Water-based single-component epoxy resin dispersion and preparation method thereof

Abstract

The invention relates to the technical field of epoxy resin, in particular to a water-based single-component epoxy resin dispersion and a preparation method thereof. The water-based single-component epoxy resin dispersion is prepared from the following components in parts by weight: 15 to 25 parts of water-based epoxy resin, 5 to 10 parts of water-soluble amine compound or water-soluble anhydride compound, 25 to 35 parts of oil phase component, 0 to 1.5 parts of initiator, 3 to 8 parts of surfactant and 95 to 145 parts of water. The water-based single-component epoxy resin dispersion prepared by the invention has relatively good light resistance.

Description

Technical Field

[0001] The present disclosure relates to the technical field of epoxy resins, and in particular to a water-based one-component epoxy resin dispersion and a preparation method thereof. Background Art

[0002] Epoxy resins have a wide range of applications, including coating materials, electrical and electronic insulation materials, and adhesives. In recent years, in particular, to improve productivity in electronic material applications, there has been a demand for one-component epoxy resin compositions with excellent curing properties and storage stability.

[0003] The Chinese invention patent with authorization announcement number CN114106757B discloses a low-precipitation single-component epoxy adhesive, its preparation method and application. The raw materials for preparing the low-precipitation single-component epoxy adhesive include the following components in parts by weight: 35-50 parts of epoxy resin; 4-12 parts of modified epoxy resin; 10-30 parts of curing agent; 0.1-1 part of stabilizer; 1-5 parts of color powder; 1-5 parts of coupling agent; 1-5 parts of accelerator; the modified epoxy resin of the invention has a significant inhibitory effect on the precipitation of epoxy adhesive, improving the current glue precipitation problem on the market; the low-precipitation single-component epoxy adhesive of the invention does not have strict requirements on the residence time outside after gluing, greatly reducing the risk of precipitation contamination of lenses and improving product yield.

[0004] The Chinese invention patent application with publication number CN116004162A discloses a UV heat-curable low-modulus epoxy resin adhesive for potting and its preparation method. Calculated by total weight, the raw material composition includes 15%-30% epoxy resin, 10%-20% toughening resin, 10%-20% thiol resin, 20%-50% filler, 0.1%-5% thixotropic agent, 0.1%-1% coupling agent, and 0.1%-5% initiator. The adhesive prepared by this invention has a low shrinkage rate, low modulus, strong adhesion to various metal composite materials, good environmental reliability, and can be quickly cured by heating, solving the problem of sealing materials between structural parts being easily damaged and failed by thermal shock.

[0005] The Chinese invention patent application with publication number CN115785871A discloses a heat-curing flame-retardant epoxy resin one-component adhesive and its preparation method, which includes the following raw materials: 50-200 parts of epoxy resin, 10-50 parts of epoxy diluent, 80-350 parts of flame-retardant filler, 5-25 parts of latent curing agent, and 1-5 parts of accelerator. The invention adopts the method of mixing and dispersing the epoxy resin, diluent, filler, etc. uniformly, and then mixing them with a modified amine curing agent to allow the amine curing agent and epoxy resin to undergo a cross-linking reaction to form a three-dimensional network structure. The flame-retardant filler added to the system can improve the flame retardant performance of the cured colloid.

[0006] However, the epoxy adhesives prepared by the above patents and prior art have poor storage stability at room temperature and still need to be cured by heating or ultraviolet irradiation. Summary of the Invention

[0007] The present disclosure provides a water-based one-component epoxy resin dispersion to address the deficiencies in the related art.

[0008] According to a first aspect of an embodiment of the present disclosure, a water-based one-component epoxy resin dispersion is provided, which comprises the following components in parts by weight: 15-25 parts by weight of a water-based epoxy resin, 5-10 parts by weight of a water-soluble amine compound or a water-soluble acid anhydride compound, 25-35 parts by weight of an oil phase component, 0-1.5 parts by weight of an initiator, 0-10 parts by weight of a surfactant, and 95-145 parts by weight of water.

[0009] In one aspect of an embodiment of the present disclosure, preferably, the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of an aqueous epoxy resin, 5-10 parts by weight of a water-soluble amine compound or a water-soluble acid anhydride compound, 25-35 parts by weight of an oil phase component, 0.5-1.5 parts by weight of an initiator, 0-0.25 parts by weight of a catalyst, 3-8 parts by weight of a surfactant, 0-8 parts by weight of a stabilizer, 110-135 parts by weight of water, and 0-5 parts by weight of a cosolvent.

[0010] In one aspect of an embodiment of the present disclosure, it is further preferred that the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-20 parts by weight of an aqueous epoxy resin, 8-10 parts by weight of a water-soluble amine compound, 25-30 parts by weight of an oil phase component, 0.5-0.8 parts by weight of an initiator, 0-0.15 parts by weight of a catalyst, 3-8 parts by weight of a surfactant, 0-5 parts by weight of a stabilizer, 120-135 parts by weight of water, 0-5 parts by weight of a cosolvent, 0-1 parts by weight of a leveling agent, and 0-1 parts by weight of a defoamer.

