A curing agent, method and application of a water-erasable two-component epoxy resin seam-beautifying agent

Abstract

The present invention discloses a curing agent, method and application of a water-erasable two-component epoxy resin seam-beautifying agent, wherein the curing agent is prepared by reacting the following components in parts by weight: a) amine compounds and derivatives thereof, b) epoxy-containing polyethers, c) epoxy compounds / epoxy resins, and d) diluents, wherein the molar ratio of components a), b), and c) is 1:(0.2-0.7):(0.2-0.7), and the addition amount of component d) is 10-50% of the total weight of components a), b), c), and d). The curing agent in the present invention has good hydrophobic properties and the ability to emulsify resins, can avoid dissolution and whitening caused by contact with water during construction, and can well erase residual materials, facilitate construction operations, and improve construction efficiency.

Description

Technical Field

[0001] The invention relates to a curing agent, in particular to a curing agent, a method and an application of a water-erasable two-component epoxy resin seam-beautifying agent. Background Art

[0002] Sealing agent is mainly used in the joints of wall and floor tiles in the living room, kitchen, bathroom, etc. Traditional seaming agent is made of oily epoxy resin and oily curing agent as bonding materials. There are generally two construction methods: 1. Before construction, you need to stick masking tape on both sides of the tile, and then tear off the masking tape after the seaming agent is hard and dry; 2. Before the seaming agent is hard and dry, use a spatula to remove the excess residual glue; these two construction methods are more troublesome to operate.

[0003] In recent years, a water-erasable caulking agent has emerged. However, most of the current water-erasable caulking agents use an external emulsifier or modify the epoxy resin component in component A to make it have an emulsifying function. It is difficult to wipe clean and leaves a lot of residue. In addition, the prepared water-erasable caulking agent is hydrophilic, so it dissolves and turns white when it comes into contact with water during wiping. After drying, obvious water stains are left, and the construction performance is poor, which affects the appearance.

[0004] Patent CN107722897A discloses an epoxy seam beautifier. When the bisphenol A epoxy resin in component A and the water-soluble polyamine epoxy adduct curing agent in component B are mixed, the formed emulsified system has amphiphilicity (hydrophilic and lipophilic), which can significantly improve the water compatibility of the system and can conveniently achieve water-erasable function within a certain period of time after the glue is applied. However, the water-soluble polyamine epoxy adduct in component B will inevitably dissolve and turn white when it comes into contact with water during construction.

[0005] Patent CN113185939A discloses a water-based caulking agent and a preparation method thereof, wherein a polyether is reacted with an epoxy resin to prepare an emulsifier, and the emulsifier is added to components A and B, respectively, to obtain a self-emulsifying resin. However, the invention requires an additional synthetic emulsifier, and the process is relatively complicated. In addition, in the absence of a catalyst, a large amount of polyether components will remain unreacted, affecting the post-curing performance. Summary of the invention

[0006] In order to solve the above technical problems, the present invention first proposes a curing agent for a water-erasable two-component epoxy resin caulking agent. The curing agent is relatively hydrophobic and has the ability to emulsify and cure resins. It can cleanly remove residues when wiping, and because of its hydrophobic properties, it avoids dissolution and whitening when wiping, which facilitates construction operations and improves workers' construction efficiency.

[0007] Based on the second aspect of the present invention, the present invention also provides a method for preparing a curing agent for a water-erasable two-component epoxy resin seam-beautifying agent, by which the hydrophobic curing agent can be simply prepared.

[0008] Based on the third aspect of the present invention, the present invention also proposes a use of the above-mentioned curing agent in the preparation of a water-erasable two-component epoxy resin seam beautifying agent.

[0009] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0010] A curing agent for a water-erasable two-component epoxy resin seam-beautifying agent is prepared by reacting the following components in parts by weight:

[0011] a) Amine compounds and their derivatives

[0012] b) Polyether containing epoxy groups

[0013] c) Epoxy compounds / epoxy resins

[0014] d) Diluent

[0015] The molar ratio of components a), b) and c) is 1:(0.2-0.7):(0.2-0.7), and the added amount of component d) is 10-50% of the total weight of components a), b), c) and d).

