OTHER POLY AROMATIC AMINES

Numerous CPs having a poly(aromatic amine) structure related to P(ANi) have been synthesized, most by electrochemical polymerization, and a few by oxidants such as Cu(Bp4)2. Indeed the oxidation potential of aromatic amine monomers such as diphenyl amine is so low that their solutions are observed to oligomerize in the presence of air alone [67]. 

Demonstrating that these low oxidation potential aromatic amines are very easy to polymerize, the Dao group subsequently reported [410] chemical polymerization with Cu(Bp4)2 xH20 oxidant/dopant for a series of Poly(N-alkyl-Diphenylamine) s. A 4-4 C-C (phenyl-phenyl) coupling mechanism was claimed for tWs polymerization. These CPs showed poor conductivities (10 S/cm) and a yellow-to-violet electrochromism. In a variant of diis syntliesis, Poly(N-alkyl-diaryl amines), i.e. with a naphthalene group replacing one of the phenyls in DPA, were chemically synthesized by Dao et al. [586]. These polymers however showed poor conductivity (10 S/cm) even in their highly doped form. The spectroelectrochemical characterization of these (see Chapter 3) showed broad-band responses characteristic of P(DPA) and its derivatives. 

Poly(5-animo-l-naphthol) synthesized by Mostefai et al. After Reference [589], reproduced with permission. 

Write down the structures of the doped and pristine forms of one member of the following classes (discussed in this chapter), and outline one chemical and one electrochemical (if available) synthesis for it P(Ac) P(DiAc) P(Py) P(ANi) P(ANi) derivatives other poly(aromatic amines). In which cases are electrochemical (or chemical) polymerizations unavailable, and why  

Enumerate the most common dopants for one member of each of the polymer classes listed in problem 1 above and briefly outline the doping method. 

---

From the difficulties encountered with interpretation of CVs which the discussions above amply show, it would appear that other voltammetric methods, especially differential methods, would have found wider application to CPs. This has unfortunately not been the case. The results in Figs. 4-17-a.b.c and 4-18 represent some of the few studies of this nature. In Fig. 4-17. the results of CV and of Differential Pulse Voltammetry (DPV) are compared. The latter is a technique in which a small potential pulse is superimposed on a staircase potential function with the difference between the post-pulse and pre-pulse current measured (inset in Fig. 4-171. The differential method yields peak-shaped curves unencumbered by residual current tails, as in CVs, and thus a clearer identification of peaks and their widths. Fig. 4-19 then shows DPV of Poly(phenylene vinylene) used to compute the bandgap, as described earlier. Normal Pulse Voltammetry (NPV), in which a sort of digital pulse-ramp is applied in place of the analog ramp of CV and the current sampled at the end of the pulse [50], has been applied to poly(l-amino pyrene) [48], yielding redox potentials as well as diffusion coefficients (Fig. 4-181. Other differential methods such as Square Wave Voltammetry have been applied to poly(aromatic amines) in the author s laboratories. There is however little other extant work with pulse voltammetry of CPs, although the very brief results above clearly provide a strong indication for it. 

What are the commonalities and differences between electrochemical properties in acetonitrile and acidic aqueous electrolyte media for poly(aromatic amines) For other CP systems ... 

Plasticiser/oil in rubber is usually determined by solvent extraction (ISO 1407) and FTIR identification [57] TGA can usually provide good quantifications of plasticiser contents. Antidegradants in rubber compounds may be determined by HS-GC-MS for volatile species (e.g. BHT, IPPD), but usually solvent extraction is required, followed by GC-MS, HPLC, UV or DP-MS analysis. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out. The determination of antioxidants in rubbers by means of HPLC and TLC has been reviewed [58], The TLC technique for antidegradants in rubbers is described in ASTM D 3156 and ISO 4645.2 (1984). Direct probe EIMS was also used to analyse antioxidants (hindered phenols and aromatic amines) in rubber extracts [59]. ISO 11089 (1997) deals with the determination of /V-phenyl-/9-naphthylamine and poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ) as well as other generic types of antiozonants such as IV-alkyl-AL-phenyl-p-phenylenediamines (e.g. IPPD and 6PPD) and A-aryl-AL-aryl-p-phenylenediamines (e.g. DPPD), by means of HPLC. 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

Examples of homopolymers are given. Poly(4-vinylphenol) was prepared as a prepolymer for the subsequent alkylation [55]. Poly[2-(4-vinylbenzyl)hydroqui-none] 65 is an example of the unhindered phenolic antioxidant for rubbers. Many homopolymers bear a hindered phenolic moiety. Homopolymer 66 was proposed for blending with BR and IR [56]. Other examples are poly[vinyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [57] (67), poly(3,5-di-/ert-butyl-4-hydroxy-benzyl methacrylate) [58] (68) or poly[iV-3,5-di-tert-butyl-4-hydroxybenzyl) male-imide] [59] (69). Numerous polymeric antioxidants are functionalized with aromatic amine groups. Poly(4-anilinophenyi methacrylate) [53] (70) serves as an example. 

