Fluorescent small molecule, fluorescent polyurethane primer as well as preparation method and application of fluorescent small molecule and fluorescent polyurethane primer

Abstract

The invention discloses a fluorescent small molecule, a fluorescent polyurethane primer as well as a preparation method and application of the fluorescent small molecule. The structural formula of the fluorescent small molecule is as follows: # imgabs0 #. Fluorescent small molecules containing reactive hydrogen react with isocyanate, and a fluorescent chromophoric group is bonded into a polyurethane molecular chain, so that the fluorescent polyurethane primer is obtained. The primer has excellent bonding performance on glass and a polyurethane base material, has stable photoluminescence performance, and has a good application prospect in the aspect of automatic production of automobile glass edge covering products.

Description

Technical Field

[0001] The present invention relates to the technical field of preparing a primer for fluorescent polyurethane, and is specifically applied to the preparation of polyurethane edge-bonding products for automotive glass, which is conducive to improving the automation degree of such products. Background Art

[0002] Due to more advantages in performance and process, polyurethane materials are widely used in the manufacture of automotive glass edge-bonding products. Currently, most manufacturers adopt the reaction injection molding process (PUR RIM), which can manufacture glass edge-bonding products with more complex shapes and more internal inserts. The general preparation process of automotive glass edge-bonding products is as follows: (1) cleaning the surface of the black frosted frame of the automotive glass; (2) coating the primer; (3) coating the polyurethane edge-bonding compound on the surface of the glass frame through the PUR RIM process. The primer applied to this field is required to have excellent adhesion performance to both the edge-bonding material and the glass substrate. Currently, the most invented primers in this field are black primers. Chinese inventions CN115678461B, CN112375484B, CN113402963B, and CN102516921B all use polyurethane prepolymer as the adhesive functional resin and carbon black as the pigment to prepare black primers. However, in actual applications, black primers sometimes require operators to visually identify whether the primer is coated and whether the coating is uniform, which hinders the full automation production of automotive glass edge-bonding products. Summary of the Invention

[0003] The purpose of the present invention is to provide a fluorescent small molecule, a fluorescent polyurethane primer and its preparation method to solve the above problems. The primer shows excellent adhesion performance to both glass and polyurethane substrates, and has stable photoluminescence performance. It can be used to identify whether the primer is coated and whether the coating is uniform through a fluorescence detection device, which is conducive to improving the automation degree of automotive glass edge-bonding products.

[0004] The first aspect of the present invention provides a fluorescent small molecule, and the structural formula of the fluorescent small molecule is as follows: 。

[0005] Preferably, the preparation method of the fluorescent molecule includes the following steps: (1) 1-Fluoro-2-nitrobenzene and alkylolamine react in organic solvent A to obtain a reaction solution; (2) The reaction solution in step (1) is processed to obtain an intermediate N-hydroxyalkyl-o-nitroaniline; (3) N-Hydroxyalkyl-o-nitroaniline is dissolved in organic solvent B, and a catalytic reduction reaction is carried out under the atmosphere of hydrogen gas and the action of a catalyst; (4) The reaction solution in step (3) is processed to obtain an o-phenylenediamine intermediate; (5) In an acidic solution, the o-phenylenediamine intermediate undergoes a cyclization reaction with alloxan monohydrate; (6) The reaction solution of step (5) is processed to obtain a fluorescent small molecule with a hydroxyl group and an imino group.

[0006] The reaction formula of the preparation method of the fluorescent molecule is as follows:

[0007] Preferably, in step (1), the alkyl alkanolamine is preferably one or more of aminomethanol, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol; the reaction temperature is 50-100 °C, and the reaction time is 4-8 h; the organic solvent A is preferably one of methanol, ethanol, acetone, etc.; the reaction preferably uses 1-fluoro-2-nitrobenzene and alkyl alkanolamine in a molar ratio of 1:1 to 1:2.

[0008] Preferably, in step (2), the post-treatment is preferably rotary evaporation and column chromatography separation, and further preferably the eluent for the column chromatography separation is a mixed solution of dichloromethane and ethyl acetate.

[0009] Preferably, in step (3), the catalyst is a Pd / C catalyst. The reaction temperature is preferably room temperature, and the reaction time is preferably 3-5 h; the organic solvent B is preferably one of methanol, ethanol, acetone, ethyl acetate, etc.

[0010] Preferably, in step (4), the post-treatment is preferably filtration and rotary evaporation.

