CN112457812A - Preparation method and application of mildew-proof yellowing-resistant transparent adhesive with strong adhesion - Google Patents
Preparation method and application of mildew-proof yellowing-resistant transparent adhesive with strong adhesion Download PDFInfo
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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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a preparation method of a transparent adhesive with strong mildew-proof yellowing resistance and strong bonding property, which comprises the following raw materials in parts by weight: 30-70 parts of silane modified polyether resin, 20-50 parts of plasticizer, 3-5 parts of filler, 10-20 parts of fumed silica, 0.5-2 parts of water removing agent, 0-0.5 part of ultraviolet absorber, 0-0.6 part of light stabilizer, 0-0.5 part of antioxidant, 0.5-3 parts of silane coupling agent, 0.1-0.4 part of catalyst and 0.1-1 part of mildew preventive for later use; the invention also discloses the application field of the transparent adhesive with strong mildew-proof and yellowing-resistant adhesion, belongs to silane modified polyether sealant, has the characteristics of environmental protection, low content of organic volatile matters, mildew resistance, yellowing resistance and strong adhesion, is used in the field of indoor home decoration, and has better application effect in materials such as doors and windows, murals, sculptures, photo frames, decorative pictures, wash basins, bathrooms, glass, PC, aluminum materials, marble, ceramic tiles and the like.
Description
Technical Field
The invention belongs to the technical field of sealants, and particularly relates to a preparation method and application of a transparent adhesive with strong mildew-proof, yellowing-resistant and bonding properties.
Background
In the field of indoor design and decoration, people have higher and higher requirements on attractiveness and environmental protection, the sealant can be used for bonding and sealing doors and windows, murals, sculptures, photo frames, decorative pictures and the like, the transparency of the sealant can be required to be high, the appearance is attractive, and the sealant can be used for bonding, sealing and waterproofing in wash basins and bathrooms. Because mould usually grows in places where water exists for a long time, such as wash basins, bathrooms and the like, the used sealant has the mould-proof effect and prevents the mould from growing.
The transparent sealant on the market mainly comprises a silicone sealant and a silane modified polyether sealant, the silicone transparent sealant has low transparency and is easy to pollute a substrate, and a large amount of white oil is doped in some components, so that the white oil can seep out after long-term use and seriously pollute the material. The silane modified polyether sealant is high in transparency, free of substrate pollution, low in content of organic volatile matters, environment-friendly and more acceptable to people, but most of silane modified polyether transparent sealants have no good mildew-proof effect, and yellowing phenomenon can be caused even if some of the sealants are used for a long time, so that attractiveness is affected, the silane modified polyether sealant is poor in adhesion to some materials, and the application range is small.
Disclosure of Invention
The invention aims to provide a preparation method of the mildew-proof yellowing-resistant transparent adhesive with strong bonding property, and the invention also aims to provide application of the mildew-proof yellowing-resistant transparent adhesive with strong bonding property in the field of indoor home decoration.
The technical problems to be solved by the invention are as follows:
in the prior art, the silicone transparent sealant has low transparency and is easy to pollute a substrate, a large amount of white oil is doped in some components, the silicone transparent sealant can seep out after long-term use and seriously pollute the material, the silane modified polyether sealant has high transparency and does not pollute the substrate, but most of the silane modified polyether transparent sealants have no good mildew-proof effect, yellowing phenomenon can be generated after long-term use of some silicone transparent sealants, the attractiveness is influenced, the adhesion to some materials is poor, and the application range is small.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a transparent adhesive with strong mildew-proof yellowing resistance and strong bonding property comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 30-70 parts of silane modified polyether resin, 20-50 parts of plasticizer, 3-5 parts of filler, 10-20 parts of fumed silica, 0.5-2 parts of water removing agent, 0-0.5 part of ultraviolet absorber, 0-0.6 part of light stabilizer, 0-0.5 part of antioxidant, 0.5-3 parts of silane coupling agent, 0.1-0.4 part of catalyst and 0.1-1 part of mildew preventive for later use;
secondly, adding the silane modified polyether resin, the plasticizer and the 90% water removal agent into a planetary stirrer, and stirring for 5-10min at the rotating speed of 30-50r/min under the normal temperature condition to obtain a base material;
thirdly, adding the filler and the fumed silica into the base material, adding the filler and the fumed silica for 3 times in equal amount, increasing the rotating speed to 500-1000r/min, stirring for 10min, adding the ultraviolet light absorber, the light stabilizer, the antioxidant and the mildew preventive, keeping the rotating speed unchanged, and continuously stirring for 20-40min to obtain a mixture;
and fourthly, adding a silane coupling agent, a catalyst and a 10% water removal agent into the mixture, and stirring for 10-20min at a rotating speed of 50-100r/min under a vacuum condition to obtain the transparent adhesive with strong mildew-proof, yellowing-resistant and bonding properties.
