Properties of wood composite plastics made from predominant Low Density Polyethylene (LDPE) plastics and their degradability in nature.

To address concerns over plastics in the global environment, this project produced three wood plastics composites (WPCs) which could divert plastics from the waste stream into new materials. The three materials made had a ratio of 85%:15%, 90%:10%, and 95%:5% low density polyethylene (LDPE) to wood powder and were produced using the dissolution method. Physical and mechanical properties of each WPC were evaluated according to Japanese Industrial Standard (JIS) A 5908:2003. Their degradation in nature was evaluated through a graveyard test and assay test conducted in Coptotermes curvignathus termites. Results showed that density, moisture content, thickness swelling and water absorption of the WPCs fulfilled the JIS standard. The mechanical properties of these composites also met the JIS standard, particularly their modulus of elasticity (MOE). Modulus of rupture (MOR) and internal bonding (IB) showed in lower values, depending on the proportion of wood filler they contained. Discoloration of the WPCs was observed after burial in the soil with spectra alteration of attenuated transmission reflectance (ATR) in the band of 500-1000 cm-1 which could be assigned to detach the interphase between wood and plastics. As termite bait, the WPCs decreased in weight, even though the mass loss was comparatively small. Micro Confocal Raman Imaging Spectrometer revealed that termite guts from insects feeding on WPCs contained small amounts of LDPE. This indicated termite can consume plastics in the form of WPCs. Thus WPCs made predominantly of plastics can be degraded in nature. While producing WPCs can assist in decreasing plastics litter in the environment, the eventual fate of the LDPE in termites is still unknown.

Chemical synthesis-free and facile preparation of magnetized polyethylene composite and its application as an efficient magnetic sorbent for some pesticides.

In this study, a magnetized polyethylene composite has been prepared using ball milling procedure and employed as an efficient sorbent in magnetic dispersive solid phase extraction combined with dispersive liquid-liquid microextraction. This method has been utilized for the extraction and preconcentration of some pesticides from fruit juices prior to their quantification by gas chromatography-flame ionization detection. The prepared sorbent consisted of the natural iron oxide (obtained from sand) coated with polyethylene. In the present work, first a few mg of the magnetic composite is added into an aqueous solution containing the analytes and vortexed. After that the analytes are eluted with iso-propanol from the surface of the composite particles separated in the presence of a strong external magnetic field. For further enrichment of the analytes, 1,2-dibromoethane (at µL-level) as an extraction solvent is mixed with the obtained eluent and hastily injected into deionized water. The composite was characterized using techniques including vibrating sample magnetometry, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, Brunauer-Emmett-Teller nitrogen sorption, and Fourier transform infrared spectrophotometry. Under optimal conditions, the method provided low limits of detection (0.94-1.9 µg L-1) and quantification (3.2-5.9 µg L-1), high enrichment factors (570-692), good linearity (r2 ≥ 0.994), and satisfactory repeatabilities (relative standard deviations ≤ 8% for intra- and inter-day precisions at a concentration of 15 µg L-1 of each analyte).

Velcrand Functionalized Polyethylene.

Velcrands are a specific class of cavitands whose complementary surfaces induce self-dimerization. The insertion of a velcrand as physical cross-linking unit into a polymer is reported. To this purpose, the velcrand was functionalized at the lower rim with an isocyanate group. The functional velcrand was reacted with poly (ethylene-co-(2-hydroxethylmethacrylate)) (PE-HEMA), a polymer equipped with free hydroxyl groups suitable for reaction with the isocyanate group. The obtained functionalized polymer was characterized by nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR), proving the introduction of velcraplexes in the polymer. Films with varying amounts of velcrands were obtained by solution casting and slow evaporation, testifying the processability of the functionalized polymers. The obtained films were used to measure the oxygen barrier properties of the functionalized material.

Biobased Poly(ethylene furanoate) Polyester/TiO2 Supported Nanocomposites as Effective Photocatalysts for Anti-inflammatory/Analgesic Drugs.

