CN107362829A - 负载型共价有机框架双金属催化剂及其制备方法和应用 - Google Patents

负载型共价有机框架双金属催化剂及其制备方法和应用 Download PDF

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CN107362829A
CN107362829A CN201610318275.9A CN201610318275A CN107362829A CN 107362829 A CN107362829 A CN 107362829A CN 201610318275 A CN201610318275 A CN 201610318275A CN 107362829 A CN107362829 A CN 107362829A
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chain olefin
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高艳安
冷文光
格日乐
董彬
王畅
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明涉及一种负载型共价有机框架双金属催化剂及其制备方法和应用，具体为以Py‑2,2’‑BPyPh COF为催化剂载体，将锰盐和钯盐负载在Py‑2,2’‑BPyPh COF孔道内得到异相催化剂Mn/Pd@Py‑2,2’‑BPyPh COF。本发明使用该催化剂成功催化了Heck‑Epoxidation串联反应，该反应产率高、催化剂可循环使用、操作简便、产物附加值高。

Description

负载型共价有机框架双金属催化剂及其制备方法和应用
技术领域
本发明涉及一种负载型共价有机框架双金属催化剂及其制备方法以及合成烯烃环氧化合物中作为催化剂的应用。
背景技术
碳-碳偶联反应是有机合成中一类重要的化学反应，该反应可以在较为温和的实验环境下将短碳链化合物高效、高选择性地转化为长碳链化合物。Heck反应是碳-碳偶联反应中的一种，其具体是指烯烃与卤代芳烃在有机钯催化剂的催化作用下转化为具有更长碳链的烯烃化合物(参考文献1：P.Pachfule,M.K.Panda,S.Kandambeth,S.M.Shivaprasad,D.Díaz Díaz and R.Banerjee,J.Mater.Chem.A，2014,2,7944.)。烯烃的环氧化反应(Epoxidation反应)则是制备烯烃环氧化合物的重要反应，该反应可以在温和的实验条件下使烯烃化合物的双键与氧化剂分子发生氧化加成反应生成对应的烯烃环氧化合物，该反应的催化剂一般可以使用锰、铁类的化合物(参考文献2：W.J.Zhang,P.P.Jiang,Y.Wang,J.Zhang and P.B.Zhang,Appl.Catal.A-Gen.,2015,489,117.)。我们设想：如果可以将钯催化剂与锰、铁催化剂复配，则可能以较短碳链的烯烃与卤代芳烃为起始原料，通过Heck反应与Epoxidation反应的连续反应直接合成出长碳链的烯烃环氧化合物。
共价有机框架(Covalent organic frameworks,COFs)材料也被称为“有机分子筛”，具有孔道结构开放有序、易于进行化学修饰改性、化学/热稳定性好等优点，是一种新型的有机聚合物多孔材料(参考文献3：A.P.A.I.Benin,N.W.Ockwig,M.O'Keeffe,A.J.Matzger and O.M.Yaghi,Science,2005,310,1166.)。近年来，以COFs为催化剂载体负载金属化合物用于制备异相反应催化剂已经成为材料领域研究的新热点。
