High-bonding-strength ceramic tile adhesive and preparation method thereof

Abstract

The invention discloses a high-bonding-strength ceramic tile adhesive and a preparation method thereof, and relates to the field of adhesives. When the ceramic tile adhesive with high bonding strength is prepared, a decaboron dodecahydrodiacetonitrile complex is subjected to a reaction with 2-butyne-3-ethylene oxide, benzotriazole, allyldimethylchlorosilane and 4-amino-2, 2, 6, 6-tetramethylpiperidine in sequence, and functionalized carborane is prepared, and the functionalized carborane is subjected to a reaction with 2-butyne-3-ethylene oxide, benzotriazole, allyldimethylchlorosilane and 4-amino-2, 2, 6, 6-tetramethylpiperidine to prepare the ceramic tile adhesive with high bonding strength. The preparation method comprises the following steps: reacting aminopropyl terminated polydimethylsiloxane with tris (4-bromophenyl) phosphine, epoxy chloropropane and copper nitrate in sequence to prepare functionalized polysiloxane; mixing the functionalized polysiloxane with epoxy resin and acetone to prepare modified epoxy resin; and mixing the modified epoxy resin with the functionalized carborane, and coating the surface of a matrix with the mixture to prepare the high-bonding-strength ceramic tile adhesive. The high-bonding-strength ceramic tile adhesive prepared by the invention has waterproof, antibacterial and anti-aging capabilities.

Description

Technical Field

[0001] The present invention relates to the field of adhesives, and particularly to a high - bonding - strength tile adhesive and a preparation method thereof. Background Art

[0002] Ceramic tile binder, also known as tile adhesive, is mainly used for pasting decorative materials such as ceramic tiles, facing tiles, floor tiles, etc. It is widely applicable to the decorative finishing places of buildings such as interior and exterior walls, floors, bathrooms, kitchens, etc. It is a very ideal bonding material. Epoxy tile adhesive is a commonly used tile adhesive, mainly composed of epoxy resin and curing agent. It is widely used for the installation and paving of various stones, ceramic tiles, and rock slabs, and is also applicable to the pasting and splicing of large - sized boards, artificial stones, jade, etc. It can be applied to almost all materials that need to be pasted, and the construction environment is clean, the efficiency is high, the comprehensive cost is low, and the bonding strength is high.

[0003] Outdoor ceramic tiles are exposed to the outdoor environment and are long - term exposed to wind, rain, sun exposure, ice and snow freezing, etc. The high temperature, ultraviolet radiation, and water erosion in the outdoor environment will all have a negative impact on the effect of the tile adhesive, resulting in the aging and falling off of the tile adhesive. Therefore, this article introduces a high - bonding - strength tile adhesive with waterproof and anti - aging capabilities and a preparation method thereof. Summary of the Invention

[0004] The purpose of the present invention is to provide a high - bonding - strength tile adhesive and a preparation method thereof to solve the problems existing in the prior art.

[0005] A high - bonding - strength tile adhesive, wherein the high - bonding - strength tile adhesive is prepared by mixing functionalized polysiloxane with epoxy resin and acetone to obtain a modified epoxy resin, and then mixing the modified epoxy resin with functionalized carborane and coating it on the surface of the substrate.

[0006] The functionalized polysiloxane is prepared by reacting aminopropyl - terminated polydimethylsiloxane with tris(4 - bromophenyl)phosphine, epichlorohydrin, and copper nitrate in sequence.

[0007] The functionalized carborane is prepared by reacting dodecahydro - dicyano - decaborane with 2 - butyne - 3 - epoxyethane, benzotriazole, allyldimethylchlorosilane, and 4 - amino - 2,2,6,6 - tetramethylpiperidine in sequence.

[0008] A preparation method of a high - bonding - strength tile adhesive, the preparation method of the high - bonding - strength tile adhesive mainly includes the following preparation steps:

[0009] (1) Mix 2-butyn-3-epoxyethane, dodecahydrodiboron diethyl cyanide complex, and acetonitrile in a molar ratio of 16 - 18:18 - 22:80 - 100. React at 80 - 90 °C, 200 - 300 r / min under nitrogen protection for 46 - 50 h, and dry at 82 - 84 °C for 8 - 12 h to obtain pre-modified carborane. Mix the pre-modified carborane and ethanol in a mass ratio of 1:35 - 45, stir at 200 - 300 r / min for 8 - 12 min, then add triethylamine in an amount of 0.03 - 0.05 times the mass of the pre-modified carborane and benzotriazole in an amount of 0.2 - 0.3 times the mass of the pre-modified carborane. React at 60 - 70 °C, 200 - 300 r / min under nitrogen protection for 46 - 50 h, filter, wash with ethanol 3 - 5 times, and vacuum dry at 75 - 85 °C for 18 - 22 h to obtain modified carborane;

[0010] (2) Mix the modified carborane, tetrahydrofuran, and n-butyllithium solution in a mass ratio of 4 - 6:17 - 18:4 - 6. Stir at -2 - 2 °C, 200 - 300 r / min under nitrogen protection for 25 - 35 min, then uniformly add allyldimethylchlorosilane in an amount equimolar to the modified carborane within 20 - 30 min. Raise the temperature to room temperature and continue stirring for 16 - 20 h. Pour into a saturated ammonium chloride aqueous solution with the same volume as the tetrahydrofuran, take the organic layer, dry, and obtain a functionalized carborane precursor. Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine, and ethanol in a mass ratio of 1:0.2 - 0.3:16 - 20. Stir at 45 - 55 °C, 200 - 300 r / min for 100 - 140 min, filter, wash, and dry to obtain functionalized carborane;

