CN114702647A - Polyacenoquinone polymer and preparation method thereof - Google Patents
Polyacenoquinone polymer and preparation method thereof Download PDFInfo
- Publication number
- CN114702647A CN114702647A CN202210450480.6A CN202210450480A CN114702647A CN 114702647 A CN114702647 A CN 114702647A CN 202210450480 A CN202210450480 A CN 202210450480A CN 114702647 A CN114702647 A CN 114702647A
- Authority
- CN
- China
- Prior art keywords
- polymer
- solid
- polyjoquinone
- modified montmorillonite
- aromatic hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 18
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 12
- 239000002135 nanosheet Substances 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000000746 purification Methods 0.000 claims description 13
- 239000002841 Lewis acid Substances 0.000 claims description 11
- 150000007517 lewis acids Chemical class 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 7
- 150000004056 anthraquinones Chemical class 0.000 claims description 7
- 239000011229 interlayer Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000138 intercalating agent Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical group [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 208000004880 Polyuria Diseases 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 22
- 239000000843 powder Substances 0.000 description 13
- 229910052901 montmorillonite Inorganic materials 0.000 description 11
- 241000221095 Simmondsia Species 0.000 description 5
- 235000004433 Simmondsia californica Nutrition 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 235000013862 Narcissus jonquilla Nutrition 0.000 description 4
- 244000223072 Narcissus jonquilla Species 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 230000003234 polygenic effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/18—Definition of the polymer structure conjugated
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The application provides a polyjoquinone polymer and a preparation method thereof, wherein the preparation method comprises the following steps: selecting modified montmorillonite as a template, and polymerizing the polycyclic aromatic hydrocarbon and acid anhydride to form the polyjonquinin polymer; the polymer has a nanosheet structure.
Description
Technical Field
The application relates to a Duoconjin polymer and a preparation method thereof, belonging to the technical field of chemical synthesis.
Background
Polygenic quinonoid polymers (PAQR for short) are intrinsic semiconductive high-molecular polymers, and have a special swimming polarization form in the molecule, so that the polygenic quinonoid polymers have a high dielectric constant and are special amphibious materials. The PAQR can be used as a semiconductive/high dielectric filler to be compounded with other matrix polymers to prepare a composite polymer material, and can also be used as a pure organic semiconductive/dielectric material to be applied to the fields of sensors and electric energy storage. The method commonly used at present comprises a solid-phase melting method, a vapor deposition method and a solution polymerization method, and is mainly prepared by polymerizing aromatic ring or heteroaromatic ring monomers and acid anhydride under the catalysis of Lewis acid. Under normal conditions, polymer chains generated in the free polymerization process are difficult to be folded and arranged in an ordered direction in a three-dimensional space, are generally intertwined, have no regularity, and the synthesized PAQR is mostly in an irregular shape. For example, Wang et al (Hollow PAQR nanostructure and its smart electrochemical activity, polymer,2016,83,129-137) disclose the synthesis of PAQR in the form of Hollow spheres using a surfactant such as sodium lauryl sulfate as a template, but the size of the resulting PAQR Hollow spheres is not uniform and is easily broken due to the poor dimensional stability of sodium lauryl sulfate. Meanwhile, the yield is low due to more side reactions and serious monomer volatilization in the current PAQR synthesis. Therefore, the realization of the controllable preparation of the PAQR morphology and the improvement of the yield are the difficulties which need to be broken through urgently in the prior art.
Disclosure of Invention
In order to solve some of the problems described above, the present application provides a method for preparing a jonquil polymer, which can prepare a jonquil polymer having a nanosheet structure.
The preparation method of the polyjoquinone polymer provided by the first aspect of the application comprises the following steps: selecting modified montmorillonite as a template, and polymerizing the polycyclic aromatic hydrocarbon and acid anhydride in the interlayer limited space of the modified montmorillonite to generate the jonquil polymer.
Optionally, the modified montmorillonite has a lewis acid as an intercalating agent.
Optionally, the Lewis acid is selected from quaternary ammonium salts, ZnCl2、AlCl3、FeCl3One kind of (1).
