Wear-resistant fluorescent waterborne polyurethane and preparation method thereof

Abstract

The invention provides wear-resistant fluorescent waterborne polyurethane and a preparation method thereof, and relates to the technical field of novel fluorescent polymer materials. The wear-resistant fluorescent waterborne polyurethane is prepared from the following raw materials in parts by weight: 5 to 15 parts of perylene bisimide modified monomer, 20 to 45 parts of oligomer polyol, 35 to 45 parts of isocyanate, 2 to 7 parts of hydrophilic monomer, 5 to 10 parts of chain extender, 2 to 5 parts of neutralizer and 0.01 to 0.1 part of catalyst, wherein the perylene bisimide modified monomer takes perylene bisimide as a center, the nitrogen end of the perylene bisimide is grafted with a cage type polysilsesquioxane group, and the bay position of the perylene bisimide is modified with a triethylene glycol group. The wear-resistant fluorescent waterborne polyurethane disclosed by the invention has high solid-state fluorescent quantum yield and excellent physical and mechanical properties.

Description

Technical Field

[0001] The invention relates to the technical field of new polymer materials, and in particular to a wear-resistant fluorescent waterborne polyurethane and a preparation method thereof. Background Art

[0002] Waterborne polyurethane is the development direction of many current industrial applications due to its advantages such as non-toxicity and environmental protection. Fluorescent waterborne polyurethane has attracted extensive attention due to its special secondary luminescence properties and its unique advantages in important applications in materials and biological sciences. However, traditional fluorescent molecules are difficult to be applied in practice due to problems such as poor compatibility and dispersibility. Therefore, actively studying a class of efficient and environmentally friendly fluorescent polyurethane materials has important practical significance and economic value.

[0003] Perylene diimide (PDI) has strong fluorescence properties and strong absorption of light from the visible light region to the infrared light region. It is considered to be a closed chromophore. Its fluorescence quantum yield is almost quantitative, and the yield and lifetime are not affected by oxygen. The unique photophysical properties have attracted the attention of researchers and broadened its application prospects in optical properties, photoelectric conversion and luminescence. The π-π conjugation degree in the plane of the perylene diimide molecule is extremely large, and its π electrons are delocalized in the molecule. The polarizability of the π electron cloud is very high, and it has an extremely high fluorescence quantum yield. However, it is precisely because of the strong conjugation that the lattice energy is greatly increased, resulting in poor solubility of most perylene diimide compounds, which in turn limits their synthesis and application. Therefore, improving the solubility of perylene derivatives and maintaining their high fluorescence quantum yields have always been a difficult problem that plagues their applications.

[0004] ZL201310223868.3, ZL201510712140.6 and ZL201910640788.5 use fluorescent dyes with hydroxyl or amino groups to graft fluorescent groups onto the molecular chain of polyurethane, but the number of fluorescent groups introduced into these fluorescent waterborne polyurethanes is small, and the weather resistance and physical properties are poor. ZL201911188645.1 introduces fluorescent composite materials such as attapulgite clay containing terminal hydroxyl groups to the molecular chain of waterborne polyurethane, but attapulgite clay is a one-dimensional material, which provides limited spatial rotation steric hindrance and dispersion solubility for the fluorescent molecule perylene imide amidation, thus having limited help in improving the fluorescence quantum yield.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a wear-resistant fluorescent waterborne polyurethane and a preparation method thereof. The wear-resistant fluorescent waterborne polyurethane of the present invention has high solid-state fluorescent quantum yield and excellent physical and mechanical properties.

[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0008] In a first aspect, the present invention provides a wear-resistant fluorescent waterborne polyurethane, wherein the raw materials for preparing the wear-resistant fluorescent waterborne polyurethane include the following components in parts by weight:

[0009]

[0010] Preferably, the perylene imide modified monomer comprises a perylene imide center, and the amino end of the perylene imide is grafted with a cage-type polysilsesquioxane group, and the bay position of the perylene imide is modified with a triethylene glycol group.

[0011] Preferably, the oligomer polyol is selected from any one of poly(1,4-butylene adipate diol), poly(1,6-hexane adipate diol), polyoxypropylene polyol or polytetramethylene glycol, or a combination of at least two thereof.

[0012] Preferably, the weight average molecular weight of the oligomer polyol is 500-4000.

[0013] Preferably, the isocyanate is selected from any one of isophorone diisocyanate, toluene diisocyanate or hexamethylene diisocyanate, or a combination of at least two thereof.

[0014] Preferably, the hydrophilic monomer is selected from dimethylolpropionic acid and / or dimethylolbutanoic acid.

[0015] Preferably, the chain extender is selected from any one of ethylene glycol, butanediol, hexanediol, ethylenediamine or diethylenetriamine, or a combination of at least two thereof.

[0016] Preferably, the neutralizing agent is selected from any one of triethylamine, sodium hydroxide or ammonia water, or a combination of at least two thereof.

[0017] Preferably, the catalyst is selected from an organotin catalyst and / or an organobismuth catalyst.

[0018] Preferably, the organotin catalyst is selected from stannous octoate and / or butyltin dilaurate.

[0019] Preferably, the organic bismuth catalyst is selected from any one of bismuth cyclohexaneate, bismuth isooctanoate or bismuth laurate, or a combination of at least two thereof.

[0020] In a second aspect, the present invention provides a method for preparing the wear-resistant fluorescent waterborne polyurethane as described in the first aspect, wherein the method for preparing the wear-resistant fluorescent waterborne polyurethane comprises the following steps:

[0021] (1) in the presence of a catalyst, a perylene imide-modified monomer, an oligomer polyol, an isocyanate and a hydrophilic monomer undergo a polymerization reaction to obtain a first product;

[0022] (2) measuring the NCO value of the first product obtained in step (1), and after the NCO value of the first product reaches a range of 1 to 3, diluting and cooling the first product, and then adding a chain extender to carry out a chain extension reaction to obtain a second product;

[0023] (3) measuring the NCO value of the second product obtained in step (1), and after the NCO value of the second product reaches a range of 1 to 2, diluting and cooling, and then adding a neutralizing agent to carry out a neutralization reaction to obtain a third product;

[0024] (4) adding water to the third product under stirring, and removing the solvent after the post-chain extension reaction is complete to obtain the wear-resistant fluorescent waterborne polyurethane.

[0025] Preferably, in step (1), the polymerization reaction temperature is 80-85° C., and the polymerization reaction time is 2-4 hours.

[0026] Preferably, in step (2), the temperature after dilution and cooling is 70-75°C.

[0027] Preferably, in step (2), the diluent used for dilution and cooling is butanone.

[0028] Preferably, in step (2), the amount of the diluent added is 5 to 10 wt%.

[0029] Preferably, in step (2), the temperature of the chain extension reaction is 70-75° C., and the time of the chain extension reaction is 1-3 h.

