CN116640244B - Membrane catalytic material for rapidly preparing high molecular weight high-regularity polyacrylate - Google Patents
Membrane catalytic material for rapidly preparing high molecular weight high-regularity polyacrylate Download PDFInfo
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- CN116640244B CN116640244B CN202310788477.XA CN202310788477A CN116640244B CN 116640244 B CN116640244 B CN 116640244B CN 202310788477 A CN202310788477 A CN 202310788477A CN 116640244 B CN116640244 B CN 116640244B
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- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 52
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002135 nanosheet Substances 0.000 claims abstract description 48
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 33
- 238000005286 illumination Methods 0.000 claims abstract description 29
- -1 acrylic ester Chemical class 0.000 claims abstract description 18
- 238000013467 fragmentation Methods 0.000 claims abstract description 17
- 238000006062 fragmentation reaction Methods 0.000 claims abstract description 17
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 15
- 230000002441 reversible effect Effects 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007888 film coating Substances 0.000 claims description 9
- 238000009501 film coating Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 239000011229 interlayer Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- IJPDPFXRBLNDPQ-UHFFFAOYSA-N 3-benzylsulfanylcarbothioylsulfanylpropanoic acid Chemical compound OC(=O)CCSC(=S)SCC1=CC=CC=C1 IJPDPFXRBLNDPQ-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- VURAQNQRBLGZAU-UHFFFAOYSA-N 2-methyl-2-tridecanethioylsulfanylpropanoic acid Chemical compound CCCCCCCCCCCCC(=S)SC(C)(C)C(O)=O VURAQNQRBLGZAU-UHFFFAOYSA-N 0.000 claims description 2
- YOQLRQUGJROXRV-UHFFFAOYSA-N benzenecarbodithioic acid;4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O.SC(=S)C1=CC=CC=C1 YOQLRQUGJROXRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000009826 distribution Methods 0.000 abstract description 17
- 239000000376 reactant Substances 0.000 abstract description 10
- 239000012298 atmosphere Substances 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 40
- 239000010408 film Substances 0.000 description 34
- 229920000642 polymer Polymers 0.000 description 20
- 230000035484 reaction time Effects 0.000 description 14
- 238000003828 vacuum filtration Methods 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- GUDPJHONHNSJBI-PMMFOGROSA-N C([ClH]([2H])([2H])([2H])([2H])[2H])(Cl)(Cl)[2H] Chemical compound C([ClH]([2H])([2H])([2H])([2H])[2H])(Cl)(Cl)[2H] GUDPJHONHNSJBI-PMMFOGROSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- DJSYWQOQABCBNU-UHFFFAOYSA-L [O-]C(C1=CC=C([C](C2=CC=C([C](C3=CC=C([C](C4=CC=C([C]5C(C=C6)=CC=C6C([O-])=O)N4)C(C=C4)=CC=C4C(O)=O)[N]3)C(C=C3)=CC=C3C(O)=O)N2)C2=CC=C5[N]2)C=C1)=O.[Zn+2] Chemical group [O-]C(C1=CC=C([C](C2=CC=C([C](C3=CC=C([C](C4=CC=C([C]5C(C=C6)=CC=C6C([O-])=O)N4)C(C=C4)=CC=C4C(O)=O)[N]3)C(C=C3)=CC=C3C(O)=O)N2)C2=CC=C5[N]2)C=C1)=O.[Zn+2] DJSYWQOQABCBNU-UHFFFAOYSA-L 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000012987 RAFT agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012690 ionic polymerization Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- PSVANWLBOGLTKZ-UHFFFAOYSA-N [Zn].C(=O)(O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 Chemical compound [Zn].C(=O)(O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2 PSVANWLBOGLTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a membrane catalytic material for rapidly preparing high molecular weight high-regularity polyacrylate, which is prepared by utilizing zinc porphyrin metal organic framework nano sheets with photocatalytic activity, and regularly stacking the nano sheets under negative pressure. Under the illumination condition, the reversible addition-fragmentation chain transfer agent is driven by pressure difference to perform in a continuous mobile phase integrated reaction mode, the reversible addition-fragmentation chain transfer agent is firstly subjected to fragmentation at the two-dimensional surface interface of the membrane under the illumination condition to generate free radicals, then acrylic ester and the free radicals perform efficient chain propagation reaction in a one-dimensional limited domain channel of the membrane catalytic material, the product flows out along with a mobile phase and is separated from the system, the rapid acrylic ester polymerization reaction is realized in an air atmosphere, the conversion rate of reactants can reach 96.5%, and meanwhile, the product has high molecular weight (can reach 10) 5 g/mol or more), narrow molecular weight distribution (PDI may be less than 1.3), high stereoregularity.
Description
Technical Field
The invention relates to the technical field of membrane catalytic materials, in particular to a zinc porphyrin metal organic framework membrane catalytic material, a preparation method thereof and application of the zinc porphyrin metal organic framework membrane catalytic material in rapid preparation of high-molecular-weight high-regularity polyacrylate.
Background
Polyacrylate is a polymer formed by taking acrylic ester molecules as monomers under the action of light, heat, an initiator and the like, has good heat stability and corrosion resistance, and is excellent in bending resistance and impact resistance, and widely used in the industries of automobiles, aviation, electronics and the like. It is also used in the fields of heat sensitive adhesive, paint, etc. because of its adhesion and good antiscale property.
The molecular weight, distribution and stereoregularity of the polyacrylate can have a significant impact on the material properties. For example: when the molecular weight of the polyacrylate is increased to 10 5 Above g/mol, the viscosity of the solvent type acrylic acid ester pressure sensitive adhesive can be increased obviously along with the increase of the molecular weight, and the holding power to stainless steel can be increased. The increase of the syndiotactic configuration of the side chain groups of the polyacrylate can raise the glass transition temperature and melting peak of the polymer, and finally improve the thermal stability of the polymer. Propylene is currently availableThe polymerization of acid esters is usually carried out by free radical or ionic polymerization, which generally ends with achiral propagating chains and does not allow regulation of the regularity of the product. However, the use of the ionic polymerization catalyst with high stereoselectivity has the problem of severe use conditions, such as the polymerization reaction temperature is required to be below minus 20 ℃, and some systems even need to be synthesized in a glove box.
