CN112724345A - Conjugated microporous polymer, preparation method thereof and application thereof in visible light induced controllable free radical polymerization - Google Patents
Conjugated microporous polymer, preparation method thereof and application thereof in visible light induced controllable free radical polymerization Download PDFInfo
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- CN112724345A CN112724345A CN202011531832.8A CN202011531832A CN112724345A CN 112724345 A CN112724345 A CN 112724345A CN 202011531832 A CN202011531832 A CN 202011531832A CN 112724345 A CN112724345 A CN 112724345A
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- phenanthridine
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- iodide
- bromide
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 39
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000011261 inert gas Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 230000001678 irradiating effect Effects 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 230000002441 reversible effect Effects 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 230000001404 mediated effect Effects 0.000 claims abstract description 13
- 238000010668 complexation reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- -1 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine iodide Chemical group 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
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- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 8
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- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 6
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- ZLSOONVQLWLPMF-UHFFFAOYSA-M 3-(3,8-diamino-6-phenylphenanthridin-5-ium-5-yl)propyl-diethyl-methylazanium;dibromide Chemical group [Br-].[Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 ZLSOONVQLWLPMF-UHFFFAOYSA-M 0.000 claims description 4
- YOXHQRNDWBRUOL-UHFFFAOYSA-N 4-(4-formyl-n-(4-formylphenyl)anilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC(C=O)=CC=1)C1=CC=C(C=O)C=C1 YOXHQRNDWBRUOL-UHFFFAOYSA-N 0.000 claims description 4
- ZCJZVMNBJKPQEV-UHFFFAOYSA-N 4-[3,5-bis(4-formylphenyl)phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC(C=2C=CC(C=O)=CC=2)=CC(C=2C=CC(C=O)=CC=2)=C1 ZCJZVMNBJKPQEV-UHFFFAOYSA-N 0.000 claims description 4
- RXFWPOMAJBVGRU-UHFFFAOYSA-N 4-[4,6-bis(4-formylphenyl)-1,3,5-triazin-2-yl]benzaldehyde Chemical compound N1=C(N=C(N=C1C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1)C1=CC=C(C=O)C=C1 RXFWPOMAJBVGRU-UHFFFAOYSA-N 0.000 claims description 4
- FRMCVETXKAMMJA-UHFFFAOYSA-N 4-[4-[3,5-bis[4-(4-formylphenyl)phenyl]phenyl]phenyl]benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=2C=C(C=C(C=2)C=2C=CC(=CC=2)C=2C=CC(C=O)=CC=2)C=2C=CC(=CC=2)C=2C=CC(C=O)=CC=2)C=C1 FRMCVETXKAMMJA-UHFFFAOYSA-N 0.000 claims description 4
- ISDBWOPVZKNQDW-UHFFFAOYSA-N 4-phenylbenzaldehyde Chemical group C1=CC(C=O)=CC=C1C1=CC=CC=C1 ISDBWOPVZKNQDW-UHFFFAOYSA-N 0.000 claims description 4
- SJPSPCODIPFASV-UHFFFAOYSA-N 5-ethyl-6-phenylphenanthridin-5-ium-3,8-diamine;iodide Chemical group [I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 SJPSPCODIPFASV-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UHLOCXITIOEOCB-UHFFFAOYSA-N COC(C(C(C(C1OC)=C=O)OC)=C=O)C1=C=O Chemical compound COC(C(C(C(C1OC)=C=O)OC)=C=O)C1=C=O UHLOCXITIOEOCB-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- XJMOSONTPMZWPB-UHFFFAOYSA-M propidium iodide Chemical group [I-].[I-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CCC[N+](C)(CC)CC)=C1C1=CC=CC=C1 XJMOSONTPMZWPB-UHFFFAOYSA-M 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- GJAJJEGWMDUKFM-UHFFFAOYSA-N 5-[3,5-bis(6-formylpyridin-3-yl)phenyl]pyridine-2-carbaldehyde Chemical compound O=Cc1ccc(cn1)-c1cc(cc(c1)-c1ccc(C=O)nc1)-c1ccc(C=O)nc1 GJAJJEGWMDUKFM-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- DBESYUOJKJZGLV-UHFFFAOYSA-N 2-iodo-2-methylpropanenitrile Chemical compound CC(C)(I)C#N DBESYUOJKJZGLV-UHFFFAOYSA-N 0.000 claims description 2
- WKZUKIUUBDORKH-UHFFFAOYSA-N 2-iodo-2-phenylacetonitrile Chemical compound N#CC(I)C1=CC=CC=C1 WKZUKIUUBDORKH-UHFFFAOYSA-N 0.000 claims description 2
- MEKNBSXCEMCLHJ-UHFFFAOYSA-N 2-iodopropanenitrile Chemical compound CC(I)C#N MEKNBSXCEMCLHJ-UHFFFAOYSA-N 0.000 claims description 2
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- 239000003086 colorant Substances 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 2
- IERHLVCPSMICTF-XVFCMESISA-N CMP group Chemical group P(=O)(O)(O)OC[C@@H]1[C@H]([C@H]([C@@H](O1)N1C(=O)N=C(N)C=C1)O)O IERHLVCPSMICTF-XVFCMESISA-N 0.000 claims 1
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- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
