CN111454455B - 一类富含poss衍生硅羟基的多孔杂化聚合物及其制备方法与催化应用 - Google Patents
一类富含poss衍生硅羟基的多孔杂化聚合物及其制备方法与催化应用 Download PDFInfo
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Abstract
一类富含POSS衍生硅羟基的多孔杂化聚合物,其结构式如下式之一所示,其由刚性的构筑单元乙烯基POSS分别与三(4‑溴苯)胺或四(4‑溴苯)甲烷通过Heck反应而制得。由于制备的多孔杂化聚合物具有大的比表面积,丰富的介孔孔隙以及原位衍生的Si‑OH活性基团,N‑PHPs和C‑PHPs作为非金属非卤素多相催化剂,可在温和条件下实现对二氧化碳的高效催化转化制备高附加值的环状碳酸酯。
Description
技术领域
本发明涉及多孔聚合物的制备和催化应用领域,具体涉及一类富含POSS衍生硅羟基的多孔杂化聚合物及其制备方法和在CO2催化转化中的应用。
背景技术
随着全球环境的日益恶化,温室气体CO2的捕集和利用显得愈发重要,而且CO2来源丰富,可作为可再生的C1资源合成高附加值的化学产品。在众多利用CO2的策略中,由CO2和环氧化合物通过环加成反应合成环状碳酸酯是最有前途的策略之一。目前,人们已经开发了许多均相和多相催化剂用于CO2转化。一般来说,均相催化剂是高效的,但是存在催化剂回收以及产物分离困难的缺陷。相对而言,多相催化剂可以解决这些问题,但大多数多相催化体系常需要高温高压的苛刻反应条件。目前,针对CO2环加成反应,不管是均相催化剂还是多相催化剂的催化活性位主要依赖具有亲核性的卤素阴离子和亲电性的金属位点,这样的催化体系是不绿色环保的。因此,构建绿色高效的非金属非卤素多相催化剂,在常压低温条件下,实现对CO2的高效转化是非常重要的研究课题。
作为一种常见的多相催化剂,多孔有机聚合物(POPs)由于具有高的表面积、可调节的化学功能和优异的化学稳定性,在CO2捕集和转化中受到越来越多的关注。POPs的这些优异特征在催化反应中,不仅可以提高催化剂对CO2的吸附能力,而且可以有效促进环氧底物的传质。此外,多种催化功能基团可以被引入到POP框架中,使其具有丰富的活性位点,可以有效的活化CO2分子和环氧底物。然而,目前POP多相催化剂中的活性位点主要是卤素阴离子位点和金属位点,用于CO2环加成反应的不含金属和卤素位点的POP催化剂非常少见。多面体低聚倍半硅氧烷(POSS)是一种新型的、纳米级的无机-有机杂化分子。由于POSS具有规整的笼状结构,功能化的可反应基团,以及优异的水热稳定性,因而被认为是构建多孔聚合物的理想构筑单元。一般来说,基于POSS的多孔杂化聚合物都具有较大的比表面积和优异的水热稳定性。然而,在制备POSS基多孔聚合物的过程中,POSS笼中的Si-C和Si-O键可能会发生部分断裂,造成笼结构发生部分坍塌,进而衍生出硅羟基(Si-OH)基团。在合成有序多孔材料的角度上看,POSS笼的破坏是不完美的;从催化应用角度上考虑,正是这些缺陷的POSS笼提供了具有催化活性的氢键供体(HBD)Si-OH基团。已有研究表明Si-OH基团可作为辅助的催化活性位点,能够极大地促进环氧化合物的活化和CO2的转化。然而,单独使用Si-OH基团作为催化活性中心的催化剂未见任何报道。因此,本专利基于POSS单元开发了一类富含POSS衍生Si-OH的多孔杂化有机聚合物,用作非金属非卤素催化剂,在无溶剂、无助催化剂条件下,实现常压温和条件下对CO2的高效催化转化。
发明内容
发明人通过大量实验研究研发了一类富含POSS衍生Si-OH的多孔杂化聚合物的制备方法,并设计合成了系列POSS基的多孔杂化聚合物N-PHPs和C-PHPs。实验研究表明,本发明中合成的N-PHPs和C-PHPs可以作为高效催化剂,应用于CO2环加成反应中。
作为本发明的第一个方面,本发明提供了一类富含POSS衍生硅羟基的多孔杂化聚合物,
其结构式如下式之一所示:
作为本发明的第二个方面,还提供了上述一类富含POSS衍生硅羟基的多孔杂化聚合物的制备方法,包括:将下式1所示乙烯基POSS与下式2所示三(4-溴苯)胺或下式3所示四(4-溴苯)甲烷溶于有机溶剂中,通过Heck反应制备所述富含POSS衍生硅羟基的多孔杂化聚合物。
