CN111100263B - Soluble linear conductive polymer and preparation method thereof - Google Patents
Soluble linear conductive polymer and preparation method thereof Download PDFInfo
- Publication number
- CN111100263B CN111100263B CN201911198554.6A CN201911198554A CN111100263B CN 111100263 B CN111100263 B CN 111100263B CN 201911198554 A CN201911198554 A CN 201911198554A CN 111100263 B CN111100263 B CN 111100263B
- Authority
- CN
- China
- Prior art keywords
- soluble linear
- equal
- pdmaema
- preparing
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 51
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 35
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002322 conducting polymer Substances 0.000 claims abstract description 17
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 16
- HMLSBRLVTDLLOI-UHFFFAOYSA-N 1-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)C(C)OC(=O)C(C)=C HMLSBRLVTDLLOI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 15
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 claims abstract description 12
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000012989 trithiocarbonate Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000000977 initiatory effect Effects 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 49
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- VMJOFTHFJMLIKL-UHFFFAOYSA-N 2-thiophen-2-ylethanol Chemical compound OCCC1=CC=CS1 VMJOFTHFJMLIKL-UHFFFAOYSA-N 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 14
- -1 N, N-dimethylaminoethyl Chemical group 0.000 abstract description 8
- 229920002319 Poly(methyl acrylate) Polymers 0.000 abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 7
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 7
- 239000012986 chain transfer agent Substances 0.000 abstract description 4
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 53
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 22
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 239000003208 petroleum Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000007710 freezing Methods 0.000 description 13
- 230000008014 freezing Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000008346 aqueous phase Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000123 polythiophene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012711 chain transfer polymerization Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001955 polymer synthesis method Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
-
- 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
- C08G2261/126—Copolymers block
-
- 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
- C08G2261/19—Definition of the polymer structure partially conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
Abstract
The invention provides a soluble linear conducting polymer and a preparation method thereof, wherein the preparation method comprises the following steps: s1: taking S-dodecyl-S '- (R, R-dimethyl-R' - (2-thienyl) ethyl acetate) trithiocarbonate as a chain transfer agent, and carrying out reversible addition-fragmentation chain transfer polymerization reaction on methyl acrylate, N-dimethylaminoethyl methacrylate and 1, 4-dioxane under the initiation of azodiisobutyronitrile to obtain polymethyl methacrylate N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate; s2: adding 3, 4-ethylenedioxythiophene N-butyl alcohol solution into polymethyl methacrylate N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate hydrochloric acid solution, and carrying out interfacial polymerization reaction under the action of a catalyst to obtain the soluble linear conducting polymer. The soluble linear conducting polymer is synthesized by adopting a reversible addition-fragmentation chain transfer polymerization and interfacial polymerization method, so that the length of a flexible chain segment of the soluble linear conducting polymer is controllable.
Description
Technical Field
The invention belongs to the field of high molecular materials, and particularly relates to a soluble linear conducting polymer and a preparation method thereof.
Background
In recent years, a class of structurally-defined novel composite polymer materials containing a flexible non-conjugated segment and a rigid conjugated segment has a far wider application range and a far higher attention than conjugated unit homopolymer materials due to the difference in structure and phase orientation. Firstly, the non-conjugation of the flexible chain segment can destroy the stacking and aggregation effects between conjugated chain segments and between molecules, generate a solubilization effect, and improve the solution processability and film-forming properties of the polymer. Secondly, under the solubilization effect of the flexible non-conjugated chain segment, a longer rigid conjugated chain segment can be introduced, so that the defect of weak mechanical strength of the small molecule conjugated material is overcome. Due to the existence of two segments with different chemical properties, namely a flexible non-conjugated segment and a rigid conjugated segment, the composite high molecular polymer has a strong tendency of self-assembly, such as assembly into a sheet structure or a cylindrical structure in a solid state. The self-assembly behavior improves the stacking density of condensed polymers and increases the contact of conducting phase regions in an insulating polymer matrix, thereby being more beneficial to the transition effect of electrons between different conducting phase regions.
Therefore, designing and constructing the novel soluble pi-conjugated system-containing polymer with definite structure, flexibility, light transparency and high electrochemical performance is one of the hotspots in the research field of the polymer synthesis method in recent years. At present, a plurality of research groups design and synthesize conductive polymers containing polythiophene branched chains to provide ideas for construction of such soluble conjugated polymer systems, such as Swager et al (ACS Macro Letters (2012), Volume 1.Iss ue 2, pages 334-. The star-shaped polymer can be applied to the fields of sensor materials, organic photoelectricity, antistatic coatings, carbon material dispersion and the like. However, the soluble aliphatic branched chain used in the synthesis method increases the solubility of the polymer and also makes the growth of the conjugated segment of the polymer difficult to control, and requires additional introduction of norbornadiene hydrogen and arylation using an expensive toxic metal catalyst to form an end cap in the cross-coupling polymerization step.
Disclosure of Invention
The invention aims to solve the problem that the growth of a conjugated chain segment is difficult to control in the synthesis process of the existing polymer simultaneously containing a flexible non-conjugated chain segment and a rigid conjugated chain segment, and provides a soluble linear conducting polymer and a preparation method thereof, which can effectively regulate and control the growth of the conjugated chain segment without introducing an end cover.
