CN115584225A - Large-plate ceramic tile back glue and preparation method thereof - Google Patents
Large-plate ceramic tile back glue and preparation method thereof Download PDFInfo
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- CN115584225A CN115584225A CN202211351833.3A CN202211351833A CN115584225A CN 115584225 A CN115584225 A CN 115584225A CN 202211351833 A CN202211351833 A CN 202211351833A CN 115584225 A CN115584225 A CN 115584225A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides a large-plate ceramic tile back glue and a preparation method thereof, belonging to the technical field of gluing; the preparation method comprises the following steps: dripping water into organic solution dissolved with long alkyl chain silane and amino silane for emulsification reaction to obtain hydrophobic SiO 2 Hollow microspheres, adding a cationic initiator to obtain hydrophobic SiO for adsorbing the initiator 2 Adding a surfactant into the hollow microspheres, adding an acrylate monomer, and performing microwave-assisted polymerization to obtain polyacrylate/SiO with a core-shell structure 2 The composite microsphere is modified by a composite silane coupling agent, mixed with acrylate emulsion and fly ash, and added withAnd carrying out thermal reaction and cooling to obtain the large-plate ceramic tile back glue. The invention overcomes the problem of poor water resistance and cohesiveness of the traditional pressure-sensitive back adhesive, improves the water resistance and cohesiveness of the whole system, finally reduces the risk of hollowing and falling of the ceramic tile, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a large-plate ceramic tile back glue and a preparation method thereof.
Background
The ceramic tile is made up by using refractory metal oxide and semimetal oxide through the processes of grinding, mixing, pressing, glazing and sintering, and is an acid-resistant and alkali-resistant ceramic or stone material for building or decoration, and is generally called as ceramic tile. The rapid development of the ceramic tile needs matched materials for paving, the existing mature paving material is cement-based ceramic tile glue compounded by cement, filler, cellulose, rubber powder and the like, and the ceramic tile glue has the advantages of scientific proportioning and stable performance; the construction thickness can be controlled and the material consumption is saved by adopting a thin pasting process in the construction; the tile glue is introduced into China from Europe, and after years of development, certain development is achieved, the popularization rate reaches about 10% of that of paving materials, but the tile glue is limited by the flatness of walls, construction habits, cost and the like, at present, C0-grade tile glue is still used as the main material, the bonding force and the stress resistance of the tile glue are weak, and the paving requirements of materials such as vitrified tiles, large plates and the like cannot be met.
Tile gum, cement yellow sand and tile gum are gradually adopted to spread and paste in recent years, and the process has the advantages that: 1) The existing construction habit can not be changed; 2) The wall surface does not need to be additionally leveled; 3) Can be used in combination with cement yellow sand and cement-based tile glue; the risk that the ceramic tile hollows out and turns is reduced. Due to the advantages, the ceramic tile back glue is subjected to rapid development and generally accepted by people. The process also has the following problems in the actual use process: 1) The working procedure is added, and the coating is required to be carried out on site; 2) The penetration and reinforcement properties are poor, and the ceramic tile with the release agent needs to be treated in advance; 3) The drying time is long, the coating needs to be spread and aired after being coated, the drying speed is greatly influenced by temperature and humidity, and the uncertainty is high; 4) The water resistance is poor, and the bonding force is weak under long-term moist or water immersion environment.
In recent years, with the development of the tile industry, the size specification of tiles is rapidly increased, the mainstream tile shapes in the market are changed from 300mm × 300mm to 400mm × 800mm, and ceramic sheets are provided by various tile manufacturers, and the size specification of the ceramic sheets is generally more than 1200mm × 2400 mm. Meanwhile, with the improvement of the tile firing process, the water absorption of the tile is also rapidly reduced, and the tile which is the mainstream in the market at present is changed from the tile with the water absorption of more than 6% to the vitrified tile with the water absorption of less than 0.5%. The increase in tile dimensional specifications and the decrease in water absorption create new challenges for tile placement. Especially, like unstable basal planes such as flue plates, elevator shafts and the like, the ceramic tile glue used alone can not meet the actual use requirements more and more. Therefore, tile glue manufacturers have gradually released gum products for paving and pasting tiles by compounding tile glue.
At present, most of tile back adhesives are double-component tile back adhesives, such as the double-component tile back adhesive disclosed by CN108048001A, the nanometer aerogel modified double-component tile back adhesive disclosed by CN109517541A and a preparation method and a use method thereof, and the tile back adhesives are complex in components and inconvenient to operate. At present, part of tile back glue is made of pressure-sensitive adhesive, and because the water resistance and the heat resistance of a polymer film are relatively poorer than those of cement-based products, when the tile back glue is made of the pressure-sensitive adhesive, the original tensile bonding strength is improved compared with that of cement mortar, but the tensile strength and the thermal aging tensile strength are reduced after soaking, and the requirements of tile bonding with low water absorption of polished tiles and the like cannot be met.
Therefore, the need exists in the art to develop a large-board tile backsize with penetration strengthening, quick drying, and water resistance to solve the problems encountered in the practical process and meet the needs of the retail market; meanwhile, the requirements in the integrated production process of the ceramic tiles and the back glue in a ceramic tile factory and the requirements in subsequent paving can be met.
