CN115572371A - 离子型多孔聚合物材料的制备方法及精油吸附脱萜的应用 - Google Patents
离子型多孔聚合物材料的制备方法及精油吸附脱萜的应用 Download PDFInfo
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- CN115572371A CN115572371A CN202211104201.7A CN202211104201A CN115572371A CN 115572371 A CN115572371 A CN 115572371A CN 202211104201 A CN202211104201 A CN 202211104201A CN 115572371 A CN115572371 A CN 115572371A
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Abstract
本发明公开了离子型多孔聚合物材料的制备方法及精油吸附脱萜的应用。首先将单体和交联剂在季铵化溶剂中反应,通过旋蒸和真空干燥除去季铵化溶剂得到季铵化产物;将季铵化产物与Lewis酸催化剂在傅克反应溶剂中反应,洗涤反应产物后,进一步索式提取,干燥后得到阴离子为Cl‑或Br‑的离子型多孔聚合物材料。将离子型多孔聚合物材料装柱后用羧酸钠甲醇溶液冲洗,得到阴离子为CnH2n+1COO‑的离子型多孔聚合物。以离子型多孔聚合物为吸附剂,采用吸附的方法分离精油中的萜类化合物及其含氧衍生物。本发明制备的离子型多孔聚合物稳定性高,制备方法相对简单,对萜类含氧衍生物的吸附速率快,容量大,选择性高,易于再生。
Description
技术领域
本发明涉及高分子材料和化学工程领域,具体涉及一种离子型多孔聚合物材料的制备方法及精油吸附脱萜的应用。
背景技术
精油广泛存在于芳香植物的根、茎、叶、花、果实等部位,通常为具有芳香气味的挥发性油状液体,在一些高档日化产品中具有很高的应用价值。此外,精油还具有镇静抗焦虑、止咳平喘和促进胃肠蠕动等生理活性作用,以及广谱高效的抗菌活性,应用于食品、医药保健品等领域。通过冷榨法、水蒸气蒸馏法和溶剂提取法等得到的粗提精油中萜烯和倍半萜烯等不饱和烃类占到了90%以上,如柠檬烯、月桂烯、松油烯、桧烯、水芹烯、姜烯等,对香气的贡献很小且易氧化产生异味;而萜类含氧衍生物所占比例很小,如芳樟醇、香叶醇、松油醇、香叶醛、橙花醛、癸醛、香芹酮、乙酸香茅酯等,却是香气的主要来源且具有较强的生物活性。脱萜,即利用分离技术实现粗提精油中大量萜类化合物与少量萜类含氧衍生物的分离,得到高纯度的萜类含氧衍生物,即风味和品质俱佳的精油。同时,剩余的萜烯类副产物是重要的化工原料,可作为无毒无害的天然溶剂应用于洗涤产品,如洗涤剂、去污剂、除胶剂等。
目前,工业上精油脱萜的主要方法是蒸馏和萃取。常压蒸馏温度过高且分离度差,不适用于热敏性精油脱萜;真空蒸馏的温度相对较低,但分离效率依赖于过程的传热传质速率,分离度不高,能耗较大;专利CN110484370A公开了一种分子蒸馏分离柑橘精油的装置及方法,但生产能力有限,对技术要求高,配套设备多,价格昂贵;专利CN103333744A公开了一种超临界色谱分离浓缩柑橘精油中含氧化合物的装置及方法,但存在工艺过程控制系统复杂,分离效率低,选择性不高等问题。溶剂萃取分离柑橘精油能耗低,操作简单,设备投入较小。专利CN111363624A公开了一种将有机盐缔合萃取剂与精油混合,进行缔合萃取脱萜的方法,但仍存在着有机盐及溶剂回收困难,需多次真空蒸馏溶剂和反萃等问题。
吸附脱萜是一种相对环保且温和的分离技术,即利用多孔吸附剂与粗提精油接触,选择性吸附其中的萜类含氧衍生物,再经过脱吸,实现萜类含氧衍生物的富集。然而目前鲜有相关专利报道,使用商业化的硅胶和活性炭作为固定相,需要大量有机溶剂洗脱,且分离能力十分有限(Iranian Journal of Pharmaceutical Sciences,2006,2(2):87-90、Journal of Chromatography A,2009,1216(14):2768-2775),进一步分离纯化需要高效液相色谱法(International Journal of Food Microbiology,2008,123(3):228-233)。因此,亟需寻找高效的吸附分离材料应用于精油脱萜。
发明内容
本发明的一个目的在于提供一种离子型多孔聚合物材料的制备方法。
本发明方法通过芳环取代的单体与交联剂超交联得到,聚合过程包含三种交联方式:一是单体中的叔胺/膦与交联剂中的苄氯发生亲核取代反应,生成季铵/鏻离子位点;二是交联剂中的苄氯在路易斯酸的催化下,与单体中的芳环发生亲电取代反应;三是交联剂之间发生傅-克烷基化反应,进一步提升交联程度,形成丰富的微孔。具体是:
步骤(1)将单体和交联剂按照摩尔比1:0.5~2溶解在季铵化溶剂中,50~100℃下反应24~72小时;
