Polystyrene Chains Research Articles

Entangled linear polymers in fast shear flows: Comparison of tube-model predictions and experimental data

This work addresses the shear response of entangled linear polymers by assessing the current state-of-the-art model and proposing alternative directions. In particular, we examine the performance of the Graham–Likhtman–McLeish–Milner (GLaMM) nonlinear tube model in fast shear flows. Predictions are compared against experimental data for well-characterized, monodisperse, entangled linear polystyrene chains. Unlike previous works using the GLaMM model, finite extensibility is accounted for. Comparison of model predictions and data not only reveals an overall reasonable performance but also highlights limitations. For example, the predictions significantly depend on whether the contribution of contour length fluctuations to the retraction rate is accounted for or not. This specific sensitivity of the model is enhanced as the Rouse–Weissenberg number increases. Possible improvement of the model by modification of the existing mechanisms/model assumptions and/or by incorporation of overlooked mechanisms such as chain tumbling and CCR-driven disentanglement (CCR-D) is discussed. As a possible way to overcome the existing limitations, we propose an alternative approach based on the time marching algorithm (TMA) and focus on the description of the steady-state regime. Compared to the GLaMM model, this approach allows us to keep track of the relaxation state of each entanglement segment in a simple way, while ensuring consistency between chain stretch and constraint release mechanisms. Moreover, it accounts for CCR-D in an indirect manner. A key ingredient is the use of the recently advanced concept of the shear blob and its dependence on the shear rate. Our simple modification of TMA reproduces the experimental steady-state viscosities accurately for all samples and for all shear rates examined.

Distributions of Deuterated Polystyrene Chains in Perforated Layers of Blend Films of a Symmetric Polystyrene-block-poly(methyl methacrylate)

We have examined the spatial distributions of polymer chains in blend films of weakly segregated polystyrene-block-poly(methyl methacrylate) [P(S-b-MMA)] and deuterated polystyrene (dPS). By fine-tuning the composition (ϕPS+dPS = 63.8 vol %) of the total PS/dPS component and annealing temperature (230 and 270 °C), P(S-b-MMA)/dPS blend films mainly form perforated layers with a parallel orientation (hereafter PLs//). The distributions of dPS in PLs// were probed by grazing-incidence small-angle neutron scattering (GISANS) and time-of-flight neutron reflectivity (ToF-NR). GISANS and ToF-NR results offer evidence that dPS chains preferentially locate at the free surface and within the PS layers for blend films that were annealed at 230 °C. Upon annealing at 270 °C, dPS chains distribute within PS layers and perforated PMMA layers. Nevertheless, dPS chains still retain a surface preference for thin films. In contrast, such surface segregation of dPS chains is prohibited for thick films when annealed at 270 °C.

Long‐term efficiency for reducing entanglements of nascent polyethylene by a polystyrene‐modified Ziegler‐Natta catalyst

AbstractThe weakly entangled ultrahigh molecular weight polyethylene (UHMWPE) was synthesized by a Ziegler‐Natta catalyst, where the titanium tetrachloride was anchored on the polystyrene (PS)‐modified silica. The PS chains were successfully incorporated into silica hierarchical pores even with the size less than 10 nm through the in situ free‐radical polymerization of styrene. The self‐diffusion coefficient and crystallization of probing molecules inside the pores were investigated by the pulsed field gradient NMR and thermoporosimetry to address the swollen behavior of incorporated PS blocks. This PS blocks compartmentalized the polyethylene chains, where the less entangled UHMWPE was synthesized with an exceptional activity at 70°C. The ubiquitous PS isolators effectively hindered the formation of chains overlaps during the polymerization, showing a long‐term efficiency to reduce the entanglements of nascent UHMWPE even at 4 h of polymerization The toughness/stiffness/strength balance of weakly entangled UHMWPE was significantly improved.

Cellulose based hyper-crosslinked polymer for efficiently recovering valuable materials from PO/SM wastewater

Herein, a TEMPO-oxidized cellulose-grafted-polystyrene hypercrosslinked polymer (TOC-PS-HCP) was synthesized facilely by TEMPO oxidation, grafting copolymerization and post crosslinking route. Based on the structural characterization, it was confirmed that TOC-PS-HCP mainly consisted of polystyrene chain on cellulose and rigid crosslinked bridge. Additionally, the as-prepared TOC-PS-HCP displayed appropriate hydrophobicity (water contact angle = 102.44°) and high specific surface area (SBET = 601.20 m2·g‐−1), which could efficiently recover ethylbenzene and styrene from PO/SM wastewater. The adsorption experiment was conducted to study the recovery performance for ethylbenzene and styrene in the aqueous phase. The results showed that TOC-PS-HCP could recover ethylbenzene and styrene quickly by adsorption process, and maintain a stable recovery rate both in different aqueous conditions and recycle experiments. The adsorption experiment in the simulated wastewater solution showed that TOC-PS-HCP exhibited the greater affinity for ethylbenzene and styrene than other substrates. Furthermore, a possible mechanism for the efficient recovery of ethylbenzene and styrene was suggested on the basis of experimental and theoretical results, which may be associated with van der Waals force and π-π stacking.

