CN108440488B - 一种有机多孔共聚物多功能仿生多相催化剂及其制备方法 - Google Patents
一种有机多孔共聚物多功能仿生多相催化剂及其制备方法 Download PDFInfo
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- CN108440488B CN108440488B CN201710083632.2A CN201710083632A CN108440488B CN 108440488 B CN108440488 B CN 108440488B CN 201710083632 A CN201710083632 A CN 201710083632A CN 108440488 B CN108440488 B CN 108440488B
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- Prior art keywords
- metalloporphyrin
- organic
- quaternary phosphonium
- phosphonium salt
- heterogeneous catalyst
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Classifications
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- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
本发明是一种基于金属卟啉和季鏻盐的有机多孔共聚物形成的多功能仿生多相催化剂及其制备方法。所述多相催化剂中,以金属卟啉和季鏻盐官能团作为主要活性物种,即金属卟啉基团充当路易斯酸,季鏻盐中的卤离子作为亲核试剂。所述含金属卟啉和季鏻盐基团的有机多孔共聚物载体是由烯烃基化金属卟啉和季鏻盐单体共聚而成。本发明提供的多相催化剂应用于环氧化合物和二氧化碳的偶联反应工艺中,聚合物骨架中丰富的N、P原子可以增加CO2的吸附;多孔有机聚合物材料能将反应底物封存并限制在纳米级的孔中,增加催化位点上的底物浓度,因此,使得该催化剂既具有极高的活性,又具有较高的稳定性的双重优势。
Description
技术领域
本发明领域属于多相催化领域,具体涉及一种应用于二氧化碳和环氧化合物偶联反应的含金属卟啉和季鏻盐共聚物多功能仿生多相催化剂及其制备方法。
背景技术
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,在大多数情况下,与通过非共价键连接成的分子网络的不稳定性相比,通过共价键连接的有机微孔聚合物,在材料孔性质得到保持的同时,分子网络结构更加稳固。另外,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。
目前,文献报道的关于二氧化碳与环氧化合物合成环状碳酸酯的催化剂主要包括离子液体、碱金属卤化物、金属salen化合物、金属卟啉化合物等均相催化剂以及金属氧化物、分子筛、离子交换树脂、介孔材料、功能性有机聚合物和金属有机框架材料等多相催化剂(Chemical Review,1996,96,51;Chemical Communications,2009,1,26;Journal ofCatalysis,2004,227,537;Chemical Record,2016,16,1339)。上述均相催化剂活性较高,但与产物分离困难,工艺复杂,且痕量金属杂质会对下游产品造成致命缺陷。另一方面,上述多相催化剂则存在活性较低,需要加入可溶性助剂或有机溶剂,活性组分易流失,重复使用性能不好等问题。
