Anti-aging easy-to-fix tile adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of polymer binders, and particularly relates to an anti-aging easy-to-fix tile adhesive and a preparation method thereof. The preparation method comprises the following steps: (1) adding amino-terminated silicon oil and an epoxy silane coupling agent into an anhydrous diluting solvent, mixing, dissolving, stirring and reacting, and removing the solvent under reduced pressure after the reaction is completed, so as to obtain an organic silicon cross-linking agent; (2) adding an organic silicon monomer and an acrylic monomer into the emulsifier aqueous solution, stirring and emulsifying uniformly, adding an initiator, and heating for polymerization reaction to obtain a silicone-acrylic emulsion; and (3) uniformly mixing the obtained organic silicon cross-linking agent with a polyether silicone oil emulsifier, adding the mixture into a silicone acrylic emulsion, heating, carrying out a thermal hydrolysis cross-linking reaction, adding a filler after the reaction is completed, and uniformly stirring and mixing to obtain the anti-aging easy-to-fix tile adhesive. The ceramic tile adhesive disclosed by the invention has the advantages of remarkably improved bonding strength, heat resistance, water resistance and aging resistance, longer opening time and easiness in gluing and tiling operation.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer binders, and particularly relates to an anti-aging and easy-to-paste tile adhesive and a preparation method thereof. Background Art

[0002] Tile adhesive is a polymer-modified cement-based material used for pasting decorative materials such as tiles, facing bricks, and floor tiles. By adding functional polymers, the bonding force and flexibility between the tile adhesive and the substrate are enhanced, and the stress generated by the thermal expansion and contraction of the bonding layer can be resisted, so as to achieve a stable bonding effect.

[0003] Functional polymers used for tile adhesives generally adopt emulsions or powder adhesives such as acrylic resins, ethylene-vinyl acetate copolymers, and polyurethane resins. For example, the invention patent with the publication number of CN 110317026 A discloses a tile adhesive, which includes the following components in parts by weight: 45-75 parts of ordinary portland cement, 80-150 parts of quartz sand, 40-60 parts of epoxy resin-modified water-based acrylic latex powder, 10-20 parts of cellulose ether, 5-10 parts of gelatin, and 2-7 parts of powdered sodium silicate. This invention improves the bonding performance of the material by mixing epoxy resin-modified water-based acrylic latex powder with ordinary portland cement and quartz sand, and it is not easy to produce hollowing phenomena. However, the anti-aging performance of simply using organic carbon chain polymer resin as the bonding functional component is insufficient.

[0004] Organosilicon materials have been widely studied in the application of tile adhesives due to their excellent anti-aging properties. For example, the invention patent with the publication number of CN 119661854A discloses a modified organosilicon polymer for tile adhesives, a tile adhesive, a preparation method and an application thereof. By reacting bis(3-aminopropyl) terminated polydimethylsiloxane with bisphenol A diglycidyl ether; then adding secondary amino silane and continuing the reaction, the modified organosilicon polymer for tile adhesives is obtained. The prepared modified organosilicon polymer can be used to prepare a high-performance tile adhesive with excellent elasticity, adhesiveness, hydrophobicity and heat resistance. However, this existing technology directly uses the modified organosilicon polymer as the main binder of the tile adhesive, resulting in a high cost. And this modified organosilicon polymer is based on the alcohol-decoupling crosslinking curing mechanism under the catalysis of organotin, with a fast curing speed and a short open time, so the time for applying glue and pasting tiles is short during the construction process, and the operation is not easy. Summary of the Invention

[0005] Aiming at the above-mentioned shortcomings and deficiencies of the prior art, the primary object of the present invention is to provide a preparation method of an anti-aging and easy-to-paste tile adhesive.

