A kind of SGP laminated glass and its production process

Abstract

The present invention discloses an SGP laminated glass and its production process. By mixing a modified resin and an SGP laminating resin and extruding and casting them into a film, a laminated film is obtained. The laminated film is placed between two pieces of glass and hot-pressed. When the modified resin and the SGP laminating resin are melted, the double bonds on the modified resin can graft with the molecular chains on the SGP laminating resin. The main body of the modified resin molecular chain is a polyurethane structure containing an organosilicon segment, which can improve the heat insulation effect of the SGP laminating resin. Moreover, the modified filler contains a multi-void structure, further enhancing the heat insulation effect. Additionally, the titanium-containing organosilicon resin segment in the modified resin, the surface of the modified filler contains tin dioxide, and the benzotriazole structure in the modified resin can increase the absorption of ultraviolet rays by the laminated film, reducing the ultraviolet irradiation.

Description

Technical Field

[0001] The present invention relates to the field of laminated glass preparation, and particularly to an SGP film laminated glass and its production process. Background Art

[0002] Laminated glass is a composite glass product made of two or more pieces of glass with one or more layers of organic polymer interlayers sandwiched between them. After special high-temperature pre-pressing (or vacuum pumping) and high-temperature and high-pressure process treatment, the glass and the interlayer are permanently bonded together. Even if the glass breaks, the fragments will be adhered to the film, and the surface of the broken glass remains clean and smooth. This effectively prevents the occurrence of fragment stabbing and penetration and falling incidents, ensuring personal safety. Most building glasses use laminated glass, not only to avoid injury accidents, but also because laminated glass has excellent anti-seismic and intrusion resistance. The interlayer can resist continuous attacks by weapons such as hammers and machetes, and can also resist bullet penetration for a considerable period of time, with a very high level of security prevention. Among the commonly used interlayers for laminated glass are: PVB, SGP, EVA, PU, etc., but the general heat insulation effect affects the use of laminated glass. Summary of the Invention

[0003] The purpose of the present invention is to provide an SGP film laminated glass and its production process, which solves the problem of the general heat insulation effect of the film in the current SGP film laminated glass.

[0004] The purpose of the present invention can be achieved by the following technical solutions:

[0005] A production process of an SGP film laminated glass specifically includes the following steps:

[0006] Step S1: Mix a modified prepolymer, ethylenediamine, and DMF, introduce nitrogen protection, and react for 2 - 3 h under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 30 - 40 °C. Then add KH560, adjust the pH value to 11 - 12, and react for 3 - 5 h to obtain a pretreated polyurethane. Mix the pretreated polyurethane, diphenylmethane diisocyanate, and DMF, introduce nitrogen protection, and react for 5 - 6 h under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 30 - 40 °C. Then add N-(2-hydroxyethyl) maleimide and continue to react for 4 - 6 h to obtain a modified polyurethane;

[0007] Step S2: Mix the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, and DMF evenly. Under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 65 - 70 °C, stir and add deionized water and hydrochloric acid, and react for 2 - 3 h. Then add tetrabutyl titanate and continue to react for 2 - 3 h. Raise the temperature to 120 - 130 °C and react for 3 - 5 h to obtain the modified resin. Mix the modified resin, SGP laminated resin, and dicumyl peroxide. Under the conditions of a feeding section temperature of 190 °C, a melting section temperature of 180 °C, and a discharging section temperature of 150 °C, extrude and cast into a film to obtain the laminated sheet. Place the laminated sheet between two pieces of glass and press at high temperature to obtain the SGP laminated glass.

[0008] The molar ratio of the isocyanate group on the modified prepolymer described in Step S1 to ethylenediamine is 1:1, and the molar ratio of the hydroxyl group on the pretreated polyurethane, diphenylmethane diisocyanate, and N-(2-hydroxyethyl) maleimide is n:n:2, where n is a natural number greater than 1.

[0009] The dosage ratios of the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, DMF, deionized water, hydrochloric acid solution, and tetrabutyl titanate described in Step S2 are 5 g:80 mg:1 mmol:10 mL:50 mL:20 mL:3 mL:1.5 mmol. The mass fraction of the hydrochloric acid solution is 10%. The weight part ratios of the modified resin and SGP laminated resin are 30 - 50:80 - 100:1 - 3.

