HDPE chemical recycling promoted by phenol solvent

The thermal cracking of HDPE in the presence of different amounts of phenol has been studied and compared with the reaction carried out without this solvent. HDPE conversion is enhanced with the amount of solvent, reaching a value of nearly 100% using a 1/10 HDPE/phenol ratio. The yield of the gaseous hydrocarbons also rose with the amount of phenol, olefins being the main products in this fraction. In all reactions, the main products of the C₅–C₃₂ fraction were linear hydrocarbons such as n-paraffins and α-olefins. The yields of both hydrocarbons increased in line with the amount of phenol. However, the increase was more significant in the case of α-olefins. All these results indicate that the phenol promotes the plastic degradation, enhancing the HDPE conversion and facilitating the formation of specific products. A reaction mechanism is proposed to explain these results, indicating random scissions and chain reactions which are favoured by the presence of this solvent during the HDPE thermal degradation.     

Fuels obtained by thermal cracking of individual and mixed polymers

Utilization of oils/waxes obtained from thermal cracking of individual LDPE (low density polyethylene), HDPE (high density polyethylene), LLDPE (linear low density polyethylene), PP (polypropylene), or cracking of mixed polymers PP/LDPE (1: 1 mass ratio), HDPE/LDPE/PP (1: 1: 1 mass ratio), HDPE/LDPE/LLDPE/PP (1: 1: 1: 1 mass ratio) for the production of automotive gasolines and diesel fuels is overviewed. Thermal cracking was carried out in a batch reactor at 450°C in the presence of nitrogen. The principal process products, gaseous and liquid hydrocarbon fractions, are similar to the refinery cracking products. Liquid cracking products are unstable due to the olefins content and their chemical composition and their properties strongly depend on the feed composition. Naphtha and diesel fractions were hydrogenated over a Pd/C catalyst. Bromine numbers of hydrogenated fractions decreased to values from 0.02 g to 6.9 g of Br₂ per 100 g of the sample. Research octane numbers (RON) before the hydrogenation of naphtha fractions were in the range from 80.5 to 93.4. After the hydrogenation of naphtha fractions, RON decreased to values from 61.0 to 93.6. Diesel indexes (DI) for diesel fractions were in the range from 73.7 to 75.6. After the hydrogenation of diesel fractions, DI increased up to 104.9.     

高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物共混体系的结晶行为

通过ＤＳＣ和ＷＡＸＤ研究了高密度聚乙烯／低密度聚乙烯／乙烯－醋酸乙烯共聚物（ＨＤＰＥ／ＬＤＰＥ／ＥＶＡ）三元共混体系的热行为和结晶性能。发现当ＨＤＰＥ含量小于４０％时，ＥＶＡ对ＬＤＰＥ起稀释剂作用，促进ＨＤＰＥ、ＬＤＰＥ的晶相分离，使ＨＤＰＥ、ＬＤＰＥ单独结晶．当ＨＤＰＥ含量高于４０％时，ＬＤＰＥ片晶进入ＨＤＰＥ晶相。形成与ＬＤＰＥ在片晶水平上的共晶。     

Copyrolysis of naphtha with polyalkene cracking products; the influence of polyalkene mixtures composition on product distribution

The steam cracking (copyrolysis) of naphtha with oils/waxes from thermal decomposition of polyalkenes has been investigated as a process for chemical recycling of plastic wastes. High-density polyethylene (HDPE), two-component mixture (LDPE/PP) and three-component mixture (HDPE/LDPE/PP) were thermally decomposed in a batch reactor at 450 °C, thus forming oil/wax products. Subsequently, these products were dissolved in heavy naphtha in the amount of 10 mass% to obtain steam cracking feedstock. The composition of gaseous and liquid products during copyrolysis was studied at 780 °C and 820 °C in dependence on residence time from 0.08 s to 0.51 s. The obtained results were compared with the product composition from steam cracking of naphtha at identical experimental conditions. The decomposition of polyalkene oils/waxes during copyrolysis was confirmed on the basis of analysis of liquid products. It was shown that more ethene and propene was formed during copyrolysis of oil/wax from HDPE in comparison with naphtha and both mixtures and so oil/wax from HDPE seems to be favourable component of steam cracking feedstock. There were slight differences between product compositions from copyrolysis of two- and three-component mixtures. The presence of HDPE in three-component mixture supported formation of gas and ethene. The presence of oil/wax form PP enhanced formation of propene and branched alkenes. For both type of polyalkenic mixtures the yields of desired low molecular alkenes and alkanes were higher or approximately the same as from naphtha. The results confirm suitability of oils/waxes from polyalkenes as a co-feed for steam cracking units.     

