CN112892603A - 一种用于氮甲酰化反应的固体多相催化剂及其制备和应用 - Google Patents
一种用于氮甲酰化反应的固体多相催化剂及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种固体多相催化剂及其制备方法和应用，更具体地，涉及一种应用于氮甲酰化反应的固体多相催化剂，由金属组分和有机配体聚合物组成，所述有机配体聚合物是含有乙烯基官能团化的膦配体单体经溶剂热聚合生成的具有大比表面积和多级孔结构的聚合物，形成配位键，高分散且稳定的存在于有机配体聚合物载体上。本发明催化剂在氮甲酰化反应中，一方面金属组分与聚合物载体中P原子之间因配位作用而稳定的存在于载体上；另一方面聚合物载体具有大比表面积和多级孔结构，金属组分可以高分散的存在于载体上，从而使本发明的固体多相催化剂具有优异的催化反应性能和稳定性，并且催化剂容易与反应物和产物分离，具有广阔工业应用前景。
Description
技术领域
本发明涉及一种用于氮甲酰化反应的固体多相催化剂及其制备方法和应用,属于多相催化技术领域。
背景技术
均相催化体系在较温和反应条件下具有较高的催化活性和目的产物的选择性，但催化剂同反应物料的分离困难。多相催化与均相催化相比最大的优点是催化剂与反应物料容易分离，存在的主要问题是反应条件苛刻，反应活性相对较低等。因此，开发兼具均相催化和多相催化优点的新型固载化多相催化剂，是科学研究的热点。近年来，多孔有机聚合物材料的设计合成逐渐成为多孔材料研究领域新的热点之一。与传统的无机微孔材料与金属有机框架材料(MOFs)相比，有机微孔聚合物的骨架由纯粹的有机分子构成，相互之间通过共价键连接，具有开放的孔道与优异的孔性质。更重要的是，由于有机化学合成方法的多样性，为有机分子网络的构建提供了丰富的合成路径和构建方式，可以通过目的性的引入功能化的有机分子使材料具有相应的性质，通过调节有机分子的结构可以调控材料的孔性质。除此以外，金属功能化的多孔有机聚合物材料可以将具有催化活性的金属活性单元定点引入到多孔有机聚合物中，实现以单原子形式高分散于有机共聚物载体中，这样不仅有利于稳定金属活性位点，而且大大提高了金属的利用效率。
胺的甲酰化反应是有机合成和医药化学重要反应之一。甲酰胺是有机合成重要的中间体，广泛用于合成各类药物。甲酰胺可以用作有机合成原料，纸张处理剂，纤维工业的柔软剂，还可以用作测定大米中氨基酸含量的分析试剂；同时甲酰胺也是优良的有机溶剂，可以用于分离氯硅烷、提纯油脂等；此外，甲酰胺具有活泼的反应性，可以发生多种反应，除了三个氢参与反应外，还可以进行脱水，脱CO，引入氨基、酰基和发生关环等反应。大量的甲酰化方法相继被报道，其中甲酰化试剂有三氯乙醛、甲酸酯、甲酸胺、甲酸等。很多氮甲酰化试剂具有试剂昂贵，副产物多等缺点，目前氮甲酰化反应试剂甲酸应用最广泛，但由于甲酸对仪器设备具有很强的腐蚀性，人们致力于发展更为清洁的反应路线。
CO2作为可再生能源有着巨大的优势，储量丰富并且无毒。但由于目前CO2的化学固定技术的成本高、效率差等缺点，限制了这一技术的商业化。自上世纪初以来，人们围绕着CO2的化学利用开展了大量的研究工作并取得了一系列进展。使用CO2作为甲酰化试剂碳源、以硅烷作为还原剂进行N-甲酰化的制备也得到了实现，但是硅烷作为还原剂导致生产成本高昂、产物分离困难，难以大规模应用。H2是当前化学工业上最为清洁、廉价的还原剂，以CO2为甲酰化碳源、H2为还原剂进行N-甲酰化胺类化合物制备无疑具有更为优良的经济性和环境友好性。因此，以工业化应用为目的，对开发以CO2为甲酰化碳源、H2为还原剂的N-甲酰化胺类化合物的制备方法具有强烈需求。
