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Synthesis and Aggregation Behavior of Poly(arylene alkenylene)s and Poly(arylene alkylene)s Having Dialkoxyphenylene and Aromatic Diimide Groups
journal contribution
posted on 2019-02-08, 19:09 authored by Li Yi Tan, Yoshitaka Tsuchido, Kohtaro Osakada, Zhengguo Cai, Yoshiaki Takahashi, Daisuke TakeuchiPolycondensation
reactions of 2,5-dialkoxy-1,4-diiodobenzene with N,N′-ω-dialkenylpyromellitic diimide and N,N′-ω-dialkenyl naphthalenetetracarboxylic
diimide in the presence of a Pd(OAc)2–NaOAc catalyst
produce six polymers containing the two aromatic groups connected
alternatingly by alkenylene spacers. 1H NMR spectrum of
a polymer prepared from 2,5-bis(dodecyloxy)-1,4-diiodobenzene and N,N′-(10-undecenyl)pyromellitic diimide (poly(1a-IA)) indicates that the polymerization involves
2,1- and 1,2-insertion of a vinyl group into the Pd–Ar bond
in 70:30 selectivity. Matrix-assisted laser deportion/ionization time-of-flight
mass spectrometry (MALDI-TOF-MS) spectra of poly(1a-IA) and a polymer from 2,5-bis(dodecyloxy)-1,4-diiodobenzene
with N,N′-dialkenyl naphthalenetetracarboxylic
diimide (poly(1a-IIA)) contained a series
of polymer fragments with Mn up to 4500.
Measurement of electrospray ionization MS (ESI-MS) of the polymers
revealed formation of cyclic molecules for 1:1 and 2:2 oligomers.
Hydrogenations of poly(1a-IA) by using [Ir(cod)(py)(PCy3)]+PF6– (cod = 1,5-cycloctadiene;
PCy3 = tricyclohexylphosphine) catalyst and of poly(1a-IIA) by a mixture of p-toluenesulfonyl
hydrazide (TSH) and tripropylamine (TPA) produce the poly(arylene
alkylene)s with saturated spacers in 93% degree of hydrogenation.
The absorption spectrum of poly(1a-IA) in
CHCl3 shows an absorption edge at 410 nm, which is at a
longer wavelength than that of a mixture of the monomers (370 nm).
Light-scattering measurement of the solution (1.00 mmol L–1) indicates the presence of aggregates with a hydrodynamic radius
of 48 nm. The polymers exhibit weak elasticity at room temperature,
as determined by dynamic viscoelasticity analysis (DMA), and it becomes
negligible on heating to 75–80 °C (polymer with pyromellitic
diimide groups) and 110–122 °C (polymer with naphthalenetetracarboxylic
diimide groups). The above properties of the polymers are attributed
to attractive interaction between the electron-rich alkoxyphenylene
and the electron-deficient aromatic diimide groups both in solution
and in the solid state.
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Keywords
CHCl 3electron-rich alkoxyphenylenehydrodynamic radiusTPAabsorption spectrum4500. Measurementelectrospray ionization MSESI-MSDMATSHPFpyromellitic diimide groups1 H NMR spectrum410 nmLight-scattering measurementcyclic moleculesMALDI-TOF-MStoluenesulfonyl hydrazidealkenylene spacersAggregation Behaviordiimide groupsM nviscoelasticity analysisabsorption edgepolymers exhibitPCy 3naphthalenetetracarboxylic diimide groupspolymer fragmentsroom temperatureIIAvinyl group48 nmIAAromatic Diimide Groups Polycondensation reactions
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