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- 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
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
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- 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
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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Abstract
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a conjugated microporous polymer, a preparation method thereof and application thereof in visible light induced controllable free radical polymerization. The method takes the synthesized conjugated microporous polymer material as a catalyst. At room temperature, adding a polymerization monomer, a catalyst, an initiator and a solvent into a Schlenk tube according to a certain proportion, and under the protection of inert gas, irradiating by using an LED lamp strip to perform reversible complexation mediated polymerization to obtain a polymer with low dispersity and various block polymers, wherein the prepared polymer chain end has good activity. The conjugated microporous polymer materials (CMPs) used in the invention can be synthesized at room temperature, so that the energy consumption is saved and the safety is higher; the conjugated microporous polymer material used in the method has the advantages of large specific surface area, high stability, accurate regulation and control of micropore size and volume, repeated use, high catalytic efficiency and strong applicability, and is suitable for large-scale application.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a conjugated microporous polymer, a preparation method thereof and application thereof in visible light induced controllable free radical polymerization.
Background
In recent years, Controlled Radical Polymerization (CRP) has been widely developed and used to prepare polymer materials having precise structures, controlled molecular weights, and uniform distribution. Methods of controlled radical polymerization are also being developed, such as nitroxide stable radical polymerization (NMP), Atom Transfer Radical Polymerization (ATRP), reversible addition-fragmentation chain transfer radical polymerization (RAFT), reversible chain transfer catalyzed polymerization (RTCP), Reversible Complex Mediated Polymerization (RCMP), and the like. These polymerization techniques open up a new way for the diversity of the polymer structure and the function. Compared with the traditional thermal initiation polymerization process, the photo-induced free radical polymerization condition is milder, which provides an important way for realizing wider application of the polymer.
Compared with other controllable active free radical polymerization, RCMP has the advantages that the catalyst is various in forms, and the RCMP is also suitable for controllable polymerization of various functional monomers. RCMP can be used for synthesizing polymers with definite composition, controllable molecular weight and uniform molecular weight, and the polymers are widely applied to the fields of clinical medicine, biomedicine, medical care, cosmetics, pesticide release and the like.
The conjugated microporous polymer materials (CMPs) are organic porous materials with a very promising prospect, have the advantages of pi-conjugation, large specific surface area, high stability, accurately controllable micropore size and volume, high chemical stability and thermal stability and the like, can be repeatedly used, have high catalytic efficiency and strong applicability, are suitable for large-scale application, and have important application in various fields such as gas adsorption, chemical sensing, heterogeneous catalysis, energy storage and conversion and the like. Conduction of electrons and holes is affected due to pi-conjugation of the conjugated microporous polymer material. Therefore, the CMPs have potential application prospects in the light-induced RCMP process.
Disclosure of Invention
The invention aims to provide a conjugated microporous polymer, a preparation method thereof and application thereof in visible light induced controllable free radical polymerization.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a preparation method of a conjugated microporous polymer by utilizing visible light to induce controllable free radical polymerization specifically comprises the following steps: at room temperature, adding a polymerization monomer, a catalyst, an initiator and a solvent into a polymerization tube according to a certain proportion, and under the protection of inert gas, irradiating by using an LED lamp strip to realize reversible complexation-mediated polymerization (RCMP), so as to obtain a polymer with low dispersity (PDI = 1.15-1.24) and various block polymers.
