Modified organic silicon polymer for ceramic tile adhesive, ceramic tile adhesive, preparation method and application

Abstract

The invention belongs to the field of ceramic tile adhesives, and particularly discloses a modified organic silicon polymer for a ceramic tile adhesive, the ceramic tile adhesive, a preparation method and application. The preparation method comprises the following steps: reacting bis (3-aminopropyl) terminated polydimethylsiloxane with bisphenol A diglycidyl ether; and then adding sec-ammonia silane and continuously reacting to obtain the modified organic silicon polymer for the ceramic tile adhesive. The prepared modified organic silicon polymer can be used for preparing high-performance ceramic tile glue with excellent elasticity, adhesion, hydrophobicity and heat resistance, the defects of traditional cement-based ceramic tile glue are overcome, and the preparation method is simple, convenient, easy to implement, environmentally friendly and wide in application prospect.

Description

Technical Field

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

[0002] Ceramic tiles are popular among people for their high strength, durability, fire resistance, bright surface and good decorative properties. They are increasingly used in wall and floor decoration. With the improvement of living quality, people's requirements for the aesthetics and functionality of building decoration materials are constantly increasing. In order to meet the needs of the market, the technology of ceramic tiles is constantly improving, developing in the direction of low water absorption, large size, high density and diversification, which puts higher requirements on ceramic tile adhesive materials.

[0003] At present, the tile adhesive (also known as tile adhesive) on the market is mainly cement mortar made of inorganic materials. It has the advantages of low cost and rich experience in use. However, since cement mortar is a rigid material, it has disadvantages such as low bonding strength, hydrophilicity, and large shrinkage deformation. In order to improve the performance of cement-based tile adhesive, a certain amount of polymer is usually added. However, cement still accounts for a large proportion in the formula. During use, drying shrinkage, temperature difference stress and uncoordinated deformation will inevitably occur, resulting in a decrease in bonding performance, which will lead to cracking and falling of tiles, which not only affects the beauty of the decorative surface, but also poses a major safety risk. Therefore, the development of an elastic tile adhesive with high bonding performance 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 polysiloxane and a preparation method thereof that enables tile adhesive to have good elasticity, water resistance and long-lasting bonding strength. Based on this, the first aspect of the present invention provides a method for preparing a modified silicone polymer for tile adhesive, comprising the following steps: After mixing bis(3-aminopropyl)-terminated polydimethylsiloxane and bisphenol A diglycidyl ether, react them at a first temperature for 5 h-9 h; then add secondary aminosilane and continue to react at the first temperature for 3 h-6 h to obtain the modified silicone polymer for tile adhesive; the first temperature is 70°C-120°C.

[0005] The present invention firstly reacts amino-terminated polysiloxane with bisphenol A diglycidyl ether to generate epoxy-terminated modified polysiloxane containing ether bonds, hydroxyl groups and phenyl groups, and then further reacts with secondary aminosilane to generate trimethoxy-terminated modified polysiloxane (i.e., the modified organic silicon polymer for tile adhesive of the present invention); the modified polysiloxane contains functional groups such as ether bonds, hydroxyl groups, amino groups and methoxy groups, which can improve its bonding performance and mechanical properties, while also maintaining good elasticity of the polysiloxane; the silicon-oxygen bonds and phenyl groups in the modified polysiloxane also make it have good heat resistance; therefore, the modified polysiloxane can be used to prepare high-performance tile adhesive with excellent elasticity, adhesion, hydrophobicity and heat resistance, avoiding the shortcomings of traditional cement-based tile adhesive.

[0006] The molar ratio of the bis(3-aminopropyl)-terminated polydimethylsiloxane, the bisphenol A diglycidyl ether and the secondary aminosilane is 1:(4-4.1):(4.1-4.2).

[0007] The molecular weight of the bis(3-aminopropyl)-terminated polydimethylsiloxane is 15000-35000. If the molecular weight is too small, the mechanical properties will be poor; if it is too large, the content of polar groups will be reduced, thereby affecting the bonding properties.

[0008] The secondary aminosilane is at least one of N-n-butyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminoisobutyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane, N-(3-dimethylaminopropyl)-3-aminopropylmethyldimethoxysilane and bis[3-(trimethoxysilyl)propyl]amine.

[0009] The second aspect of the present invention provides a modified organic silicon polymer 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 silicon polymer for tile adhesive. In addition to the above modified organic silicon polymer for tile adhesive, the tile adhesive also includes nano calcium carbonate, heavy calcium carbonate, fumed silica, vinyl trimethoxy silane and dibutyl tin dilaurate.

[0010] Wherein, the mass ratio of the modified silicone polymer for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate, the fumed silica, the vinyl trimethoxy silane and the dibutyl tin dilaurate is 100:50:160:8:5:0.6.

[0011] A fourth aspect of the present invention provides a method for preparing the above-mentioned tile adhesive, comprising the following steps: The modified silicone polymer for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate and the fumed silica are mixed, and then stirred under vacuum at 120°C for 2 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.

