CN113896704A - 一种多孔自聚合离子液体催化合成环状碳酸酯的方法 - Google Patents
一种多孔自聚合离子液体催化合成环状碳酸酯的方法 Download PDFInfo
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Abstract
本发明涉及一种多孔自聚合离子液体催化合成环状碳酸酯的方法,该方法以二氧化碳和环氧化合物为反应物,以多孔自聚合离子液体为催化剂,催化合成环状碳酸酯。本发明可以高效、高选择性合成环状碳酸酯,且其中的催化剂合成简便、条件温和,反应体系中无需添加剂或助催化剂,同时实现催化剂的循环使用。
Description
技术领域
本发明涉及多相催化及CO2资源化利用的绿色催化领域,尤其涉及一种多孔自聚合离子液体催化合成环状碳酸酯的方法。
背景技术
二氧化碳过度排放及其引发的全球环境变化是当今社会最大的环境问题之一。在全球碳中和的大背景下,寻求高效、低碳、绿色方案,将丰富、可再生的二氧化碳定向转化为各种燃料与化工原料,可在一定程度上缓解环境问题,实现将二氧化碳变废为宝的高值化利用。其中,CO2与环氧化合物的环加成反应,由于具有原子经济性和环境友好的特点,在合成化学与化学工业中占据重要地位。其产物环状碳酸脂,在锂离子电池、聚碳酸酯以及燃料添加剂工业中具有广泛应用。因此,开发更加清洁、绿色、高效的催化合成体系具有重要应用价值与可持续发展意义。
已经有大量文献报道用于CO2与环氧化合物环加成制备环状碳酸酯的催化体系,如二元催化剂Salen-金属配合物与季铵盐(中国专利CN104496959B)、碱金属盐(Chem.Rev., 2007, 107, 2365)、离子液体(Fuel, 2017, 200, 316)和金属卤化物(TetrahedronLett., 2004, 45, 8307)等。报道的均相催化剂虽然活性较高,但其后处理与回收过程通常伴随一系列高能耗操作。开发一种具有高效、高选择性、易回收的非均相催化剂仍是人们研究的重要方向。
针对离子液体高黏度、低传质速率的不足,利用其功能基团可优化、结构模板可调节的特点,通过交联聚合制备聚合离子液体是近几年的热点方向,如氨基丙烯酸类离子液体聚合物(中国专利CN109134420B)、丙烯酸酯类离子液体聚合物(中国专利CN112159386A)、季膦类聚离子液体(中国专利CN105367541B;Chem. Commun., 2015, 51,15708)、聚苯乙烯为载体的磷盐催化剂(中国专利CN1314680C)、苯乙烯等为交联剂的咪唑盐有机聚合物(中国专利CN107537575B)、离子液体功能化金属卟啉基有机聚合物(中国专利CN112023980A)等均被广泛研究。但由于交联剂(苯乙烯等)的使用,报道的催化体系通常活性位点密度减少,需要较之于均相体系更苛刻的条件,甚至有些还需要添加额外的助催化剂及溶剂来促使反应进行。
发明内容
本发明所要解决的技术问题是提供一种高效、高选择性的多孔自聚合离子液体催化合成环状碳酸酯的方法。
为解决上述问题,本发明所述的一种多孔自聚合离子液体催化合成环状碳酸酯的方法,其特征在于:该方法以二氧化碳和环氧化合物为反应物,以多孔自聚合离子液体为催化剂,催化合成环状碳酸酯。
本发明反应通式为:
式中:R1、R2均为H、CnH2n+1、CH2X、CnH2nX、C6H5、CH3O-C6H4、X-C6H4 (n=1~6,X=Cl、Br)。
所述催化剂的用量为环氧化合物的0.1~5 mol%。
所述催化合成的条件是指CO2压力为0.1~5 MPa,温度为50~140℃,反应时间0.5~12 h。