The invention provides a soluble linear conductive polymer, which has a structural formula as follows:
The preparation method of the soluble linear conducting polymer comprises the following steps:
s1: taking S-dodecyl-S '- (R, R-dimethyl-R' - (2-thienyl) ethyl acetate) trithiocarbonate (DTTC-Th) as a chain transfer agent, and carrying out reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) on Methyl Acrylate (MA), N-dimethylaminoethyl methacrylate (DMAEMA) and 1, 4-dioxane under the initiation of Azobisisobutyronitrile (AIBN) to obtain polymethyl methacrylate (PDMAEMA-b-PMA-Th);
s2: adding 3, 4-Ethylenedioxythiophene (EDOT) N-butyl alcohol solution into N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate (PDMAEMA-b-PMA-Th) hydrochloric acid solution, and carrying out interfacial polymerization (interfacial protocol) under the action of a catalyst to obtain the N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate-b-poly-3, 4-ethylenedioxythiophene (PDMAEMA-b-PMA-b-PEDOT), namely the soluble linear conductive polymer.
The synthetic route of the preparation process is as follows:
wherein n is more than or equal to 1 and less than or equal to 10, x is more than or equal to 50 and less than or equal to 100, and y is more than or equal to 5 and less than or equal to 15.
Further, in step S1, the reaction temperature of the reversible addition-fragmentation chain transfer polymerization reaction is 65 to 75 ℃. In a preferred embodiment, the reaction time is 2-6 h, and the reaction is performed under stirring at 300-600 r/min. The reaction speed is too high when the temperature is too high, the structure of a product is influenced, and the process is influenced when the temperature is too low.
Further, in step S1, the mass ratio of S-dodecyl-S' - (R, R-dimethyl-R "- (2-thienyl) ethyl acetate) trithiocarbonate (DTTC-Th), Methyl Acrylate (MA), N-dimethylaminoethyl methacrylate (DMAEMA), 1, 4-dioxane, and Azobisisobutyronitrile (AIBN) is (0.04 to 0.06) g: (0.05-0.08) g: (1.2-1.8) g: 1mL of: (0.0014-0.0018) g.
Further, the reaction temperature of the interfacial polymerization in the step S2 is 20 to 30 ℃. In a preferred embodiment, the reaction time is 24-48 h.
Further, in step S2, the mass ratio of polymethyl methacrylate N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate (PDMAEMA-b-PMA-Th) to 3, 4-Ethylenedioxythiophene (EDOT) is (8-12): (2-3).
Further, the catalyst in step S2 is selected from any one of ferric trichloride, a persulfate, and a perchlorate.
Further, the concentration of PDMAEMA-b-PMA-Th in the poly N, N-dimethylaminoethyl methacrylate-b-poly methyl acrylate (PDMAEMA-b-PMA-Th) hydrochloric acid solution is 0.02-0.06 g/mL. PDMAEMA-b-PMA-Th is dissolved in hydrochloric acid solution to form a water phase, and the hydrochloric acid can be used as a solvent and can also protonate a polymer chain.
Further, the concentration of EDOT in the n-butanol solution of 3, 4-Ethylenedioxythiophene (EDOT) is 0.005-0.015 g/mL. Dissolving EDOT in n-butanol to form an oil phase, mixing with a hydrochloric acid solution of PDMAEMA-b-PMA-Th to form a water-oil interface, and carrying out polymerization reaction on the PDMAEMA-b-PMA-Th and the EDOT at the water-oil interface.
Further, the chain transfer agent S-dodecyl-S '- (R, R-dimethyl-R' - (2-thienyl) ethyl acetate) trithiocarbonate (DTTC-Th) in the step S1 is prepared by the method comprising the following steps: mixing S-dodecyl-S ' - (R, R ' -dimethyl-R ' -acetic acid) trithiocarbonate (DTTC), 2-thiophene ethanol, dicyclohexyl carbodiimide and 4-dimethylamino pyridine for reaction to obtain S-dodecyl-S ' - (R, R-dimethyl-R ' - (2-thienyl) ethyl acetate) trithiocarbonate (DTTC-Th).
Further, the reaction temperature for synthesizing the S-dodecyl-S '- (R, R-dimethyl-R' - (2-thienyl) ethyl acetate) trithiocarbonate (DTTC-Th) is 20-30 ℃. In a preferred embodiment, the reaction time is 20-24 hours, and the reaction is performed under stirring at 300-600 r/min.
Further, the mass ratio of the S-dodecyl-S ' - (R, R ' -dimethyl-R ' -acetic acid) trithiocarbonate (DTTC), 2-thiophene ethanol, dicyclohexyl carbodiimide and 4-dimethylamino pyridine is (3-5): (1-3): (2-4): (0.1-0.2).