在这里，我们将联吡啶与亚胺键这两种含氮配体同时引入到二维COFs材料中。其中的联吡啶可以与二氯化锰发生选择性的络合负载，而亚胺键则可以与醋酸钯发生配位作用实现对钯催化剂的负载。这样一来，两种金属催化剂都可以被负载到COFs框架中，最终得到一种新型的异相催化剂，命名为Mn/Pd@Py-2,2’-BPyPh COF。我们使用该催化剂成功催化了Heck-Epoxidation串联反应，即以短链烯烃和卤代苯衍生物为起始原料，连续反应得到了最终产物：长链烯烃氧化物。催化剂经多次循环使用仍能保持高活性，COFs框架的孔道结构也没有发生破坏或堵塞，证明该材料具有优异的异相反应催化性能。
发明内容
本发明提供一种负载型共价有机框架双金属催化剂及其制备方法和合成烯烃环氧化合物中作为催化剂的应用。所述负载型共价有机框架双金属催化剂是一种新型的异相催化剂，具体为在共价有机框架(COFs)材料中负载锰元素、钯元素，并且将其用于Heck-Epoxidation串联反应合成烯烃环氧化合物。
为实现本发明目的，所采用的技术方案为：
一种负载型共价有机框架双金属催化剂，以Py-2,2’-BPyPh COF为催化剂载体，将锰盐和钯盐负载在Py-2,2’-BPyPh COF孔道内得到异相催化剂Mn/Pd@Py-2,2’-BPyPh COF，其中Py-2,2’-BPyPh COF的结构式为：
所述Py-2,2’-BPyPh COF按照参考文献中报道的方法进行合成；
参考文献为：Towards covalent organic frameworks with predesignable andaligned open docking sites，Xiong Chen,Ning Huang,Jia Gao,Hong Xu,Fei Xu andDonglin Jiang，Chem.Commun.,2014,50,6161。
本发明催化剂载体按照参考文献的方法进行合成，但是并不限制于其中的具体参数和反应条件，在参考文献方法的操作下，能得到该载体结构的，均可作为本发明的载体进行使用。
所述锰盐为MnCl2.nH2O n＝0,1,2,3,4、Mn(OAc)2或MnSO4中的一种或两种以上；所述钯盐为Pd(OAc)2、PdCl2或Pd(PPh3)4中的一种或两种以上；锰盐与钯盐之间不发生聚集，均匀分散在Py-2,2’-BPyPh COF中。
锰盐以Mn元素计，于催化剂中的负载量为0.5-2wt％；钯盐以Pd元素计，于催化剂中的负载量为5-10wt％。
Mn/Pd@Py-2,2’-BPyPh COF中Mn元素与Pd元素的摩尔比为1-8:10。
一种上述负载型共价有机框架双金属催化剂的制备方法:按照如下步骤制备：
1)将Py-2,2’-BPyPh COF与锰盐溶液混合搅拌2h-24h，之后抽滤除去溶液相得固体粉末，洗涤，于60-120℃烘干得Mn@Py-2,2’-BPyPh COF；
2)将Mn@Py-2,2’-BPyPh COF与钯盐溶液混合搅拌2h-24h，之后抽滤除去溶液相得固体粉末，洗涤，于60-120℃烘干得Mn/Pd@Py-2,2’-BPyPh COF。
步骤1)中，所述锰盐为MnCl2.nH2O n＝0,1,2,3,4、Mn(OAc)2或MnSO4中的一种或两种以上，所述锰盐溶液的溶剂为甲醇、乙醇或乙腈中的一种或两种以上，锰盐溶液中锰盐质量百分含量为0.1-5.0wt.％，洗涤方式为：甲醇和/或水洗涤两次以上，可使用布氏漏斗，洗涤抽滤至滤液无色为止；
步骤2)中，所述钯盐为Pd(OAc)2、PdCl2或Pd(PPh3)4中的一种或两种以上，钯盐溶液的溶剂为二氯甲烷、四氢呋喃或甲醇中的一种或两种以上，钯盐溶液中钯盐质量百分含量为0.1-5.0wt.％，洗涤方式为：二氯甲烷洗涤两次以上；可使用布氏漏斗，洗涤抽滤至滤液无色为止。
本发明还提供一种负载型共价有机框架双金属催化剂于Heck-Epoxidation串联反应中的应用。
