Abiotic and biotic degradation of oxo-biodegradable foamed polystyrene

An alternative for improving the degradability of polyolefins and polystyrene is the addition of pro-oxidant substances to their formulations. The materials obtained are then called oxo-biodegradable. This work aimed to assess the biotic and abiotic degradation of atactic polystyrene (PS), utilising as test material foamed PS plates used in the manufacture of trays, formulated with Co- and Mn-based pro-oxidant additives. The plates were exposed to artificial weathering (ultraviolet radiation and heat) and were periodically analysed for changes in structural properties. The oxidised surface residues detached from the samples were incubated in a stabilised compost of urban waste (58 °C) or in an aqueous mineral medium (25 °C), the latter being inoculated with urban waste compost and also with a microbial consortium. It was found that the molar masses of the eroded materials from the pro-oxidant activated samples were significantly lower than the initial sample molar masses, with simultaneous incorporation of oxygen into the chains during the accelerated weathering. These samples underwent biodegradation and gave mineralisation values of 2-5% over 2-3 months of incubation in compost and perlite or in mineral aqueous medium. Biodegradation of the residues from the samples not containing pro-oxidant additives was also observed, but at levels which were lower than those obtained for oxo-biodegradable samples.     

Mechanisms of chain scission and the role of oxidation products in the oxidative radiolysis of ethylenepropylene copolymer

Many works have been devoted to the photo-oxidation of polyolefins but numerous questions remain. The aim of this paper is to constitute a complementary source of informations leading to the radiation oxidation mechanism of these polymers which could explain the chain scission process the basis of the alteration of mechanical and physical properties of polyolefins. It can be seen from our results that the hydroperoxides and the ketones are primary products of the reaction. A new secondary reaction efficiently leading to the alteration of mechanical properties has been proposed.     

Identification of degradation products of antioxidants in polyolefins by liquid chromatography combined with atmospheric pressure photoionisation mass spectrometry

Round robin tests have revealed the trend that the concentration of stabilizers in polyolefins is usually underestimated. However, it is still unclear whether this underestimation is due to systematic errors of the analysis procedures or to degradation of the stabilizers during the production of the round robin sample itself. Within the present work, the degradation pathways of six common antioxidants (ADK Stab AO-60, Everfos 168, Kinox 30, Irganox 3114, Irganox 1076, and Cyanox 1790) were investigated. Methods based on high-performance liquid chromatography with UV detection or hyphenated with mass spectrometry (employing either an ion trap or a quadrupole/time-of-flight instrument) were developed, whereby the suitability of atmospheric pressure photoionisation was studied and compared with the performance of more established ionisation techniques like electrospray ionisation and atmospheric pressure chemical ionisation. While ADK Stab, Kinox 30, Everfos 168, and Irganox 1076 turned out to be thermally stable at 115 °C, Irganox 3114 and Cyanox 1790 were partly degraded by oxidation. In the presence of talcum, which is a widely used inorganic filler for polyolefins, additional degradation reactions such as the cleavage of ester bonds and the loss of tert-butyl groups were observed at elevated temperature.     

A review on the development of liquid chromatography systems for polyolefins

Polyolefins are the most widely produced synthetic polymer commodity and are found in countless applications ranging from bottles, packaging films to bullet-proof jackets, etc. Such widely different applications rely on high variability in the physical properties of polyolefins, which is a result of variations in microstructure, chemical composition and molar mass. Though polyolefins contain only carbon (C) and hydrogen (H) atoms, the microstructures of polyolefins are extremely variable, differing in the nature of the monomers (e.g. ethylene versus propylene), the degree of branching, chemical composition in the case of copolymers and finally their molar masses. Production, research and development of polyolefins require the analysis of polyolefin samples in terms of all these parameters. Development of efficient and robust analytical techniques based on the interactive LC is reviewed. The needed computational/theoretical studies to understand the retention mechanism in the newly developed chromatography systems are discussed.     

