WO2020151001A1 - 一种超疏水高比表面积微孔聚合物吸附材料的制备方法 - Google Patents

一种超疏水高比表面积微孔聚合物吸附材料的制备方法 Download PDF

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WO2020151001A1
WO2020151001A1 PCT/CN2019/073203 CN2019073203W WO2020151001A1 WO 2020151001 A1 WO2020151001 A1 WO 2020151001A1 CN 2019073203 W CN2019073203 W CN 2019073203W WO 2020151001 A1 WO2020151001 A1 WO 2020151001A1
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surface area
specific surface
high specific
trinaphthylbenzene
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杨坤
龚俐
任柳芬
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Zhejiang University
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    • C—CHEMISTRY; METALLURGY
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    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
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    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

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  • the invention relates to a preparation method of a superhydrophobic high specific surface area microporous polymer adsorption material, which belongs to the technical field of polymer materials.
  • VOCs Volatile organic compounds
  • Adsorption technology has become the preferred method of VOCs treatment due to its economic and high efficiency advantages.
  • the core of adsorption technology is to select adsorption materials with high specific surface area and high adsorption capacity.
  • Activated carbon as a traditional VOCs adsorption material, has disadvantages such as pore blockage and small adsorption capacity, and due to the existence of oxygen-containing functional groups on the surface, water molecules will compete for the adsorption sites of biochar for VOCs under actual conditions (relative humidity>5%) , Thereby reducing the adsorption capacity of biochar for VOCs. Therefore, the development of adsorbents with high specific surface area and hydrophobic surface is of great significance for the treatment of VOCs.
  • Hypercrosslinked polymers have a wide range of applications in the fields of adsorption and separation of gas and water compounds and heterogeneous catalysis due to their high specific surface area, low skeleton density, and stable physical and chemical properties.
  • organic molecules such as benzene, biphenyl and triphenylbenzene are used as monomers, and HCPs are synthesized by adding dimethyl formal (FDA) as crosslinking agents. Due to the introduction of alkoxy groups in the crosslinking agent, Reduce the hydrophobicity of the material. Wang et al.
  • the object of the present invention is to provide a method for preparing a microporous polymer absorbent material with superhydrophobicity and high specific surface area.
  • the present invention adopts the following technical scheme: a preparation method of superhydrophobic high specific surface area microporous polymer adsorbent material, the method is: 1,3,5-trinaphthylbenzene, chloroalkane, and Lewis acid are mixed uniformly in proportion, Polymerize at 0°C ⁇ 400°C for 15min ⁇ 100h, cool to room temperature, soak, wash, filter, and then soak with organic solvent, wash, filter, and dry to obtain superhydrophobic micropores with high specific surface area. Polymer absorbent material.
  • the ratio of the mass of 1,3,5-trinaphthylbenzene (g) to the volume (mL) of chloroalkanes is 1:1 ⁇ 1:500, and the molar ratio of Lewis acid to 1,3,5-trinaphthylbenzene is 1 :1 ⁇ 200:1.
  • chloroalkane is selected from methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride.
  • the Lewis acid is selected from anhydrous aluminum chloride, anhydrous ferric chloride, and anhydrous tin chloride.
  • the concentration of the hydrochloric acid is 0.001 mol/L to 10 mol/L.
  • the organic solvent is selected from methanol, ethanol, acetone, acetonitrile, and n-hexane.
  • the beneficial effect of the present invention is that: the present invention is based on the Fuchs alkylation reaction, and the one-step method does not require an external crosslinking agent, and obtains a superhydrophobic high specific surface area microporous (average pore diameter of 1.69nm) polymer adsorbent material, which not only has a high specific surface area (The specific surface area of Langmuir is up to 2800m 2 /g), and it is super-hydrophobic (water contact angle can reach 160°).
  • the material can be used as a potential adsorbent for the adsorption and separation of gas molecules and compounds in water.
  • Figure 2 The water contact angle diagram of the absorbent material obtained in Example 3.
  • the naphthyl group is used as the monomer building group to increase the reactive sites of the monomer and the ⁇ - ⁇ conjugation effect.
  • 1,3,5-trinaphthylbenzene is used as the monomer
  • the chloroalkane is used as the solvent and crosslinking agent.
  • a superhydrophobic high specific surface area microporous polymer adsorbent (average pore diameter of 1.69nm) was synthesized by a one-step method without the need for an external crosslinking agent in high yield. It not only has a high specific surface area (Langmuir The specific surface area is up to 2800m 2 /g), and it is superhydrophobic (water contact angle up to 160°).
  • the material can be used as a potential adsorbent for the adsorption and separation of gas molecules and compounds in water. The present invention will be further described below in conjunction with embodiments and drawings.
  • the obtained product is soaked and washed with 5 mol/L hydrochloric acid and acetonitrile, filtered and dried to obtain a superhydrophobic high specific surface area microporous polymer adsorption material.
  • the obtained product is soaked and washed with 9 mol/L hydrochloric acid and n-hexane, filtered and dried to obtain a superhydrophobic high specific surface area microporous polymer adsorption material.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