[0016] On the one hand, the curing agent has the functions of emulsifying the resin and curing the resin at the same time, which not only simplifies the construction process, but also makes the prepared two-component epoxy resin seam beautifying agent water-erasable.

[0017] On the other hand, the curing agent is hydrophobic as a whole after adjusting the raw material selection and proportion, which can avoid dissolution, whitening and the like when in contact with water, thereby improving the water-erasability of the caulking agent.

[0018] As a preferred embodiment, component a) is selected from aliphatic amines, alicyclic amines, aromatic amines, preferably one or more of diethylenetriamine, triethylenetetramine, polyetheramine, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-cyclohexanedimethylamine, N-aminoethylpiperazine, N-aminopropylcyclohexylamine, and m-xylylenediamine.

[0019] As a preferred embodiment, component b) is selected from polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether with a weight average molecular weight of 100-10000, preferably polyethylene glycol diglycidyl ether with a weight average molecular weight of 200, 400, or 1000.

[0020] As a preferred embodiment, component c) is selected from one or more of epoxy resin E51, epoxy resin E44, epoxy resin E20, benzyl glycidyl ether, phenyl glycidyl ether, C12-C14 glycidyl ether, butyl glycidyl ether, 1,4-butanediol diglycidyl ether, and 1,2-ethylene glycol diglycidyl ether.

[0021] As a preferred embodiment, component d) is selected from one or more of water, benzyl alcohol and ethanol.

[0022] A method for preparing a curing agent for the water-erasable two-component epoxy resin seam-beautifying agent as described above comprises the following steps:

[0023] 1) Add component b) dropwise into the reactor containing component a), heat to 70-100°C and stir to react for 1-3h;

[0024] 2) adding component c) or a mixture thereof with component d) into the above reactor and stirring the reaction for 1-4 hours;

[0025] 3) After the reaction temperature is lowered, the remaining component d) is added to the reaction mixture and stirred evenly to obtain the curing agent. Preferably, after the reaction temperature is lowered to 30-50°C, the remaining component d) is added.

[0026] A curing agent for the water-erasable two-component epoxy resin seam-beautifying agent as described above or a curing agent for the water-erasable two-component epoxy resin seam-beautifying agent prepared by the method described above is used in the preparation of the water-erasable two-component epoxy resin seam-beautifying agent.

[0027] A water-erasable two-component epoxy resin seam beautifying agent is obtained by mixing component A and component B in equal amounts; wherein component A comprises the following raw materials in parts by weight:

[0028]

[0029] Component B includes the following raw materials in parts by weight:

[0030] Curing agent 10-35 parts

[0031] Quartz sand 50-80 parts

[0032] 5-20 parts of other fillers;

[0033] Wherein, the curing agent is the curing agent of the water-erasable two-component epoxy resin seam-beautifying agent described above or the curing agent of the water-erasable two-component epoxy resin seam-beautifying agent prepared by the method described above.

[0034] As a preferred embodiment, the epoxy resin is selected from one or more of epoxy resin E51, epoxy resin E54, epoxy resin E44, and modified epoxy resins with emulsification function.

[0035] As a preferred embodiment, the fumed silica is a hydrophilic / hydrophobic fumed silica with a particle size of 10-500 nanometers;

[0036] Preferably, the quartz sand is selected from quartz sand of different colors with a mesh size of 10-200;

[0037] Preferably, other fillers are selected from one or more of toner, calcium carbonate, barium sulfate, white cement and bentonite.