[0006] Another object of the present invention is to provide an anti-aging and easy-to-paste tile adhesive prepared by the above method.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] A preparation method of an anti-aging and easy-to-stick tile adhesive, comprising the following preparation steps:

[0009] (1) Add amino-terminated silicone oil and epoxy group-containing silane coupling agent to an anhydrous diluting solvent, mix and dissolve, and stir for reaction. After the reaction is completed, remove the solvent under reduced pressure to obtain an organosilicon crosslinking agent;

[0010] (2) Add organosilicon monomers and acrylic monomers to an aqueous solution of an emulsifier, stir and emulsify evenly, add an initiator, and heat for polymerization reaction to obtain a silicon-acrylic emulsion;

[0011] (3) Mix the organosilicon crosslinking agent obtained in step (1) with a polyether silicone oil emulsifier evenly, add it to the silicon-acrylic emulsion in step (2), heat for hydrolysis crosslinking reaction, and after the reaction is completed, add a filler and stir to mix evenly to obtain an anti-aging and easy-to-stick tile adhesive.

[0012] The amino-terminated silicone oil described in step (1) uses amino-terminated silicone oil (bis(3-aminopropyl) terminated polydimethylsiloxane) with a number-average molecular weight of 1000-20000. It is a conventional raw material in the art, and its structural formula is as follows:

[0013]

[0014] The epoxy group-containing silane coupling agent described in step (1) uses 3-(2,3-epoxypropoxy)propyltrimethoxysilane or 3-(2,3-epoxypropoxy)propyltriethoxysilane.

[0015] The molar ratio of the amino-terminated silicone oil and the epoxy group-containing silane coupling agent described in step (1) is 1:3-5. Under the above molar ratio conditions, an organosilicon crosslinking agent with multiple crosslinking active sites can be obtained. The synthesis of the organosilicon crosslinking agent of the present invention involves the following reaction formula:

[0016]

[0017] Both ends of the above organosilicon crosslinking agent contain a large number of active silane oxy groups, which can effectively carry out hydrolysis crosslinking reaction with the silanol groups after hydrolysis of the organosilicon monomers in the silicon-acrylic emulsion, thereby improving the water resistance and heat resistance of the resin; at the same time, the remaining uncrosslinked silanol coupling groups after its hydrolysis can continuously enhance the binding force with the filler and the matrix, thereby improving the bonding strength and the operable time; in addition, it introduces a polysiloxane chain with good anti-aging property and flexibility, thereby improving the anti-aging property and bonding stability of the obtained tile adhesive.

[0018] The anhydrous diluting solvent described in step (1) uses one or several of toluene, xylene, petroleum ether, and carbon tetrachloride.

[0019] The temperature of the stirring reaction in step (1) is 40-80°C, and the time is 2-6h.

[0020] In step (2), the organosilicon monomer is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane.

[0021] In step (2), the acrylic monomer is one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0022] In step (2), the mass ratio of the added organosilicon monomer to the acrylic monomer is 0.1-0.4:1.

[0023] In step (2), the aqueous emulsifier solution is an aqueous solution of sodium allyloxyhydroxypropylsulfonate, ammonium allyloxynonylphenol polyoxyethylene ether sulfate, ammonium alkylphenol polyoxyethylene ether sulfate, allyloxynonylphenol polyoxyethylene ether, or alkylphenol polyoxyethylene ether with a mass concentration of 4%-8%.

[0024] In step (2), the initiator is ammonium persulfate or potassium persulfate, and the addition amount of the initiator is 0.2%-0.8% of the total mass of the polymerization monomers; the temperature of the heating polymerization reaction is 60-80°C, and the time is 2-4h.

[0025] In step (2), the solid content of the silicone-acrylic emulsion is 20%-50%.

[0026] In step (3), the dosage of the polyether silicone emulsifier is 5%-20% of the mass of the organosilicon crosslinking agent; the addition amount of the organosilicon crosslinking agent is 5%-20% of the total mass of the organosilicon monomer and the acrylic monomer in step (2); the temperature of the hydrolysis crosslinking reaction is 40-80°C, and the time is 1-3h.

