Modified silicone resin for tile adhesive, tile adhesive, preparation method and application thereof

Abstract

The present invention belongs to the field of tile adhesive, and specifically discloses a modified silicone resin for tile adhesive, tile adhesive, and a preparation method and application. The present invention is prepared by mixing alkyl silane, 3-acetoxypropyltrimethoxysilane and a methyl end-capping agent in an aqueous solution system, then adding an acidic cation exchange resin, and heating the mixture for low-temperature polycondensation and then continuing the polycondensation; then adding an epoxy resin, a silane-terminated polyether, a methyl end-capping agent and a vinyl end-capping agent for reaction; after filtering and removing the resin, vacuum removing low-boiling substances, adding trimethoxysilane and a platinum catalyst for reaction; then vacuum removing low-boiling substances to obtain the modified silicone resin for tile adhesive. The modified silicone resin for tile adhesive prepared by the present invention has the advantages of excellent bonding strength, elasticity, waterproofness and aging resistance, solves the problems existing in traditional cement-based tile adhesive, and the preparation method is simple and easy, environmentally friendly, and has broad application prospects.

Description

Technical Field

[0001] The invention belongs to the field of tile adhesive, and in particular relates to a modified organic silicon resin for tile adhesive, the tile adhesive, and a preparation method and application thereof. Background Art

[0002] As people's living standards improve, their requirements for the quality of their living environment are also rising. Buildings must not only meet functionality, safety and durability, but also comfort and aesthetics. Ceramic tiles are increasingly used as wall and floor finishing materials in people's daily lives due to their advantages of high strength, durability, fire resistance, bright surface and good decorative properties. Therefore, the use of tile adhesive is also increasing.

[0003] Tile glue is also called tile adhesive. Currently, the main type of tile glue on the market is cement mortar made of inorganic materials. The advantages are low cost and rich experience in use, but there are also obvious disadvantages, such as cement mortar is a rigid material, low bonding strength, non-waterproof, large shrinkage deformation, etc. The performance of polymer-modified cement mortar has been improved to a certain extent, but its main component is still cement, and the performance improvement is limited. During the use of traditional tile glue with cement mortar as the main material, due to the drying shrinkage of cement mortar, foundation settlement, and inconsistent deformation caused by temperature and humidity changes of various materials, the tiles and exterior walls move differently, causing cracking and debonding, and eventually causing the tiles to fall off, posing a great safety risk. Therefore, the development of a high-performance tile glue is of great significance to the development of the construction industry. Summary of the invention

[0004] The purpose of the present invention is to solve the deficiencies of the prior art and provide a modified silicone resin and a preparation method thereof that enables tile adhesive to have good elasticity, adhesion and waterproofness. Based on this, the first aspect of the present invention provides a preparation method of a modified silicone resin for tile adhesive, comprising the following steps: Alkyl silane, 3-acetoxypropyltrimethoxysilane and a first methyl end-capping agent are mixed in an aqueous solution system, and then an acidic cation exchange resin is added, and the mixture is kept warm for 2 h-4 h at a first temperature of 20°C-40°C; then the mixture is kept warm for 1 h-3 h at a second temperature of 60°C-90°C; then epoxy resin, silane-terminated polyether, a second methyl end-capping agent and a vinyl end-capping agent are added, and the mixture is kept warm for 2 h-5 h at the second temperature; then the acidic cation exchange resin is filtered out, low-boiling substances are removed in vacuo, and then trimethoxysilane and a platinum catalyst are added, and the mixture is kept warm for 3 h-6 h at a third temperature of 60°C-80°C; then the low-boiling substances are removed in vacuo to obtain the modified silicone resin for tile adhesive.

