Rare earth complex, rare earth composition and preparation method and application thereof

Abstract

The invention relates to a rare earth complex, a rare earth composition and a preparation method and application thereof, the chemical composition general formula of the rare earth complex is (Ln1xLn2yLn31-x-y) n (A) 3, Ln1, Ln2 and Ln3 independently represent trivalent rare earth ions except Sc < 3 + > and Pm < 3 + > respectively, x + y is greater than or equal to 0 and less than or equal to 1, and n is equal to 1 or 2; a represents an organic ligand A, is selected from benzophenone ultraviolet absorbers, and has a structure shown as a formula (I). According to the rare earth complex provided by the invention, the benzophenone ultraviolet light absorber is adopted as a ligand, the stability is high, the functions of the benzophenone ultraviolet light absorber are reutilized, ultraviolet light absorption is enhanced, harmful ultraviolet light is converted into red light or infrared light, a good temperature conversion effect is generated by utilizing the heating effect of the benzophenone ultraviolet light absorber, and the cost is relatively low. Meanwhile, the rare earth composition prepared from the specific rare earth complex can be combined with a polymer matrix to prepare a rare earth polymer photo-thermal material, and the rare earth polymer photo-thermal material has good stability and weather resistance, is wide in application field and has great economic benefits.

Description

[0001] This application claims the priority of patent application No. 202311478466.8 (the prior application date is November 8, 2023, and the name of the invention is a rare earth complex, rare earth polymer luminescent material, and preparation method and application thereof). Technical Field

[0002] The present invention relates to the technical field of photothermal materials, and in particular to a rare earth complex, a rare earth composition, and a preparation method and application thereof. Background Art

[0003] In order to achieve efficient ultraviolet absorption, researchers have prepared a series of ultraviolet absorbers with efficient ultraviolet absorption properties. Ultraviolet absorbers can convert the absorbed high-energy ultraviolet light into harmless heat. According to their structure, they can be divided into benzophenones, salicylates, benzotriazoles, substituted acrylonitriles and triazines. Among them, benzophenone ultraviolet absorbers have become the most widely used ultraviolet absorbers because of their high ultraviolet absorption performance and selective absorption of ultraviolet light, as well as the advantages of optimizing their ultraviolet absorption ability and compatibility with the matrix by adjusting the groups on the chain segments. However, benzophenone ultraviolet absorbers also have their inherent disadvantages: such as easy sublimation and poor stability. Therefore, they can be complexed with metal ions to improve their stability and absorption performance and achieve synergistic effects.

[0004] Rare earth ions have a stable fluorescence effect and a long fluorescence lifetime due to their rich energy levels. They also generate heat through non-radiative transitions. Therefore, many scholars have combined the characteristics of the two to prepare some multifunctional photothermal therapeutic agents with good photoacoustic imaging (PA) and targeted photothermal therapy (PTT). Lanthanide rare earth elements have some effects that other materials cannot achieve as photothermal conversion materials. General photothermal materials can only convert light energy into heat energy and achieve the effect through thermal effects, while lanthanide rare earth elements such as neodymium (Nd), ytterbium (Yb), and erbium (Er) have both near-infrared fluorescence and photothermal effects. It can be applied to heating fabrics, fluorescence imaging, biological probes, photothermal therapy (PTT) materials and other fields.

[0005] Based on this, a good fluorescence effect is achieved by combining benzophenone complexes with rare earth ions, and the heating effect of red light and infrared light is fully utilized to achieve good photothermal performance. However, after the two form a complex, their molecular weight becomes larger, resulting in a decrease in the compatibility and stability of the rare earth complex in the polymer matrix. Therefore, it is of great significance to improve the compatibility and stability of the rare earth complex in the polymer matrix to improve the practical application performance of rare earth polymer photothermal materials. Summary of the invention

[0006] In order to solve the above technical problems, the purpose of the present invention is to provide a rare earth complex, a rare earth composition, and a preparation method and application thereof. The rare earth composition is obtained by modifying the rare earth complex, and then a rare earth polymer photothermal material with low production cost and good weather resistance (water washing resistance and aging resistance) is prepared.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a rare earth complex, the chemical composition formula of the rare earth complex is (Ln1 x Ln2 y Ln3 1-x-y ) n (A) 3 , where Ln1, Ln2 and Ln3 independently represent the 3+ and Pm 3+ Other trivalent rare earth ions, 0≤x+y≤1, n=1 or 2;

[0009] A represents an organic ligand A, which is selected from benzophenone ultraviolet absorbers, and has a structure as shown in formula (I):

[0010]

[0011] Among them, R 1 -R 9 are independently selected from hydrogen atoms, C 1 -C 12 Alkyl, C 1 -C 12 Alkoxy, hydroxyl, C 1 -C 12 Alkyleneoxy, C 1 -C 12 Alkyloxy, phenoxy, carboxyl, nitro, amino, C 1 -C 12 N-substituted amino, cyano, phenyl, halogen or C 1 -C 12 Any one of the halogen-substituted alkyl groups.

[0012] The rare earth complex provided by the present invention is combined with rare earth ions and benzophenone ultraviolet absorbers, and ultraviolet light can be converted into red light or near-infrared light, with good luminous intensity and stability, and can be doped with high concentrations of polymer matrix, and has good dispersibility. Benzophenone ultraviolet absorbers have good stability themselves, and can strongly absorb ultraviolet light of 290-380nm at the same time. The aromatic ring structure in the structure can produce fierce π-π* electronic transitions when excited by ultraviolet light. At the same time, since ligand A has multiple coordination sites, through the effect of deprotonation of phenolic hydroxyl groups, the effects of coordinated coordination bonds and metal bonds can be coordinated with rare earth ions, and heteronuclear rare earth ions are added at the same time, which can produce the effect of energy concentration to the luminescent center, and can significantly improve the luminous intensity of the complex, and convert it into red light or near-infrared light under the excitation of ultraviolet light, thereby realizing the characteristics of photoluminescence, and then through the effect of red light and infrared light heating, the harmful ultraviolet light is converted into a rising temperature. Moreover, since benzophenone ultraviolet absorbers have long carbon chains, they are conducive to being dispersed in polymer matrix and improving compatibility. Since benzophenone ultraviolet absorbers and inert rare earth ions are easily available, the production cost is relatively low.

[0013] Among them, the value of x+y is 0-1, for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0014] Preferably, the value of x is 0-1, for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0015] Preferably, the value of y is 0-1, for example, it can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0016] Further preferably, the C 1 -C 12 The alkoxy group includes C 1 -C 12 It is any one of the straight-chain alkoxy groups, preferably any one of the methoxy group, the ethoxy group, the straight-chain octyloxy group or the straight-chain dodecyloxy group.

