新型聚醚离子液体的制备及其改性PP与催化性能研究

发布时间：2018-07-11 11:42

本文选题：聚醚离子液体 + 改性　；参考：《沈阳工业大学》2017年硕士论文

【摘要】：首先通过环氧氯丙烷开环聚合及与N-甲基咪唑反应合成了氯化1-羟基聚醚-3-甲基咪唑离子液体([HO-PECH-MIM]Cl),然后利用活性端基转化技术制备出氯化1-羧基聚醚-3-甲基咪唑离子液体([HOOC-PECH-MIM]Cl)及氯化1-氨基聚醚-3-甲基咪唑离子液体([H_2N-PECH-MIM]Cl)。采用IR与HNMR检测仪对以上三种聚醚离子液体的化学结构进行分析。将合成的聚醚咪唑离子液体与聚丙烯(PP)熔融共混,得到聚醚咪唑离子液体/PP复合材料,且对得到的复合材料的力学性能与结晶结构等进行了表征与性能测试。再将上述聚醚离子液体分别负载无机粒子硅和金属锆,得到硅胶负载聚醚离子液体与负载锆型聚醚咪唑离子液体催化剂,采用红外(IR)和核磁(HNMR)对上述制备的负载型聚醚离子液体化学结构进行分析,同时采用热重分析仪(TGA)与电镜扫描仪(SEM)对其热性能与表观形貌进行测定。再将三种聚醚离子液体及其负载硅/锆的聚醚离子液体分别催化二氧化碳(CO2)与环氧丙烷(PO)合成碳酸丙烯酯(PC),优化工艺参数,对影响催化性能的因素如压力、温度、催化剂用量等进行考察,建立催化机理模型。实验结果表明,新型聚醚离子液体与负载型聚醚离子液体均制备成功,且纯度较高,而负载后的聚醚离子液体的相态发生了改变,具有很好的热稳定性。实验结果说明,当聚醚离子液体的含量为6%时,材料的拉伸强度提高了31%,弯曲强度提高了11%,而当聚醚咪唑离子液体含量为9%时,改性后PP的冲击强度相比之前提高了约132%,而断裂伸长率则提高了75%。这说明聚醚离子液体改性后的PP强度和韧性均有显著变化,其原因是聚醚离子液体起到了成核剂的作用,使PP结晶结构发生改变,同时聚醚离子液体特有的柔性长链,使其能与PP基体很好地相容,对PP起到增强增韧作用。催化实验结果说明,制备的新型聚醚离子液体催化剂催化转化CO2与PO反应合成碳酸丙烯酯的效果很好,且催化过程操作简单,反应时间短,催化剂易分离,催化剂重复使用多次后催化性能仍然很稳定,这为实现固定床连续催化反应提供数据基础,同时也为二氧化碳的直接高效利用提供了有效途径。
[Abstract]:At first, 1-hydroxypolyether 3-methyl imidazole chloride ionic liquid ([HO-PECH-MIM] Cl) was synthesized by ring-opening polymerization of epichlorohydrin and reaction with N- methyl imidazole, and then 1-carboxyl polyether 3-methyl imidazole chloride was prepared by active terminal conversion technique. [HOOC-PECH-MIM] Cl and 1-aminopolyether 3-methyl imidazole chloride ([H2N-PECH-MIM] Cl). The chemical structures of the above three polyether ionic liquids were analyzed by IR and HNMR. The polyether imidazole ionic liquid / PP composites were prepared by melt blending the synthesized polyether imidazole ionic liquids with polypropylene (PP). The mechanical properties and crystalline structure of the composites were characterized and tested. Then the above polyether ionic liquids were loaded with inorganic particles silicon and metal zirconium respectively to obtain silica gel supported polyether ionic liquids and zirconium type polyether imidazole ionic liquid catalysts. The chemical structure of the supported polyether ionic liquids was analyzed by IR and HNMR, and the thermal properties and morphology were measured by thermogravimetric analyzer (TGA) and electron microscope scanner (SEM). Three polyether ionic liquids and polyether ionic liquids loaded with silicon / zirconium were used to catalyze the synthesis of propylene carbonate (PC) from carbon dioxide (CO _ 2) and propylene oxide (PO) respectively. The catalyst dosage was investigated and the catalytic mechanism model was established. The experimental results show that both the new polyether ionic liquid and the supported polyether ionic liquid have been prepared successfully, and the purity of the polyether ionic liquid is high. However, the phase state of the loaded polyether ionic liquid has changed and has good thermal stability. The experimental results show that when the content of polyether ionic liquid is 6, the tensile strength and bending strength of the material are increased by 31 and 11, respectively, and when the content of polyether imidazole ionic liquid is 9, The impact strength of the modified PP was increased by about 132 and the elongation at break was increased by 75%. This shows that the strength and toughness of PP modified by polyether ionic liquid have significant changes, the reason is that the polyether ionic liquid acts as a nucleating agent, which changes the crystalline structure of PP and the flexible long chain of polyether ionic liquid. It can be well compatible with PP matrix and plays a reinforcing and toughening role on PP. The results of catalytic experiments show that the new polyether ionic liquid catalyst is effective in the catalytic conversion of CO _ 2 and PO to propylene carbonate, and the catalytic process is simple, the reaction time is short, and the catalyst is easy to be separated. After repeated use of the catalyst, the catalytic performance is still very stable, which provides a data basis for the continuous catalytic reaction in a fixed bed, and also provides an effective way for the direct and efficient utilization of carbon dioxide.
【学位授予单位】：沈阳工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O645.1;O643.36

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