A preparation method of epoxy resin top coating curing agent

Abstract

The present invention relates to a method for preparing an epoxy resin topcoat curing agent, wherein 1,3-cyclohexanedimethylamine and diethylenetriamine can react with the epoxy groups at both ends of polyethylene glycol glycidyl ether in step S1 according to their respective production ratios to complete the first step of addition, the product in step S1 reacts with the epoxy resin in S2 to complete the second step of addition, and in step S3, diethylenetriamine and succinic anhydride react to produce products of amide and imide groups and complete the third step of addition with the product in step S2, and finally decompression distillation removes most of the solvent to obtain a topcoat curing agent. The present invention aims to provide a method for preparing an epoxy resin topcoat curing agent, the obtained product can quickly cure epoxy resin grinding stone material, and the obtained product has high strength, corrosion resistance, and high surface finish.

Description

Technical Field

[0001] The invention relates to the technical field of polymer composite materials, and in particular to a method for preparing an epoxy resin surface coating curing agent. Background Art

[0002] Epoxy resin terrazzo, also known as epoxy terrazzo flooring, is a new type of flooring that imitates the construction of terrazzo flooring. Epoxy terrazzo flooring is mostly used for the decoration of floors in high-end places. At present, the epoxy resin terrazzo curing agent uses a combination of polyetheramine as the main material and isophorone diamine as the auxiliary material as the main amine raw material to achieve epoxy resin terrazzo with yellowing resistance, high gloss and strong hardness after curing. However, the curing agent with polyetheramine as the main body has a slow curing speed. Therefore, on this basis, nonylphenol is often added to adjust the curing speed of the polyetheramine system. Nonylphenol is difficult to degrade, and the United Nations Environment Program has included it in the list of "Persistent Toxic Chemical Pollutants (PTS)". It was found that my country did not directly authorize the use of nonylphenol, but stipulated the limit requirements for nonylphenol. Therefore, the use of a curing agent that does not use polyetheramine as the main material can reduce or even avoid the practical use of nonylphenol, and it has a fast curing speed, high product strength and corrosion resistance, and high surface finish.

[0003] Based on the above situation, the market is in urgent need of a preparation method for an epoxy resin topcoat curing agent that can accelerate its curing speed, provide a product with high strength, corrosion resistance and high surface finish. Summary of the invention

[0004] The invention aims to provide a method for preparing an epoxy resin topcoat curing agent, which can accelerate its curing speed, and the product has high strength, corrosion resistance and high surface finish.

[0005] The above technical purpose of the present invention is achieved by the following technical scheme: a method for preparing an epoxy resin topcoat curing agent, the raw material components comprising 1,3-cyclohexanedimethylamine, diethylenetriamine, polyethylene glycol glycidyl ether, epoxy resin solution, succinic anhydride and a capping agent;

[0006] The preparation method of the top coating curing agent comprises:

[0007] Step S1, after heating 1,3-cyclohexanedimethylamine and diethylenetriamine, adding polyethylene glycol glycidyl ether solution dropwise at a uniform speed at a temperature of 55-65° C., and reacting for a period of time after the addition is completed;

[0008] Step S2, heating the material of step S1 to 60-70° C., adding epoxy resin solution dropwise at a uniform speed, and reacting for a period of time after the addition is completed;

[0009] Step S3, heating the mixture of diethylenetriamine and succinic anhydride to a temperature of 120-130° C. to react for a period of time;

[0010] Step S4, mixing the material after the reaction in step S2 with the material in step S3, controlling the temperature at 75-85° C., adding the end-capping agent solution dropwise at a uniform speed, and reacting for a period of time after the addition is completed;

[0011] Step S5, distilling the material obtained in step S4 under reduced pressure to remove most of the solvent to obtain a top coating curing agent.

[0012] As a further configuration of the present invention, in step S1, the molar ratio of 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether is 1-1.2:1:1.7-2.

[0013] As a further configuration of the present invention, the epoxy resin solution in step S2 is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the molar number of bisphenol A epoxy resin E51 to the molar number of polyethylene glycol glycidyl ether in step S1 is 0.4-0.5:1.

[0014] As a further configuration of the present invention, the molar ratio of diethylenetriamine to succinic anhydride in step S3 is 1.5-1.8:1.

[0015] As a further configuration of the present invention, the molar ratio of diethylenetriamine in step S1 to diethylenetriamine in step S3 is 4-6:1.