[0011] Preferably, in step (5), the reaction temperature is 70-100 °C, and the reaction time is 4-8 h; the acidic solution is preferably one of 5%-10% hydrochloric acid solution and 5%-10% acetic acid solution; further preferably, the o-phenylenediamine intermediate and alloxan monohydrate react in a molar ratio of 1:1 to 1:4.

[0012] Preferably, in step (6), the post-treatment is preferably rotary evaporation and recrystallization, and further preferably the recrystallization solvent is a mixed solution of ethyl acetate and ethanol.

[0013] The second aspect of the present invention provides a fluorescent polyurethane primer, which is composed of component A and component B: Component A, by mass, includes: 1-10 parts of polyester polyol A, 1-20 parts of polyester polyol B, 1-5 parts of small molecule polyol, 1-5 parts of fluorescent small molecule, 1-5 parts of silane coupling agent A, 0.1-1 part of catalyst, and 50-90 parts of organic solvent; Component B, by mass parts, includes: 85 to 100 parts of polyisocyanate A and 1 to 15 parts of isocyanate modified by silane coupling agent.

[0014] Further, the polyester polyol A is an aliphatic polyester diol with a number average molecular weight of 3000 to 5000. Further preferably, it is one or more of Qingdao Xinyutian POL-1232, POL-322, POL-A3500, Perstorp 2402A, 2302AJ, 2304, 2403D, Asahi Kasei XCP-R4500H, XCP-5000B, XCP-4000PM.

[0015] Further, the polyester polyol B is an aromatic polyester diol with a number average molecular weight of 500 to 1500. Further preferably, it is obtained by polycondensation reaction of aromatic acid or acid anhydride with aliphatic alcohol. The aromatic acid is selected from one or more of terephthalic acid, phthalic acid, isophthalic acid, and the aromatic acid anhydride is selected from phthalic anhydride, and the aliphatic alcohol is selected from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol.

[0016] Further, the isocyanate modified by silane coupling agent is obtained by reacting polyisocyanate B with silane coupling agent B. The dosage of polyisocyanate B is preferably 2 to 25 parts, the dosage of silane coupling agent B is preferably 1 to 15 parts, and the reaction temperature is preferably 50 to 80 °C. Further preferably, polyisocyanate B is one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate trimer; further preferably, silane coupling agent B is one of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, anilinopropyltrimethoxysilane, N-n-butyl-3-aminopropyltrimethoxysilane.

[0017] Further, the small molecule polyol is preferably one or more of neopentyl glycol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, trimethylolpropane.

[0018] Further, the silane coupling agent A is preferably one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltriethoxysilane, 3-aminoethylaminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane.

[0019] Further, the catalyst is preferably one or more of dibutyltin dilaurate, dimethyltin dioctanoate, bismuth neodecanoate, bismuth isooctanoate, stannous octoate, triethylamine, triethylenediamine, and bis(2,2-morpholinoethyl) ether.

[0020] Further, the organic solvent is preferably one or more of acetone, methyl ethyl ketone, propylene glycol methyl ether acetate, ethyl acetate, butyl acetate, isobutyl acetate, isobutyl ketone, and cyclohexanone.

[0021] Further, the polyisocyanate A is preferably one or more of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane-4,4-diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, and carbodiimide-modified diphenylmethane diisocyanate.

[0022] The third aspect of the present invention provides a method for preparing a fluorescent polyurethane primer, comprising the following steps: (1) Prepare component A: Weigh and measure polyester polyol A, polyester polyol B, small molecule polyol, fluorescent small molecule, silane coupling agent A, catalyst, and organic solvent, and mix them evenly; (2) Prepare component B: Weigh and measure polyisocyanate A and isocyanate modified with silane coupling agent, and mix them evenly; (3) Prepare the primer: Mix component A and component B evenly.

[0023] Preferably, the mass ratio of component A to component B is 5:1 to 1:1.

[0024] The fourth aspect of the present invention provides a use of the fluorescent polyurethane primer, and the fluorescent polyurethane primer is used for the adhesion of polyurethane edge wrapping materials and automotive glass substrates.