Preferably, the preparation method of the filler comprises the following steps:
step S11, adding silicon dioxide and absolute ethyl alcohol into a beaker, controlling the temperature to be 50-60 ℃, carrying out ultrasonic dispersion for 20-40min under the condition of frequency being 30-50kHz, then adding a silane coupling agent KH-550 into the beaker, controlling the temperature to be 78 ℃, carrying out reaction for 10-20h under the condition of rotating speed being 200 plus one year per minute, cooling to room temperature after the reaction is finished, washing a reactant for 3-5 times by deionized water, drying in a drying oven at the temperature of 60-80 ℃ to constant weight to obtain modified silicon dioxide, adding the modified silicon dioxide, acetone and coumarin-3-carboxylic acid into the beaker, carrying out reaction for 10h under the condition of rotating speed being 800 plus one year per minute, then carrying out centrifugal treatment, washing the precipitate for 3 times by deionized water, and drying in the drying oven at the temperature of 60 ℃ for 10-12h to obtain a composite material 1;
step S12, adding isopropanol, deionized water and N, N-2-dimethyl dodecyl tertiary amine into a four-neck flask, keeping the temperature at 30 ℃, reacting for 20min under the condition of the rotation speed of 200 and 300r/min, dropwise adding epoxy chloropropane into the four-neck flask, heating to 50 ℃, reacting for 8-10h under the condition of the unchanged rotation speed, removing the organic solvent in a rotary evaporator at 60 ℃ after the reaction is finished, and finally washing twice with diethyl ether to obtain quaternary ammonium salt;
step S13, adding chitosan, deionized water and isopropanol into a four-mouth beaker, keeping the temperature at 30 ℃, reacting for 35min under the condition that the rotating speed is 200 plus materials and 300r/min, adding the quaternary ammonium salt and sodium hydroxide solid obtained in the step S12 into the four-mouth beaker, wherein the quaternary ammonium salt and the sodium hydroxide solid are added in 4 times in equal amount, the interval is 1h every time, after all the quaternary ammonium salt and the sodium hydroxide solid are added, heating to 85 ℃, continuously reacting for 48h without changing the rotating speed, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the mass fraction of 25% to adjust the pH value to 7-8, treating for 24h by using a Soxhlet extractor, and finally drying in a constant-temperature drying box with the temperature of 100 ℃ to constant weight to obtain;
step S14, adding the intermediate and dimethylformamide into a three-neck flask, keeping the temperature at 60 ℃, keeping the rotation speed at 150-;
and S15, adding the composite material 1, the composite material 2 and dimethyl sulfoxide into a three-neck flask, keeping the temperature at 60 ℃, reacting for 0.5h under the condition of the rotating speed of 150-.
Preferably, the amount ratio of the silica, the absolute ethyl alcohol and the silane coupling agent KH-550 in the step S11 is 3 g: 60mL of: 1-3mL, wherein the dosage ratio of the modified silicon dioxide, the acetone and the coumarin-3-carboxylic acid is 1 g: 60mL of: 1-1.5 g; in the step S12, the dosage ratio of the isopropanol, the deionized water, the N, N-2-dimethyl dodecyl tertiary amine and the epichlorohydrin is 120 mL: 60mL of: 18 g: 16g of a mixture; in the step S13, the dosage ratio of the chitosan, the deionized water, the isopropanol, the quaternary ammonium salt and the sodium hydroxide is 2 g: 10mL of: 10mL of: 7 g: 25g of the total weight of the mixture; in the step S14, the dosage ratio of the intermediate, the dimethylformamide, the isopropanol and the epichlorohydrin is 1 g: 20mL of: 5mL of: 8 mL; in the step S15, the usage ratio of the composite material 1, the composite material 2, the dimethyl sulfoxide and the beta-cyclodextrin dispersion is 1 g: 1 g: 20mL of: 20mL, wherein the beta-cyclodextrin dispersion liquid is prepared by mixing a sodium hydroxide solution with the concentration of 0.1mol/L and beta-cyclodextrin according to the dosage ratio of 20 mL: 2g of the above-mentioned materials are mixed.
According to the invention, silane coupling agent KH-550 is used for carrying out surface modification on silicon dioxide, coumarin-3-carboxylic acid with certain antibacterial performance and bioactivity is hybridized with modified silicon dioxide to obtain silicon dioxide loaded with antibacterial factors, namely composite material 1, quaternary ammonium salt is prepared, chitosan quaternary ammonium salt composite material, namely composite material 2 is prepared, and finally composite material 1 and composite material 2 are mixed with beta-cyclodextrin dispersion liquid to prepare the filler, the composite material 1 and composite material 2 are used as core materials, beta-cyclodextrin is used as a wall material, the synergistic antibacterial effect of the quaternary ammonium salt, chitosan and coumarin-3-carboxylic acid is utilized, the filler is added into the sealant, antibacterial molecules are slowly released, and the sealant has high-efficiency and lasting antibacterial performance.
Preferably, the coupling agent is prepared by the following method: the method comprises the steps of fully replacing a 1L-capacity three-neck flask with a reflux cooler, a stirrer and a thermometer by dry nitrogen, adding 405g of 1-vinyl-3, 4-epoxycyclohexane, 0.1g of Speirer catalyst with the mass fraction of Pt being 2%, 8.1g of acetonitrile and 8.1g of methanol into the three-neck flask, heating to 60 ℃ under the protection of nitrogen, reacting for 6 hours under the condition of the rotation speed of 100-200r/min, adding 375g of trimethoxy silane, controlling the reaction temperature to be 60-75 ℃, continuously stirring and reacting for 2 hours under the condition of the rotation speed unchanged, distilling the reaction liquid at the temperature of 111-120 ℃ after the reaction is finished, and collecting a distillation product 2- (3, 4-epoxycyclohexyl) ethyltrialkoxy silane, namely the coupling agent.
Preferably, the catalyst is prepared by the following method: heating and refluxing 0.2mol of acetic acid and 0.3mol of dibutyltin oxide in 50mL of toluene for 1-3h, adding 0.3mol of gamma-aminopropyl methyldimethoxysilane in the reflux product, and uniformly stirring to prepare the tin-based composite catalyst, namely the catalyst.
Preferably, the silane modified polyether resin is a polyether with both end groups being trimethoxy silane end capping, such as 3368T resin of New Material science and technology, Inc. of Ringrui ocean Antai, and HMS-1303 resin of Huangjiang Huangma science and technology, Inc. More preferably, the silane-modified polyether resin is 40 to 60 parts by weight.
Preferably, the plasticizer is one or more selected from diisononyl phthalate, diisodecyl phthalate and diisononyl cyclohexane-1, 2-dicarboxylate, mixed in any proportion.
Preferably, the fumed silica is hydrophobic fumed silica, the water removal agent is vinyl trimethoxy silane, the ultraviolet absorber is a formamidine ultraviolet absorber, the antioxidant is 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, and the mildew preventive is 4, 5-dichloro-2-octyl-3 (2H) -isothiazolinone.
Preferably, the light stabilizer is one or more of light stabilizers 234, 292, 622, 770, 776 and 788 mixed in any proportion.
