WO2023193476A1 - 一种具有荧光特性的水性聚氨酯涂料及其制备方法 - Google Patents

一种具有荧光特性的水性聚氨酯涂料及其制备方法 Download PDF

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WO2023193476A1
WO2023193476A1 PCT/CN2022/140261 CN2022140261W WO2023193476A1 WO 2023193476 A1 WO2023193476 A1 WO 2023193476A1 CN 2022140261 W CN2022140261 W CN 2022140261W WO 2023193476 A1 WO2023193476 A1 WO 2023193476A1
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water
rare earth
based polyurethane
organic complex
polyurethane coating
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PCT/CN2022/140261
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French (fr)
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路芳
史华红
麦裕良
李岱远
梁东
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佛山华铕光电材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/22—Luminous paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to the technical field of water-based coatings, and in particular to a water-based polyurethane coating with fluorescent properties and a preparation method thereof.
  • Water-based coatings are increasingly favored by people as an environmentally friendly coating material.
  • Water-based fluorescent coatings have low VOC content, are safe to paint, and cause little harm to construction workers and the surrounding environment. They emit fluorescence after being excited and can be used in anti-counterfeiting, lighting, decoration, public transportation and other fields, and have important promotion value.
  • the main fluorescent substances that can be used in fluorescent coatings are: 1. Inorganic luminescent materials, which have good stability but are difficult to disperse in aqueous media; 2. Traditional organic fluorescent materials are simple to synthesize and have certain solubility in aqueous media.
  • Organic rare earth luminescent materials These materials are simple to prepare, have high luminous intensity and good color purity, but have poor dispersion in aqueous media. Therefore, there is an urgent need for a fluorescent material that has obvious fluorescence phenomenon, good dispersion in aqueous media, no pollution and no toxicity, and is easy to use, easy to apply and promote.
  • the present invention solves the problems existing in the prior art and provides a water-based polyurethane coating with fluorescent characteristics and a preparation method thereof.
  • the water-based coating prepared by the rare earth organic complex proposed by the present invention has low VOC content and is safe in construction. After coating, It is transparent in appearance and has high gloss. Through the ultraviolet light-excited fluorescence characteristics of rare earth organic complexes, the coating has only ultraviolet light recognition properties after being coated and formed into a film.
  • the purpose of the invention is to provide a water-based polyurethane coating with fluorescent characteristics, which is composed of the following parts by mass of raw materials: 50 to 70 parts of water-based polyurethane, 5 to 40 parts of rare earth organic complex aqueous dispersion, and 0.5 to 2 parts of additives.
  • the rare earth organic complex is a rare earth organic complex with a structural formula of LnL 1 L 2 , where Ln represents the central rare earth ion, and Ln is selected from neodymium, europium, dysprosium, holmium, Any one of erbium, thulium, ytterbium and lutetium, L 1 represents the first organic ligand, L 1 is selected from bipyridine triazole compounds, phenanthroline triazole compounds, quinoline triazole compounds and compounds containing Any of the 1,2,3-triazole compounds substituted by nitrogen bidentate heterocyclic rings, L 2 represents the second organic ligand, and L 2 is selected from the group that can form N ⁇ N ⁇ N coordination with the central rare earth ion. Functionalized ionic liquids.
  • the water-based polyurethane coating is composed of the following parts by mass of raw materials: 50 to 68 parts by mass of water-based polyurethane, 6.5 to 40 parts of rare earth organic complex aqueous dispersion, 0.7 to 1.7 parts of additives, and 4 to 10 parts of alcohol. The remainder is water. Water can be added according to actual needs.
  • the rare earth organic complex used in the present invention has the advantages of good dispersion in aqueous medium, high fluorescence intensity and good photostability.
  • the water-based coating prepared by this rare earth organic complex has low VOC content and is safe to construct. It appears transparent and has high gloss after coating. Through the ultraviolet light-excited fluorescence characteristics of the rare earth organic complex, the coating has a Only UV recognition properties.
  • the L 2 is pyridine ditetrazole functionalized ionic liquid or terpyridine functionalized ionic liquid.
  • the rare earth organic complex is selected from at least one of the following compounds:
  • Ln is independently selected from any one of neodymium, europium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;
  • R 1 and R 2 are respectively selected from hydrogen or methyl;
  • R 3 is selected from trifluoromethyl or amino;
  • R 4 and R 5 are respectively selected from hydrogen or methyl;
  • R 6 is selected from trifluoromethyl or amino;
  • R 7 is selected from hydrogen or methyl; R 8 is selected from trifluoromethyl or amino.
  • the rare earth organic complex is prepared by the following steps: 1) preparation of LnL 1 ; 2) synthesis of the second ligand terpyridine functionalized ionic liquid Tpy-mim 2 ; 3) combining LnL 1 and Tpy- mim 2 was dispersed in methanol, reacted at 75°C-85°C for 3.5-4.5 hours under stirring, poured into diethyl ether, filtered, and the precipitate was washed with diethyl ether and dried to obtain the amphiphilic rare earth organic complex LnL 1 Tpy-mim 2 .