[0010] Furthermore, the modified prepolymer is prepared by the following steps:

[0011] Step A1: Mix p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate evenly and place them in a mortar. Under the condition of a temperature of 20 - 25 °C, grind for 20 - 30 min to obtain the azo dye. Mix the azo dye, ethanol, and sodium hydroxide solution evenly. Under the conditions of a rotation speed of 600 - 800 r / min and a temperature of 80 - 85 °C, stir and add sodium dithionite and react for 1 - 1.5 h to obtain Intermediate 1.

[0012] Step A2: Mix metallic magnesium, iodine, and tetrahydrofuran evenly, introduce nitrogen protection. Under the conditions of a rotation speed of 60 - 80 r / min and a temperature of 20 - 25 °C, stir and add 2-bromothiophene, raise the temperature to 60 - 70 °C, and react for 3 - 5 h to obtain Intermediate 2. Mix Intermediate 1, Intermediate 2, and tetrahydrofuran evenly. Under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 60 - 70 °C, react for 5 - 6 h to obtain the modifier.

[0013] Step A3: Mix the modifier, diethanolamine, and DMF evenly, introduce nitrogen for protection, and under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 20 - 25 °C, stir and add sodium hydroxide until the pH value reaches 10 - 11, react for 3 - 5 h, adjust the pH to neutral to obtain the modified monomer. Mix the modified monomer, diphenylmethane diisocyanate, and DMF, and under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 40 - 50 °C, react for 2 - 4 h to obtain the modified prepolymer.

[0014] Further, the molar ratio of p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate described in Step A1 is 1:1.1:1:1, and the dosage ratio of azo dye, ethanol, sodium hydroxide solution, and sodium dithionite is 25 mmol:50 mL:50 mL:82 mmol.

[0015] Further, the dosage ratio of magnesium metal, iodine, tetrahydrofuran, and 2-bromothiophene described in Step A2 is 1.1 mol:1 mol:100 mL:1 mol, and the molar ratio of Intermediate 1 and Intermediate 2 is 1:1.

[0016] Further, the molar ratio of the modifier and diethanolamine described in Step A3 is 1:1, and the molar ratio of the modified monomer and diphenylmethane diisocyanate is 1:2.1.

[0017] Further, the modified filler is prepared by the following steps:

[0018] Step B1: Mix triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, and deionized water evenly, and under the conditions of a rotation speed of 150 - 200 r / min and a temperature of 80 - 85 °C, stir and add tetraethyl orthosilicate, KH550, and ethanol, react for 4 - 6 h, then centrifuge to remove the supernatant. Add the substrate to the hydrochloric acid solution, and under the conditions of a frequency of 20 - 30 kHz and a temperature of 20 - 25 °C, perform ultrasonic treatment for 5 - 10 min, then raise the temperature to 60 - 70 °C and keep warm for 5 - 7 h to obtain amino-functionalized nano-silica.

[0019] Step B2: Mix the amino-functionalized nano-silica, tin tetrachloride, and ethanol evenly, and under the conditions of a rotation speed of 120 - 150 r / min and a temperature of 30 - 40 °C, stir and add deionized water and ammonia water until the pH reaches 10 - 12, stir for 10 - 15 min, then raise the temperature to 150 - 160 °C and react for 20 - 25 h to obtain the modified nano-silica. Disperse the modified nano-silica in ethanol, introduce nitrogen for protection, and under the conditions of a rotation speed of 300 - 500 r / min and a temperature of 30 - 40 °C, stir and add 3-isocyanatopropyltriethoxysilane and react for 2 - 3 h to obtain the modified filler.

[0020] Furthermore, the dosage ratio of triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, deionized water, tetraethyl orthosilicate, KH550 and ethanol described in step B1 is 65 mg: 380 mg: 550 mg: 25 mL: 10 mmol: 5 mmol: 5 mL, and the dosage ratio of the base material to the hydrochloric acid solution is 1 mg: 1 mL, and the mass fraction of the hydrochloric acid solution is 5%.

[0021] Furthermore, the dosage ratio of the amino-functionalized nano-silica, tin tetrachloride, ethanol and deionized water described in step B2 is 2 g: 2 mmol: 10 mL: 10 mL, and the molar ratio of the amino group on the surface of the modified nano-silica to 3-isocyanatopropyltriethoxysilane is 1:1.

