WO2020221240A1 - Method for preparing tourmaline containing anthraquinone compound by means of thiol-ene click chemistry and application thereof - Google Patents

Method for preparing tourmaline containing anthraquinone compound by means of thiol-ene click chemistry and application thereof Download PDF

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WO2020221240A1
WO2020221240A1 PCT/CN2020/087433 CN2020087433W WO2020221240A1 WO 2020221240 A1 WO2020221240 A1 WO 2020221240A1 CN 2020087433 W CN2020087433 W CN 2020087433W WO 2020221240 A1 WO2020221240 A1 WO 2020221240A1
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tourmaline
anthraquinone compound
mercaptopropyl
organic solvent
parts
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PCT/CN2020/087433
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French (fr)
Chinese (zh)
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严滨
叶茜
许美兰
曾孟祥
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厦门理工学院
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Definitions

  • Nitrate is another chemical substance that is harmful to the human body and the environment.
  • Ammonia nitrogen and nitrate nitrogen contained in over-applied chemical fertilizers, domestic sewage, manure, industrial sewage, etc. enter the natural environment through soil and water bodies, and are one of the main substances that cause eutrophication of water bodies.
  • Conventional biochemical treatment processes generally can only convert ammonia nitrogen into nitrate nitrogen, and the reduction of nitrate nitrogen cannot be efficiently completed in general treatment processes because of the low denitrification efficiency.
  • redox mediators containing quinone groups can effectively accelerate the biotransformation process of azo dyes and nitrates, and increase the degradation rate.
  • the redox mediator containing quinone groups has the disadvantages of low molecular weight, which is easy to lose when directly added to the water treatment system, causing secondary pollution and high continuous feeding cost. Fixing the quinone group-containing redox mediator on a physical carrier that is insoluble in water is a relatively feasible industrialized method. It has the advantage of being reusable, not easy to lose, and avoiding secondary pollution.
  • the Chinese authorized invention patent with the authorized announcement number CN101862680B discloses a method for preparing a porous inorganic filler to fix a quinone compound, which effectively improves the degradation rate of azo dyes.
  • the preparation method is to plate ⁇ -alumina on the surface of the porous inorganic filler, and then treat it with 3-aminotriethoxysilane to make the surface of the porous inorganic filler contain primary amino groups, and then pass the primary amino groups and anthracene containing sulfonyl chloride groups.
  • the quinone compound reacts to obtain a porous inorganic filler containing quinone groups on the surface.
  • This method has the following problems: (1) The reaction steps are long, time-consuming, the final yield is low, and the cost is high; (2) The use of anthraquinone compounds containing sulfonyl chloride groups can easily generate hydrogen chloride gas when exposed to water vapor, which is dangerous Therefore, the production environment needs to be strictly controlled during use, which causes inconvenience and cost increase; (3) Although porous inorganic fillers have a large specific surface area, the internal porous structure is easily blocked by the flora in practical applications and cannot function. Only the quinone-based compound on the surface can play a role.
  • Redox mediators containing quinone groups can be reversibly reduced and oxidized as electron mediators. Therefore, they have the ability to act as electron carriers in multiple redox reactions, accelerating the transfer of electrons from the primary electron donor to the final electron acceptor. Therefore, the rate of biological redox reaction increases by one to several orders of magnitude. Therefore, improving the electron transfer ability of the redox mediator can further accelerate the redox ability of organisms. However, the electron transfer ability of the redox mediator itself remains basically unchanged. One way is to improve the electron transfer ability of the environment in which it is located, so that it accelerates the biodegradation of azo dyes, nitrates, etc. faster.
  • the mercapto-ene click chemistry reaction has the characteristics of high efficiency, rapidity, mild reaction conditions, high product yield and simple operation. In recent years, more and more applications have been applied to the modification of materials.
  • the purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing tourmaline containing anthraquinone compound by mercapto-ene click chemistry.
  • Another object of the present invention is to provide an application of tourmaline containing an anthraquinone compound.
  • a method for preparing tourmaline containing anthraquinone compound by mercapto-ene click chemistry includes the following steps:
  • step one Add the mercaptopropyl-modified tourmaline, the allyloxy anthraquinone compound, the second organic solvent and the photoinitiator obtained in step one into the container.
  • the main wavelength is 365nm and the light intensity is 10-200W/
  • the filtered solid was washed 3 times with absolute ethanol, and dried to obtain tourmaline containing anthraquinone compound.
  • the weight ratio of the first organic solvent, mercaptopropyl silane coupling agent, dilute hydrochloric acid and tourmaline in step one is 1:0.1-0.3:0.01:0.5-1.
  • the weight ratio of the first organic solvent, mercaptopropyl silane coupling agent, dilute hydrochloric acid and tourmaline can be 1:0.1:0.01:0.5, 1:0.2:0.01:0.5, 1:0.3:0.01:0.5, 1:0.1 :0.01:1, 1:0.2:0.01:1 or 1:0.3:0.01:1, but not limited to those listed above.
  • the first organic solvent in step one and the second organic solvent in step two are selected from methanol, absolute ethanol, isopropanol, n-propanol, ethyl acetate, butyl acetate, tetrahydrofuran, and methyl ethyl ketone One or more of, toluene and xylene.
  • the first organic solvent is selected from one or more of methanol, absolute ethanol, isopropanol and ethyl acetate.
  • the second organic solvent is selected from one or more of tetrahydrofuran, toluene, butyl acetate and methyl ethyl ketone.
  • the mercaptopropyl silane coupling agent in step 1 is selected from 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane One or more of silane and 3-mercaptopropylmethyldiethoxysilane.
  • the average particle size of the tourmaline in step 1 is 0.1 ⁇ m to 1 cm.
  • the average particle size of tourmaline may be 1 ⁇ m, 5 ⁇ m, 10 ⁇ m, 20 ⁇ m, 50 ⁇ m, 100 ⁇ m, 150 ⁇ m, 200 ⁇ m, 500 ⁇ m, 1 mm, or 5 mm, but is not limited to the above list.
  • the weight ratio of the mercaptopropyl-modified tourmaline, the allyloxy-containing anthraquinone compound, the second organic solvent and the photoinitiator in step 2 is 1:0.1-0.3:2-10:0.03-0.06.
  • the weight ratio of mercaptopropyl modified tourmaline, allyloxy-containing anthraquinone compound, second organic solvent and photoinitiator can be 1:0.1:3:0.03, 1:0.1:3:0.05, 1:0.2:5 :0.04, 1:0.2:5:0.06 or 1:0.3:8:0.06, but not limited to the above list.
  • the allyloxy-containing anthraquinone compound in step 2 is selected from 1-allyloxy-4-hydroxyanthraquinone-9,10-dione and 1-amino-4-allyloxyanthracene One or two of quinones.
  • Chinese invention authorized patent discloses the preparation method of 1-allyloxy-4-hydroxyanthraquinone-9,10-dione.
  • the photoinitiator in step 2 is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, benzophenone, 2,4-dihydroxybenzophenone, 2 -Hydroxy-2-methyl-1-phenylacetone (1173), 1-hydroxycyclohexylphenylketone (184), 2-methyl-2-(4-morpholinyl)-1-[4- (Methylthio)phenyl)-1-acetone (907), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-acetone (659), 2 ,4,6-Trimethylbenzoyl-diphenylphosphine oxide (TPO) and 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester (TPO-L) one or more Kind.
  • benzoin benzoin dimethyl ether
  • the photoinitiator can be selected from one or more of benzoin dimethyl ether, benzoin butyl ether and benzoin ethyl ether.
