Copolymerization Of Ethylene Research Articles

Molecular dynamics study of free volume coalescence around nonyl ethoxylate in polyethylene with vinyl acetate‐modified branches

AbstractPolyethylene (PE) is susceptible to environmental stress cracking (ESC). In the presence of an amphiphilic compound and subjected to stress, ESC starts with cavitation followed by slow crack growth and ends with brittle fracture. In this study, we used molecular dynamics simulation to study how branch ends which were chemically modified with vinyl acetate groups affect free volume coalescence around an amphiphilic compound, nonyl ethoxylate (NE), dispersed in branched PE models. Branch ends modified with vinyl acetate significantly impact the free volume coalescence dynamics around NE. Compared with methyl branch ends, vinyl acetate branch ends show a much higher affinity, as quantified by the corresponding radial distribution functions, for the hydrophilic ethylene oxide‐segment of NE. However, this is not the case for the hydrophobic ethylene‐segment. Interestingly, vinyl acetate branch ends tend to reduce the power (amplitude) of the free volume size fluctuations around both the ethylene oxide‐ and ethylene‐segments. Indeed, the powers of the fluctuations with different PE branching characteristics decrease with increasing vinyl acetate concentration. We believe that free volume coalescence leads to cavitation and that vinyl acetate branches could inhibit cavitation, thereby crack propagation in PE. The power results seem to be consistent with the experimental observation that the addition of copolymer ethylene vinyl acetate to low‐density polyethylene improves the ESC resistance of the blend.Highlights Vinyl acetate branches reduce free volume coalescence activities. Vinyl acetate branches are attracted to the hydrophilic segment of NE. Cavitation likely starts from the free volume coalescence around NE.

Patterning of COC Polymers by Middle‐Energy Ion Beams for Selective Cell Adhesion in Microfluidic Devices

AbstractMicrofluidic devices play a crucial role in advanced cell biology applications, including cell separations, cultivations, migration and interaction studies, diagnostic devices, and organ‐on‐chips. One of the frequent purposes of such devices is the ability to selectively address the attachment of cells at defined locations on the surface. This study explores the application of middle‐energy carbon, oxygen, and nitrogen ions to locally modify the surface of cyclic olefin copolymer (COC) thermoplastic material, allowing selective cell growth on patterned polymer surfaces. The investigation considers ion element type, ion beam energy, and ion irradiation fluence, analyzing their influence on the modification effect. Characterization of the modified surfaces involves various surface‐analytical methods such as contact angle, energy dispersive spectroscopy (SEM‐EDX), atomic force microscopy (AFM), x‐ray photoelectron spectroscopy (XPS), rutherford backscattering spectrometry (RBS), and elastic recoil detection analysis (ERDA). The study extends to practical aspects, with a representative cancer cell line, MCF‐7, grown on the patterned surface to evaluate the degree of selective attachment. Additionally, the stability of the irradiated patterns is tested under elevated temperatures beyond the glass transition temperature (Tg), demonstrating the compatibility of the approach with hot embossing technology. The findings underscore the potential of ion beam treatment for COC in cell‐biology‐related applications, offering insights into surface modification techniques for enhanced functionality in microfluidic devices.

The third compound promoted ethylene homopolymerization and copolymerization with 1-octene by using metallocene catalyst

The third compound promoted ethylene homopolymerization and copolymerization with 1-octene by using metallocene catalyst

The Third Compound Promoted Copolymerization of Ethylene with 4‐Penten‐1‐ol by Using Metallocene Catalyst

AbstractOlefin coordination copolymerization with polar monomers is an important topic both in academia and industry. During copolymerization, polar monomers will seriously reduce the polymerization activity and the molecular weight of the copolymer, making it difficult to balance the two and the polar monomer incorporation at the same time. In this study, a metallocene catalyst, Ph2C(Cp)(Flu)ZrCl2, is used for the copolymerization of ethylene with 4‐penten‐1‐ol. The incorporation of 4‐penten‐1‐ol can be effectively increased by the introduction of the steric phenol as the third component (TC). Depending on the cocatalyst, the activity or molecular weight can be improved. It is believed that the promotion effect may work by the interaction of the steric phenol with the catalyst or cocatalyst. It is also suggested that in this system, polymerization is terminated by deactivation‐chain transfer mechanism rather than β‐X elimination due to back‐biting.

