CN102504251B - Conductive copolymer material and synthesizing method and application thereof - Google Patents
Conductive copolymer material and synthesizing method and application thereof Download PDFInfo
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- CN102504251B CN102504251B CN 201110343667 CN201110343667A CN102504251B CN 102504251 B CN102504251 B CN 102504251B CN 201110343667 CN201110343667 CN 201110343667 CN 201110343667 A CN201110343667 A CN 201110343667A CN 102504251 B CN102504251 B CN 102504251B
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 229920001577 copolymer Polymers 0.000 title abstract 6
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 65
- 239000002070 nanowire Substances 0.000 claims abstract description 48
- MNKRTDOUBUSQHX-UHFFFAOYSA-N 2,4-dihydroxy-2-methyl-3-oxopentanoic acid Chemical compound CC(O)C(=O)C(C)(O)C(O)=O MNKRTDOUBUSQHX-UHFFFAOYSA-N 0.000 claims description 61
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 61
- 239000011701 zinc Substances 0.000 claims description 61
- 229910052725 zinc Inorganic materials 0.000 claims description 61
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 60
- DZLGZIGLHCRIMF-UHFFFAOYSA-N 4-pyridin-4-ylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=NC=C1 DZLGZIGLHCRIMF-UHFFFAOYSA-N 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 32
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002322 conducting polymer Substances 0.000 claims description 25
- 229920001940 conductive polymer Polymers 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 20
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 19
- 229910052740 iodine Inorganic materials 0.000 claims description 19
- 239000011630 iodine Substances 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 235000014655 lactic acid Nutrition 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- GZUBBCPCJHBRDY-UHFFFAOYSA-N 2-pyridin-4-ylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=NC=C1 GZUBBCPCJHBRDY-UHFFFAOYSA-N 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 claims description 3
- 230000007847 structural defect Effects 0.000 abstract 1
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000000018 DNA microarray Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
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- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- BXQBCBDSICIEOD-UHFFFAOYSA-N [Zn].C(C(O)C)(=O)C(C(=O)O)(O)C Chemical compound [Zn].C(C(O)C)(=O)C(C(=O)O)(O)C BXQBCBDSICIEOD-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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Abstract
The invention discloses a conductive copolymer material. The conductive copolymer material is a nanometer polypyrrole molecular conductive wire with a one-dimensional molecular chain structure. Due to the adoption of the nanometer polypyrrole molecular conductive wire with the one-dimensional molecular chain structure, the structural defects of polypyrrole molecules are effectively overcome, the delocalization degree of electric charge on the nanometer polypyrrole molecular wire is improved, and the conductive copolymer material has high conductivity. Moreover, the invention further provides a method for synthesizing the conductive copolymer material and an application of the conductive copolymer material.
Description
[technical field]
The present invention relates to conductivity high molecule nanometer synthetic field, particularly a kind of conducting polymer materials and synthetic method thereof and application.
[background technology]
Polypyrrole has broad application prospects, as on various devices such as battery, electrical condenser, biosensor and DNA chip as studying the most a kind of conducting polymer composite at present.In recent years, researcher has been opened up a series of novel method for synthesizing have different nanometers and micrometer structure with preparation polypyrrole.Wherein, template be study the method for the synthetic polypyrrole of success, current template has microporous polymer, microporous inorganic thing (microporous aluminum oxide film, micropore silicon) and molecular sieve etc., these templates are also referred to as " hard template ".Yet, because pyrroles self has the constitutional features in α, β bifunctional polymerizable site, when synthetic, very easily form crosslinked higher-dimension polymer architecture.Because polypyrrole is a kind of any solvent polymkeric substance of not fusion again that is insoluble to, its chain structure is still not fully aware of at present, therefore, adopt the polypyrrole of polymerization under the conventional open system, the polymerization position is uncertain, and easily form branched polypyrrole, chain structure that it is generally acknowledged polypyrrole is the pyrroles unit cross-link bond planar array form altogether with α-α key and some alpha-beta keys and β-β key, yet, in fact only be to exist with desirable like this form less than 2/3rds pyrroles unit, this drawbacks limit structurally of the polypyrrole of polymerization the delocalization degree of electric charge on polymer chain, reduce its electroconductibility.At present, the method for the synthetic two-dimensional layer hole of report and three-dimensional inserting hole load aggregation thing is arranged, yet the conductivity of the polymkeric substance that aforesaid method is synthetic is still lower.
