy resin emulsion which comprises the following raw materials in parts by weight: 57-80 parts of polyethylene glycol monomethyl ether; 1-4 parts of diisocyanate; 10-25 parts of liquid epoxy resin; 0.1-0.2 part of a catalyst; 600-950 parts of solid epoxy resin; 90-120 parts of a cosolvent; 600-950 parts of water. The invention introduces high molecular weight polyethylene glycol monomethyl ether on an epoxy resin molecular skeleton by a chemical grafting method to prepare a nonionic epoxy resin emulsifier with activity and emulsification functions, and combines a phase inversion technology to prepare the nonionic aqueous epoxy resin emulsion with good storage stability, fine dispersed phase particles and uniform particle size distribution.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and particularly relates to a non-ionic water-based epoxy resin emulsion and a preparation method thereof.
Background
Due to the characteristics of the nonpolar oily resin, the epoxy resin is only dissolved in organic solvents such as ketone, ether, aromatic hydrocarbons and the like, the volatilization of the organic solvents easily causes environmental pollution and harm to human bodies, and the flammable and explosive characteristics of the organic solvents also increase the potential safety hazards in the transportation and storage processes of products. Therefore, with the development of science and technology, the enhancement of environmental awareness and the consideration of safety, in order to meet the requirement of environmental protection, the traditional solvent-based epoxy coating has gradually faded out of the market, and the development of the water-based epoxy resin has become a new research direction. In recent decades, the application of water-based epoxy has replaced solvent-based epoxy in various fields, such as metal anticorrosive paint, exterior wall paint, exterior package paint for daily necessities, inner coating of food cans, paint for building industry, and the like. At present, the comprehensive performance of the waterborne epoxy resin reaches the level of solvent-based epoxy, even the performance of some aspects exceeds that of the traditional solvent-based epoxy resin, and the waterborne epoxy resin has the advantages of no toxicity, no pollution, simple and convenient construction, production cost reduction and the like, so that the research on a waterborne system of the epoxy resin has great significance.
The preparation of the water-based epoxy resin mainly comprises 3 methods of a mechanical method, a phase inversion method and chemical modification at present, and mainly surrounds two main types of ionic and nonionic epoxy emulsions for preparation. The self-emulsifying epoxy resin emulsion prepared by the chemical modification method has the characteristics of capability of modifying the performance of a coating film according to requirements, no need of adding an emulsifier, small particle size of a dispersed phase, good storage stability and the like, and is a hotspot of research in the field by people at present.
The epoxy resin emulsion prepared by the chemical modification method has 3 types of nonionic type, cationic type and anionic type, wherein the domestic research reports of the cationic type are less. The preparation process of the nonionic and anionic epoxy emulsions is simple and reliable, and the performances of the prepared emulsions are closer to those of solvent-based epoxy, so that the preparation of the epoxy emulsion with high performance ratio becomes the main direction of the current water-based epoxy field.
However, the method for preparing the nonionic epoxy emulsion is generally an external emulsifier method, but the emulsion obtained by the method has poor stability, and the water resistance and the salt spray resistance of a coating film are poor; to overcome the disadvantages of external emulsifiers, reactive epoxy emulsifiers were later developed and combined with phase inversion techniques to produce stable epoxy emulsions. According to the domestic and foreign literature patents, the emulsion has good storage stability when the average particle size of the dispersed phase particles of the emulsion is about 1-3 μm. However, most of the current patents report that the nonionic active epoxy emulsifier is synthesized, or the synthesis steps are complicated, and the process is complex and uncontrollable; or low molecular weight polyether amine is adopted for modification, but the storage stability of the obtained epoxy emulsion is not good; the modification by using expensive high molecular weight polyetheramine and the re-emulsification of solid epoxy resin have the defects of high cost, unfavorable popularization and the like.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a nonionic aqueous epoxy resin emulsion, which comprises the following raw materials in parts by weight: 57-80 parts of polyethylene glycol monomethyl ether; 1-4 parts of diisocyanate; 10-25 parts of liquid epoxy resin; 0.1-0.2 part of a catalyst; 600-950 parts of solid epoxy resin; 90-120 parts of a cosolvent; 600-950 parts of water.
