Polyolefin photo-stabilisation mechanisms. Reactions of tetramethylpiperidine derivatives in model systems

The relative rate of cyclohexyl radical scavenging by oxygen or 4-oxo-2,2,6,6-tetramethylpiperidino-N-oxyl has been measured at 25°C, together with the relative rates of cyclohexyl peroxy radical attack on cyclohexane or substituted hydroxylamines derived from 2,2,6,6-tetramethylpiperidine. These competitive processes are important in the stabilisation of polymers against photo-oxidative destruction by piperidine derivatives. Peroxy radical scavenging by the substituted hydroxylamine appears to be considerably more important than alkyl radical scavenging by the nitroxide, although both processes are essential for prolonged ultra violet (uv) stabilisation of a polymer. However, a comparison of experimental photo-protection with that predicted by the measured rate constant ratios shows that other processes are needed to account entirely for the observed stabilisation. Other factors which may be involved in piperidine photo-protection of polymers include thermal decomposition of the substituted hydroxylamine to reform nitroxide in polar(oxidised) zones and especially the association of nitroxides with hydroperoxide groups (the dominant photo-initiator in degrading polyolefins).     

Some mechanistic insights in the behaviour of thiol containing antioxidant polymers in lignin oxidation processes

Modified polyethylene glycol polymers are described in which thiol containing groups have been added via a simple esterification step. The resultant thiol end-capped polyethers retain the antioxidant behaviours of the monomeric thiols, but mitigate essentially completely the undesirable properties of the monomers, including offensive odour, volatility, and insolubility in aqueous solvents. This concept substantially enhances the number of potential practical applications of the thiol containing polymers as compared to the monomeric substances. A class of polyethylene glycols substituted with thiolactic acid or thioglycolic acid is described with potential in the pulp and paper industry, for the inhibition of radical induced oxidative processes including brightness reversion in lignin containing papers. Several techniques are used to elucidate aspects of the mechanism by which such thiols are effective: a novel photoacoustic technique demonstrates the scavenging effects of the thiol end capped polyethylene glycols towards alkoxy radicals. ESR studies demonstrate the ability of these thiol polymers to quench both the exogenous “phenoxy” radicals present in CTMP and TMP papers as well as the enhanced radical signal resulting from irradiation of these papers. The strong uv absorbance of these relatively persistent phenoxy radicals may decrease the optimal initial brightness of papers made from mechanical pulps.     

Thermal Analysis of Polypropylene Hydroperoxide

Studies on the low temperature oxidation of polyolefins have been the subject matter of several investigations because of interest in understanding the aging and weathering of polymers. One of the key steps in such an oxtdatton is the formation of hydroperoxide. Estimation of the hydroperoxide in oxidized samples, which is conventionally done by iodometric titrations, is quite important to gain knowledge about the kinetics and mechanism of the process. The present investigation is the first report of the thermal analysis of polypropylene hydroperoxide samples from two angles: (1) the thermal behavior of its decomposition and (2) whether such an analysis leads to knowledge of the concentration of hydroperoxide in the sample.     

The effect of thermal processing on PVC—Part V: The effect of thiotin stabilisers on heat and light stability

The stabilisation mechanisms of dibutyltin maleate (DBTM) and of dioctyltin bis(isooctyl thioglycollate) (DOTG) have been compared under conditions of thermal processing and photo-oxidation. DBTM and DOTG both function by neutralising evolved hydrogen chloride but DOTG has an additional ability to remove isolated double bonds, thus stabilising the polymer against further thermal oxidative degradation. During uv irradiation, DBTM functioned as a weak photo-stabiliser, whereas DOTG behaved as a photo-pro-oxidant, although it was an efficient colour stabiliser. The pro-oxidant effect is attributed to the rapid photolysis of sulphoxides formed by reaction of either the thioglycollate or the modified polymer with hydroperoxide.     

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.     

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.     

