CN116178608A - Method for preparing two-dimensional copolymer by utilizing hydrogen bond induction assembly - Google Patents
Method for preparing two-dimensional copolymer by utilizing hydrogen bond induction assembly Download PDFInfo
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- CN116178608A CN116178608A CN202310268246.6A CN202310268246A CN116178608A CN 116178608 A CN116178608 A CN 116178608A CN 202310268246 A CN202310268246 A CN 202310268246A CN 116178608 A CN116178608 A CN 116178608A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 61
- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000006698 induction Effects 0.000 title abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000010257 thawing Methods 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000001553 co-assembly Methods 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 16
- 230000009471 action Effects 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 239000000725 suspension Substances 0.000 description 12
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 4
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- COUSKCJMTHTAAP-UHFFFAOYSA-N 3,5-bis(prop-2-enoylamino)benzoic acid Chemical compound OC(=O)C1=CC(NC(=O)C=C)=CC(NC(=O)C=C)=C1 COUSKCJMTHTAAP-UHFFFAOYSA-N 0.000 description 2
- SDAHLXVKOXYTMO-UHFFFAOYSA-N 3,5-di(prop-2-enoyloxy)benzoic acid Chemical compound OC(=O)C1=CC(OC(=O)C=C)=CC(OC(=O)C=C)=C1 SDAHLXVKOXYTMO-UHFFFAOYSA-N 0.000 description 2
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- QWMJEUJXWVZSAG-UHFFFAOYSA-N (4-ethenylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=C)C=C1 QWMJEUJXWVZSAG-UHFFFAOYSA-N 0.000 description 1
- VXFRCHRNRILBMZ-UHFFFAOYSA-N 1,2,3,4,5,6-hexaethynylbenzene Chemical compound C#CC1=C(C#C)C(C#C)=C(C#C)C(C#C)=C1C#C VXFRCHRNRILBMZ-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- GQWAOUOHRMHSHL-UHFFFAOYSA-N 4-ethenyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C=C)C=C1 GQWAOUOHRMHSHL-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 241001428384 Zamora Species 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- -1 graphite alkynes Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/22—Oxygen
-
- 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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/26—Nitrogen
- C08F212/28—Amines
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
- C08F230/065—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron the monomer being a polymerisable borane, e.g. dimethyl(vinyl)borane
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to the technical field of preparation of two-dimensional polymer materials, in particular to a method for preparing a two-dimensional copolymer by utilizing hydrogen bond induction assembly, which comprises the following steps: the amphiphilic monomer containing the hydrogen bond donor/acceptor structure is co-assembled with the common amphiphilic monomer without the hydrogen bond donor/acceptor structure: adding an amphiphilic monomer containing a hydrogen bond donor/acceptor structure into deionized water, adding alkali, oscillating to dissolve the amphiphilic monomer, adding a common amphiphilic monomer without the hydrogen bond donor/acceptor structure, uniformly mixing, and standing to form a two-dimensional supermolecule solution; and adding an initiator into the two-dimensional supermolecule solution, and performing in-situ free radical polymerization at 70 ℃ after three rounds of oxygen removal and nitrogen gas introduction operations to obtain the two-dimensional copolymer. The invention is that the action of the self hydrogen bond of the amphiphilic monomer containing the hydrogen bond supply/receptor structure can induce the common amphiphilic monomer without the hydrogen bond supply/receptor structure to orient so as to form a two-dimensional supermolecule, and then the two-dimensional supermolecule is polymerized in situ to form a two-dimensional copolymer.
Description
Technical Field
The invention relates to the technical field of preparation of two-dimensional high polymer materials, in particular to a method for preparing a two-dimensional copolymer by utilizing hydrogen bond induction assembly.
Background
Over the last decade, we have witnessed the rapid development of a unique class of synthetic polymers, two-dimensional polymers with independent covalent lamellar structures of atomic or molecular thickness, which are covalently linked in both directions by monomers. The catalyst has the characteristics of large specific surface area, light weight, high structural controllability, rich chemical active sites and the like, so that the catalyst has potential application value in the aspects of electronics, biomedicine, catalytic sensing, separation, filtration membrane and the like. However, the current methods for preparing two-dimensional copolymers are still not mature enough and are a few distances from real commercial use.