[0016] As a further configuration of the present invention, in step S1, polyethylene glycol glycidyl ether is added dropwise at a uniform speed within 1.5 hours, and the reaction is carried out for 2.5 to 3 hours after the addition is completed.

[0017] As a further configuration of the present invention, in step S2, the epoxy resin solution is added dropwise at a uniform speed within 2.0 hours, and the reaction is carried out for 2.5 to 3 hours after the addition is completed.

[0018] As a further configuration of the present invention, the reaction time in step S3 is 3 to 5 hours.

[0019] As a further configuration of the present invention, the end-capping agent in step S4 is any one of phenyl glycidyl ether and benzyl glycidyl ether, and the total molar ratio of the end-capping agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.45-0.5:1.

[0020] As a further configuration of the present invention, in step S4, the end-capping agent solution is added dropwise at a uniform speed within 1 hour, and the reaction is carried out for 2 to 2.5 hours after the addition is completed.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. A method for preparing an epoxy resin top coating curing agent provided by the present invention. 1,3-cyclohexanedimethylamine is an alicyclic amine, and diethylenetriamine is an aliphatic amine. According to their respective production ratios, they can react with the epoxy groups at both ends of polyethylene glycol glycidyl ether in step S1 to complete the first step of addition. The product in step S1 reacts with the epoxy resin in S2 to complete the second step of addition. In step S3, diethylenetriamine reacts with succinic anhydride to produce products of amide and imide groups and complete the third step of addition with the product in step S2. Finally, the product obtained by removing most of the solvent by reduced pressure distillation can quickly cure the epoxy resin grindstone material. The obtained product has high strength, corrosion resistance and high surface finish.

[0023] 2. The present invention provides a method for preparing an epoxy resin top coating curing agent. When 1,3-cyclohexanedicarboxylic acid and diethylenetriamine are added to the epoxy resin through polyethylene glycol glycidyl ether, the curing agent can simultaneously play an emulsifying and curing role, and the chain length is increased, which not only improves the cross-linking density of the epoxy cured product, but also allows the benzene ring, hydroxyl, secondary amine and other groups on the main chain to react with the amide, imide, carboxyl and other groups generated in the reaction in step S3, which can further improve the cross-linking density and mechanical strength of the epoxy cured product, and improve the overall strength and smoothness of the product.

[0024] 3. The present invention provides a method for preparing an epoxy resin top coating curing agent, wherein the end-capping agent used is any one of phenyl glycidyl ether and benzyl glycidyl ether, which can reduce the particle size of the generated curing agent emulsion, promote the contact between the curing agent and the epoxy resin grinding stone material, and increase the curing speed, making the curing speed fast.

[0025] 4. The present invention provides a method for preparing an epoxy resin top coating curing agent. The amide, imide, carboxyl and other products contained in the reaction product of step S3 can accelerate the reaction rate of the capping agent and the product of step S2, and can form a stable functional group structure with the functional group of the epoxy resin, thereby improving its crosslinking density and mechanical strength. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1

[0028] A preparation method of epoxy resin top coating curing agent:

[0029] Step S1, after heating 1,3-cyclohexanedimethylamine and diethylenetriamine, polyethylene glycol glycidyl ether is uniformly added dropwise at a temperature of 55° C. within 1.5 hours, and after the addition is completed, the mixture is reacted for 2.5 hours, and the molar ratio of 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether is 1:1:1.7;

[0030] Step S2, heating the material of step S1 to 60°C, uniformly adding epoxy resin solution dropwise within 2.0 hours, and reacting for 2.5 hours after the addition is completed, wherein the epoxy resin solution is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the molar number of bisphenol A epoxy resin E51 to the molar number of polyethylene glycol glycidyl ether in step S1 is 0.4:1;

[0031] Step S3, heating the mixture of diethylenetriamine and succinic anhydride to 120° C. and reacting for 3 hours, wherein the molar ratio of diethylenetriamine to succinic anhydride is 1.5:1, and the molar ratio of diethylenetriamine in this step to the diethylenetriamine in step S1 is 1:4;

[0032] Step S4, mixing the material after the reaction in step S2 with the material in step S3, controlling the temperature at 75°C, uniformly adding phenyl glycidyl ether solution within 1 hour, reacting for 1.5 hours after the addition, and the total molar ratio of the end-capping agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.45:1;

[0033] Step S5, distilling the material obtained in step S4 under reduced pressure to remove most of the solvent to obtain a top coating curing agent.