[0022] The beneficial effects of the present invention: A kind of SGP laminated glass prepared by the present invention is obtained by mixing and extruding a modified resin and an SGP lamination resin to form a film, and then placing the laminated film between two pieces of glass and pressing at high temperature. The modified resin uses a modified prepolymer and ethylenediamine as raw materials, so that the isocyanate group on the modified prepolymer reacts with the amino group on the ethylenediamine to form an amino-terminated structure, and then reacts with KH560, so that the epoxy group on KH560 reacts with the amino group to obtain a pretreated polyurethane. The pretreated polyurethane reacts with diphenylmethane diisocyanate, so that the hydroxyl group on the pretreated polyurethane reacts with the isocyanate group on the diphenylmethane diisocyanate, and then is capped with N-(2-hydroxyethyl) maleimide to obtain a modified polyurethane. The modified polyurethane, modified filler, dimethyldiethoxysilane and tetrabutyl titanate are hydrolyzed and condensed to obtain a modified resin.

[0023] The modified prepolymer uses p-chloro-o-nitroaniline and p-hydroxystyrene as raw materials, forms an azo dye under the action of sodium nitrite and potassium bisulfate, treats the azo dye with sodium dithionite to form a benzotriazole structure to obtain intermediate 1, treats 2-bromothiophene with metallic magnesium and iodine to form thiophene-based magnesium bromide to obtain intermediate 2, reacts intermediate 1 and intermediate 2, so that the chlorine atom site on intermediate 1 reacts with the magnesium bromide group on intermediate 2 to obtain a modifier, reacts the modifier with ethylene glycol amine, so that the double bond on the modifier and the secondary amine on the ethylene glycol amine undergo Michael addition to obtain a modified monomer, and reacts the modified monomer with diphenylmethane diisocyanate to obtain a modified prepolymer.

[0024] The modified filler is prepared by polycondensation using tetraethyl orthosilicate and KH550 as raw materials, and using triethanolamine, cetyltrimethylammonium bromide, and sodium trifluoroacetate as surfactants and templating agents, so that the prepared nano-silica contains micropores, and amino-functionalized nano-silica is obtained. Tin dioxide is embedded in the micropores of the amino-functionalized nano-silica using tin tetrachloride as a raw material to obtain modified nano-silica. The amino groups on the modified nano-silica are reacted with 3-isocyanatopropyltriethoxysilane, so that the amino groups on the modified nano-silica react with the isocyanate groups on 3-isocyanatopropyltriethoxysilane to obtain the modified filler.

[0025] When the modified resin and the SGP laminated resin are melted, the double bonds on the modified resin can graft with the molecular chains on the SGP laminated resin. The main body of the modified resin molecular chain is a polyurethane structure containing an organosilicon segment, which can improve the heat insulation effect of the SGP laminated resin. Moreover, the modified filler contains a multi-void structure, which further improves the heat insulation effect. In addition, the titanium-containing organosilicon resin segment in the modified resin, the tin dioxide on the surface of the modified filler, and the benzotriazole structure in the modified resin can increase the absorption of ultraviolet rays by the laminated film and reduce the ultraviolet irradiation. Specific Embodiments

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0027] Example 1

[0028] A production process of SGP film laminated glass specifically includes the following steps:

[0029] Step S1: Mix the modified prepolymer, ethylenediamine, and DMF, introduce nitrogen protection, and react for 2 h under the conditions of a rotation speed of 150 r / min and a temperature of 30 °C. Then, add KH560, adjust the pH value to 11, and react for 3 h to obtain the pretreated polyurethane. Mix the pretreated polyurethane, diphenylmethane diisocyanate, and DMF, introduce nitrogen protection, and react for 5 h under the conditions of a rotation speed of 150 r / min and a temperature of 30 °C. Then, add N-(2-hydroxyethyl) maleimide and continue to react for 4 h to obtain the modified polyurethane;

[0030] Step S2: Mix the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, and DMF evenly. Under the conditions of a rotation speed of 120 r / min and a temperature of 65 °C, stir and add deionized water and hydrochloric acid, and react for 2 h. Then add tetrabutyl titanate and continue to react for 2 h. Raise the temperature to 120 °C and react for 3 h to obtain the modified resin. Mix the modified resin, SGP laminated resin, and dicumyl peroxide, and under the conditions of a feeding section temperature of 190 °C, a melting section temperature of 180 °C, and a discharging section temperature of 150 °C, extrude and cast into a film to obtain the laminated film. Place the laminated film between two pieces of glass and press at high temperature to obtain the SGP film laminated glass.

