Thermal insulation type ionic interlayer and method for producing the same

Abstract

This invention relates to the field of interlayer membrane technology, specifically a heat-insulating ionic interlayer membrane and its preparation method. The method involves using hollow silica nanotubes as fillers, epoxy resin-modified polyurethane emulsion as a base material, and adding additives to prepare a heat-insulating coating, which is then coated onto the ionic interlayer membrane to form a heat-insulating layer. The hollow silica nanotubes are aminated using 3-aminopropyltriethoxysilane, and maleimide is synthesized by dehydration condensation of furan-2,5-dione and amino groups to obtain maleimide-modified hollow silica nanotubes. Furan carboxylic acid imidazole salt polyionic liquid is grafted onto the nanotubes using the Diels-Alder reaction to obtain composite hollow silica nanotubes. Aminated glass fibers, composite hollow silica nanotubes, epoxy resin-modified polyurethane emulsion, and additives are mixed to obtain a reinforcing layer coating. This reinforcing layer coating is then coated onto the lower surface of the ionic interlayer membrane to form a reinforcing layer.

Description

Technical Field

[0001] This invention relates to the field of interlayer membrane technology, specifically to a heat-insulating ionic interlayer membrane and its preparation method. Background Technology

[0002] With increasing demands for safety, functionality, and energy efficiency in the automotive, electronics, medical, and construction industries, ionomer interlayers, widely used in laminated glass, have become a research hotspot. While traditional ionomer interlayers offer good transparency, adhesion, and impact resistance, their performance in sound insulation, heat insulation, antibacterial properties, and flame retardancy is insufficient, thus limiting their application range. For example, in medical or public facilities, a lack of antibacterial properties can lead to microbial growth, and insufficient flame retardancy can pose safety hazards.

[0003] Currently, methods to improve the performance of interlayer membranes mainly include filler modification, multilayer composites, and the addition of functional additives. For example, adding hollow glass microspheres can improve its heat and sound insulation properties, adding antibacterial agents such as nano-silver and quaternary ammonium salts can improve its antibacterial properties, and adding halogenated or phosphorus-based flame retardants can improve its flame retardancy. However, a single filler or additive is difficult to meet the comprehensive performance requirements, and the addition of a large amount of multiple fillers or additives will weaken its mechanical strength. At the same time, there are also problems such as easy migration and poor durability, which makes it difficult to meet the diversified needs of the current market. Summary of the Invention

[0004] The purpose of this invention is to provide a heat-insulating ionic intermediate membrane and its preparation method, so as to solve the problems in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0006] A heat-insulating ionic interlayer film, comprising, from top to bottom, a PET release layer, a heat-insulating layer, an ionic interlayer film layer, a reinforcing layer, and a PET release layer;

[0007] The reinforcing layer is composed of: aminated glass fiber, composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives.

[0008] The heat insulation layer is composed of: composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives.

[0009] Furthermore, the additives are one or a combination of leveling agents and defoamers.

[0010] Furthermore, by mass, the raw material composition of the reinforcing layer is: 1-3 parts of aminated glass fiber, 2-6 parts of composite hollow silica nanotubes, 22-34 parts of epoxy resin modified polyurethane emulsion, and 1-2 parts of additives.

[0011] Furthermore, the mass ratio of composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives in the heat insulation layer is 2:17.5:0.5.

[0012] Furthermore, the preparation of epoxy resin modified polyurethane emulsion includes the following steps:

[0013] (1) Under a nitrogen atmosphere, dimer acid and N,N-dimethylformamide are mixed, and a mixture of 4-dimethylaminopyridine and N,N-dimethylformamide is added. Then, a mixture of N,N'-dicyclohexylcarbodiimide and N,N-dimethylformamide, and a mixture of pentanediamine and N,N-dimethylformamide are added sequentially. The mixture is kept at 18-25℃ for 14-15h, washed, cooled, washed again, and dried to obtain dimer acid polyamide.

[0014] (2) Under nitrogen protection, epoxy resin, γ-aminopropyltriethoxysilane and dibutyltin dilaurate are mixed and stirred in an oil bath at 50-55℃ for 3-4 hours to obtain modified epoxy resin.

[0015] (3) Under a nitrogen atmosphere, polytetrahydrofuran ether diol was vacuum dehydrated for 2 hours, cooled to 50°C, isophorone diisocyanate and dibutyltin dilaurate were added, the temperature was raised to 78-82°C and kept for 3-4 hours, a mixture of modified epoxy resin and N-methylpyrrolidone was added, the temperature was kept for 50-70 minutes, 2,2-dimethylolbutyric acid and N-methylpyrrolidone were added and the temperature was kept for 2-3 hours, the mixture was stirred for 30-40 minutes, dimer acid polyamide was added, the temperature was kept for 50-70 minutes, furan carboxylic acid imidazole salt polyionic liquid and acetone were added, the temperature was lowered to 45-50°C, triethylamine was added to neutralize, the temperature was cooled to 18-25°C, deionized water was added to emulsify, and epoxy resin modified polyurethane emulsion was obtained.

