A water-based environmentally friendly two-component tile adhesive and preparation method thereof

Abstract

The present invention belongs to the technical field of polymer materials and adhesives, and discloses a water-based environmentally friendly two-component tile adhesive and a preparation method thereof. The two-component tile adhesive comprises a liquid material and a powder material; the liquid material comprises the following components in parts by weight: 50 to 80 parts of acrylic emulsion, 20 to 30 parts of organosilicon-modified polyurethane emulsion, and 0 to 30 parts of water; the powder material comprises the following components in parts by weight: 50 to 80 parts of silicate cement, 20 to 30 parts of quartz sand, and 2 to 10 parts of white carbon black. The organosilicon-modified polyurethane emulsion is obtained by reacting a terminal hydroxyl polyether-modified polydimethoxysiloxane with a diisocyanate, and then undergoing hydrophilic chain extension, neutralization and emulsification. The tile adhesive of the present invention uses a specific organosilicon-modified polyurethane emulsion and an acrylic emulsion for compounding, which can significantly improve the bonding force, water resistance and heat resistance of the tile adhesive.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and adhesives, and specifically relates to a water-based environmentally friendly two-component tile adhesive and a preparation method thereof. Background Art

[0002] Tile adhesives mainly include cementitious adhesives (a powdery mixture of hydraulic cementitious materials, aggregates, additives, etc.), disperslon adhesives (an organic adhesive composed of water-based polymer emulsions, additives and mineral fillers, etc.) and reaction resin adhesives (a single-component or multi-component mixture of synthetic resins, mineral fillers and additives, an adhesive cured by chemical reaction). Among them, cementitious adhesives have lower costs, but poor adhesion, flexibility and weather resistance; reaction resin adhesives have better adhesion and weather resistance, but slightly poorer stability and higher requirements for construction conditions; disperslon adhesives have been widely used due to their good stability and easy construction.

[0003] At present, the paste-like emulsion-based adhesives on the market mainly use acrylic acid solution, styrene acrylic emulsion, and polyvinyl acetate emulsion as water-based polymer emulsion components. However, single polymer emulsions generally have the defects of insufficient bonding strength, poor water resistance and heat resistance. Patent CN 115260947 A discloses a tile adhesive, which uses acrylic emulsion and water-based polyurethane emulsion as colloidal components. The coating has good bonding properties. By adding polyurethane emulsion, it can effectively improve the problem of large water absorption of acrylic emulsion, give the tile adhesive good water resistance under the premise of good flexibility, and improve the immersion bonding performance. However, the use of ordinary water-based polyurethane emulsion compound has limited effect on improving the water resistance and heat resistance of tile adhesive.

[0004] Therefore, developing a tile adhesive with strong bonding force, good water resistance and heat resistance has broad market prospects. Summary of the invention

[0005] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a water-based environmentally friendly two-component tile adhesive.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned water-based environmentally friendly two-component tile adhesive.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A water-based environmentally friendly two-component tile adhesive, comprising a liquid material and a powder material;

[0009] The liquid material comprises the following components in parts by weight: 50 to 80 parts of acrylic emulsion, 20 to 30 parts of organosilicon-modified polyurethane emulsion, and 0 to 30 parts of water;

[0010] The powder comprises the following components in parts by weight: 50-80 parts of Portland cement, 20-30 parts of quartz sand, and 2-10 parts of white carbon black;

[0011] The organosilicon-modified polyurethane emulsion is prepared by the following method:

[0012] Add terminal hydroxyl polyether modified polydimethoxysiloxane, diisocyanate and organotin catalyst into a reaction kettle and stir to mix evenly, heat to 70-85°C and stir to react until the NCO group content is 0.5%-2%, then add DMPA (2,2-dihydroxymethylpropionic acid) or DMBA (2,2-dihydroxymethylbutyric acid) butanone solution and continue to stir to react until the NCO group content is less than 0.2%, after the reaction is completed, cool to below 50°C, add triethylamine acetone solution for neutralization, then add deionized water for stirring and emulsification, and evaporate the organic solvent under reduced pressure to obtain an organosilicon modified polyurethane emulsion.

