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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 3 2022 21
ISSN 0005-2531 (Print)
UDC 547.553.1
PROPERTIES OF POLYMERS BASED ON AROMATIC DIAMINES A.A.Medjidov, S.Z.Ismayilova, G.M.Ganzayeva, S.A.Agaeva, S.N.Qasimova
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
Received 28.01.2022 Accepted 08.02.2022
This review provides detailed information on the synthesis, structure, properties, methods for studying, and areas of application conductive polymers synthesized on the basis of phenylenediamines. Conductive polymers based on phenylenediamines are cationic salts of highly conjugated polymers and are synthesized by electrochemical or chemical oxidation. Chemical oxidative polymerization has led to the formation of various functional polymers. Depending on the reaction conditions, polyphenylenedia-mines are produced as powders, colloidal dispersions, thin films, or composites. The close similarity of the chemical structure of polyanilines and polyphenylenediamines endows both groups with some similar properties, such as, for example, redox activity. They act as reductants of noble-metal compounds to the corresponding metals. Due to electrical conductivity and redox activity, as well as the dependence of electrical conductivity on the degree of protonation, it is possible to create various sensors based on polyphe-nylenediamines. In addition, polyphenylenediamines can be used as one of the components of composite materials, for example, in anticorrosion coatings. In general, some main groups of applications for poly-phenylenediamines can be distinguished. The literature indicates a number of areas of their application; they include the corrosion protection of metals, catalysis, electrorheology, sensors, energy-conversion devices, electrochromism, noble-metal recovery, and water treatment. At the same time, polymers of phe-nylenediamines can be used in medicine, unlike aniline and its oligomers, which have potential toxicity.
Keywords: poly(o-phenylenediamine), poly(m-phenylenediamine), poly(p-phenylenediamine), phe-nylenediamine, conducting polymers, redox-active polymers, conductivity.
doi.org/10.32737/0005-2531-2022-3-21-44 Introduction
Phenylenediamines, "amino anilines", are closely related to aniline, and they can similarly be oxidized to the corresponding oligomers and polymers [26, 27]. Like the polyaniline derivative, poly(phenylenediamines) are used as sensors, catalysts, electrodes in electric batteries, etc. [1-8].
In particular, in recent decades, wide attention has been drawn to the study of the adsorption characteristics of poly(phenylenediamine) due to its excellent redox reversibility and chelating ability [9-12], which allows them to be used to remove various metal ions from water, such as Cr(VI) [13], Hg(II) [14], and Ag(I) [15].
Among the three isomers of poly(pheny-lenediamine)s, poly(m-phenylenediamine) (PmPD) as an adsorbent possesses some important virtues: (I) it is insoluble in common solvent, (II) has high water permeability, (III) can be produced in high yields, (IV) and its synthesis doesn't involve high temperature or acidic solvents. Many developments of poly(m-pheny-
lenediamine) have been made by Li and groups of Stejskal, in terms of molecular structures [16], monomer conversion efficiency [17] and morphology [15].
It is advisable to compare the properties of phenylenediamine polymers with the properties of polyaniline. Polyaniline, one of the most studied conducting polymers [18-23], is valued for its conductivity, redox activity, and espon-sivity to external stimuli. The conductivity of standard polyaniline is of the order of units S cm-1 [24] and it has a semiconducting character. The redox activity manifests itself in the ability of the polymer to be oxidized or reduced, and this property is used in energy conversions and corrosion protection. The pH-dependent transition of a conducting salt to a non-conducting base illustrates the ability of polyaniline to respond to external stimuli by the change in conductivity or colour, a feature valuable in sensors. Finally, the polymer character accounts for its mechanical properties [25] and endows poly-
aniline with materials features.
Polyphenylendiamines easily prepared by chemical or electrochemical oxidation. The close similarity of the chemical structure of polyaniline and polyphenylenediamines gives both groups some similar properties, for example, such as redox activity. Polymers of phe-nylenediamines may find uses especially in biomedical applications [28], where the potential toxicity of aniline and its oligomers is feared.
Considering the terminology, the term "poly(o-phenylenediamine)" will be used below to denote the polymer derived from o-phenylenediamine, although various synonyms are found in the literature, e.g., poly-o-phe-nylenediamine, poly(1,2-phenylenediamine) or poly(1,2-diaminobenzene). The same principle applies to poly(m-phenylenediamine) and po-ly(p-phenylenediamine).
The history of phenylenediamines oxidation is associated with a photographic process. o-Phenylenediamine and especially substituted p-phenylenediamines have been used as developers in photography to reduce silver halides to silver metal and thus to convert the latent image to a negative and, subsequently, to a positive picture. The reduction of silver ions, and the consequent oxidation of phenylenediamines, took place under alkaline conditions. The formation of brown oxidation products was prevented as much as possible in black-and-white photography and exploited in coupling reactions to produced dyes in a colour process.
The oxidation of aniline with peroxydi-sulfate is accelerated by small amounts of p-phenylenediamine [29-35]. This applies also to the electrochemical polymerization of aniline [36, 37]. This illustrates the link between the oxidations of these two monomers. It was proposed that p-phenylenediamine participates in the generation of initiation centres that start the propagation of polyaniline chains. This is indirectly supported by the observation that o-phenylene-diamine has no or only a marginal effect on the rate of aniline oxidation and m-phenylene-diamine significantly retards this process, obviously by producing "incorrect" initiation centres. The addition of p-phenylenediamine not
only accelerates the oxidation of aniline but it changes its morphology from globular to nano-fibres [38-40] and, consequently, the physical properties of polyaniline are also altered. A similar effect of m-phenylenediamine was also found [41].
Preparation
Oxidative polymerization
Phenylenediamines have two primary amino groups that can be used in the oxidative linkage of monomers [44-47]. Various polymer structures resulting from this process can be proposed. The polyaniline-like chain with pendant amino groups is probably the most obvious [48-50] (Figure 1a). Especially at higher oxi-dant concentration, however, both amino groups may be involved in producing a phenazine-like ladder structure (Fig. 1b) [51-58].
