Chromatography Of Polymers Research Articles

Impact of surfactant raw material variability on extrudate clarity appearance (transparency) in HME continuous manufacturing

The appearance of an extrudate formulation was monitored during hot-melt extrusion (HME) continuous manufacturing over 3 days. The formulation matrix consisted of a polymeric component, copovidone, and a low molecular weight surfactant, polysorbate 80. Based on studies prior to the continuous manufacturing, the desired appearance of the target extrudate is translucent. Although process parameters such as feed rate and screw speed were fixed during the continuous manufacturing, the extrudate appearance changed over time from turbid to translucent. For root-cause investigation, the extrudates were analyzed offline by differential scanning calorimetry (DSC) and advanced polymer chromatography (APC™). Although the polysorbate 80 content of both turbid and translucent extrudates was within target, the glass transition temperature of the turbid extrudate was 2 °C above expected value. The observed turbidity was traced to lot-to-lot variability of the polysorbate 80 used in the continuous manufacturing, where APC™ analysis revealed that the relative content of the low molecular weight component varied from 23% to 27% in correlation with the evolution from turbid to translucent extrudates. This work stresses the importance of taking feeding material variability into account during continuous manufacturing.

Concentration‐driven morphology change of a self‐aggregated amino acid‐inspired fluorescence‐active copolymer for sustained release of hydrophobic drug

AbstractThe development of amphiphiles for sustained drug delivery represents a promising approach in biomedical fields. Polymeric self‐assembly with a hydrophobic core offers plenty of opportunities to encapsulate hydrophobic drugs for facilitating targeted delivery to the specific sites of action. Herein, N‐Boc tryptophan has been used to develop a hydrophobic monomer, Boc‐tryptophan‐HEMA (HBT). The HBT monomer has further been grafted on modified alginic acid through the RAFT technique to synthesize a unique amphiphilic copolymer with fluorescence characteristics. The advanced polymer chromatography demonstrates a narrow distribution curve, signifying the living nature of polymerization. The copolymer has exhibited self‐aggregation behavior with two distinct shapes at two different critical aggregation concentrations (CAC). The concentration‐dependent shape variation has been investigated using FESEM and TEM analyses, further supported by a small‐angle x‐ray scattering analysis. The self‐aggregation behavior of the copolymer facilitates the uptake of a model hydrophobic drug (naproxen) and its release in a sustained manner with varied rates at two different concentrations.

Molecularly imprinted polymers using high-performance liquid chromatography to detect and determine ethion pesticide in apricot, grapes, strawberry and soil samples

ABSTRACT This paper demonstrates the synthesis of molecularly imprinted polymers-solid phase extraction-liquid chromatography method at room temperature using bulk polymerisation of ethion pesticide, by high sensitivity, low costs and high stability. By making MIP for ethion as ethion-MIP, which could be detected with a UV-Vis spectrophotometer at 276 nm, a functional monomer of acrylic acid with cross-linking ethylene glycol dimethyl acrylate. The high-performance liquid chromatography methods developed in this study are accurate, sensitive, and precise to apricot, grapes, strawberry and soil samples. The elution process to the template ethion from the ethion-MIP, caused by minimum volume using solution of 1.0 mL of methanol-acetic acid (9:1) was obtained. Different factors affecting the reaction were studied and optimised. The calibration plot is linear in the concentration range of (0.02 to 1.0 µg mL−1). The relative standard deviations of (±2.0%) and detection limit of the method are 0.02 µg mL−1, and the maximum imprinting factor of ethion-MIP was 6.8 mgg−1. The results obtained the evidence of efficiency and reliability of the method for the ethion pesticide analysis and estimation for the capacitance of molecular imprinted polymer, analytical technical method by molecularly imprinted polymer and high-performance liquid chromatography.