The invention combines two controllable polymer modes of reversible addition-fragmentation chain transfer polymerization (RAFT) and improved interfacial polymerization (MIP) to prepare the soluble linear conductive polymer containing the soft soluble chain segment and the rigid conjugated chain segment with definite structure. Firstly, using N, N-dimethylaminoethyl methacrylate (DMAEMA) and Methyl Acrylate (MA) as monomers to carry out RAFT polymerization to prepare a soluble linear block copolymer PDMAEMA-b-PMA-Th with a thiophene active group at the tail end, then preparing a polymer polythiophene monomer at a water-oil two-phase interface between a PDMAEMA-b-PMA-Th hydrochloric acid solution and an EDOT N-butyl alcohol solution, and finally preparing and separating out a soluble conductive polymer containing a conjugated chain segment by utilizing the solubility of a product.
Compared with the prior art, the invention has the following beneficial effects:
(1) the soluble linear conducting polymer synthesized by the reversible-fragmentation chain transfer polymerization method has the characteristics of controllable structure, controllable molecular weight, narrow molecular weight distribution and the like, the prepared soluble linear conducting polymer has narrow molecular weight distribution, the molecular weight is linearly related to the polymerization time, and the molecular weight of a flexible part chain segment can be adjusted by controlling the polymerization time.
(2) Meanwhile, the soluble linear conducting polymer is synthesized by combining an interfacial polymerization mode, and can be polymerized by using a conjugated monomer without solubilizing side groups.
(3) The monomer in the method for synthesizing the soluble linear conducting polymer is expected to be expanded to pyrrole, aniline and fluorene monomers besides thiophene monomers.
Drawings
FIG. 1 is a kinetic diagram of the process of synthesizing PDMAEMA-Th;
FIG. 2 is an IR spectrum of PDMAEMA-b-PMA-Th and PDMAEMA-b-PMA-b-PEDOT;
FIG. 3 shows PDMAEMA-b-PMA-b-PEDOT1An H-NMR spectrum;
FIG. 4 is a cyclic voltammetry curve for PDMAEMA-b-PMA-b-PEDOT.
Detailed Description
The soluble linear conducting polymer is synthesized by adopting a reversible addition-fragmentation chain transfer polymerization and interfacial polymerization method, so that the length of a flexible chain segment of the soluble linear conducting polymer is controllable, and the technical scheme of the invention is further explained by combining specific embodiments.
Example 1
This example provides a soluble linear conductive polymer, which is prepared by the following steps:
s1: taking S-dodecyl-S '- (R, R-dimethyl-R' - (2-thienyl) ethyl acetate) trithiocarbonate (DTTC-Th) as a chain transfer agent, and carrying out reversible addition-fragmentation chain transfer polymerization reaction on Methyl Acrylate (MA), N-dimethylaminoethyl methacrylate (DMAEMA) and 1, 4-dioxane under the initiation of Azodiisobutyronitrile (AIBN) to obtain polymethyl methacrylate (PDMAEMA-b-PMA-Th);
s2: under the action of a catalyst, adding an N-butyl alcohol solution of 3, 4-Ethylenedioxythiophene (EDOT) into a hydrochloric acid solution of polymethyl methacrylate N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate (PDMAEMA-b-PMA-Th), and carrying out interfacial polymerization to obtain the soluble linear conductive polymer, namely the polymethyl methacrylate N, N-dimethylaminoethyl methacrylate-b-polymethyl acrylate-b-poly-3, 4-ethylenedioxythiophene (PDMAEMA-b-PMA-b-PEDOT).
Specifically, step S1 includes the steps of:
(1) synthesis of DTTC-Th
2.2g of DTTC, 1g of 2-thiopheneethanol, 1.5g of dicyclohexylcarbodiimide, 0.07g of 4-dimethylaminopyridine and 5mL of tetrahydrofuran were charged into a 25mL flask, dissolved with stirring at 300r/min, and then the flask was rapidly degassed by freezing 3 times and then placed in an oil bath at 25 ℃ for reaction for 25 hours. And after the reaction is finished, filtering the mixed solution, concentrating, and separating a product by using a gel chromatographic column to obtain DTTC-Th.
Wherein the DTTC can be prepared according to the methods disclosed in Macromolecules (2002), Volume 35, Issue 18, pages 6754-6756. The specific synthesis method comprises the following steps: dodecyl mercaptan (10.1g) and trioctylmethylammonium chloride (0.81g) were dissolved in acetone (30.7mL), purged with nitrogen, stirred rapidly, and cooled to 10 ℃. A50% NaOH solution (4.2g) was slowly added dropwise thereto, and after dropping over 15 minutes, the mixture was stirred for another 15 minutes to obtain a milky white reaction solution. Slowly dropping CS2Acetone (3.8g/5g), the reaction solution is orange yellow after 20 minutes of dripping, trichloromethane (8.9g) is slowly dripped, and the solution is light yellow after 5 minutes of stirring. A50% NaOH solution (40g) was added dropwise thereto, and the mixture was stirred for 3 hours.
