Molecular precursors, thermal condensation

Typical characterization of the thermal conversion process for a given molecular precursor involves the use of thermogravimetric analysis (TGA) to obtain ceramic yields, and solution NMR spectroscopy to identify soluble decomposition products. Analyses of the volatile species given off during solid phase decompositions have also been employed. The thermal conversions of complexes containing M - 0Si(0 Bu)3 and M - 02P(0 Bu)2 moieties invariably proceed via ehmination of isobutylene and the formation of M - O - Si - OH and M - O - P - OH linkages that immediately imdergo condensation processes (via ehmination of H2O), with subsequent formation of insoluble multi-component oxide materials. For example, thermolysis of Zr[OSi(O Bu)3]4 in toluene at 413 K results in ehmination of 12 equiv of isobutylene and formation of a transparent gel [67,68]. 

By analogy with B-trialkylaminoborazi ne and polyborazine derived therefrom, the first route envisioned to poly(borylaminoborazine) was the thermal condensation of molecular precursors under a convenient atmosphere. As detailed earlier the innovative idea behind this procedure is to tailor the polymeric precursor structure by increasing the distance between the two borazinic rings. For that purpose, we explored... 

Such approach of the synthesis by solid-state reaction is especially attractive with precursors that present silanol functions. Here again, the supramo-lecular association promoted by these functions combined with their reactivity allows to directly transform by a simple thermal treatment a molecular precursor to a polymeric hybrid material. Liu, et al. have reported on the possibility to polycondense silanols in the solid state [95], and Corriu et al. have obtained the formation of layered materials by condensation of bis-trisilanol precursors [96,97],... 

One of the basic properties of siloxenes is their general insolubility in organic solvents, a fact that strongly impedes physical and structural characterization. As a result, the question arose as to whether structurally better defined siloxene-like polymers with improved solubility can be assembled in a stepwise manner starting from appropriate molecular precursors, and whether the properties of siloxene, such as the intense photoluminescence, can be matched. We thus attempted to rebuild the proposed structure of Kautsky-siloxene by the controlled hydrolysis of cyclic or linear oligosilanes bearing hydrolytically labile substituents followed by the thermal condensation to polymeric siloxanes. The general route is outlined in Scheme 16.1. 

A change of alkoxy group leads to the formation of new types of molecular precursors with different volatilities, thermal stabilities, and with a wide range of chemical properties toward the hydrolysis and condensation reactions. 

Not only must precursor fibers be self-supporting as extruded, they must also remain intact (e.g. not melt or creep) during pyrolytic transformation to ceramic fibers. Thus, precursor fibers (especially melt spun fibers) must retain some chemical reactivity so that the fibers can be rendered infusible before or during pyrolysis. Infusibility is commonly obtained through reactions that provide extensive crosslinking. These include free radical, condensation, oxidatively or thermally induced molecular rearrangements. 

The telechelica,(i -bis(2,6-dimethylphenol)-poly(2,6-dimethylphenyl-ene oxide) (PP0-20H) [174-182] is of interest as a precursor in the synthesis of block copolymers [175] and thermally reactive oligomers [179]. The synthesis has been accomplished by five methods. The first synthetic method was the reaction of a low molecular weight PPO with one phenol chain end with 3,3, 5,5 -tetramethyl-l,4-diphenoquinone. This reaction occurred by a radical mechanism [174]. The second method was the electrophilic condensation of the phenyl chain ends of two PPO-OH molecules with formaldehyde [177,178], The third method consists of the oxidative copolymerization of 2,6-dimethylphenol with 2,2 -di(4-hydroxy-3,5-di-methylphenyl)propane [176-178]. This reaction proceeds by a radical mechanism. A fourth method was the phase transfer-catalyzed polymerization of 4-bromo-2,6-dimethylphenol in the presence of 2,2-di(4-hy-droxy-3,5-dimethylphenyl)propane [181]. This reaction proceeded by a radical-anion mechanism. The fifth method developed was the oxidative coupling polymerization of 2,6-dimethylphenol (DMP) in the presence of tetramethyl bisphenol-A (TMBPA) [Eq. (57)] [182],... 

The examination of structure/property relations of molecular educts and resulting ceramics required the synthesis of stoichiometrically and stmcturally different precursors. A variety of synthesis routes for Si-B-N-C precursors fiom organosilanes, silazanes, and boron compounds have been reported in recent years [3 - 5]. As an example, Riedel obtained a polymeric precursor via hydroboration of methylvinyldichlorosilane and subsequent condensation of the hydroboration product with ammonia (Eq. 1). Pyrolysis led to silicoboron carbonitride ceramics exhibiting thermal stability up to 2000 °C [6]. 

Pillared clays, layered silicates whose sheets have been permanently propped open by thermally stable molecular props, were used as templates to load various organic precursors.The pore diameters of resulting carbon materials range from 8 to 22 A, and the mass fractal dimension varies from 2.5 to 2.9, which are accessible to lithium ions when the intercalation process takes place in a lithium secondary battery. An approach to pyrolyse aromatic hydrocarbons such as pyrene within a pillared clay was also reported, in which the pillared clay serves two functions.It acts as the inorganic template around which the carbon can be formed, and it also functions as an acid catalyst to promote condensation of the aromatics similar to the Scholl reaction. The resulting carbon materials have pore sizes from 15 to 50... 

For example, it is possible to prepare hyperbranched polyimides from 3,5-dimethoxyphenol and 4-nitrophthalonitrile in the presence of diphenyl(2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate (DBOP) as a condensation agent at room temperature. Hyperbranched polyimide was obtained through thermal or chemical imidization of the precursor (polyamic acid) (Scheme 1.3) [19]. The obtained hyperbranched polyimide had a relatively great molecular mass (A/ ) of about 190000gmor but low inhinsic viscosity of 0.30 dLg . Therefore, it had a compact configuration and the lack of entanglement of polymer chains. The polymer obtained via chemical imidization was soluble in apiotic polar solvents such as tetrahydrofuran (THF), while the polymer from thermal imidization was insoluble in any solvents. 

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