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Poly(phenylacetylene)s Carrying Siloxy, Carbonate, and Hydroxy Groups: Synthesis and Properties
Author(s) -
Saeed Irfan,
Shida Yuichi,
Khan Fareha Zafar,
Shiotsuki Masashi,
Masuda Toshio
Publication year - 2008
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.200800029
Subject(s) - monomer , phenylacetylene , polymer chemistry , polymer , chemistry , polymerization , solubility , catalysis , polyimide , yield (engineering) , organic chemistry , materials science , layer (electronics) , metallurgy
t ‐Butyldimethylsilyl ( t ‐BDMS) and t ‐butoxycarbonyl ( t ‐Boc) protected 3‐ and 4‐hydroxyphenylacetylene monomers were synthesized and polymerized using [(nbd)RhCl] 2 ( 1 ) and [(nbd)RhBPh 4 ] ( 2 ) catalysts. The t ‐BDMS‐containing polymers [poly( 3a ) and poly( 4a )] were obtained in good yield (45–69%) while the t ‐Boc‐protected monomers polymerized in a high yield [poly( 5a ) and poly( 6a ): 80–100%]. The use of KN(SiMe 3 ) 2 as a cocatalyst in conjunction with 1 led to a dramatic increase in the molecular weight of the polymers. The acid‐catalyzed removal of the t ‐BDMS group afforded the naked hydroxy‐containing polymers [poly( 3b ) and poly( 4b )] which cannot be obtained directly by the polymerization of the corresponding monomers. The polymers containing protected OH moieties were more soluble in less polar solvents, whereas their deprotected counterparts displayed good solubility in polar protic or highly polar aprotic solvents. The attempts to accomplish the free‐standing membrane fabrication by solution casting were successful only for poly( 3a ) and an augmentation in the gas permeability was discerned in comparison with the unsubstituted poly(phenylacetylene) and poly( o ‐methylphenylacetylene).