技术领域：Technical field:
本发明属于无机功能材料技术领域，特别涉及一种超分子结构酚酞或其类似物插层紫外阻隔材料及其制备方法。The invention belongs to the technical field of inorganic functional materials, and in particular relates to a supramolecular structure phenolphthalein or its analog intercalated ultraviolet blocking material and a preparation method thereof.
背景技术：Background technique:
环境污染带来紫外线的大幅度增加，因紫外线所产生的光化学作用和生物学效应十分显著，引起沥青以及其他高分子聚合材料老化，致使其性能降低，粘度增加，软化点升高，因此有必要研究高效的抗紫外添加剂。酚酞的英文名称为phenolphthalein，简写为PPN，在220～310nm波段具有良好紫外阻隔性能，外观为纯白色粉末，室温下不溶于水，溶于NaOH溶液中，是一种常用的溶液pH指示剂。Environmental pollution has brought about a substantial increase in ultraviolet rays. The photochemical and biological effects produced by ultraviolet rays are very significant, causing asphalt and other polymer materials to age, resulting in reduced performance, increased viscosity, and increased softening point. Therefore, it is necessary to Research on efficient anti-ultraviolet additives. The English name of phenolphthalein is phenolphthalein, abbreviated as PPN. It has good UV blocking performance in the 220-310nm band, and its appearance is pure white powder. It is insoluble in water at room temperature and soluble in NaOH solution. It is a commonly used solution pH indicator.
水滑石(Layered Double Hydroxides，简写为LDHs)是一类重要的新型无机功能材料，利用水滑石具有的插层组装性能和良好的光热稳定性，将其作为添加剂或载体具有很高的应用价值。Hydrotalcite (Layered Double Hydroxides, abbreviated as LDHs) is an important new class of inorganic functional materials. Using hydrotalcite's intercalation assembly performance and good photothermal stability, it has high application value as an additive or carrier .
发明内容：Invention content:
本发明的目的是提供一种超分子结构酚酞或其类似物插层紫外阻隔材料及其制备方法。The object of the present invention is to provide a supramolecular structure phenolphthalein or its analog intercalated ultraviolet blocking material and its preparation method.
本发明的技术方案是：以硝酸根插层镁铝水滑石为前体，采用离子交换法将酚酞或其类似物插入到硝酸根插层镁铝水滑石前体层间，组装得到晶相结构良好、性能优异的酚酞或其类似物插层镁铝水滑石。The technical scheme of the present invention is: using nitrate intercalated magnesium aluminum hydrotalcite as a precursor, using ion exchange method to insert phenolphthalein or its analogs into the interlayers of nitrate intercalated magnesium aluminum hydrotalcite precursor, and assembling to obtain a good crystal phase structure, Phenolphthalein or its analogs intercalated magnesium aluminum hydrotalcite with excellent performance.
本发明所述的超分子结构酚酞或其类似物插层紫外阻隔材料的化学式为[Mg2+1-xAl3+x(OH)2]x+(A2-)x/2·mH2O，其中x是Al3+/(Mg2++Al3+)物质的量之比，0.29≤x≤0.36；m为层间结晶水分子数，0.5≤m≤1；A2-为酚酞或其类似物离子。The chemical formula of the supramolecular structure phenolphthalein or its analogue intercalated ultraviolet blocking material described in the present invention is [Mg2+1-x Al3+x (OH)2 ]x+ (A2- )x/2 mH2 O , where x is the ratio of the amount of Al3+ /(Mg2+ +Al3+ ), 0.29≤x≤0.36; m is the number of interlayer crystal water molecules, 0.5≤m≤1; A2- is phenolphthalein or its analog ions.
