Preparation method of palladium complex and conjugated aromatic polymer

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...

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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.

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