作为优选,所述的单体为2-苯基咪唑啉、1-苯基咪唑、2-苯基苯并咪唑、1-三苯甲基咪唑、2,4,5-三苯基咪唑、三苯基膦、二苯基丙基膦、苯基二丙基膦、1,3-双(二苯基膦)丙烷中的一种。进一步优选,单体为2-苯基咪唑啉或1-三苯甲基咪唑,空间位阻更小,亲和性更强的单体有利于与交联剂中的苄氯发生亲核取代反应,生成丰富离子位点的同时增加交联度。
作为优选,所述的交联剂为1,4-对二氯苄、4,4'-二氯甲基联苯、1,3,5-三(氯甲基)-苯、9,10-二(氯甲基)蒽、1,3,5-三[4-(氯甲基)苯基]苯、1,4-对二溴苄、4,4'-二溴甲基联苯、1,3,5-三(溴甲基)-苯中的一种。进一步优选,交联剂为4,4'-二氯甲基联苯,得到更加规则的孔结构和更多的微孔。
所述的季铵化溶剂为乙腈、乙醇、异丙醇、甲醇中的一种。
步骤(2)通过旋蒸方法除去季铵化溶剂,然后70~100℃下真空干燥12~36小时,得到季铵化产物。
步骤(3)将季铵化产物和Lewis酸催化剂加入傅克反应溶剂中,在氮气保护条件下,70~100℃反应12~36小时;加入的Lewis酸催化剂的摩尔量为步骤(1)中单体摩尔量和交联剂摩尔量总量的2~6倍。
所述的Lewis酸催化剂为无水FeCl3、无水AlCl3、无水ZnCl2、无水SnCl4、无水TiCl4中的一种。
所述的傅克反应溶剂为无水1,2-二氯乙烷、无水二氯甲烷、无水硝基苯中的一种。
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,70~100℃下真空干燥12~36小时,得到阴离子为Cl-或Br-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-或Br-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.02~0.2g/mL的羧酸钠甲醇溶液冲洗5~10天,使阴离子充分交换,所述的羧酸钠为CnH2n+1COONa,n=2~8;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为CnH2n+1COO-的离子型多孔聚合物,n=2~8。
本发明的另一个目的是提供按照以上方法制备的离子型多孔聚合物材料。该离子型多孔聚合物材料的比表面积均在685m2/g以上,平均孔径在2.3~2.7nm之间,孔径分布较窄,集中在微/介孔范围,离子含量为0.96~1.22mmol/g。
该离子型多孔超交联聚合物材料的阴离子为Cl-、Br-或CnH2n+1COO-,n=2~8。作为优选,阴离子为Cl-。
本发明的第三个目的是提供该离子型多孔聚合物材料在精油吸附脱萜上的应用。
具体是以离子型多孔聚合物材料为吸附剂,采用吸附分离方法,分离精油中的萜类化合物及其含氧衍生物。
所述的吸附分离方法采用静态釜式吸附分离、固定床吸附分离或模拟移动床吸附分离。
静态釜式吸附分离具体如下:
步骤(a)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于稀释溶剂得到稀释精油加入釜中,其中,每克离子型多孔聚合物质量加入稀释精油0.1~0.5L,10~60℃下搅拌2~6小时。所述的稀释溶剂为正戊烷、正己烷、环己烷、正庚烷、正辛烷中的一种或混合体系。
步骤(b)过滤步骤(a)中固液混合体系,将滤得固体置于釜中,加入脱附溶剂,每克滤得固体质量加入脱附溶剂0.1~0.5L,10~60℃下搅拌2~6小时。作为优选,脱附温度高于吸附温度20~30℃。
步骤(c)用脱附溶剂在10~60℃下洗涤步骤(b)中脱附后固体,每克脱附后固体质量用0.1~0.5L脱附溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
所述的脱附溶剂为甲醇、乙醇、异丙醇、丙酮、正丁醇中的一种或混合体系。
固定床吸附分离具体如下:
步骤(A)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,10~60℃下将所述上柱液通入吸附柱,流速为5~30倍床层体积/小时。所述的稀释溶剂为正戊烷、正己烷、环己烷、正庚烷、正辛烷中的一种或混合体系。
步骤(B)10~60℃下向吸附柱中通入脱附溶剂,流速为5~30倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物。作为优选,脱附温度高于吸附温度20~30℃。
所述的脱附溶剂为甲醇、乙醇、异丙醇、丙酮、正丁醇中的一种或混合体系。
步骤(C)10~60℃下用脱附溶剂继续冲洗吸附柱0.5~1小时,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
与活性炭、分子筛等商业化的多孔吸附剂相比,本发明的离子型多孔聚合物材料中含有丰富的离子位点,可以与含氧萜烯之间形成较强的多重氢键相互作用,选择性吸附萜烯氧化物;与萜类化合物之间的作用力较弱,对其的吸附量很小,从而实现萜烯和萜烯氧化物的吸附分离。
与现有技术相比,本发明具有如下有益效果:
(1)本发明所制备的离子型多孔聚合物将离子位点很好的结合在聚合物骨架中,不仅克服了离子液体粘度大、扩散慢的缺点,同时发挥了离子位点对萜烯氧化物良好的选择性识别吸附能力;丰富的微介孔结构保证了离子位点与吸附质充分接触,并增大了传质速率。该类材料具有高热稳定性和化学稳定性,有机组分不易流失,易回收,能减少对环境的污染,具有良好的分离应用前景。
(2)本发明使用的离子型多孔聚合物兼具离子位点对萜烯氧化物良好的选择性识别吸附能力以及聚合物的多孔性,对萜烯氧化物表现出较高的吸附容量和选择性。在优化条件下,可以得到纯度不低于80%的萜类含氧衍生物,并且回收率在85%以上,显著优于常规的商业化吸附剂。
(3)本发明采用的离子型多孔聚合物与精油分子的吸附结合属于物理作用,因此,采用极性溶剂在较低温度下洗脱即可实现萜烯氧化物的回收和吸附材料的再生。
附图说明
图1为本发明一实施例中离子型多孔超交联聚合物的固体核磁谱图;
图2为本发明一实施例中离子型多孔超交联聚合物的N2(77K)吸附等温线图;
图3为本发明一实施例中离子型多孔超交联聚合物的孔径分布图;
图4为本发明一实施例中离子型多孔超交联聚合物的XPS结果图;
图5为本发明一实施例中离子型多孔超交联聚合物的扫描电镜图;
图6为本发明一实施例中离子型多孔超交联聚合物的热重结果图;
图7为本发明另一实施例中离子型多孔超交联聚合物的固体核磁谱图;
图8为本发明另一实施例中离子型多孔超交联聚合物的XPS结果图;
图9为本发明一个实施例中单体和交联剂摩尔比1:1的离子型多孔超交联聚合物的扫描电镜图;
图10为本发明另一个实施例中单体和交联剂摩尔比1:1的离子型多孔超交联聚合物的扫描电镜图;
图11为本发明再一个实施例中己酸根阴离子功能化聚合物的红外谱图;
图12为一个实施例所得静态吸附等温线图。
图13为另一个实施例所得静态吸附等温线图;
图14为一个实施例所得动态吸附曲线图;
图15为另一个实施例所得动态吸附曲线图;
图16为实施例所得固定床穿透曲线图。
具体实施方式
离子型多孔聚合物材料制备方法实施例如下:
实施例1.
步骤(1)将14.6克(0.1mol)2-苯基咪唑啉和25.1克(0.1mol)4,4'-二氯甲基联苯溶解在乙醇溶剂中,60℃下反应60小时;
步骤(2)通过旋蒸方法除去乙醇溶剂,然后80℃下真空干燥24小时,得到季铵化产物;
步骤(3)将季铵化产物和105.1克(0.6mol)无水FeCl3加入无水1,2-二氯乙烷溶剂中,在氮气保护条件下,85℃反应24小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,80℃下真空干燥30小时,得到阴离子为Cl-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.05g/mL的羧酸钠甲醇溶液冲洗7天,使阴离子充分交换,羧酸钠为C4H9COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C4H9COO-的离子型多孔聚合物。
实施例2.
步骤(1)将14.4克(0.1mol)1-苯基咪唑和35.0克(0.2mol)1,4-对二氯苄溶解在乙腈溶剂中,50℃下反应72小时;
步骤(2)通过旋蒸方法除去乙腈溶剂,然后70℃下真空干燥36小时,得到季铵化产物;
步骤(3)将季铵化产物和80.0克(0.6mol)无水AlCl3加入无水二氯甲烷溶剂中,在氮气保护条件下,90℃反应15小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,100℃下真空干燥15小时,得到阴离子为Cl-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.02g/mL的羧酸钠甲醇溶液冲洗10天,使阴离子充分交换,羧酸钠为C2H5COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C2H5COO-的离子型多孔聚合物。
实施例3.
步骤(1)将19.4克(0.1mol)2-苯基苯并咪唑和26.8克(0.12mol)1,3,5-三(氯甲基)-苯溶解在异丙醇溶剂中,80℃下反应54小时;
步骤(2)通过旋蒸方法除去异丙醇溶剂,然后100℃下真空干燥12小时,得到季铵化产物;
步骤(3)将季铵化产物和150.0克(1.1mol)无水ZnCl2加入无水硝基苯溶剂中,在氮气保护条件下,85℃反应24小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,90℃下真空干燥24小时,得到阴离子为Cl-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.2g/mL的羧酸钠甲醇溶液冲洗5天,使阴离子充分交换,羧酸钠为C3H7COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C3H7COO-的离子型多孔聚合物。
实施例4.
