Tinuvins

Hydroxy-5-methyl-phenyl)benztriazole (Tinuvin P, Ciba-Geigy)... 

Under long-wavelength UV light (A = 365 nm) the 2-(2-hydroxyphenyl)-benztri-azoles yielded yellow-green fluorescent chromatogram zones, which were, in the cases of Tinuvin P (hRi 20 — 25) and Tinuvin 343 (2-[2-hydroxy-3-(l-methylpropyl)-5-ter/-butylphenyl]benztriazole hR( 45 — 50), suitable for quantitation. 

Figure 13.21 shows the resolution of a dozen polymer additives at very high resolution using chloroform as the mobile phase. Tinuvin 622 will elute in pure chloroform whereas Chimassorb 944 and many other hindered amine light stabilizers (HALS) will not. With the addition of 1% triethyl amine to the chloroform, however, virtually all HALS will elute. 

FIGURE 13.21 A series of polymer additives using the infrared detector at 5.78 micron. Efficiencies were calculated using the last peak, Tinuvin P, and a plate count of 290,000 was achieved. 

The first column corresponds to six-membered transition states where two types can be differentiated situation A, where the proton transfer leads to a neutral tautomer, and situation B (often Tinuvin P or TIN 75), where the proton transfer leads to a zwitterionic tautomer (Scheme 25). 

The closed cycle of interconversions occurs on an ultrafast time scale. Femtosecond studies (95CPL35) of the ESIPT rearrangement of 347 (R = Me) (commercial name Tinuvin-P) carried out over a wide spectral range... 

Figure 12.1 Analysis of Tinuvin 1577 in 30% virgin olive oil (in hexane), showing (a) the gas cliromatogram comparing the pure oil with a sample at the Tinuvin 1577 detection limit concentration, and (b) the coixesponding liquid chromatogram. Reprinted from Journal of High Resolution Chromatography, 20, A. L. Baner and A. Guggenberger, Analysis of Tinuvin 1577 polymer additive in edible oils using on-line coupled HPLC-GC , pp. 669-673, 1997, with pennission from Wiley-VCH.

Figure 12.7 Cliromatograms of a polycarbonate sample (a) microcolumn SEC ti ace (b) capillary GC ti ace of inti oduced fractions. SEC conditions fused-silica (30 cm X 250 mm i.d.) packed with PL-GEL (50 A pore size, 5 mm particle diameter) eluent, THE at aElow rate of 2.0ml/min injection size, 200 NL UV detection at 254 nm x represents the polymer additive fraction ti ansfeired to EC system (ca. 6 p-L). GC conditions DB-1 column (15m X 0.25 mm i.d., 0.25 pm film thickness) deactivated fused-silica uncoated inlet (5 m X 0.32 mm i.d.) temperature program, 100 °C for 8 min, rising to 350 °C at a rate of 12°C/min flame ionization detection. Peak identification is as follows 1, 2,4-rert-butylphenol 2, nonylphenol isomers 3, di(4-tert-butylphenyl) carbonate 4, Tinuvin 329 5, solvent impurity 6, Ii gaphos 168 (oxidized). Reprinted with permission from Ref. (14).

A. L. Baner and A. Guggenberger, Analysis of Tinuvin 1577 polymer additive in edible oils using on-line coupled HPLG-GG , J. High Resolut. Chromatogr. 20 669 - 673 (1997). 

The early recognition of the role of stable nitroxyl free radicals, e.g., 2,2,6,6-tetramethyl-4-oxopiperidine, and their hindered amine precursors, in polymer stabilization soon led to the development of the hindered amine light stabilizer (HALS) class of photoantioxidants. The first HALS, Tinuvin 770, AO-33, (commercialized in 1974) proved to offer much higher UV-stabil-ity to polymers than any conventional UV-stabilizer available at the time such as UV-absorbers, nickel compounds and benzoates. Table 3). 

The photostabilizing efficiency of polymer-bound HALS in i-PP and E-P copolymers were studied and compared with commercial HALS (i.e., Tinuvin 770 and Chimassorb 944) by measuring the carbonyl index at 1720 cm. Plots of carbonyl index versus irradiation... 

Di-rerf-butyl cresol Ionol100 Tinuvin-P Irganox 1076... 

To obtain representative samples from nonhomoge-neous sample materials, such as polymer compounds, particle-size reduction techniques need often to be applied (not for film) [50]. Also, for destructive inpolymer additive analysis it is advantageous to change the physical state of solid samples to provide a larger surface area per unit mass. Complete extraction is sometimes achieved only after grinding the sample. Typically, Perlstein [51] has reported recoveries of only 59 % for extraction of Tinuvin 320 from unground PVC after 16 h of Soxhlet extraction with diethyl ether while recoveries rise to 97 % for ground polymer. 

Applications Caceres et al. [114] compared various methods for extraction of Tinuvin 770 and Chimas-sorb 944 from HDPE pellets, namely room temperature diffusion in CHC13 (20 % extraction), ultrasonica-tion (20% extraction), Soxtec extraction with DCM (nonsolvent) (50 % extraction), dissolution (dichloroben-zene)/precipitation (2-propanol) (65-70% recovery) and boiling under reflux with toluene (solvent) at 160 °C (95 % extraction). By changing conditions (nature of solvent, T, t) similar comparisons do not have much added value. Table 3.6 compares the results of reflux extraction and MAE for additives in LDPE [115]. 

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