The preparation method of the two-dimensional copolymer material in the prior art mainly comprises three steps: a top-down stripping method, a bottom-up interfacial method and a solution direct synthesis method. The top-down stripping method is to use a certain means to destroy the weak interaction between the three-dimensional material layer with a regular structure and the interlayer so as to obtain the two-dimensional material with a regular structure. For example in Berlanga, i.; ruiz-Gonz lez, m.l.; gonz lez-Calset, J.M.; fierro, j.l.g.; mas-ballese, r.; zamora, F.delivery of Layered Covalent Organic Frameworks.Small 2011,7,1207-1211 the authors herein dispersed the borate-linked COF-8 in neat methylene chloride and sonicated to give thin layer nanoplatelets having a thickness of 4-10 nanometers. The method has the advantages that the obtained two-dimensional material has a regular and definite structure and is easy to characterize. But using this method is not controllable with respect to the thickness and size of the two-dimensional material and it is inevitable to bring about defects during the peeling process.
The bottom-up interfacial method is to limit the polymerization reaction to one interface artificially provided so that the reaction proceeds only on a two-dimensional plane. For example in Matsuoka, r.; sakamoto, r.; hoshiko, k.; sasaki, s; masunaga, h.; nagashio, k.; nishihara, h.crystal Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid interface j.am.chem.soc.2017,139, 3145-3152-the authors herein successfully prepared two-dimensional graphite alkynes at the interface of two immiscible solvents, the upper aqueous layer containing copper acetate and pyridine as catalysts for homogeneous coupling of acetylene and the lower dichloromethane layer containing hexaethynylbenzene monomer. And (3) under the inert atmosphere at room temperature, the two-dimensional covalent network grows through continuous catalytic coupling reaction for 24 hours, and the multilayer graphene film is generated at the liquid-liquid interface. However, generally due to the limited area of the interface, it remains a challenge to prepare two-dimensional copolymers in large quantities by an interface-assisted process.
The solution direct synthesis method means that a monolayer or oligomer two-dimensional copolymer can be directly synthesized in a solution without external assistance. The method is that monomer molecules are self-assembled in a solvent through non-covalent acting forces such as pi-pi stacking, hydrogen bonding, hydrophile-hydrophobic, electrostatic repulsion and the like among molecules to form a two-dimensional structure, and then in-situ free radical polymerization is carried out to form the two-dimensional covalent copolymer. The two-dimensional copolymer prepared by the method does not need stripping, has rich yield, but has certain requirements on the structural design of monomer molecules.
The name of the method is a method for preparing a two-dimensional polymer based on hydrogen bonding (publication number is CN 114591457A), which discloses that an amphiphilic monomer containing a hydrogen bonding donor/acceptor is self-assembled in an aqueous solution to form a two-dimensional supermolecule, and free radical polymerization reaction is carried out in a limited space of the two-dimensional supermolecule to obtain the two-dimensional polymer. In its specification, 3, 5-diacryloyloxybenzoic acid is disclosed as being unable to spontaneously form two-dimensional supramolecules and thus give two-dimensional polymers, suggesting that hydrogen bonding is critical for directed assembly to form two-dimensional structures. It follows that the common amphiphilic monomers cannot form a two-dimensional structure by themselves during polymerization.
Disclosure of Invention
The technical problem to be solved by the invention is how to provide a method for preparing a two-dimensional copolymer by using a common amphiphilic monomer.
The invention solves the technical problems by the following technical means:
in one aspect, the present invention provides a method for preparing a two-dimensional copolymer using hydrogen bond induced assembly, comprising the steps of:
(1) Amphiphilic monomers containing hydrogen bond donor or acceptor structures are co-assembled with common amphiphilic monomers: adding an amphiphilic monomer containing a hydrogen bond donor or acceptor structure into deionized water, then adding organic alkali or inorganic alkali, oscillating to dissolve the amphiphilic monomer, then adding a common amphiphilic monomer, uniformly mixing, and standing for a period of time to form a two-dimensional supermolecule solution;
(2) Polymerization reaction: and adding a free radical initiator into the two-dimensional supermolecule solution, and performing in-situ free radical polymerization at a certain temperature after three rounds of oxygen removal and nitrogen gas introduction operations to obtain the two-dimensional copolymer.