[0016] Furthermore, the preparation of composite hollow silica nanotubes includes the following steps:

[0017] 1) Mix polyethylene glycol hexadecyl ether and cyclohexane, heat in a water bath to 48-52℃, add nickel chloride solution, add hydrazine hydrate, keep warm for 2-3h, add diethylamine, add tetraethyl silicate, continue to keep warm for 2-3h, centrifuge, add to hydrochloric acid, stir for 4-5h, centrifuge, wash, freeze dry to obtain hollow silica nanotubes;

[0018] 2) Hollow silica nanotubes, γ-aminopropyltriethoxysilane, deionized water, and sodium carbonate were mixed and stirred at 78-80℃ for 46-48h. After centrifugation, washing, and drying, aminated hollow silica nanotubes were obtained. Aminated hollow silica nanotubes, furan-2,5-dione, and chlorobenzene were mixed and ultrasonically dispersed for 10min. Under a nitrogen atmosphere, the mixture was kept at 128-130℃ for 2-3h, cooled to 18-25℃, and a sodium acetate acetic anhydride solution was added. Under a nitrogen atmosphere, the mixture was kept at 130℃ for 60-70min, cooled, centrifuged, washed, and dried to obtain maleimide-modified hollow silica nanotubes.

[0019] 3) Mix maleimide-modified hollow silica nanotubes, dimethyl sulfoxide, and furanyl carboxylic acid imidazole salt polyionic liquid, ultrasonically disperse for 10-20 min, heat to 75-80℃ and keep warm for 2-3 h to obtain composite hollow silica nanotubes.

[0020] Furthermore, 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.

[0021] Furthermore, the mass ratio of maleimide-modified hollow silica nanotubes to furanylcarboxylic acid imidazole salt polyionic liquid is 3:4.

[0022] Furthermore, the preparation of furan carboxylic acid imidazole salt polyionic liquid includes the following steps:

[0023] A. Mix 3-bromopropionic acid, anhydrous ethanol and 1-vinylimidazole, reflux at 75°C for 22-24 h, cool to 18-25°C, rotary evaporate, add anhydrous acetonitrile to precipitate, centrifuge, wash, freeze dry to obtain 1-vinyl-3-carboxyethylimidazole bromide.

[0024] B. Mix 1-vinyl-3-carboxyethyl imidazolium bromide, anhydrous methanol, and azobisisobutyronitrile, and keep at 58-62℃ for 8-9 hours under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazolium bromide).

[0025] C. Mix poly(1-vinyl-3-carboxyethylimidazolium bromide), N,N-dimethylformamide, and sodium furan-2-carboxylate, dialyze with deionized water for 22-24 h, and freeze-dry to obtain furan-carboxylate imidazolium salt polyionic liquid.

[0026] Furthermore, a method for preparing a heat-insulating ionic interlayer membrane includes the following steps:

[0027] S1: A heat-insulating coating is obtained by mixing composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives.

[0028] S2: Apply heat-insulating coating to the upper surface of the ionic intermediate film layer to form a heat-insulating layer;

[0029] S3: Aminated glass fiber, composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives are mixed to obtain a reinforcing coating layer.

[0030] S4: Apply the reinforcing layer coating to the lower surface of the ionic interlayer to form a reinforcing layer; cover the reinforcing layer and the heat insulation layer with a PET release layer to obtain a heat-insulating ionic interlayer.

[0031] Compared with the prior art, the beneficial effects of the present invention are:

[0032] This invention provides a heat-insulating ionic interlayer membrane and its preparation method. Through composition and process design, a multilayer composite ionic interlayer membrane with excellent mechanical strength, heat insulation, antibacterial properties, flame retardancy, and self-healing properties is obtained.

[0033] To improve the heat and sound insulation properties of the interlayer membrane, this invention uses hollow silica nanotubes with high specific surface area and unique hollow structure synthesized by template method as fillers, epoxy resin modified polyurethane emulsion as base material, and adds additives to prepare a heat insulation coating, which is then coated on the ionic interlayer membrane layer to form a lightweight heat insulation layer with excellent barrier properties.

[0034] To improve the uniformity of hollow silica nanotube dispersion in the base material, 3-aminopropyltriethoxysilane was used to aminate the hollow silica nanotubes, and maleimide was synthesized by dehydration condensation of furan-2,5-dione and amino groups to obtain maleimide-modified hollow silica nanotubes, thereby improving the flame retardancy and aging resistance of the insulation layer. Then, furan carboxylic acid imidazole salt polyionic liquid was grafted using the Diels-Alder reaction to obtain composite hollow silica nanotubes. The furan carboxylic acid imidazole salt polyionic liquid is a carboxyl imidazole polyionic liquid containing furan structure, synthesized from 1-vinylimidazolium. The introduction of the ionic liquid significantly improves the heat insulation, antibacterial, flame retardant and stability of the hollow silica nanotubes. The introduction of dynamic reversible bonds in the composite hollow silica nanotubes endows the insulation layer with rapid self-healing properties, and the introduction of multiple active sites in the composite hollow silica nanotubes improves its bonding strength with the base material and enhances the stability of the insulation layer.