[0017] Preferably, the organic ligand A comprises

[0018] Any one of .

[0019] Preferably, the trivalent rare earth ions include Eu 3+ 、Sm 3+ , Yb 3+ , Er 3+ ,La 3+ , Y 3+ 、Nd 3+ or Gd 3+ Any one or a combination of at least two of the following, typical but non-limiting combinations include Eu 3+ with La 3+ The combination of Eu 3+ With Y 3+ The combination of Eu 3+ With Gd 3+ Combination of Nd 3+ with La 3+ Combination of Nd 3+ With Y 3+ Combination of Nd 3+ With Gd 3+ Combination of Sm 3+ With Y 3+ The combination of Yb 3+ With Gd 3+ The combination of Eu 3+ 、Sm 3+ with La 3+ The combination of Yb 3+ , Er 3+ With Gd 3+ A combination of, or, Eu 3+ 、Nd 3+ ,La 3+ , Y 3+ With Gd 3+ Combination of, preferably Eu 3+ 、Nd 3+ ,La 3+ , Y 3+ or Gd 3+ Any one or a combination of at least two.

[0020] In a second aspect, the present invention provides a method for preparing the rare earth complex as described in the first aspect, the preparation method comprising the following steps:

[0021] The rare earth salt, the organic ligand and the alkaline substance are mixed and reacted.

[0022] Preferably, the rare earth salt comprises any one of rare earth nitrate, rare earth chloride, rare earth sulfate, rare earth nitrate hydrate, rare earth chloride hydrate or rare earth sulfate hydrate, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of rare earth nitrate and rare earth chloride, a combination of rare earth chloride and rare earth sulfate, a combination of rare earth nitrate and rare earth sulfate, a combination of rare earth nitrate, rare earth chloride hydrate and rare earth sulfate hydrate, or a combination of rare earth chloride, rare earth sulfate and rare earth nitrate hydrate.

[0023] Further preferably, the rare earth salt includes europium nitrate, europium trichloride, europium nitrate hexahydrate, europium trichloride hexahydrate, samarium nitrate, samarium trichloride, samarium nitrate hexahydrate, samarium trichloride hexahydrate, neodymium nitrate, neodymium trichloride, neodymium nitrate hexahydrate, neodymium trichloride hexahydrate, ytterbium nitrate, ytterbium trichloride, ytterbium nitrate hexahydrate, ytterbium trichloride hexahydrate, erbium nitrate, erbium trichloride, erbium nitrate hexahydrate, erbium trichloride hexahydrate, lanthanum nitrate, lanthanum trichloride, lanthanum nitrate hexahydrate, lanthanum trichloride hexahydrate, yttrium nitrate, yttrium trichloride, yttrium nitrate hexahydrate, yttrium trichloride hexahydrate, gadolinium nitrate, gadolinium trichloride, gadolinium nitrate hexahydrate or gadolinium trichloride hexahydrate, any one or a combination of at least two.

[0024] Preferably, the molar ratio of the rare earth salt to the organic ligand is (1-5):1, for example, 1:1, 2:1, 3:1, 4:1 or 5:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] Preferably, the alkaline substance comprises any one of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate, potassium carbonate, aqueous ammonia or triethylamine, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of sodium hydroxide and sodium bicarbonate, a combination of sodium carbonate and potassium hydroxide, a combination of aqueous ammonia and triethylamine, a combination of sodium hydroxide, potassium carbonate and aqueous ammonia, or a combination of potassium hydroxide, sodium bicarbonate and triethylamine, preferably sodium hydroxide and / or potassium hydroxide.

[0026] Preferably, the mixing is carried out in a solvent as a medium. Exemplarily, the solvent includes ethanol.

[0027] Preferably, the reaction temperature is 50-60°C, for example, 50°C, 52°C, 54°C, 55°C, 56°C, 58°C or 60°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] Preferably, the reaction time is 6-24 h, for example, 6 h, 10 h, 15 h, 20 h or 24 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] Preferably, the reaction is followed by purification and drying.

[0030] Preferably, the reagent used for purification includes an organic solvent.

[0031] Preferably, the organic solvent comprises any one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, ether, dimethylformamide or dimethyl sulfoxide, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of toluene and ethyl acetate, a combination of acetone and tetrahydrofuran, a combination of dichloromethane and tetrachloromethane, a combination of toluene, ethyl acetate and acetone, a combination of tetrahydrofuran, dichloromethane and tetrachloromethane, or a combination of ether, dimethylformamide and dimethyl sulfoxide.

[0032] In a third aspect, the present invention provides a rare earth composition, which comprises a base resin, an accelerator, a curing agent and the rare earth complex described in the first aspect.

[0033] In the present invention, the rare earth complex is dispersed in the matrix resin, which can effectively protect the rare earth complex from oxidative decomposition, aggregation quenching or long-term ultraviolet light irradiation inactivation, thereby improving its stability. Combined with the specific combination of the accelerator and the curing agent, the rare earth complex can be modified so that the prepared rare earth polymer photothermal material has good weather resistance.

[0034] Preferably, the base resin comprises any one of oils, natural resins, phenolic resins, asphalt resins, alkyd resins, amino resins, nitrocellulose resins, epoxy resins, acrylic resins or polyester resins, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of oils and natural resins, a combination of phenolic resins and asphalt resins, a combination of alkyd resins and amino resins, a combination of nitrocellulose resins and epoxy resins, a combination of acrylic resins and polyester resins, or a combination of oils, epoxy resins and acrylic resins.

[0035] Preferably, the accelerator includes any one of cobalt naphthenate, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), benzyldimethylamine (BDMA), triethylamine, triethanolamine, o-hydroxybenzyldimethylamine (DMP-10), N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea, N-(5-chloro-2-hydroxybenzene)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea, N-(4-chloro-2-hydroxybenzene)-N',N'-dimethylurea, phenol, o-cresol, and a boron trifluoride complex, or a combination of at least two thereof.

[0036] Preferably, the mass of the accelerator is 0.1-1wt% of the base resin, for example, it can be 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt% or 0.9wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0037] Preferably, the curing agent includes any one of methyl ethyl ketone peroxide, N,N-dimethylethanolamine, bisphenol A, nonylphenol, resorcinol, m-phenylenediamine, tertiary amines, imidazole derivatives, substituted ureas, organic guanidine derivatives, acetylacetone or triphenylphosphine, or a combination of at least two thereof.