  • LnL 1 is bis[3-trifluoromethyl-5-(1,10-phenanthrolin-2-yl)-1,2,4-1H triazole] europium(III), bis[3-tri Fluoromethyl-5-(2,2'-bipyridin-6-yl)-1,2,4-1Htriazole]terbium(III) or bis[3-trifluoromethyl-5-(quinoline -2-yl)-1,2,4-1H triazole] europium (III).
  • Rare earth organic complex luminescent materials have the advantages of simple preparation, high luminous intensity, and good color purity.
  • currently commercialized rare earth organic complex luminescent materials generally have problems such as difficulty in dispersing in aqueous media and poor photostability, which limits their use in aqueous media. applications in the environment.
  • the present invention first uses bipyridine triazole compounds, phenanthroline triazole compounds, quinoline triazole compounds, nitrogen-containing bidentate heterocyclic substituted 1,2,3-triazole compounds, which have conjugated planes. and a compound with a stronger rigid structure as the first ligand to enhance the fluorescence emission intensity of the complex and improve the photostability. It has been reported that rare earth organic complexes with these structures have excellent photostability.
  • an ionic liquid containing nitrogen atoms is selected as the second ligand, which coordinates with rare earth ions through N ⁇ N ⁇ N to form an amphiphilic complex.
  • the rare earth complex is "solubilized" into the aqueous medium to improve the complex quality. Dispersibility in aqueous media.
  • the self-assembled aggregates of this amphiphilic rare earth complex can effectively shield the quenching effect produced by the solvent and the rare earth itself, thereby improving the energy between the ligand and the rare earth ion. transmission efficiency and further improve its luminous performance.
  • the mass ratio of LnL 1 to Tpy-mim 2 is 1:(1.2 ⁇ 2), the mass concentration of LnL 1 dispersed in methanol is 0.005 ⁇ 0.05g/mL, and the volume ratio of methanol to diethyl ether is 1 :(3 ⁇ 7). More preferably, the mass ratio of LnL 1 to Tpy-mim 2 is 1: (1.2-1.7), and the mass concentration of LnL 1 dispersed in methanol is 0.005-0.033g/mL.
  • the water-based polyurethane is water-based aliphatic anionic polyurethane resin or silicone-modified water-based polyurethane emulsion.
  • the solid content of the water-based polyurethane is 35% to 50%.
  • Water-based polyurethane uses water as the medium and has the advantages of low organic volatile emissions, high safety factor, and good low-temperature flexibility. It is the most ideal connecting material for water-based coatings.
  • the concentration of the rare earth organic complex in the rare earth organic complex aqueous dispersion is 0.01 to 0.1 g/mL. More preferably, the concentration of the rare earth organic complex is 0.02 to 0.08 g/mL.
  • the auxiliary agent includes one or more of wetting agent, defoaming agent, leveling agent and film-forming auxiliary agent. More preferably, the wetting agent is surface wetting agent FC-4430, the defoaming agent is defoaming agent BYK-019, and the mass ratio of wetting agent to defoaming agent is 3/4 to 8/9.
  • the present invention also protects the preparation method of the above-mentioned water-based polyurethane coating with fluorescent characteristics, which includes the following steps:
  • Methods for applying the water-based polyurethane coating include: dipping coating, coating coating, spray coating, spin coating, etc.
  • the present invention also protects the application of the above-mentioned water-based polyurethane coating with fluorescent properties in the fields of anti-counterfeiting, lighting, decoration or public transportation.
  • the present invention has the following advantages:
  • the present invention forms an amphiphilic complex by selecting appropriate amphiphilic ligands to coordinate with rare earth ions.
  • This complex is It has good dispersion in aqueous media, and also has the advantages of high fluorescence intensity and good photostability.
  • the first ligand selected for the rare earth organic complex proposed by the present invention enables the complex to have excellent luminescence properties and photostability, and the second ligand can form N ⁇ N ⁇ N coordination with the rare earth ions, giving the rare earth complex Good water dispersibility and stability.
  • the self-assembled aggregates of this amphiphilic rare earth organic complex can also effectively shield the quenching effect produced by the solvent and the rare earth itself, further improving its luminescence performance.
  • the first ligand and the second ligand can form a 9-coordination complex with rare earth ions, which effectively reduces the adverse effects of the coordination of water molecules in the aqueous medium on the luminescence intensity and stability of the complex.
  • the water-based polyurethane coating with fluorescent characteristics provided by the present invention is pollution-free and non-toxic, and is easy to popularize and apply.
  • Figure 1 is an excitation spectrum chart of the luminescent coating in Example 1.
  • Figure 2 is an emission spectrum chart of the luminescent coating in Example 1.
  • Figure 3 is a photograph of the luminescent coating in Example 1 under sunlight.
  • Figure 4 is a picture of the luminescent coating of Example 1 under ultraviolet light irradiation.
  • the surface wetting agent FC-4430 was purchased from 3M Company
  • the defoaming agent BYK-019 was purchased from BYK, Germany
  • the water-based polyurethane was purchased from Anhui Anda Huatai New Materials Co., Ltd., with the product number of AH-1502E13.