As a preferable technical scheme, the molecular weight of the polyethylene glycol monomethyl ether is more than or equal to 4500 g/mol.
As a preferable technical scheme, the diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and dicyclohexyl diisocyanate.
As a preferred technical scheme, the liquid epoxy resin is a multifunctional liquid epoxy resin with low molecular weight.
As a preferable technical scheme, the liquid epoxy resin is F44 epoxy resin and/or E44 epoxy resin.
As a preferable technical scheme, the catalyst is one or two of dibutyltin dilaurate, stannous octoate and bismuth isooctanoate.
As a preferable technical scheme, the solid epoxy resin is E20 epoxy resin and/or E12 epoxy resin.
As a preferable technical scheme, the cosolvent is selected from one or two of butanone, N-methyl pyrrolidone, propylene glycol methyl ether acetate and propylene glycol methyl ether.
The second aspect of the present invention provides a preparation method of the nonionic aqueous epoxy resin emulsion, comprising the following steps:
(1) heating and melting polyethylene glycol monomethyl ether, adding diisocyanate, and reacting under the action of a catalyst;
(2) adding liquid epoxy resin in the step (1), reacting at the temperature of 80-110 ℃ for 3-7h to obtain a nonionic active epoxy resin emulsifier;
(3) and (3) adding the solid epoxy resin and the cosolvent in the step (2), melting and stirring uniformly, and dropwise adding water to prepare the water-based epoxy resin emulsion.
The third aspect of the invention provides a coating, which comprises the nonionic waterborne epoxy resin emulsion and a curing agent.
Has the advantages that: the invention introduces high molecular weight polyethylene glycol monomethyl ether with easily available, cheap and hydrophilic materials on an epoxy resin molecular skeleton by a chemical grafting method to prepare the nonionic epoxy resin emulsifier with activity and emulsification function, and combines a phase inversion technology to prepare the nonionic waterborne epoxy resin emulsion with good storage stability, fine dispersed phase particles and uniform particle size distribution.
The epoxy resin emulsion prepared by the invention has simple and controllable process, cheap and easily obtained materials, can be stored at room temperature for more than half a year without sedimentation, has the average particle size of 1-3 mu m of dispersed phase particles of the obtained emulsion, and has the following excellent performances after being compounded with a matched curing agent: the paint film has excellent comprehensive performances of good water resistance, no damage of a paint film with the resistance of positive and reverse impact of 50cm, no damage of a paint film with the resistance of positive impact of 50cm at minus 30 ℃, more than HB hardness, 0 grade of adhesive force lattice method, more than 500h of salt spray resistance and the like.
Detailed Description
For purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range from "1 to 10" should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, and the like.
In order to solve the problems, the invention provides a nonionic water-based epoxy resin emulsion which comprises the following raw materials in parts by weight: 57-80 parts of polyethylene glycol monomethyl ether; 1-4 parts of diisocyanate; 10-25 parts of liquid epoxy resin; 0.1-0.2 part of a catalyst; 600-950 parts of solid epoxy resin; 90-120 parts of a cosolvent; 600-950 parts of water.
As a preferred embodiment, the polyethylene glycol monomethyl ether has a molecular weight of 4500g/mol or greater.
One end of a molecular chain of the polyethylene glycol monomethyl ether contains hydroxyl, and the other end of the molecular chain of the polyethylene glycol monomethyl ether contains methoxyl without active hydrogen groups; the molecular weight of the methoxypolyethylene glycols may be, for example, 4500g/mol, 10000g/mol, 20000 g/mol; the commodity brands corresponding to the molecular weights of 4500g/mol, 10000g/mol and 20000g/mol are respectively MPEG-4500, MPEG-10000 and MPEG-20000; preferably, the molecular weight of the polyethylene glycol monomethyl ether is 4500 g/mol.
As a preferred embodiment, the diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, preferably toluene diisocyanate.
As a preferred embodiment, the liquid epoxy resin is a low molecular weight multifunctional liquid epoxy resin; preferably, the liquid epoxy resin is F44 epoxy resin and/or E44 epoxy resin.
The F44 and E44 are epoxy resin marks and are well known to those skilled in the art.