[0030] Preferably, in step (3), the temperature after dilution and cooling is below 40°C.

[0031] Preferably, in step (3), the diluent used for dilution and cooling is acetone.

[0032] Preferably, in step (3), the amount of the diluent added is 5 to 10 wt %.

[0033] Preferably, in step (3), the temperature of the neutralization reaction is below 40° C., and the time of the neutralization reaction is 20 to 40 minutes.

[0034] Preferably, the perylene imide modified monomer is prepared by the following steps:

[0035] (a) performing a bromination reaction on perylenetetracarboxylic dianhydride to obtain perylenetetracarboxylic dianhydride with bromine substituted at the bay position;

[0036] (b) the bromine-substituted perylenetetracarboxylic dianhydride reacts with a cage-type polysilsesquioxane to obtain a compound POSS-PDIBr-POSS;

[0037] (c) The compound POSS-PDIBr-POSS reacts with triethylene glycol to obtain the perylene imide modified monomer POSS-PDITEG-POSS.

[0038] Preferably, in step (a), the specific steps of the bromination reaction are:

[0039] Perylenetetracarboxylic dianhydride and concentrated sulfuric acid are mixed, stirred for the first time, iodine is added, stirred for the second time, and then the temperature is raised to the reaction temperature, and bromine is added dropwise to carry out bromination reaction to obtain a reaction solution containing perylenetetracarboxylic dianhydride substituted with bromine at the bay position.

[0040] Preferably, in step (a), the ratio of the added amount of perylenetetracarboxylic dianhydride to concentrated sulfuric acid is 1 mol: (4-6) mL.

[0041] Preferably, in step (a), the molar ratio of perylenetetracarboxylic dianhydride to iodine is 1:(0.01-0.05).

[0042] Preferably, in step (a), the temperatures of the first stirring and the second stirring are each independently 20 to 30° C., and the times of the first stirring and the second stirring are each independently 1 to 3 hours.

[0043] Preferably, in step (a), the molar ratio of perylenetetracarboxylic dianhydride to bromine is 1:(1-3).

[0044] Preferably, in step (a), the time for adding bromine dropwise is within 4 hours.

[0045] Preferably, in step (a), the reaction temperature is 80-90° C., and the reaction time is 12-18 h.

[0046] Preferably, step (a) further comprises the following post-processing steps:

[0047] The unreacted bromine in the reaction solution is blown away with nitrogen, and the reaction solution is cooled and then ice water is added to precipitate a solid and filter it. The filtered solid is washed with water until the pH value is neutral, and dried to obtain the perylenetetracarboxylic dianhydride with bromine substituted at the bay position.

[0048] Preferably, in step (b), the specific steps of the reaction are:

[0049] The cage-type polysilsesquioxane, bromine-substituted perylenetetracarboxylic dianhydride at the bay position, imidazole and o-dichlorobenzene are mixed, heated and stirred, then cooled, chloroform is added, and the mixture is dispersed in ethanol and hydrochloric acid solution to react to obtain a reaction solution containing the compound POSS-PDIBr-POSS.

[0050] Preferably, in step (b), the molar ratio of the bromine-substituted perylenetetracarboxylic dianhydride at the bay position to the cage-type polysilsesquioxane is 1:(2-2.2).

[0051] Preferably, in step (b), the mass ratio of the bromine-substituted perylenetetracarboxylic dianhydride at the bay position to imidazole is 1:(5-7).

[0052] Preferably, in step (b), the temperature of the heating and stirring is 155-165° C., and the time of the heating and stirring is 2-4 h.

[0053] Preferably, in step (b), the volume ratio of the ethanol to the hydrochloric acid solution is 1:(0.8-1.2).

[0054] Preferably, in step (b), the concentration of the hydrochloric acid solution is 1 to 3 mol / L.

[0055] Preferably, in step (b), the reaction temperature is 20-30° C., and the reaction time is 8-16 h.

[0056] Preferably, step (b) further comprises the following post-processing steps:

[0057] The reaction solution was washed to neutrality with alkaline solution, and after removing water, column chromatography was performed to purify the compound POSS-PDIBr-POSS.

[0058] Preferably, in step (b), the alkali solution is a mixture of sodium bicarbonate and sodium carbonate.

[0059] Preferably, in step (b), anhydrous calcium carbonate is used for dewatering.

[0060] Preferably, in step (b), the eluent of the column chromatography is a mixture of ethyl acetate and n-hexane in a volume ratio of 25:1.

[0061] Preferably, in step (c), the specific steps of the reaction are:

[0062] The compound POSS-PDIBr-POSS is dissolved in tetrahydrofuran, and potassium carbonate, 18-crown-hexaether and triethylene glycol are added in sequence to react to obtain a reaction solution containing the perylene imide modified monomer.

[0063] Preferably, in step (c), the molar ratio of the compound POSS-PDIBr-POSS, potassium carbonate, 18-crown-hexaether and triethylene glycol is 1:(3-5):(3-5):(2-2.2).

[0064] Preferably, in step (c), the reaction temperature is 20 to 30° C., and the reaction time is 1 to 3 hours.

[0065] Preferably, step (c) further comprises the following post-processing steps:

[0066] The reaction solution was concentrated and then extracted, and the organic phase was collected, dried, and then concentrated again, and column chromatography was performed to obtain the perylene imide modified monomer POSS-PDITEG-POSS.

[0067] Preferably, in step (c), the extraction solvents used in the extraction are water and chloroform.

[0068] Preferably, in step (c), the eluent of the column chromatography is a mixture of ethyl acetate and n-hexane in a volume ratio of 25:1.

[0069] Compared with the prior art, the present invention has the following beneficial effects:

[0070] (1) The POSS-modified perylene diimide (PDI) monomer POSS-PDITEG-POSS provided by the present invention greatly enhances the solubility of PDI molecules in most organic solvents due to the rich alkyl chains on the surface of POSS, and greatly improves the fluorescence quantum yield of this type of molecule due to the spatial rotation steric hindrance effect of POSS.

[0071] (2) The present invention modifies the oligomers of ethylene glycol at the bay position, so that the modified monomers can be embedded into the molecular chain of waterborne polyurethane through the reaction of -OH group and isocyanate, and the obtained fluorescent waterborne polyurethane has good weather resistance and physical and mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0073] Figure 1 This is a schematic diagram of the cross-sectional structure of the composite membrane provided by the present invention.

[0074] Among them, 101 is a back protection layer, 102 is a substrate layer, 103 is a bonding layer, and 104 is a front structural layer. DETAILED DESCRIPTION

[0075] Unless otherwise defined herein, scientific and technological terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0076] It should be noted that specific details are described in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in a variety of other ways different from those described herein, and those skilled in the art can make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0077] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but it will be appreciated by those skilled in the art that the following embodiments and examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified, proceed according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0078] In a first aspect, the present invention provides a wear-resistant fluorescent waterborne polyurethane, wherein the raw materials for preparing the wear-resistant fluorescent waterborne polyurethane include the following components in parts by weight:

[0079]

[0080]

[0081] In the raw materials for preparing the wear-resistant fluorescent waterborne polyurethane, the content of the perylene imide modified monomer is 5 to 15 parts, for example, it can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc.

