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(3-Hexyne, 4-0Ctyne, and 5-Decyne) by WCI6 · Ph4sn and Moci5

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(3-Hexyne, 4-0Ctyne, and 5-Decyne) by WCI6 · Ph4sn and Moci5 Polymer Journal, Vol. 13, No. 3, pp 301-303 (1981) NOTE Polymerization of Symmetrical Dialkylacetylenes (3-Hexyne, 4-0ctyne, and 5-Decyne) by WCI6 · Ph4 Sn and MoCI5 · Ph4 Sn Toshio MASUDA, Yoshinori KUWANE, and Toshinobu HIGASHIMURA Department of Polymer Chemistry, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606, Japan. (Received October 6, 1980) KEY WORDS Coordination Polymerization I 3-Hexyne I 4-0ctyne I 5- Decyne I Tungsten Hexachloride I Molybdenum Pentachloride I Tetraphenyltin I Polyene I Fairly many studies have appeared on the acetylenes (3-hexyne, 4-octyne, and 5-decyne) by use polymerization of acetylene and monosubstituted of WC16- and MoCI5 -based catalysts and with the acetylenes, and several transition-metal catalysts are characterization of polymers formed. now known to provide high polymers. 1 The poly­ merization of disubstituted acetylenes, however, EXPERIMENTAL remains appreciably difficult, and virtually re­ stricted to the following cases: hexafiuoro-2-butyne Dialkylacetylenes (3-hexyne, 4-octyne, and 5- (anionic catalyst; insoluble polymer),2 dicyanoacet­ decyne; Tokyo Chemical Industry Co.) were used ylene (anionic catalysts; polymer molecular weight, without further purification (purities> 99%). Unless MW 500),3 1-phenylpropyne (WCI6 · Ph4Sn; poly­ otherwise stated, polymerizations were carried out mer MW 6000),4 diphenylacetylene (anionic cata­ at 30°C in toluene for 24 h under a dry nitrogen lysts; polymer MW 1800)5 (WCI6 · Ph4Sn; in­ atmosphere; [M]0 =1.0 mol dm- 3 , [Cat]=30 mmol soluble polymer), 6 1-chloro-2-phenylacetylene dm- 3 . The 1 : I mixtures of tetraphenyltin and (Mo(COkhv; polymer MW 4 x 105),7 and dialkyl­ either WC16 or MoCI5 in solution were aged at 30°C acetylenes8 -lo (vide infra). for 15 min before use as catalysts.12 Monomer Mauret et a!. obtained a mixture of linear consumptions and polymer yields were determined polymer and cyclic trimer in the reaction of 3- by gas chromatography and gravimetry, respec­ hexyne catalyzed by diarylcobalts.8·9 The polymer tively. was insoluble in organic solvents and susceptible to air oxidation. Very recently, Katz and Lee obtained RESULTS AND DISCUSSION mostly insoluble polymers in the polymerization of 2-butyne, 4-octyne, and cyclooctyne by tungsten­ Polymerization of Dialkoylacetylenes carbene complexes. 10 The WC16 · Ph4Sn catalyst is known to effect the 12 We have reported that WC16- and MoCI5 -based polymerization of phenylacetylene, l-phenyl­ catalysts are very effective for the polymerization of propyne,4 and cyclopenteneY This catalyst poly­ aromatic acetylenes including disubstituted acet­ merized 3-hexyne to afford a methanol-insoluble ylenes.4·6·7 ·11 Now it seems appropriate to study polymer in high yield in toluene solution within whether these catalysts can polymerize aliphatic several hours (Table I). The polymerization pro­ disubstituted acetylenes as well. This paper deals ceeded almost quantitatively in halogenated hy­ with the polymerization