The solubility of aromatic diamine polymers exhibits a significant dependence on their macromolecular structures. The PoPD and PpPD polymers basically with linear and/or ladder structures were soluble in DMSO, DMF, and NMP and partly soluble in THF and acetone; PmPD obtained by chemical oxidative polymerization with (NH4)2S2O8 as oxidant in HCl solution is insoluble in most solvents. The insolubility of PmPD and TAB polymer should be due to their three-dimensional network struc-
139
tures shown in Figure 1139. The solubility and molecular weight of polymers depended on the monomer and solution composition that was used for the polymerization. However, the solubility of polymers was nearly independent of the reaction time of polymer synthesis [139].
The ladder structure can be represented as two intertwined polyaniline chains. The viability of such concept has been confirmed by model calculations [59]. The ladder structure is widely accepted in the literature because it can be created, in principle, from any phenylenedi-amine isomer [60-62] (Figure 2). The oxidation products, however, have different properties and also their structures are likely to be different. Others chain constitutions, including branched or crosslinked chains, can be proposed and are most probably met in practice.
Fig. 1. Various polymer structures phenylenediamines: a) polyaniline-like, b) phenazine-like ladder structure .
Fig. 2. The ladder structure phenylenediamine isomers
Three comments about the effect of reaction conditions are pertinent:
1. The oxidation of aniline is highly dependent on pH. Neutral aniline molecules, which dominate in solutions of low acidity, are easily oxidized to aniline oligomers. The protonated form of aniline, anilinium cations, are oxidized with difficulty but they participate in the growth of polyaniline chains once these have been initiated. For that reason the oxidation fate of pheny-lenediamines will depend on the protonation state of their amino groups. The situation is even more complicated by the fact that, during the bonding of molecules, hydrogen atoms are released as protons. The acidity of the reaction medium thus increases correspondingly. The reaction route thus may change in the course of oxidation.
2. The oxidation potential of the oxidant has a marked influence on the course of aniline oxidation [63]. Strong oxidants, such peroxydi-sulfate, yield polyaniline, while weaker oxi-dants, such as hydrogen peroxide or silver nitrate, often yield non-conducting aniline oligo-mer even in strongly acidic media [64]. This fact has to be takes into account also in the oxidation of phenylenediamines. The oxidation products obtained under variable acidity of the reaction medium and various oxidation potentials or both will produce different products.
3. It is well-known that the oxidation of aniline may lead to various oxygencontaining constitutional units, especially quinonediimines or benzoquinones. Benzoquinones may further couple with aniline molecules [64]. It is highly probable that similar reactions will be involved in the oxidation of phenylenediamines. Phe-nylenediamines can couple with quinones and the chemistry of oxidation thus may be complex and lead to products that have not yet been considered in the literature.
4. There are two distinct groups of syntheses, chemical oxidations using chemical oxi-dants and electrochemical oxidations. The former group produces bulk quantities, usually as powders, the latter yields thin films deposited at the electrode surface.
Poly(o-phenylenediamine)
Many studies state the formation of poly(o-phenylenediamine) during the oxidation of o-phenylenediamine with ammonium peroxy-disulfate [50, 58, 62-71], iron(III) chloride [7275], iron(III) sulfate [76], hydrogen peroxide [77] or potassium dichromate [78-80]. The oxidation occurred in an acidic aqueous environment, and in exceptional cases the reaction was reported only in water [50, 81].Also, the oxidation with copper(II) sulfate took place in the
absence of added acid [82]. The oxidation of o-phenylenediamine with iron(III) chloride has also been carried out at the chloroform-water interface [73].
However, other studies have reported that chemical oxidation of o-phenylenediamine gives only dimer [83, 84], 2,3-diaminophenazine, trimer [85], tetramer [86], or hexamer [87]. This is especially true for the oxidation of o-phenylenedi-amine with iron(III) chloride [83, 84, 88]. Another study suggests that 2,3-diaminophenazine can also polymerize, at least electrochemically [89].
Noble metal compounds, such as palladium acetate [90, 91], silver nitrate [87, 88], or tetrachloroauric acid [55, 68, 92, 93], represent a separate group of oxidizing agents. In these cases, the resulting oligomers or polymers are accompanied by noble metal nanoparticles resulting from the reduction of the corresponding compounds. Oxidation of o-phenylenediamine with silver nitrate is supposed to give o-benzoquinone instead of oligomers of o-phenylenediamine [94]. Experiments on the oxidation of aniline in an aqueous medium show that the formation of oxygen-containing compounds is possible [25], and oxygen atoms will come from water molecules.
Poly(m-phenylenediamine)
Poly(m-phenylenediamine) was prepared by the oxidation of m-phenylediamine with peroxydisulfate in acidic aqueous solution [52,62,65,95-98], in concetrated hydrochloric acid [60] or in water [97,99-103]. The presence of copper(II) ions promoted the oxidation [145]. The typical yields were 60-70%. The oxidation of m-phenylenediamine has also been carried out under alkaline conditions [104-107] but, in analogy with polyaniline [25], under such conditions the formation of polymers is unlikely. The oxidation of m-phenylenediamine with silver nitrate produced nanoparticles with silver core and poly(m-phenylenediamine) shell [108].