[0025] The use of the present invention is to improve the adhesion performance between the skylight glass and the polyurethane edge wrapping material. Compared with the existing primer technology, the present invention has the following beneficial effects: (1) By reacting the self-made fluorescent small molecule with isocyanate, the fluorescent group is bonded to the polyurethane chain, and the introduction amount of the fluorescent group can be adjusted according to needs, and it has stable fluorescent performance; (2) The polyester polyols with different molecular weight ranges that can be designed in structure mainly improve the film-forming adhesion performance of the primer, and the compound use of silane coupling agent and silane-modified isocyanate can also improve the wettability and adhesion of the primer to the substrate, so that the prepared primer shows excellent adhesion performance to both inorganic glass and polyurethane substrates; (3) In actual application, the primer can be distinguished whether it is coated and whether the coating is uniform through a fluorescent detection device, and it can be widely used in the automated production of automotive glass edge wrapping products. Description of the Drawings

[0026] Figure 1 1H NMR characterization spectrum of N-(2-hydroxyethyl)-o-nitroaniline 1 ; Figure 2 1H NMR characterization spectrum of N-(2-hydroxyethyl)-o-nitroaniline 13 C NMR characterization spectrum; Figure 3 1H NMR characterization spectrum of fluorescent small molecule 1 1 ; Figure 4 1H NMR characterization spectrum of fluorescent small molecule 1 13 C NMR characterization spectrum; Figure 5 Fluorescence characterization spectrum of fluorescent small molecule 1. Detailed implementation manners

[0027] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. The dosage of each component is in parts by weight. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the described embodiments of the present invention fall within the scope of protection of the present invention.

[0028] Nuclear magnetic resonance characterization was performed using a Bruker AVANCE 500 nuclear magnetic resonance spectrometer, and fluorescence characterization was performed using a Horiba FluoroMax-4 fluorescence spectrometer.

[0029] Example 1

[0030] (1) In 100 mL of ethanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 2-aminoethanol (3.05 g, 50 mmol) were reacted under reflux at 83 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography separation was performed using dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain N-(2-hydroxyethyl)-o-nitroaniline (the nuclear magnetic resonance characterization spectra are shown in Figure 1 and Figure 2 , 1 1H NMR (CD3OD, 500 MHz): δ [ppm] = 8.14 - 8.11 (m, 1H), 7.51 - 7.46 (m, 1H), 7.04 - 7.02 (m, 1H), 6.69 - 6.65 (m, 1H), 3.83 - 3.80 (m, 2H), 3.49 - 3.46 (m, 2H); 1313C NMR (CD3OD, 125 MHz): δ [ppm] = 146.9, 137.4, 127.5, 116.3, 115.3, 61.1, 45.9.). Subsequently, N-(2-hydroxyethyl)-o-nitroaniline (5.47 g, 30 mmol) was dissolved in 50 mL of methanol. In a hydrogen atmosphere, Pd / C (Xi'an Kaili New Materials, palladium content 5%, 0.25 g) was used as a catalyst, and the reaction was carried out at room temperature for 3 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product of o-phenylenediamine intermediate. Then, in 50 mL of 5% hydrochloric acid solution, the crude product of o-phenylenediamine intermediate (3.81 g, 25 mmol) and alloxan monohydrate (6.08 g, 38 mmol) were reacted at 85 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized with a mixed solvent of ethyl acetate and ethanol (mass ratio 1:1) to obtain the fluorescent small molecule 1 with a hydroxyl group and an imino group (the NMR characterization spectrum is shown in Figure 3 and Figure 4 , 1 1H NMR (DMSO-d6, 500 MHz): δ[ppm] = 11.38 (s, 1H), 8.13 - 8.10 (m, 1H), 8.06 - 8.04 (m, 1H), 7.94 - 7.90 (m, 1H), 7.65 - 7.61 (m, 1H), 4.94 (br. s, 1H), 4.70 (t, J = 6.0 Hz, 2H), 3.82 (t, J = 5.9 Hz, 2H); 13 13C NMR (DMSO-d6, 125 MHz): δ [ppm] = 159.7, 155.5, 150.6, 138.4, 134.8, 134.6, 133.4, 131.5, 125.9, 117.1, 57.4, 46.6; the fluorescence characterization spectrum is shown in Figure 5 , and the fluorescence emission wavelength is 513 nm), and the molecular structure is as follows:

[0031] (2) 5 parts of POL-322, 12 parts of polyester polyol B (a resin with a number average molecular weight of about 1500 obtained by polycondensing terephthalic acid, isophthalic acid, ethylene glycol, and neopentyl glycol in a molar ratio of 1.0:0.9:1.1:1.0), 3 parts of diethylene glycol, 2 parts of fluorescent small molecule 1, 2 parts of 3-aminopropyltriethoxysilane, 0.2 part of bismuth isooctanoate, and 76 parts of butyl acetate were stirred and mixed evenly to obtain the component A of the primer; (3) Mix 90 parts of isophorone diisocyanate and 10 parts of isocyanate modified with silane coupling agent (prepared by reacting 20 parts of polymethylene polyphenyl isocyanate and 9.5 parts of γ-mercaptopropyltrimethoxysilane at an oil bath temperature of 70 °C) evenly to obtain Component B of the primer; (4) Preparation of the primer: Mix the above Component A and Component B evenly at a mass ratio of 4:1.

