Variations in the mechanical properties of end products from mixed plastics

From well selected polymers, using an experimental plan methodology, we show the different influences (nature, processing conditions, composition) on the properties of end products from mixed plastics such as strain and stress at rupture, flexural modulus, impact strength and extrusion flow rate. From models, it is possible to adjust necessary formulations to obtain a good quality level and, eventually, an improvement of poor properties. Mixed plastics can be considered as a polyethylene matrix containing other polymers such as polypropylene (PP), polystyrene (PS) or poly(vinyl chloride) (PVC). Poly(ethylene terephthalate) (PET) is neglected in this study. Properties such as strain at rupture or impact strength are drasticly affected by the level of polypropylene, polystyrene or poly(vinyl chloride): 5 or 10% nullify these properties. Other properties such as stress at rupture, flexural modulus or extrusion flow rate highly depend on the relative ratio of polymers. To improve the poor properties or to obtain a good level in a property, it is necessary to add well adapted compatibilizers or to dope the mixed plastics material by one of the polymers.     

Tetrazole-containing paired polymers

Paired polymers are obtained by the reaction between linear poly(5-vinyltetrazole) and poly(vinyl chloride) in the presence of triethylamine. Poly(vinyl chloride) plays the role of a macromolecular alkylating agent with respect to the tetrazole-containing polymer. The combination of two types of covalently linked macromolecules promotes in the paired polymers the manifestation of some properties typical for both homopolymers.     

Mechanical,thermal and barrier properties of pectin/cellulose nanocrystal nanocomposite films and their effect on the storability of strawberries (Fragaria ananassa)

In this work, two formulations of pectin/cellulose nanocrystals/glycerol nanocomposites were employed as packaging to extend storage life of strawberries. The effects of incorporating cellulose nanocrystals extracted from bleached Kraft wood pulp on the mechanical, thermal, and barrier properties of pectin‐based nanocomposites were evaluated. Nanocomposite films with different filler levels of cellulose nanocrystals (1, 2, 4 and 8% w/w) were prepared by casting. Compared with the neat film of pectin, improvements in the mechanical properties of the nanocomposites were observed, but these films became fragile. To improve the film flexibility, glycerol was added as a plasticizer and then new variations in the mechanical, thermal, and barrier properties of these nanocomposites were evaluated. The effects of nanocomposite films on storability of strawberries were compared with Poly vinyl chloride packaging films. The Poly vinyl chloride film and the nanocomposites showed similar behavior regarding weight loss by the strawberries, especially in the initial days of storage. The results show that pectin/cellulose nanocrystals/glycerol nanocomposites could be considered as a viable packaging alternative for replaced the Poly vinyl cloride film. Copyright © 2015 John Wiley & Sons, Ltd.     

The influence of different fillers on mechanical and physical properties of high-molecular-weight biodegradable aliphatic polyesters

Poly(ethylene succinate) and poly(butylene succinate) are synthetic biodegradable polymers, and much attention is paid to study the properties of pure polymers and the polymers modified by different comonomers and filling materials. The literature data on the physical properties of these polymers vary widely depending on their method of preparation and subsequent modifications. Most of the studies deal with low- and moderate-molecular-weight polymers or commercial grade polymers, modified by different comonomers and chain-extension agents. The data on pure high-molecular-weight polymers are scarce. In this work, we have prepared high-molecular-weight (MW range of (1.4–1.8) × 10⁵) poly(ethylene succinate) and poly(butylene succinate) by direct polycondensation at 200°C in a nitrogen flow without chain-extension agents. We have further studied the properties of pure polymers and examined the effect of different fillers (carbon nanotubes, SiO₂, Aerosil®) on the mechanical and physical properties of these polymers. Because of high-molecular-weight, the polymers possess increased tensile and storage moduli and thermostability. Even very low filler contents (up to 1 wt %) have a pronounced influence on the polymer properties: the polymer tensile and the storage modulus increases, the elongation at break decreases, and the thermal stability of the polymers decreases slightly. The effects of fillers are less pronounced compared with those for low- and moderate-molecular-weight polymers. When mixed together, poly(ethylene succinate) and poly(butylene succinate) crystallize independently from each other as evident from the mechanical and thermal analysis data.     

