Heat insulation type ionic intermediate film and preparation method thereof

Abstract

The invention relates to the technical field of intermediate membranes, in particular to a heat insulation type ionic intermediate membrane and a preparation method thereof.The heat insulation type ionic intermediate membrane is characterized in that hollow silicon dioxide nanotubes serve as filler, epoxy resin modified polyurethane emulsion serves as a base material, auxiliaries are added to prepare a heat insulation coating, and the ionic intermediate membrane layer is coated with the heat insulation coating to form a heat insulation layer; the preparation method comprises the following steps: carrying out amination on a hollow silicon dioxide nanotube by using 3-aminopropyltriethoxysilane, carrying out dehydration condensation on furan-2, 5-diketone and an amino group to synthesize maleimide so as to obtain a maleimide modified hollow silicon dioxide nanotube, and grafting furan carboxylic acid imidazolium salt polyionic liquid by using a Diels-Alder reaction so as to obtain a composite hollow silicon dioxide nanotube; aminated glass fibers, composite hollow silicon dioxide nanotubes, epoxy resin modified polyurethane emulsion and auxiliaries are mixed, and a reinforcing layer coating is obtained; and coating the lower surface of the ionic intermediate film layer with a reinforcing layer coating to form the reinforcing layer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of interlayer film, in particular to a heat insulation type ionic interlayer film and a preparation method thereof. BACKGROUND

[0002] With the increasing demand for safety, functionality and energy saving in the fields of automobile, electronics, medical treatment and construction, ionic interlayer film widely used in laminated glass has become a research hotspot. Although traditional ionic interlayer film has good transparency, adhesion and impact resistance, it is insufficient in sound insulation, heat insulation, antibacterial property and flame retardancy, thereby limiting its application range. For example, in medical treatment or public facilities, the lack of antibacterial property can cause microbial breeding, and the lack of flame retardancy can cause safety hazards.

[0003] At present, the methods for improving the performance of interlayer film mainly include filler modification, multi-layer compounding and addition of functional additives. For example, hollow glass microbeads are added to improve the heat and sound insulation, nano-silver, quaternary ammonium salt and other antibacterial agents are added to improve the antibacterial property, and halogen or phosphorus flame retardants are added to improve the flame retardancy. However, a single filler or additive is difficult to meet the comprehensive performance requirements, and a large amount of multiple fillers or additives can weaken the mechanical strength, and also have the problems of easy migration and poor durability, which are difficult to meet the diversified needs of the existing market. SUMMARY

[0004] The present application aims to provide a heat insulation type ionic interlayer film and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the present application provides the following technical scheme: A heat insulation type ionic interlayer film, comprising, from top to bottom, a PET release layer, a heat insulation layer, an ionic interlayer film layer, a reinforcing layer and a PET release layer. The raw material composition of the reinforcing layer comprises amino glass fiber, composite hollow silica nanotube, epoxy resin modified polyurethane emulsion and additive. The raw material composition of the heat insulation layer comprises composite hollow silica nanotube, epoxy resin modified polyurethane emulsion and additive.

[0006] Further, the additive is one or a combination of leveling agent and defoaming agent.

[0007] Further, the raw material composition of the reinforcing layer comprises, in mass fraction, 1-3 parts of amino glass fiber, 2-6 parts of composite hollow silica nanotube, 22-34 parts of epoxy resin modified polyurethane emulsion and 1-2 parts of additive.

[0008] Further, the mass ratio of composite hollow silica nanotube, epoxy resin modified polyurethane emulsion and additive in the heat insulation layer is 2:17.5:0.5.

[0009] Further, the preparation of the epoxy resin modified polyurethane emulsion comprises the following steps: (1) under nitrogen atmosphere, mix dimer acid and N,N-dimethylformamide, add the mixed solution of 4-dimethylaminopyridine and N,N-dimethylformamide, successively add the mixed solution of N,N'-dicyclohexyl carbodiimide and N,N-dimethylformamide, the mixed solution of pentanediamine and N,N-dimethylformamide, incubate at 18-25℃ for 14-15h, wash, cool, wash, dry, and obtain dimer acid polyamide; (2) under nitrogen protection, mix epoxy resin, γ-aminopropyl triethoxysilane and dibutyltin dilaurate, stir in 50-55℃ oil bath for 3-4h, and obtain modified epoxy resin; (3) under nitrogen atmosphere, vacuum dehydrate polytetrahydrofuran ether glycol for 2h, cool to 50℃, add isophorone diisocyanate and dibutyltin dilaurate, warm up to 78-82℃ and incubate for 3-4h, add the mixed solution of modified epoxy resin and N-methyl pyrrolidone, incubate for 50-70min, add 2,2-dimethylol butyric acid and N-methyl pyrrolidone, continue to incubate for 2-3h, stir for 30-40min, add dimer acid polyamide, continue to incubate for 50-70min, add furan carboxylic acid imidazole salt poly ionic liquid and acetone, cool down to 45-50℃, add triethylamine for neutralization, cool down to 18-25℃, add deionized water for emulsification, and obtain epoxy resin modified polyurethane emulsion.