Disclosure of Invention
The invention aims to provide a large-plate ceramic tile back glue and a preparation method thereof, the large-plate ceramic tile back glue has excellent adhesive property and mechanical property, has better water resistance and freeze-thaw resistance, can quickly permeate into a ceramic tile blank to form tight connection, overcomes the problem of poor water resistance and adhesion of the traditional pressure-sensitive back glue, improves the water resistance and adhesion of the whole system, finally reduces the risk of hollowing and falling of the ceramic tile, and has wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a large-plate ceramic tile back glue, which comprises the steps of dripping water into an organic solution dissolved with long alkyl chain silane and aminosilane for emulsification reaction to obtain hydrophobic SiO 2 Dispersing the hollow microspheres in water, adding cationic initiator, and stirringHydrophobic SiO for adsorbing initiator obtained after reaction 2 Further adding a surfactant into the hollow microspheres, stirring for reaction, adding an acrylate monomer, and performing microwave-assisted polymerization to obtain polyacrylate/SiO with a core-shell structure 2 And (3) modifying the composite microspheres by using a composite silane coupling agent, mixing the modified composite microspheres with the acrylate emulsion and the fly ash, heating for reaction, and cooling to room temperature to obtain the large-plate ceramic tile back glue.
As a further improvement of the invention, the method comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving long alkyl chain silane and amino silane in an organic solvent to obtain an oil phase; adding water drop into oil phase, adding emulsifier, stirring, emulsifying, reacting, centrifuging, washing, and drying to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: hydrophobic SiO prepared in the step S1 2 Uniformly dispersing the hollow microspheres in water, adding a cationic initiator, stirring for reaction, centrifuging, washing and drying to obtain hydrophobic SiO adsorbing the initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: hydrophobic SiO for adsorbing the initiator prepared in the step S2 2 Dispersing the hollow microspheres in water, adding a surfactant, stirring for reaction, adding an acrylate monomer, performing microwave-assisted polymerization, centrifuging, washing and drying to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
s4, modifying the microspheres: the polyacrylate/SiO with the core-shell structure prepared in the step S3 2 Dispersing the composite microspheres in an ethanol water solution, adding a composite silane coupling agent, centrifuging, washing and drying to obtain modified microspheres;
s5, preparing a large-plate ceramic tile back glue: and (5) mixing the acrylate emulsion, the modified microspheres prepared in the step (S4) and the fly ash, heating for reaction, uniformly stirring, and cooling to room temperature to obtain the large-plate ceramic tile back glue.
As a further improvement of the invention, the long alkyl chain silane in the step S1 is selected from at least one of dodecyl trimethoxy silane, hexadecyl trimethoxy silane and octadecyl trimethoxy silane; the aminosilane is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and diethylenetriaminopropyltrimethoxysilane; the emulsifier is at least one selected from tween-20, tween-40, tween-60 and tween-80; the mass ratio of the long alkyl chain silane to the amino silane is 5-7; the emulsification condition is 12000-15000r/min emulsification for 3-5min, and the reaction time is 3-5h.
As a further improvement of the invention, the cationic initiator in step S2 is 2,2-azobisisobutylamidine hydrochloride; the hydrophobic SiO 2 The mass ratio of the hollow microspheres to the cationic initiator is 100; the stirring reaction time is 0.5-1h.
As a further improvement of the present invention, in step S3, the surfactant is a cationic surfactant or an anionic surfactant, and the anionic surfactant is at least one selected from sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium tetradecyl benzene sulfonate, sodium tetradecyl sulfate, sodium tetradecyl benzene sulfonate, sodium hexadecylbenzene sulfate, sodium hexadecylbenzene sulfonate, sodium octadecyl benzene sulfonate, and sodium octadecyl benzene sulfonate; the cationic surfactant is selected from at least one of cetyl trimethyl sodium bromide, cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride and dodecyl dimethyl benzyl ammonium chloride; preferably, the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio is 5-7:3.
As a further improvement of the invention, the acrylate monomer in step S3 is selected from butyl acrylate, methyl acrylate, ethyl acrylate, 2-methyl acrylateAt least one of methyl methacrylate and ethyl 2-methacrylate; hydrophobic SiO of the adsorption initiator 2 The mass ratio of the hollow microspheres to the surfactant to the acrylate monomer is 10-5:7-12; the microwave power in the microwave-assisted polymerization is 1000-1200W, and the polymerization time is 1-3h.
As a further improvement of the invention, the core-shell structured polyacrylate/SiO in step S4 2 The mass ratio of the composite microspheres to the composite silane coupling agent is 10; the composite silane coupling agent is selected from at least one of KH550, KH560, KH570, KH580, KH590, KH602 and KH792, preferably, the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 3-5:2.