[0082] In the preparation raw materials of the wear-resistant fluorescent water-based polyurethane, the content of oligomer polyol is 20 to 45 parts, for example, it can be 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 45 parts, etc.

[0083] In the raw materials for preparing the wear-resistant fluorescent water-based polyurethane, the content of isocyanate is 35 to 45 parts, for example, it can be 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, etc.

[0084] In the raw materials for preparing the wear-resistant fluorescent waterborne polyurethane, the content of the hydrophilic monomer is 2 to 7 parts, for example, it can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, etc.

[0085] In the preparation raw materials of the wear-resistant fluorescent waterborne polyurethane, the content of the chain extender is 5 to 10 parts, for example, it can be 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, etc.

[0086] In the preparation raw materials of the wear-resistant fluorescent water-based polyurethane, the content of the neutralizer is 2 to 5 parts, for example, it can be 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5 parts, etc.

[0087] In the raw materials for preparing the wear-resistant fluorescent waterborne polyurethane, the content of the catalyst is 0.01 to 0.1 parts, for example, it can be 0.01 parts, 0.02 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.08 parts, 0.1 parts, etc.

[0088] In the present invention, the raw materials for preparing the wear-resistant fluorescent waterborne polyurethane contain a specific proportion of perylene imide modified monomers, so that the solid-state fluorescent quantum yield and physical and mechanical properties of the wear-resistant fluorescent waterborne polyurethane are significantly improved.

[0089] As an optional embodiment, the perylene imide modified monomer includes a perylene imide (PDI) center, and the amino end of the perylene imide is grafted with a cage-type polysilsesquioxane group (POSS), and the bay position of the perylene imide is modified with a triethylene glycol group (TEG).

[0090] In the present invention, a caged polysilsesquioxane group (POSS) is first grafted onto the amino end of perylene imide; it should be noted that caged polysilsesquioxane (POSS) is an important inorganic nanoparticle modified particle with large size, high thermal and chemical stability. The eight-cornered alkyl chain can react with other organic molecules to form an organic-inorganic nanohybrid material. As such a nanometer-sized modification group, POSS greatly enhances the solubility of PDI molecules in most organic solvents. Due to the spatial rotation steric hindrance effect of POSS, this type of derivative produces an aggregated molecular stacking different from general PDI, which greatly improves the solid-state fluorescence quantum yield of this type of molecule.

[0091] In the present invention, a triethylene glycol group (TEG) is also modified at the bay position of the perylene imide; it should be noted that the modification of the bay position of the PDI molecule by the triethylene glycol group allows the modified monomer to be embedded in the waterborne polyurethane molecular chain through the reaction of the -OH group with isocyanate, and the obtained fluorescent waterborne polyurethane has good weather resistance and physical and mechanical properties.

[0092] As an optional embodiment, the structural formula of the perylene imide modified monomer is shown in Formula I below:

[0093]

[0094] As an optional embodiment, in the above formula I, R is selected from isobutyl

[0095] As an optional embodiment, the oligomer polyol is selected from any one of poly(1,4-butylene adipate diol), poly(1,6-hexane adipate diol), polyoxypropylene polyol or polytetramethylene glycol, or a combination of at least two thereof.

[0096] As an optional embodiment, the weight average molecular weight of the oligomer polyol is 500-4000, for example, it can be 500, 600, 700, 800, 900, 1000, 1200, 1400, 1500, 1600, 1800, 2000, 2500, 3000, 3500, 4000, etc.

[0097] As an optional embodiment, the isocyanate is selected from any one of isophorone diisocyanate, toluene diisocyanate or hexamethylene diisocyanate, or a combination of at least two thereof.

[0098] As an optional embodiment, the hydrophilic monomer is selected from dimethylol propionic acid and / or dimethylol butyric acid.

[0099] As an optional embodiment, the chain extender is selected from any one of ethylene glycol, butanediol, hexanediol, ethylenediamine or diethylenetriamine, or a combination of at least two thereof.

[0100] As an optional embodiment, the neutralizing agent is selected from any one of triethylamine, sodium hydroxide or ammonia water, or a combination of at least two of them.

[0101] As an optional embodiment, the catalyst is selected from an organic tin catalyst and / or an organic bismuth catalyst.

[0102] As an optional embodiment, the organic tin catalyst is selected from stannous octoate and / or butyltin dilaurate.

[0103] As an optional embodiment, the organic bismuth catalyst is selected from any one of bismuth cyclohexaneate, bismuth isooctanoate or bismuth laurate, or a combination of at least two thereof.

[0104] In a second aspect, the present invention provides a method for preparing the wear-resistant fluorescent waterborne polyurethane as described in the first aspect, wherein the method for preparing the wear-resistant fluorescent waterborne polyurethane comprises the following steps:

[0105] (1) in the presence of a catalyst, a perylene imide-modified monomer, an oligomer polyol, an isocyanate and a hydrophilic monomer undergo a polymerization reaction to obtain a first product;

[0106] (2) measuring the NCO value of the first product obtained in step (1), and after the NCO value of the first product reaches a range of 1 to 3, diluting and cooling the first product, and then adding a chain extender to carry out a chain extension reaction to obtain a second product;

[0107] (3) measuring the NCO value of the second product obtained in step (1), and after the NCO value of the second product reaches a range of 1 to 2, diluting and cooling, and then adding a neutralizing agent to carry out a neutralization reaction to obtain a third product;

[0108] (4) adding water to the third product under stirring, and removing the solvent after the post-chain extension reaction is complete to obtain the wear-resistant fluorescent waterborne polyurethane.

[0109] As an optional embodiment, in step (1), the polymerization reaction temperature is 80-85°C, for example, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, etc., and the polymerization reaction time is 2-4h, for example, 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.5h, 3.6h, 3.8h, 4h, etc.

[0110] As an optional embodiment, in step (2), the NCO value of the first product reaches 1 to 3, for example, it can be 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, 2.2, 2.4, 2.5, 2.6, 2.8, 3, etc.

[0111] As an optional embodiment, in step (2), the temperature after dilution and cooling is 70-75°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, etc.

[0112] As an optional embodiment, in step (2), the diluent used for dilution and cooling is butanone.

[0113] As an optional embodiment, in step (2), the added amount of the diluent is 5-10wt%, for example, it can be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc.

[0114] It should be noted that the amount of diluent added here refers to the percentage of the content of the diluent to the total mass of the diluent and the first product.

[0115] As an optional embodiment, in step (2), the temperature of the chain extension reaction is 70-75°C, for example, it can be 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, etc., and the time of the chain extension reaction is 1-3h, for example, it can be 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, etc.

