High-performance silicone waterproofing agent and preparation method thereof

Abstract

The application discloses a kind of high-performance organic silicon waterproof agent and preparation method thereof, belong to organic silicon waterproof agent technical field.The high-performance organic silicon waterproof agent, according to weight fraction, including following raw materials: alkyl alkoxysilane 100 parts, anhydrous ethanol 40~60 parts, deionized water 20~40 parts, glacial acetic acid 0.1~0.5 parts, silane coupling agent 0~5 parts, epoxy silicone oil 0~10 parts, epoxy resin 0~5 parts and curing agent 0.1~0.5 parts;Wherein, the mass of silane coupling agent, epoxy silicone oil is not 0.It is as follows: alkyl alkoxysilane is added dropwise deionized water, acetic acid mixed solution, after reaction, neutralization is filtered to obtain silicon resin prepolymer, then silane coupling agent, epoxy silicone oil, epoxy resin and curing agent are added, and a kind of high-performance organic silicon waterproof agent is prepared after a period of time preparation.The preparation method of high-performance organic silicon waterproof agent provided by the application is simple, and the material prepared has good waterproofness and can be used in highway waterproof field.

Description

Technical Field

[0001] The present invention belongs to the technical field of organosilicon waterproofing agents, and in particular to a high-performance organosilicon waterproofing agent and a preparation method thereof. Background Art

[0002] In the construction of highway bridge projects, the waterproof construction of the pavement base is critical and has an important impact. The quality of its waterproofing has an important impact and direct correlation on the use function and life of the highway bridge.

[0003] Silicone waterproofing agent has the characteristics of good waterproofness, easy construction, non-toxicity, and no pollution to the environment. It can seal the internal pores of asphalt pavement to prevent water from seeping in, thereby solving the problem of water damage to the pavement.

[0004] Solvent-based silicone waterproofing agents contain silicone resin prepolymers as their active ingredient. As the solvent evaporates during curing, a hydrophobic molecular film forms on the road surface, blocking water penetration and improving its waterproofing properties. This film does not affect internal water drainage, making the road "breathable." However, silicone resin alone has low strength, making the waterproof layer easily damaged. Therefore, it needs to be reinforced with other components to extend its service life.

[0005] Chinese patent application number 202110484140.0 addresses the issues of low waterproofing efficiency, long curing time, and poor aging resistance of organosilicon waterproofing agents. It provides an organosilicon waterproofing agent made by combining a silane coupling agent with an MQ silicone resin. The compound is formed by the mutual dissolution of the silane coupling agent and the MQ silicone resin, with the MQ silicone resin comprising 10-90% by weight. The combination of MQ silicone resin and silane coupling agent exhibits a synergistic effect, while the addition of modified polypropylene strengthens the bond between the waterproofing agent and concrete, achieving a maximum bond strength of 4.9 MPa. However, this method still suffers from issues such as high solids content and high cost.

[0006] Chinese patent application number 202211641427.0 discloses a silicone waterproofing agent and a preparation method thereof. The silicone waterproofing agent is made of the following raw materials in parts by weight: 120-200 parts of diisocyanate; 50-100 parts of epoxy-terminated polyether; 90-120 parts of aminosiloxane; 90-120 parts of alkylsiloxane; 90-110 parts of alcohol solvent; and 400 parts of deionized water. The silicone waterproofing agent uses diisocyanate, epoxy-terminated polyether, aminosiloxane, alkylsiloxane, alcohol solvent and deionized water as raw materials to form urea segments and polyether segments. Through the complementary cooperation of the two, the toughness and strength of the waterproofing agent material are comprehensively improved, and the crack resistance of the waterproof layer is effectively improved. However, the process route of the method is long and the industrialization cost is high. Summary of the Invention

[0007] In order to solve the above problems, the application provides a high-performance organic silicon waterproof agent and a preparation method thereof, the high-performance organic silicon waterproof agent is low in cost, good in adhesion, high in strength, excellent in waterproof performance, and can be used in the field of highway waterproofing, and the preparation method is simple and easy to implement.

[0008] The high-performance organic silicon waterproof agent comprises the following raw materials in parts by weight: alkyl alkoxysilane 100 parts, anhydrous ethanol 40-60 parts, deionized water 20-40 parts, glacial acetic acid 0.1-0.5 parts, silane coupling agent 0-5 parts, epoxy silicone oil 0-10 parts, epoxy resin 0-5 parts, and curing agent 0.1-0.5 parts; wherein the mass of the silane coupling agent, the epoxy silicone oil, and the epoxy resin is not 0.