[0031] The molar ratio of the isocyanate group on the modified prepolymer described in Step S1 to ethylenediamine is 1:1, and the molar ratio of the hydroxyl group on the pretreated polyurethane, diphenylmethane diisocyanate, and N-(2-hydroxyethyl) maleimide is 1:1:2.

[0032] The dosage ratio of the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, DMF, deionized water, hydrochloric acid solution, and tetrabutyl titanate described in Step S2 is 5 g: 80 mg: 1 mmol: 10 mL: 50 mL: 20 mL: 3 mL: 1.5 mmol. The mass fraction of the hydrochloric acid solution is 10%, and the weight ratio of the modified resin to the SGP laminated resin is 30:80:1.

[0033] The modified prepolymer is prepared by the following steps:

[0034] Step A1: Mix p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate evenly and place them in a mortar. Under the condition of a temperature of 20 °C, grind for 20 min to obtain the azo dye. Mix the azo dye, ethanol, and sodium hydroxide solution evenly. Under the conditions of a rotation speed of 600 r / min and a temperature of 80 °C, stir and add sodium dithionite and react for 1 h to obtain Intermediate 1;

[0035] Step A2: Mix metallic magnesium, iodine, and tetrahydrofuran evenly, introduce nitrogen protection. Under the conditions of a rotation speed of 60 r / min and a temperature of 20 °C, stir and add 2-bromothiophene, raise the temperature to 60 °C, and react for 3 h to obtain Intermediate 2. Mix Intermediate 1, Intermediate 2, and tetrahydrofuran evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 60 °C, react for 5 h to obtain the modifier;

[0036] Step A3: Mix the modifier, diethanolamine, and DMF evenly, introduce nitrogen for protection, stir and add sodium hydroxide at a rotation speed of 120 r / min and a temperature of 20 °C until the pH value reaches 10, react for 3 h, adjust the pH to neutral to obtain the modified monomer. Mix the modified monomer, diphenylmethane diisocyanate, and DMF, and react for 2 h at a rotation speed of 120 r / min and a temperature of 40 °C to obtain the modified prepolymer.

[0037] The molar ratio of p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate described in Step A1 is 1:1.1:1:1, and the dosage ratio of azo dye, ethanol, sodium hydroxide solution, and sodium dithionite is 25 mmol:50 mL:50 mL:82 mmol.

[0038] The dosage ratio of magnesium metal, iodine, tetrahydrofuran, and 2-bromothiophene described in Step A2 is 1.1 mol:1 mol:100 mL:1 mol, and the molar ratio of Intermediate 1 and Intermediate 2 is 1:1.

[0039] The molar ratio of the modifier and diethanolamine described in Step A3 is 1:1, and the molar ratio of the modified monomer and diphenylmethane diisocyanate is 1:2.1.

[0040] The modified filler is prepared by the following steps:

[0041] Step B1: Mix triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, and deionized water evenly, stir and add tetraethyl orthosilicate, KH550, and ethanol at a rotation speed of 150 r / min and a temperature of 80 °C, react for 4 h, centrifuge to remove the supernatant, add the substrate to the hydrochloric acid solution, and perform ultrasonic treatment for 5 min at a frequency of 20 kHz and a temperature of 20 °C, then raise the temperature to 60 °C and keep warm for 5 h to obtain amino-functionalized nano-silica.

[0042] Step B2: Mix the amino-functionalized nano-silica, tin tetrachloride, and ethanol evenly, stir and add deionized water and ammonia water to adjust the pH to 10 at a rotation speed of 120 r / min and a temperature of 30 °C, stir for 10 min, then raise the temperature to 150 °C and react for 20 h to obtain the modified nano-silica. Disperse the modified nano-silica in ethanol, introduce nitrogen for protection, stir and add 3-isocyanatopropyltriethoxysilane at a rotation speed of 300 r / min and a temperature of 30 °C, and react for 2 h to obtain the modified filler.

[0043] The dosage ratio of triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, deionized water, tetraethyl orthosilicate, KH550 and ethanol described in step B1 is 65 mg: 380 mg: 550 mg: 25 mL: 10 mmol: 5 mmol: 5 mL. The dosage ratio of the base material to the hydrochloric acid solution is 1 mg: 1 mL, and the mass fraction of the hydrochloric acid solution is 5%.

[0044] The dosage ratio of the amino-functionalized nano-silica, tin tetrachloride, ethanol and deionized water described in step B2 is 2 g: 2 mmol: 10 mL: 10 mL. The molar ratio of the amino groups on the surface of the modified nano-silica to 3-isocyanatopropyltriethoxysilane is 1:1.