[0038] The technical solution of the present invention has the following advantages:

[0039] (1) The present invention creatively selects to carry out technical modification and innovation on the curing agent in the two-component seam beautifying agent, so that the curing agent component has good hydrophobicity and the ability to emulsify resin, which can avoid dissolution and whitening caused by contact with water during construction, and can well wipe away the residual materials, facilitate construction operation, and improve construction efficiency;

[0040] (2) The present invention can select different amine raw materials and epoxy-containing compounds with different structures to prepare seam-beautifying curing agents with different segment lengths, different systems, different mechanical strengths, and different properties, thereby meeting various application requirements.

[0041] (3) The two-component seam-beautifying agent curing agent of the present invention can be used alone or in combination with other epoxy resin curing agents, and has a wide range of applications. DETAILED DESCRIPTION

[0042] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0043] The names, abbreviations and sources of the main chemicals used in the examples of the present invention are shown in the following table. Unless otherwise specified, all reagents used were of chemical analytical grade.

[0044] Table 1. Main raw material information

[0045]

[0046]

[0047] The main testing methods involved in the embodiments of the present invention are as follows:

[0048] <1> Operation time: Test the gel time of the prepared two-component epoxy resin caulking agent at 25°C. The gel time is the operation time.

[0049] <2> Sample hardness test: Put 10g of the prepared two-component epoxy resin caulking agent into a disposable cup at 25°C, and use a hardness tester to test the hardness of the sample after curing for 1d and 2d;

[0050] <3> Emulsion particle size: After the synthesized curing agent and epoxy resin E51 are mixed in equal amounts, dilute with water to 40% solid content under stirring to form an emulsion. Then use a particle size analyzer to test the particle size of the emulsion; the smaller the particle size, the better the emulsification and the better the water erasability;

[0051] <4> Wipeability test: Place the prepared two-component epoxy resin caulking agent on the floor tiles and wipe it with a wet rag. If it can be completely wiped off after 2-3 wipes without any dissolution or whitening, it is considered to be a better grade and recorded as "excellent". If it can be completely wiped off after 4-6 wipes with no dissolution or whitening to a certain extent, it is considered to be a good grade and recorded as "good". If it cannot be wiped off after 6-10 wipes, it is considered to be a worse grade and recorded as "poor".

[0052] The following Examples 1-7 are used to prepare different curing agents for water-erasable two-component epoxy resin seam beautifying agents:

[0053] [Example 1]

[0054] Preparation of curing agent A:

[0055] Preparation of curing agent A:

[0056] 10.3 g (0.1 mol) of diethylenetriamine was added to a reaction container, heated to 70°C, and 12 g of polyethylene glycol diglycidyl ether 225 (0.02 mol) was added dropwise under stirring, and the mixture was reacted for 1 h. 7.6 g (0.02 mol) of epoxy resin E51 was continued to be added dropwise under stirring, and after reacting for 1 h, the mixture was cooled to 30°C, 5 g of deionized water was added, and the mixture was stirred evenly to obtain curing agent A.

[0057] [Example 2]

[0058] Preparation of curing agent B:

[0059] 5.1 g (0.05 mol) of diethylenetriamine and 10.5 g (0.05 mol) of 4,4'-diaminodicyclohexylmethane were added to a reaction container, heated to 90°C, and 16 g of polyethylene glycol diglycidyl ether 215 (0.04 mol) was added dropwise under stirring, and the reaction was continued for 2 hours; 15.2 g (0.04 mol) of epoxy resin E51 was continued to be added dropwise under stirring, and after reacting for 2 hours, the temperature was lowered to 50°C, 15 g of benzyl alcohol was added, and the curing agent B was obtained after stirring evenly.

[0060] [Example 3]

[0061] Preparation of curing agent C:

[0062] 11.5 g (0.05 mol) of polyetheramine D230 and 10.5 g (0.05 mol) of 4,4'-diaminodicyclohexylmethane were added to a reaction container, heated to 100°C, and 14 g of polyethylene glycol diglycidyl ether 205 (0.07 mol) was added dropwise under stirring, and the reaction was carried out for 3 hours; 15.2 g (0.04 mol) of epoxy resin E51 and 5 g (0.04 mol) of benzyl glycidyl ether were continued to be added dropwise under stirring, and after reacting for 3 hours, the temperature was lowered to 70°C, 28 g of benzyl alcohol was added, and the curing agent C was obtained after stirring evenly.

