CN103254426B - 一种卟啉聚合物及其合成方法 - Google Patents
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Abstract
本发明涉及一种卟啉聚合物及其合成方法，以含有氰基芳香醛和新蒸吡咯为原料，有机丙酸作催化剂，利用高温加热或微波加热方法制备卟啉，再以此产物为原料经过无机/有机酸催化制得高比表面积的卟啉聚合物。本发明以卟啉为单体，通过调控卟啉结构和聚合条件，可以控制卟啉聚合物的孔径和比表面积，提高卟啉类光敏剂的敏化效果及其重复使用率，本聚合物不含金属，大大降低光催化反应成本。
Description
技术领域
本发明涉及一种新型卟啉聚合物及其合成方法。制得的卟啉聚合物比表面积较高，孔径可以调控，应用于光催化反应提高催化效率，降低反应成本。属于聚合物合成领域。
背景技术
卟啉(porphyrin)是由四个吡咯通过亚甲基相连而形成的共轭大环化合物。卟啉及其衍生物如血红素(铁卟啉)、血蓝素(铜卟啉)、维生素B12(钴卟啉)、叶绿素(镁卟啉)等广泛存在于生物体内与催化、氧的输运和能量转移等相关的重要细胞器中。卟啉具有优异的光、电、仿生等性能，在光学材料、化学催化、电致发光材料、分子靶向药物等不同领域均有潜在的应用前景，是目前研究的热点之一。
卟啉化合物的单重态和三重态能级接近，使其容易从单重激发态跃迁至三重激发态。在氧气和可见光存在下，由单重态转化为活化的三重态，活化三重态光敏剂与周围氧发生能量交换，产生有效的氧化剂——单线态氧，可以应用于光动力治疗和降解酚类有机污染物。目前光敏剂多使用过渡金属配合物，价格昂贵，且多为均相催化，不利于催化剂的回收利用。
本发明以卟啉为单体，通过调控卟啉结构和聚合条件，控制卟啉聚合物的孔径和比表面积，以提高卟啉类光敏剂的重复使用率。本聚合物不含金属，且能回收利用，能大大降低成本。
发明内容
为克服上述技术缺陷，本发明的目的是提供一种新型卟啉聚合物的合成方法，并首次将该新型卟啉聚合物应用在光降解酚类有机污染物方面。
本发明涉及一种孔径可控的新型卟啉聚合物及其制备方法，所述卟啉聚合物的通式如图1所示，图1中的R＝-Ar-R'-Ar-其中Ar为
R'＝–(CH2)0–8–
本发明通过聚合物中R基团链的长短实现孔径的调控，其中R基团的一端连接含醛基的芳香化合物，另一端连接含氰基的芳香化合物。首先利用醛基芳香化合物制备含有芳氰基的卟啉，然后将含芳氰基的卟啉聚合得到卟啉聚合物。
由于卟啉母体容易到达三重态，敏化基态氧气生成单线态氧(强氧化剂)，因此，卟啉聚合物可作为光催化氧化剂，且其空穴结构又可作为光催化的分子反应器。鉴于此，卟啉聚合物的孔径、比表面积以及芳香化合物与卟啉母体的共轭程度会影响其催化作用。
卟啉聚合物的制备方法及其性能描述如下：
1.聚合原料的合成：meso-5,10,15,20-四(氰基)卟啉的合成
将对氰基苯甲醛和新蒸吡咯分别溶解在适量丙酸中，在氮气保护下，用恒压分液漏斗将新蒸吡咯的丙酸溶液，慢慢滴加到对氰基苯甲醛的丙酸溶液中，油浴加热或微波加热到80-140℃，持续20-60min，冷却至室温，过滤，滤饼用乙醇洗涤，用柱色谱提纯。
2.目标卟啉聚合物的合成
将meso-5,10,15,20-四(氰基)卟啉溶解在甲苯类溶剂中，或者无需溶剂，在N2保护下缓慢滴加三氟甲磺酸，在-30–140℃(高温下可用微波加热)下搅拌，反应结束，过滤，用去离子水和乙醇洗涤除去多余的丙酸，得到紫黑色卟啉聚合物。
此卟啉聚合物合成方法简单，聚合程度可以通过反应溶剂、酸催化剂量、反应温度和反应时间进行调控。
3.目标卟啉聚合物的光氧化性质测试