[0011] (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide in a mass ratio of 1:0.08 - 0.12:20 - 26, stir at 200 - 300 r / min and 85 - 95 °C for 11 - 13 h, pour into deionized water, let stand for 22 - 26 h, filter, wash with deionized water 3 - 5 times, and vacuum dry at 45 - 55 °C for 11 - 13 h to obtain pre-modified polysiloxane; mix the pre-modified polysiloxane, epichlorohydrin, and additive A-50 in a mass ratio of 3 - 5:1:0.2 - 0.3, react at 106 - 110 °C and 200 - 300 r / min for 4.5 - 5.5 h, add an equal mass of sodium hydroxide aqueous solution of the pre-modified polysiloxane, cool to 50 - 60 °C, continue to stir for 25 - 35 min, remove the aqueous phase, wash with ethanol 3 - 5 times, and vacuum dry at -10 - 0 °C for 22 - 26 h to obtain modified polysiloxane; mix the modified polysiloxane, methanol, and copper nitrate in a mass ratio of 1:6 - 8:0.1 - 0.2, react at 65 - 75 °C and 200 - 300 r / min for 55 - 65 min, and vacuum dry at -10 - 0 °C for 22 - 26 h to obtain functionalized polysiloxane;

[0012] (4) Mix the functionalized polysiloxane, epoxy resin, and solvent evenly in a mass ratio of 1:3 - 5:18 - 22 to obtain modified epoxy resin, mix the modified epoxy resin and functionalized carborane evenly in a mass ratio of 25:2 - 3, coat on the surface of the substrate, and let stand at room temperature for 24 - 28 h to obtain tile adhesive; mix the modified epoxy resin and functionalized carborane evenly in a mass ratio of 25:2 - 3 to obtain tile adhesive.

[0013] As an optimization, the n-butyllithium solution described in step (2) is a 1.6 M n-butyllithium hexane solution.

[0014] As an optimization, the specific operation of the washing described in step (2) is to wash with ethanol 3 - 5 times.

[0015] As an optimization, the specific operation of the drying described in step (2) is to dry at -10 - 0 °C under vacuum conditions for 22 - 26 h.

[0016] As an optimization, the molecular weight of the aminopropyl-terminated polydimethylsiloxane described in step (2) is 1000.

[0017] As an optimization, the sodium hydroxide aqueous solution described in step (3) is a 0.1 M sodium hydroxide aqueous solution.

[0018] As an optimization, the solvent described in step (4) is acetone.

[0019] As an optimization, the prepared tile adhesive is prepared and used immediately, coated on the surface of the substrate, and let stand at room temperature for 24 - 28 h.

[0020] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0021] When preparing the tile adhesive with high bonding strength, the present invention reacts dodecahydrodiazoniatedecaborate complex with 2-butyn-3-epoxyethane, benzotriazole, allyldimethylchlorosilane and 4-amino-2,2,6,6-tetramethylpiperidine in sequence to obtain functionalized carborane; reacts aminopropyl-terminated polydimethylsiloxane with tris(4-bromophenyl)phosphine, epichlorohydrin and copper nitrate in sequence to obtain functionalized polysiloxane; mixes the functionalized polysiloxane with epoxy resin and acetone to obtain modified epoxy resin; mixes the modified epoxy resin with the functionalized carborane, coats it on the surface of the substrate, and obtains the tile adhesive with high bonding strength.

[0022] First, react dodecahydrodiazoniatedecaborate complex with 2-butyn-3-epoxyethane, benzotriazole, allyldimethylchlorosilane and 4-amino-2,2,6,6-tetramethylpiperidine in sequence to obtain functionalized carborane; react dodecahydrodiazoniatedecaborate complex with 2-butyn-3-epoxyethane in sequence to generate carborane. Carborane has good thermal stability, chemical stability and electrochemical properties, and will not easily decompose or change. The introduction of carborane can form a protective boron oxide passivation layer on the material surface. This passivation layer can effectively prevent the direct contact between oxygen and the inside of the material in a high-temperature environment, thereby enhancing the anti-aging effect of the material; then react with benzotriazole to introduce benzimidazole. Benzimidazole can bind to the proteins on the bacterial cell membrane, block the protein synthesis of bacteria, and thus inhibit its growth and division to achieve an antibacterial effect; finally react with allyldimethylchlorosilane and 4-amino-2,2,6,6-tetramethylpiperidine to introduce hindered amine. The hindered amine can capture the free radicals generated by photoinitiation, thereby reducing the damage of free radicals to polymer materials to achieve an anti-aging effect, and the secondary amine formed by the reaction of the amino group and the alkene can react with the epoxy group to play the role of a curing agent.