Optionally, the quaternary ammonium salt is selected from one of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride.
Optionally, the molar ratio of the modified montmorillonite to the fused ring aromatic hydrocarbon to the anhydride is 1-2:1: 1.
Optionally, the fused ring aromatic hydrocarbon is an aromatic ring monomer or a heteroaromatic ring monomer. Optionally, the polycyclic aromatic hydrocarbon is selected from any one or a combination of anthracene, anthraquinone and pyrene.
Optionally, the acid anhydride is selected from one or a combination of more of pyromellitic dianhydride, tetrachloro acid anhydride and tetrabromo acid anhydride.
More specifically, the preparation method of the jojoba quinone polymer comprises the following steps: selecting modified montmorillonite as a template, adding the modified montmorillonite, polycyclic aromatic hydrocarbon and anhydride into a first solvent, and uniformly mixing; carrying out suction filtration and drying after ultrasonic treatment to obtain a first solid; heating the first solid for reaction, and cooling to room temperature after the reaction is finished to obtain a second solid; purifying the second solid to obtain the polyjoquinone polymer.
Optionally, the first solvent is selected from acetone, ethanol or methanol.
Optionally, the time of the ultrasonic treatment is 10-24 h.
Optionally, the first solid is transferred to a muffle furnace for temperature rise reaction, wherein the reaction temperature is 310-360 ℃, and the reaction time is 15-24 hours.
Optionally, the second solids purification process comprises: and sequentially selecting hydrochloric acid, water, ethanol, toluene and hydrofluoric acid as purification solvents to purify the obtained second solid.
In a second aspect, the present application provides a jojoba quinone polymer, which can be prepared by the preparation method described in any of the above technical schemes, and the jojoba quinone polymer has a nanosheet structure.
Compared with the prior art, the beneficial effect of this application is:
according to the preparation method of the polygenic quinone polymer, modified montmorillonite is used as a template and a catalyst at the same time, and condensed ring aromatic hydrocarbon and acid anhydride are polymerized in a confined space between layers of the montmorillonite to generate the nano-sheet polygenic quinone polymer, so that the controllable morphology of PAQR is realized; meanwhile, due to the limiting effect of the montmorillonite, the polycyclic aromatic hydrocarbon and the anhydride are not easy to volatilize and escape in the heating process, and the yield of the PAQR is improved; is beneficial to promoting the application research of PAQR.
According to the preparation method of the jonqr polymer, the prepared PAQR has uniform appearance, no impurities and high product purity; and the process method is simple, and the reaction condition is mild.
The method for preparing a jojoba quinone polymer according to at least one embodiment of the present disclosure can prepare an organic polymer having a nano-sheet structure in which carbon and oxygen are main components. The prepared polymer is of a lamellar structure, can be applied to the fields of energy storage, composite materials and the like, and has wide application prospect.
Drawings
FIG. 1 is a TEM and elemental mapping picture of a PAQR slab;
FIG. 2 is a phase diagram and a height diagram of AFM testing of PAQR slabs;
FIG. 3 is a TEM image of synthesized PAQR under the no-template condition.
Detailed Description
The technical solutions of the present application are explained in detail below with reference to specific embodiments, however, it should be understood that the structures and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
The application provides a preparation method of a polygenetic quinone Polymer (PAQR), which introduces modified montmorillonite with Lewis acid as an intercalating agent into a reaction system, the two-dimensional lamellar structure of the montmorillonite is used as a template for PAQR growth, and the Lewis acid is used as a catalyst for PAQR polymerization, so that the modified montmorillonite has the functions of the template and the catalyst, can induce the ordered polymerization of reaction monomers in the application in two-dimensional directions, and improves the degree of order of polymer chains, thereby realizing controllable appearance, being beneficial to improving the structural stability of the polygenetic quinone polymer and expanding the application field of the polygenetic quinone polymer.
