High-performance organosilicon waterproofing agent and preparation method thereof

Abstract

The invention discloses a high-performance organosilicon waterproofing agent and a preparation method thereof, and belongs to the technical field of organosilicon waterproofing agents. The high-performance organosilicon waterproofing agent is prepared from the following raw materials in parts by weight: 100 parts of alkyl alkoxy silane, 40 to 60 parts of absolute ethyl alcohol, 20 to 40 parts of deionized water, 0.1 to 0.5 part of glacial acetic acid, 0 to 5 parts of silane coupling agent, 0 to 10 parts of epoxy silicone oil, 0 to 5 parts of epoxy resin and 0.1 to 0.5 part of curing agent, wherein the mass sum of the silane coupling agent, the epoxy silicone oil, the epoxy resin and the curing agent is greater than 0. The preparation method comprises the following steps: dropwise adding a deionized water and acetic acid mixed solution into alkyl alkoxy silane, reacting, neutralizing and filtering to obtain a silicon resin prepolymer, adding the silane coupling agent, the epoxy silicone oil, the epoxy resin and the curing agent, and reacting for a period of time to obtain the high-performance organosilicon waterproofing agent. The preparation method of the high-performance organosilicon waterproofing agent provided by the invention is simple, and the prepared material has good waterproofness and can be used in the field of highway waterproofing.

Description

Technical Field

[0001] The 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, thus solving the problem of water damage to the pavement.

[0004] The active ingredient of solvent-based silicone waterproofing agent is silicone resin prepolymer. During the curing and solvent volatilization, a hydrophobic molecular film will be formed on the road surface, blocking water penetration and improving the road's waterproof performance. It does not affect the drainage of water inside the road, making the road "breathable". However, the strength of pure silicone resin is low, and the waterproof layer is easily damaged. It is necessary to introduce other components to reinforce it, thereby extending the service life of the waterproof layer.

[0005] The Chinese patent with application number 202110484140.0 provides a silicone waterproofing agent made of silane coupling agent and MQ silicone resin to solve the problems of low waterproofing efficiency, long curing time, and poor aging resistance of silicone waterproofing agents. The silicone waterproofing agent is formed by the mutual dissolution of silane coupling agent and MQ silicone resin, and the weight proportion of MQ silicone resin is 10-90%. The composite of MQ silicone resin and silane coupling agent can play a synergistic enhancement role. At the same time, the addition of modified polypropylene can enhance the bonding force between the waterproofing agent and concrete, and the maximum bonding strength reaches 4.9MPa. However, the method still has problems such as high solid 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 to 200 parts of diisocyanate; 50 to 100 parts of terminal epoxy polyether; 90 to 120 parts of aminosiloxane; 90 to 120 parts of alkyl siloxane; 90 to 110 parts of alcohol solvent; 400 parts of deionized water; the silicone waterproofing agent uses diisocyanate, terminal epoxy polyether, aminosiloxane, alkyl siloxane, 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, but the method has a long process route and a high industrialization cost. Summary of the invention

[0007] In view of the above problems, the present invention provides a high-performance organosilicon waterproofing agent and a preparation method thereof. The high-performance organosilicon waterproofing agent has low cost, good adhesion, high strength, and excellent waterproofness, and can be used in the field of highway waterproofing; the preparation method of the high-performance organosilicon waterproofing agent is simple and easy.

[0008] The high-performance organic silicone waterproofing agent comprises the following raw materials, measured by weight: 100 parts of alkyl alkoxy silane, 40 to 60 parts of anhydrous ethanol, 20 to 40 parts of deionized water, 0.1 to 0.5 parts of glacial acetic acid, 0 to 5 parts of silane coupling agent, 0 to 10 parts of epoxy silicone oil, 0 to 5 parts of epoxy resin and 0.1 to 0.5 parts of curing agent; wherein the sum of the masses of the silane coupling agent, epoxy silicone oil, epoxy resin and curing agent is greater than 0.

[0009] The invention uses alkyl alkoxy silane as the main raw material, drops a mixed solution of deionized water and glacial acetic acid, neutralizes and filters after reaction to obtain a silicone resin prepolymer, then adds a silane coupling agent, epoxy silicone oil, epoxy resin and a curing agent, and reacts for a period of time to prepare a high-performance silicone waterproofing agent.

[0010] Preferably, the alkylalkoxysilane includes one or more of methyltriethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-octyltriethoxysilane, vinyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane or tetraethoxysilane.

[0011] Preferably, the silane coupling agent includes one or more of γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexane)ethyltrimethoxysilane or 2-(3,4-epoxycyclohexane)ethyltriethoxysilane.

[0012] More preferably, the silane coupling agent is γ-glycidyloxypropyltriethoxysilane.

[0013] Preferably, the viscosity of the epoxy silicone oil is 45 to 220 cSt, and the epoxy value is 0.02 to 0.05 mol / 100 g.

[0014] More preferably, the viscosity of the epoxy silicone oil is 100-140 cSt, and the epoxy value is 0.030-0.032 mol / 100 g.

[0015] Preferably, the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol 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 completed;

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

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

[0023] The present invention firstly 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 0.5-1h.

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

[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. In the present invention, a small amount of epoxy resin and curing agent are added to the silicone resin prepolymer. The epoxy resin and the 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, the strength and bonding performance of the waterproofing agent material can be further improved by adding a small amount;

[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 by way of 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 organic silicon waterproofing agent comprises the following raw materials, measured 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, 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 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, react for 2 hours, and 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 basically 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 basically 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 silicone waterproofing agent in Examples 1 to 5 are shown in Table 1.

