Silicone oil, TPU intermediate film for laminated glass and preparation method of TPU intermediate film

Abstract

The invention relates to the technical field of laminated glass, in particular to silicone oil, a TPU intermediate film for laminated glass and a preparation method of the TPU intermediate film. Vinyl-terminated silicone oil and a fluorine-containing acrylic monomer are adopted to initiate polymerization, a fluorine element is introduced into a silicone oil chain to enhance the optical performance of the silicone oil, and then a click reaction is performed to obtain hydroxyl-terminated fluorine-containing silicone oil; the modified polyurethane is prepared by reacting the modified polyurethane with epoxy resin and a polyurethane prepolymer; the problem that single silicone oil is different from polyurethane and epoxy resin in compatibility is greatly solved, modified polyurethane with excellent performance is comprehensively obtained, and a TPU intermediate film obtained by processing the modified polyurethane has clearer transparency and higher impact resistance.

Description

Technical Field

[0001] The invention relates to the technical field of laminated glass, in particular to silicone oil, a TPU intermediate film for laminated glass and a preparation method thereof. Background Art

[0002] Laminated glass is a composite glass product with higher safety, which includes at least two pieces of glass, with one or more layers of organic polymer film sandwiched between adjacent pieces of glass, and is treated with special high temperature and high pressure to make the glass and the intermediate film permanently bonded together. Laminated glass has good sound insulation, heat insulation, noise prevention, buffering, energy absorption and other functions, and is widely used in high-speed trains, military and civilian helicopters, passenger planes, transport planes, bulletproof armor, cars and buildings.

[0003] For laminated glass, the interlayer plays a very important role in the overall impact resistance and optical properties. Common interlayers for laminated glass include: polyvinyl butyral (PVB) film, ethylene-vinyl acetate copolymer (EVA) film, ionic interlayer (SGP), XIR interlayer and thermoplastic polyurethane (TPU) film, among which TPU interlayer has high strength and impact resistance, excellent elasticity and cold and aging resistance, high light transmittance and low haze, which has obvious advantages over ordinary glass. Therefore, as the demand for laminated glass in modern buildings increases year by year, TPU interlayer laminated glass has huge room for development. With the vigorous development of SGP interlayer, PVB interlayer, etc., the market has put forward higher requirements for the various properties of TPU interlayer. Summary of the invention

[0004] In view of the above problems existing in the prior art, the object of the present invention is to provide a silicone oil. Another object of the present invention is to provide a TPU intermediate film for laminated glass prepared using the silicone oil. Still another object of the present invention is a method for preparing the silicone oil and the TPU intermediate film for laminated glass.

[0005] The high transparency and impact resistance of TPU interlayer for laminated glass are its most important properties. High transparency can make the laminated glass clearer; impact resistance can absorb impact force and resist damage to the glass by load.

[0006] Therefore, the performance of TPU intermediate film directly determines the quality of laminated glass. In order to obtain laminated glass with better quality, the applicant will enhance and improve the performance of TPU intermediate film. The focus of the present invention is to enhance and modify the transparency and impact resistance of TPU intermediate film. Based on this, the present invention is designed to use epoxy resin to improve polyurethane. However, considering that epoxy resin can enhance the transparency of TPU intermediate film, it has a great negative impact on impact resistance. Therefore, it is further considered to add silicone oil with toughening effect to modify polyurethane in coordination with epoxy resin. However, in actual experiments, it is found that the TPU intermediate film obtained by simply using silicone oil and epoxy resin to modify polyurethane has a certain degree of weakening in transparency and toughness. The reason is analyzed and it is believed that there is a certain degree of compatibility difference between silicone oil and polyurethane and epoxy resin, which in turn causes the transparency and toughness of TPU intermediate film to decay. On the other hand, since fluorine atoms have a strong ability to bind electrons, and have a small polarizability, a low refractive index, and a high electronegativity; therefore, the scheme of the present invention further uses vinyl-terminated silicone oil and fluorine-containing acrylic monomers to initiate polymerization, introduces fluorine elements into the silicone oil chain to enhance its optical properties, and then obtains hydroxyl-terminated fluorine-containing silicone oil through a click reaction, and then further reacts it with epoxy resin and polyurethane prepolymer (wherein, since both the epoxy resin and the hydroxyl-terminated fluorine-containing silicone oil contain hydroxyl groups, they can react with the isocyanate groups on the polyurethane prepolymer) to obtain modified polyurethane, and thus a TPU intermediate film with excellent performance is prepared by processing; this scheme solves the compatibility problem of silicone oil with polyurethane and epoxy resin, and at the same time, since the silicone oil is modified and fluorine elements are introduced into its chain, a TPU intermediate film with high transparency and high impact resistance is finally obtained.