The following photoconductive polymers can also be clarified as polymers of aromatic amines poly(N-vinylphenothiazine) and poly(N-vinylphenoxazine ° and poly(N-acrylodibenzazepine) ° Poly(N-vinylcarbazole) is basically a modified vinyldiphenylamine polymer . It has yet to be detemined if the transport characteristics of PVK with the diphenyl amino group forced into planarity are different from those of poly(N-vinyldiphenylamine) which would possess a greater freedom of rotation. The properties of PVK have been discussed in many articles and reviews [for example see Ref. ]. Several articles and patents have been published recently which deal with carbazole containing polymers other than PVK, and copolymers of N-vinylcarbazole with some other monomers. 

The preparation of these photoanalogs of GTP is simple and can be used practically without modification for the radioactive microsynthesis of other photoactivated or chemically specific affinity analogs of GTP. It cannot be concluded, however, that the several groups attached to the nucleotide may disturb its function. In our case, for example, a GTP derivative similar in structure to the y-(4-azidobenzyl) amide of GTP, but containing an aromatic amine, the y-(4-azido) anilide of GTP, is almost without inhibitory ability for the cell-free poly (U)-dependent synthesis of polyphenylalanine and does not form a ternary complex with ribosomes and elongation factor G. 

It is found Fig.1 that RIE depend on the time. Also, the straight lines gives in Fig.1 are extraploted to find the final time and the results are summarized in Table I.From Table 1 it can be seen that poly(organophosphazene) films have higher RIE than LMR. Also, poly-(organophosphazene) films with aromatic amines have good RIE properties in comparison with others. 

Finally, C—N bond formation has been also accomplished through aerobic oxidative amination of arylboronic acids (Evans-Chan-Lam coupling) under poly-NHC-copper(II) catalysis. In particular, azoles and aromatic amines were successfully coupled with arylboronic acid using catalyst 73, with catalytic efficiencies comparable to those of other previously reported copper(II)-based catalytic systems for this reaction. 

Other commercially available nylons such as nylon 610 (using sebacic acid, HO— CO—(CH2)8C0—OH) are based on aliphatic dyads. The and can be increased by incorporating cyclic or aromatic structures into the backbone. The nylons in Table 17.3, l.C, can be made by interfacial polymerization (see Section 5.3), since the amide formation is rapid between aroyl chlorides and aromatic amines. Two aromatic nylons (aramids), poly(/ -phenylene terephthalamide) and poly(m-phenylene... 

The oxidative coupling of 2,6-dimethylphenol to yield poly(phenylene oxide) represents 90—95% of the consumption of 2,6-dimethylphenol (68). The oxidation with air is catalyzed by a copper—amine complex. The poly(phenylene oxide) derived from 2,6-dimethylphenol is blended with other polymers, primarily high impact polystyrene, and the resulting alloy is widely used in housings for business machines, electronic equipment and in the manufacture of automobiles (see Polyethers, aromatic). A minor use of 2,6-dimethylphenol involves its oxidative coupling to... 

Poly(phenylene ether). The only commercially available thermoplastic poly(phenylene oxide) PPO is the polyether poly(2,6-dimethylphenol-l,4-phenylene ether) [24938-67-8]. PPO is prepared by the oxidative coupling of 2,6-dimethylphenol with a copper amine catalyst (25). Usually PPO is blended with other polymers such as polystyrene (see PoLYETPiERS, Aromatic). However, thermoplastic composites containing randomly oriented glass fibers are available. 

It is also possible to prepare them from amino acids by the self-condensation reaction (3.12). The PAs (AABB) can be prepared from diamines and diacids by hydrolytic polymerization [see (3.12)]. The polyamides can also be prepared from other starting materials, such as esters, acid chlorides, isocyanates, silylated amines, and nitrils. The reactive acid chlorides are employed in the synthesis of wholly aromatic polyamides, such as poly(p-phenyleneterephthalamide) in (3.4). The molecular weight distribution (Mw/Mn) of these polymers follows the classical theory of molecular weight distribution and is nearly always in the region of 2. In some cases, such as PA-6,6, chain branching can take place and then the Mw/Mn ratio is higher. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

---