[0027] In the present invention, by adding the polyether silicone emulsifier, on the one hand, it can better promote the mixing of the organosilicon crosslinking agent in the silicone-acrylic emulsion, thereby improving its crosslinking modification effect. On the other hand, it can be used as an antifoaming agent and a leveling agent for the finally obtained tile adhesive, improving the workability of the tile adhesive.

[0028] In step (3), the filler is one or more of portland cement, calcium carbonate, and silica white; the addition amount of the filler is 10%-60% of the mass of the silicone-acrylic emulsion.

[0029] An anti-aging and easy-to-paste tile adhesive is prepared by the above method.

[0030] Compared with the prior art, the beneficial effects of the present invention are:

[0031] (1) The tile adhesive of the present invention uses a silicone-acrylic emulsion as the main binder and is mixed and cross-linked and modified with a specific silicone cross-linking agent. On the one hand, the cross-linking enhances the cohesion, improves the polymer bonding strength, heat resistance and water resistance; on the other hand, the silicone cross-linking agent introduces a polysiloxane chain with good anti-aging property and flexibility, thereby improving the anti-aging property and bonding stability of the obtained tile adhesive.

[0032] (2) The present invention introduces a large number of hydrolyzed silanol coupling groups through the silicone cross-linking agent, which can continuously carry out coupling reactions with the filler and the bonding matrix, thereby significantly improving the bonding strength and open time of the tile adhesive, and making it easier to apply the adhesive for tiling. Detailed implementation mode

[0033] The present invention will be further described in detail below in conjunction with the embodiments, but the implementation modes of the present invention are not limited thereto.

[0034] Example 1

[0035] A preparation method of an anti-aging and easy-to-apply tile adhesive includes the following preparation steps:

[0036] (1) The amino-terminated silicone oil with an average molecular weight of 5000 and 3-(2,3-epoxypropoxy)propyltrimethoxysilane are added to toluene solvent for mixing and dissolution. The molar ratio of the amino-terminated silicone oil to the epoxy group silane coupling agent is 1:4.4, and then the temperature is raised to 60 °C and stirred for 4 h. The amino group is completely reacted by titration method, and the toluene solvent is removed under vacuum to obtain the silicone cross-linking agent.

[0037] (2) The organosilicon monomer γ-methacryloxypropyltrimethoxysilane, methyl methacrylate and butyl acrylate are added to an aqueous solution of 5% emulsifier (nonylphenol polyoxyethylene ether) according to the mass ratio of 0.3:0.5:0.5 and stirred until emulsified evenly. Under nitrogen protection, the temperature is raised to 75 °C, and 0.4% ammonium persulfate is added and kept warm for reaction for 3 h to obtain a silicone-acrylic emulsion with a solid content of 40%.

[0038] (3) 10 parts of the silicone cross-linking agent obtained in step (1) and 1 part of polyether silicone oil emulsifier are mixed evenly, added to 200 parts of the silicone-acrylic emulsion in step (2), and continue to keep warm at 70-75 °C for hydrolysis cross-linking reaction for 2 h, and then 40 parts of portland cement, 20 parts of calcium carbonate and 10 parts of white carbon black are added and stirred and mixed evenly to obtain the anti-aging and easy-to-apply tile adhesive.

[0039] Example 2

[0040] A preparation method of an anti-aging and easy-to-apply tile adhesive includes the following preparation steps:

[0041] (1) Add the amino-terminated silicone oil with an average molecular weight of 2000 and 3-(2,3-epoxypropoxy)propyltriethoxysilane into toluene solvent and mix them until dissolved. The molar ratio of the amino-terminated silicone oil to the epoxy-functional silane coupling agent is 1:4.0. Then, heat up to 50 °C and stir for 6 h. Determine that the amino groups have completely reacted by titration method, and remove the toluene solvent under vacuum to obtain the silicone crosslinking agent.

