The effect of divinylsulfone on the irradiation crosslinking of polypropylene

Polypropylene films were irradiated with ⁶⁰Co γ-rays in divinylsulfone (DVS) or butadiene (BD) gases. The variations of the intrinsic viscosities of the samples irradiated in vacuum or in DVS with dose showed usual patterns but the variation of the latter was somewhat more rapid. The intrinsic viscosity of the sample irradiated in BD could not be measured due to the early appearance of gel. The gel fraction of the sample irradiated in DVS appeared at lower dose than that irradiated in vacuum, but the former did not increase as much as the latter. The gel fraction of the sample irradiated in BD increased remarkably. The concentrations of the two kinds of double bonds increased in the sample irradiated in BD but levelled off gradually with dose. ESR study showed that the polypropylene radical reacted with DVS to form anisotropic radicals. The mechanisms of the effects of both reagents on irradiation of polypropylene were discussed.     

The effect of annealing on the elastoplastic response of isotactic polypropylene

Four series of tensile loading-unloading tests are performed on isotactic polypropylene in the sub-yield domain of deformations at room temperature. In the first series, injection-molded specimens are used as produced, whereas in the other series the samples are annealed for 24 h at 120, 140 and 160 °C, which covers the low-temperature region and an initial part of the high-temperature region of annealing temperatures. A constitutive model is developed for the elastoplastic behavior of a semicrystalline polymer. The stress-strain relations are determined by five adjustable parameters that are found by fitting the experimental data. The effect of annealing is analyzed on the material constants.     

The effect of gamma-irradiation on the morphology of quenched isotactic polypropylene

Wide-angle X-ray diffraction, differential scanning calorimetry and gel-permeation chromatography measurements have been used to investigate the effect of low absorbed doses of γ-radiation, up to 100 kGy, on isotactic polypropylene (iPP). The bimodal endotherm for the sample quenched in iced water was attributed to the presence of both “smectic” and monoclinic crystalline phases. The changes in the morphology, molecular weight distribution, decrease of melting temperature and heat of fusion with absorbed dose are related to the radiation processes in pure iPP.     

Heat treatment of isotactic polypropylene: the effect of free quenching from the melt state

Studying the effect of quenching from the melt state on the structure and impact resistance of Isotactic polypropylene (iPP) was the major aim of this work. Various tests were applied to confirm changes that occur to iPP, namely impact tests, WAXD, FTIR, and the density. The quenching from the melt state to different temperatures decreased the values of Izod impact strength for all the quenching temperatures. The FTIR result showed a decrease in the crystallinity of the polymer at the free quenching temperature of 20?°C. The X-ray diffraction study revealed that the α structure dominates the main morphology of iPP.     

The effect of morphology on thermal stability of isotactic polypropylene in air

Summary The studies on thermooxidative degradation of isotactic polypropylene films with different morphological structure were carried out in the air in temperature range 85–145 °C. The various crystallinity degrees and morphologies of PP films were obtained by cooling the melt and crystallization at different temperatures. The studies on structural changes going together with degradation and on the kinetics of chain scission have shown that this reaction occurs in two stages. The first is connected with consumption of oxygen dissolved in the initial films and the second is controlled by its diffusion into the films. The rates of degradation and structural changes occurring simultaneously depend not only on the initial crystallinity but also on morphology of the systems under study.With 8 figures and 1 tableDedicated to Prof. G. Rehage on occasion of his 60th birthday     

The effect of temperature on peroxide initiated crosslinking of polypropylene

Crosslinking of polypropylene at 10–220° was investigated. The process was initiated by radicals formed either by thermal or by u.v. decomposition of dicumyl peroxide. It was found that fragmentation of macroradicals is the most important reaction during thermal initiation and the crosslinking efficiency increases with decreasing temperature. For u.v. initiation, several chemical and physical factors are important; the efficiency is highest at 65–80°.     

Pressure dependence of free radical decay in irradiated isotactic polypropylene

Free radicals were generated in isotactic polypropylene by gamma-irradiation. The samples were annealed at pressures between 1 and 8000 atm and temperatures between 60 and 110°. The concentration of free radicals was estimated by the ESR method. The rate constants of free radical decay were determined for various pressures and temperatures. The rate constant of free radical decay decreases with increasing pressure while the activation energy increases. The relationship between the kinetics of molecular motion and the kinetics of free radical decay is discussed.     

An ESR study of the decay reaction of isotactic polypropylene peroxy radicals in air

The decay of peroxy radicals trapped in irradiated isotactic polypropylene has been studied by ESR in air at various temperatures between 284 and 309 K. All the ESR spectra obtained at the various reaction stages are shown to be composed of two components arising from a mobile fraction and an immobile fraction. Only the mobile peroxy radicals decay; those belonging to the immobile fraction are stable. Various reaction mechanisms are examined in order to explain the experimental results; it is concluded that the decay reaction is controlled by diffusion of peroxy radicals and that the immobile peroxy radicals play no role in the decay reaction. Intermolecular hydrogen abstraction of the peroxy radicals, rather than intramolecular abstraction, is suggested as the rate-determining reaction.     