一种具有超疏水高比表面积微孔聚合物吸附材料的制备方法，以1,3,5-三萘基苯为单体，路易斯酸为催化剂，氯烷烃为溶剂，一步法无需外加交联剂反应制备得到超疏水高比表面积微孔聚合物吸附材料。所得吸附材料的平均孔径为1.69nm，Langmuir比表面积达2800m 2/g，水接触角可达160°，不仅具有高比表面积，而且具有超疏水性。该材料可作为潜在吸附剂应用于气体分子及水体中化合物的吸附与分离。

Description

一种超疏水高比表面积微孔聚合物吸附材料的制备方法 技术领域
本发明涉及一种超疏水高比表面积微孔聚合物吸附材料的制备方法，属于高分子材料技术领域。
背景技术
挥发性有机化合物(VOCs)不仅对人类健康造成损害，例如：致癌、毒性效应，还会破坏臭氧，引发光化学烟雾等。吸附技术由于具有经济、高效等优势，成为VOCs治理的首选方法。吸附技术的核心是选择具有高比表面积、高吸附容量的吸附材料。活性炭作为传统的VOCs吸附材料，存在孔堵塞、吸附容量小等缺点，并且由于表面含氧官能团的存在，在实际条件下(相对湿度>5％)水分子会竞争生物炭对VOCs的吸附位点，从而降低生物炭对VOCs的吸附容量。因此开发具有高比表面积且表面疏水的吸附剂对于VOCs的治理具有重要意义。
超交联聚合物(HCPs)由于具有高比表面积、低骨架密度，稳定的物化性质等特性在气体和水中化合物的吸附分离以及非均相催化等领域具有广泛的应用。目前，以苯、联苯、三苯基苯等有机分子为单体，通过外加二甲基缩甲醛(FDA)等为交联剂，反应合成HCPs，由于交联剂中烷氧基的引入，降低材料的疏水性。Wang等以苯、联苯、三苯基苯为有机分子单体，在无需外加交联剂的条件下合成的HCPs具有更高的比表面积和狭窄的孔径分布。据我们所知，目前具有超疏水性的高比表面积HCPs(S BET>1500m 2/g)还未有报道。
发明内容
针对以上存在的问题，本发明目的是提供一种具有超疏水高比表面积微孔聚合物吸附材料的制备方法。
本发明采用如下技术方案：一种超疏水高比表面积微孔聚合物吸附材料的制备方法，该方法为：将1,3,5-三萘基苯、氯烷烃、路易斯酸按比例混合均匀，在0℃～400℃条件下聚合反应15min～100h，冷却至室温，将所得产物分别经盐酸浸泡、洗涤，过滤，然后用有机溶剂浸泡、洗涤，过滤，干燥后得到超疏水高比表面积微孔聚合物吸附材料。1,3,5-三萘基苯质量(g)与氯烷烃的体积(mL)比为1:1～1:500，路易斯酸与1,3,5-三萘基苯的摩尔比为1:1～200:1。
进一步地，所述氯烷烃选自二氯甲烷、1,2-二氯乙烷、三氯甲烷、四氯化碳。
进一步地，路易斯酸选自无水氯化铝、无水氯化铁、无水氯化锡。
进一步地，所述盐酸浓度为0.001mol/L～10mol/L。
进一步地，所述的有机溶剂选自甲醇、乙醇、丙酮、乙腈、正己烷。
本发明的有益效果在于：本发明基于付克烷基化反应，一步法无需外加交联剂，获得超疏水高比表面积微孔(平均孔径为1.69nm)聚合物吸附材料，不仅具有高比表面积(Langmuir比表面积达2800m 2/g)，而且具有超疏水性(水接触角可达160°)。该材料可作为潜在吸附剂应用于气体分子及水中化合物的吸附与分离。
附图说明
图1：实施例3所得的吸附材料的氮气吸附等温线。
图2：实施例3所得的吸附材料的水接触角图。
具体实施方式
将萘基作为单体构建基团，增加单体的反应活性位点和π-π共轭效应，以1,3,5-三萘基苯为单体，氯烷烃做溶剂和交联剂，基于付克烷基化反应，通过一步法无需外加交联剂高产率合成制备得到了一种超疏水高比表面积微孔聚合物吸附材料(平均孔径为1.69nm),不仅具有高比表面积(Langmuir比表面积达2800m 2/g)，而且具有超疏水性(水接触角可达160°)。该材料可作为潜在吸附剂应用于气体分子及水中化合物的吸附与分离。下面结合实施例和附图对本发明做进一步说明。