[0011] In one aspect of an embodiment of the present disclosure, specifically, the aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-20 parts by weight of an aqueous epoxy resin, 8-10 parts by weight of a water-soluble amine compound, 25-30 parts by weight of an oil phase component, 0.5-0.8 parts by weight of an initiator, 0-0.15 parts by weight of a catalyst, 3-8 parts by weight of a surfactant, 0-5 parts by weight of a stabilizer, and 120-135 parts by weight of water.

[0012] In one aspect of an embodiment of the present disclosure, more specifically, the aqueous one-component epoxy resin dispersion contains the following components in parts by weight: 16 parts by weight of an aqueous epoxy resin, 8 parts by weight of a water-soluble amine compound, 28 parts by weight of an oil phase component, 2 parts by weight of a phospholipid, 0.6 parts by weight of an initiator, 0.05 parts by weight of a catalyst, 3 parts by weight of a surfactant, and 1 part by weight of a stabilizer.

[0013] In one aspect of the embodiments of the present disclosure, the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine or isophoronediamine; the water-soluble acid anhydride compound is selected from maleic anhydride or phthalic anhydride.

[0014] In one aspect of an embodiment of the present disclosure, the water-based epoxy resin is prepared by hydrating the epoxy resin, and the hydration modification step includes the following: Step 1-a: adding 1,4-butanediol diglycidyl ether and polyethylene glycol to a reaction vessel, heating to 70°C-80°C and maintaining stirring to allow the reactants to completely melt.

[0015] Step 2-a: Dissolve K2S2O8 in water to obtain a solution and add it dropwise to the reaction vessel of step 1-a, react for 20-70 minutes, then raise the temperature to 150°C-180°C, and then measure the epoxy value of the system once every 30 minutes using the hydrochloric acid-acetic acid method; at the end of the reaction, obtain the product of step 2-a.

[0016] Step 3-a: providing an epoxy resin and an aqueous isocyanate emulsion; dissolving the epoxy resin and aqueous isocyanate emulsion in ethyl acetate, heating to 60°C-70°C while stirring, then adding the product of step 2-a, and reacting for 3-5 hours to obtain a water-based epoxy resin.

[0017] In one aspect of an embodiment of the present disclosure, in step 3-a, the epoxy resin may be selected from E-20, E-44, E-51, NPEL-128, YLE-1300A, etc., but is not limited thereto.

[0018] In one aspect of the embodiments of the present disclosure, the water-based one-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer water phase component contains the oil phase component, and the oil phase component also contains the inner water phase component; and the outer water phase component contains water-based epoxy resin; the inner water phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound.

[0019] In one aspect of the embodiments of the present disclosure, preferably, the water-based one-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer water phase component contains the oil phase component, and the oil phase component also contains the inner water phase component; and the outer water phase component contains water-based epoxy resin; the inner water phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound, and a curing agent, and the curing agent is selected from water-soluble compounds.

[0020] In one aspect of the embodiments of the present disclosure, preferably, the water-based one-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer water phase component contains the oil phase component, and the oil phase component also contains the inner water phase component; and the outer water phase component contains water-based epoxy resin; the inner water phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound; the oil phase component contains a curing agent, and the curing agent is selected from oil-soluble compounds.

[0021] In one aspect of the embodiments of the present disclosure, the initiator is selected from a photoinitiator, a thermal initiator or a cationic initiator.

[0022] In one aspect of the embodiments of the present disclosure, the oil phase component is selected from tributyrin, triolein, tripalmitin, tristearin, diolein, 1,3-dipalmitoyl-2-oleoyl glycerol, distearin, dilaurin, dimyristin or dilinolein.

[0023] In one aspect of the embodiments of the present disclosure, the oil phase component further comprises a phospholipid; the phospholipid is selected from lecithin, soybean lecithin, cephalin, dioleoylphosphatidylcholine, hydrogenated soybean lecithin, distearoylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, dioleoylphosphatidylcholine, distearoylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol, dioleoylphosphatidylglycerol or phosphatidylethanolamine.

[0024] In one aspect of the embodiments of the present disclosure, the mass ratio of the phospholipids to the oil phase component is selected from 1:(10-30).

[0025] In one aspect of the embodiments of the present disclosure, the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole.

[0026] In one aspect of the disclosed embodiments, the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60, or Tween 80.

[0027] In one aspect of the embodiments of the present disclosure, the stabilizer is selected from gelatin, carrageenan oligosaccharide or sodium alginate. The present disclosure may add or not add a stabilizer according to actual needs.

