Determination of polymer additives using analytical pyrolysis

When analyzing a polymeric material using pyrolysis-GC, the majority of the peaks seen are degradation products from the polymer matrix, but there may be specific compounds present resulting from the presence of antioxidants, plasticisers, stabilizers, flame retardants and other additives. Some of these compounds may be volatile or semi-volatile and appear as intact molecules, while others are larger and only appear as fragments after the pyrolysis. In understanding the pyrolysis of the complete system, it is important to understand the behavior of such additives under the thermal conditions used to analyze the polymer matrix.This paper presents data for several polymer additives, showing their contribution to the analytical results when studying typical polymers using Py-GC/MS. Specific types of additives include phenolic antioxidants, hindered amine light stabilizers, phthalates and phosphites.It was determined that for some additives, especially when analyzing simple polymers, co-analysis of the polymer and additive was feasible. For other, more complex formulas, a multi-step approach permitted a thermal separation of compound families and simplified the analysis. For some additives, especially in the parts-per-million range, pyrolysis with selected or extracted ion mass spectrometry was the most informative.     

Polymeric p-benzoquinone–tin derivatives as thermal stabilizers for rigid poly(vinyl chloride). II. Evaluation of the stabilizing efficiency

The polymeric p-benzoquinone-tin derivatives obtained from the reaction of p-benzoquinone with tin tetrachloride in the absence of solvent have been investigated as thermal stabilizers for rigid PVC at 200°C by measuring the rate of dehydrochlorination. The results reveal the greater stabilizing efficiency of the investigated products in relation to dibutyltin maleate and the basic lead stabilizers commonly used in industry. Evidence has been accumulated that the quinone and metallic elements (Sn? Sn bonds) of the stabilizer participate in the stabilization process by trapping the radical intermediates of degradation and blocking the odd electron sites formed on the polymer chains. Although stabilizers with high quinone content provide greater stabilization in the early stages of degradation, their efficiency sharply decreases in subsequent stages. On the other hand, stabilizers of high tin content effectively prohibit the dehydrochlorination reaction at all stages of degradation. On an equivalent basis of metal content, the results clearly demonstrate the greater stabilizing efficiency of tin atoms when found in direct contact in the stabilizer molecule. The mechanism of stabilization suggested to account for the results obtained may be considered as additional evidence in support of the radical nature of the dehydrochlorination reaction.     

Quantum mechanical criteria for choosing appropriate voltage stabilization additives for polyethylene

One of the major application fields for solid dielectric polymers is their use as insulating materials for power cables. Since the electrical aging of the insulating polymeric materials is one of the most important factors affecting the service lifetime of power cables, developing a model which can be used to design materials with an improved resistance to electrical degradation would be highly beneficial. We developed a model for the electrical field within the polymer material contaminated with a sharp conducting defect (a metallic needle) and defined a parameter characterizing the resistance of polymer to electrical treeing. The model was used to analyse data for the electrical degradation of polyethylene stabilized with polycyclic aromatic hydrocarbons. Based on quantum mechanically calculated electron affinities and ionisation potentials of the stabilizer molecules, we discovered that if a molecule is to be considered for voltage stabilization use it has to have a specific combination of the ionisation potential and adiabatic electron affinity. The model allows for a choice of appropriate voltage stabilizers based on theoretical calculations only and can help to facilitate any experimental study for choosing appropriate voltage stabilizer additives.     

Effect of natural antioxidants on the stability of polypropylene films

A preliminary study on the efficiency of agri-food industry wastes as stabilizers for polypropylene (PP) films is reported. Several analytical techniques were employed to evaluate the stabilization effectiveness of the additives. DSC and CL analysis performed on unaged samples confirmed the antioxidant activity of natural additives, and provided the following order of efficiency: red grape seeds > white grape seeds > tomato extracts. The films were also artificially aged at 70 °C, and FTIR spectroscopy confirmed the stabilization trend obtained from the unaged films. Kinetic analysis of TG data alongside tensile tests indicated that the tomato extract is a good thermal and processing stabilizer, but it is sensitive to oxidation. In contrast, grape seeds provide long-term stabilization to PP under conditions of oxidative degradation. Our results show that tomato and wine processing by-products have good potential to be exploited as a low-cost source of value-added phytochemicals.     

