Short Polymerization Time Research Articles

Optimizing light and heavy aromatic ratios in fluid catalytic cracking slurry oil for mesophase pitch with wide-area optically anisotropic texture

Aromatics are the preponderant component of fluid catalytic cracking (FCC) slurry oil, with notable differences in molecular structure between the light and heavy aromatics. The effect of these differences on the formation and optically anisotropic texture of mesophase remains elusive, impeding the preparation of high-quality mesophase pitch. This paper aims to regulate the ratio of light to heavy aromatics in the FCC slurry oil for optimizing the optically anisotropic texture of mesophase pitch. The results show that the heavy aromatics possess higher aromaticity, longer alkane side chains, larger molecular size and more reactive structures (methylene bridges, n-alkane structures) compared with the light aromatics. As an “accelerator”, heavy aromatics can form mesophase quickly. Light aromatics not only served as a “diluent,” but also assumed the function of a “lubricant”, which facilitated the orderly arrangement of aromatic molecular lamellar. The system exhibits moderate reactivity that inhibits excessive condensation and modifies the structural orientation of pyrolysis products with the 2/5 ratio of light to heavy aromatics. Under these conditions, a high-quality mesophase pitch (d002 = 3.485 Å, Lc = 19.832 Å) with wide-area optically anisotropic texture, suitable softening point (262 °C) and short polymerization time (t = 5.5 h) was obtained. This work provides theoretical support for the preparation of high-quality mesophase pitch by regulating the components of slurry oil.

PISOX Copolyesters-Bio- and CO2-Based Marine-Degradable High-Performance Polyesters.

Oxalate esters and isosorbide serve as intriguing polymer building blocks, as they can be sourced from renewable resources, such as CO2 and glucose, and the resulting polyesters offer outstanding material properties. However, the low reactivity of the secondary hydroxyl groups makes it difficult to generate high-molecular-weight polymers from isosorbide. Combining diaryl oxalates with isosorbide appears to be a promising approach to produce high-molecular-weight isosorbide-based polyoxalates (PISOX). This strategy seems to be scalable, has a short polymerization time (<5 h), and uniquely, there is no need for a catalyst. PISOX demonstrates outstanding thermal, mechanical, and barrier properties; its barrier to oxygen is 35 times better than PLA, it possesses mechanical properties comparable to high-performance thermoplastics, and the glass transition temperature of 167 °C can be modified by comonomer incorporation. What makes this high-performance material truly exceptional is that it decomposes into CO2 and biomass in just a few months in soil under home-composting conditions and it hydrolyzes without enzymes present in less than a year in 20 °C water. This unique combination of properties has the potential to be utilized in a range of applications, such as biomedical uses, water-resistant coatings, compostable plastic bags for gardening and agriculture, and packaging plastics with diminished environmental impact.

Electrochemical visualization of latent fingerprints using polyphenazine dyes on brass cartridges

This work is focused on the visualization of latent fingerprints left on unfired brass cartridges. Polymer films were prepared from 2 mM neutral red or 5 mM toluidine blue using two different electrochemical methods (cyclic voltammetry or chronoamperometry) with relatively short polymerization times. The conditions for the deposition of conductive polymers, poly(neutral red) and poly(toluidine blue), from a neutral medium (phosphate buffer with 0.1 M KNO3 or 0.1 M KNO3, respectively) were optimized to produce high-quality visualization of the remaining fingerprints on the brass substrates. The surface morphology and quality of the polymer films after the electrochemical deposition of both polyphenazine dyes were characterized by stereomicroscope. Phenazine dyes, which were used for the visualization of fingerprints, have been shown to provide different degrees of homogeneity in the deposited film. Furthermore, the dependence of the stability of the monomer solutions on their age, use, and storage conditions are discussed. Finally, a methodology is proposed for how to apply this technique of visualizing latent fingerprints with observed details of papillary lines in forensic practice.Graphical abstract

Thermochemical and rheological characterization of highly reactive thermoset resins for liquid moulding.

Highly reactive thermosets are currently expanding the processability of high-performance structures for transportation industry. The short polymerization time makes it a suitable process to replace metallic structures with polymer matrix-based composite materials. The resin characterization is a fundamental step to obtain the properties and the associated constitutive models, which are required to design and optimize the manufacturing process parameters of composite materials. However, the short time on polymerization requires to use the characterization equipment at their performance capability limits. This work presents a comprehensive methodology to characterize the thermo-chemical properties of highly reactive resin systems, which are relevant for resin impregnation into the preform for liquid injection processes. Four different commercial resin systems are analyzed in this study. Experimental methodologies are analyzed and adapted for best data acquisition at high temperature isothermals. Based on the experimental data, Cure kinetics and viscosity equation-based models are used to describe the behaviour of these complex resin systems. Processing maps are developed based on the cure kinetics and viscosity models to predict the processability time for specific process conditions than can be used on liquid injection moulding processes.