[0045] Example 2

[0046] A production process of SGP film laminated glass specifically includes the following steps:

[0047] Step S1: Mix the modified prepolymer, ethylenediamine and DMF, introduce nitrogen protection, and react for 3 h under the conditions of a rotation speed of 150 r / min and a temperature of 35 °C. Then add KH560, adjust the pH value to 11, and react for 4 h to obtain the pretreated polyurethane. Mix the pretreated polyurethane, diphenylmethane diisocyanate and DMF, introduce nitrogen protection, and react for 6 h under the conditions of a rotation speed of 150 r / min and a temperature of 35 °C. Then add N-(2-hydroxyethyl) maleimide and continue to react for 5 h to obtain the modified polyurethane.

[0048] Step S2: Mix the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol and DMF evenly, stir and add deionized water and hydrochloric acid under the conditions of a rotation speed of 120 r / min and a temperature of 68 °C, and react for 3 h. Then add tetrabutyl titanate and continue to react for 2 h. Raise the temperature to 125 °C and react for 4 h to obtain the modified resin. Mix the modified resin, SGP laminated resin and dicumyl peroxide, and extrude and cast into a film under the conditions of a feeding section temperature of 190 °C, a melting section temperature of 180 °C, and a discharging section temperature of 150 °C to obtain the laminated film. Place the laminated film between two pieces of glass and press at high temperature to obtain the SGP film laminated glass.

[0049] The molar ratio of the isocyanate groups on the modified prepolymer described in step S1 to ethylenediamine is 1:1, and the molar ratio of the hydroxyl groups on the pretreated polyurethane, diphenylmethane diisocyanate and N-(2-hydroxyethyl) maleimide is 2:2:2.

[0050] The dosage ratios of the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, DMF, deionized water, hydrochloric acid solution and tetrabutyl titanate described in step S2 are 5 g: 80 mg: 1 mmol: 10 mL: 50 mL: 20 mL: 3 mL: 1.5 mmol. The mass fraction of the hydrochloric acid solution is 10%, and the weight part ratio of the modified resin and the SGP laminated resin is 40: 90: 2.

[0051] The modified prepolymer described above is prepared by the following steps:

[0052] Step A1: Mix p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite and potassium bisulfate evenly and place them in a mortar. Under the condition of a temperature of 20 °C, grind for 25 min to obtain an azo dye. Mix the azo dye, ethanol and sodium hydroxide solution evenly. Under the conditions of a rotation speed of 600 r / min and a temperature of 80 °C, stir and add sodium dithionite, and react for 1.5 h to obtain intermediate 1;

[0053] Step A2: Mix metallic magnesium, iodine and tetrahydrofuran evenly, introduce nitrogen protection. Under the conditions of a rotation speed of 60 r / min and a temperature of 25 °C, stir and add 2-bromothiophene, heat up to 65 °C, and react for 4 h to obtain intermediate 2. Mix intermediate 1, intermediate 2 and tetrahydrofuran evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 65 °C, react for 6 h to obtain a modifier;

[0054] Step A3: Mix the modifier, diethanolamine and DMF evenly, introduce nitrogen protection. Under the conditions of a rotation speed of 150 r / min and a temperature of 20 °C, stir and add sodium hydroxide until the pH value is 10, react for 4 h, adjust the pH to neutral to obtain a modified monomer. Mix the modified monomer, diphenylmethane diisocyanate and DMF, and under the conditions of a rotation speed of 120 r / min and a temperature of 45 °C, react for 3 h to obtain a modified prepolymer.

[0055] The molar ratio of p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite and potassium bisulfate described in step A1 is 1: 1.1: 1: 1, and the dosage ratios of the azo dye, ethanol, sodium hydroxide solution and sodium dithionite are 25 mmol: 50 mL: 50 mL: 82 mmol.

[0056] The dosage ratios of metallic magnesium, iodine, tetrahydrofuran and 2-bromothiophene described in step A2 are 1.1 mol: 1 mol: 100 mL: 1 mol, and the molar ratio of intermediate 1 and intermediate 2 is 1: 1.

[0057] The molar ratio of the modifier and diethanolamine described in step A3 is 1: 1, and the molar ratio of the modified monomer and diphenylmethane diisocyanate is 1: 2.1.

