Polystyrene photodegradation with a novel titanium dioxide/poly(ethylene oxide)/methyl linoleate paint photocatalyst system

The photodegradation of a polystyrene (PS) film was performed by a titanium dioxide (TiO₂)/poly(ethylene oxide) (PEO)/methyl linoleate (ML) paint photocatalyst system. The PS surface was catalytically photodegraded by the TiO₂/PEO component, and a conjugated carbon–carbon double bond was partially produced. A crosslinking reaction occurred between the PS carbon–carbon double bond and radical spices; as a result, the photodegradation diffusion into the inner region was blocked. The additional ML component certainly blocked the crosslinking reaction and accelerated the photodegradation rate. The fraction of less than 10,000 molecular weight of the 4‐h‐photodegaraded film with the TiO₂/PEO/ML paint was 15.1%, and its photodegradation yield increased four times compared with that with the TiO₂/PEO one. The weight loss values of the photodegraded PS part were 9.9, 10.7, and 11.7% at 4, 8, and 12 h, respectively, and gradually increased with increasing irradiation time. Some part of the film was violently photodegraded by the paint, and its photocatalytic effect lasted. The ML was graft‐polymerized into the film, and a phase separation was caused. The photodegradation behavior between the 0.05‐ and 0.1‐mm films was remarkably different; this showed that the diffusion of the ML radical was affected by the film thickness. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modification of polypropylene through intercrosslinking graft copolymerization of poly(vinyl alcohol): Synthesis and characterization

Modification of polypropylene (PP) has been successfully carried out through intercrosslinking of poly(vinyl alcohol) (PVA), by chemical graft copolymerization method using benzoyl peroxide (BPO) as radical initiator. Prior to grafting, PP was irradiated by gamma rays at a constant dose rate of 3.40 kGy/h to introduce hydroperoxide groups. Optimum conditions pertaining to maximum percentage of grafting were evaluated as a function of different reaction parameters. Maximum percentage ofgrafting of PVA (75%) was obtained at [BPO] = 5.51 × 10^?2 mol/L in 120 min at 70°C using 15 mL of water. Characterization of pristine PP and PP‐g‐PVA was carried out by FTIR, thermogravimetric analysis, and scanning electron micrography. Swelling studies were carried out in pure, binary, ternary, and quaternary solvent systems comprising of water, ethanol (EtOH), dimethylsulfoxide (DMSO) and N, N‐dimethylformamide (DMF) in different ratios. Maximum swelling values of PP‐g‐PVA (both composite and true graft) was observed in pure DMSO followed by DMF, EtOH, and water and it was also higher than that observed in mixed solvent system. Water retention studies of pristine PP and PP‐g‐PVA (both composite and true graft) were investigated at different time periods, temperature, and pH. Maximum % water retention of PP‐g‐PVA (composite) (108%) was observed in 8 h at 50°C in neutral medium (pH = 7). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Starch‐grafted polypropylene: Synthesis and characterization

Graft copolymerization of starch has been carried out onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. The maximum percentage of grafting (115%) of starch onto PP was obtained at optimum conditions of BPO concentration, 1.239 × 10⁻³ moles; temperature, 65°C; in 120 min. using 30 mL of water. Swelling studies were carried out in pure, binary, ternary and quaternary solvent systems comprising of water, ethanol (EtOH), dimethylsulphoxide (DMSO), and N,N‐dimethylformamide (DMF) in different ratios. Maximum swelling is observed in DMSO and DMF, followed by EtOH and least in water for true graft. Water retention studies of pristine PP and PP‐g‐Starch (both composite and true graft) were investigated at different time periods, temperature and pH. The composite contains grafted PP, unreacted starch and unreacted PP whereas true graft is the product from which both unreacted polymers have been removed. Maximum % water retention of PP‐g‐Starch (composite) (110%) was observed in 8 h at 50°C in neutral medium (pH = 7). The graft copolymers were characterized by FTIR, DTG, DTA, TGA, and SEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of polypropylene‐grafted gelatin