Preferably, the invention is used in the field of indoor home decoration, and has good application effect on the adhesion of materials such as doors and windows, murals, sculptures, photo frames, decorative pictures, wash basins, bathrooms, glass, PC, aluminum materials, marble, ceramic tiles and the like.
The invention has the beneficial effects that:
1. the transparent adhesive prepared by the invention belongs to silane modified polyether sealant, has the characteristics of environmental protection and low content of organic volatile matter, compared with silicone sealant and polyurethane sealant, the silicone sealant and the polyurethane sealant have better environmental protection property, belong to environment-friendly products, the prepared transparent adhesive has the characteristics of mildew resistance, yellowing resistance and strong adhesion, most of the transparent adhesives on the market belong to silicone products, the transparency is not high, a few of the transparent adhesives belong to silane modified polyether sealant products, but do not have the mildew-proof effect, but also is not resistant to yellowing, mold is bred if the transparent adhesive is used for a long time, the yellowing phenomenon is generated, the appearance is influenced, and the transparent adhesive on the market can only be used for bonding materials such as glass, PC, aluminum materials and the like, the transparent adhesive prepared by the invention has good adhesive effect on glass, PC, aluminum materials, marble, ceramic tiles and other substrates.
2. The invention uses silane coupling agent KH-550 to modify the surface of silicon dioxide, mixes coumarin-3-carboxylic acid with certain antibacterial property and bioactivity with modified silicon dioxide to obtain silicon dioxide loaded with antibacterial factors, namely composite material 1, then prepares quaternary ammonium salt, then prepares chitosan quaternary ammonium salt composite material, namely composite material 2, and finally mixes composite material 1 and composite material 2 with beta-cyclodextrin dispersion liquid to prepare the filler, takes composite material 1 and composite material 2 as core materials, takes beta-cyclodextrin as wall material, utilizes the synergistic bacteriostasis of quaternary ammonium salt, chitosan and coumarin-3-carboxylic acid to add into the sealant, slowly releases antibacterial molecules, so that the sealant has high efficiency and lasting antibacterial property, and adopts self-made coupling agent, the self-made catalyst has higher catalytic activity compared with the conventional dibutyltin dilaurate, and the used amount of the catalyst is less under the condition of reaching the same curing speed.
3. The ultraviolet light absorber is a formamidine ultraviolet light absorber, can effectively absorb ultraviolet light with the wavelength of 240-350nm, has the maximum absorption peak of 308nm, can almost completely absorb the ultraviolet light in the wave band of 300-330nm, specifically has the functions of quenching singlet oxygen, decomposing hydroperoxide into inactive substances and the like, enables high molecular polymers to eliminate or slow down photochemical reaction possibility under the radiation of light, prevents or delays the process of photoaging, prolongs the service life of the sealant and improves yellowing resistance, and the added fumed silica also has a certain shielding effect on the ultraviolet light and reduces the decomposition of the ultraviolet light on an organic coating.
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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a transparent adhesive with strong mildew-proof yellowing resistance and strong bonding property comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 30 parts of silane modified polyether resin, 20 parts of plasticizer, 3 parts of filler, 10 parts of fumed silica, 0.5 part of water removal agent, 0.1 part of ultraviolet light absorber, 0.1 part of light stabilizer, 0.1 part of antioxidant, 0.5 part of silane coupling agent, 0.1 part of catalyst and 0.1 part of mildew preventive for later use;
secondly, adding the silane modified polyether resin, the plasticizer and the 90% water removal agent into a planetary stirrer, and stirring for 8min at the rotating speed of 40r/min under the normal temperature condition to obtain a base material;
thirdly, adding filler and fumed silica into the base material, adding the filler and the fumed silica for 3 times in an equivalent manner, increasing the rotating speed to 500r/min, stirring for 10min, adding the ultraviolet light absorber, the light stabilizer, the antioxidant and the mildew preventive, keeping the rotating speed unchanged, and continuously stirring for 20min to obtain a mixture;
and fourthly, adding a silane coupling agent, a catalyst and a 10% water removal agent into the mixture, and stirring for 10min at a rotating speed of 50r/min under a vacuum condition to obtain the transparent adhesive with strong mildew-proof, yellowing-resistant and bonding properties.
Preferably, the preparation method of the filler comprises the following steps:
step S11, adding silicon dioxide and absolute ethyl alcohol into a beaker, controlling the temperature to be 50 ℃, performing ultrasonic dispersion for 20min under the condition of frequency being 30kHz, then adding a silane coupling agent KH-550 into the beaker, reacting for 10h under the conditions of temperature being 78 ℃ and rotation speed being 200r/min, cooling to room temperature after the reaction is finished, washing reactants for 3 times by deionized water, drying in an oven at 60 ℃ to constant weight to obtain modified silicon dioxide, adding the modified silicon dioxide, acetone and coumarin-3-carboxylic acid into the beaker, reacting for 10h under the condition of rotation speed being 800r/min, then performing centrifugal treatment, washing precipitates for 3 times by deionized water, and drying for 10h in the oven at 60 ℃ to obtain a composite material 1;
step S12, adding isopropanol, deionized water and N, N-2-dimethyl dodecyl tertiary amine into a four-neck flask, keeping the temperature at 30 ℃, reacting for 20min under the condition of the rotating speed of 200r/min, dropwise adding epoxy chloropropane into the four-neck flask, then heating to 50 ℃, reacting for 8h under the condition of the rotating speed being unchanged, removing an organic solvent in a rotary evaporator at 60 ℃ after the reaction is finished, and finally washing twice with diethyl ether to obtain a quaternary ammonium salt;
step S13, adding chitosan, deionized water and isopropanol into a four-mouth beaker, keeping the temperature at 30 ℃, reacting for 35min under the condition of a rotating speed of 200r/min, adding the quaternary ammonium salt and sodium hydroxide solid obtained in the step S12 into the four-mouth beaker, adding the quaternary ammonium salt and the sodium hydroxide solid in 4 times at an equal amount, wherein each time interval is 1h, after all the quaternary ammonium salt and the sodium hydroxide solid are added, heating to 85 ℃, continuously reacting for 48h without changing the rotating speed, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the mass fraction of 25%, adjusting the pH value to 7, treating for 24h by using a Soxhlet extractor, and finally drying in a constant-temperature drying oven at 100 ℃ to constant weight to obtain an intermediate;
step S14, adding the intermediate and dimethylformamide into a three-neck flask, reacting for 0.5h under the conditions that the temperature is kept at 60 ℃ and the rotating speed is 150r/min, then adding isopropanol and epichlorohydrin, continuously reacting for 8h under the condition that the rotating speed is unchanged, adding a sodium bicarbonate solution with the mass fraction of 25% into the three-neck flask to adjust the pH value to 7, washing and filtering for 3 times by using a mixed solution of methanol and deionized water according to the volume ratio of 20:1 after the reaction is finished, and then putting the mixture into a 50 ℃ oven to dry to constant weight to obtain a composite material 2;
and step S15, adding the composite material 1, the composite material 2 and dimethyl sulfoxide into a three-neck flask, keeping the temperature at 60 ℃, reacting for 0.5h under the condition of the rotating speed of 150r/min, then adding beta-cyclodextrin dispersion liquid, increasing the rotating speed to 350r/min, reacting for 4h, washing and filtering for three times by using a mixed solution of methanol and deionized water according to the volume ratio of 20:3 after the reaction is finished, and finally drying in a 60 ℃ drying oven to constant weight to obtain the filler.