[0051] Table 1 Components of high performance organosilicon waterproofing agents in Examples 1 to 5

[0052]

[0053]

[0054] The viscosity of the high-performance organosilicon waterproofing agents prepared in Examples 1 to 5 was measured using a rotational viscometer.

[0055] 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 the sample is stirred, (6±1) g of the sample is poured into a dried and weighed culture dish (m0) and the bottom is flattened, and it is immediately weighed (m1). It is placed at room temperature for 24 hours to react completely, and then placed in an oven heated to (120±2)°C, kept at a constant temperature for 3 hours, taken out and cooled in a desiccator for 2 hours, and then weighed (m2). The solid content X is calculated according to formula (I):

[0056] X = (m2-m0) / (m1-m0) × 100% formula (I);

[0057] 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 in it, and represents the total weight of the culture dish and the sample after the reaction is completed.

[0058] 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", and the specific steps are as follows: assemble and install the pavement water permeability meter, turn off the switch, fill the measuring cylinder with water, turn on the switch to exhaust, and then refill with water; turn on the switch, start timing when the liquid level drops to the 100mL scale, record the instrument tube scale once every 60s until the water level drops by 500mL, and the pavement water permeability coefficient C w Calculate according to formula (II):

[0059] C w =(V2-V1) / (t2-t1)×100% formula (II);

[0060] 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.

[0061] The water absorption ratio test of the high-performance organosilicon waterproofing agent prepared in Examples 1 to 5 was carried out with reference to JC / T 902-2002 "Organosilicon Waterproofing Agent for Building Surfaces", and the specific steps are as follows:

[0062] Add waterproofing agent to a container with a mesh shelf, the liquid level of the waterproofing agent is about 7mm higher than the shelf, place the mortar block that has been dried at 105℃ for 4h and placed at room temperature for 24h on the shelf, soak in the waterproofing agent for 20s, take out and spin dry, and place at room temperature for 3d, with the immersed surface (experimental surface) facing up. Add distilled water to a container with a mesh shelf, the liquid level of the water is about 3mm higher than the shelf, place the mortar block treated with waterproofing agent (weight W0) on the shelf with the experimental surface facing down, take out after immersion for 24h, dry the surface moisture with a napkin, and weigh it immediately (W1). At the same time, the untreated mortar block is also immersed in water. The weight before immersion is recorded as M0, and the weight after immersion in distilled water for 24h is recorded as M1. The water absorption ratio B is calculated according to formula (III) to formula (V):

[0063] A1=(W1-W0) / W0×100%Formula (III);

[0064] A0 = (M1-M0) / M0×100% formula (IV);

[0065] B = A1 / A0×100% formula (V);

[0066] Where A0 and A1 represent the water absorption before and after treatment, respectively, and B represents the water absorption ratio.

[0067] The tensile strength, elongation at break and tear strength of the high-performance silicone waterproofing agents prepared in Examples 1 to 5 were tested with reference to GB / T 16777-2008 “Test methods for building waterproof coatings”. Each group of tests was performed three times, and the average of the three results was taken.

[0068] The performance test data of the high-performance organosilicon waterproofing agent prepared in Examples 1 to 5 are shown in Table 2.

[0069] Table 2 Summary of sample performance test results

[0070]

[0071] As shown in Table 2, the prepared silicone waterproofing agent has both good waterproofing properties 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 of the silicone resin and the epoxy resin.

[0072] It should be understood that the above embodiments are only used to illustrate the present invention and are not used to limit the scope of protection of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims

1. A high-performance silicone waterproofing agent, characterized in that: Calculated in parts by weight, the raw materials include: 100 parts of alkyl alkoxy silane, 40-60 parts of anhydrous ethanol, 20-40 parts of deionized water, 0.1-0.5 parts of glacial acetic acid, 0-5 parts of silane coupling agent, 0-10 parts of epoxy silicone oil, 0-5 parts of epoxy resin and 0.1-0.5 parts of curing agent; among which, the sum of the masses of the silane coupling agent, epoxy silicone oil, epoxy resin and curing agent is greater than 0.

2. The high-performance organic silicon waterproofing agent according to claim 1, characterized in that: The alkylalkoxysilane includes one or more of methyltriethoxysilane, dimethyldiethoxysilane, propyltriethoxysilane, n-octyltriethoxysilane, vinyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane or tetraethoxysilane; the silane coupling agent includes 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 45-220cSt, and the epoxy value is 0.02-0.05moL / 100g; the epoxy resin includes one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin or aliphatic glycidyl ether epoxy resin; the curing agent is an acid anhydride curing agent.

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

4. The high-performance organic silicon waterproofing agent according to claim 2, characterized in that: The acid anhydride curing agent is phthalic anhydride.

5. The high performance organosilicon waterproofing agent according to claim 2, 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.

6. The high-performance silicone waterproofing agent according to claim 2, characterized in that: The acid anhydride curing agent is phthalic anhydride.

7. A method for preparing the high-performance organosilicon waterproofing agent according to any one of claims 1 to 6, 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 completed; S3, after cooling to room temperature, adding alkaline substances to neutralize to a pH of 6.5 to 7.5, and filtering to obtain a silicone resin prepolymer; S4, adding silane coupling agent, epoxy silicone oil, epoxy resin and curing agent, and obtaining the high-performance silicone waterproofing agent after the reaction is completed.

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

9. The method for preparing a high-performance organosilicon waterproofing agent according to claim 7, 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.

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

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