[summary of the invention]
Based on this, be necessary to provide a kind of conducting polymer materials with high electrical conductivity energy.
A kind of conducting polymer materials, described conducting polymer materials are the nanometer polypyrrole molecular wire with molecular chain structure of one dimension.
In addition, also be necessary to provide a kind of preparation method of above-mentioned conducting polymer materials.
A kind of method of compositing conducting polymer materials comprises the steps:
Step 1: synthetic materials is that two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the organic frame of zinc, and described organic frame has nano pore;
Step 2: described organic frame is carried out drying, in inert gas atmosphere, described organic frame is soaked in the pyrrole monomer solution then, described pyrrole monomer is loaded on the described organic frame;
Step 3: load is had the organic frame of pyrrole monomer under-10 ℃～-20 ℃ temperature, be soaked in the organic solution of iodine that concentration is 0.01mol/L～0.1mol/L, place polymerization reaction take place under the room temperature then, obtain the organic frame of loaded with nano polypyrrole molecular wire; And
Step 4: the organic frame of described loaded with nano polypyrrole molecular wire is separated and purifying, obtain described conducting polymer materials, described conducting polymer materials is the nanometer polypyrrole molecular wire with molecular chain structure of one dimension.
In a preferred embodiment, in the step 1, the method of described synthetic organic frame comprises: 4-(4-pyridyl) phenylformic acid, lactic acid and zinc nitrate hexahydrate are added N successively according to 1: 0.8～1.2: 1～2 molar ratio, be mixed with the mixing solutions that total concn is 0.18mol/L～0.28mol/L in the dinethylformamide, be that insulation was carried out hydro-thermal reaction in 48 hours～72 hours under 90 ℃～140 ℃ the closed environment then in temperature with described mixing solutions, obtain described organic frame after the cooling.
In a preferred embodiment, in the step 3, the organic solution of described iodine is the hexane solution of iodine or the cyclohexane solution of iodine.
In a preferred embodiment, in the step 4, the method of described separation and purifying comprises: the organic frame of described loaded with nano polypyrrole molecular wire is soaked in the ammonia soln of 0.1mol/L～1mol/L, treat the dissolving of described organic frame after, filter and remove molecular weight less than 500 molecule.
In a preferred embodiment, the method for described filtration is the semi-permeable membranes filtration method.
In a preferred embodiment, described molecular weight is 4-(4-pyridyl) benzoic acid molecule and lactic acid molecules less than 500 molecule.
In a preferred embodiment, in the step 2, described rare gas element is nitrogen.
The present invention also provides the application of above-mentioned conducting polymer materials on battery, electrical condenser, biosensor or DNA chip.
In the method for above-mentioned compositing conducting polymer materials, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that employing contains one dimension rigidity nanoporous closes the zinc organic frame and does template, and two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the BODY WITH SQUARE APERTURE that the zinc organic frame has nanometer, the rigidity hole wall that aromatic nucleus is formed and advantage cheap and easy to get, its hole wall is rich in electronics, thereby reach entering and locating of accurate control pyrrole monomer molecule, substep is introduced oxygenant iodine and pyrrole monomer, reference is optimized the polymerization environment, realized that successfully pyridine monomer closes the orderly polymerization of zinc organic frame camber containing two 4-of nano pore (4-pyridyl) phenylformic acid lactyl-lactic acid, the nanometer polypyrrole molecular wire of the molecular chain structure with one dimension that obtains, effectively solved polypyrrole molecule defective structurally, improved the delocalization degree of electric charge on the nanometer polypyrrole molecular wire, therefore, above-mentioned conducting polymer materials has higher electroconductibility.