In the step S11, the dosage ratio of the silicon dioxide, the absolute ethyl alcohol and the silane coupling agent KH-550 is 3 g: 60mL of: 1mL, and the dosage ratio of the modified silicon dioxide, the acetone and the coumarin-3-carboxylic acid is 1 g: 60mL of: 1g of a compound; in the step S12, the dosage ratio of the isopropanol, the deionized water, the N, N-2-dimethyl dodecyl tertiary amine and the epichlorohydrin is 120 mL: 60mL of: 18 g: 16g of a mixture; in the step S13, the dosage ratio of the chitosan, the deionized water, the isopropanol, the quaternary ammonium salt and the sodium hydroxide is 2 g: 10mL of: 10mL of: 7 g: 25g of the total weight of the mixture; in the step S14, the dosage ratio of the intermediate, the dimethylformamide, the isopropanol and the epichlorohydrin is 1 g: 20mL of: 5mL of: 8 mL; in the step S15, the usage ratio of the composite material 1, the composite material 2, the dimethyl sulfoxide and the beta-cyclodextrin dispersion is 1 g: 1 g: 20mL of: 20mL, wherein the beta-cyclodextrin dispersion liquid is prepared by mixing a sodium hydroxide solution with the concentration of 0.1mol/L and beta-cyclodextrin according to the dosage ratio of 20 mL: 2g of the above-mentioned materials are mixed.
The coupling agent is prepared by the following method: the coupling agent is prepared by the steps of fully replacing a 1L-capacity three-neck flask with a reflux cooler, a stirrer and a thermometer by dry nitrogen, adding 405g of 1-vinyl-3, 4-epoxycyclohexane, 0.1g of Speirer catalyst with the mass fraction of Pt being 2%, 8.1g of acetonitrile and 8.1g of methanol into the three-neck flask, heating to 60 ℃ under the protection of nitrogen, reacting for 6 hours, adding 375g of trimethoxy silane, controlling the reaction temperature to be 60 ℃ under the condition of 100r/min rotation speed, continuously stirring for reacting for 2 hours, distilling the reaction liquid at 111 ℃ after the reaction is finished, and collecting a distillation product 2- (3, 4-epoxycyclohexyl) ethyl trialkoxy silane, namely the coupling agent.
The catalyst is prepared by the following method: heating and refluxing 0.2mol of acetic acid and 0.3mol of dibutyltin oxide in 50mL of toluene for 1 hour, adding 0.3mol of gamma-aminopropyl methyldimethoxysilane in the reflux product, and uniformly stirring to prepare the tin-based composite catalyst, namely the catalyst.
The silane modified polyether resin is 3368T resin of New Material science and technology Limited of Ringoceanic Antai of Jiangsu, the plasticizer is selected from diisononyl phthalate, the fumed silica is hydrophobic fumed silica, the water removing agent is vinyltrimethoxysilane, the ultraviolet light absorber is a formamidine ultraviolet light absorber, the antioxidant is 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, the mildew preventive is 4, 5-dichloro-2-octyl-3 (2H) -isothiazolinone, and the light stabilizer is light stabilizer 234.
Example 2
A preparation method of a transparent adhesive with strong mildew-proof yellowing resistance and strong bonding property comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 50 parts of silane modified polyether resin, 40 parts of plasticizer, 4 parts of filler, 15 parts of fumed silica, 1 part of water removal agent, 0.2 part of ultraviolet light absorber, 0.2 part of light stabilizer, 0.2 part of antioxidant, 1 part of silane coupling agent, 0.3 part of catalyst and 0.5 part of mildew preventive for later use;
secondly, adding the silane modified polyether resin, the plasticizer and the 90% water removal agent into a planetary stirrer, and stirring for 8min at the rotating speed of 40r/min under the normal temperature condition to obtain a base material;
thirdly, adding filler and fumed silica into the base material, adding the filler and the fumed silica for 3 times in an equivalent manner, increasing the rotating speed to 800r/min, stirring for 10min, adding the ultraviolet light absorber, the light stabilizer, the antioxidant and the mildew preventive, keeping the rotating speed unchanged, and continuously stirring for 30min to obtain a mixture;
and fourthly, adding a silane coupling agent, a catalyst and a 10% water removal agent into the mixture, and stirring for 15min at a rotating speed of 80r/min under a vacuum condition to obtain the transparent adhesive with strong mildew-proof, yellowing-resistant and bonding properties.