Preferably, when carrying out RCMP, the catalyst is conjugated microporous polymer materials (CMPs) having the following molecular structure:
wherein: r is trimesic aldehyde, trialdehyde phloroglucinol, 1,3, 5-tris (p-formylphenyl) benzene, tris (4-formylphenyl) amine, 2,4, 6-tris (4-formylphenyl) -1, 3, 5-triazine, tris (4-formylbiphenyl) amine, 1,3, 5-tris (4 ' -formyl [1,1 ' -biphenyl ] -4-yl) benzene, benzo [1,2-b:3,4-b ': 5,6-b ' ] trithiophene-2, 5, 8-trialdehyde, [1,3, 5-trimethyl-2, 4, 6-tris (4 ' -formylphenyl) ] benzene, 1,3, 5-trimethoxy-2, 4, 6-trimethyloylbenzene, 1,3, 5-tris (2-formylpyridin-5-yl) benzene, M is ethidium bromide, propidium bromide, ethidium iodide, propidium iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine bromide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine iodide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine bromide, 3, 8-diamino-6-phenyl-5-propyl-phenanthridine iodide, and 3, 8-diamino-6-phenyl-5-propyl-phenanthridine bromide.
Preferably, the preparation method of the conjugated microporous polymer materials (CMPs) is as follows: the aldehyde monomer is obtained by condensation reaction with amino monomer in the presence of solvent and catalyst. The solvent is one or more of 1, 4-Dioxane (Dioxane), 1,3, 5-trimethylbenzene (Mesitylene), N-dimethylacetamide (DMAc) or N, N-Dimethylformamide (DMF); the catalyst is 3M or 6M acetic acid (AcOH); the aldehyde monomer is trimesic aldehyde, trialdehyde phloroglucinol, 1,3, 5-tri (p-formylphenyl) benzene, tri (4-formylphenyl) amine, 2,4, 6-tri (4-formylphenyl) -1, 3, 5-triazine, tri (4-formylbiphenyl) amine, 1,3, 5-tri (4 ' -formyl [1,1 ' -biphenyl ] -4-yl) benzene, benzo [1,2-b:3,4-b ': 5,6-b ' ] trithiophene-2, 5, 8-trialdehyde, [1,3, 5-trimethyl-2, 4, 6-tri (4 ' -formylphenyl) ] benzene, 1,3, 5-trimethoxy-2, 4, 6-trimethyloylbenzene, 1,3, 5-tris (2-formylpyridin-5-yl) benzene; the amino monomer is ethidium bromide, propidium bromide, ethidium iodide, propidium iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine iodide, one of 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine bromide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine iodide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine bromide, 3, 8-diamino-6-phenyl-5-propyl-phenanthridine iodide, and 3, 8-diamino-6-phenyl-5-propyl-phenanthridine bromide; the temperature of the condensation reaction is 25 ℃; the time for the condensation reaction was 48 h.
Preferably, when the RCMP polymerization reaction is carried out, the polymerized monomers are tert-butyl methacrylate (tBMA), benzyl methacrylate (BzMA), Methyl Methacrylate (MMA), Butyl Acrylate (BA), phenyl methacrylate (PhMA), Butyl Methacrylate (BMA), Glycidyl Methacrylate (GMA), Methyl Acrylate (MA), tert-butyl methacrylate (t-butyl methacrylate) (tBMA)t-BuMA), methoxyethyl methacrylate (MEMA) or hydroxyethyl methacrylate (HEMA).
Preferably, the RCMP polymerization is carried out with 2-iodo-2-methylpropanenitrile (CP-I); 2-iodopropionitrile (CE-I), alpha-iodophenylacetic acid ethyl ester (PhE-I), alpha-iodophenylacetonitrile (PhCN-I), and 2-iodo-2-methyl malonic acid diethyl ester (EEMA-I).
