On the polymerization reactivity of fluorinated vinyl monomers

Abstract

The polymerization reactivities of α,β,β‐trifluorovinyl compounds (CF2=CF—R) and α‐trifluoromethylvinyl compounds (CH2=C(CF3)—R) are discussed since these monomers have scarcely been investigated and hardly yielded corresponding homopolymers, although tetrafluoroethylene and chlorotrifluoroethylene have been studied under radical polymerization conditions. In the case of α,β,β‐trifluorostyrene, a homopolymer is obtained in low yields by anionic polymerization and it is concluded that the reaction takes place without any side reactions once the reaction has started, since simple addition polymerization is observed and the molecular weight distribution is very narrow. Anionic polymerization of hexafluorobuta‐1,3‐diene is successfully achieved by the addition reaction of living end to the 2‐carbon of hexafluorobuta‐1,3‐diene followed by isomerization to produce excellently high thermostable polymers. ω‐Trifluorovinyloxyfluoroalkyl alcohol produces a polyether via a polyaddition reaction under anionic conditions. The homopolymers of α‐trifluoromethylacrylates are quantitatively obtained under anionic polymerization conditions. α‐Trifluoromethylstyrene derivatives are likely to polymerize under radical conditions, but are not well‐studied. The radical polyaddition reaction of perfluoroisopropenyl esters in 1,4‐dioxane, diethyl ether or 1,2‐dimethoxyethane yields the polymers possessing the solvent moiety in the polymer main chain, respectively. It is clearly demonstrated that each fluorinated vinyl monomer discussed in this article demands its own reaction conditions. Therefore, more experimental data on the polymerization of these individual monomers is needed, including research on developing the reactions discovered in the organofluorine chemistry field to the preparation of polymers.

Novel fluorinated polymers by radical polyaddition: Inspiration and progress

“…3 The investigation on the anionic polymerization reactivity of fluorinated monomers such as 1,2,2-trifluorostyrene [CF 2 ACFOC 6 H 5 ], ␣-trifluoromethylstyrene [CH 2 AC(CF 3 )OC 6 H 5 ], 1,4-and 1,2-addition polymerization of hexafluoro-1,3-butadiene [CF 2 ϭCFO CFACF 2 ], and hexafluoro-1,2-epoxypropane is still interesting because no appropriate answers have been obtained under radical reaction conditions. [2][3][4] The study on the radical polyaddition started from the new findings in 1993 on the way of the investigation on the anionic polymerization reactivity of fluorinated vinyl monomers. A senior student in the undergraduate school did not pass over a trace amount of the addition product of BPFP with THF.…”

“…21,22 We discussed examination of the polymerization reactivity of BPFP and came to the conclusion that the study on the polymerization of fluorinated vinyl monomers was the role of my laboratory because it had a long history of investigation on their polymerization reactivity, especially in the field of anionic polymerization. [2][3][4] (1)…”

“…Trifluorovinyl [CF 2 ACFO] derivatives except tetrafluoroethylene and chlorotrifluoroethylene have scarcely yielded corresponding homopolymers with radical and anionic initiators although several hydrocarbon analogs are easily polymerized under conventional polymerization conditions.…”

Synthesis of novel fluorinated polymers: facile carbon–carbon bond formation aided by fluorine substituents

“…A termination reaction may take place, as a-trifluoromethylstyryl anion was not observed to react with other vinyl monomers in a study on anionic copolymerizations with hydrocarbon analogs. 2,3 The inability of the a-trifluoromethylstyryl anion to serve as a propagating living end may be due to the high electron-withdrawing effect of fluorine substituents or the abstraction of fluorine by a carbanion as a side reaction. The polymerization profile of a-difluoromethylstyrene (CH 2 ¼C(CHF 2 )-C 6 H 5 ) was found to be similar to that of a-trifluoromethylstyrene.…”

“…2,3 The e-values of these monomers are generally larger than those of hydrocarbon analogs, as summarized in Table 1. Radical addition reactions of fluorinated vinyl monomers with cyclic ethers and alcohols have also been reported as these vinyl compounds are generally good radical acceptors.…”