CN109400922B - 超交联多孔聚离子液体材料的制备方法及应用 - Google Patents
超交联多孔聚离子液体材料的制备方法及应用 Download PDFInfo
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- CN109400922B CN109400922B CN201811258110.2A CN201811258110A CN109400922B CN 109400922 B CN109400922 B CN 109400922B CN 201811258110 A CN201811258110 A CN 201811258110A CN 109400922 B CN109400922 B CN 109400922B
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- ionic liquid
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- chloride
- tertiary amine
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- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 42
- 239000011344 liquid material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002608 ionic liquid Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 32
- -1 alkenyl tertiary amine Chemical class 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 25
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 10
- 238000004132 cross linking Methods 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 claims description 4
- VTPQLJUADNBKRM-UHFFFAOYSA-N 1-(bromomethyl)-4-ethenylbenzene Chemical compound BrCC1=CC=C(C=C)C=C1 VTPQLJUADNBKRM-UHFFFAOYSA-N 0.000 claims description 4
- KKLSEIIDJBCSRK-UHFFFAOYSA-N 1-(chloromethyl)-2-ethenylbenzene Chemical compound ClCC1=CC=CC=C1C=C KKLSEIIDJBCSRK-UHFFFAOYSA-N 0.000 claims description 4
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 4
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 4
- LFINSDKRYHNMRB-UHFFFAOYSA-N diazanium;oxido sulfate Chemical compound [NH4+].[NH4+].[O-]OS([O-])(=O)=O LFINSDKRYHNMRB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 claims description 2
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 claims description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical group N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 claims description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
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- 238000006555 catalytic reaction Methods 0.000 abstract description 5
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- 238000000034 method Methods 0.000 abstract description 3
- 238000012719 thermal polymerization Methods 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