本发明所述的超分子结构酚酞或其类似物插层紫外阻隔材料的制备方法，其特征在于，其具体制备步骤为：The preparation method of supramolecular structure phenolphthalein or its analog intercalation ultraviolet barrier material of the present invention is characterized in that, its specific preparation steps are:
A.配制浓度为0.02-0.2mol/L的硝酸根插层镁铝水滑石前体悬浮液；A. preparation concentration is the nitrate radical intercalation magnesium aluminum hydrotalcite precursor suspension of 0.02-0.2mol/L;
B.将酚酞或其类似物溶于除去CO2的去离子水中配制成浓度为0.04-0.4mol/L的溶液，用NaOH调节溶液pH值为11-12；B. phenolphthalein or its analogs are dissolved in the deionized water that removes CO2 and are formulated into a solution with a concentration of 0.04-0.4mol/L, and the pH value of the solution is adjusted to 11-12 with NaOH;
C.在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，酚酞或其类似物与硝酸根插层镁铝水滑石前体中硝酸根摩尔数比值为(1-4):1，氮气保护下，快速搅拌，在60-100℃温度下，优选80-95℃，晶化6-18小时，过滤、洗涤，干燥得到超分子结构酚酞或其类似物插层紫外阻隔材料。C. Under the protection of nitrogen, the solution of step B is added to the suspension of step A and mixed quickly, the molar ratio of nitrate in the precursor of phenolphthalein or its analogue and nitrate intercalation magnesium aluminum hydrotalcite is (1-4) : 1, under the protection of nitrogen, stir rapidly, at a temperature of 60-100° C., preferably 80-95° C., crystallize for 6-18 hours, filter, wash, and dry to obtain supramolecular structure phenolphthalein or its analog intercalation UV-blocking material .
所述的硝酸根插层镁铝水滑石前体的结构式为[Mg2+1-xAl3+x(OH)2]x+(NO3-)x·mH2O，其中x是Al3+/(Mg2++Al3+)物质的量之比，0.29≤x≤0.36；m为层间结晶水分子数，0.5≤m≤1。The structural formula of the nitrate intercalation magnesium aluminum hydrotalcite precursor is [Mg2+1-x Al3+x (OH)2 ]x+ (NO3- )x mH2 O, wherein x is Al3+ / (Mg2+ +Al3+ ) material ratio, 0.29≤x≤0.36; m is the number of interlayer crystal water molecules, 0.5≤m≤1.
上述制备得到的超分子结构酚酞或其类似物插层紫外阻隔材料作为沥青、塑料、橡胶的紫外阻隔剂的应用。The supramolecular structure phenolphthalein or its analog intercalation ultraviolet barrier material prepared above is used as the ultraviolet barrier agent of asphalt, plastics and rubber.
本发明的有益效果是：The beneficial effects of the present invention are:
1.本发明将酚酞或其类似物阴离子插入水滑石层间，利用水滑石特有的空间限域作用，使酚酞或其类似物在水滑石层间的构象发生变化，建立全分子的大共轭体系，共轭性的增加使得酚酞或其类似物对紫外线的吸收作用极大增强，扩大了吸收范围，提高了吸收强度，产生优异的紫外吸收性能，结合水滑石层板本身的紫外屏蔽性能，使该材料具有优异的紫外阻隔性能；1. The present invention inserts phenolphthalein or its analog anions into the hydrotalcite layer, utilizes the unique space confinement effect of hydrotalcite to change the conformation of phenolphthalein or its analog between the hydrotalcite layers, and establishes a macroconjugate of the whole molecule system, the increase in conjugation greatly enhances the absorption of phenolphthalein or its analogs to ultraviolet rays, expands the absorption range, improves the absorption intensity, and produces excellent ultraviolet absorption properties. Combined with the ultraviolet shielding properties of the hydrotalcite laminate itself, Make the material have excellent UV barrier properties;
2.本发明首次插层制备得到了层间阴离子为二价的酚酞或其类似物插层水滑石材料，且酚酞价格低于通常的有机插层试剂，这为大规模应用提供了可能；2. The first intercalation preparation of the present invention has obtained the interlayer hydrotalcite material whose interlayer anion is divalent phenolphthalein or its analogs, and the price of phenolphthalein is lower than that of common organic intercalation reagents, which provides the possibility for large-scale application;
3.本发明制备的超分子结构酚酞或其类似物插层紫外阻隔材料对220-400nm波段的紫外阻隔率高于95％，具有优良的紫外阻隔性能，拓展了紫外线阻隔剂的范围；3. The supramolecular structure phenolphthalein or its analogs intercalated UV blocking material prepared by the present invention has a UV blocking rate higher than 95% for the 220-400nm band, has excellent UV blocking performance, and expands the range of UV blocking agents;
4.用本发明制备的超分子结构酚酞或其类似物插层紫外阻隔材料作为沥青、塑料、橡胶的添加剂可使其抗紫外老化的能力大幅度提高，延长使用寿命。4. Using the supramolecular structure phenolphthalein or its analogs intercalated ultraviolet barrier material prepared by the present invention as an additive for asphalt, plastics and rubber can greatly improve its anti-ultraviolet aging ability and prolong its service life.
附图说明Description of drawings
图1为实施例1制备的MgAl-PPN-LDHs的XRD图。FIG. 1 is an XRD pattern of MgAl-PPN-LDHs prepared in Example 1.