Investigation of catalytic degradation of high-density polyethylene by hydrocarbon group type analysis

Catalytic degradation of waste high-density polyethylene (HDPE) to hydrocarbons by ZSM-5, zeolite-Y, mordenite and amorphous silica–alumina were carried out in a batch reactor to investigate the cracking efficiency of catalysts by analyzing the oily products including paraffins, olefins, naphthenes and aromatics with gas chromatography/mass spectrometry (GC/MS). Catalytic degradation of HDPE with zeolite-Y, mordenite and amorphous silica–alumina yielded 71–82 wt.% oil fraction, which mostly consisted of C₆–C₁₂ hydrocarbons, whereas ZSM-5 yielded much lower 35% oil fraction, which mostly consisted of C₆–C₁₂ hydrocarbons. Both all zeolites and silica–alumina increased olefin content in oil products, and ZSM-5 and zeolite-Y particularly enhanced the formation of aromatics and branched hydrocarbons. ZSM-5 among zeolites showed the greatest catalytic activity on cracking waste HDPE to light hydrocarbons, whereas mordenite produced the greatest amount of coke. Amorphous silica–alumina also showed a great activity on cracking HDPE to lighter olefins in high yield, but no activity on aromatic formation.     

Thermal degradation behaviour of radiation grafted FEP-g-polystyrene sulfonic acid membranes

The thermal degradation behaviour and the gaseous products of FEP-g-polystyrene sulfonic acid membranes prepared by radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films and the subsequent sulfonation were studied using thermal gravimetric analysis coupled with Fourier transform infrared spectrometry (TGA/FTIR). The membranes were found to have a three-step degradation behaviour due to water removal, elimination of sulfonic acid groups and decomposition of the FEP matrix. The evolving gaseous products were identified using FTIR analysis. The degree of grafting was found to have a strong effect on the weight loss in the membranes, whilst the degradation temperatures of the individual membrane components were shown to be independent of the degree of grafting.     

Separation and characterization of products from thermal cracking of individual and mixed polyalkenes

Low-density polyethylene (LDPE), polypropylene (PP), and their mixture in the mass ratio of 1: 1 (LDPE/PP) were thermally decomposed in a batch reactor at 450°C. The formed gaseous and oil/wax products were separated and analyzed by gas chromatography. The oils/waxes underwent both atmospheric and vacuum distillation. Densities, molar masses and bromine numbers of liquid distillates and distillation residues were determined. The first distillate fraction from the thermally decomposed LDPE contained mostly linear alkanes and alk-1-enes ranging from C₆ to C₁₃ (boiling point up to 180°C). The second distillate fraction was composed mostly of hydrocarbons C₁₁ to C₂₂ (boiling point up to 330°C). 2,4-Dimethylhept-1-ene was the major component of the first distillate fraction obtained from the product of PP decomposition, while in the 2nd distillate fraction it was 2,4,6,8-tetramethylundec-1-ene. The yields of some gaseous or liquid hydrocarbons obtained by distillation from thermally degraded LDPE/PP differed from the values corresponding to the decomposition of individual plastics due to the mutual influence of polyalkenes during their thermal cracking. Similarly, the yields of propene and methylpropene in the gaseous phase were higher in the case of mixture. Whereas the content of C₉ to C₁₇ alkanes and alkenes in the distillates separated from the liquid mixture obtained by the decomposition of LDPE/PP decreased, the formation of 2,4,6,8,10,12-hexamethylpentadec-1-ene remained unchanged. The corresponding mechanisms of thermal cracking were discussed.     