Miscible blends of amorphous polymers

Thirty-five polymethacrylate/chlorinated polymer blends were investigated by differential scanning calorimetry. Poly(ethyl), poly(n-propyl), poly(n-butyl), and poly(n-amyl methacrylate)s were found to be miscible with poly(vinyl chloride) (PVC), chlorinated PVC, and Saran, but immiscible with a chlorinated polyethylene containing 48% chlorine. Poly(methyl) (PMMA), poly(n-hexyl) (PHMA), and poly(n-lauryl methacrylate)s were found to be immiscible with the same chlorinated polymers, except the PMMA/PVC, PMMA/Saran, and PHMA/Saran blends, which were miscible. A high chlorine content of the chlorinated polymer and an optimum CH₂/COO ratio of the polymethacrylate are required to obtain miscibility. However, poly(methyl), poly(ethyl), poly(n-butyl), and poly(n-octadecyl acrylate)s were found to be immiscible with the same chlorinated polymers, except with Saran, indicating a much greater miscibility of the polymethacrylates with the chlorinated polymers as compared with the polyacrylates.     

聚氯乙烯/层状双氢氧化物纳米复合材料研究进展

聚氯乙烯(PVC)/层状双氢氧化物(LDHs)纳米复合材料相比于纯聚氯乙烯具有更好的热稳定性、力学性能、阻燃抑烟性、耐候性与耐光性等,是一种性能优异并具有广泛应用前景的新型聚合物基纳米复合材料。本文首先介绍了LDHs的化学组成和结构特点,并对其制备过程和性质特点进行了分析和探讨;然后综述了PVC/LDH纳米复合材料的制备、结构表征及性能等方面的最新研究进展,重点阐述了LDHs的表面有机化处理及其对PVC/LDH纳米复合材料制备与性能的重要作用;最后对其应用前景进行展望。     

Poly(lactic acid)‐based nanocomposites

Classic plastics accumulate in nature causing environmental pollution, yet as a counterbalance they benefit society in many ways. They are versatile, cost‐effective, and can be tailored to have desired properties. The global environment has led to the fabrication of commodity plastics from environmentally degradable polymers. Poly(lactic acid) (PLA) is the most promising among the environmentally friendly polymers available. PLA‐based plastics have mechanical, thermal, and transparency similar to traditional plastics, and they can be molded and fabricated using the same equipment and procedures. Their material properties are enhanced through nanocomposites, compatibilizers, plasticizers, and other fillers (flame retardant, ultraviolet filter, etc.). This review summarizes mass production techniques and property reinforcements (focusing on nanocomposites and plasticizers) for PLA‐based plastics for commodity use. Copyright © 2016 John Wiley & Sons, Ltd.     

Porous product with reduced apparent density keeps good mechanical properties. Extruded composites of poly(vinyl chloride) blown under microwave irradiation

New foaming method, enhanced by microwave irradiation, was elaborated and applied to obtain porous poly(vinyl chloride) and its composites with fine cell structure. The so called “thermal runaway” effect was observed during the heating of poly(vinyl chloride) under microwave irradiation. The temperature of this effect decreases as a result of additives incorporation into polymer matrix. Microwave irradiation allowed effective heating of extruded poly(vinyl chloride) and its composites with carbon black (CB) filler, behind the extruder head and decomposing azodicarbonamide (ADC) to obtain porous products. The use of CB additive to poly(vinyl chloride) significantly increased its ability to be heated under microwave irradiation as well as improved the cell structure and decreased the apparent density of final products.Among additionally used fillers (1 wt%) the montmorillonite caused the apparent density decrease of foamed materials ca. 10%, however beneficially influenced on the quality of cells structure, giving the products with isotropic cells and the highest cell density as well as keeping the tensile strength on similar level as in the case of the materials with CB and ADC only.     

