CN110194831A - It can be with the thiophene ethynyl polymer and preparation method of the orderly super group dress of carbon nanotube - Google Patents
It can be with the thiophene ethynyl polymer and preparation method of the orderly super group dress of carbon nanotube Download PDFInfo
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229930192474 thiophene Natural products 0.000 title claims abstract description 40
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 29
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- MPKQTNAUFAZSIJ-UHFFFAOYSA-N thiophene-3,4-diol Chemical compound OC1=CSC=C1O MPKQTNAUFAZSIJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001338 self-assembly Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- -1 3,4- dibutoxy thiophene Bis- hexyloxy thiophene Chemical compound 0.000 claims description 3
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims description 2
- 210000003097 mucus Anatomy 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- 238000005893 bromination reaction Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical group CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- XWEYATZFSPHATJ-UHFFFAOYSA-N 3,4-dibutoxythiophene Chemical compound CCCCOC1=CSC=C1OCCCC XWEYATZFSPHATJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- TWVGAEQMWFGWDX-UHFFFAOYSA-N acetylene;thiophene Chemical group C#C.C=1C=CSC=1 TWVGAEQMWFGWDX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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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
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- 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
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- 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
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3328—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms alkyne-based
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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
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/415—Sonogashira / Hagihara reactions
Abstract
The invention belongs to organic supermolecular field of material technology, specially a kind of thiophene ethynyl polymer and preparation method thereof that can be filled with the orderly super group of carbon nanotube.The main chain of Inventive polymers is thiophene -2- acetylene, side chain is the alkoxy containing different length carbochain.Preparation method are as follows: with 3,4- dihydroxy thiophene for starting material, etherified reaction, then bromo- 3, the 4- dialkoxythiophene of 2,5- bis- is obtained through bromination reaction；It reacts to obtain double trimethyl silicon substrate thiophene with trimethyl silicane ethyl-acetylene again；Both-end alkynes thiophene intermediate is obtained after removing TMS protecting group again, then Sonogashira occurs with bromo- 3, the 4- dialkoxythiophene of 2,5- bis- and reacts to obtain thiophene acetenyl high molecular polymer.The super assembly system of main chain π-π absorption, side chain winding can be formed between thiophene acetenyl high molecular polymer of the invention and carbon nanotube, the compound which fills System forming is with good stability, has a good application prospect.
Description
Technical field
The invention belongs to organic supermolecular field of material technology, and in particular to one kind can be with the orderly super group dress of carbon nanotube
Thiophene ethynyl polymer and preparation method thereof.
Technical background
Self assembly (self-assembly), refer to basic structural unit (molecule, nano material, micron or more large scale
Substance) spontaneously form a kind of technology of ordered structure.During self assembly, basic structural unit is based on non-covalent bond
Spontaneous tissue or a stabilization, the structure with certain regular geometric appearance are collected as under interaction.
Carbon nanotube is a kind of monodimension nanometer material with hexagonal structure for main linking group, and surface has abundant
Pi-electron has excellent mechanics, electricity and chemical property, is to be widely used in that preparation is military, civilian aspect is light high-strength answers
Condensation material.Carbon nanotube has a single wall and multi wall, and the distribution of carbon nanotube sizes range is bigger, common diameter in 2~100 nm,
Length is at 10 ~ 200 μm.Since, there are stronger Van der Waals force, carbon nanotube is often in reunion, winding or knotting shape between tube wall
State.Meanwhile the chemical structure of carbon nanotube is sufficiently stable, this also makes it with composite bodies compound tense interface cohesion and loosely
Gu also constraining the industrial application of carbon nanotube to limit the performance of the excellent properties of composite material.
Summary of the invention
In order to overcome the defect of existing carbon nanotube dispersion easy to reunite, difficult, the present invention provide a kind of stability it is good, can be with carbon
The thiophene ethynyl polymer and preparation method thereof of the orderly super group dress of nanotube.
Provided by the invention can be with thiophene -2- acetylene with the thiophene ethynyl polymer of the orderly super group dress of carbon nanotube
For main chain, using alkoxy as the high molecular polymer of side chain, the high molecular polymer can with various sizes of carbon nanotube it
Between can by main chain π-π adsorb, side chain be wound Supramolecular self assembly system, the super group fill System forming thiophene acetenyl
Polymer/carbon nano-tube compound is with good stability, has a good application prospect in the composite.