Modification of polypropylene (PP) has been successfully carried out by graft copolymerization of gelatin, by chemical method using benzoyl peroxide (BPO) as radical initiator. PP was preirradiated by gamma rays at a constant dose rate of 3.40 kGy/h before grafting to introduce hydroperoxide groups. Optimum conditions pertaining to maximum percentage of grafting were evaluated as a function of different reaction parameters. Maximum percentage of grafting of gelatin (115%) was obtained at BPO concentration = 4.132 × 10^?2 mol/L in 120 min at 70°C using 30 mL of water. Characterization of PP‐g‐gelatin was carried out through FTIR, thermogravimetric analysis, and scanning electron microscopy. Swelling studies were carried out in pure, binary, ternary, and quaternary solvent systems comprising distilled water, ethanol, dimethylsulphoxide (DMSO), and N,N‐dimethylformamide (DMF) in different ratios. Maximum swelling of PP‐g‐gelatin (both composite and true graft) was observed in pure solvents that is, DMSO followed by DMF, ethanol, and water and was higher than that observed in the mixed solvent system. Water retention studies of unmodified PP, that is, pristine PP and PP‐g‐gelatin (both composite and true graft) were investigated at different time periods, temperatures and pH. Maximum % water retention for PP‐g‐gelatin (composite; 170%) was observed in 8 h at 50°C in neutral medium (pH = 7). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of polypropylene graft copolymers from a hydroxyl‐groups‐containing polypropylene precursor via atom‐transfer radical polymerization

Isotactic polypropylene graft copolymers, isotactic[polypropylene‐graft‐poly(methyl methacrylate)] (i‐PP‐g‐PMMA) and isotactic[polypropylene‐graft‐polystyrene] (i‐PP‐g‐PS), were prepared by atom‐transfer radical polymerization (ATRP) using a 2‐bromopropionic ester macro‐initiator from functional polypropylene‐containing hydroxyl groups. This kind of functionalized propylene can be obtained by copolymerization of propylene and borane monomer using isospecific MgCl₂‐supported TiCl₄ as catalyst. Both the graft density and the molecular weights of i‐PP‐based graft copolymers were controlled by changing the hydroxyl group contents of functionalized polypropylene and the amount of monomer used in the grafting reaction. The effect of i‐PP‐g‐PS graft copolymer on PP‐PS blends and that of i‐PP‐g‐PMMA graft copolymer on PP‐PMMA blends were studied by scanning electron microscopy. Copyright © 2006 Society of Chemical Industry     

Multiwalled carbon nanotubes‐based polypropylene composites: Influence of interfacial interaction on the crystallization behavior of polypropylene

Composites of polypropylene (PP) and multi‐walled carbon nanotubes (MWCNTs) were prepared via melt‐mixing utilizing Li‐salt of 6‐amino heaxanoic acid (Li‐AHA) modified MWCNTs in the presence of a compatibilizer (polypropylene‐g‐maleic anhydride; PP‐g‐MA). Improved interaction between the anhydride group of PP‐g‐MA and the amine functionality of Li‐AHA was confirmed via FTIR and Raman spectroscopic analysis. A higher glass transition temperature (T_g) of the PP phase has been observed in these composites as compared to pristine MWCNTs‐based composites. The crystallization temperature (T_c) of the PP phase was increased as a function of pristine MWCNTs concentration in PP/MWCNTs composites indicating hetero‐nucleating action of MWCNTs. However, T_c value was decreased in the presence of Li‐AHA modified MWCNTs indicating the adsorbed Li‐AHA on the MWCNTs surface. Moreover, T_c value was higher in the presence of Li‐AHA modified MWCNTs with PP‐g‐MA as compared to that of without PP‐g‐MA, suggesting the desorbed Li‐AHA from the MWCNTs surface due to melt‐interfacial reaction. Further, MWCNTs were extracted by hot vacuum filtration technique from PP/MWCNTs composites containing Li‐AHA and PP‐g‐MA. The isothermal crystallization kinetics showed a variation in crystallization behavior of the PP phase in the corresponding composites as compared to the “extracted MWCNTs.” POLYM. ENG. SCI., 57:183–196, 2017. © 2016 Society of Plastics Engineers     

Dehydrochlorination of poly(vinyl chloride) modified with titanium dioxide/poly(ethylene oxide) based paint photocatalysts