In the preparation method of the jonquil polymer in the embodiment, a one-step synthesis method is adopted, and the synthesis of the PAQR is realized at a high temperature by controlling the proportion of reaction monomers and the reaction temperature, so that the PAQR of the nanosheet layer is obtained.
In the embodiment, modified montmorillonite is used as a template, and the polycyclic aromatic hydrocarbon and acid anhydride are polymerized in the interlayer limited space of the modified montmorillonite to generate the polyprovincial quinone polymer.
Montmorillonite is a silicate of a layered structure with metal cations adsorbed between layers. In the embodiment, the intercalation agent can enter between the sheets of the montmorillonite through the ion exchange effect to increase the distance between the sheets, and then the polymer monomer can enter between the layers to be polymerized in the limited space between the layers to generate the polymer with the nano-sheet structure.
The preparation method comprises the following specific steps:
selecting modified montmorillonite taking Lewis acid as an intercalating agent as a template, and adding the modified montmorillonite, polycyclic aromatic hydrocarbon and acid anhydride into a first solvent for uniform mixing; carrying out suction filtration and drying after ultrasonic treatment to obtain a first solid; heating the first solid for reaction, and cooling to room temperature after the reaction is finished to obtain a second solid; purifying the second solid to obtain the polyjoquinone polymer.
As an alternative embodiment, the modified montmorillonite takes Lewis acid as an intercalating agent, and the Lewis acid can be selected from quaternary ammonium salt and ZnCl2、AlCl3、FeCl3And the like. The montmorillonite intercalated with the Lewis acid can simultaneously play the roles of a template and a catalyst, so that the reaction efficiency is higher, and the reaction flow is simpler; meanwhile, the obtained product has uniform appearance and higher purity.
As an alternative embodiment, the mole ratio of the modified montmorillonite to the fused ring aromatic hydrocarbon to the anhydride is 1-2: 1-1.5: 1-1.5; preferably, the molar ratio is 1-2:1:1, for example, can be 1: 1:1,1.2: 1:1,1.5: 1:1,1.8: 1:1,2: 1:1, etc.
As an optional embodiment, the polycyclic aromatic hydrocarbon is an aromatic ring monomer or a heteroaromatic ring monomer, and any one or a combination of more of anthracene, anthraquinone, pyrene and the like can be selected.
As an alternative embodiment, the acid anhydride can be selected from one or a combination of more of pyromellitic dianhydride, tetrachloro acid anhydride, tetrabromo acid anhydride and the like.
As an alternative embodiment, the first solvent is selected from acetone, ethanol or methanol.
As an alternative embodiment, the time of the ultrasonic treatment is 10-24h, such as 12h, 15h, 18h, 20h, 22h and the like.
As an alternative embodiment, the first solid is transferred into a muffle furnace for temperature rise reaction, the reaction temperature is 300-310 ℃, and the reaction time is 15-24 hours; for example, reaction at 300 ℃ for 22 hours, reaction at 305 ℃ for 20 hours, reaction at 310 ℃ for 18 hours, and the like.
As an alternative embodiment, the second solid purification process comprises: and sequentially selecting hydrochloric acid, water, ethanol, toluene and hydrofluoric acid as purification solvents to purify the obtained second solid.
The application can prepare PAQR with a nano-sheet structure, and the main components of the PAQR are carbon and oxygen; the modified montmorillonite is simultaneously used as a template and a catalyst to realize the controllable preparation of the sheet PAQR; the prepared PAQR lamella has uniform thickness and easy purification, can be applied to the fields of film capacitors, sensors and the like, and has wide application prospect.
Example 1
The preparation method of the polyjoquinone polymer comprises the following steps:
1mol of anthraquinone, 1mol of pyromellitic dianhydride and 1mol of organic modified montmorillonite (the interlayer insertion agent is quaternary ammonium salt) are put into 300mol of acetone and mixed evenly.
And (4) performing ultrasonic treatment for 24 hours, performing suction filtration, and drying to obtain a first solid.