[0035] To further improve the mechanical strength and impact resistance of the interlayer membrane, aminated glass fiber, composite hollow silica nanotubes, epoxy resin-modified polyurethane emulsion, and additives are mixed to obtain a reinforcing layer coating. The aminated glass fiber is modified by an aminosilane coupling agent. The reinforcing layer coating is applied to the upper surface of the ionic interlayer membrane to form a reinforcing layer. By controlling the ratio of aminated glass fiber, composite hollow silica nanotubes, and epoxy resin-modified polyurethane emulsion in the reinforcing layer, a complex cross-linked network is constructed, thereby effectively improving the mechanical strength of the interlayer membrane.

[0036] Both the sound insulation layer and the reinforcing layer use epoxy resin-modified polyurethane emulsion as the base material. The epoxy resin-modified polyurethane emulsion is made from polytetrahydrofuran ether diol and isophorone diisocyanate as raw materials. Under the action of the catalyst dibutyltin dilaurate, a prepolymer is obtained. Epoxy resin modified with aminosilane coupling agent is used as a modifier, amino-terminated dimer acid polyamide synthesized from dimer acid is used as a chain extender, and furan carboxylic acid imidazole salt polyionic liquid is used as a capping agent. This results in a waterborne polyurethane emulsion with high adhesion, high light transmittance, flame retardancy, antibacterial properties, and self-healing function. This gives the reinforcing layer and the heat insulation layer excellent self-healing properties, which can effectively relieve stress concentration, prevent coating cracking or peeling, and thus extend service life. Detailed Implementation

[0037] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0038] It should be noted that if the embodiments of the present invention involve directional indicators such as up, down, left, right, front, and back, these directional indicators are only used to explain the relative positional relationship and movement of components in a specific posture. If the specific posture changes, the directional indicators will also change accordingly. Furthermore, the technical solutions of the various embodiments can be combined with each other, but this must be based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such a combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0039] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0040] Example 1: A method for preparing a heat-insulating ionic interlayer membrane, comprising the following steps:

[0041] S1: A heat-insulating coating is obtained by mixing composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives.

[0042] S2: Apply heat-insulating coating to the upper surface of the ionic intermediate film layer to form a heat-insulating layer;

[0043] The additive is an antifoaming agent;

[0044] The mass ratio of composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives in the heat insulation layer is 2:17.5:0.5.

[0045] The preparation of the epoxy resin modified polyurethane emulsion includes the following steps:

[0046] (1) Under a nitrogen atmosphere, 6g of dimer acid and 10mL of N,N-dimethylformamide were mixed, and a mixture of 0.6g of 4-dimethylaminopyridine and 5mL of N,N-dimethylformamide was added. Then, a mixture of 4.2g of N,N'-dicyclohexylcarbodiimide and 5mL of N,N-dimethylformamide and a mixture of 2.1g of pentanediamine and 10mL of N,N-dimethylformamide were added sequentially. The mixture was kept at 18℃ for 15h, washed, cooled, washed again, and dried to obtain dimer acid polyamide.

[0047] (2) Under nitrogen protection, 1.5g of epoxy resin, 0.2g of γ-aminopropyltriethoxysilane and 1 drop of dibutyltin dilaurate were mixed and stirred in an oil bath at 50°C for 4 hours to obtain modified epoxy resin.

[0048] (3) Under a nitrogen atmosphere, 20g of polytetrahydrofuran ether diol was vacuum dehydrated for 2h, cooled to 50℃, 14g of isophorone diisocyanate and 3 drops of dibutyltin dilaurate were added, the temperature was raised to 78℃ and kept for 4h, 1.5g of modified epoxy resin and 5mL of N-methylpyrrolidone mixture were added, the temperature was kept for 50min, 1.6g of 2,2-dihydroxymethylbutyric acid and 5mL of N-methylpyrrolidone were added and the temperature was kept for 2h, stirred for 30min, 0.5g of dimer acid polyamide was added, the temperature was kept for 50min, 0.6g of furan carboxylic acid imidazole salt polyionic liquid and 5mL of acetone were added, the temperature was lowered to 45℃, 1.2g of triethylamine was added to neutralize, the temperature was cooled to 18℃, deionized water was added to emulsify, and an epoxy resin modified polyurethane emulsion with a solid content of 30% was obtained.