将卟啉聚合物和1,5-二羟基萘的溶液混合，室温下搅拌，在光源为30W的氙灯照射下进行反应，光强度为300W/m2，反应开始后每2–20min取样，离心分离，取上层清液，测定溶液中1,5-二羟基萘在301nm的吸光度变化，以及产物胡桃醌在420nm的吸光度变化，计算光催化氧化的产率，总反应时间为1–4h。
此卟啉聚合物无需过渡金属辅助聚合，自身可跃迁至三重态，敏化基态氧气，生成具有强氧化性的单线态氧，降低了光催化氧化反应成本，转化率达到90％以上。
附图说明
图1为卟啉聚合物的通式的结构图；
其中，图1中的R＝-Ar-R'-Ar-其中Ar为
R'＝–(CH2)0–8–
具体实施方式
下面将结合具体实例来详叙本发明的技术特点。
实施例1：meso-5,10,15,20-四(氰基)卟啉的普通加热合成
先将1.31g对氰基苯甲醛溶解在20mL丙酸中，将新蒸吡咯0.737g(11mmol,0.76mL)溶解到10mL丙酸中。然后在氮气保护下将吡咯的丙酸溶液缓慢滴加到对氰基苯甲醛的丙酸溶液中，加热至80℃反应1h，冷却至室温，过滤，滤饼用无水乙醇洗涤。用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体。
实施例2：meso-5,10,15,20-四(氰基)卟啉的普通加热合成
先将1.31g对氰基苯甲醛溶解在20mL丙酸中，将新蒸吡咯0.737g(11mmol,0.76mL)溶解到10mL丙酸中。然后在氮气保护下将吡咯的丙酸溶液缓慢滴加到对氰基苯甲醛的丙酸溶液中，加热至100℃反应1h，冷却至室温，过滤，滤饼用无水乙醇洗涤。用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体。
实施例3：meso-5,10,15,20-四(氰基)卟啉的普通加热合成
先将1.31g对氰基苯甲醛溶解在20mL丙酸中，将新蒸吡咯0.737g(11mmol,0.76mL)溶解到10mL丙酸中。然后在氮气保护下将吡咯的丙酸溶液缓慢滴加到对氰基苯甲醛的丙酸溶液中，加热至120℃反应0.5h，冷却至室温，过滤，滤饼用无水乙醇洗涤。用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体。
实施例4：meso-5,10,15,20-四(氰基)卟啉的微波合成
先将1.31g对氰基苯甲醛溶解在20mL丙酸中，将新蒸吡咯0.737g(11mmol,0.76mL)溶解到10mL丙酸中。然后在氮气保护下将吡咯的丙酸溶液缓慢滴加到对氰基苯甲醛的丙酸溶液中，微波加热至80℃，反应1h，冷却至室温，抽滤，滤饼用无水乙醇洗涤。用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体。
实施例5：meso-5,10,15,20-四(氰基)卟啉的微波合成
先将1.31g对氰基苯甲醛溶解在20mL丙酸中，将新蒸吡咯0.737g(11mmol,0.76mL)溶解到10mL丙酸中。然后在氮气保护下将吡咯的丙酸溶液缓慢滴加到对氰基苯甲醛的丙酸溶液中，微波加热至100℃，反应0.5h，冷却至室温，抽滤，滤饼用无水乙醇洗涤。用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体。
实施例6：meso-5,10,15,20-四(氰基)卟啉的微波合成
先将1.31g对氰基苯甲醛溶解在20mL丙酸中，将新蒸吡咯0.737g(11mmol,0.76mL)溶解到10mL丙酸中。然后在氮气保护下将吡咯的丙酸溶液缓慢滴加到对氰基苯甲醛的丙酸溶液中，微波加热至140℃，反应0.4h，冷却至室温，抽滤，滤饼用无水乙醇洗涤。用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体。
