Phosphorescence from commercial polyolefins and polyamides: Effects of thermal and photochemical oxidation

A study of the phosphorescence emission from the commercial polyolefins, polyethylene, polypropylene and poly-4-methylpentene-1 and the polyamides, nylon 6/6, 6, 11 and 12 is presented and the origin of the emission discussed. Impurity centres in the polymer are responsible for the emission, being present either as groups directly attached to the polymer backbone or as discrete molecules within the polymer matrix. These impurities can play an important part in the thermal and photochemical oxidation of the polymer. Therefore, changes in the phosphorescence spectra can provide valuable information on the mechanisms of both degradation processes.     

Biodegradation of montmorillonite filled oxo‐biodegradable polyethylene

Oxo‐biodegradation of polyethylene has been well studied with different pro‐oxidants and it has been shown that pro‐oxidants have limited role in the oxidation of polyethylene and do not have any role in microbial growth. However, in few recent studies, montmorillonite clay has been reported to promote the growth of microbes by keeping the pH of the environment at levels conducive to growth. In an attempt to improve the overall oxo‐biodegradation of polyethylene, montmorillonite nanoclay has been used in this study along with a pro‐oxidant. Film samples of oxo‐biodegradable polyethylene (OPE) and oxo‐biodegradable polyethylene nanocomposite (OPENac) were subjected to abiotic oxidation followed by microbial degradation using microorganism Pseudomonas aeruginosa. The progress of degradation was followed by monitoring the chemical changes of the samples using high‐temperature gel permeation chromatography (GPC) and infrared spectroscopy (FTIR). The growth of bacteria on the surface of the polymer was monitored using environmental scanning electron microscopy. GPC data and FTIR results have shown that the abiotic oxidation of polyethylene is influenced significantly by the pro‐oxidant but not by nanoclay. But, the changes in molecular weight distribution and FTIR spectra for the biodegraded samples indicate that the growth rate of P. aeruginosa on OPENac is significantly greater than that on OPE. It indicates that nanoclay, by providing a favourable environment, helps in the growth of the microorganism and its utilisation of the polymer surface and the bulk of the polymer volume. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Photochemical degradation of thermoplastics

The general mechanism of polymer photodegradation is outlined, and various aspects are then discussed with reference to polyolefins, particularly polyethylene. It is shown that various impurities accelerate degradation and that carbonyl groups play a complex role in the process. Polyolefins can be stabilised against photodegradation by incorporation of suitable u.v. stabilisers or pigments, and the principles involved, including the synergism between u.v. stabilisers and antioxidants, are discussed.     

Lifetime prediction of biodegradable polymers

The determination of the safe working life of polymer materials is important for their successful use in engineering, medicine and consumer-goods applications. An understanding of the physical and chemical changes to the structure of widely-used polymers such as the polyolefins, when exposed to aggressive environments, has provided a framework for controlling their ultimate service lifetime by either stabilising the polymer or chemically accelerating the degradation reactions. The recent focus on biodegradable polymers as replacements for more bio-inert materials such as the polyolefins in areas as diverse as packaging and as scaffolds for tissue engineering has highlighted the need for a review of the approaches to being able to predict the lifetime of these materials. In many studies the focus has not been on the embrittlement and fracture of the material (as it would be for a polyolefin) but rather the products of degradation, their toxicity and ultimate fate when in the environment, which may be the human body. These differences are primarily due to time-scale. Different approaches to the problem have arisen in biomedicine, such as the kinetic control of drug delivery by the bio-erosion of polymers, but the similarities in mechanism provide real prospects for the prediction of the safe service lifetime of a biodegradable polymer as a structural material. Common mechanistic themes that emerge include the diffusion-controlled process of water sorption and conditions for surface versus bulk degradation, the role of hydrolysis versus oxidative degradation in controlling the rate of polymer chain scission and strength loss and the specificity of enzyme-mediated reactions.     