2012年,韩金玉等人(化学工业与工程,2012,1:1)报道了季鏻盐离子液体/卤化锌催化CO2与环氧烷烃的环加成反应。制备了一种由氯化锌和己基十四烷基季鏻盐离子液体组成的Lewis酸/碱复合催化体系,将其用于环氧烷烃的环与二氧化碳的加成反应,表现出了较高的催化活性,但是为均相催化体系,面临催化剂回收使用难等问题。
2013年,Ema等人(Green Chem,2013,15,2485)制备了一种有机‐无机杂化催化剂,即将刚性的卟啉分子通过共价键负载于氧化铁上,该催化剂在CO2与环氧化物加成反应中,表现出了高的催化活性,但其循环稳定性能较差,活性组分易于流失。
2014年,Ema等人(J.Am.Chem.Soc.2014,136,15270)合成了双功能化的卟啉催化剂,即将离子液体通过共价键嫁接到卟啉分子上,在CO2与环氧化物加成反应中,表现出了超高的催化活性,但是其仍属于均相催化体系,仍面临着催化剂回收困难等问题。
2015年,Zhang等人(Chemical Communications,2015,51,15708)用付克交联的方法把季鏻盐交联成了超交联聚合物,并且探究了这类催化剂在CO2与环氧化合物加成中的应用,发现加入ZnBr2助剂后催化剂活性明显提升,并且催化剂具有很好的底物适用性。但是催化剂活性还有待于进一步提升。
乙烯基聚合的多孔有机聚合物材料具有高比表面积、多级孔结构和易修饰等特点。作为催化材料,由于其独特的溶胀性能,其孔道内的活性中心可被大量利用。肖丰收等报道了乙烯基聚合的金属卟啉多孔材料用于催化二氧化碳和环氧化合物偶联加成制环状碳酸酯(Journal of Catalysis,2016,338,202‐209)。邓伟侨等报道了通过sonogashira偶联形成的基于salen‐金属单元的多孔有机聚合物用于催化二氧化碳和环氧化合物偶联加成制环状碳酸酯(Nature Communications,2013,4,1960)。但是,上述催化体系需加入季铵盐类助催化剂,导致产物分离提纯困难。为解决上述问题,我们通过同时引入乙烯基金属卟啉(作为路易斯酸与环氧氧化合物作用诱导开环)和季鏻盐(开环亲核试剂),形成多功能性质的双活化模式,既提高了协同催化活性,又有效地固载了金属,防止了金属的流失。
发明内容
本发明的目的在于提供一种应用于催化二氧化碳和环氧化合物偶联加成的,基于金属卟啉和季鏻盐有机共聚物多功能仿生多相催化剂及其制备方法。
本发明的技术方案
一种基于金属卟啉,季鏻盐有机多孔共聚物多功能仿生多相催化剂及其制备方法,其特征在于:所述多相催化剂中以金属卟啉和季鏻盐官能团作为活性组分,并通过烯烃基化金属卟啉和季鏻盐单体,按照摩尔比1:1~1:50共聚得到的有机共聚物作为载体。聚合物骨架中丰富的N、P原子可以增加CO2的吸附,即增加“CO2捕获能力”。
所述的含有烯烃基的有机金属卟啉配体和含有烯烃基的季鏻盐的功能化官能团优选为末端烯烃官能团。所述含有末端烯烃官能团的金属卟啉优选为四苯乙烯基化金属卟啉,其中金属最佳为镁,锌,钴,铝,铬等。所述的含有末端烯烃的季鏻盐最佳为甲基‐三(4‐乙烯苯)氯化鏻,甲基‐三(4‐乙烯苯)溴化鏻,甲基‐三(4‐乙烯苯)碘化鏻,乙基‐三(4‐乙烯苯)氯化鏻,乙基‐三(4‐乙烯苯)溴化鏻,乙基‐三(4‐乙烯苯)碘化鏻。所述的有机混聚物载体具有多级孔结构,比表面积为100~3000m2/g,同时含有大孔、中孔和微孔,孔容为0.1~5.0cm3/g,孔径分布在0.2~50.0nm。
所述的多相催化剂是将烯烃官能团化的卟啉单体金属化后和季鏻盐混合,采用溶剂热聚合方法,在添加或不添加交联剂的情况下,经自由基引发剂引发金属卟啉和季鏻盐中的烯烃基发生聚合反应,生成具有多级孔结构含金属卟啉和季鏻盐的多功能仿生多相共聚物既作为载体,又作为活性组分。
多相催化剂的制备方法:
a)在273~473K,惰性气氛下,在有机溶剂中,加入四苯乙烯基官能团化的卟啉单体(附图说明,图1‐L1),加入有机碱,再加入有路易斯酸性的金属前驱体,室温搅拌6~24h,得到的混合物过滤,水洗,25~100℃真空抽走溶剂。