  • a tourmaline containing an anthraquinone compound prepared by the method described in any one of the above embodiments.
  • Tourmaline also called tourmaline, is a compound composed of borate, silicate and various metal elements, which has pyroelectric and piezoelectric properties.
  • the two ends of the tourmaline crystal will have different positive and negative charges, which is the unique thermoelectricity of tourmaline.
  • the two ends of tourmaline are under pressure, they will also have different electric charges.
  • the present invention utilizes the thermoelectricity and piezoelectricity of tourmaline, and when the surface is modified with an anthraquinone-containing compound and applied to water treatment, as the temperature of the water body changes and/or the pressure on the tourmaline caused by the flow of the water body, This results in the generation of positive and negative charges on both ends of the tourmaline, and the generated positive and negative charges increase the conductivity of the surrounding water, and therefore can enhance the accelerated degradation of azo dyes and nitrates by the anthraquinone compound as a redox mediator.
  • the mercapto-ene click chemistry reaction is a kind of green chemistry with high efficiency, high conversion rate, fast reaction (many reactions can be completed in a few minutes or even less than a minute), mild reaction conditions (no need for high temperature and high pressure), product yield
  • the characteristics of high efficiency and simple operation have been more and more used in the modification of materials in recent years.
  • the present invention uses low-priced tourmaline as the physical carrier, which has a wide range of sources and low cost;
  • the present invention has fewer reaction steps, simple reaction process, no need for heating and pressure, and low cost;
  • the tourmaline containing the anthraquinone compound obtained in the present invention can significantly increase the biodegradation rate of azo dyes and nitrates, and can continue to be used after simple treatment.
  • the present invention utilizes the thermoelectricity and piezoelectricity of tourmaline to make the tourmaline containing anthraquinone compound more quickly promote the azo dye, under the condition of environmental temperature change and/or pressure on both ends of the tourmaline. Degradation of nitrates, etc.
  • FT-IR analysis shows that the product has a strong sharp absorption peak at 1668cm -1 , which is the characteristic absorption peak of the carbonyl group on the anthraquinone structure, and a moderately sharp absorption peak appears at 1599cm -1 , which is the hydrocarbon on the benzene ring
  • the characteristic absorption peak indicates that the anthraquinone compound is fixed on the surface of tourmaline.
  • the elemental analysis method was used to determine the S content of the tourmaline before and after the fixation.
  • the content of the anthraquinone compound on the surface of the tourmaline 1 was calculated to be 1.96 mmol/g.
  • the elemental analysis method was used to determine the S content of the tourmaline before and after the fixation, and the content of the anthraquinone compound on the surface of the tourmaline 3 was calculated to be 1.51 mmol/g.
  • the elemental analysis method was used to determine the S content of the tourmaline before and after the fixation, and the content of the anthraquinone compound on the surface of the tourmaline 5 was calculated to be 1.44 mmol/g.
  • Azo dye degradation acceleration effect test 2g of blank tourmaline, 2g of Examples 1-5 and 2g of the products of Comparative Examples 1-2 grafted on the surface of anthraquinone compounds were washed with physiological saline three times, and then added to 200ml containing The azo dye degradation strain GYZ (staphylococcus sp.) of 120 mg/L acid red B was tested for decolorization at a stirring speed of 10 rpm in several growth phases, and the concentration of acid red B was measured over time. The results are shown in Table 1.
  • Nitrate degradation acceleration effect test 2g of blank tourmaline, 2g of Example 1-5 and 2g of Comparative Example 1-2 were surface-grafted with anthraquinone compounds after being washed 3 times with normal saline, and then added to 200ml containing logarithm The test was performed in the 150mg/L nitrate wastewater of denitrifying microorganisms during the growth period at a stirring speed of 10rpm to determine the change of nitrate concentration over time. The results are shown in Table 2.
  • Stability test Wash 2g of the tourmaline grafted with anthraquinone compound on the surface of Examples 1-5 with physiological saline for 3 times, and then add it to 200ml of azo dye degradation strain GYZ (staphylococcus sp.) containing logarithmic growth phase. Decolorization test was carried out in 120mg/L of Acid Red B, and the concentration of Acid Red B after 8 hours was measured. After the test, the tourmaline grafted with anthraquinone compound on the surface was washed and dried with water and absolute ethanol, and then subjected to the decolorization test with Acid Red B for 8 hours according to the above method, and the test was repeated 12 times.
  • azo dye degradation strain GYZ staphylococcus sp.
  • test process of Examples 1-3 was carried out at a stirring speed of 10 rpm, and the test process of Examples 4-5 was carried out at a temperature change of 1 °C/min at 25-30°C.
  • the results are shown in Table 3. Shown.
  • the tourmaline grafted with an anthraquinone compound on the surface of the present invention has a significant effect of promoting the degradation of nitrate, and as the content of the anthraquinone compound increases, the degradation of nitrate is faster.
  • the content of the anthraquinone compound grafted on the surface of tourmaline in Examples 3 and 5 is significantly lower than that of Comparative Example 1, but the degradation effect on nitrate is similar.
  • the test of Comparative Example 4 and Comparative Example 2 has the same result. Therefore, the tourmaline containing the anthraquinone compound of the present invention can degrade nitrate more quickly.
  • the tourmaline grafted with an anthraquinone compound on the surface obtained in the present invention has a good promoting effect on the biodegradation of azo dyes and nitrates, and has good stability, can be used repeatedly, and can be widely used in water treatment .

Abstract

The present invention relates to the field of water treatment for wastewater containing pollutants, and specifically relate to a method for preparing tourmaline containing an anthraquinone compound by means of thiol-ene click chemistry and an application thereof. A mercaptopropyl silane coupling agent reacts with tourmaline to obtain mercaptopropyl-modified tourmaline, and the mercaptopropyl-modified tourmaline then undergoes a thiol-ene click chemistry reaction with an allyloxy-containing anthraquinone compound to obtain tourmaline the surface of which contains the anthraquinone compound. The tourmaline the surface of which contains the anthraquinone compound may significantly accelerate the degradation of azo dyes and may be used repeatedly. Furthermore, the sources of the raw materials are broad, there are few reaction steps and costs are low, and said tourmaline may be widely used in the treatment of wastewater containing azo dyes and nitrates.

Description

巯基烯点击化学制备含有蒽醌化合物的电气石的方法及应用Method and application for preparing tourmaline containing anthraquinone compound by mercaptoene click chemistry 技术领域Technical field
本发明涉及水处理工程领域，具体涉及一种巯基-烯点击化学制备含有蒽醌化合物的电气石的方法及应用。The invention relates to the field of water treatment engineering, in particular to a method and application for preparing tourmaline containing anthraquinone compounds by mercapto-ene click chemistry.
背景技术Background technique
随着社会和经济的发展，人口不断增长，为了满足人们对工农业产品越来越高的要求，通过人工手段合成了大量的化学物质，这些化学物质的制造和使用造成许多含重金属和难生物降解污染物的废水排放进入动植物和人类赖以生存的环境，最终对人体健康和整个自然界生态圈都造成严重危害。偶氮染料是难生物降解化学物质的一种，因其合成工艺简单、成本低廉、染色性能突出等特点，已成为纺织品服装在印染工艺中应用最广泛、用量最大的一类合成染料。在印染过程中约有10-15％的染料会流失到印染废水中，这些印染废水的排放会对受纳水体产生严重危害，其中就包括偶氮染料。With the development of society and economy, the population continues to grow. In order to meet people's increasingly high requirements for industrial and agricultural products, a large number of chemical substances have been synthesized by artificial means. The manufacture and use of these chemical substances have caused many heavy metals and difficult organisms. The waste water that degrades pollutants is discharged into the environment where animals, plants and humans depend, and ultimately causes serious harm to human health and the entire natural ecosystem. Azo dyes are a kind of difficult-to-biodegradable chemical substances. Because of their simple synthesis process, low cost and outstanding dyeing performance, they have become the most widely used and the largest amount of synthetic dyes in textiles and clothing in the printing and dyeing process. In the printing and dyeing process, about 10-15% of the dyes will be lost to the printing and dyeing wastewater. The discharge of these printing and dyeing wastewater will cause serious harm to the receiving water body, including azo dyes.