[0010] Further, the preparation of the composite hollow silica nanotube comprises the following steps: 1) mix polyethylene glycol hexadecyl ether and cyclohexane, warm up in water bath to 48-52℃, add nickel chloride solution, add hydrazine hydrate, incubate for 2-3h, add diethylamine, add tetraethyl silicate, continue to incubate for 2-3h, centrifuge, add to hydrochloric acid, stir for 4-5h, centrifuge, wash, freeze-dry, and obtain hollow silica nanotube; 2) mix hollow silica nanotube, γ-aminopropyl triethoxysilane, deionized water and sodium carbonate, stir at 78-80℃ for 46-48h, centrifuge, wash, dry, and obtain aminated hollow silica nanotube; mix aminated hollow silica nanotube, furan-2,5-dione and chlorobenzene, ultrasonic dispersion for 10min, incubate at 128-130℃ for 2-3h under nitrogen atmosphere, cool down to 18-25℃, add sodium acetate acetic anhydride solution, incubate at 130℃ for 60-70min under nitrogen atmosphere, cool down, centrifuge, wash, dry, and obtain maleimide modified hollow silica nanotube; 3) mixing the maleimide modified hollow silica nanotube, dimethyl sulfoxide, furan carboxylic acid imidazole salt poly ionic liquid, ultrasonic dispersion for 10-20 min, heating to 75-80 DEG C for 2-3 h, to obtain the composite hollow silica nanotube.

[0011] Further, the mass ratio of polytetrahydrofuran ether diol, isophorone diisocyanate, modified epoxy resin, dimer acid polyamide, furan carboxylic acid imidazole salt poly ionic liquid is 20:14:1.5:0.5:0.6.

[0012] Further, the mass ratio of maleimide modified hollow silica nanotube, furan carboxylic acid imidazole salt poly ionic liquid is 3:4.

[0013] Further, the preparation of furan carboxylic acid imidazole salt poly ionic liquid includes the following steps: A. mixing 3-bromopropionic acid, anhydrous ethanol, 1-vinylimidazole, refluxing at 75 DEG C for 22-24 h, cooling to 18-25 DEG C, rotary evaporation, adding anhydrous acetonitrile to precipitate, centrifuging, washing, and freeze-drying to obtain 1-vinyl-3-carboxyethyl imidazole bromide; B. mixing 1-vinyl-3-carboxyethyl imidazole bromide, anhydrous methanol, azobis isobutyronitrile, and heating at 58-62 DEG C for 8-9 h under nitrogen protection to obtain poly (1-vinyl-3-carboxyethyl imidazole bromide) salt; C. mixing poly (1-vinyl-3-carboxyethyl imidazole bromide) salt, N,N-dimethylformamide, and sodium furan-2-carboxylate, dialyzing with deionized water for 22-24 h, and freeze-drying to obtain furan carboxylic acid imidazole salt poly ionic liquid.

[0014] Further, a preparation method of a heat insulation type ionic intermediate film includes the following steps: S1: mixing the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the auxiliary agent to obtain a heat insulation coating; S2: coating the heat insulation coating on the upper surface of the ionic intermediate film layer to form a heat insulation layer; S3: mixing the aminated glass fiber, the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the auxiliary agent to obtain a reinforcing layer coating; S4: coating the reinforcing layer coating on the lower surface of the ionic intermediate film layer to form a reinforcing layer; covering a PET release layer on the reinforcing layer and the heat insulation layer to obtain a heat insulation type ionic intermediate film.

[0015] Compared with the prior art, the present application has the following advantages: The present application provides a heat insulation type ionic intermediate film and a preparation method thereof. Through component and process design, a multi-layer composite ionic intermediate film with excellent mechanical strength, heat insulation, antibacterial property, flame retardancy, and self-repairing property is obtained.

[0016] The present application is to improve the thermal and sound insulation properties of the intermediate film. Hollow silica nanotubes with high specific surface area and unique hollow structure synthesized by the template method are used as fillers. Epoxy resin modified polyurethane emulsion is used as the base material. Additives are used to prepare thermal insulation coating, which is coated on the ionic intermediate film layer to form a light, excellent barrier performance thermal insulation layer. To improve the uniformity of hollow silica nanotubes in the base material, 3-aminopropyl triethoxysilane is used to modify the hollow silica nanotubes, and maleimide is synthesized by dehydrating condensation of furan-2,5-dione and amino groups to obtain maleimide modified hollow silica nanotubes, thereby improving the flame retardance and aging resistance of the thermal insulation layer. Then, by Diels-Alder reaction, furan carboxylic acid imidazole salt polyionic liquid is grafted to obtain composite hollow silica nanotubes. The furan carboxylic acid imidazole salt polyionic liquid is a carboxylic acid imidazole salt polyionic liquid containing furan structure synthesized from 1-vinylimidazole. The introduction of ionic liquid greatly improves the thermal insulation, antibacterial, flame retardance and stability of hollow silica nanotubes. The introduction of dynamic reversible bonds in composite hollow silica nanotubes gives the thermal insulation layer fast self-healing property. The introduction of multiple active sites in composite hollow silica nanotubes improves the bonding strength with the base material and improves the stability of the thermal insulation layer.

[0017] To further improve the mechanical strength and impact resistance of the intermediate film, aminosilane coupling agent is used to modify the glass fibers, and composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion and additives are mixed to obtain a reinforcing layer coating. The aminosilane coupling agent is used to modify the glass fibers. The reinforcing layer coating is coated on the surface of the ionic intermediate film layer to form a reinforcing layer. By controlling the amount ratio of aminosilane coupling agent, composite hollow silica nanotubes and epoxy resin modified polyurethane emulsion in the reinforcing layer, a complex crosslinking network is constructed to effectively improve the mechanical strength of the intermediate film.