Correlation of thermal degradation mechanisms: Polyacetylene and vinyl and vinylidene polymers

The thermal degradation of poly(vinyl bromide) (PVB), poly(vinyl chloride) (PVC), poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc), poly(vinyl fluoride) (PVF), poly(vinylidene chloride) (PVC₂), and poly(vinylidene fluoride) (PVF₂) has been studied by direct pyrolysis–mass spectrometry (DP-MS) and flash pyrolysis–gas chromatography–mass spectrometry techniques. Vinyl and vinylidene polymers exhibit two competitive thermal degradation processes: (1) HX elimination with formation of polyene sequences which undergo further moleculaar rearrangements, and (2) main-chain cleavage with formation of halogenated or oxigenated compounds. The overall thermal degradation process depends on the prevailing decomposition reaction in each polymer; therefore, different behaviors are observed. The thermal degradation of polyacetylene (PA) has also been studied and found important for the elucidation of the thermal decomposition mechanism of the title polymers.     

Re-use of chlorine-containing polymers

Poly(vinyl chloride) (PVC) and some other chlorine-containing polymers belong to one of the most widely applied groups of thermoplastics. Their main disadvantage is the rather limited thermal stability, which requires the addition of heat stabilizers to prevent dehydrochlorination and discolouration. Hydrogen chloride is also the main volatile decomposition product during combustion of PVC; therefore, PVC-waste is less suited for the so-called thermal recycling. For the re-use of PVC and similar polymers it is necessary to characterize these products by molecular weight (or at least viscometry), internal double bonds and other defect structures, stability against the influence of heat (and in some cases of light) and a few other properties. The application of these methods for deciding about the re-usability of PVC roofing sheets and for the injection moulding of PVC scrap is demonstrated.     

Stereoregularity of poly(vinyl ether)

α-Methylvinyl isobutyl and methyl ethers were polymerized cationically and the structure of the polymers was studied by NMR. Poly(α-methylvinyl methyl ether) polymerized with iodine or ferric chloride as catalyst was found to be almost atactic, whereas poly(α-methylvinyl isobutyl ether) polymerized in toluene with BF₃OEt₂ or AlEt₂Cl as catalyst was found to be isotactic. In both cases, the addition of polar solvent resulted in the increase of syndiotactic structure as is the case with polymerization of alkyl vinyl ether. tert-Butyl vinyl ether was polymerized, and the polymer was converted into poly(vinyl acetate), the structure of which was studied by NMR. A nearly linear relationship between the optical density ratio D₇₂₂/D₇₃₆ in poly(tert-butyl vinyl ether) and the isotacticity of the converted poly(vinyl acetate) was observed.     

Preparation method for noble metal-polymer matrix nanocomposites

A method is described for the preparation of new nanocomposites based on poly(ethylene terephthalate), poly(vinyl chloride), and polypropylene on the one hand and on noble metals (Ag and Pt) on the other. The method comprises the formation of nanoporous polymer matrices by crazing the polymers with simultaneous incorporation of noble metal precursors (AgNO₃ or H₂PtCl₆) into the matrices. Subsequent in situ reduction of the precursors yields the metal-polymer nanocomposites. Prospects for the practical application of the developed method for the production of metal-polymer nanocomposites are discussed.     

