CN114702647B - Polymeroquinone polymer and preparation method thereof - Google Patents
Polymeroquinone polymer and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 17
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 239000011229 interlayer Substances 0.000 claims description 9
- 238000000746 purification 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
- 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
- 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
- 238000010438 heat treatment 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
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000009830 intercalation Methods 0.000 claims description 5
- 230000002687 intercalation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 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
- 230000008569 process Effects 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 compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 13
- 229910052901 montmorillonite Inorganic materials 0.000 description 11
- 239000000138 intercalating agent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 238000004146 energy storage Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000203 mixture Substances 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
- 238000012360 testing method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 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
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 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
- 238000005342 ion exchange Methods 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
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet 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
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- 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
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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
- 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
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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
- 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
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- 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 polycoanone polymer and a preparation method thereof, wherein the preparation method comprises the following steps: selecting modified montmorillonite as a template, and polymerizing polycyclic aromatic hydrocarbon and anhydride into the polyconfiguration quinone polymer; the polymer has a nanolamellar structure.
Description
Technical Field
The application relates to a polycoanone polymer and a preparation method thereof, belonging to the technical field of chemical synthesis.
Background
The polycoanone polymer (polyacenequinoneredical polymers, PAQR for short) is an intrinsic semi-conductive high molecular polymer, and the special floating polarization form in the molecule of the polycoanone polymer has higher dielectric constant, so that the polycoanone polymer is a special 'amphibian' material. 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 be used as a pure organic semiconductive/dielectric material to be applied to the fields of sensors and electric energy storage. The methods commonly used at present are a solid-phase melting method, a vapor deposition method and a solution polymerization method, and are mainly prepared by polymerizing aromatic ring or heteroaromatic ring monomers and acid anhydride under the catalysis of Lewis acid. In general, polymer chains generated in the free polymerization process are difficult to fold and arrange along an ordered direction in a three-dimensional space, are generally intertwined, have no regularity, and have irregular morphology. For example, wang et al (Hollow PAQR nanostructure and its smart electrorheological activity, polymer,2016,83,129-137) disclose the synthesis of PAQR in a hollow sphere structure using a surfactant such as sodium dodecyl sulfate as a template, but the obtained PAQR hollow spheres are not uniform in size and are easily broken due to poor dimensional stability of sodium dodecyl sulfate. Meanwhile, the PAQR is synthesized at present, and the side reaction is more, so that the monomer volatilizes seriously, and the yield is lower. Therefore, realizing controllable preparation of PAQR morphology and improving yield at the same time is a difficult point of breaking through 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 polyconfiguration quinone polymer, which can prepare a polyconfiguration quinone polymer with a nano lamellar structure.
The preparation method of the polycoanone polymer provided in the first aspect of the application comprises the following steps: the modified montmorillonite is selected as a template, and the polycyclic aromatic hydrocarbon and the anhydride are polymerized in the interlayer limited space of the modified montmorillonite to generate the polyconfiguration quinone polymer.
Optionally, the modified montmorillonite has lewis acid as an intercalation agent.
Alternatively, the Lewis acid is selected from quaternary ammonium salts, znCl 2 、AlCl 3 、FeCl 3 One of them.
Alternatively, the quaternary ammonium salt is one of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide and dioctadecyl dimethyl ammonium chloride.
Optionally, the molar ratio of the modified montmorillonite, the polycyclic aromatic hydrocarbon and the anhydride is 1-2:1:1.
Optionally, the polycyclic 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 more than one of anthracene, anthraquinone and pyrene.
Optionally, the anhydride is any one or a combination of more than one of pyromellitic dianhydride, tetrachloroanhydride and tetrabromoanhydride.
More specifically, the preparation method of the spinuloid polymer comprises the following steps: selecting modified montmorillonite as a template, and adding the modified montmorillonite, the polycyclic aromatic hydrocarbon and the anhydride into a first solvent for uniform mixing; performing ultrasonic treatment, and performing suction filtration and drying to obtain a first solid; heating the first solid for reaction, and cooling to room temperature after the reaction is completed to obtain a second solid; purifying the second solid to obtain the spinuloid polymer.
Alternatively, the first solvent is selected from acetone, ethanol or methanol.
Optionally, the time of the ultrasonic treatment is 10-24 hours.
Optionally, the first solid is transferred to a muffle furnace for heating reaction at 310-360 ℃ for 15-24 hours.
Optionally, the second solid purification process comprises: sequentially selecting hydrochloric acid, water, ethanol, toluene and hydrofluoric acid as purifying solvents to purify the obtained second solid.
In a second aspect, the present application provides a polycoagulant quinone polymer, which can be prepared by the preparation method according to any of the foregoing technical schemes, and the polycoagulant quinone polymer has a nano lamellar structure.