Electron paramagnetic resonance of ultraviolet-irradiated polyolefins

If films of polyolefins are ultraviolet-irradiated at liquid nitrogen temperature, alkyl radicals which can be examined by EPR are produced. No EPR spectra are observed from polyolefins irradiated at room temperature in air. Ultraviolet irradiation of polyolefins containing small alkyl side chains generally produces radicals corresponding to the pendant group or methyl radicals if the side chains contain a methyl branch. For some polymers the radical species could not be identified with certainty. Stabilization studies indicate that an optimum concentration of ultraviolet stabilizer is necessary for maximum stabilization of polyolefins. Preliminary results of EPR studies of the ultraviolet irradiation of various polyolefins are given, and some possible radical species are discussed.     

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.     

Molecularly imprinted polymer-based electrochemical sensors for biopolymers

Electrochemical synthesis and signal generation dominate among the almost 1200 articles published annually on protein-imprinted polymers. Such polymers can be easily prepared directly on the electrode surface, and the polymer thickness can be precisely adjusted to the size of the target to enable its free exchange. In this architecture, the molecularly imprinted polymer (MIP) layer represents only one ‘separation plate’; thus, the selectivity does not reach the values of ‘bulk’ measurements. The binding of target proteins can be detected straightforwardly by their modulating effect on the diffusional permeability of a redox marker through the thin MIP films. However, this generates an ‘overall apparent’ signal, which may include nonspecific interactions in the polymer layer and at the electrode surface. Certain targets, such as enzymes or redox active proteins, enables a more specific direct quantification of their binding to MIPs by in situ determination of the enzyme activity or direct electron transfer, respectively.     

Size-exclusion chromatography (SEC) of branched polymers and polysaccharides

Branched polymers are among the most important polymers, ranging from polyolefins to polysaccharides. Branching plays a key role in the chain dynamics. It is thus very important for application properties such as mechanical and adhesive properties and digestibility. It also plays a key role in viscous properties, and thus in the mechanism of the separation of these polymers in size-exclusion chromatography (SEC). Critically reviewing the literature, particularly on SEC of polyolefins, polyacrylates and starch, we discuss common pitfalls but also highlight some unexplored possibilities to characterize branched polymers. The presence of a few long-chain branches has been shown to lead to a poor separation in SEC, as evidenced by multiple-detection SEC or multidimensional liquid chromatography. The local dispersity can be large in that case, and the accuracy of molecular weight determination achieved by current methods is poor, although hydrodynamic volume distributions offer alternatives. In contrast, highly branched polymers do not suffer from this extensive incomplete separation in terms of molecular weight.     

Examination of polyolefins-organic compounds interactions by inverse gas chromatography

The investigations of interactions between polyolefins and test solutes at temperatures 58–122°C were carried out in the work. The test solutes were intentionally selected as representatives of the most important groups of compounds occurring in technological oils, which may be used as additives in conditions of industrial decomposition of polyolefins in Poland. For this purpose both the Flory-Huggins theory and inverse gas chromatography (IGC) were used. On the basis of retention data the values of both interaction and solubility parameters of analyzed polymers were determined. Solubility parameter δ and interaction parameter χ are related to some heat quantities e.g. excess free energy of mixing. It was observed influence of molecular mass and existence of chain branches on the values of the parameters. The obtained values allowed determination of influence of composition change of typical technological oils on their interactions with polymers and, at the same time, on course of charge preparation in these processes.     

Photostabilizing activity of tertiary hindered amines

The influence of the N-alkyl group of tertiary hindered amines on the photostabilization of polymers was studied. The photostabilizing effects of the tertiary amine derivatives of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine ( 1a ) in polypropylene were compared. All tertiary amine derivatives having α-H to hindered N showed higher effectiveness than 1a . Model liquid phase photoxidations were carried out by irradiating (UV-lamp) the solutions of tertiary hindered amines containing tert-butyl hydroperoxide as a photoinitiator. The tertiary hindered amines were oxidized more easily than corresponding parent hindered amine and converted to the parent amine, which was identified as its salt, resulting from the carboxylic acid produced from the N-alkyl group by oxidation. The thermal reaction of the tertiary hindered amines with tert-butyl hydroperoxide was also studied in the liquid phase. The tertiary hindered amines decomposed tert-butyl hydroperoxide more rapidly than the parent secondary hindered amine, and generated the parent amine. It was also found that the photostabilizing effects of tertiary hindered amines for polyolefins were higher than that of the parent secondary hindered amine.     

