MS silane modified tile adhesive and preparation method thereof

Abstract

The invention belongs to the technical field of polymer materials and binders, and particularly relates to an MS silane modified tile adhesive and a preparation method thereof. The preparation method comprises the following steps: firstly, carrying out addition reaction on hydrogen-containing silicone oil and an allyl polyether compound to obtain a hydroxyl polyether modified silicone oil intermediate, and then adding an isocyanate silane compound to carry out catalytic reaction to obtain an MS silane modifier; the preparation method comprises the following steps: carrying out emulsion copolymerization on an organic silicon monomer, an acrylic monomer and an acrylate monomer to obtain an organic silicon modified acrylic emulsion; and adding the obtained MS silane modifier into the organic silicon modified acrylic emulsion to carry out hydrolysis cross-linking reaction, then adding a filling agent, and uniformly stirring and mixing to obtain the MS silane modified tile adhesive. The MS silane modifier which is good in compatibility, excellent in water resistance and heat resistance and has the hydrolysis crosslinking characteristic is adopted for modifying the silicone acrylic resin binder, and the binding power, the water resistance and the heat resistance of the tile adhesive can be remarkably improved.

Description

Technical Field

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

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

[0003] The current MS silane is mainly a silane-terminated polyether polymer. For example, Wang Hongyu et al. disclosed a wet-curing elastic adhesive with α-silane-terminated polyether as a polymer (2010.18, China Building Waterproofing, 22-24). The resulting product has a strong adjustable formula and can be used to prepare adhesives for various purposes. However, the terminal silane content of pure silane-terminated polyether is limited, so the reaction and curing speed are slow, and it is not suitable for water-based bonding systems. In addition, although pure silane-terminated polyether has good elasticity, the bonding strength is still limited, and it is not suitable for application scenarios with high bonding strength requirements, such as stable bonding of tiles. Summary of the invention

[0004] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a method for preparing MS silane-modified tile adhesive.

[0005] Another object of the present invention is to provide a MS silane-modified tile adhesive prepared by the above method.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A method for preparing MS silane-modified tile adhesive comprises the following preparation steps:

[0008] (1) Preparation of MS silane modifier: adding hydrogen-containing silicone oil and allyl polyether compound to an organic solvent, mixing and dissolving them uniformly, then adding vinyl platinum catalyst (platinum (0)-divinyltetramethyldisiloxane complex) and heating and stirring to react to obtain a hydroxy polyether modified silicone oil intermediate, then adding isocyanate silane compound and organic tin catalyst to continue heat preservation reaction, after the reaction is completed, removing the organic solvent under reduced pressure to obtain MS silane modifier;

[0009] (2) Preparation of silicone-modified acrylic emulsion: adding silicone monomer, acrylic acid monomer and acrylate monomer to an emulsifier aqueous solution and stirring to emulsify uniformly, then adding an initiator and heating to initiate a reaction to obtain silicone-modified acrylic emulsion;

[0010] (3) Adding the MS silane modifier obtained in step (1) to the organosilicon-modified acrylic emulsion in step (2) to carry out a hydrolysis and cross-linking reaction, and then adding a filler and stirring and mixing evenly to obtain a MS silane-modified tile adhesive.

[0011] The preparation of the MS silane modifier of the present invention involves the following reaction formula:

[0012]

[0013] The MS silane modifier of the present invention contains a polysiloxane main chain with excellent water resistance and heat resistance, and contains a polyether chain with good compatibility with acrylic emulsion, and contains an alkoxy group that can undergo hydrolysis and cross-linking reaction with silicone-modified acrylic polymer. By cross-linking and modifying acrylic polymer, the bonding force, water resistance and heat resistance of tile adhesive can be significantly improved.

[0014] The hydrogen-containing silicone oil in step (1) is a side chain hydrogen-containing silicone oil with an average molecular weight of 1000 to 10000 g / mol and a hydrogen content of 0.2% to 1.0% (wt.%) or a side chain and end group hydrogen-containing silicone oil.