硝酸盐是另一类对人体和环境具有较大危害的化学物质。过度施用的化肥、生活污水及粪便、工业污水等含有的氨态氮及硝态氮，经由土壤、水体等进入自然环境，是引发水体富营养化的主要物质之一。常规生化处理工艺一般只能将氨态氮转变为硝态氮，硝态氮的还原因为反硝化效率低而在一般处理工艺中无法高效完成。Nitrate is another chemical substance that is harmful to the human body and the environment. Ammonia nitrogen and nitrate nitrogen contained in over-applied chemical fertilizers, domestic sewage, manure, industrial sewage, etc., enter the natural environment through soil and water bodies, and are one of the main substances that cause eutrophication of water bodies. Conventional biochemical treatment processes generally can only convert ammonia nitrogen into nitrate nitrogen, and the reduction of nitrate nitrogen cannot be efficiently completed in general treatment processes because of the low denitrification efficiency.
因此，对这类废水的处理越发受到重视，其中主要的处理方法是化学法和生物法。生物法的应用前景更好，尤其厌氧-好氧工艺是处理这类废水的最有效也是最广泛使用的方法，如何提高微生物还原染料、硝酸根的速率一直是这类工艺的重点。Therefore, more and more attention is paid to the treatment of this type of wastewater, and the main treatment methods are chemical and biological methods. Biological methods have better application prospects, especially the anaerobic-aerobic process is the most effective and widely used method for treating this type of wastewater. How to increase the rate of microbial reduction of dye and nitrate has always been the focus of this type of process.
研究者发现含有醌基的氧化还原介体能够有效的加速偶氮染料、硝酸盐等的生物转化过程，提高降解速率。而含醌基的氧化还原介体由于分子量较小，直接加入到水处理体系中易流失造成二次污染和连续投料成本高的缺点。将含醌基的氧化还原介体固定在不溶于水的物理载体上，是比较可行的工业化方法，既有可以反复利用的优点，又不容易流失，避免二次污染的发生。Researchers have found that redox mediators containing quinone groups can effectively accelerate the biotransformation process of azo dyes and nitrates, and increase the degradation rate. However, the redox mediator containing quinone groups has the disadvantages of low molecular weight, which is easy to lose when directly added to the water treatment system, causing secondary pollution and high continuous feeding cost. Fixing the quinone group-containing redox mediator on a physical carrier that is insoluble in water is a relatively feasible industrialized method. It has the advantage of being reusable, not easy to lose, and avoiding secondary pollution.
授权公告号CN101862680B的中国授权发明专利公开了一种多孔无机填料固定醌化合物的制备方法，有效提高了对偶氮染料的降解速率。该制备方法是在多孔无机填料表面镀上γ-氧化铝，然后用3-氨基三乙氧基硅烷处理，使得多孔无机填料表面含有伯氨基，再通过该伯氨基与含有磺酰氯基团的蒽醌化合物反应，得到表面含有醌基的多孔无机填料。该方法存在以下的问题：(1)反应步骤长，耗时长，最终收率低，成本高；(2)使用含有磺酰氯基团的蒽醌化合物在接触水汽时很容易产生氯化氢气体，危险性大，因此使 用时需要严格控制生产环境，造成操作不方便和成本提高；(3)多孔无机填料虽然比表面积大，但是内部的多孔结构在实际应用时容易被菌群堵塞，不能发挥作用，往往只有表面的醌基化合物能发挥作用。The Chinese authorized invention patent with the authorized announcement number CN101862680B discloses a method for preparing a porous inorganic filler to fix a quinone compound, which effectively improves the degradation rate of azo dyes. The preparation method is to plate γ-alumina on the surface of the porous inorganic filler, and then treat it with 3-aminotriethoxysilane to make the surface of the porous inorganic filler contain primary amino groups, and then pass the primary amino groups and anthracene containing sulfonyl chloride groups. The quinone compound reacts to obtain a porous inorganic filler containing quinone groups on the surface. This method has the following problems: (1) The reaction steps are long, time-consuming, the final yield is low, and the cost is high; (2) The use of anthraquinone compounds containing sulfonyl chloride groups can easily generate hydrogen chloride gas when exposed to water vapor, which is dangerous Therefore, the production environment needs to be strictly controlled during use, which causes inconvenience and cost increase; (3) Although porous inorganic fillers have a large specific surface area, the internal porous structure is easily blocked by the flora in practical applications and cannot function. Only the quinone-based compound on the surface can play a role.
含有醌基的氧化还原介体作为电子传递体，能够可逆的被还原和氧化，因此其具有可在多个氧化还原反应中作为电子载体的能力，加速电子从初级电子供体传递到最终电子受体，从而使得生物氧化还原反应的速率提高一到几个数量级。因此提高氧化还原介体的电子传递能力，能更加加速生物的氧化还原能力。但氧化还原介体本身的电子传递能力基本上保持不变，一种方法是提高其所处环境的传递电子的能力，使得其加速偶氮染料、硝酸盐等的生物降解更快。Redox mediators containing quinone groups can be reversibly reduced and oxidized as electron mediators. Therefore, they have the ability to act as electron carriers in multiple redox reactions, accelerating the transfer of electrons from the primary electron donor to the final electron acceptor. Therefore, the rate of biological redox reaction increases by one to several orders of magnitude. Therefore, improving the electron transfer ability of the redox mediator can further accelerate the redox ability of organisms. However, the electron transfer ability of the redox mediator itself remains basically unchanged. One way is to improve the electron transfer ability of the environment in which it is located, so that it accelerates the biodegradation of azo dyes, nitrates, etc. faster.
巯基-烯点击化学反应具有高效、快速、反应条件温和、产物收率高和操作简单等特点，近些年越来越多的应用在材料的改性上。The mercapto-ene click chemistry reaction has the characteristics of high efficiency, rapidity, mild reaction conditions, high product yield and simple operation. In recent years, more and more applications have been applied to the modification of materials.
发明内容Summary of the invention
本发明的目的在于克服现有技术缺陷，提供一种巯基-烯点击化学制备含有蒽醌化合物的电气石的方法。The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing tourmaline containing anthraquinone compound by mercapto-ene click chemistry.
本发明的另一个目的在于提供一种含有蒽醌化合物的电气石的应用。Another object of the present invention is to provide an application of tourmaline containing an anthraquinone compound.
