CN104292249B - A kind of covalency organic frame taking thienothiophene boric acid as part and preparation method thereof - Google Patents
A kind of covalency organic frame taking thienothiophene boric acid as part and preparation method thereof Download PDFInfo
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- CN104292249B CN104292249B CN201410385211.1A CN201410385211A CN104292249B CN 104292249 B CN104292249 B CN 104292249B CN 201410385211 A CN201410385211 A CN 201410385211A CN 104292249 B CN104292249 B CN 104292249B
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- boric acid
- thienothiophene
- organic frame
- covalency organic
- covalency
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- 239000004327 boric acid Substances 0.000 title claims abstract description 29
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 title claims abstract description 27
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000010276 construction Methods 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000012265 solid product Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 5
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002732 mesitylenes Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000005199 trimethylbenzenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/05—Cyclic compounds having at least one ring containing boron but no carbon in the ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to organic functional material technical field, especially relate to a kind of covalency organic frame taking thienothiophene boric acid as part, its structure is as follows, A kind of preparation method of the covalency organic frame taking thienothiophene boric acid as part as: thienothiophene boric acid part is dissolved in the solvent of thienothiophene boric acid, be under 110-120 DEG C, the pressure reaction condition that is 1-2MPa in temperature, reaction 48-72h, dry, obtain the covalency organic frame taking thienothiophene boric acid as part. A kind of covalency organic frame taking thienothiophene boric acid as part provided by the invention, it is a kind of covalency organic frame forming by autohemagglutination, compound with regular structure, aperture ratio is compared with homogeneous, be insoluble to and common are machine solvent, at high temperature still can keep original structure, there is higher chemical stability and heat endurance.<!--2-->
Description
Technical field
The present invention relates to organic functional material technical field, especially relate to a kind of taking thienothiophene boric acid asCovalency organic frame that part autohemagglutination forms and preparation method thereof.
Background technology
The synthetic technology of framework is more and more subject to domestic and international scientist's attention in recent years, the current overwhelming majority'sFramework is metal organic frame (MOF), and metal covalency organic frame (MOF) material has on syntheticVery large flexibility, and compound with regular structure are the important crystalline form porous materials of a class, at gas storage and transportation, lightElectrical domain has a wide range of applications, but this class material of metal covalency organic frame (MOF) exists obviouslyDefect, reason is because metal covalency organic frame (MOF) material is by metal ion and organic ligandThe material forming by coordinate bond, its skeleton easily caves in, and has therefore greatly limited this class materialExtensive use. Since Yaghi group in 2005 reports the first covalency organic frame (COF) material,Covalency organic frame (COF) causes various countries scientist's vast concern especially, covalency organic frame (COF)Become the class new material occurring after metal-organic framework (MOFs), development trend instantlyImprovement and the regulation and control of more accurately structure prediction, NW-TFT and function. Covalency organic frame (COF)Synthesis and structure be to be all formed by connecting by strong covalent bond (B-O, C-O, B-C), there is porousThe design feature of material. These materials are all by C, H, and O, N, the light element compositions such as B, have than tableThe advantages such as area is large, and density is low, particularly have a large amount of conjugated systems, and parallel stacks between layersLong-pending structure has open duct, is easily excited being subject to illumination electronics, and electronics is easily transmission in material,They have potential application prospect at aspects such as gas storage, catalysis, separation, optics and chemical sensitisations.
Report is mainly the covalency organic frame (COF) that copolymerization forms at present, its synthetic reaction condition ratioHarsher, the aperture of formation, duct inequality, limited its possibility of applying widely. Up to the present,There is not yet a kind of covalency organic frame (COF) forming with thienothiophene boric acid autohemagglutination at photoelectric materialThe report of middle application.
Summary of the invention
The object of the present invention is to provide a kind of covalency organic frame taking thienothiophene boric acid as part andPreparation method is a kind of covalency organic frame forming by autohemagglutination, by its reaction temperature of strict controlAnd reaction pressure, obtain a kind of aperture ratio compared with homogeneous, regular covalency organic frame.
The technical solution adopted for the present invention to solve the technical problems is: a kind of with thienothiophene boric acid for joiningThe covalency organic frame of body, has following construction unit:
Or
A preparation method for covalency organic frame taking thienothiophene boric acid as part, comprises the steps:
Thienothiophene boric acid part is dissolved in the solvent of thienothiophene boric acid, in temperature isUnder the reaction condition that 110-120 DEG C, pressure are 1-2MPa, reaction 48-72h, dries, and obtains with thienoThienyl boric acid is the covalency organic frame of part.
Particularly, described solvent is Isosorbide-5-Nitrae dioxane and 1,3, the complex solvent of 5 trimethylbenzenes.
Particularly, the volume ratio of described Isosorbide-5-Nitrae dioxane and 1,3,5 trimethylbenzenes is 1:0.5-3.
Particularly, described thienothiophene boric acid is thieno [3,2-b] thiophene 2,5-boric acid or thieno 2,2-thiophene-5,5-thienyl boric acid.
The invention has the beneficial effects as follows: a kind of covalency taking thienothiophene boric acid as part provided by the inventionOrganic frame is a kind of covalency organic frame forming by autohemagglutination, by its reaction temperature of strict controlAnd reaction pressure, obtain a kind of aperture ratio compared with homogeneous, regular covalency organic frame, be insoluble to and common areMachine solvent, at high temperature still can keep original structure, has higher chemical stability and heat endurance,Not only there is a large amount of conjugated systems, and parallel packed structures has open duct between layers,Be subject to illumination electronics and be easily excited, electronics is easily transmission in material, at optics and chemical sensitisation etc.There is potential application prospect aspect, and it will be a kind of extraordinary photoelectric material. One provided by the inventionThe preparation method of the covalency organic frame taking thienothiophene boric acid as part, method is simple, easily controls,Be conducive to industrialized production.
