Water-based two-component ceramic tile adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of polymer materials and binders, and discloses a water-based two-component ceramic tile binder and a preparation method thereof. The water-based double-component ceramic tile adhesive comprises a liquid material and a powder material, the liquid material is an organic silicon modified acrylic emulsion with the solid content of 30%-50%; the powder material comprises Portland cement, quartz sand and white carbon black. The organic silicon modified acrylic emulsion is obtained by carrying out hydrolysis cross-linking reaction on modified acrylic resin emulsion through a specific dendritic macromolecular cross-linking agent. According to the ceramic tile adhesive, the acrylic emulsion is subjected to cross-linking modification by adopting the dendritic macromolecular cross-linking agent, so that the adhesive strength, the water resistance and the heat resistance of the ceramic tile adhesive can be remarkably improved. And the preparation method of the dendritic macromolecular cross-linking agent is simple, wide in raw material source, low in preparation cost and easy for industrial production.

Description

Technical Field

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

[0002] Tile adhesives are a commonly used building adhesive material. According to their composition systems, they mainly include cement-based adhesives (cementitous adhesive, a powdery mixture composed of hydraulic binders, aggregates, additives, etc.), paste-like emulsion-based adhesives (disperslon adhesive, an organic adhesive composed of aqueous polymer emulsions, additives, and mineral fillers), and reactive resin adhesives (reactionresin adhesive, a one-component or multi-component mixture composed of synthetic resins, mineral fillers, and additives, and cured through chemical reactions). Among them, cement-based adhesives have a lower cost, but poor adhesion, flexibility, and weather resistance; reactive resin adhesives have good adhesion and weather resistance, but slightly poor stability and high requirements for construction conditions; paste-like emulsion-based adhesives have been widely used due to their advantages such as good stability and easy construction.

[0003] Among them, acrylic emulsion tile adhesives have been widely used in the field of building adhesives due to their advantages of using an aqueous system and low VOC environmental protection. However, pure acrylic polymer emulsions generally have defects such as insufficient adhesion, poor water resistance, and poor heat resistance. Therefore, providing an aqueous environmentally friendly tile adhesive with excellent adhesion, water resistance, and heat resistance, which can ensure the firm adhesion of tiles to the substrate, is suitable for humid environments, and can adapt to the thermal expansion and contraction differences between tiles and the substrate, reducing the risk of hollowing and peeling, has broad market prospects. Summary of the Invention

[0004] Aiming at the above-mentioned disadvantages and deficiencies of the prior art, the primary object of the present invention is to provide an aqueous two-component tile adhesive.

[0005] Another object of the present invention is to provide a preparation method of the above-mentioned aqueous two-component tile adhesive.

[0006] The object of the present invention is achieved by the following technical solutions:

[0007] An aqueous two-component tile adhesive, comprising a liquid material and a powder material; the liquid material is an organosilicon-modified acrylic emulsion with a solid content of 30% to 50%; the powder material includes portland cement, quartz sand, and silica white.

[0008] The organosilicon-modified acrylic emulsion is prepared by the following method:

[0009] (1) Add polyetheramine and epoxy group silane coupling agent into an anhydrous diluting solvent, mix and dissolve them, then stir and react at a temperature of 20 - 50 °C for 0.5 - 4 h. After the reaction is completed, remove the solvent under reduced pressure to obtain a macromolecular crosslinking agent;

[0010] (2) Add organosilicon monomer and acrylic monomer into an aqueous solution of emulsifier, stir and emulsify evenly, then add an initiator and heat for polymerization reaction for 2 - 4 h, and then add the macromolecular crosslinking agent obtained in step (1) for hydrolysis crosslinking reaction for 1 - 3 h to obtain an organosilicon-modified acrylic emulsion.

[0011] The weight part ratio of each component in the powder material is: 50 - 80 parts of portland cement, 20 - 30 parts of quartz sand, and 2 - 10 parts of white carbon black.

[0012] In step (1), the polyetheramine used is a bifunctional polyetheramine (D series) or trifunctional polyetheramine (T series) with a molecular weight of 400 - 5000.

[0013] In step (1), the epoxy group silane coupling agent used is 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0014] In step (1), the molar ratio of the polyetheramine to the epoxy group silane coupling agent is 1:3 - 7. Under the above molar ratio conditions, a dendritic macromolecular crosslinking agent can be obtained.

[0015] The silane oxy groups contained in the above dendritic macromolecular crosslinking agent can effectively carry out hydrolysis crosslinking reaction with the organosilicon monomer segments in the modified acrylic resin, thereby improving water resistance and heat resistance; at the same time, the remaining uncrosslinked silanol coupling groups after its hydrolysis can significantly enhance the binding force with the powder material and the substrate, thereby improving the adhesive force; in addition, the flexible polyether chain contained in it can effectively avoid the reduction of flexibility caused by crosslinking, thereby improving the adhesive stability.