[0012] The beneficial effects of the present invention are as follows: the modified silicone polymer prepared by the present invention can be used to prepare high-performance tile adhesive with excellent elasticity, adhesion, hydrophobicity and heat resistance, avoiding the shortcomings of traditional cement-based tile adhesives, and the preparation method is simple and easy, environmentally friendly, and has broad application prospects. DETAILED DESCRIPTION

[0013] 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.

[0014] Example 1 A modified organic silicon polymer for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of bis(3-aminopropyl)-terminated polydimethylsiloxane (molecular weight of 15,000) and 9.08 parts by mass of bisphenol A diglycidyl ether were added into a reactor, stirred evenly at room temperature, heated to 70°C and kept warm for 9 h, then 6.43 parts by mass of N-n-butyl-3-aminopropyltrimethoxysilane was added, and the reaction was continued for 6 h to obtain the modified silicone polymer for tile adhesive, which was recorded as modified silicone polymer 1.

[0015] An elastic tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of modified silicone polymer 1, 50 parts by mass of nano calcium carbonate, 160 parts by mass of heavy calcium carbonate and 8 parts by mass of fumed silica were added into a power mixer and mixed for 30 min. The mixture was heated to 120°C and mixed under vacuum for 2 h. The mixture was then cooled to 38°C, 5 parts by mass of vinyl trimethoxy silane and 0.6 parts by mass of dibutyl tin dilaurate were added, mixed for 15 min, and degassed under vacuum to obtain a tile adhesive, which was recorded as elastic tile adhesive 1.

[0016] Example 2 A modified organic silicon polymer for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of bis(3-aminopropyl)-terminated polydimethylsiloxane (molecular weight 20,000) and 6.99 parts by mass of bisphenol A diglycidyl ether were added into a reactor, stirred evenly at room temperature, heated to 120°C and kept warm for 5 h, then 4.65 parts by mass of N-ethyl-3-aminoisobutyltrimethoxysilane was added, and the reaction was continued for 3 h to obtain the modified silicone polymer for tile adhesive, which was recorded as modified silicone polymer 2.

[0017] An elastic tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of modified silicone polymer 2, 50 parts by mass of nano calcium carbonate, 160 parts by mass of heavy calcium carbonate and 8 parts by mass of fumed silica were added into a power mixer and mixed for 30 min. The mixture was heated to 120 °C and mixed under vacuum for 2 h. The mixture was then cooled to 38 °C, 5 parts by mass of vinyl trimethoxy silane and 0.6 parts by mass of dibutyl tin dilaurate were added, mixed for 15 min, and degassed under vacuum to obtain a tile adhesive, which was recorded as elastic tile adhesive 2.

[0018] Example 3 A modified organic silicon polymer for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of bis(3-aminopropyl)-terminated polydimethylsiloxane (molecular weight 25,000) and 5.51 parts by mass of bisphenol A diglycidyl ether were added into a reactor, stirred evenly at room temperature, heated to 80°C and kept warm for 8 h, then 4.34 parts by mass of N-cyclohexyl-3-aminopropyltrimethoxysilane was added, and the reaction was continued for 4 h to obtain the modified silicone polymer for tile adhesive, which was recorded as modified silicone polymer 3.

[0019] An elastic tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of modified silicone polymer 3, 50 parts by mass of nano calcium carbonate, 160 parts by mass of heavy calcium carbonate and 8 parts by mass of fumed silica were added into a power mixer and mixed for 30 min. The mixture was heated to 120 °C and mixed under vacuum for 2 h. The mixture was then cooled to 38 °C, 5 parts by mass of vinyl trimethoxy silane and 0.6 parts by mass of dibutyl tin dilaurate were added, mixed for 15 min, and degassed under vacuum to obtain a tile adhesive, which was recorded as elastic tile adhesive 3.

[0020] Example 4 A modified organic silicon polymer for tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of bis(3-aminopropyl)-terminated polydimethylsiloxane (molecular weight 30,000) and 4.63 parts by mass of bisphenol A diglycidyl ether were added into a reactor, stirred evenly at room temperature, heated to 90°C and kept warm for 7 h, then 3.41 parts by mass of N-(3-dimethylaminopropyl)-3-aminopropylmethyldimethoxysilane was added, and the reaction was continued for 5 h to obtain a modified silicone polymer for tile adhesive, which was recorded as modified silicone polymer 4.

[0021] An elastic tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of modified silicone polymer 4, 50 parts by mass of nano calcium carbonate, 160 parts by mass of heavy calcium carbonate and 8 parts by mass of fumed silica were added into a power mixer and mixed for 30 min. The mixture was heated to 120 °C and mixed under vacuum for 2 h. The mixture was then cooled to 38 °C, 5 parts by mass of vinyl trimethoxy silane and 0.6 parts by mass of dibutyl tin dilaurate were added, mixed for 15 min, and degassed under vacuum to obtain a tile adhesive, which was recorded as elastic tile adhesive 4.