[0049] The preparation of the composite hollow silica nanotubes includes the following steps:

[0050] 1) Mix 4g of polyethylene glycol hexadecyl ether and 10mL of cyclohexane, heat in a water bath to 48℃, add 1mL of 0.8mol / L nickel chloride solution, add 0.25mL of hydrazine hydrate, keep warm for 2h, add 0.5mL of diethylamine, add 1.5mL of tetraethyl silicate, keep warm for another 2h, centrifuge, add to 3mol / L hydrochloric acid, stir for 4h, centrifuge, wash, freeze dry to obtain hollow silica nanotubes;

[0051] 2) Mix 1.5g hollow silica nanotubes, 15mL γ-aminopropyltriethoxysilane, 10mL deionized water, and 100mg sodium carbonate. Stir at 80℃ for 48h, centrifuge, wash, and dry to obtain aminated hollow silica nanotubes; mix 150mg aminated hollow silica nanotubes, 0.75g furan-2,5-dione, and 13mL chlorobenzene. Disperse ultrasonically for 10min, keep warm at 130℃ for 2h under nitrogen atmosphere, cool to 1℃, add 5mL of acetic anhydride solution of 10mg / mL sodium acetate, keep warm at 130℃ for 60min under nitrogen atmosphere, cool, centrifuge, wash, and dry to obtain maleimide-modified hollow silica nanotubes;

[0052] 3) Mix 3g of maleimide-modified hollow silica nanotubes, 20mL of dimethyl sulfoxide, and 4g of furanyl carboxylic acid imidazole salt polyionic liquid, ultrasonically disperse for 10min, heat to 75℃ and keep warm for 3h to obtain composite hollow silica nanotubes.

[0053] The preparation of the furan carboxylic acid imidazole salt polyionic liquid includes the following steps:

[0054] A. Mix 0.01 mol 3-bromopropionic acid, 10 mL anhydrous ethanol, and 0.01 mol 1-vinylimidazole, reflux at 75 °C for 22 h, cool to 18 °C, rotary evaporate, add anhydrous acetonitrile to precipitate, centrifuge, wash, and freeze dry to obtain 1-vinyl-3-carboxyethylimidazole bromide.

[0055] B. Mix 0.02 mol of 1-vinyl-3-carboxyethyl imidazolium bromide, 40 ml of anhydrous methanol, and 0.04 g of azobisisobutyronitrile, and keep warm at 58 °C for 9 h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazolium bromide).

[0056] C. Mix 2.5g of poly(1-vinyl-3-carboxyethylimidazolium bromide), 10mL of N,N-dimethylformamide, and 1.1g of sodium furan-2-carboxylate, keep warm at 68℃ for 24h, dialyze with deionized water for 22h, and freeze dry to obtain furan-carboxylate imidazolium salt polyionic liquid.

[0057] S3: Aminated glass fiber, composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives are mixed to obtain a reinforcing coating layer.

[0058] S4: Apply the reinforcing layer coating to the lower surface of the ionic interlayer to form a reinforcing layer; cover the reinforcing layer and the heat insulation layer with a PET release layer to obtain a heat-insulating ionic interlayer;

[0059] The reinforcing layer is composed of the following raw materials by weight: 1 part aminated glass fiber, 2 parts composite hollow silica nanotubes, 22 parts epoxy resin modified polyurethane emulsion, and 1 part additive.

[0060] Example 2: A method for preparing a heat-insulating ionic interlayer membrane, comprising the following steps:

[0061] S1: A heat-insulating coating is obtained by mixing composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives.

[0062] S2: Apply heat-insulating coating to the upper surface of the ionic intermediate film layer to form a heat-insulating layer;

[0063] The mass ratio of composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives in the heat insulation layer is 2:17.5:0.5.

[0064] The additive is an antifoaming agent;

[0065] The preparation of the epoxy resin modified polyurethane emulsion includes the following steps:

[0066] (1) Under a nitrogen atmosphere, 6g of dimer acid and 10mL of N,N-dimethylformamide were mixed, and a mixture of 0.6g of 4-dimethylaminopyridine and 5mL of N,N-dimethylformamide was added. Then, a mixture of 4.2g of N,N'-dicyclohexylcarbodiimide and 5mL of N,N-dimethylformamide and a mixture of 2.1g of pentanediamine and 10mL of N,N-dimethylformamide were added sequentially. The mixture was kept at 20℃ for 14.5h, washed, cooled, washed again, and dried to obtain dimer acid polyamide.

[0067] (2) Under nitrogen protection, 1.5g of epoxy resin, 0.2g of γ-aminopropyltriethoxysilane and 1 drop of dibutyltin dilaurate were mixed and stirred in an oil bath at 53°C for 3.5h to obtain modified epoxy resin.

[0068] (3) Under a nitrogen atmosphere, 20g of polytetrahydrofuran ether diol was vacuum dehydrated for 2h, cooled to 50℃, 14g of isophorone diisocyanate and 3 drops of dibutyltin dilaurate were added, the temperature was raised to 80℃ and kept for 3.5h, 1.5g of modified epoxy resin and 5mL of N-methylpyrrolidone mixture were added, the temperature was kept for 60min, 1.6g of 2,2-dihydroxymethylbutyric acid and 5mL of N-methylpyrrolidone were added and the temperature was kept for 2.5h, stirred for 35min, 0.5g of dimer acid polyamide was added, the temperature was kept for 60min, 0.6g of furan carboxylic acid imidazole salt polyionic liquid and 5mL of acetone were added, the temperature was lowered to 48℃, 1.2g of triethylamine was added to neutralize, the temperature was cooled to 20℃, deionized water was added to emulsify, and an epoxy resin modified polyurethane emulsion with a solid content of 30% was obtained.