[0038] Preferably, the mass of the curing agent is 0.1-1wt% of the base resin, for example, it can be 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt% or 0.9wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] Preferably, the mass of the rare earth complex is 0.1-10wt% of the base resin, for example, it can be 0.2wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt% or 9wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0040] Preferably, the rare earth composition further comprises a dispersant and other additives.

[0041] Preferably, the dispersant includes any one of a cationic dispersant, an anionic dispersant, an electrically neutral dispersant, a nonionic dispersant or a polymeric super dispersant, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of a cationic dispersant and an electrically neutral dispersant, a combination of an anionic dispersant and a nonionic dispersant, a combination of a polymeric super dispersant and a cationic dispersant, or a combination of a cationic dispersant, a nonionic dispersant and a polymeric super dispersant.

[0042] Preferably, the mass of the dispersant is 0-30wt% of the base resin, for example, it can be 0.2wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt% or 28wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0043] Preferably, the other additives include any one of a drying agent, a toughening agent, an emulsifier, a thickener, a defoamer, a leveling agent, an anti-skinning agent, a matting agent, a mildew preventer or an antistatic agent, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of a drying agent and a toughening agent, a combination of an emulsifier and a thickener, a combination of a defoamer and a leveling agent, a combination of an anti-skinning agent and a matting agent, a combination of a mildew preventer and an antistatic agent, or a combination of a drying agent, a defoamer and a leveling agent.

[0044] Preferably, the mass of the other additives is 0-10wt% of the base resin, for example, it can be 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 2wt%, 5wt%, 8wt% or 10wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] In a fourth aspect, the present invention provides a method for preparing the rare earth composition according to the third aspect, the preparation method comprising the following steps:

[0046] The base resin, the rare earth complex, the accelerator and the curing agent are mixed to obtain the rare earth composition.

[0047] Preferably, the mixing is performed in a solvent.

[0048] Preferably, the solvent comprises any one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, ether, dimethylformamide or dimethyl sulfoxide, or a combination of at least two thereof.

[0049] In a fifth aspect, the present invention provides an application of the rare earth composition as described in the third aspect, wherein the rare earth composition is applied to any one of warming clothing, fluorescent coating, anti-counterfeiting coating or agricultural film;

[0050] Alternatively, the rare earth composition is applied to metal surface modification, solar cell surface modification, ceramic surface modification or preparation of photothermal therapy materials.

[0051] The rare earth composition provided by the present invention significantly improves its compatibility, dispersibility and stability through the combination of specific raw materials, making its application more convenient, greatly expanding its application field, and further improving its economic benefits.

[0052] In a sixth aspect, the present invention provides a rare earth polymer photothermal material, which comprises a polymer matrix and the rare earth composition described in the third aspect.

[0053] In the present invention, the base resin contained in the specific rare earth composition has good compatibility with the polymer matrix, so that a "bridge" can be built between the rare earth complex and the polymer matrix, promoting the complex combination between the rare earth complex and the polymer matrix, thereby improving the stability and weather resistance of the obtained rare earth polymer photothermal material.

[0054] Preferably, the polymer matrix includes any one of low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, polyacrylic acid, polyvinyl alcohol, polybutene, ethylene-vinyl acetate resin, polymethyl methacrylate, polyvinyl chloride, polyester, nylon, acrylic fiber, polypropylene, vinylon or chlorofiber, or a combination of at least two thereof. Typical but non-limiting combinations include a combination of low-density polyethylene and polypropylene, a combination of linear low-density polyethylene and polyacrylic acid, a combination of medium-density polyethylene and polyvinyl alcohol, a combination of high-density polyethylene and polybutene, a combination of ethylene-vinyl acetate resin, polymethyl methacrylate and polyester, a combination of polyvinyl chloride, nylon and acrylic fiber, or a combination of polypropylene, vinylon and chlorofiber.

[0055] Preferably, the mass ratio of the polymer matrix to the rare earth complex in the rare earth composition is 1:(0.001-0.1), for example, it can be 1:0.002, 1:0.004, 1:0.006, 1:0.008, 1:0.01, 1:0.02, 1:0.05, 1:0.08 or 1:0.09, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, and it is further preferably 1:(0.002-0.02).

[0056] In the present invention, the polymer matrix is ​​matched with the specific content of the rare earth complex in the specific rare earth composition, so that the obtained rare earth polymer photothermal material can effectively reduce the usage of the rare earth complex while maintaining good weather resistance, thereby reducing the economic cost.

[0057] In a seventh aspect, the present invention provides a method for preparing the rare earth polymer photothermal material as described in the sixth aspect, the preparation method comprising the following steps:

[0058] The rare earth composite is combined with a polymer matrix to obtain the rare earth polymer photothermal material.

[0059] In the present invention, the rare earth composition formed by the specific combination of the base resin, the accelerator and the curing agent can achieve good protection of the rare earth complex, making the rare earth complex not easy to migrate and having good dispersibility. Not only the compatibility of the rare earth complex in the polymer matrix in the prepared rare earth polymer photothermal material is greatly improved, but also its stability is improved, thereby improving the stability and weather resistance of the obtained rare earth polymer photothermal material.

[0060] Preferably, the combined method includes any one of dipping, spraying, brushing, and electrospinning, or a combination of at least two of them. Typical but non-limiting combinations include a combination of dipping and coating, a combination of dipping and spraying, a combination of brushing and electrospinning, a combination of dipping and electrostatic spraying, or a combination of dipping, spraying, and electrospinning.

[0061] Further preferably, the combining method is spraying and / or brushing.

[0062] Compared with the dipping process, the spraying or brushing process is more convenient to operate and can well control the dosage of the rare earth composition, thereby achieving the purpose of regulating the loading amount of the rare earth complex; at the same time, local spraying or brushing can be performed according to actual conditions, which has strong operability, not only saving costs, but also enabling the rare earth composition to form a film on the surface of the polymer matrix, thereby improving its weather resistance (water washing and aging resistance); compared with the electrospinning process, the spraying or brushing process conditions have simpler and milder requirements, strong plasticity, more convenient operation and the scope of action can be limited to the surface, thereby achieving efficient utilization of the rare earth composition and saving costs.

