CN113968884B - 一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 - Google Patents
一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用 Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 5
- -1 diphosphoramide rare earth metal Chemical class 0.000 claims abstract description 32
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
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Abstract
本发明提供了一种新型双磷酰胺稀土金属配合物、制备方法及催化聚合应用，属于催化技术领域。该双磷酰胺稀土金属配合物将含有不同取代基的多齿磷酰胺配体与稀土金属卤化物反应，催化剂易提纯，产率良好；该双磷酰胺稀土金属催化剂可直接用于催化环内酯的聚合反应，聚合条件温和，可以制备较高分子量且聚合物的分子量分布较窄的聚合物。
Description
技术领域
本发明属于催化技术领域，具体涉及一种多齿稀土金属配合物，并提供了其制备方法和应用。
背景技术
随着废弃塑料在全球的富集，不可降解的传统塑料带来的危害越来越大，因此开发新型环保，可降解的高分子材料尤为重要。其中以聚乳酸为代表的生物质可降解塑料，通常以玉米、甘蔗等可再生的生物质为原料，其来源充分且可再生。聚乳酸的生产过程低碳环保、其制品使用后可以降解，实现在自然界中的循环。同时随着高分子材料需求的增加，合成功能化的高分子材料尤为重要。聚丙交酯(PLA)又称为聚乳酸，因其良好的生物相容性和易降解、无污染被广泛应用在各个行业，尤其是在医药行业,被用作外科缝合材料和药物缓释载体等,发挥了巨大的作用。因此，设计一种具有高活性催化环内酯的聚合的催化剂是非常有意义的。
发明内容
本发明的目的之一在于提供一种新型双磷酰胺稀土金属配合物；本发明目的之二在于提供一种新型稀土金属配合物的制备方法；本发明的目的之三在于提供一种新型双磷酰胺稀土金属配合物在催化环内酯及其衍生物聚合领域的应用。
本发明的技术方案：
一种新型双磷酰胺稀土金属配合物，其结构式如下：
其中，Ln是稀土金属，为钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥；
X是胺基之间的连接取代基，为2，2-二甲基丙基、乙基或反式-1，2-环己基；
E是磷上的取代基，为氧、硫或硒；
R是磷上的烷基取代基，为异丙基、叔丁基或苯基。
一种新型双磷酰胺稀土金属配合物的制备方法，步骤如下：
(1)制备新型双磷酰胺稀土金属配合物
在氮气氛围下，将氢化钾加入到0.07～0.1M的双磷酰胺配体的四氢呋喃溶液中，氢化钾与双磷酰胺配体的摩尔比为2.05～2.1，室温反应4小时；然后将上述混合液加入到与三卤化稀土(LnX3，其中Ln是稀土金属，为钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥，X是卤素，为氯、溴、碘中的一种)的四氢呋喃悬浊液中，在85℃反应12小时，得到新型双磷酰胺稀土金属配合物；其中，双磷酰胺配体与三卤化稀土的摩尔比为2.05～2.1。
一种新型双磷酰胺稀土金属配合物的应用，新型双磷酰胺稀土金属配合物可直接用于催化环内酯及其衍生物的聚合反应。
催化聚合反应的步骤如下：
在氮气氛围下，称取一定比例的环内酯和双磷酰胺稀土金属配合物有机良溶剂中进行聚合反应；反应1min～24h后，加入链终止剂，使反应中止；将反应液用析出液进行沉降，析出聚合物，并在40℃～70℃下真空干燥至恒重。
其中，所述的环内酯与双磷酰胺稀土金属配合物的摩尔比为100～1500:1；反应体系中四齿稀土金属配合物的浓度为1×10-3～5×10-2mol/L。
所述的环内酯类型为L-丙交酯、ε-己内酯、rac-丙交酯、meso-丙交酯、γ- 戊内酯及其衍生物的一种或两种。
所述的有机良溶剂为石油醚、正戊烷、正己烷、正辛烷、苯、甲苯、间二甲苯、邻二甲苯、对二甲苯、溴苯、氯苯、二氯甲烷或四氢呋喃中的一种或两种以上混合；优选四氢呋喃、二氯甲烷、甲苯。
所述的链终止剂为甲醇、乙醇、正丁醇、异丁醇、异丙醇，以及含HCl的上述醇溶液；其中含HCl的体积比为5％～10％。
本发明的有益效果：(1)本发明所述的双磷酰胺配体，反应操作简便易行，原料易得且易于修饰；(2)本发明所述的新型双磷酰胺稀土金属配合物可直接用于催化环内酯的聚合反应。
附图说明
图1为配合物(L1-Ce)K的31PNMR谱图；
图2为配合物(L2-Ce)K的31PNMR谱图；
图3为配合物(L3-Ce)K的31PNMR谱图；
图4为所制备聚丙交酯的凝胶色谱图；
图5为所制备聚己内酯的凝胶色谱图。
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-Ce)K催化剂的制备
氮气氛围下，将氢化钾(0.03g,0.7481mmol)加入到双磷酰胺配体(1.005g，2mmol)的四氢呋喃(4ml)中，室温反应4小时。然后将其加入到与四氢呋喃配位的溴化铈(0.3798g，1mmol)的四氢呋喃溶液中，在85℃反应12小时。过滤，得到双磷酰胺铈配合物L1-Ce，产量0.5g，产率72％。配合物(L1-Ce)K 核磁磷谱如附图1所示。