The beneficial effects are that: the invention discloses a two-dimensional copolymer which is prepared by dispersing an amphipathic monomer containing a hydrogen bond donor or acceptor structure and a common amphipathic monomer in a solvent together, inducing the common amphipathic monomer which cannot form a two-dimensional structure to orient by the action force of the hydrogen bond of the amphipathic monomer containing the hydrogen bond donor or acceptor structure so as to assemble a lamellar, and then adding an initiator to initiate double bonds in a hydrophobic layer in situ to perform free radical polymerization reaction.
Preferably, the time of standing is 1-2 hours; the temperature is 60-80 ℃.
Preferably, the amphiphilic monomer structure containing the hydrogen bond donor or acceptor structure contains a benzene ring and two double bonds.
Preferably, the general amphiphilic monomer has the structural formula:
preferably, the co-assembly comprises the steps of: 1-10 parts of amphiphilic monomer containing hydrogen bond donor or acceptor structure are weighed into a polymerization bottle, 5-50 parts of solvent is added, and ultrasonic dispersion is carried out; adding 1-10 parts of organic base or inorganic base into a polymerization bottle, and shaking uniformly to obtain a transparent solution; and then weighing 10-100 parts of common amphiphilic monomer, adding into 5-50 parts of solvent, vibrating to dissolve the common amphiphilic monomer, uniformly mixing the two parts of solution, and standing for 1-2 hours at room temperature to obtain the co-assembled supermolecule solution.
Preferably, the organic base is one of 1, 3-tetramethyl guanidine and triethylamine; the inorganic alkali is one of sodium hydroxide and potassium hydroxide; the solvent is deionized water.
Preferably, the in situ radical polymerization reaction comprises the steps of: freezing the two-dimensional supermolecule solution by liquid nitrogen to remove air, thawing, filling nitrogen, and repeating the operation for three times; then weighing 2-4% of initiator of the two monomers into a polymerization bottle, and polymerizing for 12-24h in an environment of 60-80 ℃; the copolymer solution was then poured into dialysis bags and dialyzed against deionized water for 24-48 hours, during which time water was changed 8-12 times.
Preferably, the initiator is one of a water-soluble initiator or an oil-soluble initiator. If the solvent used is a water-soluble solvent, a water-soluble initiator is used; if the solvent used is not a water-soluble solvent, an oil-soluble initiator is used.
More preferably, the water-soluble initiator comprises one of potassium persulfate or ammonium persulfate; the oil-soluble initiator comprises one of azodiisobutyronitrile, azodiisoheptonitrile and dibenzoyl peroxide.
In another aspect, the present invention provides a two-dimensional copolymer prepared by the above method.
The invention has the advantages that:
1. the invention discloses a two-dimensional copolymer which is prepared by dispersing an amphipathic monomer containing a hydrogen bond donor or acceptor structure and a common amphipathic monomer in a solvent together, inducing the common amphipathic monomer which cannot form a two-dimensional structure to orient by the action force of the hydrogen bond of the amphipathic monomer containing the hydrogen bond donor or acceptor structure so as to assemble a lamellar, and then adding an initiator to initiate double bonds in a hydrophobic layer in situ to perform free radical polymerization reaction.
2. The invention can prepare a plurality of common amphiphilic monomers which can not form a lamellar layer into a two-dimensional copolymer without stripping operation, and has simple synthesis method and rich yield; in addition, the use of toxic and harmful reagents is not involved in the preparation process, and severe experimental conditions are not needed, so that the method is beneficial to green sustainable development.
3. The method for preparing the two-dimensional copolymer from the common amphiphilic monomer by hydrogen bond induction assembly can prepare the two-dimensional copolymer into a product with high added value according to different functional groups carried by the common amphiphilic monomer, and can improve mechanical performance or conductivity.