Photo-stabilising action of ortho-hydroxy aromatic compounds in polypropylene film: UV absorption versus radical scavenging

The relative importance of uv absorption and radical scavenging in the photo-stabilisation of polypropylene film by various concentrations of 4-methoxy and 4-n-octoxy substituted 2-hydroxybenzophenones and 2(2′-hydroxy-3′-t-butyl-5′-methyl phenyl)-5-chlorobenzotriazole is examined using infra-red and second-order derivative uv absorption spectroscopy and hydroperoxide analysis. Under both photolysis with polychromatic light wavelengths greater than 300 nm and photo-sensitised oxidation with monochromatic light of mainly 365 nm, the additives were considerably more effective photo-stabilisers when present in the polymer than when used as screens. Only under exposure to far uv light of 254 nm wavelength at 0·5 and 1·0% w/w of additives was any evidence of screening important. At 0·01% w/w concentration both the ortho-hydroxybenzophenones sensitised the photo-oxidation of the polymer and this correlated with higher concentration levels of hydroperoxide in the polymer films, confirming the pro-oxidant behaviour of these additives. Enhanced photo-protection by long n-alkyl groups in the 4-position of ortho-hydroxybenzophenones under photo-sensitised oxidation is associated with the lower mobility of the n-alkyl radical and cage effects in the polymer encouraging radical recombination. These conclusions are confirmed by solution photolysis experiments in the absence and presence of cumene hydroperoxide. The results clearly show that whilst reversible proton transfer may be important for protecting the additive itself, a mechanism involving uv absorption is of little or no importance in photo-stabilisation.     

Hindered Amine Light Stabilizers: A proposed photo-stabilization mechanism

Hindered amines are known to act as good photo-oxidative stabilizers for polymers, but controversy still surrounds the mechanism whereby this is achieved. The significance of complex formation between hindered amines and hydroperoxide groups in the mechanism is questioned, and the inability of hindered amines, or their nitroxide derivatives, to act as excited state quenchers is demonstrated. A mechanism involving complexation of trace transition metal impurities is proposed to account for the photo-stabilizing ability of these compounds.     

Oxidative destruction of polymers under mechanical load

An influence of tensile stress on the rate of oxidative destruction of polydienes and polyolefins under the action of ozone has been found; the influence of molecular and submolecular parameters and macrochain segmental mobility on the kinetics of oxidation of polymers is discussed. It is shown that chemical processes, with sp³ to sp² carbon atom rehybridization in the main chain, can change the reactivity of molecules under the action of structural deformations. Both acceleration and deceleration of bimolecular reactions have been found.     

Polyolefin/layered silicate nanocomposites with functional compatibilizers

Polymer nanocomposites containing layered silicates have been considered as a new generation of composite materials due to their expected unique properties attributed to the high aspect ratio of the inorganic platelets. Nevertheless, addition of layered silicates to polyolefins mostly results in phase separated systems because of the incompatibility of the silicates with the non-polar polyolefins. Functional compatibilizers are required to enhance the interactions and alter the structure from phase separated micro-composites to intercalated and exfoliated nanocomposites. Commercial macromolecular compatibilizers (mainly maleic-anhydride-functionalized polyolefins) are most commonly used to improve the interfacial bonding between the fillers and the polymers whereas specifically synthesized functional homopolymers or copolymers have been utilized as well. In this article, we are reviewing a number of investigations, which studied the influence on the composite structure of various parameters like the compatilizer to inorganic ratio, the type and content of the functional groups and the molecular weight of the functional additive, the miscibility between the matrix polymer and the compatibilizer, the kind of surfactants modifying the inorganic surface, the processing conditions, etc. The most important results obtained utilizing maleic-anhydride-functionalized polyolefins are discussed first, whereas a summary is presented then of the studies performed utilizing other functional oligomers/polymers. X-ray diffraction and transmission electron microscopy studies supported by rheology indicate that the most important factor controlling the structure and the properties is the ratio of functional additive to organoclay whereas the miscibility between the matrix polymer and the compatibilizer is a prerequisite.     