实施例2
(L2-Ce)K催化剂的制备
催化剂的制备过程和实施例1中的制备方法相同，催化剂的制备方法如下：
具体步骤与实施例1中方法类似，不同的是采用配体H2L2替代了上文中的配体H2L1,得到配合物(L2-Ce)K，产量0.6g，产率为70％。配合物(L2-Ce) K核磁磷谱如附图2所示。
实施例3
(L3-Ce)K催化剂的制备
催化剂的制备过程和实施例1中的制备方法相同，催化剂的制备方法如下：
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，得到配合物(L3-Ce)K产量0.5g，产率为72％。配合物(L3-Ce) K核磁磷谱如附图3所示。
实施例4
手套箱中，将双磷酰胺稀土金属催化剂L1-Ce(10μmol)催化剂和rac-丙交酯依次加入到10mL反应瓶中，rac-丙交酯与双磷酰胺稀土金属配合物的摩尔比为200:1，加入2mL的THF，在室温下搅拌反应60min；聚合终止过程为：加入乙醇作为链终止剂，使反应中止；将反应液用无水乙醇进行沉降，析出固体聚合物，最后，将聚合物在45℃下真空干燥至恒重，得到聚丙交酯0.288g，产率 100％。聚丙交酯GPC图如附图4所示。
实施例5
手套箱中，将双磷酰胺稀土金属催化剂L1-Ce(15μmol)催化剂和ε-己内酯依次加入到20mL反应瓶中，ε-己内酯与双磷酰胺稀土金属配合物的摩尔比为 500:1，加入适量的THF溶剂，在室温下搅拌反应12h；聚合终止过程为：加入甲醇作为链终止剂，使反应中止；将反应液用无水甲醇进行沉降，析出固体聚合物，最后，将聚合物在45℃下真空干燥至恒重，得到聚己内酯0.82g，产率 96％。聚己内酯GPC图如附图5所示。
Claims (10)
1.一种双磷酰胺稀土金属配合物，其特征在于，该双磷酰胺稀土金属配合物的结构式如下：
其中，Ln是稀土金属，为铈；
X是胺基之间的连接取代基，为2，2-二甲基丙基，乙基或反式-1，2-环己基；
E是磷上的取代基，为氧、硫或硒；
R是磷上的取代基，为异丙基、叔丁基或苯基。
2.一种如权利要求1所述的双磷酰胺稀土金属配合物的制备方法，其特征在于，步骤如下：
在氮气氛围下，将氢化钾加入到0.07～0.1M的双磷酰胺配体的四氢呋喃溶液中，氢化钾与双磷酰胺配体的摩尔比为2.05～2.1，室温反应4小时；然后将上述混合液加入到与三卤化稀土LnX3的四氢呋喃悬浊液中，在85℃反应12小时，得到双磷酰胺稀土金属配合物；其中，双磷酰胺配体与三卤化稀土的摩尔比为2.05～2.1；
其中，Ln是稀土金属，为铈。
3.一种如权利要求1所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，该催化剂能够直接用于催化环内酯的开环聚合反应，得到环境友好的高分子材料。
4.根据权利要求3所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，直接用于催化环内酯的开环聚合反应，催化聚合反应的步骤如下：
在氮气氛围下，双磷酰胺稀土金属配合物催化环内酯在有机良溶剂条件下进行聚合；反应1min～24h后，加入链终止剂，使反应中止；将反应液用析出液进行沉降，析出聚合物，并在40℃～70℃下真空干燥至恒重。
5.根据权利要求4所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，用于开环聚合反应，所述的环内酯与双磷酰胺稀土金属配合物的摩尔比为100～5000:1；反应体系中双磷酰胺稀土金属配合物的浓度为1×10-3～5×10-2mol/L。
6.根据权利要求4所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，用于催化环内酯聚合反应所述的环内酯为L-丙交酯、ε-己内酯、rac-丙交酯、meso-丙交酯、γ-戊内酯的一种或两种以上组合。
7.根据权利要求4或5所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，用于催化的环内酯的聚合反应，所述的有机良溶剂为石油醚、正戊烷、正己烷、正辛烷、苯、甲苯、间二甲苯、邻二甲苯、对二甲苯、溴苯、氯苯、二氯甲烷或四氢呋喃中的一种或两种以上混合。
8.根据权利要求6所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，用于催化的环内酯的聚合反应，所述的有机良溶剂为石油醚、正戊烷、正己烷、正辛烷、苯、甲苯、间二甲苯、邻二甲苯、对二甲苯、溴苯、氯苯、二氯甲烷或四氢呋喃中的一种或两种以上混合。
9.根据权利要求4、5或8所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，用于聚合反应，所述的链终止剂为甲醇、乙醇、正丁醇、异丁醇、异丙醇，以及含HCl的上述醇溶液；其中含HCl的体积比为5％～10％。
10.根据权利要求7所述的双磷酰胺稀土金属配合物作为催化剂的应用，其特征在于，用于聚合反应，所述的链终止剂为甲醇、乙醇、正丁醇、异丁醇、异丙醇，以及含HCl的上述醇溶液；其中含HCl的体积比为5％～10％。
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