The preparation method of the filler comprises the following steps:
step S11, adding silicon dioxide and absolute ethyl alcohol into a beaker, controlling the temperature to be 55 ℃, ultrasonically dispersing for 30min under the condition of frequency 40kHz, then adding a silane coupling agent KH-550 into the beaker, reacting for 15h under the conditions of temperature of 78 ℃ and rotation speed of 250r/min, cooling to room temperature after the reaction is finished, washing reactants for 4 times by deionized water, drying in an oven at 70 ℃ to constant weight to obtain modified silicon dioxide, adding the modified silicon dioxide, acetone and coumarin-3-carboxylic acid into the beaker, reacting for 10h under the condition of rotation speed of 900r/min, then carrying out centrifugal treatment, washing precipitates for 3 times by deionized water, and drying in the oven at 60 ℃ for 11h to obtain a composite material 1;
step S12, adding isopropanol, deionized water and N, N-2-dimethyl dodecyl tertiary amine into a four-neck flask, keeping the temperature at 30 ℃, reacting for 20min under the condition of the rotating speed of 250r/min, dropwise adding epoxy chloropropane into the four-neck flask, then heating to 50 ℃, reacting for 9h under the condition of the rotating speed being unchanged, removing an organic solvent in a rotary evaporator at 60 ℃ after the reaction is finished, and finally washing twice with diethyl ether to obtain a quaternary ammonium salt;
step S13, adding chitosan, deionized water and isopropanol into a four-mouth beaker, keeping the temperature at 30 ℃, reacting for 35min under the condition of a rotating speed of 250r/min, adding the quaternary ammonium salt and sodium hydroxide solid obtained in the step S12 into the four-mouth beaker, adding the quaternary ammonium salt and the sodium hydroxide solid in 4 times at an equal amount, wherein each time interval is 1h, after all the quaternary ammonium salt and the sodium hydroxide solid are added, heating to 85 ℃, continuously reacting for 48h without changing the rotating speed, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the mass fraction of 25%, adjusting the pH value to 7, treating for 24h by using a Soxhlet extractor, and finally drying in a constant-temperature drying oven at 100 ℃ to constant weight to obtain an intermediate;
step S14, adding the intermediate and dimethylformamide into a three-neck flask, reacting for 0.5h under the conditions that the temperature is kept at 60 ℃ and the rotating speed is 20r/min, then adding isopropanol and epichlorohydrin, continuously reacting for 8h under the condition that the rotating speed is unchanged, adding a sodium bicarbonate solution with the mass fraction of 25% into the three-neck flask to adjust the pH value to 7, washing and filtering for 3 times by using a mixed solution of methanol and deionized water according to the volume ratio of 20:1 after the reaction is finished, and then putting the mixture into a 50 ℃ oven to dry to constant weight to obtain a composite material 2;
and step S15, adding the composite material 1, the composite material 2 and dimethyl sulfoxide into a three-neck flask, keeping the temperature at 60 ℃, reacting for 0.5h under the condition of the rotating speed of 200r/min, then adding beta-cyclodextrin dispersion liquid, increasing the rotating speed to 400r/min, reacting for 4h, washing and filtering for three times by using a mixed solution of methanol and deionized water according to the volume ratio of 20:3 after the reaction is finished, and finally drying in a 60 ℃ drying oven to constant weight to obtain the filler.
In the step S11, the dosage ratio of the silicon dioxide, the absolute ethyl alcohol and the silane coupling agent KH-550 is 3 g: 60mL of: 2mL, the dosage ratio of the modified silicon dioxide, the acetone and the coumarin-3-carboxylic acid is 1 g: 60mL of: 1.3 g; in the step S12, the dosage ratio of the isopropanol, the deionized water, the N, N-2-dimethyl dodecyl tertiary amine and the epichlorohydrin is 120 mL: 60mL of: 18 g: 16g of a mixture; in the step S13, the dosage ratio of the chitosan, the deionized water, the isopropanol, the quaternary ammonium salt and the sodium hydroxide is 2 g: 10mL of: 10mL of: 7 g: 25g of the total weight of the mixture; in the step S14, the dosage ratio of the intermediate, the dimethylformamide, the isopropanol and the epichlorohydrin is 1 g: 20mL of: 5mL of: 8 mL; in the step S15, the usage ratio of the composite material 1, the composite material 2, the dimethyl sulfoxide and the beta-cyclodextrin dispersion is 1 g: 1 g: 20mL of: 20mL, wherein the beta-cyclodextrin dispersion liquid is prepared by mixing a sodium hydroxide solution with the concentration of 0.1mol/L and beta-cyclodextrin according to the dosage ratio of 20 mL: 2g of the above-mentioned materials are mixed.
The coupling agent is prepared by the following method: the coupling agent is prepared by the steps of fully replacing a 1L-capacity three-neck flask with a reflux cooler, a stirrer and a thermometer by dry nitrogen, adding 405g of 1-vinyl-3, 4-epoxycyclohexane, 0.1g of Speirer catalyst with the mass fraction of Pt being 2%, 8.1g of acetonitrile and 8.1g of methanol into the three-neck flask, heating to 60 ℃ under the protection of nitrogen, reacting for 6 hours, adding 375g of trimethoxy silane, controlling the reaction temperature to be 70 ℃ under the condition of 150r/min, continuously stirring for reacting for 2 hours under the condition of constant rotating speed, distilling the reaction liquid at the temperature of 115 ℃ after the reaction is finished, and collecting a distillation product 2- (3, 4-epoxycyclohexyl) ethyl trialkoxy silane, namely the coupling agent.
The catalyst is prepared by the following method: heating and refluxing 0.2mol of acetic acid and 0.3mol of dibutyltin oxide in 50mL of toluene for 2h, adding 0.3mol of gamma-aminopropyl methyldimethoxysilane in the reflux product, and uniformly stirring to prepare the tin-based composite catalyst, namely the catalyst.