Compared with the prior art, the beneficial effects of this application are:
according to the preparation method of the multi-layer and multi-layer quinone polymer, modified montmorillonite is used as a template and a catalyst at the same time, polycyclic aromatic hydrocarbon and anhydride are polymerized in a montmorillonite interlayer limited space to generate the nano-layer and multi-layer quinone polymer, so that the morphology of PAQR is controllable; meanwhile, due to the limiting effect of montmorillonite, polycyclic aromatic hydrocarbon and anhydride are not easy to volatilize and escape in the heating process, so that the yield of PAQR is improved; is beneficial to promoting the application research of PAQR.
The preparation method of the polycoagulant quinone polymer has the advantages that the PAQR prepared by the preparation method is uniform in appearance, free of impurities and high in product purity; and the process method is simple, and the reaction condition is mild.
The preparation method of the polycoanone polymer according to at least one embodiment of the present application can prepare an organic polymer having a nano lamellar structure whose main components are carbon and oxygen. The prepared polymer has 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 sheet;
FIG. 2 is a phase diagram and height diagram of AFM testing of PAQR sheets;
fig. 3 is a TEM photograph of the synthesis of PAQR under template-free conditions.
Detailed Description
The following detailed description of the embodiments of the present application is provided in connection with specific embodiments, however, it should be understood that structures and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.
The application provides a preparation method of a polycistronic quinone Polymer (PAQR), which introduces modified montmorillonite with Lewis acid as an intercalation agent into a reaction system, wherein a 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, and can induce the ordered polymerization of a reaction monomer in the application in the two-dimensional direction, so that the order degree of a polymer chain is improved, the shape is controllable, the structural stability of the polycistronic quinone polymer is improved, and the application field is enlarged.
The preparation method of the polycoagulant polymer in the embodiment adopts a one-step synthesis method, and the PAQR of the nano-sheet is obtained by controlling the proportion of the reaction monomers and the reaction temperature and realizing the synthesis of the PAQR at high temperature.
In the embodiment, modified montmorillonite is used as a template, and polycyclic aromatic hydrocarbon and anhydride are polymerized in an interlayer limited space of the modified montmorillonite to generate the polyconfiguration quinone polymer.
Montmorillonite is a silicate with a layered structure in which metal cations are adsorbed between layers. In this embodiment, the intercalating agent may enter between the montmorillonite sheets by ion exchange to increase the spacing between the sheets, and then the polymer monomer may enter between the sheets to polymerize in the confined space between the sheets to form a polymer of nano-lamellar structure.
The preparation method comprises the following specific steps:
modified montmorillonite with Lewis acid as an intercalation agent is selected as a template, and the modified montmorillonite, the polycyclic aromatic hydrocarbon and the anhydride are added into a first solvent and uniformly mixed; performing ultrasonic treatment, and performing suction filtration and drying to obtain a first solid; heating the first solid for reaction, and cooling to room temperature after the reaction is completed to obtain a second solid; purifying the second solid to obtain the spinuloid polymer.
As an alternative embodiment, the modified montmorillonite has Lewis acid as intercalation agent, and the Lewis acid can be quaternary ammonium salt or ZnCl 2 、AlCl 3 、FeCl 3 And the like. The montmorillonite intercalated with Lewis acid can play a role of a template and a catalyst at the same time, 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 molar ratio of modified montmorillonite, polycyclic aromatic hydrocarbon and anhydride is 1-2:1-1.5:1 to 1.5; preferably, the molar ratio is 1-2:1:1, for example, may be 1:1:1,1.2:1:1,1.5:1:1,1.8:1:1,2:1:1, etc.
As an alternative embodiment, the polycyclic aromatic hydrocarbon is an aromatic ring monomer or a heteroaromatic ring monomer, and any one or a combination of several of anthracene, anthraquinone, pyrene and the like can be selected.
As an alternative embodiment, the acid anhydride may be any one or a combination of several of pyromellitic dianhydride, tetrachloroanhydride, tetrabromoanhydride, etc.
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 10-24 hours, for example 12 hours, 15 hours, 18 hours, 20 hours, 22 hours, etc.
As an alternative embodiment, the first solid is transferred to a muffle furnace for heating reaction at 300-310 ℃ for 15-24 hours; for example, at 300℃for 22 hours, at 305℃for 20 hours, at 310℃for 18 hours, etc.
As an alternative embodiment, the second solid purification process comprises: sequentially selecting hydrochloric acid, water, ethanol, toluene and hydrofluoric acid as purifying solvents to purify the obtained second solid.
The PAQR with the nano lamellar structure can be prepared, and the main components of the PAQR are carbon and oxygen; the modified montmorillonite is used as a template and a catalyst at the same time, so that the controllable preparation of the lamellar PAQR is realized; the prepared lamellar PAQR has uniform thickness, is easy to purify, 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 polycoanone polymer comprises the following steps:
1mol of anthraquinone, 1mol of pyromellitic dianhydride and 1mol of organically modified montmorillonite (the interlayer intercalating agent of which is quaternary ammonium salt) are placed in 300mol of acetone and mixed uniformly.
