Dielectric polyethers

Solvent for Displacement Reactions. As the most polar of the common aprotic solvents, DMSO is a favored solvent for displacement reactions because of its high dielectric constant and because anions are less solvated in it (87). Rates for these reactions are sometimes a thousand times faster in DMSO than in alcohols. Suitable nucleophiles include acetyUde ion, alkoxide ion, hydroxide ion, azide ion, carbanions, carboxylate ions, cyanide ion, hahde ions, mercaptide ions, phenoxide ions, nitrite ions, and thiocyanate ions (31). Rates of displacement by amides or amines are also greater in DMSO than in alcohol or aqueous solutions. Dimethyl sulfoxide is used as the reaction solvent in the manufacture of high performance, polyaryl ether polymers by reaction of bis(4,4 -chlorophenyl) sulfone with the disodium salts of dihydroxyphenols, eg, bisphenol A or 4,4 -sulfonylbisphenol (88). These and related reactions are made more economical by efficient recycling of DMSO (89). Nucleophilic displacement of activated aromatic nitro groups with aryloxy anion in DMSO is a versatile and useful reaction for the synthesis of aromatic ethers and polyethers (90). 

Further lowering the dielectric constants has been achieved by preparing highly fluorinated polyethers without any sulfone, ketone, or other polarizable groups.239 241 Typically, the /jara-lluorinc atoms on highly fluorinated aromatic compounds, such as hexafluorobenzene and decafluorobiphenyl, are activated and thus can go through aromatic nucleophilic substitution with HFBPA under typical reaction conditions (Scheme 6.31).217... 

Dielectric relaxation studies of phosphorylated polyethers from — 180° to 200 °C have been used to study their structures. The magnitude of the dielectric constants of high-phosphonic-acid-content polymers is much larger than predicted, which suggests a microphase-separated structure. Conductance studies on some aryl- and alkyl-phosphonium salts showed a higher conductance for the halides than for the nitrate. ... 

Recently the synthesis and characterization of novel fluorinated poly(aryl ether)s containing perfluorophenylene moieties " " was also reported. These fluorinated polyethers were prepared by reaction of decafluorobiphenyl with bisphenols. These polymers exhibit low dielectric constants, low moisture absorption, and excellent thermal and mechanical properties. Tough, transparent films of the polymers were prepared by solution-casting or compression-molding. The fluorinated poly(aryl ether)s containing perfluorophenylene moieties are good candidates for use as coatings in microelectronics applications. 

The discriminative uptake of alkali metal cations by biological systems, through their membranes, has been an area of much interest. In the membrane, the cations must pass through a lipid bilayer of low dielectric constant and this has led to the proposition that the cation could be selectively transferred via a carrier molecule, or through a suitably donor-lined pore.7-9 As a consequence of their selective properties, the polyethers and cryptands have been investigated as speculative models for the above process and selectivity sequences have been established. 

Much attention has been paid to the synthesis of fluorine-containing condensation polymers because of their unique properties (43) and different classes of polymers including polyethers, polyesters, polycarbonates, polyamides, polyurethanes, polyimides, polybenzimidazoles, and epoxy prepolymers containing pendent or backbone-incorporated bis-trifluoromethyl groups have been developed. These polymers exhibit promise as film formers, gas separation membranes, seals, soluble polymers, coatings, adhesives, and in other high temperature applications (103,104). Such polymers show increased solubility, glass-transition temperature, flame resistance, thermal stability, oxidation and environmental stability, decreased color, crystallinity, dielectric constant, and water absorption. 

The use of cyclic (crown) polyethers and cryptates to enhance metal solubilities also opens up many interesting possibilities for studying expanded-metal compounds in the low-dielectric-constant solvents... 

Dielectric relaxation study of two-phase microstructures in segmented copolymers was first attempted by North and his co-workers (55, 57,58,59). Dielectric measurements down to 10 5Hz were made on MDI-based segmented polyether- and polyester-urethanes using a dc transient technique. These materials displayed large, low-frequency... 

This paper presents some of our results on the synthesis and structure of thermotropic main-chain liquid crystalline polyethers based on bis(4-hydroxy-phenoxy)-p-xylene. It also deals with two areas in the field of liquid crystalline polymers that have received only little attention, namely the dielectric relaxation (5-10 and Gedde, U.W. Liu, F. Hult, A. Gustafsson, A. Jonsson, H. Boyd, R.H. Polymer submitted) and the kinetics of isotropic-mesomorphic state transitions (11-14. 32). They are both very important for the understanding of the nature of the mesomorphic state in polymers and for the understanding of similarities and differences of physical phenomena between liquid crystalline and semi-crystalline polymers. 

Figure 4. Measured e spectra at 24°C for O, a segmented polyether-polyurethane (UET46-1) and , a segmented polyether-polyester (H49). Measurements were made with the steady-state response dielectric spectrometer.

Dielectric Properties and Electret Behavior of Complexed Polyethers... 

Polarity varies widely from one polymer to the next. PDMS has a dielectric constant of only 2.8 [13], meaning that its polarity is close to that of toluene. Solid PEG has a Kamlett-Taft k (polarity/polarizability) value of 0.86 and an Ej(30) value of 45.7 [19], The r(30) value implies a polarity comparable to MeCN or DMSO while the n value is surprisingly high for an entirely saturated structure. Ohno and Kawanabe showed that the Ej(30) of a polyether increases with molar mass and calculated that the E-j-(30) values of PEG and PPG with infinite chain lengths would be 46.6 and 38.5 kcal mol [20]. Thus PPG is significantly less polar, matching the polarity of butyl acetate. 

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