CN113185701B - Metal porphyrin-based porous polymer, preparation thereof and application thereof in catalyzing addition reaction of carbon dioxide and epoxide ring - Google Patents
Metal porphyrin-based porous polymer, preparation thereof and application thereof in catalyzing addition reaction of carbon dioxide and epoxide ring Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 7
- 238000007259 addition reaction Methods 0.000 title description 3
- 125000003700 epoxy group Chemical group 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- MFRNCWXCWOKOGV-UHFFFAOYSA-N C=CC1=CC=C(CC2=CC(C=C(C=C3)NC3=CC(C=C3)=NC3=C3)=NC2=C(CC2=CC=C(C=C)C=C2)C2=C(CC4=CC=C(C=C)C=C4)C(C4=NC=CC=C4)=C3N2CC2=CC=C(C=C)C=C2)C=C1 Chemical compound C=CC1=CC=C(CC2=CC(C=C(C=C3)NC3=CC(C=C3)=NC3=C3)=NC2=C(CC2=CC=C(C=C)C=C2)C2=C(CC4=CC=C(C=C)C=C4)C(C4=NC=CC=C4)=C3N2CC2=CC=C(C=C)C=C2)C=C1 MFRNCWXCWOKOGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002118 epoxides Chemical class 0.000 claims abstract 7
- 238000006243 chemical reaction Methods 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- SBTXZBOBSRZUPE-UHFFFAOYSA-N 5,10,15,20-tetrapyridin-2-yl-21,23-dihydroporphyrin Chemical compound c1cc2nc1c(-c1ccccn1)c1ccc([nH]1)c(-c1ccccn1)c1ccc(n1)c(-c1ccccn1)c1ccc([nH]1)c2-c1ccccn1 SBTXZBOBSRZUPE-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 6
- 150000008045 alkali metal halides Chemical class 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- RJNDIQOADACMRL-UHFFFAOYSA-N C=CC1=CC=C(CC2=C(C=C(C=C3)N=C3C=C(C=C3)NC3=CC(C=C3)=NC3=C3)NC3=C2C2=NC=CC=C2)C=C1 Chemical compound C=CC1=CC=C(CC2=C(C=C(C=C3)N=C3C=C(C=C3)NC3=CC(C=C3)=NC3=C3)NC3=C2C2=NC=CC=C2)C=C1 RJNDIQOADACMRL-UHFFFAOYSA-N 0.000 claims description 2
- JGZKUKYUQJUUNE-UHFFFAOYSA-L magnesium;ethoxyethane;dibromide Chemical compound [Mg+2].[Br-].[Br-].CCOCC JGZKUKYUQJUUNE-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 21
- 239000002608 ionic liquid Substances 0.000 abstract description 8
- -1 halogen ions Chemical class 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 150000002924 oxiranes Chemical group 0.000 description 10
- 150000001450 anions Chemical class 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 4
- 238000005956 quaternization reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical group C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention provides a preparation method of a metal porphyrin-based porous polymer, which comprises the steps of obtaining poly tetra (4-vinylbenzyl) -pyridyl porphyrin through solution thermal polymerization, and then complexing the poly tetra (4-vinylbenzyl) -pyridyl porphyrin with metal salt and carrying out ion exchange to obtain the metal porphyrin-based porous polymer. The metal porphyrin-based porous polymer has both ionic liquid and metal porphyrin, contains a metal active center, halogen ions, N + ions and a porous structure, is used as a catalyst for catalyzing the cycloaddition reaction of carbon dioxide and epoxide, and shows high-efficiency catalytic activity and high selectivity at normal pressure and at lower temperature.
Description
Technical Field
The invention belongs to the field of material preparation and application, and relates to a metal porphyrin-based porous polymer, preparation thereof and application thereof in catalyzing addition reaction of carbon dioxide and epoxide.