[0023] Secondly, the aminopropyl-terminated polydimethylsiloxane is reacted with tris(4-bromophenyl)phosphine, epichlorohydrin and copper nitrate in sequence to prepare a functionalized polysiloxane; the functionalized polysiloxane is mixed with epoxy resin and acetone to prepare a modified epoxy resin; the modified epoxy resin is mixed with functionalized carborane and coated on the surface of the substrate to prepare a tile adhesive with high bonding strength; when the aminopropyl-terminated polydimethylsiloxane is reacted with tris(4-bromophenyl)phosphine, epichlorohydrin and copper nitrate in sequence, a dense hydrophobic layer can be formed on the surface of the substrate. This hydrophobic layer is composed of long-chain polysiloxane molecules. Since the hydrophobic groups on the polysiloxane molecular chain are arranged outward, it is difficult for water molecules to wet and penetrate this film. When water contacts the hydrophobic layer, its surface tension increases significantly, resulting in water droplets presenting a spherical or hemispherical shape, thus endowing the material with good waterproof performance; the complex formed by organic phosphorus and copper ions has the function of inhibiting thermal oxidation, that is, the copper ion loses an electron, making the peroxide radical generate a negative ion and slowing down the chain growth reaction of the radical, thereby enabling the material to have an anti-aging effect; and copper ions are introduced. Copper ions can combine with fatty acids in the cell membrane, causing it to lose electrons and lose its function, and then destroying the cell membrane of microorganisms, causing them to die. It can also combine with carboxyl groups in the cell wall, resulting in the destruction of the cell wall, thus achieving an antibacterial effect. Detailed implementation mode

[0024] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0025] Example 1:

[0026] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0027] (1) Mix 2-butyn-3-epoxyethane, dodecahydrodicyano complex of decaborane and acetonitrile in a molar ratio of 16:18:80, react at 80°C, 200 r / min under nitrogen protection for 46 h, and dry at 82°C for 8 h to obtain pre-modified carborane; mix the pre-modified carborane and ethanol in a mass ratio of 1:35, stir at 200 r / min for 8 min, then add triethylamine 0.03 times the mass of the pre-modified carborane and benzotriazole 0.2 times the mass of the pre-modified carborane, react at 60°C, 200 r / min under nitrogen protection for 46 h, filter, wash with ethanol 3 times, and vacuum dry at 75°C for 18 h to obtain modified carborane;

[0028] (2) Mix the modified carborane, tetrahydrofuran, and 1.6 M n-butyllithium hexane solution in a mass ratio of 4:17:4. Stir at -2 °C, 200 r / min under nitrogen protection for 25 min. Then, uniformly add an equimolar amount of allyldimethylchlorosilane to the modified carborane within 20 min. Raise the temperature to room temperature and continue stirring for 16 h. Pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran. Take the organic layer and dry it under vacuum at -10 °C for 22 h to obtain a functionalized carborane precursor. Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine, and ethanol in a mass ratio of 1:0.2:16. Stir at 45 °C, 200 r / min for 100 min, filter, wash with ethanol three times, and dry under vacuum at -10 °C for 22 h to obtain functionalized carborane;

[0029] (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide in a mass ratio of 1:0.08:20. Stir at 200 r / min and 85 °C for 11 h. Pour it into deionized water, let it stand for 22 h, filter, wash with deionized water three times, and dry under vacuum at 45 °C for 11 h to obtain a pre-modified polysiloxane. Mix the pre-modified polysiloxane, epichlorohydrin, and additive A-50 in a mass ratio of 3:1:0.2. React at 106 °C, 200 r / min for 4.5 h. Add a 0.1 M sodium hydroxide aqueous solution with the same mass as the pre-modified polysiloxane. Cool down to 50 °C and continue stirring for 25 min. Remove the aqueous phase, wash with ethanol three times, and dry under vacuum at -10 °C for 22 h to obtain a modified polysiloxane. Mix the modified polysiloxane, methanol, and copper nitrate in a mass ratio of 1:6:0.1. React at 65 °C, 200 r / min for 55 min, and dry under vacuum at -10 °C for 22 h to obtain a functionalized polysiloxane;

[0030] (4) Mix the functionalized polysiloxane, epoxy resin, and acetone uniformly in a mass ratio of 1:3:18 to obtain a modified epoxy resin. Mix the modified epoxy resin and the functionalized carborane uniformly in a mass ratio of 25:2 to obtain a tile adhesive.

[0031] Example 2:

[0032] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0033] (1) Mix 2-butyn-3-epoxyethane, dodecahydrodicyanoethylborate and acetonitrile in a molar ratio of 17:20:90. React at 85 °C, 250 r / min under nitrogen protection for 48 h, and dry at 83 °C for 10 h to obtain pre-modified carborane. Mix the pre-modified carborane and ethanol in a mass ratio of 1:40, stir at 250 r / min for 10 min, then add triethylamine in an amount 0.04 times the mass of the pre-modified carborane and benzotriazole in an amount 0.25 times the mass of the pre-modified carborane. React at 65 °C, 250 r / min under nitrogen protection for 48 h, filter, wash 4 times with ethanol, and vacuum dry at 80 °C for 20 h to obtain modified carborane;

[0034] (2) Mix the modified carborane, tetrahydrofuran and 1.6 M n-butyllithium hexane solution in a mass ratio of 5:17.5:5. Stir at 0 °C, 250 r / min under nitrogen protection for 30 min, then uniformly add allyldimethylchlorosilane in an amount equimolar to the modified carborane within 25 min. Raise the temperature to room temperature and continue stirring for 18 h. Pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran, take the organic layer, and dry at -5 °C under vacuum for 24 h to obtain a functionalized carborane precursor. Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine and ethanol in a mass ratio of 1:0.25:18, stir at 50 °C, 250 r / min for 120 min, filter, wash 4 times with ethanol, and vacuum dry at -5 °C under vacuum for 24 h to obtain functionalized carborane;