图2为酚酞的TG-DSC谱图。Figure 2 is the TG-DSC spectrum of phenolphthalein.
图3为实施例1制备的MgAl-PPN-LDHs的TG-DSC谱图。Fig. 3 is the TG-DSC spectrogram of the MgAl-PPN-LDHs prepared in Example 1.
图4为实施例1的紫外反射谱图，其中：a是硝酸根插层镁铝水滑石前体，b是酚酞，c是MgAl-PPN-LDHs。Figure 4 is the ultraviolet reflection spectrum of Example 1, wherein: a is the precursor of nitrate intercalated magnesium aluminum hydrotalcite, b is phenolphthalein, and c is MgAl-PPN-LDHs.
图5为实施例4的紫外反射谱图，其中：a是邻甲酚酞，b是MgAl-OPPN-LDHs。Figure 5 is the ultraviolet reflection spectrum of Example 4, wherein: a is o-cresolphthalein, and b is MgAl-OPPN-LDHs.
具体实施方式detailed description
实施例1：Example 1:
步骤A：将30.72g(0.12mol)的固体Mg(NO3)2·6H2O和22.51g(0.06mol)的固体Al(NO3)3·9H2O，溶于除CO2的去离子水中，配制成150mL的混合盐溶液；称取14.4g的NaOH，溶于除CO2去离子水中，配成150mL碱溶液；室温下将两种溶液以相同的流速加入旋转膜反应器中快速成核，将得到的浆液移至500mL烧瓶，80℃晶化8小时，离心洗涤，至pH约为7，60℃干燥12小时，得到硝酸根插层镁铝水滑石前体，其结构式为Mg0.64Al0.36(OH)2(NO3-)0.36·0.9H2O；Step A: 30.72g (0.12mol) of solid Mg(NO3 )2 6H2 O and 22.51g (0.06mol) of solid Al(NO3 )3 9H2 O were dissolved in deionized CO2 In water, prepare 150mL of mixed salt solution; weigh 14.4g of NaOH, dissolve inCO2 -deionized water, and prepare 150mL of alkali solution; transfer the obtained slurry to a 500mL flask, crystallize at 80°C for 8 hours, centrifuge and wash until the pH is about 7, and dry at 60°C for 12 hours to obtain a nitrate-intercalated magnesium aluminum hydrotalcite precursor, whose structural formula is Mg0.64 Al0.36 (OH)2 (NO3- )0.36 0.9H2 O;
取上述产物22.81g(0.01molNO3—)在三口烧瓶中用除CO2的去离子水超声分散，配制成75mL悬浮液；Take 22.81g (0.01molNO3-) of the above-mentioned product in athree -necked flask and use deionized water de-CO2 to ultrasonically disperse and prepare a 75mL suspension;
步骤B：称取6.36g(0.02mol)酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值为12；Step B: Weigh 6.36g (0.02mol) of phenolphthalein and dissolve it in 75mL of deionized water withCO2 removed, add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to 12;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与酚酞摩尔比为1:2，在80℃下晶化10小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构酚酞插层紫外阻隔材料，记为MgAl-PPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly. The molar ratio of nitrate and phenolphthalein in the precursor of nitrate intercalated magnesium aluminum hydrotalcite is 1:2, crystallize at 80°C After 10 hours of deionization, centrifugation, washing with CO2 deionized water to a pH of about 7, and drying at 60°C for 12 hours, the supramolecular structure phenolphthalein intercalated UV blocking material was obtained, which was denoted as MgAl-PPN-LDHs.
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.64Al0.36(OH)2(In2-)0.18·H2O，In2-为酚酞阴离子。Characterization of the obtained product by XRD, IR, and elemental analysis shows that its chemical formula is Mg0.64 Al0.36 (OH)2 (In2- )0.18 ·H2 O, and In2- is a phenolphthalein anion.
通过X射线粉末衍射(XRD)、红外(IR)、元素分析表征，显示酚酞阴离子已组装进了水滑石层间并发生了构象变化。对其进行的热重差热分析(TG-DSC)结果见图1、图2，结果表明其插层产物的初始分解温度为280℃，比PPN的初始分解温度稍有提高。用紫外可见分析方法测定的紫外反射曲线见图3，由图3看出其对220-400波段范围的紫外线反射率低于5％。Characterized by X-ray powder diffraction (XRD), infrared (IR), and elemental analysis, it was shown that phenolphthalein anions had assembled into the interlayers of hydrotalcites and undergone conformational changes. The results of thermogravimetric differential thermal analysis (TG-DSC) are shown in Figure 1 and Figure 2. The results show that the initial decomposition temperature of the intercalation product is 280°C, which is slightly higher than that of PPN. The ultraviolet reflection curve measured by the ultraviolet-visible analysis method is shown in Figure 3, and it can be seen from Figure 3 that its ultraviolet reflection rate to the 220-400 band range is lower than 5%.