Reversible addition-fragmentation chain transfer (RAFT) polymerization is a novel radical polymerization mode, and photo-initiated radical polymerization is realized by introducing a photocatalyst and a RAFT agent, so that heating and thermal initiator are not needed, the influence of oxygen on polymerization can be overcome, and the start and stop of polymerization can be controlled. RAFT polymerization studies have focused mainly on increasing the polymerization rate to obtain a large molecular weight and a narrow molecular weight distribution, but current studies have difficulty in satisfying the above three points and have little attention on the stereoregularity of the polymerization product. In addition, heterogeneous catalysts need to solve the problem of coagulation due to poor dispersibility during polymerization, which is disadvantageous for control of process conditions.
Disclosure of Invention
In order to overcome the defects of low product stereoregularity, long reaction time, low molecular weight, complex and harsh reaction conditions and the like in the existing acrylate polymerization and heterogeneous catalysis RAFT polymerization. The invention provides a zinc porphyrin metal organic framework film catalytic material for acrylate polymerization reaction, a preparation method and application thereof; the membrane catalytic material is formed by stacking zinc porphyrin metal organic framework nano sheets with photocatalytic activity under negative pressure, and has a one-dimensional limiting channel perpendicular to a plane. Under the illumination condition, the RAFT agent generates free radicals under the catalysis of zinc porphyrin centers on the surface of the membrane catalytic material, then takes pressure difference as driving force, and performs efficient chain propagation reaction with acrylate monomers in a one-dimensional limiting channel of the membrane catalytic material, the product flows out along with a mobile phase and is separated from the system, and finally, the RAFT polymerization of the acrylate monomers with high speed (reaction time is less than 10 minutes) and high conversion rate (the conversion rate of reactants can be up to 96.5%) is realized in air atmosphere, and the product has high molecular weight (up to 10) 5 g/mol or more), narrow molecular weight distribution (PDI may be less than 1.3), high stereoregularity.
The invention aims at realizing the following technical scheme:
a method of preparing a membrane catalytic material, the method comprising the steps of:
and (3) performing vacuum suction filtration on the zinc porphyrin metal organic framework nano sheet dispersion liquid to prepare a membrane, and sequentially performing negative pressure drying treatment and heat treatment on the obtained membrane to obtain the membrane catalytic material.
According to an embodiment of the invention, the membrane catalytic material is used for catalyzing the polymerization of acrylic esters.
According to an embodiment of the invention, the zinc porphyrin metal organic framework nano-sheets are few-layer and/or single-layer zinc porphyrin metal organic framework nano-sheets.
According to the embodiment of the invention, the thickness of the zinc porphyrin metal organic framework nano-sheet is 0.5-2.2 nm, for example, 0.5 nm, 0.9 nm, 1.4 nm, 1.9 nm or 2.2 nm.
According to an embodiment of the invention, the diameter of the zinc porphyrin metal organic framework nanoplatelets is >200 nm.
According to the embodiment of the invention, the zinc porphyrin metal organic framework nano-sheet dispersion liquid is dimethyl sulfoxide dispersion liquid of zinc porphyrin metal organic framework nano-sheets.
According to an embodiment of the invention, the concentration of the zinc porphyrin metal organic framework nano-sheet dispersion liquid is 0.1-1.0 mg/mL, for example, 0.1 mg/mL, 0.2 mg/mL, 0.4 mg/mL, 0.5 mg/mL, 0.6 mg/mL, 0.8 mg/mL or 1 mg/mL. The thickness of the membrane catalytic material can be adjusted by adjusting the concentration of the zinc porphyrin metal organic frame nano-sheet dispersion liquid or the suction filtration volume of the dispersion liquid, for example, the greater the concentration of the zinc porphyrin metal organic frame nano-sheet dispersion liquid or the suction filtration volume of the dispersion liquid, the thicker the prepared membrane catalytic material; the smaller the concentration of the zinc porphyrin metal organic framework nano-sheet dispersion or the suction filtration volume of the dispersion, the thinner the thickness of the prepared film catalytic material.
According to the embodiment of the invention, a membrane formed by stacking a plurality of layers of zinc porphyrin metal organic framework nano sheets with a certain thickness is prepared on a porous substrate by adopting a vacuum filtration method, and the specific process is shown in fig. 2.
Wherein the porous substrate is made of polytetrafluoroethylene filter membrane.
Wherein the pore diameter of the porous substrate is 0.1-0.2 μm, for example 0.1 μm.
According to the embodiment of the invention, the vacuum degree of vacuum filtration by adopting a vacuum filtration method is 1-5 Pa.
According to the embodiment of the invention, zinc porphyrin metal organic framework nano sheet dispersion liquid is added into a filter cup matched with vacuum filtration equipment, and a vacuum pump is started to carry out vacuum filtration.
According to an embodiment of the present invention, the drying process is a negative pressure drying process, which is a drying process performed under a negative pressure condition; the negative pressure drying treatment is, for example, to continue the negative pressure suction filtration in this state directly without disassembling the suction filtration device after the dispersion liquid is suction-filtered.
According to an embodiment of the present invention, the temperature of the drying treatment is room temperature, and the time of the drying treatment is 6 to 24 hours, for example, 12 hours.
According to an embodiment of the present invention, the temperature of the heat treatment is 60 to 120 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, or 120 ℃; the heat treatment time is 12 to 36 hours, for example, 24 hours. Through heat treatment, the bonding solvent molecules among the zinc porphyrin metal organic framework nano-sheets can be removed, and defects generated by irregular stacking of the nano-sheets in the membrane are repaired, so that more regular one-dimensional domain-limited channels are generated, and the method is used for preparing high-molecular-weight high-regularity polyacrylate by catalyzing a membrane reactor.