步骤(1)将31.0克(0.1mol)1-三苯甲基咪唑和20.1克(0.8mol)4,4'-二氯甲基联苯溶解在甲醇溶剂中,70℃下反应48小时;
步骤(2)通过旋蒸方法除去甲醇溶剂,然后90℃下真空干燥15小时,得到季铵化产物;
步骤(3)将季铵化产物和260.5克(1mol)无水SnCl4加入无水1,2-二氯乙烷溶剂中,在氮气保护条件下,75℃反应36小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,85℃下真空干燥24小时,得到阴离子为Cl-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.15g/mL的羧酸钠甲醇溶液冲洗6天,使阴离子充分交换,羧酸钠为C4H9COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C4H9COO-的离子型多孔聚合物。
实施例5.
步骤(1)将29.6克(0.1mol)2,4,5-三苯基咪唑和41.3克(0.15mol)9,10-二(氯甲基)蒽溶解在甲醇溶剂中,100℃下反应24小时;
步骤(2)通过旋蒸方法除去甲醇溶剂,然后80℃下真空干燥20小时,得到季铵化产物;
步骤(3)将季铵化产物和270.3克(1mol)无水FeCl3加入无水二氯甲烷溶剂中,在氮气保护条件下,80℃反应24小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,75℃下真空干燥30小时,得到阴离子为Cl-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.1g/mL的羧酸钠甲醇溶液冲洗8天,使阴离子充分交换,羧酸钠为C5H11COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C5H11COO-的离子型多孔聚合物。
实施例6.
步骤(1)将26.2克(0.1mol)三苯基膦和22.5克(0.05mol)1,3,5-三[4-(氯甲基)苯基]苯溶解在乙醇溶剂中,90℃下反应36小时;
步骤(2)通过旋蒸方法除去乙醇溶剂,然后75℃下真空干燥30小时,得到季铵化产物;
步骤(3)将季铵化产物和170.3克(0.9mol)无水TiCl4加入无水硝基苯溶剂中,在氮气保护条件下,90℃反应12小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,80℃下真空干燥24小时,得到阴离子为Cl-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.12g/mL的羧酸钠甲醇溶液冲洗7天,使阴离子充分交换,羧酸钠为C6H13COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C6H13COO-的离子型多孔聚合物。
实施例7.
步骤(1)将22.8克(0.1mol)二苯基丙基膦和15.8克(0.06mol)1,4-对二溴苄溶解在乙腈溶剂中,50℃下反应60小时;
步骤(2)通过旋蒸方法除去乙腈溶剂,然后85℃下真空干燥20小时,得到季铵化产物;
步骤(3)将季铵化产物和130.3克(0.5mol)无水SnCl4加入无水1,2-二氯乙烷溶剂中,在氮气保护条件下,80℃反应30小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,90℃下真空干燥15小时,得到阴离子为Br-的离子型多孔聚合物材料;
步骤(5)将阴离子为Br-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.15g/mL的羧酸钠甲醇溶液冲洗5天,使阴离子充分交换,羧酸钠为C7H15COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C7H15COO-的离子型多孔聚合物。
实施例8.
步骤(1)将19.4克(0.1mol)苯基二丙基膦和43.2克(0.18mol)4,4'-二溴甲基联苯溶解在乙醇溶剂中,75℃下反应48小时;
步骤(2)通过旋蒸方法除去乙醇溶剂,然后95℃下真空干燥12小时,得到季铵化产物;
步骤(3)将季铵化产物和136.3克(1mol)无水ZnCl2加入无水二氯甲烷溶剂中,在氮气保护条件下,70℃反应36小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,70℃下真空干燥36小时,得到阴离子为Br-的离子型多孔聚合物材料;
步骤(5)将阴离子为Br-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.08g/mL的羧酸钠甲醇溶液冲洗9天,使阴离子充分交换,羧酸钠为C8H17COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C8H17COO-的离子型多孔聚合物。
实施例9.
步骤(1)将41.2克(0.1mol)1,3-双(二苯基膦)丙烷和35.4克(0.1mol)1,3,5-三(溴甲基)-苯溶解在异丙醇溶剂中,65℃下反应60小时;
步骤(2)通过旋蒸方法除去异丙醇溶剂,然后80℃下真空干燥30小时,得到季铵化产物;
步骤(3)将季铵化产物和29.9克(0.8mol)无水AlCl3加入无水硝基苯溶剂中,在氮气保护条件下,100℃反应12小时;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,100℃下真空干燥12小时,得到阴离子为Br-的离子型多孔聚合物材料;
步骤(5)将阴离子为Br-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.16g/mL的羧酸钠甲醇溶液冲洗6天,使阴离子充分交换,羧酸钠为C3H7COONa;用硝酸酸化的硝酸银检测流出液,达到无白色沉淀后,用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为C3H7COO-的离子型多孔聚合物。
以实施例1~9中步骤(4)或步骤(5)制得的离子型多孔聚合物材料(阴离子为Cl-、Br-或CnH2n+1COO-,n=2~8)为吸附剂,采用吸附分离方法,分离精油中的萜类化合物及其含氧衍生物。具体实施例如下:
实施例10.