[0042] (2) Add the organosilicon monomer γ-methacryloxypropyltrimethoxysilane, acrylic acid, 2-hydroxyethyl methacrylate, and butyl acrylate into the aqueous solution of 4% emulsifier (nonylphenol polyoxyethylene ether) according to the mass ratio of 0.2:0.1:0.4:0.5, stir and emulsify evenly. Under nitrogen protection, heat up to 75 °C, add 0.4% ammonium persulfate, and keep the temperature for reaction for 3 h to obtain the silicone-acrylic emulsion with a solid content of 30%.

[0043] (3) Mix 5 parts of the silicone crosslinking agent obtained in step (1) with 1 part of the polyether silicone oil emulsifier evenly, add it into 200 parts of the silicone-acrylic emulsion in step (2), continue to keep the temperature at 70 - 75 °C for hydrolysis crosslinking reaction for 2 h, then add 40 parts of portland cement, 20 parts of calcium carbonate, and 10 parts of silica white, stir and mix evenly to obtain the anti-aging and easy-to-paste tile adhesive.

[0044] Example 3

[0045] A preparation method of an anti-aging and easy-to-paste tile adhesive, comprising the following preparation steps:

[0046] (1) Add the amino-terminated silicone oil with an average molecular weight of 1000 and 3-(2,3-epoxypropoxy)propyltriethoxysilane into toluene solvent and mix them until dissolved. The molar ratio of the amino-terminated silicone oil to the epoxy-functional silane coupling agent is 1:3.0. Then, heat up to 40 °C and stir for 4 h. Determine that the amino groups have completely reacted by titration method, and remove the toluene solvent under vacuum to obtain the silicone crosslinking agent.

[0047] (2) Add the organosilicon monomer vinyltrimethoxysilane, acrylic acid, 2-hydroxyethyl methacrylate, and butyl acrylate into the aqueous solution of 4% emulsifier (nonylphenol polyoxyethylene ether) according to the mass ratio of 0.1:0.2:0.3:0.5, stir and emulsify evenly. Under nitrogen protection, heat up to 75 °C, add 0.4% ammonium persulfate, and keep the temperature for reaction for 3 h to obtain the silicone-acrylic emulsion with a solid content of 30%.

[0048] (3) Mix 5 parts of the silicone crosslinking agent obtained in step (1) with 1 part of the polyether silicone oil emulsifier evenly, add it into 100 parts of the silicone-acrylic emulsion in step (2), continue to keep the temperature at 70 - 75 °C for hydrolysis crosslinking reaction for 2 h, then add 20 parts of portland cement, 5 parts of calcium carbonate, and 5 parts of silica white, stir and mix evenly to obtain the anti-aging and easy-to-paste tile adhesive.

[0049] Example 4

[0050] A preparation method of an anti-aging and easy-to-stick tile adhesive, comprising the following preparation steps:

[0051] (1) Add amino-terminated silicone oil with an average molecular weight of 10,000 and 3-(2,3-epoxypropoxy)propyltrimethoxysilane to toluene solvent for mixing and dissolving. The molar ratio of amino-terminated silicone oil to epoxy group-containing silane coupling agent is 1:5.0. Then heat up to 70 °C and stir for reaction for 5 h. Determine that the amino group has completely reacted by titration method, and remove the toluene solvent under vacuum to obtain an organosilicon crosslinking agent.

[0052] (2) Add organosilicon monomer γ-methacryloxypropyltriethoxysilane, hydroxyethyl methacrylate, and butyl acrylate in a mass ratio of 0.4:0.4:0.6 to an aqueous solution of 6% emulsifier (nonylphenol polyoxyethylene ether) and stir to emulsify evenly. Heat up to 75 °C under nitrogen protection, add 0.4% ammonium persulfate and keep the temperature for reaction for 3 h to obtain a silicon-acrylic emulsion with a solid content of 45%.