[0013] The terminal hydroxyl polyether modified polydimethoxysiloxane is a conventional raw material in the art, and its structural formula is as follows:

[0014]

[0015] Where A is -CH2CH2CH2(OCH2CH2) a (OCH2CH(CH3)) b OH-terminated hydroxyl polyether; n is an integer of 1 to 50, a is an integer of 1 to 20, and b is an integer of 0 to 10.

[0016] The diisocyanate is preferably hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI).

[0017] The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate added is 1:1.5-2 (OH / NCO).

[0018] The organotin catalyst is preferably dibutyltin dilaurate.

[0019] The added amount of DMPA or DMBA is preferably 1% to 5% of the total mass of the terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate; the added amount of triethylamine is 1% to 5% of the total mass of the terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate.

[0020] The solid content of the organosilicon-modified polyurethane emulsion is 30% to 50%.

[0021] The acrylic emulsion includes pure acrylic emulsion, silicone acrylic emulsion, styrene acrylic emulsion, acetic acid acrylic emulsion and the like commonly used in the market; more preferably, the acrylic emulsion is a silicone-modified acrylic emulsion prepared by the following method:

[0022] (1) adding hydroxyl-terminated polyether-modified polydimethoxysiloxane, isocyanate ethyl acrylate and an organotin catalyst into a reaction kettle and stirring and mixing them evenly, heating to 70-85° C. and stirring and reacting until the NCO group content is less than 0.1%, thereby obtaining an organosilicon-modified acrylate macromonomer;

[0023] (2) adding the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer into the emulsifier aqueous solution and stirring to emulsify uniformly, heating to 60-80° C. under nitrogen protection, adding an initiator and maintaining the temperature for reaction, thereby obtaining an organosilicon-modified acrylic emulsion.

[0024] The raw materials such as the terminal hydroxyl polyether modified polydimethoxysiloxane and the organotin catalyst used in the preparation process of the acrylic emulsion are from the same source as the raw materials used in the preparation process of the organosilicon modified polyurethane emulsion, and will not be described in detail here.

[0025] The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to isocyanate ethyl acrylate added in step (1) is 1:1.5-2.

[0026] The acrylic acid monomer in step (2) is (meth)acrylic acid; the acrylic acid ester monomer is one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0027] The mass ratio of the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer added in step (2) is 1:1-3:2-4.

[0028] The emulsifier aqueous solution in step (2) is an aqueous solution of sodium allyloxyhydroxypropane sulfonate, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, alkylphenol polyoxyethylene ether ammonium sulfate, allyloxy nonylphenol polyoxyethylene ether, and alkylphenol polyoxyethylene ether with a mass concentration of 4% to 8%.

[0029] The initiator in step (2) is ammonium persulfate or potassium persulfate, and the amount of the initiator added is 0.2% to 0.8% of the total mass of the polymerization monomers.

[0030] The solid content of the organosilicon-modified acrylic emulsion is 30% to 60%.

[0031] The preparation method of the above-mentioned water-based environmentally friendly two-component tile adhesive comprises the following preparation steps:

[0032] (a) adding acrylic emulsion and organosilicon-modified polyurethane emulsion into a mixing tank, stirring and mixing, and then adding water to adjust the solid content to 30% to 50% to obtain a liquid material;

[0033] (b) Add silicate cement, quartz sand and white carbon black into a dry powder mixer and stir to mix well to obtain powder.

[0034] When the water-based environmentally friendly two-component tile adhesive obtained by the present invention is used, the liquid material and the powder material are directly mixed in a mass ratio of 2 to 4:1 and then applied.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The tile adhesive of the present invention is composed of liquid and powder, and has good adhesion and environmental protection characteristics of water as a dispersion medium. It is an anti-stripping treatment agent and enhancer with strong adhesion. It can solve the delamination of vitrified tiles, marble, granite and the like with low water absorption, and can effectively solve the problem of hollowing and falling tiles.

[0037] (2) The present invention uses a specific silicone-modified polyurethane emulsion and an acrylic emulsion for compounding, which can significantly improve the bonding strength, water resistance and heat resistance of the tile adhesive.