The reaction solution was transferred to a beaker, 75mL of water was added, the pH was about 6, 12.5mL of concentrated HCl was added and acidified, stirred rapidly, and acetone was evaporated. And (5) carrying out suction filtration and collecting filter residues. Dissolving the filter residue in 50mL of ethanol, performing suction filtration, and collecting the filtrate. The ethanol was evaporated and dried to give a yellow crude product. And recrystallizing the crude product in normal hexane, and drying to obtain a yellow solid product.
(2) Synthesis of PDMAEMA-Th
15.7g DMAEMA, 0.36g DTTC-Th, 0.016g AIBN and 10mL 1, 4-dioxane were added into a 25mL flask, dissolved under stirring at 300r/min, and the flask was rapidly degassed by freezing 3 times and then placed in a 70 ℃ oil bath for reaction for 4 hours. After the reaction is finished, the reaction solution is cooled at room temperature, and the reaction solution is dropwise added into 200mL of petroleum ether to obtain a precipitate. And (3) placing the precipitate at 25 ℃ for vacuum drying for 24h to obtain PDMAEMA-Th.
(3) Synthesis of PDMAEMA-b-PMA-Th
A100 mL flask was charged with 8.5g of PDMAEMA-Th, 2.6g of MA, 0.016g of AIBN and 36mL of 1, 4-dioxane, dissolved with stirring at 300r/min, rapidly degassed by freezing 3 times, and then placed in a 70 ℃ oil bath for reaction for 4 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 400mL of petroleum ether to obtain a precipitate, and finally, drying the precipitate at 25 ℃ in vacuum for 24h to obtain PDMAEMA-b-PMA-Th.
Step S2 specifically includes the following steps:
(4) synthesis of PDMAEMA-b-PMA-b-PEDOT
0.1g of PDMAEMA-b-PMA-Th was dissolved in 3.5mL of 1mol/L hydrochloric acid aqueous solution to give a PDMAEMA-b-PMA-Th hydrochloric acid solution having a concentration of 0.028g/mL as an aqueous phase. 0.1g of EDOT was dissolved in 10mL of n-butanol to give a solution of EDOT in n-butanol at a concentration of 0.01g/mL as the oil phase. After 1.5mL of 0.1mol/L ferric chloride aqueous solution was added to the above PDMAEMA-b-PMA-Th hydrochloric acid solution, EDOT n-butanol solution was slowly added and interfacial polymerization was started. The reactor was sealed and allowed to stand at room temperature for 24 h. After the reaction was complete, the aqueous phase was removed, centrifuged at high speed and added to 15mL NaHCO3THF mixture (NaHCO in it)30.25mol/L, deprotonation and pH adjustment) and stirred rapidly until no bubbles overflow. Then, the mixture was filtered, and the filtrate was concentrated and precipitated in 50mL of petroleum ether. And drying the precipitate at 25 ℃ in vacuum for 24 hours to obtain the soluble linear conducting polymer PDMAEMA-b-PMA-b-PEDOT.
The kinetic diagram (first order correlation) of the process of polymerizing PDMAEMA-Th from DMAEMA, DTTC-Th and the like in the step (2) is shown in FIG. 1. FIG. 1 reflects that the polymer chain growth has a certain correlation with time, and the polymer chain growth can be controlled by controlling the time.
The infrared spectrum of the PDMAEMA-b-PMA-Th synthesized in the step (3) is shown as a curve a in FIG. 2, and the wavelength is 850cm–1、988cm–1The two weak peaks indicate successful grafting of the thiophene group onto the polymer chain.
Method for preparing PDMAEMA-b-PMA-b-PEDOT1The H-NMR spectrum and the infrared spectrum are respectively shown in FIG. 3 and curve b of FIG. 2, and the wavelength in curve b of FIG. 2 is 1360cm-1The peak of (A) is a stretching vibration peak of a carbon-oxygen single bond in a PEDOT chain segment, and the chemical shift of hydrogen on a methylene in the PEDOT chain segment is 4.42-3.78 ppm in figure 3, which shows that the PEDOT chain segment (namely a 3, 4-ethylene dioxythiophene rigid chain segment) is successfully polymerized on a flexible chain segment of PDMAEMA and PMA, so that PDMAEMA-b-PMA-b-PEDOT is successfully synthesized.
Meanwhile, a cyclic voltammetry curve of PDMAEMA-b-PMA-b-PEDOT is shown in FIG. 4, a quasi-rectangular voltammetry curve shows that the whole process has redox reaction characteristics, and PDMAEMA-b-PMA-b-PEDOT has electrochemical activity.
Example 2
This example provides a soluble linear conductive polymer, which is prepared by the following steps:
(1) synthesis of DTTC-Th
2.5g of DTTC, 1.1g of 2-thiopheneethanol, 2.5g of dicyclohexylcarbodiimide, 0.08g of 4-dimethylaminopyridine and 5mL of tetrahydrofuran were charged into a 25mL flask, dissolved with stirring at 400r/min, and then the flask was rapidly degassed by freezing 3 times and then placed in an oil bath at 30 ℃ for reaction for 30 hours. And after the reaction is finished, filtering the mixed solution, concentrating, and separating a product by using a gel chromatographic column to obtain DTTC-Th.