步骤(1)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于正戊烷得到稀释精油,加入釜中;每克离子型多孔聚合物质量加入稀释精油0.2L,10℃下搅拌6小时;
步骤(2)过滤固液混合体系,将滤得固体置于釜中,加入甲醇溶剂,每克滤得固体质量加入甲醇溶剂0.2L,10℃下搅拌6小时;
步骤(3)用甲醇溶剂在10℃下洗涤脱附后固体,每克脱附后固体质量用0.5L甲醇溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例11.
步骤(1)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于正己烷得到稀释精油,加入釜中;每克离子型多孔聚合物质量加入稀释精油0.1L,20℃下搅拌5小时;
步骤(2)过滤固液混合体系,将滤得固体置于釜中,加入乙醇溶剂,每克滤得固体质量加入乙醇溶剂0.3L,50℃下搅拌3小时;
步骤(3)用乙醇溶剂在20℃下洗涤脱附后固体,每克脱附后固体质量用0.4L乙醇溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例12.
步骤(1)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于环己烷得到稀释精油,加入釜中;每克离子型多孔聚合物质量加入稀释精油0.3L,30℃下搅拌5小时;
步骤(2)过滤固液混合体系,将滤得固体置于釜中,加入脱附溶剂,每克滤得固体质量加入脱附溶剂0.1L,60℃下搅拌2小时;脱附溶剂为甲醇和乙醇的混合体系;
步骤(3)用脱附溶剂在30℃下洗涤脱附后固体,每克脱附后固体质量用0.4L脱附溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例13.
步骤(1)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于正庚烷得到稀释精油,加入釜中;每克离子型多孔聚合物质量加入稀释精油0.5L,40℃下搅拌4小时;
步骤(2)过滤固液混合体系,将滤得固体置于釜中,加入正丁醇溶剂,每克滤得固体质量加入正丁醇溶剂0.5L,40℃下搅拌4小时;
步骤(3)用正丁醇溶剂在40℃下洗涤脱附后固体,每克脱附后固体质量用0.3L正丁醇溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例14.
步骤(1)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于正辛烷得到稀释精油,加入釜中;每克离子型多孔聚合物质量加入稀释精油0.4L,25℃下搅拌5小时;
步骤(2)过滤固液混合体系,将滤得固体置于釜中,加入丙酮溶剂,每克滤得固体质量加入丙酮溶剂0.4L,50℃下搅拌3小时;
步骤(3)用丙酮溶剂在50℃下洗涤脱附后固体,每克脱附后固体质量用0.2L丙酮溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例15.
步骤(1)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于稀释溶剂得到稀释精油,加入釜中;每克离子型多孔聚合物质量加入稀释精油0.3L,60℃下搅拌2小时;稀释溶剂为正己烷和环己烷的混合体系;
步骤(2)过滤固液混合体系,将滤得固体置于釜中,加入异丙醇溶剂,每克滤得固体质量加入异丙醇溶剂0.3L,60℃下搅拌2小时;
步骤(3)用异丙醇溶剂在60℃下洗涤脱附后固体,每克脱附后固体质量用0.1L异丙醇溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例16.
步骤(1)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,60℃下将上柱液通入吸附柱,流速为5倍床层体积/小时;
步骤(2)60℃下向吸附柱中通入甲醇溶剂,流速为5倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(3)60℃下用甲醇溶剂继续冲洗吸附柱0.5小时,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例17.
步骤(1)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,40℃下将上柱液通入吸附柱,流速为10倍床层体积/小时;
步骤(2)50℃下向吸附柱中通入乙醇溶剂,流速为10倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(3)20℃下用乙醇溶剂继续冲洗吸附柱1小时,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例18.
步骤(1)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,30℃下将上柱液通入吸附柱,流速为15倍床层体积/小时;
步骤(2)60℃下向吸附柱中通入脱附溶剂,脱附溶剂为甲醇和乙醇的混合体系,流速为15倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(3)40℃下用脱附溶剂继续冲洗吸附柱40分钟,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例19.
步骤(1)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,20℃下将上柱液通入吸附柱,流速为20倍床层体积/小时;
步骤(2)40℃下向吸附柱中通入异丙醇溶剂,流速为20倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(3)30℃下用异丙醇溶剂继续冲洗吸附柱45分钟,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例20.
步骤(1)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,25℃下将上柱液通入吸附柱,流速为25倍床层体积/小时;
步骤(2)50℃下向吸附柱中通入丙酮溶剂,流速为25倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(3)20℃下用异丙醇溶剂继续冲洗吸附柱50分钟,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例21.