[0038] (3) The present invention can further adopt a specific silicone-modified acrylic emulsion. Compared with the silicone-acrylic emulsion prepared by conventional short-chain organosilanes, on the one hand, the mixing compatibility of acrylic emulsion and silicone-modified polyurethane emulsion is improved, and the compounding performance is further improved; on the other hand, the introduction of long-chain silicone side chains and cross-linked structures further improves the adhesion, water resistance and heat resistance of the tile adhesive. DETAILED DESCRIPTION

[0039] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0040] Example 1

[0041] A water-based environmentally friendly two-component tile adhesive, comprising a liquid material and a powder material;

[0042] The liquid material comprises the following components in parts by weight: 60 parts of pure acrylic emulsion (commercially available, solid content 48%), 25 parts of organosilicon-modified polyurethane emulsion (solid content 42%), and 2.7 parts of water.

[0043] The powder comprises the following components in parts by weight: 70 parts of silicate cement, 25 parts of quartz sand, and 5 parts of white carbon black.

[0044] The organosilicon-modified polyurethane emulsion is prepared by the following method:

[0045] The terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 2000, and the terminal hydroxyl polyether is propyl polyoxyethylene ether with an average molecular weight of 800) is dehydrated under reduced pressure, added into a reaction kettle, and stirred and mixed evenly with hexamethylene diisocyanate (HDI) and a catalytic amount of dibutyltin dilaurate. The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to HDI is 1:1.8. The temperature is raised to 80°C and stirred for 2.5 hours. The NCO content of the product is detected to be 1.02%. Add 2.4% DMPA butanone solution of the total mass of terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate and continue to stir and react for 1.5 hours. The NCO group content of the product is detected to be 0.16%. After the reaction is completed, the temperature is lowered to below 50°C, and triethylamine acetone solution with the same mass as DMPA is added for neutralization and stirring reaction for 0.5 hours. Deionized water is added and stirred for emulsification, and the organic solvent (acetone and butanone) is evaporated under reduced pressure. Deionized water is added during the evaporation process to obtain a silicone modified polyurethane emulsion with a solid content of 42%.

[0046] Example 2

[0047] A water-based environmentally friendly two-component tile adhesive, comprising a liquid material and a powder material;

[0048] The liquid material comprises the following components in parts by weight: 80 parts of pure acrylic emulsion (commercially available, solid content 48%), 20 parts of organosilicon-modified polyurethane emulsion (solid content 50%), and 7.6 parts of water.

[0049] The powder comprises the following components in parts by weight: 50 parts of silicate cement, 30 parts of quartz sand, and 10 parts of white carbon black.

[0050] The organosilicon-modified polyurethane emulsion is prepared by the following method:

[0051] The terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 1000, and the terminal hydroxyl polyether is propyl polyoxyethylene polyoxypropylene ether with an average molecular weight of 600) is dehydrated under reduced pressure, and then added into the reaction kettle with isophorone diisocyanate (IPDI) and a catalytic amount of dibutyltin dilaurate, and stirred and mixed evenly. The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to IPDI is 1:1.5. The temperature is raised to 75°C and stirred for 3 hours. The NCO group content of the product is detected to be 0.85%. , then add DMPA butanone solution with a total mass of 1.8% of terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate, continue to stir and react for 2 hours, and the NCO group content of the product is detected to be 0.13%. After the reaction is completed, the temperature is lowered to below 50°C, and then triethylamine acetone solution with the same mass as DMPA is added for neutralization and stirring reaction for 0.5 hours, and then deionized water is added for stirring and emulsification, and the organic solvent (acetone and butanone) is evaporated under reduced pressure. Deionized water is added during the evaporation process to obtain a silicone-modified polyurethane emulsion with a solid content of 50%.

[0052] Example 3

[0053] A water-based environmentally friendly two-component tile adhesive, comprising a liquid material and a powder material;

[0054] The liquid material comprises the following components in parts by weight: 50 parts of pure acrylic emulsion (commercially available, with a solid content of 48%) and 30 parts of organosilicon-modified polyurethane emulsion (with a solid content of 36%).