[0005] The present invention utilizes the hydrolysis and polycondensation reaction of silane and the polycondensation reaction of hydroxyl-containing epoxy resin, first prepares a modified silicone resin intermediate, and then further prepares a methoxy-terminated modified silicone resin for tile adhesive by a silylation reaction. Specifically, the present invention firstly hydrolyzes and polycondenses alkylsilane and 3-acetoxypropyltrimethoxysilane at a relatively low temperature for a period of time, and then further reacts by heating, thereby avoiding the problem of gelling due to excessively fast reaction, and then adding epoxy resin can solve the side reaction of epoxy group ring opening, and at the same time, by introducing acetoxy and epoxy resin, the bonding strength of the final product can be significantly improved, and by introducing polyether segments, the elasticity of the final product can be significantly improved. The modified silicone resin for tile adhesive prepared by the present invention has high silane-oxygen bond energy and low surface energy, so that it has good heat resistance and waterproof performance. In addition, the present invention introduces a capped methoxy group by a silylation reaction, and adds a suitable catalyst and other auxiliary agents, so that moisture curing can be achieved, and the construction process is convenient.

[0006] Wherein, the above-mentioned alkylsilane is one or two of methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane and propyltriethoxysilane. The above-mentioned first methyl end-capping agent and the above-mentioned second methyl end-capping agent are one or two of hexamethyldisiloxane, trimethylmethoxysilane and trimethylethoxysilane. The above-mentioned epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and hydrogenated bisphenol A epoxy resin. The above-mentioned silane-terminated polyether is at least one of dimethoxy-terminated polyether and trimethoxy-terminated polyether. The above-mentioned vinyl end-capping agent is one or two of divinyltetramethyldisiloxane, vinyldimethylmethoxysilane and vinyldimethylethoxysilane. The above-mentioned platinum catalyst is a platinum complex (Kaster catalyst), and the content is 1000 ppm-6000 ppm in terms of the mass percentage of metal platinum.

[0007] Among them, the mass ratio of the above-mentioned alkyl silane, the above-mentioned 3-acetoxypropyltrimethoxysilane, the sum of the above-mentioned first methyl end-capping agent and the above-mentioned second methyl end-capping agent, the above-mentioned acidic cation exchange resin, the above-mentioned epoxy resin, the above-mentioned silane end-capping polyether, the above-mentioned vinyl end-capping agent, the above-mentioned trimethoxysilane and the above-mentioned platinum catalyst is 100: (2-4): (20-30): (18-28): (2-5): (8-16): (3-6): (1-2): (0.2-1).

[0008] Among them, if the amount of 3-acetoxypropyltrimethoxysilane is too small, the bonding performance is limited, while if it is too much, it will lead to increased costs and almost no improvement in bonding performance; if the amount of end-capping agent is too small, it will lead to insufficient end-capping and easy gelation, and too much will affect the mechanical properties; if the amount of acidic cation exchange resin is too small, it will lead to the problems of slow reaction and insufficient reaction of the present invention, while if it is too much, it will lead to problems of too fast reaction, easy gelation and high cost; if the amount of epoxy resin is too small, the bonding performance is limited, while if it is too much, it will affect the elasticity of the final product; if the amount of silane-terminated polyether is too small, the elasticity is limited, while if it is too much, it will affect the mechanical properties; if the amount of trimethoxysilane is too small, the cross-linking degree is too small, thereby affecting the mechanical properties, while if it is too much, it will also lead to too large a cross-linking degree, thereby affecting the mechanical properties; if the amount of platinum catalyst is too small, the catalytic activity is insufficient, affecting the comprehensive performance of the product, while if it is too much, it will bring higher costs.

[0009] In the step of mixing the alkylsilane, 3-acetoxypropyltrimethoxysilane and the first methyl end-capping agent in the aqueous solution system, the mass ratio of the alkylsilane to water is 100:(25-40).

[0010] The second aspect of the present invention provides a modified organic silicone resin for tile adhesive prepared by the above preparation method, and based on this, the third aspect of the present invention provides a tile adhesive comprising the above modified organic silicone resin for tile adhesive. In addition to the above modified organic silicone resin for tile adhesive, the tile adhesive also includes nano calcium carbonate, heavy calcium carbonate, titanium dioxide, fumed silica, vinyl trimethoxy silane and dibutyl tin dilaurate.