Poly(p-phenylenediamine)
The oxidation of p-phenylenediamine usually occurred in hydrochloric acid solutions [32, 35, 41, 46, 52, 61, 62, 65, 96, 109-114]. Ammonium or potassium peroxydisulfate was
currently used as oxidant, similarly to the oxidations of aniline. Under such conditions the oxidation proceeds at acidic pH. The effect of the acidity conditions on the properties of the oxidation products was investigated [62]. Other oxidants have also been reported, for example, silver nitrate [115, 116], nickel(II) chloride [45], copper(II) chloride [117], graphene oxide [118] and vanadium(V) oxide [119]. Blue colouration has been observed in the ealy stages of oxidation, the final products were brown or black. Aerial oxygen oxidized p-phenylenedi-amine to a red product [45]. The formation of a polymer without any added oxidant [49, 58] has also been described. Under such conditions, UV-irradiation was used to promote the reaction [49]. Oxidations have been carried out at room temperature, and exceptionally at 800C with graphene oxide as oxidant [118], at 1180C in glacial acetic acid [58] or in an autoclave at 1800C [119].
Chemical properties
Salt-base transition
The transformation of a salt into a base under alkaline conditions, i.e., deprotonation, for polyaniline [7, 23, 62], which is accompanied by a decrease in conductivity from units to 10-9 Smxm-1, is also observed for polyphenylenedi-amines. The equilibrium between the salt and base forms probably occurs with the participation of polyphenylenediamines as shown in Figure 3, but this process has not been systematically investigated. As shown in Figure 3 a, amino groups can form the corresponding salts with acids to form a conducting structure [181].
Reduction of silver salts
The special relation between phenylene-diamines and silver dates since the times of photography. At present, however, its meaning has shifted to a new level. Polyphenylenedia-mines are able to act as reductants of noble metals compounds in general and of silver cations in particular. Such a reaction can be used for the preparation of conducting composites.
Poly(o-phenylenediamine) was used to reduce silver ions to metallic silver and composites containing up to 35 wt.% silver were obtained [95].
I
H H
Fig. 3. The poly(p-phenylenediamine) salt (a) is deprotonated in alkaline solution to the corresponding base (b). The process is reversible181.
The conductivity increased by four orders of magnitude after deposition of silver but still remained low, of the order of 10 8 S cm 1. The nanofibres of o-phenylenediamine dimers were similarly able to reduce silver ions to metallic silver; the silver nanoparticles had the size of tens of nanometres [88]. Poly(o-phenylene-diamine) nanospheres were exposed to silver nitrate solution and silver nanoparticles were produced on them [71]. An additional reductant, ascorbic acid, however, had been present in the synthesis. Similarly, electropolymerized poly(o-phenylenediamine) film was used for the elec-trodeposition of silver nanoparticles [120, 121] but the reduction ability of the polymer film may have also played a role.
Poly(m-phenylenediamine) was used for the adsorption of silver ions [122, 123], and the adsorption of 1.7 g of silver ions per 1 g of polymer was found. In such a case, however, the chemical reduction of silver ions with poly(m-phenylenediamine) to metallic silver [124] is more probable than mere adsorption. Poly(m-phenylenediamine) was similarly used to reduce silver nitrate to metallic silver [103]. In this case, however, another reductant, sodium boro-hydride, was present in the system.
Physical properties Conductivity
The oxidation of o-phenylenediamine with peroxydisulfate yielded a product with a conductivity of 10-12 S cm-1 [62, 65]. In some cases, the authors mention that the conductivity of similar samples was 10-10 S cm [15], below 10-8 S cm-1 [58] or 10-7 S cm-1 [126]. The oxidation with iron(III) chloride was reported to give a dimer only, 2,3-diaminophenazine, which had a conductivity of 10-6 S cm-1 [83, 84].
The synthesis described above was carried out at room temperature, and elevated temperature was used only in exceptional cases. The oxidation product prepared at 1180C in glacial acetic acid had a conductivity of 10-10 _ i -12 S cm [95], which was again reduced to <10
S cm-1 after conversion to a base form [95]. The synthesis carried out in an aqueous medium at 700C led to a product with conductivity 10 S cm-1 [15]. The decomposition of peroxydisul-fate at such temperatures should be considered. The oxidation product of m-phenylene-
diamine had a conductivity of 10-11 S cm-1 [62,
__ i
65], which dropped to 10 S cm after depro-
tonation with ammonia solution. A surprisingly
—3 _ 1
high conductivity of the order of 10 S cm
was also reported [52]. The electrochemically prepared polymer was non-conducting [127].
Poly(p-phenylenediamine) salt is also rated as a non-conducting polymer. Its conductivity varied between 10-10-10-9 S cm-1 [44, 57, 58, 62, 65, 128]. The conductivity was often found to be below the lower limitation of the instruments [111,129]. The higher order of 10 6 S cm-1 [109] has also been reported. Considerably higher conductivity, 10-4 S cm-1, was found for poly(p-phenylenediamine) intercalated in montmorillonite [46]. No EPR signal, however, was detected in the samples, and conductivity by diamagnetic charge carriers was therefore suggested. The electropolymerized p-phenylene-diamine was non-conducting and passivated the electrode [122].
When p-phenylenediamine was oxidized together with aniline, the conductivity of the products increased linearly on a semilogarith-mic scale from 10 9 to 101 S cm 1 with increasing mole fraction of aniline in the reaction mixture [44, 51, 57, 167, 128, 130]. This suggests that a statistical copolymer was produced. When the analogous oxidation of aniline was carried out with m-phenylenediamine, nonconducting polymers were produced when m-phenylenediamine prevailed in the reaction mixture, and only at high aniline content did the conductivity increase [44]. The formation of a mixture of corresponding homopolymers, rather than a copolymerization, would explain such behavior. Similar behaviour was observed also for the joint oxidations of aniline and o-phenylenediamine[15, 44].