[0055] The powder comprises the following components in parts by weight: 80 parts of silicate cement, 20 parts of quartz sand, and 2 parts of white carbon black.

[0056] The organosilicon-modified polyurethane emulsion is prepared by the following method:

[0057] The terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 3000, and the terminal hydroxyl polyether is propyl polyoxyethylene ether with an average molecular weight of 1200) is added into a reaction kettle after decompression dehydration, toluene diisocyanate (TDI) and a catalytic amount of dibutyltin dilaurate, and stirred and mixed evenly. The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to TDI is 1:1.9. The temperature is raised to 85°C and stirred for 2.5 hours. The NCO content of the product is detected to be 1.31%. Add 3.0% of the total mass of terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate DMBA butanone solution and continue stirring to react for 2 hours. The NCO group content of the product is detected to be 0.18%. After the reaction is completed, the temperature is lowered to below 50°C, and triethylamine acetone solution with the same mass as DMBA is added for neutralization and stirring reaction for 0.5 hours. Deionized water is added and stirred for emulsification, and the organic solvents (acetone and butanone) are evaporated under reduced pressure. Deionized water is added during the evaporation process to obtain a silicone modified polyurethane emulsion with a solid content of 36%.

[0058] Example 4

[0059] A water-based environmentally friendly two-component tile adhesive, compared with Example 1, uses silicone acrylic emulsion (commercially available, solid content 48%) to replace pure acrylic emulsion, and the rest is the same.

[0060] Example 5

[0061] A water-based environmentally friendly two-component tile adhesive, compared with Example 1, uses silicone-modified acrylic emulsion (solid content 48%) to replace pure acrylic emulsion, and the rest is the same.

[0062] The preparation method of the organosilicon-modified acrylic emulsion is:

[0063] (1) Add terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 2000, and the terminal hydroxyl polyether is propyl polyoxyethylene ether with an average molecular weight of 800) and ethyl isocyanate acrylate in a molar ratio of 1:1.8 and a catalytic amount of dibutyltin dilaurate into a reaction kettle and stir to mix evenly. Heat to 80° C. and stir to react for 4 hours. The NCO group content of the product is detected to be 0.09%, thereby obtaining a silicone modified acrylate macromonomer.

[0064] (2) Add the organosilicon-modified acrylate macromonomer, acrylic acid, methyl methacrylate and butyl acrylate in a mass ratio of 1:1.5:1:1.5 to a 5% aqueous solution of an emulsifier (composed of allyloxy nonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stir to emulsify evenly. Heat to 75°C under nitrogen protection, add 0.4% ammonium persulfate and keep warm for 4 hours to obtain an organosilicon-modified acrylic emulsion.

[0065] Comparative Example 1

[0066] A water-based environmentally friendly two-component tile adhesive, compared with Example 1, uses commercially available polyurethane emulsion (R8402B water-based polyurethane emulsion of Guangzhou Ruilin New Materials Co., Ltd., solid content 42%) to replace the silicone-modified polyurethane emulsion, and the rest is the same.

[0067] Comparative Example 2

[0068] A water-based environmentally friendly two-component tile adhesive, compared with Example 5, uses commercially available polyurethane emulsion (Guangzhou Ruilin New Materials Co., Ltd., R8402B water-based polyurethane emulsion, solid content 42%) to replace the silicone-modified polyurethane emulsion, and the rest is the same.

[0069] The tile adhesives of the above embodiments and comparative examples were subjected to performance tests, wherein the liquid material and the powder material were mixed at a mass ratio of 2:1, and the test standard was JC / T 547-2017. The test results are shown in Table 1 below.

[0070] Table 1

[0071]

[0072]

[0073] From the comparison results of Examples 1 to 4 and Comparative Example 1 in Table 1, it can be seen that the specific organosilicon-modified polyurethane emulsion and acrylic emulsion used in the present invention can significantly improve the bonding force, water resistance and heat resistance of the tile adhesive compared with conventional polyurethane emulsions. From the comparison results of Example 5 with Examples 1 to 4 and Comparative Example 2, it can be seen that the organosilicon-modified acrylic emulsion of the present invention and the organosilicon-modified polyurethane emulsion are used in combination, and the bonding force, water resistance and heat resistance of the obtained tile adhesive are further significantly improved compared with conventional acrylic emulsions.

