N-(Substituted phenyl) itaconimides as organic stabilizers for plasticized poly(vinyl chloride) against photo-degradation

Several N-(substituted phenyl)itaconimide derivatives, N-(RPh)II (R: -NO₂, -COOH, -H, -OH, -OMe, -Me, -Cl, or -Br), have been investigated as organic photo-stabilizers for poly(vinyl chloride) (PVC) plasticized with dioctyl phthalate (DOP). Their stabilizing efficiencies are evaluated by measuring the length of the induction period (Ts), the period during which no detectable amounts of hydrogen chloride gas could be observed, and also from the rate of dehydrochlorination as measured by continuous potentiometric determination, and the extent of discolouration of the degraded polymer. The efficiencies are also evaluated by determining the amount of gel formation as well as the intrinsic viscosity of the insoluble and the soluble fractions of the degraded polymer, respectively. The results have proved the greater stabilizing efficiency of the N-(RPh)II derivatives relative to that of the phenyl salicylate UV absorber which is a commonly used industrial stabilizer. A radical mechanism is proposed to account for the stabilizing action of the investigated products.     

Synergistic effect of maleimido phenyl urea derivatives mixed with some commercial stabilizers on the efficiency of thermal stabilization of PVC

Four novel antimicrobial maleimido phenyl urea stabilizers 1–4 were synthesized from N-[4-(chlorocarbonyl) phenyl] maleimide with phenyl urea and its derivatives (p-methyl, o-chloro and p-carboxy). The effect of mixing maleimido phenyl urea stabilizer 2 with each of the reference stabilizers, dibasic lead carbonate (DBLC), cadmium-barium-zinc stearate (Cd-Ba-Zn stearate) or n-octyltin mercaptide (n-OTM), on the stabilization efficiency in thermal degradation of rigid PVC at 180 °C in air, has been investigated. Mixing was effected in the range of 0–100 wt% of stabilizer 2 relative to each of the reference stabilizers. The stabilizing efficiency was evaluated by measuring the length of the thermal stability period (Ts), the period during which no detectable amount of hydrogen chloride gas could be observed, and also from the rate of dehydrochlorination as measured by continuous potentiometric determination, and by the extent of discoloration of the degraded polymer samples. The results show a true synergistic effect from the combination of stabilizer 2 with any of the reference stabilizers. Mixing of the stabilizers improves the Ts values, decreases the rate of dehydrochlorination and lowers the extent of discoloration of the polymer. The maximum synergism was attained when stabilizer 2 is mixed with either of the three reference stabilizers in equivalent weight ratio (50%/50%). The observed synergism may be attributed to the different mechanisms by which the investigated and the reference stabilizers work.     

Vanillin–Schiff’s bases as organic thermal stabilizers and co-stabilizers for rigid poly(vinyl chloride)

Vanillin–Schiff’s bases (VSB) were examined as thermal stabilizers and co-stabilizers for rigid poly(vinyl chloride) (PVC) in air at 180 °C. Their high stabilizing efficiency were shown by their high thermal stability value (Ts), which is the time elapsed for the detection of HCl gas, if compared with dibasic lead carbonate and cadmium–zinc soap reference stabilizers used industrially, with better extent of discoloration. Blending these derivatives with reference stabilizers in different ratios greatly lengthens the thermal stability and the extent of discoloration of the PVC.Condensation products of Vanillin with amines are very active biologically, besides having good complexation ability with metal ions. The Ni²⁺ and Co²⁺ complexes of VSB derivatives gave better thermal stability and less discoloration than the parent organic stabilizer. Also, blending these complexes with either of the used reference stabilizers in different ratios gave better thermal stability and lower extent of discoloration. Thermogravimetric analysis confirmed the improved stability of PVC in the presence of the VSB derivatives, compared to blank PVC, PVC stabilized with reference stabilizers and PVC stabilized with binary mixture of VSB derivatives with reference stabilizer.The stabilizing efficiency of Vanillin–Schiff’s base (VSB) derivatives is attributed to the replacement of the labile chlorine atoms on the PVC chains by a relatively more stable moiety of the organic stabilizer.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XIII: Eugenol (4-allyl-2-methoxy-phenol)