[0063] [Example 4]

[0064] Preparation of curing agent D:

[0065] 7.3 g (0.05 mol) of triethylenetetramine and 8.5 g (0.05 mol) of isophorone diamine were added to a reaction container, heated to 80°C, and 10.8 g of polypropylene glycol diglycidyl ether 207 (0.02 mol) was added dropwise under stirring, and the mixture was reacted for 1.5 h; 15.2 g (0.04 mol) of epoxy resin E51 and 4.5 g of phenyl glycidyl ether were continued to be added dropwise under stirring, and the mixture was reacted for 1.5 h, then the mixture was cooled to 50°C, 14 g of benzyl alcohol was added, and the mixture was stirred evenly to obtain curing agent D.

[0066] [Example 5]

[0067] Preparation of curing agent E:

[0068] 17 g (0.1 mol) of isophorone diamine was added to a reaction container, heated to 85°C, and 28 g of polyethylene glycol diglycidyl ether 215 (0.07 mol) was added dropwise under stirring, and the mixture was reacted for 2 h. 11.4 g (0.03 mol) of epoxy resin E51 was continued to be added dropwise under stirring, and the mixture was reacted for 1 h. The mixture was cooled to 40°C, 22 g of benzyl alcohol was added, and the mixture was stirred evenly to obtain a two-component seam beautifying agent curing agent E.

[0069] [Example 6]

[0070] Preparation of curing agent F:

[0071] 14.2 g (0.1 mol) of cyclohexanedimethylamine was added to a reaction container, heated to 95°C, and 12 g of polyethylene glycol diglycidyl ether 215 (0.03 mol) was added dropwise under stirring, and the mixture was reacted for 1.5 h. 15.2 g (0.04 mol) of epoxy resin E51 was continued to be added dropwise under stirring, and the mixture was reacted for 2 h. The mixture was cooled to 45°C, 9 g of benzyl alcohol was added, and the mixture was stirred evenly to obtain a two-component caulking agent curing agent F.

[0072] [Example 7]

[0073] Preparation of curing agent G:

[0074] 13.6 g (0.1 mol) of m-phenylenediamine was added to a reaction container, heated to 75°C, and 30 g of polyethylene glycol diglycidyl ether 225 (0.03 mol) was added dropwise under stirring, and the reaction was continued for 1.5 h; 20 g (0.02 mol) of a mixture of epoxy resin E20 and 10 g of benzyl alcohol was continued to be added dropwise under stirring, and the reaction was continued for 2.5 h, then the temperature was lowered to 55°C, 15 g of benzyl alcohol was added, and the mixture was stirred evenly to obtain a two-component seam beautifying agent curing agent G.

[0075] [Comparative Example 1]

[0076] The curing agent was prepared by a method substantially the same as that in Example 1, except that polyethylene glycol diglycidyl ether 225 was not added and the amount of epoxy resin E51 added was 15.2 g (0.04 mol).

[0077] [Comparative Example 2]

[0078] The curing agent was prepared by a method substantially the same as that in Example 1, except that the epoxy resin E51 was not added and the amount of polyethylene glycol diglycidyl ether 225 added was 24 g (0.04 mol).

[0079] [Comparative Example 3]

[0080] The curing agent was prepared by a method substantially the same as in Example 1, except that the amount of epoxy resin E51 added was modified to 38 g (0.1 mol).

[0081] [Comparative Example 4]

[0082] The curing agent was prepared by a method substantially the same as in Example 1, except that the amount of polyethylene glycol diglycidyl ether 225 added was modified to 48 g (0.08 mol).

