Polymerization of Si‐containing acetylenes. XIV. Polymerization of diphenylacetylenes with bulky silyl groups and polymer properties

Abstract

Polymerization and polymer properties of diphenylacetylenes with bulky silyl groups (SiMe2–i‐Pr, SiMe2–t‐Bu, SiMe2Ph, SiEt3) at para or meta position were studied under comparison with those of the SiMe3 derivatives. The present monomers polymerized in good yields with TaCl5‐cocatalysts to form high molecular‐weight polymers (Mw > 4 × 105). The polymer yields of para‐substituted monomers were similar to that of the SiMe3 derivative, while those of meta substituted monomers were lower than that of m‐SiMe3 derivative. Most of the polymers were totally soluble in common solvents such as toluene and CHCl3, although the polymers with p‐SiMe2–t‐Bu and p‐SiMe2Ph groups were partly insoluble in all solvents. These polymers resembled SiMe3‐containing homologues in the UV‐visible absorption and thermal stability. The oxygen permeability coefficients of these polymers were in the range of 10−9−10−8 cm3 (STP) cm/(cm2·s cm Hg)—lower than those of the corresponding SiMe3‐containing polymers. © 1993 John Wiley & Sons, Inc.

Synthesis of Poly(diphenylacetylene) Membranes by Desilylation of Various Precursor Polymers and Their Properties

“…The P(O 2 ) values of membranes 2f and 2g with silyl groups at meta position were 1700 and 1000 barrers, respectively, which are slightly higher than those of para-substituted analogues (2a, 1500 barrers; 2b, 500 barrers; 2 with p-SiMe 2 -t-Bu is insoluble 14 ). Unfortunately, the oxygen permeability of their desilylated membranes (3f and 3g) could not be measured because their desilylation did not proceed completely.…”

Enhancement of oxygen permeability by copolymerization of silyl group-containing diphenylacetylenes with tert-butyl group-containing diphenylacetylene and desilylation of copolymer membranes

“…Phenylacetylene (Aldrich), triethylamine, triphenylphosphine, copper(I) iodide, dichlorobis(triphenylphosphine) palladium(II), p-bromo-tert-butylbenzene, 1,4-dibromobenzene, triuoroacetic acid (TFA), n-butyllithium hexane solution (1.6 M), chlorotrimethylsilane, chlorotriethylsilane, chlorodimethyln-octylsilane, chlorotriphenylsilane, and common solvents (Wako Pure Chemical) were used without further purication. 1-Phenyl-2-(p-trimethylsilyl)phenylacetylene (TMSDPA), 9 1phenyl-2-(p-triethylsilyl)phenylacetylene (TESDPA), 13 1-phenyl-2-(p-dimethyl-n-octylsilyl)phenylacetylene (DMOSDPA), 10 1phenyl-2-(p-triphenylsilyl)phenylacetylene (TPSDPA), 14 and 1phenyl-2-(p-tert-butyl)phenylacetylene (TBDPA) 11 were synthesized according to the literatures.…”

Synthesis, characterization, and gas permeation properties of the silyl derivatives of cellulose acetate

“…One of them, poly(1-trimethylsilyl-1-propyne) [poly(TMSP)] is the most gas-permeable material, and many studies concerning the gas permeation properties of this polymer have been reported till today [13,16,[20][21][22][23][24][25]. Most of poly(1-aryl-2-phenylacetylenes) having spherical substituents on the phenyl moiety also exhibit high gas permeability [14,[26][27][28][29][30]. For instance, the oxygen permeability coefficient (P O 2 ) of poly[1-phenyl-2-(p-trimethylsilyl)phenylacetylene] [poly(TMSDPA)] is 1500 barrers [27], which is appreciably high among all the synthetic polymers.…”