CN106496530A - 一种多孔有机聚合物骨架材料及其制备方法与应用 - Google Patents
一种多孔有机聚合物骨架材料及其制备方法与应用 Download PDFInfo
- Publication number
- CN106496530A CN106496530A CN201710008667.XA CN201710008667A CN106496530A CN 106496530 A CN106496530 A CN 106496530A CN 201710008667 A CN201710008667 A CN 201710008667A CN 106496530 A CN106496530 A CN 106496530A
- Authority
- CN
- China
- Prior art keywords
- organic polymer
- framework material
- porous organic
- porous
- polymer framework
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 230000001699 photocatalysis Effects 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 150000003568 thioethers Chemical class 0.000 claims abstract description 9
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 8
- 150000002466 imines Chemical class 0.000 claims abstract description 6
- 150000003462 sulfoxides Chemical class 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 241000238370 Sepia Species 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 210000000988 bone and bone Anatomy 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229960001866 silicon dioxide Drugs 0.000 claims description 4
- 230000005284 excitation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 150000008376 fluorenones Chemical class 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241001263092 Alchornea latifolia Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- GBTRMNJQEKCYRN-UHFFFAOYSA-N fluoren-2-one Chemical compound C1=CC=CC2=CC3=CC(=O)C=CC3=C21 GBTRMNJQEKCYRN-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000010970 precious metal Substances 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
本发明的一种多孔有机聚合物骨架材料及其制备方法与应用属于化学及新材料技术领域。以2,7‑二‑(氮‑咔唑基)‑9芴酮为结构基元，通过二甲醇缩甲醛作为交联剂，在路易斯酸催化剂的催化下获得以亚甲基联接的多孔有机聚合物骨架材料，所述的多孔有机聚合物骨架材料可应用于光催化有机胺选择性合成亚胺或光催化硫醚选择性合成亚砜。本发明具有操作简单、反应条件温和、适用性广泛等特点。
Description
技术领域
本发明属于化学及新材料技术领域,具体涉及一种多孔有机聚合物材料及其制备方法和应用。
背景技术
与传统的化石能源相比，光能是一种廉价清洁、无污染的绿色能源。它在自然界中储藏丰富，而且使用起来非常简便，具有很高的潜在应用前景。随着人们对工业生产所造成的环境汚染的关注日益密切，光能的有效利用己成为当今的热点研究课题。
多孔有机聚合物是一类新型的多孔材料，其具有高的比表面积、低的骨架密度以及优秀的化学稳定性等独特的性质，已在气体储存、吸附与分离、多相催化、能量存储、有机光电子等领域表现出潜在的应用。相比于分子筛和金属有机骨架等，多孔有机聚合物的优势在于可以选择具有特定功能的有机结构基元通过多种合成反应途径来制备，进而调节聚合物的孔参数与骨架性质。
