Corrosion-resistant epoxy resin modified polyurethane sealing waterproof material and preparation method thereof

Abstract

The invention relates to the technical field of polyurethane coatings, in particular to a corrosion-resistant epoxy resin modified polyurethane sealing waterproof material and a preparation method thereof. The invention discloses an epoxy resin composition, which comprises a component A, a component B and a component C, the component A comprises polyether polyol and toluene diisocynate, the component B comprises epoxy resin, a diluent and a catalyst, and the component C comprises a chain extender, a plasticizer and an amine curing agent; the weight ratio of the component A to the component B to the component C is 1: (0.3-1.5): (0.3-1.5). The waterproof material prepared by the invention can be used for bonding a wet interface, and has excellent corrosion resistance at the same time.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane coatings. Specifically, it relates to a corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material and its preparation method. Background Art

[0002] In the concrete projects of ocean engineering, sewage treatment plants, and chemical plants, the maintenance and protection of concrete structures are the key to ensuring the long-term stable operation of the structures. Since concrete structures are often in complex and variable environmental conditions, such as salt erosion in the ocean, alkaline corrosion in sewage treatment plants, and chemical substance erosion in chemical plants, therefore, how to effectively protect concrete from these factors has become a problem that must be faced in the engineering design and construction process. The existing protective materials on the market mainly include epoxy resins, polyurethanes, and silicone materials. Epoxy resins are widely used in many projects due to their good corrosion resistance and chemical resistance. However, the brittleness of epoxy resins makes traditional epoxy coatings difficult to adapt to such changes. Polyurethane, as an elastomeric material, although it has a certain elasticity, its corrosion resistance is relatively weak, and it cannot form a firm bond with a wet interface. In addition, ordinary polyurethane waterproof coatings often lack sufficient corrosion resistance, which limits their application in special environments such as ocean engineering.

[0003] Chinese Patent Application CN109355049A discloses a high-elastic epoxy sealant for wet base surfaces, which consists of component A and component B with a weight ratio of 1:1; component A is composed of raw materials in the following mass percentages: bisphenol A type E51 epoxy resin 40-50%, long-chain active diluent 8-15%, additives 2-5%, fumed silica 2-4%, filler 30-39%; component B is composed of raw materials in the following mass percentages: polyetheramine 10-15%, special modified curing agent 20-30%, polyurethane-based active toughening agent 15-20%, DMP-30 accelerator 1-3%, fumed silica 2-4%, filler 30-39%. The epoxy sealant prepared by this invention maintains the high adhesiveness of epoxy resin-based waterproof materials, can play a good bonding role on various wet and complex base surfaces, and does not require the use of a primer. However, this invention does not involve corrosion resistance, which limits the application range of the sealant. Summary of the Invention

[0004] In the first aspect of the present invention, a corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material is provided, and the components include: component A, component B, and component C. Component A includes polyether polyol and toluene diisocyanate, component B includes epoxy resin, diluent, and catalyst, and component C includes chain extender, plasticizer, and amine curing agent.

[0005] Optionally, the weight ratio of the component A, component B and component C is 1:(0.3-1.5):(0.3-1.5).

[0006] Optionally, the weight ratio of the component A, component B and component C is 1:(0.5-1):(0.5-1).

[0007] It is found in the research of this application that by limiting the weight ratio of the component A, component B and component C to 1:(0.3-1.5):(0.3-1.5), the toughness and strength of the material can be balanced. It may be that the configuration of the interpenetrating polymer network (IPN) of epoxy resin and polyurethane is affected by the compounding ratio of component B and component C. Excessive component B will occupy the crosslinking sites and hinder the movement of polyurethane segments, while excessive component C will dilute the effect of the chain extender and weaken the ductility of the molecular chain.

[0008] The weight ratio of the polyether polyol and toluene diisocyanate is (1-2):1.

[0009] Optionally, the weight ratio of the polyether polyol and toluene diisocyanate is (1-1.5):1.

[0010] By weight percentage, the component B includes 45-60% of epoxy resin, 2-7% of catalyst, and the balance is made up by diluent.

[0011] Optionally, by weight percentage, the component B includes 50-55% of epoxy resin, 3-5% of catalyst, and the balance is made up by diluent.

[0012] By weight percentage, the component C includes 5-20% of chain extender, 50-70% of plasticizer, and the balance is made up by amine curing agent.