Brief description of the drawings
Fig. 1 is polycrystalline X-ray diffraction (PXRD) figure of covalency organic frame of the present invention, and wherein A isThe PXRD figure of embodiment 1 end product, B is the PXRD figure of embodiment 2 end products, C is realThe PXRD figure that executes example 3 end products, D is the PXRD of embodiment 4 end products. Can from figureFind out at the covalency organic frame of differential responses condition gained and all there is meso-hole structure.
Fig. 2 is the TEM figure of embodiments of the invention 1 end product.
Detailed description of the invention
Below in conjunction with specific embodiment, further the present invention is set forth, should be understood that and only quote embodimentBe used for illustrating the present invention, limit the scope of the invention and be not used in.
Embodiment 1
By 227mmg (1mmol) thieno [3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml1,4 dioxane and 1,3, in the mixed solution of 5 trimethylbenzene volume ratio 1:0.5, then place it in temperatureBe to react 48h in 110 DEG C and the pressure autoclave that is 1MPa, the product obtaining filters, incited somebody to actionThe solid product of having filtered cleans and removes impurity with oxolane or acetone, and then filters, and finally willIts solid product is placed on 50 DEG C of vacuum drying chambers and dries, and obtains 160mmg powder, productive rate 70%. As Fig. 1Shown in Fig. 2, can find out at the covalency organic frame of gained and all there is meso-hole structure. Its reaction equation is as followsShown in:
Embodiment 2
By 227mmg (1mmol) thieno [3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml1,4 dioxane and 1,3, in the mixed solution of 5 trimethylbenzene volume ratio 1:1, then place it in temperatureBe to react 48h in 110 DEG C and the pressure autoclave that is 1MPa, the product obtaining filters, incited somebody to actionThe solid product of having filtered cleans and removes impurity with oxolane or acetone, and then filters, and finally willIts solid product is placed on 50 DEG C of vacuum drying chambers and dries, and obtains 168mmg powdered product, and its productive rate is 74%.As shown in Figure 1, can find out at the covalency organic frame of gained and all there is meso-hole structure.
Embodiment 3
By 227mmg (1mmol) thieno [3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml1,4 dioxane and 1,3, in the mixed solution of 5 trimethylbenzene volume ratio 1:3, then place it in temperatureBe to react 48h in 110 DEG C and the pressure autoclave that is 1MPa, the product obtaining filters, incited somebody to actionThe solid product of having filtered cleans and removes impurity with oxolane or acetone, and then filters, and finally willIts solid product is placed on 50 DEG C of vacuum drying chambers and dries, and obtains 157.7mmg powdered product, and its productive rate is69%. As shown in Figure 1, can find out at the covalency organic frame of gained and all there is meso-hole structure.
Embodiment 4
By 227mmg (1mmol) thieno [3,2-b] thiophene 2,5-boric acid (TTBA) is dissolved in 10ml1,4 dioxane and 1,3, in the mixed solution of 5 trimethylbenzene volume ratio 1:1, then place it in temperatureBe to react 48h in 120 DEG C and the pressure autoclave that is 2MPa, the product obtaining filters, incited somebody to actionThe solid product of having filtered cleans and removes impurity with oxolane or acetone, and then filters, and finally willIts solid product is placed on 50 DEG C of vacuum drying chambers and dries, and obtains 165mmg powdered product, and its productive rate is 73%.As shown in Figure 1, can find out at the covalency organic frame of gained and all there is meso-hole structure.
Taking above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, related workPersonnel can, not departing from the scope of this invention technological thought, carry out various change and amendment completely.The technical scope of this invention is not limited to the content on description, must be according to claim scopeDetermine its technical scope.
Claims (4)
1. the covalency organic frame taking thienothiophene boric acid as part, is characterized in that having following construction unit:
2. a preparation method for the covalency organic frame taking thienothiophene boric acid as part as claimed in claim 1, its spyLevy and be to comprise the steps:
Thienothiophene boric acid part is dissolved in solvent, is the reaction condition that 110-120 DEG C, pressure are 1-2MPa in temperatureUnder, reaction 48-72h, dries, and obtains the covalency organic frame taking thienothiophene boric acid as part,
Described thienothiophene boric acid part is thieno [3,2-b] thiophene 2,5-boric acid.
3. the preparation method of a kind of covalency organic frame taking thienothiophene boric acid as part as claimed in claim 2, its spyLevy and be: described solvent is the complex solvent of Isosorbide-5-Nitrae-dioxane and 1,3,5-trimethylbenzene.
4. the preparation method of a kind of covalency organic frame taking thienothiophene boric acid as part as claimed in claim 3, its spyLevy and be: the volume ratio of described Isosorbide-5-Nitrae-dioxane and 1,3,5-trimethylbenzene is 1:0.5-3.
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| CN102933588A (en) * | 2010-04-07 | 2013-02-13 | 康奈尔大学 | Covalent organic frameworks and methods of making same |
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| CN102933588A (en) * | 2010-04-07 | 2013-02-13 | 康奈尔大学 | Covalent organic frameworks and methods of making same |
Non-Patent Citations (2)
| Title |
|---|
| "A Photoconductive Thienothiophene-Based Covalent Organic Framework Showing Charge Transfer Towards Included Fullerene";Dogru M et al;《Angew. Chem》;20130204;第125卷;第2992–2996页 * |
| "Vibrational Properties of Boroxine Anhydride and Boronate Ester Materials: Model Systems for the Diagnostic Characterization of Covalent Organic Frameworks";Smith M K et al;《Chemistry of Materials》;20140529;第26卷;第3781−3795页 * |
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