Preparation And Properties Of Metal-Thioether Reversible Coordination Functional Polymer Materials

Recently,in order to meet the needs of the development of technology,to prepare the smart materials which used in construction,electronics,military,and aerospace fields have attached more and more attention.Compared with the other materials,smart polymer materials have great advantages,such as simple preparation,strong molecular design,low density and inexpensive.Self-healing was an important function of smart polymer materials in the practical application,and the Self-healing polymers could achieve repair by heating or illumination to enhance the strength and prolong service life of materials.Therefore,self-healing polymers have been widely used in the fields of construction,communications,transportation,national defense,medical and daily necessities.In addition,the stimuli-responsive function of smart polymer which can be responsive to thermal,light and chemical,is also an important component.In this paper,a series of smart polymer materials with self-repairing function and stimuli response function was prepared by combining metal-thioether reversible coordination interactions with thermoplastic polymers.Firstly,a series of thioether-based diblock polymers with different molecular weights were prepared by Reversible Addition-Fragmentation Chain Transfer polymerization?RAFT?,and then combining with noble metal Silver bis?trifluoromethanesulfonamide??Ag?NTf₂??to prepare poly?methyl methacrylate?-b-Poly?methyl thioethyl acrylate-co-butyl acrylate?-silver?PMMA-b-P?BA-co-MTEA?-Ag?hybrid polymers.Two ways of crosslinking inside the polymer are involved:?1?There is microphase separation in the block polymer,and the glassy PMMA domain acts as a physical crosslinker for the polymer continuum;?2?The silver-thioether coordination interaction in polymers acts as a chemical crosslinker causing polymers to form crosslinked network structures.The Ag-thioether Reversible coordination hybrid polymers have excellent mechanical properties,the strain at break can reach 1000%,and the stress at break can reach 1-5 MPa.Meanwhile,the polymers exhibit good self-healing ability and the recovery rate can reach 80%.In addition,the polymers have the thermal processing properties of thermoplastic materials and can be prepared into desired shapes by thermal processing.Secondly,based on the study of Ag-thioether reversible coordination hybrid polymers,the cheaper and more versatile copper?I?-thioether reversible coordination hybrid block polymers?poly?methyl methacrylate?-b-Poly?methyl thioethyl acrylate-co-butyl acrylate?-silver?PMMA-b-P?BA-co-MTEA?-Ag??with dual-crosslinked structure were prepared.Those polymers exhibite excellent mechanical properties,and the strain at break can be up to 700%,and the breaking strength can be up to 7.5 MPa.At the same time,the polymers also have excellent self-healing properties?recovery rate up to 30%?and thermal processing properties.Notably,the films of copper?I?–thioether block polymers exhibited very fast responses toward hydrochloric acid vapor and hydrogen peroxide solution by color changing.The irreversible sensory properties of these hybrid materials make them suitable for applications in industries as flexible membrane sensors and disposable oxidant testing plastics.