Designing drones by combining finite element and atomistic simulations: a didactic approach

A didactic multiscale approach for drone modeling is proposed. Specifically, we investigate the drone structure at both macroscopic and microscopic scales, by making use of finite element and atomistic simulations, respectively. The structural analysis is performed with the aim to equip the drone with specific sensors and measuring instruments capable to detect the existence of volcanic ash, SO 2 , CO 2 and other pollutants in the atmosphere after a volcanic eruption. We show that, by modeling the tubular structure of the drone with a sandwich constituted by a a polystyrene core, carbon fiber skins and epoxy matrix, a weight saving of 7 grams for each drone arm can be obtained, in comparison to the standard commercial drones, although a slight worsening of the mechanical performances is observed. In addition, the molecular structure of the polystyrene chains has been investigated by using atomistic Molecular Dynamics simulations, providing further information on the local structure of the polymer chains. Additional improvements of the weight saving could be obtained by means of the the topological optimization techniques on the body of the drone and on the supports for landing.

Exploration on structural rules of highly efficient flame retardant unsaturated polyester resins

Owing to the lack of research on structure-activity relationship and interaction mechanism between unsaturated polyester resins (UPR) and flame retardants, it has been a big challenge to prepare high-efficiency flame retardants for UPR in industry. In this research, to explore structural rules of high-efficiency flame retardants, several polymeric flame retardants were synthesized with varied main-chain, side-chain, phosphorus valence states and contents of flame retardant elements. The thermal stabilities of flame retardants and UPR composites were firstly assessed. It has been found the interaction existed between flame retardants and UPR, through transesterification reaction and β scission pathway in polyester and polystyrene chains. With only 15 wt% of PCH3-S, UPR composites can reach V0 rating in UL-94. The PHRR and THR values can be maximumly decreased by 71.66 % and 77.67 %, with 20 wt% of PB-S. It has been found flame retardants with sulfone group and + 3 valence state of phosphorus in molecular backbone can release SO2 and phosphorus containing compounds in gaseous phase, which diluted fuel fragments and catalyzed H⋅ and HO⋅ radical removal. The mechanism for improved flame retardancy of UPR composites with various polymeric flame retardants were discussed in detail. Some general rules for highly efficient flame retardant UPR can be summarized: First, gaseous phase flame retardant mechanism plays the major role in improvement of flame retardant performance of UPR composites; Second, the combination of + 3 valence state of phosphorus structures, higher phosphorus contents and sulfone groups effectively improves the flame retardant efficiency of flame retardants.

Influence of Osmotic Pressure on Nanostructures in Thin Films of a Weakly-Segregated Block Copolymer and Its Blends with a Homopolymer.

We studied the influence of osmotic pressure on nanostructures in thin films of a symmetric weakly-segregated polystyrene-block-poly (methyl methacrylate), P(S-b-MMA), block copolymer and its mixtures with a polystyrene (PS) homopolymer of various compositions. Thin films were deposited on substrates through surface neutralization. The surface neutralization results from the PS mats, which were oxidized and cross-linked by UV-light exposure. Thus, thermal annealing produced perpendicularly oriented lamellae and perforated layers, depending on the content of added PS chains. Nevertheless, a mixed orientation was obtained from cylinders in thin films, where a high content of PS was blended with the P(S-b-MMA). A combination of UV-light exposure and acetic acid rinsing was used to remove the PMMA block. Interestingly, the treatment of PMMA removal inevitably produced osmotic pressure and consequently resulted in surface wrinkling of perpendicular lamellae. As a result, a hierarchical structure with two periodicities was obtained for wrinkled films with perpendicular lamellae. The formation of surface wrinkling is due to the interplay between UV-light exposure and acetic acid rinsing. UV-light exposure resulted in different mechanical properties between the skin and the inner region of a film. Acetic acid rinsing produced osmotic pressure. It was found that surface wrinkling could be suppressed by reducing film thickness, increasing PS content and using high-molecular-weight P(S-b-MMA) BCPs.