In the present study, polymer supported nanocomposites, consisting of bio-based poly(ethylene furanoate) polyester and TiO2 nanoparticles, were prepared and evaluated as effective photocatalysts for anti-inflammatory/analgesic drug removal. Nanocomposites were prepared by the solvent evaporation method containing 5, 10, 15, and 20 wt% TiO2 and characterized using Fourier Transform Infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Thin films of them have been prepared by the melt press and optimization of the photocatalytic procedure was conducted for the most efficient synthesized photocatalyst. Finally, mineralization was evaluated by means of Total organic carbon (TOC) reduction and ion release, while the transformation products (TPs) generated during the photocatalytic procedure were identified by high-resolution mass spectrometry.

Chemical stabilization of polymers: Implications for dermal exposure to additives.

Technical benefits of additives in polymers stand in marked contrast to their associated health risks. Here, a multi-analyte method based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) was developed to quantify polymer additives in complex matrices such as low-density polyethylene (LDPE) and isolated human skin layers after dermal exposure ex vivo. That way both technical aspects and dermal exposure were investigated. The effects of polymer additivation on the material were studied using the example of LDPE. To this end, a tailor-made polymer was applied in aging studies that had been furnished with two different mixtures of phenol- and diarylamine-based antioxidants, plasticizers and processing aids. Upon accelerated thermo-oxidative aging of the material, the formation of LDPE degradation products was monitored with attenuated total reflectance-Fourier transformed infrared (ATR-FTIR) spectroscopy. Compared to pure LDPE, a protective effect of added antioxidants could be observed on the integrity of the polymer. Further, thermo-oxidative degradation of the additives and its kinetics were investigated using LDPE or squalane as matrix. The half-lives of additives in both matrices revealed significant differences between the tested additives as well as between LDPE and squalane. For instance, 2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol (Antioxidant 2246) showed a half-life 12 times lower when incorporated in LDPE as compared to squalane. As a model for dermal exposure of consumers, human skin was brought into contact with the tailor-made LDPE containing additives ex vivo in static Franz diffusion cells. The skin was then analyzed for additives and decomposition products. This study proved 10 polymer additives of diverse pysicochemical properties and functionalities to migrate out of the polymer and eventually overcome the intact human skin barrier during contact. Moreover, their individual distribution within distinct skin layers was demonstrated. This is exemplified by the penetration of the procarcinogenic antioxidant N-phenylnaphthalen-2-amine (Neozon D) into the viable epidermis and the permeation through the skin of the neurotoxic plasticizer N-butylbenzenesulfonamide (NBBS). In addition, the analyses of additive degradation products in the isolated skin layers revealed the presence of 2-tert-butyl-4-methylphenol in all layers after contact to a polymer with substances of origin like Antioxidant 2246. Thus, attention needs to be paid to absorption of polymer additives together with their degradation products when it comes to dermal exposure assessment.

A DFT Study on the Co-polymerization of CO2 and Ethylene: Feasibility Analysis for the Direct Synthesis of Polyethylene Esters.

The co-polymerization of CO2 with the non-polar monomer ethylene, though highly desirable, still presents a challenge whereas the palladium-catalyzed CO/C2 H4 co-polymerization is well understood. Building on this analogy, the goal of this study was to elucidate the feasibility of developing suitable catalysts for co-polymerizing CO2 with ethylene to polyethylene esters. Computational methods based on density functional theory were hereby employed. In the search for new catalyst lead structures, a closed catalytic cycle was identified for the palladium-catalyzed CO2 /C2 H4 co-polymerization reaction. The computational study on palladium complexes with a substituted anionic 2-[bis(2,4-dimethoxyphenyl)-phosphine]-benzene-2-hydroxo ligand revealed key aspects that need to be considered when designing ligand sets for potential catalysts for the non-alternating co-polymerization of CO2 and ethylene.