As a further improvement of the invention, in the step S5, the mass ratio of the acrylate emulsion to the modified microspheres to the fly ash is 30-50; the heating temperature is 50-70 ℃, and the reaction time is 2-4h.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 5-7 parts by weight of long alkyl chain silane and 10-15 parts by weight of aminosilane in 100 parts by weight of organic solvent to obtain an oil phase; adding 40-50 weight parts of water into 100 weight parts of oil phase, adding 1-2 weight parts of emulsifier, stirring, emulsifying at 12000-15000r/min for 3-5min, reacting for 3-5h, centrifuging, washing, and drying to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Uniformly dispersing the hollow microspheres in 200 parts by weight of water, adding 1-2 parts by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 0.5-1h, centrifuging, washing and drying to obtain hydrophobic SiO (silicon dioxide) adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Dispersing hollow microspheres in 100 parts by weight of water, adding 3-5 parts by weight of surfactant, stirring for reaction, adding 7-12 parts by weight of acrylate monomer, and performing 1000-1200W microwave assistancePolymerizing for 1-3h, centrifuging, washing and drying to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 5-7:3;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the space formed by the staggered layer between dodecyl group and octadecyl group provides abundant space for the polymerization of the acrylate monomer, which is beneficial to the occurrence of polymerization reaction, so that the mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide can promote the formation of a polymer layer to play a role in synergy.
S4, modification of microspheres: 10 parts by weight of polyacrylate/SiO with a core-shell structure prepared in the step S3 2 Dispersing the composite microspheres in 50 parts by weight to 70wt% of ethanol aqueous solution, adding 2 parts by weight to 3 parts by weight of composite silane coupling agent, centrifuging, washing and drying to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 3-5:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 30-50 parts by weight of acrylate emulsion, 10-12 parts by weight of modified microspheres prepared in the step (S4) and 5-7 parts by weight of fly ash, heating to 50-70 ℃, reacting for 2-4h, uniformly stirring, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Preferably, the organic solvent is at least one selected from dichloromethane, chloroform, carbon tetrachloride, ethyl acetate, methyl acetate, butyl acetate, petroleum ether, diethyl ether, n-hexane and cyclohexane.
The invention further protects the large-plate ceramic tile back glue prepared by the preparation method.
The invention has the following beneficial effects:
the invention firstly drops water and emulsifier through organic solution dissolved with mixed silane, including long alkyl chain silane and amino silane, forms tiny water-in-oil drops through emulsification, amino part on amino silane faces inwards, hydrates to form alkaline environment,thereby promoting the silane part to be hydrolyzed, continuously consuming the silane and forming SiO 2 Shell layer with long alkyl chain part of the long alkyl chain silane facing outwards to obtain SiO 2 The surface of the hollow microsphere contains a large amount of long alkyl chain silane, so that a good hydrophobic effect is achieved; due to SiO 2 The hollow structure of the microspheres enables the gum to have good heat insulation and sound insulation effects.
The cation initiator is positively charged and is easy to react with the prepared hydrophobic SiO 2 Hollow microsphere negatively charged SiO 2 The shell layer is subjected to electrostatic adsorption, so that the shell layer is adsorbed on the surface of the microsphere, and after the shell layer is further dispersed in water, the hydrophobic end added with the surfactant is forced to face hydrophobic SiO 2 The preparation method comprises the following steps of forcing a hydrophilic end on a surfactant to face a water phase to finally form a double-layer structure, then adding an acrylate monomer, dispersing the acrylate monomer in a hydrophobic double-layer space, and carrying out encapsulation polymerization under the conditions of microwave radiation and the presence of an initiator to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres; because the inner layer is SiO 2 The structure obviously enhances the mechanical property of the polymer;
then, the prepared polyacrylate/SiO with the core-shell structure 2 The composite microspheres have the modification effect of a composite silane coupling agent, wherein the composite silane coupling agent is a mixture of KH570 and KH550, double bonds of the KH570 can be bonded with the shell polyacrylate, amino groups of the KH550 can form hydrogen bonds with ester groups of the shell polyacrylate, so that the composite silane coupling agent can be coupled on the microspheres, the other end of the composite silane coupling agent is a siloxane part, and after the fly ash is added, the siloxane part can be coupled with SiO in the fly ash 2 The components are coupled, so that the modified microsphere and the fly ash are coupled, and meanwhile, the modified microsphere has good compatibility in the acrylate emulsion because the shell layer is polyacrylate, so that the problem of poor compatibility of the fly ash in the acrylate emulsion is solved.
The large-plate tile back glue introduces the fly ash component, can perform secondary hydration with the cement mortar, obviously improves the bonding capability of the tile back glue and the cement mortar, and improves the water resistance and the freeze-thaw resistance of the tile back glue. Under the condition of sufficient water, the hydration reaction rate of cement and fly ash can be accelerated, the fly ash glass body is disintegrated to generate a large amount of C-S-H gel, the structure is more compact, and the bonding capability of the back adhesive and cement mortar of the large-plate ceramic tile is improved, so that the bonding capability is obviously improved.
The back glue for the large-plate ceramic tile, which is prepared by the invention, has excellent adhesive property and mechanical property, better water resistance and freeze-thaw resistance, can quickly permeate into a ceramic tile blank to form a tight link, overcomes the problem that the traditional pressure-sensitive back glue is poor in water resistance and adhesiveness, improves the water resistance and adhesiveness of the whole system, finally reduces the risk of hollowing and falling of the ceramic tile, and has a wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The acrylate emulsion was DURAMUL PR 3500 available from Xin Simo, US, inc.
