Polyarylene polymers

Another important factor affecting the electronic properties is the steric barrier to planarity along the polymer chain. Since polyheterocycles and polyarylenes must adopt a planar geometry in the ionized state to form quinoid-like segments, steric factors that limit the ability of the polymer to adopt geometries which are planar with respect to adjacent rings have a detrimental effect on the electronic properties (181). 

L V. Krivoshei and V. M. Skorobogatov, Polyacetylene and Polyarylenes. Synthesis and Conductive Properties, Polymer Monographs Vol. 10, Gordon and Breach, Philadelphia, 1991. 

As early as 1952, Flory [5, 6] pointed out that the polycondensation of AB -type monomers will result in soluble highly branched polymers and he calculated the molecular weight distribution (MWD) and its averages using a statistical derivation. Ill-defined branched polycondensates were reported even earlier [7,8]. In 1972, Baker et al. reported the polycondensation of polyhydrox-ymonocarboxylic acids, (OH)nR-COOH, where n is an integer from two to six [ 9]. In 1982, Kricheldorf et al. [ 10] pubhshed the cocondensation of AB and AB2 monomers to form branched polyesters. However, only after Kim and Webster published the synthesis of pure hyperbranched polyarylenes from an AB2 monomer in 1988 [11-13], this class of polymers became a topic of intensive research by many groups. A multitude of hyperbranched polymers synthesized via polycondensation of AB2 monomers have been reported, and many reviews have been published [1,2,14-16]. 

U. Scherf and K. Mullen, Polyarylenes and poly(arylene vinylenes), 7. A soluble ladder polymer via bridging of functionalized poly(p-phenylene)-precursors, Makromol. Chem., Rapid Commun., 12 489-497, 1991. 

This research was an attempt to develop new polymers with the mechanical properties of polyarylene ethers and the dielectric properties of fluoropolymers. After initially testing the viability of the [2n+ 2n] cyclodimerization reaction for preparing high-molecular-weight polymers and testing the dielectric properties of these polymers, two polymers (one thermoplastic and one thermoset) were prepared in larger quantities to evaluate the thermal and mechanical performance of these novel compositions. The high Te thermoset was also quantitatively tested for thermal/oxidative stability. 

A substantial intramolecular protective effect by phenyl groups in polymers is shown by the low G values for Hz and crosslinking in polystyrene (substituent phenyl) and in polyarylene sulfones (backbone phenyl), as well as many other aromatic polymers. The relative radiation resistance of different aromatic groups in polymers has not been extensively studied, but appears to be similar, except that biphenyl provides increased protection. Studies on various poly(amino acid)s indicate that the phenol group is particularly radiation resistant. 

Of all the hydrocarbon-based PEMs, this group most likely has the largest variety of different systems. This is probably due to the wealth of prior knowledge of the nonsulfonated analogues that have been developed over the last several decades as well as the general expectation of higher thermal stability, better mechanical properties, and increased oxidative stability over polystyrene-based systems. Within the context of this section, polyarylenes are systems in which an aryl or heteroaryl ring is part of the main chain of the polymer. This section will, therefore, include polymers such as sulfonated poly (ether ether ketone) and sulfonated poly(imides) but will not include systems such as sulfonated polystyrene, which will be covered in Section 3.3.I.3. 

Xing, D. and Kerres, J. 2006. Improved performance of sulfonated polyarylene ethers for proton exchange membrane fuel cells. Polymers for Advanced Technologies 17 591-597. 

Figure 20. Electro-osmotic drag coefficients of diverse membranes based on perfluorinated polymers (Dow - and Nafion/silica composites ) and polyarylenes (S—PEK/ PSU blends, ionically cross-linked S—PEK/PBP ), as a function of the solvent (water/methanol) volume fraction Xy (see text for references). Lines represent data for Nafion and S—PEK (given for comparison) for data points, see Figure 15. Dashed lines correspond to the maximum possible electro-osmotic drag coefficients for water and methanol, as indicated (see text).

There have been isolated QSPR studies of a number of other polymer properties. These include the dielectric constant [144], the dielectric dissipation factor (tan 8) [168], the solubility parameter [169], the molar thermal decomposition function [170], the vitrification temperature of polyarylene oxides [171], and quantities relating to molecularly imprinted polymers [172, 173]. The interested reader is referred to the literature for further information. 

Sulfonation is very useful chemical modification of polymer, as it induces high polarity in the polymer changing its chemical as well as physical properties. Sulfonated polymers are also important precursors for ionomer formation [75]. There are reports of sulfonation of ethylene-propylene diene terpolymer (EPDM) [76, 77], polyarylene-ether-sulfone [78], polyaromatic ether ketone [79], polyether ether ketone (PEEK) [80], styrene-ethylene-butylene-styrene block copolymer, (SEBS) [81]. Poly [bis(3-methyl phenoxy) phosphozene] [82], Sulfonated polymers show a distinct peak at 1176 cm"1 due to stretching vibration of 0=S=0 in the -S03H group. Another peak appears at 881 cm 1 due to stretching vibration of S-OH bond. However, the position of different vibrational bands due to sulfonation depends on the nature of the cations as well as types of solvents [75, 76]. 

Horhold found that the action spectrum of phenyl-substituted polyarylene-vinylenes shifts substantially to longer wavelengths when the photoconductor probe is simultaneously irradiated by UV light from another source31. The action spectrum of photoconductivity of the polymer subjected to UV radiation is the same as the action spectrum of photoconductivity of the cation radical of the same polymer... 

Many amine-copper complexes, as well as a few amine complexes of other metals, and certain metal oxides have since been shown to induce similar reactions (17, 18, 22, 23, 30). This chapter is concerned largely with the mechanism of oxidative polymerization of phenols to linear polyarylene ethers most of the work reported has dealt with the copper-amine catalyzed oxidation of 2,6-xylenol, which is the basis for the commercial production of the polymer marketed under the trade name PPO, but the principal features of the reaction are common to the oxidative polymerization of other 2,6-disubstituted phenols. 

In polyesterification and other polycondensation reactions, polymer molecules condense with one another by the same mechanism by which they add monomer units. There is no immediately apparent explanation, however, for the coupling of two polyarylene ether molecules of structure I. Three possible routes were first outlined by Finkbeiner (13), and each has received some support since. 

Polyarylenes, in particular different types of poly(arylene ether ketone)s, have been the focus of much hydrocarbon membrane research in recent years. - - With good chemical and mechanical stability under PEM fuel cell operating conditions, the wholly aromatic polymers are considered to be the most promising candidates for high-performance PEM fuel cell applications. Many different types of these polymers are readily available and with good process capability. Some of these membranes are commercially available, such as poly(arylene sulfone)s and poly(arylene... 

A polyarylene, 123, containing a chiral binaphthyl group has been synthesized via the Suzuki coupling reaction.207 The polymer may have a helical structure segmented by a phenylene group. Another optically active polyarylene has been synthesized and its conformation has been considered.208... 

Because polyfluorenes have undoubtedly emerged as a very attractive class of blue-emitting polymers, not surprisingly, a number of synthesis methods have been applied for the preparation of polyfluorenes and polyarylenes [20],... 

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