Effects of extra irradiation on surface and bulk properties of PMPC-grafted cross-linked polyethylene.

Sterilization using high-energy irradiation is an important aspect of implementing an ultra-high molecular weight polyethylene acetabular liner in total hip arthroplasty (THA). In this study, we evaluate the effects of extra irradiations such as gamma-ray or plasma irradiation during sterilization of the poly(2-methacryloyloxyethyl phosphorylcholine [MPC]) (PMPC) surface and cross-linked polyethylene (CLPE) substrate of a PMPC-grafted CLPE acetabular liner. The PMPC-grafted surface yielded high wettability and low friction properties regardless of the extra irradiations as compared with untreated CLPE. During a hip simulator test, wear resistance of the PMPC-grafted CLPE liner was maintained after extra irradiation, which is due to the high wettability characteristics of the PMPC surface. In particular, the PMPC-grafted CLPE liner treated with plasma irradiation showed greater wettability and wear resistance than that with gamma-ray irradiation. However, we could not clearly observe the changes in chemical properties and morphology of the PMPC surface after both extra irradiations. The physical and mechanical properties attributed to CLPE substrate performance were also unchanged. In contrast, PMPC-grafted CLPE treated with plasma irradiation showed improved oxidation resistance as compared to that treated with gamma-ray irradiation after accelerated aging. Thus, we conclude that PMPC-grafted CLPE with plasma irradiation has promise as a lifelong solution for bearing in THA.

Changing the renewable fuel standard to a renewable material standard: bioethylene case study.

The narrow scope of the U.S. renewable fuel standard (RFS2) is a missed opportunity to spur a wider range of biomass use. This is especially relevant as RFS2 targets are being missed due to demand-side limitations for ethanol consumption. This paper examines the greenhouse gas (GHG) implications of a more flexible policy based on RFS2, which includes credits for chemical use of bioethanol (to produce bioethylene). A Monte Carlo simulation is employed to estimate the life-cycle GHG emissions of conventional low-density polyethylene (LDPE), made from natural gas derived ethane (mean: 1.8 kg CO2e/kg LDPE). The life-cycle GHG emissions from bioethanol and bio-LDPE are examined for three biomass feedstocks: U.S. corn (mean: 97g CO2e/MJ and 2.6 kg CO2e/kg LDPE), U.S. switchgrass (mean: -18g CO2e/MJ and -2.9 kg CO2e/kg LDPE), and Brazilian sugar cane (mean: 33g CO2e/MJ and -1.3 kg CO2e/kg LDPE); bioproduct and fossil-product emissions are compared. Results suggest that neither corn product (bioethanol or bio-LDPE) can meet regulatory GHG targets, while switchgrass and sugar cane ethanol and bio-LDPE likely do. For U.S. production, bioethanol achieves slightly greater GHG reductions than bio-LDPE. For imported Brazilian products, bio-LDPE achieves greater GHG reductions than bioethanol. An expanded policy that includes bio-LDPE provides added flexibility without compromising GHG targets.

Synthesis of poly(ethylene furandicarboxylate) polyester using monomers derived from renewable resources: thermal behavior comparison with PET and PEN.

Poly(ethylene-2,5-furandicarboxylate) (PEF) is a new alipharomatic polyester that can be prepared from monomers derived from renewable resources like furfural and hydroxymethylfurfural. For this reason it has gained high interest recently. In the present work it was synthesized from the dimethylester of 2,5-furandicarboxylic acid and ethylene glycol by applying the two-stage melt polycondensation method. The thermal behavior of PEF was studied in comparison to its terephthalate and naphthalate homologues poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN), which were also synthesized following the same procedure. The equilibrium melting point of PEF was found to be 265 °C while the heat of fusion for the pure crystalline PEF was estimated to be about 137 J g(-1). The crystallization kinetics was analyzed using various models. PET showed faster crystallization rates than PEN and this in turn showed faster crystallization than PEF, under both isothermal and non-isothermal conditions. The spherulitic morphology of PEF during isothermal crystallization was investigated by polarized light microscopy (PLM). A large nucleation density and a small spherulite size were observed for PEF even at low supercoolings, in contrast to PET or PEN. Thermogravimetric analysis indicated that PEF is thermally stable up to 325 °C and the temperature for the maximum degradation rate was 438 °C. These values were a little lower than those for PET or PEN.