[0011] Among them, the mass ratio of the modified silicone resin for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate, the titanium dioxide, the fumed silica, the vinyl trimethoxysilane and the dibutyl tin dilaurate is 100:40:150:20:10:6:0.5.

[0012] A fourth aspect of the present invention provides a method for preparing the above-mentioned tile adhesive, comprising the following steps: The modified silicone resin for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate, the titanium dioxide and the fumed silica are mixed, and then vacuum stirred at 110°C for 2.5 hours, then cooled to below 40°C, and the vinyl trimethoxysilane and the dibutyl tin dilaurate are added, mixed and vacuum degassed to obtain the tile adhesive.

[0013] The beneficial effects of the present invention are as follows: the modified silicone resin for tile adhesive prepared by the present invention has the advantages of excellent bonding strength, elasticity, waterproofness and aging resistance, solves the problems existing in traditional cement-based tile adhesive, and the preparation method is simple and easy, environmentally friendly, and has broad application prospects. DETAILED DESCRIPTION

[0014] The following will be combined with the embodiments to clearly and completely describe the concept and technical effects of the present invention so as to fully understand the purpose, scheme and effect of the present invention. It should be noted that the embodiments and features in the embodiments of the present invention can be combined with each other without conflict.

[0015] Example 1 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of methyltrimethoxysilane, 2 parts by mass of 3-acetoxypropyltrimethoxysilane, 20 parts by mass of hexamethyldisiloxane and 40 parts by mass of deionized water were added into the reactor and stirred evenly, then 6 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 20°C for 4 h; then the temperature was raised to 90°C and kept at this temperature for 3 h; then 5 parts by mass of bisphenol A epoxy resin (SM828, Sanmu), 18 parts by mass of dimethoxy-terminated polyether (S203H, Zhonghua), 10 parts by mass of hexamethyldisiloxane and 3 parts by mass of divinyltetramethyldisiloxane were added, and the mixture was kept at 90°C for 2 h; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, then 1 part by mass of trimethoxysilane and 0.2 parts by mass of Custer catalyst (with a platinum content of 6000 ppm) were added, and the mixture was kept at 60°C for 6 h. h; and then vacuuming to remove low-boiling substances to obtain the modified organic silicone resin for tile adhesive, which is recorded as modified organic silicone resin 1.

[0016] A high-performance tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of modified silicone resin 1, 40 parts by mass of nano-calcium carbonate, 150 parts by mass of heavy calcium carbonate, 20 parts by mass of titanium dioxide and 10 parts by mass of fumed silica were added into a power mixer and mixed for 25 min. The mixture was heated to 110°C, vacuumed and stirred for 2.5 h, then cooled to 36°C, 6 parts by mass of vinyltrimethoxysilane and 0.5 parts by mass of dibutyltin dilaurate were added, mixed for 20 min, vacuumed and degassed to obtain a tile adhesive, which was recorded as high-performance tile adhesive 1.

[0017] Example 2 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of methyltriethoxysilane, 2.5 parts by mass of 3-acetoxypropyltrimethoxysilane, 18 parts by mass of trimethylmethoxysilane and 35 parts by mass of deionized water were added to the reactor and stirred evenly, then 9 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 30°C for 2 h; then the temperature was raised to 70°C and kept at this temperature for 2.5 h; then 4 parts by mass of bisphenol F epoxy resin (ZLF-170B, Zhilun), 22 parts by mass of trimethoxy-terminated polyether (SAX530, Zhonghua), 5 parts by mass of trimethylmethoxysilane and 5 parts by mass of vinyldimethylmethoxysilane were added, and the mixture was kept at 70°C for 3 h; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, and then 1.5 parts by mass of trimethoxysilane and 0.4 parts by mass of Custer catalyst (platinum content was 2000 ppm) were added, and the mixture was kept at 80°C for 3.5 h. h; and then vacuuming to remove low-boiling substances to obtain the modified organic silicone resin for tile adhesive, which is recorded as modified organic silicone resin 2.