[0032] Example 2

[0033] (1) In 100 mL of methanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 3-amino-1-propanol (5.26 g, 70 mmol) react under reflux conditions at 70 °C for 4 h. After the reaction is completed, it is concentrated by rotary evaporation, and then column chromatography separation is carried out using dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain N-(3-hydroxypropyl)-o-nitroaniline. Subsequently, dissolve N-(3-hydroxypropyl)-o-nitroaniline (5.89 g, 30 mmol) in 50 mL of methanol, and in a hydrogen atmosphere, use Pd / C (Xi'an Kaili New Materials, palladium content is 5%, 0.32 g) as the catalyst and react at room temperature for 4 h. After the reaction is completed, it is filtered and concentrated by rotary evaporation to obtain the crude product o-phenylenediamine intermediate. Then, in 50 mL of 5% acetic acid solution, the crude product o-phenylenediamine intermediate (4.16 g, 25 mmol) and alloxan monohydrate (4.0 g, 25 mmol) react at 70 °C for 8 h. After the reaction is completed, it is concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 1:1) to obtain the fluorescent small molecule 2 with a hydroxyl group and an imino group, and the molecular structure is shown as follows:

[0034] (2) Mix 6 parts of 2302AJ, 12 parts of polyester polyol B (a resin with a number average molecular weight of about 1000 obtained by polycondensing terephthalic acid, isophthalic acid, 1,4-butanediol, and neopentyl glycol in a molar ratio of 1.1:0.8:1.8:0.3), 3 parts of 1,2-propanediol, 2 parts of fluorescent small molecule 2, 3 parts of 3-aminopropyltrimethoxysilane, 0.1 part of dibutyltin dilaurate, 45 parts of acetone, and 30 parts of butyl acetate evenly to obtain Component A of the primer; (3) Mix 70 parts of dicyclohexylmethane-4,4-diisocyanate, 20 parts of diphenylmethane diisocyanate, and 10 parts of isocyanate modified with silane coupling agent (prepared by reacting 20 parts of hexamethylene diisocyanate trimer and 7 parts of γ-mercaptopropyltrimethoxysilane at an oil bath temperature of 80 °C) evenly to obtain Component B of the primer; (4) Preparation of the primer: Mix the above Component A and Component B evenly at a mass ratio of 3:1.

[0035] Example 3

[0036] (1)In 100 mL of ethanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 2-amino-1,3-propanediol (9.11 g, 100 mmol) were reacted under reflux at 83 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography was carried out using dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain 2-(2-nitroanilino)-1,3-propanediol. Subsequently, 2-(2-nitroanilino)-1,3-propanediol (6.37 g, 30 mmol) was dissolved in ethanol, and in a hydrogen atmosphere, Pd / C (Xi'an Kelixin New Materials, palladium content 5%, 0.25 g) was used as the catalyst, and the reaction was carried out at room temperature for 3 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product of o-phenylenediamine intermediate. Then, in 50 mL of 5% hydrochloric acid solution, the crude product of o-phenylenediamine intermediate (4.56 g, 25 mmol) and alloxan monohydrate (16.01 g, 100 mmol) were reacted at 80 °C for 6 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 3:2) to obtain the fluorescent small molecule 3 with a hydroxyl group and an imino group, and the molecular structure is shown below:

[0037] (2)3 parts of XCP-4000PM, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 1000 obtained by polycondensation of terephthalic acid, isophthalic acid, 1,4-butanediol, and neopentyl glycol in a molar ratio of 1.1:0.8:1.8:0.3), 2 parts of 1,2-propanediol, 2 parts of fluorescent small molecule 3, 3 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.2 part of dibutyltin dilaurate, 45 parts of methyl ethyl ketone, and 30 parts of butyl acetate were stirred and mixed evenly to obtain the component A of the primer; (3)80 parts of dicyclohexylmethane-4,4-diisocyanate, 10 parts of carbodiimide-modified diphenylmethane diisocyanate, and 10 parts of isocyanate modified with a silane coupling agent (prepared by reacting 10 parts of isophorone diisocyanate and 10 parts of 3-aminopropyltrimethoxysilane at an oil bath temperature of 60 °C) were mixed evenly to obtain the component B of the primer; (4)Preparation of the primer: The above component A and component B were mixed evenly according to a mass ratio of 3:1.

