CN110835343B - 一种含p、n多孔有机笼配体及其制备和应用 - Google Patents

一种含p、n多孔有机笼配体及其制备和应用 Download PDF

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CN110835343B
CN110835343B CN201810941094.0A CN201810941094A CN110835343B CN 110835343 B CN110835343 B CN 110835343B CN 201810941094 A CN201810941094 A CN 201810941094A CN 110835343 B CN110835343 B CN 110835343B
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丁云杰
李存耀
汪文龙
严丽
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明公开了一种含P、N多孔有机笼配体及其制备方法和应用，含P、N多孔有机笼配体以醛基、氨基等官能团功能化的P、N配体为单体，以相应的多元胺或多元醛为共单体交联而成。所合成的P、N多孔有机笼配体具有稳定的独特孔结构，可用于选择性吸附分离气体。P、N多孔有机笼配体形成的络合物催化剂具有均相反应和多相回收的特点，反应时P、N多孔有机笼配体与过渡金属形成的催化剂处于均相反应状态，反应物和催化中心充分接触，保证了良好的催化性能，反应结束后加入醇类溶剂，P、N多孔有机笼配体络合物催化剂从反应体系中结晶出来，可较为简易的实现催化剂的回收。

Description

一种含P、N多孔有机笼配体及其制备和应用
技术领域
本发明属于材料合成领域，具体涉及一种含P、N多孔有机笼配体及其制备方法和应用。
背景技术
2009年，英国利物浦大学的Cooper教授课题组(Nature materials,2009,8(12):973)首次成功合成了2+3和4+6的多孔有机笼Porous Organic Cages(POCs)。设计合成的POCs最大的比表面积可达730m2g-1。在后续的研究中(Nature Reviews Materials,2016,1(9):16053)，作者发现该类型的POCs材料溶于二氯甲烷等溶剂，可在甲醇等溶液中结晶出来，POCs材料在气体分离，催化等领域展示出了很好的应用前景。
P、N配体在过渡金属络合物催化的氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应和CO2环加成反应等反应中具有广泛的应用。以氢甲酰化反应为例，烯烃氢甲酰化反应被认为是均相催化工业实施最成功的典范，该反应过程将原料烯烃和合成气(CO/H2)接近100％选择性的转化为比原料烯烃多一个碳原子的醛。醛是用途广泛的化学中间体，其后续转化产品醇，酸，酯和脂肪胺等都是非常重要的精细化工产品，广泛用作有机溶剂、增塑剂和表面活性剂等。
目前全世界通过氢甲酰化生产的醛约为1200万吨/年，这里面有50％左右的醛是丙烯氢甲酰化生产的丁醛。表1叙述了已经工业应用的五代催化剂的丙烯氢甲酰化生产工艺条件和催化性能比较，已经工业化的五代催化剂前四代为均相催化过程，第五代为两相催化过程，但是这五种过程始终没有解决反应过程中金属及配体的流失问题。
已经工业化的五代催化技术催化剂回收利用困难，金属及配体流失严重，生产成本较高。为了能简易地实现催化剂的循环使用，人们在氢甲酰化催化剂均相催化多相化领域做了大量的工作，但是传统的均相催化多相化方法暴露出一系列需要解决和克服的问题，尤其是多相化后催化剂稳定性差，活性组分流失严重等(J.Mol.Catal.A-Chem.,2002,182:107-123；Eur.J.Org.Chem.,2012,2012:6309-6320)。