Synergistic effect of maleimido phenyl urea derivatives mixed with some commercial stabilizers on the efficiency of thermal stabilization of PVC

Four novel antimicrobial maleimido phenyl urea stabilizers 1–4 were synthesized from N-[4-(chlorocarbonyl) phenyl] maleimide with phenyl urea and its derivatives (p-methyl, o-chloro and p-carboxy). The effect of mixing maleimido phenyl urea stabilizer 2 with each of the reference stabilizers, dibasic lead carbonate (DBLC), cadmium-barium-zinc stearate (Cd-Ba-Zn stearate) or n-octyltin mercaptide (n-OTM), on the stabilization efficiency in thermal degradation of rigid PVC at 180 °C in air, has been investigated. Mixing was effected in the range of 0–100 wt% of stabilizer 2 relative to each of the reference stabilizers. The stabilizing efficiency was evaluated by measuring the length of the thermal stability period (Ts), the period during which no detectable amount of hydrogen chloride gas could be observed, and also from the rate of dehydrochlorination as measured by continuous potentiometric determination, and by the extent of discoloration of the degraded polymer samples. The results show a true synergistic effect from the combination of stabilizer 2 with any of the reference stabilizers. Mixing of the stabilizers improves the Ts values, decreases the rate of dehydrochlorination and lowers the extent of discoloration of the polymer. The maximum synergism was attained when stabilizer 2 is mixed with either of the three reference stabilizers in equivalent weight ratio (50%/50%). The observed synergism may be attributed to the different mechanisms by which the investigated and the reference stabilizers work.     

Influence of typical stabilizers on the aging behavior of EVA foils for photovoltaic applications during artificial UV-weathering

Ethylene vinyl acetate copolymer (EVA) is the most commonly used embedding material in crystalline silicon photovoltaics. It is responsible for fixing module components, electrical isolation and protecting cells against mechanical and environmental stresses. The degradation of EVA during weathering can cause adhesion loss, the so called delamination, and yellowing of the foil, resulting in a drop of module efficiency. In order to improve the long-term stability, several stabilizers including UV-absorber, hindered amine light stabilizer and phosphite are added to the polymer. However, the exact influence of the different stabilizers on failure mechanisms has not yet been identified in detail. Therefore, different EVA foils containing variable additive formulations were exposed to artificial UV-irradiation at 50 °C. As a result, delayed EVA degradation could be observed depending on stabilizers added. On the other hand, some of the tested additives were found to be involved in delamination and yellowing processes.     

Design of Drug-Like Protein–Protein Interaction Stabilizers Guided By Chelation-Controlled Bioactive Conformation Stabilization

Protein–protein interactions (PPIs) of 14-3-3 proteins are a model system for studying PPI stabilization. The complex natural product Fusicoccin A stabilizes many 14-3-3 PPIs but is not amenable for use in SAR studies, motivating the search for more drug-like chemical matter. However, drug-like 14-3-3 PPI stabilizers enabling such studies have remained elusive. An X-ray crystal structure of a PPI in complex with an extremely low potency stabilizer uncovered an unexpected non-protein interacting, ligand-chelated Mg²⁺ leading to the discovery of metal-ion-dependent 14-3-3 PPI stabilization potency. This originates from a novel chelation-controlled bioactive conformation stabilization effect. Metal chelation has been associated with pan-assay interference compounds (PAINS) and frequent hitter behavior, but chelation can evidently also lead to true potency gains and find use as a medicinal chemistry strategy to guide compound optimization. To demonstrate this, we exploited the effect to design the first potent, selective, and drug-like 14-3-3 PPI stabilizers.     

Studies on the Stabilization of Modified Lyocell Solutions

Additives with functional properties makes the Lyocell process a versatile tool for the creation of new innovative materials beyond the textile sector. Occupying functional groups or active surfaces the additives emphasize the suitability of Lyocell fibers, but simultaneously enhance the complexity of chemical reactions in cellulose/N-methylmorpholine-N-oxide (NMMO) solutions, respectively. Concerning to the concentration acidic ion exchange resins, activated charcoals, carbon black etc. shift the start of decomposition to lower temperatures, decrease the viscosity, enhance the formation of amines as the main degradation products or cause autocatalytic reactions. New routes in stabilization of modified Lyocell solutions applying a polymeric stabilizer system are described. Using calorimetric, UV/VIS, ESR and HPLC analysis the degradation processes and thermal stability of modified Lyocell solutions compared to the unstabilized were studied. Moreover, as kinetic investigations show a distinguished behavior for modified solutions autocatalytic reactions can be suppressed by the stabilizing system. ESR kinetic study of radicals reveals that formation and recombination rates of radical reactions depend on cellulose concentration in Lyocell solutions and additional ingredients.     