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- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000013315 hypercross-linked polymer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000779 poly(divinylbenzene) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
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- 238000007614 solvation Methods 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
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Abstract
本发明提供一种离子热聚合制备超交联多孔聚离子液体材料的方法及其应用,首先将烯基叔胺与氯乙腈或者将氰基叔胺与烯丙基卤代物或者苯乙烯苄基卤代物进行季铵化,并通过离子交换引入合适配阴离子,在氯化铝/氯化钠复合熔盐体系中进行离子热烯基聚合和氰基交联,得超交联多孔聚离子液体材料,所得材料有广泛的应用前景。本发明的优点:(1)产率高,为91~98%;(2)制备材料比表面积大,在250m2/g以上;(3)材料具有全离子液体骨架,活性组分含量高;(4)制备过程简便,原料易得;(5)材料应用广泛,通过调整原料、配阴离子及聚合条件,可有效调节材料结构,可用于催化、气体吸附、废水处理等领域;(6)材料可回收重用。
Description
技术领域
本发明涉及一种超交联多孔聚离子液体材料的制备方法及应用,属于高分子化学合成技术领域。
背景技术
离子液体性能优异,应用广泛,但存在回收难、价格贵、粘度高、降解差、无法成型等缺点。固载化可较好解决以上问题,但传统负载法将大体积离子液体接枝在载体上,易造成孔道堵塞,负载量低。多孔聚离子液体结合离子液体特定性能和高分子可加工成型、稳定持久、结构可调等优点,在催化、吸附分离、电化学等领域有广泛应用。
多孔聚离子液体,特别是纯聚离子液体骨架多孔材料研究较少,最常用合成方法是复合共聚。韩布兴课题组[Y.Xie,Angew.Chem.Int.Ed.2007,46:7255]将乙烯咪唑离子液体与二乙烯苯共聚,制备了催化性能优于离子液体及其自聚物的交联聚合材料。肖丰收课题组[F.Liu,J.Am.Chem.Soc.2012,134:16948]采用乙烯咪唑与二乙烯苯共聚、季铵化及离子交换,合成材料对生物柴油制备表现了优于硫酸活性。但共聚材料孔道源于聚二乙烯苯,离子液体接枝在聚合链上,非离子液体骨架,仍属负载型。Yuan等[Q.Zhao,Adv.Mater.2015,27:2913]将聚离子液体与有机多酸进行离子交联,形成多孔聚离子液体复合材料,通过调节羧酸结构和合成过程,可调控材料孔结构和形貌,成功用于CO2吸附、催化、高敏传感器等。但这类材料是聚离子液体复合物,离子交联稳定性未知,且无离子交换能力。单体直接聚合是最简便合成多孔聚离子液体材料的方法,但由于离子液体单体的极性较大,在聚合过程中随着聚合链的增长,链间极性增强,极易沉淀析出,因此,超交联聚离子液体制备的关键是形成高溶胀刚性超交联聚合网络。超交联聚合网络需在强溶剂化作用下形成,保证聚合链充分溶胀,溶剂挥发后,聚合链倾向收缩紧密堆积,降低表面能,但刚性超交联结构限制构象转换,阻止收缩,原溶剂占据空间成为孔结构。与中性聚合物不同,聚离子链极性大,随反应进行,极性持续增加,易过早从溶剂沉淀析出,形成紧密堆积的无孔结构。而双键聚合过程为自由基链式反应,交联聚合反应同时进行时,过程控制困难。为解决以上问题,本发明将烯基叔胺与氯乙腈或者将氰基叔胺与烯丙基卤代物或者苯乙烯苄基卤代物进行季铵化,形成刚性烯氰离子液体单体,选择低熔点的氯化铝/氯化钠复合熔盐作为反应介质,先进行自由基聚合,制备高分子量的线性聚合链,利用聚离子链与熔盐间强静电库仑作用,促进其在熔盐中溶胀,接着,升温进行氰基交联聚合,利用氯化铝强酸性和离子热强化条件,保证形成高溶胀刚性超交联聚离子液体网络,并通过配阴离子调节离子液体单体的溶解性和聚合网络的溶胀情况,制备超交联多孔聚离子液体。
发明内容
本发明的目的是为了解决上述现有技术的不足而提供一种超交联多孔聚离子液体材料的制备方法。
为了实现上述目的,本发明所设计的一种超交联多孔聚离子液体材料的制备方法,其将烯基叔胺与氯乙腈或者将氰基叔胺与溴丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种进行季铵化,形成刚性烯氰离子液体单体,并通过离子交换引入配阴离子,接着,在氯化铝/氯化钠复合熔盐体系中进行离子热烯基聚合和氰基交联,得到超交联多孔聚离子液体材料。
所述熔盐为氯化铝/氯化钠复合熔盐,与离子液体单体间存在强静电库仑作用,强酸性氯化铝能促进交联完成,能很好溶胀交联聚离子液体网络,形成交联聚离子液体凝胶,熔盐中氯化铝/氯化钠的质量比为100∶15~45。
优选的,所述烯基叔胺为4-乙烯吡啶、2-乙烯吡啶、2-乙烯咪唑、三烯丙胺中的一种;所述氰基叔胺为4-氰基吡啶或2-氰基吡啶。
优选的,通过离子交换将卤素离子交换成四氟硼酸根、六氟磷酸根、二氰胺根、三氟甲磺酸根、双三氟甲磺酰亚胺根离子中的一种,调整相应配阴离子,改变离子液体单体及交联聚合网络的溶胀度,调节超交联聚离子液体材料的比表面。
上述一种超交联多孔聚离子液体材料的制备方法,其具体的操作步骤如下:
步骤一,刚性烯氰离子液体单体的制备;
将烯基叔胺与氯乙腈或者将氰基叔胺与溴丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种,按物质量之比为1∶1进行混合,加入阻聚剂,阻聚剂用量为总质量的1%,加入乙酸乙酯或四氢呋喃,配成40%的溶液后,在50~80℃下搅拌5~72h后得到相应离子液体,依次用乙酸乙酯、乙醚进行洗涤3次后,在60℃进行真空干燥,得刚性双烯离子液体单体,将刚性烯氰离子液体单体溶于一定有机溶剂后,配成质量比浓度为10~50%的溶液,加入含配阴离子盐中进行交换,盐的摩尔用量为单体的1.5倍,在50~80℃下加热搅拌,并加入1%的阻聚剂,交换后过滤除去相应盐,重复交换3次,减压脱除溶剂得相应配阴离子的刚性烯氰离子液体单体;
步骤二,多孔聚离子液体材料制备;
将上述步骤一种制备的离子液体单体与质量比为100∶15~45的氯化铝/氯化钠复合盐进行研磨混合,在手套箱研磨30min以上,控制单体与熔盐的质量百分比1∶10~45,加入引发剂过氧硫酸铵,用量为离子液体单体的1%,均匀混合后,转入管式马弗炉,在氮气保护下,置于100~150℃下加热聚合反应4~12h,继续升温至180~260℃下加热氰基缩合交联反应6~24h,冷却至室温,将凝胶产物加入10%的稀盐酸中,进行加热回流,去除熔盐,所得聚离子液体依次用乙酸乙酯、乙醚洗涤3次,进行80℃烘箱中干燥12h,即得多孔聚离子液体材料。
上述一种超交联多孔聚离子液体材料的应用,其根据实际应用的要求,引入相应配阴离子,进行催化、气体吸附、废水处理方面的应用,材料经过滤回收可进行重复使用。
与背景技术相比,本发明的优点是:(1)产率高,为91~98%;(2)制备材料比表面积大,在250m2/g以上;(3)材料具有全离子液体骨架,活性组分含量高;(4)制备过程简便,原料易得;(5)材料应用广泛,通过调整原料、配阴离子及聚合条件,可有效调节材料结构,可用于催化、气体吸附、废水处理、分离等领域;(6)材料回收重用简便,可通过过滤回收。
具体实施方式
下面结合实施例对本发明进一步说明。
实施例1
本发明提供的一种超交联多孔聚离子液体材料的制备方法,其具体的操作步骤如下:
步骤一,刚性烯氰离子液体单体的制备;
称将乙烯咪唑与氯乙腈按物质量之比为1∶1进行混合,加入阻聚剂,阻聚剂用量为总质量的1%,加入四氢呋喃,配成40%的溶液后,在70℃下搅拌48h后得到相应离子液体,依次用乙酸乙酯、乙醚进行洗涤3次后,在60℃进行真空干燥,得刚性烯氰离子液体单体,将刚性烯氰离子液体单体溶于一定丙酮溶剂后,配成质量比浓度为30%的溶液,加入含六氟磷酸钾溶液中进行交换,盐的摩尔用量为单体的1.5倍,在40℃下加热搅拌,并加入1%的阻聚剂,交换后过滤除去相应盐,重复交换3次,减压脱除溶剂得相应PF6 -的刚性烯氰离子液体单体;
步骤二,多孔聚离子液体材料制备;
将离子液体单体与质量比为100:35的氯化铝/氯化钠复合盐进行研磨混合,在手套箱研磨30min以上,控制单体与熔盐的质量百分比为1:30,加入引发剂过氧硫酸铵,用量为离子液体单体的1%,均匀混合后,转入管式马弗炉,在氮气保护下,置于120℃下加热聚合反应8h,继续升温至230℃下加热氰基缩合交联反应12h,冷却至室温,将凝胶产物加入10%的稀盐酸中,进行加热回流,去除熔盐,所得的聚离子液体依次用乙酸乙酯、乙醚洗涤3次,进行80℃烘箱中干燥12h,即得多孔聚离子液体材料,比表面积为348m2/g。
实施例2-7
除以下不同外,其余与实施例1相同,分别采用表1所示的叔胺化合物和卤代烃。
表1
实施例8-12
除以下不同外,其余与实施例1相同,分别采用表2所示的配阴离子。
表2
实施例12-14
除以下不同外,其余与实施例1相同,分别采用表3所示的单体与熔盐的质量百分比。
表3
实施例15
以实施例9的超交联聚离子液体材料催化苯甲醛与氰乙酸乙酯的脑文格反应。将苯甲醛与氰乙酸乙酯按摩尔比1:1.5进行混合,加入质量比1%的催化剂进行70℃加热搅拌4小时,GC测定收率达99%。催化剂经过滤回收,洗涤烘干后,重用8次,催化活性不变。
实施例16
以实施例1的超交联聚离子液体材料用于二氧化碳的吸附。取一定量的超交联聚离子液体材料,抽真空后,通入二氧化碳气体至大气压,然后,氮气吹扫后,GC在线测量二氧化碳的吸附量。结果表明材料对二氧化碳吸附具有很好的性能,吸附量高达30mg/g。
实施例17
以实施例5的超交联聚离子液体材料用于甲基橙染料废水处理。取甲基橙含量为40mg/L的废水中加入3%的超交联聚离子液体吸附剂,在室温搅拌30min后,采用紫外分光光度计测试,甲基橙的脱除率在99%,得无色透明水溶液。通过乙醇洗涤多次后,吸附剂可以重复循环使用。
以上仅为本发明的优选实施方式,应当指出,对于有机化学合成技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种超交联多孔聚离子液体材料的制备方法,其特征在于:将烯基叔胺与氯乙腈或者将氰基叔胺与溴丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种进行季铵化,形成刚性烯氰离子液体单体,并通过离子交换引入配阴离子,接着,在氯化铝/氯化钠复合熔盐体系中进行离子热烯基聚合和氰基交联,所述熔盐中氯化铝/氯化钠的质量比为100∶15~45,得到超交联多孔聚离子液体材料。
2.根据权利要求1所述的一种超交联多孔聚离子液体材料的制备方法,其特征在于:所述烯基叔胺为4-乙烯吡啶、2-乙烯吡啶、2-乙烯咪唑、三烯丙胺中的一种;所述氰基叔胺为4-氰基吡啶或2-氰基吡啶。