[0007] In addition, since the TPU structure contains amino groups and unsaturated bonds that are easily oxidized, it is easily affected by ultraviolet rays, resulting in photo-oxidation aging, which in turn causes the TPU intermediate film to turn yellow and its performance (including mechanical, bonding, temperature resistance, etc.) to decline. Once the TPU intermediate film in the laminated glass is photo-oxidized and aged, it not only affects the appearance, but also poses certain safety hazards. At the same time, it is also impossible to remedy the problem, and the entire glass can only be replaced, which will also cause "labor and cost". Therefore, in the present invention, 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and hydrogen-containing silicone oil are reacted by hydrosilylation to prepare an anti-ultraviolet yellowing agent. The anti-ultraviolet yellowing agent contains a benzotriazole structure, which has the function of absorbing ultraviolet light, and can give the TPU resin excellent anti-ultraviolet oxidation performance, while the hydrogen-containing silicone oil can improve the resin aging performance to a certain extent. In addition, the hydrogen-containing silicone oil can give the anti-ultraviolet yellowing agent compatibility in the modified polyurethane, thereby improving the anti-ultraviolet yellowing agent's ability to act. The anti-ultraviolet yellowing agent can greatly prevent the TPU interlayer from photo-oxidation and aging, so that the TPU interlayer can maintain stable performance for a long time, thereby ensuring the quality of laminated glass.

[0008] The specific technical solutions of the present invention are as follows: The preparation method of silicone oil comprises the following steps: adding fluorine-containing acrylic monomer, vinyl-terminated silicone oil and ammonium persulfate into a reaction kettle, stirring and mixing uniformly, stirring and reacting at 70-85°C for 1-6 hours, cooling to room temperature, separating the ammonium persulfate, adding mercapto alcohol and a photoinitiator, stirring and mixing uniformly, and irradiating under ultraviolet light of 350-370nm for 1-20 minutes to obtain hydroxyl-terminated fluorine-containing silicone oil.

[0009] Further, the fluorine-containing acrylic monomer includes a combination of one or more of perfluoropropylene, trifluoropropylene, 2,2,3,3-tetrafluoropropylene, 1,1,3,3-tetrafluoropropylene and 2-phenylpentafluoropropylene; the mercapto alcohol includes any one of 4-mercaptobenzyl alcohol, 2-mercaptobenzyl alcohol, 2-mercaptoethanol and 3-mercapto-2-butanol.

[0010] Furthermore, the mass ratio of the fluorinated acrylic monomer, the vinyl-terminated silicone oil, the ammonium persulfate, the mercapto alcohol and the photoinitiator is (5-10):(0.5-2):(0.03-0.06):(0.5-1):(0.001-0.005).

[0011] The silicone oil prepared by the above method.

[0012] The method for preparing a TPU interlayer film for laminated glass comprises the following steps: S1: polyurethane prepolymer reacts with hydroxyl-terminated fluorinated silicone oil and epoxy resin to obtain modified polyurethane; S2: 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole reacts with hydrogen-containing silicone oil to obtain an anti-ultraviolet yellowing agent; S3: after the modified polyurethane, the anti-ultraviolet yellowing agent and the curing agent are uniformly mixed, the mixture is injected into a mold, and the mixture is cured and dried to obtain a TPU intermediate film; The preparation method of the anti-ultraviolet yellowing agent is as follows: 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, hydrogenated silicone oil and chloroplatinic acid are added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 50-70° C. for 1-4 hours, and the reaction was terminated to obtain the anti-ultraviolet yellowing agent.

[0013] Furthermore, the mass ratio of the 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and the hydrogen-containing silicone oil is (0.1-0.5):2; and the amount of chloroplatinic acid added is 1-3% of the total mass of the reactants.

