CN108129669A - 一种salen多孔有机聚合物及金属配合物及应用 - Google Patents
一种salen多孔有机聚合物及金属配合物及应用 Download PDFInfo
- Publication number
- CN108129669A CN108129669A CN201611087520.6A CN201611087520A CN108129669A CN 108129669 A CN108129669 A CN 108129669A CN 201611087520 A CN201611087520 A CN 201611087520A CN 108129669 A CN108129669 A CN 108129669A
- Authority
- CN
- China
- Prior art keywords
- polymer
- salen
- aldehyde
- diamines
- adjustable
- 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.)
- Pending
Links
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 9
- 150000004696 coordination complex Chemical class 0.000 title claims description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 150000002466 imines Chemical class 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001455 metallic ions Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- HSTOKWSFWGCZMH-UHFFFAOYSA-N 3,3'-diaminobenzidine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 HSTOKWSFWGCZMH-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- MTHSAJBPTNOBRW-UHFFFAOYSA-N phenyl 2,3-diaminobenzoate Chemical compound NC1=CC=CC(C(=O)OC=2C=CC=CC=2)=C1N MTHSAJBPTNOBRW-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 21
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000000523 sample Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- -1 alkynes alkynes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006352 cycloaddition reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 239000013479 COF-300 Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种salen多孔有机聚合物的合成及其金属配位聚合物的合成与应用。所述的salen多孔有机聚合物是基于三醛与二胺通过缩合作用生成亚胺键而构建起来的一个多孔体系,骨架含salen配体。该材料制备时,将二胺溶液滴加到三醛溶液中,回流后即可得到聚合物。本发明所述聚合物具有较高的比面积与微孔结构。并且可以与多种金属进行配位进一步用于催化反应、气体吸附、荧光探针的应用中。
Description
技术领域
本发明涉及一种Salen多孔聚合物的合成以及其金属配位聚合物的合成与应用。所述的聚合物是基于三醛与二胺通过缩合作用生成亚胺键而构建起来的一个多孔体系,富含salen配体。本发明所述聚合物具有较高的比面积与微孔结构。并且可以与多种金属进行配位进一步用于催化反应,气体吸附,荧光探针的应用中。
背景技术
多孔材料一直以来都是研究热点。从传统的无极多孔材料如沸石和活性炭等到最近的新兴有机多孔聚合物,人们逐渐掌握了控制材料中孔的大小、分布情况以及表面选择功能化的技能。与无机材料不同,有机多孔材料的孔道结构主要依靠单体的刚性结构支撑形成,而无需添加任何模板剂,所以构筑材料的单体一般都是刚性的有机分子(比如芳香环骨架)。通过选择具有不同长度和空间构象的合成单体,人们能够得到具有不同孔径的有机多孔聚合物材料;通过控制合成条件和选择不同的制备方法可以获得不同孔径分布的有机多孔聚合物。另外,根据所要合成的有机聚合物的应用拉力选择具有相应官能团或者结构的单体可以选择性的在材料的表面进行功能化(Pro.Polym.Sci.,2012,37,530-563)。有机多孔材料的前期研究,主要是发展不同策略通过不同的有机化学反应实现材料的构建。通常的构建手段有:酸催化下的缩合反应,过度金属催化的偶联反应,付克烷基化反应,炔炔三聚反应,Scoll偶联以及“Click”反应等。因为具有以上优点,有机多孔聚合物已经被广泛地应用到气体吸附存储、气体分离、传感和光电等领域(Chem.Soc.Rev.,2013,42:8012-8031);随着催化的发展,功能化有机多孔聚合物在多相催化领域中的研究越来越受到人们的关注