[0028] In one aspect of the embodiments of the present disclosure, the co-solvent is selected from methanol, ethanol, n-propanol or isopropanol.

[0029] In one aspect of the embodiments of the present disclosure, the defoaming agent and the leveling agent can be arbitrarily selected from defoaming agents and leveling agents commonly used in the art, and are not limited thereto.

[0030] According to the second aspect of the embodiment of the present disclosure, a method for preparing the aforementioned aqueous one-component epoxy resin dispersion is provided; the aqueous one-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; the method includes a process of first preparing an oil-in-water type emulsion dispersion and then preparing an oil-in-water type multiple emulsion dispersion; the method includes the following steps: when the initiator is selected from a water-soluble compound: Step 1-b: dispersing a water-soluble amine compound or a water-soluble acid anhydride compound, and the initiator into water to obtain a first aqueous solution.

[0031] Step 2-b: providing an oil phase component, adding a surfactant to the oil phase component; adding the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion.

[0032] Step 3-b: preparing a water-based epoxy resin by hydrating and modifying an epoxy resin; and dispersing the water-based epoxy resin in water to obtain a second aqueous solution.

[0033] Step 4-b: adding the water-in-oil emulsion dispersion prepared in step 2-b dropwise to the second aqueous solution at a stirring rate of 2500-3000 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0034] When the initiator is selected from oil-soluble compounds: Step 1-c: dispersing a water-soluble amine compound or a water-soluble acid anhydride compound into water to obtain a third aqueous solution.

[0035] Step 2-c: providing an oil phase component, dispersing the initiator and surfactant in the oil phase component; adding the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion.

[0036] Step 3-c: preparing a water-based epoxy resin by hydrating and modifying the epoxy resin; and dispersing the water-based epoxy resin in water to obtain a fourth aqueous solution.

[0037] Step 4-c: adding the water-in-oil emulsion dispersion prepared in step 2-c dropwise to the fourth aqueous solution at a stirring rate of 2500-3000 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0038] In one aspect of the embodiments of the present disclosure, when the initiator is selected from oil-soluble compounds, the oil phase component may contain phospholipids.

[0039] In one aspect of the embodiments of the present disclosure, the method includes the following steps: Step 1-d: dispersing a water-soluble amine compound, a catalyst and a co-solvent in water to obtain a fifth aqueous solution; wherein the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine or diethylaminopropylamine; and the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole.

[0040] Step 2-d: providing an oil phase component, dispersing the surfactant and the initiator in the oil phase component; adding the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; wherein the oil phase component is selected from tributyrin, triolein, tripalmitin, tristearin, diolein, 1,3-dipalmitoyl-2-oleoyl glycerol, distearin, dilaurin, dimyristin or dilinolein; the oil phase component The composition further comprises a phospholipid; the phospholipid is selected from lecithin, soybean lecithin, cephalin, dioleoylphosphatidylcholine, hydrogenated soybean lecithin, distearoylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, dioleoylphosphatidylcholine, distearoylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol, dioleoylphosphatidylglycerol or phosphatidylethanolamine; the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; the initiator is selected from oil-soluble compounds.

[0041] Step 3-d: preparing a water-based epoxy resin by hydrating and modifying the epoxy resin; dispersing the water-based epoxy resin in water, and adding a stabilizer and a defoaming agent to obtain a sixth aqueous solution.

[0042] Step 4-d: adding the water-in-oil emulsion dispersion prepared in step 2-d dropwise to the sixth aqueous solution at a stirring rate of 2500-3000 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0043] In one aspect of the embodiments of the present disclosure, the method includes the following steps: Step 1-e: dispersing a water-soluble amine compound, a catalyst, an initiator and a co-solvent in water to obtain a seventh aqueous solution; wherein the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine or diethylaminopropylamine; the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; and the initiator is selected from a water-soluble compound.

[0044] Step 2-e: providing an oil phase component and dispersing the surfactant in the oil phase component; adding the first aqueous solution dropwise to the oil phase component at a stirring rate of 1500-1800 r / min to obtain a water-in-oil emulsion dispersion; wherein the oil phase component is selected from tributyrin, triolein, tripalmitin, tristearin, diolein, 1,3-dipalmitoyl-2-oleoyl glycerol, distearin, dilaurin, dimyristin or dilinolein; and the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80.

[0045] Step 3-e: preparing a water-based epoxy resin by hydrating and modifying the epoxy resin; dispersing the water-based epoxy resin in water, and adding a stabilizer and a defoaming agent to obtain an eighth aqueous solution.

[0046] Step 4-e: adding the water-in-oil emulsion dispersion prepared in step 2-e dropwise to the eighth aqueous solution at a stirring rate of 2500-3000 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion.