综上所述，对于适用于实际工业应用的氮甲酰化反应，绿色高效可回收利用的催化剂是该领域的主要研究方向。
发明内容
为了解决上述问题，本发明的目的在于提供一种由有机配体聚合物负载金属活性组分的固体多相催化剂及其制备方法和应用。
为此，本发明提供一种应用于氮甲酰化反应的固体多相催化剂，其特征在于：所述固体多相催化剂由金属组分和有机配体聚合物组成，其中所述金属组分是金属Ru、Pd、Ir、Rh、Ni、Mo、Cu或Fe中的一种或几种，所述有机配体聚合物是含有乙烯基官能团化的膦配体单体经溶剂热聚合生成的具有大比表面积和多级孔结构的聚合物，所述金属组分与所述有机配体聚合物骨架中的P原子形成配位键，高分散且稳定的存在于有机配体聚合物载体上。
在一个优选实施方案中，所述金属组分在所述固体多相催化剂总重量中占0.01-40.0％。
在一个优选实施方案中，所述含有乙烯基官能团化的膦配体，是选自以下官能团化有机膦配体中的一种或几种：
在一个优选实施方案中，所述有机配体聚合物的比表面积为100-3000m2/g，孔容为0.1-5.0cm3/g，孔径分布在0.1-100.0nm。
在一个优选实施方案中，所述固体多相催化剂的制备方法，包括制备步骤如下：a)在273-473K和惰性气体保护氛围下，在含有乙烯基官能团化的膦配体单体的溶剂中，加入自由基引发剂，搅拌0.5-100小时；b)在273-473K和惰性气体保护氛围下，将步骤a)的溶液在水热高压釜中静置0.5-100小时，进行溶剂热聚合反应；c)将步骤b)结束后在273-473K温度条件下真空抽除溶剂，即得到所述有机配体聚合物；d)将所述有机配体聚合物置于含有活性金属组分的溶剂中，在273-473K和惰性气体保护氛围下搅拌0.5-100小时，然后在273-473K温度条件下真空抽除溶剂，即得到由有机配体聚合物负载活性金属组分的所述固体多相催化剂。
在一个优选实施方案中，所述催化剂制备方法步骤a)和d)中使用的溶剂是苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷、二氯乙烷或去离子水中的一种或几种；步骤a)中使用的自由基引发剂是过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或几种。
在一个优选实施方案中，所述催化剂制备方法中所述自由基引发剂与所述有机单体的重量比为1:500-1:5。
在一个优选实施方案中，所述的固体多相催化剂在氮甲酰化反应中的应用，是指在所述固体多相催化剂存在下使有机胺原料与CO2/H2混合气在固定床、滴流床、浆态床或釜式反应器中进行所述氮甲酰化反应，其中反应温度为293-573K，反应压力为0.05-20.0MPa,液时空速为0.01-20.0h-1,气体空速为100-20000h-1。
在一个优选实施方案中，惰性气体保护氛围为氮气，氩气，氖气，氦气中的一种或二种以上。
本发明产生的有益效果包括但不限于以下方面：
本发明的固体多相催化剂与现有的氮甲酰化催化剂相比，催化剂制备方法简单；金属组分与聚合物载体中P原子之间因配位作用而稳定的存在于载体上；聚合物载体具有大比表面积和多级孔结构，金属组分可以高分散的存在于载体上，从而使本发明的固体多相催化剂具有优异的催化反应性能及较高的稳定性。此外，本发明的催化剂在宏观上是多相催化剂，因此在回收循环利用和与反应物及产物的分离等方面具有明显的优越性，具有广阔的工业应用前景。
