Functionalization and Applications of Telechelic Oligopropylenes:  Preparation of α,ω-Dihydroxy- and Diaminooligopropylenes

Abstract

Difunctional propylene oligomers which may be used for preparing novel block copolymers were synthesized from telechelic oligomers containing two terminal vinylidene double bonds (PP-TVDs). The PP-TVDs were converted to α,ω-dihydroxyoligopropylenes (PP-OHs) in good yield by hydroboration with BH3·THF or 9-BBN, followed by oxidation. Multiple NMR signals from the α-methylene protons and the β-methyl carbons were ascribed to epimers formed during the hydroboration. α,ω-Diaminooligopropylene (PP-NH2) was prepared from PP-OH via tosylate and azide. Copolymerizations of PP-NH2 with terephthalic acid were carried out, and copolymers with molecular weights larger than that of the parent polymer were obtained.

Preparation of telechelic oligomers by thermal degradation of propylene copolymers

“…The variable f TVD in Table 1 represents the average number of terminal vinylidene groups per molecule and is discussed below. 13 C NMR spectra of the nonvolatile oligomers obtained by controlled thermal degradation of poly(propylene-ran-ethylene) are shown in Figs. 5 and 6, and the 1 H spectrum in Fig.…”

“…Moreover, we have reported a mechanism for thermal degradation accounting for the structure of products obtained from polyisobutylene [10] and polystyrene [11]. We have also reported its application to the conversion of the terminal double bond to functional groups and copolymerization of the telechelic oligomer with terminal double bond(s) obtained from polypropylene [12][13][14].…”

“…13 C NMR spectrum of nonvolatile oligomer obtained by controlled thermal degradation of poly(propylene-ran-1-butene).…”

Functionalization and applications of telechelic oligopropylenes. II. Introduction of succinic anhydride units and preparation of multiblock copolyolefins by polycondensation

“…copolyolefins, which have dissociable bonds in the main chain, can be prepared by the previously described esterification polycondensation of iPP-MA, and telechelic oligomers such as iPP-OH have already been reported by us. 5 A copolyolefin (iPP-b-iPP) was prepared from equimolar amounts of iPP-MA [M n ¼ 2.4 Â 10 3 , weight-average molecular weight/number-average molecular weight (M w /M n ) ¼ 1.5] and iPP-OH (M n ¼ 2.1 Â 10 3 , M w /M n ¼ 1.8) with catalytic amounts of p-toluenesulfonic acid. Figure 3 shows GPC curves of iPP-MA, iPP-OH, and iPP-b-iPP.…”

Development of materials and technologies for control of polymer recycling

“…The terminal vinylidene double bond groups were modified into various a,o-bifunctional groups as shown in Scheme 2, 26 for example, a,o-dibromoisobutyrate to allow them to function as bifunctional macroinitiators: Br-iPP-Br. Triblock copolymers: PS-iPP-PS and PMMA-iPP-PMMA were obtained by atom transfer radical polymerization of St and methyl methacrylate , respectively, using Br-iPP-Br.…”