Synthesis and characterization of poly[[o-(trimethylsilyl)phenyl]acetylene]

Masuda, Toshio; Hamano, Toshiyuki; Tsuchihara, Kenji; Higashimura, Toshinobu

doi:10.1021/ma00207a023

Cited by 106 publications

(38 citation statements)

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“…74 The product polymer possessed the conjugated main-chain structure and was amorphous. The polymer was in the form of a dark purple solid (k max 542 nm), completely dissolved in common organic solvents such as toluene and CHCl 3 , forming a strong membrane by solution casting, and did not lose weight below 280 8C in air, being thermally stable.…”

Section: Silicon-containing Polyacetylenesmentioning

confidence: 99%

Substituted polyacetylenes

Masuda

2006

J. Polym. Sci. A Polym. Chem.

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389

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This article reviews the chemistry of substituted polyacetylenes developed by our research group, more specifically, development of polymerization catalyst, synthesis of new polymers, elucidation of their structure, investigation of their properties, and development of their functions. The main features are as follows: a number of catalysts based on group 5, 6, and 9 transition metals (Nb, Ta, Mo, W, and Rh) have been developed, which include living polymerization catalysts. By using these catalysts, many new substituted polyacetylenes have been synthesized, whose molecular weights are very high (Mw = 104−106). Most of the polymers are soluble in many common solvents and stable enough in the air unlike polyacetylene. Some of these polymers exhibit interesting functions including high gas permeability and photoelectronic properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 165–180, 2007

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Section: Silicon-containing Polyacetylenesmentioning

confidence: 99%

Substituted polyacetylenes

Masuda

2006

J. Polym. Sci. A Polym. Chem.

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389

222

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“…These polymers can be regarded as polyacetylene grafted with methyl or phenyl side groups. More recently, various soluble di-substituted polyacetylene derivatives, including poly(diphenylacetylene), poly(1-alkyl-2-phenylacetylene), poly(1-chloro-2-phenylacetylene) and poly(1-phenyl-2-p-(triphenylsilyl)phenylacetylene) have been synthesized [257,258]. In contrast to SCHEME 2. non-substituted trans-polyacetylene, intense green and blue EL emissions have been demonstrated for LEDs based on some of the di-substituted polyacetylene derivatives [259], and the spectral narrowing of emission associated with stimulated emission was also observed upon intense optical excitation of certain of the di-substituted polyacetylenes [259].…”

Section: Conjugated Polymersmentioning

confidence: 99%

Advanced syntheses and microfabrications of conjugated polymers, C60-containing polymers and carbon nanotubes for optoelectronic applications

Dai

1999

Polym. Adv. Technol.

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“…[(o-Trimethylsilyl)phenyl]acetylene, 19 tert-butylacetylene, 20 • 21 and l-chloro-l-octyne 22 were synthesized according to the literature methods and purified by distillation. Norbornene was distilled from CaH 2 and stored as toluene solution.…”

Section: Methodsmentioning

confidence: 99%

Metathesis Polymerization of Substituted Acetylenes and Norbornene by M(CO)6-Ph2CCl2-hν (M=Mo, W) Catalysts

Misumi

Tamura

Nakako

et al. 1998

Polym J

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ABSTRACT:The M(CO)6-Ph2 CCl2-hv (M = W, Mo) systems worked as effective catalysts in the metathesis polymerization of substituted acetylenes and norbornene. Thus, W(CO) 6-Ph 2 CC1 2 -hv polymerized phenylacetylene in toluene at 30''C for 24 h to provide a polymer with M w 30000 in 70% yield, and polymerized norbornene at 60°C to give a polymer with M., 26000 quantitatively. Ph 2 CCl2 and ultraviolet (UV) irradiation were essential for the catalytic activity. However, Ph 2 CC1 2 was sufficient in catalytic amounts unlike the M(CO) 6---CC14-hv systems which require CC14 as solvent. A maximum was seen in catalytic activity at [Ph2CCl2]/[M]=0.5-2. The molecular weight of the poly(phenylacetylene) was higher than those for MCl"-based catalysts.KEY WORDS Metathesis Polymerization / Substituted Acetylene / Norbornene / Diphenyldichloromethane / Ultraviolet Irradiation / It is well known that ring-opening metathesis polymerization of cycloolefins is effected by various transition metal catalysts. 1 -3 Such catalysts include transition metal chloride-organometallic cocatalyst systems, 1 -3 metallacyclobutanes, 4 -6 Schrock-type metal carbenes, 7 ruthenium carbenes developed by Grubbs et al. 8 Groups 5 and 6 transition metal chloride-based catalysts,9 Schrock-type metal carbenes, 10 • 11 etc. are effective in metathesis polymerization of substituted acetylenes as well. Polymerization of phenylacetylene readily proceeds in the presence of metal chloride-based catalysts, but the molecular weight of the formed polymer is around 5000 at highest probably due to the Lewis acidity of the catalysts. 9 Group 6 transition metal hexacarbonyl-based catalysts, M(CO) 6 -CClchv (M = W, Mo), induce metathesis polymerization of both cycloolefins 12 · 13 and substituted acetylenes. 14 • 15 The Lewis acidity of these catalysts is lower than those of metal chlorides, and consequently the molecular weight of the poly(phenylacetylene) produced by the W(COkbased catalyst reaches almost a hundred thousand. A requirement for the M(C0) 6 -based catalysts is that CC1 4 must be used as solvent; otherwise sufficient catalytic activity is not attained. It is assumed that a metal carbene, which serves as active species, is generated by CO elimination from M(CO) 6 by ultraviolet (UV) irradiation and subsequent reactions of M(CO) 5 with CC1 4 , and so forth. 16 Further, generation of tungsten diphenylcarbene as an intermediate in the W(CO) 6 -Ph 2 CC1 2 -hv system was suggested on the basis of a finding that the presence of 2-ethoxynorbornene in this system leads to the formation of a diphenylcarbene adduct. 17 Taking this into account, we examined Ph 2 CCl 2 in place of CC14 in the W(CO) 6 -CC1 4 -hv system to find that the W(CO) 6 -Ph2CC12-hv system polymerizes phenylacetylene. 18 In the present study, we investigated the polymerization of substituted acetylenes and norbornene by the M(CO)6-Ph2CC12-hv (M = W, Mo) systems in detail to clarify the effectiveness of Ph 2 CC1 2 as second catalyst component 1 To whom all correspondence should be addressed. a...

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Synthesis and characterization of poly[[o-(trimethylsilyl)phenyl]acetylene]

Cited by 106 publications

References 0 publications

Substituted polyacetylenes

Substituted polyacetylenes

Advanced syntheses and microfabrications of conjugated polymers, C60-containing polymers and carbon nanotubes for optoelectronic applications

Metathesis Polymerization of Substituted Acetylenes and Norbornene by M(CO)6-Ph2CCl2-hν (M=Mo, W) Catalysts

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