[0009] The application uses alkyl alkoxysilane as the main raw material, drops the mixed solution of deionized water and glacial acetic acid, obtains a silicon resin prepolymer after reaction and neutralization and filtration, and then adds the silane coupling agent, the epoxy silicone oil, the epoxy resin, and the curing agent to prepare the high-performance organic silicon waterproof agent after a period of reaction.

[0010] Preferably, the alkyl alkoxysilane comprises one or more of methyl triethoxysilane, dimethyl diethoxysilane, propyl triethoxysilane, n-octyl triethoxysilane, vinyl triethoxysilane, dodecyl triethoxysilane, phenyl triethoxysilane, or tetraethoxysilane.

[0011] Preferably, the silane coupling agent comprises one or more of γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, 2-(3,4-epoxycyclohexane) ethyl trimethoxysilane, or 2-(3,4-epoxycyclohexane) ethyl triethoxysilane.

[0012] Further preferably, the silane coupling agent is γ-glycidoxypropyl triethoxysilane.

[0013] Preferably, the epoxy silicone oil has a viscosity of 45-220 cSt and an epoxy value of 0.02-0.05 moL / 100 g.

[0014] Further preferably, the epoxy silicone oil has a viscosity of 100-140 cSt and an epoxy value of 0.030-0.032 moL / 100 g.

[0015] Preferably, the epoxy resin comprises one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, or aliphatic glycidyl ether epoxy resin.

[0016] Preferably, the curing agent is an acid anhydride curing agent.

[0017] More preferably, the acid anhydride curing agent is phthalic anhydride.

[0018] The method for preparing the high-performance organosilicon waterproofing agent comprises the following steps:

[0019] S1. Stir and mix anhydrous ethanol and alkyl alkoxy silane evenly;

[0020] S2, adding a mixture of deionized water and glacial acetic acid dropwise, heating and stirring after the addition is complete;

[0021] S3, after cooling to room temperature, adding alkaline substance to neutralize to pH 6.5-7.5, and filtering to obtain silicone resin prepolymer;

[0022] S4, adding silane coupling agent, epoxy silicone oil, epoxy resin and curing agent, and obtaining the high-performance organosilicon waterproofing agent after the reaction is completed.

[0023] The present invention first prepares a silicone resin prepolymer as the main component of the waterproofing agent. In the process, the strength of the waterproofing agent is enhanced mainly through the curing reaction of the epoxy resin, and the compatibility of the material is improved by using a silane coupling agent and epoxy silicone oil.

[0024] Preferably, in step S1, the stirring temperature is controlled at 30-50°C and the stirring time is 0.5-1 h.

[0025] To promote the reaction to generate the silicone resin prepolymer, preferably, in step S2, the heating temperature is 60-100° C., and the stirring time is 2-4 h.

[0026] Preferably, in step S3, the alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, anhydrous sodium carbonate or anhydrous potassium carbonate.

[0027] More preferably, the alkaline substance is anhydrous sodium carbonate.

[0028] Preferably, in step S4, the reaction temperature is 60-100° C. and the reaction time is 0.5-2 h.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. The present invention adds a small amount of epoxy resin and curing agent to the silicone resin prepolymer. The epoxy resin and curing agent are cured to form a cross-linked structure. The strength of the epoxy resin after curing is dozens of times that of the silicone resin. Therefore, by adding a small amount, the strength and bonding performance of the waterproofing agent material can be further improved.

[0031] 2. The present invention improves the compatibility of silicone resin prepolymer and epoxy resin by adding silane coupling agent and epoxy silicone oil, so that the performance of the two can complement each other and have good toughness and strength;

[0032] 3. The present invention adopts anhydride curing agent to provide a weakly acidic environment, which can increase the curing rate of the waterproofing agent and shorten the construction time without affecting the storage stability of the waterproofing agent. DETAILED DESCRIPTION

[0033] The technical scheme of the present invention is further described below through examples. The raw materials used in the examples can be purchased from the market or prepared by conventional methods.

[0034] Example 1

[0035] A high-performance organosilicon waterproofing agent comprises the following raw materials, measured in parts by weight: 70 parts of methyltriethoxysilane, 20 parts of dimethyldiethoxysilane, 10 parts of tetraethoxysilane, 40 parts of anhydrous ethanol, 20 parts of deionized water, 0.1 parts of glacial acetic acid, 5 parts of γ-glycidyloxypropyltriethoxysilane, 10 parts of epoxy silicone oil (viscosity of 100 cSt and epoxy value of 0.03 mol / 100 g), 5 parts of bisphenol A epoxy resin, and 0.5 parts of phthalic anhydride.