The thiophene ethynyl polymer provided by the invention that can be filled with the orderly super group of carbon nanotube, general structure such as following formula
It is shown:
Wherein, n is the natural number greater than zero, R group C4H9Or C6H13。
The present invention also provides the preparations of the above-mentioned thiophene acetenyl high molecular polymer that can be filled with the orderly super group of carbon nanotube
Method, specific steps are as follows:
(1) with 3,4- dihydroxy thiophene 1 for raw material, 3,4- dialkoxythiophene 2 is made under alkaline condition, then anti-through bromo
It answers, bromo- 3, the 4- dialkoxythiophene 3 of 2,5- bis- is made；
(2) above-mentioned bromo- 3, the 4- dialkoxythiophene 3 of 2,5- bis- is reacted with trimethyl silicane ethyl-acetylene, obtains double trimethyl silicanes
Base thiophene intermediate 4, thiophene intermediate 4 obtain both-end alkynes thiophene intermediate 5 after removing TMS；
(3) Sonogashira coupling is occurred into for both-end alkynes thiophene intermediate 5 and the bromo- 3,4- dialkoxythiophene 3 of 2,5- bis- instead
It answers, the product of generation is thiophene acetenyl high molecular polymer 6.
In some embodiments, the specific steps of the Sonogashira coupling reaction are as follows: under nitrogen protection, by 2,
Reaction is added in the bromo- 3,4- dialkoxythiophene 3 of 5- bis-, both-end alkynes thiophene intermediate 5, CuI, tetra-triphenylphosphine palladium, triphenylphosphine
In bottle, toluene, triethylamine are added.After nitrogen displacement, reacted under (65--75 DEG C (preferably 70 DEG C)) under high temperature, again through extracting
Take, dry, concentration obtains yellow mucus, then obtain yellow solid powder through methanol/tetrahydrofuran repeated precipitation process.
In some embodiments, 3, the 4- dialkoxythiophene 2 is 3,4- dibutoxy thiophene or 3, bis- hexyloxy of 4-
Thiophene.
In some embodiments, the molar ratio of 3, the 4- dialkoxythiophene 2 and bromine water is 1:(2.1 ~ 2.5).
The present invention also provides the thiophene acetenyl high molecular polymers of any above method synthesis.
The present invention also provides a kind of carbon nanotube Supramolecular self assembly system, the functional mass in the self-assembly system is
Any above-mentioned thiophene acetenyl high molecular polymer.
The present invention also provides any above-mentioned thiophene acetenyl high molecular polymers in preparing carbon nano tube compound material
Application.
Beneficial effects of the present invention
(1) main chain absorption occurs between thiophene acetenyl high molecular polymer provided by the present invention and carbon nanotube, side chain twines
It around effect, is acted on by π-π, under the premise of not destroying carbon nanotube, realizes the Supramolecular self assembly to carbon nanotube, thus
Realize the dispersion to carbon nanotube；
(2) in order to guarantee the intrinsic property of carbon nanotube, promote carbon nanometer under the premise of not destroying carbon nano tube surface structure
The dispersibility of pipe, the present invention provides a kind of high molecular polymers based on thiophene acetylene, and the polymer is in conventional organic solvent
Under the action of, the effective dispersing Nano carbon tubes of energy set so as to push the application of carbon nanotube in the composite in instrument
Standby, medical instruments field has larger application potential；
(3) synthetic method of the invention is simple, easy to operate, and for technological parameter convenient for control, raw material and instrument and equipment are low in cost.
Detailed description of the invention
Fig. 1 is the nmr spectrum of 3,4- dialkoxythiophene 2a.
Fig. 2 is the nmr spectrum of the bromo- 3,4- dialkoxythiophene 3a of 2,5- bis-.
Fig. 3 is the nmr spectrum of double trimethyl silicon substrate thiophene intermediate 4a.
Fig. 4 is the nmr spectrum of both-end alkynes thiophene intermediate 5a.
Fig. 5 is the nmr spectrum of thiophene acetenyl high molecular polymer 6a.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Specification
Attached drawing is used to provide further understanding of the present application, and illustrative embodiments of the present application and the description thereof are used to explain the present application,
It does not constitute an undue limitation on the present application.
Unless otherwise specified, all technical and scientific terms used herein has general with the application technical field
The logical normally understood identical meanings of technical staff.
Embodiment 1.
The preparation flow of thiophene acetenyl high molecular polymer 6a:
。
The step of synthesis of intermediate 2a~5a is reported referring to Chem. Eur. J. 2011,17,1473-1484 into
Row.