[0016] In step (1), the anhydrous diluting solvent used is one or more of acetone, ethanol, propanol, and ethyl acetate.

[0017] In step (2), the organosilicon monomer used is one or more of vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropyltriethoxysilane.

[0018] 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.

[0019] In step (2), the mass ratio of the silicone monomer to the acrylic monomer added is 0.1 - 0.4:1.

[0020] In step (2), the emulsifier aqueous solution 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%.

[0021] 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 for the heating-induced reaction is 60 - 80°C.

[0022] In step (2), the addition amount of the macromolecular crosslinking agent is 5% - 20% of the total mass of the polymerization monomers; the temperature for the hydrolysis crosslinking reaction is 30 - 60°C.

[0023] The preparation method of the above water-based two-component tile adhesive includes the following preparation steps:

[0024] (a) Add portland cement, quartz sand, and white carbon black to a dry powder mixer and stir evenly to obtain a powder material;

[0025] (b) Divide or use the liquid material and the powder material according to a mass ratio of 2 - 4:1 to obtain a water-based two-component tile adhesive.

[0026] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0027] (1) The tile adhesive of the present invention uses a dendritic macromolecular crosslinking agent to crosslink and modify the acrylic emulsion, which can significantly improve its adhesive force, water resistance, and heat resistance.

[0028] (2) The preparation method of the dendritic macromolecular crosslinking agent adopted by the present invention is simple, the raw materials are widely available, the preparation cost is low, and it is easy to industrialize production. Detailed Embodiments

[0029] The present invention will be further described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto.

[0030] Example 1

[0031] An aqueous two-component tile adhesive, comprising a liquid material and a powder material; the liquid material is an organosilicon-modified acrylic emulsion prepared by the following method:

[0032] (1) A difunctional polyetheramine with an average molecular weight of 2000 (D-2000, a polypropylene oxide compound capped with a primary amino group, primary amine rate 97.6%) and an epoxy group silane coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane are added to acetone solvent for mixing and dissolution. The molar ratio of the polyetheramine to the epoxy group silane coupling agent is 1:4.2. Then, the temperature is raised to 40 °C and stirred for reaction for 2 h. After the reaction is completed, the solvent is removed under reduced pressure to obtain a macromolecular crosslinking agent, and the tertiary amine rate of the product is measured to be 91.8%.

[0033] The synthesis reaction formula of the macromolecular crosslinking agent in this example is as follows:

[0034]

[0035] (2) The organosilicon monomer γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, and butyl acrylate are added to a 5% aqueous solution of an emulsifier (nonylphenol polyoxyethylene ether) according to a mass ratio of 0.3:0.5:0.5 and stirred until emulsified evenly. Under nitrogen protection, the temperature is raised to 75 °C, 0.4% ammonium persulfate is added, and the reaction is carried out for 3 h while maintaining the temperature. Then, the temperature is lowered to 50 °C, and the macromolecular crosslinking agent obtained in step (1) is added for hydrolysis crosslinking reaction for 1.5 h. The addition amount of the macromolecular crosslinking agent is 15% of the total mass of the polymerization monomers, and an organosilicon-modified acrylic resin emulsion with a solid content of 42% is obtained.

[0036] The preparation method of the powder material is: Portland cement, quartz sand, and white carbon black are added to a dry powder mixer according to a weight ratio of 70:25:5 and stirred evenly to obtain the powder material.

[0037] The liquid material and the powder material are packaged or used according to a mass ratio of 3:1 to obtain the aqueous two-component tile adhesive.

[0038] Example 2

[0039] An aqueous two-component tile adhesive, comprising a liquid material and a powder material; the liquid material is an organosilicon-modified acrylic emulsion prepared by the following method:

[0040] (1) A trifunctional polyetheramine with an average molecular weight of 3000 (T-3000, primary amine rate 97.1%) and an epoxy group silane coupling agent 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane are added to acetone solvent for mixing and dissolution. The molar ratio of the polyetheramine to the epoxy group silane coupling agent is 1:6.3. Then, the temperature is raised to 40 °C and stirred for reaction for 2 h. After the reaction is completed, the solvent is removed under reduced pressure to obtain a macromolecular crosslinking agent, and the tertiary amine rate of the product is measured to be 90.5%.