[description of drawings]
Fig. 1 is the schema of method of the compositing conducting polymer materials of an embodiment;
Fig. 2 is the synoptic diagram of method of the compositing conducting polymer materials of an embodiment;
Fig. 3 is the testing conductive device synoptic diagram of embodiment one;
Fig. 4 closes the infrared spectra of zinc organic frame for two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of the loaded with nano polypyrrole molecular wire of embodiment one;
Fig. 5 for embodiment one-pyridyl) phenylformic acid lactyl-lactic acid two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that closes zinc organic frame (curve A) and loaded with nano polypyrrole molecular wire closes the thermogravimetric curve figure of zinc organic frame (curve B);
Fig. 6 closes the X-ray diffraction graphic representation that two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid in zinc organic frame (curve D), the step (1) closes zinc organic frame (curve E) and the former framework of computer simulation (curve F) for the nanometer polypyrrole molecular wire (curve C) of embodiment one, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of having removed DMF;
Fig. 7 is that the preceding organic frame of the polymerization reaction take place of embodiment one is schemed the adsorption and desorption curve (curve H) of nitrogen adsorption and desorption curve (curve G) and the organic frame behind the polymerization reaction take place of nitrogen;
Fig. 8 is the sem photograph of the nanometer polypyrrole molecular wire of embodiment one;
Fig. 9 is the transmission electron microscope picture of the nanometer polypyrrole molecular wire of embodiment one;
Figure 10 is that the I that the ethanol stripping is used in the back takes place the polyreaction of embodiment one
3-The ultraviolet absorption curve figure of ion.
[embodiment]
Mainly reaching specific embodiment below by reference to the accompanying drawings is described in further detail conducting polymer materials and synthetic method thereof and application.
The conducting polymer materials of one embodiment, this conducting polymer materials are the nanometer polypyrrole molecular wire with molecular chain structure of one dimension.
As shown in Figures 1 and 2, a kind of method of compositing conducting polymer materials comprises the steps:
Step S1: synthetic materials is that two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the organic frame of zinc, and organic frame has nano pore.In the present embodiment, the method of synthetic organic frame comprises: 4-(4-pyridyl) phenylformic acid, lactic acid and zinc nitrate hexahydrate are added N successively according to 1: 0.8～1.2: 1～2 molar ratio, be mixed with the mixing solutions that total concn is 0.18mol/L～0.28mol/L in the dinethylformamide, be that insulation was carried out hydro-thermal reaction in 48 hours～72 hours under 90 ℃～140 ℃ the closed environment then in temperature with mixing solutions, obtain organic frame after the cooling.In a preferred embodiment, hydro-thermal reaction is airtight the carrying out of hydrothermal reaction kettle of band polytetrafluoroethylsubstrate substrate, can place baking oven to carry out hydro-thermal reaction hydrothermal reaction kettle, temperature is preferably 110 ℃, preferred soaking time is 72 hours, at room temperature cool off then, obtain the organic frame of colourless block crystallization.In the present embodiment, earlier 4-(4-pyridyl) phenylformic acid is added N, in the dinethylformamide, add lactic acid again, add zinc nitrate hexahydrate preparation mixing solutions then, the preferred proportion of 4-(4-pyridyl) phenylformic acid, lactic acid and zinc nitrate hexahydrate is 1: 1: 1.5; The total concn of mixing solutions is preferably 0.23mol/L.This organic frame has the characteristics of unique regular, nano grade pore, and it is assembled by coordinate bond by organic ligand and inorganic metal center, convenient and simple land productivity is removed organic frame with having weakly alkaline ammoniacal liquor, in addition, this organic frame has the not available advantage of a large amount of traditional molecular sieves, as uncommon hole shape, gentleer synthesis condition and the potential controllability to hole size and size.
Step S2: organic frame is carried out drying, in inert gas atmosphere, organic frame is soaked in the pyrrole monomer solution then, pyrrole monomer is loaded on the organic frame.In the present embodiment, with organic frame under 200 ℃ of vacuum conditions dry 10 hours, remove the DMF in the organic frame.Rare gas element can be preferably nitrogen for gases such as nitrogen, helium, argon gas.
Step S3: load is had the organic frame of pyrrole monomer under-10 ℃～-20 ℃ temperature, be soaked in the organic solution of iodine that concentration is 0.01mol/L～0.1mol/L, place polymerization reaction take place under the room temperature then, obtain the organic frame of loaded with nano polypyrrole molecular wire.In the present embodiment, the organic solution of iodine is the hexane solution of iodine or the cyclohexane solution of iodine.Elemental iodine is as the oxygenant of polyreaction, and iodine is reduced to I after polyreaction takes place
3-Ion is again good polymer-doped dose simultaneously, has further improved the electroconductibility of polymkeric substance.In a preferred embodiment, soaking temperature is preferably-16 ℃, and the volumetric molar concentration of iodine is 0.05mol/L in the organic solution of iodine.
