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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inorganic and organometallic polymers and materials 2 (1992), S. 29-45 
    ISSN: 1572-8870
    Keywords: Polysilenes ; polysilanes ; liquid crystals ; mesophases ; birefringence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract (I) Ordered and disordered polysilane copolymers: Condensation of ClSiMe2Si(n-Hex)2SiMe2Cl with Na/K in toluene at 90°C produced a polymer with a strongly bimodal molecular weight distribution. The high-M w and low-M w portions were separated by fractional precipitation with 2-propanol, and the properties of the two fractions were investigated.29Si-NMR spectra show that the low-M w fraction is fully ordered but the high-M w fraction is randomized. (II) Liquid crystalline polysilanes: Condensation ofn-Bu(n-Hex)SiCl2 with Na in toluene led to a homopolymer which is a rubbery solid at 25°C. The polymer undergoes a second-order transition at −45°C and a first-order (melt) transition at −20°C. X-ray diffraction shows that the polymer has the same structure, a columnar hexagonal lattice, in all three phases; from −20 to 〉200°C, it exists in a columnar liquid crystalline mesophase. Similar hexagonal mesophases were observed at 25°C for the family of copolymers, (n-Hex2Si) n (Alk2Si) m , Alk =n-Pentyl,n-Bu,n-Pr, Et, Me.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of inorganic and organometallic polymers and materials 1 (1991), S. 545-565 
    ISSN: 1572-8870
    Keywords: Polysilanes ; sigma-pi conjugation ; mesophases ; polymer crystals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Polymers of structure (SiR2SiR2-C ≡ C-SiR2′SiR2′-C ≡ C) n , in which ethynylene units alternate with disilylene units, have been prepared by two routes: (a) condensation of dichlorodisilanes with dilithium derivatives of 1,2-diethynyldisilanes and (b) ring-opening polymerization of strained cyclic disilanylene-acetylnes, (SiR2SiR2C ≡ C)2. The polymers display UV absorption near 240 nm indicative of σ − π conjugation between the Si2 and the C ≡ C moieties. Polymers with R=R′=n-Bu or R=n-Bu, R′=Ph, undergo solid-state transitions to form liquid crystalline mesophases resembling those observed for many poly(silylenes). Single crystals were obtained for the polymer with R=R′=CH3, by precipitation from dilute cyclohexane solution. The solid-state properties and structures of this family of polymers are discussed.
    Type of Medium: Electronic Resource
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