3.根据权利要求1所述的一种超交联多孔聚离子液体材料的制备方法,其特征在于:通过离子交换将卤素离子交换成四氟硼酸根、六氟磷酸根、二氰胺根、三氟甲磺酸根、双三氟甲磺酰亚胺根离子中的一种。
4.根据权利要求1-3中任一项所述的一种超交联多孔聚离子液体材料的制备方法,其特征是包含以下的具体操作步骤:
步骤一,刚性烯氰离子液体单体的制备;
将烯基叔胺与氯乙腈或者将氰基叔胺与溴丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种,按物质量之比为1∶1进行混合,加入阻聚剂,阻聚剂用量为总质量的1%,加入乙酸乙酯或四氢呋喃,配成40%的溶液后,在50~80℃下搅拌5~72h后得到相应离子液体,依次用乙酸乙酯、乙醚进行洗涤3次后,在60℃进行真空干燥,得刚性双烯离子液体单体,将刚性烯氰离子液体单体溶于一定有机溶剂后,配成质量比浓度为10~50%的溶液,加入含配阴离子盐中进行交换,盐的摩尔用量为单体的1.5倍,在50~80℃下加热搅拌,并加入1%的阻聚剂,交换后过滤除去相应盐,重复交换3次,减压脱除溶剂得相应配阴离子的刚性烯氰离子液体单体;
步骤二,多孔聚离子液体材料制备;
将上述步骤一种制备的离子液体单体与质量比为100∶15~45的氯化铝/氯化钠复合盐进行研磨混合,在手套箱研磨30min以上,控制单体与熔盐的质量百分比1∶10~45,加入引发剂过氧硫酸铵,用量为离子液体单体的1%,均匀混合后,转入管式马弗炉,在氮气保护下,置于100~150℃下加热聚合反应4~12h,继续升温至180~260℃下加热氰基缩合交联反应6~24h,冷却至室温,将凝胶产物加入10%的稀盐酸中,进行加热回流,去除熔盐,所得聚离子液体依次用乙酸乙酯、乙醚洗涤3次,进行80℃烘箱中干燥12h,即得多孔聚离子液体材料。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101723852A (zh) * | 2008-10-20 | 2010-06-09 | 浙江医药股份有限公司新昌制药厂 | 新型功能离子液体催化缩合芳香醛和活泼亚甲基化合物的方法 |
CN102728403A (zh) * | 2012-07-17 | 2012-10-17 | 石家庄学院 | 合成α-氰基肉桂酸乙酯的有机固体碱催化剂、其制备方法及其应用 |
CN104610486A (zh) * | 2015-02-04 | 2015-05-13 | 杭州锐沃科技有限公司 | 一种离子液体功能化超交联聚合物及其制备方法与应用 |
CN107814932A (zh) * | 2017-11-10 | 2018-03-20 | 山东师范大学 | 一种聚离子液体有机多孔聚合物及制备方法与应用 |
CN109400923A (zh) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | 一种超交联多孔聚离子液体材料的制备方法及应用 |
CN109400781A (zh) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | 一种超交联多孔聚离子液体材料的制备方法及其应用 |
CN109400771A (zh) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | 超交联多孔聚离子液体材料的制备方法及其应用 |
-
2018
- 2018-10-26 CN CN201811258110.2A patent/CN109400922B/zh not_active Expired - Fee Related
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101723852A (zh) * | 2008-10-20 | 2010-06-09 | 浙江医药股份有限公司新昌制药厂 | 新型功能离子液体催化缩合芳香醛和活泼亚甲基化合物的方法 |
CN102728403A (zh) * | 2012-07-17 | 2012-10-17 | 石家庄学院 | 合成α-氰基肉桂酸乙酯的有机固体碱催化剂、其制备方法及其应用 |
CN104610486A (zh) * | 2015-02-04 | 2015-05-13 | 杭州锐沃科技有限公司 | 一种离子液体功能化超交联聚合物及其制备方法与应用 |
CN107814932A (zh) * | 2017-11-10 | 2018-03-20 | 山东师范大学 | 一种聚离子液体有机多孔聚合物及制备方法与应用 |
CN109400923A (zh) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | 一种超交联多孔聚离子液体材料的制备方法及应用 |
CN109400781A (zh) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | 一种超交联多孔聚离子液体材料的制备方法及其应用 |
CN109400771A (zh) * | 2018-10-26 | 2019-03-01 | 绍兴文理学院 | 超交联多孔聚离子液体材料的制备方法及其应用 |
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