Drawings
FIG. 1 shows nuclear magnetic resonance hydrogen spectrum of amphiphilic monomer DBA containing hydrogen bond donor or acceptor structure 1 HNMR) map;
FIG. 2 shows the hydrogen nuclear magnetic resonance spectrum of DBA and sodium p-styrenesulfonate in example 1 of the present invention 1 HNMR) map;
FIG. 3 is a graph of a Transmission Electron Microscope (TEM) of DBA copolymerized with sodium p-styrenesulfonate in example 1 of the present invention;
FIG. 4 is a graph of a copolymerization Optical Microscope (OM) of DBA and sodium p-styrenesulfonate in example 1 of the present invention;
FIG. 5 is an Atomic Force Microscope (AFM) image of DBA and sodium p-styrenesulfonate in example 1 of the present invention;
FIG. 6 is a graph showing the mechanical properties (tensile) of a DBA and sodium p-styrenesulfonate copolymer film prepared in example 1 of the present invention;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the copolymerization of ABA and sodium p-styrenesulfonate in comparative example 1 of the present invention;
FIG. 8 shows the hydrogen nuclear magnetic resonance spectrum of DBA and 4-vinylbenzoic acid copolymerization in example 2 of the present invention 1 HNMR) map;
FIG. 9 is a graph of a copolymerization Optical Microscope (OM) of DBA and 4-vinylbenzoic acid in example 2 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
In examples 1 to 4 of the present application, the method of using the hydrogen bonding action of the amphiphilic monomer 3, 5-diacrylamidobenzoic acid (DBA) containing a hydrogen bond donor or acceptor structure to induce the oriented assembly and in situ polymerization of the general amphiphilic monomer into a two-dimensional copolymer is utilized, but the amphiphilic monomer containing a hydrogen bond donor or acceptor structure is not limited to the DBA of the examples of the present application, and may be other amphiphilic monomers containing a hydrogen bond donor or acceptor structure.
Preparation of amphiphilic monomer 3, 5-diacrylamidobenzoic acid (DBA) containing hydrogen bond donor or acceptor structure
3,5 diaminobenzoic acid (2.00 g,13.14 mmol) was weighed into a reaction flask, 50mL of ethyl acetate was added, then potassium carbonate (36.32 g,262.80 mmol) was weighed and dissolved in 50mL of deionized water, the two solutions were mixed under ice bath stirring for 0.5h, then acryloyl chloride (4.76 g,52.56 mmol) was slowly added dropwise, the ice bath was removed after the dropwise addition was completed, and stirring was continued at room temperature for 4h. After the reaction is finished, separating liquid to remove an organic layer, acidifying the rest aqueous solution, namely, generating a large amount of precipitate, extracting solid by using ethyl acetate, then spin-drying the solvent, flushing the obtained solid by using deionized water, and then placing the solid into a vacuum drying oven to be dried for 24 hours to obtain the target micromolecule DBA. The nuclear magnetic resonance hydrogen spectrum is shown in figure 1. The method for preparing DBA in the present invention is not limited to the other methods.
Example 1
A method for preparing a two-dimensional copolymer by utilizing hydrogen bond induction assembly specifically comprises the following steps:
(1) Preparation of two-dimensional supramolecular solutions
DBA (200 mg,0.77mmol, ten parts) was weighed and added to 50mL of deionized water and dispersed ultrasonically for 20min to obtain a grey purple suspension, then (88.7 mg,0.77mmol, ten parts) of organic base 1,3 tetramethyl guanidine was added to the suspension, the grey purple suspension was immediately clear and transparent, sodium p-styrenesulfonate (1.58 g,7.7mmol, one hundred parts) was weighed and added to 50mL of deionized water, and after dissolution, the mixture was mixed with DBA solution uniformly and allowed to stand at room temperature for 1 hour to obtain a two-dimensional supramolecular solution.