按添加3wt％分别制成PPN/BN、MgAl-PPN-LDHs/BN样品模及纯BN(沥青)样品模。在紫外加速老化箱中对样品模照射4天后，分别测照射前后3个样品的粘度和软化点。纯BN老化前后的120℃粘度由0.860Pa·s增加到0.930Pa·s，增加了0.07Pa·s；PPN/BN老化前后120℃粘度由1.133Pa·s增加到1.214Pa·s，增加了0.081Pa·s；MgAl-PPN-LDHs/BN老化前后120℃粘度由0.80Pa·s增加到0.834Pa·s，增加了0.034Pa·s；纯BN老化前后的软化点由45.6℃增加到48℃，增加了2.4℃，PPN/BN老化前后软化点由47℃增加到49.2℃，增加了2.2℃，MgAl-PPN-LDHs/BN老化前后软化点由46℃增加到46.8℃，增加了0.8℃。加入MgAl-PPN-LDHs的沥青具有更优良的耐紫外老化性能。PPN/BN, MgAl-PPN-LDHs/BN sample molds and pure BN (asphalt) sample molds were made respectively by adding 3wt%. After irradiating the sample mold in the ultraviolet accelerated aging box for 4 days, measure the viscosity and softening point of the three samples before and after irradiation respectively. The viscosity of pure BN before and after aging at 120°C increased from 0.860Pa·s to 0.930Pa·s, an increase of 0.07Pa·s; the viscosity of PPN/BN before and after aging at 120°C increased from 1.133Pa·s to 1.214Pa·s, an increase of 0.081 Pa s; the viscosity of MgAl-PPN-LDHs/BN before and after aging at 120°C increased from 0.80Pa s to 0.834Pa s, an increase of 0.034Pa s; the softening point of pure BN before and after aging increased from 45.6°C to 48°C, The softening point of PPN/BN increased by 2.4°C from 47°C to 49.2°C before and after aging, an increase of 2.2°C, and the softening point of MgAl-PPN-LDHs/BN increased from 46°C to 46.8°C before and after aging, an increase of 0.8°C. The asphalt added with MgAl-PPN-LDHs has better UV aging resistance.
实施例2：Example 2:
步骤A：制备硝酸根插层镁铝水滑石前体悬浮液，方法与实施例1中步骤A相同；Step A: Prepare the precursor suspension of nitrate intercalated magnesium aluminum hydrotalcite, the method is the same as step A in Example 1;
步骤B：称取3.18g(0.01mol)酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值为11；Step B: Weigh 3.18g (0.01mol) of phenolphthalein and dissolve it in 75mL of deionized water de-CO2 , add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH of the solution to 11;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与酚酞摩尔比为1:1，在90℃下晶化8小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构酚酞插层紫外阻隔材料，记为MgAl-PPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly, the molar ratio of nitrate and phenolphthalein in the precursor of nitrate intercalation magnesium aluminum hydrotalcite is 1:1, crystallize at 90 °C After 8 hours, centrifuge, wash withCO2 -deionized water until the pH is about 7, and dry at 60°C for 12 hours to obtain a supramolecular structure phenolphthalein-intercalated UV-blocking material, which is denoted as MgAl-PPN-LDHs.
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.64Al0.36(OH)2(In2-)0.17·0.95H2O，In2-为酚酞阴离子。Characterization of the obtained product by XRD, IR, elemental analysis, etc. shows that its chemical formula is Mg0.64 Al0.36 (OH)2 (In2- )0.17 ·0.95H2 O, and In2- is a phenolphthalein anion.
MgAl-PPN-LDHs的起始分解温度为280℃，对220-400nm波段的紫外反射率低于5％。The initial decomposition temperature of MgAl-PPN-LDHs is 280°C, and the ultraviolet reflectivity of the 220-400nm band is lower than 5%.