Eugenol (4-allyl-2-methoxy-phenol) has been examined as a thermal stabilizer and co-stabilizer for rigid PVC in air, at 180 °C. Its high stabilizing efficiency is detected by its high thermal stability value (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide.Blending this organic stabilizer with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate together with the longer extent of discolouration of PVC stabilized by eugenol as compared with the blank and the samples stabilized with reference commercial stabilizers.A probable mechanism for the stabilizing action of eugenol has been proposed. The stabilizing efficiency is attributed partially to the stabilizer's ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XI: Anthraquinone derivatives

Anthraquinone and 1-aminoanthraquinone derivatives have been examined as thermal stabilizers or co-stabilizers for rigid PVC in air, at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (Ts) when compared with some of the common reference stabilizers used industrially such as dibasic lead carbonate, calcium-zinc soap and octyl tin mercaptide. Blending these organic stabilizers with some of the reference stabilizers in different ratios had synergistic effect on both the induction period and the dehydrochlorination rate.A probable mechanism for the stabilizing mode of these derivatives has been proposed. The stabilizing efficiency is attributed partially to the stabilizers' ability to intervene in the radical chain degradation process of PVC and to the replacement of the labile chlorine atoms on PVC chains by a relatively more stable moiety of the organic stabilizer.     

Organic thermal stabilizers for rigid poly(vinyl chloride). Part XII: N-phenyl-3-substituted-5-pyrazolone derivatives

N-phenyl-3-substituted-5-pyrazolone derivatives have been examined as thermal stabilizers or co-stabilizers for rigid PVC in air, at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (T_s) when compared with some of the common reference stabilizers used industrially, such as dibasic lead carbonate, calcium-zinc soap and n-octyl tin mercaptide. Blending these derivatives with some of the reference stabilizers in different ratios had a synergistic effect on both the induction period and the dehydrochlorination rate.A probable mechanism for the stabilizing mode of N-phenyl-3-substituted-5-pyrazolone derivatives has been proposed. The stabilizing efficiency is attributed at least partially to the ability of the organic stabilizer to be incorporated in the polymeric chains, thus disrupting the chain degradation.     

Novel antimicrobial and antitumor organic thermal stabilizers for rigid Poly (vinyl chloride)

Pyrazolodithiones of expected biological activity were examined as thermal stabilizers and co-stabilizers for rigid poly(vinyl chloride) (PVC) in air at 180?°C. Their high stabilizing efficiency were shown by their high thermal stability values (T _s), which is the time needed for the liberation of HCl gas, if compared with dibasic lead carbonate (DBLC) and calcium?Czinc soap (Ca?CZn soap) reference stabilizers used industrially, with better extent of discoloration. Blending these derivatives with reference stabilizers in different ratios greatly lengthens the thermal stability value and improves the extent of discoloration of the PVC. The structure of the novel organic stabilizers was confirmed by elemental analysis, FTIR, Mass spectra, and ¹H-NMR. Thermogravimetric analyses confirmed the improved stability of PVC in the presence of the investigated organic stabilizers, compared to blank PVC and PVC stabilized with the reference stabilizers. Also, GPC measurements were done to investigate the changes occurred in the molecular masses of the degraded samples of PVC in presence of the newly synthesized stabilizers. The stabilizing efficiency of pyrazolodithiones is attributed to the replacement of the labile chlorine atoms on the PVC chains by a relatively more stable moiety of the organic stabilizer. The investigated stabilizers showed a good antimicrobial activity toward two kinds of bacteria, Escherichia coli and Staphylococcus aureus; and also toward two kinds of fungi, Aspergillus flavus and Candida albicans. They also exhibited antitumor activity against both liver and colon human cell lines.     

Antimicrobial agents as photostabilizers for rigid poly(vinyl chloride)