本发明的技术方案如下：The technical scheme of the present invention is as follows:
一种巯基-烯点击化学制备含有蒽醌化合物的电气石的方法，包括以下步骤，A method for preparing tourmaline containing anthraquinone compound by mercapto-ene click chemistry includes the following steps:
一、将第一有机溶剂、巯丙基硅烷偶联剂和质量浓度0.1wt％的稀盐酸在室温下搅拌0.5-1小时，加入到电气石中，升温至不超过80℃，反应1-5小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石；1. Stir the first organic solvent, mercaptopropyl silane coupling agent and 0.1wt% dilute hydrochloric acid at room temperature for 0.5-1 hour, add to tourmaline, heat up to no more than 80℃, react 1-5 After hours, cool down, filter, filter out the solid, wash 3 times with absolute ethanol, and dry to obtain mercaptopropyl modified tourmaline;
二、将步骤一得到的巯丙基改性电气石、含烯丙氧基蒽醌化合物、第二有机溶剂和光引发剂加入到容器中，室温搅拌下在主波长365nm，光强度10-200W/cm的紫外光下照射1-30min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石。2. Add the mercaptopropyl-modified tourmaline, the allyloxy anthraquinone compound, the second organic solvent and the photoinitiator obtained in step one into the container. Under stirring at room temperature, the main wavelength is 365nm and the light intensity is 10-200W/ After irradiating 1-30min under UV light of cm, filtered, the filtered solid was washed 3 times with absolute ethanol, and dried to obtain tourmaline containing anthraquinone compound.
优选的，步骤一中所述第一有机溶剂、巯丙基硅烷偶联剂、稀盐酸和电气石的重量比为1:0.1-0.3:0.01:0.5-1。第一有机溶剂、巯丙基硅烷偶联剂、稀盐酸和电气石的重量比可以是1:0.1:0.01:0.5、1:0.2:0.01:0.5、1:0.3:0.01:0.5、1:0.1:0.01:1、1:0.2:0.01:1或1:0.3:0.01:1，但并不局限于以上所列。Preferably, the weight ratio of the first organic solvent, mercaptopropyl silane coupling agent, dilute hydrochloric acid and tourmaline in step one is 1:0.1-0.3:0.01:0.5-1. The weight ratio of the first organic solvent, mercaptopropyl silane coupling agent, dilute hydrochloric acid and tourmaline can be 1:0.1:0.01:0.5, 1:0.2:0.01:0.5, 1:0.3:0.01:0.5, 1:0.1 :0.01:1, 1:0.2:0.01:1 or 1:0.3:0.01:1, but not limited to those listed above.
更优选的，步骤一中所述第一有机溶剂和步骤二中所述第二有机溶剂选自甲醇、无水乙醇、异丙醇、正丙醇、乙酸乙酯、乙酸丁酯、四氢呋喃、甲乙酮、甲苯和二甲苯中的一种或几种。More preferably, the first organic solvent in step one and the second organic solvent in step two are selected from methanol, absolute ethanol, isopropanol, n-propanol, ethyl acetate, butyl acetate, tetrahydrofuran, and methyl ethyl ketone One or more of, toluene and xylene.
在一种更优选的方案中，第一有机溶剂选自甲醇、无水乙醇、异丙醇和乙酸乙酯中的一种或几种。In a more preferred embodiment, the first organic solvent is selected from one or more of methanol, absolute ethanol, isopropanol and ethyl acetate.
在一种更优选的方案中，第二有机溶剂选自四氢呋喃、甲苯、乙酸丁酯和甲乙酮中的一种或几种。In a more preferred embodiment, the second organic solvent is selected from one or more of tetrahydrofuran, toluene, butyl acetate and methyl ethyl ketone.
更优选的，步骤一中所述巯丙基硅烷偶联剂选自3-巯丙基三甲氧基硅烷、3-巯丙基三乙氧基硅烷、3-巯丙基甲基二甲氧基硅烷和3-巯丙基甲基二乙氧基硅烷中的一种或几种。More preferably, the mercaptopropyl silane coupling agent in step 1 is selected from 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane One or more of silane and 3-mercaptopropylmethyldiethoxysilane.
更优选的，步骤一中所述电气石的平均粒径0.1μm～1cm。电气石的平均粒径可以是1μm、5μm、10μm、20μm、50μm、100μm、150μm、200μm、500μm、1mm或5mm，但并不局限于以上所列。More preferably, the average particle size of the tourmaline in step 1 is 0.1 μm to 1 cm. The average particle size of tourmaline may be 1 μm, 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 150 μm, 200 μm, 500 μm, 1 mm, or 5 mm, but is not limited to the above list.
优选的，步骤二中所述巯丙基改性电气石、含烯丙氧基蒽醌化合物、第二有机溶剂和光引发剂的重量比为1:0.1-0.3:2-10:0.03-0.06。巯丙基改性电气石、含烯丙氧基蒽醌化合物、第二有机溶剂和光引发剂的重量比可以为1:0.1:3:0.03、1:0.1:3:0.05、1:0.2:5:0.04、1:0.2:5:0.06或1:0.3:8:0.06，但并不局限于以上所列。Preferably, the weight ratio of the mercaptopropyl-modified tourmaline, the allyloxy-containing anthraquinone compound, the second organic solvent and the photoinitiator in step 2 is 1:0.1-0.3:2-10:0.03-0.06. The weight ratio of mercaptopropyl modified tourmaline, allyloxy-containing anthraquinone compound, second organic solvent and photoinitiator can be 1:0.1:3:0.03, 1:0.1:3:0.05, 1:0.2:5 :0.04, 1:0.2:5:0.06 or 1:0.3:8:0.06, but not limited to the above list.
更优选的，步骤二中所述含烯丙氧基蒽醌化合物选自1-烯丙氧基-4-羟基蒽醌-9,10-二酮和1-氨基-4-烯丙氧基蒽醌中的一种或两种。More preferably, the allyloxy-containing anthraquinone compound in step 2 is selected from 1-allyloxy-4-hydroxyanthraquinone-9,10-dione and 1-amino-4-allyloxyanthracene One or two of quinones.
公开号CN101108795A中国发明授权专利公开了1-烯丙氧基-4-羟基蒽醌-9,10-二酮的制备方法。The publication number CN101108795A Chinese invention authorized patent discloses the preparation method of 1-allyloxy-4-hydroxyanthraquinone-9,10-dione.
2009年3月出版的《长沙理工大学学报(自然科学版)》(第6卷第1期,77-82页)《共价固定1-氨基-4-烯丙氧基蒽醌的荧光传感器的制备及其在奥硝唑测定中的应用》报导了采用1-氨基-4-羟基蒽醌和溴丙烯制备1-氨基-4-烯丙氧基蒽醌的方法。"Journal of Changsha University of Science and Technology (Natural Science Edition)" (Volume 6, Issue 1, Pages 77-82), published in March 2009, "Covalently immobilized 1-amino-4-allyloxyanthraquinone fluorescence sensor Preparation and its application in the determination of ornidazole" reported the use of 1-amino-4-hydroxyanthraquinone and bromopropene to prepare 1-amino-4-allyloxyanthraquinone.
更优选的，步骤二中所述光引发剂选自安息香、安息香双甲醚、安息香***、安息香丁醚、安息香异丙醚、二苯甲酮、2,4-二羟基二苯甲酮、2-羟基-2-甲基-1-苯基丙酮(1173)、1-羟基环己基苯基甲酮(184)、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮(907)、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮(659)、2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)和2,4,6-三甲基苯甲酰基苯基膦酸乙酯(TPO-L)中的一种或几种。More preferably, the photoinitiator in step 2 is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, benzophenone, 2,4-dihydroxybenzophenone, 2 -Hydroxy-2-methyl-1-phenylacetone (1173), 1-hydroxycyclohexylphenylketone (184), 2-methyl-2-(4-morpholinyl)-1-[4- (Methylthio)phenyl)-1-acetone (907), 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-acetone (659), 2 ,4,6-Trimethylbenzoyl-diphenylphosphine oxide (TPO) and 2,4,6-trimethylbenzoylphenylphosphonic acid ethyl ester (TPO-L) one or more Kind.