实施例3：Example 3:
步骤A：制备硝酸根插层镁铝水滑石前体悬浮液，方法与实施例1中步骤A相同；Step A: Prepare the precursor suspension of nitrate intercalated magnesium aluminum hydrotalcite, the method is the same as step A in Example 1;
步骤B：称取12.73g(0.04mol)酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值为11.5；Step B: Weigh 12.73g (0.04mol) of phenolphthalein and dissolve it in 75mL of deionized water withCO2 removed, add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to 11.5;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与酚酞摩尔比为1:4，在95℃下晶化6小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构酚酞插层紫外阻隔材料，记为MgAl-PPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly. The molar ratio of nitrate and phenolphthalein in the precursor of nitrate intercalated magnesium aluminum hydrotalcite is 1:4, crystallize at 95°C After 6 hours of deionization, centrifugation, washing with CO2 deionized water to a pH of about 7, and drying at 60°C for 12 hours, the supramolecular structure phenolphthalein intercalation UV-blocking material was obtained, denoted as MgAl-PPN-LDHs.
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.64Al0.36(OH)2(In2-)0.19·0.9H2O，In2-为酚酞阴离子。The obtained product was characterized by XRD, IR, elemental analysis, etc., and its chemical formula was Mg0.64 Al0.36 (OH)2 (In2- )0.19 ·0.9H2 O, and In2- was a phenolphthalein anion.
MgAl-PPN-LDHs的起始分解温度为283℃，对220-400nm波段的紫外反射率均低于5％。The initial decomposition temperature of MgAl-PPN-LDHs is 283°C, and the ultraviolet reflectivity of the 220-400nm band is lower than 5%.
实施例4：Example 4:
步骤A：制备硝酸根插层镁铝水滑石前体悬浮液，方法与实施例1中步骤A相同；Step A: Prepare the precursor suspension of nitrate intercalated magnesium aluminum hydrotalcite, the method is the same as step A in Example 1;
步骤B：称取13.85g(0.04mol)邻甲酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值约为12；Step B: Weigh 13.85g (0.04mol) of o-cresolphthalein and dissolve it in 75mL of deionized water withoutCO2 , add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to about 12;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与邻甲酚酞摩尔比为1:4，在90℃下晶化6小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构邻甲酚酞插层紫外阻隔材料，记为MgAl-OPPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly. The molar ratio of nitrate and o-cresolphthalein in the precursor of nitrate intercalation magnesium aluminum hydrotalcite is 1:4, at 90°C Crystallize for 6 hours, centrifuge, wash with CO2 deionized water until the pH is about 7, and dry at 60°C for 12 hours to obtain a supramolecular structure o-cresolphthalein intercalated UV barrier material, which is denoted as MgAl-OPPN-LDHs .
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.64Al0.36(OH)2(In2-)0.19·0.5H2O，In2-为邻甲酚酞阴离子。Characterization of the obtained product by XRD, IR, elemental analysis, etc. shows that its chemical formula is Mg0.64 Al0.36 (OH)2 (In2- )0.19 ·0.5H2 O, and In2- is o-cresolphthalein anion.
MgAl-OPPN-LDHs对220-400nm波段的紫外反射率均低于5％。The ultraviolet reflectivity of MgAl-OPPN-LDHs to 220-400nm band is lower than 5%.
实施例5：Example 5:
步骤A：将46.08g(0.15mol)的固体Mg(NO3)2·6H2O和22.51g(0.06mol)的固体Al(NO3)3·9H2O，溶于除CO2的去离子水中，配制成150mL的混合盐溶液；称取16.8gNaOH，溶于除CO2去离子水中，配成150mL碱溶液；室温下将两种溶液以相同的流速加入旋转膜反应器中快速成核，将得到的浆液移至500mL烧瓶，80℃晶化8小时，离心洗涤，至pH约为7，60℃干燥12小时，得到硝酸根插层镁铝水滑石前体，其结构式为Mg0.71Al0.29(OH)2(NO3-)0.29·0.8H2O；Step A: Dissolve 46.08g (0.15mol) of solid Mg(NO3 )2 6H2 O and 22.51g (0.06mol) of solid Al(NO3 )3 9H2 O in deionized CO2 In water, prepare 150mL of mixed salt solution; weigh 16.8gNaOH, dissolve in CO2 deionized water, and make 150mL alkali solution; add the two solutions into the rotating membrane reactor at the same flow rate at room temperature for rapid nucleation, The obtained slurry was transferred to a 500mL flask, crystallized at 80°C for 8 hours, centrifuged and washed until the pH was about 7, and dried at 60°C for 12 hours to obtain the precursor of nitrate intercalated magnesium aluminum hydrotalcite, whose structural formula was Mg0.71 Al0.29 ( OH)2 (NO3- )0.29 0.8H2 O;
取上述产物26.09g(0.01molNO3)在三口烧瓶中用除CO2的去离子水超声分散，配制成75mL悬浮液；Take 26.09g (0.01molNO3 ) of the above product and ultrasonically disperse it in a three-necked flask with deionized water de-CO2 to prepare a 75mL suspension;
步骤B：称取6.36g(0.02mol)酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值约为11；Step B: Weigh 6.36g (0.02mol) of phenolphthalein and dissolve it in 75mL of deionized water withCO2 removed, add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to about 11;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与酚酞摩尔比为1:2，在80℃下晶化10小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构酚酞插层紫外阻隔材料，记为MgAl-PPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly. The molar ratio of nitrate and phenolphthalein in the precursor of nitrate intercalated magnesium aluminum hydrotalcite is 1:2, crystallize at 80°C After 10 hours of deionization, centrifugation, washing with CO2 deionized water to a pH of about 7, and drying at 60°C for 12 hours, the supramolecular structure phenolphthalein intercalated UV blocking material was obtained, which was denoted as MgAl-PPN-LDHs.