The silane modified polyether resin is 3368T resin of New Material science and technology Limited of Ringoceanic Antai of Jiangsu, the plasticizer is selected from diisononyl phthalate, the fumed silica is hydrophobic fumed silica, the water removing agent is vinyltrimethoxysilane, the ultraviolet absorber is a formamidine ultraviolet absorber, the antioxidant is 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, the mildew preventive is 4, 5-dichloro-2-octyl-3 (2H) -isothiazolinone, and the light stabilizer is light stabilizer 234.
Example 3
A preparation method of a transparent adhesive with strong mildew-proof yellowing resistance and strong bonding property comprises the following steps:
firstly, preparing the following raw materials in parts by weight: 70 parts of silane modified polyether resin, 50 parts of plasticizer, 5 parts of filler, 20 parts of fumed silica, 2 parts of water removal agent, 0.5 part of ultraviolet absorber, 0.6 part of light stabilizer, 0.5 part of antioxidant, 3 parts of silane coupling agent, 0.4 part of catalyst and 1 part of mildew preventive for later use;
secondly, adding the silane modified polyether resin, the plasticizer and the 90% water removal agent into a planetary stirrer, and stirring for 10min at the normal temperature at the rotating speed of 50r/min to obtain a base material;
thirdly, adding filler and fumed silica into the base material, adding the filler and the fumed silica for 3 times in an equivalent manner, increasing the rotating speed to 1000r/min, stirring for 10min, adding the ultraviolet light absorber, the light stabilizer, the antioxidant and the mildew preventive, keeping the rotating speed unchanged, and continuously stirring for 40min to obtain a mixture;
and fourthly, adding a silane coupling agent, a catalyst and a 10% water removal agent into the mixture, and stirring for 20min at a rotating speed of 100r/min under a vacuum condition to obtain the transparent adhesive with strong mildew-proof, yellowing-resistant and bonding properties.
The preparation method of the filler comprises the following steps:
step S11, adding silicon dioxide and absolute ethyl alcohol into a beaker, controlling the temperature to be 60 ℃, performing ultrasonic dispersion for 40min under the condition of the frequency of 50kHz, then adding a silane coupling agent KH-550 into the beaker, reacting for 20h under the conditions of the temperature of 78 ℃ and the rotating speed of 300r/min, cooling to room temperature after the reaction is finished, washing reactants for 5 times by deionized water, drying in an oven at 80 ℃ to constant weight to obtain modified silicon dioxide, adding the modified silicon dioxide, acetone and coumarin-3-carboxylic acid into the beaker, reacting for 10h under the condition of the rotating speed of 1000r/min, then performing centrifugal treatment, washing precipitates for 3 times by deionized water, and drying in the oven at 60 ℃ for 12h to obtain a composite material 1;
step S12, adding isopropanol, deionized water and N, N-2-dimethyl dodecyl tertiary amine into a four-neck flask, keeping the temperature at 30 ℃, reacting for 20min under the condition of the rotating speed of 300r/min, dropwise adding epoxy chloropropane into the four-neck flask, then heating to 50 ℃, reacting for 10h under the condition of the rotating speed being unchanged, removing an organic solvent in a rotary evaporator at 60 ℃ after the reaction is finished, and finally washing twice with diethyl ether to obtain a quaternary ammonium salt;
step S13, adding chitosan, deionized water and isopropanol into a four-mouth beaker, keeping the temperature at 30 ℃, reacting for 35min under the condition of a rotating speed of 300r/min, adding the quaternary ammonium salt and sodium hydroxide solid obtained in the step S12 into the four-mouth beaker, adding the quaternary ammonium salt and the sodium hydroxide solid in 4 times at an equal amount, wherein each time interval is 1h, after all the quaternary ammonium salt and the sodium hydroxide solid are added, heating to 85 ℃, continuously reacting for 48h without changing the rotating speed, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the mass fraction of 25%, adjusting the pH value to 8, treating for 24h by using a Soxhlet extractor, and finally drying in a constant-temperature drying oven at 100 ℃ to constant weight to obtain an intermediate;
step S14, adding the intermediate and dimethylformamide into a three-neck flask, keeping the temperature at 60 ℃, reacting for 0.5h at the rotating speed of 300r/min, then adding isopropanol and epichlorohydrin, continuing to react for 8h at the constant rotating speed, adding a sodium bicarbonate solution with the mass fraction of 25% into the three-neck flask to adjust the pH value to 8, washing and filtering for 3 times by using a mixed solution of methanol and deionized water according to the volume ratio of 20:1 after the reaction is finished, and then putting the mixture into a 50 ℃ oven to dry to constant weight to obtain a composite material 2;
and step S15, adding the composite material 1, the composite material 2 and dimethyl sulfoxide into a three-neck flask, keeping the temperature at 60 ℃, reacting for 0.5h under the condition of the rotating speed of 300r/min, then adding beta-cyclodextrin dispersion liquid, increasing the rotating speed to 450r/min, reacting for 4h, washing and filtering for three times by using a mixed solution of methanol and deionized water according to the volume ratio of 20:3 after the reaction is finished, and finally drying in a 60 ℃ drying oven to constant weight to obtain the filler.
In the step S11, the dosage ratio of the silicon dioxide, the absolute ethyl alcohol and the silane coupling agent KH-550 is 3 g: 60mL of: 3mL, and the dosage ratio of the modified silicon dioxide, the acetone and the coumarin-3-carboxylic acid is 1 g: 60mL of: 1.5 g; in the step S12, the dosage ratio of the isopropanol, the deionized water, the N, N-2-dimethyl dodecyl tertiary amine and the epichlorohydrin is 120 mL: 60mL of: 18 g: 16g of a mixture; in the step S13, the dosage ratio of the chitosan, the deionized water, the isopropanol, the quaternary ammonium salt and the sodium hydroxide is 2 g: 10mL of: 10mL of: 7 g: 25g of the total weight of the mixture; in the step S14, the dosage ratio of the intermediate, the dimethylformamide, the isopropanol and the epichlorohydrin is 1 g: 20mL of: 5mL of: 8 mL; in the step S15, the usage ratio of the composite material 1, the composite material 2, the dimethyl sulfoxide and the beta-cyclodextrin dispersion is 1 g: 1 g: 20mL of: 20mL, wherein the beta-cyclodextrin dispersion liquid is prepared by mixing a sodium hydroxide solution with the concentration of 0.1mol/L and beta-cyclodextrin according to the dosage ratio of 20 mL: 2g of the above-mentioned materials are mixed.
