CN112079790B - 一种绿色荧光的双胺-噁唑啉锌配合物、制备方法和应用 - Google Patents
一种绿色荧光的双胺-噁唑啉锌配合物、制备方法和应用 Download PDFInfo
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- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
本发明提供了一种绿色荧光的双胺‑噁唑啉锌配合物、制备方法和应用，属于发光材料催化技术领域。该配合物可采用含有不同取代基的双胺‑噁唑啉配体与二乙基锌直接反应和纯化得到，配合物产率高且纯度高。以380nm为激发波长，双胺‑噁唑啉锌配合物呈现绿色荧光，最大发射波长为491‑495nm，双胺‑噁唑啉锌配合物的荧光寿命为10‑10.75μs。并且，双胺‑噁唑啉锌配合物可直接用于催化环内酯的开环聚合反应，具有较高的催化活性，得到一系列具有特定结构的高分子材料。
Description
技术领域
本发明属于发光材料催化技术领域，具体涉及一种绿色荧光的双胺-噁唑啉锌配合物，并提供了其制备方法和应用。
背景技术
发光材料作为一种重要的功能材料，在医学、工业、国防、农业等领域具有广泛的应用。虽然稀土发光配合物具有色纯度高、光吸收能力强、荧光寿命和发光谱带窄等优点，但稀土开采难度大、价格昂贵限制了稀土发光配合物在材料的大规模应用，所以开发性能优良的过渡金属配合物发光材料具有重要的经济价值和社会意义。
发明内容
本发明的目的之一在于提供一种具有绿色荧光的双胺-噁唑啉锌配合物的制备方法；本发明的目的之二在于提供双胺-噁唑啉锌配合物在催化环内酯开环聚合领域的应用。
本发明的技术方案：
一种绿色荧光的双胺-噁唑啉锌配合物，其结构式如下：
其中，R1是噁唑啉环与氮相邻碳上的取代基，为氢原子或甲基；
R2是噁唑啉环与氮相邻碳上的取代基，为氢原子、甲基、异丙基、叔丁基、苯基、苄基或金刚烷基。
一种绿色荧光的双胺-噁唑啉锌配合物的制备方法，步骤如下：
在氮气保护和低温条件下，将二乙基锌和双胺-噁唑啉配体在0.01M～0.1M的四氢呋喃溶液中混合，反应12～24小时，减压除去溶剂，重结晶后得到双胺-噁唑啉锌配合物；其中，双胺-噁唑啉配体与二乙基锌中金属的摩尔比为1:1～1.3。
双胺-噁唑啉锌配合物在491-495nm发出强的绿色荧光，具有良好的稳定性，可作为光化学传感器和荧光发生器件等领域。
双胺-噁唑啉锌配合物可催化环内酯的开环聚合反应，催化聚合反应的步骤如下：
在氮气保护条件下，环内酯和双胺-噁唑啉锌配合物按比例混合，聚合反应开始；一定时间后，加入链终止剂，使聚合反应中止；聚合物采用析出液使其沉淀析出，所得聚合物在40℃～70℃下真空干燥至恒重。
其中，环内酯与双胺-噁唑啉锌配合物的摩尔比为100～5000:1；反应体系中双胺-噁唑啉锌配合物的浓度为1×10-3～5×10-2mol/L。
所述的环内酯类型可为L-丙交酯、D-丙交酯、rac-丙交酯、meso-丙交酯、β-丁内酯、ε-己内酯或γ-戊内酯。
所述的有机溶剂为苯、甲苯、对二甲苯、间二甲苯、邻二甲苯、氯苯、对二氯苯、间二氯苯、邻二氯苯、四氢呋喃或二氯甲烷；优选甲苯或四氢呋喃。
所述的链终止剂为无水乙醇或含HCl的乙醇溶液；其中，含HCl的乙醇溶液，HCl与乙醇的体积比为5％～10％。
本发明的有益效果：(1)本发明所述的具有绿色荧光的双胺-噁唑啉锌配合物的制备方法，其中双胺-噁唑啉配体可直接与二乙基锌反应，配合物产率高(88.9％–95.6％)且产品纯度较高；(2)本发明所述的双胺-噁唑啉锌配合物在491-495nm发出强的绿色荧光，具有良好的稳定性，可作为光化学传感器和荧光发生器件等领域；(3)本发明所述的双胺-噁唑啉锌配合物可直接用于催化环内酯的开环聚合反应。
附图说明
图1是L1-Zn配合物的核磁氢谱。
图2是L1-Zn配合物的荧光谱图。
图3是L2-Zn配合物的核磁氢谱。
图4是L2-Zn配合物的紫外谱图。
图5是聚丙交酯GPC图。
图6是聚己内酯GPC图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下将结合实施例进行阐述本发明。
实施例1
L1-Zn配合物的制备(L1代表甲基取代的双胺-噁唑啉配体)
氮气保护下，将二乙基锌(0.415ml，0.415mmol)和双胺-噁唑啉配体H2L1(0.2g，0.377mmol)分别溶于5ml四氢呋喃，-78℃下将二乙基锌溶液逐滴加入到配体溶液中，缓慢升至室温反应12h，真空减压除去溶剂，得到L1-Zn配合物0.210g，产率95.6％。L1-Zn配合物核磁氢谱如图1所示。L1-Zn配合物荧光谱图如图2所示。
