CN109331877B - 一种离子型微孔聚合物催化剂及其制备方法和应用 - Google Patents

一种离子型微孔聚合物催化剂及其制备方法和应用 Download PDF

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CN109331877B
CN109331877B CN201811454881.9A CN201811454881A CN109331877B CN 109331877 B CN109331877 B CN 109331877B CN 201811454881 A CN201811454881 A CN 201811454881A CN 109331877 B CN109331877 B CN 109331877B
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徐丹
吴铎
朱海
齐浩军
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Abstract

本发明公开了一种离子型微孔聚合物催化剂及其制备方法和应用,属于催化剂制备技术领域。本发明使用便宜易得的单体,经由简单的有机合成反应制备了双功能催化剂,将双金属催化中心和亲核试剂同时引入到多孔聚合物中,并且亲核试剂分散密度高,该低成本的催化剂在0.1‑0.7MPa,25‑90℃条件催化二氧化碳转化为环碳酸脂。本发明利用简单的合成方法以及低成本的原料,达到与高成本的催化剂相近的催化效果,且该催化剂可以重复使用。

Description

一种离子型微孔聚合物催化剂及其制备方法和应用
技术领域
本发明涉及一种离子型微孔聚合物催化剂及其制备方法和应用,属于催化剂制备技术领域。
背景技术
二氧化碳的排放量正在逐年增加,设计制备对二氧化碳具有捕获与存储特性的材料以及关注CO2的化学利用迫在眉睫。二氧化碳作为便宜、易得的碳1构筑基元,以其为原料来制备高附加值化学产品也因此倍受关注。催化剂在二氧化碳转化过程中发挥着重要的作用。将催化中心和催化助剂同时引入到多孔聚合物中,以该双功能聚合物为非均相催化剂,催化二氧化碳与环氧烷烃的反应,使其转化为环碳酸脂,对于该种材料的制备是目前二氧化碳减排研究的热点。现有的能够在较温和条件下催化反应的催化剂制备步骤较多,单体需要合成,并且存在催化助剂不能回收再利用的问题。因此,开发一种合成方法简单,原料成本低,并且能够达到在较温和条件下进行催化的双功能催化剂,成为亟待解决的问题。
发明内容
为解决上述问题,本发明的催化剂在微孔聚合物中引入双金属催化中心,离子型聚合物内分散着高密度亲核试剂,如Br-或Cl-,利用双金属的协同催化作用,以及高密度分散的亲核试剂使该催化在较温和的反应条件下(0.1-0.7MPa,25-90℃),实现二氧化碳的催化转化。
本发明的第一个目的是提供一种离子型微孔聚合物催化剂,由单体A、单体B和单体C聚合而成;所述单体C作为连接基团;其中,单体A、单体B和单体C的结构式如下所示:
单体A:
Figure BDA0001887501570000021
单体B:
Figure BDA0001887501570000022
单体C:
Figure BDA0001887501570000023
其中,M、P为两种不同的金属离子;
X、Y单独选自Cl、Br或OAc,a、b分别为2或3;
Z为Cl或Br。
在本发明的一种实施方式中,所述单体A和单体B的摩尔比为4:1-1:4,单体C的摩尔数为单体A和单体B的总摩尔数的2-5倍。
在本发明的一种实施方式中,所述催化剂的一种结构示意图如下所示:
Figure BDA0001887501570000024
在本发明的一种实施方式中,所述M、P单独选自Al、Zn、Mg、Ni、Cr、Cu或者Co,且M、P不相同。
在本发明的一种实施方式中,所述M优选为Al,所述P优选为Zn。
在本发明的一种实施方式中,所述离子型微孔聚合物催化剂的比表面积为25-100m2/g。
本发明的第二个目的是提供所述催化剂的制备方法,包括:将单体A和单体B在交联剂单体C的作用下,在60-120℃反应12-36h,聚合得到所述离子型微孔聚合物催化剂;其中,单体A、单体B和单体C的结构式分别如下所示:
单体A:
Figure BDA0001887501570000031
单体B:
Figure BDA0001887501570000032
单体C:
Figure BDA0001887501570000033
其中,M、P为两种不同的金属离子;
X、Y单独选自Cl、Br或OAc,a、b分别为2或3;
Z为Cl或Br。
在本发明的一种实施方式中,所述方法按照如下步骤进行:
(1)采用咪唑分别与两种金属卤化物或醋酸盐进行反应,制备得到两种四咪唑基金属单体(单体A和单体B);
(2)将步骤(1)得到的两种四咪唑基金属单体溶入有机溶剂中,然后加入1,4-对二卤苄(单体C),反应得到所述催化剂。
在本发明的一种实施方式中,在步骤(1)中,咪唑与金属离子的摩尔比为4:1-8:1。
在本发明的一种实施方式中,在步骤(1)中,反应条件为25℃-40℃反应2-12小时。
在本发明的一种实施方式中,在步骤(2)中,单体A和单体B的摩尔比为1:4-4:1。
在本发明的一种实施方式中,在步骤(2)中,单体C的添加量,按摩尔数计,为四咪唑基金属单体总摩尔数的2-5倍。
在本发明的一种实施方式中,在步骤(2)中,反应条件为60-120℃反应12-36h。
在本发明的一种实施方式中,所述制备方法具体包括:
(1)咪唑与金属卤化物按照摩尔比4-5:1溶于甲醇中,25℃-40℃搅拌反应2-12小时,除去甲醇,然后用四氢呋喃冲洗,干燥后得到四咪唑基金属单体(单体A);
(2)按照步骤(1)的方法,采用与步骤(1)不相同的金属离子,制备另一种四咪唑基金属单体(单体B);
(3)按照摩尔比4:1-1:4将步骤(1)和步骤(2)制备得到的单体A和单体B溶于有机溶剂,然后加入单体A和单体B总摩尔数2-5倍的单体C,60-120℃搅拌反应12-36h;冷却过滤后,依次采用二氯甲烷和甲醇洗涤固体,再采用二氯甲烷与甲醇体积比为1-3:1的混合液进行索氏抽提12-36h,最后干燥得到催化剂。
在本发明的一种实施方式中,咪唑与金属卤化物的反应式为:
Figure BDA0001887501570000041
在本发明的一种实施方式中,所述有机溶剂为N-甲基吡咯烷酮或二甲基甲酰胺。
本发明的第三个目的是提供所述催化剂在二氧化碳减排中的应用。
在本发明的一种实施方式中,应用所述的离子型微孔聚合物催化剂催化二氧化碳与环氧烷烃反应转化为环碳酸脂。
本发明的有益效果在于:
本发明使用便宜易得的单体,经由简单的有机合成反应制备了双功能催化剂,将双金属催化中心和亲核试剂同时引入到多孔聚合物中,并且亲核试剂分散密度高,该低成本的催化剂在0.1-0.7MPa,25-90℃条件催化二氧化碳转化为环碳酸脂。本发明利用简单的合成方法以及低成本的原料,达到与高成本的催化剂相近的催化效果,且该催化剂可以重复使用。
附图说明
图1是苯基碳酸乙烯酯的氢谱。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,以使本领域的技术人员可以更好地理解本发明并能予以实施,但所举实施例不作为对本发明的限定。
实施例1:催化剂cat-Al-Zn的制备
四咪唑基铝单体的制备:咪唑(4.2mmol,0.29g),三氯化铝(1mmol,133.4mg)溶于甲醇30ml,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Al。
四咪唑基锌单体的制备:咪唑(4.2mmol,0.29g),氯化锌(1mmol,136.3mg)溶于甲醇,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Zn。
1-Al(1mmol,0.41g),1-Zn(1mmol,0.41g)溶于25ml NMP中,加入1,4-对二氯苄(5mmol,0.9g)或1,4-对二溴苄,80℃搅拌30h,反应停止,冷却至室温,抽滤,依次用CH2Cl2和CH3OH洗涤固体,索氏提取30h(提取液为CH2Cl2与CH3OH体积比为1.5:1的混合液),最后70℃真空干燥12h即得催化剂cat-Al-Zn。
取50mg实施例1制备得到的cat-Al-Zn,1ml苯基环氧乙烷,二氧化碳压力为0.7MPa,90℃下反应48h,得到苯基碳酸乙烯酯的产率为85%。产物核磁如图1所示。
实施例2:
四咪唑基钴单体的制备:咪唑(4.2mmol,0.29g),醋酸钴(1mmol,177.0mg)溶于甲醇30ml,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Co。
四咪唑基锌单体的制备:咪唑(4.2mmol,0.29g),氯化锌(1mmol,136.3mg)溶于甲醇,30℃搅拌12小时,除去甲醇,抽滤,用THF冲洗,干燥,得到单体1-Zn。
1-Co(1mmol,0.45g),1-Zn(1mmol,0.41g)溶于25ml NMP中,加入1,4-对二氯苄(5mmol,0.9g)或1,4-对二溴苄,80℃搅拌30h,反应停止,冷却至室温,抽滤,依次用CH2Cl2和CH3OH洗涤固体,索氏提取30h(提取液为CH2Cl2与CH3OH体积比为1.5:1的混合液),最后70℃真空干燥12h即得催化剂cat-Co-Zn。
取50mg cat-Co-Zn,1mL苯基环氧乙烷,二氧化碳压力为0.7MPa,90℃下反应48h,得到苯基碳酸乙烯酯的产率为70%。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例,本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换,均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (7)

