High-strength ceramic tile binder and preparation method thereof

Abstract

The invention belongs to the technical field of polymer materials and binders, and particularly relates to a high-strength ceramic tile binder and a preparation method thereof. The method comprises the following preparation steps: (1) adding polyether polyol, an isocyanate-based silane coupling agent and an organic tin catalyst into an organic solvent, and mixing and reacting to obtain an MS polymer; (2) mixing and reacting vinyl MQ silicon resin and a hydrogen-containing silane coupling agent under the condition of a hydrosilylation catalyst to obtain an activity enhancer; and (3) uniformly stirring and mixing the MS polymer, the activity enhancer, the filler, the plasticizer and the catalyst under an anhydrous condition to obtain the high-strength ceramic tile adhesive. According to the ceramic tile adhesive disclosed by the invention, the low-cost MS polymer is used as the base adhesive, and the product obtained by reacting the vinyl MQ silicon resin with the hydrogen-containing silane coupling agent is used as the activity enhancer, so that the bonding strength, heat resistance and water resistance of the ceramic tile adhesive can be remarkably improved.

Description

Technical Field

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

[0002] MS polymer is a silane-terminated polyether polymer, which has good water and weather resistance, high and low temperature resistance, and high elastic properties, and has been widely used in the fields of bonding, caulking, sealing, waterproofing, and reinforcement in construction engineering and decoration.

[0003] Patent CN 114249886 A discloses an anti-aging modified silane-terminated polyether resin, an MS nail-free glue and a preparation method thereof, which are prepared from a silane-terminated polyether resin and a reactive functional auxiliary agent. However, the main bonding resin, the silane-terminated polyether resin, is prepared by the catalytic reaction of acrylate-terminated polyether and vinyl silane under an olefin metathesis catalyst, and the olefin metathesis reaction catalyst is a ruthenium-based metal catalyst or a molybdenum-based metal catalyst, and its preparation method is complex and the cost is high.

[0004] Wang Hongyu et al. disclosed a moisture-curing elastic adhesive using α-silane-terminated polyether as a polymer (2010.18, China Building Waterproof, 22~24), and the obtained product has strong formula adjustability and can be used to prepare adhesives for various different purposes. However, the raw material source of α-alkoxysilane is limited and the cost is high. Currently, the reaction-based silane raw materials on the market are generally γ-alkoxysilanes (such as 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane, etc.). The problems of γ-alkoxysilane-terminated polyether are low moisture-curing crosslinking activity and poor bonding performance, resulting in inapplicability to application scenarios with high requirements for bonding strength. Summary of the Invention

[0005] Aiming at the above-mentioned disadvantages and deficiencies of the prior art, the primary object of the present invention is to provide a preparation method of a high-strength tile adhesive.

[0006] Another object of the present invention is to provide a high-strength 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 a high-strength tile adhesive includes the following preparation steps:

[0009] (1) Preparation of MS polymer: Polyether polyol, isocyanate group silane coupling agent and organotin catalyst are added to an organic solvent and mixed for reaction to obtain an MS polymer;

[0010] (2)Preparation of the activity enhancer: The vinyl MQ silicone resin and the hydrosilane coupling agent are mixed and reacted under the condition of a hydrosilylation catalyst to obtain the activity enhancer;

[0011] (3)Preparation of the high-strength tile adhesive: The MS polymer, the activity enhancer, the filler, the plasticizer and the catalyst are stirred and mixed evenly under anhydrous conditions to obtain the high-strength tile adhesive.

[0012] In step (1), the polyether polyol used is polyethylene glycol or polypropylene glycol with a number average molecular weight of 3000 - 15000.

[0013] In step (1), the isocyanate group-containing silane coupling agent used is 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane.

[0014] In step (1), the molar ratio of the polyether polyol to the isocyanate group-containing silane coupling agent in the reaction is 1:2.

[0015] In step (1), the synthesis principle of the MS polymer is that the hydroxyl group of the polyether polyol reacts with the isocyanate group of the isocyanate group-containing silane coupling agent under the condition of an organotin catalyst to form a silicone-capped polyurethane structure.

[0016] In step (1), the organotin catalyst is dibutyltin dilaurate.

[0017] In step (1), the organic solvent is one or more of acetone, ethyl acetate, N,N-dimethylformamide, and tetrahydrofuran.

[0018] In step (1), the temperature of the mixing reaction is 50 - 70 °C, and the time is 1 - 4 h.