Ultrasonic treatment is carried out for 24 hours, and the first solid is obtained after suction filtration and drying.
Transferring the dried first solid into a muffle furnace, and setting a heating program as follows: raising the temperature to 100 ℃ at room temperature, 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 of 300 ℃ to 310 ℃ and preserving heat for 20 hours; cooling to room temperature gave a second solid.
The powder of the second solid obtained was placed in a Soxhlet extractor, and sequentially purified using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, respectively, and finally the montmorillonite template was washed off with 200ml of hydrofluoric acid to obtain 1.49g of black solid powder (yield: 35%), thereby obtaining the multi-layer-structured polycoanone polymer.
And (3) observing the obtained polyconfiguration quinone polymer under a transmission electron microscope to obtain TEM and element mapping pictures shown in fig. 1, wherein the PAQR is clearly visible in the pictures to form a lamellar structure, and meanwhile, the porous carbon film on the lower copper mesh is clearly visible, so that the PAQR is a very thin lamellar.
Further, AFM test was performed on the obtained polyconquinone polymer to obtain a phase diagram and a height diagram of the PAQR sheet shown in fig. 2, from which the thickness of the sheet was found to be about 6.0nm. The multi-layer quinone polymer obtained in the embodiment is of a nano lamellar structure, and can be applied to the fields of capacitors, sensors and the like.
Example 2
The preparation method of the polycoanone polymer comprises the following steps:
1mol of anthracene, 1mol of pyromellitic dianhydride and 1mol of organically modified montmorillonite (the interlayer intercalating agent is ZnCl) 2 ) Placing in 300mol of acetone, and mixing uniformly.
Ultrasonic treatment is carried out for 24 hours, and the first solid is obtained after suction filtration and drying.
Transferring the dried first solid into a muffle furnace, and setting a heating program as follows: raising the temperature to 100 ℃ at room temperature, 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 of 300 ℃ to 310 ℃ and preserving heat for 20 hours; cooling to room temperature gave a second solid.
The powder of the second solid obtained was placed in a Soxhlet extractor, and sequentially purified using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, respectively, and finally the montmorillonite template was washed off with 200ml of hydrofluoric acid to obtain 1.39g of black solid powder (yield: 35%), thereby obtaining the multi-layer-structured polycoanone polymer.
This example is similar to the spinodal polymer obtained in example 1, and also has a lamellar structure.
Example 3
The preparation method of the polycoanone polymer comprises the following steps:
1.1mol of pyrene, 1.1mol of tetrachloroanhydride and 1.2mol of modified montmorillonite (the interlayer intercalating agent is AlCl) 3 ) Placed in 320mol of acetoneIs evenly mixed.
Ultrasonic treatment is carried out for 24 hours, and the first solid is obtained after suction filtration and drying.
Transferring the dried first solid into a muffle furnace, and setting a heating program as follows: raising the temperature to 100 ℃ at room temperature, 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 of 300 ℃ to 310 ℃ and preserving heat for 20 hours; cooling to room temperature gave a second solid.
The powder of the second solid obtained was placed in a Soxhlet extractor, and sequentially purified using 220ml of hydrochloric acid, 550ml of water, 350ml of ethanol and 120ml of toluene as purification solvents, respectively, and finally the montmorillonite template was washed off with 180ml of hydrofluoric acid to obtain 1.56g of black solid powder (yield: 32%), thereby obtaining the multi-layer-structured polycoanone polymer.
This example is similar to the spinodal polymer obtained in example 1, and also has a lamellar structure.
Example 4
The preparation method of the polycoanone polymer comprises the following steps:
1mol of anthraquinone, 1mol of tetrabromoanhydride and 1mol of modified montmorillonite (the interlayer intercalating agent is FeCl) 3 ) Placing in 280mol of acetone, and uniformly mixing.
Ultrasonic treatment is carried out for 24 hours, and the first solid is obtained after suction filtration and drying.
Transferring the dried first solid into a muffle furnace, and setting a heating program as follows: raising the temperature to 100 ℃ at room temperature, 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 of 300 ℃ to 310 ℃ and preserving heat for 20 hours; cooling to room temperature gave a second solid.
The powder of the second solid obtained was placed in a Soxhlet extractor, and sequentially purified using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, respectively, and finally the montmorillonite template was washed off with 150ml of hydrofluoric acid to obtain 1.58g of black solid powder (yield: 32%), thereby obtaining the multi-layer-structured polycoanone polymer.
This example is similar to the spinodal polymer obtained in example 1, and also has a lamellar structure.