of symmetrical dialkyl- drocarbons. Thus, WC16 · Ph4Sn is much more 301 T. MASUDA, Y. KuwANE, and T. HIGASHIMURA Table I. Polymerization of 3-hexyne" Table II. Polymerization of 4-octyne and 5-decyne" Polymer No. Catalyst Solvent Polymer yield/%b No. Monomer Catalyst Solvent yield/%b WC16 ·Ph4 Sn Toluene 87 · 2' WCI 6 ·Ph4 Sn Toluene 71 I 4-0ctyne WCI6 Ph4 Sn Toluene 70 · 3 WCI6 ·Ph4 Sn CCI4 95 2 4-0ctyne MoCI5 Ph4 Sn Toluene 13 · 4 WCI 6 ·Ph4 Sn (CH2 Cl)2 96 3 5-Decyne WCI6 Ph4 Sn Toluene 61 5-Decyne WCI · Ph Sn 5 MoCI5 · Ph4 Sn Toluene 16 4 6 4 CCI4 57 · 6 WCI6 Toluene 0 5 5-Decyne WCI6 Ph4 Sn (CH2 Cl)2 65 · 7 MoCI5 Toluene 3 6 5-Decyne MoCI5 Ph4 Sn Toluene 10 8 WC16 · (\/2)CH30H Toluene 0 "Polymerized at 30°C for 24h: [M] =1.0 mol dm- 3 , 9 MoCI5 · (l/2)CH3 0H Toluene 8 0 [Cat]=30 mmol dm- 3 . 10 Fe(acach · 3Et3 Al Toluene II Ti(On-Bu)4 · 4Et3 Al Toluene b Methanol-insoluble polymer. 12 TiC14 · 3Et3 Al Toluene " Polymerized at 30°C for 24 h: [M]0 = 1.0 mol dm- 3 , sterically-hindered acetylenes like dialkylacetylenes. [Cat]=30 mmol dm- 3 . The results for the polymerizations of 4-octyne b Methanol-insoluble polymer. ' Polymerized for I h. and 5-decyne are shown in Table II. 4-0ctyne and 5- decyne were also polymerized in fairly high yields by WCI6 · Ph4 Sn. As the alkyl group became longer, the active than any other catalysts ever used for the polymer yield decreased (3-hexyne > 4-octyne > 5- polymerization of dialkylacetylenes. 8 -lo The decyne). The solvent effects on the polymerization MoCI5 · Ph4 Sn catalyst was less active, but it also of 5-decyne were similar to those for 3-hexyne. The gave a methanol-insoluble polymer. chlorides of W and Mo by themselves and the The polymerization of 3-hexyne by WC16 · Ph4 Sn Ziegler-type catalysts described above did not and MoCI5 · Ph4 Sn produced small amounts of polymerize 5-decyne. methanol-soluble oligomer (2-1 0% of the whole products) in addition to the methanol-insoluble Properties and Structure of Polymers polymer. Hexaethylbenzene (cyclic trimer) was not The elemental compositions of polymers agreed found in the oligomeric product. well with the theoretical values: e.g., Poly(3-hexyne) On the other hand,WC16 and MoCI5 were, by (Table I, No. I) Calcd for (C6 H10)": C, 87.73%; H, themselves, practically inactive for the poly­ 12.27%. Found: C, 87.56%; H, 12.12%. Poly(4- merization of 3-hexyne (see Table 1). Certain octyne) (Table II, No. I) Calcd for (C8 H14)": C, oxygen-containing compounds, such as water and 87.19%; H, 12.81%, Found: c, 87.18%; H, 12.83%. methanol, serve as cocatalysts for the WC16 - and Poly(5-decyne) (Table II, No. 3) Calcd for MoCI5 -catalyzed polymerization of phenylacety­ (C 10H 18)": C, 86.88%; H, 13.12%. Found C, lene." Methanol, however, was hardly effective as 86.29%; H, 13.20%. a cocatalyst in the present polymerization. The poly(dialkylacetylene)s obtained had the · Ziegler-type catalysts are known to bring about form of white powder. No softening point was the polymerization of acetylenes: for example, iron observed below 300°C. In the differential thermal 14 (Ill) chelates-3Et3Al for l-alkynes and phenyl­ analysis, the polymers showed no endo- or exo­ 6 acetylene, 15 Ti(On-Bu)4 · 4Et3Al