Cyclic olefin copolymer (COC) as a promising biomaterial for affecting bacterial colonization: investigation on Vibrio campbellii

Cyclic olefin copolymer (COC) has emerged as an interesting biocompatible material for Organ-on-a-Chip (OoC) devices monitoring growth, viability, and metabolism of cells. Despite ISO 10993 approval, systematic investigation of bacteria grown onto COC is a still not documented issue.This study discusses biofilm formations of the canonical wild type BB120 Vibrio campbellii strain on a native COC substrate and addresses the impact of the physico-chemical properties of COC compared to conventional hydroxyapatite (HA) and poly(dimethylsiloxane) (PDMS) surfaces.An interdisciplinary approach combining bacterial colony counting, light microscopy imaging and advanced digital image processing remarks interesting results. First, COC can reduce biomass adhesion with respect to common biopolymers, that is suitable for tuning biofilm formations in the biological and medical areas. Second, remarkably different biofilm morphology (dendritic complex patterns only in the case of COC) was observed among the examined substrates. Third, the observed biofilm morphogenesis was related to the interaction of COC with the conditioning layer of the planktonic biological medium. Fourth, Level Co-occurrence Matrix (CGLM)-based analysis enabled quantitative assessment of the biomass textural fractal development under different coverage conditions. All of this is of key practical relevance in searching innovative biocompatible materials for pharmaceutical, implantable and medical products.

Modified Bitumen Materials from Kazakhstani Oilfield

The oil bitumen BND 90/130, produced at the “LLP SP Caspi Bitum” with the modifier, which consists of copolymer of ethylene with butyl acrylate and glycidyl methacrylate taken in an amount of 0.5–1.6 wt%, and the tire reclaim (4–20 wt%), which is the destructate of mesh elastomers of different chemical nature, was modified; possibility of using the developed bitumen-elastomer binders in road asphalt concrete was justified. Modification of bitumen with a copolymer of ethylene with butyl acrylate and glycidyl methacrylate leads to an improvement in the properties of road bitumen: the softening point, hardness, deformability at low temperatures, elasticity, and adhesion to metal and mineral filler increase. It was shown that ethylene with butyl acrylate and glycidyl methacrylate chemically interacts with the functional groups of bitumen asphaltenes through the epoxy group of glycidyl methacrylate. Analysis of the spectra and group composition indicates an increased content of high molecular weight asphaltenes in the modified bitumen with a slight increase in structuring resins. It has been established that bitumen modified with rubber crumbs of 0.6–1.0 mm in size has high elasticity. The most effective composition of a bitumen-regenerated composite material based on tire reclaim has been determined. In terms of the totality of physicochemical and operational characteristics and comparative cost, the most acceptable is the bitumen-regenerated composition (with a regenerate content of 20%) and is superior in the complex of properties to bitumen modified with an optimal content of ethylene with butyl acrylate and glycidyl methacrylate (1.6%). The technology for modifying bitumen with tire reclaim is less time-consuming, more economically profitable, and environmentally effective, since it utilizes large-tonnage waste of worn-out tires. The resulting bitumen-polymer compositions have a high positive set of properties: softening point, hardness, elasticity, frost resistance, and low-temperature characteristics.

Monomer-Recyclable Polyester from CO2 and 1,3-Butadiene.

Synthesis of monomer-recyclable polyesters solely from CO2 and bulk olefins holds great potential in significantly reducing CO2 emissions and addressing the issue of plastic pollution. Due to the kinetic disadvantage of direct copolymerization of CO2 and bulk olefins compared to homopolymerization of bulk olefins, considerable research attention has been devoted to synthesis of polyester via the ring-opening polymerization (ROP) of a six-membered disubstituted lactone intermediate, 1,2-ethylidene-6-vinyl-tetrahydro-2H-pyran-2-one (𝜹-L), obtained from telomerization of CO2 and 1,3-butadiene. However, the conjugate olefin on the six-membered ring of 𝜹-L leads to serious Michael addition side reactions. Thus, the selective ROP of 𝜹-L, which can precisely control the repeating unit for the production of polyesters potentially amenable to efficient monomer recycling, remains an unresolved challenge. Herein, the first example of selective ROP of 𝜹-L is reported using a combination of organobase and N,N'-Bis[3,5-bis(trifluoromethyl)phenyl]urea as the catalytic system. Systematic modifications of the substituent of the urea show that the presence of electron-deficient 3,5-bis(trifluoromethyl)-phenyl groups is the key to the extraordinary selectivity of ring opening over Michael addition. Efficient monomer recovery of oligo(𝜹-L) is also achieved under mild catalytic conditions.

Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

Noncovalent Ni–Phenyl Interactions Promoted α-Diimine Nickel-Catalyzed Copolymerization of Ethylene and Methyl Acrylate

Promotion of chain growth and suppression of chain transfer by 2-methoxy group in diarylmethyl moiety in pyridine-imine nickel- and palladium-catalyzed ethylene (co)polymerization

Diarylmethyl substituents are commonly used to prevent chain transfer in late-transition metal-catalyzed ethylene polymerization. However, this substituent is not effective in inhibiting chain transfer in the pyridine-imine system. In this study, we introduced substituents at the 2-position of the diarylmethyl moiety to synthesize high molecular weight polyethylene in the pyridine-imine system. Using this strategy, we synthesized two pyridine-imine ligands with either ethyl or methoxy at the 2-position diarylmethyl moiety, along with their corresponding nickel and palladium complexes. These complexes were then utilized for ethylene (co)polymerization. The catalysts with OMe exhibited significantly higher polymerization activity (an order of magnitude, 105 vs. 104 g/(mol Ni·h)) compared to the corresponding Et catalysts. In addition, it was found that polyethylene produced from nickel and palladium catalysts with OMe has higher molecular weights than that produced from ethyl nickel and palladium catalysts. The nickel system produces polyethylene with a molecular weight up to an order of magnitude higher (an order of magnitude, 13.0–13.6 vs. 3.1–4.0 kg/mol). Similar results were also observed in the palladium-catalyzed copolymerization of ethylene with MA. Notably, the palladium catalyst with OMe has a significantly higher capacity for MA insertion (three times, 1.68–4.74 vs. 5.00–11.73 mol%) than the ethyl palladium catalyst, despite their similar spatial steric structures. The observed phenomenon may be attributed to the weak interaction between OMe and the metal center. In addition, 13C NMR analysis showed that the palladium-catalyzed polyethylene and E-MA copolymers are hyperbranched polymers, with the polar groups located at the ends of the branches.

Dynamics and Internal Structure Evolution during the Glass Transition of the Ethylene-Cyclic Olefin Copolymers: A Molecular Dynamics Simulation.

Amorphous ethylene-cyclic olefin copolymers (COCs) which can be used in cell phone lenses and prefilled syringes have attracted increasing attention due to their excellent and tunable thermal properties. In order to better explain the influence of COC microstructure (cyclic olefin types and content) on the glass transition mechanism, we used molecular dynamics (MD) simulations to track the evolution of free volume, diffusion coefficients, atomic mobility, trans conformation probabilities, and characteristic parameters of α-relaxation kinetics during the quenching process. MD results show that for the classic COC E-co-NB (ethylene-norbornene copolymer), an increase in cyclic olefin content from 25 to 50 mol % reduces atomic mobility, limiting the molecular chain movement at higher temperatures and improving Tg. Compared to NB, the more rigid rings in tricyclopentadiene (TCPD) and exo-1,4,4a,9,9a,10-hexahydro-9,10(1',2')-bridged phenylidene-1,4-bridged methylideneanthracene (HBM) have the following effects: (1) reducing the thermal expansion coefficient and overall chain mobility; (2) enhancing the diffusion energy barrier; (3) promoting the formation of local ordered structures; (4) accelerating α-relaxation dynamics at high temperatures and improving the dynamic fragility m. These lead to an upward shift in the temperature region where chain movement is limited and thus improve Tg and high-temperature dimensional stability. In this simulation, the correlation equation between Tg, m, and the microstructural parameters of COCs is established, which is of great significance for the development of COCs with high performance.