  • a method for preparing a water-based polyurethane coating with fluorescent properties including the following steps:
  • Step one start with Prepare N-oxy-1,10-phenanthroline as raw material, and then prepare 2-cyano-1,10-phenanthroline; the second step: use 2-cyano-1,10-phenanthroline Roline is used as raw material to prepare 3-trifluoromethyl-5-(1,10-phenanthrolin-2-yl)-1,2,4-1H triazole.
  • the relevant preparation is carried out with reference to patent CN 103172649 B.
  • Step 3 Reaction of 3-trifluoromethyl-5-(1,10-phenanthrolin-2-yl)-1,2,4-1H triazole and europium trichloride hexahydrate under alkaline conditions Bis[3-trifluoromethyl-5-(1,10-phenanthrolin-2-yl)-1,2,4-1H triazole] europium(III) was prepared.
  • Bis[3-trifluoromethyl-5-(1,10-phenanthrolin-2-yl)-1,2,4-1H triazole] europium(III) was prepared.
  • For related preparation please refer to patent CN113801651A. conduct.
  • Second ligand Tpy-mim 2 The preparation route is as follows:
  • FIG. 1 The excitation spectrum of the luminescent coating is shown in Figure 1. It can be seen from Figure 1 , Rare earth organic complexes have maximum absorption at wavelengths 273nm and 375nm, which correspond to ultraviolet light, indicating that rare earth organic complexes can absorb ultraviolet light for photoconversion.
  • Figure 2 shows the fluorescence emission spectrum of the luminescent coating. It can be seen that the characteristic fluorescence emission spectrum of the europium (III) element is produced in the wavelength range of 580 to 700nm.
  • Figure 3 is a photo of the transparent coating under sunlight. It can be seen that the coating coated on the PET film has the characteristics of high transmittance and low haze. The coating can emit uniform and strong red fluorescence under 365nm ultraviolet light, as shown in Figure 4.
  • a method for preparing a water-based polyurethane coating with fluorescent properties including the following steps:
  • Step one start with Prepare N-oxy-2,2'-bipyridine as raw material, and then prepare 6-cyano-2,2'-bipyridine; second step: use 6-cyano-2,2'-bipyridine as raw material 3-Trifluoromethyl-5-(2,2'-bipyridin-6-yl)-1,2,4-1H triazole was prepared.
  • the relevant preparation was carried out with reference to patent CN 103044466 B.
  • Step 3 Prepare by reacting 3-trifluoromethyl-5-(2,2'-bipyridin-6-yl)-1,2,4-1H triazole and terbium trichloride hexahydrate under alkaline conditions Bis[3-trifluoromethyl-5-(2,2'-bipyridin-6-yl)-1,2,4-1H triazole]terbium (III) is obtained.
  • the related preparation is carried out with reference to patent CN113801651A.
  • the coating can emit uniform green fluorescence under 365nm ultraviolet light.
  • a method for preparing a water-based polyurethane coating with fluorescent properties including the following steps:
  • Step one start with Prepare N-oxy-quinoline as raw material, and then prepare 2-cyanoquinoline; second step: use 2-cyanoquinoline as raw material to prepare 3-trifluoromethyl-5-(quinoline-2 -1,2,4-1H triazole, the related preparation is carried out with reference to patent CN 108191827 A.
  • the coating can emit uniform red fluorescence under 365nm ultraviolet light.
  • a method for preparing a water-based polyurethane coating with fluorescent properties including the following steps:
  • the coating can emit uniform and strong red fluorescence under 365nm ultraviolet light.
  • test items and test methods are as follows:
  • the functional film is tested for light transmittance and haze.
  • a fluorescence spectrometer was used to test the luminescence performance of the functional film. Test conditions: scanning speed 1200nm/min, photomultiplier tube voltage 400V, Slit (ex/em) 5.0nm/5.0nm.
  • the coating prepared by using the rare earth organic complex aqueous dispersion of the present invention has very good transparency and fluorescent properties.
  • the water-based polyurethane coating with fluorescent properties described in the present invention is beneficial to the development of water-based fluorescent coatings. Promotion and development are of practical significance.