[0041] (2) Add the organosilicon monomer γ-methacryloxypropyltrimethoxysilane, acrylic acid, hydroxyethyl methacrylate, and butyl acrylate to 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, heat up to 75 °C under nitrogen protection, add 0.4% ammonium persulfate, keep the temperature for reaction for 3 h, then cool down to 50 °C, add the macromolecular crosslinking agent obtained in step (1) for hydrolysis crosslinking reaction for 2 h. The addition amount of the macromolecular crosslinking agent is 10% of the total mass of the polymerization monomers, and an organosilicon-modified acrylic resin emulsion with a solid content of 35% is obtained.

[0042] The preparation method of the powder material is as follows: Add portland cement, quartz sand, and white carbon black to a dry powder mixer according to the weight ratio of 76:20:4, stir and mix evenly to obtain the powder material.

[0043] Pack or use the liquid material and the powder material according to the mass ratio of 3:1 to obtain a water-based two-component tile adhesive.

[0044] Example 3

[0045] A water-based two-component tile adhesive, comprising a liquid material and a powder material; the liquid material is an organosilicon-modified acrylic emulsion prepared by the following method:

[0046] (1) Add the bifunctional polyetheramine with an average molecular weight of 400 (D-400, primary amine rate 98.0%) and the epoxy group silane coupling agent 3-(2,3-epoxypropoxy)propyltriethoxysilane to the ethyl acetate solvent, mix and dissolve. The molar ratio of the polyetheramine to the epoxy group silane coupling agent is 1:4.2, then heat up to 20 °C and stir for reaction for 3 h. After the reaction is completed, remove the solvent under reduced pressure to obtain a macromolecular crosslinking agent, and the measured tertiary amine rate of the product is 93.6%.

[0047] (2) Add the organosilicon monomer γ-methacryloxypropyltrimethoxysilane, acrylic acid, hydroxyethyl methacrylate, and butyl acrylate to 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, heat up to 75 °C under nitrogen protection, add 0.4% ammonium persulfate, keep the temperature for reaction for 3 h, then cool down to 40 °C, add the macromolecular crosslinking agent obtained in step (1) for hydrolysis crosslinking reaction for 1 h. The addition amount of the macromolecular crosslinking agent is 5% of the total mass of the polymerization monomers, and an organosilicon-modified acrylic resin emulsion with a solid content of 32% is obtained.

[0048] The preparation method of the powder material is as follows: Add portland cement, quartz sand, and white carbon black to a dry powder mixer according to the weight ratio of 80:20:2, stir and mix evenly to obtain the powder material.

[0049] Pack or use the liquid material and the powder material according to the mass ratio of 3:1 to obtain a water-based two-component tile adhesive.

[0050] Example 4

[0051] An aqueous two-component tile adhesive, comprising a liquid material and a powder material; the liquid material is an organosilicon-modified acrylic emulsion prepared by the following method:

[0052] (1) A trifunctional polyetheramine with an average molecular weight of 5000 (T-5000, primary amine ratio 97.5%) and an epoxy group silane coupling agent 3-(2,3-epoxypropoxy)propyltriethoxysilane are added to acetone solvent and mixed and dissolved. The molar ratio of polyetheramine to epoxy group silane coupling agent is 1:5, then the temperature is raised to 50 °C and stirred for reaction for 3 h. After the reaction is completed, the solvent is removed under reduced pressure to obtain a macromolecular crosslinking agent, and the tertiary amine ratio of the product is measured to be 82.8%.

[0053] (2) An organosilicon monomer γ-methacryloxypropyltriethoxysilane, hydroxyethyl methacrylate, and butyl acrylate are added to a 6% aqueous solution of an emulsifier (nonylphenol polyoxyethylene ether) according to a mass ratio of 0.4:0.4:0.6 and stirred and emulsified evenly. Under nitrogen protection, the temperature is raised to 75 °C, 0.4% ammonium persulfate is added and kept warm for reaction for 3 h, then the temperature is lowered to 60 °C, and the macromolecular crosslinking agent obtained in step (1) is added for hydrolysis crosslinking reaction for 3 h. The addition amount of the macromolecular crosslinking agent is 20% of the total mass of the polymerization monomers, and an organosilicon-modified acrylic resin emulsion with a solid content of 47% is obtained.

[0054] The preparation method of the powder material is: Portland cement, quartz sand, and white carbon black are added to a dry powder mixer according to a weight ratio of 60:30:10 and stirred and mixed evenly to obtain the powder material.

[0055] The liquid material and the powder material are packaged or used according to a mass ratio of 3:1 to obtain an aqueous two-component tile adhesive.

[0056] Comparative Example 1

[0057] An aqueous two-component tile adhesive, compared with Example 1, the liquid material is an organosilicon-modified acrylic emulsion prepared by the following method:

[0058] An organosilicon monomer γ-methacryloxypropyltrimethoxysilane, methyl methacrylate, and butyl acrylate are added to a 5% aqueous solution of an emulsifier (nonylphenol polyoxyethylene ether) according to a mass ratio of 0.3:0.5:0.5 and stirred and emulsified evenly. Under nitrogen protection, the temperature is raised to 75 °C, 0.4% ammonium persulfate is added and kept warm for reaction for 3 h, then the temperature is lowered to 50 °C, and an epoxy group silane coupling agent 3-(2,3-epoxypropoxy)propyltrimethoxysilane is added for hydrolysis crosslinking reaction for 1.5 h. The addition amount of the epoxy group silane coupling agent is 15% of the total mass of the polymerization monomers, and an organosilicon-modified acrylic resin emulsion with a solid content of 42% is obtained.

[0059] 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.

[0060] Table 1

[0061]

[0062] From the above results, it can be seen that the present invention uses a specific macromolecular cross-linking agent to cross-link and modify the acrylic emulsion. Compared with the small-molecule silane coupling agent, it can significantly improve its adhesion, water resistance and heat resistance. It shows that the macromolecular cross-linking agent of the present invention can better carry out hydrolysis cross-linking reaction with the organosilicon monomer segment in the modified acrylic resin, and can better carry out coupling reaction with the powder material and the base layer, improving the bonding effect between the resin, the powder material and the base layer, so as to achieve better bonding performance and bonding stability.

[0063] The above embodiments are 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 are all included in the protection scope of the present invention.

Claims

1. An aqueous two-component tile adhesive, characterized in that, It includes liquid material and powder material; the liquid material is an organosilicon-modified acrylic emulsion with a solid content of 30% - 50%; the powder material contains portland cement, quartz sand and silica white. The organosilicon-modified acrylic emulsion is prepared by the following method: (1) Add polyetheramine and epoxy group silane coupling agent into an anhydrous dilution solvent for mixing and dissolving, then stir and react at a temperature of 20 - 50 °C for 0.5 - 4 h. After the reaction is completed, remove the solvent under reduced pressure to obtain a macromolecular crosslinking agent. (2) Add organosilicon monomers and acrylic monomers into an aqueous solution of emulsifier and stir to emulsify evenly, then add an initiator and heat for polymerization reaction for 2 - 4 h, and then add the macromolecular crosslinking agent obtained in step (1) for hydrolysis crosslinking reaction for 1 - 3 h to obtain an organosilicon-modified acrylic emulsion.

2. The water-based two-component tile adhesive according to claim 1, characterized in that, The weight ratio of each component in the powder material is: 50 - 80 parts of portland cement, 20 - 30 parts of quartz sand, and 2 - 10 parts of silica white.

3. A water-based two-component tile adhesive according to claim 1, characterized in that, In step (1), the polyetheramine used is a bifunctional polyetheramine or trifunctional polyetheramine with a molecular weight of 400 - 5000; the epoxy group silane coupling agent used is 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldiethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

4. The water-based two-component tile adhesive according to claim 3, wherein, The molar ratio of the polyetheramine to the epoxy group silane coupling agent is 1:3 - 7.

5. A water-based two-component tile adhesive according to claim 1, characterized in that, In step (1), the anhydrous dilution solvent used is one or more of acetone, ethanol, propanol, and ethyl acetate.

6. The water-based two-component tile adhesive according to claim 1, characterized in that, In step (2), the organosilicon monomers used are one or more of vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane; the acrylic monomers used are 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, 2-hydroxypropyl methacrylate.

7. The water-based two-component tile adhesive according to claim 6, characterized in that, The mass ratio of the organosilicon monomers to the acrylic monomers added is 0.1 - 0.4:

1.

8. A water-based two-component tile adhesive according to claim 1, characterized in that, In step (2), the aqueous solution of 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 for the heating and initiation reaction is 60 - 80 °C.

9. A water-based two-component tile adhesive according to claim 1, characterized in that, In step (2), the addition amount of the macromolecular crosslinking agent is 5% - 20% of the total mass of the polymerization monomers; the temperature of the hydrolysis crosslinking reaction is 30 - 60 °C.

10. A method for preparing an aqueous two-component tile adhesive according to any one of claims 1 to 9, characterized in that, It includes the following preparation steps: (a) Add portland cement, quartz sand and silica white into a dry powder mixer and stir evenly to obtain powder material. (b) Divide or use the liquid material and the powder material according to a mass ratio of 2 to 4:1 to obtain an aqueous two-component ceramic tile adhesive.

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