[0018] A high-performance tile adhesive, the preparation method of which is basically the same as that of Example 1, except that the modified silicone resin 1 in Example 1 is replaced by a modified silicone resin 2.

[0019] Example 3 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of propyltrimethoxysilane, 3 parts by mass of 3-acetoxypropyltrimethoxysilane, 19 parts by mass of trimethylethoxysilane and 30 parts by mass of deionized water were added into the reactor and stirred evenly, then 7 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 25 °C for 3 h; then the temperature was raised to 80 °C and kept at this temperature for 1 h; then 3 parts by mass of hydrogenated bisphenol A epoxy resin (HY-600, Fitch), 28 parts by mass of dimethoxy-terminated polyether (SAX260, Zhonghua), 6 parts by mass of trimethylethoxysilane and 3 parts by mass of vinyldimethylethoxysilane were added, and the mixture was kept at 80 °C for 5 h; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, then 1 part by mass of trimethoxysilane and 0.8 parts by mass of Custer catalyst (with a platinum content of 3000 ppm) were added, and the mixture was kept at 70 °C for 4 h. h; and then vacuuming to remove low-boiling substances to obtain the modified organic silicone resin for tile adhesive, which is recorded as modified organic silicone resin 3.

[0020] A high-performance tile adhesive, the preparation method of which is basically the same as that of Example 1, except that the modified silicone resin 1 in Example 1 is replaced by the modified silicone resin 3.

[0021] Example 4 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of propyltriethoxysilane, 3.5 parts by mass of 3-acetoxypropyltrimethoxysilane, 21 parts by mass of trimethylmethoxysilane and 32 parts by mass of deionized water were added to the reactor and stirred evenly, then 10 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 35°C for 2 h; then the temperature was raised to 70°C and kept at this temperature for 2 h; then 4 parts by mass of bisphenol A epoxy resin (GELR-128, Hongchang), 24 parts by mass of dimethoxy-terminated polyether (SAX350, Zhonghua), 7 parts by mass of trimethylmethoxysilane and 4 parts by mass of divinyltetramethyldisiloxane were added, and the mixture was kept at 70°C for 4 h; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, and then 1.5 parts by mass of trimethoxysilane and 0.6 parts by mass of Custer catalyst (platinum content was 2500 ppm) were added, and the mixture was kept at 60°C for 5 h. h; and then vacuuming to remove low-boiling substances to obtain the modified organic silicone resin for tile adhesive, which is recorded as modified organic silicone resin 4.

[0022] A high-performance tile adhesive, the preparation method of which is basically the same as that of Example 1, except that the modified silicone resin 1 in Example 1 is replaced by a modified silicone resin 4.

[0023] Example 5 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of methyltrimethoxysilane, 4 parts by mass of 3-acetoxypropyltrimethoxysilane, 16 parts by mass of hexamethyldisiloxane and 25 parts by mass of deionized water were added into the reactor and stirred evenly, then 12 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 40 °C for 2 h; then the temperature was raised to 60 °C and kept at this temperature for 3 h; then 2 parts by mass of bisphenol F epoxy resin (ZLF-160B, Zhilun), 26 parts by mass of trimethoxy-terminated polyether (SAX590, Zhonghua), 4 parts by mass of hexamethyldisiloxane and 6 parts by mass of divinyltetramethyldisiloxane were added, and the mixture was kept at 60 °C for 3 h; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, then 2 parts by mass of trimethoxysilane and 1 part by mass of Custer catalyst (platinum content was 1000 ppm) were added, and the mixture was kept at 70 °C for 4 h. h; and then vacuuming to remove low-boiling substances to obtain the modified organic silicone resin for tile adhesive, which is recorded as modified organic silicone resin 5.

[0024] A high-performance tile adhesive, the preparation method of which is basically the same as that of Example 1, except that the modified silicone resin 1 in Example 1 is replaced by a modified silicone resin 5.

[0025] Comparative Example 1 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of methyltrimethoxysilane, 20 parts by mass of hexamethyldisiloxane and 40 parts by mass of deionized water were added into a reaction kettle and stirred evenly, and then 6 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 20°C for 4 hours; then the temperature was raised to 90°C and kept at this temperature for 3 hours; then 18 parts by mass of dimethoxy-terminated polyether (S203H, Zhonghua), 10 parts by mass of hexamethyldisiloxane and 3 parts by mass of divinyltetramethyldisiloxane were added, and the mixture was kept at 90°C for 2 hours; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, and then 1 part by mass of trimethoxysilane and 0.2 parts by mass of Custer catalyst (with a platinum content of 6000 ppm) were added, and the mixture was kept at 60°C for 6 hours; then low-boiling substances were removed by vacuum to obtain the modified silicone resin for tile adhesive, which was recorded as modified silicone resin 6.

[0026] A tile adhesive, the preparation method of which is basically the same as that of Example 1, except that the modified silicone resin 1 in Example 1 is replaced by a modified silicone resin 6.

[0027] Comparative Example 2 A modified silicone resin for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of methyltrimethoxysilane, 2 parts by mass of 3-acetoxypropyltrimethoxysilane, 20 parts by mass of hexamethyldisiloxane and 40 parts by mass of deionized water were added into a reaction kettle and stirred evenly, then 6 parts by mass of acidic cation exchange resin were added, and the mixture was kept at 20°C for 4 h; then the temperature was raised to 90°C and kept at this temperature for 3 h; then 5 parts by mass of bisphenol A epoxy resin (SM828, Sanmu), 10 parts by mass of hexamethyldisiloxane and 3 parts by mass of divinyltetramethyldisiloxane were added, and the mixture was kept at 90°C for 2 h; then the acidic cation exchange resin was filtered out, low-boiling substances were removed by vacuum, then 1 part by mass of trimethoxysilane and 0.2 parts by mass of Custer catalyst (platinum content of 6000 ppm) were added, and the mixture was kept at 60°C for 6 h; then low-boiling substances were removed by vacuum to obtain the modified silicone resin for tile adhesive, which was recorded as modified silicone resin 7.

[0028] A tile adhesive, the preparation method of which is basically the same as that of Example 1, except that the modified silicone resin 1 in Example 1 is replaced by a modified silicone resin 7.

[0029] Effect detection test The performance tests of the tile adhesives prepared in Examples 1-5 and Comparative Examples 1-2 were respectively carried out, specifically including: 1. Determine the bonding strength and tensile properties of tile adhesive according to GB / T 41156-2021.

[0030] 2. Determine the water impermeability of tile adhesive according to GB / T 16777-2008.

[0031] The results are shown in Table 1 and Table 2, where the data in parentheses are the cohesive failure rates.

[0032] Table 1 Table 2 As can be seen from Table 1-2, the tile adhesive prepared with the modified silicone resin in Examples 1-5 has excellent bonding strength, resistance to low temperature, alkaline water, freeze-thaw and heat aging, good elasticity and excellent waterproof performance, and has very good comprehensive performance.

[0033] It can be seen from Comparative Example 1 that the introduction of acetoxy, epoxy resin, etc. can significantly enhance the bonding performance of tile adhesive, improve the durability of tile adhesive, and avoid safety hazards caused by cracking and falling of tiles.

[0034] It can be seen from Comparative Example 2 that the introduction of polyether segments can significantly improve the elasticity of tile adhesive, and the elastic bonding can follow the differential deformation of tiles and substrates, offset stress, and significantly reduce related safety risks.