Schiff碱反应通常是指含有氨基和醛基的化合物通过缩合作用生成亚胺键的反应,反应生成的亚胺键可以继续与氨基反应生成缩醛胺化合物。Schiff碱反应是一个受热力学控制的可逆反应,因此那些在动力学控制下得到的中间产物经过足够长的反应时间后会转变成热力学更加稳定的产物。人们很早就将它应用与有机多孔材料的合成,希望能够制备出更加稳定的材料。Yaghi等人根据Schiff碱反应原理制备出晶态的COF-300聚合物,又一次掀起了Schiff碱反应在有机多孔聚合物合成中应用中的热潮(J.Am.Chem.Soc.,2009,131,4470-4571)。与其他有机多孔聚合物相似,基于Schiff碱反应的有机多孔聚合物也被用于气体吸附于分离、催化、环境中重金属离子的吸附以及有机光电领域。
发明内容
本发明涉及一种Salen多孔聚合物的合成以及其金属配位聚合物的合成与应用。所述的聚合物是基于三醛与二胺通过缩合作用生成亚胺键而构建起来的一个多孔体系,富含salen配体。本发明所述聚合物具有较高的比表面积与微孔结构。并且能与多种金属进行配位进一步用于催化反应、气体吸附及荧光探针的应用中。
本发明涉及的制备方法如下:该材料制备时,将二胺的醇溶液缓慢滴加到三醛溶液中,反应后即可得到聚合物。在甲醇溶液中与金属离子进行配位得到金属配合物多孔有机聚合物。
具体可按如下步骤操作:
1)三醛的溶解:称取一定量的三醛(三醛1,2,3,4)于单口烧瓶中,加入溶剂室温搅拌下使其溶解,溶剂可以是二氯甲烷,三氯甲烷,1,2-二氯乙烷,四氢呋喃,N,N-二甲基甲酰胺,甲苯等。
2)salen聚合物的制备:在搅拌条件下,向上述溶液中缓慢滴加二胺的醇溶液,二胺为乙二胺,1,2-丙二胺,1,3-丙二胺,己二胺,癸二胺,环己二胺,邻苯二胺,对苯二胺,均苯四胺,3,3’-二氨基联苯胺,二氨基苯甲酸苯酯,醇为甲醇,乙醇,异丙醇,乙二醇。滴加完毕后搅拌反应。合成过程中温度为20℃-100℃,搅拌时间1min-24h,三醛与二胺的摩尔比在1:1-1:5之间可调,三醛溶液与二胺醇溶液的体积比例在0.1-10之间可调;
3)干燥:将步骤(2)的产物抽滤,用乙醇洗涤,室温干燥制得本发明的产品1;
4)金属配位:将步骤(3)的产物分散在甲醇溶液中(6mg/mL),缓慢加入金属盐的甲醇溶液(10mg/mL),反应2-24h。金属可以为Co,Zn,Cu,Fe,Mn,V,Ru,Ni,Al,Mg,Sn,Pd。
5)干燥:将步骤(4)的产物抽滤,用乙醇洗涤,室温干燥制得本发明的产品2。
本发明的制备方法具有如下优点:
1.一步法构建多孔有机聚合物体系;
2.反应条件温和,温度较低,能耗少;
3.此方法可制备高含量的salen多孔有机聚合物。
本发明制备的材料具有如下优点:
1.制备的材料具有良好的机械稳定性、热稳定性及溶剂稳定性,不溶于有机溶剂,如甲醇,乙醇,二氯甲烷,四氢呋喃,1,4-二氧六环,N,N-二甲基甲酰胺,甲苯等;
2.制备的材料都具有大的比表面积和孔容以及丰富的微孔,可作气体吸附使用;
3.制备的材料可与各种金属离子配位制得金属配合物多孔有机聚合物,可以作为多功能催化剂使用。
附图说明
图1.为实施例1中所得多孔聚合物材料的扫描电子显微镜(SEM)照片。
图2.为实施例4中所得多孔聚合物的SEM照片。
图3.为实施例7中所得多孔聚合物的SEM照片。
图4.为实施例8中所得多孔聚合物的SEM照片。
图5.为实施例1,7中所得多孔聚合物的氮气吸脱附曲线。
图6.为实施例1,7中所得多孔聚合物的孔径分布。
图7.为实施例4,8中所得多孔材料的氮气吸脱附曲线。
图8.为实施例4,8中所得材料的孔径分布。
图9.为实施例11中环氧丙烷水合反应中的催化结果。
图10.为实施例12中环氧丙烷水合反应中的催化结果。
图11.为实施例13中环氧丙烷的二氧化碳还加成反应的结果。
具体实施方式
为了进一步说明本发明,列举以下实施实例,但它并不限制各附加权利要求所定义的发明范围。
实施例1
称取60mg 1号水杨醛于单口瓶中,加入1mL二氯甲烷搅拌溶解,缓慢加入环己二胺的乙醇溶液(17mg环己二胺,3mL乙醇)。滴加的过程中反应液逐渐变黄,搅拌1-2min后有黄色沉淀生成。在80℃搅拌回流1h。产物经过滤,乙醇洗涤,室温干燥最终得到黄色轻质粉末。SEM结果表明得到的产品为棒状和块状的材料,BET比表面积为470m2/g;孔容为0.32cm3/g;(图1)
实施例2
采用实施例1的制备过程,与其不同之处在于水杨醛用1mL甲苯溶解。SEM结果表明得到的产品为块状的材料,BET比表面积为20m2/g;孔容为0.05cm3/g;