Preferably, the RCMP polymerization reaction is carried out by using one or no solvent selected from N, N-Dimethylformamide (DMF), Tetrahydrofuran (THF), Toluene (Toluene), Anisole (Anisole), 1, 4-Dioxane (Dioxane), dimethyl sulfoxide (DMSO), and Acetone (Acetone).
Preferably, the light source is 13 mW m when RCMP polymerization is carried out-2, 15 mW cm-2The irradiation time of the LED lamp strips with various colors is 12 h.
Preferably, the RCMP polymerization is carried out with the inert gas being one of nitrogen or argon.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention provides a conjugated microporous polymer using visible light to induce controllable free radical polymerization and a preparation method thereof, which takes conjugated microporous polymer materials (CMPs) as catalysts, has large specific surface area, high stability, controllable micropore size and volume, repeated use, high catalytic efficiency and strong applicability, and is suitable for large-scale application.
(2) The conjugated microporous polymer prepared by visible light induced controllable free radical polymerization and the preparation method thereof can obtain a polymer with low dispersity (PDI = 1.15-1.24) and various block polymers in a short time; and a high conversion of the polymerization system is achieved.
(3) The polymer chain end prepared by the conjugated microporous polymer induced by visible light and polymerized by the controllable free radicals and the preparation method thereof has good activity.
(4) The conjugated microporous polymer prepared by visible light-induced controllable free radical polymerization and the preparation method thereof provided by the invention utilize light-induced polymerization reaction, save energy consumption and are green and environment-friendly.
(5) The catalyst used in the method is different from the synthesis of Conjugated Organic Frameworks (COFs), the synthesis of conjugated microporous polymer materials (CMPs) can be realized at room temperature, the energy consumption is saved, and the safety is higher.
Drawings
FIG. 1 is a schematic representation of the photo-induced reversible complexation-mediated polymerization process of the product of example 1.
Figure 2 is the XRD pattern of the product of example 1.
FIG. 3 is an XPS plot of the product of example 1.
Figure 4 is a TEM image of the product of example 1.
FIG. 5 shows the molecular weights of example 2 obtained by catalysis of reversible complexation-mediated polymerization with 20 mg of the product of example 1 ((R))M n) Graph of relationship between degree of dispersion (PDI) and conversion。
FIG. 6 is a graph of the polymerization kinetics obtained in example 2 by catalyzing reversible complexation mediated polymerization with 20 mg of the product of example 1.
FIG. 7 shows the molecular weights of example 4 obtained by catalysis of reversible complexation-mediated polymerization with 10 mg of the product of example 1: (M n) Graph of the relationship between degree of dispersion (PDI) and conversion.
FIG. 8 is a plot of the polymerization kinetics obtained for the catalytic reversible complexation-mediated polymerization of example 4 using 10 mg of the product of example 1.
FIG. 9 is a Gel Permeation Chromatography (GPC) graph of BzMA monomer chain extension polymerization using PMMA-I as a macroinitiator.
FIG. 10 is a plot of polymerization kinetics for an on/off lamp control experiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1:
(1) synthesis of EB-CMPs Br: ethidium bromide (177 mg, 0.45 mmol) and trimesic aldehyde (48 mg, 0.3 mmol) were placed in a Schlenk tube (5 mL), 1, 4-Dioxane (Dioxane) (10 mL) was added, and acetic acid (3M, 0.5 mL) was added as a catalyst. After 5 minutes of ultrasound, stirring for 3 days at 25 ℃ under the protection of inert gas to obtain reddish brown powder. Washed with tetrahydrofuran and water, and washed with tetrahydrofuran by soxhlet extraction for 1 day. Vacuum drying to obtain finished product EB-CMPs Br.
(2) Synthesis of EB-CMPs: 15 mL of H was prepared2O/CH3OH（VWater (W):VMethanol=1: 1) solution; dissolving sodium iodide (NaI) in the solvent until the solution is saturated; 1.5 g of EB-CMPs Br powder is dispersed in the saturated solution and stirred for 24 hours; after filtration and washing 3 times with 20 mL of distilled water. Repeating the above operation for 3 times to obtain finished product EB-CMPs I.
FIG. 2 is an XRD pattern of the product of example 1, and it can be seen that example 1 has some crystallinity, and is a conjugated microporous polymer material (CMPs).
