Pyrazoline polymers

Although the cross-linked pyrazoline polymer is insoluble in common organic solvents by virtue of the crosslinks present, it was discovered that films of this material could be cast onto a variety of substrates from a suspension in a swelling solvent such as benzene. The ability to cast films is presumably related to the substantial change in polymer resin morphology after the coupling reaction has proceeded. The initial resin is hard, spherical and white in color, while the reacted bead is powdery, irregular in appearance and yellow, the color of the pyrazoline monomer. 

These differences in film morphology were also reflected as differences in film formation conditions, film adhesion, and in electrochemical properties. The pyrazoline beads readily formed films from solvents such as benzene. For the phenoxy TTF system, however, only CH2Cl2 was effective in forming films. In general, the TTF cross-linked polymers were found to be less adherent to the metallized substrates than the pyrazoline cross-linked polymers. Electro-chemically, it was found that the pyrazoline films showed complete activity after one potential sweep. The TTF polymer films, on the other hand, required from 5 to 20 cycles to reach full electrochemical activity as evidenced by a constant voltammogram with cycling. Furthermore, it was observed that the TTF polymer films were much less electroactive than the pyrazoline materials as shown by optical densities and total coulombs passed which were several times less for the TTF systems. 

Figure 9. Schematic of electron transport at metal-pyrazoline cross-linked polymer interfaces...

An important point is that the electrochemically driven charge transport in these polymeric materials is not dependent on the presence of mixed valence interactions which are well known to give rise to electronic conductivity — in a number of cation radical crystalline salts. This is clearly seen from the absorption spectrum of the electrochemically oxidized pyrazoline films (Figure 8) which show no evidence for the mixed valence states that are the structural electronic prerequisites for electrical conductivity in the crystalline salts. A more definitive confirmation of this point is provided by the absorption spectrum (Figure 10) of electrochemically oxidized TTF polymer films which shows... 

Poly(chalcones) (183), which themselves are the products of Knoevenagel condensation of aromatic dialdehydes and diacetyl compounds, have been transformed into polylpyrazo-lines) (185) by reaction with phenylhydrazine (184) (72MI11107). The reaction (Scheme 88) was conveniently conducted in excess phenylhydrazine and yielded polymers which were described as being brilliantly fluorescent in solution. The poly(pyrazolines) (185) exhibited glass transition temperatures between 150 and 210 °C and were stable, in some cases, up to 630 °C. 

Pyrazolines have also been incorporated as modifying groups by 1,3-addition of azomethine ylides to the carbon-carbon double bond of unsaturated poly(esters) (186 Scheme 89) (68MI11100). Poly(isoxazolines) were prepared in similar fashion by reaction of an unsaturated polymer with a nitrile oxide (75MI11106). 

On the other hand, pyrazoline and pyrazole derivatives are successfully used for material science tasks. For example, triarylpyrazolines are used in the synthesis of green electroluminescent polymers for light-emitting diodes [18], Some aromatic substituted 2-pyrazolines are effective organic luminophores [19,20], fluorophores [21] and scintillating materials [20, 22]. 

Another method for the preparation of polymers containing pyrazoline fragments was suggested in [18]. Poly (9i/-fluoren-2,7-ylene)- / -[3,5-bis(l,4-phenylene)-4,5-dihydro-1-phenylpyrazole] 53 was synthesized by the reaction of pyrazoline 51 and fluorene-2,7-bis(trimethylene boronate) 52 in toluene in the presence of a catalyst, Pd(PPh3)4, with 85% yield. 

The current organic photoreceptors are triarylamines, triarylmethanes, hy-drazones, oxadiazoles, pyrazolines, oxazoles, and more recently, stilbene derivatives. The polymer matrix, on the other hand, is constituted by polyesters and polycarbonates (Fig. 5). The common presence of aromatic amines as substituents in all these materials contributes to efficient hole transport [44]. The nonbonding electron pair on the nitrogen atom, in fact, confers on these molecules a low oxidation potential, and consequently, the production of a chemically stable radical cation with the possibility of an effective overlap of nonbonding molecular orbitals between neighboring molecules. 

Hole transport in polymers occurs by charge transfer between adjacent donor functionalities. The functionalities can be associated with a dopant molecule, pendant groups of a polymer, or the polymer main chain. Most literature references are of doped polymers. The more common donor molecules include various arylalkane, arylamine, enamine, hydrazone, oxadiazole, oxazole, and pyrazoline derivatives. Commonly used polymers are polycarbonates, polyesters, and poly(styrene)s. Transport processes in these materials are unipolar. The mobilities are very low, strongly field and temperature dependent, as well as dependent on the dopant molecule, dopant concentration, and the polymer host This chapter reviews hole transport in polymers and doped polymers of potential relevance to xerography. The organization is by chemical classification. The discussion mainly includes molecularly doped, pendant, and... 

Naito and Kanemitsu (1996) investigated the relationship between the prefactor mobilities, zero-field mobilities, and the glass transition temperatures of OX doped polyarylate (PA), PC, poly(methyl methacrylate) (PMMA), PS, poly(vinyl chloride) (PVC), polyethylene terephthalate) (PET), and poly(vinyl butyral) (PVB), DEH doped PC, 5(p-diethylaminophenyl)-l-phenyl-3-(/ -diethylaminostyryl)-2-pyrazoline (DEASP) doped PS, and DEASP doped PC. OX, DEH, and DEASP are highly polar molecules with similar dipole moments. By modifying the polymer, the glass transition temperature can be varied over... 

Solid-phase synthesis of substituted pyrazolones 550 from polymer-bound /3-keto esters 549 has been described (Scheme 68) <2001EJ01631>. Trisubstituted pyrazole carboxylic acids were prepared by reaction of polymer-bound arylidene- or alkylidene-/3-oxo esters with phenylhydrazines <1999S1961>. 2-(Pyrazol-l-yl)pyrimi-dine derivatives were prepared by cyclocondensation of ethyl acetoacetate and (6-methyl-4-oxo-3,4-dihydropyrimi-din-2-yl)hydrazine with aromatic aldehydes <2004RJC423>. Reactions of acylated diethyl malonates with hydrazine monohydrochloride in ethanol afforded 3,4-disubstituted-pyrazolin-5-ones <2002T3639>. Reactions of hydrazines with A -acetoacetyl derivatives of (45 )-4-benzyloxazolidin-2-one (Evans oxazolidinone) and (2R)-bornane-10,2-sultam (Oppolzer sultam) in very acidic media gave pyrazoles retaining the 3(5)-chiral moiety <1999S157>. 

Many derivatives have been prepared from ferrocene monocarboxylic acid (S). Acetylferrocene was reduced by lithium aluminum hydride to the carbinol, and this was then converted into vinylferrocene. From this, polymers and copolymers with other polymerizable substances have been obtained. The polymers are easily obtainable in the cationic form and in the reduced, uncharged form, which are interconvertible (5). Urethanes (3), amino acids and urea, hydantoin and pyrazoline derivatives with ferrocenyl substituents have also been prepared (100, 178). 

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