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Method for preparing conductive conjugated polymer by heterogeneous catalytic carbon-carbon bond coupled reaction

A technology of conjugated polymers and homogeneous catalytic carbon, which is applied in the field of heterogeneously catalyzed carbon-carbon bond coupling reaction to prepare conductive conjugated polymers, which can solve the problems of difficult removal, reduction of polymer purity and performance, and metal ligands. Expensive and other issues

Active Publication Date: 2015-06-17
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] First: Under the conditions of the polymerization reaction, the Pd complex will irreversibly decompose to form free palladium nanoparticles, which are difficult to remove and bring harm to the performance of the polymer.
[0005]Second: The aryl group in the phosphine ligand can enter the catalytic cycle through the exchange reaction to generate other coupling by-products, resulting in end-capping of the polymer, terminating the reaction, and reducing the molecular weight ; At the same time, the aryl exchange causes the phosphorus atom in the ligand to be introduced into the polymer chain, reducing the purity and performance of the polymer
[0006]Third: metal ligands are generally expensive and not recyclable, toxic and easily oxidized by air
The solvent needs to be fully degassed before the reaction, which brings inconvenience to operation and storage, and becomes one of the bottlenecks in the large-scale synthesis of high-purity conductive conjugated polymers.

Method used

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  • Method for preparing conductive conjugated polymer by heterogeneous catalytic carbon-carbon bond coupled reaction
  • Method for preparing conductive conjugated polymer by heterogeneous catalytic carbon-carbon bond coupled reaction
  • Method for preparing conductive conjugated polymer by heterogeneous catalytic carbon-carbon bond coupled reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] Pd / C catalyzed the Suzuki coupling polymerization between monomer 1 and monomer 2 to obtain polymer P1. Implementation process: Add 2,5-dioctyl-3,6-bis(3-bromo)phenylpyrrolo[3,4-c]-pyrrole-1,4-dione (monomer 1,102.4 mg,0.15mmol), N-(2-ethylhexyl)-2,7-(bis 4',4',5',5'-tetramethyl-1',3',2'-dioxaboron Pentacycl-2-yl)-9hydro-carbazole (monomer 2, 79.7mg, 0.15mmol), 8mg 10wt% Pd / C (0.0075mmol), K 2 CO 3 (69mg, 5.0mmol) and 6mL mixed solvent (3mL DMF, 3mL THF and 0.25mL H 2 O). in N 2 Stir and warm up to 85°C under protection, and react for 72h. The polymer was precipitated in methanol, filtered and washed successively with methanol, acetone, n-hexane and chloroform in a Soxhlet extractor. The final chloroform extract was rotary evaporated under reduced pressure to obtain the product, which was dried in vacuo at 75° C. overnight to obtain 87 mg of polymer with a yield of 72%. 1 H NMR (300 MHz, CDCl 3, ppm): 7.81 (br, 6H), 7.53 (br, 6H), 7.06~7.16 (br, 2H), 3.88 (br, 6...

Embodiment 2

[0041] Pd / C catalyzed the Suzuki coupling polymerization between monomer 2 and monomer 3 to obtain polymer P2. The reaction formula is as follows:

[0042]

[0043] Implementation process:

[0044] The synthesis method of P2 is the same as that of P1, and the yield is 68%. 1 H NMR (300 MHz, CDCl 3 , ppm): 9.0 (br, 2H), 8.11 (br, 3H), 7.56 (br, 5H), 4.05 (br, 6H), 1.25-1.58 (br, 27H), 0.88 (br, 18H). 1 See attached for HNMR spectrum figure 2 .

[0045] GPC analysis and AAS detection confirmed that the molecular weight and metal Pd residue of polymer P2 obtained under Pd / C catalysis were 13000 and 56 ppm respectively, and the yield was 68%. As a comparative study, under the same conditions, the homogeneous Pd(PPh 3 ) 4 The molecular weight and metal Pd residue of the polymer P2 obtained under the catalysis were 12000 and 3350 ppm respectively, and the yield was 45%. The measured indicators were all lower than the Pd / C catalyst.

Embodiment 3

[0047] Pd / C catalyzed the Heck coupling polymerization between bromoarene monomer 4 and monomer 6 to obtain polymer P3. The reaction formula is as follows:

[0048]

[0049] Implementation process:

[0050] Add 1,4-dibromo-2,5-di-n-octyloxybenzene (monomer 4) 0.25mmol, 1,4-divinylbenzene (monomer 6) 0.25mmol, 13mg10wt%Pd / C0.0125mmol and K 2 CO 3 (104mg, 0.75mmol), dissolved in a mixed solvent of 6mL NMP and 5 drops of deionized water (ca. 0.25mL). in N 2 Stir and warm up to 135°C under protection, and react for 72h. The polymer was precipitated in methanol, filtered and washed successively with methanol, acetone, n-hexane and chloroform in a Soxhlet extractor. The final chloroform extract was rotary evaporated under reduced pressure to obtain the product, which was dried in vacuum at 75° C. overnight to obtain a polymer with a yield of 45%. 1 H NMR (300 MHz, CDCl 3 ,ppm):7.53(br,Ar H,6H),7.14(br,vinyl H,4H),4.08(br,-OCH 2 -,4H),1.89(br,-CH 2 -,4H),1.57(br,-CH 2 ...

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Abstract

The invention relates to a method for preparing a conductive conjugated polymer by heterogeneous catalytic carbon-carbon bond coupled reaction. The method comprises a step of synthetizing the conductive conjugated polymer with high purity by using a heterogeneous palladium catalyst for carbon-carbon (C-C) coupling polymerization. Compared with the product obtained by performing catalytic polymerization with the traditional homogeneous catalyst Pd (PPh3)4, the conductive conjugated polymer prepared by reacting ligand-free solid supported palladium carbon (Pd / C) catalytic Suzuki, Heck and Stille C-C coupled reaction has the advantages of higher molecular weight, higher yield and lower metal palladium residues and the like. A new method is provided for preparing the conductive conjugated polymer with high purity and low cost.

Description

technical field [0001] The invention relates to a preparation method of a conductive conjugated polymer, in particular to a method for preparing a conductive conjugated polymer by heterogeneously catalyzing a carbon-carbon bond coupling reaction. Background technique [0002] Conductive conjugated polymers have broad application prospects in nonlinear optics, organic solar cells, field-effect transistors, and organic light-emitting diodes. Heck, Suzuki and Stille build C(sp 2 )-(sp 2 ) C-bond coupling reaction has become a very important and effective tool for the synthesis of conductive conjugated polymers. [0003] So far, the preparation of conductive conjugated polymers by reactions such as Suzuki (Suzuki), Heck (Heck) and Stille (Stille) all use soluble homogeneous palladium catalysts [such as Pd(PPh 3 ) 4 , or Pd(OAc) 2 , Pd 2 (dba) 3 / PPh 3 , Pd 2 (dba) 3 / P(t-Bu) 3 ,Pd(PPh 3 ) 2 Cl 2 , PdCl 2 (dppf) and Pd(OAc) 2 / P(Tol) 3 etc.], these ligand-type ho...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08G61/12C08G61/02
Inventor 陈红征刘诗咏施敏敏李寒莹
Owner ZHEJIANG UNIV