P、N配体在过渡金属络合物催化的偶联反应、硅氢加成反应、加氢反应和CO2环加成反应等反应同样面临着均相催化剂回收困难，而传统固载化手段制备的多相催化剂性能和稳定性出现大幅度下降的问题。借用相应的P、N多孔有机笼配体与过渡金属配位形成的络合物催化剂在某些溶剂中溶解，某些溶剂中析出的特点，有望解决烯烃氢甲酰化反应，偶联反应、硅氢加成反应、加氢反应和CO2环加成反应等反应均相络合物催化剂分离回收的问题。然而，POCs从首次报道至今，还没有P、N配体功能化的多孔有机笼配体见诸于文献报道，P、N配体多孔有机笼配体的合成一直面临着巨大的挑战。
表1已经工业化的五代催化剂丙烯氢甲酰化生产工艺条件和催化性能比较[a]
发明内容
为了解决上述问题，本发明的目的在于提供一种含P、N多孔有机笼配体及其制备方法和应用。
本发明的技术方案为：
将醛基、氨基等官能团功能化的P、N配体和多元胺或多元醛共单体在溶剂中充分溶解混合后，在特定温度下静置或者搅拌，使得P、N配体和共单体中的官能团充分反应，生成具有特定孔结构的P、N多孔有机笼配体。
所述的P、N多孔有机笼配体具有特定的孔结构，比表面积为0～3000m2/g，优选范围为10～1000m2/g，孔容为0～10.0cm3/g，优选为0.5～2.0cm3/g，孔径分布在0.01～100.0nm，优选为0.5～20.0nm。
含P、N多孔有机笼配体的具体合成步骤为：
a)惰性气体气氛273～473K下，在溶剂中加入醛基、氨基等官能团功能化的P、N配体、多元胺或多元醛共单体、添加或不添加催化剂，将混合物静置或搅拌0.1～500小时，优选的静置或搅拌时间范围为10～60小时；
b)将步骤a)制得的含有P和/或N多孔有机笼配体的混合溶液浓缩，加入醇类溶剂，多孔有机笼配体结晶沉淀下来；
c)将步骤b)得到的P、N多孔有机笼配体沉淀过滤、洗涤并干燥后得到含P、N多孔有机笼配体产品；
P、N多孔有机笼配体与过渡金属形成的络合物催化剂的制备方法为：
d)惰性气体气氛273～473K下，在含有活性金属组分前驱体的溶剂中，加入步骤c)得到的多孔有机笼配体，搅拌0.1～100小时，优选搅拌时间范围0.1～20小时，之后，室温条件下真空抽除溶剂，得到P、N多孔有机笼配体与过渡金属形成的络合物催化剂。
步骤a)和d)中所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳、乙酸乙酯、甲酸甲酯、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷、环己烷、二甲亚砜、N,N-二甲基甲酰胺或四氢呋喃中一种或两种以上；
步骤b)中所述的醇类溶剂为水、甲醇、乙醇、正丙醇、异丙醇、正丁醇等中的一种或两种以上；
步骤c)中的洗涤溶剂可选水、甲醇、乙醇、正丙醇、异丙醇、正丁醇等中的一种或两种以上，干燥方法可选常压干燥、减压干燥、喷雾干燥、沸腾干燥和冷冻干燥中的一种或两种以上。
步骤a)中所述的醛基、氨基等官能团功能化的P、N配体在溶剂中的浓度范围为0.01-1000g/L，优选为0.1-10g/L，醛基、氨基等官能团功能化的P、N与共单体的摩尔比为0.01:1～100:1，优选为0.1:1-10:1，在添加催化剂的条件下，催化剂可选为盐酸、醋酸、硫酸、磷酸、硝酸中的一种或两种以上，醛基、氨基等官能团功能化的P、N配体单体与催化剂的摩尔比为10000:1-100:1，步骤a)、b)和c)中所述惰性气体选自Ar、He、N2和CO2中的一种或两种以上。
步骤d)中所述的活性组分为Rh、Co、Ni、Ir、Pd或Pt中的一种或两种以上，其中Rh的前驱体为RhH(CO)(PPh3)3、Rh(CO)2(acac)、RhCl3、Rh(CH3COO)2中的一种或两种以上；Co的前驱体为Co(CH3COO)2、Co(CO)2(acac)、Co(acac)2、CoCl2中的一种或两种以上；Ni的前驱体为Ni(CH3COO)2、Ni(CO)2(acac)、Ni(acac)2、NiCl2中的一种或两种以上；Ir的前驱体为Ir(CO)3(acac)、Ir(CH3COO)3、Ir(acac)3、IrCl4中的一种或两种以上；Pd的前驱体为Pd(CH3COO)2、Pd(acac)2、PdCl2、Pd(PPh3)4、PdCl2(CH3CN)2中的一种或两种以上；Pt的前驱体为Pt(acac)2、PtCl4、PtCl2(NH3)2中的一种或两种以上；P、N配体多孔有机笼配体与活性组分的摩尔比为100:1-1:1，优选为10:1-1:1。
