CN117088919B - Catalyst for thiophene monomer polymerization and polythiophene - Google Patents

Catalyst for thiophene monomer polymerization and polythiophene Download PDF

Info

Publication number
CN117088919B
CN117088919B CN202311353118.8A CN202311353118A CN117088919B CN 117088919 B CN117088919 B CN 117088919B CN 202311353118 A CN202311353118 A CN 202311353118A CN 117088919 B CN117088919 B CN 117088919B
Authority
CN
China
Prior art keywords
catalyst
polymerization
thiophene
thiophene monomer
polymerizing
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
Application number
CN202311353118.8A
Other languages
Chinese (zh)
Other versions
CN117088919A (en
Inventor
施信波
甘志韬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chain Walk New Material Technology Guangzhou Co ltd
Original Assignee
Chain Walk New Material Technology Guangzhou Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chain Walk New Material Technology Guangzhou Co ltd filed Critical Chain Walk New Material Technology Guangzhou Co ltd
Priority to CN202311353118.8A priority Critical patent/CN117088919B/en
Publication of CN117088919A publication Critical patent/CN117088919A/en
Application granted granted Critical
Publication of CN117088919B publication Critical patent/CN117088919B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds
    • C07F15/0066—Palladium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • 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
    • C08G2261/40—Polymerisation processes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention discloses a catalyst for thiophene monomer polymerization and polythiophene, wherein the structural formula of the catalyst for thiophene monomer polymerization is shown as formula (I):the method comprises the steps of carrying out a first treatment on the surface of the The catalyst for thiophene monomer polymerization provided by the invention can be used for preparing P3HT with high molecular weight, high regularity and narrow molecular weight distribution by catalytic polymerization at high temperature, and has wide application prospects in the fields of solar cells, organic transistors, electrochromic devices, chemical sensors, electromagnetic shielding materials and the like.