Transferring the dried first solid into a muffle furnace, and setting the temperature program as follows: raising the room temperature to 100 ℃, and preserving the heat for 1 hour; heating to 150 deg.c at 100 deg.c and maintaining for 1 hr; raising the temperature to 200 ℃ at 150 ℃, and preserving the heat for 1 hour; raising the temperature to 250 ℃ at 200 ℃, and preserving the heat for 1 hour; raising the temperature to 300 ℃ at 250 ℃, and preserving the heat for 1 hour; raising the temperature to 310 ℃ at 300 ℃, and preserving the heat for 20 hours; cooling to room temperature to obtain a second solid.
And (3) putting the obtained second solid powder into a Soxhlet extractor, sequentially purifying by respectively using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, and finally washing away the montmorillonite template by using 200ml of hydrofluoric acid to obtain 1.49g of black solid powder (the yield is 35%), thereby obtaining the polyjonqine polymer with the lamellar structure.
The obtained polyjonqin polymer is observed under a transmission electron microscope to obtain a TEM and element mapping picture shown in figure 1, and the PAQR is clearly seen to be in a lamellar structure, and meanwhile, the porous carbon film on the lower copper mesh is clearly seen, which indicates that the PAQR is a very thin lamellar.
The obtained polyjoquinone polymer was subjected to AFM test to obtain a phase diagram and a height diagram of the PAQR sheet shown in FIG. 2, from which it was found that the thickness of the sheet was about 6.0 nm. Therefore, the polyjonqin polymer obtained by the embodiment is of a nano-sheet structure and can be applied to the fields of capacitors, sensors and the like.
Example 2
The preparation method of the polyjoquinone polymer comprises the following steps:
1mol of anthracene, 1mol of pyromellitic dianhydride and 1mol of organically modified montmorillonite (the interlayer insertion agent is ZnCl)2) Placing the mixture in 300mol of acetone and mixing the mixture evenly.
And (4) performing ultrasonic treatment for 24 hours, performing suction filtration, and drying to obtain a first solid.
Transferring the dried first solid into a muffle furnace, and setting the temperature program as follows: raising the room temperature to 100 ℃, and preserving the heat for 1 hour; raising the temperature to 150 ℃ at 100 ℃, and preserving the heat for 1 hour; raising the temperature to 200 ℃ at 150 ℃, and preserving the heat for 1 hour; raising the temperature to 250 ℃ at 200 ℃, and preserving the heat for 1 hour; raising the temperature to 300 ℃ at 250 ℃, and preserving the heat for 1 hour; raising the temperature to 310 ℃ at 300 ℃, and preserving the heat for 20 hours; cooling to room temperature to obtain a second solid.
And (3) putting the obtained second solid powder into a Soxhlet extractor, sequentially purifying by respectively using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, and finally washing away the montmorillonite template by using 200ml of hydrofluoric acid to obtain 1.39g of black solid powder (the yield is 35%), thereby obtaining the polyjonqine polymer with the lamellar structure.
This example is similar to the polyjoquinone polymer obtained in example 1, and has a lamellar structure.
Example 3
The preparation method of the polyjoquinone polymer comprises the following steps:
1.1mol of pyrene, 1.1mol of tetrachloro acid anhydride and 1.2mol of modified montmorillonite (the interlayer insertion agent is AlCl)3) Placing the mixture into 320mol of acetone and uniformly mixing.
And (4) performing ultrasonic treatment for 24 hours, performing suction filtration, and drying to obtain a first solid.
Transferring the dried first solid into a muffle furnace, and setting the temperature program as follows: raising the room temperature to 100 ℃, and preserving the heat for 1 hour; heating to 150 deg.c at 100 deg.c and maintaining for 1 hr; raising the temperature to 200 ℃ at 150 ℃, and preserving the heat for 1 hour; raising the temperature to 250 ℃ at 200 ℃, and preserving the heat for 1 hour; raising the temperature to 300 ℃ at 250 ℃, and preserving the heat for 1 hour; raising the temperature to 310 ℃ at 300 ℃, and preserving the heat for 20 hours; cooling to room temperature to obtain a second solid.