The effect of the addition of polypropylene grafted SiO2 nanoparticle on the crystallization behavior of isotactic polypropylene

The crystallization behavior of isotactic polypropylene (iPP)/silica particle (SiO₂, 26 nm) nanocomposite has been investigated. In addition to the non surface-modified SiO₂, iPP grafted SiO₂ was synthesized and adopted to this study with an aim to understand the role of grafted polymer chain on the crystallization process. The crystallization rate of non surface-modified iPP/SiO₂ composite stays constant up to 1 vol%. It suggests the very weak nucleation ability of nano-sized silica particle. While large acceleration effect was observed for iPP-grafted SiO₂/iPP composite. The spherulite density increased with increasing SiO₂ contents, and more interestingly, the spherulite growth rate also increased. This finding leads to the conclusion that the grafted iPP chain has a plasticizing effect that reduces the chain entanglements at the interface. Further increase in SiO₂ contents, the crystallization rate, the spherulite density, and the spherulite growth rate showed the steep decreases at higher SiO₂ content range regardless of the surface modifications of SiO₂. It was attributed to the confinement of matrix chain since the inter-particle distance of adjacent SiO₂ approaches to the end-to-end distance of matrix chain, which a large molecular motion is restricted. Moreover, the average size of SiO₂ aggregation in iPP matrix was successfully evaluated by analyzing the contents dependence of the growth rate, assuming that the inter-particle distance with zero growth rate coincided with end-to-end distance of matrix iPP chain.     

The effect of specific nucleation on tensile mechanical behaviour of isotactic polypropylene

Commercial-grade isotactic polypropylene was modified with a specific β-nucleation agent NJ-Star (N,N^′-dicyclohexylnaphthalene-2,6-dicarboxamide) in concentrations 0.03, 0.10 wt.% and with a specific α-nucleating agent Millad 3988 (1,2:3,4-bis-O-(3,4-dimethylbenzylidene)sorbitol) in a concentration of 1.0 wt.%. Specimens for mechanical studies were prepared by injection moulding. Two types of tensile mechanical testing were performed at room temperature: (1) stress-strain test encompassing the plastic behaviour well behind the yield point and (2) tensile creep in the region of non-linear viscoelasticity. The results derived from the stress-strain traces show a distinct decrease in Young's modulus and yield stress for samples containing the crystalline β-phase as compared with non-nucleated and α-nucleated samples. This decrease was more pronounced with samples containing the lower β-nucleant concentrations (0.03 wt.%). Higher compliance of specimens containing the β-phase was also manifested in their creep behaviour. However, the creep rate of the specimen with the higher nucleant content (0.10 wt.%) did not rise with time so that its creep curve intersected the creep curves of non-nucleated and α-nucleated samples. Thus, at creep times longer than 1000 min, the sample with 0.1 wt.% of the β-nucleant showed a lower compliance than non-nucleated polypropylene and at 10 000 min reached the compliance of the α-nucleated sample. The different softening effect of the β-phase in the high-strain and low-strain regions has been ascribed to a specific structure of the amorphous interlayer induced by the presence of the β-crystallites.     

The effect of specific nucleation on molecular and supermolecular orientation in isotactic polypropylene

The molecular and supermolecular orientation, morphology and structural changes observed during cold drawing of injection moulded isotactic polypropylene modified by specific α, and β nucleating agents were studied by polarised photoacoustic FTIR spectroscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Significantly lower molecular orientation was found in the core of the β-nucleated injection moulded specimens as compared to unmodified and α-nucleated materials. This has been ascribed to the fast growth of the β-crystallites which inevitably dislocates the flow-induced orientation within the crystalline regions and in their vicinity. Moreover, it was found that the presence of the developed β-crystallites distinctly diminishes the efficiency of the orientational solid-state drawing assessed on both levels of the hierarchical structure (molecular and crystalline). This structural observation is directly connected with macroscopic softening effect of the β-phase: lowering the yield stress and flattening the neck shoulder. Thus, the interrelation between the microstructural and macroscopic effects of the β-phase could be described as a feedback process.     

Solvent effect on the reactivity of trichloromethylperoxy radicals

The solvent effect on the rate of reaction of organic reductants with trichloromethylperoxy radicals can be adequaetly described by multiparameter linear equations. The major factor affecting the reaction rate is the solvent cohesion, enhancing the cage effect.     

Solvent effect on the reactivity of arylsulfanyl radicals

The rate of reaction of p-aminophenylsulfanyl radicals with styrenes decreases as a result of solvation of the initial reactants. The determining factor in the reaction with styrene is specific solvation, and in the reaction with α-methylstyrene, nonspecific solvation.     

