Toward Biodegradable Chain-Growth Polymers and Polymer Particles: Re-Evaluation of Reactivity Ratios in Copolymerization of Vinyl Monomers with Cyclic Ketene Acetal Using Nonlinear Regression with Proper Error Analysis

Abstract

Recycling and biodegradability of chain-growth polymers is an important and growing topic. Introducing ester bonds in polymers via cyclic ketene acetals (CKAs) is an interesting route to create (bio)­degradability. Incorporation of CKA monomers is controlled by reactivity ratios. Reactivity ratios of different CKA/vinyl monomer systems published in the literature were re-evaluated with the nonlinear least-squares method, taking into account the error in the 1H NMR measurements of monomer fractions in copolymers. This study confirms that the nonlinear least-squares method should be used instead of Fineman–Ross or Kellen–Tudos methods. Re-evaluated values suggest that reactivity ratios of CKA/vinyl monomer systems follow a family-like behavior.

Connecting polymer synthesis and chemical recycling on a chain-by-chain basis: a unified matrix-based kinetic Monte Carlo strategy

“…One way to improve the biodegradability of vinyl polymers is the insertion of chemically less stable ester linkages in the polymer backbone during the synthesis, ideally each 10 th or 20 th monomer unit. 27,28 Upon hydrolyis (Figure 5(b)) such (co)polymers chains are converted into functional oligomers which can either be upcycled to new polymer products or biodegraded by bacteria. However, as vizualized in Figure 10(b) (fMMA,0=fMDO,0=0.5), these ester linkages are not included exactly every 10 th or 20 th unit in the backbone.…”

“…the development of vinyl pseudo-homopolymers with (bio)degradable ester linkages has been explored through radical ROP of vinyl monomers with cyclic ketene acetal monomers (CKA's). 26,27 In the context of next-generation PMMA synthesis one can put forward the polymerization of MMA and 2-methylene-1,3dioxepane (MDO). The (bio)degradation proceeds in two distinct stages, with in the first stage hydrolysis of the ester groups resulting in vinyl oligomer formation and in the second stage the biodegradation of these oligomers by bacteria.…”

“…The (bio)degradation proceeds in two distinct stages, with in the first stage hydrolysis of the ester groups resulting in vinyl oligomer formation and in the second stage the biodegradation of these oligomers by bacteria. 27,28 As for the conventional thermochemical recycling it is essential to know the location of the degradable functional groups in the vinyl-like chains as they are triggering the degradation. Recent work of Gigmes et al 26 already highlighted the need of suited reactivity ratios under batch conditions.…”

Prediction of the Oligomer Distribution after Degradation of (Co)Polymers with Inserted Break Points

“…[ 4–6 ] In our group we are working on the cyclic ketene acetal family of monomers (CKA) with 2‐methylene‐1,3‐dioxepane (MDO) as the most frequently studied monomer. [ 7–9 ] These monomers insert ester bonds in the polymers produced by radical polymerization through radical ring‐opening polymerization.…”

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

“…Even though their rROP has been known since the eighties,v ery few mechanistic studies have been performed and no clear structure-reactivity relationships have been established for those monomers. [10,32,33] Indeed, the major drawback of this family of monomer is related to the competition between the ring-opening process and the undesired direct vinyl propagation that leads to polyacetal (Scheme 2). Thus,f or the majority of CKA monomers,t he resultant polymer is arandom copolymer of ester and acetal units.…”