步骤(1)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,10℃下将上柱液通入吸附柱,流速为30倍床层体积/小时;
步骤(2)10℃下向吸附柱中通入正丁醇溶剂,流速为30倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(3)10℃下用正丁醇溶剂继续冲洗吸附柱1小时,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环。
实施例22.
称取14.6g(0.1mol)2-苯基咪唑啉,25.1g(0.1mol)4,4'-二氯甲基联苯溶解于200mL乙腈中,80℃搅拌48小时。反应完成后旋蒸除去大部分溶剂,80℃真空干燥24小时,完成初步季铵化交联。将彻底干燥的产物、无水FeCl3(64.8g,0.4mol)和无水1,2-二氯乙烷200mL在氮气保护的条件下80℃反应24小时。反应结束后冷却至室温,抽滤,得到的固体产物依次用乙醇、稀盐酸、纯净水洗涤,然后用乙醇作为溶剂索式提取至提取器内溶液无色,80℃真空干燥24小时得到29.0g深棕色固体粉末,其分子结构如下所示,产率73%,核磁结果如图1所示。
实施例23.
77K下实施例22所得离子型多孔聚合物的N2等温吸附如图2所示,结果表明,离子型多孔聚合物BET比表面积为972m2/g,微孔比表面积604m2/g,总孔容0.57cm3/g,微孔孔容0.29cm3/g,平均孔径2.3nm,孔径分布相对较窄,如图3所示,集中在微/介孔范围。XPS N1s谱图结果如图4所示,计算得离子含量1.22mmol/g,扫描电镜结果如图5所示,热重结果如图6所示。
实施例24.
称取31.4g(0.1mol)1-三苯甲基咪唑,25.1g(0.1mol)4,4'-二氯甲基联苯溶解于200mL乙腈中,80℃搅拌48小时。反应完成后旋蒸除去大部分溶剂,80℃真空干燥24小时,完成初步季铵化交联。将彻底干燥的产物、无水FeCl3(64.8g,0.4mol)和无水1,2-二氯乙烷200mL在氮气保护的条件下80℃反应24小时。反应结束后冷却至室温,抽滤,得到的固体产物依次用乙醇、稀盐酸、纯净水洗涤,然后用乙醇作为溶剂索式提取至提取器内溶液无色,80℃真空干燥24小时得到45.1g深棕色固体粉末,产率80%,核磁结果如图7所示。
实施例25.
77K下N2等温吸附结果表明,实施例24所得离子型多孔聚合物BET比表面积为911m2/g,微孔比表面积586m2/g,总孔容0.59cm3/g,微孔孔容0.27cm3/g,平均孔径2.6nm,孔径分布相对较窄,集中在微/介孔范围,XPS N1s谱图结果如图8所示,计算得离子含量0.44mmol/g。
实施例26.
分别称取1-苯基咪唑和1,4-对二溴苄,溶解于200mL乙腈中,80℃搅拌48小时。反应完成后旋蒸除去大部分溶剂,80℃真空干燥24小时,完成初步季铵化交联。将彻底干燥的产物、无水FeCl3,摩尔量为单体摩尔量和交联剂摩尔量总量的4倍,无水1,2-二氯乙烷200mL,在氮气保护的条件下80℃反应24小时。反应结束后冷却至室温,抽滤,得到的固体产物依次用乙醇、稀盐酸、纯净水洗涤,然后用乙醇作为溶剂索式提取至提取器内溶液无色,80℃真空干燥24小时,单体和交联剂摩尔比1:1的离子型多孔超交联聚合物的扫描电镜图如图9所示。
实施例27.
分别称取1-苯基咪唑和4,4'-二溴甲基联苯,溶解于200mL乙腈中,80℃搅拌48小时。反应完成后旋蒸除去大部分溶剂,80℃真空干燥24小时,完成初步季铵化交联。将彻底干燥的产物、无水FeCl3,摩尔量为单体摩尔量和交联剂摩尔量总量的4倍,无水1,2-二氯乙烷200mL,在氮气保护的条件下80℃反应24小时。反应结束后冷却至室温,抽滤,得到的固体产物依次用乙醇、稀盐酸、纯净水洗涤,然后用乙醇作为溶剂索式提取至提取器内溶液无色,80℃真空干燥24小时,单体和交联剂摩尔比1:1的离子型多孔超交联聚合物的扫描电镜图如图10所示。
实施例28.
称取2.00g实施例22所得离子型多孔聚合物浸泡在甲醇溶液中,湿法装柱,用0.1g/mL的己酸钠甲醇溶液冲洗一周,使阴离子充分交换。用硝酸酸化的硝酸银检测流出液,无白色沉淀,然后用纯净水冲洗除去残留己酸钠,冻干后得到阴离子为C5H10COO-的离子型多孔聚合物。
实施例29.
