Reversible Addition–Fragmentation Chain Transfer Polymerization of Vinyl Chloride

Abstract

Controlled/“living” radical polymerization (CLRP) of vinyl chloride (VC) via the reversible addition–fragmentation chain transfer (RAFT) process is reported for the first time. The cyanomethyl methyl­(phenyl)­carbamodithioate (CMPCD) was found to be an efficient RAFT agent enabling the CLRP polymerization of VC monomer under certain experimental conditions. Two different radical initiators, having very distinct half-life times at room temperature, were employed in this study. The kinetic studies of RAFT polymerization of VC show a linear increase of the molecular weight with the monomer conversion and the lowest polydispersity (PDI) ever reported for poly­(vinyl chloride) (PVC) synthesized with CLRP method (PDI ∼ 1.4). The resulting PVC was fully characterized using the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), 1H nuclear magnetic resonance spectroscopy (1H NMR), and gel permeation chromatography (GPC) techniques. The 1H NMR and MALDI-TOF-MS analysis of PVC prepared via RAFT polymerization method have shown the absence of structural defects and the presence of chain-end functional groups. The “livingness” of the PVC was also confirmed by a successful reinitiation experiment. The suitability of the RAFT agent was also confirmed via high-level ab initio molecular orbital calculations.

Synthesis and Reactivity of Mononuclear Iron Models of [Fe]‐Hydrogenase that Contain an Acylmethylpyridinol Ligand

“…The series of less intensive peaks (Figure 9b) cannot be ascribed to any chain‐end structures expected. The presence of these peaks is probably due to the occurrence of the fragmentation during ionization in the MALDI–TOF MS analysis, as reported by other authors 36–41…”

Solution and aqueous miniemulsion polymerization of vinyl chloride mediated by a fluorinated xanthate

“…16 CLRP of VC via RAFT method by using dithiocarbonate cyanomethyl methyl(phenyl)carbamodithioate as RAFT agent and tetrahydrofuran (THF) as sovlent. 23 Living character of this RAFT polymerization was confirmed by the kinetics and chain extension of PVC macromolecular chain transfer agent with VC monomer. As the industrial polymerizations of VC are generally carried out in water, development of VC RAFT (co)polymerization in an environmentally benign solvent will be of academic and industrial importance.…”

Living Radical Polymerization by the RAFT Process – A Third Update

“…[21] In recent work, it has been used for controlling the polymerization of VAc [366] and VC. [529] Further details of RAFT polymerization using 'switchable' RAFT agents that can be switched to offer good control over polymerization of both MAMs and LAMs and a route to poly-MAM-b-polyLAM has been reported. [530][531][532] [310] MA [182] BA [182] 348 [311] B/AN [312] 73 S S * St [313,314] BD [315] NIPAm [316] St/MAH [313] St [315] St-b-(St/BD) [314,315] St-b-(St/MAH) [313] ((St/MAH)-b-St) [313] 74 S S * MAA/EGDMA [291] 75 poly(3-hexylthiophene) macro-RAFT agent…”

“…A [522] St [522] 257 [539] St [539] St-b-MA [539] St-b-AN [539] St-b-NIPAm [539] 258 N S S CN A* VAc [366] VC [529] …”