FIG. 3 is an XPS plot of the product of example 1, showing the elemental composition and content of example 1.
Fig. 4 is a TEM image of the product of example 1, and it can be seen that the pore size distribution of example 1 is relatively uniform.
Example 2:
20 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 4).
FIG. 1 is a schematic view of a polymerization process; FIG. 5 shows the molecular weights of example 2 obtained by catalysis of reversible complexation-mediated polymerization with 20 mg of the product of example 1 ((R))M n) Graph of the relationship between degree of dispersion (PDI) and conversion. FIG. 7 shows the molecular weights of example 4 obtained by catalysis of reversible complexation-mediated polymerization with 10 mg of the product of example 1 ((R))M n) Graph of degree of dispersion (PDI) versus conversion; FIG. 6 shows the dynamic curve of polymerization catalyzed by reversible complexation mediated by 20 mg of the product of example 1 in example 2, and FIG. 8 shows the dynamic curve of polymerization catalyzed by reversible complexation mediated by 10 mg of the product of example 1 in example 4, which combine to show that under the polymerization conditions, a polymer with controllable molecular weight and uniform distribution can be obtained.
Example 3:
40 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 5).
Example 4:
10 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 3).
Example 5:
5 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 2).
Example 6:
MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were added to a 25 mL Schlenk tube under inert gas with a white LED strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 1).
Example 7:
20 mg of the product from example 1, MMA (4 mL, 37.2 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 6).
Example 8:
20 mg of the product of example 1 was taken and MMA (1 mL)9.3 mmol) and CP-I (21 uL, 0.186 mmol) were added to a 25 mL Schlenk tube under inert gas with a white LED strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting the mixture with tetrahydrofuran and removing the catalyst through a filter head, the conversion, molecular weight and dispersion parameters were measured by Gel Permeation Chromatography (GPC) (see table 1, entry 7).
Example 9:
10 mg of the product from example 1, MMA (1 mL, 9.3 mmol), CP-I (11 uL, 0.094 mmol), 1 mL of DMF, DMSO or acetone were taken in a 25 mL Schlenk tube and under inert gas with a white LED strip (13W m)-1，15 mW cm-2) And (4) irradiating. A trace amount of the mixture was taken at a predetermined time, diluted with tetrahydrofuran, and the catalyst was removed through a filter head, and then parameters such as conversion, molecular weight, and dispersion were measured by Gel Permeation Chromatography (GPC) (catalytic results with DMF as a solvent are shown in Table 1, entry 8; catalytic results with DMSO as a solvent are shown in Table 1, entry 9; and catalytic results with acetone as a solvent are shown in Table 1, entry 10).
Example 10:
20 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) Irradiated and polymerized for 10 h, and sampled. Monomer conversion was determined with a minor mixture (conversion = 41.25%). The product was swollen in a small amount of THF (1 mL) and the catalyst was removed via filter head for the first time; precipitation with 8 mL of ether, centrifugation and re-swelling with THF-ether precipitation-centrifugation cycles were performed 2 times. And drying the precipitate in vacuum to obtain the macromolecular initiator PMMA-I. The molecular weight and the degree of dispersion were determined by Gel Permeation Chromatography (GPC) ((M n=4100, PDI=1.15）。
10 mg of the product from example 1, the macroinitiator PMMA-I (100 mg, 0.0244 mmol), BzMA (0.83 mL, 4.88 mmol), PhMA (0.76 mL, 4.88 mmol), BMA (0.78 mL, 4.88 mmol) or MMA (0.52 mL, 4.88 mmol) are taken in a 25 mL Schlenk tube and, under inert gas, underWhite LED lamp strip (13W m)-1，15 mW cm-2) And (4) irradiating. After 18 h, the trace amount of the mixture was diluted with tetrahydrofuran, and the catalyst was removed by filtration through a filter head and then measured by Gel Permeation Chromatography (GPC).
FIG. 9 is a GPC chart of chain extension polymerization of BzMA monomer using PMMA-I as macroinitiator, and it can be seen that the peak of GPC curve after polymerization is shifted to the left significantly, the molecular weight is larger, indicating that PMMA-I initiated polymerization, and the GPC curve is shifted all the way to the left, indicating that the polymer chain end has good chain end fidelity.
