阅读说明：本技术 一种玻璃夹胶的制备方法及夹胶玻璃 (Preparation method of glass laminated adhesive and laminated glass ) 是由 石云 于 2017-12-29 设计创作，主要内容包括：本发明提供一种玻璃夹胶的制备方法及夹胶玻璃,玻璃夹胶的原料包括聚甲基丙烯酸甲酯100份、聚氨酯树脂15～20份、二氧化锆微球3～8份、二氧化硅微球6～8份、改性LDHs10～20份、植酸2～5份、稀土氧化物0.1～1份。其中,改性LDHs通过以下步骤制备：将水溶性二价金属盐、水溶性三价金属盐和沉淀剂分散于水中,滴加聚磷酸盐溶液,在80～100℃条件下反应6～36h得到。改性LDHs通过聚磷酸盐插层改性,具有良好的阻燃效果。在聚甲基丙烯酸甲酯基体中加入改性LDHs,能够赋予玻璃夹胶良好的阻燃性,同时加入二氧化锆微球、二氧化硅微球、植酸等,能够赋予玻璃夹胶出色的耐高温性能和防辐射性能。(The invention provides a preparation method of glass doubling and glass doubling, wherein the raw materials of the glass doubling comprise 100 parts of polymethyl methacrylate, 15-20 parts of polyurethane resin, 3-8 parts of zirconium dioxide microspheres, 6-8 parts of silicon dioxide microspheres, 10-20 parts of modified LDHs10, 2-5 parts of phytic acid and 0.1-1 part of rare earth oxide. The modified LDHs is prepared by the following steps: dispersing water-soluble divalent metal salt, water-soluble trivalent metal salt and a precipitator in water, dropwise adding a polyphosphate solution, and reacting at 80-100 ℃ for 6-36 hours to obtain the water-soluble metal salt. The modified LDHs is modified by polyphosphate intercalation, and has good flame retardant effect. The glass doubling adhesive is endowed with good flame retardance by adding the modified LDHs into the polymethyl methacrylate matrix, and excellent high-temperature resistance and radiation resistance can be endowed by adding the zirconium dioxide microspheres, the silicon dioxide microspheres, the phytic acid and the like.)

1. The preparation method of the glass doubling is characterized by comprising the following steps:

(1) preparing materials: preparing the following raw materials in parts by weight: 100 parts of polymethyl methacrylate, 15-20 parts of polyurethane resin, 3-8 parts of zirconium dioxide microspheres, 6-8 parts of silicon dioxide microspheres, 10-20 parts of modified LDHs, 2-5 parts of phytic acid and 0.1-1 part of rare earth oxide;

wherein the modified LDHs are prepared by the following steps: dispersing water-soluble divalent metal salt, water-soluble trivalent metal salt and a precipitator in water, dropwise adding a polyphosphate solution, and reacting at 80-100 ℃ for 6-36 hours to obtain the compound;

(2) the silica microspheres are pretreated according to the following steps: dispersing the silicon dioxide microspheres in alkaline aqueous solution containing dopamine, stirring for reaction for 15-25 h, cleaning and drying to obtain modified SiO₂(ii) a Dropwise adding 2-4% by mass of dilute ammonia water into 10-15 g/L of silver nitrate solution to obtain silver ammonia solution; under the ice-bath condition, the modified SiO₂Adding the mixture into the silver ammonia solution, reacting for 40-60 min, filtering, washing, and freeze-drying to obtain the silicon dioxide microspheres;

(3) dispersing the silicon dioxide microspheres and the zirconium dioxide microspheres obtained in the step (2) in a first solvent, sequentially adding phytic acid and a first mass part of polymethyl methacrylate, mixing, and removing the first solvent to obtain a first mixture;

(4) dispersing the modified LDHs in a second solvent, adding the polyurethane resin, heating to 120-150 ℃, stirring for 2-3 h, and then carrying out ultrasonic treatment for 30-50 min to obtain a second mixture;

(5) and melting and blending the first mixture, the second mixture, a second mass part of the polymethyl methacrylate and the rare earth oxide to obtain the glass doubling.

2. The preparation method of the glass clip according to claim 1, wherein the molar ratio of the divalent metal salt, the trivalent metal salt and the polyphosphate is 2-3: 1: 0.5-1.