Combined thermogravimetry and fourier transform infrared spectroscopy techniques for gas evolution analysis

The usefulness of thermogravimetry has been amply demonstrated for a wide variety of material analysis applications. In many instances, however, additional information is required for adequate characterization of the sample and its thermal decomposition behaviour. In this respect, the analysis of evolved gases, or condensed liquids, has proven a highly useful approach. Among the various physical methods used for analysis of the thermal degradation products, infrared spectroscopy has often been found very powerful, being versatile, rapid and widely accessible. In this study, we report a simple new approach in which the evolved gases and condensed liquids from the thermal decomposition of various products are recuperated in an infrared gas cell and on a PVC membrane filter, respectively. The gaseous components were analysed by transmission FT-IR, and the condensed liquid products were examined directly on the PVC membrane by FT-IR in the internal reflexion mode. The technique was used, for example, to examine the pyrolysis products (gases and liquid) of Koberit, a proposed substitute for asbestos. The method was also applied to the study of chemically derivatized asbestos materials in an attempt to unravel the surface chemical modifications.     

Thermal degradation of polyethylene

Thermal degradation of low-density polyethylene (LDPE) in the temperature range from 450 to 525°C has been studied using a sieve-bottom reactor with inert gas as heat-transferring agent bubbled through the PE melt. Temperature dependence of the degradation rate was determined. Full degradation of LDPE into gaseous and wax-like hydrocarbons (alkanes and 1-alkenes) was achieved. Temperature rise and prolonging of the contact time increased the yield of the gaseous hydrocarbons and decreased the molecular weight of the wax-like product.     

A comparative study on thermal and catalytic degradation of polybutylene terephthalate

A comparative study on the thermal and catalytic degradation of polybutylene terephthalate (PBT) at atmospheric pressure was conducted. The weight loss of PBT under thermal degradation was significantly influenced by the temperature between 360 °C and 380 °C, but little affected by the PBT particle size. Four groups of catalysts include metal chloride, metal oxide, metal acetate, and metal copper powder were used to test PBT degradation activity. Copper (II) chloride is the most active one for increasing the percentage PBT weight loss more than 100% in comparison with the result of thermal degradation at a temperature of 360 °C for 30 min. PBT and catalyst mixtures can be prepared by impregnation and physical method, the former resulted in a better PBT degradation. The percentage PBT weight loss in the presence of CuCl₂ increased steadily between 320 °C and 380 °C which was different from the results of thermal degradation. The time for obtaining a same percentage PBT weight loss reduced effectively when compared to the catalytic to thermal degradation. The weight ratio of CuCl₂/PBT was tested between 0 and 0.2 and the optimal ratio was 0.1. The gaseous product distribution analyzed by GC/MS for PBT thermal and catalytic degradation revealed almost the same and the major products were ethane, carbon monoxide, carbon dioxide, 1-butene, 2-butene, 1,3-butadiene, and butadiene dimmer. But the relative abundance of major products was changed, especially for 1,3-butadiene increased dramatically, and a new chlorocompound was produced in catalytic degradation. In condensed liquid product, both the number and the molar mass of components were more and greater than that of in gaseous product and 4-heptylacetophenone was the most abundance product. In PBT catalytic degradation, 4-heptylacetophenone and some products were decreased and some even disappeared completely while the abundance of benzoic acid increased and three new products were generated.     

Rare-earth-catalyzed C-H bond addition of pyridines to olefins

An efficient and general protocol for the ortho-alkylation of pyridines via C-H addition to olefins has been developed, using cationic half-sandwich rare-earth catalysts, which provides an atom-economical method for the synthesis of alkylated pyridine derivatives. A wide range of pyridine and olefin substrates including α-olefins, styrenes, and conjugated dienes are compatible with the catalysts.     

The effect of fullerene on the resistance to thermal degradation of polymers with different degradation processes

Investigations were made about the effect of fullerene (C₆₀) on the resistance to thermal degradation of high density polyethylene (HDPE), polypropylene (PP), polymethyl methacrylate (PMMA), and bisphenol A polycarbonate (PC) matrix by using thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. The results showed that the influences of C₆₀ on the resistance to the thermal degradation of different polymers were dependent on their thermal degradation mechanism. The resistance to the thermal degradation of HDPE, PP, and PMMA were improved with the addition of C₆₀, especially for HDPE matrix, which indicated that the radical trapping played a dominant role. PP and PMMA released more gaseous products at high temperature by the random scission of C–C backbone; owing to the lower bond dissociation energy of C–C in the backbone for the existence of side chains. Meanwhile, the steric hindrance of side chains also made the radicals hard to recombine with each other and accelerated the random scission, leading to the less effect on the resistance to the thermal degradation of PP and PMMA. However, few changes of resistance to the thermal degradation were found in PC matrix with the addition of C₆₀ for its non-radical degradation mechanism.     