[0034] Example 2

[0035] A preparation method of epoxy resin top coating curing agent:

[0036] Step S1, after mixing 1,3-cyclohexanedimethylamine and diethylenetriamine and heating them, polyethylene glycol glycidyl ether was uniformly added dropwise at a temperature of 65° C. within 1.5 hours, and after the addition was completed, the mixture was reacted for 3 hours, and the molar ratio of 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether was 1.2:1:2;

[0037] Step S2, heating the material of step S1 to 70°C, uniformly adding epoxy resin solution dropwise within 2.0 hours, and reacting for 3 hours after the addition is completed, wherein the epoxy resin solution is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the molar number of bisphenol A epoxy resin E51 to the molar number of polyethylene glycol glycidyl ether in step S1 is 0.5:1;

[0038] Step S3, heating the mixture of diethylenetriamine and succinic anhydride to 130° C. and reacting for 5 hours, wherein the molar ratio of diethylenetriamine to succinic anhydride is 1.8:1, and the molar ratio of diethylenetriamine in this step to the diethylenetriamine in step S1 is 1:6;

[0039] Step S4, mixing the material after the reaction in step S2 with the material in step S3, controlling the temperature at 85°C, uniformly adding benzyl glycidyl ether solution within 1 hour, reacting for 2 hours after the addition, and the total molar ratio of the end-capping agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.5:1;

[0040] Step S5, distilling the material obtained in step S4 under reduced pressure to remove most of the solvent to obtain a top coating curing agent.

[0041] Example 3

[0042] A preparation method of epoxy resin top coating curing agent:

[0043] Step S1, after mixing 1,3-cyclohexanedimethylamine and diethylenetriamine and heating them, polyethylene glycol glycidyl ether was uniformly added dropwise at a temperature of 60° C. within 1.5 hours, and reacted for 3 hours after the addition was completed, and the molar ratio of 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether was 1.1:1:1.9;

[0044] Step S2, heating the material of step S1 to 65°C, uniformly adding epoxy resin solution dropwise within 2.0 hours, and reacting for 2.75 hours after the addition is completed, wherein the epoxy resin solution is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the mole number of bisphenol A epoxy resin E51 to the mole number of polyethylene glycol glycidyl ether in step S1 is 0.45:1;

[0045] Step S3, heating the mixture of diethylenetriamine and succinic anhydride to 125°C for 4 hours, wherein the molar ratio of diethylenetriamine to succinic anhydride is 1.7:1, and the molar ratio of diethylenetriamine in this step to the diethylenetriamine in step S1 is 1:5;

[0046] Step S4, mixing the material after the reaction in step S2 with the material in step S3, controlling the temperature at 80° C. and uniformly adding benzyl glycidyl ether solution dropwise within 1 hour, reacting for 1.75 hours after the addition is completed, and the total molar ratio of the end-capping agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.475:1;

[0047] Step S5, distilling the material obtained in step S4 under reduced pressure to remove most of the solvent to obtain a top coating curing agent.

[0048] Example 4

[0049] A preparation method of epoxy resin top coating curing agent:

[0050] Step S1, after mixing 1,3-cyclohexanedimethylamine and diethylenetriamine and heating them, polyethylene glycol glycidyl ether was uniformly added dropwise at a temperature of 60° C. within 1.5 hours, and reacted for 3 hours after the addition was completed, and the molar ratio of 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether was 1.1:1:1.9;

[0051] Step S2, heating the material of step S1 to 65°C, uniformly adding epoxy resin solution dropwise within 2.0 hours, and reacting for 2.75 hours after the addition is completed, wherein the epoxy resin solution is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the mole number of bisphenol A epoxy resin E51 to the mole number of polyethylene glycol glycidyl ether in step S1 is 0.45:1;

[0052] Step S4, controlling the temperature of the material after the reaction in step S2 to 80°C, uniformly adding benzyl glycidyl ether solution dropwise within 1 hour, reacting for 1.75 hours after the addition is completed, and the total molar ratio of the end-capping agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.475:1;

[0053] Example 5

[0054] A preparation method of epoxy resin top coating curing agent:

[0055] Step S1, after mixing 1,3-cyclohexanedimethylamine and diethylenetriamine and heating them, polyethylene glycol glycidyl ether was uniformly added dropwise at a temperature of 60° C. within 1.5 hours, and reacted for 3 hours after the addition was completed, and the molar ratio of 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether was 1.1:1:1.9;

