Phenanthrene polymer

As has been described in Chapter 4, random copolymers of styrene (St) and 2-(acrylamido)-2-methylpropanesulfonic acid (AMPS) form a micelle-like microphase structure in aqueous solution [29]. The intramolecular hydrophobic aggregation of the St residues occurs when the St content in the copolymer is higher than ca. 50 mol%. When a small mole fraction of the phenanthrene (Phen) residues is covalently incorporated into such an amphiphilic polyelectrolyte, the Phen residues are hydrophobically encapsulated in the aggregate of the St residues. This kind of polymer system (poly(A/St/Phen), 29) can be prepared by free radical ter-polymerization of AMPS, St, and a small mole fraction of 9-vinylphenanthrene [119]. 

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... 

Poly(methyl methacrylate) [PMMA] is an excellent polymer for studying photoresist dissolution because of its minimal swelling characteristic. For this work, PMMA molecules were labelled with phenanthrene (Phe) dye since its fluorescence is quenched by MEK. In addition, this dye has the advantage of forming few excimers (23-241 which results in self-quenching. Thus, the reduction in fluorescence intensity of PMMA-Phe is virtually solely due to MEK quenching. Consequently, the permeation of MEK into a PMMA film can be monitored from fluorescence intensity decay. 

Fig. 15.8 Redox-active polymers for heterogeneous dehydrogenation catalysis, (a) trimerized phenanthrene quinone [42], (b) benzoquinone biphenyl copolymer [41], (c) polynaphthoquinone [40], (d) polyaniline [43], (e) pyrolyzed polyacrylonitrile [44].

Although such reactions and the consequences with respect to contaminant fate have primarily focused on soluble humic materials (Carter Suffet, 1982 Madhun et al., 1986 Traina et al., 1989 Morra et al., 1990 Puchalski et al., 1992 Engebretson von Wandruszka, 1994), the participation of microbial products in similar reactions is possible. Dohse and Lion (1994) showed that extracellular bacterial polymers enhanced the transport of phenanthrene in sand columns. The mobilization of contaminants might be beneficial to bioremediation if degradation reactions are not inhibited and substrate bioavailability is increased. Conversely, increased contaminant transport may increase the potential for contaminant movement and likewise the extent of environmental contamination. 

Dohse, D. M. Lion, W. (1994). Effect of microbial polymers on the sorption and transport of phenanthrene in a low-carbon sand. Environmental Science Technology, 28, 541—8. 

To demonstrate the UV crosslinkability of the polymers formed having pendant acyloxyimino groups, copolymers of bisphenol diacrylate and 1,6 hexanediol diacrylate were prepared by thermal methods with 5% (by weight) of pyrene oxime acrylate and phenanthrene oxime acrylate, both of which have considerable absorption in the region of 320-360 nm. The polymerization was stopped before the gel point and the prepolymer solutions were then irradiated with light from a monochromator at the maximum of... 

Fig. 8. Aromatic ring systems in Murchison polymer (Hayatsu et al., 1977, 1980a). Gentle oxidation converts substituents to COOH groups, but leaves ring systems intact. In addition to the ring systems shown, methyl naphthalene and methyl phenanthrene were also identified (Hayatsu et al., 1980a)...

A fairly similar material has been obtained in an FTT synthesis extended over 6 months (Hayatsu et al., 1977). Upon pyrolysis, it gave a mass spectrum resembling that of the Murchison polymer (Fig. 9). The spectrum shows mainly benzene, naphthalene, and their alkyl derivatives, as well as alkyl-indanes, fluorene, anthra-cene/phenanthrene, alkenes, alkanes, and alkylphenols (Hayatsu et al., 1977). This material has not been studied by the more informative, gentle oxidation methods. 

J.Y. Kim, C. Cohen. M. L. Shuler, and L. W. Lion, Use of amphiphilic polymer particles for in-situ extraction of sorbed phenanthrene from a contaminated aquifer materials. Environ. Sci. Technol. 34 (2000) pp. 4133-4139. 

Phosphorescence studies in isobutylene-methyl methacrylate-1-naphthyl-methyl methacrylate co-polymer provided evidence to show that in very dilute solution the chain collapses into more compact structures, and intramolecular excimer formation in poly-(2-vinylnaphthalene) has been shown to exhibit non-Stokes-Einstein behaviour. Laser photolysis of polymers containing phenanthryl groups, such as poly-(9-vinylphenanthrene), indicates the presence of plural dimer sites having different geometries owing to the stacking effect of phenanthrene chromophores. In poly-(2-naphthyl methacrylate). 