Characterisation of historic plastics using terahertz time-domain spectroscopy and pulsed imaging

Terahertz (THz) time-domain spectroscopy and 3D THz pulsed imaging have been explored with regard to polymer materials, both commodity and historic polymers. A systematic spectroscopic study of a wide range of different polymer materials showed significant differences in their spectra. Polyolefins and polystyrenes generally exhibit lower absorption than other examined polymers, various cellulose derivates, poly(vinyl chloride), poly(methyl methacrylate), polyamide, hard rubber and phenol formaldehyde resin, the last of these exhibiting the most intense absorption over the entire range, 0.15–4.2 THz. It was also examined how the presence of plasticisers in poly(vinyl chloride), the presence of fillers in polypropylene, and the degree of branching in polyethylene and polystyrene affect the spectra; inorganic fillers in polypropylene affected the absorption most. With 3D THz pulsed imaging, features in polymer objects were explored, appearing either as integral parts of the material (coatings and pores in foams) or as a consequence of physical deterioration (cracks, delamination). All of these features of various complexities can be successfully imaged in 3D. Terahertz technology is thus shown to have significant potential for both chemical and structural characterisation of polymers, which will be of interest to heritage science, but also to the polymer industry and development of analytical technologies in general.     

Graft Copolymers with a Backbone of Polyvinyl Chloride): Synthesis,Properties, and Applications

Poly(vinyl chloride) (PVC) has occupied the most important position among the general purpose plastics, but its industrial applications are limited due to its inferior thermal stability and mechanical properties. It has been observed that the removal of tertiary or allylic chlorine atoms or some other abnormal and unstable structures from polymeric chains, by graft copolymerization with vinyl monomers, improves the thermal stability and mechanical properties (such as softening temperature, rigidity, anticreep properties, impact strength, and tensile strength) of PVC to a large extent.     

Influence of chemical structure on the optical properties of new side-chain polymers containing cholesterol

Poly[1-(cholesteryloxyhexyloxy)ethylene] (PHET) and poly[1-(cholesteryloxycarbonyl-hexyloxy)ethylene] (PHES) were prepared by reacting poly(vinyl alcohol) with cholesteryloxyhexyloxy bromides (CHB) or cholesteryloxycarbonylhexyloxy bromides (CEHB), and their thermal and optical properties were investigated. PHET and PHES exhibited monotropic cholesteric phases; however, their thermal behaviours depended on the cholesteryl groups and alkylene spacers with different chemical structures. PHET did not display reflection colours over its entire cholesteric range, whereas PHES did display reflection colours. These results suggested that the thermal stability and helical twisting power (HTP) of these polymers strongly depend on the difference in the chemical structures of the flexible spacer via cholesterol. The mesophase properties of PHET and PHES differed substantially from those of poly(cholesteryl-ω-acryloyloxyalkanoates). The results indicate that the mode of chemical linkage between the side-chain group and the main chain as well as that between the alkylene spacer and side chain play important roles in determining the thermal stability, mesophorphic structure and HTP of the cholesteric mesophases.     

Preparation and characterization of poly(vinyl alcohol)/organo-modified cloisite Na+ with chiral L-leucine amino acid/TiO2 nanocomposites

Poly(vinyl alcohol)/organo-clay/TiO₂ nanocamposites films were prepared with 10 wt % of organo-nanoclay and various amount of TiO₂ nanoparticles. Cloisite Na⁺ has been modified via cation exchange reaction using ammonium salt of natural L-leucine amino acid as a cationic surfactant. After that poly(vinyl alcohol)/organo-nanoclay/TiO₂ nanocomposites were synthesized by dispersion of TiO₂ on the surfaces of organo-nanoclay in poly(vinyl alcohol) matrix by using ultrasonic energy. Three nanocomposites with different loading of TiO₂ were prepared and characterized by X-ray diffraction, fourier transform infrared spectroscopy, field emission type scanning electron microscope, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis and ultraviolet-visible transmission spectra. The results showed that the organo-nanoclay and TiO₂ were dispersed homogeneously in poly(vinyl alcohol) matrix and also showed improvement in their thermal properties compared with the pure poly(vinyl alcohol).     