Description

Catalyst for thiophene monomer polymerization and polythiophene
Technical Field
The invention relates to the technical field of thiophene organic photoelectric materials, in particular to a catalyst for thiophene monomer polymerization and polythiophene.
Background
Poly 3-hexylthiophene belongs to polythiophene polymers, and has wide application prospects in the fields of solar cells, organic transistors, electrochromic devices, chemical sensors, electromagnetic shielding materials and the like due to excellent electro-optic performance, environmental stability and dissolubility.
Poly (3-hexylthiophene) (P3 HT) as a low-cost commercial conjugated polymer Hole Transport Material (HTM) has the advantage of easy preparation without any dopant. In addition, its high hydrophobicity provides better stability for the solar cell. P3HT has been widely used as an HTM in perovskite solar cells, as well as a polymer interlayer between the perovskite layer and the HTM. To date, perovskite solar cells using P3HT as HTM or polymer interlayer in their structure have efficiencies as high as 23%.
While P3HT, which is of high molecular weight and structured, has more excellent electrical and optical properties, has relatively high carrier mobility, either in a pure film or in a blended film with PCBM. The McCullough method can synthesize P3HT of a higher structured structure, but the McCullough method has high raw material cost, the reaction must be performed at a low temperature, and the production process is complicated. Therefore, development of a catalyst capable of catalyzing and preparing P3HT at high temperature is a need for solving the problems.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide a catalyst for thiophene monomer polymerization, which can be used for preparing P3HT with high molecular weight, high regularity and narrow molecular weight distribution by catalytic polymerization at high temperature.
The invention aims to provide a catalyst for thiophene monomer polymerization, which has a structural formula shown in a formula (I):
wherein R is selected from alkyl with carbon number more than 2 or substituted alkyl, and the substituent of the substituted alkyl comprises at least one of alkenyl, alkynyl, aryl, naphthyl, acenaphthylenyl, camphene, cycloalkyl, cycloalkenyl and cycloalkynyl;
R 1 、R 2 independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, cycloalkynyl, naphthyl, acenaphthylenyl, camphene, benzhydryl, trityl, and the like,。
Preferably, the structural formula of the catalyst for thiophene monomer polymerization is shown as a formula (I):
wherein R is selected from tert-butyl, xylyl and trityl, R 1 、R 2 Independently selected from isopropyl, tert-butyl, benzhydryl, and,。
More preferably, the structural formula of the catalyst for thiophene monomer polymerization is shown as formula (I):
wherein R is selected from tert-butyl, R 1 、R 2 Independently selected from t-butyl, benzhydryl, benzyl,。
More preferably, the structural formula of the catalyst for thiophene monomer polymerization is shown as formula (I):
wherein R is selected from xylyl and trityl, R 1 、R 2 Independently selected from isopropyl and benzhydryl.
Still another object of the present invention is to provide a method for preparing the catalyst for polymerizing thiophene monomers, comprising the steps of:
ligandAnd (COD) PdCl 2 And (3) reacting to obtain the catalyst for polymerizing thiophene monomers.
Preferably, the ligand is associated with (COD) PdCl 2 The molar ratio of (2) is 1.5-2.5: 1.
more preferably, the ligand is bound to (COD) PdCl 2 The molar ratio of (2): 1.
preferably, the reaction temperature is 60-100 ℃ and the reaction time is 0.3-0.8 h.
More preferably, the temperature of the reaction is 80 ℃ and the time is 0.5h.
Preferably, the preparation method of the ligand comprises the following steps:
substituted anilinesWith alcohol->Reacting to obtain the ligand;
wherein R is 3 Selected from the group consisting of hydrogen, t-butyl, xylyl, and trityl.
Preferably, the substituted anilinesWith alcohol->The molar ratio of (3) is 0.45-3.3: 1.
preferably, the catalyst of the reaction comprises ZnCl 2 /HCl。
Another object of the present invention is to provide a polythiophene prepared by polymerizing thiophene monomers under the catalysis of the catalyst for polymerizing thiophene monomers.
Preferably, the molar ratio of the catalyst for thiophene monomer polymerization to thiophene monomer is 0.0015-0.0035: 1.
more preferably, the molar ratio of the catalyst for thiophene monomer polymerization to thiophene monomer is 0.0025:1.
preferably, the thiophene monomer includes 2-bromo-3-hexylthiophene.
Preferably, organic acids and inorganic bases are also added to the polymerization.
Preferably, the molar ratio of the organic acid to the thiophene monomer is 2-4: 1.
more preferably, the molar ratio of the organic acid to the thiophene monomer is 3:1.
preferably, the molar ratio of the inorganic base to the thiophene monomer is 1-2: 1.
preferably, the molar ratio of the inorganic base to the thiophene monomer is 1.4:1.
more preferably, the organic acid comprises pivalic acid.
More preferably, the inorganic base comprises anhydrous potassium carbonate.
Preferably, the reaction temperature of the polymerization is 80-120 ℃, and the reaction time of the polymerization is 12-36 h.