[0116] As an optional embodiment, in step (3), the NCO value of the second product is in the range of 1 to 2, for example, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, etc.

[0117] As an optional embodiment, in step (3), the temperature after dilution and cooling is below 40°C, for example, it can be 40°C, 39°C, 38°C, 37°C, 36°C, 35°C, 34°C, 32°C, 30°C, 25°C, 20°C, 15°C, etc.

[0118] As an optional embodiment, in step (3), the diluent used for dilution and cooling is acetone.

[0119] As an optional embodiment, in step (3), the added amount of the diluent is 5-10wt%, for example, it can be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc.

[0120] It should be noted that the amount of diluent added here refers to the percentage of the content of the diluent in the total mass of the diluent and the second product.

[0121] As an optional embodiment, in step (3), the temperature of the neutralization reaction is below 40°C, for example, it can be 40°C, 39°C, 38°C, 37°C, 36°C, 35°C, 34°C, 32°C, 30°C, 25°C, 20°C, 15°C, etc., and the time of the neutralization reaction is 20 to 40 min, for example, it can be 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min, 40 min, etc.

[0122] As an optional embodiment, the perylene imide modified monomer is prepared by the following steps:

[0123] (a) Perylenetetracarboxylic dianhydride is subjected to bromination reaction to obtain perylenetetracarboxylic dianhydride with bromine substituted at the bay position; the reaction formula is as follows:

[0124]

[0125] (b) The perylenetetracarboxylic dianhydride substituted with bromine at the bay position reacts with a cage-type polysilsesquioxane to obtain a compound POSS-PDIBr-POSS; the reaction formula is as follows:

[0126]

[0127] (c) the compound POSS-PDIBr-POSS reacts with triethylene glycol to obtain the perylene imide modified monomer POSS-PDITEG-POSS; the reaction formula is as follows:

[0128]

[0129] As an optional embodiment, in step (a), the specific steps of the bromination reaction are:

[0130] Perylenetetracarboxylic dianhydride and concentrated sulfuric acid are mixed, stirred for the first time, iodine is added, stirred for the second time, and then the temperature is raised to the reaction temperature, and bromine is added dropwise to carry out bromination reaction to obtain a reaction solution containing perylenetetracarboxylic dianhydride substituted with bromine at the bay position.

[0131] As an optional embodiment, in step (a), the ratio of the added amount of perylenetetracarboxylic dianhydride and concentrated sulfuric acid is 1 mol:(4-6) mL, for example, it can be 1 mol:4 mL, 1 mol:4.5 mL, 1 mol:5 mL, 1 mol:5.5 mL, 1 mol:6 mL, etc.

[0132] As an optional embodiment, in step (a), the mass percentage of the concentrated sulfuric acid is 98%.

[0133] As an optional embodiment, in step (a), the molar ratio of perylenetetracarboxylic dianhydride to iodine is 1:(0.01-0.05), for example, it can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, etc.

[0134] As an optional embodiment, in step (a), the temperature of the first stirring is 20-30°C, for example, it can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc., and the time of the first stirring is 1-3h, for example, it can be 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, etc.

[0135] As an optional embodiment, in step (a), the temperature of the second stirring is 20-30°C, for example, it can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc., and the time of the second stirring is 1-3h, for example, it can be 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, etc.

[0136] As an optional embodiment, in step (a), the molar ratio of perylenetetracarboxylic dianhydride to bromine is 1:(1-3), for example, it can be 1:1, 1:1.2, 1:1.4, 1:1.5, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.5, 1:2.6, 1:2.8, 1:3, etc.

[0137] As an optional embodiment, in step (a), the time for adding bromine dropwise is within 4 hours, for example, it can be 4 hours, 3.9 hours, 3.8 hours, 3.7 hours, 3.6 hours, 3.5 hours, 3.4 hours, 3.2 hours, 3 hours, etc.

[0138] As an optional embodiment, in step (a), the reaction temperature is 80-90°C, for example, it can be 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, etc., and the reaction time is 12-18h, for example, it can be 12h, 13h, 14h, 15h, 16h, 17h, 18h, etc.

[0139] As an optional embodiment, step (a) further includes the following post-processing steps:

[0140] The unreacted bromine in the reaction solution is blown away with nitrogen, and the reaction solution is cooled and then ice water is added to precipitate a solid and filter it. The filtered solid is washed with water until the pH value is neutral, and dried to obtain the perylenetetracarboxylic dianhydride with bromine substituted at the bay position.

[0141] As an optional embodiment, in step (b), the specific steps of the reaction are:

[0142] The cage-type polysilsesquioxane, bromine-substituted perylenetetracarboxylic dianhydride at the bay position, imidazole and o-dichlorobenzene are mixed, heated and stirred, then cooled, chloroform is added, and the mixture is dispersed in ethanol and hydrochloric acid solution to react to obtain a reaction solution containing the compound POSS-PDIBr-POSS.

[0143] As an optional embodiment, in step (b), the molar ratio of the bromine-substituted perylenetetracarboxylic dianhydride at the bay position to the cage-type polysilsesquioxane is 1:(2-2.2), for example, 1:2, 1:2.05, 1:2.1, 1:2.15, 1:2.2, etc.

[0144] As an optional embodiment, in step (b), the mass ratio of the bromine-substituted perylenetetracarboxylic dianhydride at the bay position to imidazole is 1:(5-7), for example, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, etc.

[0145] As an optional embodiment, in step (b), the heating and stirring temperature is 155-165°C, for example, it can be 155°C, 156°C, 157°C, 158°C, 159°C, 160°C, 162°C, 163°C, 164°C, 165°C, etc., and the heating and stirring time is 2-4h, for example, it can be 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.5h, 3.6h, 3.8h, 4h, etc.

[0146] As an optional embodiment, in step (b), the volume ratio of ethanol to hydrochloric acid solution is 1:(0.8-1.2), for example, it can be 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, etc.

[0147] As an optional embodiment, in step (b), the concentration of the hydrochloric acid solution is 1-3 mol / L, for example, it can be 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.8 mol / L, 2 mol / L, 2.2 mol / L, 2.4 mol / L, 2.6 mol / L, 2.8 mol / L, 3 mol / L, etc.

[0148] As an optional embodiment, in step (b), the reaction temperature is 20-30°C, for example, it can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc., and the reaction time is 8-16h, for example, it can be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, etc.

[0149] As an optional embodiment, step (b) further includes the following post-processing steps:

[0150] The reaction solution was washed to neutrality with alkaline solution, and after removing water, column chromatography was performed to purify the compound POSS-PDIBr-POSS.

[0151] As an optional embodiment, in step (b), the alkali solution is a mixture of sodium bicarbonate and sodium carbonate.

[0152] As an optional embodiment, in step (b), anhydrous calcium carbonate is used for dewatering.