And (3) putting the obtained second solid powder into a Soxhlet extractor, sequentially purifying by using 220ml of hydrochloric acid, 550ml of water, 350ml of ethanol and 120ml of toluene as purification solvents respectively, and finally washing away the montmorillonite template by using 180ml of hydrofluoric acid to obtain 1.56g of black solid powder (the yield is 32%), thereby obtaining the polyjonqine polymer with the lamellar structure.
This example is similar to the polyjoquinone polymer obtained in example 1, and has a lamellar structure.
Example 4
The preparation method of the polyjoquinone polymer comprises the following steps:
1mol of anthraquinone, 1mol of tetrabromo anhydride and 1mol of modified montmorillonite (I), (II)The interlaminar intercalator is FeCl3) Putting the mixture into 280mol of acetone and mixing the mixture evenly.
And (4) performing ultrasonic treatment for 24 hours, performing suction filtration, and drying to obtain a first solid.
Transferring the dried first solid into a muffle furnace, and setting the temperature program as follows: raising the room temperature to 100 ℃, and preserving the heat for 1 hour; heating to 150 deg.c at 100 deg.c and maintaining for 1 hr; raising the temperature to 200 ℃ at 150 ℃, and preserving the heat for 1 hour; raising the temperature to 250 ℃ at 200 ℃, and preserving the heat for 1 hour; raising the temperature to 300 ℃ at 250 ℃, and preserving the heat for 1 hour; raising the temperature to 310 ℃ at 300 ℃, and preserving the heat for 20 hours; cooling to room temperature to obtain a second solid.
And (3) putting the obtained second solid powder into a Soxhlet extractor, sequentially purifying by respectively using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, and finally washing away the montmorillonite template by using 150ml of hydrofluoric acid to obtain 1.58g of black solid powder (the yield is 32%), thereby obtaining the polyjonqine polymer with the lamellar structure.
This example is similar to the polyjoquinone polymer obtained in example 1, and has a lamellar structure.
Example 5
The preparation method of the polyjoquinone polymer comprises the following steps:
1mol of anthraquinone, 1mol of anthracene, 2mol of tetrabromo anhydride and 2.3mol of organic modified montmorillonite (the interlayer insertion agent is quaternary ammonium salt) are put into 600mol of acetone and mixed evenly.
And (4) carrying out ultrasonic treatment for 24 hours, carrying out suction filtration, and drying to obtain a first solid.
Transferring the dried first solid into a muffle furnace, and setting the temperature program as follows: raising the room temperature to 100 ℃, and preserving the heat for 1 hour; heating to 150 deg.c at 100 deg.c and maintaining for 1 hr; raising the temperature to 200 ℃ at 150 ℃, and preserving the heat for 1 hour; raising the temperature to 250 ℃ at 200 ℃, and preserving the heat for 1 hour; raising the temperature to 300 ℃ at 250 ℃, and preserving the heat for 1 hour; raising the temperature to 310 ℃ at 300 ℃, and preserving the heat for 20 hours; cooling to room temperature to obtain a second solid.
And (3) putting the obtained second solid powder into a Soxhlet extractor, sequentially purifying by using 400ml of hydrochloric acid, 1000ml of water, 600ml of ethanol and 200ml of toluene as purification solvents respectively, and finally washing away the montmorillonite template by using 500ml of hydrofluoric acid to obtain 3.16g of black solid powder (the yield is 33%), thereby obtaining the polyjonqine polymer with the lamellar structure.
This example is similar to the polyjoquinone polymer obtained in example 1, and has a lamellar structure.
Comparative example 1
The preparation method of the polyjoquinone polymer comprises the following steps:
1mol of anthraquinone, 1mol of pyromellitic dianhydride and 1mol of ZnCl2Placing the mixture in the porcelain and mixing the mixture evenly. And transferred to a muffle furnace, and the temperature program was set to: raising the room temperature to 100 ℃, and preserving the heat for 1 hour; heating to 150 deg.c at 100 deg.c and maintaining for 1 hr; raising the temperature to 200 ℃ at 150 ℃, and preserving the heat for 1 hour; raising the temperature to 250 ℃ at 200 ℃, and preserving the heat for 1 hour; raising the temperature to 300 ℃ at 250 ℃, and preserving the heat for 1 hour; raising the temperature to 310 ℃ at 300 ℃, and preserving the heat for 20 hours; cooling to room temperature to obtain black solid powder.