[0058] The modified filler is prepared by the following steps:

[0059] Step B1: Mix triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate and deionized water evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 85 °C, stir and add tetraethyl orthosilicate, KH550 and ethanol. After reacting for 5 h, centrifuge to remove the supernatant. Add the substrate to the hydrochloric acid solution. Under the conditions of a frequency of 25 kHz and a temperature of 20 °C, perform ultrasonic treatment for 8 min, then raise the temperature to 65 °C and keep warm for 6 h to obtain amino-functionalized nano-silica.

[0060] Step B2: Mix the amino-functionalized nano-silica, stannic chloride and ethanol evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 35 °C, stir and add deionized water and ammonia water until the pH reaches 10. After stirring for 10 min, raise the temperature to 155 °C and react for 23 h to obtain modified nano-silica. Disperse the modified nano-silica in ethanol, protect it by introducing nitrogen. Under the conditions of a rotation speed of 500 r / min and a temperature of 35 °C, stir and add 3-isocyanatopropyltriethoxysilane and react for 2 h to obtain the modified filler.

[0061] The dosage ratios of triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, deionized water, tetraethyl orthosilicate, KH550 and ethanol in Step B1 are 65 mg: 380 mg: 550 mg: 25 mL: 10 mmol: 5 mmol: 5 mL. The dosage ratio of the substrate to the hydrochloric acid solution is 1 mg: 1 mL, and the mass fraction of the hydrochloric acid solution is 5%.

[0062] The dosage ratios of the amino-functionalized nano-silica, stannic chloride, ethanol and deionized water in Step B2 are 2 g: 2 mmol: 10 mL: 10 mL. The molar ratio of the amino group on the surface of the modified nano-silica to 3-isocyanatopropyltriethoxysilane is 1:1.

[0063] Example 3

[0064] A production process of SGP film laminated glass specifically includes the following steps:

[0065] Step S1: Mix the modified prepolymer, ethylenediamine, and DMF, and introduce nitrogen for protection. React for 3 h under the conditions of a rotation speed of 200 r / min and a temperature of 40 °C. Then add KH560, adjust the pH value to 12, and react for 5 h to obtain the pretreated polyurethane. Mix the pretreated polyurethane, diphenylmethane diisocyanate, and DMF, introduce nitrogen for protection, and react for 6 h under the conditions of a rotation speed of 200 r / min and a temperature of 40 °C. Then add N-(2-hydroxyethyl) maleimide and continue to react for 6 h to obtain the modified polyurethane;

[0066] Step S2: Mix the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, and DMF evenly. Stir and add deionized water and hydrochloric acid under the conditions of a rotation speed of 150 r / min and a temperature of 70 °C. React for 3 h, then add tetrabutyl titanate and continue to react for 3 h. Raise the temperature to 130 °C and react for 5 h to obtain the modified resin. Mix the modified resin, SGP laminated resin, and dicumyl peroxide, and extrude and cast into a film under the conditions of a feeding section temperature of 190 °C, a melting section temperature of 180 °C, and a discharging section temperature of 150 °C to obtain the laminated film. Place the laminated film between two pieces of glass and press at high temperature to obtain the SGP laminated glass.

[0067] The molar ratio of the isocyanate group on the modified prepolymer described in Step S1 to ethylenediamine is 1:1, and the molar ratio of the hydroxyl group on the pretreated polyurethane, diphenylmethane diisocyanate, and N-(2-hydroxyethyl) maleimide is 3:3:2.

[0068] The dosage ratio of the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, DMF, deionized water, hydrochloric acid solution, and tetrabutyl titanate described in Step S2 is 5 g:80 mg:1 mmol:10 mL:50 mL:20 mL:3 mL:1.5 mmol. The mass fraction of the hydrochloric acid solution is 10%, and the weight ratio of the modified resin to the SGP laminated resin is 50:100:3.

[0069] The modified prepolymer is prepared by the following steps:

[0070] Step A1: Mix p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate evenly and place them in a mortar. Grind for 30 min at a temperature of 25 °C to obtain the azo dye. Mix the azo dye, ethanol, and sodium hydroxide solution evenly, stir and add sodium dithionite under the conditions of a rotation speed of 800 r / min and a temperature of 85 °C, and react for 1.5 h to obtain Intermediate 1;

[0071] Step A2: Mix magnesium metal, iodine, and tetrahydrofuran evenly, introduce nitrogen for protection, stir and add 2-bromothiophene under the conditions of a rotation speed of 80 r / min and a temperature of 25 °C, raise the temperature to 70 °C, and react for 5 h to obtain Intermediate 2. Mix Intermediate 1, Intermediate 2, and tetrahydrofuran evenly, and react for 6 h under the conditions of a rotation speed of 200 r / min and a temperature of 70 °C to obtain a modifier.