[0038] Example 4

[0039] (1) In 100 mL of ethanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 3-amino-1,2-propanediol (7.29 g, 80 mmol) were refluxed at 83 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography separation was carried out using dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain 2-[(2-nitrophenyl)amino]-1,3-propanediol. Subsequently, 2-[(2-nitrophenyl)amino]-1,3-propanediol (6.37 g, 30 mmol) was dissolved in ethanol, and in a hydrogen atmosphere, Pd / C (Xi'an Kaile New Materials, palladium content 5%, 0.25 g) was used as the catalyst, and the reaction was carried out at room temperature for 3 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product o-phenylenediamine intermediate. Then, in 50 mL of 5% acetic acid solution, the crude product o-phenylenediamine intermediate (4.56 g, 25 mmol) and alloxan monohydrate (8.0 g, 50 mmol) were reacted at 80 °C for 6 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 3:2) to obtain the fluorescent small molecule 4 with hydroxyl and imino groups, and the molecular structure is shown as follows:

[0040] (2) 5 parts of 2304, 2 parts of XCP-5000B, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 500 obtained by polycondensation of terephthalic acid, isophthalic acid, ethylene glycol, and butanediol in a molar ratio of 1.1:0.8:1.0:1.1), 2 parts of diethylene glycol, 2 parts of fluorescent small molecule 4, 3 parts of 3-ureidopropyltriethoxysilane, 0.3 part of dibutyltin dilaurate, 40 parts of methyl ethyl ketone, and 30 parts of butyl acetate were stirred and mixed evenly to obtain the component A of the primer; (3) 80 parts of isophorone diisocyanate, 10 parts of polymethylene polyphenyl isocyanate, and 10 parts of isocyanate modified with a silane coupling agent (prepared by reacting 10 parts of isophorone diisocyanate and 10 parts of N-butyl-3-aminopropyltrimethoxysilane at an oil bath temperature of 50 °C) were mixed evenly to obtain the component B of the primer; (4) Preparation of the primer: The above component A and component B were mixed evenly at a mass ratio of 1:1.

[0041] Example 5

[0042] (1) In 100 mL of methanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 2-aminoethanol (4.58 g, 75 mmol) were refluxed at 70 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography was carried out using a mixture of dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain N-(2-hydroxyethyl)-o-nitroaniline. Subsequently, N-(2-hydroxyethyl)-o-nitroaniline (5.47 g, 30 mmol) was dissolved in 50 mL of ethanol, and in a hydrogen atmosphere, Pd / C (Xi'an Kelai New Materials, palladium content 5%, 0.25 g) was used as the catalyst, and the reaction was carried out at room temperature for 4 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product o-phenylenediamine intermediate. Then, in 50 mL of 5% hydrochloric acid solution, the crude product o-phenylenediamine intermediate (3.81 g, 25 mmol) and alloxan monohydrate (12.01 g, 75 mmol) were reacted at 75 °C for 6 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 1:1) to obtain the fluorescent small molecule 1 with a hydroxyl group and an imino group.

[0043] (2) 2 parts of POL-1232, 3 parts of 2402A, 12 parts of polyester polyol B (a resin with a number average molecular weight of about 500 obtained by polycondensation of terephthalic acid, isophthalic acid, ethylene glycol, and 1,4-butanediol in a molar ratio of 1.1:0.8:1.0:1.1), 3 parts of neopentyl glycol, 2 parts of fluorescent small molecule 1, 2 parts of 3-aminopropyltriethoxysilane, 0.1 part of dibutyltin dilaurate, 0.1 part of triethylamine, 40 parts of cyclohexanone, and 36 parts of isobutyl acetate were stirred and mixed evenly to obtain the component A of the primer. (3) 90 parts of dicyclohexylmethane-4,4-diisocyanate and 10 parts of isocyanate modified with a silane coupling agent (prepared by reacting 20 parts of polymethylene polyphenyl isocyanate and 11.5 parts of γ-mercaptopropyltriethoxysilane at an oil bath temperature of 70 °C) were mixed evenly to obtain the component B of the primer. (4) Preparation of the primer: The above component A and component B were mixed evenly at a mass ratio of 5:1.