The invention also provides a membrane catalytic material prepared by the method.
According to an embodiment of the present invention, the thickness of the membrane catalytic material is 2 to 30 μm, for example, 2 μm, 3 μm, 4 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, 16 μm, 18 μm, 20 μm, 22 μm, 25 μm, 28 μm or 30 μm; the thin film catalytic material has low mechanical property, is easy to crack in the subsequent catalytic polymerization reaction process, has long vacuum filtration time in the film forming process, is easy to introduce excessive defects in the preparation process, and reduces the structural order of the one-dimensional nano finite field channel provided by the reactive molecules.
According to an embodiment of the invention, the membrane catalytic material is a zinc porphyrin metal organic framework membrane.
According to the embodiment of the invention, the interlayer spacing of the membrane catalytic material is 0.45-0.50 nm, and the aperture perpendicular to the two-dimensional plane is 0.85-1.00 nm; illustratively, the membrane catalytic material has a layer spacing of 0.45 nm, 0.46 nm, 0.47 nm, 0.48 nm, 0.49 nm, or 0.50 nm, and a pore size perpendicular to the two-dimensional plane of 0.85 nm, 0.89 nm, 0.93 nm, or 0.97 nm.
The invention also provides application of the membrane catalytic material in preparation of polyacrylate.
According to an embodiment of the invention, the use of the membrane catalytic material for the preparation of high molecular weight highly structured polyacrylates.
According to an embodiment of the invention, the use of the membrane catalytic material for the rapid preparation of high molecular weight highly structured polyacrylates.
According to an embodiment of the invention, the membrane catalytic material is used for rapidly preparing high molecular weight high-regularity polyacrylate under air atmosphere.
According to the embodiment of the invention, the membrane catalytic material is used for preparing the high-molecular-weight high-regularity polyacrylate in an air atmosphere and at a temperature ranging from 30 ℃ to 50 ℃.
According to the embodiment of the invention, the membrane catalytic material is used for preparing the high-molecular-weight high-regularity polyacrylate in an air atmosphere rapidly at a temperature ranging from 30 ℃ to 50 ℃ and with high conversion rate.
According to an embodiment of the invention, the high molecular weight means a molecular weight of 10 5 g/mol or more, i.e. the polyacrylate has a molecular weight of 10 5 g/mol.
According to an embodiment of the invention, the polyacrylate has a narrow molecular weight distribution, which means that the PDI is less than 1.3, i.e. the PDI of the polyacrylate is less than 1.3.
According to an embodiment of the invention, the fast means that the reaction time is less than 10 minutes, such as less than or equal to 8 minutes.
According to an embodiment of the present invention, the high conversion rate refers to a conversion rate of 65% or more, such as 65-96.5%, for example 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96% or 96.5%.
According to the embodiment of the invention, the temperature range of 30-35 ℃ can be realized under the condition of room temperature only by utilizing illumination without heating, and the temperature range of 35-50 ℃ can be realized by utilizing illumination and heating by a heating device.
According to an embodiment of the present invention, the polyacrylate is prepared from raw materials including an acrylate molecule, a reversible addition-fragmentation chain transfer agent, and a tertiary amine.
The invention also provides a preparation method of the polyacrylate, which comprises the following steps:
a) Dissolving acrylic ester, reversible addition-fragmentation chain transfer agent and tertiary amine in an organic solvent to obtain a film-coating reaction solution;
b) Under the illumination condition, the pressure difference drives the film passing reaction solution to pass through the film catalytic material to carry out acrylic ester polymerization reaction.
According to an embodiment of the present invention, in step a), the molar ratio of the acrylate to the reversible addition-fragmentation chain transfer agent is 50-300:1, for example 200:1.
According to an embodiment of the present invention, in step a), the acrylic acid ester is at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, benzyl acrylate and pentyl acrylate.
According to an embodiment of the present invention, in step a), the reversible addition-fragmentation chain transfer agent is selected from at least one of 3-benzylsulfanyl thiocarbonylsulfanyl propionic acid, 2- (n-butyltrithiocarbonate) -propionic acid, 4-cyano-4- [ (dodecyl-thioether thiocarbonyl) thioether ] pentanoic acid, 2- (dodecylthiocarbonylthio) -2-methylpropionic acid, 4-cyanopentanoic acid dithiobenzoic acid and cumyl benzodithioformate.
According to an embodiment of the present invention, in step a), the molar ratio of the acrylate to the tertiary amine is 25 to 200:1, for example 25:1, 75:1, 150:1 or 200:1.
According to an embodiment of the invention, in step a), the tertiary amine is selected from triethylamine and/or triethanolamine.
According to an embodiment of the present invention, in the step a), the molar ratio of the acrylic acid ester to the organic solvent is 1:0.5-2.0, for example, 1:0.5, 1:0.8, 1:1.2, 1:1.6 or 1:2.0.
According to an embodiment of the invention, in step a), the organic solvent is selected from dimethyl sulfoxide.
According to an embodiment of the present invention, in the step b), the polymerization reaction is driven by a pressure difference under the illumination condition and is performed in a continuous mobile phase aggregation reaction mode, the reversible addition-fragmentation chain transfer agent is firstly fragmented at the two-dimensional surface interface of the membrane under the illumination condition to generate free radicals, then the acrylate and the free radicals are efficiently reacted in a one-dimensional limiting domain channel of the membrane catalytic material, and the product flows out of the system along with the mobile phase, and the specific process is shown in fig. 3.
According to an embodiment of the invention, in step b), the reaction time is less than 10 minutes, for example 1, 5, 8 or 10 minutes.
According to an embodiment of the invention, in step b), the illumination has a wavelength in the range of 350 to 1000 nm, for example 470 nm, and the illumination has an intensity in the range of 10 to 120 mW/cm 2 For example 20 mW/cm 2 、40 mW/cm 2 、60 mW/cm 2 、80 mW/cm 2 、100 mW/cm 2 Or 120 mW/cm 2 。
Light according to an embodiment of the invention, in step b), the illumination is, for example, by obliquely covering the film surface.