3. The method of claim 1, wherein the rare earth oxide is pre-treated prior to use according to the following steps: dissolving the rare earth oxide in nitric acid, adding a molecular sieve, carrying out ultrasonic treatment for 1-2 h, and carrying out heat treatment for 1-2 h at 600-900 ℃, wherein the mass ratio of the rare earth oxide to the molecular sieve is 0.1-0.2: 1.

4. The method according to claim 1, wherein the first solvent is selected from one or more of chloroform, dichloromethane, acetone, toluene, and tetrahydrofuran, and the second solvent is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

5. The method for preparing glass cement according to claim 1, wherein the mass ratio of the first mass part of the polymethyl methacrylate to the second mass part of the polymethyl methacrylate is 1:3 to 5.

6. The method for preparing glass cement according to claim 1, wherein in the step (3), the mass-to-volume ratio of the first mass part of the polymethyl methacrylate to the first solvent is 1 g: 5-10 mL.

7. The method for preparing a glass cement according to claim 1, wherein in the step (5), the melt blending conditions are as follows: in an internal mixer, firstly, blending for 6-8 min at the temperature of 130-150 ℃ and the rotating speed of 80-100 rpm, then heating to 180-190 ℃, and blending for 10-12 min at the rotating speed of 150-180 rpm.

8. Laminated glass, characterized in that it is produced according to the following steps:

the preparation method of any one of claims 1 to 7, wherein the glass rubber is prepared by dissolving the glass rubber in DMF to obtain a rubber solution with a solid content of 40-60%;

providing a first glass substrate and a second glass substrate, coating the glue solution between the first glass substrate and the second glass substrate, and heating, applying and maintaining pressure under vacuum negative pressure to enable the glue solution to bond the first glass substrate and the second glass substrate together; wherein the pressure is 10-15 Mpa, and the pressing time is 20-40 min.

Technical Field

The invention relates to the field of glass, and in particular relates to a preparation method of glass laminated glue and laminated glass.

Background

Laminated glass is a composite glass product formed by sandwiching one or more layers of organic polymer intermediate films (glass laminating adhesives) between two or more pieces of glass and permanently bonding the glass and the intermediate films into a whole through special high-temperature and other processes.

The laminated glass is safe glass and has good impact resistance, penetration resistance, safety, noise reduction, ultraviolet resistance and the like. With the development of times, laminated glass is widely applied to building doors and windows, lighting ceilings, skylights, suspended ceilings, aquariums and the like due to unique properties of the laminated glass. With the diversification of the demand of people on laminated glass, the glass is required to have the original characteristics, and other special properties such as stability, heat resistance, flame retardance and the like are required.

At present, the existing laminated glass is generally a glass combination which is formed by two or more pieces of glass and PVB glass sandwiched between the two or more pieces of glass, and the two or more pieces of glass are firmly bonded into a whole after being heated and pressurized. The PVB glass doubling has poor heat-insulating property and flame-retardant effect, and the application of the doubling glass is limited.

Disclosure of Invention

The invention aims to provide glass laminating adhesive which has high flame retardance, good thermal stability, certain cooling effect and wide application range.

The technical problem to be solved by the invention is realized by adopting the following technical scheme.

The invention provides glass doubling which mainly comprises the following raw materials in parts by weight: 100 parts of polymethyl methacrylate, 15-20 parts of polyurethane resin, 3-8 parts of zirconium dioxide microspheres, 6-8 parts of silicon dioxide microspheres, 10-20 parts of modified LDHs, 2-5 parts of phytic acid and 0.1-1 part of rare earth oxide.

Wherein the modified LDHs are prepared by the following steps: dispersing water-soluble divalent metal salt, water-soluble trivalent metal salt and a precipitator in water, dropwise adding a polyphosphate solution, and reacting at 120-180 ℃ for 6-36 hours to obtain the water-soluble metal salt.

The glass doubling of the embodiment of the invention has the beneficial effects that:

polymethyl methacrylate is a superior transparent material, has light weight, toughness, high light transmittance, high and balanced mechanical properties and good processing performance. Polymethyl methacrylate is used as a base material of glass doubling, and modified LDHs are added. The modified LDHs is characterized in that polyphosphoric acid ions are intercalated into the modified layered clay, the LDHs and the polyphosphoric acid ions can be uniformly mixed at a molecular level, the LDHs and the polyphosphoric acid ions can be synergized, and the modified LDHs is added into a polymer matrix, so that the flame retardant effect of glass laminating can be effectively improved, and the modified LDHs is halogen-free, and is safer and more environment-friendly.