本发明提供的含P、N多孔有机笼配体与过渡金属形成的络合物催化剂适用于烯烃的氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应和CO2环加成反应等反应。反应时P、N多孔有机笼配体与过渡金属形成的催化剂处于均相反应状态，反应物和催化中心充分接触，保证了良好的催化性能，反应结束后加入醇类溶剂，P、N多孔有机笼配体络合物催化剂从反应体系中结晶出来，可容易的实现催化剂的回收。并且可以通过调变P、N多孔有机笼配体的构造结构进而调节P、N配体的电子效应和立体效应，控制最终形成的络合物催化剂的性能，以适用于不同底物，不同工艺的氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应和CO2环加成反应等反应。
本发明的原理为：
本发明制备的含P、N多孔有机笼配体保留了P、N配体良好的配体性质，并且由于P、N多孔有机笼配体的特定构造，P、N多孔有机笼配体具有与相应的P、N配体不同的电子效应及立体效应，同时，P、N多孔有机笼配体的NHx基团具有碱性改变腔体的化学环境，因而，P、N多孔有机笼配体与过渡金属形成的络合物催化剂(如，经典的三苯基膦的Rh-P催化剂体系)展示出了独特的催化性能。
P、N多孔有机笼配体形成的络合物催化剂具有均相反应、多相回收的特点，反应时P、N多孔有机笼配体与过渡金属形成的催化剂处于均相反应状态，反应物和催化中心充分接触，保证了良好的催化性能，反应结束后加入醇类溶剂，P、N多孔有机笼配体络合物催化剂从反应体系中结晶出来，可容易实现催化剂的回收。
本发明的有益效果为：
本发明制备的含P、N多孔有机笼配体中的P、N配体可与活性金属进行有效的配位形成络合物催化剂。由于多孔有机笼配体在二氯甲烷等溶剂中溶解性良好，在甲醇等溶剂中可结晶出来。因而P、N多孔有机笼配体形成的络合物催化剂具有均相反应、多相回收的特点，反应时P、N多孔有机笼配体与过渡金属形成的催化剂处于均相反应状态，反应物和催化中心充分接触，保证了良好的催化性能，反应结束后加入醇类溶剂，P、N多孔有机笼配体络合物催化剂从反应体系中结晶出来，可较为容易实现催化剂的回收。并且由于P、N多孔有机笼配体的特定构造，P、N多孔有机笼配体具有与相应的P、N配体不同的电子效应及立体效应，同时，P、N多孔有机笼配体的NHx基团具有碱性改变腔体的化学环境，因而，P、N多孔有机笼配体与过渡金属形成的络合物催化剂(如，经典的三苯基膦的Rh-P催化剂体系)展示出了独特的催化性能。本发明提供的含P、N多孔有机笼配体及其相应的络合物催化剂的制备方法为烯烃氢甲酰化反应、偶联反应、硅氢加成反应、加氢反应和CO2环加成反应等反应提供了新的工业化技术。
附图说明
图1是典型的醛基官能团化的PPh3单体的合成路线图。
图2是典型的含PPh3多孔有机笼配体的合成技术路线示意图。
图3是含P、N多孔有机笼配体合成所需单体的结构示意图，其中，L1-L53为醛基或氨基官能团化的P、N配体单体，L54-L65为多元醛和多元胺共单体。
图4为典型的醛基官能团化的PPh3配体单体(附图3L1)的1H谱图。
图5为典型的醛基官能团化的PPh3配体单体(附图3L1)的13C谱图。
图6为典型的醛基官能团化的PPh3配体单体(附图3L1)的31P谱图。
图7为N2氛围下实施例1合成的含PPh3多孔有机笼配体热重曲线。
图8为N2氛围下实施例1合成的含PPh3多孔有机笼配体的1H谱图。
图9为实施例1获得的PPh3多孔有机笼配体的N2物理吸附曲线。