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Abstract

一种具有荧光特性的水性聚氨酯涂料及其制备方法，该水性聚氨酯涂料由以下质量份的原料组成：水性聚氨酯50～70份，稀土有机配合物水分散液5～40份，助剂0.5～2份，酒精3～10份，余量为水；所述的稀土有机配合物是结构式为LnL1 L2的稀土有机配合物，其中，Ln表示中心稀土离子，Ln选自钕、铕、镝、钬、铒、铥、镱和镥中的任意一种，L1表示第一有机配体，L1选自联吡啶三唑类化合物、邻菲啰啉三唑类化合物、喹啉三唑类化合物和含氮双齿杂环取代的1,2,3‑三唑类化合物中的任意一种，L2表示第二有机配体，L2选自能与中心稀土离子形成N^N^N配位的功能化离子液体，该具有荧光特性的水性聚氨酯涂料无污染无毒害，易于推广应用。

Description

一种具有荧光特性的水性聚氨酯涂料及其制备方法 技术领域：
本发明涉及水性涂料技术领域，具体涉及一种具有荧光特性的水性聚氨酯涂料及其制备方法。
背景技术：
随着全球性环境污染和生态环境破坏程度的加剧，人们越来越关注生命，环保意识不断增强，水性涂料作为一种环境友好型涂料材料受到人们的日益青睐。水性荧光涂料VOC含量低，涂装安全，对施工人员和周围环境几乎没有伤害，激发后发射出荧光，可应用于防伪、照明、装饰、公共交通等领域，具有重要的推广价值。目前，可用于荧光涂料的荧光物质主要有：1、无机发光材料，其稳定性好，但在水性介质中难以分散；2、传统的有机荧光材料，合成简单，水性介质中有一定的溶解性，但多为日光激发，且多数发光不稳定；3、有机稀土发光材料，此类材料制备简单，发光强度高，色纯度好，但在水性介质中分散性差。因此，急需一种荧光现象明显，水性介质中分散性好，无污染无毒害，同时使用方便，易于应用和推广的荧光材料。
发明内容：
本发明解决了现有技术存在的问题，提供一种具有荧光特性的水性聚氨酯涂料及其制备方法，本发明提出的通过稀土有机配合物制备的水性涂料VOC含量低，施工安全，其涂布后表观透明且具有高光泽度，通过稀土有机配合物紫外光激发荧光的特性，使涂料涂布成膜后具有仅紫外光识别特性。
本发明的目的是提供一种具有荧光特性的水性聚氨酯涂料，由以下质量份的原料组成： 水性聚氨酯50～70份，稀土有机配合物水分散液5～40份，助剂0.5～2份，酒精3～10份，余量为水；所述的稀土有机配合物是结构式为LnL 1L 2的稀土有机配合物，其中，Ln表示中心稀土离子，Ln选自钕、铕、镝、钬、铒、铥、镱和镥中的任意一种，L 1表示第一有机配体，L 1选自联吡啶三唑类化合物、邻菲啰啉三唑类化合物、喹啉三唑类化合物和含氮双齿杂环取代的1,2,3-三唑类化合物中的任意一种，L 2表示第二有机配体，L 2选自能与中心稀土离子形成N^N^N配位的功能化离子液体。
优选地，所述的水性聚氨酯涂料，由以下质量份的原料组成：水性聚氨酯50～68份，稀土有机配合物水分散液6.5～40份，助剂0.7～1.7份，酒精4～10份，余量为水。水根据实际需要添加即可。
本发明采用的稀土有机配合物具有水性介质中分散性好，荧光强度高，光稳定性好的优点。这种稀土有机配合物制备的水性涂料VOC含量低，施工安全，其涂布后表观透明且具有高光泽度，通过稀土有机配合物紫外光激发荧光的特性，使涂料涂布成膜后具有仅紫外光识别特性。
优选地，所述的L 2为吡啶二四氮唑功能化离子液体或三联吡啶功能化离子液体。
优选地，所述的稀土有机配合物选自以下化合物中的至少一种：
Figure PCTCN2022140261-appb-000001
Figure PCTCN2022140261-appb-000002
其中，式(Ⅰ)、式(Ⅱ)和式(Ⅲ)中，Ln分别独立选自钕、铕、镝、钬、铒、铥、镱、镥中的任意一种；
式(Ⅰ)中，R 1、R 2分别选自氢或甲基；R 3选自三氟甲基或氨基；
式(Ⅱ)中，R 4、R 5分别选自氢或甲基；R 6选自三氟甲基或氨基；
式(Ⅲ)中，R 7选自氢或甲基；R 8选自三氟甲基或氨基。
进一步优选，所述的稀土有机配合物由如下步骤制备得到：1)LnL 1的制备；2)第二配体三联吡啶功能化离子液体Tpy-mim 2的合成；3)将LnL 1、Tpy-mim 2分散于甲醇中，搅拌下75℃-85℃反应3.5-4.5小时，倒入乙醚中，过滤，沉淀物用乙醚清洗，干燥，得到两亲性稀土有机配合物LnL 1Tpy-mim 2。
LnL 1为二[3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)、二[3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑]合铽(Ⅲ)或二[3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)。
稀土有机配合物发光材料具有制备简单，发光强度高，色纯度好的优点，但目前商业化 的稀土有机配合物发光材料普遍存在水性介质中难以分散及光稳定性差的问题，限制了其在水性环境中的应用。本发明首先采用联吡啶三唑类化合物、邻菲啰啉三唑类化合物、喹啉三唑类化合物、含氮双齿杂环取代的1,2,3-三唑类化合物这些具有共轭平面和刚性较强结构的化合物作为第一配体，增强配合物的荧光发射强度和提高光稳定性，已有报道证明这些结构的稀土有机配合物具有优异的光稳定性。接下来，选取含有氮原子的离子液体作为第二配体，与稀土离子通过N^N^N配位形成两亲性配合物，将稀土配合物“增溶”到水性介质中，提高配合物在水性介质中的分散性，此外，这种两亲性稀土配合物自主装得到的聚集体可以有效的屏蔽溶剂及稀土自身所产生的淬灭效应，从而改善配体与稀土离子之间的能量传递效率，进一步提高其发光性能。