Statistical Copolymers Comprising Bio‐Based Aromatic Methacrylate Segments and Their Influence on the Glass Transition Temperature

AbstractSynthesis of statistical copolymers is described from bio‐based 4‐(4‐methacryloyloxyphenyl)butan‐2‐one (1) with an aliphatic methacrylate, such asn‐butyl methacrylate (2),N,N‐(dimethylamino)ethyl methacrylate (3), and lauryl methacrylate (4), using mostly dimethyl sulfoxide as solvent in the free radical polymerization. Though4 is insoluble in dimethyl sulfoxide, diethyl carbonate is the preferred solvent for the copolymerization using this monomer although both yield and molecular weight are lower even for poly(4‐(4‐methacryloyloxyphenyl)butan‐2‐one) than using dimethyl sulfoxide as solvent.1H NMR spectroscopic analysis gives information about the content on the monomer segments in all copolymers. Furthermore, elementary analysis additionally supports the results obtained for the copolymers made from1 and3. As shown by the copolymerization diagrams and the copolymerization parameters, the copolymerization of1with2is a nearly ideal copolymerization using short polymerization time (20 min). Extending the polymerization time results in slight deviation from an ideal copolymerization. Furthermore, the glass transition temperature of the copolymers determined by DSC and calculated using both the Fox equation and the Gibbs‐DiMarzio equation show the strong influence of the copolymer composition. As expected, the glass transition temperature increases with increasing content on aromatic segments in the copolymer that may be interesting for application in coatings and adhesives, respectively.

Rapid Ring-Opening Polymerization of γ-Butyrolactone toward High-Molecular-Weight Poly (γ-butyrolactone) by an Organophosphazene Base and Bisurea Binary Catalyst.

The low temperature condition, long reaction time and associated high energy inputs involved in the polymerization process still hampered the scalable production of poly(γ-butyrolactone) (PγBL) via ring-opening polymerization (ROP) of low strained γBL due to its unfavorable thermodynamics. In this contribution, we presented the rapid ROP of γBL using a bisurea in combination with an organophosphazene base as the binary catalyst. Well-defined PγBL samples with various terminal groups were prepared by using different alcohol initiators. The bisurea as a co-catalyst exhibited much higher catalytic activity even compared to the most active monourea in previous report as supported by the kinetic experiments. A moderate monomer conversion of 61% was achieved within 10 mins, producing high-molecular-weight PγBL with Mn up to 37.5 kDa and good mechanical properties. The short polymerization time considerably reduced the energy cost for the ROP of γBL conducted at low temperature condition. This study may clear away obstacles for the scalable production and practical applications for PγBL.

Effect of Polymerization Time on the Binding Properties of Ciprofloxacin-Imprinted nanoMIPs Prepared by Solid-Phase Synthesis.

An innovative approach to imprinted nanoparticles (nanoMIPs) is represented by solid-phase synthesis. Since the polymeric chains grow over time and rearrange themselves around the template, the binding properties of nanoMIPs could depend on the polymerization time. Here we present an explorative study about the effect of different polymerization times on the binding properties of ciprofloxacin-imprinted nanoMIPs. The binding properties towards ciprofloxacin were studied by measuring the binding affinity constants (Keq) and the kinetic rate constants (kd, ka). Furthermore, selectivity and nonspecific binding were valued by measuring the rebinding of levofloxacin onto ciprofloxacin-imprinted nanoMIPs and ciprofloxacin onto diclofenac-imprinted nanoMIPs, respectively. The results show that different polymerization times produce nanoMIPs with different binding properties: short polymerization times (15 min) produced nanoMIPs with high binding affinity but low selectivity (Keq > 107 mol L−1, α ≈ 1); medium polymerization times (30 min–2 h) produced nanoMIPs with high binding affinity and selectivity (Keq ≥ 106 mol L−1, α < 1); and long polymerization times (>2 h) produced nanoMIPs with low binding affinity, fast dissociation kinetics and low selectivity (Keq ≤ 106 mol L−1, kdis > 0.2 min−1, α ≈ 1). The results can be explained as the combined effect of rearrangement and progressive stiffening of the polymer chains around the template molecules.