(2) Synthesis of PDMAEMA-Th
16.7g DMAEMA, 0.4g DTTC-Th, 0.02g AIBN and 10mL 1, 4-dioxane were added to a 25mL flask, dissolved with stirring at 400r/min, and the flask was rapidly degassed by freezing 3 times and then placed in a 75 ℃ oil bath for reaction for 5 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 200mL of petroleum ether for precipitation to obtain a precipitate, and performing vacuum drying at 25 ℃ for 24h to obtain PDMAEMA-Th.
(3) Synthesis of PDMAEMA-b-PMA-Th
10g of PDMAEMA-Th, 3.0g of MA, 0.02g of AIBN and 36mL of 1, 4-dioxane were added to a 100mL flask, dissolved with stirring at 400r/min, and after rapidly freezing and degassing the flask 3 times, the flask was placed in a 75 ℃ oil bath and reacted for 5 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 400mL of petroleum ether to obtain a precipitate, and carrying out vacuum drying at 25 ℃ for 24h to obtain PDMAEMA-b-PMA-Th.
(4) Synthesis of PDMAEMA-b-PMA-b-PEDOT
0.15g of PDMAEMA-b-PMA-Th was dissolved in 3.5mL of 1mol/L hydrochloric acid aqueous solution to give a PDMAEMA-b-PMA-Th hydrochloric acid solution having a concentration of 0.043g/mL as an aqueous phase. 0.1g of EDOT was dissolved in 10mL of n-butanol to give a solution of EDOT in n-butanol at a concentration of 0.01g/mL as the oil phase. To the above PDMAEMA-b-PMA-Th hydrochloric acid solution was added 1.0mL of 0.1And (3) slowly placing the EDOT n-butanol solution on the aqueous solution after mol/L of ferric trichloride aqueous solution, starting interfacial polymerization, sealing the reactor, and standing for 24 hours at room temperature. After the reaction was complete, the aqueous phase was removed, centrifuged at high speed and added to 15mL NaHCO3NaHCO with concentration of 0.25mol/L3In the THF mixture, the mixture was stirred rapidly until no bubbles were able to escape. After filtration, the clear solution was taken, concentrated and precipitated in 50mL of petroleum ether. And drying the precipitate in vacuum at 25 ℃ for 24h to obtain PDMAEMA-b-PMA-b-PEDOT.
Example 3
(1) Synthesis of DTTC-Th
2.2g of DTTC, 1g of 2-thiopheneethanol, 1.5g of dicyclohexylcarbodiimide, 0.07g of 4-dimethylaminopyridine and 5mL of tetrahydrofuran were charged into a 25mL flask, dissolved with stirring at 500r/min, and then the flask was rapidly degassed by freezing 3 times and then placed in an oil bath at 35 ℃ for reaction for 30 hours. And after the reaction is finished, filtering the mixed solution, concentrating, and separating a product by using a gel chromatographic column to obtain DTTC-Th.
(2) Synthesis of PDMAEMA-Th
15.7g DMAEMA, 0.36g DTTC-Th, 0.016g AIBN and 10mL 1, 4-dioxane were added into a 25mL flask, dissolved with stirring at 500r/min, and the flask was rapidly degassed by freezing 3 times and then placed in a 65 ℃ oil bath for reaction for 5 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 200mL of petroleum ether for precipitation to obtain a precipitate, and performing vacuum drying at 25 ℃ for 24h to obtain PDMAEMA-Th.
(3) Synthesis of PDMAEMA-b-PMA-Th
A100 mL flask was charged with 8.5g of PDMAEMA-Th, 2.6g of MA, 0.016g of AIBN and 36mL of 1, 4-dioxane, dissolved with stirring at 500r/min, rapidly degassed by freezing 3 times, and then placed in a 65 ℃ oil bath for reaction for 5 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 400mL of petroleum ether to obtain a precipitate, and carrying out vacuum drying at 25 ℃ for 24h to obtain PDMAEMA-b-PMA-Th.
(4) Synthesis of PDMAEMA-b-PMA-b-PEDOT
0.2g of PDMAEMA-b-PMA-Th was dissolved in 3.5mL of 1mol/L hydrochloric acid aqueous solution to give a PDMAEMA-b-PMA-Th hydrochloric acid solution having a concentration of 0.057g/mL as an aqueous phase. 0.1g of EDOT is dissolved in 10EDOT n-butanol solution at a concentration of 0.01g/mL was obtained in mL n-butanol as the oil phase. Adding 1.5mL of 0.1mol/L ferric trichloride aqueous solution into the PDMAEMA-b-PMA-Th hydrochloric acid solution, slowly placing the EDOT n-butanol solution on the aqueous solution, starting interfacial polymerization, sealing the reactor, and standing at room temperature for 24 h. After the reaction was complete, the aqueous phase was removed, centrifuged at high speed and added to 15mL NaHCO3NaHCO with concentration of 0.25mol/L3In the THF mixture, the mixture was stirred rapidly until no bubbles were able to escape. After filtration, the clear solution was taken, concentrated and precipitated in 50mL of petroleum ether. And drying the precipitate in vacuum at 25 ℃ for 24h to obtain PDMAEMA-b-PMA-b-PEDOT.