进一步优选，所述的LnL 1与Tpy-mim 2的质量比为1:(1.2～2)，LnL 1分散于甲醇中的质量浓度为0.005～0.05g/mL，甲醇与乙醚的体积比为1：(3～7)。再进一步优选，所述的LnL 1与Tpy-mim 2的质量比为1:(1.2～1.7)，LnL 1分散于甲醇中的质量浓度为0.005～0.033g/mL。
优选地，所述的水性聚氨酯为水性脂肪族阴离子聚氨酯树脂或有机硅改性水性聚氨酯乳液。所述的水性聚氨酯的固含量为35％～50％。水性聚氨酯以水为介质，具有有机挥发物排放低、安全系数高、低温柔韧性好的优点，是水性涂料最理想的连接料。
优选地，所述的稀土有机配合物水分散液中稀土有机配合物的浓度为0.01～0.1g/mL。进一步优选，稀土有机配合物的浓度为0.02～0.08g/mL。
优选地，所述的助剂包括润湿剂，消泡剂，流平剂和成膜助剂中的一种或几种。进一步优选，润湿剂为表面润湿剂FC-4430，消泡剂为消泡剂BYK-019，润湿剂与消泡剂的质量比为3/4～8/9。
本发明还保护上述具有荧光特性的水性聚氨酯涂料的制备方法，包括以下步骤：
(1)将稀土有机配合物分散于水中，制成稀土有机配合物水分散液；
(2)将稀土有机配合物水分散液、酒精和助剂搅拌均匀后，加入水性聚氨酯，再根据需要补充水调整粘度后制得具有荧光特性的水性聚氨酯涂料。
涂布该水性聚氨酯涂料的方法，包括：浸渍涂布、涂覆涂布、喷射涂布及旋转涂布等。
本发明还保护上述具有荧光特性的水性聚氨酯涂料在防伪、照明、装饰或公共交通领域中的应用。
本发明与现有技术相比，具有如下优点：
(1)一般情况下，稀土有机配合物在水中难以分散，本发明根据相似相容原理，通过选用适宜的两亲性配体与稀土离子配位形成两亲性配合物，这种配合物在水性介质中分散性好，同时还具有荧光强度高，光稳定性好的优点。
(2)本发明提出的稀土有机配合物选用的第一配体使得配合物具有优异的发光性能和光稳定性，第二配体能与稀土离子形成N^N^N配位，赋予稀土配合物良好的水分散性和稳定性。这种两亲性稀土有机配合物自主装得到的聚集体还可以有效的屏蔽溶剂及稀土自身所产生的淬灭效应，进一步提高其发光性能。
(3)本发明中第一配体和第二配体可以与稀土离子形成9配位配合物，有效的降低了水性介质中水分子配位对配合物发光强度和稳定性的不利影响。
(4)本发明提供的具有荧光特性的水性聚氨酯涂料无污染无毒害，易于推广应用。
附图说明
图1为实施例1中的发光涂层的激发光谱图。
图2为实施例1中的发光涂层的发射光谱图。
图3为实施例1中的发光涂层在日光下的照片。
图4为实施例1的发光涂层在紫外灯照射下的图片。
具体实施方式：
以下实施例是对本发明的进一步说明，而不是对本发明的限制。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。除特别说明，本文中的实验材料和试剂均为本技术领域常规市购产品。
下述实施例中表面润湿剂FC-4430购自3M公司，消泡剂BYK-019购自德国毕克，水性聚氨酯购自安徽安大华泰新材料有限公司，货号为AH-1502E13。
实施例1
一种具有荧光特性的水性聚氨酯涂料的制备方法，包括如下步骤：
(1)二[3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)的制备二[3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)制备路线如下：
第一步：
Figure PCTCN2022140261-appb-000003
第二步：
Figure PCTCN2022140261-appb-000004
第三步：
Figure PCTCN2022140261-appb-000005
第一步：以
Figure PCTCN2022140261-appb-000006
为原料制备得到N-氧-1,10-邻菲罗啉，继而制得2-氰基-1,10-邻菲罗啉；第二步：以2-氰基-1,10-邻菲罗啉为原料制得3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑，相关的制备参照专利CN 103172649 B进行。
第三步：碱性条件下，3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑和六水合三氯化铕反应制得二[3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)，相关的制备参照专利CN113801651A进行。
(2)第二配体Tpy-mim 2的制备
第二配体Tpy-mim 2
Figure PCTCN2022140261-appb-000007
制备路线如下：
Figure PCTCN2022140261-appb-000008
化合物1的制备：
将4.84g 2-乙酰吡啶，3.32g 3,5-二甲氧基苯甲醛，3.08g KOH溶于100mL无水乙醇，加入60mL氢氧化铵水溶液(质量分数25％)，60℃下搅拌10h。过滤收集沉淀，用无水乙醇洗涤2次，之后用MeOH为溶剂进行重结晶，得到白色粉末状化合物1，产率为40％。
1H NMR(400MHz,CDCl 3,ppm)δ8.76(6H,m),7.99(2H,s),7.49(2H,s),7.07(2H,s),6.58(1H,s),3.94(6H,s)。
化合物2的制备：
将9.3g化合物1加入到150mL HBr水溶液(质量分数48wt％)中，130℃下搅拌6h。旋蒸除去溶剂，向剩余物中加入100mL饱和碳酸氢钠溶液，室温下搅拌2h。过滤，粗产物用无水乙醇重结晶，得到化合物2。产率为90％。
1H NMR(400MHz,DMSO-d 6,ppm)δ8.75(2H,d),8.69(2H,d),8.66(2H,s),8.08(2H,t),7.63(2H,m),6.83(2H,d),6.41(1H,s).