[0018] Epoxy resin modified polyurethane emulsion is used as the base material in the sound insulation layer and the reinforcing layer. The epoxy resin modified polyurethane emulsion is obtained by using polytetrahydrofuran ether diol and isophorone diisocyanate as raw materials, and a catalyst dibutyltin dilaurate. The epoxy resin modified by aminosilane coupling agent is used as a modifier. Amino-terminated dimer acid polyamide is synthesized by using dimer acid as a raw material. Furan carboxylic acid imidazole salt polyionic liquid is used as a capping agent to obtain a water-based polyurethane emulsion with high adhesion, high light transmittance, flame retardance, antibacterial property and self-repairing function. The reinforcing layer and the thermal insulation layer have excellent self-repairing property, which can effectively alleviate stress concentration and avoid coating cracking or peeling, thereby prolonging the service life. DETAILED DESCRIPTION

[0019] The technical solutions in the present application will be described clearly and completely below in connection with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present application.

[0020] It should be noted that if the embodiments of the present application involve directional indications such as up, down, left, right, front, back, the directional indications are only used to explain the relative position relationship, movement condition and the like between components in a certain specific posture, and if the specific posture changes, the directional indications will also change accordingly. In addition, the technical solutions of each embodiment can be combined with each other, but it must be based on the fact that the technical solutions can be realized by those skilled in the art, and when the combination of technical solutions contradicts each other or cannot be realized, it shall be considered that the combination of technical solutions does not exist and is not within the protection scope of the present application.

[0021] The technical solutions of the present application will be described in further detail below in connection with specific embodiments. It should be understood that the following embodiments are only used to explain the present application, and are not used to limit the present application.

[0022] Embodiment 1: A preparation method of a heat insulation type ionic interlayer film, comprising the following steps: S1: mixing composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion and an additive to obtain a heat insulation coating; S2: coating the heat insulation coating on the upper surface of the ionic interlayer film to form a heat insulation layer; The additive is a defoaming agent; The mass ratio of the composite hollow silica nanotubes, the epoxy resin modified polyurethane emulsion and the additive in the heat insulation layer is 2:17.5:0.5; The preparation of the epoxy resin modified polyurethane emulsion comprises the following steps: (1) Under a nitrogen atmosphere, 6 g of dimer acid, 10 mL of N,N-dimethylformamide are mixed, a mixed solution of 0.6 g of 4-dimethylaminopyridine and 5 mL of N,N-dimethylformamide is added, a mixed solution of 4.2 g of N,N'-dicyclohexyl carbodiimide and 5 mL of N,N-dimethylformamide is added, a mixed solution of 2.1 g of pentanediamine and 10 mL of N,N-dimethylformamide is added, and the mixture is incubated at 18°C for 15 h, and then washed, cooled, washed and dried to obtain a dimer acid polyamide; (2) Under nitrogen protection, 1.5 g of epoxy resin, 0.2 g of γ-aminopropyl triethoxysilane and 1 drop of dibutyl tin dilaurate are mixed, and stirred in a 50°C oil bath for 4 h to obtain a modified epoxy resin; (3) Under nitrogen atmosphere, 20 g of polytetrahydrofuran ether glycol was vacuum dehydrated for 2 h, cooled to 50℃, 14 g of isophorone diisocyanate, 3 drops of dibutyl tin dilaurate were added, warmed to 78℃ for 4 h, 1.5 g of modified epoxy resin, 5 mL of N-methyl pyrrolidone mixture was added, and the mixture was kept for 50 min, 1.6 g of 2,2-dimethylol butyric acid, 5 mL of N-methyl pyrrolidone was added and the mixture was kept for 2 h, stirred for 30 min, 0.5 g of dimer acid polyamide was added, and the mixture was kept for 50 min, 0.6 g of furan carboxylic acid imidazole salt poly ionic liquid, 5 mL of acetone was added, cooled to 45℃, 1.2 g of triethylamine was added for neutralization, cooled to 18℃, and deionized water was added for emulsification, to obtain an epoxy resin modified polyurethane emulsion with a solid content of 30%; The preparation of the composite hollow silica nanotube includes the following steps: 1) 4 g of polyethylene glycol hexadecyl ether, 10 mL of cyclohexane were mixed, the water bath was warmed to 48℃, 1 mL of 0.8 mol / L nickel chloride solution was added, 0.25 mL of hydrazine hydrate was added, and the mixture was kept for 2 h, 0.5 mL of diethylamine was added, 1.5 mL of tetraethyl silicate was added, and the mixture was kept for 2 h, centrifuged, added to 3 mol / L hydrochloric acid, stirred for 4 h, centrifuged, washed, and freeze-dried to obtain hollow silica nanotubes; 2) 1.5 g of hollow silica nanotubes, 15 mL of γ-aminopropyl triethoxysilane, 10 mL of deionized water, and 100 mg of sodium carbonate were mixed, stirred at 80℃ for 48 h, centrifuged, washed, and dried to obtain amino-modified hollow silica nanotubes; 150 mg of amino-modified hollow silica nanotubes, 0.75 g of furan-2,5-dione, and 13 mL of chlorobenzene were mixed, ultrasonically dispersed for 10 min, kept at 130℃ for 2 h under nitrogen atmosphere, cooled to 1℃, 5 mL of 10 mg / mL sodium acetate in acetic anhydride solution was added, kept at 130℃ for 60 min under nitrogen atmosphere, cooled, centrifuged, washed, and dried to obtain maleimide-modified hollow silica nanotubes; 3) 3 g of maleimide-modified hollow silica nanotubes, 20 mL of dimethyl sulfoxide, and 4 g of furan carboxylic acid imidazole salt poly ionic liquid were mixed, ultrasonically dispersed for 10 min, warmed to 75℃ for 3 h to obtain composite hollow silica nanotubes; The preparation of the furan carboxylic acid imidazole salt poly ionic liquid includes the following steps: A. 0.01 mol of 3-bromopropionic acid, 10 mL of anhydrous ethanol, and 0.01 mol of 1-vinylimidazole were mixed, refluxed at 75℃ for 22 h, cooled to 18℃, rotary evaporated, precipitated with anhydrous acetonitrile, centrifuged, washed, and freeze-dried to obtain 1-vinyl-3-carboxyethyl imidazole bromide; B. 0.02 mol 1-vinyl-3-carboxyethyl imidazole bromide, 40 ml anhydrous methanol, 0.04 g azobisisobutyronitrile were mixed, and incubated at 58℃ for 9 h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazole bromide) salt; C. 2.5 g poly(1-vinyl-3-carboxyethyl imidazole bromide) salt, 10 ml N,N-dimethylformamide, 1.1 g sodium furan-2-carboxylate were mixed, incubated at 68℃ for 24 h, dialyzed with deionized water for 22 h, and freeze-dried to obtain furan carboxylic acid imidazole salt polyionic liquid; S3: The amino glass fiber, the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the auxiliary agent were mixed to obtain a reinforcing layer coating; S4: The reinforcing layer coating was coated on the lower surface of the ionic intermediate film layer to form a reinforcing layer; and the PET release layer was covered on the reinforcing layer and the heat insulation layer to obtain a heat insulation type ionic intermediate film. The raw material composition of the reinforcing layer, in mass fraction, was as follows: 1 part of amino glass fiber, 2 parts of composite hollow silica nanotube, 22 parts of epoxy resin modified polyurethane emulsion, and 1 part of auxiliary agent.