[0153] As an optional embodiment, in step (b), the eluent of the column chromatography is a mixture of ethyl acetate and n-hexane in a volume ratio of 25:1.

[0154] As an optional embodiment, in step (c), the specific steps of the reaction are:

[0155] The compound POSS-PDIBr-POSS is dissolved in tetrahydrofuran, and potassium carbonate, 18-crown-hexaether and triethylene glycol are added in sequence to react to obtain a reaction solution containing the perylene imide modified monomer.

[0156] As an optional embodiment, in step (c), the molar ratio of the compound POSS-PDIBr-POSS, potassium carbonate, 18-crown-hexaether and triethylene glycol is 1:(3-5):(3-5):(2-2.2);

[0157] The first "3-5" may be, for example, 3, 3.5, 4, 4.5, 5, etc.;

[0158] The second "3-5" may be, for example, 3, 3.5, 4, 4.5, 5, etc.;

[0159] Here, “2-2.2” can be, for example, 2, 2.05, 2.1, 2.15, 2.2, etc.

[0160] As an optional embodiment, in step (c), the reaction temperature is 20-30°C, for example, it can be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc., and the reaction time is 1-3h, for example, it can be 1h, 1.2h, 1.4h, 1.5h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.5h, 2.6h, 2.8h, 3h, etc.

[0161] As an optional embodiment, step (c) further includes the following post-processing steps:

[0162] The reaction solution was concentrated and then extracted, and the organic phase was collected, dried, and then concentrated again, and column chromatography was performed to obtain the perylene imide modified monomer POSS-PDITEG-POSS.

[0163] As an optional embodiment, preferably, in step (c), the extraction solvents used in the extraction are water and chloroform.

[0164] As an optional embodiment, in step (c), the eluent of the column chromatography is a mixture of ethyl acetate and n-hexane in a volume ratio of 25:1.

[0165] As an optional implementation, Figure 1 As shown, the present invention provides a composite film, which includes a back protective layer, a substrate layer, a bonding layer and a front structural layer stacked in sequence from bottom to top; wherein, the wear-resistant fluorescent water-based polyurethane described in the first aspect is used to prepare the back protective layer.

[0166] The present invention is further described below by means of specific examples and comparative examples. However, it should be understood that these examples are only used for more detailed description and should not be construed as limiting the present invention in any form.

[0167] Preparation Example 1

[0168] This preparation example provides a perylene imide-modified monomer, which is prepared by the following steps:

[0169] (a) Perylenetetracarboxylic dianhydride (32 g, 81.4 mmol) and concentrated sulfuric acid (98%, 450 mL) were first mixed and stirred at room temperature for 2 h, and then iodine (0.77 g, 3.03 mmol) was added and stirred for 2 h; then, the reaction temperature was increased to 85°C, and bromine (9.2 mL, 180 mmol) was added dropwise within 4 h, and the reaction was continued for 16 h; after the reaction was completed, the unreacted bromine was blown off with nitrogen, cooled to room temperature, ice water was carefully added, filtered, and washed with distilled water until neutral to obtain a crude product, which was dried in a vacuum oven at 100°C to obtain perylenetetracarboxylic dianhydride PDIBr with bromine substituted at the bay position, which was used for the next reaction without purification.

[0170] (b) POSS (4.54 g, 5.2 mmol), PDIBr (1.44 g, 2.6 mmol), imidazole (9.2 g) and o-dichlorobenzene (ODCB, 10 mL) were placed in a round-bottom flask, condensed and refluxed, heated in an oil bath at 160 °C under argon atmosphere, and stirred for 3 h; then, cooled, 30 mL of chloroform was added, and the mixture was dispersed in 50 mL of ethanol and 50 mL of 2N HCl solution overnight; after the reaction, NaHCO 3 Solution and Na 2 CO 3The solution was washed until neutral, and after dehydration with anhydrous calcium carbonate, column chromatography (volume ratio of ethyl acetate:n-hexane=25:1) was performed to separate and purify the target product POSS-PDIBr-POSS.

[0171] (c) Add 100 mg of the compound POSS-PDIBr-POSS (1.00 eq) to a round-bottom three-necked flask, dissolve it in 20 mL of THF, and then add 4.00 eq of K 2 CO 3 and 4.00eq of 18-crown-hexaether, and then add slightly more than 2.00eq of triethylene glycol, and stir at room temperature for 2h to stop the reaction. During the short period of time at the beginning of stirring, the solution will gradually change color; after stopping the reaction, the sample is subjected to rotary evaporation to obtain a concentrate, which is then extracted with water and chloroform, and then dried, spin-dried, and separated by column chromatography (the volume ratio of ethyl acetate:n-hexane = 25:1) to obtain the target product, perylene imide modified monomer POSS-PDITEG-POSS.

[0172] Comparative Preparation Example 1

[0173] This comparative preparation example provides a perylene imide modified monomer, and the perylene imide modified monomer is prepared by the following steps:

[0174] (a) Perylenetetracarboxylic dianhydride (32 g, 81.4 mmol) and concentrated sulfuric acid (98%, 450 mL) were first mixed and stirred at room temperature for 2 h, and then iodine (0.77 g, 3.03 mmol) was added and stirred for 2 h; then, the reaction temperature was increased to 85°C, and bromine (9.2 mL, 180 mmol) was added dropwise within 4 h, and the reaction was continued for 16 h; after the reaction was completed, the unreacted bromine was blown off with nitrogen, cooled to room temperature, ice water was carefully added, filtered, and washed with distilled water until neutral to obtain a crude product, which was dried in a vacuum oven at 100°C to obtain perylenetetracarboxylic dianhydride PDIBr with bromine substituted at the bay position, which was used for the next reaction without purification.

[0175] (b) In a round-bottom three-necked flask, 100 mg of perylenetetracarboxylic dianhydride PDIBr (1.00 eq) was added and dissolved in 20 mL of THF. Then, 4.00 eq of K 2 CO 3 and 4.00eq of 18-crown-hexaether, and then add slightly more than 2.00eq of triethylene glycol, and stir at room temperature for 2h to stop the reaction. During the short period of time at the beginning of stirring, the solution will gradually change color; after stopping the reaction, the sample is subjected to rotary evaporation to obtain a concentrate, which is then extracted with water and chloroform, and then dried, spin-dried, and separated by column chromatography (the volume ratio of ethyl acetate:n-hexane = 25:1) to obtain the target product, perylene imide modified monomer PDITEG.