Some amide derivatives of ethylene glycol‐bis(2‐aminoethylether)‐N,N,N^′,N^′‐tetraacetic acid (EGTA) have been prepared via their coupling with different aniline derivatives: amino, methyl, chloro, and hydroxy aniline. The EGTA amide derivatives were characterized, and their antimicrobial activities were evaluated. These antimicrobial agents have been investigated as photostabilizers for rigid poly(vinyl chloride) (PVC), suspension PVC, with a K value of 70. Their stabilizing efficiencies were evaluated by determining the percentage of weight loss, the intrinsic viscosities, as well as the amount of formed gel of the photodegraded PVC. The extent of discoloration and the change in the mechanical properties of the photodegraded polymer were also evaluated. The applied materials reduced the loss in weight that resulted from HCl evolution during photodegradation. Both viscosity and gel content measurements showed also a decrease in their values during the degradation process. The decrease in the percentage of gel formation upon applying the investigated photostabilizers reflects the lowering in extent of cross‐linking of the polymer, which implies preserving the mechanical properties of PVC. The extent of discoloration was also improved in the presence of the investigated compounds. The results have proved a greater stabilizing efficiencies of the antimicrobial EGTA amide derivatives than that of the phenyl salicylate ultraviolet (UV) absorber, which is commonly used as an industrial stabilizer. A radical mechanism was proposed to account for the stabilizing action of the investigated products. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermal degradation behaviour of poly(vinyl chloride) in the presence of poly(N′-acryloyl benzhydrazide)

The thermal degradation behaviour of poly(vinyl chloride), PVC, in the presence of poly(N′-acryloyl benzhydrazide), PABH, has been studied using continuous potentiometric determination of the evolved hydrogen chloride gas from the degradation and by measuring the extent of discoloration of the degraded samples. Blending this polymeric additive with dibasic lead carbonate, DBLC, reference stabilizer in different ratios had synergistic effects on both the thermal stability and the extent of discoloration of PVC.     

Itaconamide derivatives as organic stabilizers for poly(vinyl chloride) against photodegradation

Itaconamide derivatives have been prepared and investigated as photo-stabilizers for rigid PVC. We investigated their stabilizing efficiencies by testing the weight loss (%) with the amount of formed gel. The results indicated a reasonable stabilizing efficiency of these derivatives compared with commercial UV absorber; phenyl salicylate. The extent of discoloration of the photodegraded polymer was also improved in the presence of the prepared compounds. Rheological properties were studied to investigate the flow behavior with providing a vision into the mechanical behavior for the tested materials. Employing the evaluated photostabilizers reflects the reduction in the extent of cross-linking of the polymer. This implies preserving the mechanical properties of PVC. A radical mechanism is proposed to account for the stabilizing action of the investigated materials. The prepared itaconamide derivatives provide appropriate photostability and mechanical properties for a durable poly(vinyl chloride).     

Effect of thermal stabilizers composed of zinc barbiturate and calcium stearate for rigid poly(vinyl chloride)

Zinc barbiturate [Zn(H₂L)₂·2H₂O, abbreviated as ZnL₂] was synthesized by a precipitation method in aqueous solution, and investigated as a co-stabilizer with calcium stearate (CaSt₂) for rigid poly(vinyl chloride) (PVC) by the discoloration test and the dehydrochlorination test at 180 °C. ZnL₂ exhibits high stabilizing effect with excellent initial colour of PVC films. In comparison with the synergistic effect of CaSt₂/ZnSt₂ stabilizers, the CaSt₂/ZnL₂ stabilizers in mass ratios ranging from 0.3/1.2 to 0.6/0.9 exhibit better synergistic effect. Moreover, PVC films stabilized by CaSt₂/ZnL₂ show better initial colour with the addition of dibenzoyl methane as an auxiliary stabilizer. The mechanism of stabilizing action of ZnL₂ is also proposed. ZnL₂ may replace the labile chlorine atoms to interrupt the formation of conjugated double bonds in PVC chains, and act as the absorber of hydrogen chloride to restrain the self-catalytic dehydrochlorination.     

Polymeric p-benzoquinone–tin derivatives as thermal stabilizers for rigid poly(vinyl chloride). II. Evaluation of the stabilizing efficiency

The polymeric p-benzoquinone-tin derivatives obtained from the reaction of p-benzoquinone with tin tetrachloride in the absence of solvent have been investigated as thermal stabilizers for rigid PVC at 200°C by measuring the rate of dehydrochlorination. The results reveal the greater stabilizing efficiency of the investigated products in relation to dibutyltin maleate and the basic lead stabilizers commonly used in industry. Evidence has been accumulated that the quinone and metallic elements (Sn? Sn bonds) of the stabilizer participate in the stabilization process by trapping the radical intermediates of degradation and blocking the odd electron sites formed on the polymer chains. Although stabilizers with high quinone content provide greater stabilization in the early stages of degradation, their efficiency sharply decreases in subsequent stages. On the other hand, stabilizers of high tin content effectively prohibit the dehydrochlorination reaction at all stages of degradation. On an equivalent basis of metal content, the results clearly demonstrate the greater stabilizing efficiency of tin atoms when found in direct contact in the stabilizer molecule. The mechanism of stabilization suggested to account for the results obtained may be considered as additional evidence in support of the radical nature of the dehydrochlorination reaction.     