在一种进一步优选的方案中，光引发剂可以选自安息香双甲醚、安息香丁醚和安息香***中的一种或几种。In a further preferred solution, the photoinitiator can be selected from one or more of benzoin dimethyl ether, benzoin butyl ether and benzoin ethyl ether.
一种上述任一实施方案所述的方法制备出的含有蒽醌化合物的电气石。A tourmaline containing an anthraquinone compound prepared by the method described in any one of the above embodiments.
一种上述任一实施方案所述的方法制备出的含有蒽醌化合物的电气石在水处理领域的应用。An application of tourmaline containing an anthraquinone compound prepared by the method described in any one of the above embodiments in the field of water treatment.
电气石也叫托玛琳，是一种硼酸盐、硅酸盐与多种金属元素组合而成的化合物，具有热电性和压电性。当电气石受到温度的变化时，电气石晶体的两端会分别带有正负不同的电荷，这是电气石独特的热电性。当电气石的两端受到压力时，也会呈现带有不同电荷的现象。本发明利用电气石的热电性和压电性，将其表面用含蒽醌化合物改性后应用于水处理时，随着水体温度的变化和/或由于水体流动产生的对电气石的压力，导致电气石的两端产生正负电荷，产生的正负电荷提高了其周围水体的导电性，因此可以提高蒽醌化合物作为氧化还原介体对偶氮染料、硝酸盐的加速降解作用。Tourmaline, also called tourmaline, is a compound composed of borate, silicate and various metal elements, which has pyroelectric and piezoelectric properties. When the tourmaline is subject to temperature changes, the two ends of the tourmaline crystal will have different positive and negative charges, which is the unique thermoelectricity of tourmaline. When the two ends of tourmaline are under pressure, they will also have different electric charges. The present invention utilizes the thermoelectricity and piezoelectricity of tourmaline, and when the surface is modified with an anthraquinone-containing compound and applied to water treatment, as the temperature of the water body changes and/or the pressure on the tourmaline caused by the flow of the water body, This results in the generation of positive and negative charges on both ends of the tourmaline, and the generated positive and negative charges increase the conductivity of the surrounding water, and therefore can enhance the accelerated degradation of azo dyes and nitrates by the anthraquinone compound as a redox mediator.
巯基-烯点击化学反应是一种绿色化学，具有反应高效、转化率高、反应快速(很多反应在几分钟甚至不到一分钟内就可以完成)、反应条件温和(无需高温高压)、产物收率高和操作简单等特点，近些年越来越多的应用在材料的改性上。The mercapto-ene click chemistry reaction is a kind of green chemistry with high efficiency, high conversion rate, fast reaction (many reactions can be completed in a few minutes or even less than a minute), mild reaction conditions (no need for high temperature and high pressure), product yield The characteristics of high efficiency and simple operation have been more and more used in the modification of materials in recent years.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明采用价格低廉的电气石作为物理载体，来源广泛、成本低；(1) The present invention uses low-priced tourmaline as the physical carrier, which has a wide range of sources and low cost;
(2)本发明的反应步骤少、反应过程简单、无需加热加压，成本低；(2) The present invention has fewer reaction steps, simple reaction process, no need for heating and pressure, and low cost;
(3)本发明无需采用易和湿气接触产生有毒有害气体的原料；(3) The present invention does not need to use raw materials that are easy to contact with moisture to produce toxic and harmful gases;
(4)本发明得到的含有蒽醌化合物的电气石可明显增速偶氮染料和硝酸盐的生物降解速率，而且经过简单的处理后，可继续使用。(4) The tourmaline containing the anthraquinone compound obtained in the present invention can significantly increase the biodegradation rate of azo dyes and nitrates, and can continue to be used after simple treatment.
(5)本发明利用电气石的热电性和压电性，在环境温度变化和/或对电气石两端产生压力的情况下，使得含蒽醌化合物的电气石更加快速的促进偶氮染料、硝酸盐等的降解。(5) The present invention utilizes the thermoelectricity and piezoelectricity of tourmaline to make the tourmaline containing anthraquinone compound more quickly promote the azo dye, under the condition of environmental temperature change and/or pressure on both ends of the tourmaline. Degradation of nitrates, etc.
具体实施方式Detailed ways
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。The technical solutions of the present invention will be further illustrated and described below through specific embodiments.
如无特别指明，以下实施方案中的份数都为重量份数。Unless otherwise specified, the parts in the following embodiments are all parts by weight.
实施例1Example 1
将100份甲醇、10份3-巯丙基三甲氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌0.5小时，加入到50份5μm电气石中，升温至50℃，反应2小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石1。100 parts of methanol, 10 parts of 3-mercaptopropyltrimethoxysilane and 1 part of 0.1wt% dilute hydrochloric acid were stirred at room temperature for 0.5 hours, added to 50 parts of 5μm tourmaline, heated to 50°C, reaction 2 After hours, the temperature was lowered, filtered, the filtered solid was washed 3 times with absolute ethanol, and dried to obtain mercaptopropyl-modified tourmaline 1.
将100份巯丙基改性电气石1、10份1-烯丙氧基-4-羟基蒽醌-9,10-二酮、300份四氢呋喃和3份安息香***加入到容器中，室温搅拌下在主波长365nm，光强度20W/cm的紫外光下照射20min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石1。Add 100 parts of mercaptopropyl-modified tourmaline 1, 10 parts of 1-allyloxy-4-hydroxyanthraquinone-9,10-dione, 300 parts of tetrahydrofuran and 3 parts of benzoin ether into the container, stirring at room temperature Irradiated under ultraviolet light with a dominant wavelength of 365 nm and a light intensity of 20 W/cm for 20 minutes, filtered, and the filtered solid was washed three times with absolute ethanol and dried to obtain tourmaline 1 containing an anthraquinone compound.
FT-IR分析，产物在1668cm -1处出现强的尖锐的吸收峰，为蒽醌结构上羰基的特征吸 收峰，在1599cm -1出现中等强度的尖锐吸收峰，为苯环上的碳氢的特征吸收峰，表明蒽醌化合物固定在电气石的表面。采用元素分析方法测定固定前后电气石的S元素含量，通过计算得到电气石1表面的蒽醌化合物含量为1.96mmol/g。 FT-IR analysis shows that the product has a strong sharp absorption peak at 1668cm -1 , which is the characteristic absorption peak of the carbonyl group on the anthraquinone structure, and a moderately sharp absorption peak appears at 1599cm -1 , which is the hydrocarbon on the benzene ring The characteristic absorption peak indicates that the anthraquinone compound is fixed on the surface of tourmaline. The elemental analysis method was used to determine the S content of the tourmaline before and after the fixation. The content of the anthraquinone compound on the surface of the tourmaline 1 was calculated to be 1.96 mmol/g.
实施例2Example 2
将100份甲醇、20份3-巯丙基三甲氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌0.5小时，加入到50份20μm电气石中，升温至50℃，反应2小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石2。100 parts of methanol, 20 parts of 3-mercaptopropyltrimethoxysilane and 1 part of 0.1wt% dilute hydrochloric acid were stirred at room temperature for 0.5 hours, added to 50 parts of 20μm tourmaline, heated to 50°C, reaction 2 After hours, the temperature was lowered, filtered, and the filtered solid was washed 3 times with absolute ethanol, and dried to obtain mercaptopropyl-modified tourmaline 2.