实施例1
加入1,3,5-三萘基苯(g)与二氯甲烷(mL)比为1:3到反应瓶，称取无水氯化铁(无水氯化铁与1,3,5-三萘基苯的摩尔比为1:1)加入反应瓶，密封。升温加热聚合，温度控制在400℃，时间为15min。冷却至室温，所得产物经0.1mol/L盐酸和甲醇浸泡、洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为95％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为1230m 2/g，水接触角为155°。
实施例2
加入1,3,5-三萘基苯(g)与二氯甲烷(mL)比为1:200到反应瓶，称取无水氯化铝(无水氯化铝与1,3,5-三萘基苯的摩尔比为100:1)加入反应瓶，密封。升温 加热聚合，温度控制在40℃，时间为72h。冷却至室温，所得产物经5mol/L盐酸和正己烷浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为123％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为1850m 2/g，水接触角为157°。
实施例3
加入1,3,5-三萘基苯(g)与1,2-二氯乙烷(mL)比为1:60到反应瓶，称取无水氯化铁(无水氯化铁与1,3,5-三萘基苯的摩尔比为50:1)加入反应瓶，密封。升温加热聚合，温度控制在80℃，时间为50h。冷却至室温，所得产物经3mol/L盐酸和丙酮浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为113％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2800m 2/g，水接触角为160°。
实施例4
加入1,3,5-三萘基苯(g)与1,2-二氯乙烷(mL)比为1:50到反应瓶，称取无水氯化锡(无水氯化锡与1,3,5-三萘基苯的摩尔比为30:1)加入反应瓶，密封。升温加热聚合，温度控制在80℃，时间为100h。冷却至室温，所得产物经5mol/L盐酸和乙腈浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为121％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2550m 2/g，水接触角为156°。
实施例5
加入1,3,5-三萘基苯(g)与三氯甲烷(mL)比为1:500到反应瓶，称取无水氯化铝(无水氯化铝与1,3,5-三萘基苯的摩尔比为200:1)加入反应瓶，密封。冰水浴温度控制在0℃，时间为72h。冷却至室温，所得产物经10mol/L盐酸和乙醇浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为103％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为1580m 2/g，水接触角为157°。
实施例6
加入1,3,5-三萘基苯(g)与三氯甲烷(mL)比为1:1到反应瓶，称取无水氯化铝(无水氯化铝与1,3,5-三萘基苯的摩尔比为80:1)加入反应瓶，密封。升温加热聚合，温度控制在80℃，时间为48h。冷却至室温，所得产物经0.001mol/L盐酸和丙酮浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为92％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2060m 2/g，水接触角为152°。
实施例7