Highly flexible and transparent amorphous indium doped tin oxide on bio-compatible polymers for transparent wearable sensors

Highly transparent and flexible amorphous Sn-doped In2O3 (a-ITO) films deposited on flexible and bio-compatible cyclic olefin polymer (COP) substrate using a direct-current magnetron sputtering at room temperature were used as flexible and transparent electrodes for transparent wearable sensors. The figure of merits (FoM) value was calculated to determine the optimal sputtering process for the a-ITO electrodes by varying the direct current power, working pressure, oxygen flow rate, and a-ITO thickness. The optimized a-ITO/COP with a high FoM value of 8.9 exhibited a low sheet resistance of 36 Ohm/square, average transmittances of 89.5 % in the visible wavelength region, and a small critical bending radius of 7 mm, which are acceptable transparent electrodes for fabrication of wearable and transparent wearable sensors. To demonstrate the feasibility of the a-ITO/COP substrate as a promising wearable sensor, we examined the performance of wearable temperature sensors, wearable heaters, and wearable glucose sensors. The successful operation of a-ITO/COP-based temperature sensors with high sensitivity, transparent heaters with a saturation temperature of 87.8 °C at 6 V, and glucose sensors with high sensitivity indicates that a-ITO/COP is a promising bio-compatible electrode for next-generation wearable bionic electronics.

Fluorosilane emulsifying chlortrifluoroethylene ternary copolymerization design towards strong adhesion, anti-corrosion, fluorescent waterborne fluorocarbon coatings for tinplate substrate

Waterborne fluorinated ethylene and vinyl ether copolymer (FEVE) coatings are progressively replacing solvent-based FEVE coatings because of their environmental friendliness. However, their practical application is limited due to the poor adhesion, waterproofing, and corrosion resistance, as well as the environmentally unfriendly nature of the small emulsifiers used. Here, a novel waterborne FEVE coating with excellent adhesion, anti-corrosion, and fluorescent properties was developed using amphiphilic fluorosilane oligomer (PFSQ) as microreactors and chlorotrifluoroethylene (CTFE), isobutyl vinyl ether (IBVE), and glycidyl methacrylate (GMA) as copolymer monomers. The introduction of fluorosilane significantly enhances the hydrophobicity of the coating (the water contact angle increased from 69.3 ± 2.4° to 131.4 ± 1.1°). The epoxy groups in the GMA units of terpolymer facilitate bonding of the coating to the substrate, enhancing the adhesion of the coating to the tinplate substrate (the lap shear strength increased from 0.47 ± 0.04 to 0.92 ± 0.01 MPa). Moreover, the interaction between the epoxy groups of GMA and the silicon hydroxyl groups of PFSQ in the synergistic network leads to the intrinsic luminescence of the coating. In addition, the coating exhibits superior corrosion resistance. The molecular structure design provides a new idea for the development of multifunctional waterborne FEVE coating.

Comparison of vacuum ultraviolet irradiation and oxygen plasma treatment as pretreatment for copper seed layer on cycloolefin polymer

This study explores the factors governing the peel strength characteristics between a cycloolefin polymer (COP) film and a copper plating layer with a copper seed layer, for applying to antenna circuits in 6 G communications. The peel strength depended on the surface modification methods as pretreatment for copper seed layer formation: vacuum ultraviolet (VUV) irradiation and oxygen plasma treatment. VUV irradiation induced a modified layer with brittleness on the COP surface, leading to substrate failure. Conversely, oxygen plasma treatment formed a quite thin modified layer and facilitated Cu2O formation by bonding functional groups on the topmost COP surface with copper in the seed layer at the interface between the COP film and the copper plating layer, resulting in interface failure rather than substrate failure. Therefore, enhancing peel strength involves preventing the formation of a modified layer on the surface and generating a significant quantity of functional groups on the topmost surface.

