CN111285986B - 含杂原子、亚胺和三嗪环结构富氮多孔聚合物及制备方法 - Google Patents
含杂原子、亚胺和三嗪环结构富氮多孔聚合物及制备方法 Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 72
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 37
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 34
- 150000002466 imines Chemical group 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920000768 polyamine Polymers 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 2
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 17
- 239000007789 gas Substances 0.000 abstract description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052740 iodine Inorganic materials 0.000 abstract description 7
- 239000011630 iodine Substances 0.000 abstract description 7
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000000944 Soxhlet extraction Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical group C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 4
- 229930192474 thiophene Chemical group 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical group C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 101710205482 Nuclear factor 1 A-type Proteins 0.000 description 3
- 101710170464 Nuclear factor 1 B-type Proteins 0.000 description 3
- 102100022162 Nuclear factor 1 C-type Human genes 0.000 description 3
- 101710113455 Nuclear factor 1 C-type Proteins 0.000 description 3
- 101710140810 Nuclear factor 1 X-type Proteins 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000013311 covalent triazine framework Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- -1 cyano compound Chemical class 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNPMXMIWHVZGMJ-UHFFFAOYSA-N pyridine-2,6-dicarbonitrile Chemical compound N#CC1=CC=CC(C#N)=N1 XNPMXMIWHVZGMJ-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XHHXPPGVKPGDAH-UHFFFAOYSA-N NC1=NC(=NC(=N1)N)C1(C(=C(C(C=C1)(N)C1=NC(=NC(=N1)N)N)N)N)N Chemical compound NC1=NC(=NC(=N1)N)C1(C(=C(C(C=C1)(N)C1=NC(=NC(=N1)N)N)N)N)N XHHXPPGVKPGDAH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000007854 aminals Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/16—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom
- C07D251/18—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to only one ring carbon atom with nitrogen atoms directly attached to the two other ring carbon atoms, e.g. guanamines
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- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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Abstract
本发明属于高分子材料领域,涉及一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物及制备方法。将用惰性气体置换好的反应瓶中加入含三嗪环和杂原子结构多元胺单体,醛基单体和非质子性有机溶剂后,再将反应瓶置换惰性气体两次以上,反应物缓慢升温至100℃‑210℃反应10h‑100h,反应结束后将混合物抽滤,并分别用极性非质子溶剂和有机溶剂清洗后,然后过滤并干燥得到产物。本发明制备得到的富氮多孔聚合物具有比表面积高、气体吸附量高的特点,并且对碘蒸气具有快速高效的吸附性能。同时本发明所涉及到的聚合物,其合成方法简单,热稳定性、化学稳定性均较好,满足气体吸附和储存、非均相催化等要求,具有很好的应用前景。
Description
技术领域
本发明属于高分子科学技术领域,涉及到功能性高分子材料及其制备方法,特别涉及到一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物及制备方法。
背景技术
多孔聚合物(POPs)是一类由有机分子通过共价键连接而成的有机多孔材料,主要有碳、氮、氧、硼等院子组成,相比于金属有机框架材料(MOFs)、活性炭和分子筛等材料,多孔聚合物可以在很大范围内通过改变构筑分子的官能团和链长以及采用不同的合成方法来调节其结构和性能,并且多孔聚合物相比于金属有机框架材料具有较高的化学稳定性和热稳定性。多孔聚合物在气体存储、吸附、分离、储能和非均相催化等方面具有潜在的应用。Thomas等人报道了ZnCl2催化二腈单体制备了CTF多孔有机聚合物,具有很高的比表面积,表现出无定型微介孔的性质。有研究也报道了含二氮杂萘酮联苯结构和三嗪环结构CTF多孔有机聚合物。但上述反应均需要在400℃以上高温反应。谭必恩等人(Angew.Chem.-Int.Edit.,2017,56(45):14149)通过醛和氨基二盐酸盐之间的缩合反应成功地在120℃温和的条件下构筑含三嗪环结构CTFs。Bhaumik等人(ACS Appl.Mater.Interfaces 2018,10,23813)报道了以1,4-双(4,6-二氨基-s-三嗪基)苯四元胺单体与醛基化合物反应合成了含三嗪环和缩醛胺结构微孔有机聚合物。
上述发明和文献均未涉及到含杂原子、亚胺和三嗪环结构富氮多孔聚合物及其制备法。关于含三嗪和亚胺结构富氮多孔聚合物及其制备法未见于有关专利技术报道,也未在国内外公开出版物中出现。
发明内容
本发明的目的在于提供一种含杂原子、亚胺和三嗪环结构的富氮多孔聚合物及其制备方法。本发明以氰基化合物为原料合成含有三嗪环和杂原子结构的多元胺,并与醛基化合物反应,合成含有三嗪环和亚胺结构的富氮多孔聚合物。本发明通过在微孔聚合物结构中引入N、O、S或P等杂原子、三嗪环结构和亚胺(N-H)结构有利于对CO2、碘蒸气、有机化合物等的高效吸附。
本发明的技术方案:
一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,聚合反应步骤如下:将用惰性气体置换好的反应瓶中加入含杂原子和三嗪环结构多元胺单体,再加入醛基单体,并加入极性非质子溶剂作为溶剂,其中,多元胺单体和醛基单体的总摩尔浓度为0.05~1mol/L,多元胺单体中氨基与醛基单体中醛基的摩尔比为1:0.9~1:1.1;将反应瓶置换惰性气体两次以上,反应物缓慢升温至100℃-210℃反应10h-100h,反应结束后将混合物过滤,并分别用极性非质子溶剂和有机溶剂清洗,然后过滤并干燥,得到含杂原子、亚胺和三嗪环结构富氮多孔聚合物。
所述的含杂原子和三嗪环结构多元胺单体的制备方法,反应式如下:
步骤如下:将二腈单体、二氰二胺和碱混合均匀,以醇醚溶剂为反应溶剂,其中,二腈单体、二氰二胺和碱的摩尔比为1:(4~10):(1.1~10),二腈单体和二氰二胺摩尔总浓度为0.05~5mol/L;在惰性气体氛围下逐步升温至80℃-160℃,反应1h-24h;将反应后得到的悬浊液倒入水中,并将产物固体滤出,用水洗2次以上,经干燥后得到含杂原子和三嗪环结构多元胺单体。
所述的碱为碱金属碳酸盐或碱金属氢氧化物中的一种或两种以上混合。
所述的醇醚溶剂为乙二醇单甲醚、乙二醇二甲醚、乙二醇单乙醚、乙二醇二乙醚、丙二醇单甲醚、丙二醇二甲醚、丙二醇单乙醚、丙二醇二乙醚中的一种或两种以上混合。
所述的极性非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、乙二醇甲醚、甲醇、乙醇、丙酮、四氢呋喃、氯仿、甲苯中的一种或两种以上混合。
所述的有机溶剂为四氢呋喃、丙酮、甲醇、乙醇、乙醚中的一种或两种以上混合。
所述的惰性气体为氮气、氩气、氦气中的一种或两种以上混合。
本发明的有益效果:
1、本发明通过N、O、S或P等杂原子、亚胺(N-H)和三嗪环等富氮结构对多孔聚合物的修饰及其对被吸附分子的协同作用,有利于多孔聚合物对CO2、碘蒸气等气体或有机化合物的高效吸附,具有高比表面积,比表面积最高可达1250m2g-1以上,在273K、1bar条件下吸附量最高可达13wt%以上,并且对碘蒸气具有快速的吸附性能,最高可在20min内吸附量可达243wt%。
2、本发明通过构筑含有微孔、介孔和大孔的多孔聚合物,既有利于对气体或有机化合物的吸附,又有利于气体分子或有机化合物在孔道中的传质,提高吸附分离效率。
3、本发明通过调节聚合单体中杂原子的结构和含量、多元胺单体的氨基含量和醛基单体的醛基含量,可以调节多孔聚合物的杂原子含量、交联密度、孔道结构,进而可以调节多孔聚合物的性能。
4、本发明所涉及到的聚合物,其合成方法简单,热稳定性、化学稳定性均较好,满足气体吸附储存环境要求,在气体吸附捕获、有机蒸汽吸附、非均相催化等领域具有很好的应用前景。
具体实施方式
以下通过实例进一步详细说明本发明涉及的含杂原子、亚胺和三嗪环结构的富氮多孔聚合物,但不表示对本发明的限制。
实施例1,含三嗪环、二氮杂萘酮联苯和亚胺结构富氮多孔聚合物PAN-TPAHPZ的制备
三[4-(4-(2-(4-氰基苯基))-2,3-二氮杂萘-1-酮)苯基]胺(TPAHPZ-TN)(2mmol),二氰二胺(12mmol),KOH(4mmol)和乙二醇甲醚(2.8mL)于三口烧瓶中混合均匀后在氮气氛围下逐步升温至160℃反应1h。将反应后得到悬浊液沉入热水,并将固体产物滤出,用热水洗涤,干燥后得到含三嗪环、二氮杂萘酮联苯结构多元胺单体TPAHPZ-TDA。
将置换好氮气的反应瓶中加入多元胺单体TPAHPZ-TDA(0.4mmol)、苯甲醛(2.4mmol)和二甲基亚砜(DMSO,2.8mL)后再置换氮气三次。反应物缓慢升温至100℃并在DMSO回流下反应100h。之后将混合物抽滤并分别用N,N-二甲基甲酰胺和甲醇清洗得到固体,再将固体粗产物分别用四氢呋喃、甲醇和丙酮索提,最后将产物干燥得到含三嗪环、二氮杂萘酮联苯和亚胺结构多孔聚合物PAN-TPAHPZ,其理论N元素含量为17.5%,O元素含量2.7%,比表面积(BET)为1054m2g-1,孔径主要分布在0.5nm~40nm,以微孔和介孔为主,含有少量大孔结构;在273K,1bar条件下为12.05wt%;在75℃条件下,多孔聚合物PAN-TPAHPZ在20min时对碘蒸气吸附量高达216wt%。
其反应式如下:
实施例2,含吡啶、三嗪环、噻吩和亚胺结构多孔聚合物PAN-POTDA的制备
称取吡啶2,6-二腈(2mmol)、二氰二胺(8mmol)、KOH(2.2mmol)和乙二醇二乙醚(200mL),将其加入三口烧瓶中混合均匀后,在氮气氛围下逐步升温至80℃,反应24h。将反应后得到的悬浊液倒入热水中,并将产物固体滤出,用热水洗,干燥后得到含吡啶和三嗪环结构多元胺单体POTDA。
将置换好氮气的反应瓶中加入多元胺单体POTDA(2.0mmol)、2-噻吩甲醛(8.0mmol)和N-甲基吡咯烷酮(NMP,200mL)后再置换氮气三次。反应物缓慢升温至210℃反应10h。之后将混合物抽滤并分别用N,N-二甲基甲酰胺和甲醇清洗得到固体,再将固体粗产物分别用四氢呋喃、乙醇和丙酮索提,最后将产物在烘干得到含吡啶、三嗪环、噻吩和亚胺结构多孔聚合物PAN-POTDAS,其理论N元素含量为22.7%,S元素含量为18.9%比表面积(BET)为1130m2g-1,以微孔和介孔为主,含有少量大孔结构;在273K,1bar条件下为13.11wt%;在75℃条件下,多孔聚合物PAN-POTDAS在20min时对碘蒸气吸附量即可达到170wt%。
其反应式如下:
实施例3,含吡啶环、三嗪环和亚胺结构多孔聚合物PAN-POTDA的制备
称取吡啶2,6-二腈(2mmol)、二氰二胺(20mmol)、KOH(20mmol)和乙二醇二乙醚(200mL),将其加入三口烧瓶中混合均匀后,在氮气氛围下逐步升温至150℃,反应10h。将反应后得到的悬浊液倒入热水中,并将产物固体滤出,用热水洗,干燥后得到含吡啶环和三嗪环结构多元胺单体POTDA。
将置换好氮气的反应瓶中加入多元胺单体POTDA(2.0mmol)、对苯二甲醛(8.0mmol)和二甲基亚砜(DMSO,60mL)后再置换氮气三次。反应物缓慢升温至180℃反应50h。之后将混合物抽滤并分别用N,N-二甲基甲酰胺和甲醇清洗得到固体,再将固体粗产物分别用四氢呋喃、乙醇和丙酮索提,最后将产物在烘干得到含吡啶环、三嗪环和亚胺结构多孔聚合物PAN-POTDA,其理论N元素含量为22.7%,比表面积(BET)为1200m2g-1,以微孔和介孔为主,含有少量大孔结构,在273K,1bar条件下为13.56wt%;在75℃条件下,多孔聚合物PAN-POTDA在20min时对碘蒸气吸附量即可达到196wt%。
其结构式如下所示:
实施例4,含三苯胺、噻吩、三嗪环和亚胺结构多孔聚合物的制备
称取4,4′,4″-三氰基三苯胺(TDATPA,2mmol)、二氰二胺(12mmol)、KOH(4mmol)和乙二醇甲醚(30mL),将其加入三口烧瓶中混合均匀后,在氮气氛围下逐步升温至150℃,反应12h。将反应后得到的悬浊液倒入热水中,并将固体产物滤出,用热水洗,经干燥后得到含三苯胺和三嗪环结构多元胺单体(TDATPA)。
将置换好氮气的反应瓶中加入TDATPA(1.0mmol),2-噻吩甲醛(6.0mmol)和DMSO(35mL)后再置换氮气三次,升温至180℃反应72小时后,将混合物抽滤并分别用N,N-二甲基甲酰胺和甲醇清洗得到固体,再将固体粗产物分别用四氢呋喃、甲醇和丙酮索提,干燥后得到含三苯胺、三嗪环、噻吩和亚胺结构多孔聚合物PAN-TDATPA,其理论N元素含量为19.7%,S元素含量为16.9%,比表面积为1254m2g-1,以微孔和介孔为主,含有少量大孔结构;在273K,1bar条件下为12.06wt%,在75℃条件下,多孔聚合物PAN-TDATPA在20min时对碘蒸气吸附量可达到243wt%。
其结构式如下所示:
Claims (9)
2.一种如权利要求1所述的含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,聚合反应步骤如下:将用惰性气体置换好的反应瓶中加入含杂原子和三嗪环结构多元胺单体,再加入醛基单体,并加入极性非质子溶剂作为溶剂,其中,多元胺单体和醛基单体的总摩尔浓度为0.05~1mol/L,多元胺单体中氨基与醛基单体中醛基的摩尔比为1:0.9~1:1.1;将反应瓶置换惰性气体两次以上,反应物缓慢升温至100℃-210℃反应10h-100h,反应结束后将混合物过滤,并分别用极性非质子溶剂和有机溶剂清洗,然后过滤并干燥,得到含杂原子、亚胺和三嗪环结构富氮多孔聚合物。
4.根据权利要求3所述的一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,所述的碱为碱金属碳酸盐或碱金属氢氧化物中的一种或两种以上混合。
5.根据权利要求3或4所述的一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,所述的醇醚溶剂为乙二醇单甲醚、乙二醇二甲醚、乙二醇单乙醚、乙二醇二乙醚、丙二醇单甲醚、丙二醇二甲醚、丙二醇单乙醚、丙二醇二乙醚中的一种或两种以上混合。
6.根据权利要求2、3或4所述的一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,所述的极性非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、乙二醇甲醚、甲醇、乙醇、丙酮、四氢呋喃、氯仿、甲苯中的一种或两种以上混合。
7.根据权利要求5所述的一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,所述的极性非质子溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、N-甲基吡咯烷酮、乙二醇甲醚、甲醇、乙醇、丙酮、四氢呋喃、氯仿、甲苯中的一种或两种以上混合。
8.根据权利要求2、3或4所述的一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,所述的有机溶剂为四氢呋喃、丙酮、甲醇、乙醇、乙醚中的一种或两种以上混合。
9.根据权利要求2、3或4所述的一种含杂原子、亚胺和三嗪环结构富氮多孔聚合物的制备方法,其特征在于,所述的惰性气体为氮气、氩气、氦气中的一种或两种以上混合。
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