Synthesis of head-to-tail and head-to-head poly(propylene-alt-methyl methaerylate)s via anionic polymerization of methyl 2,4-alkadienoates. 2. Synthesis and thermal properties
A. Takasu et al., Synthesis of head-to-tail and head-to-head poly(propylene-alt-methyl methaerylate)s via anionic polymerization of methyl 2,4-alkadienoates. 2. Synthesis and thermal properties, MACROMOLEC, 34(18), 2001, pp. 6235-6242
Two methyl 2,4-alkadienoates, i.e., methyl 2,4-dimethyl-2,4-pentadienoate (
MDMPd) and methyl 2-methyl-2,4-hexadienoate (MMHd), were polymerized using
t-BuLi or t-BuMgCl as the initiator in toluene. H-1 and C-13 NMR and IR ana
lyses demonstrated that complete trans 1,4-addition was achieved in the pol
ymerizations. Addition of methylaluminum bis(2,6-di-tert-butyl-4-methylphen
oxide) produced polymers with relatively narrow molecular weight distributi
ons (M-w/M-n = 1.1-1.2) at 0 degreesC. Hydrogenation of poly(MDMPd) and pol
y(MMHd) with p-toluenesulfonylhydrazide produced head-to-tail (H-T) and hea
d-to-head (H-H) poly(propylene-alt-methyl methacrylate)s, respectively. The
thermal properties of H-H poly(propylene-alt-methyl methacrylate) and H-T
poly(propylene-alt-methyl methacrylate) were different. Differential scanni
ng calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) measurements i
ndicated that both the H-T and H-H copolymers were amorphous. The glass tra
nsition temperature of the H-H copolymer is approximately 30 degreesC highe
r than that of the H-T copolymer. According to thermogravimetric (TG) analy
sis, the H-H copolymer is more thermally stable than the H-T copolymer.