Radical polymerization of methyl trans‐β‐vinylacrylate

Abstract

SYNOPSISMethyl trans-P-vinylacrylate (MVA) undergoes radical polymerization with a,a'-azobis(isobutyronitri1e) (AIBN) in bulk and solution. The polymer obtained consists of 85% trans-l,4 and 15% truns-3,4 units. Poly(MVA) (PMVA) is readily soluble in common organic solvents, but insoluble in n-hexane and petroleum ether. PMVA exhibits a glass transition at 6"C, and loses no weight up to 300°C in nitrogen. The kinetics of MVA homopolymerization with AIBN was investigated in benzene. The rate of polymerization (R,) can be expressed by R,, = k[AIBN]o.5[MVA]'.o, and the overall activation energy has been calculated to be 94 kJ/mol. The propagation radical of MVA at 80°C was detected by ESR spectroscopy, which indicated that the unpaired electron of the propagating radical was completely delocalized over the three ally1 carbons. Furthermore, the steady-state concentration of the propagating radical of MVA a t 60°C was determined by ESR spectroscopy, and the propagation rate constant (kp) was calculated to be 1.25 X 10' L/mol.s. Monomer reactivity ratios in copolymerization of MVA ( M 2 ) with styrene ( M , ) are r1 = 0.16 and r2 = 4.9, from which Q and e values of MVA are calculated as 4.2 and -0.32, respectively. 0 1995 John Wiley & Sons, Inc.

Stereospecific Polymerization of Dialkyl Muconates through Free Radical Polymerization: Isotropic Polymerization and Topochemical Polymerization

“…Butadienes. The trans-1,4-polymerizations through radical polymerization in isotropic media have also been reported for several other butadiene derivatives, for example, 2,4-pentadienoic acid and its esters [25][26][27][28] and 2,4-hexadienoates (alkyl sorbates). 28 The preferred trans-1,4-propagation of these diene monomers is accounted for by similar conformations of the propagating radicals depicted in Chart 3, where X is CO 2 R, CH 3 , or H. Thus the stereoselectivity is determined by the conformation of the propagating chain end during the free radical polymerization of the muconates and other related substituted butadienes.…”

Poly(isoprenecarboxylates) from Glucose via Anhydromevalonolactone

“…( Z )-3-Methylpenta-2,4-dienoic acid (or isoprenecarboxylic acid, 6-H , Figure ) has been prepared from anhydromevalonolactone ( 3 ). , However, we can find no reports of the polymerization of 6-H or any of its esters ( 6-R ). In contrast, 4-methylpenta- 2,4-dienoate ( 7 ), sorbic acid esters ( 8 ), pentadienoates ( 9 ), and 3-methylene-4-pentenoates ( 10 ) have all been polymerized under one or more of radical, anionic, or cationic conditions. Light-induced topochemical polymerizations of the related dienoate salts 11a – d have also been described .…”

“…For example, methyl penta-2,4-dienoate (9 or β-vinyl acrylate) has been radically polymerized to give a homopolymer comprising an 85:15 mixture of backbone repeat units arising from competitive 1,4-vs 1,2-addition. 7 Finally, we also note the recent work of Boday and co-workers, who polymerized "methylidenelactide" 10 and pointed out that this compound was one of only a few examples of acrylate-like monomers in which all atoms are bioderived (the others arising from itaconic or levulinic acid or via bioengineered routes to acrylic acid from sugars). 11 We report here the preparation of a series of esters derived from 6-H and their radical polymerization to poly-(isoprenecarboxylates).…”

Polymerization of 1,3-Dienes with Functional Groups. 1. Free-Radical Polymerization of 2-Triethoxymethyl-1,3-butadiene

“…To our knowledge, 1,3-butadiene derivatives having a carboxyl group and its ester at the 2 position have not been isolated whereas its isomer, ethyl 2,4-pentadienoate, was synthesized and polymerized under ordinary reaction condition. 3 2-Cyano-1,3butadiene is reported to dimerize upon heating under polymerization conditions. 4 These reactions are presumably due to the high tendency of the reactants to form Diels-Alder dimers, which is caused by the electronwithdrawing character of the functional group.…”

“…On the other hand, some functional groups, especially those substituted at the 2 position of the butadienyl frame, decrease the stability of the monomer. To our knowledge, 1,3-butadiene derivatives having a carboxyl group and its ester at the 2 position have not been isolated whereas its isomer, ethyl 2,4-pentadienoate, was synthesized and polymerized under ordinary reaction condition . 2-Cyano-1,3-butadiene is reported to dimerize upon heating under polymerization conditions .…”