化合物3的制备：
称取3.4g化合物2，24.2g 1,6-二溴正己烷，6.9g K 2CO 3，加入300mL无水丙酮，N 2气氛下，80℃下回流搅拌24h。冷却后过滤，产物用CH 2CL 2洗涤2次。旋蒸除去有机溶剂，向剩余物中加入1000mL CH 2Cl 2，用饱和的NaCl溶液(3*500mL)萃取。加入无水Na 2SO 4干燥过夜，旋蒸除去有机溶剂，用硅胶色谱柱(PE/乙酸乙酯＝2/1)对产物进行提纯，得到白色粉末状化合物3，产率为84％。
1HNMR(400MHz,CDCl 3)δ8.85(6H,m),8.04(2H,s),7.57(2H,m),7.16(2H,s),6.51(1H,s),4.09(4H,m),3.38(4H,m),1.90(8H,dd),1.15(8H,s).
第二配体Tpy-mim 2的制备：
称取2g化合物3，1.64g 1-甲基咪唑，加入100mL乙腈，70℃搅拌10h。冷却后过滤，沉淀用乙腈洗涤2次，真空干燥得到产物，产率为85％。
1H NMR(400MHz,DMSO-d 6,ppm)δ9.15(2H,s),8.65(2H,d),8.75(2H,d),8.68(2H,s),8.16(2H,td),7.69(2H,d),7.65(2H,d),7.84(2H,dd),6.83(2H,d),6.53(1H,s),4.12(4H,t),4.03(4H,t),3.81(6H,s),1.83(4H,m),1.72(4H,m),1.48(4H,m),1.31(4H,m).
(3)稀土有机配合物水分散液的制备
将1g二[3-三氟甲基-5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)和1.2g Tpy-mim 2分散于100mL甲醇中，搅拌下80℃反应4小时，倒入300mL乙醚中，过滤，沉淀物用乙醚清洗三次，40℃干燥5h，得到两亲性稀土有机配合物。将2g上述两亲性稀土有机配合物分散于100mL水中，得到稀土有机配合物水分散液。
(4)具有荧光特性的水性聚氨酯涂料的制备
将0.8g表面润湿剂FC-4430，0.9g消泡剂BYK-019，10g酒精，40g步骤(3)制得 的稀土有机配合物水分散液，用高速分散机搅拌1h(转速600r/min)。加入50g水性聚氨酯AH-1502E13，用高速分散机继续搅拌1h(转速600r/min)，放置1h消泡，得到水性聚氨酯涂料。
用线棒涂布器把上述水性聚氨酯涂料均匀涂布于PET薄膜上，80℃下固化30min即可得透明涂层，该发光涂层的激发光谱如图1所示，从图1可以看出，稀土有机配合物在波长273nm和375nm处有最大吸收，这两处对应于紫外光，说明稀土有机配合物可以吸收紫外光进行光转换作用。图2为发光涂层的荧光发射光谱，可以看出在580～700nm波长范围内都产生了铕(Ⅲ)元素的特征荧光发射光谱，其中以λ cm＝619nm的 5D 0→ 7F 2电偶极跃迁的荧光相对强度为最强。图3为透明涂层在日光下的照片，可以看出涂布在PET薄膜上的涂层具有高透过率和低雾度的特点。该涂层在365nm紫外灯光照下可以发出均匀且强的红色荧光，如图4所示。
实施例2
一种具有荧光特性的水性聚氨酯涂料的制备方法，包括如下步骤：
(1)二[3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑]合铽(Ⅲ)的制备
二[3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑]合铽(Ⅲ)的制备路线如下：
第一步：
Figure PCTCN2022140261-appb-000009
第二步：
Figure PCTCN2022140261-appb-000010
第三步：
Figure PCTCN2022140261-appb-000011
第一步：以
Figure PCTCN2022140261-appb-000012
为原料制备得到N-氧-2,2’联吡啶，继而制得6-氰基-2,2’-联吡啶；第二步：以6-氰基-2,2’-联吡啶为原料制得3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑，相关的制备参照专利CN 103044466 B进行。
第三步：碱性条件下，3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑和六水合三氯化铽反应制得二[3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑]合铽(Ⅲ)，相关的制备参照专利CN113801651A进行。
(2)第二配体Tpy-mim 2的制备参照实施例1步骤(2)进行。
(3)稀土有机配合物水分散液的制备
将1g二[3-三氟甲基-5-(2,2’-联吡啶-6-基)-1,2,4-1H三唑]合铽(Ⅲ)和1.5g Tpy-mim 2分散于30mL甲醇中。搅拌下80℃反应4小时，倒入150mL乙醚中，过滤，沉淀物用乙醚清洗三次，40℃干燥5h得到两亲性稀土有机配合物。将2g上述稀土有机配合物分散于25mL水中，得到稀土有机配合物水分散液。