Studying the stability of polymer nanoparticles by size exclusion chromatography of radioactive polymers

The properties of nanomedicines will influence how they can deliver drugs to patients reproducibly and effectively. For conventional pharmaceutical products, Chemistry, Manufacturing and Control (CMC) documents require monitoring stability and storage conditions. For nanomedicines, studying these important considerations is hindered by a lack of appropriate methods. In this paper, we show how combining radiolabelling with size exclusion chromatography, using a method called SERP (for Size Exclusion of Radioactive Polymers), can inform on the in vitro degradation of polymer nanoparticles. Using nanoparticles composed of biodegradable poly(lactic acid) (PLA) and poly(lactic-co-glycolic acid) (PLGA), we show that SERP is more sensitive than dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA) to detect degradation. We also demonstrate that the properties of the polymer composition and the nature of the aqueous buffer affect nanoparticle degradation. Importantly, we show that minute changes in stability that cannot be detected by DLS and NTA impact the pharmacokinetic of nanoparticles injected in vivo. We believe that SERP might prove a valuable method to document and understand the pharmaceutical quality of polymer nanoparticles.

Study of Synthesis of Dual-Curing Thermoplastic Polyurethane Hot-Melt Adhesive and Optimization by Using Gray Relational Analysis to Apply in Fabric Industry to Solve Seamless Bonding Issues.

People wear clothes for warmth, survival and necessity in modern life, but in the modern era, eco-friendliness, shortened production times, design and intelligence also matter. To determine the relationship between data series and verify the proximity of each data series, a gray relational analysis, or GRA, is applied to textiles, where seamless bonding technology enhances the bond between components. In this study, a polyurethane prepolymer, 2-hydroxyethyl acrylate (2-HEA) as an end-capping agent and n-octyl acrylate (ODA) as a photoinitiator were used to synthesize a dual-curing polyurethane hot-melt adhesive. Taguchi quality engineering and a gray relational analysis were used to discuss the influence of different mole ratios of NCO:OH and the effect of the molar ratio of the addition of octyl decyl acrylate on the mechanical strength. The Fourier transform infrared spectroscopy (FTIR) results showed the termination of the prepolymer's polymerization reaction and the C=O peak intensity at 1730 cm-1, indicating efficient bonding to the main chain. Advanced Polymer Chromatography (APC) was used to investigate the high-molecular-weight (20,000-30,000) polyurethane polymer bonded with octyl decyl acrylate to achieve a photothermosetting effect. The thermogravimetric analysis (TGA) results showed that the thermal decomposition temperature of the polyurethane hot-melt adhesive also increased, and they showed the highest pyrolysis temperature (349.89 °C) for the polyhydric alcohols. Furthermore, high peel strength (1.68 kg/cm) and shear strength (34.94 kg/cm2) values were detected with the dual-cure photothermosetting polyurethane hot-melt adhesive. The signal-to-noise ratio was also used to generate the gray relational degree. It was observed that the best parameter ratio of NCO:OH was 4:1 with five moles of monomer. The Taguchi quality engineering method was used to find the parameters of single-quality optimization, and then the gray relation calculation was used to obtain the parameter combination of multi-quality optimization for thermosetting the polyurethane hot-melt adhesive. The study aims to meet the requirements of seamless bonding in textile factories and optimize experimental parameter design by setting target values that can effectively increase production speed and reduce processing time and costs as well.

Evaluation of the state of practice asphalt binder and mixture tests for assessing the compatibility of complex asphalt materials

The present study aims to evaluate binder and mixture testing methods for capturing the compatibility of complex asphalt materials consisting of different virgin binder sources, reclaimed asphalt pavement (RAP) materials and recycling agents (RA). Binder evaluation methods include the saturate, aromatic, resin and asphaltene (SARA) fractionation, advanced polymer chromatography (APC) analysis, differential scanning calorimeter (DSC) and rheological measurements. Mixture performance tests include the complex modulus (E*), direct tension cyclic fatigue (DTCF), disk-shaped compact tension (DCT) and semi-circular bending (SCB) fracture tests. The results from the testing and analysis indicate that the rheological characterisation of asphalt binder or mixture may not capture the incompatibility between virgin binder, RAP and RA. Binder DSC analysis as well as mixture fracture tests have shown promise to evaluate the compatibility of complex asphalt materials with different virgin binders, RAP and RA, as well as the effect of incompatibility on mixture performance.