第一步为Heck反应，以短链烯烃与卤代苯衍生物为底物，Mn/Pd@Py-2,2’-BPyPhCOF为催化剂，制备长链烯烃；第二步为Epoxidation反应，Heck反应结束后的体系中通入空气，制备最终产物长链烯烃氧化物。
具体为：
第一步为Heck反应：以短链烯烃和卤代苯衍生物为底物，无水碳酸钾或三乙基胺或吡啶为助催化剂，Mn/Pd@Py-2,2’-BPyPh COF为催化剂，乙腈或N,N’-二甲基乙酰胺或甲苯为溶剂，在N2保护下加热反应6-24h得到长链烯烃；第二步为Epoxidation反应：向Heck反应结束后的体系中加入异丁醛做为助还原剂(Heck反应与Epoxidation反应属于连续的串联反应，Heck反应结束后，直接向体系中加入其它所需物质)，并通入空气继续室温反应4-12h得到最终产物长链烯烃氧化物；
第二步Epoxidation反应结束后，固相通过过滤分离，剩余含有产物长链烯烃氧化物的液相部分通过旋转蒸发或蒸馏的方式除去溶剂得最终产物长链烯烃氧化物。
本发明反应过程中，优选的短链烯烃：卤代苯衍生物：催化剂：助催化剂：助还原剂的摩尔比＝1.2～1:1:0.001～0.01:3～5:2～3。
其中，所述短链烯烃包括苯乙烯、丙烯、丁烯或己烯。
所述卤代苯衍生物的分子式为RPhX，其中Ph为苯环，X选自Cl、Br、I中的一种或两种以上，R选自H、CH3、OCH3、CN、NO2中的一种或两种以上，Ph上的取代基个数为1个、2个、3个或4个。
本发明所述Mn/Pd@Py-2,2’-BPyPh COF催化剂的有益效果为:
1.Mn/Pd@Py-2,2’-BPyPh COF具有较高的比表面积(1562m2/g)和开放的一维孔道结构，孔道尺寸分布均一(2.0nm)，这些都有利于反应底物和产物的扩散传输。由于负载的Mn和Pd分别与联吡啶和亚胺键配位，因此这两种催化剂在COFs框架中都能够以分子的状态有效分散，避免了因催化剂分子聚集导致的催化活性下降。
2.首次提出利用COFs材料做载体可控负载两种以上的金属化合物用于催化串联反应。
3.Mn/Pd@Py-2,2’-BPyPh COF对一系列Heck-Epoxidation连续反应都表现出了高产率(>80％)。催化剂循环使用3次以上催化性能没有出现明显下降。
4.所有的反应和操作过程简单方便，原料的价格相对较低，而最终产物烯烃氧化物则是一类重要的化工原料，具有较高的附加值。
5.本发明所述的新型异相催化剂Mn/Pd@Py-2,2’-BPyPh COF用于催化连续反应合成烯烃环氧化合物，催化剂特殊而又精巧的结构设计有利于促进催化反应的顺利进行、反应底物种类可扩展、反应产率高、催化剂可循环使用、操作简便、产物附加值高。
附图说明
图1为实施例2制备催化剂的反应式；
图2为实施例2Heck-Epoxidation反应的反应式。
具体实施方式
下面结合具体实施例对本发明进一步描述，但本发明的保护范围并不仅限于此。
实施例1
催化剂的制备：
第一步：在室温条件下，将Py-2,2’-BPyPh COF与MnCl2.4H2O的甲醇溶液(10-30g/L)混合搅拌12h，让锰盐通过渗透扩散作用进入COFs的孔道中并与联吡啶配位生成Mn@Py-2,2’-BPyPh COF。反应后抽滤除去溶液相，固体粉末经甲醇、水洗涤后，烘干备用。Mn元素的负载量为0.5-2wt％。
第二步：在室温条件下，将Mn@Py-2,2’-BPyPh COF与Pd(OAc)2的二氯甲烷溶液(10-30g/L)混合搅拌12h，让钯盐通过渗透扩散作用进入COFs的孔道中与亚胺键配位，制备得到同时负载锰、钯双金属的COFs材料Mn/Pd@Py-2,2’-BPyPh COF。反应后抽滤除去溶液相，固体粉末经二氯甲烷洗涤后，烘干备用。Pd元素的负载量为5-10wt％。
Heck-Epoxidation反应：
第三步：以Mn/Pd@Py-2,2’-BPyPh COF为异相催化剂(5-10mg)，连续催化Heck-Epoxidation串联反应。