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.71Al0.29(OH)2(In2-)0.15·0.72H2O，In2-为酚酞阴离子。Characterization of the obtained product by XRD, IR, elemental analysis, etc. shows that its chemical formula is Mg0.71 Al0.29 (OH)2 (In2-)0.15 · 0.72H2 O, and In2- is a phenolphthalein anion.
MgAl-PPN-LDHs的起始分解温度为285℃，对220-400nm波段的紫外反射率均低于5％。The initial decomposition temperature of MgAl-PPN-LDHs is 285°C, and the ultraviolet reflectivity of the 220-400nm band is lower than 5%.
实施例6：Embodiment 6:
步骤A：制备硝酸根插层镁铝水滑石前体悬浮液，方法与实施例4中步骤A相同；Step A: preparing the nitrate intercalation magnesium aluminum hydrotalcite precursor suspension, the method is the same as step A in Example 4;
步骤B：称取3.18g(0.01mol)酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值约为12；Step B: Weigh 3.18g (0.01mol) of phenolphthalein and dissolve it in 75mL of deionized water withCO2 removed, add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to about 12;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与酚酞摩尔比为1:1，在95℃下晶化6小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构酚酞插层紫外阻隔材料，记为MgAl-PPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly, the molar ratio of nitrate and phenolphthalein in the precursor of nitrate intercalated magnesium aluminum hydrotalcite is 1:1, crystallize at 95 °C After 6 hours, centrifuge, wash withCO2 -deionized water until the pH is about 7, and dry at 60°C for 12 hours to obtain a supramolecular structure phenolphthalein-intercalated UV-blocking material, which is denoted as MgAl-PPN-LDHs.
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.72Al0.28(OH)2(In2-)0.14·0.5H2O，In2-为酚酞阴离子。XRD, IR, elemental analysis and other characterizations of the obtained product show that its chemical formula is Mg0.72 Al0.28 (OH)2 (In2- )0.14 ·0.5H2 O, and In2- is a phenolphthalein anion.
MgAl-PPN-LDHs的起始分解温度为283℃，对220-400nm波段的紫外反射率均低于5％。The initial decomposition temperature of MgAl-PPN-LDHs is 283°C, and the ultraviolet reflectivity of the 220-400nm band is lower than 5%.
实施例7：Embodiment 7:
步骤A：制备硝酸根插层镁铝水滑石前体悬浮液，方法与实施例4中步骤A相同；Step A: preparing the nitrate intercalation magnesium aluminum hydrotalcite precursor suspension, the method is the same as step A in Example 4;
步骤B：称取12.73g(0.04mol)酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值约为12；Step B: Weigh 12.73g (0.04mol) of phenolphthalein and dissolve it in 75mL of deionized water withCO2 removed, add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to about 12;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与酚酞摩尔比为1:4，在90℃下晶化18小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构酚酞插层紫外阻隔材料，记为MgAl-PPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly, the molar ratio of nitrate and phenolphthalein in the precursor of nitrate intercalation magnesium aluminum hydrotalcite is 1:4, crystallize at 90 °C After 18 hours of deionization, centrifugation, washing with CO2 deionized water to a pH of about 7, and drying at 60°C for 12 hours, the supramolecular structure phenolphthalein intercalated UV blocking material was obtained, which was denoted as MgAl-PPN-LDHs.
