Preparation method of palladium complex and conjugated aromatic polymer

A technology of palladium complexes and conjugated aromatics, which is applied in the field of preparation of palladium complexes and conjugated aromatics polymers, can solve the problems of unfavorable oxidative addition, difficult coordination, poor oil solubility, etc., and achieve good catalytic effect

Active Publication Date: 2014-09-17
CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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  • Summary
  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

[0004] Although the hydrophilic series of ligands TPPMS, TPPDS, TPPTS and Pd(OAc) 2 The two-component catalytic system of composition can improve the molecular weight of polymkeric substance, but there is unfavorable influence in the ligand that this method adopts and metal palladium salt two-component catalyst: 1) the sulfonate group that ligand has in the catalytic system has Too strong water solubility and poor oil solubility will make the catalyst form in the water phase, and it is difficult to enter the organic phase, which is not conducive to oxidative addition with the polymerization monomer in the polymerization reaction; 2) because the ligand has too much Strong water solubility and poor oil solubility. When the palladium intermediate is located at the two-phase interface during the polymerization process, the ligand is extremely difficult to coordinate with the palladium intermediate, causing the palladium intermediate to decompose and aggregate to form palladium black, which makes the catalyst inactive.

Method used

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  • Preparation method of palladium complex and conjugated aromatic polymer
  • Preparation method of palladium complex and conjugated aromatic polymer
  • Preparation method of palladium complex and conjugated aromatic polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Embodiment 1: the synthesis of 3-(diphenylphosphine) benzenesulfonic acid (3-TPPMSH)

[0079] In a 250ml three-neck round bottom flask, add 20ml of fuming sulfuric acid (Oleum), and add 10g of triphenylphosphine (PPh) in batches in an ice-water bath under an argon atmosphere. 3 ), stirred until completely dissolved, then raised the temperature to 93°C and stirred for 2h. After cooling to room temperature, add 20 g of ice and 100 ml of distilled water, add NaOH aqueous solution to adjust the reaction solution to neutral, and precipitate a white solid, which is recrystallized twice from distilled water after filtration to obtain 3 g of bright white crystalline powder sodium sulfonate ligand, sulfonic acid The yield of sodium ligand was 20%. Sodium sulfonate ligand is dissolved in hydrochloric acid methanol solution to obtain 3-TPPMSH, and the reaction formula is shown in the following formula:

[0080]

[0081] Carry out nuclear magnetic resonance analysis to interme...

Embodiment 2

[0082] Embodiment 2: the synthesis of 4-(diphenylphosphine) benzoic acid (4-TPPMC)

[0083] In a 500ml three-necked round-bottomed flask, 6g of KOH and 300ml of dimethyl sulfoxide (DMSO) were added under the protection of argon. After adding 10.4ml of diphenylphosphine, a red reaction solution was obtained. Stir at room temperature for 2h, add 7.26 g p-fluorobenzonitrile, the reaction solution immediately produces a white precipitate, and after stirring for 0.5h, the precipitate is filtered and recrystallized twice with methanol to obtain 13.75g bright white crystal 4-(diphenylphosphine)benzonitrile, 4-(diphenylphosphine) The yield of phenylphosphine)benzonitrile was 80%. Product 4-(diphenylphosphine) benzonitrile is carried out nuclear magnetic resonance analysis, and characterizing result is as follows: 1 H NMR (CDCl 3 , 300MHz): δ=7.30-7.39(m, 12H), 7.57ppm(d, J=6.9Hz, 2H); 31 P { 1 H}NMR (CDCl 3 , 161.9Hz): δ=-4.67ppm(s). It can be seen that 4-(diphenylphosphine)benzo...

Embodiment 3

[0087] Embodiment 3: the synthesis of 3-(diphenylphosphine) benzoic acid (3-TPPMC)

[0088] In a 500ml three-neck round bottom flask, add 6gKOH and 300ml dimethyl sulfoxide (DMSO) under the protection of argon, after adding 10.4ml diphenylphosphine, a red reaction solution is obtained, stir at room temperature for 2h, add 7.26g Fluorobenzonitrile, the reaction solution produced white precipitate immediately, after stirring for 0.5h, the precipitate was filtered and recrystallized twice with methanol to obtain 12g bright white crystal 3-(diphenylphosphine)benzonitrile, 3-(diphenylphosphine) ) Benzonitrile productive rate is 70%. Product 3-(diphenylphosphine) benzonitrile is carried out nuclear magnetic resonance analysis, and characterizing result is as follows: 1 H NMR (CDCl 3 , 400MHz): δ=7.27-7.31(m, 4H), 7.375(d, J=5.2Hz, 6H), 7.44(d, J=7.6Hz, 1H), 7.48-7.55(m, 2H), 7.60ppm (d, J=7.6Hz, 1H); 31 P { 1 H}NMR (CDCl 3 , 161.9Hz): δ=-5.83ppm(s). It can be seen that 3-(diphen...

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Abstract

The present invention provides a palladium complex with a structure such as formula (I) or formula (II), wherein X is a halogen; L is a phosphine ligand or a nitrogen-containing ligand; G is a sulfonic acid group, a carboxylic acid group, a phosphonic acid group , a hydroxyl group or a polyether chain; the position of the G is at the para or meta position of the L; n is a positive integer; m is 2, 3 or 4. The invention also provides a preparation method of the palladium complex and a method for preparing the conjugated arene polymer by using the palladium complex catalyst. Due to the introduction of neutral hydrophilic substituents in the palladium complex catalyst ligand, the palladium complex catalyst has amphiphilicity and can be dissolved in both the water phase and the organic phase, and the catalyst is easy to carry out oxidative addition with the polymerized monomer, and The metal transfer step can be promoted, and the coupling polymerization reaction can be carried out continuously and rapidly, so high molecular weight conjugated arene polymers can be obtained, PdX2(L-Gn)2 (I); Pd(L-Gn)m (II).

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a preparation method of a palladium complex and a conjugated arene polymer. Background technique [0002] Suzuki coupling polymerization refers to the coupling reaction of organic boron compound and organic halogen compound under the action of catalyst. This method was first applied by Schluter in 1989. After more than 20 years, the coupling reaction of small molecules has made great progress in terms of catalyst activity, yield, simplified operation and optimized reaction conditions, but there has been little improvement in coupling polymerization. . The existing coupling polymerization generally uses zero-valent tetrakis(triphenylphosphine) palladium as a catalyst, and the polymerization monomers are reacted in a two-phase reaction system of an organic phase and an alkaline aqueous solution. The problem with this method is that during the reaction, the polymerized monomers are dissol...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F19/00C08G61/02
Inventor 程延祥李静付宏伟胡盼李晓张子龙
Owner CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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