将100份巯丙基改性电气石2、20份1-烯丙氧基-4-羟基蒽醌-9,10-二酮、500份四氢呋喃和4份安息香双甲醚加入到容器中，室温搅拌下在主波长365nm，光强度100W/cm的紫外光下照射5min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石2。Add 100 parts of mercaptopropyl modified tourmaline 2, 20 parts of 1-allyloxy-4-hydroxyanthraquinone-9,10-dione, 500 parts of tetrahydrofuran and 4 parts of benzoin dimethyl ether into the container, room temperature Under stirring, irradiate with ultraviolet light with a dominant wavelength of 365 nm and a light intensity of 100 W/cm for 5 minutes, filter, and filter the solid, wash it with absolute ethanol 3 times, and dry to obtain tourmaline 2 containing an anthraquinone compound.
采用元素分析方法测定固定前后电气石的S元素含量，通过计算得到电气石2表面的蒽醌化合物含量为1.74mmol/g。The elemental analysis method was used to determine the S content of the tourmaline before and after the fixation. The content of the anthraquinone compound on the surface of the tourmaline 2 was calculated to be 1.74 mmol/g.
实施例3Example 3
将100份无水乙醇、30份3-巯丙基三乙氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌1小时，加入到100份100μm电气石中，升温至70℃，反应3小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石3。100 parts of absolute ethanol, 30 parts of 3-mercaptopropyltriethoxysilane and 1 part of dilute hydrochloric acid with a mass concentration of 0.1wt% were stirred at room temperature for 1 hour, added to 100 parts of 100μm tourmaline, and heated to 70°C , React for 3 hours, cool down, filter, filter the solid, wash 3 times with absolute ethanol, and dry to obtain mercaptopropyl-modified tourmaline 3.
将100份巯丙基改性电气石3、30份1-烯丙氧基-4-羟基蒽醌-9,10-二酮、800份甲苯和6份安息香双甲醚加入到容器中，室温搅拌下在主波长365nm，光强度150W/cm的紫外光下照射3min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石3。Add 100 parts of mercaptopropyl modified tourmaline 3, 30 parts of 1-allyloxy-4-hydroxyanthraquinone-9,10-dione, 800 parts of toluene and 6 parts of benzoin dimethyl ether into the container, room temperature Under stirring, irradiate with ultraviolet light with a dominant wavelength of 365 nm and a light intensity of 150 W/cm for 3 minutes, filter, and filter the solid, wash it with absolute ethanol 3 times, and dry to obtain tourmaline 3 containing an anthraquinone compound.
采用元素分析方法测定固定前后电气石的S元素含量，通过计算得到电气石3表面的蒽醌化合物含量为1.51mmol/g。The elemental analysis method was used to determine the S content of the tourmaline before and after the fixation, and the content of the anthraquinone compound on the surface of the tourmaline 3 was calculated to be 1.51 mmol/g.
实施例4Example 4
将100份无水乙醇、20份3-巯丙基三乙氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌1小时，加入到50份500μm电气石中，升温至70℃，反应3小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石4。100 parts of absolute ethanol, 20 parts of 3-mercaptopropyltriethoxysilane and 1 part of 0.1wt% dilute hydrochloric acid were stirred at room temperature for 1 hour, added to 50 parts of 500μm tourmaline, and heated to 70°C , Reacted for 3 hours, cooled, filtered, filtered the solid, washed with absolute ethanol 3 times, and dried to obtain mercaptopropyl-modified tourmaline 4.
将100份巯丙基改性电气石4、20份1-氨基-4-烯丙氧基蒽醌、500份甲苯和4份安息香双甲醚加入到容器中，室温搅拌下在主波长365nm，光强度100W/cm的紫外光下照射10min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石4。Add 100 parts of mercaptopropyl-modified tourmaline 4, 20 parts of 1-amino-4-allyloxyanthraquinone, 500 parts of toluene and 4 parts of benzoin dimethyl ether into the container, stirring at room temperature at the dominant wavelength of 365nm, Irradiate under ultraviolet light with a light intensity of 100 W/cm for 10 min, filter, and filter the solid, wash it with absolute ethanol 3 times, and dry to obtain tourmaline 4 containing an anthraquinone compound.
采用元素分析方法测定固定前后电气石的S元素含量，通过计算得到电气石4表面的蒽醌化合物含量为1.25mmol/g。The elemental analysis method was used to determine the S content of the tourmaline before and after the fixation, and the content of the anthraquinone compound on the surface of the tourmaline 4 was calculated to be 1.25 mmol/g.
实施例5Example 5
将100份无水乙醇、15份3-巯丙基三乙氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌0.5小时，加入到50份100μm电气石中，升温至70℃，反应4小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石5。100 parts of absolute ethanol, 15 parts of 3-mercaptopropyltriethoxysilane and 1 part of 0.1wt% dilute hydrochloric acid were stirred at room temperature for 0.5 hours, added to 50 parts of 100μm tourmaline, and heated to 70°C , React for 4 hours, cool down, filter, filter the solid, wash 3 times with absolute ethanol, and dry to obtain mercaptopropyl-modified tourmaline 5.
将100份巯丙基改性电气石5、25份1-氨基-4-烯丙氧基蒽醌、300份四氢呋喃和4份安息香双甲醚加入到容器中，室温搅拌下在主波长365nm，光强度150W/cm的紫外光下照射5min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石5。Add 100 parts of mercaptopropyl-modified tourmaline 5, 25 parts of 1-amino-4-allyloxyanthraquinone, 300 parts of tetrahydrofuran and 4 parts of benzoin dimethyl ether into the container, stirring at room temperature at the dominant wavelength of 365nm, Irradiate with UV light with a light intensity of 150 W/cm for 5 min, filter, and filter the solid, wash it with absolute ethanol 3 times, and dry to obtain tourmaline 5 containing anthraquinone compound.
采用元素分析方法测定固定前后电气石的S元素含量，通过计算得到电气石5表面的蒽醌化合物含量为1.44mmol/g。The elemental analysis method was used to determine the S content of the tourmaline before and after the fixation, and the content of the anthraquinone compound on the surface of the tourmaline 5 was calculated to be 1.44 mmol/g.
对比例1Comparative example 1
将100份甲醇、15份氯丙基三甲氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌0.5小时，加入到100份20μm滑石粉中，升温至50℃，搅拌反应3小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到氯丙基修饰滑石粉。100 parts of methanol, 15 parts of chloropropyltrimethoxysilane and 1 part of 0.1wt% dilute hydrochloric acid were stirred at room temperature for 0.5 hours, added to 100 parts of 20μm talc, heated to 50°C, stirred for 3 hours , Cooling, filtering, filtering the solid, washing 3 times with absolute ethanol, and drying to obtain chloropropyl modified talc.
将容器置于14℃的水浴中，依次加入100份氯丙基修饰滑石粉、12份1-氨基蒽醌、300份四氢呋喃和8.1份三乙胺，搅拌反应8小时，升温至55℃，搅拌5小时，过滤，滤出固体用去离子水清洗3次，再用无水乙醇清洗3次，干燥，得到表面固定有蒽醌化合物的滑石粉。采用元素分析方法测定固定前后滑石粉的N元素含量，通过计算得到滑石粉表面的蒽醌化合物含量为1.70mmol/g。Place the container in a water bath at 14°C, add 100 parts of chloropropyl modified talc, 12 parts of 1-aminoanthraquinone, 300 parts of tetrahydrofuran and 8.1 parts of triethylamine in sequence, stir and react for 8 hours, heat up to 55°C, and stir After 5 hours, filter, the filtered solid was washed 3 times with deionized water, then washed 3 times with absolute ethanol, and dried to obtain talc powder with an anthraquinone compound fixed on the surface. The elemental analysis method was used to determine the N element content of the talc before and after the fixation, and the content of the anthraquinone compound on the surface of the talc was calculated to be 1.70 mmol/g.