The latest results on imprinted chiral footprints [154] have shown that enantioselective catalysis (hydrolysis) does occur, and based on kinetic measurement the authors believe that this is due to an enantioselective mechanism. Kaiser and Andersson also chose aluminium doped silica as a polymeric material to obtain phenanthrene imprints and their work has been discussed earlier [52]. No selectivity towards the template was observed when imprinted silica was used as stationary phase. Only relative retention and capacity factors increased. Furthermore, even after careful extraction in a Soxhlet, the polymer still leaked phenanthrene. They also found that diazomethane yields a side reaction forming long alkyl chains. Finally they attempted to rej at the work of Morihara et al. [150-155]. but were not able to detect any selectivity using dibenzamide as the template and instead found that the template decomposes into at least five different products when adsorbed on the silica. Clearly further work is required on these systems. 

The role of free volume on TICT emission of dimethylaminobenzonitrile and related compounds has been examined in polymeric media . The increase in emission with increase in free volume rules out the possibility of specific solute-solvent interactions being responsible for TICT emission in PVA polymer matrices. Fluorescence quenching of phenanthrene and chrysene by KI in met ha nol-et ha no.l, s olu t ion s shows both electron transfer processes and exciplex formation between aromatic hydrocarbon and perturber are important. ... 

They are well known as compounds which are photoohemically very reactive. The excited singlet and triplet states are the photochemically reactive states,and they also can participate in energy transfer reactions (2,3i10,11). Some of these compoxmds such as anthracene,phenanthrene,pyrene added to polyethylene effect the photodegradation of polymer (118,... 

Phenanthrene is a biphenyl with an ethene bridge. Poly(2,7-phenanthryl-ene)s 81 have been prepared by polymer-analogous McMurry coupling of precursor poly(2-acyl-p-phenylene)s 82 (Scheme 36) [111]. 

Anthracene and phenanthrene are stereoisomers that are crystals in pure form. Anthracene is a pale yellow crystal, while phenanthrene exhibits a yellow to brown hue. Besides its common name, anthracene is referred to as anthracin, green oil, or paranaphthalene. The compound is commercially produced by recovery from the coal tar distillation fraction known as anthracene oil or green oil. Anthracene is the key ingredient in the production of anthraquinone. However, it and phenanthrene are also used for the manufacture of dyes, fibers, plastics, and wood preservatives. ° Phenanthrene, also known as phenanthrin, can be produced by high-temperature fractional distillation of coal tar oil. It is additionally used for the oxidation of diphenic acid for use in polymers, as well as the production of chemical softeners, explosives, and some pharma-ceuticals. Recent research has extended the application of both isomers to scintillation counters, semiconductors, and photoconductors. ... 

A synthesis of substituted phenanthrenes has been reported using the bicyclooctadienes (61) as starting material. The process makes use of the nucleofugal group on C-8 and follows the path outlined in Scheme 3. This involves a di-rr-methane bridging process followed by the collapse of the intermediate biradical (62). Normal di-Ti-methane behaviour is reported in the acetophenone-sensitized irradiation of the isoquinolinone derivative (63a). This yields the two products (64) and (65) as a 3 1 mixture in a total yield of 75%. An N-oxide derivative gave a brown polymer with little evidence for the formation of di-n-methane products. The influence of ring substituents was also studied for the derivatives (63b, d) and the results of this are shown in Scheme 4. The authors conclude that the cyclization process is under LUMO control. Irradiation of the dihydropyridine (66) affords the oxidised pyridine (67) as the major product. A minor product (68) is also formed by a di-ir- methane process. ... 

Oxygen Quenching in Poly(vinyl acetate) Particles. In order to study a system in which fluorescent groups could be Introduced into both the stabilizer and core polymers, we turned our attention to poly(vinyl acetate) [PVAc] particles sterically stabilized by poly(2-ethylhexyl methacrylate) [PEHMA] (14,15). Phenanthrene [Phe] was chosen as the fluorescence sensor. It was Introduced into the stabilizer by mixing a small amount (ca. 1%) of 9-phenanthrylmethyl methacrylate 1. with EHMA in the synthesis of PEHMA. It was introduced into the core polymer by mixing a trace (ca. 0.01%) of J with VAc in the presence of unlabelled PEHMA in the particle synthesis step. 

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