[0015] The molecular formula of the allyl polyether compound in step (1) is H2C=CH-CH2O-[CH2CH2O] m -[CH(CH3)CH2O] n H, m, and n are integers of 0 to 20.

[0016] Preferably, the added amount of the allyl polyether compound is 0.5 to 3 times the mass of the hydrogen-containing silicone oil.

[0017] The organic solvent in step (1) is one or a mixed solvent of two or more selected from the group consisting of benzene, toluene, ethyl acetate and acetone.

[0018] The temperature of the heating stirring reaction and the heat preservation reaction in step (1) is 70-90° C., the time of the heating stirring reaction is 2-8 hours, and the time of the heat preservation reaction is 1-5 hours.

[0019] The isocyanate silane compound in step (1) is 3-isocyanate propyl trimethoxy silane or 3-isocyanate propyl triethoxy silane; the amount of the isocyanate silane compound added is 0.6 to 1 times the molar amount of the allyl polyether compound.

[0020] The organosilicon monomer in step (2) is vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane or γ-methacryloxypropyltriethoxysilane.

[0021] 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.

[0022] The mass ratio of the organic silicon monomer, acrylic acid monomer and acrylic ester monomer added in step (2) is 0.2-0.5:1:0.5-1.

[0023] 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%.

[0024] 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 polymerized monomers; the temperature of the heating initiation reaction is 60 to 80° C., and the time is 2 to 6 hours.

[0025] The solid content of the organosilicon-modified acrylic emulsion in step (2) is 20% to 50%.

[0026] The amount of the MS silane modifier added in step (3) is 20% to 50% of the solid content in the silicone-modified acrylic emulsion; the temperature of the hydrolysis and cross-linking reaction is 30 to 80° C., and the time is 1 to 6 hours.

[0027] The filler in step (3) is one or more of silicate cement, calcium carbonate and white carbon black; the amount of the filler added is 10% to 60% of the mass of the silicone-modified acrylic emulsion.

[0028] A MS silane modified tile adhesive is prepared by the method.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] (1) The tile adhesive of the present invention uses an acrylic resin with good bonding properties as the main adhesive, and is modified by an MS silane modifier which has good compatibility, excellent water resistance and heat resistance and can undergo hydrolysis and cross-linking reaction with an organosilicon-modified acrylic polymer, thereby significantly improving the bonding strength, water resistance and heat resistance of the tile adhesive.

[0031] (2) The present invention allows the MS silane modifier to undergo a hydrolysis and crosslinking reaction with the organosilicon-modified acrylic emulsion in advance, so that the alkoxy groups in the MS silane modifier can be fully hydrolyzed and partially crosslinked with the silane groups in the organosilicon-modified acrylic polymer, thereby increasing the polymerization strength and improving the storage stability after subsequent mixing with the filler. The remaining uncrosslinked silanol groups can be further dehydrated and condensed during the subsequent adhesive liquid construction drying and curing process, thereby improving the adhesive film's adhesion, water resistance, and heat resistance. DETAILED DESCRIPTION

[0032] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0033] Example 1

[0034] A method for preparing MS silane-modified tile adhesive comprises the following preparation steps:

[0035] (1) Preparation of MS silane modifier: Hydrogenated silicone oil with an average molecular weight of 1000 g / mol and a hydrogen content of 1.0% and allyl polyethylene glycol APEG-400 are added to a mixed solvent of toluene:ethyl acetate with a volume ratio of 1:2 and mixed and dissolved evenly. The amount of APEG-400 added is 1.5 times the mass of the hydrogenated silicone oil. Then, 0.01% of the system mass of vinyl platinum catalyst is added and heated to 80-85°C and stirred for reaction for 5 hours to obtain a hydroxy polyether modified silicone oil intermediate. Then, 0.6 times the molar amount of APEG-400 3-isocyanate propyl trimethoxysilane and 0.2% of the system mass of dibutyltin dilaurate catalyst are added and the reaction is continued for 2 hours of heat preservation. After the reaction is completed, the organic solvent is removed under reduced pressure to obtain the MS silane modifier.

[0036] (2) Preparation of silicone-modified acrylic emulsion: The silicone monomer γ-methacryloxypropyltrimethoxysilane and acrylic acid, methyl methacrylate, and butyl acrylate were added in a mass ratio of 0.2:1:0.3:0.5 to a 5% aqueous solution of an emulsifier (composed of allyloxynonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stirred for uniform emulsification. The temperature was raised to 75°C under nitrogen protection, and 0.4% ammonium persulfate was added and the reaction was maintained at this temperature for 4 hours to obtain a silicone-modified acrylic resin emulsion with a solid content of 36%.

[0037] (3) Add 10 parts by mass of the MS silane modifier obtained in step (1) to 100 parts of the organosilicon-modified acrylic emulsion in step (2), heat and stir at 45-50° C. for 2 h to carry out hydrolysis and cross-linking reaction, then add 20 parts of silicate cement, 10 parts of calcium carbonate and 5 parts of white carbon black and stir to mix evenly to obtain MS silane-modified tile adhesive.

[0038] Example 2

[0039] A method for preparing MS silane-modified tile adhesive comprises the following preparation steps:

[0040] (1) Preparation of MS silane modifier: Hydrogenated silicone oil with an average molecular weight of 5000 g / mol and a hydrogen content of 0.55% and allyl polyethylene glycol APEG-700 are added to a mixed solvent of toluene:ethyl acetate with a volume ratio of 1:2 and mixed and dissolved evenly. The amount of APEG-700 added is 1.2 times the mass of the hydrogenated silicone oil. Then, 0.01% of the system mass of vinyl platinum catalyst is added and heated to 80-85°C and stirred for reaction for 5 hours to obtain a hydroxy polyether modified silicone oil intermediate. Then, 0.8 times the molar amount of APEG-700 3-isocyanate propyl trimethoxysilane and 0.2% of the system mass of dibutyltin dilaurate catalyst are added and the reaction is continued for 2 hours of heat preservation. After the reaction is completed, the organic solvent is removed under reduced pressure to obtain the MS silane modifier.

[0041] (2) Preparation of silicone-modified acrylic emulsion: The silicone monomer γ-methacryloxypropyltrimethoxysilane and acrylic acid, methyl methacrylate, and butyl acrylate were added in a mass ratio of 0.3:1:0.3:0.4 to a 5% aqueous solution of an emulsifier (composed of allyloxynonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stirred for uniform emulsification. The temperature was raised to 75°C under nitrogen protection, and 0.4% ammonium persulfate was added and the reaction was maintained at this temperature for 4 hours to obtain a silicone-modified acrylic resin emulsion with a solid content of 36%.

[0042] (3) Add 15 parts by mass of the MS silane modifier obtained in step (1) to 100 parts of the organosilicon-modified acrylic emulsion in step (2), heat and stir at 55-60° C. for 2 h to carry out hydrolysis and cross-linking reaction, then add 20 parts of silicate cement, 10 parts of calcium carbonate and 5 parts of white carbon black and stir to mix evenly to obtain MS silane-modified tile adhesive.

[0043] Example 3

[0044] A method for preparing MS silane-modified tile adhesive comprises the following preparation steps:

[0045] (1) Preparation of MS silane modifier: Hydrogenated silicone oil with an average molecular weight of 10,000 g / mol and a hydrogen content of 0.24% and allyl polyethylene glycol APEG-800 are added to a mixed solvent of toluene:ethyl acetate with a volume ratio of 1:2 and mixed and dissolved evenly. The amount of APEG-800 added is 0.8 times the mass of the hydrogenated silicone oil. Then, 0.01% of the system mass of vinyl platinum catalyst is added and heated to 80-85°C and stirred for reaction for 5 hours to obtain a hydroxy polyether modified silicone oil intermediate. Then, 1 times the molar amount of APEG-800 3-isocyanate propyl triethoxysilane and 0.2% of the system mass of dibutyltin dilaurate catalyst are added and the reaction is continued for 2 hours of heat preservation. After the reaction is completed, the organic solvent is removed under reduced pressure to obtain the MS silane modifier.

[0046] (2) Preparation of silicone-modified acrylic emulsion: The silicone monomer γ-methacryloxypropyltriethoxysilane and acrylic acid, methyl methacrylate, and butyl acrylate were added in a mass ratio of 0.4:1:0.3:0.3 to a 5% aqueous solution of an emulsifier (composed of allyloxynonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stirred for uniform emulsification. The temperature was raised to 75°C under nitrogen protection, and 0.4% ammonium persulfate was added and the reaction was maintained at this temperature for 4 hours to obtain a silicone-modified acrylic resin emulsion with a solid content of 36%.

[0047] (3) Add 18 parts by mass of the MS silane modifier obtained in step (1) to 100 parts of the organosilicon-modified acrylic emulsion in step (2), heat and stir at 65-70° C. for 2 h to carry out hydrolysis and cross-linking reaction, then add 20 parts of silicate cement, 10 parts of calcium carbonate and 5 parts of white carbon black and stir to mix evenly to obtain MS silane-modified tile adhesive.

[0048] Comparative Example 1

[0049] An organosilicon-modified acrylic tile adhesive, compared with Example 1, does not contain MS silane modifier, and its preparation steps are as follows:

[0050] (1) The preparation of silicone-modified acrylic emulsion is the same as that in Example 1.

[0051] (2) Add 20 parts by mass of silicate cement, 10 parts by mass of calcium carbonate and 5 parts by mass of white carbon into 100 parts by mass of the organosilicon-modified acrylic emulsion of step (1), stir and mix them evenly, to obtain an organosilicon-modified acrylic tile adhesive.

[0052] Comparative Example 2

[0053] A MS silane-modified tile adhesive, compared with Example 1, uses conventional silane-terminated polyether to replace the MS silane modifier, and the preparation steps are as follows:

[0054] (1) Preparation of silane-terminated polyether: polyethylene glycol PEG-400 is added to a mixed solvent of toluene:ethyl acetate in a volume ratio of 1:2 and mixed and dissolved uniformly, and then 3-isocyanatepropyltrimethoxysilane (2 times the molar amount of PEG-400) and dibutyltin dilaurate (0.2% by mass of the system) are added to continue the reaction at the same temperature for 2 hours. After the reaction is completed, the organic solvent is removed under reduced pressure to obtain a silane-terminated polyether.

[0055] (2) The preparation of silicone-modified acrylic emulsion is the same as that in Example 1.

[0056] (3) Add 10 parts by mass of the silane-terminated polyether obtained in step (1) to 100 parts of the silicone-modified acrylic emulsion in step (2), heat-insulate and stir at 45-50° C. for 2 h to carry out hydrolysis and cross-linking reaction, then add 20 parts of silicate cement, 10 parts of calcium carbonate and 5 parts of white carbon black and stir to mix evenly to obtain a conventional silane-terminated polyether modified tile adhesive.

[0057] The tile adhesives of the above embodiments and comparative examples were subjected to performance tests in accordance with JC / T 547-2017. The test results are shown in Table 1 below.

[0058] Table 1

[0059]

[0060] From the results in Table 1, it can be seen that the present invention can significantly improve the adhesion, water resistance and heat resistance of the obtained tile adhesive by modifying the acrylic resin binder with a specific MS silane modifier. And the improvement effect of the MS silane modifier of the present invention is further significantly improved compared with the conventional silane-terminated polyether modifier. The reason is that the introduction of long-chain polysiloxane can further improve the water resistance and heat resistance, and the high content of silane hydrolysis cross-linking groups can improve the cross-linking strength with the silicone-modified acrylic resin, thereby improving the adhesion, water resistance and heat resistance.