[0014] Furthermore, hydroxyl-terminated fluorinated silicone oil, epoxy resin and acetone are added to the polyurethane prepolymer, stirred and mixed evenly, the temperature is kept constant, the reaction is stirred for 1 to 6 hours, and the reaction is terminated to obtain a modified polyurethane; wherein, by weight, 40 parts of polyurethane prepolymer, 5 to 15 parts of hydroxyl-terminated fluorinated silicone oil, 2 to 10 parts of epoxy resin, and 50 parts of acetone.

[0015] Furthermore, the preparation method of the polyurethane prepolymer is as follows: adding diol to a reaction kettle, vacuum dehydrating the reaction kettle at 100-110° C. for 0.5-2 h, cooling the reaction kettle to 60-85° C., adding diisocyanate and a catalyst dropwise therein under an inert atmosphere, stirring the reaction for 1-6 h, and terminating the reaction to obtain a polyurethane prepolymer; The diol includes a combination of one or more of PEG-200, PEG-400, PEG-600, polycaprolactone diol, polycarbonate diol and polytetramethylene ether diol; the diisocyanate includes a combination of one or more of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate; the catalyst includes any one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, N,N-dimethylcyclohexylamine and N-methylmorpholine; the mass ratio of the diol, diisocyanate and catalyst is 10:(5~8):(0.005~0.5).

[0016] Furthermore, in S3, by weight, the modified polyurethane, the anti-ultraviolet yellowing agent, and the curing agent are 70 to 90 parts, 0.5 to 4 parts, and 5 to 12 parts.