In a preferred embodiment, the catalyst is one or two of dibutyltin dilaurate, stannous octoate and bismuth isooctanoate.
As a preferred embodiment, the solid epoxy resin is E20 epoxy resin and/or E12 epoxy resin, preferably E20 epoxy resin.
The E12 and E20 are epoxy resin grades and are well known to those skilled in the art.
As a preferred embodiment, the cosolvent is selected from one or two of butanone, N-methylpyrrolidone, propylene glycol methyl ether acetate and propylene glycol methyl ether.
The second aspect of the present invention provides a preparation method of the nonionic aqueous epoxy resin emulsion, comprising the following steps:
(1) heating and melting polyethylene glycol monomethyl ether, adding diisocyanate, and reacting under the action of a catalyst;
(2) adding liquid epoxy resin in the step (1), reacting at the temperature of 80-110 ℃ for 3-7h to obtain a nonionic active epoxy resin emulsifier;
(3) and (3) adding the solid epoxy resin and the cosolvent in the step (2), melting and stirring uniformly, and dropwise adding water to prepare the water-based epoxy resin emulsion.
Wherein, in the step (1), the reaction temperature is 50-90 ℃ and the reaction time is 3-7 h.
Polyethylene glycol monomethyl ether and diisocyanate are reacted under the action of catalyst to obtain polyethylene glycol monomethyl ether with isocyanate at one end, and the chemical reaction formula is shown in the following formula (I);
in the step (2), after the liquid epoxy resin is added, under the action of a catalyst, hydroxyl on the main chain of the liquid epoxy resin reacts with polyethylene glycol monomethyl ether with isocyanate at one end to obtain a nonionic active epoxy resin emulsifier, wherein the chemical reaction formula is shown as the following formula (II);
in the step (3), the melting temperature is 80-120 ℃, and the stirring speed is 1500-.
In the step (3), the water is not particularly limited, and is preferably deionized water; and dropwise adding deionized water to prepare the water-based epoxy resin emulsion by a phase inversion method.
The deionized water refers to pure water from which impurities in the form of ions are removed, and can be prepared by self or purchased.
The invention implants a polyethylene glycol monomethyl ether structure with high surface activity, reasonable H L B value, higher molecular weight (molecular weight of 4500g/mol or more), low cost, easy obtainment and hydrophilicity on the main chain of liquid epoxy resin by a simple controllable chemical grafting method, and obtains a non-ionic active epoxy resin emulsifier with hydrophilicity based on the epoxy group and lipophilic benzene ring structure of the liquid epoxy resin, the benzene ring structures of the solid epoxy resin and the non-ionic active epoxy resin emulsifier are fully wetted and wound by a cosolvent, the lipophilic parts of the solid epoxy resin and the emulsifier rapidly form oil-in-water particles in the phase conversion process of dropping deionized water, and the hydrophilic chain segment polyethylene glycol monomethyl ether in the emulsifier has the characteristic of enough chain length (molecular weight of above 4500 g/mol), can rapidly wrap the oily particles and can extend enough long chain segments to be dispersed in the water phase, thereby achieving the purpose of rapidly dispersing the water phase and obtaining the water-based epoxy resin emulsion.
The third aspect of the invention provides a coating, which comprises the nonionic waterborne epoxy resin emulsion and a curing agent.
The curing agent is not particularly limited, and is preferably hensmei Aradur3986 curing agent;
wherein: the nonionic water-based epoxy resin emulsion and the curing agent are proportioned according to the equivalent ratio of epoxy value to active hydrogen of 1: 0.9.
