Synthesis and Structure in Solution of Poly[(−)-menthyl propiolate] as a New Class of Helical Polyacetylene

Nakako, Hideo; Nomura, Ryoji; Tabata, Masayoshi; Masuda, Toshio

doi:10.1021/ma981630c

Cited by 124 publications

(69 citation statements)

References 15 publications

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“…89 Recently there are fairly many examples of helical substituted polyacetylenes; for example, induced helices based on the combinations of poly(p-carboxyphenylacetylene) and its analogues with low molecular weight compounds, 29,90 helical poly(p-alkoxy-m,m-dihydroxyphenylacetylene) synthesized by using chiral Rh catalyst systems, 28,91 and poly(menthyl/chiral alkyl propiolates). 92,93 The most salient feature of helical poly(Npropargylamides) developed by us is that the helix is mainly induced by the intramolecular hydrogen bonding between amide groups in the side chain.…”

Section: Helical Structurementioning

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: Helical Structurementioning

confidence: 99%

Substituted polyacetylenes

Masuda

2006

J. Polym. Sci. A Polym. Chem.

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389

222

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“…23 More specifically, the poly(propiolic ester)s obtained with Rh catalysts have high cis contents, while trans-rich polymers are obtained with Mo and W catalysts. Actually poly(2) samples were prepared in this study by using [(nbd)RhCl] 2 , MoOCl 4 /n-Bu 4 Sn, and WOCl 4 / n-Bu 4 Sn to compare the geometric structure with that obtained with Ru catalyst 1 (Table III), and the 1 H NMR spectra of the poly(2)s were depected in Figure 1.…”

Section: Structure and Properties Of Poly(2)mentioning

confidence: 99%

“…Rh catalysts can polymerize only monosubstituted acetylenes such as phenylacetylene and its ring-substituted derivatives, 6-11 N-propargylamides, 12-17 and propiolic esters. [19][20][21][22][23] The Rh-catalyzed polymerization proceeds by the insertion mechanism, and features excellent tolerance to polar subsituents in the monomer 24,25 and protic solvents. 26 The Rh-based polymers generally possess high cis stereoregularity, which is indispensable for the formation of helical structures of poly(N-propargylamide)s.…”

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confidence: 99%

Polymerization of Substituted Acetylenes by the Grubbs–Hoveyda Ru Carbene Complex

Katsumata

Shiotsuki

Kuroki

et al. 2005

Polym J

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ABSTRACT:Polymerization of various mono-and disubstituted acetylenes was investigated by using GrubbsHoveyda catalyst (1). Hexyl propiolate (2) and 1-phenyl-2-(p-trimethylsilyl)phenylacetylene (3) Substituted polyacetylenes have been gathering much attention due to their potential applications to material-separation membranes, and optoelectronic and related fields.1 These polymers have been obtained by polymerization of corresponding acetylenic monomers in the presence of transition metal catalysts. Catalysts including group 5 and 6 transition metal and Rh have traditionally been employed to induce their polymerization. Among them, halides of early transition metals such as TaCl 5 , NbCl 5 , MoCl 5 , and WCl 6 in conjunction with organometallic cocatalysts polymerize various mono-and disubstituted acetylenes to give high molecular weight polymers in good yield. Some well-defined Ta, Mo, and W carbenes, so-called Schrock carbenes, induce living polymerization of substituted acetylenes. [2][3][4][5] This implies that the group 5 and 6 transition metal-catalyzed polymerization proceeds by the metathesis mechanism. One of the drawbacks of the early transition metal is that they are readily deactivated by polar groups in the monomer and polymerization solvents because of their high oxophilicity.Another type of catalysts frequently used for the polymerization of substituted acetylenes are rhodium (Rh) catalysts. Rh catalysts can polymerize only monosubstituted acetylenes such as phenylacetylene and its ring-substituted derivatives, 6-11 N-propargylamides, 12-17 and propiolic esters. [19][20][21][22][23] The Rh-catalyzed polymerization proceeds by the insertion mechanism, and features excellent tolerance to polar subsituents in the monomer 24,25 and protic solvents. 26 The Rh-based polymers generally possess high cis stereoregularity, which is indispensable for the formation of helical structures of poly(N-propargylamide)s. 12-17A huge number of studies on the synthesis and catalysis of ruthenium (Ru) carbene complexes have been reported in these several years. Ru carbene complexes represented by Grubbs' first-and secondgeneration catalysts exhibit high activity in olefin metathesis reactions such as ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), cross metathesis (CM). 27 Compared to early transition metal-based metathesis catalysts, Ru carbene complexes display tolerance against protic functional groups in these metathesis reactions as well as considerable stability to oxygen and moisture. It should also be noted that many Ru complexes have well-defined carbene structures, which enables to directly generate carbene-type active species without adding cocatalysts. The Grubbs' second-generation complex reportedly reacts with diphenylacetylene stoichiometrically to afford 3 -vinylcarbene complex, which is regarded as an intermediate of the polymerization of acetylenes.28 Ru-catalyzed polymerizations of acetylene 29 and diyne compounds 30,31 have recently been reported. Though an Ru carbene ...

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“…It has been reported that the peaks of cis protons in the 1 H NMR spectrum of poly(N-propargylalkylamides) are very broad due to the limited main chain mobility [9]. On the contrary, the 1 H NMR spectra of the present poly(propargyl esters) usually showed sharp signals of the cis protons, indicating that their main chain is enough flexible like those of poly(propiolic esters) [19].…”

Section: Figurementioning

confidence: 76%

Synthesis of Poly(propargyl esters) with Rhodium Catalysts and Their Characterization

et al. 2006

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SummaryPropargyl esters (HC≡CCH 2 OC(=O)R; 1: R = n-C 5 H 11 , 2: R = CH 3 , 3: R = CHBrCH 3 , 4: R = C 6 H 5 , 5: R = C(C 6 H 5 ) 3 ) were polymerized by using (nbd)RhPh 3 ) (nbd = 2,5-norbornadiene) to produce poly(1)-poly(5) with molecular weights in the range of M n = 4,900-40,000. Poly(1), poly(3) and poly(4) were readily soluble in common organic solvents such as toluene, THF and CHCl 3 , and poly(2) showed similar solubility behavior except that it was insoluble in THF. Poly(5) did not dissolve in any organic solvent. Poly(1) was yellow oil, while poly(2)-poly(5) were yellow solids. Poly(1)-poly(4) exhibited UV-vis absorptions in a range of 300-425 nm, which are attributed to the conjugation of the main chain. All the polymers were thermally stable up to 150-200 o C.

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Synthesis and Structure in Solution of Poly[(−)-menthyl propiolate] as a New Class of Helical Polyacetylene

Cited by 124 publications

References 15 publications

Substituted polyacetylenes

Substituted polyacetylenes

Polymerization of Substituted Acetylenes by the Grubbs–Hoveyda Ru Carbene Complex

Synthesis of Poly(propargyl esters) with Rhodium Catalysts and Their Characterization

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