Step S4: the organic frame separation and purification with loaded with nano polypyrrole molecular wire, obtain conducting polymer materials, conducting polymer materials is the nanometer polypyrrole molecular wire with molecular chain structure of one dimension.In the present embodiment, the method for separation and purification comprises: the organic frame of loaded with nano polypyrrole molecular wire is soaked in 0.1mol/L～1mol/L ammonia soln, treats the organic frame dissolving, filtration removal molecular weight is the molecule less than 500 then.In the present embodiment, the solubility of ammonia soln is preferably 0.5mol/L; The method of filtering is the semi-permeable membranes filtration method, and semi-permeable membranes gets off molecular weight more than or equal to 500 molecular retentions, and molecular weight sees through semi-permeable membranes less than 500 molecule; Molecular weight is 4-(4-pyridyl) phenylformic acid and lactic acid less than 500 molecule.
Above-mentioned conducting polymer materials can be used at battery, electrical condenser, biosensor or DNA chip.
In the method for above-mentioned compositing conducting polymer materials, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that employing contains one dimension rigidity nanoporous closes the zinc organic frame and does template, and two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the BODY WITH SQUARE APERTURE that the zinc organic frame has nanometer, the rigidity hole wall that aromatic nucleus is formed and advantage cheap and easy to get, its hole wall is rich in electronics, thereby reach entering and locating of accurate control pyrrole monomer molecule, substep is introduced oxygenant iodine and pyrrole monomer, reference is optimized the polymerization environment, realized that successfully pyridine monomer closes the orderly polymerization of zinc organic frame camber containing two 4-of nano pore (4-pyridyl) phenylformic acid lactyl-lactic acid, the nanometer polypyrrole molecular wire of the molecular chain structure with one dimension that obtains, effectively solved polypyrrole molecule defective structurally, improved the delocalization degree of electric charge on the nanometer polypyrrole molecular wire, therefore, above-mentioned conducting polymer materials has higher electroconductibility.
Below be the specific embodiment part, the equipment that is used for the testing conductive rate among the following embodiment is U.S.'s Keithley 2400, and room temperature is 25 ℃, and compressing tablet pressure is 50atm, adopts spun gold to do electrode, and conductive silver glue is as tackiness agent.
Embodiment 1
(1) synthetic two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the zinc organic frame
1 mole of 4-(4-pyridyl) phenylformic acid is added N, in the dinethylformamide, add 0.8 molar lactic acid again, at room temperature use magnetic stirrer 10 minutes in the air, add 1 mole of zinc nitrate hexahydrate again, continue to stir 5 minutes, be mixed with the mixing solutions that total concn is 0.18mol/L, it is 23ml that mixing solutions is transferred to volume, airtight in the hydrothermal reaction kettle of band polytetrafluoroethylsubstrate substrate, hydrothermal reaction kettle is placed baking oven, hydro-thermal reaction was carried out in insulation in 72 hours under temperature is 110 ℃, cooling at room temperature then, and two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that obtains having nano pore closes the zinc organic frame.
(2) the preparation load has two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame
Two 4-in (1) (4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame under 200 ℃ of vacuum conditions dry 10 hours, remove DMF, then two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame in the atmosphere of nitrogen, be soaked in the pyrrole monomer solution, make pyrrole monomer be full of two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close the zinc organic frame, make pyrrole monomer load to two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close on the zinc organic frame.
(3) two 4-of loaded with nano polypyrrole molecular wire (4-pyridyl) phenylformic acid lactyl-lactic acid closes the zinc organic frame
Having two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame load in (2) is soaked under-16 ℃ temperature in the hexane solution of iodine that concentration is 0.05mol/L, after 48 hours, place polymerization reaction take place under the room temperature, treat whole organic frame blackening, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that namely obtains loaded with nano polypyrrole molecular wire closes the zinc organic frame.
(4) separation and purification
Two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of loaded with nano polypyrrole molecular wire is closed the zinc organic frame to be soaked in the 0.05mol/L ammonia soln, the organic frame dissolving, the nanometer polypyrrole molecular wire that comprises in the organic frame is released, adopt the dialysis tubing with semi-permeable membranes material to filter then to remove molecular weight for less than 500 molecule, the material that is trapped on the dialysis tubing is the nanometer polypyrrole molecular wire.