实施例2
L2-Zn配合物的制备(L2代表异丙基取代的双胺-噁唑啉配体)
配合物的制备过程和实施例1中的制备方法相同，配合物的制备方法如下：
具体步骤与实施例1中方法类似，不同的是采用配体H2L2替换了上文中的配体H2L1。得到L2-Zn配合物0.203g，产率91.9％。L2-Zn配合物核磁氢谱如图3所示。L2-Zn配合物紫外谱图如图4所示。
实施例3
L3-Zn配合物的制备(L3代表苯基取代的双胺-噁唑啉配体)
配合物的制备过程和实施例1中的制备方法相同，配合物的制备方法如下：
具体步骤与实施例1中方法类似，不同的是采用配体H2L3替代了上文中的配体H2L1。得到L3-Zn配合物0.195g，产率88.9％。
实施例4
手套箱中，向20mL反应瓶中依次加入L1-Zn(10μmol，5.90mg)催化剂和rac-丙交酯(2mmol，288.3mg)，加入3mLTHF溶剂，在室温下搅拌反应30min；聚合终止过程为：加入链终止剂，中止反应；反应液用无水乙醇析出固体聚合物，并用无水乙醇多次洗涤所得到的聚合物，最后，将聚合物在45℃下真空干燥至恒重，得到256.8mg聚丙交酯，转化率为99％，聚合活性为88.85kg·mol-1·h-1。聚丙交酯GPC图如图5所示。
实施例5
过程同实施例4，不同的是催化剂由L2-Zn换成L1-Zn，将环内酯由rac-丙交酯换成L-丙交酯，反应得到243.3mg聚L-丙交酯，转化率为98％，聚合活性为83.57kg·mol-1·h-1。
实施例6
手套箱中，向20mL反应瓶中依次加入L1-Zn(10μmol，5.90mg)催化剂和ε-己内酯(2mmol，228mg)，加入3mL甲苯溶剂，在室温下搅拌反应3h；聚合终止过程为：加入链终止剂，中止反应；反应液用无水乙醇析出固体聚合物，并用无水乙醇多次洗涤所得到的聚合物，最后，将聚合物在45℃下真空干燥至恒重，得到218mg聚己内酯，转化率为95.6％，聚己内酯分子量为35744g·mol-1。聚己内酯GPC图如图6所示。
实施例7
过程同实施例6，不同的是催化剂由L2-Zn换成L1-Zn，反应得到243.3mg聚己内酯，转化率为98％，聚己内酯分子量为30700g·mol-1。
实施例8
过程同实施例6，不同的是将环内酯由ε-己内酯换成β-丁内酯，反应得到150.3mg聚丁内酯，转化率为87.29％，聚丁内酯分子量为28975g·mol-1。
Claims (8)
1.一种绿色荧光的双胺-噁唑啉锌配合物，其特征在于，该绿色荧光的双胺-噁唑啉锌配合物的结构式如下：
其中，R1是噁唑啉环与氮相邻碳上的取代基，为氢原子或甲基；
R2是噁唑啉环与氮相邻碳上的取代基，为氢原子、甲基、异丙基、叔丁基、苯基、苄基或金刚烷基。
2.如权利要求1所述的双胺-噁唑啉锌配合物的制备方法，其特征在于，步骤如下：
在氮气保护和低温条件下，将二乙基锌和双胺-噁唑啉配体在0.01M～0.1M的四氢呋喃溶液中混合，反应12～24小时，减压除去溶剂，重结晶后得到双胺-噁唑啉锌配合物；其中，双胺-噁唑啉配体与二乙基锌中金属的摩尔比为1:1～1.3。
3.如权利要求1所述的双胺-噁唑啉锌配合物作为光化学传感器或荧光发生器件的应用，其特征在于，所述双胺-噁唑啉锌配合物在491-495nm发出强的绿色荧光。
4.如权利要求1所述的双胺-噁唑啉锌配合物用于催化环内酯的开环聚合反应的应用，其特征在于，催化聚合反应的步骤如下：
在氮气保护条件下，环内酯和双胺-噁唑啉锌配合物按比例混合，聚合反应开始；一定时间后，加入链终止剂，使聚合反应中止；聚合物采用析出液使其沉淀析出，所得聚合物在40℃～70℃下真空干燥至恒重；
其中，环内酯与双胺-噁唑啉锌配合物的摩尔比为100～5000:1；反应体系中双胺-噁唑啉锌配合物的浓度为1×10-3～5×10-2mol/L。
5.如权利要求4所述的应用，其特征在于，所述的环内酯为L-丙交酯、D-丙交酯、rac-丙交酯、meso-丙交酯、β-丁内酯、ε-己内酯或γ-戊内酯。
6.如权利要求4或5所述的应用，其特征在于，所述的催化环内酯的开环聚合反应中使用有机溶剂，所述的有机溶剂为苯、甲苯、对二甲苯、间二甲苯、邻二甲苯、氯苯、对二氯苯、间二氯苯、邻二氯苯、四氢呋喃或二氯甲烷。
7.如权利要求4或5所述的应用，其特征在于，所述的链终止剂为无水乙醇。
8.如权利要求6所述的应用，其特征在于，所述的链终止剂为无水乙醇。
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