b)在273~473K,惰性气氛下,在有机溶剂中,加入四苯乙烯官能团化的金属卟啉(附图1,L2)和乙烯基化的季鏻盐(附图1,L3),添加或不添加交联剂,再加入自由基引发剂,混合后,将混合物搅拌0.1~100h,优选的搅拌时间范围为0.1~1h。
c)将步骤a)制得的混合溶液转移至合成高压釜中,323~473K,惰性气体气氛下,采用溶剂热聚合法,静置1~100h进行聚合反应,得到一种含金属卟啉和季鏻盐的有机共聚物。
d)将步骤b)得到的共聚物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有金属卟啉和季鏻盐的有机共聚物,即作为催化环氧化合物与二氧化碳偶联反应的多功能仿生多相催化剂。多功能仿生多相催化剂作为催化环氧化合物与二氧化碳偶联反应的催化剂,在环氧化合物和二氧化碳的偶联反应中表现出高的催化活性和稳定性。
所述多相催化剂中,以金属卟啉和季鏻盐官能团作为主要活性物种,即金属卟啉基团充当路易斯酸,季鏻盐中的卤离子作为亲核试剂。所述含金属卟啉和季鏻盐基团的有机多孔共聚物载体是由烯烃基化金属卟啉和季鏻盐单体共聚而成。本发明提供的多相催化剂应用于环氧化合物和二氧化碳的偶联反应工艺中,此类多功能仿生多相催化剂适用于固定床、浆态床、釜式反应器和滴流床等反应器中。
本发明的反应原理
本发明将典型的卟啉单体(porphyrin)上引入四苯乙烯基(vinyl),将其金属化后,再将季鏻盐也引入乙烯基,在高压釜中利用溶剂热聚合法,使之聚合形成高比表面积和多级孔道结构的有机共聚物,充分综合了金属卟啉(作为路易斯酸活化环氧化合物)和季鏻盐(作为开环亲核试剂))的各自优势。值得一提的是,该聚合物骨架中丰富的N、P原子可以增加CO2的吸附,即增加“CO2捕获能力”;多孔有机聚合物材料能将反应底物封存并限制在纳米级的孔中,增加催化位点上的底物浓度;通过溶剂热聚合合成的乙烯基多孔有机聚合物表现出了较好的溶胀特性。上述这些有利的特性,使得该催化剂既具有极高的活性,又具有较高的稳定性的双重优势。
本发明的有益效果
本发明所述的多相催化剂骨架中含有金属卟啉和季鏻盐结构单元,其中金属卟啉中金属与卟啉分子形成的共价键有利于活性金属的高分散,提高了金属的利用效率,且不易流失,共聚物具有高比表面积多孔级结构,具备载体和配体的双重功能,活性金属组分和聚合物中另一功能组分季鏻盐形成协同催化作用,极大地提高了催化活性。此类多功能仿生多相催化剂适用于固定床、浆态床、釜式反应器和滴流床等反应工艺,本发明所提供的多级孔结构含金属卟啉和季鏻盐有机共聚物多功能仿生多相催化剂应用于二氧化碳和环氧乙烷的偶联加成反应合成环状碳酸酯之中,能够显著提高催化反应活性。也可以在室温下利用二氧化碳合成出环状碳酸酯。降低了环碳酸酯工业化生产的成本,催化剂稳定性好,产品和催化剂的分离简单高效,为环碳酸酯的生产提供了新的工业催化剂。
附图说明
图1为典型的烯烃基功能化的卟啉,金属化的卟啉和季鏻盐。
图2是聚合技术路线示意图。
图3是聚合中用到的交联剂。
图4是实施例1乙烯基官能团化的Vinyl PILC2Br的1H谱。
图5是实施例1乙烯基官能团化的Vinyl PILC2Br的13C谱。
图6是实施例1Mg‐porphyrin&phos@POP固体13C谱
图7是实施例1在N2氛围下催化剂热重曲线。
图8是实施例1Mg‐porphyrin&phos@POP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
下述实施例对本发明进行更好的说明,不限制本发明所要保护的范围。
实施例1