Example 1
The embodiment provides a preparation method of a large-plate ceramic tile back glue, which specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 5 parts by weight of dodecyl trimethoxy silane and 10 parts by weight of N-beta (aminoethyl) -gamma-aminopropyl trimethoxy silane in 100 parts by weight of dichloromethane to obtain an oil phase; dripping 40 weight parts of water into 100 weight parts of oil phase, adding 1 weight part of tween-20, stirring for 2 min, emulsifying for 3min at 12000r/min, reacting for 3h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 deg.C for 2h to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, performing ultrasonic treatment for 20min at 1000W, adding 1 part by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 0.5h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO (silicon dioxide) for adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Adding hollow microspheres into 100 parts by weight of water, performing ultrasonic dispersion at 1000W for 15min, adding 3 parts by weight of surfactant, stirring for reaction for 30min, adding 7 parts by weight of ethyl acrylate, performing microwave-assisted polymerization at 1000W for 1h, centrifuging at 3000r/min for 15min, washing with clear water, and drying at 70 ℃ for 2h to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 5:3;
s4, modification of microspheres: 10 parts by weight of polyacrylate/SiO with a core-shell structure prepared in the step S3 2 Adding the composite microspheres into 50 parts by weight of 50wt% ethanol aqueous solution, stirring for 15min, adding 2 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 3:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 30 parts by weight of acrylate emulsion, 10 parts by weight of modified microspheres prepared in the step (S4) and 5 parts by weight of fly ash, heating to 50 ℃ for reaction for 2 hours, stirring for 30 minutes, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Example 2
The embodiment provides a preparation method of a large-plate ceramic tile back glue, which specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 7 parts by weight of octadecyl trimethoxy silane and 15 parts by weight of N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane in 100 parts by weight of petroleum ether to obtainTo an oil phase; dripping 50 weight parts of water into 100 weight parts of oil phase, adding 2 weight parts of Tween-60, stirring for 2 min, emulsifying for 5min at 15000r/min, reacting for 5h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, performing ultrasonic treatment at 1000W for 20min, adding 2 parts by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 1h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain hydrophobic SiO (silicon dioxide) adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 5 parts by weight of surfactant, stirring for reaction for 40min, adding 12 parts by weight of acrylate monomer, carrying out microwave-assisted polymerization for 3h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 7:3;
s4, modifying the microspheres: 10 parts by weight of polyacrylate/SiO with a core-shell structure prepared in the step S3 2 Adding the composite microspheres into 50 parts by weight of 70wt% ethanol aqueous solution, stirring for 15min, adding 3 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio of the composite silane coupling agent to the KH550 is 5:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 50 parts by weight of acrylate emulsion, 12 parts by weight of modified microspheres prepared in the step (S4) and 7 parts by weight of fly ash, heating to 70 ℃, reacting for 4 hours, stirring for 30 minutes, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Example 3
The embodiment provides a preparation method of a large-plate ceramic tile back glue, which specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 6 parts by weight of hexadecyl trimethoxy silane and 12 parts by weight of gamma-aminopropyl triethoxy silane in 100 parts by weight of ethyl acetate to obtain an oil phase; dripping 45 weight parts of water into 100 weight parts of oil phase, adding 1.5 weight parts of Tween-80, stirring for 20min, emulsifying for 4min at 13500r/min, reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, performing ultrasonic treatment at 1000W for 20min, adding 1.5 parts by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 1h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain hydrophobic SiO (silicon dioxide) adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 4 parts by weight of surfactant, stirring for reacting for 35min, adding 10 parts by weight of butyl acrylate, carrying out microwave-assisted polymerization for 2h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 6:3;
s4, modification of microspheres: 10 parts by weight of the polyacrylate/SiO with the core-shell structure prepared in the step S3 2 Adding the composite microspheres into 50 parts by weight of 60wt% ethanol aqueous solution, stirring for 15min, adding 2.5 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 4:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 40 parts by weight of acrylate emulsion, 11 parts by weight of modified microspheres prepared in the step (S4) and 6 parts by weight of fly ash, heating to 60 ℃, reacting for 3 hours, stirring for 30 minutes, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Example 4
Compared with the example 3, the surfactant is single dodecyl trimethyl ammonium bromide, and other conditions are not changed.
Example 5
Compared with example 3, the surfactant is single octadecyl trimethyl ammonium bromide, and other conditions are not changed.
Example 6
Compared with example 3, the composite silane coupling agent is single KH570, and other conditions are not changed.
Example 7
Compared with example 3, the composite silane coupling agent is single KH550, and other conditions are not changed.
Comparative example 1
In contrast to example 3, step S2 was not included, but the initiator was added after the monomer addition, all other conditions being unchanged.