(2) Preparation of two-dimensional copolymers
The preparation method comprises the steps of using potassium persulfate as an initiator, freezing and pumping air of a two-dimensional supermolecular solution by using liquid nitrogen, thawing, filling nitrogen, repeating the operation for three times, adding potassium persulfate (91.8 mg,0.3mmol and 4% parts), polymerizing at 70 ℃ for 12 hours, dialyzing for 48 hours by using a dialysis bag with the molecular weight cutoff of 8000-14000 after the polymerization is finished, and changing water for 8-12 times to finally obtain the two-dimensional copolymer. The nuclear magnetic resonance hydrogen spectrum of the two-dimensional copolymer is shown in FIG. 2.
A Transmission Electron Microscope (TEM) image of the obtained copolymer is shown in FIG. 3, and the morphology of the two-dimensional copolymer sheet prepared by the embodiment can be seen from the TEM image, and the dimension can reach one micron to two microns. The copolymer was dispersed in deionized water and observed with an Optical Microscope (OM), and a large number of lamellae were found in fig. 4. Atomic Force Microscopy (AFM) showed that the two-dimensional copolymer sheets prepared had a thickness of about 1.497nm, which is about 2 times the thickness of 0.7nm for sodium styrene sulfonate as simulated by Chem 3D, indicating the formation of a two-dimensional copolymer with a bilayer.
The two-dimensional polymer obtained by copolymerizing DBA and sodium p-styrenesulfonate is formed into a film by a solution casting method, and then the mechanical property is tested by an electronic universal tensile testing machine, and the result is shown in figure 6, the higher the copolymerization ratio is, the better the tensile property is.
Comparative example 1
The specific implementation steps are as follows:
(1) First, 3, 5-diacryloyloxybenzoic acid (ABA) was synthesized: 3,5 dihydroxybenzoic acid (3.08 g,20 mmol) was weighed into a reaction flask and 2.35g aqueous sodium hydroxide solution (100 mL) was added; after stirring at 5℃for 20min, acryloyl chloride (6.5 mL,80 mmol) was slowly added dropwise, and the mixture was allowed to react at room temperature for 6h. After the reaction is finished, the reaction solution is acidified to generate a large amount of sediment, and the sediment is washed by a large amount of deionized water. Finally, drying in a vacuum drying oven to obtain white solid, namely the target product ABA.
(2) ABA (200 mg,0.77mmol, ten parts) was weighed into 50mL deionized water and dispersed ultrasonically for 20min, then (88.7 mg,0.77mmol, ten parts) organic base 1,3 tetramethylguanidine was added, and the mixture was clarified by shaking, sodium p-styrenesulfonate (317.5 mg,1.54mmol, twenty parts) was weighed into 50mL deionized water, and after dissolution was mixed with ABA solution uniformly, and allowed to stand at room temperature for 1-2 hours to obtain a supramolecular solution.
(3) The preparation method comprises the steps of using potassium persulfate as an initiator, freezing and pumping air of a supermolecule solution by using liquid nitrogen, thawing and filling nitrogen, repeating the operation for three times, adding potassium persulfate (33.3 mg,0.12mmol and 4% parts), polymerizing at 70 ℃ for 12 hours, dialyzing for 48 hours by using a dialysis bag with the molecular weight cutoff of 8000-14000 after the polymerization is finished, and changing water for 8-12 times to finally obtain copolymer dialysate.
A small amount of the copolymer dialysate was taken and lyophilized in a freeze dryer for 72 hours to give a white copolymer solid, which was subjected to Scanning Electron Microscopy (SEM) to find no lamellar formation (see FIG. 7). The comparative example can show that the lack of hydrogen bonding can not induce the oriented assembly of common amphiphilic monomers and can not form a two-dimensional copolymer; the hydrogen bond acting force is very important for inducing the common amphiphilic monomer to orient to form a two-dimensional lamellar.