Monitoring the degradation of stabilization systems in polypropylene during accelerated aging tests by liquid chromatography combined with atmospheric pressure chemical ionization mass spectrometry

Degradation pathways of three commonly used antioxidants were successfully studied by using accelerated aging tests for polymers. Additionally, thermal stability and resistance to discoloration of seven stabilizers were investigated by aging pure stabilizers dissolved in the polymer-mimicking solvent squalane. Methods based on high-performance liquid chromatography hyphenated with highly sensitive tandem mass spectrometric detection (HPLC-MS) were developed for structural elucidation of degradation products. Subsequent quantification was done using UV-detection. While Irganox 1330, Irganox 3114 and Cyanox 1790 showed a similar degradation mechanism with highly colored decomposition products, no corresponding oxidized species could be found for other stabilizers and less discoloration was observed. For Irganox 1010, hydrolysis was the preferred degradation mechanism, leading to products with an increased solubility in water. Therefore this stabilizer is less suitable for materials intended for water applications. In the aged materials previously unknown degradation mechanisms were observed for Irganox 1010 and Irgafos 168 which also contribute to the inhibition of autoxidation of the polymer.     

How will additives shape the future of plastics?

Additives are essential components of plastic formulations providing maintenance and/or modification of polymer properties, performance and long-term use. The extension of polymer properties by additives has played a substantial role in the growth of plastics. At the beginning of the plastics age additives were used mainly to maintain polymer properties and to help plastics to survive heat treatment during transforming processes. The next generation of additives provided extension of service life as well as modification of mechanical and physical properties. These well-established additives - antioxidants, heat stabilizers, light stabilizers and others - cover the requirements of standard plastics and today's mass applications. The more recent developments of high-performance additives address more stringent or new requirements, more severe processing and use conditions and/or environmental concerns, but still with the main target of maintaining plastic properties. The future will introduce more and more new effects and functionalities through additives in plastic applications tailoring the properties of polymers and offering a vast potential of innovation in the plastics area. Recent examples of emerging technologies show that additives will not only modify the polymer itself and add new properties, but can also, when incorporated into the plastic, beneficially impact properties, which are of high value for the user. The paper shows the role of additives used in plastics from the past to the present with the focus on stabilization and performance of additives incorporated during melt processing, and outlines future trends.     

Additives for controlled degradation of agricultural plastics: ENVIROCARETM

ENVIROCARE^TM additives are specialty chemicals that can be added to conventional thermoplastic polymers to obtain degradable agricultural plastic articles. Their main benefits are connected with their possible incorporation in “commodity plastics”. This allows the production of degradable agriculture plastic articles processable with standard manufacturing machines, without negative effects on the main properties of the plastic article and with evident costs advantages. Furthermore, required outdoor exposure lifetimes for different articles and different environmental conditions can be modulated with the incorporation of the appropriate additive loading in the plastic and with combinations of selected stabilizers. Mulch films, small tunnel films, banana bags and sleeves, direct covers, non-woven, ropes, twines and pots are convenient agricultural applications for this technology. ENVIROCARE^TM products induce plastic degradation following a two steps mechanism: first the plastic is photo- and thermo-oxidized during the outdoor exposure; once the degradation process has been activated by light or heat, ENVIROCARE^TM acts by increasing the degradation rate and degradation continues until the article is totally degraded. Since degradation is both photolytically and thermally triggered, degradation occurs both at the surface and in the soil. Experimental laboratory results allow the assessment of the contribution of different important parameters - i.e. type of polymer, type of article, presence of other stabilizers/additives or pigments, different environmental conditions- on the control of the article lifetime and degradation. Field exposure in different environments integrates the test results and allows for the design of the additive systems adapted to the specific needs.     