[0069] The preparation of the composite hollow silica nanotubes includes the following steps:

[0070] 1) Mix 4g of polyethylene glycol hexadecyl ether and 10mL of cyclohexane, heat in a water bath to 50℃, add 1mL of 0.8mol / L nickel chloride solution, add 0.25mL of hydrazine hydrate, keep warm for 2.5h, add 0.5mL of diethylamine, add 1.5mL of tetraethyl silicate, keep warm for another 2.5h, centrifuge, add to 3mol / L hydrochloric acid, stir for 4.5h, centrifuge, wash, freeze dry to obtain hollow silica nanotubes;

[0071] 2) Mix 1.5g hollow silica nanotubes, 15mL γ-aminopropyltriethoxysilane, 10mL deionized water, and 100mg sodium carbonate. Stir at 80℃ for 48h, centrifuge, wash, and dry to obtain aminated hollow silica nanotubes; mix 150mg aminated hollow silica nanotubes, 0.75g furan-2,5-dione, and 13mL chlorobenzene. Disperse ultrasonically for 10min, keep warm at 129℃ for 2.5h under nitrogen atmosphere, cool to 20℃, add 5mL of acetic anhydride solution of 10mg / mL sodium acetate, keep warm at 130℃ for 65min under nitrogen atmosphere, cool, centrifuge, wash, and dry to obtain maleimide-modified hollow silica nanotubes;

[0072] 3) Mix 3g of maleimide-modified hollow silica nanotubes, 20mL of dimethyl sulfoxide, and 4g of furanyl carboxylic acid imidazole salt polyionic liquid, sonicate for 15min, heat to 78℃ and keep warm for 2.5h to obtain composite hollow silica nanotubes.

[0073] The preparation of the furan carboxylic acid imidazole salt polyionic liquid includes the following steps:

[0074] A. Mix 0.01 mol 3-bromopropionic acid, 10 mL anhydrous ethanol, and 0.01 mol 1-vinylimidazole, reflux at 75 °C for 23 h, cool to 20 °C, rotary evaporate, add anhydrous acetonitrile to precipitate, centrifuge, wash, and freeze dry to obtain 1-vinyl-3-carboxyethylimidazole bromide.

[0075] B. Mix 0.02 mol of 1-vinyl-3-carboxyethyl imidazolium bromide, 40 ml of anhydrous methanol, and 0.04 g of azobisisobutyronitrile, and keep at 60 °C for 8.5 h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazolium bromide).

[0076] C. Mix 2.5g of poly(1-vinyl-3-carboxyethylimidazolium bromide), 10mL of N,N-dimethylformamide, and 1.1g of sodium furan-2-carboxylate, keep warm at 69℃ for 23h, dialyze with deionized water for 23h, and freeze dry to obtain furan-carboxylate imidazolium salt polyionic liquid.

[0077] S3: Aminated glass fiber, composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives are mixed to obtain a reinforcing coating layer.

[0078] S4: The reinforcing layer coating is applied to the lower surface of the ionic intermediate film layer to form a reinforcing layer; a PET release layer is covered on the reinforcing layer and the heat insulation layer to obtain a heat-insulating ionic intermediate film; by mass parts, the raw material composition of the reinforcing layer is: 2 parts of aminated glass fiber, 4 parts of composite hollow silica nanotubes, 29 parts of epoxy resin modified polyurethane emulsion, and 1.5 parts of additives.

[0079] Example 3: A method for preparing a heat-insulating ionic interlayer membrane, comprising the following steps:

[0080] S1: A heat-insulating coating is obtained by mixing composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives.

[0081] S2: Apply heat-insulating coating to the upper surface of the ionic intermediate film layer to form a heat-insulating layer;

[0082] The mass ratio of composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives in the heat insulation layer is 2:17.5:0.5.

[0083] The additive is an antifoaming agent;

[0084] The preparation of the epoxy resin modified polyurethane emulsion includes the following steps:

[0085] (1) Under a nitrogen atmosphere, 6g of dimer acid and 10mL of N,N-dimethylformamide were mixed, and a mixture of 0.6g of 4-dimethylaminopyridine and 5mL of N,N-dimethylformamide was added. Then, a mixture of 4.2g of N,N'-dicyclohexylcarbodiimide and 5mL of N,N-dimethylformamide and a mixture of 2.1g of pentanediamine and 10mL of N,N-dimethylformamide were added sequentially. The mixture was kept at 25℃ for 14h, washed, cooled, washed again, and dried to obtain dimer acid polyamide.