所述环氧化合物的结构为:
所述多孔自聚合离子液体由烯基和羟基双官能化的咪唑盐类化合物单体通过自聚合反应获得,且咪唑N原子上分别连有烯基和烷基醇片段,其结构通式如下:
本发明与现有技术相比具有以下优点:
1、本发明以具有多孔结构和高活性位点密度的自聚型聚离子液体为多相催化剂,实现二氧化碳和环氧化物在温和条件下,高效催化环加成反应制备环状碳酸酯,过程中无需任何助催化剂。
2、本发明自聚合反应得到的多孔自聚合离子液体,具有丰富的咪唑基碱性位以及长链烷基醇酸性位,高密度双活性位点有效促进了CO2溶解与活化,避免了嵌段聚合类离子液体片段结构不均匀及催化过程中催化剂用量大的问题;同时多孔自聚合离子液体具有丰富的孔结构,可高效富集周围微环境中的CO2,明显提升反应体系的传质效率。
3、本发明多孔自聚合离子液体为多相催化剂,避免了均相体系的后处理过程,是一条更绿色的合成路线。
4、本发明催化剂合成简便、条件温和,反应体系中无需添加剂或助催化剂,同时实现催化剂的循环使用。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细的说明。
图1为本发明实施例1中自聚合离子液体a-p的红外光谱表征。
图2为本发明催化剂a-p的循环稳定性测试图。
具体实施方式
一种多孔自聚合离子液体催化合成环状碳酸酯的方法,该方法以二氧化碳和环氧化合物为反应物,以多孔自聚合离子液体为催化剂,催化剂的用量为环氧化合物的0.1~5mol%,在CO2压力为0.1~5 MPa、温度为50~140℃、反应时间0.5~12 h的条件下催化合成环状碳酸酯。
其中:环氧化合物的结构为:
多孔自聚合离子液体由烯基和羟基双官能化的咪唑盐类化合物单体通过自聚合反应获得,且咪唑N原子上分别连有烯基和烷基醇片段,其结构通式如下:
m, n=1~12,p=0~12,x= Cl、Br、I,优先选择Cl和Br。
多孔自聚合离子液体的聚合过程可以采用超临界CO2为软模板剂,通过引发剂诱导聚合,聚合后CO2气体逸出制得,也可以采用本领域公知的其他能够实现多孔结构以及高位点密度的策略和方法来合成。
本发明经典合成方法如下:
在273~393 K,在少量溶剂中加入1~8 mol/L烯基与羟基双官能团化的离子液体单体,加入0.1~5%单体质量的自由基引发剂混合后,搅拌0.5~10小时,得到混合溶液;将混合溶液转移至超临界CO2装置中,在7.5~30 MPa高压CO2气氛、温度为30~100 ℃条件下进行热聚合反应,得到一种自聚合离子液体聚合物混合物;该混合物快速泄至常压,在室温条件下真空抽除少许溶剂,经干燥即得具有多孔结构的自聚合离子液体。
实施例1 多孔自聚合离子液体a-p的合成:
在1 ml乙醇溶剂中加入1 mmol苯乙烯基羟乙基双官能团化的离子液体单体,加入自由基引发剂偶氮二异丁腈(1%)混合后,鼓入氮气后搅拌0.5小时;将制得的混合溶液转移至超临界CO2装置中,高压CO2气氛(17 MPa)温度80 ℃下,进行聚合反应4 h,得到自聚合离子液体聚合物a;将所得聚合物,在室温条件下真空抽除少许溶剂,得到具有多孔结构的自聚合离子液体聚合物。在真空烘箱中60℃下干燥12 h获得多孔自聚合离子液体a-p,数均分子量为7610。
对所得多孔自聚合离子液体a-p进行红外表征,如图1所示。由图1可以看出, 3095cm-1附近的红外吸收峰为咪唑环阳离子中C-H键的伸缩振动, 1565 cm-1为咪唑环的骨架振动,1602 cm-1附近为苯环环呼吸红外吸收特征峰,1450 cm-1附近为饱和碳氢键的吸收峰,1080 cm-1为碳氧键、3378 cm-1附近为羟基的伸缩振动,由于聚离子液体的吸潮性导致吸收峰显著宽化。综合以上,可以看出自聚合的离子液体中单体结构及羟乙基官能团得以保持。
