Photochemical [2 + 2] Cycloaddition Enables the Synthesis of Highly Thermally Stable and Acid/Base-Resistant Polyesters from a Nonpolymerizable α,β-Conjugated Valerolactone.

We report a simple strategy to transform a nonpolymerizable six-membered α,β-conjugated lactone, 5,6-dihydro-2 H -pyran-2-one ( DPO ), into polymerizable bicyclic lactones via photochemical [2 + 2] cycloaddition. Two bicyclic lactones, M1 and M2 , were obtained by the photochemical [2 + 2] cycloaddition of tetramethylethylene and DPO . Ring-opening polymerization (ROP) of M1 and M2 catalyzed by diphenyl phosphate (DPP), La[N(SiMe 3 ) 2 ] 3 , and 1- tert -butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris (dimethylamino) phosphoranylide-namino]-2λ 5 , 4λ 5 -catenadi(phosphazene) ( t Bu-P 4 ) were conducted. M1 is highly polymerizable, either DPP or La[N(SiMe 3 ) 2 ] 3 could catalyze its living ROP under mild conditions, affording the well-defined PM1 with a predictable molar mass and low dispersity. M2 could only be polymerized with t Bu-P 4 as the catalyst, also generating the same polymer PM1 . PM1 has high thermal stability, with a T d,5% being up to 376 °C. Ring-opening copolymerization (ROcP) of M1 and δ-valerolactone (δ-VL) catalyzed by La[N(SiMe 3 ) 2 ] 3 afforded a series of random copolymers with enhanced thermal stabilities. Both PM1 and the copolymer containing 10 mol % M1 exhibited excellent resistance to acidic and basic hydrolysis. Our results demonstrate that direct photochemical [2 + 2] cycloaddition of α,β-conjugated valerolactone is not only a strategy to tune its polymerizability, but also allows for the synthesis of highly thermally stable aliphatic polyesters, inaccessible by other methods.