[0023] Example 2: A heat insulation type ionic intermediate film preparation method, comprising the following steps: S1: The composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the auxiliary agent were mixed to obtain a heat insulation coating; S2: The heat insulation coating was coated on the upper surface of the ionic intermediate film layer to form a heat insulation layer; The mass ratio of the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the auxiliary agent in the heat insulation layer was 2:17.5:0.5; The auxiliary agent was a defoaming agent; The preparation of the epoxy resin modified polyurethane emulsion included the following steps: (1) Under a nitrogen atmosphere, 6 g dimer acid, 10 ml N,N-dimethylformamide were mixed, 0.6 g 4-dimethylaminopyridine, 5 ml N,N-dimethylformamide were added, 4.2 g N,N'-dicyclohexyl carbodiimide, 5 ml N,N-dimethylformamide were added, 2.1 g pentanediamine, 10 ml N,N-dimethylformamide were added, and incubated at 20℃ for 14.5 h, and then washed, cooled, washed, and dried to obtain dimer acid polyamide; (2) Under nitrogen protection, 1.5 g epoxy resin, 0.2 g γ-aminopropyl triethoxysilane, and 1 drop of dibutyl tin dilaurate were mixed, and stirred in a 53℃ oil bath for 3.5 h to obtain modified epoxy resin; (3) Under nitrogen atmosphere, 20 g of polytetrahydrofuran ether glycol was vacuum dehydrated for 2 h, cooled to 50℃, 14 g of isophorone diisocyanate, 3 drops of dibutyl tin dilaurate were added, warmed to 80℃ for 3.5 h, 1.5 g of modified epoxy resin, 5 mL of N-methyl pyrrolidone mixture was added, and kept for 60 min, 1.6 g of 2,2-dimethylol butyric acid, 5 mL of N-methyl pyrrolidone was added and kept for 2.5 h, stirred for 35 min, 0.5 g of dimer acid polyamide was added, and kept for 60 min, 0.6 g of furan carboxylic acid imidazole salt poly ionic liquid, 5 mL of acetone was added, cooled to 48℃, 1.2 g of triethylamine was added for neutralization, cooled to 20℃, and deionized water was added for emulsification to obtain an epoxy resin modified polyurethane emulsion with a solid content of 30%; The preparation of the composite hollow silica nanotube includes the following steps: 1) 4 g of polyethylene glycol hexadecyl ether, 10 mL of cyclohexane were mixed, the water bath was warmed to 50℃, 1 mL of 0.8 mol / L nickel chloride solution was added, 0.25 mL of hydrazine hydrate was added, and kept for 2.5 h, 0.5 mL of diethylamine was added, 1.5 mL of tetraethyl silicate was added, and kept for 2.5 h, centrifuged, added to 3 mol / L hydrochloric acid, stirred for 4.5 h, centrifuged, washed, and freeze-dried to obtain a hollow silica nanotube; 2) 1.5 g of hollow silica nanotube, 15 mL of γ-aminopropyl triethoxysilane, 10 mL of deionized water, and 100 mg of sodium carbonate were mixed, stirred at 80℃ for 48 h, centrifuged, washed, and dried to obtain an amino-modified hollow silica nanotube; 150 mg of the amino-modified hollow silica nanotube, 0.75 g of furan-2,5-dione, and 13 mL of chlorobenzene were mixed, ultrasonically dispersed for 10 min, kept at 129℃ for 2.5 h under nitrogen atmosphere, cooled to 20℃, 5 mL of 10 mg / mL sodium acetate in acetic anhydride solution was added, kept at 130℃ for 65 min under nitrogen atmosphere, cooled, centrifuged, washed, and dried to obtain a maleimide-modified hollow silica nanotube; 3) 3 g of the maleimide-modified hollow silica nanotube, 20 mL of dimethyl sulfoxide, and 4 g of furan carboxylic acid imidazole salt poly ionic liquid were mixed, ultrasonically dispersed for 15 min, warmed to 78℃ and kept for 2.5 h to obtain a composite hollow silica nanotube; The preparation of the furan carboxylic acid imidazole salt poly ionic liquid includes the following steps: A. 0.01 mol of 3-bromopropionic acid, 10 mL of anhydrous ethanol, and 0.01 mol of 1-vinylimidazole were mixed, refluxed at 75℃ for 23 h, cooled to 20℃, rotary evaporated, precipitated with anhydrous acetonitrile, centrifuged, washed, and freeze-dried to obtain 1-vinyl-3-carboxyethyl imidazole bromide; B. 0.02 mol 1-vinyl-3-carboxyethyl imidazole bromide, 40 ml anhydrous methanol, 0.04 g azobisisobutyronitrile were mixed, and the mixture was kept at 60°C for 8.5 h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazole bromide) salt; C. 2.5 g poly(1-vinyl-3-carboxyethyl imidazole bromide) salt, 10 ml N,N-dimethylformamide, 1.1 g sodium furan-2-carboxylate were mixed, and the mixture was kept at 69°C for 23 h, then dialyzed with deionized water for 23 h, and freeze-dried to obtain furan carboxylic acid imidazole salt polyionic liquid; S3: The amino glass fiber, the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the additive were mixed to obtain a reinforcing layer coating; S4: The reinforcing layer coating was coated on the lower surface of the ionic intermediate film layer to form a reinforcing layer; and the PET release layer was covered on the reinforcing layer and the heat insulation layer to obtain a heat insulation type ionic intermediate film; the raw material composition of the reinforcing layer, by mass fraction, was as follows: amino glass fiber 2 parts, composite hollow silica nanotube 4 parts, epoxy resin modified polyurethane emulsion 29 parts, and additive 1.5 parts.

[0024] Example 3: A heat insulation type ionic intermediate film preparation method, comprising the following steps: S1: The composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the additive were mixed to obtain a heat insulation coating; S2: The heat insulation coating was coated on the upper surface of the ionic intermediate film layer to form a heat insulation layer; The mass ratio of the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the additive in the heat insulation layer was 2:17.5:0.5; The additive was a defoaming agent; The preparation of the epoxy resin modified polyurethane emulsion included the following steps: (1) Under a nitrogen atmosphere, 6 g dimer acid, 10 ml N,N-dimethylformamide were mixed, and a mixture of 0.6 g 4-dimethylaminopyridine, 5 ml N,N-dimethylformamide was added, followed by sequentially adding a mixture of 4.2 g N,N'-dicyclohexyl carbodiimide, 5 ml N,N-dimethylformamide, a mixture of 2.1 g pentanediamine, and 10 ml N,N-dimethylformamide, and the mixture was kept at 25°C for 14 h, and then washed, cooled, washed, and dried to obtain dimer acid polyamide; (2) Under nitrogen protection, 1.5 g epoxy resin, 0.2 g γ-aminopropyl triethoxysilane, and 1 drop of dibutyltin dilaurate were mixed, and the mixture was stirred in a 55°C oil bath for 3 h to obtain modified epoxy resin; (3) Under nitrogen atmosphere, 20 g of polytetrahydrofuran ether glycol was vacuum dehydrated for 2 h, cooled to 50℃, 14 g of isophorone diisocyanate, 3 drops of dibutyl tin dilaurate were added, warmed to 82℃ for 3 h, 1.5 g of modified epoxy resin, 5 mL of N-methyl pyrrolidone mixture was added, and the temperature was maintained for 70 min. 1.6 g of 2,2-dimethylol butyric acid, 5 mL of N-methyl pyrrolidone was added and the temperature was maintained for 3 h. After stirring for 40 min, 0.5 g of dimer acid polyamide was added and the temperature was maintained for 70 min. 0.6 g of furan carboxylic acid imidazole salt poly ionic liquid, 5 mL of acetone was added, and the temperature was reduced to 50℃. 1.2 g of triethylamine was added for neutralization. After cooling to 25℃, deionized water was added for emulsification to obtain an epoxy resin modified polyurethane emulsion with a solid content of 30%; The preparation of the composite hollow silica nanotube includes the following steps: 1) 4 g of polyethylene glycol hexadecyl ether, 10 mL of cyclohexane were mixed, and the temperature was raised to 52℃ in a water bath. 1 mL of 0.8 mol / L nickel chloride solution was added, followed by 0.25 mL of hydrazine hydrate. The temperature was maintained for 3 h. 0.5 mL of diethylamine was added, followed by 1.5 mL of tetraethyl silicate. The temperature was maintained for another 3 h. Centrifugation was performed, and the product was added to 3 mol / L hydrochloric acid. Stirring was performed for 5 h. Centrifugation, washing, and freeze-drying were performed to obtain the hollow silica nanotube; 2) 1.5 g of hollow silica nanotube, 15 mL of γ-aminopropyl triethoxysilane, 10 mL of deionized water, and 100 mg of sodium carbonate were mixed and stirred at 80℃ for 48 h. Centrifugation, washing, and drying were performed to obtain the amino-modified hollow silica nanotube. 150 mg of the amino-modified hollow silica nanotube, 0.75 g of furan-2,5-dione, and 13 mL of chlorobenzene were mixed and ultrasonically dispersed for 10 min. Under nitrogen atmosphere, the temperature was maintained at 130℃ for 2 h. After cooling to 25℃, 5 mL of 10 mg / mL sodium acetate in acetic anhydride solution was added. The temperature was maintained at 130℃ for 70 min under nitrogen atmosphere. Cooling, centrifugation, washing, and drying were performed to obtain the maleimide-modified hollow silica nanotube; 3) 3 g of the maleimide-modified hollow silica nanotube, 20 mL of dimethyl sulfoxide, and 4 g of furan carboxylic acid imidazole salt poly ionic liquid were mixed and ultrasonically dispersed for 20 min. The temperature was raised to 75℃ and maintained for 3 h to obtain the composite hollow silica nanotube; The preparation of the furan carboxylic acid imidazole salt poly ionic liquid includes the following steps: A. 0.01 mol of 3-bromopropionic acid, 10 mL of anhydrous ethanol, and 0.01 mol of 1-vinylimidazole were mixed and refluxed at 75℃ for 24 h. The temperature was cooled to 25℃, and rotary evaporation was performed. Anhydrous acetonitrile was added for precipitation. Centrifugation, washing, and freeze-drying were performed to obtain 1-vinyl-3-carboxyethyl imidazole bromide; B. 0.02 mol 1-vinyl-3-carboxyethyl imidazole bromide, 40 mL anhydrous methanol, 0.04 g azobisisobutyronitrile were mixed, and incubated at 62°C for 8 h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazole bromide) salt; C. 2.5 g poly(1-vinyl-3-carboxyethyl imidazole bromide) salt, 10 mL N,N-dimethylformamide, 1.1 g sodium furan-2-carboxylate were mixed, and incubated at 70°C for 22 h, dialyzed with deionized water for 24 h, and freeze-dried to obtain furan carboxylic acid imidazole salt polyionic liquid; S3: Amino glass fiber, composite hollow silica nanotube, epoxy resin modified polyurethane emulsion, and auxiliary were mixed to obtain a reinforcing layer coating; S4: The reinforcing layer coating was coated on the lower surface of the ionic intermediate film layer to form a reinforcing layer; and the PET release layer was overlaid on the reinforcing layer and the thermal insulation layer to obtain a heat insulation type ionic intermediate film; the raw material composition of the reinforcing layer, by mass fraction, was as follows: amino glass fiber 3 parts, composite hollow silica nanotube 6 parts, epoxy resin modified polyurethane emulsion 34 parts, and auxiliary 2 parts.

[0025] Comparative Example 1: Using Example 3 as a control group, the composite hollow silica nanotube was replaced with hollow silica nanotube, and other procedures were normal.

[0026] Comparative Example 2: Using Example 3 as a control group, the epoxy resin modified polyurethane emulsion was replaced with modified epoxy resin, and other procedures were normal.

[0027] The preparation of the amino glass fiber in the examples and comparative examples included the following steps: 2 g glass fiber, 20 mL γ-aminopropyl triethoxysilane, and 10 mL deionized water were mixed, 2 drops of ammonia water were added dropwise, and incubated at 80°C for 44 h, followed by centrifugation, washing, and drying to obtain amino glass fiber; The thickness of the reinforcing layer in the examples and comparative examples was 0.2 mm; and the thickness of the thermal insulation layer was 0.2 mm.

[0028] The sources of the raw materials used (only as an exemplary example) were as follows: Ionic interlayer (SGP, 0.3 mm): Dongguan Qun'an Plastic Industry Co., Ltd.; PET release layer (PET release film, 0.2 mm), glass fiber (1 µm, AR), pentanediamine (462-94-2, 98%), epoxy resin (E51, 99%): commercially available; defoamer M101: Shandong Dayi Chemical Co., Ltd.; furan-2,5-dione (99.5%): Tianjin Kemio Chemical Reagent Co., Ltd.; acetic anhydride 242845: Merck reagent; dimer acid D304162, 4-dimethylaminopyridine D1092074, γ-aminopropyltriethoxysilane A107147, dibutyltin dilaurate D100274, polytetrahydrofuran ether glycol P117874, isophorone diisocyanate I109582, 2,2-dimethylol butyric acid B115196, polyethylene glycol hexadecyl ether P684403, hydrazine hydrate H431263, tetraethyl silicate T110595, 1-vinylimidazole V109377, azobis isobutyronitrile A434183, sodium furan-2-carboxylate (prepared from furan acid F111223): Aldrich reagent; N,N-dimethylformamide, N,N'-dicyclohexyl carbodiimide, N-methyl pyrrolidone, acetone, triethylamine, cyclohexane, nickel chloride, hydrochloric acid, sodium carbonate, diethylamine, 3-bromopropionic acid, chlorobenzene, sodium acetate, dimethyl sulfoxide, anhydrous ethanol, anhydrous acetonitrile, anhydrous methanol, analytically pure, commercially available.