[0072] Step A3: Mix the modifier, diethanolamine, and DMF evenly, introduce nitrogen for protection, stir and add sodium hydroxide until the pH value reaches 11 under the conditions of a rotation speed of 150 r / min and a temperature of 25 °C, react for 5 h, adjust the pH to neutral to obtain a modified monomer. Mix the modified monomer, diphenylmethane diisocyanate, and DMF, and react for 4 h under the conditions of a rotation speed of 150 r / min and a temperature of 50 °C to obtain a modified prepolymer.

[0073] The molar ratio of p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate described in Step A1 is 1:1.1:1:1, and the dosage ratio of azo dye, ethanol, sodium hydroxide solution, and sodium dithionite is 25 mmol:50 mL:50 mL:82 mmol.

[0074] The dosage ratio of magnesium metal, iodine, tetrahydrofuran, and 2-bromothiophene described in Step A2 is 1.1 mol:1 mol:100 mL:1 mol, and the molar ratio of Intermediate 1 and Intermediate 2 is 1:1.

[0075] The molar ratio of the modifier and diethanolamine described in Step A3 is 1:1, and the molar ratio of the modified monomer and diphenylmethane diisocyanate is 1:2.1.

[0076] The modified filler is prepared by the following steps:

[0077] Step B1: Mix triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, and deionized water evenly, stir and add tetraethyl orthosilicate, KH550, and ethanol under the conditions of a rotation speed of 200 r / min and a temperature of 85 °C, react for 6 h, then centrifuge to remove the supernatant. Add the substrate to a hydrochloric acid solution, and perform ultrasonic treatment for 10 min under the conditions of a frequency of 30 kHz and a temperature of 25 °C, then raise the temperature to 70 °C and keep warm for 7 h to obtain amino-functionalized nano-silica.

[0078] Step B2: Mix the aminated nano-silica, tin tetrachloride, and ethanol evenly. Under the conditions of a rotation speed of 150 r / min and a temperature of 40 °C, stir and add deionized water and ammonia water until the pH reaches 12. After stirring for 15 min, raise the temperature to 160 °C and react for 25 h to obtain modified nano-silica. Disperse the modified nano-silica in ethanol, protect it by introducing nitrogen. Under the conditions of a rotation speed of 500 r / min and a temperature of 40 °C, stir and add 3-isocyanatopropyltriethoxysilane and react for 3 h to obtain the modified filler.

[0079] The dosage ratios of triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, deionized water, tetraethyl orthosilicate, KH550, and ethanol described in Step B1 are 65 mg: 380 mg: 550 mg: 25 mL: 10 mmol: 5 mmol: 5 mL, and the dosage ratio of the base material to the hydrochloric acid solution is 1 mg: 1 mL, and the mass fraction of the hydrochloric acid solution is 5%.

[0080] The dosage ratios of the aminated nano-silica, tin tetrachloride, ethanol, and deionized water described in Step B2 are 2 g: 2 mmol: 10 mL: 10 mL, and the molar ratio of the amino group on the surface of the modified nano-silica to 3-isocyanatopropyltriethoxysilane is 1:1.

[0081] Comparative Example 1

[0082] In this comparative example, compared with Example 1, nano-silica is used to replace the modified filler, and the remaining steps are the same.

[0083] Comparative Example 2

[0084] In this comparative example, compared with Example 1, aminated nano-silica is used to replace the modified nano-silica, and the remaining steps are the same.

[0085] Comparative Example 3

[0086] In this comparative example, compared with Example 1, diphenylmethane diisocyanate is used to replace the modified prepolymer, and the remaining steps are the same.

[0087] Comparative Example 4

[0088] In this comparative example, compared with Example 1, SGP laminated film is used to replace the laminated film, and the remaining steps are the same.

[0089] Make specimens with a volume of 1 m 3 in size from the laminated glass and ordinary glass prepared in Examples 1-3 and Comparative Examples 1-4. Simulate the sun light artificially, irradiate for 8 h, and compare the temperature difference with that in the space of ordinary glass. The test results are shown in the following table.

[0090]

[0091] As can be seen from the above table, the present application has a good heat insulation effect.