Determination of hexamethylphosphoramide and other highly polar phosphoramides in water samples using reversed-phase liquid chromatography/electrospray ionization time-of-flight mass spectrometry

The widely used solvent hexamethylphosphoramide (HMPA) and its biological (metabolic) and chemical (abiotic) phosphoramide-based oxidation products may cause adverse health effects through occupational exposure and intake of contaminated groundwater. However, no current methods exist for the separation and the detection of the many polar HMPA oxidation products. Thus, we developed a new RPLC/ESI-TOF-MS method and further investigated the chromatographic performances of two columns (i.e., XTerra Phenyl and XBridge Phenyl). In addition, the impact of (forced) acid hydrolysis for optimized chromatographic performance of the XTerra Phenyl column is investigated. The XTerra Phenyl column showed the best separation of the less polar major metabolic oxidation products pentamethylphosphoramide and hydroxymethyl-pentamethylphosphoramide, however, only after treating the column with formic acid (acid-treated). The XTerra column separated most of the investigated HMPA oxidation products (11 of 16 compounds) in a single chromatographic run. In contrast, the XBridge Phenyl column requires one method for the less polar and another method for the more polar oxidation products. However, this results in an overall better separation performance of the XBridge Phenyl column, especially for the less polar major abiotic oxidation products hydroxymethyl-pentamethylphosphoramide and formyl-pentamethylphosphoramide, as well as for 11 highly polar oxidation products (R(S)>1.5). The RPLC/ESI-TOF-MS method presented and validated in this study is the first analytical method that can be used to separate and detect HMPA (LOD 0.10 μM without preconcentration) and all of its oxidation products.     

Characterization of polypropylene�Cpolyethylene blends by temperature rising elution and crystallization analysis fractionation

The introduction of single-site catalysts in the polyolefins industry opens new routes to design resins with improved performance through multicatalyst-multireactor processes. Physical combination of various polyolefin types in a secondary extrusion process is also a common practice to achieve new products with improved properties. The new resins have complex structures, especially in terms of composition distribution, and their characterization is not always an easy task. Techniques like temperature rising elution fractionation (TREF) or crystallization analysis fractionation (CRYSTAF) are currently used to characterize the composition distribution of these resins. It has been shown that certain combinations of polyolefins may result in equivocal results if only TREF or CRYSTAF is used separately for their characterization.     

Evaluation of the melt stabilization performance of hydroxytyrosol (3,4-dihydroxy-phenylethanol) in polypropylene

The use of hydroxytyrosol (3,4-dihydroxy-phenylethanol) as a potential alternative to synthetic compounds in the melt stabilization of polyolefins is considered. Hydroxytyrosol was found to play a role in enhancing the oxidative stability of olive oil, and a similar reduction in polyolefins’ thermo-oxidative degradation during processing is expectable. Rheological tests (melt flow index and viscosity vs. shear rate) showed the good antioxidant performance of hydroxytyrosol during polypropylene processing as was also demonstrated by the increase in apparent activation energies and oxidation induction parameters after addition to polypropylene (0.1 wt%). Results were compared to those obtained for a commercial synthetic phenolic antioxidant and for a natural compound widely used in polymer stabilization (α-tocopherol). The main conclusion of this work is the good performance of hydroxytyrosol in polypropylene stabilization during processing and consequently the possibility of its use in formulations with improved resistance to oxidative degradation.     

Specific features of formation and properties of hydroperoxides of polyolefins

Oxidized polyolefins may contain hydroperoxide groups but hydroxyl, carbonyl and other oxygen-containing groups also may be distributed in the polymer. The distribution of these groups and their proportions depend on oxygen pressure and other reaction conditions. Properties of hydroperoxides are functions of the conditions prevailing during the oxidation of the polyolefin. The mechanism of hydroperoxide formation during oxidation of polyolefins is discussed.     

Pyrolysis of mixed polyolefins in a fluidised-bed reactor and on a pyro-GC/MS to yield aliphatic waxes

Polyolefins (PE, PP and PS) were pyrolysed in a fluidised-bed reactor on kilogram scale at 510°C. Pyrolysis products were analysed with GC, GC/MS and other methods. It was shown that valuable products, mostly aliphatic waxes, are received from polyolefins. It was also investigated if mixtures of different polyolefins (PE, PP, PS) interact with each other in fluidised bed pyrolysis yielding different pyrolysis products than received from the pure, individual polyolefins. The same polymer mixtures were also analysed using a pyro-GC/MS-device.     

