Thermal oxidation of isotactic polypropylene synthesized with a metallocene catalyst

The mechanism and kinetics of thermal oxidation of metallocene PP are investigated. It is shown that the rate of oxidation of the samples synthesized at a high temperature (40–70°C) is higher than that of the samples synthesized at a low temperature (20 and 30°C). The composition of oxidation products of PP samples; the kinetics of the accumulation of these products; and changes in structural, thermal, and thermophysical parameters during oxidation are analyzed in detail. Our data indicate that the oxidation of low-temperature samples and the oxidation of high-temperature samples obey different mechanisms. The oxidation of low-temperature samples corresponds to the radical-chain process, in which the intramolecular transfer of kinetic chains prevails. High-temperature samples are characterized by the intermolecular transfer of oxidation kinetic chains, which leads to the degradation of macromolecules. It is inferred that the rate and mechanism of thermal oxidation are determined by the microstructure of polymer chains.     

Thermal oxidation of clay-nanoreinforced polypropylene

The thermo-oxidation process at low temperatures for a montmorillonite-nanoreinforced polypropylene (PP) was studied. Experimental aging kinetic data at 100, 80 and 60 °C have been obtained and compared with a computational simulation in which a kinetic model based on the closed loop approach was used. As a result, it has been found that the montmorillonite role is not limited to a role of inert filler in the polymer matrix but induces a slight catalytic effect leading to induction period reduction. This effect has been well simulated by increasing initial hydroperoxyde concentration. The consequences of kinetic control by oxygen diffusion have also been investigated by using micro ATR-FTIR mapping to assess concentration profiles of the oxidation products across the sample thickness. It has been found that the oxidized layer thickness is close to 17 μm for the pure polypropylene whereas it is around 10 μm for the nanocomposite at 100 °C. These profile variations have been attributed to differences in oxygen diffusion coefficient values. Simulations based on the kinetic model including diffusion-reaction coupling describe these profiles well.     

Thermal degradation study of isotactic polypropylene using factor-jump thermogravimetry

The degradation of isotactic polypropylene in the range 390–465°C was studied using factor-jump thermogravimetry. The degradations were carried out in vacuum and at pressures of 5 and 800 mm Hg of N₂, flowing at 100–400 standard mL/s. At 800 mm Hg this corresponds to linear rates of 1–4 mm/s. In vacuum bubbling in the sample caused problems in measuring the rate of weight loss. The apparent activation energy was estimated as 61.5 ± 0.8 kcal/mol (257 ± 3 kJ/mol). In slowly flowing N₂ at 800 mm Hg pressure the activation energy was 55.1 ± 0.2 kcal/mol (230 ± 0.8 kJ/mol) for isotactic polypropylene and 51.1 ± 0.5 kcal/mol (214 ± 2 kJ/mol) for a naturally aged sample of atactic polypropylene. For isotactic polypropylene degrading at an external N₂ pressure of 5 mm Hg the apparent activation energy was 55.9 ± 0.3 kcal/mol (234 ± 1 kJ/mol). A simplified degradation mechanism was used with estimates of the activation energies of initiation and termination to give an estimate of 29.6 kcal/mol for the ß-scission of tertiary radicals on the polypropylene backbone. Initiation was considered to be backbone scission ß to allyl groups formed in the termination reaction. For initiation by random scission of the polymer backbone, as in the early stages of thermal degradation, an overall activation energy of 72 kcal/mol is proposed. The difference between vacuum and in-N₂ activation energies is ascribed to the latent heat contributions of molecules which do not evaporate as soon as they are formed. At these imposed rates of weight loss the average molecular weights of the volatiles in vacuum and in 8 and 800 mm H_g N₂ are in the ratios 1–1/2–1/9.     

Thermal degradation behaviour of isotactic polypropylene blended with lignin

The influence of lignin on the thermal degradation of isotactic polypropylene, investigated by thermogravimetric analysis, is reported in this article. Polypropylene blends containing 5 and 15 wt% of lignin were prepared by mixing the components in a screw mixer. An increase in the thermal degradation temperature of the blends was observed as a function of lignin content, in both oxidative and non-oxidative conditions. The increase is noticeably marked for the experiments carried out in air atmosphere, where the interactions between the polypropylene and the lignin lead to the formation of a protective surface able to reduce the oxygen diffusion towards the polymer bulk. Morphological analyses were carried out with optical and electronic microscopy, to evaluate the degree of dispersion of the lignin in the polypropylene matrix. X-ray techniques were employed to study the influence of lignin on the structure of the blended polypropylene.     