The effect of hindered amine light stabilizers on the photooxidative stability of high-density polyethylene

The photoprotective effectiveness of various polymeric and nonpolymeric hindered amine light stabilizers (HALS) was determined by exposing samples of high-density polyethylene (HDPE) containing these additives to ultraviolet (UV) light and measuring the resultant oxygen uptake characteristics. Values of the initial quantum yield for oxygen uptake calculated for these formulations indicate that the higher molecular weight HALS compounds are less effective photostabilizers than the nonpolymeric HALS, and this is partly attributable to their decreased mobility in the polymer matrix. It was further found that the addition of an ultraviolet absorber (UVA) to a formulation containing a polymeric HALS compound enhances its photostability, although this phenomenon may be partly due to synergism between the UVA and the antioxidant, the latter having been added as part of the base stabilization. The antagonism which exists between certain sulfur-containing antioxidants and HALS compounds was also investigated and it was found that the lower molecular weight sulfur-containing antioxidants exhibit the greatest degree of antagonism. The results confirm that the mobility in the polymer matrix of the stabilizer system can serve as an explanation of its effectiveness. The article provides evidence that the technique of oxygen uptake monitoring is a sensitive and rapid method of assessment of polymer photostability in the presence of stabilizer systems.     

Separation and characterization of oligomeric hindered amine light stabilizers using high‐performance liquid chromatography with UV and quadrupole time‐of‐flight mass spectrometric detection

Hindered amine light stabilizers are an important class of stabilizers that protect synthetic polymers from degradation and thus from changing mechanical and optical properties. The current study presents an HPLC method capable of separating oligomeric hindered amine light stabilizers on a commercially available stationary phase, employing an MS‐compatible novel mobile phase. Based on the exact masses observed with Q‐TOF‐MS, a comprehensive characterization of five different types of oligomeric hindered amine light stabilizers was achieved, leading to structural information not included in the datasheets provided by the suppliers. For the different investigated hindered amine light stabilizers, a number of recurring units up to 17 and a molecular weight of 5200 g/mol were detected. Furthermore, the analysis of stabilizer extracts of processed polypropylene samples containing different types of hindered amine light stabilizers revealed significant differences in the oligomeric pattern between standards and polymer samples. Thus, changes in the analytes’ oligomeric pattern resulting from processing or aging of polymer materials can be monitored with the presented method.     

Effect of stabilizer and pigment on photodegradation of polypropylene as revealed by macromolecule scission and crosslinking measurements

Photodegradation depth-profiles have been generated using computer-aided molecular weight distribution analysis for 3 mm thick polypropylene injection moldings containing (i) a stabilizing package that included hindered amine light stabilizers and a phenolic stabilizer, (ii) titanium dioxide pigment and (iii) both the pigment and the stabilizing package. The inhibiting effect of the additives has been determined quantitatively by comparing macromolecule scission and crosslinking rates with those in samples containing no stabilizer or pigment. TiO₂ pigment gave more effective protection against molecular degradation than the stabilizer package; there was very little advantage to be gained by adding stabilizer when the pigment was present. The inhibition caused by having pigment or stabilizer present was measured to be very large: degradation was reduced by at least a factor of 10 and often by a factor of several hundred times. The relative amount of scission and crosslinking differed according to the additives present and the depth from the exposed surface: high reaction rates favoured scission and lower reaction rates resulted in a higher relative crosslinking concentration.     

SYNTHESIS AND CHARACTERIZATION OF NEW STABILIZERS WITH OPTIMAL MOLECULAR WEIGHT*

Over 2×10~8 tons of polymers are produced every year, and a large portion of polymers faces the degradationproblem. There are many effective methods to protect polymers against degradation and the addition of stabilizers to polymerremains the most convenient and effective way of enhancing polymer life and performance. In this article, a series of effectivestabilizers with optimal molecular weight (MW), including common, monomeric and polymeric stabilizers (antioxidant andlight stabilizer) were synthesized using isocyanation, controlled isocyanation, hydrosilylation, epoxide addition, macro-reaction of stabilizing functional compounds and polymerization of monomeric stabilizers. The structure and performance ofthese new stabilizers were characterized by using IR, NMR, MS, UV-spectra XPS and elemental analysis. The currentdevelopment of stabilizer synthesis was also reviewed.     