[0063] Compared with the prior art, the present invention has at least the following beneficial effects:

[0064] (1) The rare earth complex provided by the present invention uses a benzophenone ultraviolet absorber as a ligand, has strong stability, reuses the function of the benzophenone ultraviolet absorber, enhances ultraviolet absorption, converts harmful ultraviolet light into red light or infrared light, and utilizes its thermogenic effect to produce a temperature conversion effect, and has low cost; further, the prepared rare earth composition is combined with a polymer matrix through a specific combining process to prepare a specific rare earth polymer photothermal material. Compared with the used benzophenone ligand itself, the rare earth polymer photothermal material has a unique structural property, so that its ultraviolet absorption ability is improved, and has a stronger photothermal conversion performance.

[0065] (2) The present invention obtains a rare earth composite by modifying a specific rare earth complex with a base resin, a promoter and a curing agent, etc., which can better protect the rare earth complex and effectively avoid the risk of structural destruction due to long-term ultraviolet light irradiation, thereby significantly reducing its stability; at the same time, it can also improve the compatibility and dispersibility of the rare earth composite with the polymer matrix, thereby further improving the stability and weather resistance of the obtained photothermal material. Combined with the advantages of the spraying process, the application of the obtained polymer photothermal material can be more convenient, greatly expanding its application field, and thus improving its economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1The temperature-time variation curves of the materials obtained in Application Example 3, Application Example 6, Comparative Application Example 1 and Comparative Application Example 3 under 340nm ultraviolet light irradiation;

[0067] Figure 2 This is a diagram showing the water washability test results of Application Example 6;

[0068] Figure 3 This is a diagram of the water washability test results of comparative application example 4. DETAILED DESCRIPTION

[0069] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following examples are only simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0070] The information of some raw materials used in the following examples, comparative examples and application examples is as follows:

[0071] 901 vinyl resin: purchased from SWAN COR 901 from SWAN New Materials Technology Co., Ltd.

[0072] Epoxy resin E44: purchased from Shandong Mantanghong New Materials Co., Ltd., 61788-97-4;

[0073] Dispersant: Japanese Kuraray PVA-105, purchased from Guangzhou Qihua Chemical Co., Ltd.;

[0074] Methyl ethyl ketone peroxide was purchased from Shangwei New Materials Technology Co., Ltd.;

[0075] Metaphenylenediamine: purchased from Shandong Mantanghong New Materials Co., Ltd.

[0076] Cobalt naphthenate: purchased from Shangwei New Materials Technology Co., Ltd.;

[0077] 2,4,6-Tris(dimethylaminomethyl)phenol (DMP-30): purchased from Shandong Mantanghong New Materials Co., Ltd.

[0078] Other raw materials and reagents are commercially available unless otherwise specified.

[0079] Preparation Example 1

[0080] This preparation example provides a rare earth complex, the chemical composition formula of which is Eu 0.5 Y 0.5 (A) 3 , where A represents an organic ligand, and its structure is shown below:

[0081]

[0082] The preparation method of the rare earth complex is as follows:

[0083] (1) dissolving 0.5 mmol of europium chloride hexahydrate and 0.5 mmol of yttrium chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0084] (2) dissolving 3.0 mmol A in 40 mL of anhydrous ethanol and 3.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution of A and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0085] (3) Slowly drop the rare earth anhydrous ethanol solution described in step (1) into the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, the reaction is carried out for 24 hours. After the reaction is completed, the solvent is dried by rotary evaporator, and organic solvent toluene is added to dissolve it, and the insoluble matter is removed. The mixture is purified by natural volatilization, and vacuum dried at 40° C. for 24 hours to obtain a yellow solid.

[0086] Preparation Example 2

[0087] This preparation example provides a rare earth complex, the chemical composition formula of which is Eu 0.5 La 0.5 (A) 3 , where A represents an organic ligand, the results are as follows:

[0088]

[0089] The preparation method of the rare earth complex is as follows:

[0090] (1) dissolving 0.5 mmol of europium chloride hexahydrate and 0.5 mmol of lanthanum chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0091] (2) dissolving 3.0 mmol A in 40 mL of anhydrous ethanol and 3.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution of A and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0092] (3) Slowly drop the rare earth anhydrous ethanol solution described in step (1) into the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, the reaction is carried out for 24 hours. After the reaction is completed, the solvent is dried by rotary evaporator, and organic solvent toluene is added to dissolve it, and the insoluble matter is removed. The mixture is purified by natural volatilization, and vacuum dried at 40° C. for 24 hours to obtain a yellow solid.

[0093] Preparation Example 3

[0094] This preparation example provides a rare earth complex, the chemical composition formula of which is Eu(A): 3 , where A represents an organic ligand, and its structure is shown below:

[0095]

[0096] The preparation method of the rare earth complex is as follows:

[0097] (1) dissolving 1.0 mmol of europium chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0098] (2) dissolving 3.0 mmol A in 40 mL of anhydrous ethanol and 3.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution of A and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0099] (3) Slowly drop the rare earth anhydrous ethanol solution described in step (1) into the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, the reaction is carried out for 24 hours. After the reaction is completed, the solvent is dried by rotary evaporator, and organic solvent toluene is added to dissolve it, and the insoluble matter is removed. The mixture is purified by natural volatilization, and vacuum dried at 40° C. for 24 hours to obtain a yellow solid.

[0100] Preparation Example 4

[0101] This preparation example provides a rare earth complex, the chemical composition formula of which is Eu 0.4 Nd 0.4 Y 0.2 (A) 3 , where A represents an organic ligand, the results are as follows:

[0102]

[0103] The preparation method of the rare earth complex is as follows:

[0104] (1) dissolving 0.4 mmol of europium chloride hexahydrate, 0.4 mmol of neodymium chloride hexahydrate, and 0.2 mmol of yttrium chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0105] (2) dissolving 3.0 mmol A in 40 mL of anhydrous ethanol and 3.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution of A and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0106] (3) Slowly drop the rare earth anhydrous ethanol solution described in step (1) into the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, the reaction is carried out for 24 hours. After the reaction is completed, the solvent is dried by rotary evaporator, and organic solvent toluene is added to dissolve it, and the insoluble matter is removed. The mixture is purified by natural volatilization, and vacuum dried at 40° C. for 24 hours to obtain a yellow solid.

[0107] Preparation Example 5

[0108] This preparation example provides a rare earth complex, the chemical composition formula of which is Nd 2 (A) 3 , where A represents an organic ligand, and its structure is shown below:

[0109]

[0110] (1) dissolving 2.0 mmol of neodymium chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0111] (2) dissolving 3.0 mmol A in 40 mL of anhydrous ethanol and 6.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution of A and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0112] (3) Slowly drop the rare earth anhydrous ethanol solution described in step (1) into the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, the reaction is carried out for 24 hours. After the reaction is completed, the solvent is dried by rotary evaporator, and organic solvent toluene is added to dissolve it, and the insoluble matter is removed. The mixture is purified by natural volatilization, and vacuum dried at 40° C. for 24 hours to obtain a yellow solid.