[0047] In one aspect of the embodiments of the present disclosure, in step 3-a, step 3-b to step 3-e, the steps of preparing a water-based epoxy resin by hydration modification of the epoxy resin are specifically as follows: 1,4-butanediol diglycidyl ether and polyethylene glycol are added to a reaction vessel, heated to 70°C-80°C and kept stirring to completely melt the reactants; K2S2O8 is dissolved in water to obtain a solution and added dropwise to the reaction vessel, reacted for 20-70 minutes, then heated to 150°C-180°C, and then the epoxy value of the system is measured once every 30 minutes using a hydrochloric acid-acetic acid method; a product is obtained at the end of the reaction; an epoxy resin and an aqueous isocyanate emulsion are provided; the epoxy resin and the aqueous isocyanate emulsion are dissolved in ethyl acetate, heated to 60°C-70°C and kept stirring, and then the product is added and reacted for 3-5 hours to obtain a water-based epoxy resin. The epoxy resin may be selected from E-20, E-44, E-51, NPEL-128, YLE-1300A, etc., but is not limited thereto.

[0048] In the present disclosure, the initiator may be selected from methyl ethyl ketone peroxide, t-butyl perbenzoate, benzoyl peroxide, t-butyl peroxyethyl octanoate or diphenoxyethyl peroxydicarbonate.

[0049] The technical solutions provided by the embodiments of the present disclosure may include the following beneficial effects: As can be seen from the above embodiments, the present disclosure prepares a water-in-oil-in-water type multiple emulsion dispersion, which is relatively stable at room temperature and pressure; and has the following advantages: (1) The present disclosure disperses the epoxy resin in the outer aqueous phase, and the curing agent water-soluble amine compound (or water-soluble acid anhydride compound) is dispersed in the inner aqueous phase. When the initiator is a water-soluble compound, the initiator is also dispersed in the inner aqueous phase; the inner aqueous phase is encapsulated by the oil phase component, and the oil phase is encapsulated by the oil phase component. The phase components are encapsulated by the outer aqueous phase; therefore, when the structure of the multiple emulsion dispersion is not destroyed, it has better stability; for example, in the prior art, the epoxy resin dispersion containing a photocuring initiator needs to be stored away from light, otherwise it will cure under light. However, when a water-in-oil-in-water type multiple emulsion dispersion prepared by the present invention is used, the photocuring initiator and the curing agent are encapsulated in the inner aqueous phase, and the epoxy resin is encapsulated in the outer aqueous phase. The three cannot mix and are therefore difficult to react, thereby having better light resistance.

[0050] (2) Similarly, when the initiator is an oil-soluble compound, the initiator is dispersed in the oil phase, the curing agent is still dispersed in the inner oil phase, and the epoxy resin is still dispersed in the outer oil phase; when the structure of the multiple emulsion dispersion is not destroyed, it has better stability; similarly, for example, in the prior art, the epoxy resin dispersion containing a photocuring initiator needs to be stored away from light, otherwise it will cure under light, but when a water-in-oil-in-water type multiple emulsion dispersion prepared by the present disclosure is used, the photocuring initiator is encapsulated in the oil phase, the curing agent is encapsulated in the inner water phase, and the epoxy resin is encapsulated in the outer water phase. Similarly, the three cannot mix, so it is difficult to react, thereby having better light resistance (in addition, phospholipids can also be added to the oil phase. The phospholipids form a bilayer at the water-oil interface, which can avoid cross-linking between the epoxy resin and the photocuring initiator).

[0051] (3) In addition, the water-in-oil-in-water type multiple emulsion dispersion prepared by the present invention is relatively stable at room temperature and pressure. However, when a very small amount of strong acid, strong base, salt, osmotic pressure regulator or demulsifier is added, the emulsion structure can be destroyed. Therefore, it can be applied to some special usage scenarios; for example, the water-in-oil-in-water type multiple emulsion dispersion containing a photocuring agent prepared by the present invention can have a certain light resistance and does not require high light-proof storage; and when curing is required, a small amount of salt or osmotic pressure regulator can be added to destroy the emulsion structure, and curing can be completed under light.

[0052] It is to be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the present disclosure and, together with the description, serve to explain the principles of the present disclosure.

[0054] Figure 1 3 is a schematic structural diagram of a water-in-oil-in-water multiple emulsion dispersion prepared according to an exemplary embodiment. DETAILED DESCRIPTION

[0055] To make the purpose, technical solutions, and advantages of this application more clear, the technical solutions of this application will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of this application, rather than all the embodiments. The relevant embodiments described herein are illustrative and are used to provide a basic understanding of this application. The embodiments of this application should not be interpreted as limiting this application.

[0056] For the sake of clarity, only some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form an unspecified range; and any lower limit may be combined with other lower limits to form an unspecified range, and similarly, any upper limit may be combined with any other upper limit to form an unspecified range. In addition, each individually disclosed point or single value may itself serve as a lower limit or upper limit and be combined with any other point or single value, or with other lower limits or upper limits, to form an unspecified range.