Online hyphenation of size-exclusion chromatography and pyrolysis-gas chromatography for polymer characterization

An understanding of the composition and molecular heterogeneities of complex industrial polymers forms the basis of gaining control of the physical properties of materials. In the current work we report on the development of an online method to hyphenate liquid polymer chromatography with pyrolysis-GC (Py-GC). The designed workflow included a 10-port valve for fractionation of the first-dimension effluent. Collected fractions were transferred to the Py-GC by means of a second LC pump, a 6-port valve was used to control injection in the Py-GC, allowing the second pump to operate continuously. The optimized large volume injection (LVI) method was capable of analyzing 117 µL of the LC effluent in a 6 min GC separation with a total cycle time of 8.45 min. This resulted in a total run time of 2.1 h while obtaining 15 Py-GC runs over the molar mass separation.The method was demonstrated on various real-life samples including a complex industrial copolymer with a bimodal molar mass distribution. The developed method was used to monitor the relative concentration of 5 different monomers over the molar mass distribution. Furthermore, the molar mass-dependent distribution of a low abundant comonomer (styrene, <1% of total composition) was demonstrated, highlighting the low detection limits and increased resolving power of this approach over e.g. online NMR or IR spectroscopy. The developed method provides a flexible and widely applicable approach to LC-Py-GC hyphenation without having to resort to costly and specialized instrumentation.

Rheology of entangled active polymer-like T. Tubifex worms

We propose a new ‘active particle’ system in which the particles are in fact polymer-like. We experimentally study the rheology of long, slender, and entangled living worms (Tubifex Tubifex, or ‘sludge worms’). Performing classical rheology experiments on this entangled polymer-like system, we find that the rheology is qualitatively similar to that of usual polymers, but, quantitatively, (i) shear thinning is reduced by activity, (ii) the characteristic shear rate for the onset of shear-thinning is given by the time scale of the activity, and (iii) the low shear viscosity as a function of concentration shows a very different scaling from that of regular polymers. The level of activity can be controlled by changing the temperature but also by adding small amounts of alcohol to make the worms temporarily inactive. I will also briefly discuss phase separation by entanglement, and our first attempts to perform hydrodynamic chromatography of these wormy polymers.

Polymers of micro(nano) plastic in household tap water of the Barcelona Metropolitan Area

Microplastics (MPLs) are emerging persistent pollutants affecting drinking water systems, and different studies have reported their presence in tap water. However, most of the work has a focus on particles in the 100–5 µm range.Here, a workflow to identify and quantify polymers of micro and nanoplastics (MNPLs), with sizes from 0.7 to 20 µm in tap water, is presented. The analytical method consisted of water fractionated filtration followed by toluene ultrasonic-assisted extraction and size-exclusion chromatography, using an advanced polymer chromatography column coupled to high-resolution mass spectrometry with atmospheric pressure photoionization source with negative and positive ionization conditions (HPLC(APC)-APPI(±)-HRMS) and normal phase chromatography HILIC LUNA® column and electrospray ionisation source in positive and negative mode (HPLC(HILIC)-ESI(±)-HRMS). The acquisition was performed in full scan mode, and the subsequent tentative identification of MNPLs polymers has been based on increasing the confirmation level, including the characterisation of monomers by using Kendrick Mass Defect (KMD) analysis, and confirmation and quantification using standards. This approach was applied to assess MNPLs in tap water samples of the Barcelona Metropolitan Area (BMA), that were collected from August to October 2020 from home taps of volunteers distributed in the 42 postal codes of the BMA.Polyethylene (PE), polypropylene (PP), polyisoprene (PI), polybutadiene (PBD), polystyrene (PS), polyamide (PA), and polydimethylsiloxanes (PDMS) were identified. PE, PP, and PA were the most highly detected polymers, and PI and PBD were found at the highest concentrations (9,143 and 1,897 ng/L, respectively).A principal component analysis (PCA) was conducted to assess differences in MNPLs occurrence in drinking water, that was provided from the two drinking water treatment plants (DWTPs) suppliers. Results showed that no significant differences (at 95% confidence level) were established between the drinking water supplies to the different areas of the BMA.