Example 4
(1) Synthesis of DTTC-Th
2.3g of DTTC, 1.1g of 2-thiopheneethanol, 1.6g of dicyclohexylcarbodiimide, 0.08g of 4-dimethylaminopyridine and 5mL of tetrahydrofuran were charged into a 25mL flask, dissolved with stirring at 600r/min, and then the flask was rapidly degassed by freezing 3 times and then placed in an oil bath at 25 ℃ for reaction for 25 hours. And after the reaction is finished, filtering the mixed solution, concentrating, and separating a product by using a gel chromatographic column to obtain DTTC-Th.
(2) Synthesis of PDMAEMA-Th
16.7g DMAEMA, 0.36g DTTC-Th, 0.016g AIBN and 10mL 1, 4-dioxane were added into a 25mL flask, dissolved with stirring at 600r/min, and the flask was rapidly degassed by freezing 3 times and then placed in a 70 ℃ oil bath for reaction for 3 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 200mL of petroleum ether for precipitation to obtain a precipitate, and performing vacuum drying at 25 ℃ for 24h to obtain PDMAEMA-Th.
(3) Synthesis of PDMAEMA-b-PMA-Th
A100 mL flask was charged with 8.5g of PDMAEMA-Th, 2.6g of MA, 0.016g of AIBN and 36mL of 1, 4-dioxane, dissolved with stirring at 600r/min, rapidly degassed by freezing 3 times, and then placed in a 70 ℃ oil bath for reaction for 3 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 400mL of petroleum ether for precipitation to obtain a precipitate, and performing vacuum drying at 25 ℃ for 24h to obtain PDMAEMA-b-PMA-Th.
(4) Synthesis of PDMAEMA-b-PMA-b-PEDOT
0.15g PDMAEMA-b-PMA-Th was dissolved in 3.5mL of 1mol/L aqueous hydrochloric acid to give a 0.043g/mL solution of PDMAEMA-b-PMA-Th in hydrochloric acid as the aqueous phase. 0.1g of EDOT was dissolved in 10mL of n-butanol to give a solution of EDOT in n-butanol at a concentration of 0.01g/mL as the oil phase. After 1.5mL of 0.1mol/L perchlorate aqueous solution is added into the PDMAEMA-b-PMA-Th hydrochloric acid solution, the EDOT n-butanol solution is slowly placed on the aqueous solution, the interfacial polymerization reaction starts, the reactor is sealed, and the mixture is stood for 24 hours at room temperature. After the reaction was complete, the aqueous phase was removed, centrifuged at high speed and added to 15mL NaHCO3NaHCO with concentration of 0.25mol/L3In the THF mixture, the mixture was stirred rapidly until no bubbles were able to escape. After filtration, the clear solution was taken, concentrated and precipitated in 50mL of petroleum ether. And drying the precipitate in vacuum at 25 ℃ for 24h to obtain PDMAEMA-b-PMA-b-PEDOT.
Example 5
(1) Synthesis of DTTC-Th
2.2g of DTTC, 1g of 2-thiopheneethanol, 1.5g of dicyclohexylcarbodiimide, 0.07g of 4-dimethylaminopyridine and 5mL of tetrahydrofuran were put into a 25mL flask, stirred to dissolve, and then the flask was rapidly frozen and degassed 3 times, and then placed in an oil bath at 25 ℃ to react for 20 hours. And after the reaction is finished, filtering the mixed solution, concentrating, and separating a product by using a gel chromatographic column to obtain DTTC-Th.
(2) Synthesis of PDMAEMA-Th
15.7g DMAEMA, 0.36g DTTC-Th, 0.016g AIBN and 10mL 1, 4-dioxane were added into a 25mL flask, and after stirring and dissolving, the flask was rapidly refrigerated and degassed 3 times and then placed in a 70 ℃ oil bath for reaction for 5 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 200mL of petroleum ether for precipitation to obtain a precipitate, and performing vacuum drying at 30 ℃ for 24h to obtain PDMAEMA-Th.
(3) Synthesis of PDMAEMA-b-PMA-Th
A100 mL flask was charged with 8.5g of PDMAEMA-Th, 2.6g of MA, 0.016g of AIBN and 36mL of 1, 4-dioxane, and after dissolution with stirring, the flask was rapidly degassed by freezing 3 times and then placed in a 70 ℃ oil bath for reaction for 5 hours. After the reaction is finished, cooling at room temperature, dropwise adding the reaction solution into 400mL of petroleum ether for precipitation to obtain a precipitate, and performing vacuum drying at 30 ℃ for 24h to obtain PDMAEMA-b-PMA-Th.