[0083]

Application examples

[0084] According to the raw material ratio in Table 2, the curing agents prepared in each embodiment and comparative example were used to prepare two-component epoxy resin seam beautifiers, and the performance tests shown in Table 3 were performed. In addition, epoxy seam beautifiers were prepared according to the method in Example 1 of patent CN107722897A, recorded as control group 1; and epoxy seam beautifiers were prepared using a commercially available seam beautifier curing agent (Tuanfeng tg-1, Anhui Tuanfeng Environmental Technology Co., Ltd.), recorded as control group 2.

[0085] Table 2, two-component epoxy resin seam sealant formula

[0086]

[0087] Table 3. Performance test of epoxy resin seam sealant

[0088]

[0089]

[0090] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A curing agent for a water-erasable two-component epoxy resin seam-beautifying agent, characterized in that: Prepared by reacting the following components in parts by weight: a) Amine compounds and their derivatives b) Polyether containing epoxy groups c) Epoxy compounds / epoxy resins d) diluent; Component a) is selected from one or more of diethylenetriamine, triethylenetetramine, polyetheramine, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-cyclohexanedimethylamine, N-aminoethylpiperazine, N-aminopropylcyclohexylamine and m-xylylenediamine; Component b) is selected from polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether having a weight average molecular weight of 100-10000; Component c) is selected from one or more of epoxy resin E51, epoxy resin E44, epoxy resin E20, benzyl glycidyl ether, phenyl glycidyl ether, C12-C14 glycidyl ether, butyl glycidyl ether, 1,4-butanediol diglycidyl ether, and 1,2-ethylene glycol diglycidyl ether; The molar ratio of components a), b), and c) is: 1:(0.2-0.7):(0.2-0.7), and the added amount of component d) is 10-50% of the total weight of components a), b), c), and d); The preparation method of the curing agent comprises the following steps: 1) Add component b) dropwise into the reactor containing component a), heat to 70-100°C and stir to react for 1-3h; 2) adding component c) or a mixture thereof with component d) into the above reactor and stirring the reaction for 1-4 hours; 3) After the reaction temperature is lowered, the remaining component d) is added into the reaction mixture and stirred evenly to obtain the curing agent.

2. The curing agent of the water-erasable two-component epoxy resin seam-beautifying agent according to claim 1, characterized in that: Component b) is selected from polyethylene glycol diglycidyl ether with a weight average molecular weight of 200, 400, and 1000.

3. The curing agent of the water-erasable two-component epoxy resin seam-beautifying agent according to claim 1 or 2, characterized in that: Component d) is selected from one or more of water, benzyl alcohol and ethanol.

4. Use of a curing agent for a water-erasable two-component epoxy resin seam-beautifying agent as claimed in any one of claims 1 to 3 in the preparation of a water-erasable two-component epoxy resin seam-beautifying agent.

5. A water-erasable two-component epoxy resin seam beautifying agent, characterized in that: The mixture is obtained by mixing component A and component B in equal amounts; wherein component A comprises the following raw materials in parts by weight: Component B includes the following raw materials in parts by weight: Curing agent 10-35 parts Quartz sand 50-80 parts 5-20 parts of other fillers; Wherein, the curing agent is the curing agent of the water-erasable two-component epoxy resin seam beautifying agent described in any one of claims 1-4.

6. The water-erasable two-component epoxy resin seam-beautifying agent according to claim 5, characterized in that: The epoxy resin is selected from one or more of epoxy resin E51, epoxy resin E54, epoxy resin E44, and modified epoxy resins with emulsification function.

7. The water-erasable two-component epoxy resin seam-beautifying agent according to claim 5 or 6, characterized in that: The fumed silica is hydrophilic / hydrophobic fumed silica with a particle size of 10-500 nanometers.

8. The water-erasable two-component epoxy resin seam-beautifying agent according to claim 7, characterized in that: The quartz sand is selected from quartz sand of different colors with a mesh size of 10-200.

9. The water-erasable two-component epoxy resin seam-beautifying agent according to claim 7, characterized in that: Other fillers are selected from one or more of toner, calcium carbonate, barium sulfate, white cement and bentonite.

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