CN112521584A - 一种卟啉类微孔聚合物的制备及其光催化应用 - Google Patents
一种卟啉类微孔聚合物的制备及其光催化应用 Download PDFInfo
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Abstract
本发明属于高分子科学技术领域，提供了一种卟啉类微孔聚合物的制备及其光催化应用。本发明的方法制备工艺简单，且作为异相催化剂用于光催化反应后有利于催化剂的回收及循环利用，是一种绿色环保的新型光催化剂，并且简化了产物的纯化步骤，降低后处理成本。我们设计了两种带有特殊官能团的卟啉单体A1和A2，在双三苯基磷二氯化钯和碘化亚铜共同作用下利用芳香炔烃和芳香卤化物通过进行Sonogashira‑Hagihara偶联反应合成五种聚卟啉。
Description
技术领域
本发明属于高分子科学技术领域，涉及一种卟啉类微孔聚合物的制备及其光催化应用。
背景技术
目前，利用结构新颖的构筑基元制备多孔有机聚合材料(POP)并应用于各类多相催化反应的研究正处于一个快速发展的阶段。迄今为止，多孔有机骨架材料主要包括超交联聚合物(HCPs)、固有微孔聚合物(PIMs)、共价有机骨架(COFs)和共轭微孔聚合物(CMPs)。POP材料中交联的开放孔道和高的比表面积有利于促进催化底物与产物的扩散和传输。然而，大部分POP材料多为纯有机多孔聚合物，材料本身不含有活性催化位点，其在多相催化领域的研究主要集中在聚合物负载型催化材料的应用。这不仅未能发挥POP作为催化材料的优势，同时还面临着负载型催化剂活性位点分布不均、纳米粒子脱落、催化效率低等问题。将催化活性位点均匀地固定在POP材料骨架中是解决这一问题的有效办法，通常的两种设计策略为：(1)通过后修饰的化学方法将功能小分子催化剂如脯氨酸、吡咯烷、卡宾等通过共价键的连接方式嫁接到已合成好的POP材料骨架当中；(2)直接利用具有催化活性的构筑基元如金属螯合席夫碱或卟啉合成POP材料。
卟啉单元是π电子大共轭平面结构，同时还具有骨架强度大、稳定性强、功能可调等特点，使它成为构筑POP材料的理想基元之一。另外，卟啉及卟啉衍生物是许多生物体内至关重要的功能性分子，尤其是在催化氧化领域，譬如对烷烃的催化氧化、对烯烃的催化氧化及环氧化、醇醛的催化氧化、硫化合物的氧化和氮化合物的氧化。但是其在催化过程中的分离，循环利用及产物纯化往往是限制其应用的关键。
发明内容
本发明目的在于解决小分子卟啉在催化过程中的分离，循环利用及产物纯化的问题，公开了五种含卟啉的微孔聚合物的制备方法，该方法制备工艺简单，且作为异相催化剂用于光催化反应后有利于催化剂的回收及循环利用，是一种绿色环保的新型光催化剂，并且简化了产物的纯化步骤，降低后处理成本。我们设计了两种带有特殊官能团的卟啉单体A1和A2，在双三苯基磷二氯化钯和碘化亚铜共同作用下利用芳香炔烃和芳香卤化物通过进行
Sonogashira-Hagihara偶联反应合成五种聚卟啉。
本发明的技术方案：
卟啉单体A1含双溴双炔基，结构如下所示：
卟啉单体A2含有四溴取代基，结构如下所示：
通过卟啉单体A1自聚制备聚卟啉1，结构如下所示：其中n＝4-100不等
通过卟啉单体A2分别与含双炔基的共聚单体R1(1,7-辛二炔)、R2(对苯二炔)、R3(联苯二炔)、R4(对萘二炔)共聚合成聚卟啉2、聚卟啉3、聚卟啉4、聚卟啉5，其中共聚单体结构如下所示：
聚卟啉2、聚卟啉3、聚卟啉4、聚卟啉5结构示意图如下所示：其中n＝4-100不等
其中R结构分别为：
一种卟啉类微孔聚合物的制备方法，步骤如下：
(1)聚卟啉1的制备方法
准确称量1摩尔当量的卟啉单体A1，与5摩尔当量的醋酸锌溶于二甲基甲酰胺里，卟啉单体A1的浓度为0.025-0.25M，110℃下反应1-24小时，将反应后的体系加水离心洗涤多次，最后烘干得到中心位置配位上金属Zn的卟啉单体A1-Zn；在手套箱里将1摩尔当量的卟啉单体A1-Zn、0.2-0.6摩尔当量的双三苯基磷二氯化钯和0.1-0.3摩尔当量的碘化亚铜催化剂溶于二甲基亚砜，卟啉单体A1-Zn的浓度在0.05-0.5M范围内，搅拌均匀后加入10-100摩尔当量的三乙胺，100℃下反应1-60分钟后体系交联溶胀，用二氯甲烷沉降离心洗涤多次，干燥后得到黑色固体粉末聚卟啉1-Zn，再用浓硫酸浸泡黑色固体粉末，洗去中心配位的金属Zn，半小时后使用去离子水离心沉降多次洗涤，烘干后得到黑色固体粉末聚卟啉1；
(2)聚卟啉2-5的制备方法
准确称量1摩尔当量卟啉单体A2，与5摩尔当量的醋酸锌溶于二甲基甲酰胺里，卟啉单体A2浓度为0.025-0.25M，110℃下反应1-24小时，将反应后的体系加水离心洗涤多次，最后烘干得到中心位置配位上金属Zn的卟啉单体A2-Zn；在手套箱里将1摩尔当量卟啉单体A2-Zn、2摩尔当量的二炔类共聚单体(1,7-辛二炔、对苯二炔、联苯二炔、对萘二炔)、0.4-1.2摩尔当量的双三苯基磷二氯化钯和0.2-0.6摩尔当量的碘化亚铜催化剂溶于二甲基亚砜，卟啉单体A2-Zn浓度在0.05-0.5M范围内，搅拌均匀后加入10-100摩尔当量的三乙胺，100℃下反应1-60分钟后体系交联溶胀，用二氯甲烷沉降离心洗涤多次，干燥后得到黑色固体粉末聚卟啉2-Zn到5-Zn，再用适量浓硫酸浸泡黑色固体粉末，洗去中心配位的金属Zn，半小时后使用去离子水离心沉降多次洗涤，烘干后得到黑色固体粉末聚卟啉2-5；
(3)聚卟啉催化氧化反应
分别准确称量1摩尔当量的苄胺(包括但不限于以下苄胺类单体)、硫醚(包括但不限于以下硫醚类单体)，缩硫酮(包括但不限于以下缩硫酮类单体)作为反应原料，同时准确0.1-1摩尔当量的聚卟啉催化剂粉末置于10mL的反应瓶里，溶剂包括但不限于二氯甲烷、氯仿、乙腈、二甲基甲酰胺、二甲基亚砜，苄胺的浓度在0.05-0.5M范围内，使用氯苯作为内标，室温下用白灯(功率范围为3W-100W)照射敞口反应1-24小时并定时取样，样品过滤后通过气相色谱谱图分析转化率。
苄胺类单体代表性结构如下：
硫醚类单体代表性结构如下：
缩硫酮类单体代表性结构如下：
本发明的有益效果：
(1)本发明提出了一类含卟啉的微孔聚合物光催化剂的制备方法，为合成新型聚卟啉材料提供了技术参考。
(2)利用具有催化活性位点的卟啉作为构筑单元合成POP，既能发挥POP作为催化材料的优势，同时解决了负载型催化剂活性位点分布不均、纳米粒子脱落、催化效率低等问题
(3)解决单体卟啉在催化过程中的分离，循环利用及产物纯化的问题，该方法制备工艺简单，且作为异相催化剂用于光催化反应后有利于催化剂的回收及循环利用，是一种绿色环保的新型光催化剂，并且简化了产物的纯化步骤，降低后处理成本。
附图说明
图1为本发明实施例1聚卟啉1的SEM图。
图2为本发明实施例2聚卟啉2的SEM图。
图3为本发明实施例2聚卟啉3的SEM图。
图4为本发明实施例2聚卟啉4的SEM图。
图5为本发明实施例2聚卟啉5的SEM图。
图6为本发明实施例1聚卟啉1的77K下N2吸脱附等温线图。
图7为本发明实施例2聚卟啉2的77K下N2吸脱附等温线图。
图8为本发明实施例2聚卟啉3的77K下N2吸脱附等温线图。
图9为本发明实施例2聚卟啉4的77K下N2吸脱附等温线图。
图10为本发明实施例2聚卟啉5的77K下N2吸脱附等温线图。
图11为本发明实施例1聚卟啉1的孔径分布图。
图12为本发明实施例2聚卟啉2的孔径分布图。
图13为本发明实施例2聚卟啉3的孔径分布图。
图14为本发明实施例2聚卟啉4的孔径分布图。
图15为本发明实施例2聚卟啉5的孔径分布图。
图16为本发明实施例3中光催化转化率随时间的变化。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1
以聚卟啉1为例：在手套箱里将150mg(0.17mmol)A1-Zn、48mg(0.068mmol)的双三苯基磷二氯化钯和6.5mg(0.034mmol)的碘化亚铜催化剂置于10mL反应瓶中，加入2-3mL的二甲基亚砜，搅拌均匀后加入0.3-3mL的三乙胺，100℃下反应10分钟后体系交联溶胀，用30-35mL的二氯甲烷在7000r/min的条件下沉降离心洗涤5-6次，干燥后得到黑色固体粉末聚卟啉1-Zn，再用15-20mL的98％浓硫酸浸泡黑色固体粉末，洗去中心配位的金属Zn，半小时后使用30-35mL的去离子水在7000r/min的条件下离心沉降洗涤5-6次，烘干后得到黑色固体粉末聚卟啉1。
实施例2
以聚卟啉2为例：在手套箱里将149mg(0.15mmol)A2-Zn、32mg(0.3mmol)的1,7-辛二炔、84mg(0.12mmol)的双三苯基磷二氯化钯和12mg(0.06mmol)的碘化亚铜催化剂置于10mL反应瓶中，加入2-3mL的二甲基亚砜，搅拌均匀后加入0.3-3mL的三乙胺，100℃下反应10分钟后体系交联溶胀，用30-35mL的二氯甲烷在7000r/min的条件下沉降离心洗涤5-6次，干燥后得到黑色固体粉末聚卟啉2-Zn，再用15-20mL的98％浓硫酸浸泡黑色固体粉末，洗去中心配位的金属Zn，半小时后使用30-35mL的去离子水在7000r/min的条件下离心沉降洗涤5-6次，烘干后得到黑色固体粉末聚卟啉2。所有聚卟啉的扫描电镜，77K下N2吸脱附等温线图，以及孔径如图1-3所示。
实施例3
以聚卟啉1光催化二苄胺为例：称量100mg(0.5mmol)二苄胺与41mg(0.05mmol)聚卟啉1置于10mL的反应瓶内，加入5-6mL的乙腈溶剂与10μl的氯苯，光照后的第0、1、2、3、4、8、12、16、24个小时从体系取样400μl，样品经220μl滤膜过滤后注入气相色谱仪，得到其谱图后通过内标法计算反应的转化率。聚卟啉催化二苄胺前24小时转化率对比如图4所示。
Claims (4)
1.一种卟啉类微孔聚合物的制备方法，其特征在于，步骤如下：
卟啉单体A1含双溴双炔基，结构如下所示：
卟啉单体A2含有四溴取代基，结构如下所示：
通过卟啉单体A1自聚制备聚卟啉1，结构如下所示：其中n＝4-100不等；
通过卟啉单体A2分别与含双炔基的共聚单体R1、R2、R3、R4共聚合成聚卟啉2、聚卟啉3、聚卟啉4、聚卟啉5，R1为1,7-辛二炔，R2为对苯二炔，R3为联苯二炔，R4为对萘二炔；其中共聚单体结构如下所示：
聚卟啉2、聚卟啉3、聚卟啉4、聚卟啉5结构示意图如下所示：其中n＝4-100不等
其中R结构分别为：
(1)聚卟啉1的制备方法
准确称量1摩尔当量的卟啉单体A1，与5摩尔当量的醋酸锌溶于二甲基甲酰胺里，卟啉单体A1的浓度为0.025-0.25M，110℃下反应1-24小时，将反应后的体系加水离心洗涤多次，最后烘干得到中心位置配位上金属Zn的卟啉单体A1-Zn；在手套箱里将1摩尔当量的卟啉单体A1-Zn、0.2-0.6摩尔当量的双三苯基磷二氯化钯和0.1-0.3摩尔当量的碘化亚铜催化剂溶于二甲基亚砜，卟啉单体A1-Zn的浓度在0.05-0.5M范围内，搅拌均匀后加入10-100摩尔当量的三乙胺，100℃下反应1-60分钟后体系交联溶胀，用二氯甲烷沉降离心洗涤多次，干燥后得到黑色固体粉末聚卟啉1-Zn，再用浓硫酸浸泡黑色固体粉末，洗去中心配位的金属Zn，半小时后使用去离子水离心沉降多次洗涤，烘干后得到黑色固体粉末聚卟啉1；
(2)聚卟啉2-5的制备方法
准确称量1摩尔当量卟啉单体A2，与5摩尔当量的醋酸锌溶于二甲基甲酰胺里，卟啉单体A2浓度为0.025-0.25M，110℃下反应1-24小时，将反应后的体系加水离心洗涤多次，最后烘干得到中心位置配位上金属Zn的卟啉单体A2-Zn；在手套箱里将1摩尔当量卟啉单体A2-Zn、2摩尔当量的含双炔基的共聚单体中的一种、0.4-1.2摩尔当量的双三苯基磷二氯化钯和0.2-0.6摩尔当量的碘化亚铜催化剂溶于二甲基亚砜，卟啉单体A2-Zn浓度在0.05-0.5M范围内，搅拌均匀后加入10-100摩尔当量的三乙胺，100℃下反应1-60分钟后体系交联溶胀，用二氯甲烷沉降离心洗涤多次，干燥后得到黑色固体粉末聚卟啉2-Zn到5-Zn，再用适量浓硫酸浸泡黑色固体粉末，洗去中心配位的金属Zn，半小时后使用去离子水离心沉降多次洗涤，烘干后得到黑色固体粉末聚卟啉2-5。
2.一种卟啉类微孔聚合物催化氧化反应，其特征在于，步骤如下：分别准确称量1摩尔当量的苄胺类单体、硫醚类单体、缩硫酮类单体作为反应原料，同时准确称量0.1-1摩尔当量的聚卟啉催化剂粉末置于溶剂中，苄胺的浓度在0.05-0.5M范围内，使用氯苯作为内标，室温下用功率范围为3W-100W的白灯照射敞口反应1-24小时并定时取样，样品过滤后通过气相色谱谱图分析转化率。
3.根据权利要求2所述的卟啉类微孔聚合物催化氧化反应，其特征在于，所述的溶剂为二氯甲烷、氯仿、乙腈、二甲基甲酰胺或二甲基亚砜。
4.根据权利要求2或3所述的卟啉类微孔聚合物催化氧化反应，其特征在于，
所述的苄胺类单体的结构如下：
所述的硫醚类单体的结构如下：
所述的缩硫酮类单体代表性结构如下：
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| CN113457643B (zh) * | 2021-07-02 | 2023-12-15 | 潍坊学院 | 卟啉-紫罗碱阳离子型多孔聚合物及其制备方法与应用 |
| CN113698579A (zh) * | 2021-07-23 | 2021-11-26 | 西北民族大学 | 卟啉型共轭微孔聚合物及其合成方法和应用 |
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| CN113769791B (zh) * | 2021-10-13 | 2023-12-12 | 泉州永悦新材料有限公司 | 一种醇解催化剂的制备方法 |
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| CN114479171B (zh) * | 2021-12-29 | 2023-02-28 | 东华大学 | 一种卟啉基共轭微孔聚合物光热转换海绵及其制备和应用 |
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