Molecular Weight Polystyrene Research Articles

Sulfenamides as Standalone Flame Retardants for Polystyrene

Efficient standalone sulfenamide based flame retardants consisting of N-benzothiazol-2-ylsulfanyl-N-tert-butyl-benzothiazole-2-sulfenamide (SF-201) or N-cyclohexylthiophthal-imide (SF-205) have been developed for bulk and expanded polystyrene (EPS). In the first set of experiments the sulfenamides were mixed with general purpose polystyrene (GPPS) in a Haake Rheocord melt blender, and in the second set of experiments suspension polymerizations of styrene were carried out in the presence of either of the sulfenamides. Under these experimental conditions SF-201 was deemed to be a more effective flame retardant than SF-205. The third set of experiments involved all the relevant steps for industrial production of EPS: Preparation of polystyrene beads containing pentane as blowing agent and SF-201 as the sole flame retardant, subsequent pre-expansion of the beads at 120 °C with steam and in the last step molding with steam to produce large EPS blocks. The prepared EPS blocks were cut into desired dimensions for EN ISO 11925-2 fire tests. The obtained beads containing SF-201 had a spherical shape and their particle size distribution as well as molecular weights were rather similar to the reference polystyrene beads. Thus, it seems that SF-201 did not have a notably negative influence in the process of breakage and coalescence of monomer/polymer droplets. In addition, the molecular weight distribution remained narrow and a slight decrease in polystyrene molecular weights were observed in comparison to neat polystyrene prepared under similar conditions. The flame retardant efficacy of SF-201 as a standalone flame retardant in EPS was high, as at 2.5 % loading of SF-201 in EN ISO 11925-2 ignitability test the EN 13501-1 E class with no flammable droplets was obtained. The thermogravimetric analysis (TGA) carried out under inert atmosphere revealed enhanced and earlier onset of polystyrene degradation in the presence of sulfenamides. The enhanced polystyrene degradation led to a lowering of melt viscosity that facilitated an effective mass transfer of fuel and heat away from the fire zone. The pyrolysis gas chromatography-mass spectrometry (PyGCMS) measurements of blends showed a lower level and number of polystyrene related degradation products (styrene, multiple dimer and trimer species) and evidence of parent SF-201 flame retardant molecule was no longer visible. Whereas new volatile amine species such as tert-butylamine and N-tert-butyl-2-benzothiazolesulfenamide were detected which relate to flame retardant activity in the condensed phase and potentially radical scavenging of key combustion radicals (H., .OH) in gas-phase.

Enhancing response time of micro-patterned thermoresponsive hydrogels by incorporation of pores

Micro-patterned hydrogels have received increasing attention in various research fields that need a fine structure and advanced functions compared to bulk hydrogels. For enhancing their performance, control of the size and distribution of pores in hydrogels is crucial. In particular, for the application of thermoresponsive hydrogels to a soft actuator, the characteristics of pores play an important role in enhancing the response time. We formed a porous structure in micro-patterns of polydiethylacrylamide (PDEAM), a thermoresponsive hydrogel, and analyzed the effect of pore size on the response time of the patterned hydrogels. Micro-patterned thermoresponsive hydrogels are fabricated by photo-crosslinking PDEAM copolymerized with benzophenone photo-crosslinker and polystyrene (PS) as a porogen. Pores sufficiently smaller than patterned objects, between a few micrometers to a few tens of micrometers, are successfully formed by controlling the content and molecular weight of PS. As the size and number of pores increase, the response time is improved, and the response time for swelling and deswelling is improved by up to 52 and 43% by blending PDEAM with 50 vol% of low molecular weight PS (5 kg/mol). This simple way to form a sub-millimeter scale hydrogel structure with controlled pores can be utilized in the emerging research fields, including 3D cell scaffolds, targeted drug delivery, and soft robotics.

Chain Transfer to Solvent and Monomer in Early Transition Metal Catalyzed Olefin Polymerization: Mechanisms and Implications for Catalysis

Even after several decades of intense research, mechanistic studies of olefin polymerization by early transition metal catalysts continue to reveal unexpected elementary reaction steps. In this mini-review, the recent discovery of two unprecedented chain termination processes is summarized: chain transfer to solvent (CTS) and chain transfer to monomer (CTM), leading to benzyl/tolyl and allyl type chain ends, respectively. Although similar transfer reactions are well-known in radical polymerization, only very recently they have been observed also in olefin insertion polymerization catalysis. In the latter context, these processes were first identified in Ti-catalyzed propene and ethene polymerization; more recently, CTS was also reported in Sc-catalyzed styrene polymerization. In the Ti case, these processes represent a unique combination of insertion polymerization, organic radical chemistry and reactivity of a M(IV)/M(III) redox couple. In the Sc case, CTS occurs via a σ-bond metathesis reactivity, and it is associated with a significant boost of catalytic activity and/or with tuning of polystyrene molecular weight and tacticity. The mechanistic studies that led to the understanding of these chain transfer reactions are summarized, highlighting their relevance in olefin polymerization catalysis and beyond.

Study on the Dissolution and Diffusion of Supercritical Carbon Dioxide in Polystyrene Melts Based on Adsorption and Diffusion Mechanism.

In order to reveal the dissolution process, the adsorption kinetics and diffusion theory are combined and used to describe the adsorption-diffusion mechanism. This can not only predict the solubility of supercritical CO2 in polymer melts but also describe two important parameters of supercritical CO2 in the dissolution process: dissolution amount and dissolution rate, which can provide a good theoretical basis for microcellular foaming. To verify the feasibility and accuracy of the theoretical calculation method, an experimental device for the volume-changing method under static condition was established. The results showed that the theoretical calculation value was in good agreement with the experimental value. In addition, the dissolution amount and dissolution rate of supercritical CO2 in three polystyrene melts with different molecular weights under different temperature and pressure conditions were measured. The results showed that the difference of polystyrene molecular weight can cause the change of dissolution rate during the dissolution process, that is, the larger the molecular weight, the slower the dissolution rate.

Molecular dynamics in the supercooled liquid and glassy states of bezafibrate and binary mixture of fenofibrate

Two solubility limited pharmaceuticals bezafibrate and fenofibrate, belonging to BCS class II drugs, were compared, by investigating molecular dynamics of the former and compared with the neat and as a probe in an apolar host polystyrene of mole. wt. 800 (PS800) of the latter by broadband dielectric spectroscopy (BDS), other supporting thermal and spectroscopic experimental means and density functional theory (DFT) calculations. The BDS experiments from frozen glassy state to vibrant molten state of the title drugs were done to explore the role of parameters describing their complex molecular dynamics and the stabiliy of amorphous phase, such as glass transition temperature (Tg), temperature dependence of α-relaxation times (τα), width of structural dispersion and its role on the occurrence of Johari-Goldstein (JG) β-relaxation, fragility index (m) and apparent activation energy of secondary processes. Realizing that most of the pharmaceuticals have narrow α-dispersion which limits the visibility of JG β-relaxation as a separate process in the dielectric window, to resolve the conundrum, we have further explored the amorphous dynamics of fenofibrate as a probein an apolar host polystyrene of molecular weight 800 (PS800) having higher Tg than the polar probe. The Tg of bezafibrate and PS800-fenofibrate mixture were determined to be 298 K and 275 K respectively, whereas the fractional exponent of Kohlrausch–Williams–Watts function βKWW of bezafibrate was determined to be 0.68 which is closer to that of fenofibrate, whereas that of PS800-fenofibrate mixture was found to be much broader with a value of 0.39, all in the vicinity of Tg. Even though βKWW decreased in binary mixture of fenofibrate when compared to its pure form due to concentration fluctuations and other aspects, but cold crystallization tendency was absent and Tg is elevated than that of fenofibrate. Due to higher Tg than that of fenofibrate, amorphous bezafibrate is more stable than fenofibrate. Finally, using quantum computational calculations using DFT, the relevant flexible parts of the two drug molecules, whose motions manifests the secondary γ-relaxation was identified by calculating potential energy barriers and dipole moments on relaxed dihedral angle scans, as no experimental technique is available for this purpose.

Glass Transition of Disentangled and Entangled Polymer Melts: Single-Chain-Nanoparticles Approach.

We study the effect of entanglements on the glass transition of high molecular weight polymers, by the comparison of single-chain nanoparticles (SCNPs) and equilibrated melts of high-molecular weight polystyrene of identical molecular weight. SCNPs were prepared by electrospraying technique and characterized using scanning electron microscopy and atomic force microscopy techniques. Differential scanning calorimetry, Brillouin light spectroscopy, and rheological experiments around the glass transition were compared. In parallel, entangled and disentangled polymer melts were also compared under cooling from molecular dynamics simulations based on a bead-spring polymer model. While experiments suggest a small decrease in the glass transition temperature of films of nanoparticles in comparison to entangled melts, simulations do not observe any significant difference, despite rather different chain conformations.

Spatial structures formation of surface-modified nanoparticles in polymer nanocomposite thin films

The spatial structures of polystyrene (PS) nanocomposite thin films containing oleic acid-modified nanoparticles were investigated. A layer of the nanoparticles was formed at the surface of the thin film under all conditions in this work. Aggregates of the nanoparticles were formed simultaneously in the film when the concentration of the nanoparticles was relatively high. The effects of the evaporation rate and the molecular weight of PS on the spatial structures of the nanoparticles in the thin films were discussed using the ratio of the time constants for phase separation (diffusion) of the nanoparticles, gravitational sedimentation of the aggregates and drying. As the ratio of the diffusion time to the drying time increased, the thickness of the nanoparticle layer and the diameter of the nanoparticle aggregates decreased, and then reached a constant value. When the ratio of the sedimentation time to the drying time was high, the relatively small aggregates were dispersed throughout the thin film since the effect of gravitational sedimentation was small.

Diffusion and Thermodynamics of Polystyrene Mixing with Block and Gradient Copolymers of Butyl Acrylate and Styrene

Phase equilibria in systems polystyrene–block and gradient n-butyl acrylate–styrene copolymers are studied for the first time using optical interferometry for polystyrene of various molecular weight and copolymers of different architecture. Phase diagrams, which are characterized by the upper critical solution temperatures, are constructed. The pair interaction parameters for these systems are calculated, and the thermodynamics of mixing of the components is evaluated. The data on the interdiffusion of polystyrene into the copolymer and the copolymer into polystyrene are obtained. The effect of the composition of copolymers on their interaction with polystyrene is analyzed. The friction coefficients of macromolecules and the diffusion coefficients of monomer units are calculated. It is shown that these values are independent of the molecular weight of the diffusant and the architecture of the copolymer.

Effect of polystyrene molecular weight and zinc oxide concentration on dewetting behavior of polymeric thin films

The separation between ultra-thin polymer film on metal oxide substrate is called dewetting. Dewetting causes the polymer films to loss their stability and other important properties, for example, the films may short circuit or reduce their transparency. Therefore, the stability of polymer thin films on substrate need to be improved. Addition of nanoparticles is one of the most popular technique used to increase the stability of polymer thin films. The correlation between the different of molecular weight and ZnO concentration on dewetting behavior was studied in this research. The appropriate concentration of ZnO on dewetting suppression in each molecular weight was examined. Furthermore, the variation of dewetting pattern in each molecular weight system was analyzed. In this research, PS (13K and 30K) solutions mixed with ZnO suspension in toluene were prepared. The concentrations of ZnO in PS solution were 0-1.0 wt%. All composite thin films were coated by spin-casting technique and annealed at a temperature of 100°C in a vacuum oven to induce dewetting behavior. The topographies of annealed thin films were studied by using Optical microscope (OM) and Scanning electron microscope (SEM). The thicknesses of thin films were examined by Atomic force microscope (AFM). The surface energies of PS and PS-ZnO composite films were measured and calculated by using contact angle measurement. From the results, we found that addition of ZnO nanoparticles at concentrations 0.7 and 1.0 wt% are the optimum concentration for dewetting inhibition of PS13K and PS30K films, respectively.

Application of 1H DOSY NMR in Measurement of Polystyrene Molecular Weights

In this work, we studied the applicability of diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR) as an alternative method in determination of polystyrene molecular weight. DOSY NMR spectroscopy allows measuring the diffusion coefficient of molecule which directly depend on hydrodynamic radius and so on, average molar mass in weight (Mw). By using commercial polystyrene (PS) standards, an external calibration curve was established. Based on the excellent linear correlation between diffusion coefficient (logD) and molecular weight (logM), the molecular weight of polystyrene can be predicted using the following equation . The validation was done by comparing with the Mw value obtained by gel permeation chromatography within less than 5% deviation. From the diffusion coefficient, some property of polystyrene in solution, such as Flory coefficient and polymer-solvent interaction, were also studied. The Flory coefficient confirmed that chloroform is a good solvent for PS.

Metagenomic Exploration of Plastic Degrading Microbes for Biotechnological Application.

Since the last few decades, the promiscuous and uncontrolled use of plastics led to the accumulation of millions of tons of plastic waste in the terrestrial and marine environment. It elevated the risk of environmental pollution and climate change. The concern arises more due to the reckless and unscientific disposal of plastics containing high molecular weight polymers, viz., polystyrene, polyamide, polyvinylchloride, polypropylene, polyurethane, and polyethylene, etc. which are very difficult to degrade. Thus, the focus is now paid to search for efficient, eco-friendly, low-cost waste management technology. Of them, degradation of non-degradable synthetic polymer using diverse microbial agents, viz., bacteria, fungi, and other extremophiles become an emerging option. So far, very few microbial agents and their secreted enzymes have been identified and characterized for plastic degradation, but with low efficiency. It might be due to the predominance of uncultured microbial species, which consequently remain unexplored from the respective plastic degrading milieu. To overcome this problem, metagenomic analysis of microbial population engaged in the plastic biodegradation is advisable to decipher the microbial community structure and to predict their biodegradation potential in situ. Advancements in sequencing technologies and bioinformatics analysis allow the rapid metagenome screening that helps in the identification of total microbial community and also opens up the scope for mining genes or enzymes (hydrolases, laccase, etc.) engaged in polymer degradation. Further, the extraction of the core microbial population and their adaptation, fitness, and survivability can also be deciphered through comparative metagenomic study. It will help to engineer the microbial community and their metabolic activity to speed up the degradation process.

Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing.

Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs were grafted with low molecular weight polystyrene (PS) chains in order to be segregated in a specific phase of the matrix to induce selective localization. After the mixing of the BCPs with 10% w/v PS-g-MNPs, nanocomposite thin films were formed by spin coating. Solvent vapor annealing (SVA) enabled the PS-g-MNPs selective placement within the PS domains of the BCPs, as revealed by atomic force microscopy (AFM). The recorded images have proven that high amounts of functionalized MNPs can be controllably localized within the same block (PS), despite the architecture of the BCPs (AB vs. ABC). The adopted lamellar structure of the “neat” BCP thin films was maintained for MNPs loading approximately up to 10% w/v, while, for higher content, the BCP adopted lamellar morphology is partially disrupted, or even disappears for both AB and ABC architectures.

Polymer Free Volume Effects on Protein Dynamics in Polystyrene Revealed by Single-Molecule Spectroscopy.

Protein-polymer interactions are critical to applications ranging from biomedical devices to chromatographic separations. The mechanistic relationship between the microstructure of polymer chains and protein interactions is challenging to quantify and not well studied. Here, single-molecule microscopy is used to compare the dynamics of two model proteins, α-lactalbumin and lysozyme, at the interface of uncharged polystyrene with varied molecular weights. The two proteins exhibit different surface interaction mechanisms despite having a similar size and structure. α-Lactalbumin exhibits interfacial adsorption-desorption with residence times that depend on polymer molecular weight. Lysozyme undergoes a continuous time random walk at the polystyrene surface with residence times that also depend on the molecular weight of polystyrene. Single-molecule observables suggest that the hindered continuous time random walk dynamics displayed by lysozyme are determined by the polystyrene free volume, a finding supported by thermal annealing and solvent quality studies. Hindered dynamics are dominated by short-range hydrophobic interactions where the contributions of electrostatic forces are negligible. This work establishes a relationship between the microscale structure (i.e., free volume) of polystyrene polymer chains to nanoscale interfacial protein dynamics.

Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly

The spontaneous formation of periodic nanopatterns through the self-assembly of block copolymer (BCP) thin films offers an enticing path to engineer functional material properties over large areas, but the prohibitively slow ordering of ultrahigh molecular weight BCPs that generate large pattern periods (>100 nm) severely restricts the design space in which BCPs may be used. Here, we demonstrate that blending lamellae-forming polystyrene-block-poly(methyl methacrylate) diblock copolymers with very low molecular weight polystyrene and poly(methyl methacrylate) homopolymers can reduce by an order-of-magnitude the times required to form ordered large period patterns through solvent vapor annealing. Using in situ grazing-incidence small-angle X-ray scattering and ex situ electron microscopy, we show that the added homopolymer plasticizers act as a “smart solvent”: They increase the mobility of the long BCP chains by amplifying the dilution effect during solvent vapor annealing but segregate to like domains du...

Phase-equilibrium measurement of a carbon dioxide/toluene/polystyrene ternary system using laser turbidimetry

The phase behavior of a carbon dioxide (CO2)/toluene (Tol)/polystyrene (PS) ternary system was measured. The measurements were performed using a synthetic method combined with a reflected light intensity measurement. The bubble points were determined by visual observation, and the cloud points were determined from the change in the reflected light intensity. The phase boundaries were measured at temperatures ranging from 313.2 K to 373.2 K and CO2 weight fractions ranging from 0.10 to 0.41. The homogeneous phase area decreased when the molecular weight of PS and/or the ratio of PS to Tol increased. It was found that the phase behavior of ternary systems, especially the liquid-liquid phase separation behavior, was altered by a change in the mutual solubility between the three components.

Influence of solvent and molecular weight in wrinkle formation in spin-cast polystyrene thin films

The surface morphology of polystyrene thin films formed from various molecular weight polystyrene and solvent conditions is studied. When spin-cast from tetrahydrofuran (THF) wrinkles are formed at the extremities that have periodicity with wavelengths in the μm range and amplitudes in the nm range but varies with molecular weight. A mixed solvent system consisting of THF and dimethylformamide (DMF) leads to periodic structures only with THF-rich compositions. THF and DMF have similar properties relevant to spin-casting: density, surface tension, molecular weight, and viscosity but different boiling points and room temperature vapor pressures, demonstrating that formation periodicity requires a volatile solvent. The formation of the surface structures is attributed to the Marangoni effect and the film thicknesses and wave parameters are shown to be consistent with literature models.

Thermal performance of nanoencapsulated phase change material in high molecular weight polystyrene

Abstract A novel nanoencapsulation of n-hexadecane in high molecular weight polystyrene nanoparticles for thermal energy storage was carried out by miniemulsion polymerization using an iron-containing imidazolium-based ionic liquid (IL) as catalyst. The particle size, morphology, molecular weight, and thermal performance of nanoparticles containing the phase change material (PCM) were measured by dynamic light scattering, transmission electron microscopy, gel permeation chromatography, and differential scanning calorimetry, respectively. The nanoparticles were regular spherical, with narrow size distribution and particle size ranged from 138 nm to 158 nm. The enthalpy of melting for the nanoencapsulated PCM increased from 19 J/g to 72 J/g, as the content of n-hexadecane used increased from 20 wt% to 50 wt%. In addition, the nanoparticles showed thermal reversibility after 100 thermal cycles. The high molecular weights of the polymer, up to 1800 kDa, that could be reached with this IL may have contributed positively to this thermal behavior.

Complexes of end-functionalized polystyrenes carrying amine end-group with transition metals: association effects in organic solvents

Linear end-functionalized polystyrenes of different molecular weights bearing amino end-group (NPS) were synthesized by anionic polymerization high vacuum techniques. The polymers were exposed to copper and iron salts (CuCl2.2H2O and FeCl3.6H2O) to form complexes with specific metal/amino molar ratios. The thermal stability of these complexes was studied by Thermogravimetric Analysis (TGA) and Differential Thermogravimetry (DTG), whereas their solution behavior was studied by Low Angle Laser Light Scattering (LALLS), Dynamic Light Scattering (DLS) and dilute solution Viscometry. Extended aggregation phenomena of these complexes were observed in organic solvents. The association behavior was influenced by the molecular weight of the polymer chain, the metal/amine group molar ratio, the chemical nature of the metal and the polarity of the solvent. A complex situation was revealed by DLS showing the existence of equilibrium between aggregates and clusters. Under the influence of shear forces applied in the capillary tube of the viscometer the clusters are disrupted.

Characterizing effects of fast melt deformation on entangled polymers in their glassy state.

Fast deformation of entangled melts is known to cause chain stretching due to affinelike straining of the entanglement network. Since the chain deformation may also result in perturbations of covalent bond angles and bond length, there are always possible enthalpic effects. In this study, we first subject polystyrene and PMMA of different molecular weights to either uniaxial melt extension or planar extension and subsequently impose rapid thermal quenching to preserve the chain deformation. Then, such pre-melt-deformed samples are annealed at various temperatures below the glass transition temperature Tg. During annealing, these samples can undergo appreciable contraction on a time scale much shorter than the alpha relaxation time. Significant retractive stress is observed when such contracting samples are held fixed during the annealing. The stress level can be nearly as high as the Cauchy stress produced during melt stretching. These observations not only allowed us to investigate glassy chain dynamics as well as the molecular nature of mechanical stress but may also suggest that pre-melt-stretched polymers can cause segmental mobilization in the glassy state. The available evidence indicates that the retractive stress is enthalpic in origin, associated with the conformational distortion at the bond level produced by melt stretching.

Correlating fragility and heterogeneous dynamics in polystyrene through single molecule studies.

Many macroscopic properties of polymers depend on their molecular weight, with one notable example being glass transition temperature: polymers with higher molecular weights typically have higher glass transition temperatures than their lower molecular weight polymeric and oligomeric counterparts. Polymeric systems close to their glass transition temperatures also exhibit interesting properties, showing both high (and molecular weight dependent) fragility and strong evidence of dynamic heterogeneity. While studies have detailed the correlations between molecular weight and fragility, studies clearly detailing correlations between molecular weight and degree of heterogeneous dynamics are lacking. In this study, we use single molecule rotational measurements to investigate the impact of molecular weight on polystyrene's degree of heterogeneity near its glass transition temperature. To this end, two types of fluorescent probes are embedded in films composed of polystyrene ranging from 0.6 to 1364.0 kg mol-1. We find correlation between polystyrene molecular weight, fragility, and degree of dynamic heterogeneity as reported by single molecule stretching exponents but do not find clear correlation between these quantities and time scales associated with dynamic exchange.