Pyrolysis of polyolefins in high-boiling solvents

The pyrolysis of polyethylene and polypropylene in vacuum residue and coal-tar pitch solvents was studied in a batch reactor at atmospheric pressure in a temperature range of 380–420°C. Aliphatic hydrocarbons and C₅–C₃₂ normal olefins and isoolefins were the main pyrolysis products of the polyolefins and vacuum residue, which also underwent thermal degradation at these temperatures. The total conversion of a polypropylene-vacuum residue mixture into gaseous and distillate products was nearly additive; upon the pyrolysis of polypropylene in pitch and of polyethylene in vacuum residue and pitch, the yield of distillate products decreased and the paraffin/olefin ratio in these products increased. The observed regularities were explained by hydrogen transfer from the solvents to the intermediate radical products of the thermal decomposition of polymer chains. The reactions of the resulting of olefins with the solvents can also occur to a lesser degree. The greatest deviations from additivity were observed in the pyrolysis of polyethylene in the solvents used.     

Biodegradation of oxo‐biodegradable polyethylene

Biodegradation of polyethylene and oxo‐biodegradable polyethylene films was studied in this work. Abiotic oxidation, which is the first stage of oxo‐biodegradation, was carried out for a period corresponding to 4 years of thermo‐oxidation at composting temperatures. The oxidation was followed by biodegradation, which was achieved by inoculating the microorganism Pseudomonas aeruginosa on polyethylene film in mineral medium and monitoring its degradation. The changes in the molecular weight of polyethylene and the concentration of oxidation products were monitored by size exclusion chromatography and Fourier transform infrared (FTIR) spectroscopy, respectively. It has been found that the initial abiotic oxidation helps to reduce the molecular weight of oxo‐biodegradable polyethylene and form easily biodegradable product fractions. In the microbial degradation stage, P. aeruginosa is found to form biofilm on polymer film indicating its growth. Molecular weight distribution data for biodegraded oxo‐biodegradable polyethylene have shown that P. aeruginosa is able to utilize the low‐molecular weight fractions produced during oxidation. However, it is not able to perturb the whole of the polymer volume as indicated by the narrowing of the polymer molecular weight distribution curve toward higher molecular fractions. The decrease in the carbonyl index, which indicates the concentration of carbonyl compounds, with time also indicates the progress of biodegradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Friction and its effect on the mechanical- to-thermal energy conversion during extrusion of poly(vinylidene chloride)

Solid state friction reduction has been found to be an effective method for extrusion stabilization of a high coefficient of friction (COF) thermally sensitive polymer. A poly(vinylidenechloride) copolymer (PVDC) was studied alone and blended with various polyolefins to change its frictional behavior. COF of the polymer rubbing on a metal surface was measured under conditions typical of an extrusion process. These results correlated well with the measured mechanical energy consumed during extrusion. Of the polyolefins studied, high and low density polyethylene were found to be very effective for lowering friction and improving extrusion performance of the PVDC. Polypropylene was found to be much less effective. Interface temperature where melting occurs due to frictionally generated heat has been experimentally shown to be a function of COF and the bulk metal temperature.     

Effect of Br gassing after Ar plasma treatment of polyolefins

For simulation and acceleration of artificial polymer ageing, polyolefin foils were exposed to low-pressure Ar plasma. Plasma particle bombardment and irradiation induce C–C and C–H bond scissions by σ?→?σ ^? excitations on the surface and in near-surface layers. Consequently, radicals are generated. They react by recombination, cross-linking, metastable trapping of the radical site or formation of olefinic double bonds. The long-living and metastable trapped C-radicals as well as double bonds in polyolefins were immediately exposed to bromine vapour without breaking the vacuum after switching-off the plasma. These reactive sites rapidly react with the molecular bromine under formation of C–Br bonds. For 5?min of argon plasma exposure, the elemental concentration of bromine was 13% for polyethylene and 22% Br/C for polypropylene as analysed by X-ray photoelectron spectroscopy. Nevertheless, not all C radical sites have reacted with bromine. Later on, when the polyolefins brought in contact with ambient air, an additional post-plasma reaction of the remaining trapped radicals with oxygen was observed. The oxygen concentrations were lower after bromine gassing, thus repressing partially the post-plasma oxidation in the analysed layer (ca. 6?nm) by radical quenching. Such bromination took place either at the surface or in near-surface layers because the Attenuated Total Reflectance (ATR)-FTIR spectra (sampling depth ca. 2500?nm) did not show significant changes for argon plasma-treated PE foils with and without bromine vapour exposure. Further addition of bromine may also occur on C=C double bonds.     

