Siloxanes thermal stability

Silane coupling agents may contribute hydrophilic properties to the interface, especially when amino functional silanes, such as epoxies and urethane silanes, are used as primers for reactive polymers. The primer may supply much more amine functionality than can possibly react with the resin at the interphase. Those amines that could not react are hydrophilic and, therefore, responsible for the poor water resistance of bonds. An effective way to use hydrophilic silanes is to blend them with hydrophobic silanes such as phenyltrimethoxysilane. Mixed siloxane primers also have an improved thermal stability, which is typical for aromatic silicones [42]. 

More recently, St. Clair and co-workers176) reported the use of aromatic amine terminated polydimethylsiloxane oligomers of varying molecular weights in an effort to optimize the properties of LARC-13 polyimides. They observed the formation of two phase morphologies with low (—119 to —113 °C) and high (293 to 318 °C) temperature Tg s due to siloxane and polyimide phases respectively. The copolymers were reported to have improved adhesive strengths and better thermal stabilities due to the incorporation of siloxanes. 

Development of several new siloxane-imide copolymers for commercial applications have also been reported by Lee 181) and Berger58). Although no information was given in terms of the chemical compositions of these materials, most of these polymers were reported to be processable by solution or melt processing techniques, most probably due to their high siloxane contents. However, due to the presence of low (—20 to —120 °C) and high (>230 °C) temperature Tg s, it was clear that multiphase copolymers have been synthesized. Molecular weights and thermal stabilities, etc, were not reported. 

In most of the studies discussed above, except for the meta-linked diamines, when the aromatic content (dianhydride and diamine chain extender), of the copolymers were increased above a certain level, the materials became insoluble and infusible 153, i79, lsi) solution to this problem with minimum sacrifice in the thermal properties of the products has been the synthesis of siloxane-amide-imides183). In this approach pyromellitic acid chloride has been utilized instead of PMDA or BTDA and the copolymers were synthesized in two steps. The first step, which involved the formation of (siloxane-amide-amic acid) intermediate was conducted at low temperatures (0-25 °C) in THF/DMAC solution. After purification of this intermediate thin films were cast on stainless steel or glass plates and imidization was obtained in high temperature ovens between 100 and 300 °C following a similar procedure that was discussed for siloxane-imide copolymers. Copolymers obtained showed good solubility in various polar solvents. DSC studies indicated the formation of two-phase morphologies. Thermogravimetric analysis showed that the thermal stability of these siloxane-amide-imide systems were comparable to those of siloxane-imide copolymers 183>. 

The synthesis of block polymers of diacetylene-silarylene and diacetylene-carboranylenesiloxane polymers (99a-e) (Fig. 61) by the polycondensation reaction of 1,4-dilithiobutadiyne with l,4-bis(dimethylchlorosilyl) benzene and/or l,7-bis(tetramethylchlorodisiloxane)-m-carborane have been reported by Sundar and Keller.129 These polymers are a hybrid between the carboranylenesiloxane and silarylene-siloxane polymers and have high char yields (up to 85%) at 1000°C in N2 and in air, reflecting the thermal stabilizing effects of the carborane and aromatic units in the polymeric backbone. 

In thick samples, a boron oxide/boron carbide crust has been detected on the surface of the polymer. This inorganic surface layer has a shielding effect on the inner polymer layers, further enhancing the thermal stability of the material. Poly(m-carborane-siloxane)s have therefore been considered as surface coatings for organic materials, providing protection from erosion effects. 

At the other end of the temperature spectrum, with high thermal stability of siloxane-modified poly(arylene carbonates) also a desired property, the onset of thermal decomposition (40) for polymers 1-12 was found to be in the range of 385-456°C (as determined from TGA curves obtained by heating polymer samples in nitrogen at a heating rate of 20°C/min.). There does not appear to be any pronounced trend in regard to variation of the thermal stability with structure in polymers 1-12. The small differences in the values of T for these polymers can be due... 

As expected, the terminal functional groups mainly determine the reactivity of these siloxane oligomers towards other reactants. The variations in the backbone composition have critical effects on the glass transition temperature, solubility parameter, thermal stability and surface behavior of the resulting oligomers(12,13). 

Silicones possess both thermal stability and good mechanical, chemical, and electric properties between —70 and 250 C. In the absence of oxygen, many linear siloxanes degrade at temperatures greater than 350 C to give cyclic products. Oxidative degradation generally occurs at lower temperatures. 

Heteroboranes, compounds where one or more of the cage borons are replaced by a main group element (33), are not themselves commercially available. However, carborane siloxanes containing w-carborane [16986-21-6], C2H12B10, are available under the trade name of Dexsil for the stationary phase in gas—liquid chromotography (qv) (34). The carborane, l,7-dicarba- / o-dodecaborane(10) (35), contributes enhanced chemical and thermal stability to the siloxane polymer. 

Several modifications of commercial silane coupling agents have been evaluated to search for improved bonding at the interface. These approaches attempt to use modifiers to counteract basic faults of the individual silanes. Some of these modifications include increased hydrophobic character, increased crosslinking of the siloxane structure, increased thermal stability, and ionomer bond formation to reduce shear degradation at the interface. 

The lanthanides find some use as stabilizers for polymers. The coating of polycarbonate with a poly(vinyl alcohol) film containing CeCl3 inhibits photodegradation of the polycarbonate.151 The naphthenates of cerium, lanthanum and yttrium act as thermal stabilizers for polyorgano-siloxanes.152... 

Silicones. Polydimethylsiloxanes, polydiphenylsiloxanes, and polymethylphenylsiloxanes are generally called silicones (see Silicon COMPOUNDS, silicones). With a repeating unit of alternating silicon—oxygen, the siloxane chemical backbone structure, silicone possesses excellent thermal stability and... 

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