Phthalocyanine polymers

Phthalocyanine Polymers. Phthalocyanin-imide polymers show an initial decomposition temperature > 500 °C both in air and inert atmosphere (Co, Ni, Cu, Zn) as expected. An increase in the concentration of metal phthalocyanine in the copolymer increases the thermal stability [70]. Poly(Cu 2,3,9,10,16,17,23,24-octacyanophthalocyanine) represents an unique polymer showing enhanced thermal stability (1.2% wt loss at 585 °C and 1.5% wt loss at 625 °C, 21.6% at 800 °C) in He atmosphere Rapid oxidation takes place on heating above 560 °C (9% wt loss at 585 °Q [99] in air. The enhanced stability of this material is different from that of monomeric metal phthalocyanine compounds which sublime and loose most of their weight around 600 °C [99]. 

Phthalocyanine Polymers. As mentioned earlier [99], thermal cyclization of poly(Cu,2,3,9,10,16,17,23,24-octacyanophthalocyanine) induces a dramatic improvement of the conductivities. The polymer, cyclized at 203 °C, has a room temperature conductivity of ca, 6.7 x 10-6(ft-1 cm- ) in air, cyclized at 400°C, the conductivity is enhanced 3 times which is claimed to be due to elimination of impurities. At 600-700 °C, large extensive cyclization (both inter and intramolecular) leads to highly conjugated structure cyclized at 900 °C, the polymer exhibits conductivity in the range 4.6-8 (ft-1 cm-1) with only ca. 21.9% weight-loss. 

Interesting results have been obtained in studies of the catalytic activity for oxidation by phthalocyanine polymers, containing different metal ions in the same molecule 87-90>. If Fe was mixed with a series of other transition metal ions, differences in activity were found to be dependent on the metal ion, and correlations between the catalytic activity and the thermal activation energy of semiconductivity were found. With copper as the second metal ion, maximum activities were found at a ratio Fe/Cu = 1. Many other chelate polymers have been tested for their oxidation activity, and a dependence of the catalytic activity on the donor properties of the ligand was found 91>92). 

Zhu J, Shen Y, Gu F, Tao J, Zhang J (2007) Preparation and photovoltaic properties of near-infrared absorbing manganese(II) phthalocyanine polymer films. Mater Lett 61(6) 1296-1298... 

DBU and its salts have been utilized in the manufacture of polyisocyanate binders (85GEP3328662), metal phthalocyanine polymers (85JAP(K)47027), and resin-sealed light-emitting apparatus (85JAP(K)70781). 

The synthesis, by Professor Malcolm Kenny at Case Western Reserve University, of a series of silicon phthalocyanine polymers (SiPc) (aggregates of the monomer of this series, m-SiPc, are discussed here) and of a series of aluminum and gallium, fluoro and chloro phthalocyanines (AIPc-Cl, GaPc-Cl, AIPc-Cl, GaPc-F) allowed us to study several oriented systems (16). 

Figure la. Silicon phthalocyanine polymer shown attached to SnO, surface. 

Scheme 4.3 Synthesis of diazophenylene-bridged phthalocyanine polymer 6.

Evaporating Al(OH)Pc and Ga(OH)Pc with aqueous HF led after heating to fluoroaluminium and fluorogallium phthalocyanine polymers [Al(F)Pc] , [Ga(F)Pc] (79)125-128). The polymers were purified by sublimation. The bond between the Pc in the staple is described as combined covalent coordinative linkage. 

The polymers deseribed so far have relatively flexible main ehains which can result in complex conformations. In some cases, they ean double baek and eross over themselves. There are also investigations on polymers whieh are eonstrained to remain in a eonformation eorresponding, at least approximately, to a straight line, but whieh have amphiphilic properties that ensme that this line is parallel to the water surfaee. Chiral molecules are one example and many polypeptides fall into this elass [107]. Another example is cofacial phthalocyanine polymers (figme C2.4.9). 

N. Brasseur, R. Ouellet, C. La Madeleine, J.E. van Lier (1999). Water-soluble aluminium phthalocyanine-polymer conjugates for PDT photodynamic activities and pharmacokinetics in tumor-bearing mice. Br. J. Cancer, 80, 1533-1541. 

In our measurements the electrical and photoelectrical properties of a series of phthalocyanine polymers were determined by using these materials in a Schottky junction devices. 

Figure 5 Solid-state absorption spectra of silicon and germanium phthalocyanine polymers.

It should be pointed out that a specific modification of Ti(0)Pc 1 (R = -H) in organic polymers is the most widely used photoconductor in bilayer photoreceptor copiers and laser printers [19]. A thin film containing ethylene-bridged silicon phthalocyanine polymer dispersed in poly(vinylidene fluoride) (1 4 by weight) obtained by casting from a DMF slurry on quartz was orientated in an electrical field [20], A double-layered receptor device for measuring the... 

A more fruitful approach has been to make stacked phthalocyanine polymers with oxygen bridges between the metals. Dehydration of phthalocyanine complexes of Si, Ge and Sn produces a face-to-face oxygen bridged stacking pattern shown in Scheme Since electrical, optical and magnetic properties of... 

The nonlinear nanolayered materials are fabricated by introducing nonlinear dyes into alternate layers of the nanolayered polymer. Nonlinear dyes with large refractive and absorptive nonlinearities have designed, synthesized, and characterized at NRL over the past several years. The nonlinear optical chromophore is typically a phthalocyanine. Polymer miscibility was achieved by peripheral substitution of the phthalocyanine. Nonlinear dyes compatible with styrenes, epoxies, (19,20) and urethane polymers (21) are available. 

Kang, T.F., G.-L. Shen, and R.-Q. Yu (1997). Voltammetric behaviour of dopamine at nickel phthalocyanine polymer modified electrodes and analytical applications. Anal. Chim. Acta 356, 245-251. 

Wen, Z.-H. and T.-F. Kang (2004). Determination of nitrite using sensors based on nickel phthalocyanine polymer modified electrodes. Talanta 62, 351-355. 

Poly(CH2-CHCOOROPc)fl C8H17 or C12H25 Side chain phthalocyanine polymers Pc substituted with various groups metal free, Cu and Ni Pc s M up to 47 000 liquid crystalline absorption and fluorescence spectroscopy. [171]... 

Poly[acrylamide-CuPc(NO)2] Side chain phthalocyanine polymer water soluble also doped with iodine photoconductivity discussed. [175]... 

---