Aromatic structures ladder-type polymers

Conj ugated Ladder Polymers. Since the 1930s double-stranded, ladder-type polymers have been prepared in a multistep process with limited success of cyclization (191,192). Other routes have also been explored such as those for poly(acrylonitrile) (193,194), poly(l,2-butadiene), poly(3,4-isoprene) (195), or poly(butadiyne)s (196). These materials were found to be poorly soluble and unworkable, with a considerable number of defects in the structure (incomplete cyclization, cross-linking, radical sites). The first successful synthesis of a ladder polymer with a completely defined structure was accomplished in 1991 by Sherf and Mullen (197). The first step was the AA/BB-t5q)e polycondensation of an aromatic diboronic acid with a substituted 2,5-dibromo-l,4-dibenzoylbenzene to give a single-stranded precursor PPP-type polymer, followed by cyclization to the ladder structure (Fig. 8). Several other examples exist that have resulted in ladder-type structures. These include angular polyacene (198,199), Diels-Alder polyaddition of AB-type diene-dienophiles (200), AA/BB-type Diels-Alder polyaddition of a bisdiene and a bisdienophile (201), thienylene imits (202),... 

An electrophilic substitution reaction has been used for the key ladderforming step in the synthesis of soluble ladder-type poly(phenylene)s [51-53]. These aromatic polymers have a ribbon-like rigid, planar structure. They are of interest because of their optical and electronic properties [51,54,55]. The preparation of these polymers was accomplished by two basic steps. The first step was the construction of a substituted poly(p-phenylene) backbone. The ladder structure was obtained by a subsequent intramolecular electrophilic ring closure reaction. For example, the syn-... 

The next two approaches for synthesizing structurally defined ladder-type oligomers and polymers, discussed in sects. 4.3. and 4.4., rest on the formation of the single-stranded intermediates via polycondensation of (aromatic) monomers, again followed by a polymer-analogous ring-closure sequence. 

The polymers from the three compounds will have ladder-type structures. However, the polymers from compounds B and C will have at least one and two skeletal bond(s) per repeating unit while a double-cyclization polymer will result from compound A. The presence of one or two consecutive single bonds between aromatic units will enhance polymer susceptibility to thermal degradation. In principle, therefore, under identical conditions the thermal stability of the resulting polymers will be A more than B more than C. 

In general, the types of polymers which have the best thermal properties are aromatic in character (often with recurring heterocyclic units), have low hydrogen content, and often have stepladder or ladder structures. Although there are numerous articles in the literature which deal with the effects of structure on stability within a given class of heat-resistant polymers, only a limited number of publications are to be found which compare the stabilities of different classes of heat-resistant polymers under controlled conditions. From Ehler s TGA studies on different classes of heat-resistant polymers, as well as from other sources, a classification can be made of the effects of structure on heat stability for several classes of compounds. For... 

As already briefly mentioned, easily the most obvious change regarding optical properties appears in the transition from the open-chain precursor polymers to the planarized PPP ladder polymers (LPPP). The primary single-stranded coupling product (a benzoyl-substituted polyphenylene) from a Suzuki-type polycondensation between an alkyl- or alkoxy-substituted 2,5-dibromo-1,4-dibenzoylbenzene derivative and 2,5-dihexyl-l,4-phenylenediboronic acid is colorless with an absorption maximum Amax of 264 nm [n-TT transition c = 39,000 L/(moI cm)l (19]. This absorption behavior supports the strongly twisted structure of the main PPP chain. The mutual distortion of the aromatic subunits reduces the conjugative interaction to a minimum, so that the typical electronic properties of a conjugated polymer are almost completely lost. 

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