[0035] (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine and dimethyl sulfoxide in a mass ratio of 1:0.1:23. Stir at 250 r / min, 90 °C for 12 h, pour it into deionized water, let it stand for 24 h, filter, wash 4 times with deionized water, and vacuum dry at 50 °C for 12 h to obtain pre-modified polysiloxane. Mix the pre-modified polysiloxane, epichlorohydrin and auxiliary A-50 in a mass ratio of 4:1:0.25. React at 108 °C, 250 r / min for 5 h, add a 0.1 M sodium hydroxide aqueous solution with the same mass as the pre-modified polysiloxane, cool down to 55 °C, continue stirring for 30 min, remove the aqueous phase, wash 4 times with ethanol, and vacuum dry at -5 °C for 24 h to obtain modified polysiloxane. Mix the modified polysiloxane, methanol and copper nitrate in a mass ratio of 1:7:0.15. React at 70 °C, 250 r / min for 60 min, and vacuum dry at -5 °C for 24 h to obtain functionalized polysiloxane;

[0036] (4) Mix the functionalized polysiloxane, epoxy resin and acetone in a mass ratio of 1:4:20 evenly to obtain modified epoxy resin. Mix the modified epoxy resin and functionalized carborane in a mass ratio of 25:2.5 evenly to obtain tile adhesive.

[0037] Example 3:

[0038] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0039] (1) Mix 2-butyn-3-epoxyethane, dodecahydrodiazene complex of decaborane and acetonitrile according to a molar ratio of 18:22:100, react at 90 °C, 300 r / min under nitrogen protection for 50 h, and dry at 84 °C for 12 h to obtain pre-modified carborane; Mix the pre-modified carborane and ethanol according to a mass ratio of 1:45, stir at 300 r / min for 12 min, then add triethylamine with a mass 0.05 times that of the pre-modified carborane and benzotriazole with a mass 0.3 times that of the pre-modified carborane, react at 70 °C, 300 r / min under nitrogen protection for 50 h, filter, wash with ethanol 5 times, and vacuum dry at 85 °C for 22 h to obtain modified carborane;

[0040] (2) Mix the modified carborane, tetrahydrofuran and 1.6 M n-butyllithium hexane solution according to a mass ratio of 6:18:6, stir at 2 °C, 300 r / min under nitrogen protection for 35 min, then uniformly add allyldimethylchlorosilane with an equimolar amount of the modified carborane within 30 min, raise the temperature to room temperature, continue to stir for 20 h, pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran, take the organic layer, and dry at 0 °C under vacuum conditions for 26 h to obtain a functionalized carborane precursor; Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine and ethanol according to a mass ratio of 1:0.3:20, stir at 55 °C, 300 r / min for 140 min, filter, wash with ethanol 5 times, and vacuum dry at 0 °C under vacuum conditions for 26 h to obtain functionalized carborane;

[0041] (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine and dimethyl sulfoxide according to a mass ratio of 1:0.12:26, stir at 300 r / min, 95 °C for 13 h, pour it into deionized water, let it stand for 26 h, filter, wash with deionized water 5 times, and vacuum dry at 55 °C for 13 h to obtain pre-modified polysiloxane; Mix the pre-modified polysiloxane, epichlorohydrin and auxiliary agent A-50 according to a mass ratio of 5:1:0.3, react at 110 °C, 300 r / min for 5.5 h, add a 0.1 M sodium hydroxide aqueous solution with the same mass as the pre-modified polysiloxane, cool down to 60 °C, continue to stir for 35 min, remove the aqueous phase, wash with ethanol 5 times, and vacuum dry at 0 °C for 26 h to obtain modified polysiloxane; Mix the modified polysiloxane, methanol and copper nitrate according to a mass ratio of 1:8:0.2, react at 75 °C, 300 r / min for 65 min, and vacuum dry at 0 °C for 26 h to obtain functionalized polysiloxane;

[0042] (4) Mix the functionalized polysiloxane, epoxy resin, and acetone evenly at a mass ratio of 1:5:22 to obtain a modified epoxy resin. Then mix the modified epoxy resin and the functionalized carborane evenly at a mass ratio of 25:3 to obtain the tile adhesive.

[0043] Comparative Example 1:

[0044] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0045] (1) Mix 2-butyn-3-epoxyethane, dodecahydrododecaborane-diethyl cyanide complex, and acetonitrile at a molar ratio of 17:20:90, react at 85 °C, 250 r / min under nitrogen protection for 48 h, and dry at 83 °C for 10 h to obtain the modified carborane.

[0046] (2) Mix the modified carborane, tetrahydrofuran, and 1.6 M n-butyllithium hexane solution at a mass ratio of 5:17.5:5, stir at 0 °C, 250 r / min under nitrogen protection for 30 min, then uniformly add an equimolar amount of allyldimethylchlorosilane of the modified carborane within 25 min, raise the temperature to room temperature, continue stirring for 18 h, pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran, take the organic layer, and dry it at -5 °C under vacuum conditions for 24 h to obtain the functionalized carborane precursor; Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine, and ethanol at a mass ratio of 1:0.25:18, stir at 50 °C, 250 r / min for 120 min, filter, wash with ethanol 4 times, and dry at -5 °C under vacuum conditions for 24 h to obtain the functionalized carborane.