Thermal degradation of thin films of isotactic polypropylene and polypropylene with ketonic additives

The rate of oxidation of 0.3–0.7 mil films of pure polypropylene is much more rapid than with thicker films. The rate of oxidation increases with the increase in the partial pressure of oxygen and with temperature. The apparent activation energy in oxygen is 22.5 keal/mole. 1,3-Diphenyl-2-propanone added to the polymer acts as an oxidation initiator while p-phenylacetophenone and 4-phenylbenzophenone slightly retard the oxidation. The effects of the additives are more pronounced when the oxidation was carried out in air or at the lower temperatures (90°C) when the oxidation was conducted in pure oxygen. The degree of crystallinity based on the infrared data was found to increase with the degree of oxidation of the polymer.     

Gamma-, photo-, and thermally-initiated oxidation of isotactic polypropylene

The detailed oxidation products have been identified and compared from the γ-, photo-, and thermally-initiated oxidation of unstabilized polypropylene films. Products were identified and quantified by a combination of iodometric analysis and infrared spectroscopy. Spectral resolution was enhanced by derivatization reactions which allow the quantification of primary, secondary, and tertiary hydroperoxide and alcohol groups as well as more reliable analysis of carbonyl species. In contrast to polyethylene oxidation which yields predominantly ketone with lesser amounts of secondary hydroperoxide and carboxylic acid, polypropylene oxidizes to give predominantly tertiary hydroperoxide and lesser quantities of secondary hydroperoxide and ketone. In addition carboxylic acid groups are a minor product except at high degrees of thermal and photoinitiated oxidation. © 1993 John Wiley & Sons, Inc.     

Thermal behavior of isotactic polypropylene freeze-extracted from solutions with varying concentrations

Isotactic polypropylene (iPP) with narrow molecular mass distribution was freeze-extracted from n-octane solutions with varying concentrations. The recovered samples were characterized by differential scanning calorimetry. It is found that the sample recovered from the very dilute solution exhibits the higher non-isothermal crystallization temperature, faster isothermal crystallization rate, and smaller Avrami index. And there should exist a critical concentration corresponding with the critical overlap concentration proposed by de Gennes in the polymer solutions. In the solution well below the critical concentration, the iPP chains were isolated from each other, resulting in an acceleration of melt crystallization for the recovered samples. It seems that the chain entanglement is a barrier to the melt crystallization of polymer.     

Unidirectional solidification of isotactic polypropylene

Thin films of isotactic polypropylene have been solidified unidirectionally by pulling specimens through a fixed temperature gradient of 5.5°/mm at rates ranging from 0.07 to 7 mm/hr. At pulling rates lower than 1.7 mm/hr, polypropylene spherulites grew preferentially in the direction of solidification with a tendency to the generation of more asymmetric spherulites at lower rates of solidification.     

Crystallization of oxidized isotactic polypropylene

The effect of processes accompanying thermal oxidation of the polymer on the characteristics of its isothermal crystallization has been revealed. It has been shown that crystallization decelerates with a rise in the degree of PP oxidation. The higher the concentration of functional groups, the stronger the deceleration. The energy of nucleation increases when passing from virgin to oxidized PP samples. The higher the concentration of carbonyl groups accumulated in polymer chains, the more pronounced this effect, although the degradation of the chains must lead to a reduction in this parameter. It has been concluded that the kinetic and thermodynamic parameters of the isothermal crystallization are applicable to investigation of processes accompanying thermal oxidation of the crystallizable polymer.     

Thermal oxidative degradation of isotactic polypropylene catalyzed by copper and copper oxide interfaces