A new technique for determining the oxidative stability of molten polymers

A new method and apparatus for determining the oxidative stability of molten polymers, especially polyolefins, is described. The apparatus consists of a laboratory scale mixer modified to allow for the continuous determination of the oxygen absorbed by the polymer. The oxygen uptake curve observed for polyolefins is of the type normally associated with the autocatalytic oxidation of hydrocarbons and yields an induction period—a traditional measure of stability. Typical results from experiments concerning the antioxidant type, antioxidant level and temperature on polyethylene stabilization are presented to illustrate the usefulness of the technique in both quality control and research applications.     

Diffusion of stabilizers in polymers. I. 2,4-dihydroxybenzophenone in polyolefins

The diffusion of the ultraviolet stabilizer 2,4-dihydroxybenzophenone in compressionmolded sheets of low-density polyethylene, high-density polyethylene, and isotactic polypropylene was investigated over the temperature range of 44–75°C. The magnitude of the diffusion coefficients for these polyolefins was found to decrease in the order low-density polyethylene > high-density polyethylene > polypropylene, the corresponding activation energies being approximately 18, 23, and 34 kcal/mole. Studies under conditions of saturation indicated that the migration of this stabilizer was confined to the more accessible amorphous regions of the polymers. The rate of loss of stabilizer from polymer samples immersed in water was also investigated at 44°C. Values of the diffusion coefficients calculated from the results of these studies were somewhat greater than those determined from the diffusion studies for the low-density polyethylene and isotactic polypropylene samples and considerably smaller in the case of high-density polyethylene. The extraction studies also permitted the quantitative evaluation of the solubilities of the stabilizer in the polymers. These were found to be 0.003, 0.03, and 0.07 wt-% for high-density polyethylene, low-density polyethylene, and polypropylene, respectively, at 44°C.     

Superficial degradation evaluated through color change in weathered orange LLDPE

We report the evaluation of superficial degradation of orange and colorless linear low density polyethylene samples exposed to weather. Color change and UV–VIS absorption were measured on samples exposed to the weather conditions of the city of Aguascalientes, Mexico, for more than a year. The color change was calculated in CIELAB units. Color change and absorption presented an exponential decay with time for orange samples, whereas they remained constant for colorless samples. No degradation products from the polymer matrix were revealed by UV–VIS spectroscopy, and apart from color change, no other degradation was noticed. © 2009 Wiley Periodicals, Inc. Col Res Appl, 34, 458–463, 2009     

Monitoring polyolefin modification along the axis of a twin screw extruder. I. Effect of peroxide concentration

The evolution of the structure of polyolefins with different ethene/propene ratios in the absence or in presence of peroxide was monitored along a twin screw extruder. Small samples were quickly collected from the melt at specific barrel locations and characterized by rheological measurements. The rheological properties of the polyolefins are hardly affected when processing is carried out in the absence of peroxide. In the presence of peroxide both branching/crosslinking and degradation occur along the extruder, until the peroxide is fully converted. The degree of branching/crosslinking and/or degradation depends on the ethene/propene ratio, on the original molecular weight of the polymer and on the amount of peroxide added. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 58–68, 2001     

基于静电分选解析聚乙烯颗粒生长与形貌演变

解析聚烯烃颗粒生长过程的形貌演变规律对认识聚合反应机理和调控产品性能至关重要。然而,聚烯烃复杂的颗粒生长行为导致极宽的粒径分布和较大的形貌差异,现有研究关注形貌均一的催化剂破碎生长成初级聚烯烃的过程,缺少对形貌各异的初级聚烯烃后续生长和形貌演化的系统研究。此外,亟需一种能够批量分选不同形貌聚烯烃的手段,支撑聚烯烃颗粒生长形貌的统计解析。基于同质同粒径颗粒摩擦荷电的形貌依赖性,开发了聚烯烃颗粒静电-形貌协同分选技术,实现了尺寸相近的不同形貌聚烯烃颗粒的批量分选,并基于此考察了聚乙烯颗粒生长过程中形貌的分化与演变规律。结果显示,聚乙烯颗粒生长过程中存在普遍的形貌劣化现象,随着粒径增大,颗粒形貌逐渐偏离标准球形;颗粒粒径、形貌、结晶度等的耦合解析表明聚乙烯颗粒存在两种可能的颗粒生长模式和形貌劣化路径：结晶速率过快导致的颗粒破碎和催化剂形貌复制效应导致的形貌劣化。研究方法和结果可为聚烯烃形貌研究和开发高性能聚烯烃催化剂提供重要支撑。     