[0113] Preparation Example 6

[0114] This preparation example provides a rare earth complex, the chemical composition formula of which is Er(A): 3 , where A represents an organic ligand, and its structure is shown below:

[0115]

[0116] The preparation method of the rare earth complex is as follows:

[0117] (1) dissolving 1.0 mmol of erbium chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0118] (2) dissolving 3.0 mmol A in 40 mL of anhydrous ethanol and 3.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution of A and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0119] (3) Slowly drop the rare earth anhydrous ethanol solution described in step (1) into the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, the reaction is carried out for 24 hours. After the reaction is completed, the solvent is dried by rotary evaporator, and organic solvent toluene is added to dissolve it, and the insoluble matter is removed. The mixture is purified by natural volatilization, and vacuum dried at 40° C. for 24 hours to obtain a yellow solid.

[0120] Comparative Preparation Example 1

[0121] This comparative preparation example provides a rare earth complex, which has the same chemical composition formula as Preparation Example 1. The only difference between the rare earth complex and Preparation Example 1 is that sodium hydroxide is not added in step (2) of the preparation method of the rare earth complex, and other raw materials, amounts and preparation methods are the same as those in Preparation Example 1.

[0122] Comparative Preparation Example 2

[0123] This preparation example provides a rare earth complex, the chemical composition formula of which is Eu(B): 3 , where B is cinnamic acid, and its structure is shown below:

[0124]

[0125] The preparation method of the rare earth complex is as follows:

[0126] (1) dissolving 1.0 mmol of europium chloride hexahydrate in 10 mL of anhydrous ethanol to obtain a rare earth anhydrous ethanol solution;

[0127] (2) dissolving 3.0 mmol B in 40 mL of anhydrous ethanol and 3.0 mmol sodium hydroxide in 10 mL of anhydrous ethanol; mixing the anhydrous ethanol solution containing B and the anhydrous ethanol solution of sodium hydroxide to obtain a mixed anhydrous ethanol solution;

[0128] (3) Slowly dropwise add the rare earth anhydrous ethanol solution described in step (1) to the mixed anhydrous ethanol solution described in step (2) under stirring at 50° C. After the dropwise addition is completed, react for 24 hours. After the reaction is completed, use a rotary evaporator to dry the solvent, add an organic solvent toluene to dissolve it, remove insoluble matter, purify it by natural volatilization, and dry it in vacuo at 40° C. for 24 hours to obtain a white solid.

[0129] Example 1

[0130] This embodiment provides a rare earth composition, which includes 901 vinyl resin, cobalt naphthenate, methyl ethyl ketone peroxide and the rare earth complex Eu described in Preparation Example 1. 0.5 Y 0.5 (A) 3 .

[0131] The preparation method of the rare earth composition is as follows:

[0132] Weigh 0.03g of rare earth complex Eu 0.5 Y 0.5 (A) 3 , after adding 30 mL of acetone to dissolve, 1.2 g of 901 vinyl resin, 12 mg of cobalt cyclohexaneate and 12 mg of methyl ethyl ketone peroxide were added and mixed to obtain the rare earth composition.

[0133] Example 2

[0134] This embodiment provides a rare earth composition, which is different from the embodiment 1 only in that the rare earth complex Eu prepared in the preparation example 1 is 0.5 Y 0.5 (A) 3 Replaced with the rare earth complex Eu described in Preparation Example 2 0.5 La 0.5 (A) 3 , other raw materials, amounts and preparation methods are the same as those in Example 1.

[0135] Example 3

[0136] This embodiment provides a rare earth composition, which is different from the embodiment 1 only in that the rare earth complex Eu prepared in the preparation example 1 is 0.5 Y 0.5 (A) 3 Replaced with the rare earth complex Eu(A) described in Preparation Example 3 3 , other raw materials, amounts and preparation methods are the same as those in Example 1.

[0137] Example 4

[0138] This embodiment provides a rare earth composition, which is different from the embodiment 1 only in that the rare earth complex Eu prepared in the preparation example 1 is 0.5 Y 0.5 (A) 3 Replaced with the rare earth complex Eu described in Preparation Example 4 0.4 Nd 0.4 Y 0.2 (A) 3 , other raw materials, amounts and preparation methods are the same as those in Example 1.

[0139] Example 5

[0140] This embodiment provides a rare earth composition, which is different from the embodiment 1 only in that the rare earth complex Eu prepared in the preparation example 1 is 0.5 Y 0.5 (A) 3 Replaced with the rare earth complex Nd described in Preparation Example 5 2 (A) 3 , other raw materials, amounts and preparation methods are the same as those in Example 1.

[0141] Example 6

[0142] This embodiment provides a rare earth composition, which is different from the embodiment 1 only in that the rare earth complex Eu prepared in the preparation example 1 is 0.5 Y 0.5 (A) 3 Replaced with the rare earth complex Er(A) described in Preparation Example 6 3 , other raw materials, amounts and preparation methods are the same as those in Example 1.

[0143] Example 7

[0144] This embodiment provides a rare earth composition, which includes epoxy resin E44, 2,4,6-tris(dimethylaminomethyl)phenol, m-phenylenediamine and the rare earth complex Eu described in Preparation Example 1. 0.5 Y 0.5 (A) 3 .

[0145] The preparation method of the rare earth composition is as follows:

[0146] Weigh 1.2 mg of rare earth complex Eu 0.5 Y 0.5 (A) 3 , after adding 30 mL of tetrahydrofuran to dissolve, 1.2 g of base resin, 1.2 mg of accelerator and 1.2 mg of curing agent were added and mixed to obtain the rare earth composition.

[0147] Example 8

[0148] This embodiment provides a rare earth composition, which includes 901 vinyl resin, cobalt naphthenate, a dispersant, methyl ethyl ketone peroxide and the rare earth complex Eu described in Preparation Example 1. 0.5 Y 0.5 (A) 3 .

[0149] The preparation method of the rare earth composition is as follows:

[0150] Weigh 0.12g of rare earth complex Eu 0.5 Y 0.5 (A) 3, after adding 30 mL of ethyl acetate to dissolve, 1.2 g of 901 vinyl resin, 6 mg of cobalt cyclohexaneate, 0.36 g of dispersant and 9 mg of methyl ethyl ketone peroxide were added and mixed to obtain the rare earth composition.