According to an embodiment of the invention, in step b), the temperature of the reaction under light conditions refers to a temperature range of 30-50 ℃, e.g. 30 ℃, 32 ℃, 33 ℃, 34 ℃,35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃, 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 48 ℃ or 50 ℃.
According to an embodiment of the present invention, in step b), the pressure difference is greater than 0.1 atm, for example greater than or equal to 0.4 atm, such as greater than or equal to 0.85 atm.
According to an embodiment of the present invention, in step b), the conversion rate of the reaction may reach 65% or more, such as 65 to 96.5%.
According to an embodiment of the invention, in step b), the reaction product has a molecular weight of up to 10 5 The g/mol or more can have a molecular weight distribution of less than 1.3 and a high stereoregularity.
According to an embodiment of the invention, the method further comprises a step of removing oxygen.
According to an embodiment of the present invention, the removal of oxygen is, for example, removal of oxygen within and on the surface of the membrane catalytic material and/or removal of oxygen in the membrane-passing reaction solution.
Illustratively, the organic solvent is driven under light conditions by a pressure differential (pressure differential greater than 0.1 atm, e.g., greater than or equal to 0.4 atm, such as greater than or equal to 0.85 atm) through the membrane catalytic material described above to remove oxygen within the membrane as well as at the membrane surface.
Illustratively, the film-coated reaction solution is added, the pressure difference is not generated, and continuous illumination is performed to remove oxygen in the reaction solution.
According to an embodiment of the present invention, the wavelength of the illumination is 350-1000 nm, for example 470-nm, and the illumination intensity is 10-120 mW/cm 2 For example 20 mW/cm 2 、40 mW/cm 2 、60 mW/cm 2 、80 mW/cm 2 、100 mW/cm 2 Or 120 mW/cm 2 The light is obliquely covered on the surface of the film.
The invention has the beneficial effects that:
the invention provides a membrane catalytic material for rapidly preparing high molecular weight high-regularity polyacrylate, which comprisesThe zinc porphyrin metal organic framework nano-sheets with photocatalytic activity are used and are regularly stacked under negative pressure to prepare the membrane catalytic material with one-dimensional limiting channels perpendicular to the plane and different in thickness. Under the illumination condition, the reversible addition-fragmentation chain transfer agent is driven by pressure difference to perform in a continuous mobile phase integrated reaction mode, the reversible addition-fragmentation chain transfer agent is firstly subjected to fragmentation at the two-dimensional surface interface of the membrane under the illumination condition to generate free radicals, then acrylic ester and the free radicals perform efficient chain propagation reaction in a one-dimensional limited domain channel of the membrane catalytic material, the product flows out along with a mobile phase and is separated from the system, the rapid acrylic ester polymerization reaction is realized in an air atmosphere, the conversion rate of reactants can reach 96.5%, and meanwhile, the product has high molecular weight (can reach 10) 5 g/mol or more), narrow molecular weight distribution (PDI may be less than 1.3), high stereoregularity. The membrane catalytic material is suitable for polymerization reactions of acrylic ester molecules with different reactivities and different sizes, and solves the problem of complicated operation of RAFT polymerization in the past.
The one-dimensional limited domain channel formed by regularly stacking zinc porphyrin metal organic frameworks of the invention enables front line molecular orbits of reactants with different reactivities and different sizes to be matched, reduces the degree of freedom of molecules, enables the molecules to orderly arrange between layers to pass through the channel, reduces the reaction activation energy, thereby realizing the rapid polymerization of acrylic ester molecules with different reactivities and different sizes under the condition of room temperature, the conversion rate of the reactants can reach 96.5 percent at most, and the product has high molecular weight (can reach 10 percent 5 g/mol or more) and narrow molecular weight distribution (PDI may be less than 1.3), and the specific orientation bond induced by the restricted domain channel may allow good stereoregularity of the product.
Drawings
FIG. 1 is a schematic diagram of the preparation process and structure of zinc porphyrin metal organic framework nano-sheets according to a preferred embodiment of the present invention.
FIG. 2 is a schematic diagram showing the preparation process and structure of a membrane catalytic material according to a preferred embodiment of the present invention.
FIG. 3 is a catalytic step and performance characterization of a membrane catalytic material according to a preferred embodiment of the present invention. Wherein, (a) a catalytic step is schematically depicted; (b) nuclear magnetic hydrogen spectrometry of a film-passing substance; (c) Nuclear magnetic carbon spectrum contrast diagram of the product under the reaction condition of the film-passing substance and the common bulk phase; (d) Gel permeation chromatography contrast for the product under common bulk reaction conditions for the transmembrane material.
Detailed Description
< Zinc porphyrin Metal organic framework nanosheets and preparation method thereof >
As mentioned above, the zinc porphyrin metal organic framework nano-sheet can be prepared by the following method: and mixing zinc porphyrin molecule dispersion liquid, copper nitrate solution, surfactant and reaction solvent, and reacting to obtain the zinc porphyrin metal organic framework nano-sheet.
In one embodiment of the present invention, the surfactant is selected from at least one of benzoic acid, biphenyl dicarboxylic acid and polyvinylpyrrolidone.
In one embodiment of the invention, the zinc porphyrin molecule is selected from zinc (II) tetra (4-carboxyphenyl) porphyrin and/or zinc (II) tetra (4-carboxybiphenyl) porphyrin, and the dispersing solvent is N, N-dimethylformamide.
In one embodiment of the present invention, the concentration of the zinc porphyrin molecule dispersion liquid is 0.5 to 5 mmol/L, for example, 0.5, 1, 2 or 5.
In one embodiment of the invention, the copper nitrate solution is an aqueous copper nitrate solution.