Sub10 μm macroporous aramid substrates with a hierarchically structured interface for organic solvent nanofiltration

Compared with traditional methods for elaborately tailoring the active layer of thin-film composite (TFC) membranes, this study focused on building novel substrates for potential applications in developing organic solvent nanofiltration (OSN) membranes. One kind of “three-parts” hierarchically structured interface with nanospheres and macro surface pores was successfully prepared via Michael addition and Schiff's base (M&S) reactions between N-(2-aminoethyl)-3-aminopropyl triethoxysilane (NAE-A) and glycerite (a natural polyphenol) in the aramid substrate. The thickness was reduced to sub10 μm with the aid of the high-speed spin coating process coupling nonsolvent-induced phase separation (HSSC-co-NIPS) method. The composition characterization results demonstrated the introduction of glycerite, and the reactions occurred in/on the substrate. Scanning electron microscopy (SEM) images clearly showed that the sub10 μm substrate contained a “three-level” hierarchically structured interface that included: (1) a “stalk-like” structure; (2) glycerite-NAE-A silane (GNAS) nanospheres; and (3) the substrate surface. These phenomena also resulted in better surface hydrophilicity. All types of organic solvents, including harsh solvents, such as tetrahydrofuran (THF) and N,N-dimethylformamide (DMF), had stable permeability within the substrate, as did apolar n-hexane and isopar™ G. Therefore, the as-prepared TFC OSN membrane, which had an extremely short polymerization time, retained broad-spectrum solvent stability and had the highest solvent permeance in acetonitrile (24.5 ± 0.4 L m−2 h−1·bar−1). In addition, the resultant TFC membrane almost completely rejected the popular macrolide antibiotic azithromycin (AZM, 748.98 g mol−1) in ethanol, which is used to treat COVID-19.

Morphometric Characteristics of Renal Vessels and Ureter Concerned on Mulages Obtained by Plastic Injections

The study was performed on a number of 48 plastic molds, obtained by injection of Technovit 7143. Technovite is a self-curing resin based on methyl methacrylate. Technovite no longer requires the use of dyes that can adversely affect the polymerization process and has a short polymerization time, making corrosion possible shortly after injection.

Effect of Acrylic Polymerization on Cytotoxicity, Residual Monomer Content and Mechanical Properties

Introduction: The aim of this study was to test and find connection between three different parameters of acrylic resins: cytotoxicity, residual monomer content in the material and flexural strength. Materials and Methods: Superacryl Plus (SpofaDental, Czech Rep.) acrylic material has been polymerized in three different ways, short-time polymerization (45 minutes), normal time (90 minutes) and long-time (7 hours 30 minutes). Flexural strength was tested in compressive instrument Shimadzu for 65 × 10 × 3.3 mm samples. Then after 24 hours the samples were broken. In 50 mm diameter and 1 mm thick samples, residual monomer was determined by gas chromatography (according to ISO standard), and the last series of the sample was used to perform cytotoxicity tests (5 mm diameter). Statistical analysis: Data were analyzed by two-way ANOVA (in GraphPad Software Inc., San Diego, CA, USA), with p-value < 0.05 as statistically significant. Results: The results from the tests show that the greatest inhibition in the development of cell cultures (VERO CCL-81) by MTT assay), was observed for the sample polymerized in the first short-time method (73.49±10%). The material also had the largest content of residual monomer 2.02±0.08% (p-value < 0.01) and lowest flexural strength 71.53±2.26 MPa. Hardened acrylic resins over 60 minutes do not adversely affect cell cultures (undisturbed growth 83.18±10.72%). The residual monomer content was below 1% (p-value < 0.01) and the mechanical resistance to fracture was over 80 MPa (p-value < 0.01). Conclusion: The use of a short polymerization method of acrylic materials can adversely affect both the mechanical properties of the prosthesis itself and its biocompatibility. From a clinical point of view, it is important to take care about the polymerization times of acrylic. Dentures for allergic patients should be carried out in long-term polymerization when the content of residual monomer is as low as possible.

Influence of butyl group of tin chloride initiators on the non-isothermal DSC ring-opening polymerization of ε-caprolactone: The studies of kinetics, mechanism and polymer synthesis

