Study On Chan-Lam Coupling Polymerization And Sonogashira Decarboxylative Coupling Polymerization

As novel materials with unique physical or chemical properties,advanced functional polymers have been widely used in many fields such as photophysics,biomedicine,materials science,nanoscience and so on.The current polymerization processes to prepare functional polymer materials might have disadvantages such as expensive raw materials,complex monomer synthesis,harsh reaction conditions,poor reaction selectivity,and environmental pollution caused by by-products,which limit the further development and application of functional polymer materials.Thus,one of the keys to promote the development of functional polymer materials is to develop new polymerization methods with simple and efficient process,mild conditions,environmental protection,high selectivity,and wide application range.Since there are numbers of mature and high-efficiency organic small molecule reactions in the field of organic synthesis,if these potential small molecule reactions can be developed into new types of polymerizations,it will be of great significance to the development of advanced functional polymer materials.Based on the Chan-Lam coupling reaction and Sonogashira decarboxylative coupling reaction of small molecules,two new types of polymerization reactions are developed in this paper,which are named Chan-Lam coupling polymerization and Sonogashira decarboxylative coupling polymerization,and they have been successfully applied to the construction of functional polymer materials with the property of aggregation-induced emission.Firstly,Chan-Lam coupling polymerization,a new type of polymerization for the construction of C-N bond was successfully developed based on the Chan-Lam coupling reaction.The Chan-Lam polymerization occurs under the catalysis of cuprous chloride at room temperature,a variety of sulfonyl azide and aryl boronic acid derivatives are used as monomers,and methanol is used as solvent.A series of polysulfonamide derivatives were prepared with ideal yield(up to 82%)and molecular weight(weight average molecular weight up to 11400).The reaction is suitable for a variety of monomers with different structures,and the resulting polymers have great solubility and thermal stability.Among these polymers,the polymer P1b/2f has good film-forming property and unique property of aggregation-induced emission,which was prepared into a uniform film by solution spin coating,and was successfully used in the production of fluorescent photopatterns.Secondly,Sonogashira decarboxylative coupling polymerization,a new type of polymerization for the construction of C-C bond was successfully developed based on the Sonogashira decarboxylative coupling reaction.The Sonogashira decarboxylative polymerization occurs under the catalysis of tetrakis(triphenylphosphine)palladium at 110?,1,8-diazabicyclo[5.4.0]undec-7-ene is used as a base,aryl dibromide compounds and butyndioic acid are used as monomers,and N-methylpyrrolidone is used as solvent.A series of poly(phenyleneethynylene)derivatives were generated with good yield(between 71%and 86%)and molecular weight(weight average molecular weight up to 18700).The reaction has well monomer applicability,and the resulting polymers have excellent thermal stability and great solubility.The thermal decomposition temperatures of these polymers are between 317? and 405?.Among them,the polymer P3a/4 has a good film-forming property and a unique property of aggregation-induced emission,which was prepared into a uniform thin film by solution spin coating,and was further used in the production of fluorescent photopatterns.