Polymérisation du chloroformiate de vinyle et de ses dérivés

Abstract

Requ le 19 juin 1984Cet article esr rle'die' a la mkmoire de Monsieur Li Xiao-Bni SYLVIANE BOIVIN, PATRICK HEMERY et SYLVIE BOILEAU. Can. J . Chem. 63, 1337Chem. 63, (1985 La polymCrisation radicalaire du chloroformiate de vinyle a CtC Ctudiee dans le chlorure de mtthylkne a 35"C, avec le peroxydicarbonate de dicyclohexyle comme amorceur. Dcs mesures cinetiques ont Ct C effectuCes par dilatomktrie dans des appareils entikrement scellts sous vide pousse. L'ordre de la rkaction de polymCrisation par rapport B la concentration en monomkre est Cgal a I et celui relatif i la concentration en amorceur est Cgal B 0,5.Par ailleurs, des polymkres nouveaux ont CtC prCparCs soit par polymCrisation radicalaire de monomeres dCrivCs du chloroformiate de vinyle, soit par modification chimique du polychloroformiate de vinyle par des amines, des alcools, des thiols, des acides carboxyliques, KCN . . . , par catalyse par transfert de phase. La structure de ces polymkres ainsi que leur comportement thermique ont Ct C examinks. SYLVIANE BOIVIN, PATRICK HEMERY, and SYLVIE BOILEAU. Can. J . Chem. 63, 1337Chem. 63, (1985. The free-radical polymerization of vinyl chloroformate has been studied in methylene chloride at 3S°C using dicyclohexyl peroxydicarbonate as initiator. Kinetic measurements performed by dilatometry under high vacuum have shown that the reaction order in monomer is equal to one whereas that in catalyst is equal to 0.5.New polymers have been prepared either by free-radical polymerization of monomers derived from vinyl chloroformate or by chemical modification of poly(viny1 chloroformate) with amines, alcohols, thiols, carboxylic acids. KCN . . . using phase transfer catalysis. The structure of these polymers as well as their thermal behaviour have becn studied.

Vinyl carbonates, vinyl carbamates, and related monomers: synthesis, polymerization, and application

“…31 Boileau et al polymerized some vinyl carbonates (2,4,5) using common thermal initiators like azobisisobutyronitrile (AIBN), BP, and dicyclohexyl peroxydicarbonate (DCPD). [32][33][34][35] These results are hardly comparable as the experiments were carried out under different conditions. However, it was pointed out that low temperature initiator DCPD is the most suitable initiator for the vinyl monomers giving polymers with higher molecular weights and better yields and therefore should be favored over BP and especially AIBN, which failed to show satisfying results in some cases.…”

“…From the class of O-vinyl thiocarbonates, only S-phenyl-Ovinyl thiocarbonate was synthesized 60,62 and polymerized. 35,37 Polymerization initiated with AIBN proceeded to higher yield than was the case for phenyl vinyl carbonate (4). Poly(O-vinyl thiocarbonates) seem to decompose at lower temperature than poly(vinyl carbonates/carbamates).…”

“…77 Boileau et al obtained high molecular weight poly(vinyl carbamates) in good yields by polymerization of a series of vinyl carbamates (25-28) using common thermal initiators like AIBN and DCPD. [33][34][35]78 Though vinyl carbonates gave low molecular weight polymers in poor yields when initiated with AIBN, polymerization of vinyl carbamates proceeded smoothly under the same conditions. From small sample data the authors concluded that the thermal stability of the polymers decreases in the following order: poly(O-vinyl carbamates) > poly(vinyl carbonates) > poly(O-vinyl thiocarbonates).…”

“…28,29 Boileau's group then continued these studies over many years. 32,34,35,78,[86][87][88] For the polymerization they used more common thermal initiators like peroxydicarbonates, peroxides and AIBN. It was shown that high molecular weight poly(vinyl carbonates/carbamates) could be obtained by post-treatment of poly(VOC-Cl) with alcohols or amines with a degree of substitution close to 100%.…”

New Sterically Stabilized Vesicles Based on Nonionic Surfactant, Cholesterol, and Poly(Ethylene Glycol)-Cholesterol Conjugates

“…Monomethoxypoly(ethylene glycol) cholesteryl carbonate (M-PEG-Chol) has been synthesized in one step by the reaction of M-PEG on CholCl, using moderate phase transfer catalysis conditions previously described for the nucleophilic substitution of poly(vinyl chloroformate) by phenol (Boivin et al, 1983(Boivin et al, , 1985(Boivin et al, , 1988. In a typical experiment, 2.5 mmol of polymer dissolved in 10 ml CH 2 Cl 2 was added dropwise to a magnetically stirred mixture containing 2.5 mmol of CholCl in 20 ml CH 2 Cl 2 , 0.125 mmol of Bu 4 N ϩ Cl Ϫ (5 mol% of each reagent), and 3.75 mmol of NaOH in water (33 weight %) as HCl scavenger.…”