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.70Al0.30(OH)2(In2-)0.15·0.7H2O，In2-为酚酞阴离子。The obtained product was characterized by XRD, IR, elemental analysis, etc., and its chemical formula was Mg0.70 Al0.30 (OH)2 (In2- )0.15 ·0.7H2 O, and In2- was a phenolphthalein anion.
MgAl-PPN-LDHs的起始分解温度为287℃，对220-400nm波段的紫外反射率均低于5％。The initial decomposition temperature of MgAl-PPN-LDHs is 287°C, and the ultraviolet reflectivity of the 220-400nm band is lower than 5%.
实施例8：Embodiment 8:
步骤A：制备硝酸根插层镁铝水滑石前体悬浮液，方法与实施例4中步骤A相同；Step A: preparing the nitrate intercalation magnesium aluminum hydrotalcite precursor suspension, the method is the same as step A in Example 4;
步骤B：称取3.46g(0.01mol)邻甲酚酞溶于75mL除CO2的去离子水中，快速搅拌条件下加入约0.03gNaOH，调节溶液pH值约为12；Step B: Weigh 3.46g (0.01mol) of o-cresolphthalein and dissolve it in 75mL of deionized water withoutCO2 , add about 0.03g of NaOH under rapid stirring conditions, and adjust the pH value of the solution to about 12;
步骤C：在氮气保护下，将步骤B的溶液加入到步骤A的悬浮液中快速混合，硝酸根插层镁铝水滑石前体中硝酸根与邻甲酚酞摩尔比为1:1，在85℃下晶化6小时，离心分离，用除CO2的去离子水洗涤至pH约为7，60℃干燥12小时，得到超分子结构邻甲酚酞插层紫外阻隔材料，记为MgAl-OPPN-LDHs。Step C: Under the protection of nitrogen, add the solution of step B to the suspension of step A and mix quickly. The molar ratio of nitrate and o-cresolphthalein in the precursor of nitrate intercalation magnesium aluminum hydrotalcite is 1:1, at 85 ℃ Crystallize for 6 hours, centrifuge, wash with CO2 deionized water until the pH is about 7, and dry at 60°C for 12 hours to obtain a supramolecular structure o-cresolphthalein intercalated UV barrier material, which is denoted as MgAl-OPPN-LDHs .
将得到的产品进行XRD、IR、元素分析等表征得出其化学式为Mg0.72Al0.28(OH)2(In2-)0.14·0.8H2O，In2-为邻甲酚酞阴离子。The obtained product was characterized by XRD, IR, elemental analysis, etc., and its chemical formula was Mg0.72 Al0.28 (OH)2 (In2- )0.14 ·0.8H2 O, and In2- was o-cresolphthalein anion.
MgAl-OPPN-LDHs对220-400nm波段的紫外反射率均低于5％。The ultraviolet reflectivity of MgAl-OPPN-LDHs to 220-400nm band is lower than 5%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410559483.9ACN104497358B (en) | 2014-10-20 | 2014-10-20 | A kind of supramolecular structure phenolphthalein or its analog intercalation ultraviolet blocking material and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410559483.9ACN104497358B (en) | 2014-10-20 | 2014-10-20 | A kind of supramolecular structure phenolphthalein or its analog intercalation ultraviolet blocking material and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN104497358A CN104497358A (en) | 2015-04-08 |
| CN104497358Btrue CN104497358B (en) | 2017-06-20 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410559483.9AActiveCN104497358B (en) | 2014-10-20 | 2014-10-20 | A kind of supramolecular structure phenolphthalein or its analog intercalation ultraviolet blocking material and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN104497358B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105347310B (en)* | 2015-11-23 | 2017-07-04 | 北京化工大学 | A kind of method for preparing high-purity calcium based hydrotalcite |
| CN107022115B (en)* | 2017-05-10 | 2019-08-13 | 北京化工大学 | A kind of intercalated houghite anti-ultraviolet ageing agent for rubber and preparation method thereof and application method |
| CN109897226B (en)* | 2019-02-19 | 2021-03-16 | 安庆北化大科技园有限公司 | Calcium carboxylic acid intercalation ultraviolet barrier material with supermolecular structure, preparation method and application |
| CN112625302B (en)* | 2020-12-20 | 2022-06-14 | 北京化工大学 | Preparation method of ultraviolet barrier material with PPN @ LDHs composite supermolecular structure |
| CN115232485B (en)* | 2022-07-13 | 2023-11-07 | 塔里木大学 | Vermiculite ultraviolet blocking material and preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766356A (en)* | 2012-07-31 | 2012-11-07 | 武汉大学 | Ultraviolet adsorption composite material and preparation method thereof |