[0029] Performance test: the reinforcing layer coating prepared in the examples and comparative examples was cured in a mold to form a sample with a length of 2 mm, a width of 2 mm, and a thickness of 0.1 mm, and the sample was tested. Thermal insulation: using a thermal conductivity instrument to detect the thermal conductivity; antibacterial property: using plate method to test with E. coli as test bacteria; flame retardancy: performing UL-94 vertical burning grade test; self-repairing property: drawing a scratch with a length of 0.5 mm, a width of 1 µm, and a depth of 0.1 mm on the surface, keeping at 80 ℃ for 24 h, and observing the length of the scratch with an electron microscope, the self-repairing rate = (L 初始划痕长度 -L 现有划痕长度 ) / L 初始划痕长度 ×100%; aging resistance: irradiating with 365 nm ultraviolet light for 72 h, then measuring the antibacterial rate again, and the difference between the change of the initial antibacterial rate and the change of the antibacterial rate is 0-1% including 1%, then the aging resistance is qualified, otherwise the aging resistance is unqualified; the results obtained are shown in Table 1. Table 1

[0030] The application provides a heat-insulating ionic interlayer and a preparation method thereof, and through component and process design, a multi-layer composite ionic interlayer with excellent mechanical strength, heat insulation, antibacterial property, flame retardancy and self-repairing property is obtained.

[0031] Comparing example 3 with comparative example 1 can know that, in order to improve the uniformity of dispersion of hollow silica nanotubes in the base material, the hollow silica nanotubes are aminated by using 3-aminopropyl triethoxysilane, and maleimide is synthesized by dehydrating condensation of furan-2,5-dione and amino to obtain maleimide modified hollow silica nanotubes, so as to improve the flame retardance and aging resistance of the thermal insulation layer, and then by using Diels-Alder reaction, furan carboxylic acid imidazole salt polyionic liquid is grafted to obtain composite hollow silica nanotubes; wherein the furan carboxylic acid imidazole salt polyionic liquid is a carboxylic acid imidazole salt polyionic liquid containing furan structure synthesized by using 1-vinylimidazole as raw material, the introduction of the ionic liquid greatly improves the thermal insulation, antibacterial, flame retardance and stability of the hollow silica nanotubes, the introduction of dynamic reversible bond in the composite hollow silica nanotubes endows the thermal insulation layer with fast self-healing property, and the introduction of multiple active sites in the composite hollow silica nanotubes improves the bonding strength of the composite hollow silica nanotubes with the base material, and improves the stability of the thermal insulation layer.

[0032] Comparing example 3 with comparative example 2 can know that, in the sound insulation layer and the reinforcing layer, the epoxy resin modified polyurethane emulsion is used as the base material, the epoxy resin modified polyurethane emulsion is prepared by using polytetrahydrofuran ether diol and isophorone diisocyanate as raw materials, under the action of a catalyst dibutyltin dilaurate to obtain a prepolymer, using amino silane coupling agent modified epoxy resin as a modifier, using amino-terminated dimer acid polyamide synthesized by using dimer acid as a raw material as a chain extender, and using furan carboxylic acid imidazole salt polyionic liquid as a capping agent to obtain a waterborne polyurethane emulsion with high adhesion, high light transmittance, flame retardance, antibacterial property and self-repairing function, which endows the reinforcing layer and the thermal insulation layer with excellent self-repairing property, can effectively relieve stress concentration, avoid coating cracking or peeling, and thus prolong the service life.

[0033] The above only describes the embodiments of the present application, and does not limit the patent scope of the present application, any equivalent structural transformation made by using the present application specification, or direct / indirect application in other related technical fields within the concept of the present application are included in the patent protection scope of the present application.

Claims

1. A heat-shielding ion-type interlayer film, characterized by, From top to bottom successively contains PET release layer, thermal insulation layer, ionic intermediate film layer, reinforcing layer, PET release layer; The raw material composition of the thermal insulation layer is: composite hollow silica nanotube, epoxy resin modified polyurethane emulsion, auxiliary agent; The raw material composition of the reinforcing layer is: aminated glass fiber, composite hollow silica nanotube, epoxy resin modified polyurethane emulsion, auxiliary agent.

2. The heat shielding type ionic interlayer film according to claim 1, wherein The auxiliary agent is one or a combination of leveling agent and defoaming agent.

3. The heat shielding type ionic interlayer film according to claim 1, wherein The mass ratio of the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion and the auxiliary agent in the thermal insulation layer is 2:17.5:0.

5.

4. The heat shielding type ionic interlayer film according to claim 1, wherein The raw material composition of the reinforcing layer is: aminated glass fiber 1-3 parts, composite hollow silica nanotube 2-6 parts, epoxy resin modified polyurethane emulsion 22-34 parts, auxiliary agent 1-2 parts, in terms of mass fraction.