[0044] Example 6

[0045] (1) In 100 mL of ethanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 3-amino-1-propanol (4.88 g, 65 mmol) were refluxed at 83 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography separation was carried out using dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain the intermediate N-(3-hydroxypropyl)-o-nitroaniline. Subsequently, N-(3-hydroxypropyl)-o-nitroaniline (5.89 g, 30 mmol) was dissolved in 50 mL of ethanol, and in a hydrogen atmosphere, with Pd / C (Xi'an Kelai New Materials, palladium content 5%, 0.32 g) as the catalyst, the reaction was carried out at room temperature for 5 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product o-phenylenediamine intermediate. Then, in 50 mL of 5% hydrochloric acid solution, the crude product o-phenylenediamine intermediate (4.16 g, 25 mmol) and alloxan monohydrate (10.01 g, 62.5 mmol) were reacted at 80 °C for 5 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 1:1) to obtain the fluorescent small molecule 2 with a hydroxyl group and an imino group.

[0046] (2) 5 parts of POL-322, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 800 obtained by polycondensation of terephthalic acid, isophthalic acid, ethylene glycol, and neopentyl glycol in a molar ratio of 1.1:0.9:1.0:1.2), 2 parts of neopentyl glycol, 2 parts of fluorescent small molecule 2, 3 parts of 3-ureidopropyltriethoxysilane, 0.2 part of bismuth isooctanoate, and 73 parts of methyl ethyl ketone were stirred and mixed evenly to obtain the component A of the primer; (3) 80 parts of isophorone diisocyanate, 10 parts of polymethylene polyphenyl isocyanate, and 10 parts of isocyanate modified with a silane coupling agent (prepared by reacting 20 parts of hexamethylene diisocyanate trimer and 8.5 parts of γ-mercaptopropyltrimethoxysilane at an oil bath temperature of 80 °C) were mixed evenly to obtain the component B of the primer; (4) Preparation of the primer: The above component A and component B were mixed evenly at a mass ratio of 4:1.

[0047] Example 7

[0048] (1) In 100 mL of ethanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 2-amino-1,3-propanediol (7.74 g, 85 mmol) were refluxed at 83 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography was carried out using a mixture of dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain 2-(2-nitroanilino)-1,3-propanediol. Subsequently, 2-(2-nitroanilino)-1,3-propanediol (6.37 g, 30 mmol) was dissolved in methanol, and in a hydrogen atmosphere, using Pd / C (Xi'an Kaili New Materials, palladium content 5%, 0.25 g) as the catalyst, the reaction was carried out at room temperature for 4 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product of o-phenylenediamine intermediate. Then, in 50 mL of 5% acetic acid solution, the crude o-phenylenediamine intermediate (4.56 g, 25 mmol) and alloxan monohydrate (7.60 g, 47.5 mmol) were reacted at 70 °C for 8 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 3:2) to obtain the fluorescent small molecule 3 with a hydroxyl group and an imino group.

[0049] (2) 2 parts of 2302AJ, 5 parts of POL-A3500, 12 parts of polyester polyol B (a resin with a number average molecular weight of about 900 obtained by polycondensation of phthalic anhydride, 1,4-butanediol, and neopentyl glycol in a molar ratio of 2:1.8:0.4), 3 parts of dipropylene glycol, 2 parts of fluorescent small molecule 3, 3 parts of 3-aminopropyltrimethoxysilane, 0.1 part of bismuth isooctanoate, 0.1 part of dibutyltin dilaurate, 40 parts of methyl ethyl ketone, 23 parts of ethyl acetate, and 10 parts of propylene glycol methyl ether acetate were stirred and mixed evenly to obtain the primer A component; (3) 80 parts of isophorone diisocyanate, 10 parts of polymethylene polyphenyl isocyanate, and 10 parts of isocyanate modified with a silane coupling agent (prepared by reacting 10 parts of isophorone diisocyanate and 10 parts of N-butyl-3-aminopropyltrimethoxysilane at an oil bath temperature of 60 °C) were mixed evenly to obtain the primer B component; (4) Preparation of the primer: The above A component and B component were mixed evenly at a mass ratio of 3.5:1.

[0050] Example 8

[0051] (1) In 100 mL of ethanol, 1-fluoro-2-nitrobenzene (7.06 g, 50 mmol) and 3-amino-1,2-propanediol (9.11 g, 100 mmol) were reacted under reflux at 83 °C for 4 h. After the reaction was completed, it was concentrated by rotary evaporation, and then column chromatography was carried out using dichloromethane and ethyl acetate (mass ratio 1:2) as the eluent to obtain 2-[(2-nitrophenyl)amino]-1,3-propanediol. Subsequently, 2-[(2-nitrophenyl)amino]-1,3-propanediol (6.37 g, 30 mmol) was dissolved in methanol, and in a hydrogen atmosphere, with Pd / C (Xi'an Kelai New Materials, palladium content 5%, 0.25 g) as the catalyst, the reaction was carried out at room temperature for 4 h. After the reaction was completed, it was filtered and concentrated by rotary evaporation to obtain the crude product o-phenylenediamine intermediate. Then, in 50 mL of 5% hydrochloric acid solution, the crude product o-phenylenediamine intermediate (4.56 g, 25 mmol) and alloxan monohydrate (13.21 g, 82.5 mmol) were reacted at 80 °C for 6 h. After the reaction was completed, it was concentrated by rotary evaporation, and then recrystallized using a mixed solvent of ethyl acetate and ethanol (mass ratio 3:2) to obtain the fluorescent small molecule 4 with a hydroxyl group and an imino group.