The oxidative degradation of isotactic polypropylene films coated on well-defined Cu(Cu₂O), CuO_0.67, and CuO films in a temperature range of 90–120°C in a quartz-spoon-gauge-reaction vessel was studied. This catalytic reaction has been compared with the oxidation of polypropylene without copper or oxide films. The reaction vessel contained, if needed, P₂O₅ and/or KOH as “getters” for H₂O and CO₂, these substances could be menitored continuously. Cu(Cu₂O) films were transformed during oxidation of the polymer to yellow CuO_0.67 below 100°C and above this temperature to black CuO in the presence of H₂O and CO₂, whereas in the absence of these compounds CuO was formed below 100°C and CuO_0.67 at 120°C. Characteristic autoxidation curves obtained in the absence of H₂O and CO₂ showed induction periods that were shorter for copper oxide-polymer interfaces than for glass-polymer interfaces (i.e., for uncatalyzed oxidation). Abnormalities were observed for Cu(Cu₂O)-polymer interfaces because of further oxidation of Cu during the reaction. The rates of oxygen consumption were faster for CuO_0.67-polymer and CuO-polymer than for the uncatalyzed reaction; the catalytic action of CuO_0.67 was somewhat larger than that of CuO. The important observation was made that the mechanism of oxidation is not the same in the absence and presence of reaction products; that is, H₂O and CO₂. This was confirmed by ion beam scattering experiments, which also revealed that an oxidation-reduction process takes place at Cu and their oxide interfaces. A mechanism for the catalytic oxidation process, based on the ease by which copper ions are released from the metal oxides at the interface, was formulated. These ions diffuse subsequently as actions of carboxylate anions into the bulk of the polymer. Arrhenius equations of oxygen consumption are given for all cases; the energy of activation calculated for the initiation of the uncatalyzed oxidation agrees with its literature value. The energy of activation for the initiation of the catalyzed reaction was a few kilocalories lower than that for the uncatalyzed reaction. Catalytic action is mainly operative for the initiation reaction at the interface and for the decomposition of hydroperoxides by copper ions. Preventing the delivery of copper ions to the polymer would be the most efficient way of inhibiting the catalysis.     

Analysis of the nonvolatile oxidation products of polypropylene I. Thermal oxidation

The nonvolatile products in thermal-oxidized polypropylene sheet have been quantitatively identified by infrared analysis and chemical reaction. The molecular weight changes with oxidation have been studied by gel-permeation chromatography. It was determined that there is a functional group at each end of a chain. A general oxidation mechanism scheme for polypropylene is presented. The discovery of γ-lactone is an indication of the importance of an intramolecular backbiting process. The overall functional group distribution is found to differ from that found in a polyethylene sheet.     

Low and high-yield isotactic polypropylene

The crystallization and melting behaviour of isotactic polypropylene (iPP) samples synthetized with different catalyst systems (low and high-yield) have been studied by differential scanning calorimetry and optical microscopy. The isothermal crystallization rates from the melt have been found to depend on the catalyst system employed and on the isotacticity index of the sample. Moreover, for low-yield iPP, Avrami analysis of the overall kinetics has provided evidence of the presence of secondary crystallization phenomena. The values of the equilibrium melting point, energy of nucleation and surface energy of folding of iPP lamellar crystals have been calculated according to the ‘Kinetic theories’ of polymer crystallization. The observed variation of such thermodynamic parameters for the various iPP samples has been accounted for by the amount and type of configurational irregularities present along the chains and by the differences in the molecular weight distribution.     

Structural-mechanical phase diagram of isotactic polypropylene

The polymorphic transformations associated with the plastic deformation of isotactic polypropylene samples of different stereoregularity, prepared with different metallocene catalysts, have been studied. Crystals of alpha or gamma forms, present in the unstretched samples, transform into the mesomorphic form by stretching. The formation of the mesophase facilitates successive further deformation up to very high strains and produces development of outstanding unusual properties of high flexibility and elasticity. The phase diagram of isotactic polypropylene, where the regions of stability of the different polymorphic forms are defined as a function of stereoregularity and degree of deformation, is reported.     

High-pressure crystallization of isotactic polypropylene droplets

Dispersions of isotactic polypropylene (PP) particles in polystyrene (PS) were produced by interfacially driven breakup of nanolayers in multilayered systems that were fabricated by means of layer-multiplying coextrusion. The droplet size was controlled by the individual PP layer thickness ranging from 12 to 200?nm. In addition, PP was melt blended with PS to produce PP droplets larger than those formed by breakup of nanolayers. The dispersions of PP particles in the PS matrix were melted and annealed under high pressure of 200?MPa. Only the largest PP droplets, with average sizes of 170?μm, crystallized predominantly in the γ form. In the 42-μm droplets obtained by breakup of 200?nm layers, a minor content of the γ form was found whereas the smaller droplets obtained by breakup of the thinner nanolayers contained the α form and/or the mesophase. The results showed that the γ phase formed only in the droplets sufficiently large to contain the most active heterogeneities nucleating PP crystallization under atmospheric pressure. It is concluded that the presence of nucleating heterogeneities is necessary for crystallization of PP in the γ form under high pressure.     

Drawing behavior of cross-linked isotactic polypropylene

The drawing behavior of cross-linked isotactic polypropylene was analysed. The crystallinity and the composition of the crystalline phase are affected by cross-linking. Structural and topological features play a significant role in the drawing behavior. The yielding, the necking phenomenon, and the ultimate properties, i.e., stress and strain at the fracture, can be correlated with the sample structure. The general picture agrees well with Peterlin's model of cold drawing.     