[0057] As used herein, the terms "comprises," "comprising," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not preclude the presence of additional identical elements in the process, method, article, or apparatus that includes the element.

[0058] In the description herein, unless otherwise specified, “above” and “below” include the number itself.

[0059] Unless otherwise specified, the terms used in this disclosure have the commonly understood meanings commonly understood by those skilled in the art. Unless otherwise specified, the numerical values ​​of the various parameters mentioned in this disclosure can be measured using various measurement methods commonly used in the art (for example, they can be tested according to the methods given in the examples of this disclosure).

[0060] The term "about" is used to describe and illustrate small changes. When used in conjunction with an event or situation, the term may refer to an example in which the event or situation occurs precisely and an example in which the event or situation occurs very approximately. For example, when used in conjunction with a numerical value, the term may refer to a variation range of less than or equal to ±10% of the numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%. In addition, amounts, ratios, and other numerical values ​​are sometimes presented in this article in a range format. It should be understood that such range formats are for convenience and brevity, and should be flexibly understood to include not only numerical values ​​explicitly designated as range limits, but also all individual numerical values ​​or subranges encompassed within the range, as if each numerical value and subrange were explicitly designated.

[0061] A list of items connected by the terms "at least one of," "at least one of," "at least one of," or other similar terms can mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; or only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A can contain a single component or multiple components. Item B can contain a single component or multiple components. Item C can contain a single component or multiple components.

[0062] The present disclosure is further described below with reference to the following examples. It should be understood that these examples are only used to illustrate the present disclosure and are not intended to limit the scope of the present disclosure.

[0063] Example 1: Example 1 includes the following steps: 1. Preparation of waterborne epoxy resin: 0.25 mol of 1,4-butanediol diglycidyl ether and 0.25 mol of polyethylene glycol are added to a reaction vessel, heated to 80°C and kept stirring to completely melt the reactants; 0.6 g of K2S2O8 is dissolved in 200 mL of water to obtain a solution, which is added dropwise to the reaction vessel, reacted for 60 min, then heated to 170°C, and then the epoxy content of the system is measured every 30 minutes using a hydrochloric acid-acetic acid method. value; the reaction was completed after 4 hours, and the product was collected; 0.20 mol of epoxy resin E-51 and aqueous isocyanate emulsion (wherein the molar amount of isocyanate was 0.12 mol; specifically, aqueous blocked polyisocyanate emulsion with a solid content of 45%, and the blocking agent was 2-butanone oxime, based on isophorone diisocyanate); the epoxy resin and aqueous isocyanate emulsion were dissolved in ethyl acetate, heated to 70°C and kept stirring, and then the above-mentioned product was added, reacted for 5 hours, and a water-based epoxy resin was obtained by rotary evaporation.

[0064] 2. Preparation of the water-in-oil-in-water multiple emulsion dispersion of Example 1: 8 parts by weight of triethylenetetramine and 0.05 parts by weight of the catalyst dimethylaminophenol were dispersed in 15 parts by weight of water to obtain aqueous solution A; 2 parts by weight of phospholipid (lecithin) were dissolved in 28 parts by weight of the oil phase component, and then 3 parts by weight of the surfactant Span 60 and 0.6 parts by weight of the photoinitiator Irgacue 250 were added to obtain an oil phase; aqueous solution A was added dropwise to the oil phase at a stirring rate of 1700 r / min to obtain a water-in-oil emulsion dispersion; 16 parts by weight of the water-based epoxy resin prepared above was dispersed in 115 parts by weight of water, and 1 part by weight of the stabilizer sodium alginate was added to obtain aqueous solution B. The above-mentioned water-in-oil emulsion dispersion was added dropwise to aqueous solution B at a stirring rate of 2800 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion of Example 1; its structure is as follows: Figure 1 shown.

[0065] Example 2-4: The steps of Example 2-4 are the same as those of Example 1, except that: in Example 2, the amount of triethylenetetramine used is changed to 4 parts by weight; in Example 3, the amount of triethylenetetramine used is changed to 12 parts by weight; in Example 4, the amount of water-based epoxy resin used is changed to 8 parts by weight; however, Examples 2-4 cannot form water-in-oil-in-water type multiple emulsion dispersions, and demulsification occurs during the preparation process.

[0066] Examples 5-7: In Example 5-7, the water-soluble epoxy resin prepared by the preparation method of the water-soluble epoxy resin provided in Example 2 of CN201410503428.8 is used to replace the water-based epoxy resin prepared in Example 1; wherein Example 5 uses 16 parts by weight of the water-soluble epoxy resin prepared in Example 2 of CN201410503428.8; Example 6 uses 10 parts by weight of the water-soluble epoxy resin prepared in Example 2 of CN201410503428.8; Example 7 uses 20 parts by weight of the water-soluble epoxy resin prepared in Example 2 of CN201410503428.8; however, Examples 5-7 cannot form water-in-oil-in-water type multiple emulsion dispersions, and demulsification occurs during the preparation process.

