Living metathesis polymerization of [o-(trifluoromethyl)phenyl]acetylene by molybdenum-based three-component catalysts

Masuda, Toshio; Mishima, Kazuhiro; Fujimori, Junichi; Nishida, Masakazu; Muramatsu, Hiroshige; Higashimura, Toshinobu

doi:10.1021/ma00031a007

Cited by 44 publications

(30 citation statements)

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“…50 Thus the polymerization by MoOCl 4 -n-Bu 4 Sn-EtOH (1:1:0.5 mol ratio) catalyst in toluene at 30 8C produced a polymer with narrow MWD; M w /M n ¼ 1.06. Upon three consecutive additions of fresh monomer feeds to completely polymerized systems, the M n of the polymer increased in direct proportion to monomer conversion, while the M w /M n remained <1.1.…”

Section: Metathesis Mechanismmentioning

confidence: 97%

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: Metathesis Mechanismmentioning

confidence: 97%

Substituted polyacetylenes

Masuda

2006

J. Polym. Sci. A Polym. Chem.

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389

222

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“…Detailed polymerization procedures were described before. 5 Monomer conversions were determined by measuring the initial and final monomer concentrations by GC (silicone DC 3 m, 170°C). The MWD curves of polymers were observed by gel permeation chromatography (GPC) using a Jasco Trirotar liquid chromatograph (Shodex A803, A804, and A805 polystyrene gel columns, eluent CHC1 3 ), and the number-and weight-average molecular weights (.M.…”

Section: Experiments Almentioning

confidence: 99%

“…The authors have found that molybdenum-based three-component catalysts, i.e., MoOClc(or MoC1 5 )-n-Bu4 SnEtOH effect living polymerization of substituted acetylenes such as l -chloro-l -octyne 3 · 4 and [o-(trifluoromethyl)phenyl]acetylene. 5 Silicon-containing polyacetylenes are characterized by unique properties like high gas permeability. 6 Examples of such polymers with high molecular weight include poly[l-(trimethylsilyl)-1-propyne] and poly [[o-(trimethylsilyl) In the present note, we report on the living polymerization of o-Me 3 SiPA effected * To whom correspondence should be addressed.…”

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confidence: 99%

Living Polymerization of [o-(Trimethylsilyl)phenyl]acetylene by Molybdenum-Based Three-Component Catalysts

Masuda

Fujimori

Rahman

et al. 1993

Polym J

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Living polymerization induced by transition-metal catalysts has recently made great progress. For instance, Grubbs 1 and Schrock 2 have developed many living systems in ringopening metathesis polymerization (ROMP) of cycloolefins by using well-defined metalcarbene initiators. The authors have found that molybdenum-based three-component catalysts, i.e., MoOClc(or MoC1 5 )-n-Bu4 SnEtOH effect living polymerization of substituted acetylenes such as l -chloro-l -octyne 3 · 4 and [o-(trifluoromethyl)phenyl]acetylene. 5 Silicon-containing polyacetylenes are characterized by unique properties like high gas permeability. 6 Examples of such polymers with high molecular weight include poly[l-(trimethylsilyl)-1-propyne] and poly [[o-(trimethylsilyl) In the present note, we report on the living polymerization of o-Me 3 SiPA effected * To whom correspondence should be addressed.by MoC1 5 -and MoOCl 4 -based catalysts and the effects of polymerization conditions on the molecular weight distribution (MWD) of polymers. The living nature of the polymerization by MoC1 5 -(or MoOC1 4 )-n-Bu 4 Sn-EtOH catalysts has been proved by both small polydispersity ratios close to unity and increases of polymer molecular weight proportional to monomer consumption. EXPERIMENT ALThe synthesis of o-Me 3 SiPA followed the same method as described previously. 8 The monomer was distilled twice at reduced pressure from calcium hydride before use: bp 85°C/IO mmHg, purity > 99% (by gas chromatography (GC)). Transition metal chlorides (Strem Chemicals; purity >99%) and organometallic cocatalysts were commercially obtained, and used without further purification with care being taken not to be decomposed by moisture and/or air. Oxygen-containing compounds such as ethanol (EtOH) were distilled before use. Toluene as polymerization solvent was purified by a standard method.All the procedures for polymerization were 535

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“…Polymerization of substituted acetylenes by group 5 and 6 transition metal catalysts is believed to proceed via metal carbenes as active species and metallacyclobutenes as intermediates (Scheme 1) 3,4) . Recently, precise synthesis of polymers aroused much attention, and living polymerization of substituted acetylenes is making remarkable progress as well as those in other polymerization processes [4][5][6][7][8][9] . We have found that the MoOCl 4 -n-Bu 4 Sn -EtOH (1 : 1 : 1)/toluene catalyst induces living polymerization of various substituted acetylenes [7][8][9] .…”

Section: Introductionmentioning

confidence: 99%

“…Recently, precise synthesis of polymers aroused much attention, and living polymerization of substituted acetylenes is making remarkable progress as well as those in other polymerization processes [4][5][6][7][8][9] . We have found that the MoOCl 4 -n-Bu 4 Sn -EtOH (1 : 1 : 1)/toluene catalyst induces living polymerization of various substituted acetylenes [7][8][9] . It is considered that n-Bu 4 Sn reacts with MoOCl 4 as alkylating agent to produce a metal carbene in this catalyst system.…”

Section: Introductionmentioning

confidence: 99%