Evolution of H2O and CO2 during the copper-catalyzed oxidation of isotactic polypropylene

The kinetics and mechanism of H₂O and CO₂ evolution during uncatalyzed and copper(oxide)-catalyzed (Cu, CuO, CuO_0.67) oxidation of isotactic polypropylene have been investigated in detail for various catalysts over a range of temperatures (90–150°C). These volatiles were determined chromatographically; H₂O and CO₂ represent the main volatiles of the oxidation, comprising about 80 mol % of all volatiles. Uncatalyzed oxidation evolves ca. 1 mol of H₂O and 1 mol of CO₂ for each unit mole of polymer oxidized, while catalyzed oxidation produces 2 mol of H₂O and ca. 1.2 mol of CO₂ for each unit mole of polymer. These results indicate that secondary as well as tertiary H atoms on the polymer chains are involved in hydroperoxide formation and decay. The oxidation mechanism has been formulated and evaluated on this basis. It consists essentially of two parallel oxidation reactions involving tertiary and secondary groups (H atoms and hydroperoxides), respectively. The mechanism can be represented by first- and pseudo-first-order reactions in series: (1) oxygen absorption showing induction periods; (2) hydroperoxide formation and decay (plateaus are reached); (3) H₂O evolution from the decay of hydroperoxides; and (4) subsequent CO₂ production involving chain scission. Arrhenius parameters for all oxidation reactions (uncatalyzed and catalyzed) are also presented. It appears that CuO_0.67 is the most efficient catalyst of those investigated.     

ESR study of the molecular dynamic of peroxyradicals in the post-irradiation oxidation of isotactic polypropylene

By adopting the modified Bloch equations, the analysis of the motion of macroperoxyradicals during the post-irradiation oxidation of isotactic polypropylene at room temperature has been performed. Rotations about the chain axis and cubic jumps are the motion of prominent importance in the early stages of reaction involving mostly radicals trapped at defects or in amorphous phase; on the other hand rotations about the C? O bonds at decreasing rates are dominant in the latter stages. Clear evidence of the progressive immobilization of peroxyradicals, which may be reckoned with monomolecular termination mechanism and of the trapping of peroxyradicals in the crystalline phase, have been obtained.     

Synthesis of polypropylene block copolymers from brominated styrene-terminated isotactic polypropylene

Isotactic polypropylene block copolymers, isotactic-polypropylene-block-poly (methyl methacrylate) (i-PP-b-PMMA) and isotactic-polypropylene-block-polystyrene (i-PP-b-PS), were prepared by atom transfer radical polymerization (ATRP) using a brominated styrene-terminated isotactic polypropylene macroinitiator synthesized from bromination of styrene-terminated isotactic polypropylene. The styrene-terminated isotactic polypropylene can be obtained by polymerization of propylene in the presence of styrene and hydrogen chain transfer agents using a rac-Me₂Si[2-methyl-4-(1-naphyl)Ind]₂ZrCl₂ as catalyst. The molecular weights of isotactic polypropylene block copolymers were controlled by altering the amount of hydrogen used in the polymerization of propylene and the amount of monomer used in the blocking reaction. The effect of i-PP-b-PS block copolymer on PP-PS blends and that of i-PP-b-PMMA block copolymer on PP-PMMA blends were studied by scanning electron microscopy.     

Inelastic neutron scattering from isotactic polypropylene

We used inelastic neutron scattering to probe the low‐energy excitations in semicrystalline isotactic polypropylenes with different degrees of crystallinity. The contributions from the amorphous and crystalline regions to the total scattering intensity were extracted under the assumption of a weighted linear contribution of the two regions in a simplified two‐phase system. The resulting intensity from the amorphous region showed a peak at 1.2 meV that was in good agreement with the previously determined boson peak characteristic of atactic polypropylene. The possibility of a contribution to the boson peak region by longitudinal acoustic mode modes that are characteristic of semicrystalline polymers and appear in the same low‐frequency region is discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2852–2859, 2001     

Melting temperature and enthalpy of isotactic polypropylene

The fusion process, melting temperature and heat of fusion of carefully crystallized fractions of isotactic polypropylene (molecular weights from 5·4 × 10⁴ to 2·2 × 10⁵) have been investigated. The equilibrium melting temperature, obtained by the extrapolation method in experiments involving very low degrees of crystallinity, corresponds to 208°. The fusion enthalpy was found to be 1·386 cal/mole. This low value and the high depression of Tm^o suggest a relatively high interfacial energy; a value of 285 erg/cm² is estimated for σ_ec.