UV-visible spectra
o-Phenylenediamine monomer has an absorption maximum at 315 nm [133]. Poly(o-phenylenediamine) has an orange-to-red colour [15, 62, 65, 101], i.e. the absorption is shifted to the visible region (Figure 4 a). Absorption bands have been observed at 260 and 420 nm [62, 75, 79] or 291 and 421 nm [131], 300 and 435 nm [126] or 416 and 490 nm [132]. The band located at -420 nm has been assigned to n-n* transition of the benzenoid and quinonoid structures [82,126,132]. A band at 573 nm was also exceptionally found and attributed to n-n*
transition associated with conjugated phenazine rings [82]. The oxidation with iron(III) chloride led to a o-phenylenediamine dimer, 2,3-diaminophenazine, which had an absorption maximum at 451 nm [83] or 437 nm [72]. The absorption band at 429 nm was observed for o-phenylenediamine hexamer [87] and 440 nm for a tetramer [133].
a
PmPD
b
PANl
1 . r . 1 c 1
300 400 500 600 700 800 900 Wavelength (nm)
Fig. 4. UV-spectra of (a) poly(1,2-phenylene-diamine), (b) poly(1,3- phenylenediamine), and (c) polyaniline colloidal dispersions stabilized with poly(N-vinylpyrrolidone) after 60-times dilution with 1 M HCl (full lines) or 1 M ammonium hydroxide (dashed lines)181.
Poly(m-phenylenediamine) powder was reported to be brown [62, 65] or black [60, 143]. UV-visible spectra were characterized by the absorption decreasing monotonously towards longer wavelengths [181], without any local maximum in 300-900 nm range (Figure 4 b).
Poly(p-phenylenediamine) is brown-to-black [65]. Optical spectra of poly(p-pheny-lenediamine) dispersed in water display local absorption maxima at 392 and 524 nm [111] or at 245 nm [133], 350-355 nm, and 540 nm [42, 133]. In other cases, bands located mainly close to 330 and 420 nm have been observed. The former was assigned to a n- n* transition in the benzenoid ring. The spectra recorded in N-methylpyrrolidone display a strong absorption band at 274 nm with a shoulder at 304 nm assigned to a n-n* transition, and a band at 450
nm associated with the presence of quinoneimi-noid units in the polymer chain [129] or again with a n-n* transition [114]. Other authors [111] reported not only a shoulder but a strong absorption band at 305 nm and a broad band at 430 nm attributed to a polaron-n transition, analogous to that in polyaniline. The assignment of the absorption bands is not unambiguous. In dimethylformamide, three bands were identified at 355, 420, and 540 nm [96].
During the oxidation of p-pheny-lenediamine after intercalation into montmoril-lonite, the resulting polymer had absorption bands at 620 and 670 nm, like polyaniline [46].
Infrared spectra
The spectra of poly(p-phenylenediamine) (Figure 5), used here for illustration, differ from the spectra of polyaniline. Absorption in the
4000 3500 3000 2S00
2000
1500
1000
500
Wavenumbers I cm"
Fig. 5. Spectra of poly(p-phenylenediamine) and polyaniline181.
region about 3034 cm-1 characteristic of the aromatic C-H stretching vibrations is higher. The band of quinonoid ring stretching vibrations at about 1573 cm-1 is present in both spectra. The band of benzenoid ring-stretching vibrations is shifted to higher wavenumbers in the spectrum of poly(p-phenylenediamine) and it is mixed with the N-H deformation vibrations.
The region of N-C stretching vibrations at about 1300 cm-1 has lower absorption in the spectrum of poly(p-phenylenediamine). The peaks of C-H in-plane deformation vibrations at about 1162 cm-1 are present in both spectra. The peaks at 699 and 503 cm-1 assigned to the vibrations of variously substituted rings are present in both spectra.
Fluorescence
The fluorescence of o-phenylenediamine oligomers was excited at 405 nm, the emission was located between 560-590 nm [131]. Ultrasensitive detecting system based on poly(p-phe-nylenediamine)(PpPD) fluorescent nanospheres is proposed [177].
Fig. 6. Fluorescence emission spectra of poly(p-phenylenediamine)177.
This detecting system shows excellent selectivity, stability, specificity and anti-interference ability. PpPD dispersed in water displayed a strong fluorescence excited (Figure 6) with 296 nm irradiation and its emission maximum was at 410 nm [114]. The fluorescence was quenched with caffeine [114] or L-cysteine [133].
ESR Spectroscopy
ESR spectroscopy is a useful technique for investigating the electron and radical in the conducting polymers. However, there are only a few reports on the ESR spectroscopy of the aromatic diamine polymers prepared by oxidative polymerization. It is suggested that pheny-lendiamine polymers exhibit a single ESR peak with a g value of 2.004-2.006 and a maximum peak width of 13-36 G [136]. Tsuchida et al. suggested that the ESR spectrum of polyazo-phenylene from pPD has a single absorption with a peak width at the maximum slope between 7 and 12 G [137]. The solidstate pPD ol-igomer by copper oxidant exhibits a sharp ESR signal at 3180 G due to a free radical inside the oligomer and a broad ESR absorption at 3165 G due to Cu2+ ion in the oligomer [138]. These signals are not affected significantly on heating, but a slight dependence on the position of the
signals on changing the central field was observed. The pPD oligomer oxidized by cobalt complex exhibits only one signal at 3200 G due to a radical. In addition, the radical in the end group of the oligomer could be stabilized by metal ions. The solid ESR spectra of pPD oli-gomer vary significantly with the oxidants used for the oxidative oligomerization.
Applications of polyphenylenediamines
Due to the low cost of the starting material and a whole range of special properties, polyphenylenediamines and its derivatives have found application in a wide range of areas. Thus, due to electrical conductivity and redox activity, as well as the dependence of electrical conductivity on the degree of protonation, it is possible to create various sensors based on pol-yphenylenediamine. In addition, polyphe-nylenediamines can be used as one of the components in composite materials, for example, in composite anti-corrosion coatings, as one of the anti-corrosion components of the composition. In general, some main groups of areas of applicability of polyphenylenediamines can be distinguished. These include electronics and radio engineering, the manufacture of membranes and various types of sensors, the creation of antistatic and anticorrosion coatings and applications in medicine and biology.