[0176] Comparative Preparation Example 2

[0177] This comparative preparation example provides a perylene imide modified monomer, and the perylene imide modified monomer is prepared by the following steps:

[0178] (a) Perylenetetracarboxylic dianhydride (32 g, 81.4 mmol) and concentrated sulfuric acid (98%, 450 mL) were first mixed and stirred at room temperature for 2 h, and then iodine (0.77 g, 3.03 mmol) was added and stirred for 2 h; then, the reaction temperature was increased to 85°C, and bromine (9.2 mL, 180 mmol) was added dropwise within 4 h, and the reaction was continued for 16 h; after the reaction was completed, the unreacted bromine was blown off with nitrogen, cooled to room temperature, ice water was carefully added, filtered, and washed with distilled water until neutral to obtain a crude product, which was dried in a vacuum oven at 100°C to obtain perylenetetracarboxylic dianhydride PDIBr with bromine substituted at the bay position, which was used for the next reaction without purification.

[0179] (b) POSS (4.54 g, 5.2 mmol), PDIBr (1.44 g, 2.6 mmol), imidazole (9.2 g) and o-dichlorobenzene (ODCB, 10 mL) were placed in a round-bottom flask, condensed and refluxed, heated in an oil bath at 160 °C under argon atmosphere, and stirred for 3 h; then, cooled, 30 mL of chloroform was added, and the mixture was dispersed in 50 mL of ethanol and 50 mL of 2N HCl solution overnight; after the reaction, NaHCO 3 Solution and Na 2 CO 3 The solution was washed to neutrality, and after dehydration with anhydrous calcium carbonate, column chromatography (volume ratio of ethyl acetate:n-hexane=25:1) was used for separation and purification to obtain the target product, perylene imide modified monomer POSS-PDIBr-POSS.

[0180] Comparative Preparation Example 3

[0181] This comparative preparation example provides a perylene imide modified monomer, which is different from Preparation Example 1 only in that POSS in step (b) is replaced by an equimolar amount of tris(hydroxymethyl)aminomethane.

[0182] Comparative Preparation Example 4

[0183] This comparative preparation example provides a perylene imide modified monomer, which is different from Preparation Example 1 only in that the triethylene glycol in step (c) is replaced by an equivalent amount of ethylene glycol.

[0184] Example 1

[0185] This embodiment provides a wear-resistant fluorescent water-based polyurethane, and the raw materials for preparing the wear-resistant fluorescent water-based polyurethane include the following components in parts by weight:

[0186]

[0187] The wear-resistant fluorescent waterborne polyurethane is prepared by the following steps:

[0188] (1) In a reaction vessel, oligomer polyol, perylene imide modified monomer, isocyanate, hydrophilic monomer and catalyst are added according to the above components and proportions, and reacted at 82° C. for 3 hours;

[0189] (2) After 3 hours, take a sample to measure the NCO value. When the value reaches the specified range (NCO value = 2), dilute with butanone and cool to 72°C. Then, add a chain extender according to the above components and proportions to carry out a chain extension reaction. Keep the temperature for 2 hours.

[0190] (3) After 2 hours, take a sample to measure the NCO value. When it reaches the specified range (NCO value = 1.4), dilute it with acetone and cool it to 40°C. Add a neutralizing agent according to the above components and proportions to carry out a neutralization reaction for 30 minutes.

[0191] (4) After the reaction is completed, deionized water is added under high-speed stirring at a speed of 2000 rpm, and after the chain extension reaction is complete, vacuum desolventization is performed to obtain a wear-resistant fluorescent water-based polyurethane.

[0192] Example 2

[0193] This embodiment provides a wear-resistant fluorescent water-based polyurethane, and the raw materials for preparing the wear-resistant fluorescent water-based polyurethane include the following components in parts by weight:

[0194]

[0195] The wear-resistant fluorescent waterborne polyurethane is prepared by the following steps:

[0196] (1) In a reaction vessel, oligomer polyol, perylene imide modified monomer, isocyanate, hydrophilic monomer and catalyst are added according to the above components and proportions, and reacted at 82° C. for 3 hours;

[0197] (2) After 3 hours, take a sample to measure the NCO value. When the value reaches the specified range (NCO value = 2), dilute with butanone and cool to 72°C. Then, add a chain extender according to the above components and proportions to carry out a chain extension reaction. Keep the temperature for 2 hours.

[0198] (3) After 2 hours, take a sample to measure the NCO value. When it reaches the specified range (NCO value = 1.4), dilute it with acetone and cool it to 40°C. Add a neutralizing agent according to the above components and proportions to carry out a neutralization reaction for 30 minutes.

[0199] (4) After the reaction is completed, deionized water is added under high-speed stirring at a speed of 2000 rpm, and after the chain extension reaction is complete, vacuum desolventization is performed to obtain a wear-resistant fluorescent water-based polyurethane.

[0200] Example 3

[0201] This embodiment provides a wear-resistant fluorescent water-based polyurethane, and the raw materials for preparing the wear-resistant fluorescent water-based polyurethane include the following components in parts by weight:

[0202]

[0203] The wear-resistant fluorescent waterborne polyurethane is prepared by the following steps:

[0204] (1) In a reaction vessel, oligomer polyol, perylene imide modified monomer, isocyanate, hydrophilic monomer and catalyst are added according to the above components and proportions, and reacted at 82° C. for 3 hours;

[0205] (2) After 3 hours, take a sample to measure the NCO value. When the value reaches the specified range (NCO value = 2), dilute with butanone and cool to 72°C. Then, add a chain extender according to the above components and proportions to carry out a chain extension reaction. Keep the temperature for 2 hours.

[0206] (3) After 2 hours, take a sample to measure the NCO value. When it reaches the specified range (NCO value = 1.4), dilute it with acetone and cool it to 40°C. Add a neutralizing agent according to the above components and proportions to carry out a neutralization reaction for 30 minutes.

[0207] (4) After the reaction is completed, deionized water is added under high-speed stirring at a speed of 2000 rpm, and after the chain extension reaction is complete, vacuum desolventization is performed to obtain a wear-resistant fluorescent water-based polyurethane.

[0208] Example 4

[0209] This embodiment provides a wear-resistant fluorescent water-based polyurethane, and the raw materials for preparing the wear-resistant fluorescent water-based polyurethane include the following components in parts by weight:

[0210]

[0211] The wear-resistant fluorescent waterborne polyurethane is prepared by the following steps:

[0212] (1) In a reaction vessel, oligomer polyol, perylene imide modified monomer, isocyanate, hydrophilic monomer and catalyst are added according to the above components and proportions, and reacted at 82° C. for 3 hours;

[0213] (2) After 3 hours, take a sample to measure the NCO value. When the value reaches the specified range (NCO value = 2), dilute with butanone and cool to 72°C. Then, add a chain extender according to the above components and proportions to carry out a chain extension reaction. Keep the temperature for 2 hours.

[0214] (3) After 2 hours, take a sample to measure the NCO value. When it reaches the specified range (NCO value = 1.4), dilute it with acetone and cool it to 40°C. Add a neutralizing agent according to the above components and proportions to carry out a neutralization reaction for 30 minutes.

[0215] (4) After the reaction is completed, deionized water is added under high-speed stirring at a speed of 2000 rpm, and after the chain extension reaction is complete, vacuum desolventization is performed to obtain a wear-resistant fluorescent water-based polyurethane.