The nanometer polypyrrole molecular wire compressing tablet that present embodiment is synthetic, form press sheet compression 100, as shown in Figure 3, adopt U.S.'s Keithley (model 2400) 200 testing conductivities to draw, the specific conductivity of the nanometer polypyrrole molecular wire press sheet compression 100 that present embodiment is synthetic is 3S/m, than two dimension or the specific conductivity (10 of three-dimensional nanometer polypyrrole molecular wire of bibliographical information
-5-10
-4S/m) 5 orders of magnitude have been improved.
Draw from Fig. 4, the characteristic peak of polypyrrole has appearred in the infrared spectra that closes the zinc organic frame at two 4-of loaded with nano polypyrrole molecular wire (4-pyridyl) phenylformic acid lactyl-lactic acid, and characteristic peak appears at 964,1043,1306 and 1558 wave number places.
From Fig. 5, draw, it is obviously different with the thermogravimetric curve that two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of loaded with nano polypyrrole molecular wire closes zinc organic frame (curve B) that two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes zinc organic frame (curve A), and this is owing to generated the polypyrrole molecule.
As shown in Figure 6, close in the X-ray diffraction curve that two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid zinc organic frame (curve D), the step (1) closes zinc organic frame (curve E) and the former framework of computer simulation (curve F) as can be seen from the nanometer polypyrrole molecular wire (curve C) of separation and purification, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of having removed DMF, the diffraction angle of the nanometer polypyrrole molecular wire (curve C) of separation and purification is the characteristic peak of polypyrrole at 17.8 and 23.3 peaks that occur.
As shown in Figure 7, organic frame before the polymerization reaction take place to the organic frame behind the adsorption and desorption curve (curve G) of nitrogen and the polymerization reaction take place to the adsorption and desorption curve (curve H) of nitrogen as can be seen, organic frame behind the polymerization reaction take place is owing to the generation of polypyrrole in the organic frame, and its adsorptive power to gas will obviously descend.
As Fig. 8 and shown in Figure 9, as can be seen, the nanometer polypyrrole molecular wire of present embodiment has the molecular chain structure of one dimension.
As shown in figure 10, from polyreaction the I that the ethanol stripping is used in the back takes place
3-Can draw I in the ultraviolet absorption curve of ion
3-The characteristic peak of ion appears at 360nm wavelength place, because after polyreaction took place, oxygenant iodine was reduced to I
3-Ion.
(1) synthetic two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the zinc organic frame
1 mole of 4-(4-pyridyl) phenylformic acid is added N, in the dinethylformamide, add 1 molar lactic acid again, at room temperature use magnetic stirrer 10 minutes in the air, add 1.5 moles of zinc nitrate hexahydrates again, continue to stir 5 minutes, be mixed with the mixing solutions that total concn is 0.23mol/L, it is 23ml that the 3rd solution is transferred to volume, airtight in the hydrothermal reaction kettle of band polytetrafluoroethylsubstrate substrate, hydrothermal reaction kettle is placed baking oven, hydro-thermal reaction was carried out in insulation in 48 hours under temperature is 140 ℃, cooling at room temperature then, and two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that obtains having nano pore closes the zinc organic frame.
(2) the preparation load has two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame
Two 4-in (1) (4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame under 200 ℃ of vacuum conditions dry 10 hours, remove DMF, then two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame in the atmosphere of nitrogen, be soaked in the pyrrole monomer solution, make pyrrole monomer be full of two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close the zinc organic frame, make pyrrole monomer load to two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close on the zinc organic frame.
(3) two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of synthetic loaded with nano polypyrrole molecular wire closes the zinc organic frame
Having two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame load in (2) is soaked under-10 ℃ temperature in the cyclohexane solution of iodine that concentration is 0.01mol/L, after 48 hours, place polymerization reaction take place under the room temperature, treat whole organic frame blackening, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that namely obtains loaded with nano polypyrrole molecular wire closes the zinc organic frame.
(4) separation and purification
Two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of loaded with nano polypyrrole molecular wire is closed the zinc organic frame to be soaked in the 0.1mol/L ammonia soln, the organic frame dissolving, the nanometer polypyrrole molecular wire that comprises in the organic frame is released, adopt the dialysis tubing with semi-permeable membranes material to filter then to remove molecular weight for less than 500 molecule, the material that is trapped on the dialysis tubing is the nanometer polypyrrole molecular wire.