The dehydrochlorination of poly(vinyl chloride) (PVC) film samples modified with titanium dioxide (TiO₂)/poly(ethylene oxide) (PEO) based paint photocatalysts [the addition of methyl linoleate (ML) or methyl oleate (MO)] was performed. After 24 h of UV photoirradiation, the sample with TiO₂/PEO showed that there existed a structure with the longest polyene length, whereas that with TiO₂/PEO/ML contained the most polyene structures. The chloroform‐soluble fraction of the sample with TiO₂/PEO contained a poly(vinyl alcohol) (PVA) structure instead of a polyene one and showed a novel method of PVA production via PVC photodegradation. The molecular weight curve of the fraction shifted slightly to a lower molecular weight compared to that without the photocatalyst; this showed that slight polymer chain scission occurred. The ¹H‐NMR and ¹³C‐NMR spectra showed that the content of PVA units was about 20%, and the PVA sequence was blocky. The fraction of the sample with TiO₂/PEO/ML contained the highest methyl group content; this showed that the branch degree was highest as was the polyene content. These highest contents were due to the existence of the grafted ML. Pyrolysis gas chromatography/mass spectroscopy measurements suggested that there existed more polyene and graft units in the chloroform‐insoluble fractions of the samples with TiO₂/PEO, TiO₂/PEO/ML, and TiO₂/PEO/MO, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40760.     

Effects of UV‐irradiation on the nonisothermal crystallization kinetics of polypropylene

The influences of UV‐induced photodegradation on the nonisothermal crystallization kinetics of polypropylene (PP) were investigated by differential scanning calorimetry. The Avrami analysis modified by Jeziorny, Ozawa method, and a method modified by Liu were employed to describe the nonisothermal crystallization process of unexposed and photodegraded PP samples. Kinetics studies reveal that the rates of nucleation and growth may be affected differently by photodegradation. A short‐term UV‐irradiation may accelerate the overall nonisothermal crystallization process of PP, but a long‐term UV‐irradiation should impede it. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and characterization of dextrin‐grafted polypropylene

We carried out the graft copolymerization of the water‐soluble natural polymer dextrin onto preirradiated polypropylene (PP) in an aqueous medium using benzoyl peroxide (BPO) as the radical initiator. PP was irradiated by γ rays from a Co⁶⁰ source at a constant dose rate of 3.40 kGy/h to introduce hydroperoxide linkages, which served as the sites for grafting. The graft copolymerization was studied as a function of different reaction parameters, and the maximum percentage grafting (P_g; 55%) of dextrin onto PP was obtained at optimum conditions of [BPO] = 5.165 × 10⁻² mol/L, temperature = 60°C in 120 min with 15 mL of water. Different grafting parameters, such as the percentage apparent grafting, percentage grafting, and percentage true grafting have been evaluated. The graft copolymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Swelling studies were carried out in pure, binary, ternary, and quaternary solvent systems composed of water, ethanol (EtOH), dimethyl sulfoxide (DMSO), and N,N‐dimethylformamide (DMF) at different ratios. The maximum swelling percentage PP‐g‐dextrin (both composite and true graft) was observed in pure DMSO and DMF followed by EtOH and water. Water‐retention studies of PP and PP‐g‐dextrin (both composite and true graft) were investigated at different time periods, temperatures, and pH values. The maximum percentage water retention of PP‐g‐dextrin (composite, 124%) was observed at 8 h and 50°C in a neutral medium (pH 7). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of Oils Extracted from Plant Seeds on the Growth and Lipolytic Activity of <Emphasis Type="Italic">Yarrowia lipolytica</Emphasis> Yeast

This study was aimed at evaluating the capability of Yarrowia lipolytica W29 for the synthesis of lipolytic enzymes in a medium containing plant oils from non‐conventional sources with some components displaying bioactivity. Oils from almond, hazelnut, and coriander seeds were obtained by using n‐hexane (Soxhlet method) and a chloroform/methanol mixture of solvents (Folch method), and their effect on the growth and lipolytic activity of Y. lipolytica was compared. A comparison of these two extraction methods showed that the extraction with n‐hexane was less effective regarding the oil extraction yields than the extraction conducted according to Folch's procedure. The lipolytic activity of the studied yeast was higher in the culture media containing oils extracted with the Soxhlet method than the Folch method but it was lower compared to olive oil medium. Among all oils tested, almond oil extracted with n‐hexane was the best inducer of extracellular lipases synthesized by Y. lipolytica. Its lipolytic activity achieved the maximum value of 2.33 U/mL after 48 h of culture. After 24 h of culture, it was close to the value obtained for the medium containing olive oil. Almond oil was a source of oleic and linoleic acids, which may determine differences in the lipolytic activity. The linoleic acid content in almond oil was higher than that found in other oils. When n‐hexane was used for extraction, the resultant oils were characterized by lower contents of polyphenols and poorer antioxidative activity.     