[0013] Optionally, by weight percentage, the component C includes 10-20% of chain extender, 60-70% of plasticizer, and the balance is made up by amine curing agent.

[0014] The hydroxyl value of the polyether polyol is 40-80mgKOH / g, the number average molecular weight is 2000-4000, the functionality is 2-4, and the viscosity at 25°C is 300-1000mPa·s.

[0015] Optionally, the hydroxyl value of the polyether polyol is 50-70mgKOH / g, the number average molecular weight is 2500-3500, the functionality is 3, and the viscosity at 25°C is 400-600mPa·s.

[0016] Optionally, the polyether polyol is selected from at least one of the following grades: Bluestar Dongda EP-330N, BASF Pluracol GP 3000, Covestro Desmophen 3900, Dow Chemical VORANOL CP 3000, Huntsman Jeffol G30-650, Shell Caradol MD30-02, Wanhua Chemical WANNATE 3000.

[0017] The epoxy resin includes at least one of E-51, E-54, E-44, F-44 phenolic epoxy resin, and alicyclic epoxy resin.

[0018] Optionally, the epoxy resin includes at least one of E-51, E-54, and E-44.

[0019] Optionally, the diluent includes at least one of ethyl acetoacetate, propylene glycol methyl ether acetate, and ethyl acetate.

[0020] Optionally, the catalyst includes at least one of phosphoric acid, p-toluenesulfonic acid, and boron trifluoride complex.

[0021] Optionally, the chain extender includes at least one of 1,4-butanediol, ethylene glycol, and neopentyl glycol.

[0022] Optionally, the plasticizer includes at least one of chlorinated paraffin, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and dioctyl sebacate.

[0023] Optionally, the amine curing agent includes at least one of triethylenetetramine, diethylenetriamine, polyetheramine, and polyamide.

[0024] The second aspect of the present invention provides a preparation method of a corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material, including the following steps:

[0025] S1, subject the polyether polyol to vacuum dehydration first and then react it with toluene diisocyanate to obtain component A;

[0026] S2, subject the epoxy resin and the diluent to vacuum dehydration first and then mix them with the catalyst to obtain component B;

[0027] S3, mix the chain extender, the plasticizer, and the amine curing agent evenly to obtain component C;

[0028] S4, mix component A, component B, and component C.

[0029] Beneficial effects

[0030] 1. By limiting the weight ratio of component A, component B and component C to 1:(0.3-1.5):(0.3-1.5), the toughness and strength of the material can be balanced.

[0031] 2. By limiting the weight ratio of polyether polyol and toluene diisocyanate to (1-2):1, the acid resistance, alkali resistance and salt resistance of the material can be further improved.

[0032] 3. By limiting the raw material composition of component B to: 45-60% epoxy resin, 2-7% catalyst, and the balance made up by diluent, the tensile strength of the material can be made ≥5MPa and the elongation at break ≥900%.

[0033] 4. By limiting the raw material composition of component C: chain extender 5-20%, plasticizer 50-70%, and amine curing agent to make up the balance, the surface drying time and actual drying time during the construction process can be effectively controlled to improve construction efficiency.

[0034] 5. The waterproof material prepared by the present invention has excellent bonding strength with both dry concrete base surfaces and wet concrete base surfaces, and the bonding strength is ≥2MPa. DETAILED DESCRIPTION

[0035] Examples 1-3, Comparative Examples 1-3

[0036] A corrosion-resistant epoxy resin modified polyurethane sealing and waterproofing material is composed of component A, component B, and component C. The specific components are shown in Table 1, wherein the suppliers and brands of the raw materials in Table 1 are shown in Table 2, and the raw material formulas of component A, component B, and component C are all calculated according to their respective weight percentages. In Examples 1-3, the weight ratios of component A, component B, and component C are 1:1:1, 1:0.75:0.75, and 1:0.5:0.5, respectively; and in Comparative Examples 1-3, the weight ratios of component A, component B, and component C are 1:2:1, 1:0.25:1, and 1:0.5:2, respectively.