[0056] Step S2, heating the material of step S1 to 65°C, uniformly adding epoxy resin solution dropwise within 2.0 hours, and reacting for 2.75 hours after the addition is completed, wherein the epoxy resin solution is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the mole number of bisphenol A epoxy resin E51 to the mole number of polyethylene glycol glycidyl ether in step S1 is 0.45:1;

[0057] Step S4, controlling the temperature of the material after the reaction in step S2 to 80°C, uniformly adding benzyl glycidyl ether solution dropwise within 1 hour, reacting for 3 hours after the addition is completed, and the total molar ratio of the end-capping agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.475:1;

[0058] Take the curing agent in Examples 1 to 5, dilute it with distilled water to obtain a diluted curing agent with a solid content of 70%. At the same time, purchase a curing agent (comparative example) on the market that is mainly composed of polyetheramine and a main amine raw material of nonylphenol. The performance of the above curing agents is compared and the performance of the above curing agents is tested. The results are shown in Tables 1 and 2, respectively. The primary amine content of the material after the reaction in step S4 of Examples 3 to 5 is determined, and the primary amine content ratio in Examples 3 to 5 is calculated. The results are shown in Table 3.

[0059] Table 1 Physical and chemical index test results of examples and comparative examples

[0060] project Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example Particle size (nm) 18.3 17.4 17.0 192 75.6 85.9 Viscosity (mpa·s) 3197 3099 3125 10265 5534 6438

[0061] Table 2 Comparison results of the embodiments and comparative examples

[0062]

[0063]

[0064] Table 3 Primary amine content ratio of Examples 3 to 5

[0065] project Proportion n(primary amine content in Example 3):(primary amine content in Example 4):(primary amine content in Example 5) 1：15.5：2.4

Claims

1. A method for preparing an epoxy resin topcoat curing agent, Features: The raw material components include 1,3-cyclohexanedimethylamine, diethylenetriamine, polyethylene glycol glycidyl ether, epoxy resin solution, succinic anhydride and a capping agent; The preparation method of the top coating curing agent comprises: Step S1, after mixing 1,3-cyclohexanedimethylamine and diethylenetriamine and heating them, at a temperature of 55-65° C., uniformly dropping a polyethylene glycol glycidyl ether solution, reacting for a period of time after the dropping is completed, wherein the molar ratio of the 1,3-cyclohexanedimethylamine, diethylenetriamine, and polyethylene glycol glycidyl ether is 1-1.2:1:1.7-2; Step S2, heating the material of step S1 to 60-70° C., uniformly dropping an epoxy resin solution, and reacting for a period of time after the dropping is completed, wherein the epoxy resin solution is a propylene glycol solution containing 50% by mass of bisphenol A epoxy resin E51, wherein the ratio of the molar number of bisphenol A epoxy resin E51 to the molar number of polyethylene glycol glycidyl ether in step S1 is 0.4-0.5:1; Step S3, heating the mixture of diethylenetriamine and succinic anhydride to 120-130° C. and reacting for a period of time, wherein the molar ratio of diethylenetriamine to succinic anhydride in step S3 is 1.5-1.8:1, and the molar ratio of diethylenetriamine in step S1 to diethylenetriamine in step S3 is 4-6:1; Step S4, mixing the material after the reaction in step S2 with the material in step S3, controlling the temperature at 75-85° C., uniformly dropping a blocking agent solution, and reacting for a period of time after the addition is completed, wherein the blocking agent is any one of phenyl glycidyl ether and benzyl glycidyl ether, and the total molar ratio of the blocking agent to 1,3-cyclohexanedimethylamine and diethylenetriamine in step S1 is 0.45-0.5:1; Step S5, distilling the material obtained in step S4 under reduced pressure to remove most of the solvent to obtain a top coating curing agent.

2. A method for preparing an epoxy resin topcoat curing agent according to claim 1, Features: In the step S1, polyethylene glycol glycidyl ether is added dropwise at a uniform speed within 1.5 hours, and the reaction is continued for 2.5 to 3 hours after the addition is completed.

3. A method for preparing an epoxy resin top coating curing agent according to claim 1, Features: In the step S2, the epoxy resin solution is added dropwise at a uniform speed within 2.0 hours, and the reaction is continued for 2.5 to 3 hours after the addition is completed.

4. A method for preparing an epoxy resin top coating curing agent according to claim 1, Features: The reaction time in step S3 is 3 to 5 hours.

5. A method for preparing an epoxy resin top coating curing agent according to claim 1, Features: In the step S4, the end-capping agent solution is added dropwise at a uniform speed within 1 hour, and the reaction is continued for 1.5 to 2 hours after the addition is completed.

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