Polystyrene magnetic nanocomposite blend: An effective, facile, and economical alternative in oil spill removal applications

Finding an efficient and economical method to remediate oil spills on water is a priority worldwide. In this article, we propose a solution to this problem using polystyrene magnetic nanocomposite blends composed of polystyrene chains grafted on the surface of silica coated on iron oxide nanoparticles and polystyrene. The hydrophobic and oleophilic magnetic polymer nanocomposite collected oil from the water surface quickly and efficiently. However, when the magnetic polymer nanocomposite was blended with polystyrene, the resulting material also absorbed oil efficiently from the water surface. The blending technique made it easier to prepare the absorbent and dramatically decreased its cost. These new absorbents absorbed oil up to 5 times their own weight in only 5 minutes. The excellent hydrophobicity, low density, and easy magnetic separation makes these new absorbents a promising alternative to recover oil from spilled in fresh and marine water.

Random copolymerization of macromonomers as a versatile strategy to synthesize mixed‐graft block copolymers

AbstractThe random copolymerization of norbornene‐functionalized macromonomers was explored as a method of synthesizing mixed‐graft block copolymers (mGBCPs). The copolymerization kinetics of a model system of polystyrene (PS) and poly(lactic acid) (PLA) macromonomers was first analyzed, revealing a gradient composition of side chains along the mGBCP backbone. The phase separation behavior of mGBCPs with PS and PLA side chains of various backbone lengths and side chain molar ratios was investigated, and increasing the backbone length was found to stabilize the phase‐separated nanostructures. The graft architecture was also demonstrated to improve the processability of the mGBCP, compared to a linear counterpart. Investigations of mGBCPs comprised of polydimethylsiloxane and poly(ethylene oxide) side chains exemplified the diverse self‐assembled morphologies, including a Frank‐Kasper A15 phase, that can be obtained with mGBCPs synthesized by random copolymerization of macromonomers. Lastly, a ternary mGBCP was synthesized by the copolymerization of three macromonomers.

Polystyrene perturbs the structure, dynamics, and mechanical properties of DPPC membranes: An experimental and computational study

Synthetic plastic oligomers can interact with the cells of living organisms by different ways. They can be intentionally administered to the human body as part of nanosized biomedical devices. They can be inhaled by exposed workers, during the production of multicomponent, polymer-based nanocomposites. They can leak out of food packaging. Most importantly, they can result from the degradation of plastic waste, and enter the food chain. A physicochemical characterization of the effects of synthetic polymers on the structure and dynamics of cell components is still lacking. Here, we combine a wide spectrum of experimental techniques (calorimetry, x-ray, and neutron scattering) with atomistic Molecular Dynamics simulations to study the interactions between short chains of polystyrene (25 monomers) and model lipid membranes (DPPC, in both gel and fluid phase). We find that doping doses of polystyrene oligomers alter the thermal properties of DPPC, stabilizing the fluid lipid phase. They perturb the membrane structure and dynamics, in a concentration-dependent fashion. Eventually, they modify the mechanical properties of DPPC, reducing its bending modulus in the fluid phase. Our results call for a systematic, interdisciplinary assessment of the mechanisms of interaction of synthetic, everyday use polymers with cell membranes.

Elasticity of single flexible polymer chains in good and poor solvents

Force versus extension curves measure entropic elasticity of single polymer chain in force spectroscopy experiments. A Worm-like Chain model is used to describe force extension experiments with an intrinsic chain parameter called persistence length, which is a measure of local bending flexibility. For flexible polymers, there is a discrepancy in estimates of persistence length in various force regimes. For instance, Atomic Force Microscopy (AFM) based pulling experiments report anomaly low values which are also inconsistent with magnetic tweezers experiments. To understand this, we investigate the role of coupling between microscopic force probe and intrinsic elasticity of polyethylene glycol chain in AFM-based experiments. We perform experiments using oscillatory rheology by providing an external excitation of fixed frequency to the probe. We show that a proper quantification of elastic response measured directly by oscillatory technique deviates significantly from conventional force-extension curves. The persistence length obtained by fitting WLC to stiffness extension data matches well with equilibrium tweezers experiments. In addition, for polystyrene chain in poor solvent no deviation in elastic response is observed between oscillatory and constant velocity pulling experiments. However, such deviation is seen for polystyrene in good solvent. We attribute this to hydrophobic interaction between monomers of polystyrene in water. Our results suggest that oscillatory rheology on single polymer chains provide quantitative estimate of its elastic response. The consistency in values of persistence length using magnetic tweezers experiments in low force regime and the AFM experiments in high force regime suggests that WLC is successful in describing the polymer elasticity in the force range typically probed in AFM experiments.