Example 2
A method for preparing a two-dimensional copolymer by utilizing hydrogen bond induction assembly specifically comprises the following steps:
(1) Preparation of two-dimensional supramolecular solutions
DBA (200 mg,0.77mmol, ten parts) was weighed into 50mL deionized water and dispersed ultrasonically for 20min to give an grey purple suspension; subsequently, to the suspension was added (88.7 mg,0.77mmol, ten parts) of the organic base 1,3 tetramethylguanidine, and the gray-purple suspension was immediately clear and transparent; 4-vinylbenzoic acid (1.141 g,7.7mmol, one hundred parts) was weighed and added to 50mL of deionized water, then sodium hydroxide (308 mg,7.7mmol, one hundred parts) was added to dissolve the solution, and then the 4-vinylbenzoic acid solution was added to the DBA solution and mixed uniformly, and allowed to stand at room temperature for 2 hours, thereby obtaining a two-dimensional supramolecular solution.
(2) Preparation of two-dimensional copolymers
The preparation method comprises the steps of using potassium persulfate as an initiator, freezing and pumping air of a two-dimensional supermolecular solution by using liquid nitrogen, thawing, filling nitrogen, repeating the operation for three times, adding potassium persulfate (91.8 mg,0.34mmol,4% parts), polymerizing at 70 ℃ for 24 hours, dialyzing for 48 hours by using a dialysis bag with the molecular weight cutoff of 8000-14000 after the polymerization is finished, and changing water for 8-12 times to finally obtain the two-dimensional copolymer. The nuclear magnetic resonance hydrogen spectrum of the two-dimensional copolymer is shown in FIG. 8.
The obtained two-dimensional copolymer was dispersed with deionized water and then observed with an Optical Microscope (OM), and the result is shown in fig. 9, from which it can be seen that the morphology of the sheet of the solid two-dimensional copolymer prepared in this example can be several tens of micrometers in size.
Example 3
(1) Preparation of two-dimensional supramolecular solutions
Monomer molecule DBA (200 mg,0.77mmol, ten parts) was weighed and added to 50mL of deionized water and dispersed ultrasonically for 20min to obtain a gray-purple suspension, then organic base 1,3 tetramethylguanidine (88.7 mg,0.77mmol, ten parts) was added to the suspension, the gray-purple suspension was immediately clear and transparent, 4-vinylphenylboronic acid (1.139 g,7.7mmol, one hundred parts) was weighed and added to 50mL of water, sodium hydroxide (616 mg,15.4mmol, two hundred parts) was added, and then mixed uniformly with DBA solution and allowed to stand at room temperature for 1.5h to obtain a two-dimensional supramolecular solution.
(2) Preparation of two-dimensional copolymers
Potassium persulfate (91.8 mg,0.34mmol,4% parts) is used as an initiator, the two-dimensional supermolecule solution is frozen by liquid nitrogen to remove air, then thawed and filled with nitrogen, the operation is repeated for three times, then the polymerization is carried out for 18 hours at 70 ℃, after the polymerization is finished, dialysis is carried out for 48 hours by using a dialysis bag with the molecular weight cutoff of 8000-14000, and water is changed for 8-12 times during the process, so that the two-dimensional copolymer is finally obtained.
Example 4
(1) Preparation of two-dimensional supramolecular solutions
Monomer molecule DBA (200 mg,0.77mmol, ten parts) is weighed and added into 100mL deionized water and dispersed for 20min by ultrasonic, gray purple suspension is obtained, then organic alkali 1, 3-tetramethylguanidine (88.7 mg,0.77mmol, ten parts) is added into the suspension, the gray purple suspension is immediately clear and transparent, 4-vinylphenyl-N, N-dimethylamine (1.241 g,7.7mmol, one hundred parts) is weighed and added into DBA solution to be uniformly mixed, and the mixture is stood for 2h at room temperature, thus obtaining the two-dimensional supermolecule solution.
(2) Preparation of two-dimensional copolymers
Potassium persulfate (91.8 mg,0.34mmol,4% parts) is used as an initiator, the supramolecular solution is frozen by liquid nitrogen to remove air, then thawed and filled with nitrogen, the operation is repeated for three times, then the mixture is polymerized for 12 hours at 70 ℃, after the polymerization is finished, the mixture is dialyzed for 48 hours by a dialysis bag with the molecular weight cutoff of 8000-14000, and water is changed for 8-12 times during the process, so that the two-dimensional copolymer is finally obtained.
