CN106008564B - 笼状2‑(2‑吡啶基)苯并咪唑锌配合物及其制备方法和应用 - Google Patents

笼状2‑(2‑吡啶基)苯并咪唑锌配合物及其制备方法和应用 Download PDF

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CN106008564B
CN106008564B CN201610380662.5A CN201610380662A CN106008564B CN 106008564 B CN106008564 B CN 106008564B CN 201610380662 A CN201610380662 A CN 201610380662A CN 106008564 B CN106008564 B CN 106008564B
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魏学红
华宇鹏
王海蟒
郭志强
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Abstract

本发明提供了一种笼状2‑(2‑吡啶基)苯并咪唑锌配合物及其制备方法和应用。该方法是以2‑(2‑吡啶基)苯并咪唑为配体，并以此配体为转移试剂，与二乙基锌试剂作用合成一种笼状的2‑(2‑吡啶基)苯并咪唑锌配合物，这种笼状的金属锌配合物可用于催化丙交酯的开环聚合。本发明配合物的制备方法简便，原料易得，反应条件温和，产率高；对丙交酯开环聚合反应合成生物可降解的聚乳酸材料具有较高催化活性，并由于这类催化剂的生物相容性好、毒性小，对环境污染小，催化反应时间短，产率高，有很好的工业应用前景。