Formation and reactivity of free radicals in 5-hydroxymethyl-2-furaldehyde--the effect on isoprenaline photostability

Solutions of glucose are used as diluents for drugs in various drug infusions. When sterilized by heat small amounts of the substance 5-hydroxymethyl-2-furaldehyde (5-HMF) is produced from glucose. At a hospital ward such infusions may be exposed to irradiation; including UV-light. The photoreactivity of the furaldehyde is investigated. It is shown to photodestabilize the catecholamine isoprenaline. It is shown to be a producer, but also a consumer, of singlet oxygen. The excited triplet, cation and anion radical have been produced by pulse radiolysis and flash photolysis and their absorbance characteristics have been determined. The triplet absorption spectrum showed absorption bands at 320 and 430 nm with molar absorption coefficients of 4700 and 2600 M-1 cm-1, respectively. The anion radical showed absorption bands at 330 and 420 nm with molar absorption coefficients of 2000 and 300 M-1 cm-1, respectively. The cation radical had an absorption band at 320 nm with a molar absorption coefficient of 5000 M-1 cm-1. The quantum yield for the production of singlet oxygen, sensitized by the 5-HMF triplet, was determined to be 0.6, whilst the quantum yield for the triplet formation was 1.0. Aqueous solutions of 5-HMF were found to photoionize to yield the hydrated electron and the cation radical of 5-HMF in a biphotonic process. The influences of pH, buffer and glucose on the formation of transients were evaluated. The reactions between 5-HMF and the solvated electron, the hydroxyl radical and the superoxide were also studied.     

Nucleation effect of adipic acid metal salts in isotactic polypropylene

Journal of Thermal Analysis and Calorimetry - A series of adipic acid metal salts as nucleating agents for isotactic polypropylene (iPP) were synthesized from adipic acid (Adi) and corresponding...     

On the reactivity of cellulose free radicals in graft copolymerization reactions

The formation and behavior of photo-and mechanoinduced free radicals in cellulose were studied by ESR spectroscopy and the capability of these free radicals to initiate graft copolymerization reactions was demonstrated. Although an 11-line ESR signal was detected from cellulose irradiated with ultraviolet (UV) light, a higher-intensity ESR signal with a five-line pattern was detected from a sample mechanically milled at 77 K. The decay of photoinduced free radicals when heated took place monotonously, whereas mechanoradicals exhibited an anomalous behavior with an increased signal intensity at 150 K before decaying at a higher temperature. Mechanoradicals have been found to react more efficiently and rapidly with oxygen and methyl methacrylate (MMA) than photoinduced free radicals. The peroxy mechanoradicals, however, were mobile and decayed more rapidly than the peroxy photoinduced radicals. Simultaneous graft copolymerizations of MMA to cellulose demonstrated that mechano-and photoinduced free radicals are capable of initiating grafting reactions, but a higher degree of grafting efficiency was obtained from cellulose treated mechanically.     

On the reactivity of diethyl hydroxyl amine toward free radicals

Diethyl hydroxyl amine is an efficient trap for alkyl, alkoxy, and peroxy radicals. The specific rate constant for the reaction of ethyl radicals (gas phase, 25°C), tert-butoxy radicals (benzene solution, 115°C), and poly (peroxystyryl) peroxy radicals (styrene solution, 50°C) were evaluated as 7.2 × 10⁵, 7.7 × 10⁷, and 2.9 × 10⁵ M^?1·sec^?1, respectively. Several possible secondary reactions of the nitroxide radicals are discussed.     

The relationship between the density of the unpaired electron and reactivity of free radicals

Theoretical and Experimental Chemistry -     

The effect of the addition of polypropylene-grafted SiO2 nanoparticle on the thermal conductivity of isotactic polypropylene

The thermal conductivity of Isotactic polypropylene (iPP)/silica particle (SiO₂, 26 nm) nanocomposite has been investigated. The untreated SiO₂ and iPP grafted onto SiO₂ were dispersed in the iPP (M _w = 2.5 × 10⁵) matrix. The molecular mass of the iPP-grafted chain, M _n, was precisely controlled to be 5.8 × 10³, 1.2 × 10⁴, and 4.6 × 10⁴. It was found that the thermal conductivities of graft-treated nanocomposites were higher than that of untreated SiO₂ composites. This implied that it is possible to achieve even higher thermal conductivity using the graft treatment. A thermal conductivity analysis conducted using a three-phase model, with considerations for thermal conductivity at interfacial layers, showed that the thermal conductivity of the interfacial layer increased significantly when a graft chain was incorporated. Moreover, the thermal conductivity per graft chain was proportional to the 1/2 power of the molecular mass ( \( M_{\text{n}}^{0.5} \) ). The results strongly suggest that the thermal conductivity pathway of interfacial layer was the main chain direction of iPP-grafted molecular chains.