Thermal behavior of polystyrene synthesized in the presence of carboxymethyl cellulose

Summary Study of the decomposition kinetics is an important tool for the development of polymer recycling in industrial scale. In this work, parameters such as activation energy, frequency factor and reaction order, were measured under dynamic conditions. Flynn-Wall-Ozawa, Van Krevelen, Horowitz-Metzger, Coats-Redfern, Madhusudanan and Vyazovkin methods were used to determine the kinetic parameters. The analysis of the results obtained by the Coats-Redfern method shows that the thermal degradation process of LDPE and HDPE corresponds to a phase boundary controlled reaction (mechanism R2). This method shows that the reaction order values of LDPE and HDPE are about 0.7 and 0.6, respectively.     

The effect of orientation on the radiation induced degradation of polymers

A study has been made of the effect of orientation on the oxidative degradation of poly(vinylchloride) (PVC), low density polyethylene (LDPE) and high density polyethylene (HDPE) under the influence of γ- and u.v.-radiation. The effect of drawing in PVC is to increase the rate of oxidative degradation; in LDPE and HDPE, this rate decreases (especially for HDPE) both under u.v. and γ-radiation.     

Tear anisotropy in films blown from polyethylenes of different macromolecular architectures

Blown films of different types of polyethylenes, such as branched low‐density polyethylene (LDPE) and linear high‐density polyethylene (HDPE), are well known to tear easily along particular directions: along the film bubble's transverse direction for LDPE and along the machine direction (MD) for HDPE. Depending on the resin characteristics and processing conditions, different structures can form within the film; it is therefore difficult to separate the effects of the crystal structure and orientation on the film tear behavior from the effects of the macromolecular architecture, such as the molecular weight distribution and long‐chain branching. Here we examine LDPE, HDPE, and linear low‐density polyethylene (LLDPE) blown films with similar crystal orientations, as verified by through‐film X‐ray scattering measurements. With these common orientations, LDPE and HDPE films still follow the usual preferred tear directions, whereas LLDPE tears isotropically despite an oriented crystal structure. These differences are attributed to the number densities of the tie molecules, especially along MD, which are considerably greater for linear‐architecture polymers with a substantial fraction of long chains, capable of significant extension in flow. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 413–420, 2005     

Degradation of pre-aged polymers exposed to simulated recycling: Properties and thermal stability

Accelerated thermal and photo-aging of four homopolymers, low-density polyethylene (LDPE), high-density polyethylene (HDPE), polypropylene (PP) and high-impact polystyrene (HIPS), was performed and the impact of subsequent reprocessing conditions on their properties studied. Polymer samples oven-aged at 100 °C for varying periods of time or UV irradiated in a Weather-o-meter (WOM) at λ = 340 nm were reprocessed in a Brabender plasticorder at 190 °C/60 rpm for 10 min. Chemical changes and the evolution of rheological and mechanical properties accompanying the gradual degradation of the individual polymers were monitored and evaluated (DSC, FTIR, colorimetric method, MFI, tensile impact strength). LDPE and HIPS were found to be more susceptible to thermo-oxidation than HDPE and PP, whereas HDPE and PP were affected to a greater extent by UV exposure; the crucial role here is being played by the stabilization of the studied resins. In HDPE the scission and crosslinking reactions competed both in thermo-and photo-degradation. In the case of LDPE, scission prevailed over branching during thermo-oxidation, whereas photo-oxidation of the same sample led predominantly to crosslinking. Abrupt deterioration of the LDPE rheological properties after one week of thermal exposure was suppressed by re-stabilization. The scission reaction was also predominant for PP during thermo-oxidation, and it took place even faster during UV exposure. In the case of HIPS a slight photo-degradation of PS matrix is accompanied by simultaneous crosslinking of the polybutadiene component.     