[0037] Table 1

[0038]

[0039] Table 2

[0040] Raw materials Supplier Grade Polyether polyol BlueStar Dongda EP-330N Toluene diisocyanate Wanhua Chemical TDI-80 Epoxy resin Nantong Xingchen Synthetic Materials Co., Ltd. E-44 Ethyl acetoacetate Jinan Yingshun Chemical Co., Ltd. 1-100 Phosphoric acid Shandong Yousuo Chemical Technology Co., Ltd. S11107200 1,4-Butanediol Jinan Xintongshun Chemical 619 Chlorinated paraffin BoHao Petroleum 52# Polyetheramine Huntsman D400

[0041] The EP-330N has a hydroxyl value of 56 mgKOH / g, a number average molecular weight of 3000, a functionality of 3, and a viscosity at 25° C. of 400-600 mPa·s.

[0042] A method for preparing a corrosion-resistant epoxy resin modified polyurethane sealing and waterproof material comprises the following steps:

[0043] Add the weighed polyether polyol to the reaction kettle, start the stirrer, heat up to 80 °C, start the vacuum pump, and slowly increase the vacuum degree to 0.095 MPa (gauge pressure negative pressure), then heat up to 120 °C and maintain for 2 h; cool down to 80 °C, add the weighed toluene diisocyanate, and stir and react under vacuum at 80 °C for 4 h, then cool down to room temperature (25 °C) to obtain Component A; add the weighed epoxy resin and ethyl acetoacetate to the reaction kettle, start the stirrer, heat up to 80 °C, start the vacuum pump, and slowly increase the vacuum degree to 0.095 MPa (gauge pressure negative pressure), then heat up to 120 °C and maintain for 2 h; cool down to 80 °C, add the weighed phosphoric acid, and stir under vacuum at 80 °C for 2 h, then cool down to room temperature (25 °C) to obtain Component B; stir the weighed 1,4-butanediol, chlorinated paraffin and polyetheramine evenly in a high-speed disperser to obtain Component C; mix Component A, Component B and Component C evenly.

[0044] Performance test methods and data

[0045] Conduct performance tests on the sealant waterproof materials prepared in the examples and comparative examples. The test methods and data are listed in Table 3.

[0046] Table 3

[0047]

[0048]

Claims

1. A corrosion-resistant epoxy resin modified polyurethane sealing waterproof material, characterized in that, The components include: Component A, Component B and Component C. Component A includes polyether polyol and toluene diisocyanate. Component B includes epoxy resin, diluent and catalyst. Component C includes chain extender, plasticizer and amine curing agent. The weight ratio of Component A, Component B and Component C is 1:(0.3 - 1.5):(0.3 - 1.5).

2. The corrosion-resistant epoxy resin modified polyurethane sealing waterproof material according to claim 1, wherein The weight ratio of Component A, Component B and Component C is 1:(0.5 - 1):(0.5 - 1).

3. The corrosion-resistant epoxy resin modified polyurethane sealing waterproof material according to claim 2, wherein, The hydroxyl value of the polyether polyol is 40 - 80mgKOH / g, the number average molecular weight is 2000 - 4000, the functionality is 2 - 4, and the viscosity at 25°C is 300 - 1000mPa·s.

4. The corrosion-resistant epoxy resin modified polyurethane sealing waterproof material according to claim 3, characterized in that The weight ratio of the polyether polyol and toluene diisocyanate is (1 - 2):

1.

5. The corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material according to claim 4, wherein The weight ratio of the polyether polyol and toluene diisocyanate is (1 - 1.5):

1.

6. The corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material according to claim 1, wherein By weight percentage, Component B includes 45 - 60% of epoxy resin, 2 - 7% of catalyst, and the diluent makes up the balance.

7. The corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material according to claim 6, characterized in that, By weight percentage, Component B includes 50 - 55% of epoxy resin, 3 - 5% of catalyst, and the diluent makes up the balance.

8. The corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material according to claim 1, characterized in that, By weight percentage, Component C includes 5 - 20% of chain extender, 50 - 70% of plasticizer, and the amine curing agent makes up the balance.

9. The corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material according to claim 8, characterized in that By weight percentage, Component C includes 10 - 20% of chain extender, 60 - 70% of plasticizer, and the amine curing agent makes up the balance.

10. A method for preparing the corrosion-resistant epoxy resin-modified polyurethane sealing waterproof material according to any one of claims 1-9, characterized in that, It includes the following steps: S1, subject the polyether polyol to vacuum dehydration first and then react it with toluene diisocyanate to obtain Component A; S2, subject the epoxy resin and diluent to vacuum dehydration first and then mix them with the catalyst to obtain Component B; S3, mix the chain extender, plasticizer and amine curing agent evenly to obtain Component C; S4, mix Component A, Component B and Component C.

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