[0052] (2) 6 parts of XCP-R4500H, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 900 obtained by polycondensation of phthalic anhydride, 1,4-butanediol, and neopentyl glycol in a molar ratio of 2:1.8:0.4), 2 parts of dipropylene glycol, 2 parts of fluorescent small molecule 4, 3 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.3 part of stannous octoate, 40 parts of methyl ethyl ketone, 20 parts of isobutyl acetate, and 12 parts of propylene glycol monomethyl ether acetate were stirred and mixed evenly to obtain the component A of the primer; (3) 70 parts of dicyclohexylmethane-4,4-diisocyanate, 20 parts of diphenylmethane diisocyanate, and 10 parts of isocyanate modified with a silane coupling agent (prepared by reacting 20 parts of hexamethylene diisocyanate trimer and 7 parts of γ-mercaptopropyltrimethoxysilane at an oil bath temperature of 70 °C) were mixed evenly to obtain the component B of the primer; (4) Preparation of the primer: The above component A and component B were mixed evenly at a mass ratio of 3:1.

[0053] Comparative Example 1 (1) 5 parts of POL-322, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 800 obtained by polycondensation of terephthalic acid, isophthalic acid, ethylene glycol, and neopentyl glycol in a molar ratio of 1.1:0.9:1.0:1.2), 2 parts of neopentyl glycol, 2 parts of dipropylene glycol, 3 parts of 3-ureidopropyltriethoxysilane, 0.2 part of bismuth isooctanoate, and 73 parts of methyl ethyl ketone were stirred and mixed evenly to obtain the component A of the primer; (2) Mix 80 parts of isophorone diisocyanate, 10 parts of polymethylene polyphenyl isocyanate, and 10 parts of isocyanate modified with silane coupling agent (prepared by reacting 20 parts of hexamethylene diisocyanate trimer and 8.5 parts of γ-mercaptopropyltrimethoxysilane under the condition of an 80 °C oil bath temperature) evenly to obtain Component B of the primer; (3) Preparation of the primer: Mix the above Component A and Component B evenly according to a mass ratio of 4:1.

[0054] Comparative Example 2 (1) Mix 5 parts of POL-322, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 800 obtained by polycondensing terephthalic acid, isophthalic acid, ethylene glycol, and neopentyl glycol in a molar ratio of 1.1:0.9:1.0:1.2), 2 parts of neopentyl glycol, 2 parts of dipropylene glycol, 0.2 parts of bismuth isooctanoate, and 76 parts of methyl ethyl ketone evenly to obtain Component A of the primer; (2) Mix 80 parts of isophorone diisocyanate, 10 parts of polymethylene polyphenyl isocyanate, and 10 parts of isocyanate modified with silane coupling agent (prepared by reacting 20 parts of hexamethylene diisocyanate trimer and 8.5 parts of γ-mercaptopropyltrimethoxysilane under the condition of an 80 °C oil bath temperature) evenly to obtain Component B of the primer; (3) Preparation of the primer: Mix the above Component A and Component B evenly according to a mass ratio of 4:1.

[0055] Comparative Example 3 (1) Mix 5 parts of POL-322, 15 parts of polyester polyol B (a resin with a number average molecular weight of about 800 obtained by polycondensing terephthalic acid, isophthalic acid, ethylene glycol, and neopentyl glycol in a molar ratio of 1.1:0.9:1.0:1.2), 2 parts of neopentyl glycol, 2 parts of dipropylene glycol, 3 parts of 3-ureidopropyltriethoxysilane, 0.2 parts of bismuth isooctanoate, and 73 parts of methyl ethyl ketone evenly to obtain Component A of the primer; (2) Mix 80 parts of isophorone diisocyanate, 10 parts of polymethylene polyphenyl isocyanate, and 10 parts of hexamethylene diisocyanate trimer evenly to obtain Component B of the primer; (3) Preparation of the primer: Mix the above Component A and Component B evenly according to a mass ratio of 4:1.