通过改变离子液体单体类型,以相同的方式可以合成其他共聚物。
实施例2 环状碳酸酯的合成:
在20 mL反应釜中,依次加入1.4 ml环氧丙烷和1 mol%多孔自聚合离子液体a-p,由控温仪控制温度稳定至80 ℃,充入CO2至2 MPa,反应8 h后,冷却至室温后缓慢泄压,气相色谱内标法确定碳酸丙烯酯收率。产品产率为95%,产物的纯度经气相色谱确定为99.3%。
实施例3 环状碳酸酯的合成:
方法同实施例2,采用压力0.1 MPa,反应时间为6 h,其他反应条件不变,得到产物碳酸丙烯酯的产率为64%。
实施例4 环状碳酸酯的合成:
方法同实施例2,采用多孔自聚合离子液体a-p与底物环氧化合物的摩尔比为0.2%,其他反应条件不变,得到产物2b的产率为87%。
实施例5 环状碳酸酯的合成:
方法同实施例2,采用反应时间为6 h,其他反应条件不变,得到产物2b的产率为90%。
实施例6 催化剂循环测试:
方法同实施例2,将催化剂离心回收后循环使用,使用5次后产物碳酸丙烯酯的产率均为90%以上,如图2所示分别为95.0,95.2,93.9,93.0,92.7。
对比例1 自聚合离子液体a-s的合成:
在5 ml乙醇溶剂中加入3 mmol苯乙烯基与羟乙基双官能团化的离子液体单体,加入自由基引发剂偶氮二异丁腈(1%)混合后,鼓入氮气后在80 ℃下温度搅拌4小时进行聚合反应,得到自聚合离子液体聚合物a;将所得聚合物,在室温条件下真空抽除少许溶剂,得到自聚合离子液体聚合物。在真空烘箱中60℃下干燥12 h获得自聚合离子液体a-s。
对比例2 环状碳酸酯的合成:
方法同实施例2,催化剂采用自聚合离子液体a-s,其他反应条件不变,得到碳酸丙烯酯的产率为77%。
对比例3 多孔自聚合离子液体b-p的合成:
方法同实施例1,离子液体为苯乙烯基单官能化的离子液体,其他反应条件不变,得到多孔自聚合离子液体b-p。该离子液体不含羟基。
对比例4 环状碳酸酯的合成:
方法同实施例2,催化剂采用多孔自聚合离子液体b-p,其他反应条件不变,得到产物碳酸丙烯酯的产率为81%。
与实施例1~2相比,对比例1~2中无孔结构特征的自聚合离子液体催化催化合成环状碳酸酯的效率由99%降低至77%;对比例3~4中,无羟乙基结构的自聚合离子液体催化催化合成环状碳酸酯的效率由99%降低至81%。由此可以看出,羟乙基结构特征及独特孔结构对自聚合离子液体发挥催化活性具有显著的促进作用。
Claims (5)
1.一种多孔自聚合离子液体催化合成环状碳酸酯的方法,其特征在于:该方法以二氧化碳和环氧化合物为反应物,以多孔自聚合离子液体为催化剂,催化合成环状碳酸酯。
2.如权利要求1所述的一种多孔自聚合离子液体催化合成环状碳酸酯的方法,其特征在于:所述催化剂的用量为环氧化合物的0.1~5 mol%。
3.如权利要求1所述的一种多孔自聚合离子液体催化合成环状碳酸酯的方法,其特征在于:所述催化合成的条件是指CO2压力为0.1~5 MPa,温度为50~140℃,反应时间0.5~12h。
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CN115181248A (zh) * | 2022-07-28 | 2022-10-14 | 东莞理工学院 | 带有季铵盐结构的多孔有机聚合物及其制备方法和应用 |
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