对比例2Comparative example 2
将100份甲醇、20份氯丙基三甲氧基硅烷和1份质量浓度0.1wt％的稀盐酸在室温下搅拌0.5小时，加入到100份100μm重质碳酸钙，升温至50℃，搅拌反应3小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到氯丙基修饰重质碳酸钙。100 parts of methanol, 20 parts of chloropropyltrimethoxysilane and 1 part of 0.1wt% dilute hydrochloric acid were stirred at room temperature for 0.5 hours, then added to 100 parts of 100μm heavy calcium carbonate, heated to 50°C, stirred for reaction 3. After hours, the temperature was lowered, filtered, the filtered solid was washed 3 times with absolute ethanol, and dried to obtain chloropropyl modified heavy calcium carbonate.
将容器置于12℃的水浴中，依次加入100份氯丙基修饰重质碳酸钙、21份1-氨基蒽醌、400份四氢呋喃和11.8份三乙胺，搅拌反应5小时，升温至60℃，搅拌5小时，过滤，滤出固体用去离子水清洗3次，再用无水乙醇清洗3次，干燥，得到表面固定有蒽醌化合物的重质碳酸钙。采用元素分析方法测定固定前后重质碳酸钙的N元素含量，通过计算得到重质碳酸钙表面的蒽醌化合物含量为1.48mmol/g。Place the container in a water bath at 12°C, add 100 parts of chloropropyl modified heavy calcium carbonate, 21 parts of 1-aminoanthraquinone, 400 parts of tetrahydrofuran and 11.8 parts of triethylamine in sequence, stir and react for 5 hours, and heat up to 60°C , Stirred for 5 hours, filtered, the filtered solid was washed 3 times with deionized water, and then washed 3 times with absolute ethanol, and dried to obtain heavy calcium carbonate with anthraquinone compound fixed on the surface. The elemental analysis method was used to determine the N element content of heavy calcium carbonate before and after fixation, and the anthraquinone compound content on the surface of heavy calcium carbonate was calculated to be 1.48 mmol/g.
测试test
偶氮染料降解加速效果测试：分别将2g空白电气石、2g实施例1-5和2g对比例1-2中表面接枝蒽醌化合物的产物用生理盐水冲洗3次后，加入到200ml含对数生长期的偶氮染料降解菌株GYZ(staphylococcus sp.)的120mg/L的酸性红B中在10rpm的搅拌转速下进行脱色测试，测定酸性红B浓度随时间的变化。结果如表1所示。Azo dye degradation acceleration effect test: 2g of blank tourmaline, 2g of Examples 1-5 and 2g of the products of Comparative Examples 1-2 grafted on the surface of anthraquinone compounds were washed with physiological saline three times, and then added to 200ml containing The azo dye degradation strain GYZ (staphylococcus sp.) of 120 mg/L acid red B was tested for decolorization at a stirring speed of 10 rpm in several growth phases, and the concentration of acid red B was measured over time. The results are shown in Table 1.
硝酸盐降解加速效果测试：分别将2g空白电气石、2g实施例1-5和2g对比例1-2中表面接枝蒽醌化合物的产物用生理盐水冲洗3次后，加入到200ml含对数生长期反硝化微生物的150mg/L的硝酸盐废水中在10rpm的搅拌转速下进行测试，测定硝酸盐浓度随时间的变化。结果如表2所示。Nitrate degradation acceleration effect test: 2g of blank tourmaline, 2g of Example 1-5 and 2g of Comparative Example 1-2 were surface-grafted with anthraquinone compounds after being washed 3 times with normal saline, and then added to 200ml containing logarithm The test was performed in the 150mg/L nitrate wastewater of denitrifying microorganisms during the growth period at a stirring speed of 10rpm to determine the change of nitrate concentration over time. The results are shown in Table 2.
稳定性测试：分别将2g实施例1-5中表面接枝蒽醌化合物的电气石用生理盐水冲洗3次后，加入到200ml含对数生长期的偶氮染料降解菌株GYZ(staphylococcus sp.)的120mg/L的酸性红B中进行脱色测试，测定8小时后酸性红B的浓度。将测试后表面接枝蒽醌化合物的电气石用清水和无水乙醇清洗干燥后再按上述方法用酸性红B进行脱色测试8小时，如此反复测试12次。其中，实施例1-3的测试过程是在10rpm的搅拌转速下进行的，实施例4-5的测试过程是再25-30℃以1℃/min的温度变化下进行的，结果如表3所示。Stability test: Wash 2g of the tourmaline grafted with anthraquinone compound on the surface of Examples 1-5 with physiological saline for 3 times, and then add it to 200ml of azo dye degradation strain GYZ (staphylococcus sp.) containing logarithmic growth phase. Decolorization test was carried out in 120mg/L of Acid Red B, and the concentration of Acid Red B after 8 hours was measured. After the test, the tourmaline grafted with anthraquinone compound on the surface was washed and dried with water and absolute ethanol, and then subjected to the decolorization test with Acid Red B for 8 hours according to the above method, and the test was repeated 12 times. Among them, the test process of Examples 1-3 was carried out at a stirring speed of 10 rpm, and the test process of Examples 4-5 was carried out at a temperature change of 1 °C/min at 25-30°C. The results are shown in Table 3. Shown.
表1酸性红B降解加速测试结果Table 1 Accelerated Test Results of Acid Red B Degradation
Figure PCTCN2020087433-appb-000001
Figure PCTCN2020087433-appb-000001
由表1可知，本发明的表面接枝蒽醌化合物的电气石具有显著的促进酸性红B偶氮染料降解的作用，而且随着蒽醌化合物含量的增加，对酸性红B的降解更快。对比实施例3和5与对比例1的测试，实施例3和5中电气石表面接枝的蒽醌化合物的含量明显低 于对比例1，但是对酸性红B染料的降解效果差不多。对比实施例4和对比例2的测试，具有同样的结果。因此，采用本发明的含有蒽醌化合物的电气石能更快的降解偶氮染料。It can be seen from Table 1 that the tourmaline grafted with an anthraquinone compound on the surface of the present invention can significantly promote the degradation of acid red B azo dyes, and as the content of the anthraquinone compound increases, the degradation of acid red B is faster. Comparing the tests of Examples 3 and 5 and Comparative Example 1, the content of the anthraquinone compound grafted on the surface of tourmaline in Examples 3 and 5 is significantly lower than that in Comparative Example 1, but the degradation effect on the acid red B dye is similar. The test of Comparative Example 4 and Comparative Example 2 has the same result. Therefore, the tourmaline containing the anthraquinone compound of the present invention can degrade the azo dye faster.
表2硝酸盐降解加速测试结果Table 2 Accelerated test results of nitrate degradation
Figure PCTCN2020087433-appb-000002
Figure PCTCN2020087433-appb-000002
由表2可知，本发明的表面接枝蒽醌化合物的电气石具有显著的促进硝酸盐降解的作用，而且随着蒽醌化合物含量的增加，对硝酸盐的降解更快。对比实施例3和5与对比例1的测试，实施例3和5中电气石表面接枝的蒽醌化合物的含量明显低于对比例1，但是对硝酸盐的降解效果差不多。对比实施例4和对比例2的测试，具有同样的结果。因此，采用本发明的含有蒽醌化合物的电气石能更快的降解硝酸盐。It can be seen from Table 2 that the tourmaline grafted with an anthraquinone compound on the surface of the present invention has a significant effect of promoting the degradation of nitrate, and as the content of the anthraquinone compound increases, the degradation of nitrate is faster. Comparing the tests of Examples 3 and 5 and Comparative Example 1, the content of the anthraquinone compound grafted on the surface of tourmaline in Examples 3 and 5 is significantly lower than that of Comparative Example 1, but the degradation effect on nitrate is similar. The test of Comparative Example 4 and Comparative Example 2 has the same result. Therefore, the tourmaline containing the anthraquinone compound of the present invention can degrade nitrate more quickly.