[0035] The above is only a preferred embodiment of the present invention. The present invention is not limited to the above implementation. As long as the technical effect of the present invention is achieved by the same means, it should belong to the protection scope of the present invention. Within the protection scope of the present invention, its technical scheme and / or implementation method can have various modifications and changes.

Claims

1. A method for preparing a modified silicone resin for tile adhesive, characterized in that: The following steps are involved: Alkyl silane, 3-acetoxypropyltrimethoxysilane and a first methyl end-capping agent are mixed in an aqueous solution system, and then an acidic cation exchange resin is added, and the mixture is kept warm for 2 h-4 h at a first temperature of 20°C-40°C; then the mixture is kept warm for 1 h-3 h at a second temperature of 60°C-90°C; then epoxy resin, silane-terminated polyether, a second methyl end-capping agent and a vinyl end-capping agent are added, and the mixture is kept warm for 2 h-5 h at the second temperature; then the acidic cation exchange resin is filtered out, low-boiling substances are removed in vacuo, and then trimethoxysilane and a platinum catalyst are added, and the mixture is kept warm for 3 h-6 h at a third temperature of 60°C-80°C; then the low-boiling substances are removed in vacuo to obtain the modified silicone resin for tile adhesive.

2. The preparation method according to claim 1, characterized in that: The alkylsilane is one or two of methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane and propyltriethoxysilane; and / or, the first methyl end-capping agent and the second methyl end-capping agent are one or two of hexamethyldisiloxane, trimethylmethoxysilane and trimethylethoxysilane.

3. The preparation method according to claim 1, characterized in that: The epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and hydrogenated bisphenol A epoxy resin; and / or the silane-terminated polyether is at least one of dimethoxy-terminated polyether and trimethoxy-terminated polyether; and / or the vinyl-terminated agent is one or two of divinyltetramethyldisiloxane, vinyldimethylmethoxysilane and vinyldimethylethoxysilane; and / or the platinum catalyst is a platinum complex, and its content is 1000 ppm-6000 ppm in terms of the mass percentage of metallic platinum.

4. The preparation method according to claim 1, characterized in that: The mass ratio of the alkylsilane, the 3-acetoxypropyltrimethoxysilane, the sum of the first methyl end-capping agent and the second methyl end-capping agent, the acidic cation exchange resin, the epoxy resin, the silane-terminated polyether, the vinyl end-capping agent, the trimethoxysilane and the platinum catalyst is 100: (2-4): (20-30): (18-28): (2-5): (8-16): (3-6): (1-2): (0.2-1).

5. A modified silicone resin for tile adhesive, characterized in that: Prepared by the preparation method according to any one of claims 1 to 4.

6. A tile adhesive, characterized in that: The raw materials include the modified silicone resin for tile adhesive as claimed in claim 5.

7. The tile adhesive according to claim 6, characterized in that: The raw materials also include nano calcium carbonate, heavy calcium carbonate, titanium dioxide, gas phase silicon dioxide, vinyl trimethoxy silane and dibutyl tin dilaurate.

8. The tile adhesive according to claim 7, characterized in that: The mass ratio of the modified silicone resin for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate, the titanium dioxide, the fumed silica, the vinyl trimethoxysilane and the dibutyl tin dilaurate is 100:40:150:20:10:6:0.

5.

9. A method for preparing a tile adhesive according to any one of claims 6 to 8, characterized in that: The following steps are involved: The modified silicone resin for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate, the titanium dioxide and the fumed silica are mixed, and then vacuum stirred at 110° C. for 2.5 h, then cooled to below 40° C., and the vinyl trimethoxysilane and the dibutyl tin dilaurate are added, mixed and vacuum degassed to obtain the tile adhesive.

10. Use of the modified silicone resin for tile adhesive according to claim 5 or the tile adhesive according to claim 6 in the field of tiles.

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