[0092] The above content is only an example and explanation of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution, as long as they do not deviate from the concept of the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.

Claims

1. A production process of SGP laminated glass, characterized in that: Specifically, it includes the following steps: Step S1: Mix the modified prepolymer, ethylenediamine, and DMF, introduce nitrogen protection, react, add KH560, react to obtain the pretreated polyurethane. Mix the pretreated polyurethane, diphenylmethane diisocyanate, and DMF, introduce nitrogen protection, react, add N-(2-hydroxyethyl) maleimide, and continue to react to obtain the modified polyurethane; Step S2: Mix the modified polyurethane, modified filler, dimethyldiethoxysilane, ethanol, and DMF, stir, add deionized water and hydrochloric acid, react, add tetrabutyl titanate, continue to react to obtain the modified resin. Mix the modified resin, SGP laminated resin, and dicumyl peroxide, extrude and cast into a film to obtain the laminated film. Place the laminated film between two pieces of glass and press at high temperature to obtain the SGP film laminated glass.

2. The production process of an SGP laminated glass according to claim 1, characterized in that: The modified prepolymer is prepared by the following steps: Step A1: Mix p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate evenly and place them in a mortar for grinding to obtain the azo dye. Mix the azo dye, ethanol, and sodium hydroxide solution, stir, add sodium dithionite, and react to obtain Intermediate 1; Step A2: Mix metallic magnesium, iodine, and tetrahydrofuran evenly, introduce nitrogen protection, stir, add 2-bromothiophene, and react to obtain Intermediate 2. Mix Intermediate 1, Intermediate 2, and tetrahydrofuran for reaction to obtain the modifier; Step A3: Mix the modifier, diethanolamine, and DMF evenly, introduce nitrogen protection, stir, add sodium hydroxide for reaction, adjust the pH to neutral to obtain the modified monomer. Mix the modified monomer, diphenylmethane diisocyanate, and DMF for reaction to obtain the modified prepolymer.

3. The production process of an SGP laminated glass according to claim 2, characterized in that: In Step A1, the molar ratio of p-chloro-o-nitroaniline, p-hydroxystyrene, sodium nitrite, and potassium bisulfate is 1:1.1:1:1, and the dosage ratio of the azo dye, ethanol, sodium hydroxide solution, and sodium dithionite is 25 mmol:50 mL:50 mL:82 mmol.

4. The production process of an SGP laminated glass according to claim 2, characterized in that: In Step A2, the dosage ratio of metallic magnesium, iodine, tetrahydrofuran, and 2-bromothiophene is 1.1 mol:1 mol:100 mL:1 mol, and the molar ratio of Intermediate 1 and Intermediate 2 is 1:

1.

5. The production process of an SGP laminated glass according to claim 2, characterized in that: In Step A3, the molar ratio of the modifier and diethanolamine is 1:1, and the molar ratio of the modified monomer and diphenylmethane diisocyanate is 1:2.

1.

6. The production process of an SGP laminated glass according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step B1: Mix triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, and deionized water, stir, add tetraethyl orthosilicate, KH550, and ethanol, react, centrifuge to remove the supernatant, add the substrate to the hydrochloric acid solution, perform ultrasonic treatment, and then heat up and keep warm to obtain the amino-functionalized nano-silica; Step B2: Mix and stir aminized nano-silica, tin tetrachloride, and ethanol, add deionized water and ammonia water, after stirring treatment, raise the temperature for reaction to obtain modified nano-silica. Disperse the modified nano-silica in ethanol, protect it by introducing nitrogen, stir and add 3-isocyanatopropyltriethoxysilane for reaction to obtain modified filler.

7. The production process of an SGP laminated glass according to claim 6, characterized in that: The dosage ratio of triethanolamine, cetyltrimethylammonium bromide, sodium trifluoroacetate, deionized water, tetraethyl orthosilicate, KH550, and ethanol described in Step B1 is 65 mg: 380 mg: 550 mg: 25 mL: 10 mmol: 5 mmol: 5 mL, and the dosage ratio of the base material and the hydrochloric acid solution is 1 mg: 1 mL.

8. The production process of an SGP laminated glass according to claim 6, characterized in that: The dosage ratio of the aminized nano-silica, tin tetrachloride, ethanol, and deionized water described in Step B2 is 2 g: 2 mmol: 10 mL: 10 mL, and the molar ratio of the amino group on the surface of the modified nano-silica and 3-isocyanatopropyltriethoxysilane is 1:1.

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