In addition, a certain amount of polyurethane resin is added into the base material, so that the bonding strength and the bonding stability of the product can be further improved, and the glass laminated adhesive is endowed with excellent high-temperature resistance.

The silicon dioxide microspheres and the zirconium dioxide microspheres have special optical specificity, are embedded into a polymethyl methacrylate matrix, have good light transmittance, and can effectively improve the light reflectivity of the material, reflect most infrared rays and ultraviolet rays and achieve the effect of radiation cooling. And the solar heat radiation is reduced, and simultaneously the daylighting and the beautiful requirements are kept, so that the energy is saved and the environment is protected.

The phytic acid can improve the oxidation resistance and weather resistance of the product and effectively prolong the service life of the product. Meanwhile, the phytic acid serving as an organic phosphorus additive can further improve the flame retardant property of the product, can also improve the adhesiveness of the silicon dioxide microspheres and the silicon dioxide microspheres with a polymer matrix, and is not easy to precipitate.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following will specifically explain the glass insert according to the embodiment of the present invention.

The embodiment of the invention provides glass doubling which mainly comprises the following raw materials in parts by weight: 100 parts of polymethyl methacrylate, 15-20 parts of polyurethane resin, 3-8 parts of zirconium dioxide microspheres, 6-8 parts of silicon dioxide microspheres, 10-20 parts of modified LDHs, 2-5 parts of phytic acid and 0.1-1 part of rare earth oxide.

Wherein the modified LDHs are prepared by the following steps: dispersing water-soluble divalent metal salt, water-soluble trivalent metal salt and a precipitator in water, dropwise adding a polyphosphate solution, and reacting at 80-100 ℃ for 6-36 hours to obtain the water-soluble metal salt.

Further, the precipitant is urea. The divalent metal salt is selected from one or more of magnesium chloride, zinc chloride, nickel chloride and calcium chloride. The trivalent metal salt is selected from one or more of aluminum chloride, ferric chloride, lanthanum chloride and cerium chloride. The molar ratio of the precipitant to the divalent metal salt is 1: 1-2.

Further, in a preferred embodiment of the present invention, the molar ratio of the divalent metal salt, the trivalent metal salt and the polyphosphate is 2-3: 1: 0.5-1. Under the proportion, the polyphosphate can be intercalated into the LDHs in a proper proportion to form a good flame retardant effect. Furthermore, the polyphosphate is selected from melamine phosphate, contains 37.5 percent of N and 13.8 percent of phosphorus in the structure, has the characteristics of no halogen, flame retardance, low smoke, low toxicity and the like, and has good stability and excellent flame retardance.

Further, in a preferred embodiment of the present invention, the rare earth oxide is pretreated before use according to the following steps: dissolving rare earth oxide in nitric acid, adding a molecular sieve, carrying out ultrasonic treatment for 1-2 h, and carrying out heat treatment for 1-2 h at 600-900 ℃, wherein the mass ratio of the rare earth oxide to the molecular sieve is 0.1-0.2: 1. Further, the rare earth oxide isLa with mass ratio of 1:1₂O₃And CeO₂. The rare earth oxide is loaded on the molecular sieve, so that the dispersion property of the rare earth oxide can be improved. On one hand, the rare earth oxide has certain catalytic performance, and can enhance the molecular weight of the polymer and improve the thermal stability and the like when being fused and blended with the polymer matrix, and on the other hand, the rare earth oxide can improve the radiation protection performance of the product.

The embodiment of the invention also provides a preparation method of the glass doubling, which comprises the following steps:

s1, dispersing the silicon dioxide microspheres and the zirconium dioxide microspheres in a first solvent, sequentially adding the phytic acid and a first mass part of polymethyl methacrylate, mixing, and removing the first solvent to obtain a first mixture;

s2, dispersing the modified LDHs in a second solvent, adding the polyurethane resin, heating to 120-150 ℃, stirring for 2-3 h, and then carrying out ultrasonic treatment for 30-50 min to obtain a second mixture;

s3, melting and blending the first mixture, the second mixture, a second mass part of the polymethyl methacrylate and the rare earth oxide to obtain the glass doubling.