[0047] (3) Mix the aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide at a mass ratio of 1:0.1:23, stir at 250 r / min, 90 °C for 12 h, pour it into deionized water, let it stand for 24 h, filter, wash with deionized water 4 times, and dry at 50 °C under vacuum for 12 h to obtain the pre-modified polysiloxane; Mix the pre-modified polysiloxane, epichlorohydrin, and additive A-50 at a mass ratio of 4:1:0.25, react at 108 °C, 250 r / min for 5 h, add a 0.1 M sodium hydroxide aqueous solution with the same mass as the pre-modified polysiloxane, cool down to 55 °C, continue stirring for 30 min, remove the aqueous phase, wash with ethanol 4 times, and dry at -5 °C under vacuum for 24 h to obtain the modified polysiloxane; Mix the modified polysiloxane, methanol, and copper nitrate at a mass ratio of 1:7:0.15, react at 70 °C, 250 r / min for 60 min, and dry at -5 °C under vacuum for 24 h to obtain the functionalized polysiloxane.

[0048] (4) Mix the functionalized polysiloxane, epoxy resin, and acetone evenly at a mass ratio of 1:4:20 to obtain a modified epoxy resin. Then mix the modified epoxy resin and the functionalized carborane evenly at a mass ratio of 25:2.5 to obtain the tile adhesive.

[0049] Comparative Example 2:

[0050] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0051] (1) Mix 2-butyn-3-epoxyethane, decaborane dodecahydro diethyl cyanide complex, and acetonitrile in a molar ratio of 17:20:90, react at 85 °C, 250 r / min under nitrogen protection for 48 h, and dry at 83 °C for 10 h to obtain pre-modified carborane; Mix the pre-modified carborane and ethanol in a mass ratio of 1:40, stir at 250 r / min for 10 min, then add triethylamine with a mass 0.04 times that of the pre-modified carborane and benzotriazole with a mass 0.25 times that of the pre-modified carborane, react at 65 °C, 250 r / min under nitrogen protection for 48 h, filter, wash with ethanol 4 times, and dry under vacuum at 80 °C for 20 h to obtain modified carborane;

[0052] (2) Mix the modified carborane, tetrahydrofuran, and 1.6 M n-butyllithium hexane solution in a mass ratio of 5:17.5:5, stir at 0 °C, 250 r / min under nitrogen protection for 30 min, then add allyldimethylchlorosilane with an equimolar amount of the modified carborane evenly within 25 min, raise the temperature to room temperature, continue to stir for 18 h, pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran, take the organic layer, and dry it at -5 °C under vacuum for 24 h to obtain the functionalized carborane precursor; Mix the functionalized carborane precursor, 1-aminopropane, and ethanol in a mass ratio of 1:0.25:18, stir at 50 °C, 250 r / min for 120 min, filter, wash with ethanol 4 times, and dry it at -5 °C under vacuum for 24 h to obtain the functionalized carborane;

[0053] (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide in a mass ratio of 1:0.1:23, stir at 250 r / min and 90 °C for 12 h, pour into deionized water, let stand for 24 h, filter, wash with deionized water 4 times, and vacuum dry at 50 °C for 12 h to obtain pre-modified polysiloxane; Mix pre-modified polysiloxane, epichlorohydrin, and additive A-50 in a mass ratio of 4:1:0.25, react at 108 °C and 250 r / min for 5 h, add an equal mass of 0.1 M sodium hydroxide aqueous solution of pre-modified polysiloxane, cool to 55 °C, continue stirring for 30 min, remove the aqueous phase, wash with ethanol 4 times, and vacuum dry at -5 °C for 24 h to obtain modified polysiloxane; Mix modified polysiloxane, methanol, and copper nitrate in a mass ratio of 1:7:0.15, react at 70 °C and 250 r / min for 60 min, and vacuum dry at -5 °C for 24 h to obtain functionalized polysiloxane;

[0054] (4) Mix functionalized polysiloxane, epoxy resin, and acetone evenly in a mass ratio of 1:4:20 to obtain modified epoxy resin, and mix the modified epoxy resin and functionalized carborane evenly in a mass ratio of 25:2.5 to obtain tile adhesive.

[0055] Comparative Example 3:

[0056] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0057] (1) Mix 2-butyn-3-epoxyethane, decaborane dodecahydro diethyl cyanide complex, and acetonitrile in a molar ratio of 17:20:90, react at 85 °C, 250 r / min under nitrogen protection for 48 h, and dry at 83 °C for 10 h to obtain pre-modified carborane; Mix pre-modified carborane and ethanol in a mass ratio of 1:40, stir at 250 r / min for 10 min, then add triethylamine 0.04 times the mass of pre-modified carborane and benzotriazole 0.25 times the mass of pre-modified carborane, react at 65 °C, 250 r / min under nitrogen protection for 48 h, filter, wash with ethanol 4 times, and vacuum dry at 80 °C for 20 h to obtain modified carborane;

[0058] (2) Mix the modified carborane, tetrahydrofuran, and 1.6 M n-butyllithium hexane solution in a mass ratio of 5:17.5:5. Stir at 0 °C, 250 r / min under nitrogen protection for 30 min. Then, uniformly add an equimolar amount of allyldimethylchlorosilane to the modified carborane within 25 min. Raise the temperature to room temperature and continue stirring for 18 h. Pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran. Take the organic layer and dry it under vacuum at -5 °C for 24 h to obtain a functionalized carborane precursor. Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine, and ethanol in a mass ratio of 1:0.25:18. Stir at 50 °C, 250 r / min for 120 min, filter, wash with ethanol 4 times, and dry under vacuum at -5 °C for 24 h to obtain the functionalized carborane;