[0216] Example 5

[0217] This embodiment provides a wear-resistant fluorescent water-based polyurethane, and the raw materials for preparing the wear-resistant fluorescent water-based polyurethane include the following components in parts by weight:

[0218]

[0219] The wear-resistant fluorescent waterborne polyurethane is prepared by the following steps:

[0220] (1) In a reaction vessel, oligomer polyol, perylene imide modified monomer, isocyanate, hydrophilic monomer and catalyst are added according to the above components and proportions, and reacted at 82° C. for 3 hours;

[0221] (2) After 3 hours, take a sample to measure the NCO value. When the value reaches the specified range (NCO value = 2), dilute with butanone and cool to 72°C. Then, add a chain extender according to the above components and proportions to carry out a chain extension reaction. Keep the temperature for 2 hours.

[0222] (3) After 2 hours, take a sample to measure the NCO value. When it reaches the specified range (NCO value = 1.4), dilute it with acetone and cool it to 40°C. Add a neutralizing agent according to the above components and proportions to carry out a neutralization reaction for 30 minutes.

[0223] (4) After the reaction is completed, deionized water is added under high-speed stirring at a speed of 2000 rpm, and after the chain extension reaction is complete, vacuum desolventization is performed to obtain a wear-resistant fluorescent water-based polyurethane.

[0224] Comparative Example 1

[0225] This comparative example provides a waterborne polyurethane, which is different from Example 1 only in that the content of the perylene imide modified monomer is reduced to 3 parts, the content of the oligomer polyol is increased to 47 parts, and the contents of other components and the preparation method are completely consistent with Example 1.

[0226] Comparative Example 2

[0227] This comparative example provides a waterborne polyurethane, which is different from Example 1 only in that the content of the perylene imide modified monomer is increased to 20 parts, the content of the oligomer polyol is reduced to 30 parts, and the contents of other components and the preparation method are completely consistent with Example 1.

[0228] Comparative Example 3

[0229] This comparative example provides a waterborne polyurethane, which is different from Example 1 only in that 5 parts of POSS-PDITEG-POSS provided in Preparation Example 1 are replaced by 5 parts of perylene imide modified monomer PDITEG provided in Comparative Preparation Example 1.

[0230] Comparative Example 4

[0231] This comparative example provides a waterborne polyurethane, which differs from Example 1 only in that 5 parts of POSS-PDITEG-POSS provided in Preparation Example 1 are replaced by 5 parts of perylene imide modified monomer POSS-PDIBr-POSS provided in Comparative Preparation Example 2.

[0232] Comparative Example 5

[0233] This comparative example provides a waterborne polyurethane, which is different from Example 1 only in that 5 parts of POSS-PDITEG-POSS provided in Preparation Example 1 are replaced by 5 parts of perylene imide modified monomer provided in Comparative Preparation Example 3.

[0234] Comparative Example 6

[0235] This comparative example provides a waterborne polyurethane, which is different from Example 1 only in that 5 parts of POSS-PDITEG-POSS provided in Preparation Example 1 are replaced by 5 parts of perylene imide modified monomer provided in Comparative Preparation Example 4.

[0236] Test Example 1

[0237] Test samples: the wear-resistant fluorescent waterborne polyurethane provided in Examples 1 to 5 and the waterborne polyurethane provided in Comparative Examples 1 to 6.

[0238] Test method:

[0239] (1) Wear resistance test:

[0240] Tested with the national standard method of 0000# steel wool ball. Fix the sample to be tested on the wear machine with the test surface facing up, cut the steel wool into the size of the abrasive and glue it to the friction head, and fix it in the fixture; select the appropriate weight and add it to the weight fixing rod above the friction head, gently lower the friction head, contact it with the surface to be tested, and start the test. The moving speed is 8cm / sec, and the number of frictions is ten times back and forth. 15s after the end of the friction, place the membrane under the lighted desk lamp for reflection observation, the observation distance is 20cm, and observe at a 45° angle to the left and right to see if there is obvious abrasion on the membrane surface; if the coating is not worn under the corresponding gram weight, it is judged to be OK, otherwise continue to increase the gram weight until the abrasion NG appears, and the highest gram weight without abrasion is the wear-resistant weight.

[0241] (2) Scratch resistance test:

[0242] According to the scratch test method of GB / T9279-1988, wipe the coating surface with 0000# steel wool. No scratch is excellent, slight scratch is good, and severe scratch is poor.

[0243] (3) Weathering performance test:

[0244] The test was carried out according to GB / T 1865-2009 Paints and varnishes - Artificial weathering and artificial radiation exposure (filtered xenon arc radiation), and the decay time of the fluorescent waterborne polyurethane film to 50% of the remaining fluorescence intensity was used as the measurement standard.

[0245] (4) Fluorescence quantum yield test:

[0246] The isosbestic point excitation-correction fluorescence emission spectrum integral area ratio method is used. The reference solution used here is rhodamine 6G ethanol solution, and its standard yield is 0.86. Rhodamine 6G ethanol solution and PDI chloroform solution are prepared, and ultraviolet-visible light absorption detection is used to ensure that the absorbance is less than 0.05. Then, the spectrum intersection point, that is, the isosbestic point, is taken as the excitation wavelength of the fluorescence spectrum, and then the fluorescence spectrum of each sample under the excitation wavelength is tested. The absorbance values ​​and fluorescence emission integral area values ​​of the two are collected, and the fluorescence quantum yield is obtained by substituting them into the formula and calculating.

[0247] Φunk=Φstd(Iunk / Istd)(Aunk / Astd)(ηunk / ηstd) 2

[0248] Wherein, Φ represents the fluorescence quantum yield, I is the integral of the fluorescence intensity, A is the ultraviolet absorption at the excitation wavelength of the fluorescence spectrum, η is the solvent refractive index, unk is the substance to be tested, and std is the standard reference.

[0249] The specific test results are shown in Table 1 below:

[0250] Table 1

[0251]

[0252] As shown in Table 1, the wear-resistant fluorescent waterborne polyurethane of the present invention has a tensile strength of more than 21 MPa, a wear resistance of more than 2000 g, excellent scratch resistance, weather resistance of more than 1550 h, and a fluorescence quantum yield of 100%. This fully demonstrates that the wear-resistant fluorescent waterborne polyurethane of the present invention has a high solid-state fluorescence quantum yield and excellent physical and mechanical properties.

[0253] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A wear-resistant fluorescent waterborne polyurethane, characterized in that: The raw materials for preparing the wear-resistant fluorescent waterborne polyurethane include the following components by weight: The perylene imide-modified monomer is centered on perylene imide, a cage-type polysilsesquioxane group is grafted to the nitrogen end of the perylene imide, and a triethylene glycol group is modified at the bay position of the perylene imide.