In one embodiment of the present invention, the concentration of the copper nitrate solution is 1 to 50 mmol/L, for example, 1 mmol/L, 5 mmol/L, 10 mmol/L, 25 mmol/L, or 50 mmol/L.
In one embodiment of the invention, the molar ratio of zinc porphyrin molecule to copper nitrate is 1:2-20, for example 1:2, 1:5, 1:10, 1:15 or 1:20.
In one embodiment of the invention, the molar ratio of zinc porphyrin molecule to surfactant is 1:200-1300, for example 1:405, 1:490, 1:735, 1:980 or 1:1225.
In one embodiment of the invention, the reaction temperature is 60-90 ℃ and the reaction time is 3-6 hours.
In one embodiment of the invention, the reaction further comprises a washing treatment after completion of the reaction.
In one embodiment of the invention, the washing treatment is to centrifuge the reacted dispersion liquid (the centrifugal rotation speed is 8000-10000 rpm), add ethanol, then carry out ultrasonic treatment for 5 min, then carry out centrifugal treatment to collect centrifugal substrates, circulate for three times, remove unreacted surfactant and zinc porphyrin molecules, and obtain pure zinc porphyrin metal organic frame nano-sheets.
In one embodiment of the invention, the zinc porphyrin metal organic framework nano-sheet dispersion liquid is prepared by the following method: mixing zinc porphyrin metal organic frame nano sheet with dispersion solvent and making ultrasonic treatment.
In one embodiment of the present invention, the time of the ultrasonic treatment is 20-60 min, and the power of the ultrasonic treatment is 100-300W, for example, 150W.
In one embodiment of the invention, the peripheral groups of the zinc porphyrin molecule have carboxyl functional groups that can crosslink with copper ions to form a double paddle wheel structure, and connect to form a metal organic framework structure. The method comprises the steps of utilizing a surfactant to induce growth, and under the condition of the existence of the surfactant, inducing the growth of the metal organic frame along a two-dimensional direction to obtain zinc porphyrin metal organic frame nano-sheets; further, after cleaning and dispersing the zinc porphyrin metal organic frame nano-sheets, a dispersion liquid comprising the zinc porphyrin metal organic frame nano-sheets is obtained, and the specific structure is shown in fig. 1.
In one embodiment of the present invention, illustratively, there is provided: taking zinc porphyrin molecule N, N-dimethylformamide dispersion liquid with the concentration of 40 mL of 1 mmol/L, adding copper nitrate solution with the concentration of 20 mL of 10 mmol/L, adding 3.6 g benzoic acid, stirring for 10 minutes, heating to 90 ℃ and stirring for 5 hours, centrifuging after the reaction is finished to remove supernatant, washing a sample with ethanol, and vacuum drying for 24 hours. Dispersing the dried substrate with 225 mL dimethyl sulfoxide, performing ultrasonic treatment for 30 min with 150W, transferring the dispersion into a reagent bottle after ultrasonic dispersion, and sealing and preserving at room temperature.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Quantitatively analyzing the film sample through nuclear magnetic resonance hydrogen spectrum, and calculating the reaction conversion rate, wherein the method specifically comprises the following steps:
using deuterated reagent (C) 2 D 6 OS) washing and collecting the membrane-passing sample, and preparing a nuclear magnetic sample. Characteristic hydrogen is present in both the reactant and product molecules. The characteristic hydrogen has a corresponding relation with the molecular number, the integral area of a single peak at different chemical displacement positions is calculated and compared through single peak fitting, the corresponding molecular number ratio is calculated, and then the reaction conversion rate is calculated.
Analyzing the purified membrane sample by gel permeation chromatography, and detecting the molecular weight of the polymerization product, wherein the method specifically comprises the following steps:
methanol was used: the polymerization product was purified by combining a petroleum ether mixed solution (volume ratio 1:1) with a centrifugation step. Preparing a gel permeation chromatography sample, and performing gel permeation chromatography characterization to characterize the molecular weight and molecular weight distribution of the gel permeation chromatography sample.
Analyzing the purified film sample through nuclear magnetic resonance carbon spectrum, and detecting the stereoregularity of a polymerization product, wherein the method specifically comprises the following steps of:
methanol was used: the polymerization product was purified by combining a petroleum ether mixed solution (volume ratio 1:1) with a centrifugation step. Using deuterated reagent (CDCl) 3 ) Nuclear magnetic samples were prepared, and characteristic carbon peaks were present for polymers of different configurations. The stereoregularity of the polymerization product is characterized by the peak shape of the characteristic carbon peak.
Example 1
Taking N, N-dimethyl methyl 40 mL zinc (4-carboxyphenyl) porphyrin (II)The amide dispersion (1 mmol/L) was stirred and then added with stirring to a mixture of 20. 20 mL aqueous copper nitrate (10 mmol/L), 3.6. 3.6 g benzoic acid and 200 mLN, N-dimethylformamide, followed by stirring for 10 minutes, and then heating to 90℃and stirring for reaction for 5 hours. After the reaction was completed and cooled to room temperature, the reaction solution was centrifuged (at 10000 rpm) to obtain a centrifugal substrate. Adding 120 mL ethanol, treating with 150W ultrasonic power for 5 minutes, centrifuging (the centrifugal speed is 8000 rpm) to collect a substrate, circulating for three times, vacuum drying for 24 hours after cleaning, and treating with 225 mL dimethyl sulfoxide with 150W ultrasonic power for 30 minutes to obtain zinc porphyrin metal organic frame nano-sheet dispersion. The mixture was stored at room temperature under sealed conditions (at a concentration of about 0.2. 0.2 mg/mL) and the dispersion was labeled Zn-PMOF. The atomic force microscope height curve of the nanosheets shows that the zinc porphyrin metal organic framework nanosheets are few-layer metal organic framework nanosheets, the thickness of the nanosheets is 1.9 nm (corresponding to the thickness of 4-5 atomic layers), and the sheet diameter is equal to that of the nanosheets>200 nm. Centrifugally drying the Zn-PMOF dispersion liquid to obtain 1700 cm in infrared spectrum data of Zn-PMOF nano sheet powder −1 The marked reduction in C=O stretching vibration compared to zinc (II) tetrakis (4-carboxyphenyl) porphyrin indicates Cu 2 (COO) 4 The formation of the paddle wheel metal nodes also means the formation of a metal-organic framework structure.
