Polymerization of some fluorine-containing phenylacetylenes

Muramatsu, Hiroshige; Ueda, Teruo; Ito, Katsukiyo

doi:10.1021/ma00150a019

Cited by 33 publications

(12 citation statements)

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“…1, Table 1) also indicated that the polydispersity index (PDI) of polymers P1 – P3 also seem to decrease as the size of the ortho ‐substituent increase from H (4.18, P1 ) through methyl (3.13, P2 ) to isopropyl (3.00, P3 ). These results are in consistent with the previous observations that the PPA s with bulkier ortho ‐alkyl substituents had a higher M w and a narrower PDI, which have been attributed to the much increased crowd of the propagating species due to the presence of the ortho ‐substituents that helps to suppress the undesired chain transfer and termination reactions 18–22…”

Section: Resultssupporting

confidence: 92%

“…Furthermore, compared with the unsubstituted PPA , the ortho ‐substituted PPA s in general showed enhanced solubility, better film‐forming property,17 higher molecular weight, and narrower molecular weight distribution 18–22. Thus, we are also interested to examine the effect of the alkyl substituents present at the ortho ‐ and meta ‐positions to the polyene backbone of these novel substituted PPA s. In this article, we report the preparations and characterizations of polymers P1–P3 (Scheme ) and compare their properties with that of PPA prepared under the same conditions.…”

Section: Introductionmentioning

confidence: 99%

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Highly fluorescent mono‐substituted poly(arylacetylene)s containing tolane chromophores

Han

Balasubramanian

2008

J. Polym. Sci. A Polym. Chem.

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A new class of highly fluorescent mono-substituted polyarylacetylenes (P1-P3) has been successfully prepared with good yields and high molecular weights from a series of phenylethynylene-substituted arylacetylenes (M1-M3), using Wbased catalyst. These polymers are readily soluble in common organic solvents (e.g., THF, toluene, and chloroform) and thermally stable up to $350 8C. Both 1 H NMR and IR studies confirmed that all the monomers were selectively polymerized at the terminal triple bond. The 1 H NMR results showed that both P1 and P2 have essentially trans-polyene backbone structures, while P3 contains significant amounts of both cis-and trans-structures. Coincidently, the photoluminescence (PL) intensity of P3 is also much lower than both P1 and P2. Nevertheless, the PL intensity of P1-P3 are all much higher than that of PPA, suggesting that the introduction of phenylethynylene group to the phenyl rings of PPAs have made the in general nonemissive PPAs to become highly photoluminescent. Most interestingly, although P1 did not contain any substituent group on its tolane pendant group, it is already highly soluble in common organic solvent and emitting blue fluorescence (416 nm) with a reasonably good quantum yield (0.36). V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: [5483][5484][5485][5486][5487][5488][5489][5490][5491][5492][5493][5494][5495][5496][5497][5498] 2008

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Section: Resultssupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Highly fluorescent mono‐substituted poly(arylacetylene)s containing tolane chromophores

Han

Balasubramanian

2008

J. Polym. Sci. A Polym. Chem.

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“…The value of σ = 0.80 obtained for P4 thus confirmed the enhanced rigidity of P4 chains in THF. The rigid conformation of poly(disubstituted acetylene)s with bulky substituents (that can be assumed from the covalent structure of these polymers) was confirmed for several polymers of this type by intrinsic viscosity vs. molecular weight measurements 71–74…”

Section: Resultsmentioning

confidence: 78%

Synthesis and Spectral Properties of Novel Poly(disubstituted acetylene)s

Duchoslavová

Sivkova

Hanková

et al. 2011

Macro Chemistry & Physics

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The synthesis of mostly new acetylenes, R1CCR2, (R1 = 4‐t‐butylphenyl; R2 = 4‐t‐butylphenyl; 4‐[(t‐butyl)(diphenyl)silyloxy]phenyl; 1‐naphthyl; 2‐naphthyl; 9‐anthryl) is reported. Their UV‐vis characteristics are discussed in comparison to the results of TD‐DFT calculations. R1CCR2 (except for R2 = 9‐anthryl) give polyacetylenic polymers—[C(R1) = C(R2)]‐n, insoluble if R1 = R2 and well soluble if R1 ≠ R2 in polymerization with TaCl5/SnBu4. Polymerizability increases with increasing monomer triple bond accessibility for the catalyst. The photoluminescence yield of the soluble polymers rises in the R2 order: 1‐naphthyl < 2‐naphthyl < 4‐[(t‐butyl)(diphenyl)silyloxy]phenyl.

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“…In the case of transition metal catalysis, it has been suggested that undesired chain transfer and termination events are limited in bulky propagating species 23–25. Remarkably, poly( o ‐CF 3 PA) obtained by catalysis of W(CO) 6 under UV irradiation exhibited higher MWs than poly( m ‐CF 3 PA) or poly( p ‐CF 3 PA), and the M w values increased with decreasing monomer concentration in solution 26…”

Section: Resultsmentioning

confidence: 99%

Synthesis of polyarylacetylenes by γ‐ray‐induced polymerization of terminal alkynes. Nanostructures of ortho‐substituted derivatives

Bassetti

Fratoddi

Lilla

et al. 2012

J. Polym. Sci. A Polym. Chem.

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Terminal aryl alkynes RC6H4CCH with substituents of different electronic properties and ring position (R = H, 4‐CF3, 4‐OMe, 2‐CF3, 2‐OMe, 2‐Me) were exposed to γ‐radiation (50–400 kGy) in organic solvents (hexane, 1,4‐dioxane, ethylacetate, methanol, tetrahydrofuran), at room temperature. The effects arising from substituent, solvent, dilution, and radiation dose allowed to define the conditions suitable for polymerization, which was favored in methanol at increasing dilution of the alkyne. Ortho‐substitution represented the key structural element in the substrate, and the derived polyarylacetylenes were characterized in detail, including gel permeation chromatography, thermal analysis, infrared, NMR, UV–vis, fluorescence, and scanning electron microscope spectroscopy. The results are consistent with the formation of irregular polymers mainly composed of trans‐transoid chains. Controlled aggregation of the polymers by means of an osmosis‐based procedure in solvent/non‐solvent mixtures allowed the formation of nanostructured materials, in particular of hollow nanospheres from THF/water. The methodology sets the basis for the development of γ‐rays‐induced polymerization of alkynes, in a transition metal catalyst‐free environment. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

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Polymerization of some fluorine-containing phenylacetylenes

Cited by 33 publications

References 0 publications

Highly fluorescent mono‐substituted poly(arylacetylene)s containing tolane chromophores

Highly fluorescent mono‐substituted poly(arylacetylene)s containing tolane chromophores

Synthesis and Spectral Properties of Novel Poly(disubstituted acetylene)s

Synthesis of polyarylacetylenes by γ‐ray‐induced polymerization of terminal alkynes. Nanostructures of ortho‐substituted derivatives

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