[0086] (2) Under nitrogen protection, 1.5g of epoxy resin, 0.2g of γ-aminopropyltriethoxysilane and 1 drop of dibutyltin dilaurate were mixed and stirred in an oil bath at 55°C for 3h to obtain modified epoxy resin.

[0087] (3) Under a nitrogen atmosphere, 20g of polytetrahydrofuran ether diol was vacuum dehydrated for 2h, cooled to 50℃, 14g of isophorone diisocyanate and 3 drops of dibutyltin dilaurate were added, the temperature was raised to 82℃ and kept for 3h, 1.5g of modified epoxy resin and 5mL of N-methylpyrrolidone mixture were added, the temperature was kept for 70min, 1.6g of 2,2-dihydroxymethylbutyric acid and 5mL of N-methylpyrrolidone were added and the temperature was kept for 3h, stirred for 40min, 0.5g of dimer acid polyamide was added, the temperature was kept for 70min, 0.6g of furan carboxylic acid imidazole salt polyionic liquid and 5mL of acetone were added, the temperature was lowered to 50℃, 1.2g of triethylamine was added to neutralize, the temperature was cooled to 25℃, and deionized water was added to emulsify to obtain epoxy resin modified polyurethane emulsion with a solid content of 30%;

[0088] The preparation of the composite hollow silica nanotubes includes the following steps:

[0089] 1) Mix 4g of polyethylene glycol hexadecyl ether and 10mL of cyclohexane, heat in a water bath to 52℃, add 1mL of 0.8mol / L nickel chloride solution, add 0.25mL of hydrazine hydrate, keep warm for 3h, add 0.5mL of diethylamine, add 1.5mL of tetraethyl silicate, keep warm for another 3h, centrifuge, add to 3mol / L hydrochloric acid, stir for 5h, centrifuge, wash, freeze dry to obtain hollow silica nanotubes;

[0090] 2) Mix 1.5g hollow silica nanotubes, 15mL γ-aminopropyltriethoxysilane, 10mL deionized water, and 100mg sodium carbonate. Stir at 80℃ for 48h, centrifuge, wash, and dry to obtain aminated hollow silica nanotubes; mix 150mg aminated hollow silica nanotubes, 0.75g furan-2,5-dione, and 13mL chlorobenzene. Disperse ultrasonically for 10min, keep warm at 130℃ for 2h under nitrogen atmosphere, cool to 25℃, add 5mL of acetic anhydride solution of 10mg / mL sodium acetate, keep warm at 130℃ for 70min under nitrogen atmosphere, cool, centrifuge, wash, and dry to obtain maleimide-modified hollow silica nanotubes;

[0091] 3) Mix 3g of maleimide-modified hollow silica nanotubes, 20mL of dimethyl sulfoxide, and 4g of furanyl carboxylic acid imidazole salt polyionic liquid, ultrasonically disperse for 20min, heat to 75℃ and keep warm for 3h to obtain composite hollow silica nanotubes.

[0092] The preparation of the furan carboxylic acid imidazole salt polyionic liquid includes the following steps:

[0093] A. Mix 0.01 mol 3-bromopropionic acid, 10 mL anhydrous ethanol, and 0.01 mol 1-vinylimidazolium, reflux at 75 °C for 24 h, cool to 25 °C, rotary evaporate, add anhydrous acetonitrile to precipitate, centrifuge, wash, and freeze dry to obtain 1-vinyl-3-carboxyethylimidazolium bromide.

[0094] B. Mix 0.02 mol of 1-vinyl-3-carboxyethyl imidazolium bromide, 40 ml of anhydrous methanol, and 0.04 g of azobisisobutyronitrile, and keep at 62 °C for 8 h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazolium bromide).

[0095] C. Mix 2.5g of poly(1-vinyl-3-carboxyethylimidazolium bromide), 10mL of N,N-dimethylformamide, and 1.1g of sodium furan-2-carboxylate, keep warm at 70℃ for 22h, dialyze with deionized water for 24h, and freeze dry to obtain furan-carboxylate imidazolium salt polyionic liquid.

[0096] S3: Aminated glass fiber, composite hollow silica nanotubes, epoxy resin modified polyurethane emulsion, and additives are mixed to obtain a reinforcing coating layer.

[0097] S4: The reinforcing layer coating is applied to the lower surface of the ionic intermediate film layer to form a reinforcing layer; a PET release layer is covered on the reinforcing layer and the heat insulation layer to obtain a heat-insulating ionic intermediate film; by mass parts, the raw material composition of the reinforcing layer is: 3 parts of aminated glass fiber, 6 parts of composite hollow silica nanotubes, 34 parts of epoxy resin modified polyurethane emulsion, and 2 parts of additives.

[0098] Comparative Example 1: Using Example 3 as the control group, hollow silica nanotubes were used to replace composite hollow silica nanotubes, while other processes were normal.

[0099] Comparative Example 2: Using Example 3 as the control group, the epoxy resin-modified polyurethane emulsion was replaced with modified epoxy resin, while other processes were normal.