Stress-Strain and Stress-Relaxation Behaviors of Solution-Coated Layers Composed of Block Copolymers Mixed with Tackifiers.

The relationship between the mechanical properties and the structure of block copolymers mixed with tackifiers whose relative solubility to the respective components of block copolymers differs was examined. Coated layers were prepared by solution coating using a block copolymer composed of polystyrene (PS) and polyisoprene (PI), which forms spherical microdomains of PS in the PI matrix, mixed with three types of tackifiers: aliphatic (C5) resin, aliphatic–aromatic (C5–C9) resin, and rosin ester (RE) resin. Furthermore, the correlation between the changes in the nanostructure and mechanical properties including the stress-relaxation behaviors was clarified by two-dimensional small-angle X-ray scattering measurement. The amount of the PI-bridge conformation in the case of C5 resin is the lowest, resulting in the lowest stress. On the contrary, the largest amount of RE resin was solubilized in the PS phase so that it can be considered that pulling out of the PS chains took place easily. We were able to explain the stress-relaxation behavior by fitting with the three-component exponent functions. The triple exponential decay functions indicate the hierarchy of the structures that are the origins of the ″fast mode″ relating to the local relaxation due to the rotation of the repeating unit of polymer chains; the ″intermediate mode″ of the disentanglement of the mid-PI chains; and the ″slow mode″ relating to, in this particular case, pulling out of the PS chains from the PS sphere.

Universal Chain-End Coupling Conditions for Brominated Polystyrenes, Polyacrylates, and Polymethacrylates

Atom transfer radical coupling (ATRC), performed with or without radical traps, has allowed for high extents of coupling (Xc) for a variety of brominated polymers, yet structurally different polymeric chain ends require unique reagents and reaction conditions. Inspired by a similar study that focused on universal conditions for the controlled polymerization of different monomers using atom transfer radical polymerization (ATRP), this work focuses on developing a single set of conditions (or conditions with as little variation as possible) that will achieve extents of coupling greater than 80% or end-brominated chains of polystyrene (PSBr), poly(methyl methacrylate) (PMMABr), and poly(methyl acrylate) (PMABr). The radical traps α-phenyl-tert-butylnitrone (PBN), 2-methyl-2-nitrosopropane (MNP), and nitrosobenzene (NBz) were chosen in this study, along with copper catalysts, reducing agents, and nitrogen-based ligands. Ultimately, a single set of effective reaction conditions was identified with the only difference being the radical trap used: MNP was effective for coupling PSBr and PMABr while NBz was necessary to achieve similarly high extents of coupling for PMMABr.

Regioselective synthesis of cellulosic janus bottlebrushes with polystyrene and poly (ε-caprolactone) side chains and their solid-state microphase separation

Regioselective synthesis of cellulosic janus bottlebrushes with polystyrene and poly (ε-caprolactone) side chains and their solid-state microphase separation

Surface Functionalization of Graphene Oxide with Polymer Brushes for Improving Thermal Properties of the Polymer Matrix

In this work, polymethyl methacrylate (PMMA) and polystyrene (PS) with controlled structures would be grafted on graphene material. The hybrid materials were prepared by coating graphene oxide (GO) with polydopamine (PDA) as a reactive underlayer and reducing agent, subsequently, surface-initiated polymerization of monomers (methyl methacrylate, styrene) based on the activators regenerated electron transfer atom transfer radical polymerization (ARGET-ATRP) technique. The polymer brush-modified graphene materials were then incorporated into the PMMA or PS matrix to get polymer nanocomposites with better thermal properties. The results of Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA) demonstrated that PMMA and PS chains were successfully anchored on the surfaces of functionalized GO sheets. The influence of the grafted polymer brush-modified GO on thermal stability of PMMA and PS was investigated by a simultaneous thermal analyzer. Thermal conductivity of the polymer nanocomposite was determined by a conductive calorimeter. The results showed that thermal stability, glass transition temperature ( T g ), and thermal conductivity of the polymer nanocomposites were obviously improved compared with pure PMMA or PS.