[0036] The preparation method of the high-performance organosilicon waterproofing agent comprises the following steps:

[0037] S1. Add 40 parts of anhydrous ethanol, 70 parts of methyltriethoxysilane, 20 parts of dimethyldiethoxysilane and 10 parts of tetraethoxysilane into a reaction kettle in sequence, raise the temperature to 40°C and keep the temperature constant for 10 minutes;

[0038] S2. Mix 20 parts of deionized water and 0.1 parts of glacial acetic acid, add dropwise over 30 minutes, heat to 70°C, and react for 4 hours;

[0039] S3. After the reaction is completed, the pH of the reaction system is adjusted to 7, and the reaction system is filtered to obtain a silicone resin prepolymer;

[0040] S4. Add 5 parts of γ-glycidyloxypropyltriethoxysilane, 10 parts of epoxy silicone oil (viscosity of 100 cSt, epoxy value of 0.03 mol / 100 g), 5 parts of bisphenol A epoxy resin and 0.5 parts of phthalic anhydride to the silicone resin prepolymer, raise the temperature to 80°C, and react for 2 hours to obtain the silicone waterproofing agent product.

[0041] Example 2

[0042] A high-performance organosilicon waterproofing agent is substantially the same as the high-performance organosilicon waterproofing agent described in Example 1, except that it does not contain γ-glycidyloxypropyltriethoxysilane.

[0043] Example 3

[0044] A high-performance organosilicon waterproofing agent is substantially the same as the high-performance organosilicon waterproofing agent described in Example 1, except that it does not contain epoxy silicone oil.

[0045] Example 4

[0046] A high-performance organosilicon waterproofing agent is substantially the same as the high-performance organosilicon waterproofing agent described in Example 1, except that it does not contain bisphenol A epoxy resin.

[0047] Example 5

[0048] A high-performance organosilicon waterproofing agent is substantially the same as the high-performance organosilicon waterproofing agent described in Example 1, except that it does not contain phthalic anhydride.

[0049] Detection and analysis

[0050] The components of the high performance organosilicon waterproofing agent in Examples 1 to 5 are shown in Table 1. Table 1 Components of the high performance organosilicon waterproofing agent in Examples 1 to 5

[0051]

[0052] The viscosity of the high-performance organosilicon waterproofing agents prepared in Examples 1 to 5 was measured using a rotational viscometer.

[0053] The solid content of the high-performance organosilicon waterproofing agent prepared in Examples 1 to 5 was tested with reference to GB / T 16777-2008 "Test Methods for Building Waterproof Coatings". The specific steps are as follows: After stirring the sample, (6±1) g of the sample was poured into a dried and weighed Petri dish (m0) and the bottom was flattened. The sample was immediately weighed (m1). The sample was placed at room temperature for 24 h to complete the reaction. The sample was then placed in an oven heated to (120±2)°C and kept at this temperature for 3 h. The sample was taken out and cooled in a desiccator for 2 h, and then weighed (m2). The solid content X was calculated according to formula (I):

[0054] X = (m2-m0) / (m1-m0) × 100% formula (I);

[0055] Where m0 represents the weight of the dry culture dish, m1 represents the total weight of the culture dish and the sample after the sample is placed, and m2 represents the total weight of the culture dish and the sample after the reaction is completed.

[0056] The water permeability coefficient of the high-performance organosilicon waterproofing agent prepared in Examples 1 to 5 was tested with reference to JTG E20-2011 "Test Procedures for Asphalt and Asphalt Mixtures in Highway Engineering". The specific steps are as follows: assemble and install a pavement water permeability meter, turn off the switch, fill the measuring cylinder with water, turn on the switch to vent, and then refill with water; turn on the switch, start timing when the liquid level drops to 100 mL, record the instrument tube scale every 60 seconds until the water level drops to 500 mL, and the pavement water permeability coefficient C is 0. w Calculate according to formula (II):

[0057] C w = (V2-V1) / (t2-t1) × 100% formula (II);

[0058] Where V1 and V2 represent the first and second instrument tube scales respectively, and t1 and t2 represent the first and second recording times respectively.

[0059] The water absorption ratio test of the high-performance organosilicon waterproofing agents prepared in Examples 1 to 5 was performed with reference to JC / T 902-2002 "Organic silicon waterproofing agents for building surfaces". The specific steps are as follows:

[0060] A waterproofing agent was added to a container with a mesh shelf, with the liquid level approximately 7 mm above the shelf. A mortar block that had been dried at 105°C for 4 hours and then stored at room temperature for 24 hours was placed on the shelf and immersed in the waterproofing agent for 20 seconds. The block was removed and shaken dry, then stored at room temperature for 3 days, with the immersed surface (experimental surface) facing upward. Distilled water was added to a container with a mesh shelf, with the liquid level approximately 3 mm above the shelf. A mortar block treated with the waterproofing agent (weight W0) was placed on the shelf with the experimental surface facing downward. After immersion for 24 hours, the block was removed, the surface moisture was blotted with a paper napkin, and the weight was immediately weighed (W1). Simultaneously, an untreated mortar block was immersed in water, with the weight before immersion recorded as M0 and the weight after immersion in distilled water for 24 hours recorded as M1. The water absorption ratio B was calculated according to formulas (III) to (V):

[0061] A1=(W1- W0) / W0×100% Formula (III);

[0062] A0=(M1- M0) / M0×100% Formula (IV);

[0063] B=A1 / A0×100% (Formula V);

[0064] Where A0 and A1 represent the water absorption before and after treatment, respectively, and B represents the water absorption ratio.