The use of polyphenylenediamines in electronics
Due to good operational stability polymers of phenylenediamines, they can be used as materials for creating various types of electronic products. Electrorheological fluids consist of suspensions of electrically polarizable particles in a non-conductive liquid carrier. When an electric field is applied, the electric dipoles organize into strands and the viscosity of the suspension increases.
Systems containing polyphenylenediamines behave in a similar way. Their electrical conductivity is quite low, but at the same time the polarizability is sufficient to obtain an ordered structure in an electric field, and thus it is possible to obtain an electrorheological response. Thus, the oxidation product of o-phe-
nylenediamine is an active agent in electrorhe-ology. Large particles dispersed in silicone oil are easily structured, transforming into chains in an electric field, which was observed using an optical microscope. Electric dipoles induced on particles of poly(m-phenylenediamine) in an electric field lead to their organization and observation of the electrorheological effect [29], in turn, poly(p-phenylenediamine) demonstrates the strongest electrorheological response compared to poly(o-phenylenediamine) and poly (m-phenylenediamine) [29].
The use of polyphenylenediamines for the creation of biosensors
Poly-phenylenediamines (PPDs) electro-synthesized from one of the three monomer isomers have found widespread use as a biosensor permselectivity barrier [196-199], although poly(ortho-phenylenediamine), PoPD, may be superior for long-term in-vivo monitoring [200]. A variety of immobilization methods for oxidase enzymes (EOx) have also been described for PPD-based biosensors, with three approaches commonly used: enzyme deposited before the PPD layer, EOx/PoPD [201-204], enzyme immobilized over PPD, PPD/EOx [201,205-207] and enzyme co-immobilized from the monomer solution, PPD-EOx [208-210].
Recently, a number of new aspects to the problem of interference at PoPD-based biosensors have been identified. First, the permselec-tivity can be undermined for biosensors with large values of Pt-insulation "edge density", such as microdisks [211]. Briefly, PoPD deposited near the electrode insulation is not as effective at blocking interference. Second, the incorporation of enzyme in the PoPD can decrease its blocking ability [211]. Third, electrosynthesis of enzyme-free PoPD in the absence of added background electrolyte can improve its perm-selective properties, apparently due to fewer ions being trapped in the polymer matrix [212].
Application of polyphenylenediamines in corrosion of metals
Corrosion is an undesirable natural process that arises from the use of metallic materials, therefore serious efforts to prevent this phe-
nomenon are ongoing through this century. Three approaches are commonly applied to reduce the rate of corrosion including cathodic protection, anodic protection (passivation), and application of barrier coatings [144]. Protective coatings have been widely used for metal corrosion control. The use of conducting polymers for the inhibition of corrosion is an area which is very recently gaining increasing attention [145].
Fig. 7. Cyclicvoltammogram of PoPD nan-ofiber coated 316L SS in 0.1 M NaCl at scan rate 50 mV s-1 146 .
PoPD nanofiber was synthesized by polymerization of o-phenylenediamine using po-lyvinylpyrrolidone(PVP) and HAuCl4. Thin, adherent and compact layer of PoPD nanofibers were coated on 316L stainlessteel (SS) by dip coating method. The evaluation of corrosion behaviors for PoPD nanofiber coated 316L SS in 3.5% NaCl revealed that the corrosion potential shifted in the nobler direction which indicates the strong adherent and inhibition effect of the PoPD nanofiber film. The EIS (electrochemical impedance spectroscopic) measurement show that the passive film of PoPD nanofiber coated on 316L SS exhibits good corrosion resistance when compared uncoated 316L SS (Figure 7). Hence, PoPD nanofiber coatings can be considered as a potential coating material for 316L SS in chloride containing medium [146].
Poly(o-phenylenediamine) and poly(o-phenylenediamine)/ZnO (PoPd/ZnO) nanocom-posites coating were prepared on type-304 aus-tenitic (SS) using H2SO4 acid as electrolyte by potentiostatic methods. The corrosion protection of polymer coatings ability was studied by-
time measurement, anodic and cathodic poten-tiodynamic polarization and impedance techniques in 3.5% NaCl as corrosive solution (Figure 8). It was found that ZnO nanoparticles improve the barrier and electrochemical anticorrosive properties of poly(o-phenylenediamine) [147].
Organic batteries based phenylendia-
mines
Fig. 8. Potentiostatic polymerization of pure PoPd (a) and PoPd/ZnO nanocom-posites coating (b) at potential 1.2 V for 1800 s147.
Redox-flow batteries
Redox-flow batteries (RFBs) are considered among the top candidates for large-scale electricity storage systems [144, 145]. This is due to their operating principle, which is very different from that of the conventional secondary batteries. When uncharged, two different redox couples or a single redox couple in their discharged states are dissolved in a supporting electrolyte and stored in separate reservoir tanks. During the charge of RFBs, these two electrolytes are simultaneously pumped into an electrode stack, wherein the redox couples are converted into their respective charged states by electrochemical oxidation and reduction reactions, respectively.
RFBs have been developed with aqueous electrolytes since the 1950s [148]. The aqueous RFBs have some drawbacks: (I) the working voltage is limited due to water electrolysis (1.23 V), and (II) they use highly corrosive electrolyte solutions (for example, concentrated sulfu-ric acid in all-vanadium RFBs). These drawbacks may be mitigated by switching to non-aqueous electrolytes, which are non-corrosive
and afford a wider electrochemical stability window compared to water [149]. Until now, however, the benefit of nonaqueous RFBs has not been fully utilized. The most critical problem is the poor solubility of redox couples in non-aqueous electrolytes, which is directly correlated with volumetric capacity. Previously, Wang et al. [147, 150] reported that the solubility of common redox couples are < 0.1 M in non-aqueous electrolytes containing >1.0 M salts.
In p-phenylenediamine two nitrogen re-dox centers can lose two electrons to form a cation radical and di-cation in sequence. As an active material in flow batteries, such a molecule could generate twice the volumetric capacity compared to that involving only one electron in the redox reaction at the same concentration of electrolyte. Therefore, the organic redox couple of PD is cost-effective as the positive electrolyte ingredient for a flow battery. However, its low solubility (<0.5 M in 1.0 M LiBF4/pro-pylene carbonate (PC) electrolyte) and poor chemical stability make its practical adoption difficult.
