CN112892605B - 用于氮甲酰化反应的具有碱性多相催化剂及制备和应用 - Google Patents
用于氮甲酰化反应的具有碱性多相催化剂及制备和应用 Download PDFInfo
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Abstract
本发明涉及一种具有碱性的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具有碱性多相催化剂,其由金属组分和有机配体共聚物组成,所述有机配体共聚物是含有乙烯基官能团化的膦配体和含有乙烯基官能团化的有机碱单体经溶剂热共聚生成的具有大比表面积和多级孔结构的共聚物。本发明催化剂一方面共聚物载体中引入有机碱,使固体多相催化剂具有碱性,促进氮甲酰化反应向正向移动,提高反应活性;另一方面金属组分与共聚物载体P原子之间因配位作用而高分散且稳定的存在于载体上。因此,本发明的具有碱性多相催化剂有优异的氮甲酰化反应性能和稳定性;且催化剂同反应物和产物易分离,具有广阔的工业应用前景。
Description
技术领域
本发明涉及一种用于氮甲酰化反应的具有碱性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
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,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。
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,是当前科学研究的热点。
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固体多相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共聚物负载金属活性组分的具有碱性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具有碱性多相催化剂,其特征在于:所述具有碱性多相催化剂由金属组分和有机配体共聚物组成,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,所述有机配体共聚物是含有乙烯基官能团化的膦配体和含有乙烯基官能团化的有机碱单体经溶剂热共聚生成的具有大比表面积和多级孔结构的共聚物,所述金属组分与所述有机配体共聚物骨架中的P原子形成配位键,高分散且稳定的存在于有机配体共聚物载体上。
在一个优选实施方案中,所述金属组分在所述具有碱性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,含有乙烯基官能团化的有机碱单体为B1-B6中的一种或几种:
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和含有乙烯基官能团化的有机碱单体摩尔比为0.1-20.0。
在一个优选实施方案中,所述有机配体共聚物的比表面积为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,所述具有碱性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和乙烯基官能团化的有机碱单体的溶剂中,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共聚物;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,即得到由有机配体共聚物负载活性金属组分的所述具有碱性多相催化剂。
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,惰性气体保护氛围为氩气,氦气,氮气,氖气中的一种或二种以上。
在一个优选实施方案中,所述的具有碱性多相催化剂在氮甲酰化反应中的应用,是指在所述具有碱性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。
本发明产生的有益效果包括但不限于以下方面:
本发明的具有碱性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;共聚物载体中引入有机碱,可以使固体多相催化剂具有碱性,促进氮甲酰化反应向正反应方向移动;金属组分与具有大比表面积和多级孔结构的共聚物载体P原子之间因配位作用而高分散且稳定的存在于载体上,使该催化剂具有优异的催化反应性能及较高的稳定性;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是本发明的具有碱性多相催化剂合成路线示意图。
图2是本发明的具有碱性多相催化剂的N2吸脱附等温曲线和孔径分布曲线图。
图3是本发明的具有碱性多相催化剂的热重曲线图。
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3.0克三(4-乙烯基苯)基膦和0.95克苯乙烯磺酸钠溶于50.0ml四氢呋喃溶剂中,向上述溶液中加入0.075克自由基引发剂偶氮二异丁腈,搅拌3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和磺酸钠的多孔有机共聚物。
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40ml四氢呋喃溶剂中,加入1.0克上述制备的含有三苯基膦和磺酸钠的多孔有机共聚物,搅拌24小时。随后,333K温度条件下真空抽除溶剂,即获得由有机配体共聚物负载金属组分的具有碱性多相催化剂。本发明的具有碱性多相催化剂合成路线示意图见图1,本发明催化剂的N2吸脱附等温曲线和孔径分布曲线图见图2,结果表明催化剂具有750m2/g的比表面积和多级孔道结构,本发明催化剂的热重曲线图见图3。
实施例2
在实施例2中,除了称取0.078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0.03克醋酸钯替代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克醋酸镍替代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,除了称取3.0克三(4-乙烯基苯)基膦和0.475克苯乙烯磺酸钠替代3.0克三(4-乙烯基苯)基膦和0.95克苯乙烯磺酸钠,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,共聚物合成过程除了用甲苯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7
在实施例7中,共聚物合成过程除了搅拌24小时替代搅拌3小时,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,除了将自由基引发剂用过氧化环己酮替代偶氮二异丁腈,其余的催化剂制备过程与实施例1相同。
实施例9
在实施例9中,除了称取自由基引发剂偶氮二异丁腈0.3克替代偶氮二异丁腈0.075克,其余的催化剂制备过程与实施例1相同。
实施例10
将上述实施例1制备的具有碱性多相催化剂0.093克装入高压釜式反应器中,加入1mmol吗啉和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,产物N-甲酰吗啉收率80%,TON为216。
实施例11
在实施例11中,除了称取1mmol二乙胺替代1mmol吗啉,其余的催化剂评价过程与实施例10相同。产物N-甲酰二乙胺收率为77%,TON为209.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)
2.根据权利要求1所述的应用,其特征在于:所述金属组分在所述具有碱性多相催化剂总重量中占0.01-40.0%。
4.根据权利要求1所述的应用,其特征在于:所述含有乙烯基官能团化的膦配体和含有乙烯基官能团化的有机碱单体摩尔比为0.1-20.0。
5.根据权利要求1所述的应用,其特征在于:所述有机配体共聚物的比表面积为100-3000m2/g,孔容为0.1-5.0cm3/g,孔径分布在0.1-100.0nm。
6.一种权利要求1-5任一所述的应用,其特征在于,所述催化剂的制备方法包括:
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和乙烯基官能团化的有机碱单体的溶剂中,加入自由基引发剂,搅拌0.5-100小时;
b)在333-473K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共聚物;
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,即得到由有机配体共聚物负载活性金属组分的所述具有碱性多相催化剂。
7.根据权利要求6所述的应用,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。
9.根据权利要求4所述的应用,其特征在于:所述含有乙烯基官能团化的膦配体和含有乙烯基官能团化的有机碱单体摩尔比为5:1。
10.根据权利要求8所述的应用,其特征在于:所述CO2原料与所述H2原料的摩尔比为1:1。
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