PMMA‐multigraft copolymers derived from linseed oil,soybean oil,and linoleic acid: Protein adsorption and bacterial adherence

Synthesis of Poly(methyl methacrylate), PMMA‐multigraft copolymers derived from linseed oil, soybean oil, and linoleic acid PMMA‐g‐polymeric oil/oily acid‐g‐poly(3‐hydroxy alkanoate) (PHA), and their protein adsorption and bacterial adherence have been described. Polymeric oil/oily acid peroxides [polymeric soybean oil peroxide (PSB), polymeric linseed oil peroxide (PLO), and polymeric linoleic acid peroxide (PLina)] initiated the copolymerization of MMA and unsaturated PHA‐soya to yield PMMA–PLO–PHA, PMMA–PSB–PHA, and PMMA–PLina–PHA multigraft copolymers. PMMA–PLina–PHA multigraft copolymers were completely soluble while PMMA–PSB–PHA and PMMA–PLO–PHA multigraft copolymers were partially crosslinked. Crosslinked parts of the PLO‐ and PSB‐multigraft copolymers were isolated by the sol gel analysis and characterized by swelling measurements in CHCl₃. Soluble part of the PLO‐ and PSB‐multigraft copolymers and completely soluble PLina‐multigraft copolymers were obtained and characterized by spectroscopic, thermal, gel permeation chromatography (GPC), and scanning electron microscopy (SEM) techniques. In the mechanical properties of the PHA–PLina–PMMA, the elongation at break is reduced up to ～ 9%, more or less preserving the high stress values at its break point (48%) when compared to PLina‐g‐PMMA. The solvent casting film surfaces were studied by means of adsorption of blood proteins and bacterial adhesion. Insertion of the PHA into the multigraft copolymers caused the dramatic increase in bacterial adhesion on the polymer surfaces. PHA insertion into the graft copolymers also increased the protein adsorption. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation of thermal‐responsive poly(propylene) membranes grafted with n‐isopropylacrylamide by plasma‐induced polymerization and their water permeation

Poly(propylene) (PP) membrane grafted with poly(N‐isopropylacrylamide) (PNIPAAm), which is known to have a lower critical solution temperature (LCST) at around 32°C, was prepared by the plasma‐induced graft polymerization technique. Graft polymerization of PNIPAAm onto a PP membrane was confirmed by microscopic attenuated total reflection/Fourier transform IR spectroscopy. The grafting yield of PNIPAAm increased with the concentration of N‐isopropylacrylamide monomer and the reaction time of graft polymerization. The average pore size of the PP membrane also affected the grafting yield. From the field emission scanning electron microscopy (FE‐SEM) measurement, we observed a morphological change in the PP‐g‐PNIPAAm membrane under wet conditions at 25°C below LCST. The permeability of water through the PP‐g‐PNIPAAm membrane was controlled by temperature. The PP‐g‐PNIPAAm membrane (PN05 and PN10) exhibited higher water permeability (L_p) than the original PP substrate membrane below LCST. As the temperature increased to above LCST, L_p gradually decreased. In addition, the graft yield of PNIPAAm and the average pore size of the PP substrate influenced water permeability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1168–1177, 2002; DOI 10.1002/app.10410     

The effects of chemical structure and synthesis method on photodegradation of polypropylene

The effects of chemical structure and synthesis method on the photodegradation behavior of polypropylene (PP) were investigated in injection‐molded samples exposed to ultraviolet radiation (UV) at 60°C. For this purpose, three PP samples with different chemical structures were chosen: two homopolymerized PP samples (H₁P, synthesized by bulk polymerization; whereas H₂P was synthesized by Ziegler–Natta catalyst) and copolymerized PP sample (CP). The photodegradation was characterized by melt flow rate and mechanical properties and Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and scanning electron microscopy. The results showed that CP possesses the most superior resistance to UV‐irradiation, followed by H₂P and then H₁P, which indicates that copolymerization with a small amount of ethylene monomer is an effective approach to obtain high stability of PP to UV‐irradiation, and synthesis methods of PP play an important role in the resistance to UV‐irradiation. Moreover, the effect of photodegradation on the thermal behaviors of H₂P was also investigated using X‐ray diffraction, differential scanning calorimetry, and dynamical mechanical thermal analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 270–279, 2005     

Flame‐retardancy properties of tris(2‐hydroxyethyl) isocyanurate based charring agents on polypropylene