Example 11:
20 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) were introduced into a 25 mL Schlenk tube under inert gas with a white LED lamp strip (13W m)-1，15 mW cm-2) Irradiating for 2h, turning off the lamp for 2h, irradiating for 2h, taking out a trace amount of the mixture every two hours, diluting with tetrahydrofuran, removing the catalyst through a filter head, and measuring parameters such as conversion rate, molecular weight and dispersion degree by using a Gel Permeation Chromatograph (GPC) to obtain FIG. 10.
FIG. 10 is a graph showing the polymerization kinetics in a time-controlled experiment, in which polymerization hardly proceeds in the dark, and the strict control of the polymerization light is shown.
Example 12:
EB-CMPs I (20 mg), MMA (2 mL, 18.6 mmol), CP-I (21 uL, 0.186 mmol) were added to a 25 mL Schlenk tube under inert gas with a white LED strip (13W m)-1，15 mW cm-2) And (4) irradiating. After taking a trace amount of the mixture at a predetermined time, diluting with tetrahydrofuran and removing the catalyst through a filter head, the monomer conversion, molecular weight and molecular weight dispersion were measured by Gel Permeation Chromatography (GPC) (table 1, entry 4). After 12 h of reaction, the Schlenk tube was washed with copious amounts of THF, the resulting catalyst was centrifuged and washed by soxhlet extraction overnight with THF solvent, and the resulting catalyst was dried under vacuum and used for the cycling experiments.
Example 13:
the product of example 1, 10 mg, CP-I (11 uL,0.094 mmol), HEMA (2.287 mL), BMA (3.013 mL), BzMA (3.195 mL), GMA (2.498 mL), PhMA (2.907 mL), t-BuMA (3.065 mL) or MEMA (1.410 mL) were added to a 25 mL Schlenk tube under inert gas with a white LED strip (13W m mL)-1，15 mW cm-2) And (4) irradiating. A trace amount of the mixture was taken at a predetermined time, diluted with tetrahydrofuran, and the catalyst was removed through a filter head, and then parameters such as conversion, molecular weight, and dispersion were measured by Gel Permeation Chromatography (GPC) (the catalytic results of HEMA, BMA, BzMA, GMA, PhMA, t-BuMA, and MEMA monomers are shown in Table 1, entry 11 to 17, respectively).
Example 14:
20 mg of the product from example 1, MMA (2 mL, 18.6 mmol) and CP-I (21 uL, 0.186 mmol) are introduced into a 25 mL Schlenk tube under inert gas with a green, white or blue LED strip (13W m)-1，15 mW cm-2) And (4) irradiating. A trace amount of the mixture was taken at a predetermined time, diluted with tetrahydrofuran, and the catalyst was removed through a filter head, and then parameters such as conversion, molecular weight, and dispersion were measured by Gel Permeation Chromatography (GPC) (green, white, or blue light are shown in Table 1, entry 18, 4, and 19, respectively).
Table 1 shows the conversion, molecular weight and degree of dispersion of the polymer as determined by Gel Permeation Chromatography (GPC) under different polymerization conditions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, substitutions, improvements and the like that are within the scope of the invention should be included in the protection scope of the present invention.
Claims (10)
1. A conjugated microporous polymer characterized by: the molecular structure of the CMPs is as follows:
wherein: r is trimesic aldehyde, trialdehyde phloroglucinol, 1,3, 5-tris (p-formylphenyl) benzene, tris (4-formylphenyl) amine, 2,4, 6-tris (4-formylphenyl) -1, 3, 5-triazine, tris (4-formylbiphenyl) amine, 1,3, 5-tris (4 ' -formyl [1,1 ' -biphenyl ] -4-yl) benzene, benzo [1,2-b:3,4-b ': 5,6-b ' ] trithiophene-2, 5, 8-trialdehyde, [1,3, 5-trimethyl-2, 4, 6-tris (4 ' -formylphenyl) ] benzene, 1,3, 5-trimethoxy-2, 4, 6-trimethyloylbenzene, 1,3, one of 5-tris (2-formylpyridin-5 yl) benzene; m is ethidium bromide, propidium bromide, ethidium iodide, propidium iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine bromide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine iodide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine bromide, 3, 8-diamino-6-phenyl-5-propyl-phenanthridine iodide, and 3, 8-diamino-6-phenyl-5-propyl-phenanthridine bromide.