(4)具有荧光特性的水性聚氨酯涂料的制备
将0.6g表面润湿剂FC-4430，0.7g消泡剂BYK-019，6g酒精，7.5g步骤(3)制得 的稀土有机配合物水分散液，用高速分散机搅拌1h(转速600r/min)。加入68g水性聚氨酯AH-1502E13，用高速分散机继续搅拌1h(转速600r/min)，放置1h消泡，得到水性聚氨酯涂料。
用线棒涂布器把上述涂料均匀涂布于PET薄膜上，80℃下固化30min即可得透明涂层，该涂层在365nm紫外灯光照下可以发出均匀的绿色荧光。
实施例3
一种具有荧光特性的水性聚氨酯涂料的制备方法，包括如下步骤：
(1)二[3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)的制备
二[3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)的制备路线如下：
第一步：
Figure PCTCN2022140261-appb-000013
第二步：
Figure PCTCN2022140261-appb-000014
第三步：
Figure PCTCN2022140261-appb-000015
第一步：以
Figure PCTCN2022140261-appb-000016
为原料制备得到N-氧-喹啉，继而制得2-氰基喹啉；第二步：以2-氰基喹啉为原料制得3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑，相关的制备参照专利CN 108191827 A进行。
第三步：二[3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)的制备：将11.5g 3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑和2.5g六水合三氯化铕分别溶于50mL乙二醇：水(V:V＝1:3)的混合溶液中。3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑溶液中加入1.2g氢氧化钠，搅拌反应30min，再加入六水合三氯化铕溶液，室温搅拌反应8h。反应结束后减压蒸馏，固体在50℃下干燥3h，得到二[3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)。
(2)第二配体Tpy-mim 2的制备参照实施例1步骤(2)进行。
(3)稀土有机配合物水分散液的制备
将1g二[3-三氟甲基-5-(喹啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)和1.7g Tpy-mim 2分散于200mL甲醇中。搅拌下80℃反应4小时，倒入1400mL乙醚中，过滤，沉淀物用乙醚清洗三次，40℃干燥5h得到改性稀土有机配合物。将2g上述改性稀土有机配合物分散于35mL水中，得到稀土有机配合物水分散液。
(4)具有荧光特性的水性聚氨酯涂料的制备
将0.3g表面润湿剂FC-4430，0.4g消泡剂BYK-019，4g酒精，6.5g步骤(3)制得的稀土有机配合物水分散液，用高速分散机搅拌1h(转速600r/min)。加入55g水性聚氨酯AH-1502E13，用高速分散机继续搅拌1h(转速600r/min)，放置1h消泡，得到具有荧光特性的水性聚氨酯涂料。
用线棒涂布器把上述涂料均匀涂布于PET薄膜上，80℃下固化30min即可得透明涂层，该涂层在365nm紫外灯光照下可以发出均匀的红色荧光。
对比例1
一种具有荧光特性的水性聚氨酯涂料的制备方法，包括如下步骤：
(1)三[5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)的制备
稀土配合物三[5-(1,10-邻菲罗啉-2-基)-1,2,4-1H三唑]合铕(Ⅲ)的制备参照专利CN 103172649 B进行，其分子式如下所示：
Figure PCTCN2022140261-appb-000017
(2)具有荧光特性的水性聚氨酯涂料的制备
将0.8g表面润湿剂FC-4430，0.9g消泡剂BYK-019，10g酒精，0.8g步骤(1)制得的稀土有机配合物，用高速分散机搅拌1h(转速600r/min)。加入50g水性聚氨酯AH-1502E13，用高速分散机继续搅拌1h(转速600r/min)，放置1h消泡，得到水性聚氨酯涂料。
对比例2
(1)三[2-噻吩甲酰三氟丙酮]合铕(Ⅲ)的制备
将4.5g 2-噻吩甲酰三氟丙酮和2.5g六水合三氯化铕分别溶于50mL乙二醇：水(V:V＝1:3)的混合溶液中。将2-噻吩甲酰三氟丙酮溶液中加入1.2g氢氧化钠，搅拌反应30min。加入六水合三氯化铕溶液，室温搅拌反应8h。反应结束后减压蒸馏，固体在50℃下干 燥3h。
Figure PCTCN2022140261-appb-000018
(2)第二配体Tpy-mim 2的制备参照实施例1步骤(2)进行。
(3)稀土有机配合物水分散液的制备