[0100] The preparation of aminated glass fibers in the examples and comparative examples includes the following steps:

[0101] Mix 2g of glass fiber, 20mL of γ-aminopropyltriethoxysilane and 10mL of deionized water, add 2 drops of ammonia, keep warm at 80℃ for 44h, centrifuge, wash and dry to obtain aminated glass fiber;

[0102] In the examples and comparative examples, the thickness of the reinforcing layer is 0.2 mm; the thickness of the heat insulation layer is 0.2 mm.

[0103] Sources of raw materials used (for illustrative purposes only):

[0104] Ionic interlayer (SGP, 0.3mm): Dongguan Qun'an Plastics Industry Co., Ltd.; PET release layer (PET release film, 0.2mm), glass fiber (1µm, 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 diol P 117874, Iophorone diisocyanate I109582, 2,2-dimethylolbutyric acid B115196, polyethylene glycol hexadecyl ether P684403, hydrazine hydrate H431263, tetraethyl silicate T110595, 1-vinylimidazolium V109377, azobisisobutyronitrile A434183, sodium furan-2-carboxylate (prepared from furoic acid F111223): Aladdin reagent; N,N-dimethylformamide, N,N'-dicyclohexylcarbodiimide, N-methylpyrrolidone, acetone, triethylamine, cyclohexane, nickel chloride, hydrochloric acid, sodium carbonate, diethylamine, 3-bromopropionic acid, chlorobenzene, sodium acetate, dimethyl sulfoxide, anhydrous ethanol, anhydrous acetonitrile, anhydrous methanol, analytical grade, commercially available.

[0105] Performance testing: The reinforcing coatings prepared in the examples and comparative examples were 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 for testing.

[0106] Thermal insulation: Thermal conductivity was measured using a thermal conductivity meter; Antibacterial properties: Escherichia coli was used as the test strain, and the plate method was employed; Flame retardancy: UL-94 vertical flammability test was performed; Self-healing property: A scratch measuring 0.5 mm in length, 1 µm in width, and 0.1 mm in depth was made on the surface, and the surface was kept at 80℃ for 24 hours. The scratch length was observed using an electron microscope, and the self-healing rate was calculated as follows: (L...) 初始划痕长度 -L 现有划痕长度 ) / L 初始划痕长度 ×100%; Aging resistance: Irradiate with 365nm ultraviolet light for 72h, and then measure the antibacterial rate. If the difference between the antibacterial rate and the initial antibacterial rate is within 0-1% (including 1%), the aging resistance is qualified; otherwise, the aging resistance is unqualified. The results are shown in Table 1.

[0107] Table 1

[0108]

[0109] This invention provides a heat-insulating ionic interlayer membrane and its preparation method. Through composition and process design, a multilayer composite ionic interlayer membrane with excellent mechanical strength, heat insulation, antibacterial properties, flame retardancy, and self-healing properties is obtained.

[0110] Comparing Example 3 with Comparative Example 1, it can be seen that, in order to improve the uniformity of hollow silica nanotube dispersion in the base material, 3-aminopropyltriethoxysilane was used to aminate the hollow silica nanotubes, and maleimide was synthesized by dehydration condensation of furan-2,5-dione and amino groups to obtain maleimide-modified hollow silica nanotubes, thereby improving the flame retardancy and aging resistance of the heat insulation layer. Then, furan carboxylic acid imidazole salt polyionic liquid was grafted using the Diels-Alder reaction to obtain... Composite hollow silica nanotubes; the furan carboxylic acid imidazole salt polyionic liquid is a carboxyimidazole polyionic liquid containing furan structure, synthesized from 1-vinylimidazole. The introduction of the ionic liquid significantly improves the thermal insulation, antibacterial, flame retardant and stability of the hollow silica nanotubes. The introduction of dynamic reversible bonds in the composite hollow silica nanotubes endows the thermal insulation layer with rapid self-healing properties. The introduction of multiple active sites in the composite hollow silica nanotubes improves its bonding strength with the base material and enhances the stability of the thermal insulation layer.

[0111] Comparing Example 3 with Comparative Example 2, it can be seen that both the sound insulation layer and the reinforcing layer use epoxy resin modified polyurethane emulsion as the base material. The epoxy resin modified polyurethane emulsion is made from polytetrahydrofuran ether diol and isophorone diisocyanate as raw materials, and a prepolymer is obtained under the action of the catalyst dibutyltin dilaurate. The epoxy resin modified with aminosilane coupling agent is used as the modifier, the amino-terminated dimer acid polyamide synthesized from dimer acid is used as the chain extender, and the furan carboxylic acid imidazole salt polyionic liquid is used as the end-capping agent. A waterborne polyurethane emulsion with high adhesion, high light transmittance, flame retardancy, antibacterial properties and self-healing function is obtained, which gives the reinforcing layer and the heat insulation layer excellent self-healing properties, can effectively relieve stress concentration, avoid coating cracking or peeling, and thus extend service life.