Light-induced catalyst and solvent-free high pressure synthesis of high density polyethylene at ambient temperature.

The combined effect of high pressure and electronic photo-excitation has been proven to be very efficient in activating extremely selective polymerisations of small unsaturated hydrocarbons in diamond anvil cells (DAC). Here we report an ambient temperature, large volume synthesis of high density polyethylene based only on high pressure (0.4-0.5 GPa) and photo-excitation (~350 nm), without any solvent, catalyst or radical initiator. The reaction conditions are accessible to the current industrial technology and the laboratory scale pilot reactor can be scaled up to much larger dimensions for practical applications. FTIR and Raman spectroscopy, and X-ray diffraction, indicate that the synthesised material is of comparable quality with respect to the outstanding crystalline material obtained in the DAC. The polydispersity index is comparable to that of IV generation Ziegler-Natta catalysts. Moreover the crystalline quality of the synthesised material can be further enhanced by a thermal annealing at 373 K and ambient pressure.

Designing polyethylenes of complex chain architectures via Pd-diimine-catalyzed "living" ethylene polymerization.

Polymer chain architecture is a critically important chain parameter governing intrinsically the properties and applications of polymers. The rapid developments in "living"/controlled polymerization techniques, particularly the controlled radical polymerization techniques, in the past two decades have enabled the precision synthesis of novel polymers having a great variety of complex yet well-defined chain architectures from various monomer stocks. For polyolefins synthesized via catalytic coordination polymerization, the design of complex chain architectures, however, has only started recently because of the relatively limited advancements in the catalytic "living" olefin polymerization technique. In this regard, the versatile Pd-diimine catalysts have provided some unprecedented opportunities, due to their outstanding features, in rendering successfully a novel class of polyethylenes of various new complex chain architectures through the "living" ethylene polymerization protocol. The complex chain architectures designed to date have included hyperbranched, hybrid hyperbranched-linear, block, gradient and block-gradient, star, telechelic, graft and comb, and surface-tethered polymer brushes. This Feature Article attempts to summarize the recent developments achieved in the area, with an emphasis on the synthetic strategies for the architectural design. These developments demonstrate the great potential for further advancements of this new exciting research area.

Ethylene polymerization by new chromium catalysts based on carborane [SSO] ligands.

Tridentate carborane [S, S, O] ligands 2a-2b [(HOC6H2R2-4,6)(CH2)SC(B10H10)C(Ph)2P=S, R = (t)Bu (2a), R = Me (2b)] were synthesized and characterized. Reaction of CrCl3(THF)3 with the sodium salts of ligands 2a and 2b afford six-coordinated chromium complexes 3a and 3b. EXAFS spectroscopy performed on complex 3a to describe the coordination chemistry of ligand 2a around chromium center. DFT calculations were also performed on complex 3a to analyze the structure. The preliminary screening results revealed that six-coordinated chromium complexes 3a-3b displayed good catalytic activities towards ethylene polymerization in the presence of modified methylaluminoxane. The effect of polymerization parameters such as cocatalyst, reaction temperature, ethylene pressure, and reaction time on polymerization behavior were investigated in detail. The polymer obtained from this homogeneous catalytic reaction has a fibroid morphology.

Sequential ROMP of cyclooctenes as a route to linear polyethylene block copolymers.