Anthraquinone derivatives as organic stabilizers for rigid poly(vinyl chloride) against photo-degradation

Anthraquinone derivatives have been prepared and investigated as photo-stabilizers for rigid PVC by measuring the extent of weight loss (%), the amount of gel formation as well as the intrinsic viscosity of the soluble fractions of the degraded polymer. The results indicated a reasonable stabilizing effect of these derivatives compared with UV-commercially used stabilizers. A synergistic effect is achieved when the anthraquinone derivatives are mixed with UV-absorbers in a weight ratio of 75% of investigated organic stabilizer and 25% of reference stabilizer.A probable radical mechanism is proposed to account for the stabilizing action of the organic investigated materials.     

Synthesis, characterization and application of enrofloxacin complexes as thermal stabilizers for rigid poly(vinyl chloride)

Synthesis and characterization of both binary Co(II)- (1), Ni(II)- (2) complexes with enrofloxacin drug (HL(1)) and ternary Co(II)- (3), Ni(II)- (4) complexes in presence of DL-alanine (H(2)L(2)) are reported using physico-chemical techniques. The antimicrobial activity of these complexes has been screened against two gram-positive and two gram-negative bacteria. Antifungal activity against two different fungi has been evaluated and compared with reference drug. All the binary and ternary complexes showed remarkable potential antimicrobial activity higher than the recommended standard agents. Ni(II)-complexes exhibited higher potency as compared to the parent drug against bacterial and fungal strain. In addition, it was of interest to investigate the reported complexes as thermal stabilizers and co-stabilizers for rigid PVC in air at 180 °C. Their high stabilizing efficiency is detected by their high induction period values (T(s)) compared with some of the common reference stabilizers used industrially, such as dibasic lead carbonate (DBLC) and calcium-zinc soap. Blending these complexes with some of the reference stabilizers in different ratios had a synergistic effect on both induction period as it gave better thermal stability and lower extent of discoloration. The stabilizing efficiency is attributed at least partially to the ability of the metal complex stabilizer to be incorporated in the polymeric chains, thus disrupting the chain degradation and replace the labile chlorine atoms on PVC chains by a relatively more s moiety of the inorganic stabilizer. Their amenability to use as a biomedical additives for PVC, has afforded them great potential for various medical applications.     

Synthesis, characterization, and thermal investigation of some transition metal complexes of benzopyran-4-one Schiff base as thermal stabilizers for rigid poly(vinyl chloride) (PVC)

New metal complexes of Schiff base (PB) prepared from condensation reaction of 2-aminopyridine and 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one with metal ions; Mn(II), Co(II), Ni(II), and Cu(II) are prepared. Different analysis tools like elemental analyses, FTIR, thermal analysis, conductivity, electronic spectra, and magnetic susceptibility measurements are all used to elucidate the structures of the newly prepared metal complexes. The free Schiff base (PB) has been examined as thermal stabilizer and co-stabilizer for rigid PVC in air, at 180 °C. Its high stabilizing efficiency is detected by its high induction period value (T _s) when compared with some of the common reference stabilizers used industrially, such as dibasic lead carbonate and calcium–zinc stearate (Ca–Zn soap). Blending Schiff base or its metal complexes with Mn(II), Co(II), Ni(II), and Cu(II) ions with the reference stabilizers in different ratios had a synergistic effect on the induction period (thermal stability). The stabilizing efficiency is attributed at least partially to the ability of the stabilizer to be incorporated in the polymeric chains, thus disrupting the chain degradation process.     

Polymerization products of p-benzoquinone as thermal stabilizers for rigid poly(vinyl chloride). Part II—Evaluation of the stabilizing efficiency

Quinone-tin polymers prepared by the cationic polymerization of p-benzoquinone with tin(II)chloride in the absence of solvent have been investigated as thermal stabilizers for rigid PVC at 180°C in air by measuring the rate of dehydrochlorination. The results reveal the higher stabilizing efficiency of these products relative to dibutyltin maleate, basic lead carbonate and barium-cadmium stearate stabilizers commonly used in industry. The induction period in the early stages of the dehydrochlorination process increases as a function of the metal content in the stabilizer molecule. The evidence indicates that the quinone and the metal part (

) of the stabilizer participate in the stabilization process by trapping the radical intermediates, as well as blocking the odd electron sites formed on the PVC chains. The mechanism of stabilization suggested to account for the results obtained supports a radical mechanism for the dehydrochlorination reaction.     