[0112] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the present invention's specification under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. A heat-shielding ion-type interlayer film, characterized by, From top to bottom successively contain 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; (1) under nitrogen atmosphere, mixed dimer acid and N,N-dimethylformamide, added 4-dimethylaminopyridine and N,N-dimethylformamide mixture, sequentially added N,N'-dicyclohexyl carbodiimide and N,N-dimethylformamide mixture, pentanediamine and N,N-dimethylformamide mixture, incubated at 18-25℃ for 14-15h, washed, cooled, washed, dried, to obtain dimer acid polyamide; (2) under nitrogen protection, mixed epoxy resin, γ-aminopropyl triethoxysilane and dibutyl tin dilaurate, stirred in 50-55℃ oil bath for 3-4h, to obtain modified epoxy resin; (3) under nitrogen atmosphere, vacuum dehydrated polytetrahydrofuran ether diol for 2h, cooled to 50℃, added isophorone diisocyanate and dibutyl tin dilaurate, warmed to 78-82℃ for 3-4h, added modified epoxy resin and N-methyl pyrrolidone mixture, incubated for 50-70min, added 2,2-dimethylol butyric acid and N-methyl pyrrolidone, continued to incubate for 2-3h, stirred for 30-40min, added dimer acid polyamide, continued to incubate for 50-70min, added furan carboxylic acid imidazole salt polyionic liquid and acetone, cooled to 45-50℃, added triethylamine for neutralization, cooled to 18-25℃, added deionized water for emulsification, to obtain epoxy resin modified polyurethane emulsion; 1) mixed polyethylene glycol hexadecyl ether and cyclohexane, water bath warmed to 48-52℃, added nickel chloride solution, added hydrazine hydrate, incubated for 2-3h, added diethylamine, added tetraethyl silicate, continued to incubate for 2-3h, centrifuged, added to hydrochloric acid, stirred for 4-5h, centrifuged, washed, freeze-dried, to obtain hollow silica nanotube; 2) mixed hollow silica nanotube, γ-aminopropyl triethoxysilane, deionized water and sodium carbonate, stirred at 78-80℃ for 46-48h, centrifuged, washed, dried, to obtain aminated hollow silica nanotube; mixed aminated hollow silica nanotube, furan-2,5-dione and chlorobenzene, ultrasonic dispersed for 10min, incubated at 128-130℃ for 2-3h under nitrogen atmosphere, cooled to 18-25℃, added sodium acetate in acetic anhydride solution, incubated at 130℃ for 60-70min under nitrogen atmosphere, cooled, centrifuged, washed, dried, to obtain maleimide modified hollow silica nanotube; 3) mixed maleimide modified hollow silica nanotube, dimethyl sulfoxide and furan carboxylic acid imidazole salt polyionic liquid, ultrasonic dispersed for 10-20min, warmed to 75-80℃ for 2-3h, to obtain composite hollow silica nanotube; A. 3-bromopropionic acid, anhydrous ethanol, 1-vinylimidazole were mixed, refluxed at 75℃ for 22-24h, cooled to 18-25℃, rotary evaporation, precipitated with anhydrous acetonitrile, centrifuged, washed, and freeze-dried to obtain 1-vinyl-3-carboxyethyl imidazole bromide; B. 1-vinyl-3-carboxyethyl imidazole bromide, anhydrous methanol, azobisisobutyronitrile were mixed, and incubated at 58-62℃ for 8-9h under nitrogen protection to obtain poly(1-vinyl-3-carboxyethyl imidazole bromide) salt; C. Poly(1-vinyl-3-carboxyethyl imidazole bromide) salt, N,N-dimethylformamide, sodium furan-2-carboxylate were mixed, dialyzed with deionized water for 22-24h, and freeze-dried to obtain furan carboxylic acid imidazole salt polyionic liquid.

2. The heat shielding type ionic interlayer film according to claim 1, wherein The auxiliary agent is one or a combination of a leveling agent and a 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, in mass fraction: 1-3 parts of aminated glass fiber, 2-6 parts of composite hollow silica nanotube, 22-34 parts of epoxy resin modified polyurethane emulsion, and 1-2 parts of auxiliary agent.

5. The heat shielding type ionic interlayer film according to claim 1, wherein In the preparation of the epoxy resin modified polyurethane emulsion, 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.

6. The heat shielding type ionic interlayer film according to claim 1, wherein In the preparation of the composite hollow silica nanotube, the mass ratio of maleimide modified hollow silica nanotube and furan carboxylic acid imidazole salt polyionic liquid is 3:

4.

7. The method for producing a heat shielding type ionic interlayer film according to any one of claims 1 to 6, wherein The method comprises the following steps: S1: mixing the composite hollow silica nanotube, the epoxy resin modified polyurethane emulsion, and the auxiliary agent to obtain a thermal insulation coating; S2: coating the thermal insulation coating on the upper surface of the ionic intermediate film layer to form a thermal 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 thermal insulation layer to obtain a heat-insulating type ionic intermediate film.

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