Polymerization of m-Chlorophenylacetylene Initiated by [Rh(norbornadiene)Cl]2-Triethylamine Catalyst Containing Long-Lived Propagation Species

Abstract

KEY WORDSLong-Lived Propagating Species / Rhodium Complex Catalyst / m-Chlorophenylacetylene / In recent years there has been a growing interest in the polymerization of aromatic acetylenes using transition metal catalysts. Several investigations have been described in the literature, 1 -4 including the living polymerization of ortho substituted phenylacetylenes by Mo-based catalyst. In our preliminary experiments, the polymerization of chlorinated phenylacetylenes, for example, o-chlorophenylacetylene ( o-CPA), m-chlorophenylacetylene (m-CPA) and pchlorophenylacetylene (p-CPA) in the presence of Rh complex-TEA catalyst was examined. Among their monomers, m-CPA was readily polymerized to quantitative conversion and the polydispersity of the resultant polymer, Poly-(m-CPA) soluble into common solvents was rather narrow. Therefore, the polymerization of m-CPA was studied using three kinds of Rh-based catalysts, i.e., Rh-TEA

Pressure-inducedcis totrans isomerization of aromatic polyacetylenes prepared using a Rh complex catalyst: A control of ?-conjugation length

“…2 It has been proposed that the effect of the solvents is to promote In a previous article we reported that phenylacetthe efficient dissociation of the dimer complex ylene (PA), 1 its homologues, 2 a-naphthylacety-[Rh(NBD)Cl] 2 into the monomeric species, which lene, 3 and alkylpropiolates, 4,5 and pentynoate 6 may be an important initiation species for this can be stereospecifically polymerized in the prespolymerization, 1,7 as shown in Scheme 1. Further, ence of a Rh complex, [Rh(norbornadiene)Cl] 2 , the structural differences observed between poly-[Rh(NBD)Cl] 2 , when triethylamine (TEA) or an pentynoates prepared with the Rh complex cataalcohol is used as the polymerization solvent and lyst and with metathesis catalysts such as WCl 6 that the helical cis-transoid isomer were selecwas interpreted in terms of the difference in geotively formed in high yields under mild conditions.…”

Helical Poly(N-propargylamide)s Derived from Lactic Acid: Effect of O-Acyl Groups on the Secondary Structures

“…Figure 1 depicts the CD and UV-vis spectra of the polymers with R 1 ¼ CH 3 and R 2 ¼ C 2 H 5 , n-C 4 H 9 , C(CH 3 ) 3 . Although poly(3) exhibited a different CD pattern from those of poly (1) and poly (2), all these polymers showed UV-vis absorption at 310 nm, indicating the absence of a substituent effect on the conjugation length.…”

“…2 When appropriately chiral groups are substituted, polyaceytlenes form a helical structure with predominantly one-handed screw sense due to the rigid main chain. In the cases of poly(1-alkyne)s, 3 poly(phenylacetylene) derivatives, 4 and poly(propiolic ester)s, 5 bulky substituents stabilize the helical structure.…”

Helical poly(phenylacetylene)s containing schiff-base and amino groups: Synthesis, secondary structures, and responsiveness to benzoic acid

“…[35][36][37] The polymerizations of monomers 1a-e were carried out in THF with [(nbd)RhCl] 2 /Et 3 N catalyst, whose results are listed in Table 1. Monomers 1a-c containing Schiff-base groups gave polymers 2a-c as methanol-insoluble products with fairly high molecular weights (M n 5 4.7 3 10 4 to 6.0 3 10 4 ) in high yields (91-97%).…”