Radiation-induced grafting of functional acrylic monomers onto polyethylene and polypropylene films using acryloyl chloride

Summary Radiation-induced graft polymerization of acryloyl chloride onto films of polyolefins (polyethylene and polypropylene) using gamma radiation was investigated in order to establish a convenient method to obtain polymer films grafted with polyacrylic esters. Grafting was carried out by three different methods; (i) direct irradiation of film in monomer solution (ii) vapor phase irradiation method, and (iii) pre-irradiation in air. The effects of monomer concentration, radiation dose and methods of grafting, on the formation of grafted polyolefins are reported in this paper. Received: 5 April 2000/Revised version: 17 November 2000/Accepted: 20 November 2000     

Photosensitized degradation of polyolefins. II

The oxydative photodegradation of polyethylene sensitized by aromatically substituted dienes such as 1,6-diphenyl-1,3,5-hexatriene (DPH) and 1,4-diphenyl-1,3-butadiene (DPB) has been investigated. The rate of degradation has been monitored by following the change of the mechanical properties of the polymer during accelerated indoor aging tests. It was found that both additives are efficient sensitizers of the photodegradation of polyethylene. The mechanism of photo-oxidation has been investigated by ESR and IR spectroscopy and it has been interpreted on the basis of a complex mechanism which includes excited singlet oxygen (¹O₂) and the products of photodegradation of the additives. Singlet oxygen, produced by DPB and DPH and/or by impurities present in the polymer, reacts with the additives themselves and, directly, with polyethylene. In turn, the products of photodegradation of the additives react with the polymer via hydrogen atom abstraction, further promoting the photodegradation. Irradiation carried out in absence of air seems to rule out the possibility of direct hydrogen atom abstraction by DPB and DPH.     

Diffusion of stabilizers in polymers. II. 2-hydroxy-4-octoxybenzophenone in polyolefins

The migration of radioactively labeled 2-hydroxy-4-octoxybenzophenone in a number of polyolefins was investigated over the temperature range 36–75°C. The rates of diffusion in the polymers studied were found to decrease in the order low-density polyethylene > high-density polyethylene ～ isotactic polypropylene, the activation energies being approximately 17, 36, and 24 kcal/mole, respectively. The results of the present study were found to be in qualitative agreement with those previously determined for the same stabilizer/polymer systems, quantitative differences being attributed to the different methods of sample preparation and the resulting differences in the morphological structures of the test specimens. The calculated solubilities of the substituted 2-hydroxybenzophenone in the various polymers were substantially higher, at a particular temperature, than the corresponding values previously determined for 2,4-dihydroxybenzophenone, being 1.4, 0.4, and 0.8 wt-% for low-density polyethylene, high-density polyethylene, and polypropylene, respectively at 75°C. Studies to determine the rate of loss of the stabilizer from polymer samples immersed in water resulted in extremely low rates of extraction, in contrast to those found for 2,4-dihydroxybenzophenone, as a result of the octoxy substituent and the resulting increase in compatibility between the stabilizer and polymer.     

金属钝化剂的研究进展

塑料和聚烯烃材料爆露在空气中被氧化降解使之失去使用价值。该问题可通过添加稳定剂解决。但是当材料与金接触时，某些金属离子或金属可加速氧化反应，这会明显降低制品的使用寿命。这时应加入金属离子钝化剂，以降低聚合物的降解。本文综述了该类产品的合成与应用，还介绍了一些工业化的品种。     

国外聚乙烯生产及消费进展

综述了国外聚乙烯生产及消费的进展,特别是重点分析了生产技术的改进及发展,如Unipol工艺、BP工艺、Spherilene工艺、Phillips工艺等技术进展。金属茂催化剂可使聚合物性能优化,并使聚烯烃经历新的革命。文章也叙述了Exxon、Dow、Mobil、BP及三井油化等公司金属茂研究开发的成果,及其在聚乙烯工业中的应用。     

The weathering degradation of polyolefins

The mechanism of weathering degradation of polyolefins is discussed. Variations in spectral radiation, temperature, density, polymer absorption spectra, orientation, and sample thickness are related to property deterioration. Organic ultraviolet stabilizers, zinc oxide stabilization, and UV catalyzed degradation are briefly reviewed.