附图说明
图1是本发明的固体多相催化剂合成路线示意图。
图2是本发明的固体多相催化剂的N2吸脱附等温曲线和孔径分布曲线图。
具体实施方式
为了更好的说明本发明的催化剂的制备方法及其在氮甲酰化反应中的应用，下面举出一些催化剂样品的制备及其在反应工艺中的应用的实施例，但本发明不限于所列举的实例。除非另有具体说明，本申请中所用的“百分比”基于重量。
实施例1
在298K和氩气保护氛围下，将10.0克三(4-乙烯基苯)基膦溶于100ml四氢呋喃溶剂中，向上述溶液中加入0.25克自由基引发剂偶氮二异丁腈，搅拌0.5小时。将搅拌好的溶液移至水热高压釜中，于373K和惰性气体保护氛围下溶剂热法聚合24h。待上述聚合后冷却至室温，333K温度条件下真空抽除溶剂，即得到含有三苯基膦的多孔有机聚合物。
在298K和惰性气体保护氛围下，称取0.0156克对伞花烃二氯化钌(Ⅱ)二聚体溶于50ml四氢呋喃溶剂中，加入1.0克上述制备的含有三苯基膦的多孔有机聚合物，搅拌24小时。随后，333K温度条件下真空抽除溶剂，即获得由有机配体聚合物负载金属组分的固体多相催化剂。本发明的固体多相催化剂合成路线示意图见图1，本发明的固体多相催化剂的N2吸脱附等温曲线和孔径分布曲线图见图2，结果表明该催化剂比表面积为1001m2/g并且具有多级孔道结构。
实施例2
在实施例2中，除了称取0.0312克对伞花烃二氯化钌(Ⅱ)二聚体替代0.0156克对伞花烃二氯化钌(Ⅱ)二聚体，其余的催化剂制备过程与实施例1相同。
实施例3
在实施例3中，除了称取0.035克氯铱酸替代0.0156克对伞花烃二氯化钌(Ⅱ)二聚体，其余的催化剂制备过程与实施例1相同。
实施例4
在实施例4中，除了称取0.1克乙酰丙酮铜(Ⅱ)替代0.0156克对伞花烃二氯化钌(Ⅱ)二聚体，其余的催化剂制备过程与实施例1相同。
实施例5
在实施例5中，聚合物合成过程除了用二氯甲烷溶剂替代四氢呋喃溶剂，其余的催化剂制备过程与实施例1相同。
实施例6
在实施例6中，聚合物合成过程除了搅拌12小时替代搅拌0.5小时，其余的催化剂制备过程与实施例1相同。
实施例7
在实施例7中，除了将自由基引发剂用过氧化二苯甲酰替代偶氮二异丁腈，其余的催化剂制备过程与实施例1相同。
实施例8
在实施例8中，除了称取自由基引发剂偶氮二异丁腈0.1克替代偶氮二异丁腈0.25克，其余的催化剂制备过程与实施例1相同。
实施例9
将上述实施例1制备的固体多相催化剂0.093克装入高压釜式反应器中，依次加入1mmol吗啉、0.3mmol磷酸钾和4ml溶剂1,3-二甲基-2-咪唑啉酮，密闭反应釜，充入CO2/H2混合气(CO2:H2＝1:1)，高压釜系统压力升至6MPa，由温度控制仪控制温度缓慢升至100℃，反应24h。反应结束后，将反应釜冷却至室温，缓慢放出过量的反应气，过滤分离出催化剂，将所得的产品加入甲苯作为内标，进入配有HP-5毛细管柱和FID检测器的HP-7890N气相色谱分析，反应物吗啉转化率85％，产物N-甲酰吗啉收率80％，TON为217。
实施例10
在实施例10中，除了称取1mmol 2,6-二甲基哌啶替代1mmol吗啉，其他的催化剂评价过程与实施例9相同。反应物2，6-二甲基哌啶转化率75％，产物2,6-二甲基-N-甲酰哌啶收率71％，TON为193。