[0151] Example 9

[0152] This embodiment provides a rare earth composition, which is different from the embodiment 1 in that 0.03g of rare earth complex Eu 0.5 Y 0.5 (A) 3 Adjusted to 4.35 mg rare earth complex Eu 0.5 Y 0.5 (A) 3 , other raw materials, contents and preparation methods are the same as those in Example 1.

[0153] Example 10

[0154] This embodiment provides a rare earth composition, which is different from the embodiment 1 in that 0.03g of rare earth complex Eu 0.5 Y 0.5 (A) 3 Adjusted to 8.7 mg rare earth complex Eu 0.5 Y 0.5 (A) 3 , other raw materials, contents and preparation methods are the same as those in Example 1.

[0155] Embodiment 11

[0156] This embodiment provides a rare earth composition, which is different from the embodiment 1 in that 0.03g of rare earth complex Eu 0.5 Y 0.5 (A) 3 Adjusted to 0.087g rare earth complex Eu 0.5 Y 0.5 (A) 3 , other raw materials, contents and preparation methods are the same as those in Example 1.

[0157] Example 12

[0158] This embodiment provides a rare earth composition, which is different from the embodiment 1 in that 0.03g of rare earth complex Eu 0.5 Y 0.5 (A) 3 Adjusted to 0.092g rare earth complex Eu 0.5 Y 0.5 (A) 3 , other raw materials, contents and preparation methods are the same as those in Example 1.

[0159] Comparative Example 1

[0160] This comparative example provides a rare earth composition, which is different from Example 1 in that the rare earth complex Eu prepared in Preparation Example 1 is 0.5 Y 0.5 (A) 3 The rare earth complex described in Comparative Preparation Example 1 was used instead, and other raw materials, amounts used and preparation methods were the same as those in Example 1.

[0161] Comparative Example 2

[0162] This comparative example provides a rare earth composition, which is different from Example 1 in that the rare earth complex Eu prepared in Preparation Example 1 is 0.5 Y 0.5 (A) 3 The organic ligand A in Preparation Example 1 was used instead, and other raw materials, amounts used and preparation methods were the same as those in Example 1.

[0163] Comparative Example 3

[0164] This comparative example provides a rare earth composition, which is different from Example 1 in that the rare earth complex Eu prepared in Preparation Example 1 is 0.5 Y 0.5 (A) 3 The rare earth complex described in Comparative Preparation Example 2 was used instead, and other raw materials, amounts used and preparation methods were the same as those in Example 1.

[0165] Application Example 1

[0166] This application example provides a rare earth polymer photothermal material, which includes polyester and the rare earth composition described in Example 1.

[0167] The preparation method of the rare earth polymer photothermal material is as follows:

[0168] 4 mL of the rare earth composition described in Example 1 was sprayed on 0.58 g of polyester fabric, and after the solvent evaporated naturally, the rare earth polymer photothermal material was obtained.

[0169] Application Example 2-6

[0170] The rare earth components used in Application Examples 2-6 are the rare earth compositions described in Examples 2-6, respectively. Other raw materials, dosages and preparation methods are the same as those in Application Example 1.

[0171] Application Example 7

[0172] This application example provides a rare earth polymer photothermal material, which includes polyester fabric and the rare earth composition described in Example 1.

[0173] The preparation method of the rare earth polymer photothermal material is as follows:

[0174] 4 mL of the rare earth composition described in Example 7 was sprayed on 0.16 g of polyester fabric, and after the solvent evaporated naturally, the rare earth polymer photothermal material was obtained.

[0175] Application Example 8

[0176] This application example provides a rare earth polymer photothermal material, which includes polyester fabric and the rare earth composition described in Example 1.

[0177] The preparation method of the rare earth polymer photothermal material is as follows:

[0178] 4 mL of the rare earth composition described in Example 8 was sprayed on 0.16 g of polyester fabric, and after the solvent evaporated naturally, the rare earth polymer photothermal material was obtained.

[0179] Application Examples 9-12

[0180] The rare earth components used in Application Examples 9-12 are the rare earth compositions described in Examples 9-12, respectively. Other raw materials, amounts used and preparation methods are the same as those in Application Example 1.

[0181] Application Example 13

[0182] This application example provides a rare earth polymer photothermal material, which includes polyester and the rare earth composition described in Example 6.

[0183] The preparation method of the rare earth polymer photothermal material is as follows:

[0184] 0.58 g of polyester fabric was placed in the rare earth composition described in Example 6, and taken out after immersion for 10 minutes. After the solvent evaporated naturally, the rare earth polymer photothermal material was obtained.

[0185] Comparative application example 1

[0186] This comparative application example provides a polymer material, which is obtained from 0.58 g of polyester fabric without any treatment.

[0187] Comparative Application Example 2

[0188] This comparative application example provides a rare earth polymer photothermal material, which differs from Application Example 1 only in that the rare earth composition obtained in Example 1 is replaced by the rare earth composition described in Comparative Example 1, and other raw materials, amounts and preparation methods are the same as those in Application Example 1.

[0189] Comparative Application Example 3

[0190] This comparative application example provides a rare earth polymer photothermal material, which differs from Application Example 1 only in that the rare earth composition obtained in Example 1 is replaced by the rare earth composition described in Comparative Example 2, and other raw materials, amounts and preparation methods are the same as those in Application Example 1.

[0191] Comparative Application Example 4

[0192] This comparative application example provides a rare earth polymer photothermal material, which includes polyester and the rare earth complex Er (A) described in Preparation Example 6. 3 .

[0193] The preparation method of the rare earth polymer photothermal material is as follows:

[0194] (1) Weigh 0.03g of rare earth complex Er(A) 3 , add 30 mL of acetone to dissolve, and obtain a rare earth complex solution;

[0195] (2) Take 4 mL of the rare earth complex solution described in step (1) and spray it on 0.58 g of polyester fabric. After the solvent evaporates naturally, the rare earth polymer photothermal material is obtained.

[0196] Comparative Application Example 5

[0197] This comparative application example provides a rare earth polymer photothermal material, which includes polyester and the rare earth complex Er (A) described in Preparation Example 6. 3 .

[0198] The preparation method of the rare earth polymer photothermal material is as follows:

[0199] (1) Weigh 0.03g of rare earth complex Er(A) 3 , add 30 mL of acetone to dissolve, and obtain a rare earth complex solution;

[0200] (2) 0.58 g of polyester fabric is placed in the rare earth complex solution described in step (1), and taken out after immersion for 10 minutes. After the solvent evaporates naturally, the rare earth polymer photothermal material is obtained.

