100th Anniversary of Macromolecular Science Viewpoint: Degradable Polymers from Radical Ring-Opening Polymerization: Latest Advances, New Directions, and Ongoing Challenges

Towards nanoparticles with site-specific degradability by ring-opening copolymerization induced self-assembly in organic medium

“…37 In the past few years, rROP of CKAs has made significant progress from both fundamental 38,39 and applicative [40][41][42][43] perspectives. 44 The rROPISA process was illustrated by the copolymerization in heptane between benzyl methacrylate (BzMA) and two different CKAs, either 2-methylene-4-phenyl-1,3-dioxolane (MPDL) or 5,6-benzo-2-methylene-1,3-dioxepane (BMDO), from a poly(lauryl methacrylate) (PLMA) macro-chain transfer agents (CTAs). 31 It led to stable diblock copolymer nanoparticles with narrow particle size distribution and tunable amounts of ester groups in the core block, and thus adjustable degradation rates of the copolymers under accelerated hydrolytic degradation conditions.…”

Synthesis of degradable and chemically recyclable polymers using 4,4-disubstituted five-membered cyclic ketene hemiacetal ester (CKHE) monomers

“…Fig. 1c and d show the 13 C NMR spectra (CDCl 3 ) of DMDL and PDMDL, respectively. Through the polymerization, the vinyl carbon (b) of DMDL (Fig.…”

“…Degradable polymers nd numerous applications in, e.g., drug delivery, packaging, and agriculture elds. [1][2][3][4][5][6][7][8][9] In the eld of radical polymerization, degradable polymers are prepared via radical ring-opening polymerization of cyclic ketene acetals (CKAs), [10][11][12][13][14] for example, gaining signicant attention. Examples of CKA are 2-methylene-1,3-dioxepane (MDO), [15][16][17][18][19][20][21][22][23] 5,6-benzo-2methylene-1,3-dioxepane (BMDO), [24][25][26] and 2-methylene-4phenyl-1,3-dioxolane (MPDL) [27][28][29][30] (Scheme 1).…”

“…The obtained homopolymers and copolymers have been exploited for applications in, e.g., packaging, agrochemical, personal care, and biomedical applications. [10][11][12][13] In the present work, we are motivated to use cyclic ketene hemiacetal esters (CKHEs) (Scheme 2) as alternatives to CKAs. A Scheme 1 CKA monomers and their possible polymerization mechanisms.…”

Vinyl Copolymers with Faster Hydrolytic Degradation than Aliphatic Polyesters and Tunable Upper Critical Solution Temperatures

“…5,6 Among them, 2-methylene-1,3-dioxepane (MDO), 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) or 2-methylene-4-phenyl-1,3-dioxolane (MPDL) are by far the most used ones. 7,8 For example, copolymerization of common vinyl monomers with CKAs by conventional free-radical polymerization or RDRP has received tremendous attention 8 to design degradable materials for applications in drug delivery, [9][10][11] marine antibiofouling technologies, [12][13][14] gene/DNA transfection, 15 tissue engineering 16 and others. 17,18 Yet, despite promising proofs of concepts, important limitations still stand, such as the poor hydrolytic degradation of CKA-containing copolymers in physiological conditions, which still cannot compete with the most popular polyesters like poly(lactic-co-glycolic acid) (PLGA) or even poly(lactic acid) (PLA).…”