Poly benzenes, structure

Example the source-based name poly[(benzene-l,2,4,5-tetracarboxylic 1,2 4,5-dianhydride)-a/t-(4,4 -oxydianiline)] is ambiguous ambiguity about the structure is removed by writing poly(amide-acid) [(benzene-1,2,4,5-tetracarboxylic 1,2 4,5-dianhydride)-a/t-(4,4 -oxydianiline)] to accompany the graphical structure-based representation... 

A large part of organic and macromolecular chemistry starts with the chemical functionalization of benzene, and benzene units serve us building blocks for important polymers. Naturally, benzene-based aromatic materials also represent an important subclass of jt-conjugaled architectures. Despite some synthetic difficulties related to the generation of structurally well-defined oligo- and poly(phenyl-... 

Recently, Tour et al. [47] described attempts to use the Bergman cyclizat produce PPP derivatives starting from substituted endiynes, e.g. poi-. 1,4-phenylene) 22 starting from l-phenyl-hex-3-en-l,5-diyne or the structurally related poly(2-phenyl-1,4-naphthalene) 23 starting from l-phenylethynyl-2-ethynyl-benzene. 

The versatility of poly(phenylcne) chemistry can also be seen in that it constitutes a platform for the design of other conjugated polymers with aromatic building blocks. Thus, one can proceed from 1,4- to 1,3-, and 1,2-phenylene compounds, and the benzene block can also be replaced by other aromatic cores such as naphthalene or anthracene, helerocyclcs such as thiophene or pyridine as well as by their substituted or bridged derivatives. Conceptually, poly(pheny ene)s can also be regarded as the parent structure of a series of related polymers which arc obtained not by linking the phenylene units directly, but by incorporation of other conjugated, e.g. olefinic or acetylenic, moieties. 

Kim and Webster [57] were the first to show that trifunctional benzene-based monomers can also be used to synthesize poly(phenylene)s, in this case hyperbranched structures 31 based on 1,3,5-trisubstituled benzene cores. They self-condensed l,3-dibromophenyl-5-boronic acid leading to the formation of soluble, hyperbranched PPP-type macromolecule 31. 

Stmcturally novel pyrazole derivatives include the propellene 2,3,4,5,6-pentakis(pyrazol-r-yl)pyridine 1 and the corresponding 3 ,5 -dimethylpyrazole derivative 2<96T11075>. Poly(pyrazol-l-ylmethyl)benzenes, such as 3, have been prepared as multidentate ligands <95AJC1587>. Solid phase synthesis of structurally diverse 1-phenylpyrazolones was reported, with application to combinatorial synthesis <96SL667>. 

For the synthesis of the target structures, it is absolutely necessary to introduce solubilizing substituents in the positions peripheral to the benzoyl substituents. The primary coupling product, 117, a poly(2,5-dibenzoyl-l,4-phenyl-ene) derivative - a poly(para-phenylene) with two benzoyl substituents in each structural unit - is, as expected, very poorly soluble. Highly substituted monomers (2,5-dibromo-l,4-bis(3,4-dihexyloxy-benzoyl)benzene), containing four solubilizing alkoxy groups per monomer unit, allow the synthesis of polymeric materials with M of about 12,000 and M, of about 22,000 [139]. 

After the first report on the crystal structure correlation between 2,5-DSP and poly-2,5-DSP crystals, a different crystallographic result was reported on a poly-2,5-DSP crystal (Meyer et al., 1978). It was reconfirmed, however, that the first structural analysis was correct (Nakanishi et al., 1979a). 2,5-DSP, crystallized from benzene solution, is highly photoreactive (a-form), while the same compound, sublimed at a rather high temperature... 

A number of bis(tacn) ligands, composed of pairs of covalently linked tacn macrocycles, can form similar structures, provided the linker group between the sandwiching macrocycles is sufficiently flexible (e.g., (556)).1411-1413 In particular, several Ni11 complexes of poly(tacn) derivatives with a central benzene have been studied, where the Ni is sandwiched between pairs of tacn macrocycles when these are attached to the ortho positions of the aromatic spacer group (e.g., (557)).1412,1413... 