[0067] Examples 8-10: In Example 8-10, a water-soluble epoxy resin prepared using the following method for preparing a water-soluble epoxy resin was used to replace the water-based epoxy resin prepared in Example 1: 0.20 mol of phenolic epoxy resin was prepared into a 30% dioxane solution; under ice water protection and at a temperature not exceeding 10°C, a 15% ethanol solution containing 0.15 mol of dimethylamine was added dropwise using a peristaltic pump; the addition time was controlled to 1 hour. A small amount of 3 g of citric acid was then added, and after sufficient dissolution, 25 mL of 30% hydrogen peroxide was slowly added dropwise. Finally, the temperature was raised to 60°C and maintained for 2 hours. After cooling, the product was collected to obtain a water-soluble epoxy resin.

[0068] Example 8 uses 16 parts by weight of the water-soluble epoxy resin prepared by the aforementioned method; Example 9 uses 10 parts by weight of the water-soluble epoxy resin prepared by the aforementioned method; Example 10 uses 20 parts by weight of the water-soluble epoxy resin prepared by the aforementioned method; however, Examples 8-10 are unable to form water-in-oil-in-water type multiple emulsion dispersions, and demulsification occurred during the preparation process.

[0069] Comparative Example 1: Comparative Example 1 includes the following steps: 1. Preparation of water-based epoxy resin: 0.25 mol of 1,4-butanediol diglycidyl ether and 0.25 mol of polyethylene glycol are added to a reaction vessel, heated to 80°C and kept stirring to completely melt the reactants; 0.6 g of K2S2O8 is dissolved in 200 mL of water to obtain a solution, which is then added dropwise to the reaction vessel, reacted for 60 minutes, then heated to 170°C, and then the epoxy content of the system is measured every 30 minutes using the hydrochloric acid-acetic acid method. value; the reaction was completed after 4 hours, and the product was collected; 0.20 mol of epoxy resin E-51 and aqueous isocyanate emulsion (wherein the molar amount of isocyanate was 0.12 mol; specifically, aqueous blocked polyisocyanate emulsion with a solid content of 45%, and the blocking agent was 2-butanone oxime, based on isophorone diisocyanate); the epoxy resin and aqueous isocyanate emulsion were dissolved in ethyl acetate, heated to 70°C and kept stirring, and then the above-mentioned product was added, reacted for 5 hours, and a water-based epoxy resin was obtained by rotary evaporation.

[0070] 2. Preparation of the oil-in-water emulsion dispersion of Comparative Example 1: Disperse 16 parts by weight of the above-prepared water-based epoxy resin, 1 part by weight of the stabilizer sodium alginate, 8 parts by weight of triethylenetetramine, and 0.05 parts by weight of the catalyst dimethylaminophenol in 130 parts by weight of water to obtain aqueous solution C.

[0071] 2 parts by weight of phospholipid (lecithin) were dissolved in 28 parts by weight of the oil phase component, and then 3 parts by weight of surfactant Span 60 and 0.6 parts by weight of photoinitiator Irgacue 250 were added to obtain an oil phase.

[0072] At a stirring rate of 1700 r / min, the oil phase was added dropwise to the aqueous solution C to obtain the oil-in-water emulsion dispersion of Comparative Example 1.

[0073] Comparative Example 2: The steps of Comparative Example 2 are the same as those of Comparative Example 1, except that phospholipid is not added in Example 2.

[0074] Light stability test of Example 1 and Comparative Examples 1-2: At room temperature and pressure, Example 1 and Comparative Examples 1-2 were irradiated with 365nm ultraviolet light. After 1 hour of irradiation, the sample of Comparative Example 1 was partially cured; the sample of Comparative Example 2 was completely cured; the sample of Example 1 was stable; after 3 hours of irradiation, the sample of Comparative Example 1 was obviously cured; the sample of Example 1 was still stable.

[0075] When 1 part by weight of a saturated sodium chloride solution was added to the sample of Example 1, the sample of Example 1 immediately experienced demulsification and then showed obvious solidification within 2 minutes.

[0076] The reason Example 1's properties are significantly superior to Comparative Example 1 is that the photoinitiator is encapsulated in the oil phase, the curing agent is encapsulated in the inner aqueous phase, and the epoxy resin is encapsulated in the outer aqueous phase; these three components are separated in pairs, and a phospholipid bilayer exists at the water / oil interface, resulting in excellent light resistance. In Comparative Example 1, the curing agent and photoinitiator are encapsulated in the oil phase, while the epoxy resin is encapsulated in the outer aqueous phase. Although a phospholipid bilayer exists at the water / oil interface, there is still a possibility of curing through the phospholipid bilayer. Furthermore, the cross-linked products produced after curing can damage the phospholipid bilayer, resulting in significantly inferior light resistance to Example 1.