The coupling agent is prepared by the following method: the coupling agent is prepared by the steps of fully replacing a 1L-capacity three-neck flask with a reflux cooler, a stirrer and a thermometer by dry nitrogen, adding 405g of 1-vinyl-3, 4-epoxycyclohexane, 0.1g of Speirer catalyst with the mass fraction of Pt being 2%, 8.1g of acetonitrile and 8.1g of methanol into the three-neck flask, heating to 60 ℃ under the protection of nitrogen, reacting for 6 hours under the condition of the rotation speed of 100-200r/min, adding 375g of trimethoxy silane, controlling the reaction temperature to be 75 ℃, continuously stirring and reacting for 2 hours under the condition of the rotation speed being unchanged, distilling the reaction liquid at the temperature of 120 ℃ after the reaction is finished, and collecting a distillation product 2- (3, 4-epoxycyclohexyl) ethyltrialkoxy silane, namely the coupling agent.
The catalyst is prepared by the following method: heating and refluxing 0.2mol of acetic acid and 0.3mol of dibutyltin oxide in 50mL of toluene for 1-3h, adding 0.3mol of gamma-aminopropyl methyldimethoxysilane in the reflux product, and uniformly stirring to prepare the tin-based composite catalyst, namely the catalyst.
The silane modified polyether resin is 3368T resin of New Material science and technology Limited of Ringoceanic Antai of Jiangsu, the plasticizer is selected from diisononyl phthalate, the fumed silica is hydrophobic fumed silica, the water removing agent is vinyltrimethoxysilane, the ultraviolet light absorber is a formamidine ultraviolet light absorber, the antioxidant is 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, the mildew preventive is 4, 5-dichloro-2-octyl-3 (2H) -isothiazolinone, and the light stabilizer is light stabilizer 234.
Comparative example 1
The filler in example 1 was removed, and the other raw materials and the preparation process were unchanged.
Comparative example 2
The coupling agent in example 2 was replaced by the coupling agent KH792, and other raw materials and preparation processes were unchanged.
Comparative example 3
The catalyst of example 3 was replaced by dibutyltin dilaurate, and the other starting materials and preparation were unchanged.
Comparative example 4
The comparison is a common sealant in the market.
The sealants of examples 1-3 and comparative examples 1-4 were tested for performance, open time: testing according to GB/T13477.5-2003; tensile strength and elongation at break: hardness according to GB/T528-1998 test: tensile shear strength as tested in GB/T531-1999: according to the test of GB/T7124, the mildew-proof performance: resistance to yellowing as tested in GB/T2591-2003: an ultraviolet aging box is used for 500 hours; the test results are shown in the following table:
as can be seen from the table above, the test results of examples 1-3 in the surface drying time, tensile strength, elongation at break, tensile shear strength, hardness and mildew resistance are superior to those of comparative examples 1-4, which shows that the sealant prepared by the invention has the characteristics of mildew resistance, yellowing resistance and excellent mechanical properties.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. The preparation method of the transparent adhesive with strong mildew-proof yellowing resistance and strong bonding property is characterized by comprising the following steps:
firstly, preparing the following raw materials in parts by weight: 30-70 parts of silane modified polyether resin, 20-50 parts of plasticizer, 3-5 parts of filler, 10-20 parts of fumed silica, 0.5-2 parts of water removing agent, 0-0.5 part of ultraviolet absorber, 0-0.6 part of light stabilizer, 0-0.5 part of antioxidant, 0.5-3 parts of silane coupling agent, 0.1-0.4 part of catalyst and 0.1-1 part of mildew preventive for later use;
secondly, adding the silane modified polyether resin, the plasticizer and the 90% water removal agent into a planetary stirrer, and stirring for 5-10min at the rotating speed of 30-50r/min under the normal temperature condition to obtain a base material;
thirdly, adding the filler and the fumed silica into the base material, adding the filler and the fumed silica for 3 times in equal amount, increasing the rotating speed to 500-1000r/min, stirring for 10min, adding the ultraviolet light absorber, the light stabilizer, the antioxidant and the mildew preventive, keeping the rotating speed unchanged, and continuously stirring for 20-40min to obtain a mixture;
and fourthly, adding a silane coupling agent, a catalyst and a 10% water removal agent into the mixture, and stirring for 10-20min at a rotating speed of 50-100r/min under a vacuum condition to obtain the transparent adhesive with strong mildew-proof, yellowing-resistant and bonding properties.
