Stereochemistry of Acrylate Polymerization in Toluene Using n-BuLi

Structurally controlled polymerizations of methacrylates and acrylates

“…74±76 The isotacticity increased with increasing polymerization temperature, and the poly(MA) obtained at 0°C, was 93% isotactic in diads. 76 The polymerization was not living even at À78°C.…”

“…76 Polymerization of primary acrylates such as ethyl (EA) and butyl (n-BuA) acrylates with t-C 4 H 9 Li/ MeAl(ODBP) 2 in toluene at À60°C gave atactic polymers. The MWDs were relatively broad, probably due to occasional end cyclization during polymerization (Table 6).…”

Stereospecific radical polymerization of fluoroalkyl acrylates

“…Because the poly(HFiPA) and poly(PFtBA) were insoluble in chloroform, a mixture of chloroform-d and 1,1,2-trifluoro-1,2,2-trichloroethane was employed as the solvent for the NMR measurements. According to the previous assignments made for other polyacrylates, 2,6 the peaks at ␦ 2.5 [poly(TFEA)] or 2.7 [poly(HFiPA) and poly(PFtBA)] and 2.4 -1.5 ppm were assigned to the main-chain methine and methylene, respectively. The methylene proton peaks are split into three parts because of the mainchain stereochemistry, which is assigned to two meso and one racemo signal as shown in the figure.…”

“…2,6 Figure 1 shows the 1 H NMR spectra of poly(TFEA), poly(HFiPA), and poly(PFtBA) obtained in this work. Because the poly(HFiPA) and poly(PFtBA) were insoluble in chloroform, a mixture of chloroform-d and 1,1,2-trifluoro-1,2,2-trichloroethane was employed as the solvent for the NMR measurements.…”

Salicylaldiminato-based cobalt(III)-, iron(III)-, and chromium(III)/methyl aluminoxane catalyst systems for polymerization of t-butyl acrylate

“…Various stereospecific polymerizations using ZieglerNatta [38], metallocene [39], anionic [40] or radical polymerization [7] have been reported earlier. Highly isotactic poly(t-BA) has been synthesized using a chiral zirconocene ([m] diad 83%) [39] or n-BuLi in the presence of LiOH ([m]-diad 85%) [41]. The highest syndiotactic diad value reported is with [r] = 63% for poly(t-BA) which was prepared by radical polymerization at low temperature [42] and a triad syndiotacticity [rr] of about 40% has been reported for anionic polymerization with diphenylmethyllithium as an initiator [43].…”