Because the epoxy group in the liquid epoxy resin with the main structure of the active epoxy resin emulsifier is not substituted, the active epoxy resin emulsifier can participate in curing film formation together with the main component solid epoxy resin, and the hydrophilic chain segment of the branched chain can effectively avoid reducing the comprehensive performance of a cured film due to the characteristic of the branched chain, the waterborne epoxy resin emulsion prepared by the invention has the following excellent comprehensive performance: the paint film has excellent comprehensive properties of good water resistance, no damage of a paint film which resists forward and backward impact of 50cm, no damage of a paint film which resists forward impact of 50cm at minus 30 ℃, more than HB of hardness, 0 grade of adhesive force lattice method, more than 500h of salt spray resistance and the like; and no special equipment and conditions are needed in the synthesis process, the process is simple, the process is easy to control, the raw materials are easy to obtain, and the cost is low.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A non-ionic water-based epoxy resin emulsion comprises the following raw materials: 63g of polyethylene glycol monomethyl ether (the molecular weight is 4500g/mol, and the trade mark is MPEG-4500); 2.5g of toluene diisocyanate; liquid epoxy E4422 g; 0.1g of dibutyltin dilaurate as a catalyst; solid epoxy resin E20700 g; 100g of cosolvent; 700g of deionized water. Wherein: the cosolvent comprises 50g of propylene glycol methyl ether acetate and 50g of propylene glycol methyl ether.
The preparation method of the nonionic water-based epoxy resin emulsion comprises the following steps:
(1) heating 63g of polyethylene glycol monomethyl ether (the molecular weight is 4500g/mol, and the trade mark is MPEG-4500) to melt, cooling to 65 +/-5 ℃, adding 2.5g of toluene diisocyanate and 0.1g of dibutyltin dilaurate, and reacting for 4 hours at the reaction temperature of 65 +/-5 ℃;
(2) adding 22g of E44 epoxy resin in the step (1), heating to 85 +/-5 ℃, and continuing to react for 4 hours to obtain a nonionic active epoxy resin emulsifier;
(3) adding 700g of E20 epoxy resin, 50g of propylene glycol methyl ether acetate and 50g of propylene glycol methyl ether in the step (2), heating to 110 +/-5 ℃, melting, stirring uniformly, cooling to 80 ℃, dropwise adding 700g of deionized water under the condition that the stirring speed is 1500r/min, and carrying out phase transformation to obtain the aqueous epoxy resin emulsion.
Example 2
A non-ionic water-based epoxy resin emulsion comprises the following raw materials: 70g of polyethylene glycol monomethyl ether (the molecular weight is 10000g/mol, and the trade mark is MPEG-10000); 1.3g of toluene diisocyanate; liquid epoxy E4412 g; 0.1g of dibutyltin dilaurate as a catalyst; solid epoxy E20820 g; 100g of cosolvent; 800g of deionized water. Wherein: the cosolvent comprises 50g of propylene glycol methyl ether acetate and 50g of propylene glycol methyl ether.
The preparation method of the nonionic water-based epoxy resin emulsion comprises the following steps:
(1) heating and melting 70g of polyethylene glycol monomethyl ether (molecular weight is 10000g/mol, trade mark is MPEG-10000), cooling to 65 +/-5 ℃, adding 1.3g of toluene diisocyanate and 0.1g of dibutyltin dilaurate, and reacting for 4 hours at the reaction temperature of 65 +/-5 ℃;
(2) adding 12g of E44 epoxy resin in the step (1), heating to 85 +/-5 ℃, and continuing to react for 4 hours to obtain a nonionic active epoxy resin emulsifier;
(3) adding 820g of E20 epoxy resin, 50g of propylene glycol methyl ether acetate and 50g of propylene glycol methyl ether in the step (2), heating to 110 +/-5 ℃, melting, stirring uniformly, cooling to 80 ℃, dropwise adding 800g of deionized water under the condition that the stirring speed is 1500r/min, and carrying out phase transformation to obtain the aqueous epoxy resin emulsion.
Example 3
A non-ionic water-based epoxy resin emulsion comprises the following raw materials: 80g of polyethylene glycol monomethyl ether (molecular weight is 20000g/mol, and the trade mark is MPEG-20000); 1.0g of diphenylmethane diisocyanate; liquid epoxy E4415 g; 0.1g of catalyst stannous octoate; solid epoxy resin E20950 g; 120g of cosolvent; 950g of deionized water. Wherein: the cosolvent comprises 60g of propylene glycol methyl ether acetate and 60g of propylene glycol methyl ether.