Surface wettability and tribological performance of Ni-based nanocomposite moulds against polymer materials

In the mass-production of microfluidic devices through micro hot embossing/injection moulding, the longevity of mould inserts is influenced by elevated adhesion and friction between the polymer and the mould. Thus, accurate prediction of mould lifespan requires a comprehensive understanding of surface wettability and tribological performance during polymer contact. The current study addresses this gap by characterizing fabricated micro-structured Ni, Ni-WS2, and Ni-PTFE nanocomposite moulds (surface morphologies, crystal structures and microhardness) to investigate inherent lubrication mechanisms. Surface wettability of mould material was systematically studied by measuring the contact angles with eight different polymer melts. Pin-on-disk tests with polymer pins made of cyclic olefin copolymer (COC 8007), polypropylene (PP), and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) were conducted to elucidate the wear resistance of the nanocomposite moulds. Pressure-dependent friction coefficient and wear resistance were further explored under increasing external loads, simulating the actual moulding processes where contact pressure may vary considerably depending on the part shape. Results indicate that Ni-WS2 exhibits the highest microhardness (532 Hv), followed by Ni-PTFE (465 Hv) and Ni (198 Hv). Notably, Ni-PTFE demonstrates exceptional hydrophobicity against all polymer melts, signifying low surface energy during polymer contact. Moreover, both nanocomposite moulds exhibit reduced friction coefficients and enhanced wear resistance across various polymers. Counterintuitively, despite its lower hardness, the Ni-PTFE mould displays superior wear resistance against the COC pin under higher loads, while the Ni-WS2 mould experiences severe adhesive wear, as observed from wear morphology and profile analysis. This finding establishes the Ni-PTFE as a promising alternative as a mould insert material for precision manufacturing.

Nickel‐ and Palladium‐Catalyzed Copolymerizations of Norbornene with Polar α‐Olefins

AbstractRecent progress regarding the copolymerization of norbornene with various polar α‐olefins catalyzed by nickel and palladium catalysts is reviewed here with special attention paid to the diverse catalyst frameworks, polar monomer scopes as well as polymer microstructures. Both the influences of steric effect and electron property of ligand substituents and the type of polar monomers on the catalytic behaviors (activity, stability, polarity tolerance, etc.) and the polymer microstructures (molecular weight and distribution, comonomer contents, etc.) have been summarized. The introduction of noncyclic‐olefins, such as polar vinyl monomers, polar higher α‐olefins, and polar styrenes, into rigid cyclic‐based polynorbornene chain resulted in significant modifications on the polarity, compatibility, thermostability, processibility, transparency, and many other properties of the material, which has also been discussed in the review. The contents of this review have been classified according to the type of polar monomers involved in the norbornene copolymerization, and each section included nickel and palladium catalysts bearing different ligand structures, which will be meaningful for the development of new types of catalysts and new families of norbornene‐based cyclic olefin copolymer materials in the future.

Mechanistic Insights into Cationic [P,O]-Pd-Catalyzed Chain-Transfer Copolymerization of Ethylene with Carbon Monoxide

Mechanistic Insights into Cationic [P,O]-Pd-Catalyzed Chain-Transfer Copolymerization of Ethylene with Carbon Monoxide

Aqueous Coordination‐Insertion Copolymerization for Producing High Molecular Weight Polar Polyolefins

AbstractHydrocarbons, when used as the medium for transition metal catalyzed organic reactions and olefin (co‐)polymerization, are ubiquitous. Environmentally friendly water is highly attractive and long‐sought, but is greatly challenging as coordination‐insertion copolymerization reaction medium of olefin and polar monomers. Unfavorable interactions from both water and polar monomer usually lead to either catalyst deactivation or the formation of low‐molecular‐weight polymers. Herein, we develop well‐behaved neutral phosphinophenolato nickel catalysts, which enable aqueous copolymerization of ethylene and diverse polar monomers to produce significantly high‐molecular‐weight linear polar polyolefins (219–549 kDa, 0.13–1.29 mol %) in a single‐component fashion under mild conditions for the first time. These copolymerization reactions occur better in water than in hydrocarbons such as toluene. The dual characteristics of high molecular weight and the incorporation of a small amount of functional group result in improved surface properties while retain the desirable intrinsic properties of high‐density polyethylene (HDPE).

Compatibilization of Polyamide 6/Cyclic Olefinic Copolymer Blends for the Development of Multifunctional Thermoplastic Composites with Self-Healing Capability.