在298K和惰性气体Ar保护氛围下,将1.0g四苯乙烯基化卟啉单体溶于150.0mL二氯甲烷溶剂中,同时加入18.1ml三乙胺和113mg MgBr2·Et2O,搅拌12h,混合物过滤,水洗,干燥,经索氏提取72h,之后40℃真空干燥24h,得到四苯乙烯基功能化的镁卟啉单体(附图1,L4)。在298K和惰性气体保护氛围下,取上述四苯乙烯基功能化的镁卟啉单体0.1g溶于12ml N,N‐二甲基甲酰胺中,再加入1.0g乙基‐三(4‐乙烯苯)溴化鏻(附图1,L5),向上述溶液中加入55mg自由基引发剂偶氮二异丁腈,搅拌2小时。将搅拌好的溶液移至高压釜中,于473K利用溶剂热聚合法聚合72h。待上述聚合后的溶液冷却至室温,40℃条件真空抽走溶剂,即得到由四苯乙烯基功能化的金属镁卟啉和乙基‐三(4‐乙烯苯)溴化鏻单体共聚的有机多孔聚合物多功能多相催化剂,命名为Mg‐porphyrin&phos@POP,经氮气吸脱附测试表征,其比表面积为558m2/g,总孔容为0.55cm3/g,根据图8(B)孔径分布曲线(由非定域密度函数理论计算所得),得知其孔径分布为0.84nm、1.43nm、2.40nm和4.14nm,主要为微孔区域和部分介孔范围内,将该催化剂应用于应用于二氧化碳和环氧化合物的偶联加成反应之中。图2是聚合技术路线示意图。
实施例2
在实施例2中,除了称取20.6mg CoCl2·6H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例3
在实施例3中,除了称取17.1mg Zn(OAc)2·2H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例4
在实施例4中,除了称取46.8mg AlCl3·6H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例5
在实施例5中,除了称取20.4mg Cr(OAc)2·2H2O,替代金属盐MgBr2·Et2O,其余的催化剂合成过程与实施例1相同。
实施例6
在实施例6中,除了称取1.0g甲基‐三(4‐乙烯苯)溴化鏻单体,替代乙基‐三(4‐乙烯苯)溴化鏻单体,其余的催化剂合成过程与实施例1相同。
实施例7
在实施例7中,除了用12.0mL四氢呋喃溶剂替代12.0mL N,N‐二甲基甲酰胺溶剂外,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,除了用12.0mL N‐甲基吡咯烷酮溶剂替代12.0mL N,N‐二甲基甲酰胺溶剂溶剂外,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,除了用423K聚合温度替代473K聚合温度外,其余的催化剂制备过程与实施例1相同。
实施例10
在实施例10中,除了用48h聚合时间替代72h聚合时间外,其余的催化剂制备过程与实施例1相同。
实施例11
在实施例11中,除了再聚合反应前于体系中加入12.0g二乙烯基苯(附图3,L1),其余的催化剂制备过程与实施例1相同。
实施例12
将上述制备的催化剂50mg装入到高压釜式反应器中,再加入环氧丙烷160mmol,密闭反应釜,充入3MPa压力的二氧化碳,由温度控制仪控制温度缓慢升至120℃,反应1h,反应结束后,将反应釜冷却到室温,缓慢放出过量的二氧化碳,过滤分离出催化剂,将所得的产品加入正丁醇作为内标,进入配有HP‐5毛细管柱和FID检测器的HP‐7890N气相色谱分析,生成碳酸丙烯酯的TOF值14800h‐1(催化剂的活性中心以镁卟啉组分进行计算,而镁含量根据ICP‐OES测得),收率为74%。
Claims (10)
1.一种有机多孔共聚物多功能仿生多相催化剂,其特征在于,所述多相催化剂中通过烯烃基化金属卟啉和含有烯烃基的季鏻盐单体,按照摩尔比1:1~1:50共聚得到的有机共聚物,其作为载体,而其中的金属卟啉和季鏻盐盐官能团作为活性组分,即有机共聚物即作为载体又作为活性组分;所述的烯烃基化金属卟啉为含有四乙烯苯基的金属卟啉,金属为镁,钴,锌,铝或铬中的一种或二种以上,其结构通式为:
其中M为Mg,Zn,Co,Al或Cr中的一种或二种以上,所述的含有烯烃基的季鏻盐为甲基-三(4-乙烯苯)氯化鏻,甲基-三(4-乙烯苯)溴化鏻,甲基-三(4-乙烯苯)碘化鏻,乙基-三(4-乙烯苯)氯化鏻,乙基-三(4-乙烯苯)溴化鏻,乙基-三(4-乙烯苯)碘化鏻中的一种或二种以上。
2.按照权利要求1所述的多相催化剂,其特征在于:所述的有机共聚物载体具有多级孔结构,比表面积为100-3000m2/g,同时含有大孔、中孔和微孔,孔容为0.1-5.0cm3/g,孔径分布在0.2-50.0 nm。
3.按照权利要求1-2任一所述的多相催化剂的制备方法,其特征在于: 所述的多相催化剂是将烯烃官能团化的卟啉配体金属化后和含有烯烃基的季鏻盐混合,采用溶剂热聚合方法,在添加或不添加交联剂的情况下,经自由基引发剂引发金属卟啉和季鏻盐中的烯烃基发生聚合反应,生成具有多级孔结构含金属卟啉和季鏻盐的多功能仿生多相共聚物催化剂,既作为载体,又作为活性组分。
4.按照权利要求3所述的制备方法,其特征在于:
a) 在 273~473K, 惰性气氛下,在有机溶剂中,加入烯烃基官能团化的卟啉单体,加入有机碱,再加入有路易斯酸性的金属前驱体,室温搅拌6~24h,得到的混合物过滤,水洗,25~100℃真空抽走溶剂,得到烯烃基官能团化的金属卟啉;
b) 在 273~473K, 惰性气氛下,在有机溶剂中,加入烯烃基官能团化的金属卟啉和含有烯烃基的季鏻盐,添加或不添加交联剂,再加入自由基引发剂,混合后,将混合物搅拌0.1-100 h;
c) 将步骤b)制得的混合溶液转移至合成高压釜中,323K-473K, 惰性气氛下,采用溶剂热聚合法,静置1-100h进行聚合反应,得到一种含金属卟啉和季鏻盐的有机共聚物;
d)将步骤c)得到的有机共聚物,在室温条件下真空抽除溶剂,即得到具有多级孔结构的含有金属卟啉和季鏻盐的有机共聚物。
5.按照权利要求4所述的制备方法,其特征在于:惰性气氛为氩气或氮气。
6.按照权利要求3所述的制备方法,其特征在于:步骤a)中所述有机溶剂为二氯甲烷、三氯甲烷、苯、甲苯、甲醇、乙醇或四氢呋喃中的一种或两种以上;所述的有机碱为三乙胺、三乙烯二胺、1,8-二氮杂二环[5,4,0]十一碳-7-烯和4-二甲胺基吡啶中的一种或两种以上;所述的金属前驱体为溴化镁***、水合醋酸锌、水合氯化钴氯化铝和氯化铬中的一种或两种以上;步骤b)中所述的有机溶剂为苯、甲苯、甲醇、乙醇、四氢呋喃、二氯甲烷或三氯甲烷中一种或两种以上;所述的交联剂为苯乙烯、乙烯、丙烯、二乙烯基苯或1,3,5-三乙炔基苯中的一种或两种以上;所述的自由基引发剂为过氧化环己酮、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两种以上。
7.按照权利要求4或6所述的制备方法,其特征在于:步骤a)中所述的金属前驱体和烯烃基官能团化的卟啉单体的摩尔比为1:1,有机碱与金属前驱体的摩尔比为10:1~1:1;步骤b)中所述的烯烃基官能团化的金属卟啉和含有烯烃基的季鏻盐的摩尔比为0.01:1~100:1,在交联剂添加的情况下,金属卟啉与交联剂的摩尔比为0.01:1~10:1, 金属卟啉与自由基引发剂的摩尔比为300:1~10:1,聚合成有机共聚物前,金属卟啉在有机溶剂中的浓度范围为0.01-1000g/L;聚合成有机共聚物后,金属的担载量为0.01~10wt%。
8.按照权利要求7所述的制备方法,其特征在于:步骤a)中有机碱与金属前驱体的摩尔比为3:1~1:1;步骤b)中所述的烯烃基官能团化的金属卟啉和含有烯烃基的季鏻盐的摩尔比为0.1:1~1:1,在交联剂添加的情况下,金属卟啉与交联剂的摩尔比为0.1:1~1:1, 金属卟啉与自由基引发剂的摩尔比为50:1~10:1,聚合成有机共聚物前,金属卟啉在有机溶剂中的浓度范围为0.1~10g/L;聚合成有机共聚物后,金属的担载量为0.01~0.2 wt%。
9.一种有机多孔共聚物多功能仿生多相催化剂的应用,其特征在于:多功能仿生多相催化剂作为催化环氧化物与二氧化碳偶联反应的催化剂,