Tris(2‐hydroxyethyl) isocyanurate based charring agent (TBCA) was synthesized by melt polycondensation with tris(2‐hydroxyethyl) isocyanurate (THEIC) and terephthalic acid as raw materials. It was characterized by Fourier transform infrared spectroscopy, elemental analysis, ¹H‐NMR, and thermogravimetric analysis (TGA). TBCA was blended with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The charring properties of TBCA was tested by flame retardancy in the PP/APP/TBCA (PP/IFR₂) composite and compared with that of the PP/APP/THEIC (PP/IFR₁) composite. The results show that PP/IFR₂ had lower flame‐retardant properties but better water resistance than that of the PP/IFR₁ composite because PP/IFR₂ could still obtain a V‐0 rating after it had been soaked in water at 70°C for 96 h, whereas PP/IFR₁ could not achieve any rating after 36 h. Their combustion performance was further evaluated by a cone calorimeter test, their thermal degradation processes were studied by TGA, and the morphology of the char residue was observed by scanning electron microscopy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41810.     

Geometrical isomerization of polyunsaturated fatty acids in physically refined rapeseed oil during plant‐scale deodorization

The effect of the operating temperature (between 220 and 270 °C) on the formation of trans isomers of linoleic and linolenic acids in physically refined rapeseed oil during deodorization in a plant‐scale semicontinuous tray‐type deodorizer (capacity 10 t/h) was investigated. The industrial procedures of physical refining consisted of a two‐step bleaching and deodorization process. The degree of isomerization of linoleic acid ranged from 0.33 to 4.77% and that of linolenic acid from 4.43 to 45.22% between 220 and 270 °C, respectively. A relation between the logarithm of the degree of isomerization and the deodorization temperature can be approximated by statistically highly significant linear functions for both linoleic and linolenic acids. Oleic acid was resistant to the heat‐induced geometrical isomerization. The values found for the ratio between the degrees of isomerization of linolenic and linoleic acids, slightly decreasing with increasing temperature, were equal to 13.6 and 12.9 at 230 and 240 °C, respectively. Two trans isomers of linoleic acid, exclusively with one double bond isomerized into trans configuration, and four trans isomers of linolenic acid, mostly with one double bond isomerized into trans configuration, were determined in deodorized rapeseed oils. Linolenic acid was observed to be the main source responsible for the formation of nearly all trans fatty acids in physically refined rapeseed oil. At 235 °C, a deodorization temperature considered as a reasonable technological compromise, the content of trans fatty acids in plant‐scale physically refined rapeseed oil was less than 1% of total fatty acids, which would be acceptable for further application.     

Influence of carboxyl and amide groups on in vitro hemocompatibility of sulfonated polypropylene non‐woven fabric

The sulfonated polypropylene non‐woven fabric (PP_NWF) was successfully fabricated via γ‐ray simultaneous radiation‐induced graft polymerization of acrylic acid (AA)/sodium styrenesulfonate (NaSS) and acrylamide (AAm)/NaSS. The existence of graft chains in both PP‐g‐P(AA‐co‐NaSS) and PP‐g‐P(AAm‐co‐NaSS) was proved by attenuated total reflection Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy. Water contact angle measurement illustrated the sulfonated PP_NWF owning good hydrophilicity. The in vitro hemocompatibility evaluation showed that both PP‐g‐P(AA‐co‐NaSS) and PP‐g‐P(AAm‐co‐NaSS) inhibited effectively the adhesion of platelets and were significantly compatible with erythrocytes. Moreover, no obvious difference was confirmed in the prevention of platelet adhesion and hemolysis ratio between carboxyl and amide groups. However, as compared with that of PP‐g‐P(AAm‐co‐NaSS), PP‐g‐P(AA‐co‐NaSS) exhibited outstanding anticoagulant activity via increased activated partial thromboplastin time and thrombin time. This result indicated that the carboxyl group but not amide group featured strong synergistic effect on the anticoagulant activity of sulfonated PP_NWF. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45915.     

Adsorption and recovery of nonionic polymers by neutralization of cellulose fiber surface charge via cationic polyamide‐epichlorohydrin resins

Gelatin‐based graft copolymers of polypropylene (PP), has been synthesized by chemical method using benzoyl peroxide (BPO), as radical initiator. Biodegradation studies of pristine PP and PP‐g‐Gelatin have been carried out by soil burial test in simple soil and soil enriched with nitrogenous content by adding urea. The microbial degradation was substantiated by the direct attack of the microbes on the grafted samples. The rate of degradation by the direct attack was fast in comparison to the degradation in soil burial studies. The biochemical tests performed on the organisms isolated from the soil, identified these organisms as Bacillus circulans, Kurthia gibsonii, and Flavobacterium sp. which helped biodegradation of PP‐g‐Gelatin samples. The degradation of the grafted samples was further confirmed by carrying out the physical characterization of the original samples and the degraded samples by SEM, XRD, and TGA. The XRD and thermal data indicate an increase in the crystallinity of the degraded samples. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Grafting of poly(3‐hydroxyalkanoate) and linoleic acid onto chitosan