[0019] In step (2), the vinyl MQ silicone resin used is a vinyl MQ silicone resin with a number average molecular weight of 2000 - 5000 and a vinyl content of 2 - 5% (mass percentage).

[0020] In step (2), the hydrosilane coupling agent used is trimethoxysilane or triethoxysilane.

[0021] In step (2), the addition amount of the hydrosilane coupling agent is 1 - 1.2 times the vinyl molar amount of the vinyl MQ silicone resin. By adding a slightly excessive hydrosilane coupling agent, the vinyl addition reaction of the vinyl MQ silicone resin to graft the silyl group can be promoted, and the excessive hydrosilane coupling agent can be removed by vacuum distillation to improve the product stability.

[0022] In step (2), the hydrosilylation catalyst used is Karstedt catalyst (platinum vinylsiloxane catalyst).

[0023] In step (2), the temperature of the mixing reaction is 50 - 70°C, and the time is 1 - 4 h.

[0024] The principle of the activity enhancer in step (2) is that the vinyl group of vinyl MQ silicone resin reacts with the silicon - hydrogen group of the hydrogen - containing silane coupling agent under the condition of a catalyst to carry out a hydrosilylation reaction, generating a high - steric - hindrance activity enhancer with a large number of active silanes on the periphery. This reaction has strong specificity and no gel phenomenon. The obtained product can significantly reduce the hydrolysis cross - linking tendency of the silane coupling agent itself, and promote the wet - curing cross - linking reaction with the terminal silane of the MS polymer. At the same time, a large number of active silanes can enhance the binding force with the filler and the bonding base surface, thus significantly improving the curing efficiency and bonding strength of the MS polymer - based adhesive.

[0025] In step (3), the filler used is one or two of calcium carbonate and silica.

[0026] In step (3), the plasticizer used is polyethylene glycol or polypropylene glycol with a number - average molecular weight of 400 - 4000.

[0027] In step (3), the catalyst is dibutyltin dilaurate.

[0028] In step (3), the mass - part ratio of each component is as follows: 100 parts of MS polymer, 1 - 10 parts of activity enhancer, 100 - 200 parts of filler, 50 - 100 parts of plasticizer, and 0.5 - 1 part of catalyst.

[0029] A high - strength tile adhesive is prepared by the above - mentioned method.

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

[0031] (1) The base adhesive of the high - strength tile adhesive of the present invention uses an MS polymer obtained by reacting polyether polyol with an isocyanate - group - containing silane coupling agent, which has the advantages of wide raw material sources and low cost.

[0032] (2) The present invention uses the product obtained by reacting vinyl MQ silicone resin with a hydrogen - containing silane coupling agent as an activity enhancer. This reaction has strong specificity, no gel phenomenon, and high synthesis stability. The obtained product has a large number of highly active silane groups, which can significantly promote the wet - curing cross - linking reaction with the terminal silane of the MS polymer, and can enhance the binding force with the filler and the bonding base surface, thus significantly improving the curing efficiency and bonding strength of the MS polymer - based adhesive. Detailed implementation mode

[0033] The following further describes the present invention in detail with reference to examples, but the implementation modes of the present invention are not limited thereto.

[0034] Example 1

[0035] A preparation method of a high-strength tile adhesive, comprising the following preparation steps:

[0036] (1) Preparation of MS polymer: Polypropylene glycol with a number-average molecular weight of 8000 and 3-isocyanatopropyltrimethoxysilane are added to an acetone solvent dehydrated by nitrogen in a molar ratio of 1:2. Then, a catalyst of dibutyltin dilaurate with a mass concentration of 0.2% is added and stirred to dissolve evenly. The mixture is heated and stirred under reflux for 3 h. After determining that the hydroxyl value of the product has completely reacted, the solvent is removed by distillation under reduced pressure to obtain the MS polymer.

[0037] (2) Preparation of the activity enhancer: Vinyl MQ silicone resin (viscosity 3800 cs) with a number-average molecular weight of 3000 and a vinyl content of 3.2 wt% and trimethoxysilane are added to a reaction flask dehydrated by nitrogen and mixed evenly. The addition amount of trimethoxysilane is 1.1 times the molar amount of vinyl contained in the vinyl MQ silicone resin. Then, a Karstedt catalyst with a concentration of 100 ppm is added, and the temperature is raised to 60 °C and stirred for 3 h. After determining that the vinyl of the product has completely reacted, the unreacted raw materials are removed by distillation under reduced pressure to obtain the activity enhancer.