[0074] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A water-based environmentally friendly two-component tile adhesive, characterized in that: Including liquid and powder; The liquid material comprises the following components in parts by weight: 50-80 parts of acrylic emulsion, 20-30 parts of silicone-modified polyurethane emulsion, and 0-30 parts of water; The powder comprises the following components in parts by weight: 50-80 parts of Portland cement, 20-30 parts of quartz sand, and 2-10 parts of white carbon black; The organosilicon-modified polyurethane emulsion is prepared by the following method: Add terminal hydroxyl polyether modified polydimethoxysiloxane, diisocyanate and organotin catalyst into a reaction kettle and stir and mix evenly, heat to 70-85°C and stir to react until the NCO group content is 0.5%-2%, then add DMPA or DMBA butanone solution and continue to stir to react until the NCO group content is less than 0.2%, cool to below 50°C after the reaction is completed, add triethylamine acetone solution for neutralization, then add deionized water for stirring and emulsification, and evaporate the organic solvent under reduced pressure to obtain organosilicon modified polyurethane emulsion; The acrylic emulsion is a silicone-modified acrylic emulsion prepared by the following method: (1) Adding terminal hydroxyl polyether modified polydimethoxysiloxane, isocyanate ethyl acrylate and organotin catalyst into a reaction kettle and stirring and mixing them evenly, heating to 70-85° C. and stirring and reacting until the NCO group content is less than 0.1%, thereby obtaining an organosilicon modified acrylate macromonomer; (2) Adding the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer into the emulsifier aqueous solution and stirring to emulsify evenly, heating to 60-80°C under nitrogen protection, adding an initiator and keeping the temperature to react, thereby obtaining an organosilicon-modified acrylic emulsion.

2. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The structural formula of the hydroxy-terminated polyether-modified polydimethoxysiloxane is as follows: ， Where A is -CH2CH2CH2(OCH2CH2) a (OCH2CH(CH3)) b OH-terminated polyether; n is an integer of 1 to 50, a is an integer of 1 to 20, and b is an integer of 0 to 10; The diisocyanate is hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate or diphenylmethane diisocyanate; The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate added is 1:1.5-2.

3. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The amount of DMPA or DMBA added is 1% to 5% of the total mass of the terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate; the amount of triethylamine added is 1% to 5% of the total mass of the terminal hydroxyl polyether modified polydimethoxysiloxane and diisocyanate.

4. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The solid content of the silicone-modified polyurethane emulsion is 30% to 50%.

5. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to isocyanate ethyl acrylate added in step (1) is 1:1.5-2.

6. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The acrylic acid monomer in step (2) is (meth)acrylic acid; the acrylic acid ester monomer is one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

7. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The mass ratio of the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer added in step (2) is 1:1~3:2~4.

8. The water-based environmentally friendly two-component tile adhesive according to claim 1, characterized in that: The emulsifier aqueous solution in step (2) is an aqueous solution of sodium allyloxyhydroxypropane sulfonate, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, alkylphenol polyoxyethylene ether ammonium sulfate, allyloxy nonylphenol polyoxyethylene ether, and alkylphenol polyoxyethylene ether with a mass concentration of 4% to 8%; the initiator is ammonium persulfate or potassium persulfate, and the amount of the initiator added is 0.2% to 0.8% of the total mass of the polymerized monomers.

9. The method for preparing a water-based environmentally friendly two-component tile adhesive according to any one of claims 1 to 8, characterized in that: The method comprises the following preparation steps: (a) adding acrylic emulsion and silicone-modified polyurethane emulsion into a mixing tank, stirring and mixing, and then adding water to adjust the solid content to 30% to 50% to obtain a liquid material; (b) Add silicate cement, quartz sand and white carbon black into a dry powder mixer and stir to obtain powder.

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