More preferably, the reaction temperature of the polymerization is 100 ℃, and the reaction time of the polymerization is 24 hours.
Preferably, the polymerization reaction solvent comprises N, N-dimethylacetamide.
Compared with the prior art, the invention has the following beneficial effects:
the catalyst for thiophene monomer polymerization provided by the invention can be used for preparing P3HT at high temperature, and the prepared P3HT has the advantages of high molecular weight, high regularity and narrow distribution, has obvious economic benefit, and has wide application prospects in the fields of solar cells, organic transistors, electrochromic devices, chemical sensors, electromagnetic shielding materials and the like.
Drawings
Fig. 1 is a nuclear magnetic resonance spectrum of a catalyst C1 for polymerizing thiophene monomers according to example 6.
Fig. 2 is a nuclear magnetic resonance spectrum of the catalyst C1 for polymerizing thiophene monomers according to example 6.
Fig. 3 is a nuclear magnetic resonance spectrum of a catalyst C2 for polymerizing thiophene monomers according to example 7.
Fig. 4 is a nuclear magnetic resonance spectrum of the catalyst C2 for polymerizing thiophene monomers according to example 7.
Fig. 5 is a nuclear magnetic resonance spectrum of a catalyst C3 for polymerizing thiophene monomers according to example 8.
Fig. 6 is a nuclear magnetic resonance spectrum of the catalyst C3 for polymerizing thiophene monomers according to example 8.
Fig. 7 is a nuclear magnetic resonance spectrum of a catalyst C4 for polymerizing thiophene monomers according to example 9.
Fig. 8 is a nuclear magnetic resonance spectrum of the catalyst C4 for polymerizing thiophene monomers according to example 9.
Fig. 9 is a nuclear magnetic resonance spectrum of the catalyst C5 for polymerizing thiophene monomers according to example 10.
Fig. 10 is a nuclear magnetic resonance spectrum of the catalyst C5 for polymerizing thiophene monomers according to example 10.
Fig. 11 is a nuclear magnetic resonance spectrum of the catalyst C6 for polymerizing thiophene monomers according to example 11.
Fig. 12 is a nuclear magnetic resonance spectrum of the catalyst C6 for polymerizing thiophene monomers according to example 11.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention. The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
In the description of the present invention, the descriptions of the terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
(COD)PdCl 2 : (1, 5-cyclooctadiene) Palladium dichloride.
The structural formulas of the catalyst, the ligand and the aniline for polymerizing thiophene monomers in each example are as follows:
the catalyst for thiophene monomer polymerization is prepared by the following reaction route:
in the following examples, the prepared P3HT was used to determine the molecular weight and molecular weight distribution of a polymer (trichlorobenzene as solvent and mobile phase, concentration 1.5 g/L, flow rate 1 mL/min) using high temperature gel permeation chromatography (HT-GPC).
Example 1
The present embodiment provides a ligand L1, which is synthesized as follows:
under nitrogen atmosphere, adding compound A1 (5 mmol) and benzhydrol (11 mmol) into a bottle, stirring at 80deg.C, condensing and refluxing for 30min (molten state), and adding prepared ZnCl by syringe 2 Concentrated HCl (wherein ZnCl) 2 (0.75 g), concentrated HCl (1 ml), at 140℃for 6h, and cooled to room temperature after the reaction. Adding a proper amount of dichloromethane, dissolving, transferring to a beaker, adding saturated sodium bicarbonate solution, regulating the pH of the solution to 7, stirring for 30min, removing zinc salt by suction filtration, separating filtrate, collecting an organic layer, adding anhydrous sodium sulfate for water removal, filtering, spin-drying, passing through a silica gel chromatographic column, spin-drying, recrystallizing (absolute ethyl alcohol), and carrying out suction filtration and drying to obtain a white compound L1, wherein the yield is 69%.
Example 2
The embodiment provides a ligand L2, and the synthesis method thereof is as follows:
under nitrogen atmosphere, adding compound A2 (5 mmol) and benzhydrol (5.5 mmol) into a bottle in turn, stirring at 80deg.C for reaction, condensing and refluxing for 30min (molten state), and adding the prepared ZnCl by a syringe 2 Concentrated HCl (wherein ZnCl) 2 (0.75 g), concentrated HCl (1 ml), at 140℃for 6h, and cooled to room temperature after the reaction. Adding a proper amount of dichloromethane, dissolving, transferring to a beaker, adding saturated sodium bicarbonate solution, regulating the pH of the solution to 7, stirring for 30min, removing zinc salt by suction filtration, separating filtrate, collecting an organic layer, adding anhydrous sodium sulfate for water removal, filtering, spin-drying after a silica gel chromatographic column, recrystallizing (absolute ethyl alcohol), and carrying out suction filtration and drying to obtain a white compound L2 with the yield of 57%.
Example 3
The embodiment provides a ligand L3, and the synthesis method thereof is as follows:
under the atmosphere of nitrogen, the compound A3 (5 mmol) and the benzhydrol (16.5 mmol) are sequentially added into a branched bottle to be stirred and reacted at 80 ℃,reflux was condensed for 30min (molten state) and then the ready-to-prepare ZnCl was added with a syringe 2 Concentrated HCl (wherein ZnCl) 2 (0.75 g), concentrated HCl (1 ml), at 140℃for 6h, and cooled to room temperature after the reaction. Adding a proper amount of dichloromethane, dissolving, transferring to a beaker, adding saturated sodium bicarbonate solution, regulating the pH of the solution to 7, stirring for 30min, removing zinc salt by suction filtration, separating filtrate, collecting an organic layer, adding anhydrous sodium sulfate for water removal, filtering, spin-drying after a silica gel chromatographic column, recrystallizing (absolute ethyl alcohol), and carrying out suction filtration and drying to obtain a white compound L3 with the yield of 72%.
Example 4
The present embodiment provides a ligand L5, which is synthesized as follows:
under nitrogen atmosphere, adding compound A5 (5 mmol) and benzhydrol (11 mmol) into a bottle, stirring at 80deg.C, condensing and refluxing for 30min (molten state), and adding prepared ZnCl by syringe 2 Concentrated HCl (wherein ZnCl) 2 (0.75 g), concentrated HCl (1 ml), at 140℃for 6h, and cooled to room temperature after the reaction. Adding a proper amount of dichloromethane, dissolving, transferring to a beaker, adding saturated sodium bicarbonate solution, regulating the pH of the solution to 7, stirring for 30min, removing zinc salt by suction filtration, separating filtrate, collecting an organic layer, adding anhydrous sodium sulfate for water removal, filtering, spin-drying after a silica gel chromatographic column, recrystallizing (absolute ethyl alcohol), and carrying out suction filtration and drying to obtain a white compound L5 with the yield of 82%.
Example 5
The present embodiment provides a ligand L6, which is synthesized as follows:
under nitrogen atmosphere, adding the compound A6 (5 mmol) and dibenzosuberol (2.31 mmol) into a bottle in turn, stirring at 80 ℃ for reaction, condensing and refluxing for 30min (molten state), and then adding the prepared ZnCl by a syringe 2 Concentrated HCl (wherein ZnCl) 2 (0.75 g), concentrated HCl (1 ml), at 140℃for 6h, and cooled to room temperature after the reaction. Adding proper amount of dichloromethane, dissolving, transferring to a beaker, adding saturated sodium bicarbonate solution, adjusting pH to 7, and stirring for 3After 0min, removing zinc salt by suction filtration, separating filtrate, collecting an organic layer, adding anhydrous sodium sulfate for water removal, filtering, spin-drying, subjecting to silica gel chromatographic column, spin-drying, recrystallizing (absolute ethyl alcohol), suction filtering, and drying to obtain white compound L6 with a yield of 72%.
Example 6
The embodiment provides a catalyst C1 for thiophene monomer polymerization, which is synthesized by the following steps:
ligand L1 (1 mmol), (COD) PdCl 2 (0.5 mmol) is dissolved in DMAC (1.5 ml), stirred and reacted for 0.5h at 80 ℃, after the reaction is cooled to be carried out, methanol is added for sedimentation, and after filtering, dissolving solid and passing through a silica gel chromatographic column, the mixture is dried by spin-drying and recrystallized (absolute ethyl alcohol), and then yellow compound C1 is obtained by suction filtration and drying, and the yield is 85%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.24-7.07 (m, 32H), 6.97-6.91 (m, 8H), 6.88 (d,J= 2.1 Hz, 2H), 6.50 (s, 2H), 6.29 (d,J= 2.0 Hz, 2H), 5.32 (s, 2H), 4.31 (s, 4H), 3.43-3.26 (m, 2H), 1.25 (d,J= 6.5 Hz, 12H).
13 C NMR (101 MHz, CDCl 3 ) δ 143.78, 141.43, 140.89, 139.39, 136.14, 132.80, 129.62, 129.49, 129.22, 128.59, 128.11, 126.92, 126.09, 125.44, 56.35, 51.79, 28.01, 23.33.
Example 7
The embodiment provides a catalyst C2 for thiophene monomer polymerization, and the synthesis method thereof is as follows:
ligand L2 (1 mmol), (COD) PdCl 2 (0.5 mmol) is dissolved in DMAC (1.5 ml), stirred and reacted for 0.5h at 80 ℃, after the reaction is cooled to be carried out, methanol is added for sedimentation, and after filtering, dissolving solid and passing through a silica gel chromatographic column, the mixture is dried by spin-drying and recrystallized (absolute ethyl alcohol), and then yellow compound C2 is obtained by suction filtration and drying, and the yield is 88%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.30-7.18 (m, 16H), 7.05 (d,J= 7.5 Hz, 4H), 6.78 (s, 4H), 5.43 (s, 2H), 4.48 (s, 4H), 3.42 (p,J= 6.6 Hz, 4H), 1.22 (d,J= 5.4 Hz, 25H).
13 C NMR (101 MHz, DMSO) δ 145.49, 139.88, 137.52, 131.56, 129.42, 128.59, 126.35, 123.53, 56.33, 27.18, 23.07.
Example 8
The embodiment provides a catalyst C3 for thiophene monomer polymerization, and the synthesis method thereof is as follows:
ligand L3 (1 mmol), (COD) PdCl 2 (0.5 mmol) was dissolved in DMAC (1.5 ml), reacted for 0.5h with stirring at 80℃until the reaction cooled to dryness, then methanol was added for sedimentation, the solid was filtered, dissolved, and after passing through a silica gel column, spin-dried, recrystallized (absolute ethanol), suction-filtered and dried to give yellow compound C3 in 84% yield.
1 H NMR (400 MHz, CDCl 3 ) δ 7.23-7.06 (m, 52H), 6.88-6.79 (m, 8H), 6.39 (d,J= 10.9 Hz, 8H), 5.19 (s, 2H), 4.12 (s, 4H).
13 C NMR (101 MHz, CDCl 3 ) δ 143.68, 141.23, 140.37, 136.04, 134.35, 130.14, 129.58, 129.09, 128.57, 128.02, 126.99, 125.97, 56.03, 51.77.