The method specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 6 parts by weight of hexadecyl trimethoxy silane and 12 parts by weight of gamma-aminopropyl triethoxy silane in 100 parts by weight of ethyl acetate to obtain an oil phase; dripping 45 weight parts of water into 100 weight parts of oil phase, adding 1.5 weight parts of Tween-80, stirring for 20min, emulsifying for 4min at 13500r/min, reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO 2 Hollow microspheres;
s2, polyacrylate/SiO of core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 4 parts by weight of surfactant, stirring for reacting for 35min, adding 10 parts by weight of butyl acrylate, adding 0.15 part by weight of 2,2-azodiisobutyramidine hydrochloride, carrying out 1100W microwave-assisted polymerization for 2h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain polyacrylate/S with a core-shell structureiO 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 6:3;
s3, modification of microspheres: 10 parts by weight of polyacrylate/SiO with a core-shell structure prepared in the step S2 2 Adding the composite microspheres into 50 parts by weight of 60wt% ethanol aqueous solution, stirring for 15min, adding 2.5 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 4:2;
s4, preparing a large-plate ceramic tile back glue: and (3) mixing 40 parts by weight of acrylate emulsion, 11 parts by weight of modified microspheres prepared in the step (S3) and 6 parts by weight of fly ash, heating to 60 ℃, reacting for 3 hours, stirring for 30 minutes, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Comparative example 2
Compared with example 3, no surfactant was added in step S3, and other conditions were not changed.
The method specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 6 parts by weight of hexadecyl trimethoxy silane and 12 parts by weight of gamma-aminopropyl triethoxy silane in 100 parts by weight of ethyl acetate to obtain an oil phase; dripping 45 weight parts of water into 100 weight parts of oil phase, adding 1.5 weight parts of Tween-80, stirring for 20min, emulsifying for 4min at 13500r/min, reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, performing ultrasonic treatment at 1000W for 20min, adding 1.5 parts by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 1h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain hydrophobic SiO (silicon dioxide) adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO 2 Preparing the composite microspheres: 10 parts by weight of the adsorbing catalyst obtained in step S2Hydrophobic SiO of hair agent 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 10 parts by weight of butyl acrylate, carrying out microwave-assisted polymerization for 2h at 1100W, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain polyacrylate/SiO 2 Compounding the microspheres;
s4, modification of microspheres: 10 parts by weight of the polyacrylate/SiO prepared in step S3 2 Adding the composite microspheres into 50 parts by weight of 60wt% ethanol aqueous solution, stirring for 15min, adding 2.5 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 4:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 40 parts by weight of acrylate emulsion, 11 parts by weight of modified microspheres prepared in the step (S4) and 6 parts by weight of fly ash, heating to 60 ℃, reacting for 3 hours, stirring for 30 minutes, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Comparative example 3
Compared to example 3, step S4 was not included, and other conditions were not changed.
The method specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 6 parts by weight of hexadecyl trimethoxy silane and 12 parts by weight of gamma-aminopropyl triethoxy silane in 100 parts by weight of ethyl acetate to obtain an oil phase; dripping 45 weight parts of water into 100 weight parts of oil phase, adding 1.5 weight parts of Tween-80, stirring for 20min, emulsifying for 4min at 13500r/min, reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, performing ultrasonic treatment at 1000W for 20min, adding 1.5 parts by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 1h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain hydrophobic SiO (silicon dioxide) adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 4 parts by weight of surfactant, stirring for reacting for 35min, adding 10 parts by weight of butyl acrylate, carrying out microwave-assisted polymerization for 2h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 6:3;
s4, preparing a large-plate ceramic tile back glue: 40 parts by weight of acrylate emulsion and 11 parts by weight of polyacrylate/SiO with the core-shell structure prepared in the step S3 2 And (3) mixing the composite microspheres and 6 parts by weight of fly ash, heating to 60 ℃, reacting for 3 hours, stirring for 30 minutes, and cooling to room temperature to obtain the large-plate ceramic tile back glue.
Comparative example 4
Compared with the example 3, the fly ash is not added in the step S5, and other conditions are not changed.
The method specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 6 parts by weight of hexadecyl trimethoxy silane and 12 parts by weight of gamma-aminopropyl triethoxy silane in 100 parts by weight of ethyl acetate to obtain an oil phase; dripping 45 weight parts of water into 100 weight parts of oil phase, adding 1.5 weight parts of Tween-80, stirring for 20min, emulsifying for 4min at 13500r/min, reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, performing ultrasonic treatment at 1000W for 20min, adding 1.5 parts by weight of 2,2-azodiisobutyl amidine hydrochloride, stirring for reaction for 1h, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain hydrophobic SiO (silicon dioxide) adsorbing an initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of the hydrophobing of the adsorption initiator obtained in step S2SiO 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 4 parts by weight of surfactant, stirring for reacting for 35min, adding 10 parts by weight of butyl acrylate, carrying out microwave-assisted polymerization for 2h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 6:3;
s4, modification of microspheres: 10 parts by weight of polyacrylate/SiO with a core-shell structure prepared in the step S3 2 Adding the composite microspheres into 50 parts by weight of 60wt% ethanol aqueous solution, stirring for 15min, adding 2.5 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 4:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 40 parts by weight of acrylate emulsion and 17 parts by weight of modified microspheres prepared in the step (S4), heating to 60 ℃, reacting for 3 hours, stirring for 30 minutes, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
Comparative example 5
Compared with example 3, no modified microspheres were added in step S5, and other conditions were not changed.