The obtained powder was placed in a soxhlet extractor and purified sequentially with 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, respectively, to obtain 0.34g of black solid powder (yield 8%), i.e. the jojoba quinone polymer. FIG. 3 is a TEM image of PAQR obtained under the condition of no template in the present embodiment, and it can be seen that the obtained sample mostly presents thick irregular bulk morphology and disordered morphology.
The embodiments described above are merely preferred embodiments of the present application, and are not intended to limit the scope of the present application, and various modifications and improvements made to the technical solutions of the present application by those skilled in the art without departing from the spirit of the present application should fall within the protection scope defined by the claims of the present application.
Claims (10)
1. A method for preparing a polyjoquinone polymer, which is characterized by comprising the following steps: and (3) selecting the modified montmorillonite as a template, and polymerizing the polycyclic aromatic hydrocarbon and the acid anhydride in the interlayer limited space of the modified montmorillonite to synthesize the polyjonqin polymer.
2. The method of claim 1, wherein the modified montmorillonite is a lewis acid as an intercalating agent.
3. The method of claim 2, wherein the Lewis acid is selected from quaternary ammonium salts, ZnCl or mixtures thereof2、AlCl3、FeCl3To (3) is provided.
4. The method of claim 3, wherein the quaternary ammonium salt is selected from dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, and dioctadecyl dimethyl ammonium chloride; the polycyclic aromatic hydrocarbon is an aromatic ring monomer or a heteroaromatic ring monomer.
5. The method for preparing a polyjoquinone polymer according to any one of claims 1 to 4, wherein the molar ratio of the modified montmorillonite, the polycyclic aromatic hydrocarbon and the acid anhydride is 1-2:1: 1.
6. The method for preparing a polyjoquinone polymer according to any one of claims 1 to 4, wherein the condensed ring aromatic hydrocarbon is selected from any one or a combination of anthracene, anthraquinone, pyrene; the acid anhydride is selected from one or a combination of more of pyromellitic dianhydride, tetrachloro acid anhydride and tetrabromo acid anhydride.
7. The process for the preparation of a polyjoquinone polymer according to any of claims 1 to 4, more specifically comprising: selecting modified montmorillonite as a template, adding the modified montmorillonite, polycyclic aromatic hydrocarbon and anhydride into a first solvent, and uniformly mixing; carrying out suction filtration and drying after ultrasonic treatment to obtain a first solid; heating the first solid for reaction, and cooling to room temperature after the reaction is finished to obtain a second solid; purifying the second solid to obtain the polyjoquinone polymer.
8. The method for producing a polyjoquinone polymer according to claim 7, wherein the first solvent is selected from acetone, ethanol or methanol; the ultrasonic treatment time is 10-24 h; the second solid purification process comprises: and sequentially selecting hydrochloric acid, water, ethanol, toluene and hydrofluoric acid as purification solvents to purify the obtained second solid.
9. The method for preparing polyuria-quinone polymer according to claim 7, wherein the first solid is transferred to a muffle furnace for reaction at 310-360 ℃ for 15-24 hours.