In the preparation method, the silicon dioxide microspheres and the zirconium dioxide microspheres are mixed with a part of polymethyl methacrylate by a solution method, so that the silicon dioxide microspheres and the zirconium dioxide microspheres can be well dispersed in a polymer matrix. Mixing a part of polymethyl methacrylate with microspheres to obtain a first mixture, mixing modified LDHs and polyurethane to obtain a second mixture, and melting and blending the first mixture and the second mixture with the rest of polymethyl methacrylate to ensure good dispersion of silicon dioxide microspheres, zirconium dioxide microspheres and modified LDHs, ensure that the materials are uniformly distributed in a polymer matrix, effectively reduce the using amount of a solvent, and realize low carbon and environmental protection.

Further, in the preferred embodiment of the present invention, the silica microspheres are pre-treated before use according to the following steps:

dispersing the silicon dioxide microspheres in alkaline aqueous solution containing dopamine, stirring for reaction for 15-25 h, cleaning and drying to obtain modified SiO₂. And dropwise adding 2-4% by mass of dilute ammonia water into 10-15 g/L of silver nitrate solution to obtain the silver ammonia solution. Under the ice-bath condition, the modified SiO₂Adding the silver-ammonia solution into the silver-ammonia solution, reacting for 40-60 min, filtering, washing, and freeze-drying.

Furthermore, in the alkaline aqueous solution containing dopamine, the concentration of the dopamine is 0.7-1 g/L, the pH value is 8-8.5, and the silica microspheres can form a proper polydopamine functional surface layer in the alkaline aqueous solution. The poly-dopamine functional surface layer has excellent surface activity and adhesion capability, silver ions can be modified on the silicon dioxide microspheres, the product has higher light reflectivity, and a better cooling effect is achieved.

In the examples of the present invention, the zirconium dioxide microspheres may be obtained commercially, or may be synthesized by a gas phase method, a liquid phase method, a solid phase method, or the like. In this example, the synthesis was performed as follows: 0.65g of ZrOCl₂·8H₂Dissolving O in isopropanol, adding 0.08g of carboxymethyl cellulose, stirring to form a reaction solution, placing the reaction solution in a microwave reactor, and reacting for 8min under the condition of 40W. After the reaction is finished, 5mol/L ammonia water is added dropwise to obtain emulsion. Then the zirconium dioxide microspheres are obtained through centrifugal separation, washing and drying.

The silicon dioxide microspheres and the zirconium dioxide microspheres can take away heat of an object through radiation, and the heat on the object is automatically radiated to an atmospheric space by infrared wavelengths of 0-13.5 microns, so that the surface temperature and the internal temperature of the object are reduced, and the effects of heat dissipation and cooling are achieved.

Further, in a preferred embodiment of the present invention, the first solvent is selected from one or more of chloroform, dichloromethane, acetone, toluene and tetrahydrofuran, and the second solvent is selected from one or more of N, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.

Further, in a preferred embodiment of the present invention, the mass ratio of the first mass part of the polymethylmethacrylate to the second mass part of the polymethylmethacrylate is 1:3 to 5.

Further, in a preferred embodiment of the present invention, in step S1, the mass-to-volume ratio of the first mass part of the polymethylmethacrylate to the first solvent is 1 g: 5-10 mL.

Further, in the preferred embodiment of the present invention, in step S3, the melt blending conditions are: in an internal mixer, firstly, blending for 6-8 min at the temperature of 130-150 ℃ and the rotating speed of 80-100 rpm, then heating to 180-190 ℃, and blending for 10-12 min at the rotating speed of 150-180 rpm. The high-speed blending is carried out at a lower temperature at present, and then the blending is carried out at a higher temperature, so that the combination property of each component can be further improved, and the product quality is improved.

The embodiment of the invention also provides laminated glass, which is prepared according to the following steps:

dissolving the prepared glass doubling adhesive in DMF to prepare an adhesive solution with solid content of 40-60%;

providing a first glass substrate and a second glass substrate, coating the glue solution between the first glass substrate and the second glass substrate, and heating, applying and maintaining pressure under vacuum negative pressure to enable the glue solution to bond the first glass substrate and the second glass substrate together; wherein the pressure is 10-15 Mpa, and the pressing time is 20-40 min. Preferably, the pressure is 12MPa and the pressing time is 25 min.

The features and properties of the present invention are described in further detail below with reference to examples.