The method specifically comprises the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 6 parts by weight of hexadecyl trimethoxy silane and 12 parts by weight of gamma-aminopropyl triethoxy silane in 100 parts by weight of ethyl acetate to obtain an oil phase; dripping 45 weight parts of water into 100 weight parts of oil phase, adding 1.5 weight parts of Tween-80, stirring for 20min, emulsifying for 4min at 13500r/min, reacting for 4h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Adding hollow microspheres into 200 parts by weight of water, carrying out ultrasonic treatment at 1000W for 20min, adding 1.5 parts by weight of 2,2-azodiisobutyl amidine hydrochloride,stirring for reaction for 1h, centrifuging at 3000r/min for 15min, washing with clear water, and drying at 70 deg.C for 2h to obtain hydrophobic SiO for adsorbing initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Adding hollow microspheres into 100 parts by weight of water, ultrasonically dispersing for 15min at 1000W, adding 4 parts by weight of surfactant, stirring for reacting for 35min, adding 10 parts by weight of butyl acrylate, carrying out microwave-assisted polymerization for 2h, centrifuging for 15min at 3000r/min, washing with clear water, and drying for 2h at 70 ℃ to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 6:3;
s4, modification of microspheres: 10 parts by weight of the polyacrylate/SiO with the core-shell structure prepared in the step S3 2 Adding the composite microspheres into 50 parts by weight of 60wt% ethanol aqueous solution, stirring for 15min, adding 2.5 parts by weight of composite silane coupling agent, centrifuging for 15min at 3000r/min, washing with clear water, and drying at 70 ℃ for 2h to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 4:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 40 parts by weight of acrylate emulsion and 17 parts by weight of fly ash, heating to 60 ℃, reacting for 3 hours, stirring for 30 minutes, and cooling to room temperature to obtain the large-plate ceramic tile back adhesive.
Test example 1
Large tile backsizers prepared in examples 1 to 7 and comparative examples 1 to 5, and a commercially available backsize were subjected to performance tests, and the results are shown in Table 1.
The standard detection is referred to JC/T547-2005 ceramic wall and floor tile adhesive and GB 24264-2009 adhesive for facing stone.
TABLE 1
As can be seen from the above table, the large-plate ceramic tile back glue prepared in the embodiments 1-3 of the present invention has good cohesiveness, good water resistance and aging resistance, and little change of the characteristics after freeze-thaw cycles.
Test example 2
After the tile adhesive was dried, the large-board tile backsize prepared in examples 1 to 7 and comparative examples 1 to 5, and the commercially available backsize, were applied to the back of the tile, which was then attached to the wall, and the properties thereof were as shown in table 2.
TABLE 2
As can be seen from the above table, the large-plate ceramic tile back glue prepared in the embodiments 1-3 of the invention has better application property. After one year, the problems of cracks, hollows, crusting, falling off and the like do not occur. In comparative examples 4 and 5, partial exfoliation occurred after one year. Comparative examples 1 to 3 exhibited a phenomenon of empty drum after one year.
Examples 4 and 5 compared with example 3, the surfactant was dodecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide alone, and the water resistance, freeze-thaw resistance, and tensile strength of the adhesive were reduced. In comparative example 2, compared to example 3, the water resistance, freeze/thaw resistance, aging resistance, and tensile bond strength were decreased without adding a surfactant in step S3. The surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the space formed by the staggered layer between dodecyl group and octadecyl group provides abundant space for the polymerization of the acrylate monomer, which is beneficial to the occurrence of polymerization reaction, so that the mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide can promote the formation of a polymer layer to play a role in synergy. The polymer shell layer is uniform and the thickness is increased due to the good polymerization environment, so that the fly ash can be uniformly coupled, the dispersibility of the fly ash in the acrylate emulsion is improved, and the comprehensive performance is improved.
In examples 6 and 7, compared with example 3, the composite silane coupling agent was KH570 or KH550 alone, and the water resistance, freeze-thaw resistance, aging resistance, and tensile adhesive bond strength were reduced. Comparative example 3 compared to example 3, without the step S4, the overall performance was significantly reduced. The polyacrylate/SiO with the core-shell structure prepared by the invention 2 The composite microspheres have the modification effect of a composite silane coupling agent, wherein the composite silane coupling agent is a mixture of KH570 and KH550, double bonds of the KH570 can be bonded with the polyacrylate of the shell layer, amino groups of the KH550 can form hydrogen bonds with ester groups of the polyacrylate of the shell layer, so that the composite silane coupling agent can be coupled on the microspheres, the other end of the composite silane coupling agent is a siloxane part, and after the fly ash is added, the siloxane part can be in contact with SiO in the fly ash 2 The components are coupled, so that the modified microsphere and the fly ash are coupled, and meanwhile, the modified microsphere has good compatibility in the acrylate emulsion because the shell layer is polyacrylate, so that the problem of poor compatibility of the fly ash in the acrylate emulsion is solved.