23.5 mL of Zn-PMOF dispersion was collected, a membrane was prepared by vacuum filtration (vacuum degree: 0.7 atm), after the solvent above the membrane was drained, the membrane was directly vacuum-filtered (vacuum degree: 0.7 atm) in this state without disassembling the filtration apparatus for 12 hours, and the apparatus was transferred to an oven for heat treatment at 80℃for 24 hours, which was designated as Zn-PMOF-80 ℃. The Zn-PMOF-80℃film cross-sectional thickness was observed by a scanning electron microscope to be about 20.1. Mu.m. X-ray diffraction data indicated that the Zn-PMOF-80℃film interlayer size was about 0.47. 0.47 nm. The data of nitrogen adsorption and desorption show that the size of a one-dimensional limiting channel of the Zn-PMOF-80 ℃ film perpendicular to a plane is about 0.93 nm. The UV visible diffuse reflectance data shows that the Zn-PMOF-80deg.C film has a light absorbance of 0.89 for 470 nm.
The Zn-PMOF-80 ℃ film is used as a catalyst to catalyze the polymerization reaction of acrylic ester, and the specific operation is as follows: 949.3. Mu.L of benzyl acrylate, 8.7. 8.7 mg were reversibly addition-fragmentationThe split chain transfer agent 3-benzylsulfanyl thiocarbonylsulfanyl propionic acid and 16.9. Mu.L triethanolamine were dissolved in 578. Mu.L dimethyl sulfoxide to give a film-coated reaction solution; the micro suction filtration device sealed with Zn-PMOF-80 ℃ film is fixed on a iron stand, and the light irradiation head of 470 and nm is fixed, so that the light irradiates to cover the surface of the film obliquely. At 120 mW/cm 2 Under the illumination intensity, 500 mu L of dimethyl sulfoxide is added into a measuring cylinder above a suction filtration device, and the organic solvent is driven by a pressure difference (0.85 atm) to pass through the membrane catalytic material. Adding 1.5. 1.5 mL membrane-passing reaction solution, and maintaining the pressure at 40. 40 mW/cm without pressure difference 2 Continuously irradiating for 30 minutes under the irradiation of light to remove oxygen in the reaction solution; after removal of the dimethyl sulfoxide flowing through the preceding step, the reaction mixture was purified at 40 mW/cm 2 Under the illumination of the (2), the reaction solution passes through a one-dimensional limiting channel of the Zn-PMOF-80 ℃ film vertical to the plane under the drive of a pressure difference (0.85 atm), reactants are polymerized in the one-dimensional limiting channel, and products flow out along with dimethyl sulfoxide. After dissolving the product with dimethyl sulfoxide-d 6, using 1 The H NMR spectrum analyzes its components and determines the conversion.
The reaction results are: the temperature of the reaction liquid in the filter cup under the illumination condition is 32 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 96.5%. The polymer had a number average molecular weight of 161868 g/mol, a weight average molecular weight of 207475 g/mol and a molecular weight distribution coefficient of 1.282. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Example 2
Other operations are the same as in example 1, except that:
18.8 mL of the Zn-PMOF dispersion was collected, a membrane was prepared by vacuum filtration (vacuum degree: 0.7 atm), after the solvent above the membrane was drained, the membrane was directly vacuum-filtered (vacuum degree: 0.7 atm) in this state without disassembling the filtration apparatus for 12 hours, and the apparatus was transferred to an oven for heat treatment at 80℃for 24 hours. The film cross-sectional thickness was observed by a scanning electron microscope to be about 15.8 μm and was designated Zn-PMOF-16. Mu.m. X-ray diffraction data indicated that the Zn-PMOF-16 μm interlayer size was about 0.47. 0.47 nm.
The Zn-PMOF-16 mu m film is used as a catalyst to catalyze the polymerization reaction of benzyl acrylate, and the reaction result is as follows: the temperature of the reaction liquid in the filter cup under the illumination condition is 32 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 93.1%. The polymer had a number average molecular weight of 153657 g/mol, a weight average molecular weight of 198367 g/mol and a molecular weight distribution coefficient of 1.291. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Example 3
Other operations are the same as in example 1, except that:
14.1 mL of Zn-PMOF dispersion was collected, a membrane was prepared by vacuum filtration (vacuum degree: 0.7 atm), after the solvent above the membrane was drained, the membrane was directly vacuum-filtered (vacuum degree: 0.7 atm) in this state without disassembling the filtration apparatus for 12 hours, and the apparatus was transferred to an oven for heat treatment at 80℃for 24 hours. The cross-sectional thickness of the film was observed by a scanning electron microscope to be about 11.7. Mu.m, and was designated as Zn-PMOF-12. Mu.m. X-ray diffraction data indicated that the Zn-PMOF-12 μm interlayer size was about 0.47. 0.47 nm.
The Zn-PMOF-12 mu m film is used as a catalyst to catalyze the polymerization reaction of benzyl acrylate, and the reaction result is as follows: the temperature of the reaction liquid in the filter cup under the illumination condition is 32 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 86.1 percent. The polymer had a number average molecular weight of 145182, g/mol, a weight average molecular weight of 188476 g/mol and a molecular weight distribution coefficient of 1.298. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Example 4
Other operations are the same as in example 1, except that:
9.5 mL of Zn-PMOF dispersion was collected, a membrane was prepared by vacuum filtration (vacuum degree: 0.7 atm), after the solvent above the membrane was drained, the membrane was directly vacuum-filtered (vacuum degree: 0.7 atm) in this state without disassembling the filtration apparatus for 12 hours, and the apparatus was transferred to an oven for heat treatment at 80℃for 24 hours. The cross-sectional thickness of the film was observed by a scanning electron microscope to be about 8.2. Mu.m, and was designated Zn-PMOF-8. Mu.m. X-ray diffraction data indicated that the Zn-PMOF-8 μm interlayer size was about 0.47. 0.47 nm.