The preparation method of the nonionic water-based epoxy resin emulsion comprises the following steps:
(1) heating and melting 80g of polyethylene glycol monomethyl ether (molecular weight is 20000g/mol, and trade mark is MPEG-20000), cooling to 65 +/-5 ℃, adding 1.0g of diphenylmethane diisocyanate and 0.1g of stannous octoate, and reacting for 4h at the reaction temperature of 65 +/-5 ℃;
(2) adding 15g of F44 epoxy resin in the step (1), heating to 85 +/-5 ℃, and continuing to react for 4 hours to obtain a nonionic active epoxy emulsifier;
(3) adding 950g of E20 epoxy resin, 60g of propylene glycol methyl ether acetate and 60g of propylene glycol methyl ether in the step (2), heating to 110 +/-5 ℃, melting, stirring uniformly, cooling to 80 ℃, dropwise adding 950g of deionized water under the condition that the stirring speed is 1500r/min, and carrying out phase transformation to obtain the aqueous epoxy resin emulsion.
Example 4
A non-ionic water-based epoxy resin emulsion comprises the following raw materials: 57g of polyethylene glycol monomethyl ether (the molecular weight is 4500g/mol, and the trade mark is MPEG-4500); 3.0g of isophorone diisocyanate; liquid epoxy E4425 g; 0.1g of catalyst bismuth isooctanoate; solid epoxy resin E12600 g; 90g of cosolvent; 600g of deionized water. Wherein: the cosolvent comprises 45g of butanone and 45g of propylene glycol methyl ether.
The preparation method of the nonionic water-based epoxy resin emulsion comprises the following steps:
(1) heating and melting 57g of polyethylene glycol monomethyl ether (the molecular weight is 4500g/mol, the trade mark is MPEG-4500), cooling to 65 +/-5 ℃, adding 3.0g of isophorone diisocyanate and 0.1g of bismuth isooctanoate, and reacting for 4 hours at the reaction temperature of 65 +/-5 ℃;
(2) adding 25g of E44 epoxy resin into the step (1), heating to 85 +/-5 ℃, and continuing to react for 4 hours to obtain a nonionic active epoxy emulsifier;
(3) adding 600g of E12 solid epoxy resin, 45g of butanone and 45g of propylene glycol methyl ether in the step (2), heating to 110 +/-5 ℃, melting and stirring uniformly, cooling to 80 ℃, dropwise adding 600g of deionized water under the condition that the stirring speed is 1500r/min, and obtaining the solid-containing water-based epoxy resin emulsion through phase transition.
Example 5
A non-ionic water-based epoxy resin emulsion comprises the following raw materials: 70g of polyethylene glycol monomethyl ether (the molecular weight is 4500g/mol, and the trade mark is MPEG-4500); 2.8g of toluene diisocyanate; liquid epoxy resin F4425 g; 0.1g of catalyst bismuth isooctanoate; solid epoxy resin E20600 g; 100g of cosolvent; 600g of deionized water. Wherein: the cosolvent comprises 50g of propylene glycol methyl ether acetate and 50g of propylene glycol methyl ether.
The preparation method of the nonionic water-based epoxy resin emulsion comprises the following steps:
(1) heating and melting 70g of polyethylene glycol monomethyl ether (the molecular weight is 4500g/mol, and the trade mark is MPEG-4500), cooling to 65 +/-5 ℃, adding 2.8g of toluene diisocyanate and 0.1g of bismuth isooctanoate, and reacting for 4 hours at the reaction temperature of 65 +/-5 ℃;
(2) adding 25g of F44 epoxy resin in the step (1), heating to 85 +/-5 ℃, and continuing to react for 4 hours to obtain a nonionic active epoxy resin emulsifier;
(3) adding 600g of E20 solid epoxy resin, 50g of propylene glycol methyl ether acetate and 50g of propylene glycol methyl ether in the step (2), heating to 110 +/-5 ℃, melting, stirring uniformly, cooling to 80 ℃, dropwise adding 600g of deionized water under the condition that the stirring speed is 1500r/min, and carrying out phase transformation to obtain the aqueous epoxy resin emulsion.
Comparative example 1
The difference between the raw materials of the nonionic epoxy resin emulsion and the preparation method is that 63g of polyethylene glycol monomethyl ether (molecular weight is 4500g/mol, trade mark is MPEG-4500) and 2.5g of toluene diisocyanate are replaced by 63g of polyethylene glycol monomethyl ether (molecular weight is 2000g/mol, trade mark is MPEG-2000) and 5.5 g of toluene diisocyanate in the same way as in example 1.