Comparative example 1, which does not include step S2, but adds the initiator after adding the monomer, has a reduced water resistance, freeze-thaw resistance, and tensile strength of the adhesive as compared to example 3. In the invention, the cationic initiator is positively charged and is easy to react with the prepared hydrophobic SiO 2 Hollow microsphere negatively charged SiO 2 The shell layer is electrostatically adsorbed to be adsorbed on the surface of the microsphere, so that the polymerization reaction can be initiated in situ. The comparative example 1 does not include S2, and the surface of the microsphere does not adsorb an initiator, so that the polymerization reaction efficiency is reduced, the effect is reduced, the formed polymer shell is not uniform, the dispersibility of the fly ash in the acrylate emulsion is influenced, and the performance is reduced.
Comparative examples 4 and 5 compared with example 3, no fly ash or modified microspheres were added in step S5The comprehensive performance of the composite material is obviously reduced. The large-plate tile back glue introduces the fly ash component, can perform secondary hydration with the cement mortar, obviously improves the bonding capability of the tile back glue and the cement mortar, and improves the water resistance and the freeze-thaw resistance of the tile back glue. Under the condition of sufficient water, the hydration reaction rate of cement and fly ash can be accelerated, the fly ash glass body is disintegrated to generate a large amount of C-S-H gel, the structure is more compact, and the bonding capability of the back adhesive and cement mortar of the large-plate ceramic tile is improved, so that the bonding capability is obviously improved. The surface of the modified particle is provided with double bonds and amino groups, the double bonds can be connected with polyacrylic ester bonds of the shell layer, the amino groups can form hydrogen bonds with ester groups of polyacrylate of the shell layer, so that the composite silane coupling agent can be coupled on the microsphere, the other end of the composite silane coupling agent is a siloxane part, and after the fly ash is added, the siloxane part can be connected with SiO in the fly ash 2 The components are coupled, so that the modified microsphere is coupled with the fly ash, and meanwhile, the modified microsphere has good compatibility in the acrylate emulsion because the shell layer is polyacrylate, so that the problem of poor compatibility of the fly ash in the acrylate emulsion is solved. Therefore, the addition of the two components has a synergistic effect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a large-plate ceramic tile back glue is characterized in that water is dripped into an organic solution dissolved with long alkyl chain silane and aminosilane for emulsification reaction to obtain hydrophobic SiO 2 Hollow microspheres, further dispersing in water, adding a cationic initiator, and stirring for reaction to obtain hydrophobic SiO for adsorbing the initiator 2 Further adding a surfactant into the hollow microspheres, stirring for reaction, adding an acrylate monomer, and performing microwave-assisted polymerization to obtain the core-shell structurepolyacrylate/SiO 2 And (3) modifying the composite microspheres by using a composite silane coupling agent, mixing the modified composite microspheres with the acrylate emulsion and the fly ash, heating for reaction, and cooling to room temperature to obtain the large-plate ceramic tile back glue.
2. The method of claim 1, comprising the steps of:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving long alkyl chain silane and amino silane in an organic solvent to obtain an oil phase; adding water drop into oil phase, adding emulsifier, stirring, emulsifying, reacting, centrifuging, washing, and drying to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: hydrophobic SiO prepared in the step S1 2 Uniformly dispersing the hollow microspheres in water, adding a cationic initiator, stirring for reaction, centrifuging, washing and drying to obtain hydrophobic SiO adsorbing the initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: hydrophobic SiO for adsorbing the initiator prepared in the step S2 2 Dispersing the hollow microspheres in water, adding a surfactant, stirring for reaction, adding an acrylate monomer, performing microwave-assisted polymerization, centrifuging, washing and drying to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
s4, modification of microspheres: the polyacrylate/SiO with the core-shell structure prepared in the step S3 2 Dispersing the composite microspheres in an ethanol water solution, adding a composite silane coupling agent, centrifuging, washing and drying to obtain modified microspheres;
s5, preparing a large-plate ceramic tile back glue: and (5) mixing the acrylate emulsion, the modified microspheres prepared in the step (S4) and the fly ash, heating for reaction, uniformly stirring, and cooling to room temperature to obtain the large-plate ceramic tile back glue.
3. The method according to claim 2, wherein the long alkyl silane in step S1 is at least one selected from the group consisting of dodecyltrimethoxysilane, hexadecyltrimethoxysilane and octadecyltrimethoxysilane; the aminosilane is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and diethylenetriaminopropyltrimethoxysilane; the emulsifier is at least one selected from tween-20, tween-40, tween-60 and tween-80; the mass ratio of the long alkyl chain silane to the amino silane is 5-7; the emulsification condition is 12000-15000r/min emulsification for 3-5min, and the reaction time is 3-5h.
4. The method of claim 2, wherein the cationic initiator in step S2 is 2,2-azobisisobutylamidine hydrochloride; the hydrophobic SiO 2 The mass ratio of the hollow microspheres to the cationic initiator is 100; the stirring reaction time is 0.5-1h.