The Zn-PMOF-8 mu m film is used as a catalyst to catalyze the polymerization reaction of benzyl acrylate, and the reaction result is as follows: the temperature of the reaction liquid in the filter cup under the illumination condition is 32 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 78.6%. The polymer had a number average molecular weight of 132762 g/mol, a weight average molecular weight of 174183 g/mol and a molecular weight distribution coefficient of 1.312. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Example 5
Other operations are the same as in example 1, except that:
4.8 mL of Zn-PMOF dispersion was collected, a membrane was prepared by vacuum filtration (vacuum degree: 0.7 atm), after the solvent above the membrane was drained, the membrane was directly vacuum-filtered (vacuum degree: 0.7 atm) in this state without disassembling the filtration apparatus for 12 hours, and the apparatus was transferred to an oven for heat treatment at 80℃for 24 hours. The cross-sectional thickness of the film was observed by a scanning electron microscope to be about 4.1. Mu.m, and was designated as Zn-PMOF-4. Mu.m. X-ray diffraction data indicated that the Zn-PMOF-4 μm interlayer size was about 0.47. 0.47 nm.
The Zn-PMOF-4 mu m film is used as a catalyst to catalyze the polymerization reaction of benzyl acrylate, and the reaction result is as follows: the temperature of the reaction liquid in the filter cup under the illumination condition is 32 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 68.9%. The polymer had a number average molecular weight of 120138 g/mol, a weight average molecular weight of 159302 g/mol and a molecular weight distribution coefficient of 1.326. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Example 6
The Zn-PMOF-4 μm film of example 5 was used as a catalyst to catalyze the polymerization of benzyl acrylate in an oven at 35℃as a result of: the temperature of the reaction liquid in the filter cup under the illumination condition is 37 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 88.3 percent. The polymer has a number average molecular weight of 132485 g/mol and a weight average molecular weight173422 g/mol and a molecular weight distribution coefficient of 1.309. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Example 7
The Zn-PMOF-4 μm film of example 5 was used as a catalyst to catalyze the polymerization of benzyl acrylate in an oven at 40℃as a result of: the temperature of the reaction liquid in the filter cup under the illumination condition is 42 ℃, the film-coating reaction time is less than 8 minutes, and the conversion rate is 93.4%. The polymer had a number average molecular weight of 143509 g/mol, a weight average molecular weight of 186131 g/mol and a molecular weight distribution coefficient of 1.297. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity showed only a single peak at 41.5 ppm of the polymerized product, indicating good stereoregularity.
Comparative example 1
40 mL tetra (4-carboxyphenyl) porphyrin in N, N-dimethylformamide dispersion (1 mmol/L) was added with stirring to prepare a mixture, and 20 mL copper nitrate aqueous solution (10 mmol/L), 3.6 g benzoic acid and 200 mLN, N-dimethylformamide were stirred for 10 minutes and mixed uniformly, and then heated to 90℃and stirred for reaction for 5 hours. After the reaction was completed and cooled to room temperature, the reaction solution was centrifuged (at 10000 rpm) to obtain a centrifugal substrate. Adding 120 mL ethanol, treating with 150W ultrasonic power for 5 minutes, centrifuging (the centrifugal speed is 8000 rpm) to collect a substrate, circulating for three times, vacuum drying for 24 hours after cleaning, and treating with 225 mL dimethyl sulfoxide with 150W ultrasonic power for 30 minutes to obtain zinc porphyrin metal organic frame nano-sheet dispersion. The mixture was stored at room temperature under sealed conditions (at a concentration of about 0.2. 0.2 mg/mL) and the dispersion was labeled as Cu-PMOF. The atomic force microscope height curve of the nano-sheet shows that the nano-sheet of the metal organic frame is a few-layer nano-sheet of the metal organic frame, the thickness of the nano-sheet is 1.8 nm (equivalent to the thickness of 4-5 atomic layers), and the sheet diameter is equal to that of the nano-sheet>200 nm. Centrifugally drying the Cu-PMOF dispersion liquid to obtain Cu-PMOF nano-sheet powder, wherein 1700 cm in infrared spectrum data of the Cu-PMOF nano-sheet powder −1 The marked reduction in C=O stretching vibration compared to zinc (II) tetrakis (4-carboxyphenyl) porphyrin indicates Cu 2 (COO) 4 The formation of the paddle wheel metal nodes also means the formation of a metal-organic framework structure.
22.3 mL of Cu-PMOF dispersion is added into an upper filter cup, a membrane is prepared by vacuum filtration (vacuum degree is 0.7 atm), after solvent above the membrane is pumped out, the vacuum filtration device is directly removed under negative pressure (vacuum degree is 0.7 atm) for 12 hours under the state, and the device is transferred into an oven for heat treatment at 80 ℃ for 24 hours, and the membrane is named as Cu-PMOF. The Cu-PMOF film cross-sectional thickness was observed by a scanning electron microscope to be about 18.7 μm. The X-ray diffraction data indicate that the Cu-PMOF film interlayer size is about 0.47 nm.