[0022] Example 5 A modified organic silicon polymer for tile adhesive, the preparation method of which comprises the following steps: 100 parts by weight of bis(3-aminopropyl)-terminated polydimethylsiloxane (molecular weight of 35,000) and 3.93 parts by weight of bisphenol A diglycidyl ether were added into a reactor, stirred evenly at room temperature, heated to 100°C and kept warm for 6 hours, then 4.07 parts by weight of [3-(trimethoxysilyl)propyl]amine was added, and the reaction was continued for 4 hours to obtain a modified silicone polymer for tile adhesive, which was recorded as modified silicone polymer 5.

[0023] An elastic tile adhesive, the preparation method of which comprises the following steps: 100 parts by mass of modified silicone polymer 5, 50 parts by mass of nano calcium carbonate, 160 parts by mass of heavy calcium carbonate and 8 parts by mass of fumed silica were added into a power mixer and mixed for 30 min. The mixture was heated to 120 °C and mixed under vacuum for 2 h. The mixture was then cooled to 38 °C, 5 parts by mass of vinyl trimethoxy silane and 0.6 parts by mass of dibutyl tin dilaurate were added, mixed for 15 min, and degassed under vacuum to obtain a tile adhesive, which was recorded as elastic tile adhesive 5.

[0024] Comparative Example 1 A tile adhesive, the preparation method of which comprises the following steps: 100 parts by weight of bis(trimethoxy)-terminated polydimethylsiloxane (molecular weight of 15,000), 50 parts by weight of nano-calcium carbonate, 160 parts by weight of heavy calcium carbonate and 8 parts by weight of fumed silica were added into a power mixer and mixed for 30 min. The mixture was heated to 120 °C and vacuum mixed for 2 h. The mixture was then cooled to 38 °C, 5 parts by weight of vinyltrimethoxysilane and 0.6 parts by weight of dibutyltin dilaurate were added, mixed for 15 min, and vacuum degassed to obtain a tile adhesive.

[0025] Effect detection test The performance tests of the tile adhesives prepared in Examples 1-5 and Comparative Example 1 were respectively carried out, specifically including: 1. Determine the bonding strength and tensile properties of tile adhesive according to GB / T 41156-2021.

[0026] 2. Determine the water impermeability of tile adhesive according to GB / T 16777-2008.

[0027] The results are shown in Table 1 and Table 2, where the data in parentheses are the cohesive failure rates.

[0028] Table 1 Table 2 It can be seen from Table 1-2 that the tile adhesive prepared by the modified silicone polymer in Example 1-5 not only has excellent bonding performance, resistance to low temperature, alkaline water, freeze-thaw and heat aging, but also has excellent elasticity and hydrophobicity.

[0029] It can be seen from Comparative Example 1 that by introducing functional groups such as ether bonds, hydroxyl groups, amino groups and phenyl groups, the comprehensive performance of tile adhesive, especially its bonding performance, can be significantly improved, thereby improving the durability of tile adhesive, avoiding cracking and falling of tiles, and reducing safety hazards.

[0030] 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 organosilicon polymer for tile adhesive, characterized in that: The following steps are involved: After mixing bis(3-aminopropyl)-terminated polydimethylsiloxane and bisphenol A diglycidyl ether, react them at a first temperature for 5 h-9 h; then add secondary aminosilane and continue to react at the first temperature for 3 h-6 h to obtain the modified silicone polymer for tile adhesive; the first temperature is 70°C-120°C.

2. The preparation method according to claim 1, characterized in that: The molar ratio of the bis(3-aminopropyl)-terminated polydimethylsiloxane, the bisphenol A diglycidyl ether and the secondary aminosilane is 1:(4-4.1):(4.1-4.2).

3. The preparation method according to claim 1, characterized in that: The molecular weight of the bis(3-aminopropyl)-terminated polydimethylsiloxane is 15,000-35,000.

4. The preparation method according to claim 1, characterized in that: The secondary aminosilane is at least one of N-n-butyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminoisobutyltrimethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropylmethyldimethoxysilane, N-(3-dimethylaminopropyl)-3-aminopropylmethyldimethoxysilane and bis[3-(trimethoxysilyl)propyl]amine.

5. A modified silicone polymer 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 material comprises the modified organic silicon polymer 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, 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 organic silicon polymer for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate, the fumed silica, the vinyl trimethoxysilane and the dibutyltin dilaurate is 100:50:160:8:5:0.

6.

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 organic silicon polymer for tile adhesive, the nano calcium carbonate, the heavy calcium carbonate and the fumed silica are mixed, and then vacuum stirred at 120° C. for 2 h, then cooled to below 40° C., the vinyl trimethoxysilane and the dibutyl tin dilaurate are added, mixed and vacuum degassed to obtain the tile adhesive.

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

Images