(4) Synthesis of PDMAEMA-b-PMA-b-PEDOT
0.1g of PDMAEMA-b-PMA-Th was dissolved in 3.5mL of 1mol/L hydrochloric acid aqueous solution to give a PDMAEMA-b-PMA-Th hydrochloric acid solution having a concentration of 0.028g/mL as an aqueous phase. 0.1g of EDOT was dissolved in 10mL of n-butanol to give a solution of EDOT in n-butanol at a concentration of 0.01g/mL as the oil phase. After adding 1.5mL of 0.1mol/L aqueous persulfate solution to the PDMAEMA-b-PMA-Th hydrochloric acid solution, the EDOT n-butanol solution was slowly added and the interfacial polymerization reaction was started. The reactor was sealed and allowed to stand at room temperature for 48 h. After the reaction was complete, the aqueous phase was removed, centrifuged at high speed and added to 15mL NaHCO3NaHCO with concentration of 0.25mol/L3In the THF mixture, the mixture was stirred rapidly until no bubbles were able to escape. After filtration, the clear solution was taken, concentrated and precipitated in 50mL of petroleum ether. And drying the precipitate in vacuum at 30 ℃ for 24h to obtain PDMAEMA-b-PMA-b-PEDOT.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A soluble linear conducting polymer of the formula:
wherein n is more than or equal to 1 and less than or equal to 10, x is more than or equal to 50 and less than or equal to 100, and y is more than or equal to 5 and less than or equal to 15.
2. A method for preparing a soluble linear conducting polymer, characterized in that: the method comprises the following steps:
s1: to be provided with
As chain transfer agents, methyl acrylate, N-dimethylaminoethyl methacrylate and 1, 4-dioxane were usedThe reversible addition-fragmentation chain transfer polymerization reaction is carried out under the initiation of azodiisobutyronitrile to obtain
S2: in that
Adding 3, 4-ethylenedioxythiophene n-butyl alcohol solution into hydrochloric acid solution, and carrying out interfacial polymerization reaction under the action of a catalyst to obtain the soluble linear conductive polymer
Wherein n is more than or equal to 1 and less than or equal to 10, x is more than or equal to 50 and less than or equal to 100, and y is more than or equal to 5 and less than or equal to 15.
3. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: in step S1, the reaction temperature of the reversible addition-fragmentation chain transfer polymerization reaction is 65-75 ℃.
4. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: in the step S1, in the step S,
the using amount ratio of the methyl acrylate to the N, N-dimethylaminoethyl methacrylate to the 1, 4-dioxane to the azobisisobutyronitrile is (0.04-0.06) g: (0.05-0.08) g: (1.2-1.8) g: 1mL of: (0.0014-0.0018) g.
5. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: in step S2, the reaction temperature of the interfacial polymerization is 20-30 ℃.
6. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: in step S2, the
The mass ratio of the 3, 4-ethylenedioxythiophene to the 3, 4-ethylenedioxythiophene is (8-12): (2-3).
7. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: in step S2, the catalyst is selected from any one of ferric trichloride, persulfate, and perchlorate.
8. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: the above-mentioned
The concentration of the hydrochloric acid solution is 0.02-0.06 g/mL.
9. The method for preparing the soluble linear conductive polymer according to claim 2, wherein: in the step S2, the concentration of 3, 4-ethylenedioxythiophene in the n-butanol solution of 3, 4-ethylenedioxythiophene is 0.005-0.015 g/mL.
10. The method for preparing a soluble linear conducting polymer according to any one of claims 2 to 9, wherein: in step S1, the method for preparing the chain transfer includes the steps of: mixing S-dodecyl-S ' - (R, R ' -dimethyl-R ' -acetic acid) trithiocarbonate, 2-thiophene ethanol, dicyclohexyl carbodiimide and 4-dimethylamino pyridine for reaction to obtain
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911198554.6A CN111100263B (en) | 2019-11-29 | 2019-11-29 | Soluble linear conductive polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911198554.6A CN111100263B (en) | 2019-11-29 | 2019-11-29 | Soluble linear conductive polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111100263A CN111100263A (en) | 2020-05-05 |
| CN111100263B true CN111100263B (en) | 2022-04-19 |
Family
ID=70420695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911198554.6A Active CN111100263B (en) | 2019-11-29 | 2019-11-29 | Soluble linear conductive polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111100263B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672000B (en) * | 2020-12-24 | 2024-01-09 | 中科院广州化学有限公司 | Linear high-conductivity organic soluble thiophene polymer and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483355A (en) * | 2013-09-22 | 2014-01-01 | 江西科技师范大学 | Monomer and polymer of 3,4-ethylenedioxythiophene (EDOT) modified by L-leucine and preparation methods for monomer and polymer |
| WO2014206044A1 (en) * | 2013-06-29 | 2014-12-31 | 华南理工大学 | Amphiphilic 4/6 miktoarm star-shaped ph-responsive copolymer and preparation method thereof |
| CN106336603A (en) * | 2015-07-09 | 2017-01-18 | 信越化学工业株式会社 | Conductive polymer composition, coated article, and patterning process |