2. The wear-resistant fluorescent waterborne polyurethane according to claim 1, characterized in that: The oligomer polyol is selected from any one or a combination of at least two of poly(1,4-butylene adipate diol), poly(1,6-hexane adipate diol), polyoxypropylene polyol or polytetramethylene glycol; Preferably, the weight average molecular weight of the oligomer polyol is 500-4000.

3. The wear-resistant fluorescent waterborne polyurethane according to claim 1, characterized in that: The isocyanate is selected from any one or a combination of at least two of isophorone diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; Preferably, the hydrophilic monomer is selected from dimethylolpropionic acid and / or dimethylolbutanoic acid.

4. The wear-resistant fluorescent waterborne polyurethane according to claim 1, characterized in that: The chain extender is selected from any one or a combination of at least two of ethylene glycol, butanediol, hexanediol, ethylenediamine or diethylenetriamine; Preferably, the neutralizing agent is selected from any one or a combination of at least two of triethylamine, sodium hydroxide or ammonia water; Preferably, the catalyst is selected from an organotin catalyst and / or an organobismuth catalyst; Preferably, the organotin catalyst is selected from stannous octoate and / or butyltin dilaurate; Preferably, the organic bismuth catalyst is selected from any one of bismuth cyclohexaneate, bismuth isooctanoate or bismuth laurate, or a combination of at least two thereof.

5. A method for preparing a wear-resistant fluorescent waterborne polyurethane according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: (1) in the presence of a catalyst, a perylene imide-modified monomer, an oligomer polyol, an isocyanate and a hydrophilic monomer undergo a polymerization reaction to obtain a first product; (2) measuring the NCO value of the first product obtained in step (1), and after the NCO value of the first product reaches a range of 1 to 3, diluting and cooling the first product, and then adding a chain extender to carry out a chain extension reaction to obtain a second product; (3) measuring the NCO value of the second product obtained in step (1), and after the NCO value of the second product reaches a range of 1 to 2, diluting and cooling, and then adding a neutralizing agent to carry out a neutralization reaction to obtain a third product; (4) adding water to the third product under stirring, and removing the solvent after the post-chain extension reaction is complete to obtain the wear-resistant fluorescent waterborne polyurethane.

6. The method for preparing the wear-resistant fluorescent waterborne polyurethane according to claim 5, characterized in that: In step (1), the polymerization reaction temperature is 80-85° C., and the polymerization reaction time is 2-4 hours; Preferably, in step (2), the temperature after dilution and cooling is 70-75°C; Preferably, in step (2), the diluent used for dilution and cooling is butanone; Preferably, in step (2), the amount of the diluent added is 5 to 10 wt %; Preferably, in step (2), the temperature of the chain extension reaction is 70-75° C., and the time of the chain extension reaction is 1-3 h; Preferably, in step (3), the temperature after dilution and cooling is below 40°C; Preferably, in step (3), the diluent used for dilution and cooling is acetone; Preferably, in step (3), the amount of the diluent added is 5 to 10 wt %; Preferably, in step (3), the temperature of the neutralization reaction is below 40° C., and the time of the neutralization reaction is 20 to 40 minutes.

7. The method for preparing the wear-resistant fluorescent waterborne polyurethane according to claim 5, characterized in that: The perylene imide modified monomer is prepared by the following steps: (a) performing a bromination reaction on perylenetetracarboxylic dianhydride to obtain perylenetetracarboxylic dianhydride with bromine substituted at the bay position; (b) the bromine-substituted perylenetetracarboxylic dianhydride reacts with a cage-type polysilsesquioxane to obtain a compound POSS-PDIBr-POSS; (c) The compound POSS-PDIBr-POSS reacts with triethylene glycol to obtain the perylene imide modified monomer POSS-PDITEG-POSS.

8. The method for preparing the wear-resistant fluorescent waterborne polyurethane according to claim 7, characterized in that: In step (a), the specific steps of the bromination reaction are: Perylenetetracarboxylic dianhydride and concentrated sulfuric acid are mixed, stirred for the first time, iodine is added, stirred for the second time, and then the temperature is raised to the reaction temperature, and bromine is added dropwise to carry out bromination reaction to obtain a reaction solution containing perylenetetracarboxylic dianhydride with bromine substituted at the bay position; Preferably, in step (a), the ratio of the added amount of perylenetetracarboxylic dianhydride to concentrated sulfuric acid is 1 mol: (4-6) mL; Preferably, in step (a), the molar ratio of perylenetetracarboxylic dianhydride to iodine is 1:(0.01-0.05); Preferably, in step (a), the temperature of the first stirring and the second stirring are each independently 20 to 30° C., and the time of the first stirring and the second stirring are each independently 1 to 3 hours; Preferably, in step (a), the molar ratio of perylenetetracarboxylic dianhydride to bromine is 1:(1-3); Preferably, in step (a), the time for adding bromine dropwise is within 4 hours; Preferably, in step (a), the reaction temperature is 80-90° C., and the reaction time is 12-18 h.

9. The method for preparing the wear-resistant fluorescent waterborne polyurethane according to claim 7, characterized in that: In step (b), the specific steps of the reaction are: The cage-type polysilsesquioxane, perylenetetracarboxylic dianhydride substituted with bromine at the bay position, imidazole and o-dichlorobenzene are mixed, heated and stirred, then cooled, chloroform is added, and the mixture is dispersed in ethanol and hydrochloric acid solution to react to obtain a reaction solution containing the compound POSS-PDIBr-POSS; Preferably, in step (b), the molar ratio of the bromine-substituted perylenetetracarboxylic dianhydride at the bay position to the cage-type polysilsesquioxane is 1:(2-2.2); Preferably, in step (b), the mass ratio of the bromine-substituted perylenetetracarboxylic dianhydride at the bay position to imidazole is 1:(5-7); Preferably, in step (b), the temperature of the heating and stirring is 155-165° C., and the time of the heating and stirring is 2-4 hours; Preferably, in step (b), the volume ratio of the ethanol to the hydrochloric acid solution is 1:(0.8-1.2); Preferably, in step (b), the concentration of the hydrochloric acid solution is 1 to 3 mol / L; Preferably, in step (b), the reaction temperature is 20-30° C., and the reaction time is 8-16 h.

10. The method for preparing the wear-resistant fluorescent waterborne polyurethane according to claim 7, characterized in that: In step (c), the specific steps of the reaction are: The compound POSS-PDIBr-POSS is dissolved in tetrahydrofuran, and potassium carbonate, 18-crown-hexaether and triethylene glycol are added in sequence to react to obtain a reaction solution containing the perylene imide modified monomer; Preferably, in step (c), the molar ratio of the compound POSS-PDIBr-POSS, potassium carbonate, 18-crown-hexaether and triethylene glycol is 1:(3-5):(3-5):(2-2.2); Preferably, in step (c), the reaction temperature is 20 to 30° C., and the reaction time is 1 to 3 hours.

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