Example 9
The present example provides a catalyst C4 for polymerizing thiophene monomers, and the synthesis method thereof is as follows.
L4 (1 mmol), (COD) PdCl 2 (0.5 mmol) is dissolved in DMAC (1.5 ml), stirred and reacted for 0.5h at 80 ℃, after the reaction is cooled to be carried out, methanol is added for sedimentation, and after filtering, dissolving solid and passing through a silica gel chromatographic column, the mixture is dried by spin-drying and recrystallized (absolute ethyl alcohol), and then yellow compound C4 is obtained by suction filtration and drying, and the yield is 85%.
1 H NMR (400 MHz, CDCl 3 ) δ 7.18 (d,J= 2.3 Hz, 4H), 4.80 (s, 2H), 1.80 (s, 9H), 1.71 (s, 12H), 1.40 (s, 15H), 1.28-1.15 (m, 19H).
13 C NMR (101 MHz, CDCl 3 ) δ 146.90, 139.76, 134.99, 123.16, 121.94, 35.81, 34.84, 34.75, 32.79, 32.65, 31.67, 31.42, 31.20, 31.12, 31.02, 30.35.
Example 10
The present example provides a catalyst C5 for polymerizing thiophene monomers, and the synthesis method thereof is as follows.
L5 (1 mmol), (COD) PdCl 2 (0.5 mmol) was dissolved in DMAC (1.5 ml), reacted for 0.5h with stirring at 80℃until the reaction cooled to dryness, then methanol was added for sedimentation, the solid was filtered, dissolved, and after passing through a silica gel column, spin-dried, recrystallized (absolute ethanol), suction-filtered and dried to give yellow compound C5 in 65% yield.
1 H NMR (400 MHz, CDCl 3 ) δ 7.26 (dd,J= 8.1, 6.5 Hz, 16H), 7.23-7.17 (m, 8H), 7.13-7.05 (m, 16H), 6.58 (s, 4H), 5.46 (s, 4H), 0.97 (s, 18H).
13 C NMR (101 MHz, CDCl 3 ) δ 142.82, 140.00, 139.42, 129.48, 128.51, 128.36, 126.52, 125.44, 52.63, 33.90, 31.26.
Example 11
The present example provides a catalyst C6 for polymerizing thiophene monomers, and the synthesis method thereof is as follows.
L6 (1 mmol), (COD) PdCl 2 (0.5 mmol) is dissolved in DMAC (1.5 ml), stirred and reacted for 0.5h at 80 ℃, after the reaction is cooled to be carried out, methanol is added for sedimentation, and after filtering, dissolving solid and passing through a silica gel chromatographic column, the mixture is dried by spin-drying and recrystallized (absolute ethyl alcohol), and then yellow compound C6 is obtained by suction filtration and drying, and the yield is 86%.
1 H NMR (400 MHz, DMSO) δ 7.40 (d,J= 7.1 Hz, 8H), 7.14 (h,J= 7.1 Hz, 24H), 6.67 (s, 4H), 5.19 (s, 4H), 4.11 (s, 4H), 3.31-3.23 (m, 8H), 2.72-2.60 (m, 9H), 0.91 (d,J= 1.8 Hz, 18H).
13 C NMR (101 MHz, DMSO) δ 140.66, 139.91, 131.04, 130.94, 127.57, 126.76, 125.89, 55.14, 33.61, 31.45.
Comparative example 1
This comparative example provides a catalyst C7 for polymerizing thiophene monomers, which is synthesized as follows.
Acetylacetone (10 mmol) and 2, 6-diisopropylaniline A7 (22 mmol) were taken and placed in a round bottom flask, 40mL of absolute ethanol was added, 1.5mL of concentrated hydrochloric acid was slowly added dropwise with vigorous stirring, the mixture was heated under reflux for 3 days, a white solid was obtained by suction filtration, redissolved in dichloromethane, and the mixture was purified by saturated NaHCO 3 The solution is adjusted to be neutral, the solvent is removed by extraction and liquid separation and reduced pressure distillation, and the light yellow solid beta-diimine L7 is obtained with the yield of 61 percent.
Weighing beta-diimine L7 (1 mmol), (COD) PdCl 2 (1 mmol) in a branched flask, 18mL of methanol was added to the flask in N 2 The reaction was refluxed for 16h under protection. After the reaction, the yellow solid was filtered off with suction and eluted rapidly through a short column of silica gel, and recrystallized from dichloromethane/n-hexane to give yellow solid C7 in 47% yield.
Catalysts C1 to C6 for thiophene monomer polymerization of examples 6 to 11 and catalyst C7 for thiophene monomer polymerization prepared in comparative example 1 are used for catalyzing polymerization of 2-bromo-3-hexylthiophene to obtain P3HT, and the specific steps are as follows:
taking a clean anhydrous anaerobic parallel reactor, respectively placing the reactor into magnetic stirrers, adding 2-bromo-3-hexylthiophene (0.5 mmol), anhydrous potassium carbonate (0.7 mmol), pivalic acid (0.15 mmol) and 4ml of N, N-dimethylacetamide as solvents into the reactor, respectively adding 0.25% of catalysts C1-C7 for thiophene monomer polymerization, and heating to 100 under natural conditions o C, stirring and reacting for 24 hours at a controlled temperature, stopping heating, adding 20ml of methanol for precipitation, separating out a reddish brown solid product, carrying out suction filtration and drying, wrapping the product with filter paper, putting the product into a Soxhlet extractor, adding n-hexane as a solvent for extraction until the siphoned solvent has no color, drying the product, weighing, and carrying out GPC characterization on the polymer. The results of the catalytic polymerization are shown in Table 1.
TABLE 1 results of polymerization of 2-bromo-3-hexylthiophene with catalysts for polymerization of different thiophene monomers.
As can be seen from Table 1, the P3HT prepared in examples 6-11 of the present invention has higher molecular weight and regularity, and narrow molecular weight distribution.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (9)