5. The heat shielding type ionic interlayer film according to claim 1, wherein The preparation of the epoxy resin modified polyurethane emulsion comprises the following steps: (1) under nitrogen atmosphere, mix dimer acid and N,N-dimethylformamide, add the mixed solution of 4-dimethylaminopyridine and N,N-dimethylformamide, successively add the mixed solution of N,N'-dicyclohexyl carbodiimide and N,N-dimethylformamide, the mixed solution of pentanediamine and N,N-dimethylformamide, and incubate at 18-25℃ for 14-15h, then wash, cool, wash, and dry to obtain dimer acid polyamide; (2) under nitrogen protection, mix epoxy resin, γ-aminopropyl triethoxysilane and dibutyltin dilaurate, and stir in an oil bath at 50-55℃ for 3-4h to obtain modified epoxy resin; (3) under nitrogen atmosphere, vacuum dehydrate polytetrahydrofuran ether diol for 2h, cool to 50℃, add isophorone diisocyanate and dibutyltin dilaurate, and incubate at 78-82℃ for 3-4h, then add the mixed solution of modified epoxy resin and N-methylpyrrolidone, incubate for 50-70min, add 2,2-dimethylol butyric acid and N-methylpyrrolidone, and continue to incubate for 2-3h, stir for 30-40min, add dimer acid polyamide, and continue to incubate for 50-70min, add furan carboxylic acid imidazole salt polyionic liquid and acetone, reduce the temperature to 45-50℃, add triethylamine for neutralization, cool to 18-25℃, add deionized water for emulsification, and obtain epoxy resin modified polyurethane emulsion.

6. The heat shielding type ionic interlayer film according to claim 1, wherein The preparation of the composite hollow silica nanotube comprises the following steps: 1) mix polyethylene glycol hexadecyl ether and cyclohexane, and heat in a water bath to 48-52℃, then add nickel chloride solution, hydrazine hydrate, continue to incubate for 2-3h, add diethylamine, and add tetraethyl silicate, continue to incubate for 2-3h, centrifuge, add to hydrochloric acid, stir for 4-5h, centrifuge, wash, and freeze-dry to obtain hollow silica nanotube; 2) mixing hollow silica nanotubes, γ-aminopropyltriethoxysilane, deionized water and sodium carbonate, stirring at 78-80℃ for 46-48h, centrifuging, washing and drying to obtain aminated hollow silica nanotubes; mixing the aminated hollow silica nanotubes, furan-2,5-dione and chlorobenzene, ultrasonic dispersion for 10min, incubating at 128-130℃ for 2-3h under nitrogen atmosphere, adding a solution of sodium acetate in acetic anhydride after cooling to 18-25℃, incubating at 130℃ for 60-70min under nitrogen atmosphere, cooling, centrifuging, washing and drying to obtain maleimide-modified hollow silica nanotubes; 3) mixing the maleimide-modified hollow silica nanotubes, dimethyl sulfoxide and furan carboxylic acid imidazole salt polyionic liquid, ultrasonic dispersion for 10-20min, incubating at 75-80℃ for 2-3h to obtain composite hollow silica nanotubes.

7. The heat-insulating ionic interlayer film according to claim 5, wherein the mass ratio of polytetrahydrofuran ether diol, isophorone diisocyanate, modified epoxy resin, dimer acid polyamide and furan carboxylic acid imidazole salt polyionic liquid is 20:14:1.5:0.5:0.

6.

8. The heat-insulating ionic interlayer film according to claim 6, wherein the mass ratio of maleimide-modified hollow silica nanotubes and furan carboxylic acid imidazole salt polyionic liquid is 3:

4.

9. The heat shielding type ionic interlayer film according to claim 5 or 6, wherein The preparation of the furan carboxylic acid imidazole salt polyionic liquid comprises the following steps: A. mixing 3-bromopropionic acid, anhydrous ethanol and 1-vinylimidazole, refluxing at 75℃ for 22-24h, cooling to 18-25℃, rotary evaporation, adding anhydrous acetonitrile for precipitation, centrifuging, washing and freeze-drying to obtain 1-vinyl-3-carboxyethyl imidazole bromide; B. mixing 1-vinyl-3-carboxyethyl imidazole bromide, anhydrous methanol and azobis isobutyronitrile, incubating at 58-62℃ for 8-9h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazole bromide) salt; C. mixing poly(1-vinyl-3-carboxyethyl imidazole bromide) salt, N,N-dimethylformamide and furan-2-carboxylic acid sodium, dialyzing with deionized water for 22-24h, and freeze-drying to obtain furan carboxylic acid imidazole salt polyionic liquid.

10. The method for producing a heat shielding type ionic interlayer film according to any one of claims 1 to 8, wherein comprises the following steps: S1: mixing the composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion and additives to obtain a heat-insulating coating; S2: coating the heat-insulating coating on the upper surface of the ionic interlayer film to form a heat-insulating layer; S3: mixing the aminated glass fiber, composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion and additives to obtain a reinforcing layer coating; S4: coating the reinforcing layer coating on the lower surface of the ionic interlayer film to form a reinforcing layer; covering a PET release layer on the reinforcing layer and the heat-insulating layer to obtain a heat-insulating ionic interlayer film.

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