2. The preparation method of the mildewproof yellowing-resistant transparent adhesive with strong bonding property according to claim 1, wherein the preparation method of the filler comprises the following steps:
step S11, adding silicon dioxide and absolute ethyl alcohol into a beaker, controlling the temperature to be 50-60 ℃, carrying out ultrasonic dispersion for 20-40min under the condition of frequency being 30-50kHz, then adding a silane coupling agent KH-550 into the beaker, controlling the temperature to be 78 ℃, carrying out reaction for 10-20h under the condition of rotating speed being 200 plus one year per minute, cooling to room temperature after the reaction is finished, washing a reactant for 3-5 times by deionized water, drying in a drying oven at the temperature of 60-80 ℃ to constant weight to obtain modified silicon dioxide, adding the modified silicon dioxide, acetone and coumarin-3-carboxylic acid into the beaker, carrying out reaction for 10h under the condition of rotating speed being 800 plus one year per minute, then carrying out centrifugal treatment, washing the precipitate for 3 times by deionized water, and drying in the drying oven at the temperature of 60 ℃ for 10-12h to obtain a composite material 1;
step S12, adding isopropanol, deionized water and N, N-2-dimethyl dodecyl tertiary amine into a four-neck flask, keeping the temperature at 30 ℃, reacting for 20min under the condition of the rotation speed of 200 and 300r/min, dropwise adding epoxy chloropropane into the four-neck flask, heating to 50 ℃, reacting for 8-10h under the condition of the unchanged rotation speed, removing the organic solvent in a rotary evaporator at 60 ℃ after the reaction is finished, and finally washing twice with diethyl ether to obtain quaternary ammonium salt;
step S13, adding chitosan, deionized water and isopropanol into a four-mouth beaker, keeping the temperature at 30 ℃, reacting for 35min under the condition that the rotating speed is 200 plus materials and 300r/min, adding the quaternary ammonium salt and sodium hydroxide solid obtained in the step S12 into the four-mouth beaker, wherein the quaternary ammonium salt and the sodium hydroxide solid are added in 4 times in equal amount, the interval is 1h every time, after all the quaternary ammonium salt and the sodium hydroxide solid are added, heating to 85 ℃, continuously reacting for 48h without changing the rotating speed, cooling to room temperature after the reaction is finished, adding a sodium bicarbonate solution with the mass fraction of 25% to adjust the pH value to 7-8, treating for 24h by using a Soxhlet extractor, and finally drying in a constant-temperature drying box with the temperature of 100 ℃ to constant weight to obtain;
step S14, adding the intermediate and dimethylformamide into a three-neck flask, keeping the temperature at 60 ℃, keeping the rotation speed at 150-;
and S15, adding the composite material 1, the composite material 2 and dimethyl sulfoxide into a three-neck flask, keeping the temperature at 60 ℃, reacting for 0.5h under the condition of the rotating speed of 150-.
3. The method for preparing the transparent adhesive with the mildew-proof, yellowing-resistant and strong adhesive property according to claim 2, wherein the amount ratio of the silicon dioxide, the absolute ethyl alcohol and the silane coupling agent KH-550 in the step S11 is 3 g: 60mL of: 1-3mL, wherein the dosage ratio of the modified silicon dioxide, the acetone and the coumarin-3-carboxylic acid is 1 g: 60mL of: 1-1.5 g; in the step S12, the dosage ratio of the isopropanol, the deionized water, the N, N-2-dimethyl dodecyl tertiary amine and the epichlorohydrin is 120 mL: 60mL of: 18 g: 16g of a mixture; in the step S13, the dosage ratio of the chitosan, the deionized water, the isopropanol, the quaternary ammonium salt and the sodium hydroxide is 2 g: 10mL of: 10mL of: 7 g: 25g of the total weight of the mixture; in the step S14, the dosage ratio of the intermediate, the dimethylformamide, the isopropanol and the epichlorohydrin is 1 g: 20mL of: 5mL of: 8 mL; in the step S15, the usage ratio of the composite material 1, the composite material 2, the dimethyl sulfoxide and the beta-cyclodextrin dispersion is 1 g: 1 g: 20mL of: 20mL, wherein the beta-cyclodextrin dispersion liquid is prepared by mixing a sodium hydroxide solution with the concentration of 0.1mol/L and beta-cyclodextrin according to the dosage ratio of 20 mL: 2g of the above-mentioned materials are mixed.
4. The preparation method of the mildewproof yellowing-resistant transparent adhesive with strong adhesive property according to claim 1, wherein the coupling agent is prepared by the following method: the method comprises the steps of fully replacing a 1L-capacity three-neck flask with a reflux cooler, a stirrer and a thermometer by dry nitrogen, adding 405g of 1-vinyl-3, 4-epoxycyclohexane, 0.1g of Speirer catalyst with the mass fraction of Pt being 2%, 8.1g of acetonitrile and 8.1g of methanol into the three-neck flask, heating to 60 ℃ under the protection of nitrogen, reacting for 6 hours under the condition of the rotation speed of 100-200r/min, adding 375g of trimethoxy silane, controlling the reaction temperature to be 60-75 ℃, continuously stirring and reacting for 2 hours under the condition of the rotation speed unchanged, distilling the reaction liquid at the temperature of 111-120 ℃ after the reaction is finished, and collecting a distillation product 2- (3, 4-epoxycyclohexyl) ethyltrialkoxy silane, namely the coupling agent.
5. The preparation method of the mildewproof yellowing-resistant transparent adhesive with strong adhesive property according to claim 1, wherein the catalyst is prepared by the following method: heating and refluxing 0.2mol of acetic acid and 0.3mol of dibutyltin oxide in 50mL of toluene for 1-3h, adding 0.3mol of gamma-aminopropyl methyldimethoxysilane in the reflux product, and uniformly stirring to prepare the tin-based composite catalyst, namely the catalyst.
6. The method for preparing the transparent adhesive with the mildew resistance, the yellowing resistance and the strong bonding property according to claim 1, wherein the silane modified polyether resin is trimethoxy silane terminated polyether with two terminal groups.
7. The method for preparing the transparent adhesive with the mildew-proof and yellowing-resistant performances according to claim 1, wherein the plasticizer is one or more selected from diisononyl phthalate, diisodecyl phthalate and diisononyl cyclohexane-1, 2-dicarboxylate, which are mixed at any ratio.
8. The method for preparing the mildewproof, yellowing-resistant and strong-adhesion transparent adhesive according to claim 1, wherein the fumed silica is hydrophobic fumed silica, the water removing agent is vinyltrimethoxysilane, the ultraviolet light absorber is a formamidine ultraviolet light absorber, the antioxidant is n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the mildew preventive is 4, 5-dichloro-2-octyl-3 (2H) -isothiazolone.
9. The method for preparing the mildewproof and yellowing-resistant adhesive strong transparent glue according to claim 1, wherein the light stabilizer is one or more of light stabilizers 234, 292, 622, 770, 776 and 788 mixed in any proportion.
10. Use of a strong transparent adhesive with mildew and yellowing resistance prepared according to any one of claims 1 to 9 in indoor home decoration.
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