[0059] (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide in a mass ratio of 1:0.1:23. Stir at 250 r / min, 90 °C for 12 h. Pour it into deionized water, let it stand for 24 h, filter, wash with deionized water 4 times, and dry under vacuum at 50 °C for 12 h to obtain a pre-modified polysiloxane. Mix the pre-modified polysiloxane, epichlorohydrin, and additive A-50 in a mass ratio of 4:1:0.25. React at 108 °C, 250 r / min for 5 h. Add a 0.1 M sodium hydroxide aqueous solution with the same mass as the pre-modified polysiloxane. Cool down to 55 °C and continue stirring for 30 min. Remove the aqueous phase, wash with ethanol 4 times, and dry under vacuum at -5 °C for 24 h to obtain the modified polysiloxane;

[0060] (4) Mix the modified polysiloxane, epoxy resin, and acetone in a mass ratio of 1:4:20 uniformly to obtain a modified epoxy resin. Mix the modified epoxy resin and the functionalized carborane in a mass ratio of 25:2.5 uniformly to obtain the tile adhesive.

[0061] Comparative Example 4

[0062] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0063] (1) Mix 2-butyn-3-epoxyethane, dodecahydrodiborane diethyl cyanide complex, and acetonitrile in a molar ratio of 17:20:90. React at 85 °C, 250 r / min under nitrogen protection for 48 h. Dry at 83 °C for 10 h to obtain a pre-modified carborane. Mix the pre-modified carborane and ethanol in a mass ratio of 1:40. Stir at 250 r / min for 10 min. Then, add triethylamine with a mass 0.04 times that of the pre-modified carborane and benzotriazole with a mass 0.25 times that of the pre-modified carborane. React at 65 °C, 250 r / min under nitrogen protection for 48 h, filter, wash with ethanol 4 times, and dry under vacuum at 80 °C for 20 h to obtain the modified carborane;

[0064] (2) Mix the modified carborane, tetrahydrofuran, and 1.6 M n-butyllithium hexane solution in a mass ratio of 5:17.5:5. Stir at 0 °C, 250 r / min under nitrogen protection for 30 min. Then, uniformly add an equimolar amount of allyldimethylchlorosilane to the modified carborane within 25 min. Raise the temperature to room temperature and continue stirring for 18 h. Pour it into a saturated ammonium chloride aqueous solution with the same volume as tetrahydrofuran. Take the organic layer and dry it under vacuum at -5 °C for 24 h to obtain a functionalized carborane precursor. Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine, and ethanol in a mass ratio of 1:0.25:18. Stir at 50 °C, 250 r / min for 120 min, filter, wash with ethanol 4 times, and dry under vacuum at -5 °C for 24 h to obtain functionalized carborane;

[0065] (3) Mix epoxy resin and acetone evenly in a mass ratio of 5:20 to obtain modified epoxy resin. Mix the modified epoxy resin and functionalized carborane evenly in a mass ratio of 25:2.5 to obtain tile adhesive.

[0066] Comparative Example 5

[0067] A preparation method of a tile adhesive with high bonding strength mainly includes the following preparation steps:

[0068] (1) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide in a mass ratio of 1:0.1:23. Stir at 250 r / min, 90 °C for 12 h, pour it into deionized water, let it stand for 24 h, filter, wash with deionized water 4 times, and dry under vacuum at 50 °C for 12 h to obtain pre-modified polysiloxane. Mix the pre-modified polysiloxane, epichlorohydrin, and auxiliary A-50 in a mass ratio of 4:1:0.25. React at 108 °C, 250 r / min for 5 h, add a 0.1 M sodium hydroxide aqueous solution with the same mass as the pre-modified polysiloxane, cool down to 55 °C, continue stirring for 30 min, remove the aqueous phase, wash with ethanol 4 times, and dry under vacuum at -5 °C for 24 h to obtain modified polysiloxane. Mix the modified polysiloxane, methanol, and copper nitrate in a mass ratio of 1:7:0.15. React at 70 °C, 250 r / min for 60 min, and dry under vacuum at -5 °C for 24 h to obtain functionalized polysiloxane;

[0069] (2) Mix the functionalized polysiloxane, epoxy resin, and acetone evenly in a mass ratio of 1:4:20 to obtain modified epoxy resin. Mix the modified epoxy resin and propylenediamine evenly in a mass ratio of 25:2.5 to obtain tile adhesive.

[0070] Test Example 1:

[0071] Antibacterial property test

[0072] The tile adhesives prepared in each example and the comparative example were coated on a polytetrafluoroethylene plate, left standing at room temperature for 26 h, peeled off, crushed to 30 mesh, 1 g was taken, and tested in accordance with GB / T 31402-2015. The selected bacterial strains were Staphylococcus aureus and Escherichia coli. The results are shown in Table 1.

[0073] Table 1

[0074]

[0075] From the comparison of the experimental data in Table 1, it can be found that the tile adhesive with high bonding strength prepared by the present invention has good antibacterial ability.