Li-ion batteries
Lithium ion batteries (LIBs) are one of the most efficient power sources for hybrid electric vehicles and portable electronic devices [152-154]. However, the low power, high cost, and safety concerns associated with LIBs limit their widespread application. To address these issues, the development of novel electrode materials with superior electrochemical performance is essential. Lithium titanate (LTO) spinel is regarded as an alternative anode material for LIBs since it exhibits no structural changes,
has good lithiumeion mobility, and presents a long and stable voltage plot of approximately 1.55 V vs. Li+/Li [155,156]. Unfortunately, the electrical conductivity of LTO is very low (<1013 S cm1), which decreases its performance at higher current densities [157,158].
The polymer of the aromatic diamine compound pephenylenediamine (pPDA), which resembles aniline, is considered to be a superior alternative to PANI. Consequently, significant effort has been devoted to investigating poly(pephenylenediamine)-reduced graphene oxide (PpPDA-RGO) as a polymer nanocompo-site in LIBs. Excellent performance has been reported with PpPDA-RGO in a supercapacitor, where the nanocomposite was synthesized in the presence of suitable oxidizing agents. Furthermore, pPDA was recently reported to be a noble reducing agent for GO. In particular, pPDA induces redox reactions with GO in the absence of other oxidants or reducing agents, producing electrically conductive PpPDA-RGO [159, 160].
Successfully prepared PG/LTO nanocom-posites via a oneestep redox reaction of pPDA and GO/LTO(reduced graphene oxide/lithium titanate) without using any other reducing agents (Figure 9).
The loading of a small amount of pPDA relative to GO effectively increased the extent of chemical reduction in the functional groups of GO. In terms of the electrochemical performance in a Li-battery anode, PG/LTO exhibited superior rate capabilities compared to GO/LTO and pristine LTO.
Fig. 9. Schematic representation of the preparation of PG/LTO nanocomposites
Excellent rate capability and cyclic stability were obtained for nanocomposites with a 3:1 ratio of pPDA:GO.
The RGO served to increase the electrical conductivity of the nanocomposites, while the presence of residual PpPDA facilitated good contact between the RGO and LTO in PG-encapsulated LTO particles. Consequently, PG/LTO displayed excellent electrochemical performance when utilized in an LIB anode [161].
Organic Radical Batteries
An organic radical battery (ORB) is a type of battery first developed in 2005 [182]. As of 2011, this type of battery was generally not available for the consumer, although their development at that time was considered to be approaching practical use [183]. ORBs are potentially more environmentally friendly than conventional metal-based batteries, because they use organic radical polymers (flexible plastics) to provide electrical power instead of metals. ORBs are considered to be a high-power alternative to the Li-ion battery. Functional prototypes of the battery have been researched and developed by different research groups and corporations including the Japanese corporation NEC[162].
The organic radical polymers used in ORBs are examples of stable radicals, which are stabilized by steric and/or resonance effects [163]. For example, the nitroxide radical in (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), the most common subunit used in ORBs, is a stable oxygen-centered molecular radical. Here, the radical is stabilized by delocalization of electrons from the nitrogen onto the oxygen. TEMPO radicals can be attached to polymer backbones to form poly(2,2,6,6-tetramethyl- piperidenyloxyl-4-yl methacrylate) (PTMA). PTMA-based ORBs have a charge-density slightly higher than that of conventional Li-ion batteries, which should theoretically make it possible for an ORB to provide more charge than a Li-ion battery of similar size and weight[163].
As of 2007, ORB research was being directed mostly towards Hybrid ORB/Li-ion batteries because organic radical polymers with appropriate electrical properties for the anode are difficult to synthesize[164].
Radical polymer batteries rely on a redox reaction of an organic radical to generate an electrochemical potential. The most studied example of such an organic radical redox reaction is that of nitroxide radicals, such as the one found on a molecule called (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl, also known as TEMPO. A nitroxide radical can be oxidized to an oxammonium cation or reduced to a hydroxylamine anion.
Na-ion batteries
Rechargeable sodium ion batteries have emerged in recent years with a flourishing research activity as they are seen as a low cost technology for grid storage applications, [165171] which could be an alternative to environmentally questionable Pb-acid or to Na-S with its high operating temperatures (300 °C). The overall abundance of sodium on Earth is estimated to be almost 1000 times that of lithium [172, 173]. Besides, over one third of the sodium can be found in seawater, which is geographically widespread and facilitates its extraction, leading to more economical resources for energy storage systems. However, the bigger ion size of Na+ ions in comparison to Li+, makes it more difficult to find host materials that can reversibly accommodate the ions in their structure during electrochemical cycling.
Several examples of organic molecules and macromolecules have been reported so far to be electrochemically active at high potentials vs. Na+/Na [174-178]. Polymers are typically included in lithium and sodium ion batteries formulations of electrodes as the binding agent that confers mechanical stability to the electrode, sticking together the active material, the electron conductive carbon and the current collector. Its presence is particularly important for long term cycling, as the interparticle contact might be lost by volume expansion and contraction concomitant with ion insertion/de-insertion.
To meet the challenge of developing low voltage anode materials that rely on sustainable and low cost precursors, has been synthesized a new family of Schiff bases. Polymeric Schiff bases have been reported to be promising materials as anodes for sodium ion batteries despite their poor processability. Has been founded that
substituting 1 in 3 p-phenylene-diamine monomer by Jeffamine® 600 g/mol in DMF leads to terpolymers with optimum electrochemical activity as well as their self-binding properties (Figure 10). The macromolecule shows a stable reversible capacity of 178 mAh/g over 25 cycles as a powder and around 185 mAh/g for the binder-free laminated electrodes with 20 wt. % carbon [178].