[0053] (3) Mix 10 parts of the organosilicon crosslinking agent obtained in step (1) with 2 parts of polyether silicone oil emulsifier evenly, add it to 120 parts of the silicon-acrylic emulsion in step (2), continue to keep the temperature at 70-75 °C for hydrolysis crosslinking reaction for 2 h, and then add 40 parts of portland cement, 20 parts of calcium carbonate, and 10 parts of white carbon black and stir to mix evenly to obtain an anti-aging and easy-to-stick tile adhesive.

[0054] Comparative Example 1

[0055] A preparation method of a tile adhesive, compared with Example 1, without adding an organosilicon crosslinking agent for hydrolysis crosslinking reaction, comprising the following preparation steps:

[0056] (1) Add organosilicon monomer γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, and butyl acrylate in a mass ratio of 0.3:0.5:0.5 to an aqueous solution of 5% emulsifier (nonylphenol polyoxyethylene ether) and stir to emulsify evenly. Heat up to 75 °C under nitrogen protection, add 0.4% ammonium persulfate and keep the temperature for reaction for 3 h to obtain a silicon-acrylic emulsion with a solid content of 40%.

[0057] (2) Take 200 parts of the silicon-acrylic emulsion in step (1), add 40 parts of portland cement, 20 parts of calcium carbonate, and 10 parts of white carbon black and stir to mix evenly to obtain an anti-aging and easy-to-stick tile adhesive.

[0058] Comparative Example 2

[0059] A preparation method of a tile adhesive, compared with Example 1, using epoxy group-containing silane coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane to replace the organosilicon crosslinking agent for hydrolysis crosslinking reaction, comprising the following preparation steps:

[0060] (1) The organosilicon monomer γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, and butyl acrylate were added to an aqueous solution of 5% emulsifier (nonylphenol polyoxyethylene ether) according to a mass ratio of 0.3:0.5:0.5, stirred and emulsified evenly. Under nitrogen protection, the temperature was raised to 75 °C, and 0.4% ammonium persulfate was added and kept warm for reaction for 3 h to obtain a silicon-acrylic emulsion with a solid content of 40%.

[0061] (2) 10 parts of epoxy group silane coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane and 1 part of polyether silicone oil emulsifier were mixed evenly, added to 200 parts of the silicon-acrylic emulsion in step (1), and kept warm at 70-75 °C for hydrolysis cross-linking reaction for 2 h. Then, 40 parts of Portland cement, 20 parts of calcium carbonate, and 10 parts of white carbon black were added and stirred and mixed evenly to obtain an anti-aging and easy-to-paste tile adhesive.

[0062] The tile adhesives of the above examples and comparative examples were subjected to performance tests, and the test standard was JC / T 547-2017. The test results are shown in Table 1 below.

[0063] Table 1

[0064]

[0065] It can be seen from the results in Table 1 that the present invention uses an organosilicon cross-linking agent to carry out hydrolysis cross-linking modification on the silicon-acrylic resin binder, which can significantly improve the bonding strength, heat resistance, water resistance, and aging resistance of the obtained tile adhesive. At the same time, it can significantly improve the tensile bonding strength after the drying time > 20 min, extend the open time of the tile adhesive, and make it easier to apply the adhesive and paste the tiles. However, the improvement effect of using a conventional silane coupling agent on the above effects is limited. The reason is that the conventional small molecule silane coupling agent is easy to hydrolyze and self-condense and cross-link to form a T-type silicone resin, which reduces the coupling effect with the silicon-acrylic resin, filler, and bonding matrix.

[0066] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and shall be included in the protection scope of the present invention.