[0017] The TPU intermediate film for laminated glass prepared by the above method.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. In the present invention, vinyl-terminated silicone oil and fluorine-containing acrylic monomer are used to initiate polymerization, and fluorine elements are introduced into the silicone oil chain to enhance its optical properties. Then, through a click reaction, hydroxyl-terminated fluorine-containing silicone oil is obtained; the hydroxyl-terminated fluorine-containing silicone oil is reacted with epoxy resin and polyurethane prepolymer to prepare modified polyurethane; the problem of differences in compatibility between single silicone oil and polyurethane and epoxy resin is greatly solved, and a modified polyurethane with excellent performance is obtained comprehensively. The TPU intermediate film processed by the silicone oil has clearer transparency and higher impact resistance; 2. In order to further enhance the light-oxidation and aging resistance of the TPU interlayer in the present invention, an anti-ultraviolet yellowing agent is prepared by reacting 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole with hydrogen-containing silicone oil through a hydrosilylation reaction; the anti-ultraviolet yellowing agent has good compatibility with modified polyurethane, can greatly improve the light-oxidation and aging resistance of the TPU interlayer, and has good stability, so that the TPU interlayer can maintain stable performance for a long time; 3. The present invention prepares a TPU intermediate film with high transparency, high impact resistance and excellent aging resistance by uniformly mixing modified polyurethane, an anti-ultraviolet yellowing agent and a curing agent, and curing and drying the mixture in a mold. The intermediate film is applied to laminated glass to greatly improve the quality and service life of the laminated glass. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0020] It should be noted that the purchasers of all raw materials involved in the present invention are not subject to any special restrictions and exemplarily include: In the following embodiments: the sources of the raw materials used are as follows: PEG-400 purity 99%, hydrogenated silicone oil purity 99.5%, CAS number: 70900-21-9, item number: 70900-21-9, purchased from Hubei Yongkuo Technology Co., Ltd.; Polycaprolactone diol, purity 99%, average molecular weight 530, purchased from Merck; Isophorone dicyanate purity 99%, dibutyltin dilaurate purity 99%, perfluoropropylene purity 99%, ammonium persulfate purity 99%, acetone purity 99%, ethylenediamine purity 99%, polyurethane purity 99%, item number: JJL36540202020202020, CAS number: 26680-22-8, all purchased from Shanghai Jinjinle Industrial Co., Ltd.; 4-Mercaptobenzyl alcohol, purity 98%, silicone oil, purity 98%, model: 201, purchased from JACS-Zhengzhou Jacks Chemical Products Co., Ltd.; Epoxy resin model: E-20, hydroxyl content 5.4%, purchased from Nanjing Zhongchun Biotechnology Co., Ltd.; Vinyl terminated silicone oil with a purity of 99%, product number: KBR-110, purchased from Huangshan Kebery Chemical Co., Ltd.; 2-(2'-Hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and chloroplatinic acid, purity 99%, were purchased from Henan Tianfu Chemical Co., Ltd.; The purity of the photoinitiator was 99%, item number: A0075, purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0021] Example 1 A method for preparing a TPU interlayer film for laminated glass, specifically comprising: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: 16 parts of perfluoropropylene, 3 parts of vinyl-terminated silicone oil and 0.08 parts of ammonium persulfate were added to a reactor, stirred and mixed evenly, stirred and reacted at 70°C for 5 hours, cooled to room temperature, and after separating the ammonium persulfate, 1.6 parts of 4-mercaptobenzyl alcohol and 0.008 parts of photoinitiator were added, stirred and mixed evenly, and irradiated under 350nm ultraviolet light for 10 minutes to terminate the reaction to obtain hydroxyl-terminated fluorinated silicone oil; S13: adding 10 parts of hydroxyl-terminated fluorinated silicone oil, 6 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70° C.), stirring and reacting for 5 hours, and terminating the reaction to obtain modified polyurethane; S2: Preparation of anti-ultraviolet yellowing agent: S21: Add 1 part of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 5 parts of hydrogenated silicone oil and 0.12 parts of chloroplatinic acid into a reaction kettle, stir and mix evenly, stir and react at 60° C. for 2 h, terminate the reaction, and obtain an anti-ultraviolet yellowing agent; S3: Preparation of TPU interlayer: S31: 86 parts of modified polyurethane, 3 parts of anti-ultraviolet yellowing agent and 10 parts of ethylenediamine are mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0022] Example 2 A method for preparing a TPU interlayer film for laminated glass, specifically comprising: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: 10 parts of perfluoropropylene, 3 parts of vinyl-terminated silicone oil and 0.08 parts of ammonium persulfate were added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 70°C for 5 hours, cooled to room temperature, and after separating the ammonium persulfate, 1.6 parts of 4-mercaptobenzyl alcohol and 0.008 parts of photoinitiator were added, stirred and mixed evenly, and irradiated under 350nm ultraviolet light for 10 minutes to terminate the reaction to obtain hydroxyl-terminated fluorinated silicone oil; S13: adding 5 parts of hydroxyl-terminated fluorinated silicone oil, 2 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70°C), stirring and reacting for 5 hours, and ending the reaction to obtain modified polyurethane; S2: Preparation of anti-ultraviolet yellowing agent: S21: 0.25 parts of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 5 parts of hydrogenated silicone oil and 0.105 parts of chloroplatinic acid are added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 60° C. for 2 hours, and the reaction was terminated to obtain an anti-ultraviolet yellowing agent; S3: Preparation of TPU interlayer: S31: 86 parts of modified polyurethane, 3 parts of anti-ultraviolet yellowing agent and 10 parts of ethylenediamine are mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0023] Example 3 A method for preparing a TPU interlayer film for laminated glass, specifically comprising: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: Add 20 parts of perfluoropropylene, 3 parts of vinyl-terminated silicone oil and 0.08 parts of ammonium persulfate into a reaction kettle, stir and mix evenly, stir and react at 70°C for 5 hours, cool to room temperature, separate the ammonium persulfate, add 1.6 parts of 4-mercaptobenzyl alcohol and 0.008 parts of photoinitiator, stir and mix evenly, irradiate under 350nm ultraviolet light for 10 minutes, terminate the reaction, and obtain hydroxyl-terminated fluorinated silicone oil; S13: adding 15 parts of hydroxyl-terminated fluorinated silicone oil, 10 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70° C.), stirring and reacting for 5 hours, and terminating the reaction to obtain modified polyurethane; S2: Preparation of anti-ultraviolet yellowing agent: S21: 1.25 parts of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 5 parts of hydrogenated silicone oil and 0.125 parts of chloroplatinic