In response to the challenges of using an inorganic electrode for the reversible accommodation of different size metal ions, an imine-rich poly(o-phenylendiamine) (PoPD) is obtained
through a rational controllable oxidization, acting as a trifunctional electrode in alkali-ion batteries. At the same time, its successful application as a versatile electrode in lithium and sodium storage (537 and 307 mAhg-1 after 300 cycles for LIBs and SIBs, respectively) extends the application range of PoPD and may even be useful for multivalent- and dual-ion batteries in the future (Figure 11). We anticipate that these findings will enlighten the design and application of organic electrode materials for cheap, green, sustainable, and versatile energy storage devices [179].
Fig. 10. Electrochemical characterization in sodium half cells (powder electrodes, 20 % wt. of C65, 19.7 mA/gactive): a) differential capacity plot of the second cycle; b) cycle life and coulombic efficiency at different rates178.
j •»
Fig. 11. DFT calculations and redox mechanism. (a) Electrochemical redox process of PoPD. (b) Major bond length change of PoPD during the reduction process. (c) Stabilization energies at vari-ous reduction stages of PoPD. (d-f) Three configurations of PoPD-K179.
Use of phenylenediamines as catalysts
High-temperature pyrolyzed FeNx/C catalyst is one of the most promising nonprecious metal electrocatalysts for oxygen reduction reaction (ORR) [213]. However, it suffers from two challenging problems: insufficient ORR activity and unclear active site structure. Herein, has been reported a FeNx/C catalyst derived from poly(m-phenylenediamine) (PmPDA-FeNx/C) that possesses high ORR activity (11.5 A g-1 at 0.80 V vs RHE) and low H2O2 yield (<1%) in acid medium (Figure 12). The PmP-DA-FeNx/C also exhibits high catalytic activity for both reduction and oxidation of H2O2. The
further has been find that the ORR activity of PmPDA-FeNx/C is not sensitive to CO and NOx but can be suppressed significantly by halide ions (e.g., Cl-, F-, and Br-) and low valence state sulfur-containing species (e.g., SCN-, SO2, and H2S). This result reveals that the active sites of the FeNx/C catalyst contains Fe element (mainly as Fem at high potentials) in acid medium. The present study has thrown a new insight into the active site nature of the FeNx/C through molecule/ion probes and is of importance in rational design of high performance FeNx/C catalysts for the ORR [180].
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Fig. 12. (a) ORR polarization curves and H2O2 yield plots of PmPDAFeNx/C catalyst prepared at different pyrolysis temperature, measured in O2-saturated 0.1 M H2SO4. Catalyst loading: 0.6 mg cm-2 ; Scan rate: 10 mV s-1 ; Rotating speed: 900 rpm. (b) Variety of ORR mass activity at 0.80 V with pyrolysis temperature. (c) Polarization and power density plots for H2O2 single fuel cell with PmPDA-FeNx/C as cathode catalyst at 80 °C180.
Fig. 13. Schematic diagram of the OLED structure
Organic light-emitting devices (OLEDs)
Organic Light Emitting Diode (OLED) are diodes in which the emitting layer is an organic compound. They consist of the following elements:
• substrates (plastic, glass, foil);
• a cathode that injects electrons into the emitting layer when current passes;
• layers of organic materials, one of which conducts holes injected by the anode, and the other conducts electrons injected by the cathode, and radiative recombination of charge carriers occurs in it;
• transparent anode, which injects holes when current passes.
The anode material is usually tin-doped indium oxide (ITO). It is transparent to visible light and has a high work function which promotes hole injection into the polymer layer. The cathode is often made of metals (aluminum and calcium) with a low work function, but sufficient to inject electrons into the polymer layer. Low-molecular organic substances (sm-OLED) and polymers are used as light-emitting materials. The latter are divided into simple polymers, organopolymer (POLED) and phosphorescent (PHOLED) compounds.
Figure 13 shows the basic OLED structure. The devices consist of a glass substrate covered with a patterned indium tin oxide (ITO) layer with 100 nm thickness, then 40 nm of the hole transport material N,N'-diphenyl-N,N'-
bi s(3 -methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), 10 nm of either 4,4-bis[4-(diphenylami-no)styryl]biphenyl(BDASBi) or 4-(2,2-diphenyl-ethenyl)-N,N-bis(4-methylphenyl)benzeneamine (PEBA) doped into 4,4-bis(N-carbazole)-biphe-nyl(CBP) (6 wt.%), 50 nm of the electron transport material 4,7-diphenyl-1,1-phenanthro-line (Bphen) and a cathode consisting of 100 nm Mg:Ag (10:1) and a 10 nm thick Ag capping layer.
Over the last decades, the mechanisms underlying the functioning of organic electronics devices have been the topic of intense research such that in particular organic light-emitting devices (OLEDs) do now rapidly mature into new applications and products [186— 188]. In such OLEDs, amorphous or non-crystalline materials are commonly employed. It has been found that these amorphous films may exhibit a preferential orientation [189] or even a particular defined local packing. This affects charge carrier transport and light emission that depend strongly on the local molecular order [190-195]. In a comprehensive study, Adachi and coworkers investigated the molecular orientation and electronic properties of a large number of organic amorphous thin film materials and found that linear or planar molecules show a tendency to orient flat with respect to the substrates [189]. Longer molecules are inclined to form films with a larger anisotropy [189].
Fig. 14. (a) Chemical structures of the a-6T and a-NPD molecules, (b) the device structure of the hole-only devices composed of ITO, a-6T, a-NPD, molybdenum oxide and Al214.