Poly(3‐hydroxy octanoate) (PHO), poly(3‐hydroxy butyrate‐co‐3‐hydroxyvalerate) (PHBV), and linoleic acid were grafted onto chitosan via condensation reactions between carboxylic acids and amine groups. Unreacted PHAs and linoleic acid were eliminated via chloroform extraction and for elimination of unreacted chitosan were used 2 wt % of HOAc solution. The pure chitosan graft copolymers were isolated and then characterized by FTIR, ¹³C‐NMR (in solid state), DSC, and TGA. Microbial polyester percentage grafted onto chitosan backbone was varying from 7 to 52 wt % as a function of molecular weight of PHAs, namely as a function of steric effect. Solubility tests were also performed. Graft copolymers were soluble, partially soluble or insoluble in 2 wt % of HOAc depending on the amount of free primary amine groups on chitosan backbone or degree of grafting percent. Thermal analysis of PHO‐g‐Chitosan graft copolymers indicated that the plastizer effect of PHO by means that they showed melting transitions T_ms at 80, 100, and 113°C or a broad T_ms between 60.5–124.5°C and 75–125°C while pure chitosan showed a sharp T_m at 123°C. In comparison of the solubility and thermal properties of graft copolymers, linoleic acid derivatives of chitosan were used. Thus, the grafting of poly(3‐hydroxyalkanoate) and linoleic acid onto chitosan decrease the thermal stability of chitosan backbone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:81–89, 2007     

Cracking formation on the surface of extruded photodegraded polypropylene plates

The cracking formation during the photodegradation of polypropylene (PP) plates (1 mm thickness), with (PPOx) and without pro‐oxidant (PP), has been investigated. The plates were produced by extrusion in an industrial production line and were exposed to ultraviolet radiation in the laboratory for periods of up to 480 hr. The samples were investigated by infrared spectroscopy—FTIR, optical light microscopy, differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The results showed that the extension of photodegradation process is more intense for PPOx than for PP samples. For both samples, cracks were formed at the surface perpendicularly to the flow‐lines. However the cracks frequency was different for both samples and sides of sample. The crack frequency was correlated with chain orientation, A₁₁₀; it was shown that lower degrees of orientation resulted in lower crack frequency. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Natural polyphenols as chain‐breaking antioxidants during methyl linoleate peroxidation

A technique based on monitoring oxygen consumption was applied to study 11 natural and model polyphenols (PP, QH₂) as well as four typical monophenolics as a chain‐breaking antioxidant during the controlled chain oxidation of methyl linoleate (ML) in bulk at 37°C. The antioxidant activities of QH₂ were characterized by two parameters: the rate constant k₁ for reaction of QH₂ with the peroxy radical ${\rm LO}_{2}^{{\bf .}} $ : (i) QH₂ + ${\rm LO}_{2}^{{\bf .}} $ → ${\rm QH}^{{\bf .}} $ + LOOH and the stoichiometric factor of inhibition, f, which shows how many kinetic chains may be terminated by one molecule of QH₂. The rate constant k₁ were reduced significantly by factor of 4 –28 as compared to these determined during the oxidation of styrene in bulk; the effect was typically more pronounced for catechol derivatives than for pyrogallol derivatives. At the same time, f for QH₂ was found to be close to two independent of the number of active OH groups, similar to that determined earlier during the inhibited oxidation of styrene. The formation of H bond between OH group of QH₂ and carboxyl group of ML is suggested as a reason for reducing effect of ML on k₁. Practical applications : This work reports rate constants for the reaction of lipid peroxyl radical with phenolics and stoichiometric coefficient of inhibition, which characterize the antioxidant activity (AOA) of 15 natural and model PP, QH₂ during the controlled peroxidation of ML. The reactivity of PP, QH₂ during the oxidation of ML is routinely lower than the reactivity during the oxidation of non‐polar model hydrocarbons. This information may be useful to estimate the AOA of natural PP, QH₂ in real systems of practical significance including plant oils, fats, food‐stuffs, biological objects, and similar.