1. 一种离子型微孔聚合物催化剂的制备方法,其特征在于,包括:将单体A和单体B在交联剂单体C的作用下,在60-120℃反应12-36 h,聚合得到所述离子型微孔聚合物催化剂;其中,单体A、单体B和单体C的结构式分别如下所示:
单体A:
Figure DEST_PATH_IMAGE002
单体B:
Figure DEST_PATH_IMAGE004
单体C:
Figure DEST_PATH_IMAGE006
Figure DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE010
其中,M为Al或Co、P为Zn;
X、Y单独选自Cl、Br或OAc,a、b分别为2或3;
Z为Cl或Br;
所述单体A和单体B的摩尔比为4:1-1:4;
所述单体C的摩尔数为单体A和单体B的总摩尔数的2-5倍。
2.根据权利要求1所述的方法,其特征在于,所述单体A或单体B的制备方法为:采用咪唑与金属的卤化物或者醋酸盐进行反应,得到单体A或单体B。
3.根据权利要求2所述的方法,其特征在于,所述咪唑与金属离子的摩尔比为4:1-8:1。
4.根据权利要求2所述的方法,其特征在于,所述咪唑与金属的卤化物或者醋酸盐进行反应的条件为25℃-40℃反应2-12小时。
5.一种权利要求1~4任一项所述的方法制备得到的离子型微孔聚合物催化剂。
6.权利要求5所述的离子型微孔聚合物催化剂在二氧化碳减排中的应用。
7.根据权利要求6所述的应用,其特征在于,应用所述的离子型微孔聚合物催化剂催化二氧化碳与环氧烷烃反应转化为环碳酸脂。
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CN101270113A (zh) * 2008-01-16 2008-09-24 兰州大学 多手性催化剂制备及在高光学活性环碳酸酯合成的应用
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