Advanced Characterization of Propylene-Based Copolymers and Olefin Block Copolymers

Summary: The newly developed interactive separation of polyolefins by high temperature liquid chromatography (HTLC) provides new information about the chemical composition distribution of polyolefin elastomers. The technique has the advantage of being quantitative in its separation, and has high resolution for the separation of polyolefins by their chemical composition without influence by cocrystallization. Chemical composition distributions can be determined for individual polymers and blends which contain the full range of comonomer typically present in polyethylene and poylypropylene homopolymers, semi-crystalline copolymers, and amorphous copolymers. HTLC analysis in combination with the other fractionation techniques, such as DSC, TREF, NMR, and xylene fractionation, can be used to estimate the amount of olefin block copolymer present in a block composite produced by chain shuttling catalysis.     

A multi-technique study of the spontaneous oxidation of N-hexane plasma polymers

Long-term compositional changes were observed when n-hexane plasma polymers were stored in air at ambient temperature. These post-deposition changes were monitored over periods exceeding one year using XPS, grazing angle FTIR, and SEM. A rapid initial increase in the oxygen content was followed by a slower oxygen uptake, which continued for many months. In contrast to the reported autocatalytic acceleration of the oxidation of polyolefins, the rate of oxidation of n-hexane plasma polymers was found to decrease continuously, and it did not proceed to the same extent toward higher oxidation states. The plasma polymer coatings did not show physical manifestations of oxidative degradation such as cracking, reduction in thickness, or loss of physical integrity. Comparison of the XPS and FTIR data suggested that the top few nanometers of the plasma polymer coatings oxidized at a faster rate than the “bulk.” The experimental data were interpreted using a model comprising reactions known from the oxidative degradation of polyolefins: carbon-centered radicals, trapped in the course of the plasma deposition, combine with atmospheric oxygen to form metastable peroxy radicals and hydroperoxides, which decompose to generate a variety of stable product groups such as hydroxyl, carbonyl, and carboxylic groups. There was broad agreement between the XPS data and the time dependence of particular species in model calculations. © 1994 John Wiley & Sons, Inc.     

Tailor-made polymers through selective modification

Despite being generally regarded as “mass materials” without a high degree of sophistication in public, plastics are revolutionizing our life with new innovations on a day-to-day basis. While stunning developments like self-healing polymers or high-performance nanocomposites are still in a basic phase of their development, recent years have seen “commodity” materials like polyolefins evolving into performance polymers with a variety of technically demanding applications. This has become possible through a selective modification of the material properties on all structural and productional levels: Catalyst and chain structure, copolymerisation and phase morphology, conventional and reactive compounding, processing and crystallinity. A state-of-art review and an outlook on future developments for polyolefins in general, but polypropylene in particular, is given.     

Vapor phase oxidative synthesis of conjugated polymers and applications

Since their discovery, electrically conductive polymers have gained immense interest both in the fields of basic and applied research. Despite their vast potential in the fabrication of efficient, flexible, and low‐cost electronic and optoelectronic devices, they are often difficult to process by wet‐chemical methods due to their very low to poor solubility in organic solvents. The use of vapor‐based synthetic routes, in which conductive polymers can be synthesized and deposited as a thin film directly on a substrate from the vapor phase, provides many unique advantages. This article discusses oxidative vapor deposition processes, primarily vapor phase polymerization and oxidative chemical vapor deposition, of conjugated polymers and their applications. The mild operating conditions (near room temperature processing) allow conformal and functional coatings of conjugated polymers on delicate substrates. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012