acid are added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 60° C. for 2 h, and the reaction was terminated to obtain an anti-ultraviolet yellowing agent; S3: Preparation of TPU interlayer: S31: 86 parts of modified polyurethane, 3 parts of anti-ultraviolet yellowing agent and 10 parts of ethylenediamine are mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0024] Based on Example 1, comparative examples 1 to 6 are set, as shown below: Comparative Example 1 Comparative Example 1 was adjusted based on Example 1: 201 silicone oil, E-20 epoxy resin and commercially available polyurethane were directly mixed evenly to obtain modified polyurethane, and other processes remained unchanged, specifically: A method for preparing TPU interlayer film for laminated glass: S1: Add 10 parts of 201 silicone oil, 6 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of commercially available polyurethane, stir and mix well to obtain modified polyurethane; S2: Preparation of anti-ultraviolet yellowing agent: S21: Add 1 part of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 5 parts of hydrogenated silicone oil and 0.12 parts of chloroplatinic acid into a reaction kettle, stir and mix evenly, stir and react at 60° C. for 2 h, terminate the reaction, and obtain an anti-ultraviolet yellowing agent; S3: Preparation of TPU interlayer: S31: 86 parts of modified polyurethane, 3 parts of anti-ultraviolet yellowing agent and 10 parts of ethylenediamine are mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0025] Comparative Example 2 Comparative Example 2 was adjusted based on Example 1 except that the fluorine element was not introduced into the vinyl-terminated silicone oil, and the other processes remained unchanged, specifically: A method for preparing TPU interlayer film for laminated glass: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: 19 parts of vinyl-terminated silicone oil, 1.6 parts of 4-mercaptobenzyl alcohol, and 0.008 parts of a photoinitiator were stirred and mixed uniformly, and irradiated under 350 nm ultraviolet light for 10 min to terminate the reaction, thereby obtaining hydroxyl-terminated silicone oil; S13: adding 10 parts of hydroxyl-terminated silicone oil, 6 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70° C.), stirring and reacting for 5 hours, and terminating the reaction to obtain modified polyurethane; S2: Preparation of anti-ultraviolet yellowing agent: S21: Add 1 part of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 5 parts of hydrogenated silicone oil and 0.12 parts of chloroplatinic acid into a reaction kettle, stir and mix evenly, stir and react at 60° C. for 2 h, terminate the reaction, and obtain an anti-ultraviolet yellowing agent; S3: Preparation of TPU interlayer: S31: 86 parts of modified polyurethane, 3 parts of anti-ultraviolet yellowing agent and 10 parts of ethylenediamine are mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0026] Comparative Example 3 Comparative Example 3 is adjusted based on Example 1: only epoxy resin is used to modify the polyurethane prepolymer, and other processes remain unchanged, specifically: A method for preparing TPU interlayer film for laminated glass: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: adding 16 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70° C.), stirring and reacting for 5 hours, and ending the reaction to obtain modified polyurethane; S2: Preparation of anti-ultraviolet yellowing agent: S21: Add 1 part of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, 5 parts of hydrogenated silicone oil and 0.12 parts of chloroplatinic acid into a reaction kettle, stir and mix evenly, stir and react at 60° C. for 2 h, terminate the reaction, and obtain an anti-ultraviolet yellowing agent; S3: Preparation of TPU interlayer: S31: 86 parts of modified polyurethane, 3 parts of anti-ultraviolet yellowing agent and 10 parts of ethylenediamine are mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0027] Comparative Example 4 Comparative Example 4 was adjusted based on Example 1, except that 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole was directly added as an anti-ultraviolet yellowing agent, and other processes remained unchanged, specifically: A method for preparing TPU interlayer film for laminated glass: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: 16 parts of perfluoropropylene, 3 parts of vinyl-terminated silicone oil and 0.08 parts of ammonium persulfate were added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 70°C for 5 hours, cooled to room temperature, and after separating the ammonium persulfate, 1.6 parts of 4-mercaptobenzyl alcohol and 0.008 parts of photoinitiator were added, stirred and mixed evenly, and irradiated under 350nm ultraviolet light for 10 minutes to terminate the reaction to obtain hydroxyl-terminated fluorinated silicone oil; S13: adding 10 parts of hydroxyl-terminated fluorinated silicone oil, 6 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70° C.), stirring and reacting for 5 hours, and terminating the reaction to obtain modified polyurethane; S2: Preparation of TPU interlayer: S21: 86 parts of modified polyurethane, 3 parts of 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and 10 parts of ethylenediamine were mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0028] Comparative Example 5 Comparative Example 5 is adjusted based on Example 1: no anti-ultraviolet yellowing agent is added, and other processes remain unchanged, specifically: A method for preparing TPU interlayer film for laminated glass: S1: Preparation of modified polyurethane: S11: 30 parts of diol (a mixture of PEG-400 and polycaprolactone diol in a mass ratio of 1:1) are added to a reaction kettle, and after vacuum dehydration treatment at 105°C for 1 hour, the temperature is lowered to 70°C, and 20 parts of isophorone dicyanate and 0.6 parts of dibutyltin dilaurate are added dropwise thereto under nitrogen protection, and the reaction is stirred for 5 hours. The reaction is terminated to obtain a polyurethane prepolymer, which is kept warm for later use; S12: 16 parts of perfluoropropylene, 3 parts of vinyl-terminated silicone oil and 0.08 parts of ammonium persulfate were added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 70°C for 5 hours, cooled to room temperature, and after separating the ammonium persulfate, 1.6 parts of 4-mercaptobenzyl alcohol and 0.008 parts of photoinitiator were added, stirred and mixed evenly, and irradiated under 350nm ultraviolet light for 10 minutes to terminate the reaction to obtain hydroxyl-terminated fluorinated silicone oil; S13: adding 10 parts of hydroxyl-terminated fluorinated silicone oil, 6 parts of E-20 epoxy resin and 50 parts of acetone to 40 parts of polyurethane prepolymer, stirring and mixing evenly, keeping the temperature constant (70° C.), stirring and reacting for 5 hours, and terminating the reaction to obtain modified polyurethane; S2: Preparation of TPU interlayer: S21: 86 parts of modified polyurethane and 10 parts of ethylenediamine were mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0029] Comparative Example 6 Commercially available polyurethane is directly processed into TPU interlayer, as follows: S1: 86 parts of commercially available polyurethane prepolymer and 10 parts of ethylenediamine were mixed evenly, injected into a mold, and cured and dried at 100° C. to obtain a TPU intermediate film.