In summary, the present invention utilizes the hydrogen bond acting force provided by the amide group in the amphiphilic monomer containing the hydrogen bond donor or acceptor structure to enable the common amphiphilic monomer incapable of forming a two-dimensional structure by itself to be assembled in a solvent in an orientation way to form a two-dimensional supermolecule, and then in-situ initiates free radical polymerization to successfully prepare the two-dimensional covalent copolymer with a bilayer. This suggests that the induced orientation forces of hydrogen bonding play an indispensable role in the stacking of molecules into two-dimensional morphologies.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a two-dimensional copolymer by hydrogen bond induced assembly, comprising the steps of:
(1) Amphiphilic monomers containing hydrogen bond donor or acceptor structures are co-assembled with common amphiphilic monomers: adding an amphiphilic monomer containing a hydrogen bond donor or acceptor structure into deionized water, then adding organic alkali or inorganic alkali, oscillating to dissolve the amphiphilic monomer, then adding a common amphiphilic monomer, uniformly mixing, and standing for a period of time to form a two-dimensional supermolecule solution;
(2) Polymerization reaction: and adding a free radical initiator into the two-dimensional supermolecule solution, and carrying out in-situ free radical polymerization at a certain temperature after three-wheel oxygen removal and nitrogen gas introduction operations to obtain the two-dimensional copolymer.
2. The method for preparing a two-dimensional copolymer by hydrogen bond induced assembly according to claim 1, wherein the amphiphilic monomer structure containing hydrogen bond donor or acceptor structure comprises a monomer containing benzene ring and two double bonds.
3. The method for preparing a two-dimensional copolymer by hydrogen bond induced assembly according to claim 1, wherein the general amphiphilic monomer has a structural formula:
4. the method for preparing a two-dimensional copolymer by hydrogen bond induced assembly according to claim 1, wherein the standing time is 1-2 hours; the temperature is 60-80 ℃.
5. A method of preparing a two-dimensional copolymer using hydrogen bond induced assembly according to claim 1, wherein the co-assembly comprises the steps of: 1-10 parts of amphiphilic monomer containing hydrogen bond donor or acceptor structure are weighed into a polymerization bottle, 5-50 parts of solvent is added, and ultrasonic dispersion is carried out; adding 1-10 parts of organic base or inorganic base into a polymerization bottle, and shaking uniformly to obtain a transparent solution; and then weighing 10-100 parts of common amphiphilic monomer, adding into 5-50 parts of solvent, vibrating to dissolve the common amphiphilic monomer, uniformly mixing the two parts of solution, and standing for 1-2 hours at room temperature to obtain the co-assembled supermolecule solution.
6. The method for preparing a two-dimensional copolymer by hydrogen bond induced assembly according to claim 5, wherein the organic base is one of 1, 3-tetramethylguanidine and triethylamine; the inorganic alkali is one of sodium hydroxide and potassium hydroxide; the solvent is deionized water.
7. The method of preparing a two-dimensional copolymer using hydrogen bond induced assembly of claim 1, wherein the in situ radical polymerization comprises the steps of: freezing the two-dimensional supermolecule solution by liquid nitrogen to remove air, thawing, filling nitrogen, and repeating the operation for three times; then weighing 2-4% of initiator of the two monomers into a polymerization bottle, and polymerizing for 12-24h in an environment of 60-80 ℃; the copolymer solution was then poured into dialysis bags and dialyzed against deionized water for 24-48 hours, during which time water was changed 8-12 times.
8. The method for preparing a two-dimensional copolymer by hydrogen bond induced assembly according to claim 1 or 7, wherein the initiator is one of a water-soluble initiator and an oil-soluble initiator.
9. The method of preparing a two-dimensional copolymer using hydrogen bond induced assembly of claim 8, wherein the water soluble initiator comprises one of potassium persulfate or ammonium persulfate; the oil-soluble initiator comprises one of azodiisobutyronitrile, azodiisoheptonitrile and dibenzoyl peroxide.
10. A two-dimensional copolymer prepared by the method for preparing a two-dimensional copolymer using hydrogen bond induced assembly according to any one of claims 1 to 9.
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