Embodiment 3
(1) synthetic two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the zinc organic frame
1 mole of 4-(4-pyridyl) phenylformic acid is added N, in the dinethylformamide, add 1.2 molar lactic acid again, at room temperature use magnetic stirrer 10 minutes in the air, add 2 moles of zinc nitrate hexahydrates again, continue to stir 5 minutes, be mixed with the mixing solutions that total concn is 0.28mol/L, it is 23ml that mixing solutions is transferred to volume, airtight in the hydrothermal reaction kettle of band polytetrafluoroethylsubstrate substrate, hydrothermal reaction kettle is placed baking oven, hydro-thermal reaction was carried out in insulation in 72 hours under temperature is 90 ℃, cooling at room temperature then, and two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that obtains having nano pore closes the zinc organic frame.
(2) the preparation load has two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame
Two 4-in (1) (4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame under 200 ℃ of vacuum conditions dry 10 hours, remove DMF, then two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame in the atmosphere of nitrogen, be soaked in the pyrrole monomer solution, make pyrrole monomer be full of two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close the zinc organic frame, make pyrrole monomer load to two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close on the zinc organic frame.
(3) two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of synthetic loaded with nano polypyrrole molecular wire closes the zinc organic frame
Having two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame load in (2) is soaked under-20 ℃ temperature in the hexane solution of iodine that concentration is 0.1mol/L, after 48 hours, place polymerization reaction take place under the room temperature, treat whole organic frame blackening, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that namely obtains loaded with nano polypyrrole molecular wire closes the zinc organic frame.
(4) separation and purification
Two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of loaded with nano polypyrrole molecular wire is closed the zinc organic frame to be soaked in the 1mol/L ammonia soln, the organic frame dissolving, the nanometer polypyrrole molecular wire that comprises in the organic frame is released, adopt semi-permeable membranes filter to remove molecular weight for less than 500 molecule then, the material that is trapped on the semi-permeable membranes is the nanometer polypyrrole molecular wire.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (1)
1. the method for a compositing conducting polymer materials is characterized in that, comprises the steps:
(1) synthetic two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid closes the zinc organic frame
1 mole of 4-(4-pyridyl) phenylformic acid is added N, in the dinethylformamide, add 1.2 molar lactic acid again, at room temperature use magnetic stirrer 10 minutes in the air, add 2 moles of zinc nitrate hexahydrates again, continue to stir 5 minutes, be mixed with the mixing solutions that total concn is 0.28mol/L, it is 23ml that mixing solutions is transferred to volume, airtight in the hydrothermal reaction kettle of band polytetrafluoroethylsubstrate substrate, hydrothermal reaction kettle is placed baking oven, hydro-thermal reaction was carried out in insulation in 72 hours under temperature is 90 ℃, cooling at room temperature then, and two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that obtains having nano pore closes the zinc organic frame;
(2) the preparation load has two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame
Two 4-in (1) (4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame under 200 ℃ of vacuum conditions dry 10 hours, remove DMF, then two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid is closed the zinc organic frame in the atmosphere of nitrogen, be soaked in the pyrrole monomer solution, make pyrrole monomer be full of two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close the zinc organic frame, make pyrrole monomer load to two 4-(4-pyridyl) phenylformic acid lactyl-lactic acid and close on the zinc organic frame;
(3) two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of synthetic loaded with nano polypyrrole molecular wire closes the zinc organic frame
Having two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of pyrrole monomer to close the zinc organic frame load in (2) is soaked under-20 ℃ temperature in the hexane solution of iodine that concentration is 0.1mol/L, after 48 hours, place polymerization reaction take place under the room temperature, treat whole organic frame blackening, two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid that namely obtains loaded with nano polypyrrole molecular wire closes the zinc organic frame;
(4) separation and purification
Two 4-(4-pyridyl) the phenylformic acid lactyl-lactic acid of loaded with nano polypyrrole molecular wire is closed the zinc organic frame to be soaked in the 1mol/L ammonia soln, the organic frame dissolving, the nanometer polypyrrole molecular wire that comprises in the organic frame is released, adopt semi-permeable membranes filter to remove molecular weight for less than 500 molecule then, the material that is trapped on the semi-permeable membranes is the nanometer polypyrrole molecular wire.
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