[0038] (3) Preparation of the high-strength tile adhesive: 100 parts by mass of the MS polymer, 6 parts by mass of the activity enhancer, 100 parts by mass of heavy calcium carbonate, 30 parts by mass of silica white, 70 parts by mass of PPG-2000 plasticizer, and 0.8 parts by mass of dibutyltin dilaurate are stirred and mixed evenly under nitrogen protection to obtain the high-strength tile adhesive.

[0039] The tile adhesive obtained in this example is subjected to performance testing, and the test standard is JC / T 547-2017. The test results show that the shear bond strength is 3.6 MPa; the shear bond strength after thermal aging is 2.9 MPa; the shear bond strength after 21 days in air and 7 days of immersion in water is 2.7 MPa.

[0040] Example 2

[0041] A preparation method of a high-strength tile adhesive, comprising the following preparation steps:

[0042] (1) Preparation of MS polymer: Polypropylene glycol with a number-average molecular weight of 5000 and 3-isocyanatopropyltriethoxysilane are added to an ethyl acetate solvent dehydrated by nitrogen in a molar ratio of 1:2. Then, a catalyst of dibutyltin dilaurate with a mass concentration of 0.2% is added and stirred to dissolve evenly. The mixture is heated to 70 °C and stirred for 2 h. After determining that the hydroxyl value of the product has completely reacted, the solvent is removed by distillation under reduced pressure to obtain the MS polymer.

[0043] (2) Preparation of the activity enhancer: Vinyl MQ silicone resin with a number-average molecular weight of 4000 and a vinyl content of 2.5 wt% (viscosity 4700 cs) and trimethoxysilane were added to a reaction flask after dehydration with nitrogen and mixed evenly. The addition amount of trimethoxysilane was 1.2 times the molar amount of vinyl contained in the vinyl MQ silicone resin. Then, a Karstedt catalyst with a concentration of 100 ppm was added, and the temperature was raised to 70 °C and stirred for reaction for 2 h. After determining that the vinyl reaction of the product was complete, the unreacted raw materials were removed by vacuum distillation to obtain the activity enhancer.

[0044] (3) Preparation of the high-strength tile adhesive: 100 parts by mass of MS polymer, 8 parts by mass of the activity enhancer, 110 parts by mass of heavy calcium carbonate, 20 parts by mass of silica, 50 parts by mass of PPG-3000 plasticizer, and 0.8 parts by mass of dibutyltin dilaurate were stirred and mixed evenly under nitrogen protection to obtain the high-strength tile adhesive.

[0045] The test results of the tile adhesive obtained in this example showed that the shear bond strength was 3.7 MPa; the shear bond strength after thermal aging was 2.8 MPa; the shear bond strength after 21 days in air and 7 days of immersion in water was 2.9 MPa.

[0046] Example 3

[0047] A preparation method of a high-strength tile adhesive, comprising the following preparation steps:

[0048] (1) Preparation of MS polymer: Polyethylene glycol with a number-average molecular weight of 3000 and 3-isocyanatopropyltriethoxysilane were added to an ethyl acetate solvent after dehydration with nitrogen at a molar ratio of 1:2, and then a dibutyltin dilaurate catalyst with a mass concentration of 0.2% was added and stirred until dissolved evenly. The temperature was raised to 50 °C and stirred for reaction for 4 h. After determining that the hydroxyl value reaction of the product was complete, the solvent was removed by vacuum distillation to obtain the MS polymer.

[0049] (2) Preparation of the activity enhancer: Vinyl MQ silicone resin with a number-average molecular weight of 5000 and a vinyl content of 2.0 wt% (viscosity 5500 cs) and trimethoxysilane were added to a reaction flask after dehydration with nitrogen and mixed evenly. The addition amount of trimethoxysilane was 1.2 times the molar amount of vinyl contained in the vinyl MQ silicone resin. Then, a Karstedt catalyst with a concentration of 100 ppm was added, and the temperature was raised to 50 °C and stirred for reaction for 4 h. After determining that the vinyl reaction of the product was complete, the unreacted raw materials were removed by vacuum distillation to obtain the activity enhancer.

[0050] (3) Preparation of high-strength tile adhesive: Stir and mix 100 parts by mass of MS polymer, 10 parts by mass of active enhancer, 120 parts by mass of heavy calcium carbonate, 20 parts by mass of silica white, 80 parts by mass of PEG-4000 plasticizer and 1.0 part by mass of dibutyltin dilaurate evenly under nitrogen protection to obtain high-strength tile adhesive.

[0051] The test results of the tile adhesive obtained in this example show that the shear bond strength is 3.8 MPa; the shear bond strength after thermal aging is 3.1 MPa; the shear bond strength after 21 days in air and 7 days of immersion in water is 2.6 MPa.

[0052] Example 4

[0053] A preparation method of high-strength tile adhesive includes the following preparation steps:

[0054] (1) Preparation of MS polymer: Add polypropylene glycol with a number average molecular weight of 12000 and 3-isocyanatopropyltrimethoxysilane into the DMF solvent dehydrated by nitrogen in a molar ratio of 1:2, then add a catalyst of dibutyltin dilaurate with a mass concentration of 0.2%, stir and dissolve evenly, heat to 60 °C and stir for reaction for 3 h, determine that the hydroxyl value of the product reacts completely, and distill off the solvent under reduced pressure to obtain MS polymer.

[0055] (2) Preparation of active enhancer: Add vinyl MQ silicone resin with a number average molecular weight of 2000 and a vinyl content of 4.6 wt% (viscosity 2200 cs) and triethoxysilane into the reaction flask dehydrated by nitrogen and mix evenly. The addition amount of triethoxysilane is 1.05 times the molar amount of vinyl contained in the vinyl MQ silicone resin. Then add a Karstedt catalyst with a concentration of 100 ppm, heat up to 60 °C and stir for reaction for 3 h, determine that the vinyl of the product reacts completely, and distill off the unreacted raw materials under reduced pressure to obtain the active enhancer.

[0056] (3) Preparation of high-strength tile adhesive: Stir and mix 100 parts by mass of MS polymer, 4 parts by mass of active enhancer, 120 parts by mass of heavy calcium carbonate, 40 parts by mass of silica white, 100 parts by mass of PPG-1000 plasticizer and 0.6 part by mass of dibutyltin dilaurate evenly under nitrogen protection to obtain high-strength tile adhesive.

[0057] The test results of the tile adhesive obtained in this example show that the shear bond strength is 3.4 MPa; the shear bond strength after thermal aging is 2.7 MPa; the shear bond strength after 21 days in air and 7 days of immersion in water is 2.7 MPa.

[0058] Example 5

[0059] A preparation method of high-strength tile adhesive includes the following preparation steps:

[0060] (1) Preparation of MS polymer: Polypropylene glycol with a number average molecular weight of 15,000 and 3-isocyanatopropyltrimethoxysilane were added to the DMF solvent dehydrated by nitrogen in a molar ratio of 1:2. Then, a catalyst of dibutyltin dilaurate with a mass concentration of 0.2% was added and stirred until dissolved evenly. The mixture was heated to 70 °C and stirred for reaction for 3 h. After determining that the hydroxyl value of the product was completely reacted, the solvent was removed by distillation under reduced pressure to obtain the MS polymer.

[0061] (2) Preparation of the activity enhancer: Vinyl MQ silicone resin with a number average molecular weight of 2,000 and a vinyl content of 4.6 wt% (viscosity 2,200 cs) and trimethoxysilane were added to a reaction flask dehydrated by nitrogen and mixed evenly. The addition amount of trimethoxysilane was 1.1 times the molar amount of vinyl contained in the vinyl MQ silicone resin. Then, a Karstedt catalyst with a concentration of 100 ppm was added, and the temperature was raised to 60 °C and stirred for reaction for 3 h. After determining that the vinyl of the product was completely reacted, the unreacted raw materials were removed by distillation under reduced pressure to obtain the activity enhancer.

[0062] (3) Preparation of the high-strength tile adhesive: 100 parts by mass of the MS polymer, 1 part by mass of the activity enhancer, 80 parts by mass of heavy calcium carbonate, 20 parts by mass of white carbon black, 60 parts by mass of PPG-400 plasticizer, and 0.5 part by mass of dibutyltin dilaurate were stirred and mixed evenly under nitrogen protection to obtain the high-strength tile adhesive.

[0063] The test results of the tile adhesive obtained in this example showed that the shear bond strength was 3.2 MPa; the shear bond strength after thermal aging was 2.5 MPa; the shear bond strength after 21 days in air and 7 days of immersion in water was 2.5 MPa.

[0064] Comparative Example 1

[0065] A preparation method of a high-strength tile adhesive, compared with Example 1, without adding the activity enhancer, and the rest are the same.

