Shunsuke Murahashi

Normal Vibrations of the Polymer Molecules of Helical Conformation. IV. Polyethylene Oxide and Polyethylene‐d4 Oxide

Polarized infrared spectra of polyethylene oxide (PEO), —(CH2CH2O)n— and PEO‐d4, —(CD2CD2O)n—, have been measured in the region from 4000 to 80 cm—1. The spectra of PEO at various temperatures (about —130°, 20°, 65°, and 80°C) were also observed, and splittings of some perpendicular bands were found at the low temperature. The selection rules for the PEO molecule are derived under the factor group D(4π/7). The normal vibrations of PEO and PEO‐d4 are calculated for the Raman‐active A1 symmetry species, the infrared‐active A2 species, and the Raman‐ and infrared‐active E1 species, by use of the GF matrix method with the Urey—Bradley force field taking into account the torsional displacement coordinates of the skeleton. The results show fairly good agreement between the observed and calculated frequencies, and give strong support to the 72 helix conformation proposed by the authors previously. The assignments of the bands are given and discussed.

Normal Vibrations of the Polymer Molecules of Helical Conformation. V. Isotactic Polypropylene and Its Deuteroderivatives

Polarized infrared spectra of isotactic polypropylene (IPP), [Complex chemical formula] were measured in the region from 4000 to 80 cm−1. The normal vibrations of these three polymers were calculated for the infrared‐ and Raman‐active A and E species, by the use of the GF‐matrix method with the Urey—Bradley force field. The results show a fairly good agreement between the observed and calculated frequencies. The assignments of the absorption bands were given, and discussions were made on the vibrational modes of the bands characteristic of the isotactic helical structures. A computation program for calculating the characteristic values and vectors of a Hermitian matrix was presented.From the normal coordinate treatment applied to the threo‐ and erythro‐ model of di‐isotactic polypropylene‐1‐d, [Complex chemical formula] it was found that the polymers prepared from trans‐ and cis‐propylene‐1‐d, CHD, CH–CH3, have threo‐ and erythro‐di‐isotactic structures, respectively, suggesting cis‐opening mechanism in t...

Normal Vibrations of the Polymer Molecules of Helical Configuration. III. Polyoxymethylene and Polyoxymethylene‐d2

Polarized infrared spectra of polyoxymethylene (POM), — (CH2O)n—, and POM‐d2, — (CD2O)n— have been measured in the region from 4000 to 100 cm—1. The spectra of POM at elevated temperatures were also observed. The selection rules for POM molecules are derived under the factor group D(10π/9). The normal vibrations of POM and POM‐d2 are calculated for the Raman active A1 symmetry species, the infrared active A2 species and the Raman and infrared active E1 species, by the use of the GF‐matrix method with the Urey—Bradley force field taking into account the torsional displacement coordinates of the skeleton. The results show fairly good agreement of the observed and calculated frequencies. The assignments of the bands are given and discussed.

Normal Vibrations of Polyacrylonitrile and Deuterated Polyacrylonitriles

Polarized infrared spectra of polyacrylonitrile, poly‐α‐deuteroacrylonitrile, poly‐β,β‐dideuteroacrylonitrile and poly‐α,β,β‐trideuteroacylonitrile have been measured in the region from 4000 to 200 cm—1. β,β‐dideuteroacrylonitrile was prepared by the hydrogen re‐exchange reaction of α,β,β‐trideuteroacrylonitrile with H2O in the presence of CaO. The calculations of the normal vibrations of polyacrylonitrile and these three polydeuteroacrylonitriles have been made, assuming a syndiotactic planar zigzag chain as the most simple model for calculation. The calculation was made by the use of the GF‐matrix method with the Urey—Bradley force field. The results show fairly good agreement between the observed and calculated frequencies. The assignments of the bands are given and discussed.

Normal Vibrations of the Polymer Molecules of Helical Conformation. VI. Polytetrahydrofuran and Deuterated Polytetrahydrofurans

Polarized infrared spectra of polytetrahydrofuran, polytetrahydrofuran‐3,3,4,4‐d4, and polytetrahydrofuran‐d8 have been measured in the region from 4000 to 400 cm−1. The selection rules for polytetrahydrofuran molecule are derived under the factor group isomorphous to D2h. The normal vibrations of these polymer molecules are calculated for the infrared active B1u, B2u, and B3u species, by the use of the GF matrix method with the Urey‐Bradley force field. The results show fairly good agreement of the observed and calculated frequencies, and give support to the 21 helix conformation, i.e., the planar zigzag conformation, reported previously. The assignments of the bands are given and discussed.

Synthesis, structure and some properties of a new polyalcohol

Abstract A new polyalcohol (CH2CH2CH(OH))n was synthesized from 1:1 ethylene/carbon monoxide alternating copolymer (polyketone) by reduction with sodium borohydride. Some structural and chemical properties are described.

Cationic Copolymerization with Depropagation. The Copolymerization of α-Methylstyrene and Styrene

ABSTRACT To evaluate the existence of the depropagation reaction in the copolymerization of vinyl monomers, the cationic copolymerization of α-methylstyrene with styrene was studied. The copolymer composition exhibited an extensive dependency on the temperature of polymerization and the monomer concentration, this fact not being explained by the Mayo-Lewis equation. Treatment of the copolymerization in terms of the depropagation reaction led to an estimate of the monomer reactivity ratio and the equilibrium constant between the polymer and the monomer of α-methylstyrene. A comparison of the equilibrium constants thus obtained with those reported in the literature indicates that the magnitude of the equilibrium constants depends on the sequence length of α-methylstyrene units. By extrapolation to long sequence length, the equilibrium constants approach the values which are reported for high molecular weight poly(α-methylstyrene).

Vinylation Reaction of Sulfonamides with Acetylene

新しい複合触媒系を用いてアセチレン加圧下における脂肪族, 芳香族スルホンアミドのビニル化反応を行ない, その反応条件を検討した。通常活性水素をもつ有機化合物のビニル化反応の触媒として有効な亜鉛化合物,カドミウム化合物,またはアルカリ金属化合物単独では,スルホンアミドのビニル化反応はほとんど進行しないか,または非常に遅い。しかしカドミウム化合物とアルカリ金属化合物の共用により,これらスルホンアミドのビニル化反応はすみやかに進行し,対応するN-ビニル化合物が好収率で得られることを見出した。スルホンアミド0.045mol, 触媒KOH-CdO 各0.005mol 使用し, アセチレン初圧25～30kg/cm2 ,反応温度150℃ でのビニル化物の収率は40～90%である。アルカリ金属水酸化物-CdO系触媒を用いたビニル化反応において,その見かけの反応速度はアセチレンの1次,触媒濃度の1次に比例する。触媒に関しては,アルカリ金属の種類によりLi<Na<K<Rb<Csの順となり,その組成についてK/Cd当量比1で反応速度は極大となる。一方,スルホン-p-置換アニリドの同触媒によるビニル化反応速度の置換基効果は, CH3O<CH3≅H<Clの順に速度は大となる。これらの複合触媒系では, スルホンアミドのカドミウム塩とアルカリ金属塩の間のコンプレックス形成によるCd-N結合のイオン性の増加が触媒活性の原因であると推定される。