Heck反应：以苯乙烯和卤代苯衍生物(摩尔比大约1:1)为原料，Mn/Pd@Py-2,2’-BPyPh COF为异相催化剂(5-10mg)，无水碳酸钾为助催化剂，乙腈为溶剂，在N2保护下加热反应6-24h得到长链烯烃。Epoxidation反应：向上述结束后的Heck反应体系中加入异丁醛做为助还原剂，并通入空气继续室温反应4-12h得到最终产物长链烯烃氧化物。所述的卤代苯衍生物，其共同特征为：分子式为RPhX，其中Ph为苯环，X选自Cl、Br、I中的一种或两种以上，R选自H、CH3、OCH3、CN、NO2中的一种或两种以上，Ph上的取代基个数为1个、2个、3个或4个。所述短链烯烃包括苯乙烯、丙烯、丁烯或己烯。Mn/Pd@Py-2,2’-BPyPh COF和无水碳酸钾做为固体相可以通过过滤分离，产物的乙腈溶液可以通过旋转蒸发或蒸馏的方式处理得到最终的固体或液体产物。
实施例2
催化剂的制备：
第一步：COFs负载Mn：
在室温条件下，将100mg Py-2,2’-BPyPh COF与172mg MnCl2.4H2O的甲醇溶液混合搅拌12h，172mg MnCl2.4H2O用10mL甲醇，让锰盐通过渗透扩散作用进入COFs的孔道中并与联吡啶配位生成Mn@Py-2,2’-BPyPh COF。反应后抽滤除去溶液相，固体粉末经甲醇、水洗涤后120℃烘干备用。
第二步：在室温条件下，将100mg Mn@Py-2,2’-BPyPh COF与137mg Pd(OAc)2的二氯甲烷溶液混合搅拌12h，137mg Pd(OAc)2用10mL二氯甲烷，让钯盐通过渗透扩散作用进入COFs的孔道中与亚胺键配位，制备得到同时负载锰、钯双金属的COFs材料Mn/Pd@Py-2,2’-BPyPh COF。反应后抽滤除去溶液相，固体粉末经二氯甲烷洗涤后120℃烘干。
Heck-Epoxidation反应：
第三步：以Mn/Pd@Py-2,2’-BPyPh COF为异相催化剂(10mg)，连续催化Heck-Epoxidation串联反应。
Heck反应：以苯乙烯(1.1mmol)和卤代苯衍生物(1.0mmol)为原料，无水碳酸钾(2.0mmol)为助催化剂，以Mn/Pd@Py-2,2’-BPyPh COF为异相催化剂(10mg)，乙腈为溶剂，在N2保护下80℃反应24h得到长链烯烃。Epoxidation反应：向上述结束后的Heck反应体系中加入异丁醛(3.0mmol)做为助还原剂，并通入空气继续室温反应12h得到最终产物长链烯烃氧化物。Mn/Pd@Py-2,2’-BPyPh COF和无水碳酸钾做为固体相可以通过过滤分离，产物的乙腈溶液可以通过旋转蒸发或蒸馏的方式处理得到最终的固体或液体产物，产率80-96％。
实施例3-5
以Mn/Pd@Py-2,2’-BPyPh COF为异相催化剂，连续催化苯乙烯和碘代苯的Heck-Epoxidation串联反应，循环使用3次催化性能没有出现明显下降，按照表1所述，其它制备、反应、测试条件，同实施例2。
表1
实施例6-8
在Mn/Pd@Py-2,2’-BPyPh COF的催化作用下，苯乙烯和不同卤素取代的芳烃反应都表现出了高产率，按照表2所述，其它制备、反应、测试条件，同实施例2。
表2
实施例9-12
在Mn/Pd@Py-2,2’-BPyPh COF的催化作用下，苯乙烯和不同氯苯衍生物反应都表现出了高产率，按照表3所述，其它制备、反应、测试条件，同实施例2。
表3
本发明首次实现了在COFs材料中可控负载两种以上金属化合物用于连续催化串联反应，催化剂特殊而又精巧的结构设计有利于促进催化反应的顺利进行、反应底物种类可扩展、反应产率高、催化剂可循环使用、操作简便、产物附加值高。

Claims (10)