2. A method of preparing the conjugated microporous polymer of claim 1, comprising the steps of: the conjugated microporous polymer is obtained by catalyzing 0.3 mmol aldehyde group monomer and 0.45 mmol amino group monomer in 10 mL solvent by 0.5 mL catalyst and performing condensation reaction in a Schlenk tube; the aldehyde monomer is trimesic aldehyde, trialdehyde phloroglucinol, 1,3, 5-tri (p-formylphenyl) benzene, tri (4-formylphenyl) amine, 2,4, 6-tri (4-formylphenyl) -1, 3, 5-triazine, tri (4-formylbiphenyl) amine, 1,3, 5-tri (4 ' -formyl [1,1 ' -biphenyl ] -4-yl) benzene, benzo [1,2-b:3,4-b ': 5,6-b ' ] trithiophene-2, 5, 8-trialdehyde, [1,3, 5-trimethyl-2, 4, 6-tri (4 ' -formylphenyl) ] benzene, 1,3, 5-trimethoxy-2, 4, 6-trimethyloylbenzene, 1,3, 5-tris (2-formylpyridin-5-yl) benzene; the amino monomer is ethidium bromide, propidium bromide, ethidium iodide, propidium iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine iodide, 3, 8-diamino-5-hexyl-6-phenyl-phenanthridine bromide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine iodide, 3, 8-diamino-5-ethyl-6- (4-nitrophenyl) -phenanthridine bromide, 3, 8-diamino-6-phenyl-5-propyl-phenanthridine iodide, and 3, 8-diamino-6-phenyl-5-propyl-phenanthridine bromide.
3. The method of claim 2, wherein: the temperature of the condensation reaction is 25 ℃; the time for the condensation reaction was 48 h.
4. The method of claim 2, wherein: the solvent is one or more of 1, 4-dioxane, 1,3, 5-trimethylbenzene, N-dimethylacetamide and N, N-dimethylformamide; the catalyst is 3M or 6M acetic acid.
5. Use of the conjugated microporous polymer of claim 1 in visible light induced controlled radical polymerization, wherein: adding a polymerization monomer, a catalyst, an initiator and a solvent into a Schlenk tube at room temperature, and under the protection of inert gas, irradiating by using an LED lamp belt to perform reversible complexation-mediated polymerization (RCMP), thereby obtaining a polymer with controllable molecular weight and uniform molecular weight distribution and various block polymers.
6. Use according to claim 5, wherein the RCMP polymerization is carried out using one or more polymerized monomers selected from the group consisting of t-butyl methacrylate, benzyl methacrylate, methyl methacrylate, butyl acrylate, phenyl methacrylate, butyl methacrylate, glycidyl methacrylate, methyl acrylate, t-butyl methacrylate, methoxyethyl methacrylate, and hydroxyethyl methacrylate.
7. The use according to claim 5, wherein the RCMP polymerization is carried out using 2-iodo-2-methylpropanenitrile; 2-iodopropionitrile, alpha-iodophenyl ethyl acetate, alpha-iodophenyl acetonitrile and 2-iodo-2-methyl diethyl malonate.
8. The use according to claim 5, wherein the RCMP polymerization is carried out in the presence of one or no solvent selected from the group consisting of N, N-dimethylformamide, tetrahydrofuran, toluene, anisole, 1, 4-dioxane, dimethyl sulfoxide and acetone.
9. The use of claim 5, wherein the LED light source is 13W cm when RCMP polymerization is performed-1, 15 mW cm-2The irradiation time of the LED lamp strips with various colors is 12 h.
10. The use according to claim 5, wherein the RCMP polymerization is carried out with the inert gas being one of nitrogen or argon.
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| CN115073685A (en) * | 2022-07-18 | 2022-09-20 | 福州大学 | Metal-free halogen-free covalent organic framework material and application thereof in catalysis of RCMP (Rich chemical Messaging protocol) |
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