加入1,3,5-三萘基苯(g)与三氯甲烷(mL)比为1:30到反应瓶，称取无水氯化锡(无水氯化锡与1,3,5-三萘基苯的摩尔比为100:1)加入反应瓶，密封。升温加热聚合，温度控制在60℃，时间为12h。冷却至室温，所得产物经7mol/L盐酸和乙醇浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为119％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2240m 2/g，水接触角为159°。
实施例8
加入1,3,5-三萘基苯(g)与四氯化碳(mL)比为1:10到反应瓶，称取无水氯化锡(无水氯化锡与1,3,5-三萘基苯的摩尔比为20:1)加入反应瓶，密封。升温加热聚合，温度控制在200℃，时间为24h。冷却至室温，所得产物经6mol/L盐酸和丙酮浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为114％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2570m 2/g，水接触角为155°。
实施例9
加入1,3,5-三萘基苯(g)与四氯化碳(mL)比为1:300到反应瓶，称取无水氯化铁(无水氯化铁与1,3,5-三萘基苯的摩尔比为100:1)加入反应瓶，密封。升温加热聚合，温度控制在120℃，时间为100h。冷却至室温，所得产物经9mol/L盐酸和正己烷浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为108％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2600m 2/g，水接触角为154°。
实施例10
加入1,3,5-三萘基苯(g)与三氯甲烷(mL)比为1:200到反应瓶，称取无水氯化铁(无水氯化铁与1,3,5-三萘基苯的摩尔比为200:1)加入反应瓶，密封。升温加热聚合，温度控制在120℃，时间为100h。冷却至室温，所得产物经10mol/L盐酸和乙腈浸泡洗涤，过滤、干燥，得到超疏水高比表面积微孔聚合物吸附材料。产率为110％，(产率＝单体质量/聚合物质量×100％)，Langmuir比表面积为2360m 2/g，水接触角为158°。
对比例1
采用二乙烯苯单体(已报道的专利CN 107602744 A)替换实施例3中的1,3,5-三萘基苯，通过大量参数优化，合成产物的比表面积最高达到890.7m 2/g。
综上案例可以看出以1,3,5-三萘基苯为单体，氯烷烃做溶剂和交联剂，基于付克烷基化反应，通过一步法无需外加交联剂合成制备得到了一种超疏水高比 表面积微孔聚合物吸附材料。

Claims (5)

  1. 一种超疏水高比表面积微孔聚合物吸附材料的制备方法，其特征在于，该方法为：将1,3,5-三萘基苯、氯烷烃、路易斯酸按比例混合均匀，在0℃～400℃条件下聚合反应15min～100h，冷却至室温，将所得产物分别经盐酸浸泡、洗涤，过滤，然后用有机溶剂浸泡、洗涤，过滤，干燥后得到超疏水高比表面积微孔聚合物吸附材料。1,3,5-三萘基苯质量(g)与氯烷烃的体积(mL)比为1:1～1:500，路易斯酸与1,3,5-三萘基苯的摩尔比为1:1～200:1。
  2. 根据权利要求1所述的制备方法，其特征在于，所述氯烷烃选自二氯甲烷、1,2-二氯乙烷、三氯甲烷、四氯化碳。
  3. 根据权利要求1所述的制备方法，其特征在于，路易斯酸选自无水氯化铝、无水氯化铁、无水氯化锡。
  4. 根据权利要求1所述的制备方法，其特征在于，所述盐酸浓度为0.001mol/L～10mol/L。
  5. 根据权利要求1所述的制备方法，其特征在于，所述的有机溶剂选自甲醇、乙醇、丙酮、乙腈、正己烷。
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