The effect of orientational changes in thin films of the non-crystalline hole transport material a-N-N'-diphenyl N-N''-bis(1 naph-thayl)-1,1'-biphenyl-4,4'-diamine (a-NPD) on the energy level alignment and the film electronic structure has been investigated by an-gleresolved ultraviolet photoelectron spectros-copy and related to the transport characteristics of hole-only devices (Figure 14). Changes in the anisotropic a-sexithiophene (a-6T) substrate from a ''standing'' to a ''flat'' molecular orientation induced by mechanical rubbing lead to molecular order and a preferential orientation in subsequently deposited thin a-NPD films and cause a reduction of the charge injection barrier at the organic/organic interface. The results show that the height of this barrier is determined by the surface dipoles of the individual organic films that relate to the orientation of
214
intramolecular polar bonds at the interface .
Conclusions
The oxidation of phenylenediamines in acidic aqueous media yields materials that are redox-active and also display potentially useful electrical, optical, and chemical properties. The synthesis of bulk quantities by chemical oxidation is simple and easy. Electrochemical oxidation has extensively been used to prepare thin films. The oxidation products are expected to be ladder polymers but both the molecular structure and polymer character still have to be confirmed and controlled. The close relation with a conducting polymer, polyaniline, inspires both future studies and applications of polyphe-nylenediamines. As all three phenylenediamine isomers can be oxidized to various products, copolymerized with aniline or with each other, the variability of the produced materials is immense. In addition, these polymers can be carbonized at elevated temperature to nitrogen-containing carbons. The most promising applications are seen in corrosion protection, electro-catalysis, energy conversions, sensing, electrical stimulation in biosciences, water purification, and in many other related fields. Such a potential for applications is unique among polymers.
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AROMATiK DlAMiNLOR OSASINDA POLlMERLORlN XÜSUSiYYOTLORl
O.O.Macidov, S.Z.ismayilova, G.M.Ganzayeva, S.A.Agayeva, S.N.Qasimova
Bu icmalda fenilendiaminlar asasinda sintez edilan keçirici polimerlarin sintezi, quruluçu, xassalari, tadqiqat metodlari va tatbiq sahalari haqqinda atrafli malumat verilir. Fenilendiaminlar asasinda sintez edilan keçirici polimerlar yüksak konyuqasiyali polimerlarin kation duzlaridir, elektrokimyavi va ya kimyavi oksidlaçma yolu ila sintez olunurlar. Kimyavi oksidlaçdirici polimerlaçma yolu ila müxtalif funksional polimerlar sintez olmuçdur. Reaksiya çaraitindan asili olaraq polifenilendiaminlar tozlar, kolloid dispersiyalar, nazik tabaqalar va ya kompozitlar çaklinda sintez olunur. Polianilin kimi, bu polimerlar da duz-turçu keçidi nûmayiç etdirirlar va redoks-aktivdirlar. Onlar nacib metal birlaçmalarinin müvafiq metallara reduksiyaedicilari kimi çixiç edirlar. Elektrik keçiriciliyina va redoks aktivliyina, elaca da elektrik keçiriciliyinin protonlaçma daracasindan asililigina göra polifenilendiaminlar asasinda müxtalif sensorlar yaratmaq mümkündür. Bundan alava, polifenilendiaminlar kompozit materiallarin tarkib hissalarindan biri kimi, masalan, antikorroziya örtüklarinda istifada edila bilar. Ümumiyyatla, polifenilendiaminlarin bazi asas tatbiq sahalarini qruplaçdirmaq olar. Odabiyyat malumatlarinda onlarin bir sira tatbiq sahalari gôstarilmiçdir; bunlara metallarin korroziyadan qorunmasi, kataliz, elektroreologiya, sensorlar, enerjiya çevrilma cihazlari, elektroxromizm, nacib metallarin barpasi va suyun tamizlanmasi daxildir. Eyni zamanda, fenilendiaminlarin polimerlari potensial toksikliya malik olan anilin va onun oliqomerlarindan farqli olaraq tibbda istifada oluna bilar.
Açar sözlar: poli(o-fenilendiamin), poli(m-fenilendiamin), poli(p-fenilendiamin), fenilendiamin, keçirici polimerlar, redoks aktiv polimerlar, elektrik keçiriciliyi.
СВОЙСТВА ПОЛИМЕРОВ НА ОСНОВЕ АРОМАТИЧЕСКИХ ДИАМИНОВ
А.А.Меджидов, С.З.Исмаилова, Г.М.Ганзаева, С.А.Агаева, С.Н.Гасымова
В данном обзоре представлена подробная информация о синтезе, строении, свойствах, методах исследования и областях применения проводящих полимеров, синтезированных на основе фенилендиаминов. Проводящие полимеры на основе фенилендиаминов представляют собой катионные соли полисопряженных систем, которые получаются методом электрохимического или химического окисления. Химическая окислительная полимеризация приводит к образованию различных функциональных полимеров. В зависимости от условий реакции полифенилендиамины получают в виде порошков, коллоидных дисперсий, тонких пленок или композитов. Близкое сходство химической структуры полианилинов и полифенилендиаминов наделяет обе группы некоторыми аналогичными свойствами, например, такими как окислительно-восстановительная активность. Они действуют как восстановители соединений благородных металлов в соответствующие металлы. Благодаря электропроводности и окислительно-восстановительной активности, а также зависимости электропроводности от степени протонирования возможно создание различных сенсоров на основе полифенилендиаминов. Кроме того, полифенилендиамины могут быть использованы как один из компонентов композиционных материалов, например, в антикоррозионных покрытиях. В целом можно выделить некоторые основные группы областей применения полифенилендиаминов.В литературе указан ряд областей их применения; они включают защиту металлов от коррозии, катализ, электрореологию, датчики, устройства преобразования энергии, электрохромизм, извлечение благородных металлов и очистку воды. В то же время полимеры фенилендиаминов могут найти применение в медицине в отличие от анилина и его олигомеров, которые обладают потенциальной токсичностью.
Ключевые слова: поли(о-фенилендиамин), поли(м-фенилендиамин), поли(п-фенилендиамин), фенилендиамин, проводящие полимеры, редокс-активные полимеры, электропроводность.
