Development Of New Polymerizations Based On C-C And C-N Triple-Bond Building Blocks

Alkynes have been used as monomers for the high reactivity of their carbon-carbon triple bonds.Developing the polymerization methodologies of alkyne and heteroatom-containing monomers to construct the polymers with C–X（X = N,O,S…）bonds not only enriches the structures of polymers,but also extends the function of materials.Hitherto,azide-alkyne and thiol-yne click polymerization have attracted wide attentions.Many linear and hyperbranched polymers have been prepared and used in the fields of medicine,biology and photoelectricity.The hydroxyl and amino monomers could generate C–O and C–N bonds with alkynes,and are more stable,safer and less-poisonous comparing to azide and thiol monomers.However,the works based on polymerizations of hydroxyl-alkyne and amino-yne are rarely reported.So it is of significance to develop the polymerizations of hydroxyl/amino and alkyne monomers.C–H activation as a powerful organic synthetic tool has been widely used in organic synthesis,bioconjugation and the preparation of medicine.But the polymerizations based on C–H activation,especially C（sp³）–H activation are rarely reported.In this thesis,the new polymerization mothodologies based on hydroxyl-alkyne,amino-yne and C（sp³）–H activation about triple monomers were explored,and functional polymers were prepared as well.Firstly,the polyhydroalkoxylation of aromatic diynes was successfully developed in the presence of a superbase of phosphazene base（t-BuP₄）.A series of soluble and regioregular antiMarkovnikov additive poly（vinyl ether）s with high molecular weights（M_w up to 40 600）were obtained in excellent yields（up to 99%）.All the polymers are thermally and morphologically stable.The tetraphenylethene（TPE）-containing poly（vinyl ether）s could show unique aggregation-enhanced emission（AEE）characteristics,whose aggregates and solids could be used for explosive detection with superamplication quenching effect.The poly（vinyl ether）s are degradable under acidic conditions.Thus,this work not only established a new polymerization but also generated series functional polymeric materials that are potentially applicable in optoelectronic and biomedical fields.What’s more,the polymerization of internal alkyne and alcohol monomers catalyzed by Pd（0）/benzoic acid through C（sp³）–H activation was well-established.Regio-and stereo-regular functional E-poly（allylic ether）s were prepared in excellent yield（up to 98%）with high molecular weight（M_w up to 21 000）and well-defined structure.The polymerization enjoys general applicability of various monomers including primary and secondary alcohols,and no byproduct generated from the polymerization,demonstrating high atom economy.These polymers have good solubility and film-forming ability.Their thin films display high refractive indices(n_632.8 = 1.6840)and narrow optical dispersions（D′ down to 0.0009）.The poly（allylic ether）s with TPE group could show unique AEE characteristics and be used in photo-pattern.The polymerization of internal alkynes and secondary amino monomers catalyzed by Pd（0）/benzoic acid through C（sp³）–H activation was exploited.A series of functional poly（allylic tertiary amine）s with regio-and stereo-regularity were prepared in excellent yield（up to 98%）with high molecular weight（M_w up to 23 400）and narrow D.The polymers have high RI of 1.8842-1.6530 at the wavelengths of 400 – 1700 nm.The poly（allylic tertiary amine）s with TPE group display unique AEE characteristics.The dilute THF solutions of these polymers could absorb UV at the wavelength of 280-400 nm well,showing the potential in ultraviolet protection.Finally,the azide-acetonitrile click polymerization（AACP）catalysted by Cs₂CO₃ in DMSO/H₂O was explored.The poly（5-amino-1,2,3-triazole）s were prepared in high yield（98%）with high molecular weight（M_w up to 204 000）via C（sp³）–H activation.Not only the aromatic azide but also the alkyl azide could be used in the AACP,showing the generality of the polymerization.