AB diblock copolymers were prepared by sequential ring-opening metathesis polymerization of cyclooctenes catalyzed by a Ru-based Grubbs catalyst. The relatively slow polymerization of cis-3-phenylcyclooct-1-ene (3PC) or cis-cyclooct-2-en-1-yl acetate (3AC) was first carried out and then followed by the faster polymerization of unsubstituted cis-cyclooctene (COE) from the active Ru-alkylidene chain ends. In contrast, simultaneous polymerization of the two monomers provides copolymers with a statistical monomer distribution owing to extensive chain transfer. The resulting poly(3PC-b-COE) and poly(3AC-b-COE) diblock copolymers were subjected to hydrogenation to selectively saturate the backbone alkenes. The consequences of architectural variance between the materials from simultaneous vs. sequential polymerizations are reflected by the contrasting thermal characteristics.

High performance polyethylene/thermoplastic starch blends through controlled emulsification phenomena.

The emulsification efficacies of a range of compatibilizers for polyethylene/thermoplastic starch blends have been studied and a detailed morphological and mechanical analysis has been conducted. It is shown that polyethylene-maleic anhydride terpolymers containing elastomeric segments provided excellent emulsification of PE/TPS blends with a fine morphology (volume diameter of 1.4 µm; number average diameter of 600 nm). The blends compatibilized with these copolymers exhibit a very high elongation at break of about 800%, the highest value ever reported for PE/TPS systems. Also, significant improvement in notched impact strength performance at interfacial saturation was found for these systems leading to specimens with an equivalent performance to pure polyethylene. An excellent correlation was found between the critical concentration for interfacial saturation and the mechanical properties, indicating the key role of morphology.

Which polyesters can mimic polyethylene?

Self-metathesis of erucic acid by [(PCy(3))(η-C-C(3)H(4)N(2)Mes(2))Cl(2)Ru = CHPh] (Grubbs second- generation catalyst) followed by catalytic hydrogenation and purification via the ester yields 1,26-hexacosanedioate (>99% purity). Polyesterification with 1,26-hexacosanediol, generated from the diester, affords polyester-26,26, which features a T(m) of 114 °C (T(c) = 92 °C, ΔH(m) = 160 J g(-1)). Ultralong-chain model polyesters-38,23 (T(m) = 109 °C) and -44,23 (T(m) = 111 °C), generated via multistep procedures including acyclic diene metathesis polymerization, underline that melting points of such aliphatic polyesters do not gradually increase with methylene sequence chain length. Available data suggest that to mimic linear polyethylenes thermal properties, even longer sequences, amounting to at least four times a fatty acid chain, fully incorporated in a linear fashion are required.

Preparation and characterization of bagasse/HDPE composites using multi-walled carbon nanotubes.

This article presents the preparation and characterization of bagasse/high density polyethylene (HDPE) composites. The effects of multi-walled carbon nanotubes (MWCNTs), as reinforcing agent, on the mechanical and physical properties were also investigated. In order to increase the interphase adhesion, maleic anhydride grafted polyethylene (MAPE) was added as a coupling agent to all the composites studied. In the sample preparation, MWCNTs and MAPE contents were used as variable factors. The morphology of the specimens was characterized using scanning electron microscopy (SEM) technique. The results of strength measurement indicated that when 1.5 wt% MWCNTs were added, tensile and flexural properties reached their maximum values. At high level of MWCNTs loading (3 or 4 wt%), increased population of MWCNTs lead to agglomeration and stress transfer gets blocked. The addition of MWCNTs filler slightly decreased the impact strength of composites. Both mechanical and physical properties were improved when 4 wt% MAPE was applied. SEM micrographs also showed that the surface roughness improved with increasing MAPE loading from 0 to 4 wt%. The improvement of physicomechanical properties of composites confirmed that MWCNTs have good reinforcement and the optimum synergistic effect of MWCNTs and MAPE was achieved at the combination of 1.5 and 4 wt%, respectively.

Specific His6-tag attachment to metal-functionalized polymersomes relies on molecular recognition.