进一步的,所述制备方法具体包括以下步骤:
S1:称取一定量的所述式1所示乙烯基POSS与所述式2所示三(4-溴苯)胺或所述式3所示四(4-溴苯)甲烷溶于有机溶剂中,得均匀溶液;
S2:将所述均匀溶液转移到反应釜中,加入碱性吸酸剂和催化剂,加热反应一段时间;
S3:反应结束后,过滤、洗涤、干燥得所述富含POSS衍生硅羟基的多孔杂化聚合物。
进一步的,所述步骤S1中,所述式1所示乙烯基POSS与所述式2所示三(4-溴苯)胺或所述式3所示四(4-溴苯)甲烷的摩尔比为1:1~3。
进一步的,所述碱性吸酸剂为K2CO3。
进一步的,所述催化剂为三苯基膦钯。
进一步的,所述步骤S2中的反应温度120℃,反应时间72h。
作为本发明的第三个方面,还提供了上述富含POSS衍生硅羟基的多孔杂化聚合物在CO2催化转化中的应用。
进一步的,所述应用具体包括:以环氧化合物为底物,以所述富含POSS衍生硅羟基的多孔杂化聚合物为催化剂,于常压CO2氛围中,在加热条件下进行CO2与环氧化合物的环加成反应。
进一步的,所述环氧化合物的结构式如下式4所示
其中,R为氯甲基、溴甲基、苯基、正丁基、正己基或苯甲氧基。
与现有技术相比,本发明的有益效果:
本发明通过乙烯基POSS与三(4-溴苯)胺或四(4-溴苯)甲烷进行Heck反应制得一类富含POSS衍生Si-OH的多孔杂化聚合物,制备工艺所需反应条件温和、反应时间短,所用设备简单,具有广阔的工业化/规模化应用前景;
通过将氢键供体Si-OH基团原位地引进到聚合物中,使得制备的聚合物有着优异的催化活性;
本发明中的富含POSS衍生Si-OH的多孔杂化聚合物在无溶剂,无助催化剂条件下,在环氧化合物与CO2环加成反应中具有优异的催化性能,且该反应还具有催化剂用量少、易于分离和回收。
附图说明
图1为实施例1中N-PHP-2,C-PHP-2的XRD谱图;
图2为实施例1中N-PHP-2,C-PHP-2的IR谱图;
图3为实施例1中N-PHP-2,C-PHP-2的SEM图;
图4为实施例1中N-PHP-2,C-PHP-2在77K下的N2吸脱附曲线和NLDFT孔径分布图;
图5-9为实施例3中各反应产物的1H NMR谱图。
具体实施方式:
下面结合实例对本发明的技术方案进行具体进行说明,需要说明的是,实施的例子仅仅对本发明的优选实例进行描述,并非对本发明的构思和范围进行限定。在不脱离本发明设计思路的前提下,本领域中专业技术人员对新型的富含POSS衍生Si-OH的多孔杂化聚合物中连接体的改变,对合成的方法进行的反应条件变化,合成聚合物比表面积的改变以及其在CO2催化转化应用方面的改变,均属于本发明的保护范围。
实施例1:富含POSS衍生Si-OH的多孔杂化聚合物N-PHPs和C-PHPs的制备
合成路线:
称取乙烯基POSS(VPOSS),三(4-溴苯)胺(TBPA)分别加入10mL N,N’-二甲基甲酰胺,搅拌使其完全溶解,将两种溶液混合装入聚四氟乙烯衬里的不锈钢反应釜中。称取碱性吸酸剂K2CO3加入2mL水,搅拌使其溶解,将其转移至上述反应釜中。接着称取催化剂三苯基膦钯加入反应釜中,搅拌均匀。将反应釜置于120℃烘箱,反应72h。反应结束,反应釜冷却至室温,将溶液移入烧杯中,然后进行抽滤,分别用四氢呋喃、去离子水和乙醇洗涤。最后,将滤饼置于真空烘箱(80℃)干燥12h,即得多孔杂化聚合物N-PHPs。通过调节VPOSS与TBPA的摩尔比(1:1~1:3),得到一系列的多孔杂化聚合物N-PHP-n(n=1,2,3)。由于得到的N-PHP-2具有最高的比表面积,适中的含氮量,选择其作为典型样品进行后续表征与应用。
使用四(4-溴苯)甲烷(TBPM)替换TBPA,以VPOSS与TBPM摩尔比为1:1~3重复上述实验即可得多孔杂化聚合物C-PHP-n(n=1,2,3)。
结构表征:
图1为实施例1制备的多孔杂化聚合物N-PHP-2和C-PHP-2的红外光谱图(POSS为多面体低聚倍半硅氧烷的英文简称,PHPs为多孔杂化聚合物的英文简称)。从图中可以看出,N-PHP-2和C-PHP-2基本保留了POSS笼的Si-O-Si结构,但是由于POSS笼中共存的Tn和Qn硅单元的坍塌与再生,它们的特征峰位置从VPOSS单体的1110cm-1处偏移到了1062,1147和1142cm-1处。其在3674/3650cm-1处的Si-OH以及967/966cm-1处的Si-O键的伸缩振动证实了N-PHP-2和C-PHP-2中Si-OH基团的存在。此外,1506cm-1处的特征峰归属于三(4-溴苯)胺中的C-N键,进一步说明了三(4-溴苯)胺单体被成功引入到聚合物骨架中。图2为N-PHP-2和C-PHP-2的XRD谱图,其在20.9°-21.5°有着明显的包峰,说明N-PHP-2和C-PHP-2为无定形结构。图3为N-PHP-2和C-PHP-2的SEM图像,表明它们具有蓬松的纳米状形貌。通过77K下的氮气吸脱附测试证实多孔杂化聚合物的多孔特性。如图4A所示,N-PHP-2和C-PHP-2等温线在低相对压力(P/P0<0.1)下表现出相当大的吸收率,在高压P/P0(0.85-0.99)下表现出一定的回滞环,表明它们具有微孔和介孔的多级孔结构。此外,它们具有较高的比表面积,分别为547和715m2g-1。利用NLDFT模型计算了样品的孔径分布,如图4B所示,聚合物N-PHP-2和C-PHP-2在1.41和1.29nm处有较窄的微孔分布,在2.89/3.32、5.44/4.54和11.17/15.31nm处出现了一些无序的介孔分布,这与N2吸附脱附等温线的类型是一致的。
实施例2:N-PHP-2和C-PHP-2催化转化CO2的反应活性对比及重复利用性
将实施例1得到的多孔杂化聚合物催化剂N-PHP-2和C-PHP-2用于CO2与环氧氯丙烷的环加成反应中。反应条件为:环氧氯丙烷(2mmol),实施例1中的催化剂(0.05g),加入25mL的反应管中,80℃下搅拌,先用连接CO2气瓶的通气管将反应管内空气排出,再用充满二氧化碳的气球(0.1MPa)插在反应管上,反应72h。反应结束后,加入一定量的乙酸乙酯稀释,室温搅拌20分钟。将溶液取出,离心,将上层清液取出,使用气相色谱(GC)分析计算产率,结果如表1所示。从表1中可以看出,在相同条件下,催化剂N-PHP-2与C-PHP-2的催化活性几乎一致,都能够表现出优异的催化活性。
表1催化剂N-PHP-2与C-PHP-2催化的CO2与环氧氯丙烷环加成反应结果
使用上述催化剂C-PHP-2重复上述实验,在同样的反应温度和反应时间条件下循环1-5次,实验结果如表2所示。从表2中可以看出,催化剂C-PHP-2具有很好的重复利用性。
表2 C-PHP-2催化的CO2与环氧氯丙烷的环加成反应的重复利用结果
实施例3:催化剂N-PHP-2和C-PHP-2在催化CO2与不同环氧化物的环加成反应中的活性对比及底物适用性
本实施例以N-PHP-2和C-PHP-2催化剂,以多种环氧化合物作为底物,进行N-PHP-2和C-PHP-2催化剂的活性对比以及CO2环加成催化反应的底物拓展性研究,环氧化合物为
其中,R为氯甲基,溴甲基,苯基,苯甲氧基,正丁基,正己基实验结果如表3所示。
从表3中数据可知,催化剂C-PHP-2的催化活性稍优于N-PHP-2,这可能是由于C-PHP-2具有很高的比表面积以及大量的介孔,利于反应中环氧底物的传质。此外,两种催化剂都能够相对温和的条件下,对惰性以及长链的环氧底物都有着较高的产率,说明上述两种催化剂有着良好的底物适用性,都能够作为高效的多相催化剂实现温和条件下对CO2的催化转化。
表3催化剂N-PHP-2与C-PHP-2催化的CO2与不同环氧化合物环加成反应性能
下面为具体的实验步骤,以C-PHP-2为例:
3.1C-PHP-2催化转化CO2与环氧溴丙烷反应的催化性能
将环氧溴丙烷(2mmol),实施例1中的C-PHP-2催化剂(0.05g),加入25mL的反应管中,80℃下搅拌,先用连接CO2气瓶的通气管将反应管内空气排出,再用充满CO2的气球(0.1MPa)插在反应管上,反应72h。反应结束后,加入一定量乙酸乙酯稀释,室温搅拌20分钟。将溶液取出,离心,将上层清液取出,使用真空旋蒸仪,将溶剂蒸出,得到的粗产品通过核磁氢谱计算产率。反应产物的1H NMR谱图如图5所示。
在类似的反应条件下,使用氧化苯乙烯,环氧丙基苯基醚,1,2-环氧己烷和1,2-环氧辛烷替换环氧溴丙烷,在其他条件不变的情况下,改变反应温度(100-120℃)来测试催化剂C-PHP-2在催化转化CO2与其他环氧化合物反应中的催化性能。反应产物1H NMR谱图如图6-9所示。
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