New synthetic method for aromatic polyketones from bis(arylsilane)s and aromatic dicarboxylic acid chlorides

A new synthetic method for aromatic polyketones was developed through Friedel–Crafts polycondensation of bis(arylsilane) monomers with aromatic dicarboxylic acid chlorides. The solution polycondensation of these monomer pairs in the presence of aluminum chloride in 1,2‐dichloroethane readily afforded aromatic polyketones having inherent viscosities up to 0.37 dL/g with the elimination of chlorotrimethylsilane. The polycondensation proceeded through aromatic electrophilic ipso substitution, the mechanism of which is very similar to that of normal Friedel–Crafts acylation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2729–2735, 2002     

Copper(I) tert-butoxide-promoted coupling of o-(1-hydroxyalkyl)arylsilanes with organic halides

Copper(I) tert-butoxide-promoted coupling of arylsilanes possessing a 1-hydroxyalkyl group at the o-position with organic halides proceeded to give disubstituted arenes. The results indicate that an intermediary arylcopper species is formed by aromatic C^sp2-to-O silyl migration.     

New regioselective synthesis of metalinked aromatic polyketones from metasubstituted bis(arylsilane)s and aromatic dicarboxylic acid chlorides

A new regioselective synthesis of metalinked aromatic polyketones was achieved for the first time. New metaconnected aromatic polyketones with inherent viscosities of up to 0.49 dL/g were regioselectively synthesized by the solution polycondensation of metasubstituted bis(arylsilane)s with aromatic dicarboxylic acid chlorides in the presence of aluminum chloride in 1,2‐dichloroethane along with the elimination of chlorotrimethylsilane. The polycondensation proceeded through aromatic electrophilic ipso‐substitution. The metalinked aromatic polyketones had considerably lower glass‐transition temperatures and 10% weight‐loss temperatures than those of their counterpart paracatenated aromatic polyketones. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1428–1434, 2003     

A study of polyurethanes synthesized from an arylsilane,bis(4,4′-phenylisocyanato)dimethylsilane,and its carbon analog, 2,2-bis(4,4′-phenylisocyanato)propane

Bis(4,4′-phenylisocyanato) dimethylsilane (SiDI) and 2,2-bis (4,4′-phenylisocyanato)propane (PrDI) were synthesized, polymerized to polyurethanes, and their chemical, thermal and physical properties studied. Nuclear magnetic resonance spectra confirm deshielding by silicon of both the phenyl ring and the urethane linkage. The glass transition temperatures, solubility parameters, and mechanical properties were independent of the diisocyanates. The silicon containing polyurethanes are more thermally stable than their carbon counterparts. © 1993 John Wiley & Sons, Inc.     

A study of polyesters synthesized from an arylsilane and its carbon analog

Bis(4,4′-benzoyl chloride) dimethylsilane (SiCO) and 2,2-bis(4,4′-benzoyl chloride) propane (CCO) were synthesized and polymerized with butanediol, resorcinol, or hydroquinone. The polymers of SiCO–hydroquinone (SiCO–Hyd) and SiCO–resorcinol (SiCO–Res) possess glass transition temperatures 25°C lower than their carbon analogs but the less aromatic SiCO–butanediol (SiCO–BDO) and CCO–butanediol (CCO–BDO) polymers have similar glass transitions. Silicon containing polymers are superior to their carbon counterparts in thermal stability. Furthermore, polyarylates of excellent thermal stability and solubility were synthesized from SiCO/terephthaloyl chloride and hydroquinone. © 1993 John Wiley & Sons, Inc.