[0065] The high-performance silicone waterproofing agents prepared in Examples 1 to 5 were tested for tensile strength, elongation at break, and tear strength in accordance with GB / T 16777-2008 “Test methods for building waterproof coatings.” Each test was performed three times, and the average of the three results was taken.

[0066] Table 2 shows the performance test data of the high-performance organosilicon waterproofing agents prepared in Examples 1 to 5.

[0067] Table 2 Summary of sample performance test results

[0068]

[0069] As shown in Table 2, the prepared silicone waterproofing agent has both good waterproofing and mechanical properties. The addition of epoxy resin and its curing agent improves the mechanical properties of the silicone resin, while the silane coupling agent and epoxy silicone oil improve the compatibility between the silicone resin and the epoxy resin.

[0070] It should be understood that the above embodiments are only intended to illustrate the present invention and are not intended to limit the scope of protection of the present invention. In addition, it should be understood that after reading the contents of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

Claims

1. A high-performance silicone waterproofing agent, characterized in that: The raw materials are as follows: 100 parts by weight of alkyl alkoxysilane, 40-60 parts by weight of anhydrous ethanol, 20-40 parts by weight of deionized water, 0.1-0.5 parts by weight of glacial acetic acid, 0-5 parts by weight of silane coupling agent, 0-10 parts by weight of epoxy silicone oil, 0-5 parts by weight of epoxy resin and 0.1-0.5 parts by weight of curing agent; wherein the weight of silane coupling agent, epoxy silicone oil and epoxy resin is not 0; the alkyl alkoxysilane includes methyltriethoxysilane, dimethyldiethoxysilane and propyltriethoxysilane. The invention relates to a novel epoxy silicone oil comprising one or more of alkyl, n-octyltriethoxysilane, vinyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane or tetraethoxysilane; the silane coupling agent comprises one or more of γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane or 2-(3,4-epoxycyclohexane)ethyltriethoxysilane; the viscosity of the epoxy silicone oil is 45-220 cSt, and the epoxy value is 0.02-0.05 mol / 100 g; the epoxy resin comprises one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin or aliphatic glycidyl ether epoxy resin; and the curing agent is an acid anhydride curing agent.

2. The high-performance organosilicon waterproofing agent according to claim 1, characterized in that: The silane coupling agent is gamma-glycidyloxypropyltriethoxysilane.

3. The high-performance organosilicon waterproofing agent according to claim 1, characterized in that: The acid anhydride curing agent is phthalic anhydride.

4. The high-performance organosilicon waterproofing agent according to claim 1, characterized in that The viscosity of the epoxy silicone oil is 100-140 cSt, and the epoxy value is 0.030-0.032 mol / 100 g.

5. The high-performance organosilicon waterproofing agent according to claim 1, characterized in that: The acid anhydride curing agent is phthalic anhydride.

6. A method for preparing the high-performance organosilicon waterproofing agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Stir and mix anhydrous ethanol and alkyl alkoxy silane evenly; S2, adding a mixture of deionized water and glacial acetic acid dropwise, heating and stirring after the addition is complete; S3, after cooling to room temperature, adding alkaline substance to neutralize to pH 6.5-7.5, and filtering to obtain silicone resin prepolymer; S4, adding silane coupling agent, epoxy silicone oil, epoxy resin and curing agent, and obtaining the high-performance organosilicon waterproofing agent after the reaction is completed.

7. The method for preparing a high-performance organosilicon waterproofing agent according to claim 6, wherein: In step S1, the stirring temperature is controlled at 30-50°C for 0.5-1 h; in step S2, the heating temperature is 60-100°C and the stirring time is 2-4 h.

8. The method for preparing a high-performance organosilicon waterproofing agent according to claim 6, characterized in that: In step S3, the alkaline substance includes one or more of sodium hydroxide, potassium hydroxide, anhydrous sodium carbonate or anhydrous potassium carbonate.

9. The method for preparing a high-performance organosilicon waterproofing agent according to claim 8, characterized in that: The alkaline substance is anhydrous sodium carbonate.

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