所述多相催化剂中通过烯烃基化金属卟啉和含有烯烃基的季鏻盐单体,按照摩尔比1:1~1:50共聚得到的有机共聚物,其作为载体,而其中的金属卟啉和季鏻盐盐官能团作为活性组分,即有机共聚物即作为载体又作为活性组分;所述的烯烃基化金属卟啉为含有四乙烯苯基的金属卟啉,金属为钴,锌,铝或铬中的一种或二种以上,其结构通式为:
其中M为Zn,Co,Al或Cr中的一种或二种以上,所述的含有烯烃基的季鏻盐为甲基-三(4-乙烯苯)氯化鏻,甲基-三(4-乙烯苯)溴化鏻,甲基-三(4-乙烯苯)碘化鏻,乙基-三(4-乙烯苯)氯化鏻,乙基-三(4-乙烯苯)溴化鏻,乙基-三(4-乙烯苯)碘化鏻中的一种或二种以上。
10.按照权利要求9所述的应用,其特征在于:所述的有机共聚物载体具有多级孔结构,比表面积为100-3000m2/g,同时含有大孔、中孔和微孔,孔容为0.1-5.0cm3/g,孔径分布在0.2-50.0 nm。
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104448283A (zh) * | 2014-11-26 | 2015-03-25 | 中国科学院长春应用化学研究所 | 一种聚碳酸酯的制备方法 |
CN105753894A (zh) * | 2016-05-09 | 2016-07-13 | 中国科学院长春应用化学研究所 | 铝系卟啉配合物与聚碳酸酯的制备方法 |
-
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- 2017-02-16 CN CN201710083632.2A patent/CN108440488B/zh active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104448283A (zh) * | 2014-11-26 | 2015-03-25 | 中国科学院长春应用化学研究所 | 一种聚碳酸酯的制备方法 |
CN105753894A (zh) * | 2016-05-09 | 2016-07-13 | 中国科学院长春应用化学研究所 | 铝系卟啉配合物与聚碳酸酯的制备方法 |
Non-Patent Citations (3)
Title |
---|
Highly recyclable polymer supported ionic liquids as efficient heterogeneous catalysts for batch and flow conversion of CO2 to cyclic carbonates;Tao Wang,et al.;《RSC Advances》;20170112;2836–2841 * |
Metalated porous porphyrin polymers as efficient heterogeneous catalysts for cycloaddition of epoxides with CO2 under ambient conditions;Zhifeng Dai,et al.;《Journal of Catalysis》;20160325;202-209 * |
Phosphonium salt and ZnX2–PPh3 integrated hierarchical POPs: tailorable synthesis and highly efficient cooperative catalysis in CO2 utilization;Cunyao Li,et al.;《J. Mater. Chem. A》;20160908;16017–16027 * |
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