表3酸性红B降解稳定性测定结果Table 3 Degradation stability test results of Acid Red B
Figure PCTCN2020087433-appb-000003
Figure PCTCN2020087433-appb-000003
Figure PCTCN2020087433-appb-000004
Figure PCTCN2020087433-appb-000004
由表3可知，本发明得到的表面接枝蒽醌化合物的电气石在促进偶氮染料生物降解中反复使用12次后还具有较好的效果。It can be seen from Table 3 that the tourmaline grafted with an anthraquinone compound on the surface obtained in the present invention has a better effect after repeated use for 12 times in promoting the biodegradation of azo dyes.
综上所述，本发明得到的表面接枝蒽醌化合物的电气石对偶氮染料和硝酸盐的生物降解具有较好的促进作用，而且稳定性好，可反复使用，在水处理中可广泛应用。In summary, the tourmaline grafted with an anthraquinone compound on the surface obtained in the present invention has a good promoting effect on the biodegradation of azo dyes and nitrates, and has good stability, can be used repeatedly, and can be widely used in water treatment .
以上所述，显示和描述了本发明的基本原理、主要特征和优点。本领域技术人员应该了解本发明不受上述实施例的限制，上述实施例仅为本发明的较佳实施例而已，不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。The above has shown and described the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments are only preferred embodiments of the present invention. The scope of implementation of the present invention cannot be limited accordingly, that is, it is made in accordance with the patent scope of the present invention and the contents of the specification. The equivalent changes and modifications of should still fall within the scope of the present invention. The scope of protection claimed by the present invention is defined by the appended claims and their equivalents.

Claims (10)

  1. 一种巯基-烯点击化学制备含有蒽醌化合物的电气石的方法，其特征在于：包括以下步骤，A method for preparing tourmaline containing anthraquinone compound by mercapto-ene click chemistry, characterized in that it comprises the following steps:
    一、将第一有机溶剂、巯丙基硅烷偶联剂和质量浓度0.1wt％的稀盐酸在室温下搅拌0.5-1小时，加入到电气石中，升温至不超过80℃，反应1-5小时，降温，过滤，滤出固体用无水乙醇清洗3次，干燥，得到巯丙基改性电气石；1. Stir the first organic solvent, mercaptopropyl silane coupling agent and 0.1wt% dilute hydrochloric acid at room temperature for 0.5-1 hour, add to tourmaline, heat up to no more than 80℃, react 1-5 After hours, cool down, filter, filter out the solid, wash 3 times with absolute ethanol, and dry to obtain mercaptopropyl modified tourmaline;
    二、将步骤一得到的巯丙基改性电气石、含烯丙氧基蒽醌化合物、第二有机溶剂和光引发剂加入到容器中，室温搅拌下在主波长365nm，光强度10-200W/cm的紫外光下照射1-30min，过滤，滤出固体用无水乙醇清洗3次，干燥，得到含有蒽醌化合物的电气石。2. Add the mercaptopropyl-modified tourmaline, the allyloxy anthraquinone compound, the second organic solvent and the photoinitiator obtained in step one into the container. Under stirring at room temperature, the main wavelength is 365nm and the light intensity is 10-200W/ After irradiating 1-30min under UV light of cm, filtered, the filtered solid was washed 3 times with absolute ethanol, and dried to obtain tourmaline containing anthraquinone compound.
  2. 根据权利要求1所述的方法，其特征在于：步骤一中所述第一有机溶剂、巯丙基硅烷偶联剂、稀盐酸和电气石的重量比为1:0.1-0.3:0.01:0.5-1。The method according to claim 1, wherein the weight ratio of the first organic solvent, mercaptopropyl silane coupling agent, dilute hydrochloric acid and tourmaline in step one is 1:0.1-0.3:0.01:0.5- 1.
  3. 根据权利要求1或2所述的方法，其特征在于：步骤一中所述第一有机溶剂和步骤二中所述第二有机溶剂选自甲醇、无水乙醇、异丙醇、正丙醇、乙酸乙酯、乙酸丁酯、四氢呋喃、甲乙酮、甲苯和二甲苯中的一种或几种。The method according to claim 1 or 2, characterized in that: the first organic solvent in step one and the second organic solvent in step two are selected from methanol, absolute ethanol, isopropanol, n-propanol, One or more of ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, toluene and xylene.
  4. 根据权利要求1或2所述的方法，其特征在于：步骤一中所述巯丙基硅烷偶联剂选自3-巯丙基三甲氧基硅烷、3-巯丙基三乙氧基硅烷、3-巯丙基甲基二甲氧基硅烷和3-巯丙基甲基二乙氧基硅烷中的一种或几种。The method according to claim 1 or 2, wherein the mercaptopropyl silane coupling agent in step 1 is selected from 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, One or more of 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane.
  5. 根据权利要求1或2所述的方法，其特征在于：步骤一中所述电气石的平均粒径0.1μm～1cm。The method according to claim 1 or 2, characterized in that the average particle size of the tourmaline in step 1 is 0.1 μm to 1 cm.
  6. 根据权利要求1所述的方法，其特征在于：步骤二中所述巯丙基改性电气石、含烯丙氧基蒽醌化合物、第二有机溶剂和光引发剂的重量比为1:0.1-0.3:2-10:0.03-0.06。The method according to claim 1, wherein the weight ratio of the mercaptopropyl-modified tourmaline, the allyloxy-containing anthraquinone compound, the second organic solvent and the photoinitiator in step two is 1:0.1- 0.3:2-10:0.03-0.06.
  7. 根据权利要求1或6所述的方法，其特征在于：步骤二中所述含烯丙氧基蒽醌化合物选自1-烯丙氧基-4-羟基蒽醌-9,10-二酮和1-氨基-4-烯丙氧基蒽醌中的一种或两种。The method according to claim 1 or 6, wherein the allyloxy-containing anthraquinone compound in step 2 is selected from 1-allyloxy-4-hydroxyanthraquinone-9,10-dione and One or two of 1-amino-4-allyloxyanthraquinone.
  8. 根据权利要求1或6所述的方法，其特征在于：步骤二中所述光引发剂选自安息香、安息香双甲醚、安息香***、安息香丁醚、安息香异丙醚、二苯甲酮、2,4-二羟基二苯甲酮、2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮、2-羟基-2-甲基-1-[4-(2-羟基乙氧基)苯基]-1-丙酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦和2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种或几种。The method according to claim 1 or 6, wherein the photoinitiator in step 2 is selected from benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, benzophenone, 2 , 4-Dihydroxybenzophenone, 2-hydroxy-2-methyl-1-phenylacetone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-(4-morpholinyl)- 1-[4-(Methylthio)phenyl]-1-acetone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-acetone, 2, One or more of 4,6-trimethylbenzoyl-diphenylphosphine oxide and ethyl 2,4,6-trimethylbenzoylphenylphosphonate.
  9. 一种权利要求1-8任一项所述的方法制备出的含有蒽醌化合物的电气石。A tourmaline containing an anthraquinone compound prepared by the method of any one of claims 1-8.
  10. 一种权利要求1-8任一项所述的方法制备出的含有蒽醌化合物的电气石在水处理领域的应用。An application of tourmaline containing an anthraquinone compound prepared by the method of any one of claims 1-8 in the field of water treatment.
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