The Cu-PMOF film is used as a catalyst to catalyze the polymerization reaction of acrylic ester, and the specific operation is as follows: 949.3. Mu.L of benzyl acrylate, 8.7. 8.7 mg of reversible addition-fragmentation chain transfer agent and 16.9. Mu.L of triethanolamine were dissolved in 578. Mu.L of dimethyl sulfoxide to give a film-coated reaction solution; the micro suction filtration device sealed with the Cu-PMOF film was fixed to a stand of iron, and the light head of 470, nm was fixed so that the light was obliquely covered on the film surface. At 120 mW/cm 2 Under the illumination intensity, 500 mu L dimethyl sulfoxide is added into a measuring cylinder above the suction filtration device, and the organic solvent passes through the membrane catalytic material through pressure difference driving. Adding 1.5. 1.5 mL membrane-passing reaction solution, and maintaining the pressure at 40. 40 mW/cm without pressure difference 2 Continuously irradiating for 30 minutes under the irradiation of light to remove oxygen in the reaction solution; after removal of the dimethyl sulfoxide flowing through the preceding step, the reaction mixture was purified at 40 mW/cm 2 Under the illumination of the (2), the reaction solution passes through a one-dimensional limited-area channel of the Cu-PMOF film perpendicular to the plane under the drive of a pressure difference (0.85 atm), reactants are polymerized in the one-dimensional channel, and the product flows out along with the dimethyl sulfoxide. After dissolving the product with dimethyl sulfoxide-d 6, using 1 The H NMR spectrum analyzes its components and determines the conversion. The temperature of the reaction solution in the filter bowl under the illumination condition is 32 ℃, and the conversion rate is 0.1%.
Comparative example 2
The Zn-PMOF nanosheets are used as catalysts to catalyze the polymerization reaction of acrylic ester, and the ratio of reactants is also the ratio which is common to the prior RAFT polymerization species as a comparison of catalyzing polymerization under the condition of non-finite fields. The specific operation is as follows: 949.3 mu L of propyleneBenzyl acid ester, 8.7 mg reversible addition-fragmentation chain transfer agent 3-benzylsulfanyl thiocarbonylsulfanyl propionic acid and 16.9 μl of triethanolamine were dissolved in 578 μl of 0.2 mg/mL Zn-PMOF nano dimethyl sulfoxide dispersion to obtain a reaction solution; the reaction solution was added to a 10 mL hour beaker, and a light irradiation head of 470 nm was fixed so that the light was irradiated to cover the reaction solution obliquely. At 40 mW/cm 2 Continuously irradiating for 30 minutes under the irradiation of light to remove oxygen in the reaction solution; then at 40 mW/cm 2 The beaker was shaken every half hour to prevent catalyst agglomeration, the reactants were polymerized in the bulk phase, and the product was aspirated with a pipette at fixed time points for analysis. After dissolving the product with dimethyl sulfoxide-d 6, using 1 The H NMR spectrum analyzes its components and determines the conversion.
The reaction results are: the conversion was 10.1% at a reaction time of 10 minutes. If the conversion rate reaches over 96.5%, the reaction time is over 150 minutes. The number average molecular weight of the bulk reaction polymer was 15680 g/mol, the weight average molecular weight was 21789/g/mol, and the molecular weight distribution coefficient was 1.390. Dissolving the purified polymer product with chloroform-d 6, using 13 C NMR spectrum analysis of its stereoregularity, the polymerization product at 41.5 ppm was multimodal and the inclusion of a peak indicates poor stereoregularity.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method of preparing a membrane catalytic material, wherein the method comprises the steps of:
vacuum filtering zinc porphyrin metal organic frame nano sheet dispersion liquid to prepare a membrane, and sequentially carrying out negative pressure drying treatment and heat treatment on the obtained membrane to obtain the membrane catalytic material;
the zinc porphyrin metal organic framework nano-sheet is prepared by the following method: and mixing zinc porphyrin molecule dispersion liquid, copper nitrate solution, surfactant and reaction solvent, and reacting to obtain the zinc porphyrin metal organic framework nano-sheet.
2. The preparation method of claim 1, wherein the zinc porphyrin metal organic framework nano-sheet has a thickness of 0.5-2.2 nm.
3. The production method according to claim 1, wherein the drying treatment is a negative pressure drying treatment, the negative pressure drying treatment is a drying treatment performed under a negative pressure condition, the temperature of the drying treatment is room temperature, and the time of the drying treatment is 6 to 24 hours;
and/or the temperature of the heat treatment is 60-120 ℃; the heat treatment time is 12-36 hours.
4. A membrane catalytic material prepared by the method of any one of claims 1-3.
5. The membrane catalytic material of claim 4, wherein the thickness of the membrane catalytic material is 2-30 μιη; and/or the interlayer spacing of the membrane catalytic material is 0.45-0.50 nm, and the aperture perpendicular to the two-dimensional plane is 0.85-1.00 nm.
6. Use of the membrane catalytic material of claim 4 or 5 for the preparation of benzyl polyacrylate.
7. A process for the preparation of benzyl polyacrylate, the process comprising the steps of:
a) Dissolving benzyl acrylate, a reversible addition-fragmentation chain transfer agent and tertiary amine in an organic solvent to obtain a film-coating reaction solution;
b) Under the illumination condition, the pressure difference drives the film passing reaction solution to pass through the film catalytic material as claimed in claim 5 or 6 to carry out acrylic ester polymerization reaction.
8. The process according to claim 7, wherein in step a), the tertiary amine is selected from triethylamine and/or triethanolamine; and/or the organic solvent is selected from dimethyl sulfoxide; and/or the reversible addition-fragmentation chain transfer agent is selected from at least one of 3-benzylsulfanyl thiocarbonylsulfanyl propionic acid, 2- (n-butyltrithiocarbonate) -propionic acid, 4-cyano-4- [ (dodecyl-thioether thiocarbonyl) thioether ] pentanoic acid, 2- (dodecyl thiocarbonylthio) -2-methylpropanoic acid, 4-cyanovaleric acid dithiobenzoic acid, and cumyl benzodithioformate; and/or the molar ratio of the acrylic ester to the reversible addition-fragmentation chain transfer agent is 50-300:1; and/or the molar ratio of the acrylic ester to the tertiary amine is 25-200:1; and/or the molar ratio of the acrylic ester to the organic solvent is 1:0.5-2.0.
9. The production method according to claim 7 or 8, wherein the method further comprises an oxygen removal step of removing oxygen in the membrane catalyst material and on the surface of the membrane catalyst material and/or removing oxygen in the membrane-passing reaction liquid.
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