Melt Copolymerization Reactions between 1,3-Bis(diethylamino)tetramethyldisiloxane and Aryldiol Derivatives

Abstract

Melt copolymerization reactions of bis(diethylamino)tetramethyldisiloxane with several aryldiols were carried out to afford poly(carbotetramethyldisiloxane)s containing fluorescent aromatic chromophore groups in the polymer main chain: poly{oxy(4,4'-biphenylene)oxytetramethyldisiloxane}, poly{oxy(1,4-phenylene)oxytetramethyldisiloxane}, poly[oxy{(4,4'-isopropylidene)diphenylene}oxytetramethyldisiloxane], poly[oxy{(4,4'-hexafluoroisopropylidene)diphenylene}oxytetramethyldisiloxane], poly{oxy(2,6-naphthalene)oxytetramethyldisiloxane}, poly[oxy{4,4'-(9-fluorenylidene)diphenylene}oxytetramethyldisiloxane], poly{oxy(fluorene-9,9-dimethylene)oxytetramethyldisiloxane}, and poly[oxy{4,4'-(9-fluorenylidene)bis(2-phenoxyethylene)}oxytetra-methyldisiloxane]. These materials are soluble in common organic solvents such as CHCl 3 and THF. The FTIR spectra of all the polymers exhibit the characteristic Si-O-C stretching frequencies at 1021-1082 cm −1 . In the THF solution, the polymeric materials show strong maximum absorption peaks at 215-311 nm, with strong maximum excitation peaks at 250-310 nm, and strong maximum fluorescence emission bands at 310-360 nm. TGA thermograms indicate that most of the polymers are stable up to 200 o C with a weight loss of less than 10% in nitrogen.

Synthesis and Photoelectronic Properties of Thermally Stable Poly[oxy(2,7-fluoren-9-onenylene)oxy(diorganosilylene)]s

“…As shown in Figure 2 and Table 1, most of the prepared polymers, 4a-d, were more stable up to 300 °C than the polycarbosiloxanes previously prepared by melt copolymerization, with a weight loss of less than 5% in nitrogen, 27,28 and approximately 63-89% of the initial polymer weights remained at 500 °C in nitrogen.…”

Synthesis and Properties of Poly[oxy(arylene)oxy(tetramethyldisilylene)]s via Melt Copolymerization Reaction

“…The polymers 4a-d contained tetramethyldisilylene and several arylene groups, such as biphenylene, isopropylidenediphenylene, fluorenedimethylene, and fluorenylidenephenoxyethylene, along the polymer main chain, and the aromatic chromophores were different from the previously reported results. [20][21][22][23][24] The objective of these melt copolymerizations was to synthesize the copolymers of poly[oxy(arylene)oxy(tetramethyldisilylene)]s with high molecular weights. The synthesized materials were characterized by several spectrophotometric methods such as Si NMR in the solution state, and by using FTIR as well as elemental analysis.…”

“…20,21 We had previously reported the preparation and excited-state energy dynamics of polycarbosilanes and polycarbogermanes containing 1,4-bis(thiophene or phenylene)buta-1,3-diyne in the polymer backbone.…”

“…29,30 We also recently reported the melt copolymerizations of bis(diethylamino)silane and bis(diethylamino)disiloxane with several aryldiols. 20,21,24 We had tried copolymerization reactions between 1,2-bis(diethylamino)tetramethyldisilane 2 carrying the functionality of diethylamine group and several diol derivatives, by using a previously reported method.…”

Grignard Metathesis Polymerization and Properties of 1,1-Disubstituted-2,5-dibromo-3,4-diphenylsiloles

“…22 The melt copolymerizations of several bis(diethylamino)silane derivatives with 2,7-dihydroxyfluoren-9-one were also examined, and were found to produce poly[oxy-(2,7-fluoren-9-onenylene)oxy(diorgnaosilylene)]s containing fluoren-9-one as a fluorescent aromatic chromophore group in the main chains. 23 Recently, the melt copolymerizations of 1,2-bis(diethylamino)tetramethyldisilane with various aryldiols were studied, and these afforded poly[oxy-(arylene)oxy(tetramethyldisilylene)]s containing fluorescent aromatic chromophore groups in the polymer main chains.…”