[0066] The test results of the tile adhesive obtained in this comparative example showed that the shear bond strength was 2.3 MPa; the shear bond strength after thermal aging was 1.8 MPa; the shear bond strength after 21 days in air and 7 days of immersion in water was 1.5 MPa.

[0067] It can be seen from the results of this comparative example that the activity enhancer of the present invention can significantly improve the bond strength, aging resistance and water resistance of the MS polymer-based adhesive.

[0068] Comparative Example 2

[0069] A preparation method of a high-strength tile adhesive, compared with Example 1, using a physical mixture of vinyl MQ silicone resin and trimethoxysilane to replace the activity enhancer, including the following preparation steps:

[0070] (1) The preparation of the MS polymer was the same as that in Example 1.

[0071] (2) Preparation of the high-strength tile adhesive: Stir and mix evenly 100 parts by mass of the MS polymer, 6 parts by mass of a mixture of vinyl MQ silicone resin (viscosity 3800 cs) and trimethoxysilane (the addition amount of trimethoxysilane is 1.1 times the molar amount of vinyl contained in the vinyl MQ silicone resin), 100 parts by mass of heavy calcium carbonate, 30 parts by mass of fumed silica, 70 parts by mass of PPG-2000 plasticizer, and 0.8 part by mass of dibutyltin dilaurate under nitrogen protection to obtain the high-strength tile adhesive.

[0072] The test results of the tile adhesive obtained in this comparative example showed that the shear bond strength was 2.7 MPa; the shear bond strength after thermal aging was 2.1 MPa; and the shear bond strength after 21 days in air and 7 days of immersion in water was 2.0 MPa.

[0073] It can be seen from the results of this comparative example that the improvement effect of using a mixture of vinyl MQ silicone resin and silane coupling agent for enhancement is limited.

[0074] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited to 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 are all included in the protection scope of the present invention.

Claims

1. A preparation method of a high-strength tile adhesive, characterized in that, It includes the following preparation steps: (1) Preparation of MS polymer: Polyether polyol, isocyanate-based silane coupling agent and organotin catalyst are added to an organic solvent and mixed for reaction to obtain an MS polymer; (2) Preparation of activity enhancer: Vinyl MQ silicone resin and hydrogen-containing silane coupling agent are mixed and reacted under the condition of a hydrosilylation catalyst to obtain an activity enhancer; (3) Preparation of high-strength tile adhesive: The MS polymer, activity enhancer, filler, plasticizer and catalyst are stirred and mixed evenly under anhydrous conditions to obtain a high-strength tile adhesive.

2. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (1), the polyether polyol used is polyethylene glycol or polypropylene glycol with a number average molecular weight of 3000 - 15000; the isocyanate-based silane coupling agent used is 3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilane; the molar ratio of the polyether polyol to the isocyanate-based silane coupling agent in the reaction is 1:

2.

3. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (1), the organotin catalyst used is dibutyltin dilaurate; the organic solvent is one or more of acetone, ethyl acetate, N,N-dimethylformamide, and tetrahydrofuran; the temperature of the mixing reaction is 50 - 70 °C, and the time is 1 - 4 h.

4. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (2), the vinyl MQ silicone resin used is vinyl MQ silicone resin with a number average molecular weight of 2000 - 5000 and a vinyl content of 2 - 5%; the hydrogen-containing silane coupling agent used is trimethoxysilane or triethoxysilane; the addition amount of the hydrogen-containing silane coupling agent is 1 - 1.2 times the vinyl molar amount of the vinyl MQ silicone resin.

5. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (2), the hydrosilylation catalyst used is Karstedt catalyst; the temperature of the mixing reaction is 50 - 70 °C, and the time is 1 - 4 h.

6. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (3), the filler used is one or two of calcium carbonate and silica.

7. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (3), the plasticizer used is polyethylene glycol or polypropylene glycol with a number average molecular weight of 400 - 4000.

8. The preparation method of a high-strength tile adhesive according to claim 1, characterized in that, In step (3), the catalyst used is dibutyltin dilaurate.

9. The preparation method of a high-strength tile adhesive according to any one of claims 1 to 8, characterized in that, The mass part ratio of each component in step (3) is: 100 parts of MS polymer, 1 - 10 parts of activity enhancer, 100 - 200 parts of filler, 50 - 100 parts of plasticizer, and 0.5 - 1 part of catalyst.

10. A high-strength tile adhesive, characterized in that, It is prepared by the method described in any one of claims 1 - 9.