实施例7：目标卟啉聚合物的普通加热合成
将50mg的meso-5,10,15,20-四(氰基)卟啉加入到50mL的二口瓶中，在N2保护下缓慢滴加进1.5mL的三氟甲磺酸，在140℃下搅拌1.5h。过滤，用去离子水和乙醇洗涤至中性，得到紫黑色卟啉聚合物。
实施例8：目标卟啉聚合物的普通加热合成
将50mg的meso-5,10,15,20-四(氰基)卟啉溶解在30mL的甲苯溶液中，在N2保护下缓慢滴加进0.1mL的三氟甲磺酸，在100℃下反应4h，过滤，用去离子水和乙醇洗涤至中性，得到黑色卟啉聚合物。
实施例9：目标卟啉聚合物的微波加热合成
将50mg的meso-5,10,15,20-四(氰基)卟啉溶解在30mL的氯苯溶液中，在N2保护下缓慢滴加进1.5mL的三氟甲磺酸，在130℃下微波反应2h，过滤，用去离子水和乙醇洗涤至中性，得到黑色卟啉聚合物。
实施例10：目标卟啉聚合物的光氧化性质测试
在烧瓶中加入10mg卟啉聚合物和30mL 1,5-二羟基萘的溶液(1×10-4mol/L)，室温下搅拌，在光源为30W的氙灯照射下进行反应，光强度为300W/m2，反应开始后每2–20min取3mL溶液，在转速为1000r·min-1下离心10min，取上层清液，用1cm比色皿测定溶液中1,5-二羟基萘在301nm的吸光度变化，以及产物胡桃醌在420nm的吸光度变化，并计算光催化氧化的产率，总反应时间为1h。
Claims (2)
1.一种卟啉聚合物的用途，该卟啉聚合物用作光催化剂，用于光降解1,5-二羟基萘有机污染物，光催化氧化的转化率达到90％以上；其通式为
R＝-Ar-R'-Ar-其中Ar为
R'＝–(CH2)0–8–；
具体步骤如下：
⑴.聚合原料meso-5,10,15,20-四(氰基)卟啉的合成
①.将含芳氰的醛类化合物溶解在20mL质量分数大于99.5％的丙酸中，将新蒸吡咯溶解到10mL质量分数大于99.5％丙酸中，含芳氰的醛类化合物与新蒸吡咯的摩尔比为1：1；
②.在氮气的保护下，将含芳氰的醛类化合物与丙酸的混合溶液加热到60-140℃，然后将新蒸吡咯的丙酸溶液缓慢滴加到含芳氰的醛类化合物的丙酸溶液中；
③.滴加完毕后，继续反应20-30min，反应物冷却至室温，从反应器中取出反应物，减压抽滤，滤饼用无水乙醇反复洗涤多次，除去丙酸；
④.将上一步得到的滤饼用二氯甲烷溶解，得到的溶液减压旋干，用柱色谱提纯，洗脱剂为二氯甲烷，得到深紫色固体粉末；
⑵.目标卟啉聚合物的合成
①.将meso-5,10,15,20-四(氰基)卟啉溶解在溶剂中，或者无需溶剂，在氮气保护下缓慢滴加三氟甲磺酸，在–30～140℃下搅拌；
②.反应结束，减压抽滤，滤饼用去离子水和乙醇洗涤至中性，得到紫黑色卟啉聚合物。
2.根据权利要求1所述的用途，其特征在于：步骤(1)中含芳氰的醛类化合物与丙酸的混合溶液的加热为微波加热。
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| Star-Shaped Donor-π-Acceptor Conjugated Oligomers with 1,3,5-Triazine Cores:Convergent Synthesis and Multifunctional Properties;Shijie Ren,et al.;《The Jounal Physical Chemistry B》;20100722;第114卷(第32期);全文 * |
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