[0030] Performance test: The TPU interlayers prepared in Examples 1 to 3 and Comparative Examples 1 to 6 were subjected to relevant performance tests, as follows: (1) Light transmittance: tested by UV-visible spectrophotometer, using an integrating sphere accessory to collect the spectrum of the TPU interlayer, with a spectral range of 400~800nm; (2) Yellowing resistance: The yellowing resistance of the TPU interlayer is tested by irradiation with a UVA340Lamp for 144 hours. The yellowing resistance is divided into 1 to 5 levels. The higher the level, the better the yellowing resistance. Level 4 is yellowing resistance and level 5 is no yellowing at all. (3) Toughness: The polyurethane adhesive corresponding to each example was processed into dumbbell specimens with dimensions of 75 mm × 25 mm × 0.6 mm and a neck width of 4 mm. Then, according to the standard GB / T 1040.3-2006, a universal testing machine was used with a force unit of 100 N and a tensile test was carried out at a speed of 200 mm / min. Each group of samples was measured 5 times to obtain the average value.

[0031] The specific test results are shown in Table 1 below: Table 1 Test results

[0032] Result analysis: From the data in Table 1 above, it can be seen that: (1) From the perspective of both cost and effect, the TPU intermediate film prepared in Example 1 has a higher cost-effectiveness, so Example 1 is the optimal example; (2) The present invention introduces fluorine elements into vinyl-terminated silicone oil in conjunction with epoxy resin to prepare modified polyurethane, and adds an anti-ultraviolet yellowing agent to the modified polyurethane, and finally prepares a TPU intermediate film. Compared with ordinary TPU films, the TPU intermediate film has better transparency and yellowing resistance, and the toughness of the TPU intermediate film is also better (excellent impact resistance); (3) Applying it to laminated glass can make the laminated glass maintain a long-term stable high transparency effect, and can also better protect the laminated glass, making the service life of the laminated glass longer.

[0033] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

Claims

1. A method for preparing silicone oil, characterized in that: Add fluorinated acrylic monomer, vinyl terminated silicone oil and ammonium persulfate into a reaction kettle, stir and mix evenly, react at 70-85°C for 1-6 hours, cool to room temperature, separate the ammonium persulfate, add mercapto alcohol and photoinitiator, stir and mix evenly, irradiate under ultraviolet light of 350-370nm for 1-20 minutes to obtain hydroxyl terminated fluorinated silicone oil.