到目前为止，以多孔有机聚合物作为非均相有机光催化剂的文献较少，而且一般是通过贵金属催化偶联的方法获得(Macromolecules 2013,46,8779；Chem.Mater.2015,27,1921；J.Mater.Chem.A 2014,2,18720；J.Am.Chem.Soc.2015,137,3265)。不但受限于单体上的反应基团，而且大大增加多孔聚合物的制备成本。因此，利用廉价的方法合成新一类具有高比表面积、良好稳定性和优秀的光催化效率的多孔有机聚合物在非均相有机光催化领域具有重要的意义。
发明内容
本发明的目的在于，针对现有技术的不足，提供一种可用于非均相有机光催化的多孔有机聚合物骨架材料及制备方法与用途。
本发明的目的是通过以下技术方案实现的：
一种多孔有机聚合物骨架材料，是以2,7-二-(氮-咔唑基)-9芴酮为结构基元，通过二甲醇缩甲醛作为交联剂，在路易斯酸催化剂的催化下获得以亚甲基联接的多孔有机聚合物骨架材料。
本发明的一种多孔有机聚合物骨架材料，所述的路易斯酸催化剂优选FeC l3或AlCl3。
一种多孔有机聚合物骨架材料的制备方法，具体步骤为：在惰性气体保护下，将2,7-二-(氮-咔唑基)-9芴酮、二甲醇缩甲醛和路易斯酸催化剂按摩尔比1～4：8：8置于容器中，向其中加入有机溶剂并混合，所述的有机溶剂的用量为每mmol2,7-二-(氮-咔唑基)-9芴酮使用1-100ml，将得到的混合液在30-120℃搅拌6-120小时，待反应结束后，将体系冷却至室温，将反应生成的固体过滤、清洗、真空干燥后得到棕褐色多孔有机聚合物骨架材料。
本发明的一种多孔有机聚合物骨架材料的制备方法中，所述的有机溶剂优选1,2-二氯乙烷或氯仿，用量优选每mmol2,7-二-(氮-咔唑基)-9芴酮使用20ml。
本发明的一种多孔有机聚合物骨架材料的制备方法中，搅拌时间优选24小时，搅拌时的温度优选80℃。
本发明的一种多孔有机聚合物骨架材料的制备方法中，所述的清洗可以按以下步骤进行：依次分别加入甲醇、水、二氯甲烷、丙酮，加入量均为反应过程中所用的2,7-二-(氮-咔唑基)-9芴酮质量的10-50倍，利用丙酮、甲醇分别索氏提取1-48小时。
本发明制备的多孔有机聚合物骨架材料具有高的比表面积、大的孔容和良好的光吸收性能，可以作为非均相催化剂应用在光催化领域。
一种多孔有机聚合物骨架材料的用途，其特征在于，将所述的多孔有机聚合物骨架材料应用于光催化有机胺选择性合成亚胺，具体操作为：在玻璃密闭反应器中加入有机胺、乙腈、多孔有机聚合物骨架材料，以氧气作为氧源，绿色的荧光灯作为激发光源，25℃下搅拌反应6～12小时，其中多孔有机聚合物骨架材料与有机胺的摩尔比为0.5～10:100，每mmol多孔有机聚合物骨架材料使用20～300ml的乙腈，反应混合物经过滤、萃取、干燥过微型硅胶柱得到亚胺产物。
一种多孔有机聚合物骨架材料的用途，其特征在于，将所述的多孔有机聚合物骨架材料应用于光催化硫醚选择性合成亚砜，具体操作为：在玻璃密闭反应器中加入硫醚、多孔有机聚合物骨架有混合溶剂，以氧气作为氧源，绿色的荧光灯作为激发光源，25℃下搅拌反应6～12小时，其中多孔有机聚合物骨架材料与硫醚的摩尔比为0.5～10:100，每mmol多孔有机聚合物骨架材料使用20～300ml混合溶剂，所述的混合溶剂是体积比为5：2的乙腈和甲醇的混合液，反应混合物经过滤、萃取、干燥过微型硅胶柱，得到亚砜产物。
在本发明的实施例中，通过测定本发明多孔有机聚合物骨架材料的傅立叶红外光谱证实材料确实是由2,7-二-(氮-咔唑基)-9芴酮与交联剂反应获得[参见：C.D.Wood,B.Tan,A.Trewin,H.J.Niu,D.Bradshaw,M.J.Rosseinsky,Y.Z.Kyimyak,N.L.Campbell,R.Kirk,E.Stockel,A.I.Cooper,Chemistry of Materials,2007,19,2034.]；通过测定氮气吸附-脱附曲线计算本发明多孔聚合物骨架材料的比表面积、孔尺寸和孔体积；通过多孔有机聚合物骨架材料的催化实验证明其催化活性。
有益效果：
1、本发明采用廉价的路易斯酸催化剂。
2、本发明采用的制备方法非常简单，反应条件温和，可以在一个反应器皿中一步完成多孔有机聚合物的合成。
3、本发明采用的合成方法具有广泛的适用性。
4、本发明合成材料可作为光催化剂，在光照的下室温即可高效催化有机胺选择性合成亚胺及硫醚选择性合成亚砜，具有高度的原子经济性。
附图说明：
图1是实施例1中的多孔有机聚合物骨架材料的傅立叶红外图谱(IR)。
图2是实施例1中的多孔有机聚合物骨架材料的热失重图谱(TGA)。
图3是实施例1中的多孔有机聚合物骨架材料的吸收图谱(IR)。
图4是实施例1中多孔有机聚合物骨架材料的氮气吸附-脱附等温线(77K)。
图5是实施例2中多孔有机聚合物骨架材料的氮气吸附-脱附等温线(77K)。
图6是实施例3中多孔有机聚合物骨架材料的氮气吸附-脱附等温线(77K)。
具体实施方式
以下实施例将有助于理解本发明，但本发明的保护范围并不限于此内容，实施例1-3为本发明的一种多孔有机聚合物骨架材料的制备方法，实施例4-5为多孔有机聚合物骨架材料在非均相光催化领域的的应用。
实施例1
在惰性气体保护下，将2,7-二-(氮-咔唑基)-9芴酮(108.5mg,0.2mmol),二甲醇缩甲醛(70.8μL,0.8mmol)和FeCl3(0.13g,0.8mmol)置于50mL圆底烧瓶中，向其中加入4mL的1,2-二氯乙烷，混合液在80℃搅拌24h。待反应结束后，将体系冷却至室温，将反应生成的固体过滤，依次用10～30毫升的甲醇、水、二氯甲烷、丙酮清洗，利用丙酮、甲醇分别索氏提取12小时。将索氏提取后的固体产物真空干燥后得到棕褐色多孔有机聚合物骨架材料。
用比表面积及孔径分析仪(JW-BK 132F)对其进行比表面积及孔径分布检测，测得比表面积为1217m2g-1。孔体积为0.92cm3g-1。孔尺寸分布在0.6、0.8、1.1、2.1nm。
实施例2
在惰性气体保护下，将2,7-二-(氮-咔唑基)-9芴酮(108.5mg,0.2mmol),二甲醇缩甲醛(35.4μL,0.4mmol)和FeCl3(0.065g,0.4mmol)置于50mL圆底烧瓶中，向其中加入4mL的1,2-二氯乙烷，混合液在80℃搅拌24h。待反应结束后，将体系冷却至室温，将反应生成的固体过滤，依次用10～30毫升的甲醇、水、二氯甲烷、丙酮清洗，利用丙酮、甲醇分别索氏提取12小时。将索氏提取后的固体产物真空干燥后得到棕褐色多孔有机聚合物骨架材料。
用比表面积及孔径分析仪(JW-BK 132F)对其进行比表面积及孔径分布检测，测得比表面积为735m2g-1。孔体积为0.50cm3g-1。孔尺寸分布在0.6、1.0、1.2、2.3nm。
实施例3
在惰性气体保护下，将2,7-二-(氮-咔唑基)-9芴酮(108.5mg,0.2mmol),二甲醇缩甲醛(106.2μL,1.2mmol)和FeCl3(0.195g,1.2mmol)置于50mL圆底烧瓶中，向其中加入4mL的1,2-二氯乙烷，混合液在80℃搅拌24h。待反应结束后，将体系冷却至室温，将反应生成的固体过滤，依次用10～30毫升的甲醇、水、二氯甲烷、丙酮清洗，利用丙酮、甲醇分别索氏提取12小时。将索氏提取后的固体产物真空干燥后得到棕褐色多孔有机聚合物骨架材料。
用比表面积及孔径分析仪(JW-BK 132F)对其进行比表面积及孔径分布检测，测得比表面积为654m2g-1。孔体积为0.48cm3g-1。孔尺寸分布在0.5、0.8、1.1、2.3nm。
实施例4
称取实施例1中制备获得的多孔有机聚合物骨架材料5毫克(0.0088mmol)，加入到反应瓶中，加入2mL乙腈和0.2mmol有机胺，在氧气条件、25℃、搅拌条件下利用绿色的荧光灯(功率30W，波长520nm)照射6小时。反应完毕后，利用1H-NMR计算产物收率，结果见表1。
表1多项催化剂催化活性举例
实施例5
称取实施例1中制备获得的多孔有机聚合物骨架材料5毫克(0.0088mmol)，加入到反应瓶中，加入2mL乙腈、0.8mL甲醇和0.2mmol硫醚，在氧气条件、25℃、搅拌下利用绿色的荧光灯(功率100W，波长520nm)照射6小时。反应完毕后，利用GC计算产物收率，结果见表2。
表2多项催化剂催化活性举例
Claims (8)
1.一种多孔有机聚合物骨架材料，是以2,7-二-(氮-咔唑基)-9芴酮为结构基元，通过二甲醇缩甲醛作为交联剂，在路易斯酸催化剂的催化下获得以亚甲基联接的多孔有机聚合物骨架材料。
2.根据权利要求1所述的一种多孔有机聚合物骨架材料，其特征在于，所述的路易斯酸催化剂是FeCl3或AlCl3。
3.一种权利要求1的多孔有机聚合物骨架材料的制备方法，具体步骤为：在惰性气体保护下，将2,7-二-(氮-咔唑基)-9芴酮、二甲醇缩甲醛和路易斯酸催化剂按摩尔比1～4：8：8置于容器中，向其中加入有机溶剂并混合，所述的有机溶剂的用量为每mmol2,7-二-(氮-咔唑基)-9芴酮使用1-100ml，将得到的混合液在30-120℃搅拌6-120小时，待反应结束后，将体系冷却至室温，将反应生成的固体过滤、清洗、真空干燥后得到棕褐色多孔有机聚合物骨架材料。
4.根据权利要求3所述的一种多孔有机聚合物骨架材料的制备方法，其特征在于，所述的有机溶剂是1,2-二氯乙烷或氯仿，用量为每mmol2,7-二-(氮-咔唑基)-9芴酮使用20ml。
5.根据权利要求3所述的一种多孔有机聚合物骨架材料的制备方法，其特征在于，搅拌时间为24小时，搅拌时的温度为80℃。
6.根据权利要求3～5任一所述的一种多孔有机聚合物骨架材料的制备方法，其特征在于，所述的清洗是按以下步骤进行的：依次分别加入甲醇、水、二氯甲烷、丙酮，加入量均为反应过程中所用的2,7-二-(氮-咔唑基)-9芴酮质量的10-50倍，利用丙酮、甲醇分别索氏提取1-48小时。
7.一种权利要求1的多孔有机聚合物骨架材料的用途，其特征在于，将所述的多孔有机聚合物骨架材料应用于光催化有机胺选择性合成亚胺，具体操作为：在玻璃密闭反应器中加入有机胺、乙腈、多孔有机聚合物骨架材料，以氧气作为氧源，绿色的荧光灯作为激发光源，25℃下搅拌反应6～12小时，其中多孔有机聚合物骨架材料与有机胺的摩尔比为0.5～10:100，每mmol多孔有机聚合物骨架材料使用20～300ml的乙腈，反应混合物经过滤、萃取、干燥过微型硅胶柱得到亚胺产物。
8.一种权利要求1的多孔有机聚合物骨架材料的用途，其特征在于，将所述的多孔有机聚合物骨架材料应用于光催化硫醚选择性合成亚砜，具体操作为：在玻璃密闭反应器中加入硫醚、多孔有机聚合物骨架有混合溶剂，以氧气作为氧源，绿色的荧光灯作为激发光源，25℃下搅拌反应6～12小时，其中多孔有机聚合物骨架材料与硫醚的摩尔比为0.5～10:100，每mmol多孔有机聚合物骨架材料使用20～300ml混合溶剂，所述的混合溶剂是体积比为5：2的乙腈和甲醇的混合液，反应混合物经过滤、萃取、干燥过微型硅胶柱，得到亚砜产物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710008667.XA CN106496530B (zh) | 2017-01-06 | 2017-01-06 | 一种多孔有机聚合物骨架材料及其制备方法与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710008667.XA CN106496530B (zh) | 2017-01-06 | 2017-01-06 | 一种多孔有机聚合物骨架材料及其制备方法与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106496530A true CN106496530A (zh) | 2017-03-15 |
| CN106496530B CN106496530B (zh) | 2018-09-11 |
Family
ID=58345092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710008667.XA Expired - Fee Related CN106496530B (zh) | 2017-01-06 | 2017-01-06 | 一种多孔有机聚合物骨架材料及其制备方法与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106496530B (zh) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109655569A (zh) * | 2019-01-31 | 2019-04-19 | 烟台大学 | 一种尿液中苯丙胺类物质的spme-gc检测方法 |
| CN110075919A (zh) * | 2019-06-04 | 2019-08-02 | 中国科学院上海高等研究院 | 含柱[5]芳烃共轭聚合物在光催化氧化硫醚中作为催化剂的用途 |
| CN110452365A (zh) * | 2019-08-01 | 2019-11-15 | 广东省工业分析检测中心 | 一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用 |
| CN111215149A (zh) * | 2020-03-10 | 2020-06-02 | 辽宁大学 | 一种MOF@POP-n复合催化剂及其制备方法和应用 |
| CN113509906A (zh) * | 2021-06-11 | 2021-10-19 | 西安交通大学 | 一种具有吸附脱硫性能的有机多孔骨架材料及其制备方法 |
| CN114933704A (zh) * | 2022-06-02 | 2022-08-23 | 南昌大学 | 一种杂原子连接的多孔有机聚合物的制备方法及其光催化解毒硫芥模拟物应用 |
-
2017
- 2017-01-06 CN CN201710008667.XA patent/CN106496530B/zh not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| COLIN D. WOOD ET AL.: "Hydrogen Storage in Microporous Hypercrosslinked Organic Polymer Networks", 《CHEM. MATER.》 * |
| ZHIYU DOU ET AL.: "Metalloporphyrin-Based Hypercrosslinked Polymers Catalyze Hetero-Diels–Alder Reactions of Unactivated Aldehydes with Simple Dienes: A Fascinating Strategy for the Construction of Heterogeneous Catalysts", 《CHEMISTRY A EUROPEAN JOURNAL COMMUNICATION 》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109655569A (zh) * | 2019-01-31 | 2019-04-19 | 烟台大学 | 一种尿液中苯丙胺类物质的spme-gc检测方法 |
| CN109655569B (zh) * | 2019-01-31 | 2021-10-26 | 烟台大学 | 一种尿液中苯丙胺类物质的spme-gc检测方法 |
| CN110075919A (zh) * | 2019-06-04 | 2019-08-02 | 中国科学院上海高等研究院 | 含柱[5]芳烃共轭聚合物在光催化氧化硫醚中作为催化剂的用途 |
| CN110075919B (zh) * | 2019-06-04 | 2022-02-22 | 中国科学院上海高等研究院 | 含柱[5]芳烃共轭聚合物在光催化氧化硫醚中作为催化剂的用途 |
| CN110452365A (zh) * | 2019-08-01 | 2019-11-15 | 广东省工业分析检测中心 | 一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用 |
| CN110452365B (zh) * | 2019-08-01 | 2022-02-11 | 广东省工业分析检测中心 | 一种共轭多孔聚合物及其制备方法与在光催化伯胺氧化制备亚胺的应用 |
| CN111215149A (zh) * | 2020-03-10 | 2020-06-02 | 辽宁大学 | 一种MOF@POP-n复合催化剂及其制备方法和应用 |
| CN111215149B (zh) * | 2020-03-10 | 2022-07-19 | 辽宁大学 | 一种MOF@POP-n复合催化剂及其制备方法和应用 |
| CN113509906A (zh) * | 2021-06-11 | 2021-10-19 | 西安交通大学 | 一种具有吸附脱硫性能的有机多孔骨架材料及其制备方法 |
| CN114933704A (zh) * | 2022-06-02 | 2022-08-23 | 南昌大学 | 一种杂原子连接的多孔有机聚合物的制备方法及其光催化解毒硫芥模拟物应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106496530B (zh) | 2018-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106496530B (zh) | 一种多孔有机聚合物骨架材料及其制备方法与应用 | |
| CN102050919B (zh) | 负载型咪唑离子液体交联聚合物纳米粒子及其制备和应用 | |
| CN107459656B (zh) | 一种离子化共价有机框架材料及其制备方法和催化应用 | |
| CN106947022B (zh) | 一种氮杂环卡宾金属多孔有机聚合物的制备及其应用 | |
| CN110746602B (zh) | 一种金属钴卟啉基多孔有机聚合物及其制备方法和应用 | |
| CN106084217B (zh) | 一种三嗪基多孔聚合物材料、Ag/三嗪基多孔聚合物催化剂及其将二氧化碳转化为炔酸的应用 | |
| CN111286010B (zh) | 一种亲油超疏水多孔芳香骨架材料及其制备方法和应用 | |
| Girija et al. | Cerium oxide nanoparticles-a green, reusable, and highly efficient heterogeneous catalyst for the synthesis of Polyhydroquinolines under solvent-free conditions | |
| CN103480353A (zh) | 一种用水热法合成碳量子点溶液制备复合纳米光催化剂的方法 | |
| CN102963877B (zh) | 一种大比表面积、高孔体积硅藻土模板炭及其制备方法 | |
| CN105251535A (zh) | 一种多孔有机聚合物材料及其制备方法 | |
| Wang et al. | Porous organic frameworks with mesopores and [Ru (bpy) 3] 2+ ligand built-in as a highly efficient visible-light heterogeneous photocatalyst | |
| CN109201113A (zh) | 一种功能化金属有机骨架复合材料及其制备方法 | |
| CN110560170A (zh) | 一种新型Pd@MOF材料及其制备方法和其在联苯制备中的应用 | |
| CN114832863B (zh) | 一种多级孔金属有机框架材料及其制备方法和应用 | |
| CN102909070A (zh) | 一种负载型手性催化剂及其制备方法 | |
| Du et al. | Dehydrative Formation of Isosorbide from Sorbitol over Poly (ionic liquid)–Covalent Organic Framework Hybrids | |
| CN107382718A (zh) | CaO/MCF介孔碱性分子筛催化醇解聚乳酸的方法 | |
| CN105665017A (zh) | 一种用于Suzuky-Miyaura偶联反应的负载型Pd催化剂及其制备方法 | |
| Tao et al. | Synthesis, characterization and photocatalytic properties of BiOBr/amidoxime fiber composites | |
| CN108276574B (zh) | 一种环己二胺基多孔共价有机骨架化合物及其制备方法 | |
| CN105778062A (zh) | 一种聚合物及其制备方法 | |
| CN105597705B (zh) | 一种具有优异co2吸附与分离性能的超微孔共价三嗪骨架材料以及制备方法 | |
| CN110201718A (zh) | 一种红磷/铁基金属有机骨架复合材料的制备及应用 | |
| CN108864435A (zh) | 一种二维共价有机框架及其制备方法和用途 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180911 |