1. The catalyst for thiophene monomer polymerization is characterized in that the structural formula of the catalyst for thiophene monomer polymerization is shown as the formula (I):
wherein R is selected from tert-butyl, xylyl and trityl, R 1 、R 2 Independently selected from isopropyl, tert-butyl, benzhydryl, and,。
2. The catalyst for polymerizing thiophene monomers according to claim 1, wherein the structural formula of the catalyst for polymerizing thiophene monomers is shown in formula (I):
wherein R is selected from tert-butyl, R 1 、R 2 Independently selected from t-butyl, benzhydryl, benzyl,。
3. The catalyst for polymerizing thiophene monomers according to claim 1, wherein the structural formula of the catalyst for polymerizing thiophene monomers is shown in formula (I):
wherein R is selected from xylyl and trityl, R 1 、R 2 Independently selected from isopropyl and benzhydryl.
4. The method for preparing a catalyst for polymerizing thiophene monomers according to any one of claims 1 to 3, comprising the steps of:
ligandAnd (COD) PdCl 2 And (3) reacting to obtain the catalyst for polymerizing thiophene monomers.
5. The method for preparing a catalyst for polymerizing thiophene monomers according to claim 4, wherein the method for preparing the ligand comprises the steps of:
substituted anilinesWith alcohol->Reacting to obtain the ligand;
wherein R is 3 Selected from the group consisting of hydrogen, t-butyl, xylyl, and trityl.
6. The use of the catalyst for polymerizing thiophene monomers according to any one of claims 1 to 3 for catalyzing the polymerization of thiophene monomers.
7. The use according to claim 6, wherein the thiophene monomer comprises 2-bromo-3-hexylthiophene.
8. Use according to claim 6, characterized in that organic acids and inorganic bases are also added in the polymerization.
9. The use according to claim 6, wherein the polymerization reaction temperature is 80-120 ℃ and the polymerization reaction time is 12-36 h.
CN202311353118.8A 2023-10-19 2023-10-19 Catalyst for thiophene monomer polymerization and polythiophene Active CN117088919B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311353118.8A CN117088919B (en) 2023-10-19 2023-10-19 Catalyst for thiophene monomer polymerization and polythiophene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311353118.8A CN117088919B (en) 2023-10-19 2023-10-19 Catalyst for thiophene monomer polymerization and polythiophene