以上已对本发明进行了详细描述，但本发明并不局限于本文所描述具体实施方式。本领域技术人员理解，在不背离本发明范围的情况下，可以作出其他更改和变形。本发明的范围由所附权利要求限定。
Claims (10)
1.一种用于氮甲酰化反应的固体多相催化剂，其特征在于：所述固体多相催化剂由金属组分和有机配体聚合物组成，其中所述金属组分是金属Ru、Pd、Ir、Rh、Ni、Mo、Cu或Fe中的一种或几种，所述有机配体聚合物是含有乙烯基官能团化的膦配体单体经溶剂热共聚生成的聚合物，所述金属组分与所述有机配体聚合物骨架中的P原子形成配位键，存在于有机配体聚合物载体上。
2.根据权利要求1所述的固体多相催化剂，其特征在于：所述金属组分在所述固体多相催化剂总重量中占0.01-40.0％(优选0.5％)。
3.根据权利要求1所述的固体多相催化剂，其特征在于：所述含有乙烯基官能团化的膦配体，是选自以下L1-L8官能团化膦配体中的一种或几种：
4.根据权利要求1所述的固体多相催化剂，其特征在于：所述有机配体聚合物的比表面积为100-3000m2/g，孔容为0.1-5.0cm3/g，孔径分布在0.1-100.0nm。
5.一种权利要求1-4任一所述的固体多相催化剂的制备方法，所述方法包括：
a)在273-473K(优选293K)和惰性气体保护氛围下，在含有乙烯基官能团化的膦配体溶剂中，加入自由基引发剂，搅拌0.5-100(优选3)小时；
b)在333K-473K(优选373K)和惰性气体保护氛围下，将步骤a)的溶液在水热高压釜中静置0.5-100(优选24)小时，进行溶剂热聚合反应；
c)将步骤b)结束后在273-473K(优选333K)温度条件下真空抽除溶剂，即得到所述有机配体聚合物；
d)将所述有机配体聚合物置于含有活性金属组分的溶剂中，在273-473K(优选293K)和惰性气体保护氛围下搅拌0.5-100(优选24)小时，然后在273-473K(优选333K)温度条件下真空抽除溶剂，即得到由有机配体聚合物负载活性金属组分的所述固体多相催化剂。
6.根据权利要求5所述的方法，其特征在于，步骤a)和d)中使用的溶剂是苯、甲苯、四氢呋喃、甲醇、乙醇、二氯甲烷、二氯乙烷或去离子水中的一种或几种；
步骤a)中使用的自由基引发剂是过氧化环己酮、过氧化二苯甲酰、叔丁基过氧化氢、偶氮二异丁腈或偶氮二异庚腈的一种或几种。
7.根据权利要求5或6所述的方法，其特征在于，所述自由基引发剂与所述有机单体的重量比为1:500-1:5(优选1：25)。
8.一种权利要求1-4任一所述的固体多相催化剂在氮甲酰化反应中的应用。
9.根据权利要求8所述的应用，其特征在于，在所述固体多相催化剂存在下使有机胺原料与CO2/H2混合气在固定床、滴流床、浆态床或釜式反应器中进行所述氮甲酰化反应，其中反应温度为293-573K(优选373K)，反应压力为0.05-20.0MPa(优选6.0MPa),液时空速为0.01-20.0h-1(优选5h-1),气体空速为100-20000h-1(优选1000h-1)，所述CO2原料与所述H2原料的摩尔比为1:1-1:100(优选1：1)。
10.根据权利要求8或9所述的应用，其特征在于，所述有机胺选自下述中的一种或二种以上：
其中R1和R2各自独立地分别选自C1-18烷基，m为1到6的整数，并且n为1到12的整数。
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