| CN104087243A (en)* | 2013-04-01 | 2014-10-08 | 上海杰事杰新材料(集团)股份有限公司 | Hydrotalcite-like ultraviolet absorbent and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333005C (en)* | 2005-12-19 | 2007-08-22 | 北京化工大学 | Supermolecular interlayer structured ultraviolet light absorbent, its preparation method and uses |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766356A (en)* | 2012-07-31 | 2012-11-07 | 武汉大学 | Ultraviolet adsorption composite material and preparation method thereof |
| CN104087243A (en)* | 2013-04-01 | 2014-10-08 | 上海杰事杰新材料(集团)股份有限公司 | Hydrotalcite-like ultraviolet absorbent and preparation method thereof |
| Title |
|---|
| 以功能为导向的插层结构功能材料结构设计及应用;王利人，等;《化学通报》;20111231;第74卷(第12期);1074-1083* |
| 插层结构功能材料的组装与产品工程;林彦军，等;《石油化工》;20121231;第41卷(第1期);1-8* |
| Publication number | Publication date |
|---|---|
| CN104497358A (en) | 2015-04-08 |
| Publication | Publication Date | Title |
|---|---|---|
| CN104497358B (en) | A kind of supramolecular structure phenolphthalein or its analog intercalation ultraviolet blocking material and preparation method thereof | |
| Chai et al. | Synthesis and UV absorption properties of 2, 3-dihydroxynaphthalene-6-sulfonate anion-intercalated Zn–Al layered double hydroxides | |
| Rajamathi et al. | On the relationship between α-nickel hydroxide and the basic salts of nickel | |
| WO2007071132A1 (en) | Supermolecular intercalation-structured uv absorber as well as its preparation method and use | |
| CN104725670B (en) | Phenol red or derivatives thereof intercalation ultraviolet blocking material of a kind of supramolecular structure and preparation method thereof | |
| CN107629310A (en) | A kind of supermolecular intercalation structure light stabilizer and preparation method thereof | |
| CN107029659A (en) | Ternary composite modified bentonite material and preparation method and application thereof | |
| CN110105298A (en) | A kind of synthesis of nitrogenous sulphur synergistic flame-retardant compound and its preparation method of intercalation modifying hydrotalcite | |
| Yan et al. | Visible‐Light Degradation of Dyes and Phenols over Mesoporous Titania Prepared by Using Anthocyanin from Red Radish as Template | |
| Zhang et al. | Synthesis and UV absorption properties of 5-sulfosalicylate-intercalated Zn–Al layered double hydroxides | |
| CN104761750B (en) | A kind of supramolecular structure p-nitrophenol or its isomers intercalation ultraviolet blocking material and preparation method thereof | |
| CN105347310B (en) | A kind of method for preparing high-purity calcium based hydrotalcite | |
| CN1850787A (en) | Supermolecular intercalation 2-phenylbenzimidazole-5-sulfonic acid, and its preparing method and use | |
| CN112390984B (en) | Cyclodextrin inclusion compound modified hydrotalcite-like flame-retardant composite material and preparation method thereof | |
| CN101173118B (en) | Supramolecular structured 2-naphthylamine-1,5-disulfonic acid intercalation ultraviolet absorption material and method for producing the same | |
| CN109897226B (en) | Calcium carboxylic acid intercalation ultraviolet barrier material with supermolecular structure, preparation method and application | |
| CN106633215A (en) | Sulfonated beta-cyclodextrin-LDH complex and synthesis method thereof | |
| CN102974303A (en) | Method for synthesizing hydrotalcite by utilizing electroplating wastewater | |
| CN103524311B (en) | The preparation method of 2-hydroxyl 4-n-hexadecane oxygen base benzophenone | |
| CN107602925A (en) | A kind of supermolecular intercalation structure anti-light aging material and preparation method thereof | |
| CN107129597A (en) | A kind of uvioresistant composite of hydrotalcite confinement synthesis Schiff base molecule, preparation method and application | |
| CN101544782A (en) | Supermolecular structural 5,5'-methylene disalicylic acid intercalation ultraviolet absorption material and preparation method thereof | |
| CN106318386A (en) | Preparation method of boron-chlorine doped carbon quantum dots | |
| CN106318387A (en) | Preparation method of boron-sulfur doped carbon quantum dots | |
| CN102766356B (en) | Ultraviolet adsorption composite material and preparation method thereof |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |