Alkynes And Sulfonyl Azides-based Multicomponent Polymerizations

The development of polymerization methodology affords polymer materials with new structures and functionalities.Multicomponent polymerizations?MCPs?as a facile tool for preparing multifunctional polymers with complicated structures have attracted increasing attention from polymer scientists,owing to their high efficiency,high atom economy,simple procedure,structural diversity,and environmental benefit.MCPs have become an emerging field in polymer science frontier.On the other hand,through polymerizations of alkynes with rich chemical properties,functional polymers with unsaturated structures and optoelectronic properties can be obtained.The preparation of functional polymer materials with complex structures usually requires multi-step synthesis and harsh conditions,which severely restricts the development of advanced materials.In this thesis,a series of alkyne-involving click reaction-mediated MCPs have been developed to prepare multifunctional polymer material with complex structure efficiently under mild conditions,which can't been prepared by other synthetic methods.The copper-catalyzed multicomponent reactions?MCRs?with alkynes and sulfonyl azides are mediated by click reaction,which possess rich reactivity and mild reaction conditions.Based on these MCRs,firstly,a facile one-pot three-component polymerization of diynes,disulfonyl azides,and iminophosphorane is developed to construct N,O,S,P-containing heteroatom-rich poly?phosphorus amidine?s with advanced functionalities.The optimized MCP proceeds at room temperature in THF under the catalysis of CuI,generating polymers with high molecular weights?up to 85 600 g/mol?in excellent yields?up to 92%?.The MCP enjoys general applicability of various monomers,and the only byproduct generated from the polymerization is nitrogen gas,demonstrating high atom economy and environmental benefit.Interestingly,the phosphorus amidine model compounds were found to possess both aggregation-induced emission?AIE?behavior and thermally-activated delayed fluorescence.The polymers generally enjoy good solubility in polar organic solvents,good film-forming ability,satisfactory thermal stability,and high refractivity.They can also function as fluorescent chemosensors for Pd²⁺ions detection with high sensitivity and selectivity.What's more,a series of efficient one-pot MCPs of diynes,disulfonyl azides,and N-protected isatins are developed to afford oxindole-containing poly?N-acylsulfonamide?s with advanced properties.After optimization of the polymerization conditions,the MCP can proceed smoothly at room temperature in DCM/t-BuOH with Cu I as catalyst and LiOH as base,generating poly?N-acylsulfonamide?s with high molecular weights of up to 30 600 g/mol in excellent yields of up to 98%.This MCP enjoys general applicability of a series of electron-rich or electron-deficient alkynes and alkyl group or aromatic group-substituted isatins and nitrogen gas as the only byproduct.The solubility and hydrophilicity of these polymers can be reversibly switched upon acidification and alkalization.Furthermore,water can be participated in the MCP as the fourth component when the MCP is conducted in DMF with CuI as catalyst and Na₂CO₃ as base,generating random copolymer consisting with 3-alkenyloxindole moieties and two chiral centers-containing 3-hydroxyindole moieties in the backbone.The unique structure of oxindole-containing poly?N-acylsulfonamide?s endows the polymers with a series of properties such as reversibly tunable solubility and hydrophilicity,photoluminescence with yellow to red emission,solvatochromism,photo-induced generation of reactive oxygen species?ROS?etc.Finally,facile MCPs of diynes,disulfonyl azides,and 2-hydroxybenzonitrile are developed to construct multifunctional iminocoumarin-containing poly?N-sulfonylimine?s.The optimized MCPs proceed at mild condition in DCM under the catalysis of CuCl,generating polymers with high molecular weights?up to 37 700 g/mol?in excellent yields?up to 96%?.The MCP enjoys general applicability of various monomers,and the only byproduct generated from the polymerization is nitrogen gas.The polymers enjoy good thermal stability.Some of them were found to possess AIE behavior.They can function as fluorescent chemosensors for Ru³⁺ions detection with high sensitivity and selectivity.They can also inhibit the growth of Staphylococcus aureus.These MCPs not only serve as a tool to connect monomeric units together in the polymer chain,but also construct new functional units in situ.These MCPs can accelerate the progress of new synthetic methodology and exploration of advanced functional materials,which can accelerate the development of polymer chemistry and polymer materials.