| CN106928414A (en) * | 2017-03-31 | 2017-07-07 | 天津大学 | A kind of preparation method of polymeric sorbent predecessor di-block copolymer |
| CN110317294A (en) * | 2018-03-30 | 2019-10-11 | 长春理工大学 | A kind of novel temperature sensitive fluorescent polymer of triphen amine and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7205368B2 (en) * | 2000-02-16 | 2007-04-17 | Noveon, Inc. | S-(α, α′-disubstituted-α′ ′-acetic acid) substituted dithiocarbonate derivatives for controlled radical polymerizations, process and polymers made therefrom |
| EP1697424A1 (en) * | 2003-12-23 | 2006-09-06 | The University Of Leeds | Polymerisation using chain transfer agents |
| WO2006086599A1 (en) * | 2005-02-11 | 2006-08-17 | Carnegie Mellon University | Modified carbon particles |
| WO2007025189A2 (en) * | 2005-08-26 | 2007-03-01 | Carnegie Mellon University | Electrically conductive blockcopolymers and controlled radical polymerization |
-
2019
- 2019-11-29 CN CN201911198554.6A patent/CN111100263B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014206044A1 (en) * | 2013-06-29 | 2014-12-31 | 华南理工大学 | Amphiphilic 4/6 miktoarm star-shaped ph-responsive copolymer and preparation method thereof |
| CN103483355A (en) * | 2013-09-22 | 2014-01-01 | 江西科技师范大学 | Monomer and polymer of 3,4-ethylenedioxythiophene (EDOT) modified by L-leucine and preparation methods for monomer and polymer |
| CN106336603A (en) * | 2015-07-09 | 2017-01-18 | 信越化学工业株式会社 | Conductive polymer composition, coated article, and patterning process |
| CN106928414A (en) * | 2017-03-31 | 2017-07-07 | 天津大学 | A kind of preparation method of polymeric sorbent predecessor di-block copolymer |
| CN110317294A (en) * | 2018-03-30 | 2019-10-11 | 长春理工大学 | A kind of novel temperature sensitive fluorescent polymer of triphen amine and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| End group removal and modification of RAFT polymers;Helen Willcock et al.;《Polymer Chemistry》;20091223;第1卷;第149-157页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111100263A (en) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6154784B2 (en) | Catalyst-free polymerization of 3,4-alkylenedioxypyrrole and 3,4-alkylenedioxyfuran | |
| CN111100263B (en) | Soluble linear conductive polymer and preparation method thereof | |
| CN113061266B (en) | High-strength ionic gel based on multiple non-covalent crosslinking effects | |
| Kotal et al. | Synthesis of semitelechelic POSS‐polymethacrylate hybrids by thiol‐mediated controlled radical polymerization with unusual thermal behaviors | |
| CN111187373B (en) | Epoxy vegetable oil nucleic acid base copolymer, preparation method thereof and application of composite material | |
| CN109134769B (en) | High-molecular method of perylene bisimide fluorescent dye | |
| US20150197585A1 (en) | Tapered block copolymer electrolytes | |
| CN105482011B (en) | A kind of preparation method of cyclic macromolecular chain-transferring agent and its ring comb-shaped polymer | |
| Zhang et al. | Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization | |
| KR100666146B1 (en) | A Novel Poly-3,4-ethylenedioxythiophene Graft Copolymer | |
| KR101669042B1 (en) | Polythiophene based-grafted copolymer and manufacturing method thereof | |
| CN105622788A (en) | Three-arm ATRP (atom transfer radical polymerization) initiator with plane conjugated structure, and preparation and application thereof | |
| CN101469041B (en) | Polymer containing benzene pyridine unit | |
| Zhao et al. | Synthesis of macroporous poly (N‐isopropylacrylamide) hydrogel with ultrarapid swelling–deswelling properties | |
| CN114395081B (en) | Star-shaped soluble conjugated polymer and preparation method and application thereof | |
| Antoun et al. | A Simple Route to Rod‐Coil Block Copolymers of Oligo‐and Polythiophenes with PMMA and Polystyrene | |
| US5789600A (en) | Polymerizable monomer containing electrolytically polymerizable groups | |
| CN101885816B (en) | Method for preparing poly(styrene-b-acrylonitrile) by two-step polymerization method | |
| US9328194B2 (en) | Benzodithiophene based copolymer containing isoindoline-1,3-diketone units and preparing method and applications thereof | |
| Jannasch | Preparation and characterisation of aggregating comblike poly (propylene oxide) | |
| Nguyen et al. | A novel conducting amphiphilic diblock copolymer containing regioregular poly (3-hexylthiophene) | |
| CN101381452B (en) | Poly(3-butylthiophen) containing function end-group and preparation method thereof | |
| CN115181252B (en) | Five-membered aromatic heterocycle fused BODIPY-based high polymer material and preparation method thereof | |
| CN114015027B (en) | Preparation method of poly (alkyl (oxy) thiophene-fullerene-polylactic acid triblock copolymer and solar cell | |
| CN109053609B (en) | Triphenylamine-triazine derivative and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 510665 Guangzhou, Guangdong, Tianhe District Province Road West, No. 318 Patentee after: Institute of chemical engineering, Guangdong Academy of Sciences Address before: 510665 Guangzhou, Guangdong, Tianhe District, Tangxia, 318 West Po Road Patentee before: GUANGDONG RESEARCH INSTITITUTE OF PETROCHEMICAL AND FINE CHEMICAL ENGINEERING |
|
| CP03 | Change of name, title or address |