[0061] 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 method for preparing MS silane-modified tile adhesive, characterized in that: The method comprises the following preparation steps: (1) Preparation of MS silane modifier: adding hydrogen-containing silicone oil and allyl polyether compound to an organic solvent and mixing and dissolving them uniformly, then adding a vinyl platinum catalyst and heating and stirring to react to obtain a hydroxy polyether modified silicone oil intermediate, then adding an isocyanate silane compound and an organic tin catalyst and continuing to heat and react, after the reaction is completed, removing the organic solvent under reduced pressure to obtain the MS silane modifier; (2) Preparation of silicone-modified acrylic emulsion: adding silicone monomer, acrylic acid monomer and acrylate monomer to an emulsifier aqueous solution and stirring to emulsify uniformly, then adding an initiator and heating to initiate a reaction to obtain silicone-modified acrylic emulsion; (3) Adding the MS silane modifier obtained in step (1) to the organosilicon-modified acrylic emulsion in step (2) to carry out a hydrolysis and cross-linking reaction, and then adding a filler and stirring and mixing evenly to obtain a MS silane-modified tile adhesive.

2. The method for preparing a MS silane-modified tile adhesive according to claim 1, characterized in that: The hydrogen-containing silicone oil in step (1) is a side chain hydrogen-containing silicone oil with an average molecular weight of 1000-10000 g / mol and a hydrogen content of 0.2%-1.0% or a side chain and end group hydrogen-containing silicone oil.

3. The method for preparing a MS silane-modified tile adhesive according to claim 2, characterized in that: The molecular formula of the allyl polyether compound in step (1) is H2C=CH-CH2O-[CH2CH2O] m -[CH(CH3)CH2O] n H, m and n are integers of 0 to 20; the added amount of the allyl polyether compound is 0.5 to 3 times the mass of the hydrogen-containing silicone oil.

4. The method for preparing a MS silane-modified tile adhesive according to claim 1, characterized in that: The organic solvent in step (1) is one or a mixed solvent of benzene, toluene, ethyl acetate and acetone; the temperature of the heating and stirring reaction and the insulation reaction is 70 to 90° C., the heating and stirring reaction time is 2 to 8 hours, and the insulation reaction time is 1 to 5 hours.

5. The method for preparing a MS silane-modified tile adhesive according to claim 1, characterized in that: The isocyanate silane compound in step (1) is 3-isocyanate propyl trimethoxy silane or 3-isocyanate propyl triethoxy silane; the amount of the isocyanate silane compound added is 0.6 to 1 times the molar amount of the allyl polyether compound.

6. The method for preparing a MS silane-modified tile adhesive according to claim 1, characterized in that: The organosilicon monomer in step (2) is vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane or γ-methacryloxypropyltriethoxysilane; the acrylic acid monomer is (meth)acrylic acid; the acrylate monomer is one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate.

7. The method for preparing a MS silane-modified tile adhesive according to claim 6, characterized in that: The mass ratio of the organic silicon monomer, acrylic acid monomer and acrylic ester monomer added is 0.2-0.5:1:0.5-1.

8. The method for preparing a MS silane-modified 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; the temperature of the heating initiation reaction is 60 to 80° C., and the time is 2 to 6 hours; the solid content of the silicone-modified acrylic emulsion is 20% to 50%.

9. The method for preparing a MS silane-modified tile adhesive according to claim 1, characterized in that: The amount of the MS silane modifier added in step (3) is 20% to 50% of the solid content in the silicone-modified acrylic emulsion; the temperature of the hydrolysis and cross-linking reaction is 30 to 80° C., and the time is 1 to 6 hours; the filler is one or more of silicate cement, calcium carbonate, and white carbon black; the amount of the filler added is 10% to 60% of the mass of the silicone-modified acrylic emulsion.

10. A MS silane modified tile adhesive, characterized in that: It is prepared by the method according to any one of claims 1 to 9.

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