[0076] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 1 in Table 1, it can be found that the antibacterial rates of Examples 1, 2, 3 are higher than that of Comparative Example 1, indicating that benzimidazole can bind to the proteins on the bacterial cell membrane, block the protein synthesis of bacteria, thereby inhibiting their growth and division, and achieving the antibacterial effect;

[0077] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that the antibacterial rates of Examples 1, 2, 3 are higher than that of Comparative Example 3, indicating that copper ions can bind to the fatty acids in the cell membrane, cause them to lose electrons and lose their functions, and further damage the cell membrane of microorganisms, causing them to die. Copper ions can also bind to the carboxyl groups in the cell wall, resulting in the destruction of the cell wall, thereby achieving the antibacterial effect.

[0078] Test Example 2:

[0079] Aging resistance test

[0080] Tempered glass with a high light transmittance of 1.6 mm was selected as the bonding specimen. Before testing, the tile adhesives prepared in each example and the comparative example were left standing at room temperature for 26 h after coating;

[0081] Thermal oxygen aging test: Using an INSTRON8501 type microcomputer controlled universal testing machine to test the room temperature single lap shear strength (LSS) of the bonding specimen. Referring to the standard GB7124-2008, aging was carried out at 300 °C for 1 h, and the shear strength was tested. The shear strength retention rate A was tested, and the shear strength retention rate A = shear strength after aging / shear strength before aging * 100%;

[0082] Photoaging test: Using an INSTRON8501 type microcomputer controlled universal testing machine to test the room temperature single lap shear strength (LSS) of the bonding specimen. Referring to the standard GB7124-2008, irradiating under a fluorescent ultraviolet lamp UV-A340 for 15 days, testing the shear strength, and testing the shear strength retention rate B. The shear strength retention rate B = shear strength after aging / shear strength before aging * 100%. The results are shown in Table 2.

[0083] Table 2

[0084] Shear strength retention rate A Shear strength retention rate B Example 1 97.0％ 97.6％ Example 2 96.8％ 97.8％ Example 3 96.7％ 97.5％ Comparative example 1 96.9％ 97.2％ Comparative example 2 96.3％ 88.6％ Comparative example 3 86.2％ 97.3％ Comparative example 4 86.0％ 97.1％ Comparative example 5 81.3％ 83.5％

[0085] From the comparison of the experimental data in Table 2, it can be found that the high-bonding-strength tile adhesive prepared by the present invention has good anti-aging ability.

[0086] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 2 in Table 2, it can be found that the shear strength retention rate B of Examples 1, 2, 3 is higher than that of Comparative Example 2, indicating that the hindered amine can capture the free radicals generated by photoinitiation, thereby reducing the damage of free radicals to polymer materials and achieving the anti-aging effect;

[0087] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 3, it can be found that the shear strength retention rate A of Examples 1, 2, 3 is higher than that of Comparative Example 3, indicating that the complex formed by organophosphorus and copper ions has the function of inhibiting thermal oxidation, that is, the copper ion loses one electron, making the peroxy free radical generate a negative ion and slowing down the chain growth reaction of free radicals, thereby achieving the anti-aging effect;

[0088] From the comparison of the experimental data of Examples 1, 2, 3 and Comparative Example 5, it can be found that the shear strength retention rate A of Examples 1, 2, 3 is higher than that of Comparative Example 5, indicating that carborane has good thermal stability, chemical stability and electrochemical properties, and will not easily decompose or change, and the introduction of carborane can form a protective boron oxide passivation layer on the material surface. This passivation layer can effectively prevent the direct contact of oxygen with the inside of the material at high temperature, thereby achieving the anti-aging effect.

[0089] Test Example 3:

[0090] Waterproof test

[0091] Test method: Coat a 0.5-mm-thick adhesive layer on the surface of tempered glass with a high light transmittance thickness of 1.6 mm for the tile adhesives prepared in each example and comparative example, and let it stand at room temperature for 26 h. Use the XHKE-CATY type contact meter produced by Chengde Xinma Testing Instrument Co., Ltd. to test the water contact angle on the surface of the tile adhesive. The test conditions are as follows: temperature is 25 °C, relative humidity is 25%, the test sample size is 4 cm * 2 cm, and the amount of deionized water used is 5 μL per drop. The results are shown in Table 3.

[0092] Table 3

[0093] Water contact angle Example 1 98.8° Example 2 98.9° Example 3 98.6° Comparative example 1 98.5° Comparative example 2 98.3° Comparative example 3 98.4° Comparative example 4 75.3° Comparative example 5 98.7°

[0094] From the comparison of the experimental data in Table 3, it can be found that the high-bonding-strength tile adhesive prepared by the present invention has good waterproof ability.

[0095] From the comparison of the experimental data of Examples 1, 2, and 3 and Comparative Example 4 in Table 3, it can be found that the water contact angles of Examples 1, 2, and 3 are larger than that of Comparative Example 4, indicating that polysiloxane can form a dense hydrophobic layer on the substrate surface. This hydrophobic layer is composed of long-chain polysiloxane molecules. Since the hydrophobic groups on the polysiloxane molecular chain are arranged outward, it is difficult for water molecules to wet and penetrate this film. When water contacts the hydrophobic layer, its surface tension increases significantly, resulting in water droplets presenting a spherical or hemispherical shape, thus achieving the waterproof effect.