Background
Porous organic materials due to their regularityThe pore channel structure with adjustable arrangement and size has the characteristics of adsorption, permeation, photoelectricity and the like, and is widely applied to the fields of gas adsorption, medium separation, heterogeneous catalysis and the like. Therefore, since its appearance, it has been widely appreciated by scientists in various fields. In 2012, Zhao et al polymerized ionic liquid CO by pairing micropores2The capture capacity is compared with that of a monomer, and the microporous polyion liquid is found to be used for CO2The capture capacity is 7 times that of The monomer (ZHao Z J, Dong H F, Zhang X P. The Research Progress of CO)2 Capture with Ionic Liquids[J]. Chinese Journal of Chemical Engineering, 2012, 20(1):120-129.)。
Based on the technical scheme, the metal porphyrin-based heterogeneous catalyst containing the porous polyion liquid is designed, firstly, a core unit containing pyridyl is selected on the structure of porphyrin, then the core unit and cheap 4-vinylbenzyl chloride are subjected to quaternization reaction to obtain a porphyrin-based ionic liquid monomer with a double bond, and then the porphyrin-based ionic liquid monomer is polymerized to realize the heterogeneous catalyst with both porous and ionic liquid structures, and the heterogeneous catalyst can be used for CO (carbon monoxide) and can be used for CO (carbon monoxide) to obtain the catalyst with both porous and ionic liquid structures2High efficiency conversion under mild condition and can be recycled.
Disclosure of Invention
The invention aims to provide a metal porphyrin-based porous polymer and a preparation method thereof;
another object of the present invention is to provide a metal porphyrin-based porous polymer as a catalyst for CO catalysis2Use in cycloaddition reactions with epoxides for the preparation of cyclic carbonates.
Mono, metal porphyrin based porous polymer and preparation thereof
The structural formula of the metal porphyrin-based porous polymer is as follows:
wherein M is Co, Mg or Zn; x is Cl, Br or I.
The preparation method of the metal porphyrin-based porous polymer comprises the following steps:
(1) preparing VBTPyPC: adding tetrapyridyl porphyrin (TPyP), 4-vinylbenzyl chloride (VBC) and 2, 6-di-tert-butyl-p-cresol (BHT) into DMF, stirring and reacting for 60-75 h at 100-120 ℃, cooling the mixture to room temperature after the reaction is finished, washing with diethyl ether, filtering to obtain purple solid, dissolving with methanol, filtering, settling with diethyl ether, and vacuum drying to obtain the tetra (4-vinylbenzyl) -pyridylporphyrin VBTPyPC. Wherein the molar ratio of the tetrapyridylporphyrin, the 4-vinylbenzyl chloride and the 2, 6-di-tert-butyl-p-cresol is 1:4: 0.5-1: 12: 0.5.
(2) Preparation of PVBTPyPC: dissolving VBTPyPC and Azobisisobutyronitrile (AIBN) in N-methylpyrrole, reacting for 60-75 h at 180-200 ℃, filtering, and refluxing and washing with DMF to remove soluble polymer to obtain brown solid poly (4-vinylbenzyl) -pyridylporphyrin PVBTPyPC. The mass ratio of VBTPyPC to azobisisobutyronitrile is 10: 1-100: 1.
(3) Preparation of MPVBTPyPC: PVBTPyPC and metal salt are added to DMF in N2Refluxing for 12-24 h at 140-160 ℃ in an atmosphere, cooling the reaction system to room temperature after the reaction is finished, and dropwise adding HCl into the reaction system in the air (or dropwise adding HCl into the reaction system in the air to oxidize the HCl into Co if the metal salt is cobalt chloride hexahydrate3+And other metal salts do not need the operation), filtering, washing and vacuum drying to obtain brown solid, namely the target product of the metal porphyrin-based porous polymer MPVBTPyPC. Wherein the metal salt is cobalt chloride hexahydrate, diethyl ether magnesium bromide or zinc acetate dihydrate; the mass ratio of the PVBTPyPC to the metal salt is 1: 1-1: 1.5.
(4) Preparation of MPVBTPyPX: adding MPVBTPyPC and alkali metal halide into deionized water, reacting for 45-50 h at normal temperature, filtering, washing and drying to obtain a brown solid, namely the target product, namely the metal porphyrin-based porous polymer MPVBTPyPX (X is Br or I, wherein X is marked as MPVBTPyPB when Br, and is marked as MPVBTPyPI when I). Wherein the alkali metal halide is NaBr or NaI; the mass ratio of MPVBTPyPC to alkali metal halide is 1: 1-1: 1.5.