[0077] Those skilled in the art will readily appreciate other embodiments of the present disclosure after considering the specification and practicing the disclosure disclosed herein. This disclosure is intended to cover any variations, uses, or adaptations of the present disclosure that follow the general principles of the present disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A water-based one-component epoxy resin dispersion, characterized in that: The aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of an aqueous epoxy resin, 5-10 parts by weight of a water-soluble amine compound or a water-soluble acid anhydride compound, 25-35 parts by weight of an oil phase component, 0-1.5 parts by weight of an initiator, 0-10 parts by weight of a surfactant, and 95-145 parts by weight of water.

2. The aqueous one-component epoxy resin dispersion according to claim 1, characterized in that The aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-25 parts by weight of an aqueous epoxy resin, 5-10 parts by weight of a water-soluble amine compound or a water-soluble acid anhydride compound, 25-35 parts by weight of an oil phase component, 0.5-1.5 parts by weight of an initiator, 0-0.25 parts by weight of a catalyst, 3-8 parts by weight of a surfactant, 0-8 parts by weight of a stabilizer, 110-135 parts by weight of water, and 0-5 parts by weight of a cosolvent.

3. The aqueous one-component epoxy resin dispersion according to claim 1, characterized in that The aqueous one-component epoxy resin dispersion comprises the following components in parts by weight: 15-20 parts by weight of an aqueous epoxy resin, 8-10 parts by weight of a water-soluble amine compound, 25-30 parts by weight of an oil phase component, 0.5-0.8 parts by weight of an initiator, 0-0.15 parts by weight of a catalyst, 3-8 parts by weight of a surfactant, 0-5 parts by weight of a stabilizer, 120-135 parts by weight of water, 0-5 parts by weight of a cosolvent, 0-1 parts by weight of a leveling agent, and 0-1 parts by weight of a defoamer.

4. The aqueous one-component epoxy resin dispersion according to claim 1, characterized in that The water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, diethylaminopropylamine or isophoronediamine; the water-soluble acid anhydride compound is selected from maleic anhydride or phthalic anhydride.

5. The aqueous one-component epoxy resin dispersion according to any one of claims 1 to 4, characterized in that The waterborne epoxy resin is prepared by subjecting the epoxy resin to hydration modification, and the hydration modification step comprises the following: step 1-a: adding 1,4-butanediol diglycidyl ether and polyethylene glycol to a reaction container, heating to 70°C-80°C and maintaining a stirring state to completely melt the reactants; step 2-a: dissolving K2S2O8 in water to obtain a solution and dropwise adding the solution to the reaction container of step 1-a, reacting for 20-70 minutes, then heating to 150°C-180°C, and then measuring the epoxy value of the system once every 30 minutes using a hydrochloric acid-acetic acid method; obtaining the product of step 2-a at the end of the reaction; step 3-a: providing an epoxy resin and an aqueous isocyanate emulsion; dissolving the epoxy resin and the aqueous isocyanate emulsion in ethyl acetate, heating to 60°C-70°C and maintaining a stirring state, then adding the product of step 2-a, reacting for 3-5 hours, and obtaining the waterborne epoxy resin.

6. The aqueous one-component epoxy resin dispersion according to claim 1, characterized in that The water-based single-component epoxy resin dispersion is a water-in-oil-in-water type multiple emulsion dispersion; in the water-in-oil-in-water type multiple emulsion dispersion, the outer water phase component contains the oil phase component, and the oil phase component also contains the inner water phase component; and the outer water phase component contains water-based epoxy resin; the inner water phase component contains a water-soluble amine compound or a water-soluble acid anhydride compound.

7. The aqueous one-component epoxy resin dispersion according to any one of claims 2 or 3, characterized in that The aqueous one-component epoxy resin dispersion satisfies at least one of the following conditions: (1) the initiator is selected from a photoinitiator, a thermal initiator or a cationic initiator; (2) the oil phase component is selected from tributyrin, triolein, tripalmitin, tristearin, diolein, 1,3-dipalmitoyl-2-oleoyl glycerol, distearin, dilaurin, dimyristin or dilinolein; (3) the oil phase component further contains phospholipids; the phospholipids are selected from lecithin, soybean lecithin, cephalin, dioleoylphosphatidylcholine, hydrogenated soybean lecithin, distearoylphosphatidylcholine, (4) the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; (5) the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; (6) the stabilizer is selected from gelatin, carrageenan oligosaccharide or sodium alginate; (7) the cosolvent is selected from methanol, ethanol, n-propanol or isopropanol.