Publications (2)

Publication Number Publication Date
CN117088919A CN117088919A (en) 2023-11-21
CN117088919B true CN117088919B (en) 2024-01-30

Family

ID=88777271

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311353118.8A Active CN117088919B (en) 2023-10-19 2023-10-19 Catalyst for thiophene monomer polymerization and polythiophene

Country Status (1)

Country Link
CN (1) CN117088919B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118085244B (en) * 2024-04-19 2024-06-25 链行走新材料科技(广州)有限公司 Bithiophene-thiophene copolymer and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003101936A1 (en) * 2002-06-03 2003-12-11 Sumitomo Chemical Company, Limited Polymerization catalysts for olefins and process for the production of olefin polymers
CN103025789A (en) * 2010-07-26 2013-04-03 综研化学株式会社 Polythiophene polymerization catalyst, and method for producing poly(substituted thiophene)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003101936A1 (en) * 2002-06-03 2003-12-11 Sumitomo Chemical Company, Limited Polymerization catalysts for olefins and process for the production of olefin polymers
CN103025789A (en) * 2010-07-26 2013-04-03 综研化学株式会社 Polythiophene polymerization catalyst, and method for producing poly(substituted thiophene)

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Novel dinuclear and trinuclear palladium b-diiminate complexes containing amido–chloro double-bridges;Alen Hadzovic et al.;《Dalton Transactions》;Scheme 3 *

Also Published As

Publication number Publication date
CN117088919A (en) 2023-11-21

Similar Documents

Publication Publication Date Title
CN117088919B (en) Catalyst for thiophene monomer polymerization and polythiophene
CN112225882B (en) N-type polymer containing non-condensed ring acceptor unit and preparation method and application thereof
CN107778319B (en) A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof
CN112300201B (en) Synthesis and preparation method of trimeric indenyl coumarin-corrole-porphyrin quaternary system star-shaped compound
CN117105990B (en) Catalyst for preparing polythiophene and P3HT material by catalysis
CN109096313B (en) Preparation method of trimeric indenyl corrole-porphyrin-fullerene star-shaped compound
CN103408756B (en) The method preparing polytriazoles of the loading type monovalence copper catalyst catalysis of recoverable and obtained polytriazoles
CN114316265B (en) Polythiourea compound and preparation method and application thereof
CN111100264A (en) Polymer containing DPP, thiophene and fluorothiophene structural units and preparation method and application thereof
WO2021174532A1 (en) Acceptor material of nitrogen-containing heterocyclic trapezoidal fused ring, and preparation method therefor and application thereof
CN114644611B (en) Naphthalene condensed ring-based electron-deficient monomer, polymer and application thereof
CN113354663A (en) Acceptor material containing nitrogen hetero-trapezoidal condensed ring, and preparation method and application thereof
CN117343105A (en) Palladium catalyst and application thereof in preparation of P3HT
CN114560964A (en) Synthetic method and application of carboxyl functional polyion liquid
CN114133391A (en) Mother nucleus substituted naphthalene diimide electrochemical polymerization monomer and preparation method thereof
CN105153182B (en) A kind of Dihydrobenzofuranes C of 5 alkyl 2,360Fullerene double adduct and its production and use
CN108794732B (en) A kind of side's acids high molecular polymer, preparation method and application
CN111068780B (en) Catalyst for preparing biphenyl and preparation method and application thereof
CN117417378A (en) Asymmetric alpha-diimine palladium catalyst and preparation method and application thereof
CN110606937B (en) Polymeric complex containing 4-vinylaniline derivative and Zn (II) and preparation method and application thereof
CN107474257B (en) Indolocarbazole covalent organic framework material and synthesis method thereof
CN113248693A (en) Wide-bandgap polymer donor material based on benzodithiazole electron-deficient unit and preparation method and application thereof
CN112608245A (en) Cationic water-soluble inclined column [6] arene and synthetic method thereof
CN113801301B (en) Isoindigo polymer of fused pyrrole ring type perylene imide with pendant gulf-position and preparation method thereof
CN111545247B (en) SBA-15 supported multiphase chiral phosphine gold catalyst 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