The kinetics of ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) initiated by tin(II) chloride (SnCl2), dibutyltin(IV) dichloride (Bu2SnCl2) and tributyltin(IV) chloride (Bu3SnCl) was successfully investigated by non-isothermal DSC technique. The steric effect of butyl group of these tin chloride initiators on the catalytic performance of the ROP of ε-CL was studied by isoconversional kinetics methods. From isoconversional kinetics analysis by both Friedman and Kissinger-Akahira-Sunose (KAS) methods, the activation energy (Ea) values for the ROP of ε-CL initiated by SnCl2 were lower than Bu2SnCl2 and Bu3SnCl, respectively. The average values of frequency factor (A) for the ROP of ε-CL with SnCl2, Bu2SnCl2 and Bu3SnCl are 2.05 × 104, 1.34 × 108 and 2.64 × 108 min-1, respectively. The kinetics results clearly demonstrated that the reactivity of SnCl2 > Bu2SnCl2 > Bu3SnCl in the ROP of ε-CL. The effectiveness of all tin chloride initiators in the synthesis of poly(ε-caprolactone) (PCL) was investigated via bulk polymerization. The highly reactive SnCl2 produced high number average molecular weight PCL (M¯n = 3.5 × 104 – 1.1 × 105) in a short polymerization time. The increasing of butyl group in tin chloride initiators reduced the effectiveness in the synthesis of high molecular weight PCL. Furthermore, the mechanism of the ROP of ε-CL with tin chloride initiators was also studied and proposed through the coordination-insertion mechanism.

SnOct2-Catalyzed Syntheses of Cyclic Poly(l-lactide)s with Catechol as Low-Toxic Co-catalyst

Polymerizations of l-lactide in bulk at 160 or 180 °C were performed with 1/1 mixtures of catechol (CA) or 4-tert-butylcatechol (BuCA) and tin(II)-2-ethylhexanoate (SnOct2) as catalysts and a variation of the Lac/Cat ratio. Weight average molar masses (Mw) up to 170,000 g mol−1 were obtained with CA and up to 120,000 g mol−1 with BuCA. The cyclic structure of the resulting poly(l-lactide)s was proven by MALDI-TOF mass spectrometry and by comparison of their hydrodynamic volumes with those of commercial linear poly(l-lactide)s. The predominance of even-numbered cycles increased with lower temperatures and shorter polymerization times. This finding indicates that the cyclic architecture is the results of a ring-expansion polymerization mechanism. Addition of silylated BuCA as co-catalyst was less favorable than addition of free BuCA.

Development of Large-Scale Stopped-Flow Technique and its Application in Elucidation of Initial Ziegler-Natta Olefin Polymerization Kinetics.

The stopped-flow (SF) technique has been extensively applied to study Ziegler–Natta (ZN) olefin polymerization kinetics within an extremely short period (typically <0.2 s) for understanding the nature of the active sites as well as the polymerization mechanisms through microstructure analyses of obtained polymers. In spite of its great applicability, a small amount of polymer that is yielded in a short-time polymerization has been a major bottleneck for polymer characterizations. In order to overcome this limitation, a large-scale SF (LSF) system has been developed, which offers stable and scalable polymerization over an expanded time range from a few tens milliseconds to several seconds. The scalability of the LSF technique has been further improved by introducing a new quenching protocol. With these advantages, the LSF technique has been effectively applied to address several unknown issues in ZN catalysis, such as the role of physical and chemical transformations of a catalyst on the initial polymerization kinetics, and regiochemistry of ZN propylene polymerization. Here, we review the development of the LSF technique and recent efforts for understanding heterogeneous ZN olefin polymerization catalysis with this new system.

Short-time polymerization and convolution kinetics in the analysis of the initiation step of isoprene polymerization over neodymium catalyst

The paper considers a convolution model for polymerization of 1,3-dienes in the presence of organometallic catalysts. It is shown that initial steps of polymerization can be represented as a set of shifted parallel reactions of the chain propagation, in which shift value are governed by the kinetics of the initiation step. In this case, polymer accumulation curve is described by an equation containing convolution of functions which allow one to solve an inverse problem of restoring the function of active site accumulation. Based on the example of isoprene polymerization over neodymium catalyst, it was demonstrated that the results of the inverse problem solution are in good agreement with the experimental data on concentration of the active sites. These data were obtained by a method of controlled introduction of inhibitor in short-time polymerization.

Simple tertiary amines as promotors in oxygen tolerant photochemically induced ATRP of acrylates

Well-defined poly(methyl acrylate) (PMA) and poly(n-butyl acrylate) (PBA) are prepared via photochemically induced atom transfer radical polymerization (photoATRP) using ppm amounts of CuBr2/tris[2-(dimethylamino)ethyl]amine (Me6TREN) catalyst complex without degassing of the polymerization mixture. The effect of light intensity and partial replacement of the excess of expensive Me6TREN ligand with cheaper tertiary amines on kinetics of the polymerization was investigated in various solvents. The addition of triethylamine to photoATRP system resulted in both significant shortening the induction period and increasing the polymerization rate. High livingness of the oxygen tolerant photoATRP system containing triethylamine was proved by chain-extension polymerizations resulting in formation of PMA-b-PBA copolymer. The presented photoATRP system can have tremendous importance from an industrial point of view since the well-defined polyacrylates can be prepared almost without any induction period and in short polymerization time without necessity of both air removal and using the excess of expensive ligand.

