Multicomponent Reactions And Polymerizaions Involving Carbon Disulfide

Multicomponent polymerization（MCP）is a powerful tool to efficiently and conveniently prepare functional polymer materials,which usually generated single polymer product.This thesis aims to explore the synthetic methods of sulfur-containing functional polymers via MCP,as sulfur-containing polymer materials have been widely used in the fields of mechanical materials,energy storage materials,and optical materials.Developing new synthetic methods can obtain more new sulfur-containing polymers with diverse structures,thereby expanding their application scenarios and promoting the further development of sulfur chemistry and sulfur-containing polymer materials.Carbon disulfide（CS₂）is a cheap and abundant chemical product that has rich chemical reactivity and is also an efficient sulfur source.However,there are currently few reports on directly using CS₂ to construct sulfur-containing polymers with rich structures.Therefore,in this thesis,a series of CS₂ based multicomponent reactions（MCRs）were developed,furthermore,some multicomponent polymerizations（MCPs）were developed,which can prepare a variety of functional sulfur-containing polymer materials with different structures.First,we explored the MCR of amine,CS₂ and isocyanide,confirmed the reaction mechanism,and successfully developed the special MCR,which could synthesis products with different structures by controlling the monomer loading ratio,that is,[amine]:[CS₂]:[isocyanide]=1:1:1 to afford isothiocyanate and thioformamide with equal equivalent;[amine]:[CS₂]:[isocyanide]=2:1:1 to afford thiourea and thioformamide with equal equivalent.Moreover,the MCP of diamine,CS₂ and monoisocyanide was successfully developed to afford polythiourea and thioformamide twin-products simultaneously in equal equivalent.A series of polythioureas with various structures were successfully prepared through this polymerization,on the other hand,the other product of polymerization,thioformamide,could be used as a thioformamide reagent to convert amino groups into thioformamide.Importantly,polythioureas with tunable compositions and sequence could be facilely constructed by one-step copolymerization or two-step tandem polymerization,achieving the tunable of the glass transition temperature of polythiourea from 19 to 143°C,and 62.3 g-scale sequence controlled polythiourea has been pre fpared in one potor the first time.These polythioureas exhibited good thermal stability,clusterization-triggered emission property and excellent glass state self-healing property.Secondly,we introduced hydrazide as a nucleophilic reagent into the reaction in order to construct new sulfur-containing units and sulfur-containing polymers,and successfully developed the MCR of hydrazides,CS₂ and isocyanide to synthesize isothiocyanatoamides and thioformamide in equal equivalent;and the new MCR of amines,CS₂,isocyanide,and hydrazide to synthesize acylthiosemicarbazides and thioformamide.Furthermore,the one pot MCP of diamines,CS₂,monoisocyanide,and dihydrazides was successfully developed to prepare polyacylthiosemicarbazides and thioformamide.Various of new polyacylthiosemicarbazides have been prepared through this polymerization,and the resulting polymers exhibits good solubility and thermal stability.In addition,these polymers also have good film-forming properties,which can be used to prepare transparent film with good mechanical properties（tensile strength of 14.73 MPa）through solution processing.This strategy also provides a new idea for constructing mechanical materials with new structures.Finally,we also challenged thiols to participate in the reaction as a nucleophilic reagent in order to construct more functional sulfur-containing polymer materials,and developed the MCR with amine,CS₂,isocyanide,and thiol to synthesize dithiourethanes and thioformamide in equal equivalent.What’s more,the corresponding MCP of diamine,CS₂,monoisocyanide,and dithiols was successfully developed to prepare polydithiourethanes and thioformamide.A series of polydithiourethanes with good thermal stability and solubility were successfully prepared via this polymerization.Importantly,these polydithiourethanes also has excellent mechanical properties with the tensile strength of 18.51 MPa and the strain at break of 513%.On the other hand,these polydithiourethanes,being stretched even to 5 times its original length,is observed to recover to its original dimension after rest for only 10 min,suggesting that this new material possess strength,toughness and elasticity.This thesis mainly developed a series of MCRs and MCPs,which have the advantages of low-cost commercially available monomers,simple operation,mild reaction conditions（room temperature,air and catalyst free）and wide applicability of monomers,which could efficiently,economically and conveniently direct convert CS₂ into a variety of sulfur-containing polymer materials（polythioureas,polyacylthiosemicarbazides and polydithiourethanes）.Meanwhile,a thioformamide compound was afforded in equivalent amount as the other twin-product,which could serve as a thioacylation reagent to transform amines to thioformamides.These MCPs enriched the sulfur-containing materials and their synthetic methods,and has great potential in constructing advanced functional materials with adjustable thermal,mechanical and optical properties.