Emission polystyrene copolymers

Recent encouraging results have been reported by Carter et al., who have obtained room temperature lifetimes in excess of 7000 h for encapsulated ITO/PPV/Ca devices at current densities of 60 mA/cm2.37 The polymer used was the PPV copolymer shown in Fig. 5.23, where the conjugation is interrupted by nonconjugated a -acetyloxy-/ -xylylene units. The efficiency of these devices was typically 0.02 lm/W. Devices operating at 80° C had lifetimes in excess of 1100 h. Carter et al., also reported devices based on the same emissive polymer giving efficiencies between 0.5 and 2 lm/W. These devices used a layer of conducting polymer (polyethylenedioxythiophene/polystyrene sulfonate) between the ITO and the PPV, and a sputtered aluminum/lithium alloy as the cathode. The devices... 

On the other hand, the excimer emission because it is 80% non-correlated with monomer trap emission and because it is effectively quenched in the copolymers even at low temperatures, must largely arise from a mobile precursor. The activation energy for hopping of this precursor is implied to be <10 cm l. This is not unreasonably low(12,17), and indeed, the zero-point energy of the phenyl chromo-phore could in principle allow completely activationless hopping (tunneling) at reasonable rates. Determination of the true situation will require measurements at still lower temperatures, which are now in progress. We note that the polystyrene emission spectrum at 4.2K reported in (Id) indicates a monomer/excitner intensity ratio nearly the same as our 20K spectra. 

Weak delayed-emission spectra of vacuum- or air-irradiated copolymer films were similar in intensity and showed a phosphorescence maximum at 432 nm with shoulders ca. 390 nm and 450 nm on excitation at 260 nm in addition to a very weak maximum at 505 nm excited at 380 nm. These spectra are close to those shown in Figure 4 for ketone phosphorescence in photooxidized polystyrene and agree reasonably well with phosphorescence spectra for model napthaleneones (15). Energetically, the quench-... 

Excimer formation has been studied in polystyrene and poly(a-alkylstyrenes)189 (PS), poly(vinylcarbazole),139>140 poly-(2-vinylnaphthalene), and poly-(4-vinyl-biphenyl).141 For polystyrene films, David et a/.189 showed that the fluorescence yield increased with increasing crystallinity, at both ambient temperature and 77 K. The contribution of excimer fluorescence yield increased in the sequence atactic (0.7) < atactic oriented (0.60) < isotactic amorphous (0.28) < isotactic crystallized (0.01), with normal yields relative to excimer given in parentheses. Similar results were obtained for poly(vinylcarbazole), PVCZ, although the contribution of excimer fluorescence at 77 was independent of crystallinity. The results can be interpreted in terms of electronic energy migration to low-energy defect sites from which excimer emission can occur. In PVCZ copolymers with fumaronitrile (10), diethyl fumarate (11), and diethyl maleate (12) (Scheme 6),... 

Most significant environmental issues with respect to block copolymer S5m-thesis relate to manufacturing process, taste and odor issues in end use, and solid waste in final disposal of these pol5uners. Manufacturing process issues relate to industrial hygiene, exposure, and volatile organic emissions. In end use, block copolymer/polystyrene blends tend to have taste and odor issues, especially for sensitive food packaging applications. 

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