1.一种负载型共价有机框架双金属催化剂，其特征在于：以Py-2,2’-BPyPh COF为催化剂载体，将锰盐和钯盐负载在Py-2,2’-BPyPh COF孔道内得到异相催化剂Mn/Pd@Py-2,2’-BPyPh COF，其中Py-2,2’-BPyPh COF的结构式为：
2.如权利要求1所述的负载型共价有机框架双金属催化剂,其特征在于:所述锰盐为MnCl2.nH2O n＝0,1,2,3,4、Mn(OAc)2或MnSO4中的一种或两种以上；所述钯盐为Pd(OAc)2、PdCl2或Pd(PPh3)4中的一种或两种以上；锰盐与钯盐之间不发生聚集，分散在Py-2,2’-BPyPh COF中。
3.如权利要求1所述的负载型共价有机框架双金属催化剂,其特征在于:锰盐以Mn元素计，于催化剂中的负载量为0.5-2wt％；钯盐以Pd元素计，于催化剂中的负载量为5-10wt％。
4.如权利要求1所述的负载型共价有机框架双金属催化剂,其特征在于:Mn/Pd@Py-2,2’-BPyPh COF中Mn元素与Pd元素的摩尔比为1-8:10。
5.一种权利要求1所述负载型共价有机框架双金属催化剂的制备方法,其特征在于:按照如下步骤制备：
1)将Py-2,2’-BPyPh COF与锰盐溶液混合搅拌2h-24h，之后抽滤除去溶液相得固体粉末，洗涤，于60-120℃烘干得Mn@Py-2,2’-BPyPh COF；
2)将Mn@Py-2,2’-BPyPh COF与钯盐溶液混合搅拌2h-24h，之后抽滤除去溶液相得固体粉末，洗涤，于60-120℃烘干得Mn/Pd@Py-2,2’-BPyPh COF。
6.如权利要求5所述的制备方法,其特征在于:
步骤1)中，所述锰盐为MnCl2.nH2O n＝0,1,2,3,4、Mn(OAc)2或MnSO4中的一种或两种以上，所述锰盐溶液的溶剂为甲醇、乙醇或乙腈中的一种或两种以上，锰盐溶液中锰盐质量百分含量为0.1-5.0wt.％，洗涤方式为：甲醇和/或水洗涤两次以上；
步骤2)中，所述钯盐为Pd(OAc)2、PdCl2或Pd(PPh3)4中的一种或两种以上，钯盐溶液的溶剂为二氯甲烷、四氢呋喃或甲醇中的一种或两种以上，钯盐溶液中钯盐质量百分含量为0.1-5.0wt.％，洗涤方式为：二氯甲烷洗涤两次以上。
7.一种权利要求1所述负载型共价有机框架双金属催化剂于Heck-Epoxidation串联反应中的应用。
8.如权利要求7所述的应用，其特征在于:第一步为Heck反应，以短链烯烃与卤代苯衍生物为底物，Mn/Pd@Py-2,2’-BPyPh COF为催化剂，制备长链烯烃；第二步为Epoxidation反应，Heck反应结束后的体系中通入空气，制备最终产物长链烯烃氧化物。
9.如权利要求8所述的应用，其特征在于:第一步为Heck反应：以短链烯烃和卤代苯衍生物为底物，Mn/Pd@Py-2,2’-BPyPh COF为催化剂，无水碳酸钾或三乙基胺或吡啶为助催化剂，乙腈或N,N’-二甲基乙酰胺或甲苯为溶剂，在N2保护下加热反应6-24h得到长链烯烃；第二步为Epoxidation反应：向Heck反应结束后的体系中加入异丁醛做为助还原剂，并通入空气继续室温反应4-12h得到最终产物长链烯烃氧化物。
10.如权利要求8或9所述的应用，其特征在于:
第二步Epoxidation反应结束后，固相通过过滤分离，剩余含有产物长链烯烃氧化物的液相部分通过旋转蒸发或蒸馏的方式除去溶剂得最终产物长链烯烃氧化物；
短链烯烃：卤代苯衍生物：催化剂：助催化剂：助还原剂的摩尔比＝1.2～1:1:0.001～0.01:3～5:2～3；
所述短链烯烃包括苯乙烯、丙烯、丁烯或己烯；
所述卤代苯衍生物的分子式为RPhX，其中Ph为苯环，X选自Cl、Br、I中的一种或两种以上，R选自H、CH3、OCH3、CN、NO2中的一种或两种以上，Ph上的取代基个数为1至4个。
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