This study investigated the self-healing properties of PA6/COC blends, in particular, the impact of three compatibilizers on the rheological, microstructural, and thermomechanical properties. Dynamic rheological analysis revealed that ethylene glycidyl methacrylate (E-GMA) played a crucial role in reducing interfacial tension and promoting PA6 chain entanglement with COC domains. Mechanical tests showed that poly(ethylene)-graft-maleic anhydride (PE-g-MAH) and polyolefin elastomer-graft-maleic anhydride (POE-g-MAH) compatibilizers enhanced elongation at break, while E-GMA had a milder effect. A thermal healing process at 140 °C for 1 h was carried out on specimens broken in fracture toughness tests, performed under quasi-static and impact conditions, and healing efficiency (HE) was evaluated as the ratio of critical stress intensity factors of healed and virgin samples. All the compatibilizers increased HE, especially E-GMA, achieving 28.5% and 68% in quasi-static and impact conditions, respectively. SEM images of specimens tested in quasi-static conditions showed that all the compatibilizers induced PA6 plasticization and crack corrugation, thus hindering COC flow in the crack zone. Conversely, under impact conditions, E-GMA led to the formation of brittle fractures with planar surfaces, promoting COC flow and thus higher HE values. This study demonstrated that compatibilizers, loading mode, and fracture surface morphologies strongly influenced self-healing performance.

Effect of Mold Materials Used During Hot Embossing on Feature Fidelity for Microfabrication in Cyclic Olefin Polymer (COP) Substrate

During the transition from research to market, the fabrication of microfluidic devices in thermoplastic substrates is inevitable. For short production runs of several hundred products, hot embossing is the typical method before moving on to a typically more expensive injection molding process for higher production volumes. In this work, we investigated the effect of mold material used during hot embossing on feature fidelity for microfabrication in cyclic olefin polymer (COP) substrate. Specifically, we designed a simple flow-focusing microfluidic device and fabricated three different molds using silicon wafer by deep reactive ion etching (DRIE), aluminum filled high temperature epoxy by soft lithography and aluminum by CNC milling. We performed hot embossing experiments with 2mm thick COP substrates and these three different molds using automatic bench top Carver hot press. Finally, we characterized the hot embossed substrates by optical and scanning electron microscopy. Fabrication results demonstrate that the mold material plays a big role in feature fidelity. Among the mold materials used, silicon substrate performed the worst based on defects after demolding. Epoxy and aluminum molds were similar in terms of microfabricated feature defects in the substrate which could be mostly attributed to their coefficient of thermal expansion (CTE). A mold material with a CTE closer to the thermoplastic will result in much better feature fidelity.

Surface functionalization of naturally occurring silicate minerals infused hydrocarbon polymer matrix for ultra‐low dielectric performance at high frequency domain

AbstractThe expanding realm of high‐frequency electronics necessitates materials with exceptional attributes: notably, a low dielectric constant (Dk) to minimize signal propagation delays, high thermal conductivity for effective heat dissipation, higher breakdown strength, and robust mechanical properties to withstand demanding operational environments. While cycloolefin copolymers (COC) excel in electrical insulation, chemical resistance, and mechanical durability, their intrinsic slightly higher dielectric constant compared to other polymers, along with challenges such as poor dispersibility and low compatibility with nanoparticles, hinder their full potential in this domain. Considering these drawbacks, this study fabricated a series of COC/mica composites by integrating natural mica particles into the COC matrix via a CTAB‐assisted surface modification of mica to enhance dispersibility and mitigating particle aggregation through in‐situ mixing and hot‐press methods. The resultant composites demonstrate an outstanding ultra‐low Dk of 1.44, marking a significant decrease of over 36% compared to pristine COC with a Dk of 2.26, along with exceptionally low dielectric loss (δ) of 0.00013 at the frequency of 10 GHz, high dielectric breakdown strength ~49.40 kV/mm and enhanced thermal conductivity up to 0.88 W/(m K) at 40% mica loading. Additionally, the composites heightened mechanical performances like tensile strength 69 MPa at 6.5% elongation at break, impact strength up to ~17.9 kJ × m−2, and exceptional water resistance with absorption below 0.097%. These exceptional ultra‐low dielectric performance with above mentioned properties can meet the stringent requirements of modern high‐frequency electronics packaging for next generation electronics development.Highlights Surface modification by CTAB enhanced homogeneous dispersibility of composites. Achieved ultra‐low dielectric constant and loss compared to pure COC. Thermal conductivity improved significantly with incorporation of mica. Unlocking high‐frequency applications potential with ultralow Dk performance.