Intermediate 2a is colourless liquid.1H NMR (500 MHz, Chloroform-d) δ 6.34 (s, 2H),
4.02 (t, J = 6.1 Hz, 4H), 1.81 – 1.69 (m, 4H), 1.58 – 1.46 (m, 4H), 0.96 (t,J = 7.6 Hz, 6H)。
Intermediate 3a is white solid.1H NMR (500 MHz, Chloroform-d) δ 4.08 (t, J = 6.1
Hz, 4H), 1.79 – 1.69 (m, 4H), 1.58 – 1.49 (m, 4H), 0.97 (t, J = 7.6 Hz, 6H)。
Intermediate 4a, white solid.1H NMR (500 MHz, Chloroform-d) δ 4.09 (t, J = 6.1
Hz, 4H), 1.77 – 1.67 (m, 4H), 1.49 – 1.39 (m, 4H), 0.95 (t, J = 7.6 Hz, 6H),
0.25 (s, 18H)。
Intermediate 5a, white solid.1H NMR (500 MHz, Chloroform-d) δ 4.07 (t, J = 6.1
Hz, 4H), 3.32 (s, 2H), 1.79 – 1.72 (m, 4H), 1.57 – 1.47 (m, 4H), 0.96 (t, J =
7.6 Hz, 6H)。
Polymer 6a: under nitrogen protection, the addition intermediate 3a(3.84 g into 250 dry mL three-necked flasks, 10
Mmol), intermediate 5a(2.76 g, 10 mmol), CuI(0.19 g, 1mmol is added), tetra-triphenylphosphine palladium (0.24 g, 0.2
Mmol) triphenylphosphine (0.13 g, 0.5 mmol), adds 100 mL of dry toluene, 20 mL of triethylamine, and nitrogen is replaced three times
It reacts 24 hours at 70 DEG C, is cooled to room temperature to reaction system afterwards, then through extraction, drying, concentrated by rotary evaporation, it is viscous to obtain yellow
Liquid, then 4.4 g of greenish yellow solid powder is recrystallized to give through methanol/tetrahydrofuran.1H NMR (500 MHz,
Chloroform-d) δ 4.03 (ddt, J = 9.1, 6.3, 3.4 Hz, 20H), 2.20 (s, 2H), 1.99 (s,
2H), 1.79-1.73 (m, 20H), 1.55-1.49 (m, 20H), 0.99-0.94 (m, 30H)。
Claims (7)
1. one kind can be shown below with the thiophene ethynyl polymer of the orderly super assembly system of carbon nanotube, general structure:
Wherein, n is the natural number greater than zero, R group C4H9Or C6H13。
2. a kind of thiophene acetenyl high molecular polymer preparation method as described in claim 1, which is characterized in that specific steps
Are as follows:
(1) 3,4- dihydroxy thiophene 1 is raw material, 3,4- dialkoxythiophene 2 is made under alkaline condition, then through bromo-reaction,
The bromo- 3,4- dialkoxythiophene 3 of 2,5- bis- is made；
(2) above-mentioned bromo- 3, the 4- dialkoxythiophene 3 of 2,5- bis- is reacted with trimethyl silicane ethyl-acetylene, obtains double trimethyl silicanes
Base thiophene intermediate 4, thiophene intermediate 4 obtain both-end alkynes thiophene intermediate 5 after removing TMS；
(3) by the generation of the bromo- 3,4- dialkoxythiophene 3 of both-end alkynes thiophene intermediate 5 and 2,5- bis-, to intersect Sonogashira anti-
It answers, the product of generation is thiophene acetenyl high molecular polymer 6.
3. preparation method as claimed in claim 2, which is characterized in that the specific steps of the Sonogashira coupling reaction are as follows:
Under nitrogen protection, by both-end alkynes thiophene intermediate 5, bromo- 3, the 4- dialkoxythiophene 3 of 2,5- bis-, CuI, tetra-triphenylphosphine palladium, three
Phenylphosphine is added in reaction flask, adds toluene, triethylamine；After nitrogen displacement, reacted under high temperature, is cooling, extracted, is dry,
Concentration, obtains yellow mucus, then obtain yellow solid powder through methanol/tetrahydrofuran precipitation method.
4. preparation method as claimed in claim 3, which is characterized in that 3, the 4- dialkoxythiophene 2 is 3,4- dibutoxy thiophene
Bis- hexyloxy thiophene of pheno or 3,4-.
5. preparation method as claimed in claim 3, which is characterized in that the molar ratio of 3,4- the bis-alkoxy thiophene 2 and bromine water
For 1:(2.0 ~ 2.5).
6. a kind of carbon nanotube Supramolecular self assembly system, functional mass is any thiophene acetenyl described in claim 1
High molecular polymer.
7. thiophene alkynyl high molecular polymer as described in claim 1, carbon nanotube supermolecule as claimed in claim 6 are certainly
The application of assembly system in the composite.
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| PCT/CN2020/094511 WO2020244608A1 (en) | 2019-06-05 | 2020-06-05 | Thiophene ethynyl polymer capable of ordered superassembly with carbon nanotube and preparation method therefor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020244608A1 (en) * | 2019-06-05 | 2020-12-10 | 复旦大学 | Thiophene ethynyl polymer capable of ordered superassembly with carbon nanotube and preparation method therefor |
| CN112442277A (en) * | 2020-11-20 | 2021-03-05 | 山东省科学院新材料研究所 | Amido high-molecular polymer/carbon nano tube compound and blending type super-assembly preparation method thereof |
| CN112552491A (en) * | 2020-12-15 | 2021-03-26 | 池州学院 | Porphyrin polymer containing 3-hexylthiophene and synthetic method thereof |
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| WO2020244608A1 (en) * | 2019-06-05 | 2020-12-10 | 复旦大学 | Thiophene ethynyl polymer capable of ordered superassembly with carbon nanotube and preparation method therefor |
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