Description

笼状2-(2-吡啶基)苯并咪唑锌配合物及其制备方法和应用
技术领域
本发明涉及催化剂制备技术领域，具体涉及一种笼状2-(2-吡啶基)苯并咪唑锌配合物及其制备方法和应用。
背景技术
基于α-羟基酸(乙二醇，乳酸)的聚酯有可降解性，同时其水解后的产物有生物相容性。其中聚乳酸(PLA)作为一种新型友好的热塑性塑料有着广泛的用途：纤维，涂料，薄膜等。乳酸合成来源是玉米、甜菜、或者其他可再生的资源，可作为一种石油衍生聚合物的替代品，进而缓解人类资源危机染。PLA不但具有一般高分子材料所具有的基本特性，而且极易改性以满足各种需要；其已在医疗、工业、农业等领域得到广泛应用，并且除具有高分子的特点外，还有良好的生物相容性且无毒性的优点，因而被认为是21世纪最有前途的可生物降解的功能材料。目前，丙交酯的开环聚合反应相对于缩聚反应有更多优点，如条件温和，单体转化率高，易得高分子量且分子量窄的聚乳酸等，而成为现今研究最深入的方法。所用催化剂主要有铝系、锌系、镁系、钙系及锡系等。锌配合物催化剂因其毒性小与可控的聚合物分子量等特点被广泛研究。但是大部分锌配合物催化剂存在常温下反应时间较长、催化产率低、聚合物分子量分布不均匀的问题。
发明内容
本发明的目的是提供一种笼状2-(2-吡啶基)苯并咪唑锌配合物及其制备方法，配合物合成简便，反应条件温和，产率高；配合物对丙交酯开环聚合反应合成生物可降解的聚乳酸材料具有在常温下反应时间短、催化产率高、聚合物分子量分布均匀的特点。
本发明提供的一种笼状2-(2-吡啶基)苯并咪唑锌配合物，其结构式为：
式中：该配合物呈现笼状构型，由四个(2-(2-吡啶基)苯并咪唑)乙基锌分子通过四个N-Zn配位键构成；其中锌原子与乙基碳原子、配体上两个氮原子及另一配体的氮原子形成四配位模式，并且每个锌原子均连接向外伸展的乙基。
本发明提供的一种笼状2-(2-吡啶基)苯并咪唑锌配合物的制备方法，包括如下步骤：
(1)将吡啶甲醛在0℃缓慢滴入到邻苯二胺的乙醇溶液中，室温反应4小时，抽干溶剂后得大量淡黄色固体，用正己烷洗涤两次，然后用无水乙醇重结晶得2-(2-吡啶基)苯并咪唑配体；反应式：
(2)在惰性气体保护下，将等当量的二乙基锌试剂在-78℃逐滴滴加到2-(2-吡啶基)苯并咪唑的正己烷溶液中，恢复室温后继续搅拌2小时，反应完毕后过滤重结晶，室温析出无色透明晶体，即为笼状2-(2-吡啶基)苯并咪唑锌配合物，产率91-94％。反应式：
步骤1)中吡啶甲醛与邻苯二胺的摩尔比为2∶1。
该催化剂可在催化丙交酯开环聚合反应中应用。
与现有技术相比本发明的优点和效果：本发明配合物的制备方法简便，原料易得，反应条件温和，产率较高；在其笼状结构上存在四个向外伸展的乙基活性基团，更有利于丙交酯开环聚合反应的进行，因此具有较高催化活性且所生成的聚乳酸分子量分布均匀，由于这类催化剂的生物相容性好、毒性小，对环境污染小，催化反应时间短，产率高，有很好的工业应用前景。
附图说明
图1本发明一种笼状2-(2-吡啶基)苯并咪唑锌配合物的单晶X射线结构图
具体实施方式：
以下仅仅为详细说明本发明而给出的具体实施例，这些实施例并非用于限制本发明的保护范围。
实施例1笼状2-(2-吡啶基)苯并咪唑锌配合物的制备
将吡啶甲醛(2.14g,20mmol)在0℃缓慢滴入到邻苯二胺(1.08g,10mmol)的乙醇溶液中，室温反应4小时，抽干溶剂后得大量淡黄色固体，分别用5mL正己烷洗涤两次，然后用无水乙醇重结晶得2-(2-吡啶基)苯并咪唑配体，产率94％；
在惰性气体保护下，将二乙基锌试剂(2.0mL，1.0M，正己烷溶液)在-78℃逐滴滴加到2-(2-吡啶基)苯并咪唑(2.31g，2mmol)的正己烷溶液中，恢复室温后继续搅拌2小时，反应完毕后过滤重结晶，室温析出无色透明晶体，即为笼状2-(2-吡啶基)苯并咪唑锌配合物，产率97％。
晶体参数：化学式：C56H52N12Zn4，三斜晶系(triclinic)，空间群P1，晶胞参数 α＝97.551(3)°，β＝107.060(3)°，γ＝105.469(3)°，V＝2920.5(5)，Z＝1。单晶结构图见图1。
部分键长：Zn1-C13 1.964(15)，Zn1-N1 2.164(16)，Zn1-N3 2.023(19)，Zn1-N5 2.105(18)，Zn2-C27 1.90(3)，Zn2-N4 2.18(2)，Zn2-N6 2.071(18)，Zn2-N8 2.023(18)，Zn3-C41 1.88(3)，Zn3-N7 2.20(2)，Zn3-N9 2.058(17)，Zn3-N11 2.133(17)，Zn4-C55 2.02(2)，Zn4-N10 2.16(2)，Zn4-N12 2.06(2)，Zn4-N2 2.083(17)；键角(°)：C13-Zn1-N3 113.6(7)，C13-Zn1-N5 118.9(6)，N3-Zn1-N1 79.7(6)，N5-Zn1-N1 95.7(6)，N3-Zn1-N5116.6(7)，C13-Zn1-N1 125.9(7)，C27-Zn2-N8 132.3(11)，C27-Zn2-N4 118.4(11)，C27-Zn2-N6 114.6(11)，N8-Zn2-N6 107.8(8)，N8-Zn2-N4 90.9(8)，N6-Zn2-N4 77.2(8)，C41-Zn3-N9 119.9(11)，C41-Zn3-N11 116.1(10)，C41-Zn3-N7 125.1(11)，N9-Zn3-N11 117.1(7)，N9-Zn3-N7 78.8(7)，N11-Zn3-N7 91.4(7)，C55-Zn4-N12 128.5(8)，C55-Zn4-N2116.4(9)，C55-Zn4-N10 122.5(8)，N12-Zn4-N2 106.6(7)，N12-Zn4-N10 76.9(7)，N2-Zn4-N10 96.2(7)。
实施例2
(1)催化剂的制备同实施例1
(2)丙交酯开环聚合：将丙交酯(1.44g,10mmol)和催化剂(0.1mmol)溶入20mL四氢呋喃溶剂中，待溶液澄清后，加入苄醇(0.4mmol)进行引发，25℃反应1小时后取少量反应混合液用于核磁1H NMR检测转化产率，然后加入0.5mL HCl(1.0M)的乙醇溶液对反应进行终止，再缓慢加入无水乙醇沉淀聚乳酸，静置后过滤，真空干燥得白色聚乳酸固体产品。转化率99％，PDI＝1.16。
实施例3
(1)催化剂的制备同实施例1
(2)丙交酯开环聚合：将丙交酯(7.20g,50mmol)和催化剂(0.1mmol)溶入30mL四氢呋喃溶剂中，待溶液澄清后，加入苄醇(0.4mmol)进行引发，25℃反应1小时后取少量反应混合液用于核磁1H NMR检测转化产率，然后加入0.5mL HCl(1.0M)的乙醇溶液对反应进行终止，再缓慢加入无水乙醇沉淀聚乳酸，静置后过滤，真空干燥得白色聚乳酸固体产品。转化率98％，PDI＝1.11。

Claims (4)

1.一种笼状2-(2-吡啶基)苯并咪唑锌配合物，其特征在于，结构式为：
2.如权利要求1所述的一种笼状2-(2-吡啶基)苯并咪唑锌配合物的制备方法，其特征在于，包括如下步骤：
1)将吡啶甲醛在0℃缓慢滴入邻苯二胺的乙醇溶液中，室温反应4小时，抽干溶剂后得大量淡黄色固体，用正己烷洗涤两次，然后用无水乙醇重结晶得2-(2-吡啶基)苯并咪唑配体；
2)在惰性气体保护下，将等当量的二乙基锌试剂在-78℃逐滴滴加到2-(2-吡啶基)苯并咪唑的正己烷溶液中，恢复室温后继续搅拌2小时，过滤重结晶，室温析出无色透明晶体即可。
3.如权利要求2所述的一种笼状2-(2-吡啶基)苯并咪唑锌配合物的制备方法，其特征在于，所述步骤1)中吡啶甲醛与邻苯二胺的摩尔比为2∶1。
4.如权利要求1所述的笼状2-(2-吡啶基)苯并咪唑锌配合物在催化丙交酯开环聚合反应制备聚乳酸材料中的应用。
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