Claims

1. A preparation method of an anti-aging and easy-to-paste tile adhesive, characterized in that, It includes the following preparation steps: (1) Add the amino-terminated silicone oil and epoxy group-containing silane coupling agent into an anhydrous diluting solvent, mix and dissolve them, and stir for reaction. After the reaction is completed, remove the solvent under reduced pressure to obtain an organosilicon crosslinking agent; (2) Add the organosilicon monomer and acrylic monomer into an aqueous solution of an emulsifier, stir and emulsify them evenly, add an initiator, and heat for polymerization reaction to obtain a silicone-acrylic emulsion; (3) Mix the organosilicon crosslinking agent obtained in step (1) with a polyether silicone oil emulsifier evenly, add it to the silicone-acrylic emulsion in step (2), and heat for hydrolysis crosslinking reaction. After the reaction is completed, add a filler and stir and mix evenly to obtain an anti-aging and easy-to-paste tile adhesive.

2. The preparation method of an anti-aging and easy-to-paste tile adhesive according to claim 1, characterized in that, In step (1), the amino-terminated silicone oil used is an amino-terminated silicone oil with a number average molecular weight of 1000 - 20000, and its structural formula is as follows: The epoxy group-containing silane coupling agent used is 3-(2,3-epoxypropoxy)propyltrimethoxysilane or 3-(2,3-epoxypropoxy)propyltriethoxysilane.

3. The preparation method of an anti-aging and easy-to-stick tile adhesive according to claim 2, wherein, The molar ratio of the amino-terminated silicone oil to the epoxy group-containing silane coupling agent is 1:3 - 5.

4. The preparation method of an anti-aging and easy-to-paste tile adhesive according to claim 1, characterized in that, In step (1), the anhydrous diluting solvent used is one or several of toluene, xylene, petroleum ether, and carbon tetrachloride; the temperature of the stirring reaction is 40 - 80 °C, and the time is 2 - 6 h.

5. The preparation method of an anti-aging and easy-to-stick tile adhesive according to claim 1, characterized in that, In step (2), the organosilicon monomer used is one or several of vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltriethoxysilane; the acrylic monomer used is one or several of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate; the mass ratio of the organosilicon monomer to the acrylic monomer added is 0.1 - 0.4:

1.

6. The preparation method of an anti-aging and easy-to-stick tile adhesive according to claim 1, characterized in that, In step (2), the aqueous solution of the emulsifier used is an aqueous solution of sodium allyloxyhydroxypropyl sulfonate, ammonium allyloxynonylphenol polyoxyethylene ether sulfate, ammonium alkylphenol polyoxyethylene ether sulfate, allyloxynonylphenol polyoxyethylene ether, or alkylphenol polyoxyethylene ether with a mass concentration of 4% - 8%; the initiator used is ammonium persulfate or potassium persulfate, and the addition amount of the initiator is 0.2% - 0.8% of the total mass of the polymerization monomers; the temperature of the heating polymerization reaction is 60 - 80 °C, and the time is 2 - 4 h.

7. The preparation method of an anti-aging and easy-to-stick tile adhesive according to claim 1, characterized in that, In step (2), the solid content of the silicone-acrylic emulsion is 20% - 50%.

8. The preparation method of an anti-aging and easy-to-paste tile adhesive according to claim 1, characterized in that, In step (3), the dosage of the polyether silicone oil emulsifier is 5% - 20% of the mass of the organosilicon crosslinking agent; the addition amount of the organosilicon crosslinking agent is 5% - 20% of the total mass of the organosilicon monomer and acrylic monomer in step (2); the temperature of the hydrolysis crosslinking reaction is 40 - 80 °C, and the time is 1 - 3 h.

9. The preparation method of an anti-aging and easy-to-paste tile adhesive according to claim 1, characterized in that, In step (3), the filler is one or more of portland cement, calcium carbonate, and silica white; the addition amount of the filler is 10% - 60% of the mass of the silicone-acrylic emulsion.

10. An anti-aging and easy-to-stick tile adhesive, characterized in that, It is prepared by the method described in any one of claims 1 - 9.

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