8. A method for preparing the aqueous one-component epoxy resin dispersion according to claim 6 or 7, characterized in that: The aqueous one-component epoxy resin dispersion is an oil-in-water type multiple emulsion dispersion; the method comprises the process of first preparing an oil-in-water type emulsion dispersion and then preparing an oil-in-water type multiple emulsion dispersion; the method comprises the following steps: when the initiator is selected from a water-soluble compound: step 1-b: dispersing a water-soluble amine compound or a water-soluble acid anhydride compound and the initiator into water to obtain a first aqueous solution; step 2-b: providing an oil phase component, adding a surfactant to the oil phase component; at a stirring rate of 1500-1800 r / min, dropwise adding the first aqueous solution to the oil phase component to obtain an oil-in-water type emulsion dispersion; step 3-b: preparing an aqueous epoxy resin by hydrating and modifying the epoxy resin; dispersing the aqueous epoxy resin into water to obtain a second aqueous solution; step 4-b: stirring the epoxy resin prepared in step 2-b at a stirring rate of 2500-3000 r / min. The oil-in-water emulsion dispersion is added dropwise to the second aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion; when the initiator is selected from oil-soluble compounds: step 1-c: dispersing a water-soluble amine compound or a water-soluble acid anhydride compound in water to obtain a third aqueous solution; step 2-c: providing an oil phase component, dispersing the initiator and the surfactant in the oil phase component; at a stirring rate of 1500-1800 r / min, the first aqueous solution is added dropwise to the oil phase component to obtain an oil-in-water emulsion dispersion; step 3-c: preparing a water-based epoxy resin by hydration modification of the epoxy resin; dispersing the water-based epoxy resin in water to obtain a fourth aqueous solution; step 4-c: at a stirring rate of 2500-3000 r / min, the oil-in-water emulsion dispersion prepared in the step 2-c is added dropwise to the fourth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

9. The method according to claim 8, characterized in that The method comprises the following steps: step 1-d: dispersing a water-soluble amine compound, a catalyst and a cosolvent in water to obtain a fifth aqueous solution; wherein the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine or diethylaminopropylamine; the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; step 2-d: providing an oil phase component, dispersing the surfactant and the initiator in the oil phase component; at a stirring rate of 1500-1800 r / min, adding the first aqueous solution dropwise to the oil phase component to obtain an oil-in-water emulsion dispersion; wherein the oil phase component is selected from tributyrin, triolein, tripalmitin, tristearin, diolein, 1,3-dipalmitoyl-2-oleoyl glycerol, distearin, dilaurin, dimyristin or dilinolein; the oil phase component further comprises phospholipids; the phospholipids are selected from egg Phospholipids, soybean lecithin, cephalin, dioleoylphosphatidylcholine, hydrogenated soybean lecithin, distearoylphosphatidylcholine, dipalmitoylphosphatidylcholine, dimyristoylphosphatidylcholine, dioleoylphosphatidylcholine, distearoylphosphatidylglycerol, dipalmitoylphosphatidylglycerol, dimyristoylphosphatidylglycerol, dioleoylphosphatidylglycerol or phosphatidylethanolamine; the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; the initiator is selected from oil-soluble compounds; step 3-d: preparing a water-based epoxy resin by hydrating and modifying the epoxy resin; dispersing the water-based epoxy resin in water, and adding a stabilizer and a defoaming agent to obtain a sixth aqueous solution; step 4-d: at a stirring rate of 2500-3000 r / min, adding the oil-in-water emulsion dispersion prepared in the step 2-d dropwise to the sixth aqueous solution to obtain the water-in-oil-in-water multiple emulsion dispersion.

10. The method according to claim 8, characterized in that The method comprises the following steps: step 1-e: dispersing a water-soluble amine compound, a catalyst, an initiator and a cosolvent in water to obtain a seventh aqueous solution; wherein the water-soluble amine compound is selected from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine or diethylaminopropylamine; the catalyst is selected from dimethylaminophenol or 2-ethyl-4-methylimidazole; the initiator is selected from a water-soluble compound; step 2-e: providing an oil phase component, dispersing the surfactant in the oil phase component; at a stirring rate of 1500-1800 r / min, dropping the first aqueous solution into the oil phase component to obtain an oil-in-water emulsion dispersion; wherein the oil phase component is selected from tributyrin, triolein, tripalmitin, tristearin, Glycerol ester, dioleyl glycerol, 1,3-dipalmitoyl-2-oleoyl glycerol, distearic glycerol, dilauric glycerol, dimyristin or dilinoleic glycerol; the surfactant is selected from Span 20, Span 40, Span 60, Span 80, Tween 20, Tween 40, Tween 60 or Tween 80; step 3-e: preparing a water-based epoxy resin by hydration modification of the epoxy resin; dispersing the water-based epoxy resin in water, and adding a stabilizer and a defoaming agent to obtain an eighth aqueous solution; step 4-e: adding the oil-in-water emulsion dispersion prepared in step 2-e dropwise to the eighth aqueous solution at a stirring rate of 2500-3000 r / min to obtain the water-in-oil-in-water multiple emulsion dispersion.

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