Poly arylene Ether s

When groups are inserted into the main chain, its regularity is disturbed and chain mobility increases (reduction of the enthalpy of melting as well as increase of the entropy of melting). Thus, polymers are formed that can be further processed from solution or in bulk. 

In cases where carbonyl or sulfonyl groups are inserted between the aromatic rings in addition to oxygen or sulfur, the resulting type of polymers is commonly classified as poly(arylene ether)s (II). 

The five classes of poly(arylene ether)s of technical interest are shown in Table 4.3. 

Poly(arylene ether)s generally exhibit high glass transition temperatures, resistance to hydrolysis, as well as an excellent thermo-oxidative stability. 

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A generalized structure of the poly(arylene ether)s can be represented as in Scheme 6.2. 

Robeson et al. studied the secondary loss transitions of a series of poly(arylene ether)s using a torsion pendulum.15 They found that the secondary loss transitions are closely related to the segmental motion of the aryl ether bonds. The secondary... 

Scheme 6.1 Examples of commercial poly(arylene ether)s.

GENERAL APPROACHES FOR THE SYNTHESIS OF POLY(ARYLENE ETHER)S 329... 

A wide variety of high-performance polymeric materials have been synthesized by incorporating thermally stable moieties such as sulfone, ketone, or aryl or alkyl phosphine oxide in addition to the ether linkage in poly(arylene ether)s. 

The general approaches for the synthesis of poly(arylene ether)s include electrophilic aromatic substitution, nucleophilic aromatic substitution, and metal-catalyzed coupling reactions. Poly(arylene ether sulfone)s and poly(arylene ether ketone)s have quite similar structures and properties, and the synthesis approaches are quite similar in many respects. However, most of the poly(arylene ether sul-fone)s are amorphous while some of the poly(arylene ether)s are semicrystalline, which requires different reaction conditions and approaches to the synthesis of these two polymer families in many cases. In the following sections, the methods for the synthesis of these two families will be reviewed. 

Poly(arylene ether)s Synthesized via other Activated Dihalides... 

Other Approaches for the Synthesis of Poly(arylene ethers)s... 

The Ullman reaction has long been known as a method for the synthesis of aromatic ethers by the reaction of a phenol with an aromatic halide in the presence of a copper compound as a catalyst. It is a variation on the nucleophilic substitution reaction since a phenolic salt reacts with the halide. Nonactivated aromatic halides can be used in the synthesis of poly(arylene edier)s, dius providing a way of obtaining structures not available by the conventional nucleophilic route. The ease of halogen displacement was found to be the reverse of that observed for activated nucleophilic substitution reaction, that is, I > Br > Cl F. The polymerizations are conducted in benzophenone with a cuprous chloride-pyridine complex as a catalyst. Bromine compounds are the favored reactants.53,124 127 Poly(arylene ether)s have been prepared by Ullman coupling of bisphenols and... 

Poly(arylene ether ketone)s can also be modified by introducing the functional groups using similar approaches to polysulfones. For example, poly(arylene ether ketone)s were sulfonated.189 In addition, o-dibenzoylbenzene moieties in the poly(arylene ether)s can be transformed to heterocycles by cyclization with small molecules. These polymers can react with hydrazine monohydrate in the presence of a mild acid in chlorobenzene or with benzylamine in a basic medium.190 Another example of the use of the o-benzyl cyclization strategy is the intramolecular ring closure of poly(arylene ketone)s containing 2,2/-dibenzoylbiphenyl units to form poly(arylene ether phenanthrenes).191... 

Phenolphthalein reacts with hydroxylamine to give 4-aminophenol and 2(4-hydroxybenzoyl)benzoic acid in high yield. 2-(4-Hydroxybenzoyl)benzoic acid reacts with hydrazine to yield phtlialazinone.194 This monomer behaves like a bisphenol and reacts with activated difluorides (Scheme 6.25).195 The resulting poly(arylene ether)s have high glass transition temperatures (over 265°C). 

Very few graft copolymers based on poly(arylene ether)s have been synthesized, probably because of their chemical inertness. Klapper et al. reported grafting the polystyrene or polyisoprene onto the poly(ether ether ketone ketone) (PEEKK) by anionic deactivation.229 The carbonyl groups on tire backbone can be attacked by the polystyrene monoanion or polyisoprene anion (Mn about 3000). Due to the steric hindrance only about 30% of tire carbonyl groups can be reacted. 

MISCELLANEOUS POLY(ARYLENE ETHER)S, POLY(ARYLENE THIOETHER)S, AND RELATED POLYMERS... 

Recently, Baneijee et al. prepared a series of difluoro monomers with pendent trifluoromethyl groups using a Pd(0)-catalyzed cross-coupling reaction (Scheme 6.32).242,243 These monomers were converted to poly(arylene ether)s by nucleophilic displacement of the halogen atoms on the benzene ring with several... 

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