Glass transition temperatures -siloxane

Silicones. Polydimethylsiloxanes, polydiphenylsiloxanes, and polymethylphenylsHoxanes are generally called siUcones (see Silicon COMPOUNDS, silicones). With a repeating unit of alternating siUcon-oxygen, the siloxane chemical backbone stmcture, siUcone possesses excellent thermal stabiUty and flexibility that are superior to most other materials. Polydimethjisiloxane provides a very low glass-transition temperature T material but is suitable for use... 

Although each of these cyclic siloxane monomers can be polymerized separately to synthesize the respective homopolymers, in practice they are primarily used to modify and further improve some specific properties of polydimethylsiloxanes. The properties that can be changed or modified by the variations in the siloxane backbone include the low temperature flexibility (glass transition temperature, crystallization and melting behavior), thermal, oxidation, and radiation stability, solubility characteristics and chemical reactivity. Table 9 summarizes the effect of various substituents on the physical properties of resulting siloxane homopolymers. The... 

The most commonly used siloxane modifiers are those having phenyl, trifluoro-propyl and cyanopropyl substituents. Introduction of phenyl units into the polydimethylsiloxane backbone either in the form of methylphenylsiloxane or diphenyl-siloxane increases the thermal and oxidative stability, glass transition temperature and the organic solubility characteristics of the resulting copolymers. At low levels (5-10 percent by weight) of incorporation, bulky phenyl groups also break up the regularity of polydimethylsiloxane chains and inhibit the crystallization (Tc... 

Values of the upper glass transition temperatures of the siloxane modified polyimides were found to be a function of both the level of incorporated siloxane as well as the siloxane molecular weight (Table II). The upper transition temperature of the solution... 

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). 

Siloxane elastomers present an attractive alternative to the butadiene acrylonitrile elastomers most often used for epoxy modification. Poly(dimethyl siloxanes) exhibit glass transition temperatures well below those of butadiene acrylonitrile modifiers (minimum —123 °C vs. about —40 °C) and also display very good thermal stability13, 14). Other favorable and potentially useful attributes include good weatherability, oxidative stability, and moisture resistance. Finally, the non-polar nature and low surface energy of poly(dimethyl siloxanes) constitute a thermodynamic driving force... 

The epoxy/siloxane/PACM-20 mixture was poured into a hot (120 °C) RTV-silicone mold of the precise shapes to be used for solid-state testing. The mixture was cured at 160 °C for 2.5 hours. The curing time and temperature chosen were considered to provide enough mobility for network formation. This conclusion was partially based on earlier studies which found a glass transition temperature of 150 °C for Epon 828/PACM-20 3S). 

Table 1. Glass Transition Temperatures of Siloxane Oligomers...

Table 1 lists the glass transition temperatures for the pertinent siloxane oligomers as a function of TFP and DP contents. The percent of each comonomer is recorded with reference to the siloxane units as well as the entire oligomer. One notes the difference that this creates between the two nominally 100% TFP siloxanes of different molecular weight. Note also the higher Tg values for the DP series at equal weight percents, a factor which limits their ease of synthesis and may affect their mobility during cure. 

The dynamic mechanical properties of the siloxane-modified epoxy networks were also investigated. The DMTA curves for the control epoxy network exhibit the two major relaxations observed in most epoxy polymers 39 40,41>. A high temperature or a transition at 150 °C corresponds to the major glass transition temperature of the network above which large chain motion takes place. The low temperature or (5 transition is a broad peak extending from —90° to 0 °C with a center near —40 °C. It has been attributed predominantly to the motion of the CH2—CH(OH)—CH2—O (hydroxyether) group of the epoxy 39-40 2 ... 

In a similar manner, the hydrosilylation-polymerization of diallyl bisphenol A (278) with 275 in the presence of a platinum catalyst affords polymer 279 that possesses a relatively high glass transition temperature for siloxane polymers (Tg = 28-34 °C) and... 

Other siloxane polymers are of interest because their very low glass transition temperatures render plasticisers superfluous. However their low polarity and high hydrophobicity means that the simple commercial polydimethyl-siloxanes have high membrane resistances [92], probably due to the low solubility of ions in such media. Plasticisers could aid this but would defeat the object of using polysiloxanes in the first place. Incorporation of more polar moieties as co-monomers in the polymer, such as cyanopropyl [93], lowered membrane resistance by a factor of up to 20, with the incorporation of triflu-oropropyl groups leading to sensors for nitrate and cations [94]. Studies have also been made on using photopolymerisable crosslinkers, for example in the construction of a nitrate sensor [95]. 

Different materials for the hydrophobic membrane in which the receptor is incorporated, have been investigated. Polysiloxanes that have the required glass transition temperature and dielectric constant provide a stable chemical system that transduces the complexation of cationic species into electronic signals. The material properties can be optimized by copolymerization of three building blocks viz. dimethyl-, (3-cyanopropyl)methyl-, and methacryloxypropylmethyl siloxane. CHEMFETs made with this terpolymer have fast response times (<. 1 sec.). With valinomycin and hemispherands (2) and (3) linear responses to changing K+ concentrations are obtained in the range 10"5 - 1.0M (55-58 mV/decade) in a solution of 0.1M NaCl. Similar devices specific for Na+ and Ca2+ have been obtained with other ionophores. 

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