The development of nanocarriers for drug/protein delivery is in focus today, as they can serve to both decrease dosages and improve localization to a desired biological compartment. A powerful tool to functionalize these carriers is specific affinity tagging supported by molecular recognition, a key principle in biology. However, the geometry of the binding region in a molecular recognition process, and thus its conformation and specificity, are in many cases poorly understood. Here, we demonstrate that short, model peptides, His(6)-tags, selectively recognize Cu(II)-trisnitrilotriacetic acid moieties (Cu(II)-trisNTA) when exposed at the surfaces of polymer vesicles designed to serve as nanocarriers or as surfaces for proteins binding. A mixture of poly(butadiene)-b-poly(ethylene oxide) (PB-b-PEO) and Cu(II)-trisNTA-functionalized PB-b-PEO diblock copolymers (10:1) self-assembles in aqueous solution, generating vesicles with a hydrodynamic radius of approximately 100 nm, as established by light scattering and TEM. Fluorescently labeled His(6) tags specifically bind to metal centers exposed on vesicles' surface, with a dissociation constant of 0.6 ± 0.2 µM, as determined by fluorescence correlation spectroscopy. The significant rearrangement in the geometry of the metal center upon peptide binding was characterized by a combination of CW-EPR, pulse-EPR, and DFT computations. Understanding the binding configuration around the metal center inside NTA pocket exposed at the surface of vesicles supports further development of efficient targetable nanocarriers that can be recognized selectively by molecular recognition in a biological environment and facilitates their immobilization on solid supports and their use in two-dimensional protein arrays.

Synthesis and preliminary evaluation of a polyolefin-based core for carrier-based root canal obturation.

INTRODUCTION: Carrier-based gutta-percha is an effective method of root canal obturation creating a 3-dimensional filling; however, retrieval of the plastic carrier is relatively difficult, particularly with smaller sizes. The purpose of this study was to develop composite carriers consisting of polyethylene (PE), hydroxyapatite (HA), and strontium oxide (SrO) for carrier-based root canal obturation. METHODS: Composite fibers of HA, PE, and SrO were fabricated in the shape of a carrier for delivering gutta-percha (GP) using a melt-extrusion process. The fibers were characterized using infrared spectroscopy and the thermal properties determined using differential scanning calorimetry. The elastic modulus and tensile strength tests were determined using a universal testing machine. The radiographic appearance was established using digital periapical radiographs. RESULTS: The composite core carrier exhibited a melting point of 111°C to 112°C, which would facilitate removal by heat application. The elastic modulus and the tensile strength were found to be lower than those of Thermafil carriers (Dentsply Tulsa Dental, Tulsa, OK). The preliminary radiographic evaluation showed that the novel composite core carrier is sufficiently radiopaque and can be distinguished from gutta-percha. CONCLUSIONS: The PE-HA-SrO composites were successfully melt processed into composite core carriers for delivering gutta-percha into the root canal space.

Synthesis of polyethylene containing allene groups: a simple and efficient route to functional polyethylene.

Allene groups are first employed as the reactive moiety in the simple and efficient synthesis of well-defined functional polyethylene. By copolymerization of ethylene with allene group substituted norbornene, the allene group is successfully introduced into the polyethylene with a high content. The retained allene groups are demonstrated to be highly reactive in following photoinduced functionalized reactions and can be efficiently converted into the functional groups without the multi-step, time consuming processes that have generally been required in previous reports, providing the side group-functionalized polyethylene with a wide range of functional group content.

Shifting from Ziegler-Natta to Philips-type catalyst? A simple and safe access to reduced titanium systems for ethylene polymerization.

Silica-supported titanium(IV) chloride is readily reduced by Mashima and co-workers' reagent (1-methyl-3,6-bis(trimethylsilyl)-1,4-cyclohexadiene) to afford materials active in ethylene polymerisation without need of aluminum alkyl cocatalyst.