Coordination studies of acyclic thioether ligands to silver(I) centers has also been studied. Poly(alkylthio)aromatic systems have been used to form supramolecular silver(I) compounds. With the ligand 2,3,5,6-tetrakis(isopropylthio)benzoquinone the compound has a linear chain structure in which silver(I) has a tetrahedral coordination.1156 A similar structure has the compound with the hexakis(methylthio)benzene,1157 but with the hexakis(tolylthio)benzene the silver... 

Fig. 9 (a) Molecular structures of novel ESIPT dyes, 2,5,-bis[5-(4-t-butylphenyl)-[l,3,4]oxadia-zol-2-yl]-phenol (SOX), and 2,5-bis[5-(4-t-butylphenyl)-[l,3,4]oxadiazol-2-yl]-benzene-l,4,-diol (DOX). (b) Emission colors in the Commission Internationale de L Eclariage (CEE) chromaticity diagram. The inner oval and the filled circle at coordinate (x,y) of (0.33, 0.33) indicate the white region and the ideal color, respectively. Note that PS and PVK denote polystyrene and poly (N-vinylcarbazole) film (reprint from ref. [91], Copyright 2005 Wiley-VCH)... 

Figure 17 shows the chemical structures of anionic amphiphile sodium-1,2-bis (tetradecylcarbonyl)ethane-l-sulfonate (2Cj4SNa)[34] and poly(ethyleneimine)(PEI). A benzene/ethanol (9 1)(WV) solution of anionic amphiphile was spread on the pure water surface or the PEI-water solution (lxlO5 unit M in monomer unit, pH=3.2) surface at a subphase temperature, Tsp of 293 K. At this pH, ca. 70 % of nitrogen atom in PEI molecule was protonated[35]. Surface pressure-area(ji-A) isotherms were measured with a microprocessor controlled film balance system. 

Oil-Based SINs. The SINs produced were based on a castor oil polyester-urethane and styrene crosslinked with 1 mole percent of technical grade (55%) divinyl benzene (DVB) (7). This structure may be written poly[(castor oil, sebacic acid, TDI)-SIN-(Styfene, DVB)], poly[(CO,SA,TDI)-SIN-(S,DVB)]. Benzoyl peroxide (BP) (0.48%) was used as the free radical initiator for the styrene and 1,4-tolylene-diisocyanate (TDI) was used as the crosslinker for the polyester prepolymer. A 500 ml resin kettle equipped with a N inlet, condenser, thermometer, and high torque stirrer was used as the polymerization reactor. 

Finally, we should mention the phenomenon of incompatibility of mixtures of polymer solutions. It applies to nearly all combinations of polymer solutions when the homogeneous solutions of two different polymers in the same solvent are mixed, phase separation occurs. For example, 10% solutions of polystyrene and poly(vinyl acetate), each in benzene, form two separated phases upon mixing. One phase contains mainly the first polymer, the other phase mainly the second polymer, but in both phases there is a certain amount of the other polymer present. This limited compatibility of polymer mixtures can be explained thermodynamically and depends on various factors, such as the structure of the macromolecule, the molecular weight, the mixing ratio, the overall polymer concentration, and the temperature. 

A poly(arylene ether phenylquinoxaline) of structure 14 was prepared by the aluminum chloride catalyzed reaction of 6,6 -bis[2-(4-phenoxyphenyl)-3-phenylquinoxaline] and isophthaloyl chloride in 1,2-dichloroethane [51]. The polymer had an inherent viscosity of 1.29 dL/g and a Tg of 224 °C. A polymer of the same chemical structure was prepared from the reaction of 3,3, 4,4 -tetraaminobiphenyl with l,3-bis(phenylglyoxalyl-4-phenoxy-4 -benzoyl)-benzene that gave a Tg of 239 °C [16], significantly higher than that prepared by the electrophilic route. In addition, a polymer of the same chemical structure (third polymer in Table 3) prepared via nucleophilic substitution exhibited a Tg of 240 °C. 

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