[0056] The adhesion performance of the primers of Examples 1 to 8 and Comparative Examples 1 to 3 was tested. Test method: The primers of the Examples and Comparative Examples were coated on the surface of the glass substrate, and glass edge-banding samples were prepared by reaction injection molding process. The peel strength between the edge-banding strip and the glass substrate was measured by a universal tensile machine using the 90° peel method, and compared with the blank sample without coating the primer. The results are shown in Table 1. When the peel strength of the bonding surface is greater than the strength of the edge-banding strip itself, the edge-banding strip breaks and cannot be completely peeled off, and the failure mode is complete cohesive failure, which can be considered the best bonding effect. From the data in Table 1, it can be seen that the primer of the present invention can significantly improve the bonding strength between the polyurethane edge-banding material and the glass substrate, and the coating has fluorescence.

[0057] Table 1 Performance table of the primers of Examples 1 to 8, Comparative Examples and blank samples

Claims

1. A fluorescent small molecule has the following structural formula: 。 2. The fluorescent small molecule according to claim 1, wherein The preparation method of the fluorescent molecule comprises the following steps: (1) 1-Fluoro-2-nitrobenzene and alkyl alkanolamine react in organic solvent A to obtain a reaction solution; (2) The reaction solution of step (1) is processed to obtain an intermediate N-hydroxyalkyl-o-nitroaniline; (3) N-Hydroxyalkyl-o-nitroaniline is dissolved in organic solvent B, and a catalytic reduction reaction is carried out under the atmosphere of hydrogen gas and the action of a catalyst; (4) The reaction solution of step (3) is processed to obtain an o-phenylenediamine intermediate; (5) In an acidic solution, the o-phenylenediamine intermediate undergoes a ring-forming reaction with alloxan monohydrate; (6) The reaction solution of step (5) is processed to obtain a fluorescent small molecule with a hydroxyl group and an imino group.

3. A fluorescent polyurethane primer containing the fluorescent small molecule according to any one of claims 1-2, which consists of component A and component B: Component A, in parts by mass, includes: 1-10 parts of polyester polyol A, 1-20 parts of polyester polyol B, 1-5 parts of small molecule polyol, 1-5 parts of fluorescent small molecule, 1-5 parts of silane coupling agent A, 0.1-1 part of catalyst, and 50-90 parts of organic solvent; Component B, in parts by mass, includes: 85-100 parts of polyisocyanate A and 1-15 parts of silane coupling agent-modified isocyanate.

4. The fluorescent polyurethane primer according to claim 3, wherein The polyester polyol A is an aliphatic polyester diol with a number average molecular weight of 3000-5000, and the polyester polyol B is an aromatic polyester diol with a number average molecular weight of 500-1500.

5. The fluorescent polyurethane primer according to claim 3, wherein The silane coupling agent-modified isocyanate is obtained by reacting polyisocyanate B with silane coupling agent B; polyisocyanate B is preferably one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, and hexamethylene diisocyanate trimer; silane coupling agent B is preferably one of γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, anilinopropyltrimethoxysilane, and N-n-butyl-3-aminopropyltrimethoxysilane.

6. The fluorescent polyurethane primer according to claim 3, characterized in that, The small molecule polyol is preferably one or more of neopentyl glycol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, and trimethylolpropane.

7. The fluorescent polyurethane primer according to claim 3, wherein The silane coupling agent A is selected from one or several of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane, γ-(2,3-epoxypropoxy)propyltriethoxysilane, 3-aminoethylaminopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane.

8. The fluorescent polyurethane primer according to claim 3, wherein The polyisocyanate A is selected from one or several of isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane-4,4-diisocyanate, polymethylene polyphenyl isocyanate, toluene diisocyanate, and carbodiimide-modified diphenylmethane diisocyanate.

9. A preparation method of the fluorescent polyurethane primer according to any one of claims 3-8, which comprises the following steps: (1) Preparation of Component A: Weigh the metered polyester polyol A, polyester polyol B, small molecule polyol, fluorescent small molecule, silane coupling agent A, catalyst, and organic solvent, and mix them evenly; (2) Preparation of Component B: Weigh the metered polyisocyanate A and isocyanate modified with silane coupling agent, and mix them evenly; (3) Preparation of the primer: Mix Component A and Component B evenly.

10. Use of the fluorescent polyurethane primer according to any one of claims 3-8, wherein the fluorescent polyurethane primer is used for bonding polyurethane edge wrapping materials and automotive glass substrates.

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