实施例3
采用实施例1的制备过程,与其不同之处在于所用的醇为乙二醇。SEM结果表明得到的产品为块状的材料,BET比表面积为1000m2/g;孔容为0.9cm3/g,在25℃、1个大气压下的二氧化碳吸附量为4.10mmol/g,CO2/N2选择性为18;
实施例4
采用实施例1的制备过程,与其不同之处在于,加入的二胺为乙二胺(9mg)。最终得到淡黄色轻质粉末。表征方法同上。SEM结果表明得到的产品为纤维状的材料,BET比表面积为464m2/g;孔容为0.64cm3/g。(图2)
实施例5
采用实施例1的制备过程,与其不同之处在于,加入的二胺为邻苯二胺(16.2mg)。最终得到深黄色轻质粉末。表征方法同上。SEM结果表明得到的产品为球形材料,BET比表面积为100m2/g;孔容为0.25cm3/g。
实施例6
采用实施例1的制备过程,与其不同之处在于,加入的三醛为2号水杨醛。最终得到淡黄色轻质粉末。表征方法同上。SEM结果表明得到的产品为棒状材料,BET比表面积为500m2/g;孔容为0.5cm3/g。
实施例7
将实施例1的产物180mg分散于30mL甲醇中。在室温下将112mg醋酸钴溶于10mL乙醇中,然后加入到25mL恒压漏斗中。惰气保护下缓慢加入到配体的溶液中,体系颜色逐渐变为红色。搅拌回流3h,冷却,抽滤,用甲醇洗涤,收集产物,真空干燥。SEM结果表明得到的产品为棒状和块状的混合物,BET比表面积为626m2/g;孔容为0.41cm3/g,在25℃、1个大气压下的二氧化碳吸附量为3.11mmol/g,CO2/N2选择性为14。(图3)
实施例8
采用实施例4的制备过程,与其不同之处在于,加入的配体材料为实施例2所得产物。表征方法同上。SEM结果表明得到的产品为球形形貌,BET比表面积为860m2/g;孔容为0.84cm3/g。(图4)
实施例9
采用实施例3的制备过程,与其不同之处在于,加入的金属盐为醋酸锌。表征方法同上。SEM结果表明得到的产品为球形形貌,BET比表面积为450m2/g;孔容为0.6cm3/g。该材料具有很强的荧光信号,可用作生物探针。
实施例10
采用实施例3的制备过程,与其不同之处在于,加入的金属盐为醋酸铜。表征方法同上。SEM结果表明得到的产品为球形形貌,BET比表面积为250m2/g;孔容为0.4cm3/g。
实施例11
将实施例7中所得产物(10mg)经对甲苯磺酸的乙醇溶液(1mg/mL,5mL)活化后,用于环氧丙烷水合反应。将10mg催化剂加入10mL反应瓶中,陆续加入350mg环氧丙烷和180mg的水,在40度下反应。反应结束后将催化剂过滤,滤液加入40mg内标辛醇,通过GC分析环氧化合物转化率和产物选择性。反应3小时后即可获得94%的丙二醇产率。
实施例12
采用实施例11的过程,与其不同之处在于,所用材料为实施例8所得产物。反应3小时后即可获得94%的丙二醇产率。
实施例13
将实施例10中所得产物用于二氧化碳与环氧烷烃的环加成反应。将20mg催化剂加入10mL反应管中,加入350mg环氧丙烷,在常温常压下反应48小时。反应48h后丙烯碳酸脂的产率为78%。
本发明涉及一种Salen多孔聚合物的合成以及其金属配位聚合物的合成与应用。具体的说是一种基于三醛与二胺通过缩合作用生成亚胺键而构建起来的一个多孔体系。其特征在于聚合物骨架富含salen配体,具有丰富的微孔,比表面积在20-2000m2/g,孔容在0.01-1cm3/g。并且能与多种金属进行配位进一步用于催化反应,气体吸附,荧光探针的应用中。该合成方法步骤少,用时短,一步法构建多孔聚合物体系,反应条件温和,温度较低,能耗少。与钴配位后形成的催化剂和其相应的均相催化剂相比,具有较高的催化活性并且可以循环使用(如图9-10所示。图9和图10分别为本实例中所得固体催化剂在环氧丙烷水合反应中的催化活性,如图所示,本实例所得固体催化剂均表现出比均相催化剂更高的催化活性)。与Zn配位后形成的催化剂在常温常压下可以催化环氧丙烷的二氧化碳环加成反应。
Claims (10)
1.一种salen多孔聚合物,其特征在于:该聚合物是基于三醛与二胺通过缩合作用生成亚胺键而构建起来的一个多孔体系,骨架含salen配体;原料三醛与二胺的摩尔比在1:1-1:5之间可调。
2.如权利要求1所述的聚合物,其特征在于:制备过程为,将二胺的醇溶液滴加到三醛的溶液中,回流后即可得到聚合物;醇为甲醇、乙醇、异丙醇、乙二醇中的一种或二种以上;三醛的溶液的溶剂为二氯甲烷、三氯甲烷、1,2-二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺、甲苯中的一种或二种以上。
3.根据权利要求1或2所述的聚合物,其特征在于:三醛为以下三醛中的一种或二种以上:
所述二胺为乙二胺、1,2-丙二胺、1,3-丙二胺、己二胺、癸二胺、环己二胺、邻苯二胺、对苯二胺、均苯四胺、3,3’-二氨基联苯胺、二氨基苯甲酸苯酯中的一种或二种以上。
4.根据权利要求2所述的制备方法,其特征在于:二胺的醇溶液的质量浓度在0.1-10mg/mL之间可调;三醛溶液的的质量浓度10-100mg/mL之间可调。
5.根据权利要求2或4所述的制备方法,其特征在于:三醛溶液与二胺醇溶液的体积比例在0.1-10之间可调。
6.根据权利要求2所述的制备方法,其特征在于:回流时间在1min-24h内可调。
7.根据权利要求1所述的salen聚合物,其特征在于:该聚合物的比表面积在20-2000m2/g之间。
8.一种金属离子配位salen多孔聚合物的金属配合物,其特征在于:权利要求1-7任一所述salen多孔聚合物能与金属离子配位;所述金属包括:Co、Zn、Cu、Fe、Mn、V、Ru、Ni、Al、Mg、Sn、Pd。
9.根据权利要求8所述的金属配合物,其特征在于:将配位金属离子的金属盐的醇溶液(2-20mg/mL之间可调)在惰性气氛下加入到salen聚合物的分散液中(1-10mg/mL之间可调),20-120℃之间反应2-24h,即可得相应的金属配合物多孔有机聚合物;salen聚合物与金属盐的质量比为1.6:1。
10.一种权利要求8或9所述的金属配合物在气体吸附或催化过程中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611087520.6A CN108129669A (zh) | 2016-12-01 | 2016-12-01 | 一种salen多孔有机聚合物及金属配合物及应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611087520.6A CN108129669A (zh) | 2016-12-01 | 2016-12-01 | 一种salen多孔有机聚合物及金属配合物及应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN108129669A true CN108129669A (zh) | 2018-06-08 |
Family
ID=62387396
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611087520.6A Pending CN108129669A (zh) | 2016-12-01 | 2016-12-01 | 一种salen多孔有机聚合物及金属配合物及应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108129669A (zh) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108864438A (zh) * | 2018-06-20 | 2018-11-23 | 上海师范大学 | 兼具核壳及多级孔结构的聚合物微球的制备方法及应用 |
CN109485866A (zh) * | 2018-11-20 | 2019-03-19 | 东南大学 | 一种三维含锌/钒手性配位聚合物及其制备方法与应用 |
CN110787651A (zh) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | 一种共价有机框架膜材料及制备方法 |
CN110790877A (zh) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | 一种共价有机框架材料及其制备、在识别手性多糖上的应用 |
CN111097531A (zh) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | 环氧化合物水合制二醇的固体催化剂、制备及应用 |
CN111732736A (zh) * | 2020-07-03 | 2020-10-02 | 遵义医科大学 | 一种Ni(II)-Salen配体金属有机框架晶体材料及其制备方法与应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013121593A1 (en) * | 2012-02-14 | 2013-08-22 | Nippon Kodoshi Corporation | Inorganic / polymeric hybrid catalytic materials with high activity in various solvents |
CN104558016A (zh) * | 2015-02-02 | 2015-04-29 | 山东大学 | 一种同时提高多孔性和二氧化碳储存量的poss基多孔材料的制备方法 |
CN104892801A (zh) * | 2015-05-25 | 2015-09-09 | 吉林大学 | 一种有机多孔材料后负载单茂铬催化剂及应用 |
CN105754588A (zh) * | 2016-04-05 | 2016-07-13 | 吉林大学 | 一种亚胺连接的发光多孔有机聚合物材料及制备方法 |
-
2016
- 2016-12-01 CN CN201611087520.6A patent/CN108129669A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013121593A1 (en) * | 2012-02-14 | 2013-08-22 | Nippon Kodoshi Corporation | Inorganic / polymeric hybrid catalytic materials with high activity in various solvents |
CN104558016A (zh) * | 2015-02-02 | 2015-04-29 | 山东大学 | 一种同时提高多孔性和二氧化碳储存量的poss基多孔材料的制备方法 |
CN104892801A (zh) * | 2015-05-25 | 2015-09-09 | 吉林大学 | 一种有机多孔材料后负载单茂铬催化剂及应用 |
CN105754588A (zh) * | 2016-04-05 | 2016-07-13 | 吉林大学 | 一种亚胺连接的发光多孔有机聚合物材料及制备方法 |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108864438A (zh) * | 2018-06-20 | 2018-11-23 | 上海师范大学 | 兼具核壳及多级孔结构的聚合物微球的制备方法及应用 |
CN108864438B (zh) * | 2018-06-20 | 2021-08-03 | 上海师范大学 | 兼具核壳及多级孔结构的聚合物微球的制备方法及应用 |
CN110787651A (zh) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | 一种共价有机框架膜材料及制备方法 |
CN110790877A (zh) * | 2018-08-01 | 2020-02-14 | 孝感市思远新材料科技有限公司 | 一种共价有机框架材料及其制备、在识别手性多糖上的应用 |
CN111097531A (zh) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | 环氧化合物水合制二醇的固体催化剂、制备及应用 |
CN111097531B (zh) * | 2018-10-25 | 2022-12-09 | 中国石油化工股份有限公司 | 环氧化合物水合制二醇的固体催化剂、制备及应用 |
CN109485866A (zh) * | 2018-11-20 | 2019-03-19 | 东南大学 | 一种三维含锌/钒手性配位聚合物及其制备方法与应用 |
CN109485866B (zh) * | 2018-11-20 | 2021-02-09 | 东南大学 | 一种三维含锌/钒手性配位聚合物及其制备方法与应用 |
CN111732736A (zh) * | 2020-07-03 | 2020-10-02 | 遵义医科大学 | 一种Ni(II)-Salen配体金属有机框架晶体材料及其制备方法与应用 |
CN111732736B (zh) * | 2020-07-03 | 2022-05-17 | 遵义医科大学 | 一种Ni(II)-Salen配体金属有机框架晶体材料及其制备方法与应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108129669A (zh) | 一种salen多孔有机聚合物及金属配合物及应用 | |
Ju et al. | Salen–porphyrin-based conjugated microporous polymer supported Pd nanoparticles: highly efficient heterogeneous catalysts for aqueous C–C coupling reactions | |
Hassan et al. | Salen-Zr (IV) complex grafted into amine-tagged MIL-101 (Cr) as a robust multifunctional catalyst for biodiesel production and organic transformation reactions | |
Dhakshinamoorthy et al. | Metal–organic frameworks as solid catalysts for the synthesis of nitrogen-containing heterocycles | |
Yang et al. | Azo-functionalized microporous organic polymers: synthesis and applications in CO 2 capture and conversion | |
Cui et al. | A stable and porous iridium (III)-porphyrin metal–organic framework: synthesis, structure and catalysis | |
Azizi et al. | Deep eutectic solvent immobilized on SBA-15 as a novel separable catalyst for one-pot three-component Mannich reaction | |
US10293335B2 (en) | Rh-C3N4 heterogeneous catalyst for preparing acetic acid by carbonylation reaction | |
Tehrani et al. | Urea-containing metal-organic frameworks as heterogeneous organocatalysts | |
CN107790184B (zh) | 一种具有可控形貌的Pd金属纳米晶体内核的Pd/UiO-66催化剂及其制备方法 | |
Jun et al. | One-pot synthesis of magnetically recyclable mesoporous silica supported acid–base catalysts for tandem reactions | |
CN110016126A (zh) | 一种共轭微孔聚合物及其制备方法与应用 | |
CN104448381B (zh) | 咪唑功能化有序介孔酚醛树脂材料的制备及其应用 | |
CN102909070B (zh) | 一种负载型手性催化剂及其制备方法 | |
CN103483360A (zh) | 金属配合物官能化zif-8材料的制备方法 | |
CN106607091B (zh) | 微孔聚合物-纳米金属粒子催化剂及其制备方法和应用 | |
Gholampour et al. | Simultaneous creation of metal nanoparticles in metal organic frameworks via spray drying technique | |
Li et al. | Highly active ultrafine Pd NPs confined in imine-linked COFs for nitrobenzene hydrogenation | |
Guo et al. | Embedded homogeneous ultra-fine Pd nanoparticles within MOF ultra-thin nanosheets for heterogeneous catalysis | |
Isaeva et al. | Preparation of novel hybrid catalyst with an hierarchical micro-/mesoporous structure by direct growth of the HKUST-1 nanoparticles inside mesoporous silica matrix (MMS) | |
Bagherzade et al. | A porous metal-organic framework (Ni-MOF): An efficient and recyclable catalyst for cascade oxidative amidation of alcohols by amines under ultrasound-irradiations | |
Saravanamurugan et al. | Transesterification reactions over morphology controlled amino-functionalized SBA-15 catalysts | |
Wang et al. | Metal-organic framework grown in situ on chitosan microspheres as robust host of palladium for heterogeneous catalysis: Suzuki reaction and the p-nitrophenol reduction | |
Xing et al. | Preparation of active and robust palladium nanoparticle catalysts stabilized by diamine-functionalized mesoporous polymers | |
Aryanejad et al. | A nanoscale Cu-metal organic framework with Schiff base ligand: Synthesis, characterization and investigation catalytic activity in the oxidation of alcohols |
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 | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180608 |