Disperse Composition of Titanium–Magnesium Catalyst Particles and trans-1,4-Polyisoprene Granules in Short-Time Polymerization

The disperse composition of trans-1,4-polyisoprene granules and supported titatium–magnesium catalyst particles in the ultrarapid polymerization of isoprene within 0.1–0.7 s is studied. It is shown that within this period the alteration of external and internal fragmentations occurs between two fractions of polymer granules that are formed by 0.1 s of polymerization and already contain significantly fragmented catalyst particles. The correlation between these processes and molecular mass characteristics of trans-1,4-polyisoprene is investigated. It is found that the external fragmentation is accompanied by a decrease in the average molecular masses of the polymer, while the internal fragmentation leads to formation of a higher molecular mass trans-1,4-polyisoprene. As a result, the fraction of polymer granules with a diameter of 7.5 μm is formed by 0.7 s of polymerization and replication to high conversions is developed on their basis.

Zn(OAc)₂-Catalyzing Ring-Opening Polymerization of N-Carboxyanhydrides for the Synthesis of Well-Defined Polypeptides.

Despite notable progress, the fabrication of well-defined polypeptides via controlled ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydrides (NCAs) using convenient catalysts under mild conditions in a relatively short polymerization time is still challenging. Herein, an easily obtained catalyst system composed of zinc acetate and aniline was explored to mediate the fast ROP of γ-benzyl-l-glutamate-N-carboxyanhydride (BLG-NCA) monomer, to produce poly(γ-benzyl-l-glutamates) (PBLGs) with controllable molecular weights and narrow dispersity. Considering the excellent cooperative action of zinc acetate and a broad scope of aniline derivatives with different functional groups to control ROP of BLG-NCA, this method may offer a useful platform enabling the rapid generation of end-functionalized PBLG and block copolymers for numerous biomedical applications.

Structural and kinetic continuum in the butadiene polymerization with titanium catalysts

The short-time polymerization of butadiene induced by heterogeneous titanium catalysts was studied for the first time. In the 0.1−0.3 s time interval, polymerization is characterized by a considerable decrease in the chain propagation rate constant and 1,4-stereospecificity of the catalysts. A structure kinetic continuum model was proposed in which the initiation step and the first propagation steps are kinetically continuous. The violation of this continuity changes the catalyst stereospecificity and creates conditions for chain transfer reactions.

Modulation of Surface-Initiated ATRP by Confinement: Mechanism and Applications.

The mechanism of surface-initiated atom transfer polymerization (SI-ATRP) of methacrylates in confined volumes is systematically investigated by finely tuning the distance between a grafting surface and an inert plane by means of nanosized patterns and micrometer thick foils. The polymers were synthesized from monolayers of photocleavable initiators, which allow the analysis of detached brushes by size-exclusion chromatography (SEC). Compared to brushes synthesized under “open” polymerization mixtures, nearly a 4-fold increase in brush molar mass was recorded when SI-ATRP was performed within highly confined reaction volumes. Correlating the SI-ATRP of methyl methacrylate (MMA), with and without “sacrificial” initiator, to that of lauryl methacrylate (LMA) and analyzing the brush growth rates within differently confined volumes, we demonstrate faster grafting kinetics with increasing confinement due to the progressive hindering of CuII-based deactivators from the brush propagating front. This effect is especially noticeable when viscous polymerization mixtures are generated and enables the synthesis of several hundred nanometer thick brushes within relatively short polymerization times. The faster rates of confined SI-ATRP can be additionally used to fabricate, in one pot, precisely structured brush gradients, when volume confinement is continuously varied across a single substrate by spatially tuning the vertical distance between the grafting and the confining surfaces.

Short-time isoprene polymerization under the action of a titanium–magnesium catalyst

The short-time polymerization of isoprene under the action of a TiCl4/MgCl2−i-Bu3Al heterogeneous catalyst has been investigated. Pulse mixing of the catalyst and monomer in a cylindrical tubular reactor with a certain length followed by ethanol injection has made it possible to carry out polymerization for 0.1−0.7 s. In the first 0.3 s, when there is a considerable rise in the activity of the catalyst, living polymerization of isoprene takes place. In this period, polyisoprene has up to 95% trans-1,4 units. Extending the polymerization time to 0.7 s diminishes the average molar mass of polyisoprene, broadens its molar mass distribution, and decreases the concentration of trans-1,4 units to 83%. The data of this study have been analyzed on the basis of the kinetic continuity of the polymer chain initiation and growth.