The photo-stabilisation of polypropylene: A review

The incorporation of antioxidants and light stabilisers in polymers is important in order to preserve their long-term use in the environment. The mechanisms of photo-stabilisation are complex and with continued research grow even more in complexity. The processes involved are further complicated by the effects of processing which can in many cases dramatically influence the performance of the additives. This review presents an in-depth account of the complex mechanisms involved in both thermal and photochemical oxidation of polyolefins, with particular emphasis on polypropylene and the interactions that take place thermally.     

Early Transition Metal Catalysis for Olefin–Polar Monomer Copolymerization

Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value-added applications. The metal catalyst-mediated copolymerization of non-polar olefins with polar comonomers represents the seemingly most straightforward, atom- and energy-efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)-catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co-monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.     

New materials from new catalysts

The polyolefins, especially polypropylene and polyethylene, industry of today is very different from that of 10 years ago. The development of highly active and stereospecific catalysts, represented by Ti/Mg supported catalysts, have made the gas-phase polymerization process practical. The trend in catalyst development is shifting from an emphasis on improving the stereospecificity and activity toward improving the polymer physical properties, processability and morphology. Many hybrid thermoplastic olefins, such as high-impact copolymers, propylene–ethylene–butene terpolymers, and very low density polyethylene, have already been developed by utilizing the features of the gas-phase polymerization process. These hybrid thermoplastic olefins cover a very broad range of products. They cannot be clearly identified as polyethylenes, polypropylenes or elastomers. Incidentally, metallocene catalysts for polyolefins have been under development for the past 15 years, and are now in the early stage of commercialization. These catalysts differ significantly from the conventional heterogeneous catalysts. They can polymerize not only ethylene, propylene and other linear α-olefins, but also styrene, cycloolefins and functional monomers In addition, they can control the microstructure of polymer molecules by varying the transition metals and the cyclopentadienyl ligands. Because of these features, we have to be confident that the development of metallocene catalysts, or more widely homogeneous catalysts, may be a dominant force throughout the 1990s in the polyolefin industries.     

Molecular interactions at the interface in blends of ester groups-functionalized polyolefins

Due to the apolarity of the aliphatic backbones, unmodified polyolefins are scarcely miscible with most of other polymers. The functionalization of preformed polyolefins is a way which has been successfully followed to improve the polymer miscibility. The functionalization of linear low density polyethylene (LLDPE) and ethylene-propylene copolymers (EP), with diethyl maleate (DEM) and dicumyl peroxide (DCP) as radical initiator, gives products containing up to 2–5 mol % of well defined functional groups (2-diethyl succinate). Intermolecular interactions of these functional groups are characterized by comparison with suitable low-molecular-weight structural models in the presence of different solvents containing acidic hydrogen atoms. On the basis of these indication evidences of interface molecular interactions in blends with halogenated polymers are described between the functionalized polyolefins and poly(vinyl chloride) (PVC), poly(vinylidene fluoride) (PVDF) or vinylidene fluoride-hexafluoropropene copolymer obtained in semiindustrial Brabender mixers. It is shown that a smooth functionalization of the polyolefins can modify the phase behaviour and structure of these systems. The FT-IR microanalysis supports the occurrence of partial miscibility phenomena which can be accounted for by specific intermolecular interactions involving the inserted functional groups and occurring mainly at the interfaces between domains of polyolefins and of the halogen-containing polymers.     

Early Transition Metal Catalysis for Olefin–Polar Monomer Copolymerization

Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value‐added applications. The metal catalyst‐mediated copolymerization of non‐polar olefins with polar comonomers represents the seemingly most straightforward, atom‐ and energy‐efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)‐catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co‐monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.     

双烯烃橡胶复分解-加氢制备端羧基聚烯烃

采用烯烃复分解法,以双烯烃橡胶为原料,在Grubbs II代催化剂和链转移剂(马来酸)的作用下制得相应的端羧基聚二烯烃,通过对甲苯磺酰肼/三正丙胺试剂对其进一步加氢得到端羧基聚烯烃.主要研究了反应时间、反应温度、橡胶中双键/催化剂摩尔比、橡胶中双键/链转移剂摩尔比等因素对产物分子量及分子量分布的影响.通过核磁共振氢谱(1H-NMR)和碳谱(13C-NMR)、红外光谱(FTIR)、凝胶渗透色谱仪(GPC)、热重分析(TGA)和示差扫描量热分析(DSC)对产物的结构和性能进行了测试表征.结果表明,通过调整橡胶中双键/催化剂的摩尔比或橡胶中双键/链转移剂的摩尔比可以调控产物的分子量.另外,采用该方法制得的端羧基聚丁二烯具有较高的反式1,4-结构含量,与原料相比其顺式1,4-结构含量大幅下降,从而对产物的性能产生一定影响;而以异戊橡胶为原料时并没有观察到该现象.端羧基聚二烯烃经加氢反应后转变成端羧基聚烯烃,具有更好的热稳定性.该方法合成步骤简单,产物分子量可控,为功能材料的制备提供了新的可能.     

