CuCl/Ph3P-catalyzed multicomponent polymerization of CO2 to prepare functional poly(alkynoate)s and fused heterocyclic polymers under atmospheric pressure and near ambient temperature

Abstract The conversion of CO2 into polymeric materials is a straightforward strategy for stable long-term carbon fixation and possible carbon revitalization if introduced with functionality. Yet, such conversion has long been compromised by expensive catalysts and harsh conditions due to the inactivity of CO2. In this work, we establish an efficient CuCl/Ph3P-catalyzed multicomponent polymerization of CO2, diynes, and dihalides under mild conditions of rt—60 °C and atmospheric pressure. The polymerization shows great monomer universality, producing diverse poly(alkynoate)s in yields up to 99% with weight-average molecular weights up to 94 000. Poly(alkynoate)s containing tetraphenylethylene (TPE) moieties show typical aggregation-induced emission features, and can specifically and sensitively detect Fe3+ ions with a low limit of detection (LOD) of 1.79 × 10−7 M. Notably, owing to lots of activated triple bonds in the main chain of poly(alkynoate)s, N-hydroxyphthalimide derivatives are facilely introduced into this polymerization in situ to establish a ‘one-pot, two-step, four-component’ tandem polymerization to produce poly(3a-hydroxyisoxazolo[3,2-a]isoindol-8(3aH)-ones)s (PHIIOs) with 100% grafting ratio. Interestingly, the fused heterocyclic PHIIO containing TPE could realize the specific and sensitive detection of Ag+ ions with a low LOD of 4.90 × 10−6 M. This work not only innovatively achieves the direct chemical fixation of CO2 into functional polymeric materials under relatively low temperatures with low-cost catalysts, but also obtains a series of polymers with controllable structure-function, which can be realized for a wide range of applications.