Example 5
The preparation method of the polycoanone polymer comprises the following steps:
1mol of anthraquinone, 1mol of anthracene, 2mol of tetrabromoanhydride and 2.3mol of organically modified montmorillonite (the interlayer intercalating agent of which is quaternary ammonium salt) are placed in 600mol of acetone and mixed uniformly.
Ultrasonic treatment is carried out for 24 hours, and the first solid is obtained after suction filtration and drying.
Transferring the dried first solid into a muffle furnace, and setting a heating program as follows: raising the temperature to 100 ℃ at room temperature, 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 of 300 ℃ to 310 ℃ and preserving heat for 20 hours; cooling to room temperature gave a second solid.
The powder of the second solid obtained was placed in a Soxhlet extractor, and sequentially purified using 400ml of hydrochloric acid, 1000ml of water, 600ml of ethanol and 200ml of toluene as purification solvents, respectively, and finally the montmorillonite template was washed off with 500ml of hydrofluoric acid to obtain 3.16g of black solid powder (yield: 33%), thereby obtaining the multi-layer-structured polycoanone polymer.
This example is similar to the spinodal polymer obtained in example 1, and also has a lamellar structure.
Comparative example 1
The preparation method of the polycoanone polymer comprises the following steps:
1mol of anthraquinone, 1mol of pyromellitic dianhydride and 1mol of ZnCl 2 Placing the mixture in the porcelain week and mixing the mixture uniformly. And transferring to a muffle furnace, wherein the temperature-raising program is set as follows: raising the temperature to 100 ℃ at room temperature, 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 of 300 ℃ to 310 ℃ and preserving heat for 20 hours; cooling to room temperature, a black solid powder was obtained.
The obtained powder was placed in a Soxhlet extractor and sequentially purified using 200ml of hydrochloric acid, 500ml of water, 300ml of ethanol and 100ml of toluene as purification solvents, respectively, to obtain 0.34g of a black solid powder (yield: 8%), thereby obtaining a polycoagulant quinone polymer. Fig. 3 is a TEM image of the PAQR obtained without the template in this example, and it can be seen from the figure that the obtained sample has a thicker irregular block morphology and a disordered morphology.
The described embodiments are merely illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the spirit of the design of the present application.
Claims (9)
1. A method for preparing a polycoanone polymer, comprising: selecting modified montmorillonite as a template, and polymerizing polycyclic aromatic hydrocarbon and anhydride into the polycistronic quinone polymer in an interlayer limited space of the modified montmorillonite; wherein,,
the modified montmorillonite takes Lewis acid or quaternary ammonium salt as an intercalation agent.
2. The method for preparing a polycoanone polymer according to claim 1, wherein the lewis acid is ZnCl 2 、AlCl 3 、FeCl 3 One of them.
3. The method for preparing a polyconfiguration quinone polymer according to claim 1, wherein the quaternary ammonium salt is one of 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.
4. A process for the preparation of a polyconfiguration quinone polymer according to any one of claims 1-3, wherein the molar ratio of modified montmorillonite, polycyclic aromatic hydrocarbon and anhydride is 1-2:1:1.
5. A method for preparing a polyconfiguration quinone polymer according to any one of claims 1-3, wherein the polycyclic aromatic hydrocarbon is selected from any one or a combination of more of anthracene, anthraquinone, pyrene; the anhydride is selected from any one or a combination of more of pyromellitic dianhydride, tetrachloroanhydride and tetrabromoanhydride.
6. A process for the preparation of a polycoanone polymer according to any one of claims 1 to 3, characterized in that it comprises more specifically: selecting modified montmorillonite as a template, and adding the modified montmorillonite, the polycyclic aromatic hydrocarbon and the anhydride into a first solvent for uniform mixing; performing ultrasonic treatment, and performing suction filtration and drying to obtain a first solid; heating the first solid for reaction, and cooling to room temperature after the reaction is completed to obtain a second solid; purifying the second solid to obtain the spinuloid polymer.
7. The method for preparing a polycoanone polymer according to claim 6, wherein the first solvent is selected from acetone, ethanol or methanol; the ultrasonic treatment time is 10-24 hours; the process of the second solid purification comprises: sequentially selecting hydrochloric acid, water, ethanol, toluene and hydrofluoric acid as purifying solvents to purify the obtained second solid.
8. The method for preparing a polycoanone polymer according to claim 6, wherein the first solid is transferred to a muffle furnace for heating reaction at 310-360 ℃ for 15-24 hours.
9. A polycoagulaquinone polymer, characterized in that it is obtained by the method for preparing polycoagulaquinone polymer according to any one of claims 1-8, and has a nano lamellar structure.
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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 | A kind of preparation method of lithium ion cell positive |
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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 | A kind of preparation method of lithium ion cell positive |
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