CN107840954A - 一种离子型聚合物及其制备和应用 - Google Patents

一种离子型聚合物及其制备和应用 Download PDF

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CN107840954A
CN107840954A CN201610826417.2A CN201610826417A CN107840954A CN 107840954 A CN107840954 A CN 107840954A CN 201610826417 A CN201610826417 A CN 201610826417A CN 107840954 A CN107840954 A CN 107840954A
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ionomer
carbon dioxide
catalyst
present
reaction
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李留义
高金伟
王瑞虎
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/063Polymers comprising a characteristic microstructure
    • B01J31/064Dendrimers
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D317/00Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10Heterocyclic 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
    • C07D317/32Heterocyclic 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
    • C07D317/34Oxygen atoms
    • C07D317/36Alkylene carbonates; Substituted alkylene carbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02Polyamines
    • C08G73/0273Polyamines containing heterocyclic moieties in the main chain

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  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Polyesters Or Polycarbonates (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明公开一种离子聚合物及其制备方法和其在常压下催化转化二氧化碳制环状碳酸酯反应中的应用,属于材料制备及催化技术领域;本发明制备的离子聚合物催化剂是含有三嗪基团和季铵盐离子基团的有机聚合物,能够在常压条件下实现高效催化转化二氧化碳制备环状碳酸酯;本发明催化反应条件温和,产率高,符合实际生产需要,具有较大的应用潜力。

Description

一种离子型聚合物及其制备和应用
技术领域
本发明涉及一种基于离子型聚合物催化剂的制备及催化二氧化碳制备环状碳酸酯的应用,为利用工业废气中二氧化碳提供潜在应用。
背景技术
二氧化碳是温室效应的主要来源,同时也是自然界中储量最丰富的C1资源,利用二氧化碳与环氧化合物反应制备环状碳酸酯是利用二氧化碳的一条低污染、环境友好的有效途径。目前,环状碳酸酯的制备方法主要是在需要高温高压的条件下进行,对设备要求较高。开发出用量小、效率高、催化条件温和等的催化剂对我国具有重大的经济和环境意义。
发明内容
本发明的目的在于克服现有技术不足,提供了一种在常压下高效催化转化二氧化碳制备环状碳酸酯的方法,具体技术方案如下:
本发明提供的催化转化二氧化碳制备环状碳酸酯的方法,其特征在于:使用离子型有机聚合物作为催化剂,三乙胺作为溶剂和共催化剂,常压条件。
本发明提供的方法以二氧化碳为原料,三乙胺作为反应溶剂和共催化剂,离子型有机聚合物作为催化剂,制备环状碳酸酯,反应压力为0.1Mpa,反应温度为25-100℃,反应时间为1-24小时,产率5-100%。
相对于传统催化方法,本发明提供了一种反应条件温和的方法,具有如下显著优点:
(1)采用三乙胺胺作为溶剂和共催化剂,对二氧化碳具有更好的吸附能力。
(2)反应体系以离子型有机聚合物为催化剂,是异相催化体系,催化剂可循环使用,有利于产物的分离。
(3)常压下催化,反应条件温和,实现了二氧化碳同时捕获和转化。
(4)本发明中的催化剂催化活性高。
附图说明
图1实施例催化剂的结构式。
图2实施例催化剂的红外谱图。
图3实施例催化剂的固体核磁谱图。
图4实施例催化剂的催化动力学曲线图
图5实施例催化剂的催化活性稳定图
具体实施方式
以下是本发明的几个实施例,进一步说明本发明,但是本发明不仅限于此。
实施例1
离子型有机聚合物催化剂的制备
将100毫克2,4,6-三(4-(溴亚甲基)苯)-1,3,5-三嗪和30毫克四甲基乙二胺溶于乙腈和甲苯的混合溶液中,搅拌,升温到100摄氏度,在100摄氏度加热反应24小时后,冷却,过滤,收集固体,80摄氏度真空干燥得到白色离子型有机聚合物催化剂粉末,产率65%。图1为实施例1所得的离子型有机聚合物的结构单元,图2为实施例1所得的离子型有机聚合物和多孔有机聚合物单体的红外谱图,图3为实施例1所得的离子型有机聚合物的固体核磁共振碳谱图,图2和3清晰的表明所制备的催化剂骨架中含有三嗪和季铵盐基团。
实施例2
催化转化二氧化碳性能测试
将1毫升三乙胺、1毫升环氧氯丙烷和20毫克离子型有机聚合物催化剂,放入反应器中,通入二氧化碳到0.1MPa,在100摄氏度加热反应1小时后,用气相色谱检测,产物为氯代碳酸丙烯酯,转化率为100%。
实施例3
类似实施例2,采用离子型有机聚合物为催化剂,改变时间等条件,反应结果如附图4。图4为实施例3所得的离子型有机聚合物催化二氧化碳和环氧氯丙烷生成氯代碳酸丙烯酯的时间反应曲线。
实施例4
类似实施例2,采用离子型有机聚合物为催化剂,催化剂循环使用6次后,转化率仍达到98%(图5),说明催化剂具有良好的可循环性能。
实施例5
类似实施例1,采用为离子型有机聚合物催化剂和三乙胺,以环氧化合物和二氧化碳为反应底物,不同环氧化合物的反应结果如下表(表1):
表1环氧化合物的催化活性
以上所述仅为本发明的代表实施例,凡是依据本发明申请专利范围内所做的修饰与变化,皆应属于本发明的涵盖范围。

Claims (3)

1.一种离子聚合物,其特征在于:聚合物中包括三嗪基团和季铵盐离子基团。
2.权利要求1所述的离子聚合物的制备方法,其特征在于:采用2,4,6-三(4-(溴亚甲基)苯)-1,3,5-三嗪和四甲基乙二胺为原料,通过季铵化反应制备。
3.权利要求1所述离子聚合物应用于催化转化二氧化碳生成环状碳酸酯的反应,其特征在于:所述反应压力为0.1Mpa,反应温度为25-100℃,反应时间为1-24小时,产率5-100%。
CN201610826417.2A 2016-09-18 2016-09-18 一种离子型聚合物及其制备和应用 Pending CN107840954A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113637163A (zh) * 2021-08-16 2021-11-12 山东大学 一种三嗪基聚离子液体及其合成方法与应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113637163A (zh) * 2021-08-16 2021-11-12 山东大学 一种三嗪基聚离子液体及其合成方法与应用

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