5. The production method according to claim 2, wherein the surfactant in step S3 is a cationic surfactant or an anionic surfactant selected from at least one of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, sodium tetradecylsulfate, sodium tetradecylbenzenesulfonate, sodium hexadecylbenzenesulfonate, sodium hexadecylsulfate, sodium hexadecylbenzenesulfonate, sodium octadecylbenzenesulfonate, sodium octadecylsulphate, sodium octadecylsulphonate; the cationic surfactant is selected from at least one of cetyl trimethyl sodium bromide, cetyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride and dodecyl dimethyl benzyl ammonium chloride; preferably, the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio is 5-7:3.
6. The method according to claim 2, wherein the acrylate monomer in step S3 is at least one selected from the group consisting of butyl acrylate, methyl acrylate, ethyl acrylate, 2-methyl methacrylate and 2-ethyl methacrylate; hydrophobic SiO of the adsorption initiator 2 The mass ratio of the hollow microspheres to the surfactant to the acrylate monomer is 10-5:7-12; the microwave power in the microwave-assisted polymerization is 1000-1200W, and the polymerization time is 1-3h.
7. The method according to claim 2, wherein the core-shell structured polyacrylate/SiO in step S4 2 The mass ratio of the composite microspheres to the composite silane coupling agent is 10; the composite silane coupling agent is at least one selected from KH550, KH560, KH570, KH580, KH590, KH602 and KH792, preferably, the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 3-5:2.
8. The preparation method according to claim 7, wherein the mass ratio of the acrylate emulsion, the modified microspheres and the fly ash in step S5 is 30-50; the heating temperature is 50-70 ℃, and the reaction time is 2-4h.
9. The preparation method according to claim 7, characterized by comprising the following steps:
s1, hydrophobic SiO 2 Preparing hollow microspheres: dissolving 5-7 parts by weight of long alkyl chain silane and 10-15 parts by weight of aminosilane in 100 parts by weight of organic solvent to obtain an oil phase; adding 40-50 weight parts of water into 100 weight parts of oil phase, adding 1-2 weight parts of emulsifier, stirring, emulsifying at 12000-15000r/min for 3-5min, reacting for 3-5h, centrifuging, washing, and drying to obtain hydrophobic SiO 2 Hollow microspheres;
s2, adsorption of an initiator: 100 parts by weight of the hydrophobic SiO prepared in step S1 2 Uniformly dispersing the hollow microspheres in 200 parts by weight of water, adding 1-2 parts by weight of 2,2-azobisisobutylamidine hydrochloride, stirring for reaction for 0.5-1h, and centrifugingWashing and drying to obtain hydrophobic SiO for adsorbing initiator 2 Hollow microspheres;
s3, polyacrylate/SiO with core-shell structure 2 Preparing the composite microspheres: 10 parts by weight of hydrophobic SiO adsorbing the initiator prepared in the step S2 2 Dispersing hollow microspheres in 100 parts by weight of water, adding 3-5 parts by weight of surfactant, stirring for reaction, adding 7-12 parts by weight of acrylate monomer, carrying out microwave-assisted polymerization for 1-3h at 1000-1200W, centrifuging, washing, and drying to obtain polyacrylate/SiO with a core-shell structure 2 Compounding the microspheres;
the surfactant is a mixture of dodecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, and the mass ratio of the dodecyl trimethyl ammonium bromide to the octadecyl trimethyl ammonium bromide is 5-7:3;
s4, modification of microspheres: 10 parts by weight of polyacrylate/SiO with a core-shell structure prepared in the step S3 2 Dispersing the composite microspheres in 50 parts by weight of 50-70wt% ethanol aqueous solution, adding 2-3 parts by weight of composite silane coupling agent, centrifuging, washing and drying to obtain modified microspheres;
the composite silane coupling agent is a mixture of KH570 and KH550, and the mass ratio is 3-5:2;
s5, preparing a large-plate ceramic tile back glue: and (3) mixing 30-50 parts by weight of acrylate emulsion, 10-12 parts by weight of modified microspheres prepared in the step (S4) and 5-7 parts by weight of fly ash, heating to 50-70 ℃, reacting for 2-4h, uniformly stirring, and cooling to room temperature to obtain the back glue for the large-plate ceramic tiles.
10. A large-board tile backsize obtainable by the process according to any one of claims 1 to 9.
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| CN113912359A (en) * | 2021-11-26 | 2022-01-11 | 佛山市卓仕高新型材料有限公司 | High-toughness tile back glue and preparation method thereof |
| CN114591462A (en) * | 2022-03-09 | 2022-06-07 | 广东巴德富新材料有限公司 | Hydrophobic high-strength high-viscosity composite ceramic tile back glue and preparation method thereof |
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| US20070213449A1 (en) * | 2006-03-08 | 2007-09-13 | 3M Innovative Properties Company | Pressure-sensitive adhesive containing silica nanoparticles |
| CN104262531A (en) * | 2014-09-22 | 2015-01-07 | 广西大学 | Unmodified silica sol/polyacrylate core-shell emulsion and preparation method thereof |
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