10. A polyjoquinone polymer characterized by having a nanosheet structure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210450480.6A CN114702647B (en) | 2022-04-27 | 2022-04-27 | Polymeroquinone polymer and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210450480.6A CN114702647B (en) | 2022-04-27 | 2022-04-27 | Polymeroquinone polymer and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114702647A true CN114702647A (en) | 2022-07-05 |
CN114702647B CN114702647B (en) | 2023-08-04 |
Family
ID=82176898
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210450480.6A Active CN114702647B (en) | 2022-04-27 | 2022-04-27 | Polymeroquinone polymer and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114702647B (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4557978A (en) * | 1983-12-12 | 1985-12-10 | Primary Energy Research Corporation | Electroactive polymeric thin films |
CN1663969A (en) * | 2005-02-24 | 2005-09-07 | 北京科技大学 | Process for preparing nano polymer with montmorillonite as template |
CN103965993A (en) * | 2014-04-27 | 2014-08-06 | 青岛科技大学 | Hollow sphere electrorheological fluid and preparation method thereof |
CN107317022A (en) * | 2017-06-28 | 2017-11-03 | 南京工业大学 | Preparation method of lithium ion battery anode |
-
2022
- 2022-04-27 CN CN202210450480.6A patent/CN114702647B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4557978A (en) * | 1983-12-12 | 1985-12-10 | Primary Energy Research Corporation | Electroactive polymeric thin films |
CN1663969A (en) * | 2005-02-24 | 2005-09-07 | 北京科技大学 | Process for preparing nano polymer with montmorillonite as template |
CN103965993A (en) * | 2014-04-27 | 2014-08-06 | 青岛科技大学 | Hollow sphere electrorheological fluid and preparation method thereof |
CN107317022A (en) * | 2017-06-28 | 2017-11-03 | 南京工业大学 | Preparation method of lithium ion battery anode |
Also Published As
Publication number | Publication date |
---|---|
CN114702647B (en) | 2023-08-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Liu et al. | Facile fabrication of three-dimensional highly ordered structural polyaniline–graphene bulk hybrid materials for high performance supercapacitor electrodes | |
Wei et al. | Polyaniline nanotubes doped with sulfonated carbon nanotubes made via a self‐assembly process | |
Zhang et al. | Recent advances in microwave initiated synthesis of nanocarbon materials | |
Xu et al. | Strong, conductive, lightweight, neat graphene aerogel fibers with aligned pores | |
Wu et al. | Morphology-controllable graphene–TiO 2 nanorod hybrid nanostructures for polymer composites with high dielectric performance | |
Sun et al. | Hierarchical structure and polymorphism of a sphere-cubic shape amphiphile based on a polyhedral oligomeric silsesquioxane–[60] fullerene conjugate | |
US11780733B2 (en) | Porous silicon and method of manufacture | |
Cao et al. | Fabrication and properties of graphene oxide-grafted-poly (hexadecyl acrylate) as a solid-solid phase change material | |
CN102398902B (en) | Method for preparing carbon nano material by using natural endellite as formwork | |
CN107963623A (en) | The method for preparing carbon material-graphene composite material film | |
Mai et al. | Polymer-directed synthesis of metal oxide-containing nanomaterials for electrochemical energy storage | |
Huang et al. | Polyaniline-intercalated graphene oxide sheet and its transition to a nanotube through a self-curling process | |
US11242258B1 (en) | Method of manufacture of porous silicon | |
US20110104040A1 (en) | Simple, effective and scalable process for making carbon nanotubes | |
KR101549732B1 (en) | Porous graphene/metal-oxide complex and method for preparing the same | |
Li et al. | Handedness inversion in preparing chiral 4, 4′-biphenylene-silica nanostructures | |
CN112679949A (en) | Conductive conjugated microporous polymer and preparation method thereof | |
KR101615604B1 (en) | Method for preparing catalyst composite including intermetallic nano particle | |
CN114702647B (en) | Polymeroquinone polymer and preparation method thereof | |
KR100999173B1 (en) | Preparative method of conductive silica nano-tube composite by using in situ polymerization of aniline | |
Du et al. | Facile synthesis of exfoliated and highly conductive poly (arylene disulfide)/graphite nanocomposites | |
Dong et al. | Characterization and comparison of conducting polyaniline synthesized by three different pathways | |
Suzuki et al. | Synthesis and characterization of Zn-doped mesoporous SnO 2 by using thermally-stable block copolymer templates | |
CN116715232B (en) | Preparation method of independently-supportable three-dimensional graphite alkyne foam and product thereof | |
CN114956053B (en) | Metal-doped polymer C 60 Two-dimensional polymerization of C 60 And preparation method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |