CN114805756B - 一种金刚烷基微孔材料及其制备方法 - Google Patents
一种金刚烷基微孔材料及其制备方法 Download PDFInfo
- Publication number
- CN114805756B CN114805756B CN202210570055.0A CN202210570055A CN114805756B CN 114805756 B CN114805756 B CN 114805756B CN 202210570055 A CN202210570055 A CN 202210570055A CN 114805756 B CN114805756 B CN 114805756B
- Authority
- CN
- China
- Prior art keywords
- adamantyl
- tetrahydrofuran
- microporous material
- dibromodiamantane
- aromatic monomer
- 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.)
- Active
Links
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 title claims abstract description 44
- 239000012229 microporous material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 claims abstract description 4
- MQFBWJOMLIHUDY-UHFFFAOYSA-N 2,3,4,5-tetraphenylthiophene Chemical compound C1=CC=CC=C1C1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)S1 MQFBWJOMLIHUDY-UHFFFAOYSA-N 0.000 claims abstract description 4
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 claims abstract description 4
- QBHWPVJPWQGYDS-UHFFFAOYSA-N hexaphenylbenzene Chemical compound C1=CC=CC=C1C(C(=C(C=1C=CC=CC=1)C(C=1C=CC=CC=1)=C1C=2C=CC=CC=2)C=2C=CC=CC=2)=C1C1=CC=CC=C1 QBHWPVJPWQGYDS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 38
- 238000004458 analytical method Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013317 conjugated microporous polymer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
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
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
- C08G61/126—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 sulfur atom in the ring
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
-
- 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
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- 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
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- 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
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- 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
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- 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
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/598—Chemical stability
-
- 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
- C08G2261/50—Physical properties
- C08G2261/61—Permeability
- C08G2261/612—Permeability for gases
-
- 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
- C08G2261/50—Physical properties
- C08G2261/61—Permeability
- C08G2261/614—Permeability for liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种金刚烷基微孔材料及其制备方法，所述制备包括以下步骤：(1)在干燥容器内加入1,3‑二溴金刚烷、芳香单体、催化剂和溶剂，混合；其中，1,3‑二溴金刚烷与芳香单体摩尔比例为1:0.3‑0.7；(2)加热至30‑100℃，反应6‑72h；(3)反应完成后，抽滤取固体部分，依次用N,N‑二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤；(4)采用四氢呋喃、甲醇或氯仿中的任意一种提取至少48h，产物在100‑150℃下真空干燥24‑48h，即得；所述芳香单体为螺二芴、四苯基噻吩、三蝶烯、六苯基苯中的任意一种。本发明制备的金刚烷基多孔材料，具有高BET表面积和孔体积、优异的物理化学稳定性和热稳定性。在有机废水及重金属污水处理、催化等方面具有潜在的应用价值。
Description
技术领域
本发明涉及材料领域，特别涉及一种金刚烷基微孔材料及其制备方法。
背景技术：
微孔有机聚合物具有高比表面积，优异的物理化学稳定性，在气体吸附及分离、废水处理、碘捕获等方面具有潜在的应用价值。
近年来，科学家通过各种反应设计制备了各种结构的微孔有机材料，如醛基与氨基反应生成的聚亚胺或聚缩醛胺、氨基与酸酐反应生成的聚酰亚胺，以及金属催化卤代化合物的偶联反应生成的共轭微孔聚合物等。1,3-二溴金刚烷作为一种二溴代试剂，价廉易得。但是目前，尚未有采用1,3-二溴金刚烷与芳香单体反应构建微孔有机聚合物的报道。
因鉴于此，特提出此发明。
发明内容
本发明的目的旨在提供一种制备金刚烷基微孔材料的方法，采用lewis酸催化直接合成，制备工艺简单，产品的性能优秀。
为了实现上述目的，本发明提供了一种金刚烷基微孔材料的制备方法，包括以下步骤：
(1)在干燥容器内加入1,3-二溴金刚烷、芳香单体、催化剂和溶剂，混合；其中，1,3-二溴金刚烷与芳香单体摩尔比例为1:0.3-0.7；
(2)加热至30-100℃，反应6-72h；
(3)反应完成后，抽滤取固体部分，依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤；
(4)采用四氢呋喃、甲醇或氯仿中的任意一种提取至少48h，产物在100-150℃下真空干燥24-48h，即得；
所述芳香单体为螺二芴、四苯基噻吩、三蝶烯、六苯基苯中的任意一种。
通过不同洗涤剂的按顺序洗涤，先除去未反应的原料或者低聚物，后洗去催化剂，最后洗去残留的酸。
优选或可选的，所述催化剂为三氯化铝、三氯化铁、三氟化硼、四氯化钛中的一种或多种的组合。
优选或可选的，所述1,3-二溴金刚烷与催化剂的质量比为1:1-5。
优选或可选的，所述溶剂为二氯甲烷、1,2-二氯乙烷、三氯甲烷、四氢呋喃中的任意一种。
优选或可选的，所述1,3-二溴金刚烷与溶剂的质量比为1:20-90。
优选或可选的，步骤(2)中反应的反应环境为惰性气体气氛。
优选或可选的，所述惰性气体气氛为氮气气氛。
优选或可选的，步骤(3)中，N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水均各洗涤4次。
优选或可选的，步骤(3)中，提取的方式为索氏抽提法，抽提时间为72h。
另一方面，本发明还提供了一种金刚烷基微孔材料，所述金刚烷基微孔材料采用权上述的制备方法制备而成。
本发明提供的一种金刚烷基微孔材料及其制备方法，采用一锅法，制备工艺简单，成本低廉。且制备出的金刚烷基多孔材料，具有高BET表面积和孔体积、优异的物理化学稳定性和热稳定性。在二氧化碳吸附及分离、二氧化硫和氨气捕获、碘捕获、有机废水及重金属污水处理、催化等方面具有潜在的应用价值。
附图说明
图1为实施例1中制得的金刚烷基微孔材料产品的结构式；
图2为实施例1中制得的金刚烷基微孔材料产品的IR分析图谱；
图3为实施例1中制得的金刚烷基微孔材料产品的TGA图谱；
图4为实施例2中制得的金刚烷基微孔材料产品的结构式；
图5为实施例2中制得的金刚烷基微孔材料产品的IR分析图谱；
图6为实施例2中制得的金刚烷基微孔材料产品的TGA图谱；
图7为实施例3中制得的金刚烷基微孔材料产品的结构式；
图8为实施例3中制得的金刚烷基微孔材料产品的IR分析图谱；
图9为实施例3中制得的金刚烷基微孔材料产品的TGA图谱；
图10为实施例4中制得的金刚烷基微孔材料产品的结构式；
图11为实施例4中制得的金刚烷基微孔材料产品的IR分析图谱；
图12为实施例4中制得的金刚烷基微孔材料产品的TGA图谱；
图13为对比例1中制得的金刚烷基微孔材料产品的结构式；
图14为对比例1中制得的金刚烷基微孔材料产品的IR分析图谱；
图15为对比例1中制得的金刚烷基微孔材料产品的TGA图谱。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
本发明实施例提供了一种金刚烷基微孔材料产品，该产品采用下述方法制备而成。
称取0.71g 1,3,-二溴金刚烷、0.38g螺二芴、0.71g三氯化铝至干燥的反应瓶内，并加入11mL二氯甲烷。
在氮气气氛下，将反应体系加热至40℃，并保温搅拌反应6h。
反应完成后，待体系自然冷却至室温，抽滤，滤饼依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤。
洗涤完成后用四氢呋喃采用索氏抽提法提取72h，将提取后的固体在140℃下真空干燥30h，即得金刚烷基微孔材料产品。
本实施例中制得的金刚烷基微孔材料产品的结构式如图1所示，IR分析图谱如图2所示，TGA分析图谱如图3所示。
实施例2
本发明实施例提供了一种金刚烷基微孔材料产品，该产品采用下述方法制备而成。
称取0.88g 1,3,-二溴金刚烷、0.58g四苯基噻吩、4.40g四氯化钛至干燥的反应瓶内，并加入28mL 1,2-二氯乙烷。
在氮气气氛下，将反应体系加热至100℃，并保温搅拌反应16h。
反应完成后，待体系自然冷却至室温，抽滤，滤饼依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤。
洗涤完成后用甲醇采用索氏抽提法提取48h，将提取后的固体在150℃下真空干燥24h，即得金刚烷基微孔材料产品。
本实施例中制得的金刚烷基微孔材料产品的结构式如图4所示，IR分析图谱如图5所示，TGA分析图谱如图6所示。
实施例3
本发明实施例提供了一种金刚烷基微孔材料产品，该产品采用下述方法制备而成。
称取0.97g 1,3,-二溴金刚烷、0.56g三蝶烯、2.00g三氯化铁至干燥的反应瓶内，并加入66mL四氢呋喃。
在氮气气氛下，将反应体系加热至60℃，并保温搅拌反应72h。
反应完成后，待体系自然冷却至室温，抽滤，滤饼依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤。
洗涤完成后用氯仿采用索氏抽提法提取60h，将提取后的固体在100℃下真空干燥48h，即得金刚烷基微孔材料产品。
本实施例中制得的金刚烷基微孔材料产品的结构式如图7所示，IR分析图谱如图8所示，TGA分析图谱如图9所示。
实施例4
本发明实施例提供了一种金刚烷基微孔材料产品，该产品采用下述方法制备而成。
称取0.59g 1,3,-二溴金刚烷、0.36g六苯基苯、1.77g三氯化铝至干燥的反应瓶内，并加入36mL二氯甲烷。
在氮气气氛下，将反应体系加热至40℃，并保温搅拌反应24h。
反应完成后，待体系自然冷却至室温，抽滤，滤饼依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤。
洗涤完成后用四氢呋喃采用索氏抽提法提取72h，将提取后的固体在120℃下真空干燥48h，即得金刚烷基微孔材料产品。
本实施例中制得的金刚烷基微孔材料产品的结构式如图10所示，IR分析图谱如图11所示，TGA分析图谱如图12所示。
对比例1
本发明对比例提供了一种金刚烷基微孔材料产品，该产品采用下述方法制备而成。
称取0.71g 1,3,-二溴金刚烷、0.53g 1,3,5,7-四苯基金刚烷、1.42g三氟化硼至干燥的反应瓶内，并加入43mL三氯甲烷。
在氮气气氛下，将反应体系加热至180℃，并保温搅拌反应24h。
反应完成后，待体系自然冷却至室温，抽滤，滤饼依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤。
洗涤完成后用四氢呋喃采用索氏抽提法提取72h，将提取后的固体在120℃下真空干燥48h，即得金刚烷基微孔材料产品。
本实施例中制得的金刚烷基微孔材料产品的结构式如图7所示，IR分析图谱如图8所示，TGA分析图谱如图9所示。
分别测定实施例1-5中制备的产品的产率、BET比表面积、微孔比表面积、微孔提及、总孔体积，结果如下表所示。
表1实施例与对比例产品性能表
由上表可见，本发明采用一锅法制备的金刚烷基微孔材料，制备方法简单，成本低廉，产率高，并通过优选作为核心的芳香单体，使制备出的金刚烷基微孔材料具备良好的BET比表面积、微孔比表面积、微孔体积和总孔体积等性能，以及优异的物理化学稳定性和热稳定性。在二氧化碳吸附及分离、二氧化硫和氨气捕获、碘捕获、有机废水及重金属污水处理、催化等方面具有潜在的应用价值。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。
Claims (10)
1.一种金刚烷基微孔材料的制备方法，其特征在于，包括以下步骤：
(1)在干燥容器内加入1,3-二溴金刚烷、芳香单体、催化剂和溶剂，混合；其中，1,3-二溴金刚烷与芳香单体摩尔比例为1:0.3-0.7；
(2)加热至30-100℃，反应6-72h；
(3)反应完成后，抽滤取固体部分，依次用N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水洗涤；
(4)采用四氢呋喃、甲醇或氯仿中的任意一种提取至少48h，产物在100-150℃下真空干燥24-48h，即得；
所述芳香单体为螺二芴、四苯基噻吩、三蝶烯、六苯基苯中的任意一种。
2.根据权利要求1所述的制备方法，其特征在于，所述催化剂为三氯化铝、三氯化铁、三氟化硼、四氯化钛中的一种或多种的组合。
3.根据权利要求2所述的制备方法，其特征在于，所述1,3-二溴金刚烷与催化剂的质量比为1:1-5。
4.根据权利要求1所述的制备方法，其特征在于，所述溶剂为二氯甲烷、1,2-二氯乙烷、三氯甲烷、四氢呋喃中的任意一种。
5.根据权利要求4所述的制备方法，其特征在于，所述1,3-二溴金刚烷与溶剂的质量比为1:20-90。
6.根据权利要求1所述的制备方法，其特征在于，步骤(2)中反应的反应环境为惰性气体气氛。
7.根据权利要求6所述的制备方法，其特征在于，所述惰性气体气氛为氮气气氛。
8.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，N,N-二甲基甲酰胺、二氯甲烷、四氢呋喃、稀盐酸溶液、去离子水均各洗涤4次。
9.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，提取的方式为索氏抽提法，抽提时间为72h。
10.一种金刚烷基微孔材料，其特征在于，采用权利要求1-9任一所述的制备方法制备而成。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210570055.0A CN114805756B (zh) | 2022-05-24 | 2022-05-24 | 一种金刚烷基微孔材料及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210570055.0A CN114805756B (zh) | 2022-05-24 | 2022-05-24 | 一种金刚烷基微孔材料及其制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805756A CN114805756A (zh) | 2022-07-29 |
| CN114805756B true CN114805756B (zh) | 2023-07-07 |
Family
ID=82516943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210570055.0A Active CN114805756B (zh) | 2022-05-24 | 2022-05-24 | 一种金刚烷基微孔材料及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805756B (zh) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200415156A (en) * | 2002-11-01 | 2004-08-16 | Sumitomo Chemical Co | Composition for forming porous organic film |
| JP2010212489A (ja) * | 2009-03-11 | 2010-09-24 | Fujifilm Corp | 組成物 |
| CN102503806A (zh) * | 2011-10-21 | 2012-06-20 | 西北师范大学 | 一种1,3,5,7-四（4-丙烯酸-苯基）金刚烷化合物的合成方法 |
-
2022
- 2022-05-24 CN CN202210570055.0A patent/CN114805756B/zh active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200415156A (en) * | 2002-11-01 | 2004-08-16 | Sumitomo Chemical Co | Composition for forming porous organic film |
| JP2010212489A (ja) * | 2009-03-11 | 2010-09-24 | Fujifilm Corp | 組成物 |
| CN102503806A (zh) * | 2011-10-21 | 2012-06-20 | 西北师范大学 | 一种1,3,5,7-四（4-丙烯酸-苯基）金刚烷化合物的合成方法 |
Non-Patent Citations (3)
| Title |
|---|
| Covalent triazine frameworks for the dynamic adsorption/separation of benzene/cyclohexane mixtures;Jun Yan;The Royal Society of Chemistry;第46卷;7580–7587 * |
| Monodispersed ultramicroporous semicycloaliphatic polyimides for the highly efficient adsorption of CO2, H2 and organic vapors;Jun Yan;The Royal Society of Chemistry;第7卷;7295–7303 * |
| 多孔共价三嗪骨架的简易合成及碘捕获研究;黄宝旺;《山东化工》;第51卷(第22期);51-54 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805756A (zh) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106967216B (zh) | 一种亚胺联接的共价有机骨架材料及其制备方法与应用 | |
| CN110218301B (zh) | 一种基于1,3,5-三(4-甲酰基苯基)苯的共轭有机微孔聚合物及其制备方法 | |
| CN107759796A (zh) | 一类多孔超交联聚合物的制备方法 | |
| CN106633033B (zh) | 含二氮杂萘酮联苯结构自具微孔共聚物及其制备方法 | |
| CN113698579B (zh) | 卟啉型共轭微孔聚合物及其合成方法和应用 | |
| CN108676150B (zh) | 利用次级结构基块构筑的多孔芳香骨架材料 | |
| CN114456338B (zh) | 一种苯并咪唑基共价有机框架材料的光催化合成方法 | |
| CN112778533A (zh) | 一种卟啉基多孔有机聚合物及其制备方法和环状碳酸酯的合成方法 | |
| CN114471487B (zh) | 一类可溶解加工的超交联多孔聚合物材料及其制备方法 | |
| CN114669332A (zh) | 一种离子型超高交联多孔有机聚合物负载钴催化剂的制备方法 | |
| CN111875761A (zh) | 一种基于四苯乙烯结构的有机多孔骨架聚合物及其合成方法 | |
| CN110090664B (zh) | 一种酸性离子液体@cof材料及其制备方法和应用 | |
| CN114805756B (zh) | 一种金刚烷基微孔材料及其制备方法 | |
| CN107698742A (zh) | 苯并二噻吩二酮基共轭微孔聚合物制备及其光催化应用 | |
| CN110938184A (zh) | 一种基于有机醛和三聚氰胺的希夫碱型生物基多孔材料及其制备方法 | |
| CN111848951A (zh) | 一种基于1,3,6,8-四（4-氨基苯基）芘的共轭有机聚合物及其制备方法 | |
| CN114195966A (zh) | 大比表面积多孔聚缩酮胺及其制备方法和应用 | |
| Sobarzo et al. | Effect of thiophene, furan moieties and zinc ions on melamine-based porous polyaminals properties and catalytic activity on CO2 cycloaddition reaction | |
| CN112547027A (zh) | 一种掺杂高岭土的共轭微孔聚合物复合材料的制备方法 | |
| CN111215149A (zh) | 一种MOF@POP-n复合催化剂及其制备方法和应用 | |
| CN117327243B (zh) | 烯烃链接的二维共价有机框架及其制备方法和应用 | |
| CN116284629B (zh) | 一种廉价多孔有机聚合物材料及其制备方法 | |
| CN113603845B (zh) | 一种含羟基多孔共价有机骨架材料及其制备方法和应用 | |
| CN115028834B (zh) | 一种聚芳基三唑及其制备方法和应用 | |
| CN117362637A (zh) | 一种超稳定疏水共价有机框架材料及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240923 Address after: Room 302, Unit 2, No. 70 Yuqinggong Road, Licang District, Qingdao City, Shandong Province, China 266100 Patentee after: Qi Feng Country or region after: China Patentee after: QINGDAO GREEN WORLD NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 750021 No. 204, Wenchang North Street, Xixia District, the Ningxia Hui Autonomous Region, Yinchuan Patentee before: BEIFANG MINZU University Country or region before: China |