for acetylene/ thermic peak below 200°C but complex exothermic and TiC14 · 3Et3Al for phenylacetylene (cyclotrimeri­ peaks above 200°C. Even though the polymers were zation).17 For the sake of comparison, the poly­ exposed to the air at room temperature for a month, merization of 3-hexyne was carried out using these no change occurred in the polymer color, elemental catalysts. Almost no methanol-insoluble polymer, compositions or IR spectra. this indicates that the however, was formed. Consequently it is concluded polymers are fairly stable against air oxidation. that Ziegler-type catalysts, which are usually hetero­ The major portions of the polymers (70-90%) geneous, are unsuitable for the polymerization of were insoluble (polymers were precipitated during 302 Polymer J., Vol. 13, No. 3, 1981 Polymerization of 3-Hexyne, 4-0ctyne, and 5-Decyne polymerization regardless of the reaction time), and n-Pr, n-Bu) was confirmed by IR and 1 H NMR even the soluble fractions became gradually in­ spectra. soluble after isolation. This seems due to cross­ linking which occurs slightly and gradually. REFERENCES The IR spectrum of poly(3-hexyne) showed the following absorptions: 2950-2850 (s), 1660-1580 I. See, for a review, M. G. Chauser, Yu. M. Rodionov, V. M. Misin, and M. I. Cherkashin, Usp. Khim., 45, (w), 1460(m), 1370(m), 1310(m), 1260(m), 1150- 695 (1976); Russ. Chern. Rev., 45, 348 (1976). 1000 (m), and 800 (m) em - 1 . The weak and broad 2. e. g., J. A. Jackson, J. Polym. Sci., Polym. Chern. Ed., absorption at 1660-1580 cm- 1 is due to the C=C 10, 2935 (1972). stretching of conjugated double bonds along the 3. e. g., M. Benes, J. Peska, and 0. Wichterle, J. Polym. main chain. The spectra of poly(4-octyne) and Sci., C, No.4, 1377 (1963). poly(5-decyne) were also similar, though a little 4. N. Sasaki, T. Masuda, and T. Higashimura, Macromolecules, 9, 664 (1976). more complex. The intensities of absorptions at 5. V. M. Misin, P. P. Kisilitsa, N. I. Bolondaeva, and 1 1150-1000 em - depended on the kind of catalysts M. I. Cherkashin, Vysokomol. Soedin., Ser. A, 18, used, (WC16 · Ph4 Sn and MoCI5 · Ph4 Sn), suggesting 1726 (1976). a difference in the geometric structure of polymers. 6. T. Masuda, H. Kawai, T. Ohtori, and T. 1 H nuclear magnetic resonance (NMR) and Higashimura, Polym. J., 11, 813 (1979). ultraviolet (UV)-visible spectra were measured 7. T. Masuda, Y. Kuwane, K. Yamamoto, and T. using the soluble part of poly(5-decyne) which was Higashimura, Polym. Bull., 2, 823 (1980). 8. P. Mauret and G. Guerch, C. R. Acad. Sci., Ser. C, more soluble than poly(3-hexyne) and poly(4- 274, 1340 (1972). 1 octyne): H NMR (CC14 ) .52.5-0.5 ppm (broad 9. P. Mauret, J. Magne, and G. Guerch, C. R. Acad. singlet); UV max (cyclohexane) 273 nm (e 450). If the Sci .. Ser. C, 275, 415 (1972). present polymerization is accompanied by isomeri­ 10. T. J. Katz and S. J. Lee, J. Am. Chern. Soc., 102, 422 zation to terminal acetylenes, the polymers formed (1980). should be colored and show olefinic-proton peaks II. T. Masuda, K. Hasegawa, and T. Higashimura, Macromolecules, 7, 728 (1974), and subsequent around t5 5-6 ppm in the 1 H NMR spectra.
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