Coprocessing of Waste Plastic and Hydrocarbons over MFI (HZSM‐5)

The thermal and catalytic degradation of high‐ and low‐density polyethylene (HDPE and LDPE, respectively) and waste plastic film (polyethylene‐based plastic wastes) were analyzed through simultaneous thermogravimetry and differential scanning calorimetry in inert atmosphere. Catalytic degradation was performed using MFI (HZSM‐5) zeolites. Although the catalyst induces a large decrease of the degradation temperature for polyethylene, it has a smaller effect on the waste plastic (WP) degradation temperature. To check the activity of the catalyst after its use in the WP degradation, experiments were conducted with fresh HDPE which confirmed a significant loss of catalytic activity. Mixtures of WP with large paraffin were also analyzed (nC₅₀). The results show that the presence of the hydrocarbon in the mixture grants some protection to the catalyst, allowing it to retain part of its activity during the process even in the presence of the waste contaminants. These findings suggest that larger hydrocarbon: waste plastic ratios promote higher protection to deactivation and that WP coprocessing with oil is feasible. Gas chromatography was used to analyze the products formed in the catalytic degradation of the WP in the presence C₅₀ hydrocarbon at a ratio of 1:12, consisting mostly of light products in the range of C₂ to C₈ hydrocarbons.     

Emanation thermal analysis of low-density polyethylene irradiated by electron beam

The thermal behaviour of low-density polyethylene (LDPE) as powder and pellet have been characterised by means of the emanation thermal analysis (ETA) during heating in air. The ETA was used in the study of LDPE polymer before and after irradiation to various doses of high energy electrons. It was shown that the ETA reflects microstructure changes taking place as the result of thermal degradation and oxidation pyrolysis of the polymer samples. It was shown in the study of LDPE products, resulting after the electron-beam treatment, that the results of ETA reflect structural changes caused by the radiation over the range of absorbed doses from 0 to 20 MGy. The annealing chemical radicals produced by the electron-beam irradiation was assessed by comparing ETA curves measured during first and second heating runs.     

Thermal degradation of polymers: Part XXVIII — Vacuum pyrolysis of poly(m-acetamidostyrene): Products volatile at ambient temperature

The products obtained on degradation of poly(m-acetamidostyrene) (Pm-AAS) in vacuo are described. The effects of molecular weight and pyrolysis temperature are discussed and compared with those observed for polystyrene (PS) under identical conditions.The liquid products of pyrolysis were separated and identified by gas-liquid chromatography and mass spectrometry. Monomer was not present in the liquid fraction from Pm-AAS and product analysis revealed significant differences in the degradation behaviour relative to PS. This behaviour was ascribed to differences in volatility of the parent monomers, their relative susceptibility to thermal polymerisation and the ability of the side grouping to undergo cleavage in the substituted polymer. Mechanisms involving side group cleavage are proposed and discussed to account for the products obtained. Quantitative studies are also described and compared with results from PS.     

Characterization of high molecular weight polyethylenes using high temperature asymmetrical flow field-flow fractionation with on-line infrared, light scattering, and viscometry detection

High temperature asymmetrical flow field-flow fractionation (HTAF4) coupled to infrared (IR), multi-angle light scattering (MALS), and viscometry (Visc) detection is introduced as a tool for the characterization of high molecular weight polyethylenes. The high molecular weight fraction strongly affects the rheological behaviour and processability of polyethylene materials and can often not be accurately resolved by current technology such as high temperature size-exclusion chromatography (HTSEC). Molecular weight (M), radius of gyration (Rg), and intrinsic viscosity [eta] of linear high density polyethylene (HDPE) and branched low density polyethylene (LDPE) samples are studied in detail by HTAF4 and are compared to HTSEC. HTAF4 showed a better separation and mass recovery than HTSEC for very high molecular weight fractions in HDPE and LDPE samples. As no stationary phase is present in an HTAF4 channel, the technique does not show the typical drawbacks associated with HTSEC analysis of high molecular weight polyethylenes, such as, exclusion effects, shear degradation, and anomalous late elution of highly branched material. HTAF4 is applied to study the relation between the molecular weight and the zero shear viscosity eta0 for high molecular weight HDPE. It was found that the zero shear viscosity values predicted from HTAF4 results are in good qualitative agreement with measured values obtained from dynamic mechanical spectroscopy (DMS) experiments, whereas eta0 values predicted from HTSEC do not show a strong correlation. The low molecular weight cutoff of HTAF4 is approximately 5x10(4) as a result of relatively large pores in the HTAF4 channel membrane. HTAF4 is, therefore, currently not suited to analyze low molecular weight materials.