The discolouration of PVC—II : Kinetic studies

On the basis of previous results, a relation has been derived between the time of the dehydrochlorination and the grade of the discolouration of PVC. The correctness of this relation is experimentally proved by investigations with samples containing metal soap stabilizers and with non-stabilized samples. The relation permits direct calculation of the rate constants and other kinetic characteristics of the propagation and termination steps for the conjugated polyenic chains. The activation energies derived are in apparently good agreement with the measured values for model compounds having similar structure. From the rate constants, conclusions can be drawn on the influence of the stabilizers on the individual steps. The experimental results obtained with stabilizer pairs support the present ideas about the mechanism of synergism; they also elucidate further details of the mechanism of stabilizing action.     

Photooxidation of poly[methyl(phenyl)silylene] and effect of photostabilizers

Poly[methyl(phenyl)silylene] (PMPSi) samples were irradiated in air atmosphere using either a weatherometer ATLAS Ci 3000+ or a mercury discharge lamp HBO 200. The kinetics of photodegradation was determined by FTIR and UV spectroscopies. The absorption changes in the siloxane, carbonyl and hydroxyl regions were monitored and analyzed. It is assumed that photodegradation of neat PMPSi in air atmosphere is an irreversible dual photoprocess consisting of primary photolysis followed by the photooxidation to oxygenated products such as siloxanes and species containing hydroxyl and carbonyl groups. Degradative changes can be retarded by the addition of photostabilizers. Triazine-based phenolic UV absorber protecting the polymer by the excited-state intramolecular proton transfer mechanism, bifunctional stabilizer (consisting of UV absorber and HAS functions) and the combination of triazine-based phenolic UV absorber with HAS was rather effective in retardation of photodegradation of PMPSi.     

Surface modification of polymers. IV. UV initiated degradation of polymers with stabilizers grafted onto the surface

Polypropylene (PP), Polyethylene (PE), and polystyrene (PS) films were grafted with glycidylmethacrylate in thin surface layers. To the oxiran groups thus grafted onto the surface three UV stabilizers were attached, 4-amino-2,2,6,6-tetramethylpiperidine (AP), 2,4-dihydroxybenzophenone (DHBP), and phenyl 4-aminosalicylate (PAS). The amount of stabilizer grafted onto the surface varied between 25 and 40 nmol/cm² depending on the polymer substrate. The samples were exposed to UV radiation in air, and the degradation and oxidation of the polymers were studied with IR, UV, and ESCA spectroscopy and by stress–strain measurements. PP grafted with AP exhibited a near 20-fold increase in lifetime compared with the unprotected PP, AP did not stabilize the PE or PS samples. DHBP was an efficient stabilizer of PE, the oxidation rate of the grafted sample being 1/2 to 1/3 of the ungrafted. A similar effect was observed when DHBP was grafted onto PP and PS. PAS underwent a rearrangement reaction when irradiated with UV light, and had only a slight stabilizing effect.     

Synergism of hindered amine light stabilizers and UV-absorbers

The synergism of hindered amine light stabilizers (HALS) and UV-absorbers is very important in the practical photo-stabilization of polymers. As very little is known, however, the relationship between the composition of the mixture of the two kinds of light stabilizer and its photo-stabilizing efficiency was investigated in four common polymers. A high level of synergism was observed in polypropylene, high density polyethylene and ABS resin. A moderate synergistic effect was obtained in polystyrene. The maximum efficiency was observed at mixing ratios of hindered amine light stabilizer to UV-absorber of about 75:25 in polypropylene and high density polyethylene, 90:10 in ABS resin and 80:20 in crystal polystyrene.The synergism is due to different stabilizing mechanisms of hindered amine light stabilizer and UV-absorber, and is explained by the diffusion of very effective hindered amine light stabilizer from the polymer bulk, which is protected by the UV-absorber, towards the surface layer where photo-oxidation proceeds.