图10为实施例1获得的PPh3多孔有机笼配体的孔径分布曲线(NLDFT计算方法)。
图11为实施例1中合成的含PPh3多孔有机笼配体的XRD衍射谱图，并且我们也测试了X射线单晶衍射，解析出结构后申请的CCDC号码为1857136。
具体实施方式
下述实施例对本发明进行更好的说明，但不限制本发明所要保护的范围。
实施例1
醛基官能团化的PPh3配体单体(附图3L1)的制备：醛基官能团化的PPh3配体的合成路线如附图1所示。25g4-溴苯甲醛二乙酸醛(96mmol)用四氢呋喃稀释10倍(体积比)后缓慢滴加到4.4g镁屑中，制得格氏试剂。2.3g三氯化磷溶解于10倍(体积比)的四氢呋喃溶液后滴加如制得的格氏试剂中，充分反应后，加入等体积的5％的HCl溶液继续反应。反应完成后，油相减压蒸馏除去大部分溶剂，经5:1的石油醚：乙酸乙酯的洗脱剂过柱子后可得淡黄色固体产品6.5g，产率60％左右。附图4、附图5和附图6分别为制备出的醛基官能团化的PPh3配体单体核磁1H、13C和31P谱图。
含PPh3多孔有机笼配体的制备：在318K和惰性气体保护氛围下，将4.29克醛基官能团化的PPh3单体(附图3，L1)溶于500.0ml四氢呋喃溶剂中，同时加入1,2环己二胺共单体2.12g(附图3中L55)，并加入1ml醋酸作为催化剂，混合溶液在该反应条件下静止60h可得含PPh3多孔有机笼配体粗产品。
含PPh3多孔有机笼配体配位的Rh基络合物催化剂的制备：称取25.8毫克乙酰丙酮羰基铑(Rh(CO)2(acac))溶于10.0ml四氢呋喃溶剂中，加入277.8毫克上述制得的含PPh3多孔有机笼配体，将此混合物在298K和惰性气体保护氛围下搅拌24小时，室温条件下真空抽除溶剂，即获得适用于烯烃氢甲酰化反应的含PPh3多孔有机笼配体配位的Rh基络合物催化剂。
实施例2
在实施例2中，除了称取2.12克附图3L57为共单体替代2.12克附图3 L55共单体外，其余的实施过程与实施例1相同。
实施例3
在实施例3中，除了不添加醋酸作为催化剂外，其余的实施过程与实施例1相同。
实施例4
在实施例4中，除了用250.0ml四氢呋喃溶剂替代500.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。
实施例5
在实施例5中，除了用500.0ml乙酸乙酯溶剂替代500.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。
实施例6
在实施例6中，除了用298K反应温度替代318K反应温度外，其余的实施过程与实施例1相同。
实施例7
在实施例7中，除了用24h反应时间替代60h反应时间外，其余的实施过程与实施例1相同。
实施例8
在实施例8中，除了用1.06g附图3中的L55共单体和1.06g附图3中的L57共单体作为混合共单体替代2.12g附图3中的L55共单体外，其余的实施过程与实施例1相同。
实施例9
在实施例9中，除了用0.56g附图3中的L63共单体(n＝1)和0.67g附图3中的L65共单体(n＝1)作为混合共单体替代2.12g附图3中的L55共单体外，其余的实施过程与实施例1相同。
实施例10
在实施例10中,称取25.7毫克乙酰丙酮钴替代乙酰丙酮羰基铑溶于10.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。
实施例11
在实施例11中,称取34.8毫克乙酰丙酮二羰基铱替代乙酰丙酮羰基铑溶于10.0ml四氢呋喃溶剂外，其余的实施过程与实施例1相同。
实施例12
在实施例12中，称取4.08g附图3中的L3替代实施例1中的L1，其余的实施过程与实施例1相同。
对比实施例13