[0096] The specific embodiments described above have further elaborated on the purpose, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A tile adhesive with high bonding strength, characterized in that, The high-adhesion-strength tile adhesive is prepared by mixing a functionalized polysiloxane with an epoxy resin and acetone to obtain a modified epoxy resin, and then mixing the modified epoxy resin with a functionalized carborane and coating the mixture on the surface of a substrate; The functionalized polysiloxane is prepared by reacting an aminopropyl-terminated polydimethylsiloxane successively with tris(4-bromophenyl)phosphine, epichlorohydrin, and copper nitrate; The functionalized carborane is prepared by reacting a decaborane dinitrile complex successively with 2-butyn-3-epoxyethane, benzotriazole, allyldimethylchlorosilane, and 4-amino-2,2,6,6-tetramethylpiperidine; 2. A preparation method of a tile adhesive with high bonding strength, characterized in that, The preparation method of the high-adhesion-strength tile adhesive mainly includes the following preparation steps: (1) Mix 2-butyn-3-epoxyethane, a decaborane dinitrile complex, and acetonitrile at a molar ratio of 16-18:18-22:80-100, react at 80-90 °C, 200-300 r / min under nitrogen protection for 46-50 h, and dry at 82-84 °C for 8-12 h to obtain a pre-modified carborane; Mix the pre-modified carborane and ethanol at a mass ratio of 1:35-45, stir at 200-300 r / min for 8-12 min, then add triethylamine in an amount of 0.03-0.05 times the mass of the pre-modified carborane and benzotriazole in an amount of 0.2-0.3 times the mass of the pre-modified carborane, react at 60-70 °C, 200-300 r / min under nitrogen protection for 46-50 h, filter, wash with ethanol 3-5 times, and vacuum dry at 75-85 °C for 18-22 h to obtain a modified carborane; (2) Mix the modified carborane, tetrahydrofuran, and a n-butyllithium solution at a mass ratio of 4-6:17-18:4-6, stir at -2-2 °C, 200-300 r / min under nitrogen protection for 25-35 min, then uniformly add an equimolar amount of allyldimethylchlorosilane to the modified carborane within 20-30 min, raise the temperature to room temperature, continue to stir for 16-20 h, pour into a saturated ammonium chloride aqueous solution with the same volume as the tetrahydrofuran, take the organic layer, dry to obtain a functionalized carborane precursor; Mix the functionalized carborane precursor, 4-amino-2,2,6,6-tetramethylpiperidine, and ethanol at a mass ratio of 1:0.2-0.3:16-20, stir at 45-55 °C, 200-300 r / min for 100-140 min, filter, wash, and dry to obtain a functionalized carborane; (3) Mix aminopropyl-terminated polydimethylsiloxane, tris(4-bromophenyl)phosphine, and dimethyl sulfoxide in a mass ratio of 1:0.08 - 0.12:20 - 26, stir at 200 - 300 r / min and 85 - 95 °C for 11 - 13 h, pour into deionized water, let stand for 22 - 26 h, filter, wash with deionized water 3 - 5 times, and vacuum dry at 45 - 55 °C for 11 - 13 h to obtain pre-modified polysiloxane; mix the pre-modified polysiloxane, epichlorohydrin, and additive A-50 in a mass ratio of 3 - 5:1:0.2 - 0.3, react at 106 - 110 °C and 200 - 300 r / min for 4.5 - 5.5 h, add an equal mass of sodium hydroxide aqueous solution of the pre-modified polysiloxane, cool to 50 - 60 °C, continue to stir for 25 - 35 min, remove the aqueous phase, wash with ethanol 3 - 5 times, and vacuum dry at -10 - 0 °C for 22 - 26 h to obtain modified polysiloxane; mix the modified polysiloxane, methanol, and copper nitrate in a mass ratio of 1:6 - 8:0.1 - 0.2, react at 65 - 75 °C and 200 - 300 r / min for 55 - 65 min, and vacuum dry at -10 - 0 °C for 22 - 26 h to obtain functionalized polysiloxane; (4) Mix the functionalized polysiloxane, epoxy resin, and solvent in a mass ratio of 1:3 - 5:18 - 22 uniformly to obtain modified epoxy resin; mix the modified epoxy resin and functionalized carborane in a mass ratio of 25:2 - 3 uniformly to obtain tile adhesive.

3. The preparation method of a high bonding strength tile adhesive according to claim 2, characterized in that, The n-butyllithium solution described in step (2) is a 1.6 M n-butyllithium hexane solution.

4. The preparation method of a high bond strength tile adhesive according to claim 2, characterized in that, The specific operation of the washing described in step (2) is to wash with ethanol 3 - 5 times.

5. The preparation method of a high bonding strength tile adhesive according to claim 2, characterized in that, The specific operation of the drying described in step (2) is to dry at -10 - 0 °C under vacuum conditions for 22 - 26 h.

6. The preparation method of a high bond strength tile adhesive according to claim 2, characterized in that, The molecular weight of the aminopropyl-terminated polydimethylsiloxane described in step (2) is 1000.

7. The preparation method of a high bond strength tile adhesive according to claim 2, characterized in that, The sodium hydroxide aqueous solution described in step (3) is a 0.1 M sodium hydroxide aqueous solution.

8. The preparation method of a high bond strength tile adhesive according to claim 2, wherein The solvent described in step (4) is acetone.

9. The tile adhesive prepared by the preparation method of a tile adhesive with high bonding strength according to claim 2 is prepared and used immediately, coated on the surface of the substrate, and left to stand at room temperature for 24 - 28 h.

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