Effects of reprocessing of oxobiodegradable and non-degradable polyethylene on the durability of recycled materials

The use of plastics is steadily increasing in our daily lives, and plastics are the fastest-growing component of the waste stream. Although the efficiency of plastic recycling is increasing, plastics are often seen as a permanent environmental problem because of littering. The introduction of oxobiodegradable polyolefins (OBDs), containing prodegradant additives, is considered to be a way to reduce this problem by enabling the fast degradation of plastics in the environment. The prodegradant additives form radicals that attack the polymer chains, causing chain scissions and generation of low molecular mass oxidation products that can be consumed by microorganisms. There is, however, a concern that the prodegradant additives will present a problem if OBD materials end up in the conventional plastic recycling streams. The present study therefore highlights the impact of mixing OBD materials with conventional polyolefins to evaluate the impact on the remaining service life of the recyclates.The study included the use of two different OBDs, mixed in different proportions (10% and 20%) in a conventional polyethylene. The remaining service life of the mixtures was evaluated by monitoring the reduction in tensile strain after exposure to thermo-oxidative degradation at 70 °C, compared with a pure polyethylene. The impact of stabilizer content in the mixtures was also evaluated together with the effect of mixing partially degraded OBDs into the recyclate.The results show that the incorporation of minor fractions of OBD materials in the existing recycling streams will not create a severe effect on the service life of the recyclates as long as the polymer mixture possesses a reasonable degree of stabilization.     

Synthesis and properties of new adducts of 2,2,6,6-tetramethylpiperidine and 2-hydroxyphenylbenzotriazole as polymer photostabilizers

The synthesis of new stabilizer type compounds (a combination between 2,2,6,6-tetramethylpiperidine and 2-hydroxyphenylbenzotriazole in one molecule) is reported. Three new polymerizable combined stabilizers as well as one unsaturated triazinyl-2,2,6,6-tetramethylpiperidine and three unsaturated triazinyl-2-hydroxyphenylbenzotriazoles as individual stabilizers were synthesized. Their copolymers and the terpolymers of the individual stabilizers with methyl methacrylate (MMA) were obtained. Chemical bonding of the stabilizers in the polymer was confirmed spectrophotometrically. The influence of these additives on the photostability of the copolymers was studied. The participation of the combined stabilizers in the polymerization did not affect considerably the rate of copolymerization, the molecular weight and polydispersity of the copolymers. A significant stabilizing effect against photodegradation was determined.     

Loss of light stabilizers from polypropylene

Loss of light stabilizers. related to 2-hydroxybenzophenone and 2-(2-hydroxyphenyl) benzotriazole. from isotactic polypropylene was measured over the range 60–120° and during storage at 25'. The light stabilizer content in polypropylene corresponded to that used in practice. The rate constants and the activation energy were calculated from the rate of loss. The influence of the structure of stabilizer on the rate of loss from polymer is discussed. The losses of stabilizers from polymer were compared with the vapour pressure of stabilizers and with the losses of stabilizers alone at 280. The rate of diffusion of stabilizers to the surface of polypropylene and the rate of even evaporation may cause a rapid diminution of stabilizer or undesirable accumulation on the polymer surface.     

Effect of chlorinated fire-retardant additives on the thermal degradation of polypropylene

Modifications in the thermal degradation mechanism of polypropylene caused by interactions between the degrading polymer, a chloroparaffin and bismuth carbonate (typical fire retardant additives) are studied.Preliminary TVA and pyrolysis-GLC results show that volatilisation of the polymer occurs at lower temperatures with production of a larger proportion of higher boiling chain fragments in the mixture than in the pure polymer.The products of a strongly exothermal reaction occurring when the two additives are heated together, as shown by DTA and TG, could play an important role in modifying the thermal degradation behaviour of polypropylene in the mixture.     

BREAKTHROUGH CHEMISTRY FOR PROCESSING STABILIZATION OF POLYPROPYLENE

Traditional stabilization systems for polypropylene are typically based on a binary combination of a phenolic antioxidant and a phosphorus based melt processing stabilizer. The phenolic antioxidant provides melt processing stability as a hydrogen atom donor and free radical scavenger; it also provides the polymer with some desired level of short-term or long-term thermal stability, simply for storage or throughout the lifetime of the final article. The phosphorus based melt processing stabilizer, usually a phosphite or phosphonite, functions as a hydroperoxide decomposer above the melting point of the polymer, during melt compounding and processing. Both chemistries work together synergistically to help maintain the original molecular architecture of the polymer.

Recently, a new class of additives, 3-aryl-benzofuranones (lactones) has been introduced and adopted commercially. Lactones are highly efficient at scavenging both carbon and oxygen centered radicals during melt processing of polyolefins. Investigations have been underway to examine the impact of low concentrations of lactone in regard to enhancing the performance of traditional stabilization systems. The presumed stabilization mechanism of a lactone and the optimum composition of ternary stabilizer blends for polypropylene are discussed.