Crystallization Elution Fractionation and Thermal Gradient Interaction Chromatography. Techniques Comparison

Summary: The chemical composition distribution has been shown to be the most critical and discriminating parameter in understanding the performance of industrial polyolefins with non homogeneous comonomer incorporation. The chemical composition distribution is being analyzed by well known techniques such as temperature rising elution fractionation, TREF, crystallization analysis fractionation, CRYSTAF and crystallization elution fractionation, CEF. These techniques separate according to crystallizability and provide a powerful and predictable separation of components based on the presence of branches, irregularities or tacticity differences, independently of the molar mass. TREF, CRYSTAF and CEF can not be used, however, for the separation of more amorphous resins, and may not always provide the best solution for complex multi-component resins due to the existence of some co-crystallization. The application of high temperature interactive HPLC to polyolefins opened a new route to characterize these types of polymers. The use of solvent gradient HPLC for separation of polyethylene and polypropylene and the developments in HPLC on carbon based columns extended further the application of high temperature HPLC in polyolefins. A new approach has been developed recently using the carbon based column but replacing solvent gradient by a thermal gradient which facilitates the analysis of polyethylene copolymers and provides a powerful tool for the analysis of elastomers. Thermal gradient interaction chromatography (TGIC) is being compared with TREF and CEF with the analysis of model samples. The advantages/disadvantages of each technique are being investigated and discussed. The combination of TGIC and TREF/CEF provides an extended range of separation of polyolefins.     

Rare earth metal initiated ring‐opening polymerization of lactones

The progress in the synthesis of organolanthanide complexes supports the exploration of these compounds as initiators for ring‐opening polymerization (ROP) of lactones. The performance of these initiators in terms of yield, molecular weight, polydispersity, stereoregularity is affected by the ligands and by the oxidation state of the respective rare earth metals. Several initiators are known to initiate living polymerization of lactones with excellent polydispersities of the thus obtained polymers. Differences in the performance of the initiators are caused by differences in the initiation mechanism, chain growth mechanism, or side reactions. ROP of lactones was extended to block‐ and graft copolymerization with polylactones, polylactides, and polyolefins either by simply utilizing living polymer chain ends, by transformation of living polymer chain ends, or by usage of polyinitiators.     

Effect of photochemical oxidation on polypropylene phosphorescence

Phosphorescence from polyolefins was studied from the aspects of excitation and emission wavelength and lifetime. Effects of photochemical oxidation on polypropylene phosphorescence are discussed in contrast to the effects of thermal oxidation.     

Photostabilisation mechanisms in polymers: A review

Key degradative processes for various polymers are itemised, together with photostabilisation mechanisms which can minimise these processes. Polymers can be conveniently classified as inherent absorbers, which absorb large amounts of solar uv, and as ‘non-absorbers’, that is polymers transparent in the near uv. The former group which includes aramids, polycarbonates and polyesters is predominantly photodegraded by primary processes causing direct bond scission and stabilisation is best effected by the use of uv absorbing additives or opaque pigments. The ‘non-absorbers’ include polyolefins and poly(vinylchloride) which are degraded as the result of oxidative chain processes initiated by chromophoric impurities. For polypropylene the dominant photooxidation product is hydroperoxide which photocleaves to initiate further oxidation. Various uv. stabilisers for polyolefins appear to owe their effectiveness to their ability to decompose hydroperoxide groups and/or to their ability to scavenge free radical intermediates in the oxidative process.     

Development of Synergistic Stabilizing Compositions for Polyolefins and Evaluation of Their Performance

A series of new synergistic polyfunctional stabilizing compositions phenol-phosphite for polyolefins were developed. Their performance as antioxidants, color stabilizers, and agents preventing thermomechanical degradation was quantitatively evaluated.