[0201] Comparative Application Example 6

[0202] This comparative application example provides a rare earth polymer photothermal material, which differs from comparative application example 5 only in that the rare earth complex Er(A) described in preparation example 6 is 3 Replaced with the rare earth complex Eu(A) described in Preparation Example 3 3 , other raw materials, dosage and preparation method are the same as those in Comparative Application Example 5.

[0203] Comparative Application Example 7

[0204] This comparative application example provides a rare earth polymer photothermal material, which differs from Application Example 1 only in that the rare earth composition described in Example 1 is replaced by the rare earth composition described in Comparative Example 3, and other raw materials, amounts and preparation methods are the same as those in Application Example 1.

[0205] The materials obtained from the above application examples 1-13 and comparative application examples 1-7 were subjected to weather resistance tests, and the test method was as follows:

[0206] (1) Washability test: The material to be tested is heated at 340nm and 0.16W / cm 2 After irradiation with ultraviolet light for 120s, the initial temperature T 0 ; The prepared polymer material was placed in 30 mL of pure water, 1 g of commercial laundry detergent was added, and it was placed in a magnetic stirrer for 30 min and then rinsed with clean water (the first wash). The temperature T after irradiation with 340 nm ultraviolet light for 120 s was tested. 1 ; In the same way, continue to test the temperature T after the second water wash 2 , Temperature after the third wash T 3 and the temperature after the fourth wash T 4 ;

[0207] Heating maintenance rate = (T 4 -T * 4 ) / (T 0 -T * 0 ), where T * 4 It represents the temperature T measured after the fourth water washing of the polymer material in comparative application example 1. 4 , T * 0 Indicates the initial temperature T measured for the polymer material in comparative application example 1 0 ;

[0208] (2) Aging resistance test: According to the national standard ISO 4892-3, the material to be tested is placed in a 340nm UV aging box for 72 hours, and its temperature value T is tested. m .

[0209] The test results are shown in Table 1.

[0210] Table 1

[0211]

[0212] “-” in the table means no data.

[0213] The test results show that:

[0214] (1) The rare earth complex, rare earth composition and rare earth polymer luminescent material provided by the present invention can absorb ultraviolet light and produce a thermogenic effect. By introducing heteronuclear rare earth ions, the luminescent effect can be significantly improved to produce a more significant thermogenic effect.

[0215] (2) By comparing Application Examples 1-13 with Comparative Application Example 1, it can be seen that the specific rare earth polymer photothermal material provided by the present invention has good photothermal conversion performance at 340nm and 0.16W / cm 2 After irradiation with ultraviolet light for 120s, the measured initial temperature T 0 Not lower than 35.8°C; and it has good water washing resistance, and its temperature rise retention rate after four water washings is more than 90%; after 72h of aging resistance test, the difference between its temperature and the initial temperature is not higher than 1.3°C, that is, the specific rare earth polymer photothermal material provided by the present invention has good aging resistance.

[0216] (3) By comparing Application Example 1 with Application Examples 9-12, it can be seen that the present invention can not only better improve the comprehensive performance of the photothermal conversion and weather resistance of the obtained rare earth polymer photothermal material by further limiting the quality of the rare earth complex, but also effectively control the amount of raw materials used, effectively avoiding the waste of raw materials, and thus reducing economic costs.

[0217] (4) By comparing Application Example 1 with Application Example 13, it can be seen that the use of a spraying method in the preparation process of the specific rare earth polymer photothermal material in the present invention can achieve the same or even slightly better technical effect as the dipping method, which is beneficial to cost saving and efficient utilization of raw materials.

[0218] (4) Through the comparison between Application Example 6 and Comparative Application Example 4, it can be seen that the rare earth composite material obtained by modifying the rare earth complex of specific structure with a specific base resin, a promoter and a curing agent can be combined with a polymer matrix to improve the compatibility and dispersibility between the specific rare earth complex and the polymer matrix, thereby obtaining a rare earth polymer photothermal material with good weather resistance (water washability and aging resistance) while ensuring good photothermal conversion performance; further, through the comparison between Application Example 6, Comparative Application Example 4 and Comparative Application Example 5, it can be seen that the rare earth polymer photothermal material of the present invention can form a dense resin film on the surface of the polymer matrix by optimizing the specific raw material composition formula and combining it with spraying, thereby obtaining a rare earth polymer photothermal material with good weather resistance and low preparation cost. In addition, Comparative Application Examples 4 and 5 jointly illustrate that when rare earth complexes are directly used in combination with polymer matrices, the resulting materials have poor water wash resistance, and their highest temperature retention rate is only 6.1%, which is much lower than the temperature retention rate of the rare earth polymer photothermal material obtained from the specific rare earth composition of the present invention.

[0219] (5) Through the comparison between Application Example 1 and Comparative Application Example 2 and Comparative Application Example 3, and the comparison between Application Example 3 and Comparative Application Example 7, it can be seen that the specific rare earth polymer photothermal material of the present invention has more excellent photothermal conversion performance.

[0220] like Figure 1 As shown, through the comparison between Application Example 3 and Application Example 6 and Comparative Application Example 1, it can be seen that the rare earth polymer photothermal material provided by the present invention can absorb ultraviolet light and produce a photothermal effect; further, through the comparison between Application Example 1 and Application Example 6 and Comparative Application Example 3, it can be seen that the specific rare earth polymer photothermal material of the present invention has a better photothermal conversion performance than the polymer material formed by the organic ligand A.

[0221] like Figure 2 As shown, under 340nm ultraviolet light irradiation, by comparing the temperature-time variation curves of the material obtained in Application Example 6 before washing and after the first, second, third and fourth washings with the temperature-time variation curves of the material obtained in Comparative Application Example 1 before washing, it can be found that the rare earth polymer luminescent material prepared from the rare earth composition provided by the present invention has good water washing resistance; Figure 3As shown, under the same 340nm ultraviolet light irradiation, by comparing the temperature-time change curves of the material obtained in Application Example 4 before washing and after the first, second, third and fourth washings with the temperature-time change curve of the material obtained in Application Example 1 before washing, it can be seen that although the rare earth polymer luminescent material prepared by the specific composition not of the present invention has good photothermal performance, its water resistance will decrease with the increase of the number of washings; Figure 2 and Figure 3 It can be seen from the comparison that the rare earth polymer luminescent material prepared from the specific rare earth composition provided by the present invention has good water wash resistance while maintaining good photothermal properties.