The synthetic route is as follows:
wherein M is Co, Mg or Zn; x is Br or I.
Characterization of bis, metalloporphyrin-based porous polymers
1. Characterization of VBTPyPC
FIG. 1 shows the reaction of VBC with TPyP to obtain VBTPyPC1H NMR spectrum. Peaks shown between 8.5ppm and 10ppm are assigned to TPyP, while peaks between 5ppm and 8.5ppm are assigned to VBC. The characteristic peak of vinyl in VBC is respectively assigned to 1 and 2, the most obvious characteristic peak in TPyP is 9, the result is that hydrogen in pyrrole ring is in the shielding area of porphyrin ring, the displacement of the presented special hydrogen is-3.0 ppm, and the results show that VBC and TPyP successfully react to generate VBTPyPC.
Research shows that tetraphenylporphyrin is substituted with halogen atom or electron withdrawing group (such as Cl, OH, etc.) and then red-shifted to different degrees, so that the pyridyl porphyrin and 4-vinyl benzyl chloride are quaternized to generate Cl with strong electron withdrawing capability-A corresponding red-shift phenomenon also occurs. As shown in FIG. 2, VBTPyPC and TPyP are both dissolved in DMF, and the results of UV-Vis show that TPyP and VBTPyPC respectively have an S band with larger absorption intensity at 417nm and 430nm, and four Q bands with lower absorption intensity at 500-700nm, which shows that the porphyrin structures of VBTPyPC and previous TPyP after quaternization are not damaged by quaternization, and the corresponding Q bands and S bands have certain red shifts, which can indicate that the quaternization reaction is successful.
2. Characterization of the Metal porphyrin-based porous Polymer
FIG. 3 is N of MPVBTPyPC2Adsorption and desorption curves. By N2The adsorption curve characterizes the pore size of the polymer, and it can be seen from FIG. 3 (a) that as the pressure increases, N increases2The adsorption capacity shows an almost linear trend, which indicates that the prepared polymer has a larger pore size. The circled part of the area in 3 (a) is enlarged, and as shown in figure 3 (b), the polymer presents hysteresis loops with IV-type curves between 0.9 and 1, and the polymerization is more intuitively illustratedThe pore diameter structure of the object is formed, and the relative surface area calculated by a BET formula is up to 4221.84m2g-1This is an epoxide and CO2The gas provides sufficient space for movement and access to the gas, and also provides epoxide and CO2Provides a sufficient place for the reaction of (2).
FIG. 4 is a TGA curve of PVBTPyPC versus CoPVBTPyPC, CoPVBTPyPB, and CoPVBTPyPI. As shown in fig. 4, compared with TGA curves of copbtpypc, copbtpypb and copbtpypi, the weight loss rate of PVBTPyPC is faster than that of copbtpypc, copbtpypb and copbtpypi at 0-50 ℃; the weight of PVBTPyPC at the stage of 50-250 ℃ is kept stable, while CoPVBTPyPC, CoPVBTPyPB and CoPVBTPyPI always lose weight at a slower speed at the stage, which is probably because at the stage of 0-250 ℃, because VBBTPyP contains four vinyl groups, the four vinyl groups are not on the same plane in the polymerization reaction, so that partial vinyl groups can not be completely reacted, the local crosslinking degree of the prepared polymer is lower, the heating can cause the part of chemical bonds to break, the PVBTPyPC can generate a higher-speed weight loss at the temperature of 0-50 ℃, and when the part of chemical bonds completely break, the weight of the PVBTPyPC is kept at a certain level; the weight loss rate of the CoPVBTPyPC, CoPVBTPyPB and CoPVBTPyPI at the front section is similar to that of the PVBTPyPC, but the weight loss rate is still equal to a certain speed at the stage of 50-200 ℃, but the weight loss percentage is less than half of that of the PVBTPyPC, which shows that the mass proportion of the PVBTPyPC is slightly reduced and the thermal stability is also improved to a certain extent after the polymer is coordinated with the metal, wherein the thermal stability of the CoPVBTPyPBr is slightly higher than that of the CoPVBTPyPCl and the CoPVBTPyPI. After 250 ℃, the overall structure of the polymer before and after coordination is destroyed at high temperature, so its quality always decreases with increasing temperature.
Fig. 5 is an SEM image of PVBTPyPC and copbtpypb (fig. 5 (a) is an SEM image of PVBTPyPC at different magnifications, and fig. 5 (b) is an SEM image of copbtpypb at different magnifications). As can be seen from fig. 5, the prepared PVBTPyPC almost consists of nanorods with different diameters, and the mutual entanglement and stacking of the nanorods leads to a fluffy polymer structure with larger pores; after the polymer is coordinated with the metal, the nanorod structures almost form a whole, so that the CoPVBTPyPB has a rough surface, which is probably because the original hollow structures are filled with metal ions after porphyrin rings are coordinated with the metal ions, and the nanorod structures are connected with each other through metal centers to form a whole. From the microscopic level, the polymer coordinated with the metal is more like a layered cloud with a rough surface, and the rough surface structure is not only favorable for the short residence of the substrate, but also provides sufficient time for halogen to attack the ring opening of the substrate, thereby improving the reaction efficiency.
Tri, metal porphyrin-based porous polymer as catalyst for catalyzing CO2Application in cycloaddition reaction with epoxide
The MPVBTPyP prepared by the invention is used as a catalyst to be applied to epichlorohydrin and CO under the mild condition without solvent and additive2The cycloaddition reaction of (3). Adding 25mg of epichlorohydrin catalyst into a 25ml Schlenk tube, adding 3ml of epichlorohydrin, and filling CO with the purity of 99.9 percent into a balloon2Stirring and reacting for 36h at the temperature of 80 ℃, cooling a reaction system to room temperature after the reaction is finished, and passing through1H NMR was used to confirm the selectivity and conversion of the desired product.
The catalytic activity of the metal porphyrin-based porous polymer is shown in table 1. Without coordination to the metal, PVBTPyPC has little catalytic activity; when PVBTPyPC is coordinated with metal Co, the conversion rate of epichlorohydrin reaches 39.4%, which shows that the existence of metal center plays a dominant role in catalyzing cycloaddition reaction. Under the same reaction conditions, the catalytic activity of CoPVBTPyPC is compared with that of small-molecule CoTPyPC, and the result shows that the catalytic activity of CoPVBTPyPC is only about 10 percent lower than that of CoTPyPC, and the TOF value is 72 times higher than that of CoTPyPC. Since the anion can be used as a nucleophilic reagent to attack the epoxide for ring opening, which plays a decisive role in the catalytic rate, we mainly investigate three common applications of Cl, Br and I in CO2The effect of the anion of the cycloaddition reaction on the reaction system, and the results of the study (numbers 2,3-5 in Table 1) show that under the same conditions, the catalytic activity order of the anion is Br in turn>I>Cl, catalyst TON with Br as anionValue 82534.1, TOF value 1880.8h-1(ii) a This may be related to nucleophilicity and leaving property of the anion, and the larger radius of the ion I is not favorable for moving in the porous of the polymer, so that the catalytic activity of the catalyst is lower than that of the catalyst containing Br. Br is therefore the optimal nucleophile to attack the epoxide and assist in the ring closure and exit of the intermediate.
a Reaction conditions ECH 38.26mmol (3ml), T =80 ℃, T =36h, Cat. 25mg, CO21 atm。
In order to obtain higher catalytic activity, the optimum reaction conditions were also investigated, mainly including reaction time, temperature and catalyst amount. As shown in fig. 6, herein by1H NMR traces the conversion of 12-48H CoPVBTPyPC to the target cyclic carbonate. Under the condition of taking CoPVBTPyPC as a catalyst, the conversion rate of the epichlorohydrin is increased along with the increase of the time, and the conversion rate of the epichlorohydrin reaches 61.5% at 48h, which shows that the time is prolonged to play a positive role in the conversion of the epichlorohydrin, and the time is obviously increased from 36h to 48h, and the conversion rate of the epichlorohydrin is increased from 39.1% to 61.5%, and is increased by about 20%. In order to save energy and time, the catalytic activity of the CoPVBTPyPB is examined under the conditions of 80 ℃ and 48h, and the experimental result shows that the catalytic conversion rate of the CoPVBTPyPB catalyst to epichlorohydrin under the same conditions reaches 80.3 percent (table 1, serial number 4) and is about 20 percent higher than that of the CoPVBTPyPC catalyst with Cl as an anion.
Under the condition of keeping other conditions unchanged, the reaction temperature is increased to 90 ℃ from 80 ℃, the catalytic activity of the CoPVBTPyPC is improved by 20 percent (Table 2), and the conversion rate of the epichlorohydrin is increased to 59.6 percent from 42.4 percent; the catalyst dosage is doubled, the conversion rate of the epichlorohydrin is only increased by less than 5 percent, and the TOF value is reduced to about 1/2, which shows that under the same conditions, the influence of the increased temperature on the conversion rate of the epichlorohydrin is larger than that of the increased time,The dosage efficiency of the catalyst is high. Therefore, we used CoPVBTPyPB as CO with the optimum reaction condition of 25mg of catalyst dosage, 90 ℃ and 48h2The catalyst for cycloaddition reaction has epoxy chloropropane converting rate as high as 92.0% and TON value as high as 109173.1.
aReaction conditions ECH 38.26mmol (3mL), CO21 atm。
In conclusion, the invention obtains poly tetra (4-vinylbenzyl) -pyridyl porphyrin through solution thermal polymerization, and then the poly tetra (4-vinylbenzyl) -pyridyl porphyrin is complexed with metal salt and ion-exchanged to obtain the metal porphyrin-based porous polymer. The metal porphyrin-based porous polymer has ionic liquid and metal porphyrin, contains a metal active center, halogen ions, N + ions and a porous structure, is used as a catalyst for catalyzing cycloaddition reaction of carbon dioxide and epoxide, and shows high-efficiency catalytic activity and high selectivity at normal pressure and low temperature. The invention investigates the influence of different metals, anions and reaction conditions on the metal, and research results show that: the Co center with the strongest Lewis acidity has the best catalytic activity among three metal centers of Co, Zn and Mg; among the three anions Cl, Br and I, better catalytic effect is shown due to the advantages that Br has strong nucleophilicity and small molecular weight and is easy to move in catalyst pores. Under the reaction conditions of 90 ℃, 48h and 25mg CoPVBTPyPBr, the conversion rate of the epichlorohydrin can reach 92.0 percent, and the excellent catalytic effect is shown.
Drawings
FIG. 1 shows the reaction of VBC with TPyP to obtain VBTPyPC1H NMR spectrum.
FIG. 2 shows the UV-Vis spectra of VBTPyPC and TPyP.
FIG. 3 is the N of MPVBTPyPX2Adsorption and desorption curves.
FIG. 4 is a TGA curve of PVBTPyPC versus CoPVBTPyPC, CoPVBTPyPB, and CoPVBTPyPI.
Figure 5 is an SEM image of PVBTPyPC and copbtpypb.
FIG. 6 is a time vs. epoxide and CO2Effect of cycloaddition reaction.
Detailed Description
The preparation of the present invention will be further illustrated by the following specific examples.
(1) Preparation of VBTPyPC
A150 mL round bottom flask was charged with tetrapyridylporphyrin (TPyP, 0.6g, 1.0 mmol), 4-vinylbenzyl chloride (VBC, 1.52g, 10 mmol), 2, 6-di-tert-butyl-p-cresol (BHT, 1.1g, 0.5 mmol), and 50mL anhydrous DMF. The reaction was stirred at 120 ℃ for 72h, and the progress of the reaction was monitored by TLC plates during the reaction. After the reaction was completed, the mixture was cooled to room temperature, washed with ether, and filtered to obtain a purple solid, which was dissolved in methanol, filtered, and then precipitated with ether, and vacuum-dried to a constant weight to obtain VBTPyPC monomer (1.1 g, yield: 90%).
(2) Preparation of PVBTPyPC
1.0g of VBTPyPC monomer is placed in a polytetrafluoroethylene cup, 50mg of Azobisisobutyronitrile (AIBN) is weighed, and 10ml of N-methylpyrrole (DMP) is weighed and added in the polytetrafluoroethylene cup for dissolution. The polytetrafluoroethylene cup was placed in a reaction vessel at 200 ℃ for 72 hours, filtered, washed with DMF until no color was evident in the filtrate, and then PVBTPyPC was placed in a 250ml round bottom flask, and 150ml of DMF was added thereto and refluxed for 12 hours to obtain brown solid PVBTPyPC (0.98 g, yield: 98%).
(3) Preparation of CoPVBTPyPC
Into a 250ml round bottom flask, 1.0g of PVBTPyPC was charged, followed by 1.01g of CoCl2∙6H2O, finally measuring 150ml of anhydrous DMF in N2Refluxing at 150 deg.C for 12h under atmosphere. After completion of the reaction, the reaction system was cooled to room temperature, and HCl (3M, 60 mL) was slowly added dropwise to the reaction system in the air. Filtration and washing with water, drying to constant weight in a vacuum oven at 50 ℃ gave brown solid CoPVBTPyPC (0.98 g, yield: 91%).
The catalytic activity of CoPVBTPyPC is shown in Table 1 (No. 3) and Table 1 (Nos. 1-3).
(4) Preparation of CoPVBTPyPB
A200 ml beaker was taken, 0.5g of CoPVBTPyPC was weighed and poured into the beaker, 0.38g of NaBr and 100ml of deionized water were added into the beaker, and then the mixture was reacted at normal temperature for 48 hours, filtered, washed and dried to obtain brown solid CoPVBTPyPB (0.52 g, yield: 92%).
The catalytic activity of CoPVBTPyPB is shown in Table 1 (No. 4) and Table 1 (No. 4-5).
Example 2
(1) Preparing VBTPyPC: the same as example 1;
(2) preparation of PVBTPyPC: the same as example 1;
(3) preparation of MgPVBTPyPC
In a 250ml round bottom flask, 1.0g PVBTPyPC was added, followed by 1.12g (CH)3CH2)2O·MgBr2Finally, 150ml of anhydrous DMF was taken in N2Refluxing at 160 deg.C for 24h under atmosphere. After the reaction was completed, the reaction system was cooled to room temperature, filtered and washed with water, and dried to constant weight in a vacuum oven at 50 ℃ to obtain MgPVBTPyPC as a brown solid (yield: 90%).
(4) Preparation of MgPVBTPyPB
Taking a 200ml beaker, weighing 0.5g of MgPVBTPyPB, pouring into the beaker, adding 0.4g of NaBr and 100ml of deionized water into the beaker, reacting for 48h at normal temperature, filtering, washing with water, and drying to obtain brown solid MgPVBTPyPB (0.52 g, yield: 92%).
The catalytic activity of MgPVBTPyPB is shown in Table 1 (number 7).
Example 3
(1) Preparing VBTPyPC: the same as example 1;
(2) preparation of PVBTPyPC: the same as example 1;
(3) preparation of ZnPVBTPyPC
In a 250ml round bottom flask, 1.0g of PVBTPyPC was added, followed by 0.96g of (CH)3COO)2Zn·2H2O, finally measuring 150ml of anhydrous DMF in N2Refluxing at 140 deg.C for 20h under atmosphere. After the reaction was completed, the reaction system was cooled to room temperature, filtered and usedWashed with water and dried in a vacuum oven at 50 ℃ to constant weight to obtain brown solid ZnPVBTPyPC (yield: 92%).
(4) Preparation of ZnPVBTPyPB
Taking a 200ml beaker, weighing 0.5g of ZnPVBTPyPB, pouring into the beaker, adding 0.4g of NaBr and 100ml of deionized water into the beaker, reacting for 48h at normal temperature, filtering, washing with water, and drying to obtain brown solid ZnPVBTPyPB (0.52 g, yield: 92%).
The catalytic activity of ZnPVBTPyPB is shown in table 1 (No. 6).
Example 4
(1) Preparing VBTPyPC: the same as example 1;
(2) preparation of PVBTPyPC: the same as example 1;
(3) preparation of copbtpypc: the same as example 1;
(4) a200 ml beaker is taken, 0.5g of CoPVBTPyPC is weighed and poured into the beaker, 0.5g of NaI and 100ml of deionized water are added into the beaker, and then the mixture reacts for 48 hours at normal temperature, is filtered, washed and dried to obtain brown solid CoPVBTPyPI (yield: 95%).
The catalytic activity of CoPVBTPyPI is shown in Table 1 (number 5).
Claims (10)
2. The method for preparing a metalloporphyrin-based porous polymer according to claim 1, comprising the following steps:
(1) preparing VBTPyPC: adding tetrapyridyl porphyrin, 4-vinylbenzyl chloride and 2, 6-di-tert-butyl-p-cresol into DMF, stirring and reacting for 60-75 h at 100-120 ℃, cooling the mixture to room temperature after the reaction is finished, washing with diethyl ether, filtering to obtain purple solid, dissolving with methanol, precipitating with diethyl ether after filtering, and drying in vacuum to obtain tetrakis (4-vinylbenzyl) -pyridylporphyrin VBTPyPC;
(2) preparation of PVBTPyPC: dissolving VBTPyPC and azobisisobutyronitrile into N-methylpyrrole, reacting for 60-75 h at 180-200 ℃, filtering, and washing with DMF (dimethyl formamide) reflux to obtain brown solid poly (4-vinylbenzyl) -pyridylporphyrin PVBTPyPC;
(3) preparation of MPVBTPyPC: PVBTPyPC and metal salt are added to DMF in N2Refluxing for 12-24 h at 140-160 ℃ in an atmosphere, after the reaction is finished, cooling a reaction system to room temperature, filtering, washing, and drying in vacuum to obtain a brown solid, namely the target product of the metal porphyrin-based porous polymer MPVBTPyPC; the metal salt is cobalt chloride hexahydrate, diethyl ether magnesium bromide or zinc acetate dihydrate.
3. The method of claim 2, wherein the step of preparing the metal porphyrin-based porous polymer comprises: the following steps are further included after the step (3): adding MPVBTPyPC and alkali metal halide into deionized water, reacting for 45-50 h at normal temperature, filtering, washing and drying to obtain brown solid, namely the target product MPVBTPyPX; the alkali metal halide is NaBr or NaI, and X is Br or I.
4. The method according to claim 2, wherein the step of preparing the metal porphyrin-based porous polymer comprises: in the step (1), the molar ratio of the tetrapyridylporphyrin, the 4-vinylbenzyl chloride and the 2, 6-di-tert-butyl-p-cresol is 1:4: 0.5-1: 12: 0.5.
5. The method of claim 2, wherein the step of preparing the metal porphyrin-based porous polymer comprises: in the step (2), the mass ratio of VBTPyPC to azobisisobutyronitrile is 10: 1-100: 1.
6. The method according to claim 2, wherein the step of preparing the metal porphyrin-based porous polymer comprises: in the step (3), the mass ratio of the PVBTPyPC to the metal salt is 1: 1-1: 1.5.
7. The method according to claim 3, wherein the step of preparing the metal porphyrin-based porous polymer comprises: the mass ratio of MPVBTPyPC to alkali metal halide is 1: 1-1: 1.5.
8. The metal porphyrin-based porous polymer as claimed in claim 1, which is used as catalyst for CO catalysis2The cycloaddition reaction of cyclic carbonate with epoxide.
9. The metalloporphyrin-based porous polymer of claim 8 as a catalyst for CO catalysis2Use of cycloaddition reaction with epoxides to produce cyclic carbonates, characterised in that: performing cycloaddition reaction by taking a metal porphyrin-based porous polymer as a catalyst and taking an epoxide and carbon dioxide as reaction substrates to obtain cyclic carbonate; the reaction temperature is 50-100 ℃, and the reaction time is 6-48 h.
10. The use of the metal porphyrin-based porous polymer as a catalyst in CO catalysis2Use of cycloaddition reaction with an epoxide to produce a cyclic carbonate, characterized in that: the epoxide is ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, styrene oxide, allyl glycidyl ether, n-butyl glycidyl ether or phenyl glycidyl ether, and the mass-volume ratio of the metal porphyrin-based porous polymer to the epoxide is 8-15 mg/mL; the pressure of carbon dioxide is 1 atm.
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