By Tsutomu Yokozawa, Naomi Ajioka, Akihiro Yokoyama (auth.), Shiro Kobayashi (eds.)
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Additional resources for New Frontiers In Polymer Synthesis
Also studied the preparation and ring-opening polymerization of cyclic oligomeric esters . 5–10% of DABCO or quinuclidine and triethylamine making up the remainder of the organic base. The diols and acid chlorides were simultaneously slowly added to a solution of the amines (pseudo-high dilution conditions). The yield of the cyclic oligomers was 49–85%. Ring-opening polymerization using tin or titanate catalysts afforded high molecular weight polyesters within minutes. For example, complete polymerization of PBT cyclic oligomer was able to be achieved at 180– 200 ◦ C (the mixture of PBT cyclic oligomers began to melt at about 140 ◦ C and was completely molten at 160–190 ◦ C), signiﬁcantly below the polymer’s melting point of 225 ◦ C, and with molecular weights as high as 445 000 (Scheme 51).
1 Transfer of Reactive Species Speciﬁc elements can transmit a reactive species, stemmed from an initiator, with elimination of small molecules. The ﬁrst category is insertion of the monomer to the terminal M–F bond (Scheme 69). The second one is transfer of the cationic species (Scheme 70). Scheme 69 Scheme 70 The polymerization of dimethylsulfoxonium methylide (17) initiated by trialkylborane, which Shea et al. developed, is classiﬁed as the ﬁrst category. Propagation involves insertion of 17 into the terminal C–B bond with elimination of DMSO.
Both the resonance effect and inductive effect of the nucleophilic site on the reactivity of the electrophilic site at the para and meta positions of the monomer are applicable, respectively. 1 Resonance Effect (Polymerization of p-Substituted Monomers) In polycondensation of some p-substituted monomers, the polymer end group was reported to become more reactive than the monomer, but the polycondensation did not precisely control the molecular weight of polymer within narrow molecular weight distributions because of the insolubility of the polymers and the contamination of step-growth condensation polymerization [294–299].
New Frontiers In Polymer Synthesis by Tsutomu Yokozawa, Naomi Ajioka, Akihiro Yokoyama (auth.), Shiro Kobayashi (eds.)