Full Paper: The objective of this work is aimed at determining the kinetics of HALS photografting in PP films as a function of the additive concentration under both natural weathering and accelerated UV conditions. The stabilizer studied had a single structure that combined HALS and a UV absorbing unit detectable at 308 nm in the UV spectrum of PP, capable of inducing a photoreaction with the polymer matrix. The kinetics of HALS photografting on PP films at various additive concentrations was determined by direct spectroscopic measurements on film samples through the absorption band of the stabilizer positioned at 308 nm in the UV spectra, which was attributed to the highly conjugated methylenic double bond. The content of free HALS was determined as a function of exposure time by UV spectroscopy for all the additive concentration ratios used. It is shown that the kinetics of HALS photografting increase with a decrease in the additive concentration ratio. The whole grafting process under conditions of natural weathering occurred in the PP film after almost 350 h of exposure, while approximately 20 h were necessary under accelerated UV conditions. Moreover, these kinetics are well described by a third order polynomial model, validated by a maximum value of the coefficient of correlation close to unity. This was also confirmed by a comparison of the time values measured at 50% of the total grafting calculated from the model with those observed experimentally. This finding was consistent with the data obtained on the free HALS content determined by UV spectroscopy.
Summary: The thermal stability of gamma irradiated low density polyethylene (LDPE) films in presence of various structures of hindered amine stabilizers (HAS) was investigated by the oxygen uptake method under constant temperature of 180 °C and normal pressure conditions. The thermo‐oxidation was run using air environment. The sigmoidal dependency of oxygen uptake allows the calculation of the main kinetic parameters: oxidation induction time and oxidation rate on the propagation step. The various steps involved in the thermal degradation process were detected by the derivative procedure applied to the dependencies of oxygen uptake on time. It was found that the kinetic parameters of the thermal degradation process, determined by oxygen uptake, revealed the antioxidant role of HAS in γ‐irradiated LDPE films by providing better stability, when compared with the unstabilized samples. Moreover, the results indicated that the dependencies of oxygen uptake on thermal degradation time involved two degradation stages: the former occurring in the ungrafted moiety and the latter taking place after the antioxidant depletion is achieved. The stabilization efficiency of these oxidation inhibitors provides satisfactory thermal resistance to LDPE films, especially those based on an alkoxyamine structure.Dependencies of oxygen uptake on time at the thermal degradation of LDPE irradiated at 812 kGy. (‐□‐) free of additive; (‐○‐) Tinuvin 123; (‐▵‐) Sanduvor PR 31; (‐⋄‐) Uvasil 299.magnified imageDependencies of oxygen uptake on time at the thermal degradation of LDPE irradiated at 812 kGy. (‐□‐) free of additive; (‐○‐) Tinuvin 123; (‐▵‐) Sanduvor PR 31; (‐⋄‐) Uvasil 299.
ABSTRACT:The photografting kinetic of a hindered amine light stabilizer (HALS) was studied in low density polyethylene (LDPE) films under natural weathering conditions. The HALS (PBH-3) was added to the polymer at a concentration of 0.3% (w/w). The photografting kinetic of polymer bound HALS (PBH-3) was determined by direct spectroscopic measurements through the absorption band area of the stabilizer centered at 308 nm in the UV spectra and 1605 cm Ϫ1 in Fourier transform IR (FTIR) spectra, which correspond to benzylidene malonate ester and benzylidene malonic groups, respectively. In parallel, measurements were carried out on the free PBH-3 content after chloroform extraction of the photostabilizer from the polymer matrix by means of UV and gas chromatography methods. The results showed that in natural weathering the grafting of PBH-3 occurred in the LDPE film after very short exposure times of 127 and 168 h as determined by UV and FTIR, respectively. Moreover, the curves describing both the photografting and the free HALS kinetics exhibited similar profiles. The mechanism of photografting implies a rapid photoreaction between the methylenic double bond of the stabilizer and the macroalkyl radicals of the polymer, resulting in formation of polymer-bonded aminyl derivatives of the stabilizer.
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