将1g三[2-噻吩甲酰三氟丙酮]合铕(Ⅲ)和1.2g Tpy-mim 2分散于100mL甲醇中。搅拌下80℃反应4小时，倒入300mL乙醚中，过滤，沉淀物用乙醚清洗三次，40℃干燥5h得到两亲性稀土有机配合物。将2g上述两亲性稀土有机配合物分散于100mL水中，得到稀土有机配合物水分散液。
(4)具有荧光特性的水性聚氨酯涂料的制备
将0.8g表面润湿剂FC-4430，0.9g消泡剂BYK-019，10g酒精，40g步骤(3)制得的稀土有机配合物水分散液，用高速分散机搅拌1h(转速600r/min)。加入50g水性聚氨酯AH-1502E13，用高速分散机继续搅拌1h(转速600r/min)，放置1h消泡，得到具有荧光特性的水性聚氨酯涂料。
用线棒涂布器把上述涂料均匀涂布于PET薄膜上，80℃下固化30min即可得透明涂层，该涂层在365nm紫外灯光照下可以发出均匀且强的红色荧光。
性能测试
对实施例1～3和对比例1～2制得的功能膜(透明涂层)进行性能测试，测试项目及测试 方法如下：
1、透明性
按JIS K-7105试验方法，对功能膜进行透光率、雾度测试。
2)发光性能测试：
采用荧光光谱仪测试功能膜的发光性能。测试条件：扫描速度1200nm/min，光电倍增管电压400V，Slit(ex/em)为5.0nm/5.0nm。
测试结果如表1所示。
表1实施例1～3和对比例1～2制得的涂料外观和功能膜性能测试结果
Figure PCTCN2022140261-appb-000019
从以上测试结果可以充分说明，本发明采用稀土有机配合物水分散液制备的涂层具有非常好的透明性和荧光性能，本发明所述的具有荧光特性的水性聚氨酯涂料有利于水性荧光涂料的推广与发展，具有实际意义。
以上实施例的说明只是用于帮助理解本发明的技术方案及其核心思想，应当指出，对于本技术领域的技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

  1. 一种具有荧光特性的水性聚氨酯涂料，其特征在于，由以下质量份的原料组成：水性聚氨酯50～70份，稀土有机配合物水分散液5～40份，助剂0.5～2份，酒精3～10份，余量为水；所述的稀土有机配合物是结构式为LnL 1L 2的稀土有机配合物，其中，Ln表示中心稀土离子，Ln选自钕、铕、镝、钬、铒、铥、镱和镥中的任意一种，L 1表示第一有机配体，L 1选自联吡啶三唑类化合物、邻菲啰啉三唑类化合物、喹啉三唑类化合物和含氮双齿杂环取代的1,2,3-三唑类化合物中的任意一种，L 2表示第二有机配体，L 2选自能与中心稀土离子形成N^N^N配位的功能化离子液体。
  2. 根据权利要求1所述的水性聚氨酯涂料，其特征在于，所述的L 2为吡啶二四氮唑功能化离子液体或三联吡啶功能化离子液体。
  3. 根据权利要求1或2所述的水性聚氨酯涂料，其特征在于，所述的稀土有机配合物选自以下化合物中的至少一种：
    Figure PCTCN2022140261-appb-100001
    Figure PCTCN2022140261-appb-100002
    其中，式(Ⅰ)、式(Ⅱ)和式(Ⅲ)中，Ln分别独立选自钕、铕、镝、钬、铒、铥、镱、镥中的任意一种；
    式(Ⅰ)中，R 1、R 2分别选自氢或甲基；R 3选自三氟甲基或氨基；
    式(Ⅱ)中，R 4、R 5分别选自氢或甲基；R 6选自三氟甲基或氨基；
    式(Ⅲ)中，R 7选自氢或甲基；R 8选自三氟甲基或氨基。
  4. 根据权利要求3所述的水性聚氨酯涂料，其特征在于，所述的稀土有机配合物由如下步骤制备得到：1)LnL 1的制备；2)第二配体三联吡啶功能化离子液体Tpy-mim 2的合成；3)LnL 1与Tpy-mim 2反应制备两亲性稀土有机配合物LnL 1Tpy-mim 2。
  5. 根据权利要求4所述的水性聚氨酯涂料，其特征在于，所述的LnL 1与Tpy-mim 2的质量比为1：(1.2～2)，LnL 1分散于甲醇中的质量浓度为0.005～0.05g/mL，甲醇与乙醚的体积比为1：(3～7)。
  6. 根据权利要求1所述的水性聚氨酯涂料，其特征在于，所述的水性聚氨酯为水性脂肪族阴离子聚氨酯树脂或有机硅改性水性聚氨酯乳液。
  7. 根据权利要求1所述的水性聚氨酯涂料，其特征在于，所述的稀土有机配合物水分散液中稀土有机配合物的浓度为0.01～0.1g/mL。
  8. 根据权利要求1所述的水性聚氨酯涂料，其特征在于，所述的助剂包括润湿剂，消泡剂， 流平剂和成膜助剂中的一种或几种。
  9. 权利要求1-8任一项所述的具有荧光特性的水性聚氨酯涂料的制备方法，其特征在于，包括以下步骤：
    (1)将稀土有机配合物分散于水中，制成稀土有机配合物水分散液；
    (2)将稀土有机配合物水分散液、酒精和助剂搅拌均匀后，加入水性聚氨酯，再根据需要补充水调整粘度后制得具有荧光特性的水性聚氨酯涂料。
  10. 权利要求1-8任一项所述的具有荧光特性的水性聚氨酯涂料在防伪、照明、装饰或公共交通领域中的应用。
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