[0222] In summary, the rare earth complex provided by the present invention adopts a benzophenone ultraviolet absorber as a ligand, has strong stability, reuses the function of the benzophenone ultraviolet absorber, enhances ultraviolet absorption, converts harmful ultraviolet rays into red light or infrared light, and utilizes its thermogenic effect to produce a temperature conversion effect, and has low cost; a rare earth composite is obtained by modifying a specific rare earth complex with a matrix resin, a promoter and a curing agent, etc., and has better compatibility with a polymer matrix, thereby improving the stability and weather resistance of the obtained photothermal material, and combining the advantages of the spraying process, thereby expanding its application field, which has great economic benefits.

[0223] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A rare earth complex, characterized in that: The chemical composition formula of the rare earth complex is (Ln1 x Ln2 y Ln3 1-x-y ) n (A) 3, wherein Ln1, Ln2 and Ln3 each independently represent 3+ and Pm 3+ Other trivalent rare earth ions, 0≤x+y≤1, n=1 or 2; A represents an organic ligand A, which is selected from benzophenone ultraviolet absorbers, and has a structure as shown in formula (I): wherein R1-R9 are independently selected from hydrogen atoms, C1-C 12 Alkyl, C1-C 12 Alkoxy, hydroxyl, C1-C 12 Alkyleneoxy, C1-C 12 Alkyloxy, phenoxy, carboxyl, nitro, amino, C1-C 12 N-substituted amino, cyano, phenyl, halogen or C1-C 12 Any one of the halogen-substituted alkyl groups.

2. The rare earth complex according to claim 1, characterized in that The organic ligand A comprises Any one of .

3. A method for preparing a rare earth complex as claimed in claim 1 or 2, characterized in that: The preparation method comprises the following steps: The rare earth salt, the organic ligand and the alkaline substance are mixed and reacted.

4. The preparation method according to claim 3, characterized in that: The rare earth salt includes any one of rare earth nitrate, rare earth chloride, rare earth sulfate, rare earth nitrate hydrate, rare earth chloride hydrate or rare earth sulfate hydrate, or a combination of at least two thereof; Preferably, the molar ratio of the rare earth salt to the organic ligand is (1-5):1; Preferably, the alkaline substance comprises any one of sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate, potassium carbonate, ammonia water or triethylamine, or a combination of at least two thereof; Preferably, the reaction temperature is 50-60°C; Preferably, the reaction time is 6-24 hours.

5. The preparation method according to claim 3 or 4, characterized in that: After the reaction, purification and drying are performed in sequence; Preferably, the reagent used for purification includes an organic solvent; Preferably, the organic solvent comprises any one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, ether, dimethylformamide or dimethyl sulfoxide, or a combination of at least two thereof.

6. A rare earth composition, characterized in that the rare earth composition comprises a base resin, an accelerator, a curing agent and the rare earth complex according to claim 1 or 2; Preferably, the matrix resin includes any one or a combination of at least two of grease, natural resin, phenolic resin, asphalt resin, alkyd resin, amino resin, nitrocellulose resin, epoxy resin, acrylic resin or polyester resin; Preferably, the accelerator comprises any one of cobalt naphthenate, 2,4,6-tris(dimethylaminomethyl)phenol, benzyldimethylamine, triethylamine, triethanolamine, o-hydroxybenzyldimethylamine, N-(2-hydroxyphenyl)-N',N'-dimethylurea, N-(2-hydroxy-4-nitrobenzene)-N',N'-dimethylurea, N-(5-chloro-2-hydroxybenzene)-N',N'-dimethylurea, N-(4-chlorophenyl)-N',N'-dimethylurea, N-(4-chloro-2-hydroxybenzene)-N',N'-dimethylurea, phenol, o-cresol, or a boron trifluoride complex, or a combination of at least two thereof; Preferably, the mass of the accelerator is 0.1-1wt% of the base resin; Preferably, the curing agent includes any one or a combination of at least two of methyl ethyl ketone peroxide, N,N-dimethylethanolamine, bisphenol A, nonylphenol, resorcinol, m-phenylenediamine, tertiary amine, imidazole derivatives, substituted urea, organic guanidine derivatives, acetylacetone or triphenylphosphine; Preferably, the mass of the curing agent is 0.1-1wt% of the base resin; Preferably, the mass of the rare earth complex is 0.1-10wt% of the base resin; Preferably, the rare earth composition further comprises a dispersant and other additives; Preferably, the dispersant includes any one or a combination of at least two of a cationic dispersant, an anionic dispersant, an electrically neutral dispersant, a nonionic dispersant or a polymeric superdispersant; Preferably, the mass of the dispersant is 0-30wt% of the base resin; Preferably, the other additives include any one or a combination of at least two of a drying agent, a toughening agent, an emulsifier, a thickener, a defoaming agent, a leveling agent, an anti-skinning agent, a matting agent, a mildew preventer or an antistatic agent; Preferably, the mass of the other additives is 0-10wt% of the base resin.

7. A method for preparing a rare earth composition as claimed in claim 6, characterized in that: The preparation method comprises the following steps: Mixing a base resin, a rare earth complex, an accelerator and a curing agent to obtain the rare earth composition; Preferably, the mixing is carried out in a solvent; Preferably, the solvent comprises any one of toluene, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, tetrachloromethane, ether, dimethylformamide or dimethyl sulfoxide, or a combination of at least two thereof.

8. A use of the rare earth composition as claimed in claim 6, characterized in that: The rare earth composition is applied to any one of warming clothing, fluorescent coatings, anti-counterfeiting coatings or agricultural films; Alternatively, the rare earth composition is applied to metal surface modification, solar cell surface modification, ceramic surface modification or preparation of photothermal therapy materials.

9. A rare earth polymer photothermal material, characterized in that: The rare earth polymer photothermal material comprises a polymer matrix and the rare earth composition according to claim 6; Preferably, the polymer matrix includes any one of low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, polyacrylic acid, polyvinyl alcohol, polybutylene, ethylene-vinyl acetate resin, polymethyl methacrylate, polyvinyl chloride, polyester, nylon, acrylic fiber, polypropylene fiber, vinylon or chlorofiber, or a combination of at least two thereof; Preferably, the mass ratio of the polymer matrix to the rare earth complex in the rare earth composition is 1:(0.001-0.1), preferably 1:(0.002-0.02).

10. A method for preparing a rare earth polymer photothermal material as claimed in claim 9, characterized in that: The preparation method comprises the following steps: Combining the rare earth composition with a polymer matrix to obtain the rare earth polymer photothermal material; Preferably, the combining method includes any one of dipping, spraying, brushing, and electrospinning, or a combination of at least two thereof.

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