为了对比，在实施例13中，我们制备了经典传统的三苯基膦配体与贵金属Rh配位的络合物催化剂。具体制备步骤为，称取25.8毫克乙酰丙酮羰基铑(Rh(CO)2(acac))溶于10.0ml四氢呋喃溶剂中，加入157.2毫克PPh3配体(保证与实施例1相同的P/Rh比)，将此混合物在298K和惰性气体保护氛围下搅拌24小时，室温条件下真空抽除溶剂，即获得适用于烯烃氢甲酰化反应的PPh3配位的Rh基络合物催化剂。
实施例14
将上述制备的催化剂10mmol溶于50ml甲苯，并加入1000mol 1-辛烯，在373K，1MPa合成气(CO:H2＝1:1)压力条件下进行氢甲酰化反应。反应5h后将反应釜冷却至室温，加入正丁醇作为内标，采用配有HP-5毛细管柱和FID检测器的Agilent-7890B气相色谱分析，反应结果列于表2。反应完成后加入50ml甲醇，含PPh3多孔有机笼配体配位的Rh基络合物催化剂即可从反应体系中结晶出来，实现催化剂的回收。
表2实施例1-13中合成的含P多孔有机笼配体比表面积和1-辛烯反应数据
*实验条件为100℃，1MPa，TOF计算时认为所有的金属均是活性位点，催化剂回收使用10次，未出现催化性能的下降。**表示反应温度为230℃，实施例10的活性组分为Co，实施例11的活性组分为Ir。

Claims (7)

1.一种含P、N多孔有机笼配体的制备方法，其特征在于:以醛基和/或氨基官能团功能化的P配体为单体，将单体和多元胺或多元醛共单体在溶剂中充分溶解混合后，静置或者搅拌，使得P配体和共单体中的官能团充分反应，生成具有特定孔结构的P、N多孔有机笼配体；
所述单体选自下述中的一种或二种以上：
所述共单体多元胺或多元醛选自下述中的一种或二种以上：
n为正整数。
2.按照权利要求1所述的制备方法，其特征在于：所述的P、N多孔有机笼配体具有特定的孔结构，比表面积为0.1-3000m2/g，孔容为0-10.0cm3/g，孔径分布在0.01-100.0nm。
3.按照权利要求2所述的制备方法，其特征在于：所述的P、N多孔有机笼配体具有特定的孔结构，比表面积为10-1000m2/g，孔容为0.5-2.0cm3/g，孔径分布在0.5-20.0nm。
4.按照权利要求1所述的制备方法，其特征在于：
含P、N多孔有机笼配体的具体合成步骤为：
a)惰性气体气氛273-473K下，在溶剂中加入醛基和/或氨基官能团功能化的P配体、多元胺或多元醛共单体、添加或不添加催化剂，将混合物静置或搅拌0.1-500小时；
b)将步骤a)制得的含有P多孔有机笼配体的混合溶液浓缩，加入醇类溶剂，多孔有机笼配体结晶沉淀下来；
c)将步骤b)得到的P、N多孔有机笼配体沉淀过滤、洗涤并干燥后得到含P、N多孔有机笼配体产品。
5.按照权利要求4所述的制备方法，其特征在于：
步骤a）中所述的溶剂为二氯甲烷、三氯甲烷、四氯化碳、乙酸乙酯、甲酸甲酯、苯、甲苯、二甲苯、正己烷、正庚烷、正辛烷、环己烷、二甲亚砜、N,N-二甲基甲酰胺或四氢呋喃中一种或两种以上；
步骤b）中所述的醇类溶剂为甲醇、乙醇、正丙醇、异丙醇、正丁醇中的一种或两种以上；
步骤c）中的洗涤溶剂可选水、甲醇、乙醇、正丙醇、异丙醇、正丁醇中的一种或两种以上，干燥方法可选常压干燥、减压干燥、喷雾干燥、沸腾干燥和冷冻干燥中的一种或两种以上。
6.按照权利要求4所述的制备方法，其特征在于：步骤a)中所述的醛基和/或氨基官能团功能化的P配体在溶剂中的浓度范围为0.01-1000g/L，醛基和/或氨基官能团功能化的P配体单体与共单体的摩尔比为0.01:1-100:1，在添加催化剂的条件下，催化剂可选为盐酸、醋酸、硫酸、磷酸、硝酸中的一种或两种以上，醛基和/或氨基官能团功能化的P配体单体与催化剂的摩尔比为10000:1-100:1，步骤a)、b）和c）中所述惰性气体选自Ar、He、N2和CO2中的一种或两种以上。
7.按照权利要求6所述的制备方法，其特征在于：步骤a)中所述的醛基和/或氨基官能团功能化的P配体在溶剂中的浓度范围为0.1-10g/L，醛基和/或氨基官能团功能化的P配体单体与共单体的摩尔比为0.1:1-10:1。
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