Comparative example 2
The difference between the raw materials of the nonionic epoxy resin emulsion and the preparation method is that 63g of polyethylene glycol monomethyl ether (molecular weight is 4500g/mol, and the trade mark is MPEG-4500) and 2.5g of toluene diisocyanate are replaced by 63g of polyethylene glycol monomethyl ether (molecular weight is 1500g/mol, and the trade mark is MPEG-1500) and 7.5 g of toluene diisocyanate in example 1. The aqueous epoxy emulsion can not be successfully prepared, or the aqueous epoxy emulsion can be directly settled and layered overnight.
Comparative example 3
The raw materials and preparation method of a nonionic epoxy resin emulsion are the same as example 1, except that 2.5g of toluene diisocyanate is replaced by 5.5 g of hexamethylene diisocyanate trimer N3300.
Performance testing
(1) The performance results of the nonionic aqueous epoxy resin emulsions prepared in the examples and comparative examples are shown in Table 1;
and (3) stability testing: the emulsion was stored at room temperature for 6 months and the appearance was observed.
TABLE 1
(2) The performance test results of paint films obtained after mixing the nonionic waterborne epoxy resin emulsions prepared in the examples and the comparative examples with a curing agent (Hensman Aradur3986 curing agent) and spraying the mixture on a tinplate for curing at room temperature for 168 hours are shown in Table 2;
wherein: the nonionic aqueous epoxy resin emulsion and the curing agent are compounded in such a ratio that the equivalent ratio of epoxy value to active hydrogen is 1:0.9, for example, the nonionic aqueous epoxy resin emulsion of example 1 and the curing agent of hensmy Aradur3986 are mixed in a mass ratio of 2.8: 1.
TABLE 2
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The nonionic water-based epoxy resin emulsion is characterized by comprising the following raw materials in parts by weight: 57-80 parts of polyethylene glycol monomethyl ether; 1-4 parts of diisocyanate; 10-25 parts of liquid epoxy resin; 0.1-0.2 part of a catalyst; 600-950 parts of solid epoxy resin; 90-120 parts of a cosolvent; 600-950 parts of water.
2. The nonionic aqueous epoxy resin emulsion according to claim 1, wherein the molecular weight of the polyethylene glycol monomethyl ether is 4500g/mol or more.
3. The non-ionic aqueous epoxy resin emulsion according to claim 1, wherein the diisocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate.
4. The non-ionic aqueous epoxy resin emulsion according to claim 1, wherein the epoxy resin is a low molecular weight multifunctional liquid epoxy resin.
5. The nonionic aqueous epoxy resin emulsion according to claim 4, characterized in that the liquid epoxy resin is F44 epoxy resin and/or E44 epoxy resin.
6. The non-ionic aqueous epoxy resin emulsion of claim 1 wherein the catalyst is one or a combination of two of dibutyltin dilaurate, stannous octoate, and bismuth isooctanoate.
7. The non-ionic aqueous epoxy resin emulsion according to claim 1, characterized in that the solid epoxy resin is an E20 epoxy resin and/or an E12 epoxy resin.
8. The non-ionic aqueous epoxy resin emulsion according to any one of claims 1 to 7, wherein the cosolvent is selected from one or a combination of two of butanone, N-methylpyrrolidone, propylene glycol methyl ether acetate and propylene glycol methyl ether.
9. A process for the preparation of a non-ionic aqueous epoxy resin emulsion according to any one of claims 1 to 8, characterized in that it comprises the following steps:
(1) heating and melting polyethylene glycol monomethyl ether, adding diisocyanate, and reacting under the action of a catalyst;
(2) adding liquid epoxy resin in the step (1), reacting at the temperature of 80-110 ℃ for 3-7h to obtain a nonionic active epoxy resin emulsifier;
(3) and (3) adding the solid epoxy resin and the cosolvent in the step (2), melting and stirring uniformly, and dropwise adding water to prepare the water-based epoxy resin emulsion.
10. A coating material comprising the nonionic aqueous epoxy resin emulsion according to any one of claims 1 to 8 and a curing agent.
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