实施例28中己酸根阴离子功能化聚合物的红外谱图如图11所示,1116cm-1处为咪唑环上被取代的N的C-N特征吸收峰,1660cm-1和1588cm-1处为咪唑骨架的特征吸收峰,3039cm-1处的吸收峰为苯环骨架上不饱和C的C-H吸收;1490cm-1处为羧酸根的特征吸收峰,2928cm-1的峰为己酸根阴离子烷基链上C-H基团的特征吸收,表明阴离子交换成功。
实施例30.
以正庚烷为稀释剂,分别配制0.2~20mg/mL的柠檬烯、芳樟醇和柠檬醛原料液。在50mL锥形瓶中加入20mL原料液和100mg实施例22中的吸附剂,密封后置于摇床中,30℃,120rpm下振荡24小时。静置1小时后吸取上清液,用气相色谱测得精油单组分的平衡浓度,计算吸附量,吸附等温线如图12所示。实施例22中的吸附剂对柠檬烯的吸附量小于5mg/g,对芳樟醇和柠檬醛的饱和吸附量分别为352和424mg/g。
实施例31.
以正庚烷为稀释剂,分别配制0.2~20mg/mL的柠檬烯、芳樟醇和柠檬醛原料液。在50mL锥形瓶中加入20mL原料液和100mg实施例24中的吸附剂,密封后置于摇床中,30℃,120rpm下振荡24小时。静置1小时后吸取上清液,用气相色谱测得精油单组分的平衡浓度,计算吸附量,吸附等温线如图13所示。实施例22中的吸附剂对柠檬烯的吸附量小于5mg/g,对芳樟醇和柠檬醛的饱和吸附量分别为186和454mg/g。
实施例32.
以正庚烷为稀释剂,分别配制10mg/mL的芳樟醇和柠檬醛原料液。在50mL锥形瓶中加入20mL原料液和100mg实施例22中的吸附剂,密封后置于摇床中,30℃,120rpm下振荡,1~120分钟内取样分析,动态吸附曲线如图14所示,对芳樟醇和柠檬醛的平衡吸附量分别为235和272mg/g。
实施例33.
以正庚烷为稀释剂,分别配制10mg/mL的芳樟醇和柠檬醛原料液。在50mL锥形瓶中加入20mL原料液和100mg实施例24中的吸附剂,密封后置于摇床中,30℃,120rpm下振荡,1~120分钟内取样分析,动态吸附曲线如图15所示。15分钟内对柠檬醛达到吸附平衡(>95%),对芳樟醇和柠檬醛的平衡吸附量分别为141和260mg/g。
实施例34.
以正庚烷为稀释剂,配制模型精油原料液,柠檬烯、芳樟醇和柠檬醛浓度分别为4.5、0.25和0.25mg/mL。在50mL锥形瓶中加入20mL原料液和100mg实施例22中的吸附剂,密封后置于摇床中,30℃,120rpm下振荡24小时。实施例22中的吸附剂对含氧萜烯的总吸附量为20.3mg/g,是活性炭的1.3倍;含氧萜烯对萜烯的分离选择性为22.5,是13X分子筛的5.0倍。
实施例35.
以正庚烷为稀释剂,配制模型精油原料液,柠檬烯、芳樟醇和柠檬醛浓度分别为9.0、0.5和0.5mg/mL。在50mL锥形瓶中加入20mL原料液和100mg实施例22中的吸附剂,密封后置于摇床中,30℃,120rpm下振荡24小时。实施例22中的吸附剂对含氧萜烯的总吸附量为43.1mg/g,是活性炭的2.1倍;含氧萜烯对萜烯的分离选择性为13.5,是13X分子筛的2.7倍。
实施例36.
将实施例22中制备的离子型多孔聚合物装入吸附柱(内径4.6mm,长度150mm),并用正庚烷冲洗压实。30℃下,将实施例27中配制的原料液通入吸附柱,流速0.5mL/min,0~150分钟内取样分析,穿透曲线如图16所示。吸附完成后,30℃下,通入乙醇脱吸,流速0.5mL/min。合并主要含有芳樟醇和柠檬醛的洗脱液,减压蒸馏,得到含氧萜烯混合物45.0mg/g吸附剂,纯度大于80%,回收率89.6%,含氧萜烯对萜烯的选择性为2.1。
Claims (10)
1.离子型多孔聚合物材料的制备方法,其特征在于:
步骤(1)将单体和交联剂按照摩尔比1:0.5~2溶解在季铵化溶剂中,50~100℃下反应24~72小时;
步骤(2)通过旋蒸方法除去季铵化溶剂,然后70~100℃下真空干燥12~36小时,得到季铵化产物;
步骤(3)将季铵化产物和Lewis酸催化剂加入傅克反应溶剂中,在氮气保护条件下,70~100℃反应12~36小时;加入的Lewis酸催化剂的摩尔量为步骤(1)中单体摩尔量和交联剂摩尔量总量的2~6倍;
步骤(4)将反应产物依次用工业乙醇、稀盐酸、纯净水洗涤,然后用工业乙醇作为溶剂,索式提取至提取器内溶液无色,70~100℃下真空干燥12~36小时,得到阴离子为Cl-或Br-的离子型多孔聚合物材料;
步骤(5)将阴离子为Cl-或Br-的离子型多孔聚合物材料浸泡在甲醇溶液中,湿法装柱,用0.02~0.2g/mL的羧酸钠甲醇溶液冲洗5~10天,使阴离子充分交换,所述的羧酸钠为CnH2n+1COONa,n=2~8;用硝酸酸化的硝酸银检测流出液,无白色沉淀,然后用纯净水冲洗除去残留羧酸钠,冻干后得到阴离子为CnH2n+1COO-的离子型多孔聚合物,n=2~8。
2.如权利要求1所述的离子型多孔聚合物材料的制备方法,其特征在于:步骤(1)中所述的单体为2-苯基咪唑啉、1-苯基咪唑、2-苯基苯并咪唑、1-三苯甲基咪唑、2,4,5-三苯基咪唑、三苯基膦、二苯基丙基膦、苯基二丙基膦、1,3-双(二苯基膦)丙烷中的一种。
3.如权利要求1所述的离子型多孔聚合物材料的制备方法,其特征在于:步骤(1)中所述的交联剂为1,4-对二氯苄、4,4'-二氯甲基联苯、1,3,5-三(氯甲基)-苯、9,10-二(氯甲基)蒽、1,3,5-三[4-(氯甲基)苯基]苯、1,4-对二溴苄、4,4'-二溴甲基联苯、1,3,5-三(溴甲基)-苯中的一种。
4.如权利要求1所述的离子型多孔聚合物材料的制备方法,其特征在于:步骤(1)中所述的季铵化溶剂为乙腈、乙醇、异丙醇、甲醇中的一种。
5.如权利要求1所述的离子型多孔聚合物材料的制备方法,其特征在于:步骤(3)中所述的Lewis酸催化剂为无水FeCl3、无水AlCl3、无水ZnCl2、无水SnCl4、无水TiCl4中的一种。
6.如权利要求1所述的离子型多孔聚合物材料的制备方法,其特征在于:步骤(3)中所述的傅克反应溶剂为无水1,2-二氯乙烷、无水二氯甲烷、无水硝基苯中的一种。
7.离子型多孔聚合物材料,按照如权利要求1、2、3、4、5或6的方法制备得到,离子型多孔超交联聚合物材料的阴离子为Cl-、Br-或CnH2n+1COO-,n=2~8。
8.如权利了要求7所述的离子型多孔聚合物材料在精油吸附脱萜上的应用,其特征在于:以离子型多孔聚合物材料为吸附剂,采用吸附分离方法,分离精油中的萜类化合物及其含氧衍生物;所述的吸附分离方法采用静态釜式吸附分离、固定床吸附分离或模拟移动床吸附分离。
9.如权利了要求8所述的离子型多孔聚合物材料在精油吸附脱萜上的应用,其特征在于,所述的静态釜式吸附分离,具体如下:
步骤(a)将离子型多孔聚合物材料置于釜中,将粗提精油溶解于稀释溶剂得到稀释精油加入釜中,其中,每克离子型多孔聚合物质量加入稀释精油0.1~0.5L,10~60℃下搅拌2~6小时;
所述的稀释溶剂为正戊烷、正己烷、环己烷、正庚烷、正辛烷中的一种或混合体系;
步骤(b)过滤步骤(a)中固液混合体系,将滤得固体置于釜中,加入脱附溶剂,每克滤得固体质量加入脱附溶剂0.1~0.5L,10~60℃下搅拌2~6小时;
步骤(c)用脱附溶剂在10~60℃下洗涤步骤(b)中脱附后固体,每克脱附后固体质量用0.1~0.5L脱附溶剂洗涤,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环;
所述的脱附溶剂为甲醇、乙醇、异丙醇、丙酮、正丁醇中的一种或混合体系。
10.如权利了要求8所述的离子型多孔聚合物材料在精油吸附脱萜上的应用,其特征在于,所述的固定床吸附分离,具体如下:
步骤(A)将离子型多孔聚合物材料装入吸附柱,将粗提精油溶解于稀释溶剂中,配成上柱液,10~60℃下将所述上柱液通入吸附柱,流速为5~30倍床层体积/小时;
所述的稀释溶剂为正戊烷、正己烷、环己烷、正庚烷、正辛烷中的一种或混合体系;
步骤(B)10~60℃下向吸附柱中通入脱附溶剂,流速为5~30倍床层体积/小时,分段收集流出液,减压蒸馏,先后分别得到萜烯和萜烯氧化物;
步骤(C)10~60℃下用脱附溶剂继续冲洗吸附柱0.5~1小时,使离子型多孔聚合物彻底再生,进入下一个吸附分离循环;
所述的脱附溶剂为甲醇、乙醇、异丙醇、丙酮、正丁醇中的一种或混合体系。
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