Glass-Transition Temperature of Cyclic Polystyrene: A Computational Study

Molecular-dynamics simulations are employed to study the glass transition of cyclic polystyrene melts. Gibbs and DiMarzio’s theory predict an increase in glass transition temperature, Tg upon lowering the length of cyclic polymer chains, which is opposite to the well-known trend for linear polymers. Their theory has been confirmed by some experiments; however, others observe a decrease in Tg upon lowering the chain length instead. When volumetric methods are employed to obtain the glass transition temperature in simulated cyclic polystyrene, a slight increase with decreasing cyclic polystyrene chain length is obtained. This increase is more pronounced when glass transition temperatures are obtained from dynamics. Both the glass transition temperature Tg obtained from diffusion data and the ideal glass transition temperature T0 obtained from the decay of the orientational autocorrelation function of the phenyl bond show a clear upturn.

Functionalization of Single-Walled Carbon Nanotubes with End-Capped Polystyrene via a Single-Step Diels-Alder Cycloaddition.

A facile, single-step, [4+2] Diels–Alder cycloaddition reaction for the surface functionalization of single-walled carbon nanotubes (SWNTs) with end-capped polystyrene chains is presented. The thermal cycloaddition reaction took place at high temperature (~230 °C) without any catalyst between the sp2 network of carbon nanotubes, which acted as dienophile, and the diphenylethylene cyclobutene (DPE-CB) terminal group of the polystyrene chain. Anionic polymerization was employed for the synthesis of the polystyrene macromolecule, and successful and quantitative end-capping reaction with the DPE-CB molecule was confirmed by matrix-assisted laser desorption/ionization time of flight mass spectroscopy. Thermogravimetric analysis revealed the wt % of the grafted macromolecule on the CNT surface as well as the grafting density of the polymer chains on the SWNTs (0.027 chains nm−2). Direct evidence for the surface functionalization and the presence of thin polystyrene film was obtained by transmission electron microscopy (TEM) and by atomic force microscopy (AFM).

Brownian Dynamics Simulations of Cavitation-Induced Polymer Chain Scission

In this study, bead–spring Brownian dynamics simulations have been employed to simulate flow-induced chain scission of isolated polystyrene chains exposed to uniaxial elongational flow and ultrasou...

Laser-assisted nanowetting (LAN): Hierarchical Nanocomposites containing polymer/gold nanorods on breath figure films

Polymer nanostructures have drawn tremendous interest in recent years owing to their unique properties and widespread applications in various fields. It is still a great challenge, however, to develop novel methods that are capable of preparing hierarchical polymer structures with patterning ability. To conquer this challenge, in this work, we demonstrate the fabrication of hierarchical structures containing polystyrene (PS)/gold nanorods (AuNRs) by combining the modified breath figure method and the laser-assisted nanowetting (LAN) method. PS/PS-AuNRs films are dipped into good/poor solvents (CHCl3/MeOH) mixture solutions using the modified breath figure method to form the porous films with micrometer-sized pores. Subsequently, the porous films are brought in contact with anodic aluminum oxide (AAO) templates and shone by laser beams. The AuNRs then absorb the laser energy and heat the surrounding polymer chains via plasmonic heating, inducing the PS chains to wet the nanopores of the AAO templates. As a result, hierarchical PS/PS-AuNRs films with controlled regions and dimensions can be obtained. This study opens a new research direction for developing hierarchical polymer structures using porous templates.

Green analogs of polybutadienes from carbon dioxide and epoxy‐based feedstocks

AbstractPolybutadiene has widespread use as a commodity as well as a specialty polymer, but currently, it is prepared from non‐renewable feedstocks. Herein, we report the synthesis of rubbery unsaturated polycarbonates (RUPCs) as green alternatives for polybutadiene. We prepared two RUPCs (respectively, denoted as RUPC1 and RUPC2) via the copolymerization of carbon dioxide (CO2) and a mixture of saturated and unsaturated long‐chain epoxides using a Co(III) catalyst. The RUPCs were reacted with a styrene monomer via free‐radical polymerization to prepare RUPC‐graft‐Polystyrene. All of the prepared polymers were characterized by 1H nuclear magnetic resonance spectroscopy and gel permeation chromatography. For RUPC, the number average molecular weight (Mn) increased by three‐fold after the grafting reaction. Differential scanning calorimetry analysis confirmed that the glass transition temperature (Tg) of the RUPCs were low (~ −40°C) and approached those of polybutadienes. After polystyrene chains had been grafted onto the RUPC backbone, the Tg increased to 81°C. These green RUPCs have the potential to replace non‐renewable polybutadiene in some applications such as high impact materials.