Pyrolysis–gas chromatographic analysis of poly(vinyl chloride). II. In situ absorption of HCl during pyrolysis and combustion of PVC

A pyrolysis–gas chromatographic technique for measuring the amount of hydrogen chloride released during the high temperature pyrolysis of poly(vinyl chloride) resins, plastisols, copolymers and compounds containing inert fillers has been developed. The technique, which is also applicable to the analysis of chlorinated polyethylene and chlorinated poly(vinyl chloride), is based on the use of a standard precursor of HCl, poly(vinyl chloride) homopolymer. The analysis has been successfully used to measure the degree of in situ absorption of HCl during pyrolysis by certain basic fillers [K₂CO₃, CaCO₃, CaO, MgO, Al(OH)₃, Na₂CO₃, Al₂O₃ and LiOH] dispersed in a poly(vinyl chloride)–o-dioctyl phthalate matrix. Combustion of a number of combustion residues (chloride determination) revealed that the amount of HCl absorbed by the basic filler was independent of the method of degradation (pyrolysis or combustion). Flammability measurements of those matrices having the same composition indicate that in situ absorption of HCl during combustion has little effect on the overall flammability of these materials.     

Poly(vinyl alcohol) Chains Grafted onto the Surface of Copper Oxide Nanoparticles: Application in Synthesis and Characterization of Novel Optically Active and Thermally Stable Nanocomposites Based on Poly(amide-imide) Containing N-trimellitylimido-L-valine Linkage

Green polymer nanocomposites (NCs) show unique properties of combining the advantages of nanofillers and organic polymers. In this study, in order to control the dispersion of nanoparticles (NPs) in a polymer matrix, first, poly(vinyl alcohol) (PVA) as a green modifier was grafted on the surface of the CuO NPs to obtain CuO-PVA nanohybrid. Then poly(amide-imide) (PAI) was synthesized by the direct step growth polymerization of N-trimellitylimido-L-valine and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) in ionic liquid medium. Finally, CuO-PVA hybrids were incorporated into the PAI matrix using ultrasonic technique for the preparation of PAI/CuO-PVA NCs. The obtained PAI/CuO-PVA NCs were characterized by different methods. The results of thermogravimetric analysis showed that thermal stability of the NCs was enhanced by incorporation of CuO-PVA nanohybrid compared to the pure PAI.     

Effect of new melamine-terephthaldehyde resin modified graphene oxide on thermal and mechanical properties of PVC

In this study a new melamine-terephthaldehyde resin modified graphene oxide was synthesized and used as a reinforcement of poly(vinyl chloride) (PVC). Characterization, morphology, thermal and mechanical properties of the nanocomposites were examined by means of attenuated total reflectance-Fourier transform infrared spectroscopy, X-ray diffraction, field emission-scanning electron microscopy, thermogravimetric analysis, differential scanning calorimeter and tensile properties. The first hydrochloric acid releasing data of poly(vinyl chloride) was removed by incorporation of the modified graphene oxide as compare to the neat polymer. The temperatures at 2 wt% losses, main decomposition temperatures, maximum decomposition temperatures, also shift to higher temperature in the corresponding nanocomposites as compared to the neat PVC. The tensile strength and elongation at break of the nanocomposite films was increased as compared to the neat PVC. The interesting results in crystallinity of PVC were observed with adding 5 wt% of the modified graphene oxide.     

Preparation and Optical Properties of New Metal/Macromolecule Architectures

Polymer nanocomposite films with unusual and anisotropic optical properties were obtained by the controlled in-situ generation of noble metal nanoparticles (NPs). Poly(vinyl alcohol) (PVA) and poly(ethylene-co-vinylalcohol) (EVAl) nanocomposites containing gold and silver NPs were efficiently produced by a photo-reduction or thermal process both operating directly in the solid state and resulted efficiently stabilized by the presence of polymer hydroxyl groups, which prevent particles agglomeration. Uniaxial drawing of the NPs/polymer composites promoted anisotropic packing of the embedded particles along the stretching direction of the film, resulting in a shift of the surface plasmon resonance well above 40 nm and thus producing a well-defined polarization-dependent colour change. Such nanostructured materials when are obtained in the form of thin films can be applied to several fields, from sensor to photonics (i.e., macromolecular strain sensor, linear absorbing polarizer).