2. The method for preparing silicone oil according to claim 1, characterized in that: The fluorine-containing acrylic monomer includes a combination of one or more of perfluoropropylene, trifluoropropylene, 2,2,3,3-tetrafluoropropylene, 1,1,3,3-tetrafluoropropylene and 2-phenylpentafluoropropylene; the mercapto alcohol includes any one of 4-mercaptobenzyl alcohol, 2-mercaptobenzyl alcohol, 2-mercaptoethanol and 3-mercapto-2-butanol.

3. The method for preparing silicone oil according to claim 1, characterized in that: The mass ratio of fluorinated acrylic monomer, vinyl terminated silicone oil, ammonium persulfate, mercapto alcohol and photoinitiator is (5~10):(0.5~2):(0.03~0.06):(0.5~1):(0.001~0.005).

4. The silicone oil prepared by the method according to any one of claims 1 to 3.

5. A method for preparing a TPU interlayer for laminated glass, characterized in that: The following steps are involved: S1: polyurethane prepolymer reacts with hydroxyl-terminated fluorinated silicone oil and epoxy resin to obtain modified polyurethane; S2: 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole reacts with hydrogen-containing silicone oil to obtain an anti-ultraviolet yellowing agent; S3: after the modified polyurethane, the anti-ultraviolet yellowing agent and the curing agent are uniformly mixed, the mixture is injected into a mold, and the mixture is cured and dried to obtain a TPU intermediate film; The preparation method of the anti-ultraviolet yellowing agent is as follows: 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole, hydrogenated silicone oil and chloroplatinic acid are added to a reaction kettle, stirred and mixed evenly, stirred and reacted at 50-70° C. for 1-4 hours, and the reaction was terminated to obtain the anti-ultraviolet yellowing agent.

6. The method for preparing the TPU interlayer for laminated glass according to claim 5, characterized in that: The mass ratio of the 2-(2'-hydroxy-3'-methallyl-5'-methylphenyl)benzotriazole and the hydrogen-containing silicone oil is (0.1-0.5):2; the amount of chloroplatinic acid added is 1-3% of the total mass of the reactants.

7. The method for preparing the TPU interlayer for laminated glass according to claim 5, characterized in that: Add hydroxyl-terminated fluorinated silicone oil, epoxy resin and acetone to the polyurethane prepolymer, stir and mix evenly, keep the temperature constant, stir and react for 1 to 6 hours, terminate the reaction, and obtain a modified polyurethane; wherein, by weight, the polyurethane prepolymer is 40 parts, the hydroxyl-terminated fluorinated silicone oil is 5 to 15 parts, the epoxy resin is 2 to 10 parts, and the acetone is 50 parts.

8. The method for preparing the TPU interlayer film for laminated glass according to claim 5 or 7, characterized in that: The preparation method of the polyurethane prepolymer is as follows: adding diol into a reaction kettle, performing vacuum dehydration treatment at 100-110° C. for 0.5-2 hours, cooling to 60-85° C., adding diisocyanate and a catalyst dropwise therein under an inert atmosphere, stirring the reaction for 1-6 hours, and terminating the reaction to obtain a polyurethane prepolymer; The diol includes a combination of one or more of PEG-200, PEG-400, PEG-600, polycaprolactone diol, polycarbonate diol and polytetramethylene ether diol; the diisocyanate includes a combination of one or more of toluene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate; the catalyst includes any one of dibutyltin dilaurate, dibutyltin diacetate, stannous octoate, N,N-dimethylcyclohexylamine and N-methylmorpholine; the mass ratio of the diol, diisocyanate and catalyst is 10:(5~8):(0.005~0.5).

9. The method for preparing a TPU interlayer for laminated glass according to claim 5, characterized in that: In S3, by weight, the modified polyurethane comprises 70 to 90 parts, the anti-ultraviolet yellowing agent comprises 0.5 to 4 parts, and the curing agent comprises 5 to 12 parts.

10. The TPU interlayer film for laminated glass prepared by the method according to any one of claims 5 to 9.

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