Dispersion polymerization of styrene/acrylonitrile in polyether stabilized by macro-RAFT agents

A series of poly(acrylate polyether)s (RPA) was designed and synthesized by reversible addition-fragmentation chain transfer (RAFT) copolymerization, which were then used as dispersants for the dispersion copolymerization of styrene/acrylonitrile in polyethers in a semicontinuous approach to prepare graft polyether polyol (POP) with high solid content. The effects of structure, dosage, and feed ratio for macro-RAFT agent RPA on the stability, viscosity, and particle size of POP were examined and discussed. The dispersion polymerization process was also characterized by gradient elution polymer chromatography, and the results indicated that RPA was rapidly consumed and block-type stabilizer formed in the initial stage of polymerization. A portion of RPA added with monomer feeding provided better stability for the semicontinuous polymerization process.

Reversible Addition–Fragmentation Chain Transfer-Mediated Amphiphilic Copolymeric Composite as a Nanocarrier for Drug Delivery Application

Magnetic core–shell nanoparticle (NP)-polymer-based composite materials, in which the stimuli-responsive polymer acts as a suitable shell, become more advantageous as nanocarriers. Here, nanocomposites comprising magneto-responsive γ-Fe2O3 NPs that incorporated amphiphilic copolymers have been synthesized. At first, the copolymer [dextran grafted with poly(N-vinyl caprolactam)] has been prepared via reversible addition–fragmentation chain transfer polymerization followed by ex situ incorporation of γ-Fe2O3 NPs. The copolymerization is living in nature as apparent from molecular weight distribution (determined using advanced polymer chromatography, i.e., APC analysis) and the reaction kinetics study. The developed nanocomposite exhibits regular core–shell morphology, where the magnetic NPs have been found to behave as the core, while the copolymer represents as the shell, as obvious from field emission scanning electron microscopy and high-resolution transmission electron microscopy analyses. The nanocarrier is non-cytotoxic and has further been studied for its effectivity as an efficient carrier for a hydrophobic drug (naproxen).

Reaction kinetics of melt post‐polycondensation process for polycarbonate in film state

AbstractMelt post‐polycondensation (MPP) process is one of manufactures industrially that can efficiently increase the molecular weight of polycarbonate (PC). Herein, the MPP experiments of several PC materials using quaternary ammonium hydroxides and alkali metal compounds as the catalyst in the film state are studied. The reaction products are characterized by Ubbelohde viscometer, DSC, 1H‐NMR, ultraviolet spectrophotometry, advanced polymer chromatography and rotational rheometer. It is found that MPP can effectively improve the intrinsic viscosity of PC. After a certain reaction time at a specific temperature, the number average molecular weight (Mn) of PC is raised from 19,000 to 54,600 g/mol. Furthermore, the 1H‐NMR results reveal that Fries rearrangement products are produced during the MPP process. Based on the functional group model, a reaction kinetic model, combining the effects of the main melt polycondensation reaction and the Fries rearrangement reaction, is established for the first time. The reaction rate constants at different temperatures and the reaction activation energies of the two PC materials are obtained. This work provides a new reaction kinetics model to guide the MPP process of PC, which contains Fries rearrangement reaction.

Synthesis and characteristic applications of silicon resins for the modifying agent in heat conduction

Heat energy retention and dissipation have become key points of global smart textiles in recent years. This study describes the designing of silicon resin by using a sol–gel process, which acts as the modifying agent for siloxane substrate. The modifying agent was effectively blocked by silicon resin mixed with the ethylene or aluminum bond group, to control the molecular weight. Advanced polymer chromatography confirmed that the number average molecular weight (Mn) of silicon resin is 41,301 g mol−1, the weight average molecular weight (Mw) is 47,982 g mol−1, and the molecular weight distribution is 1.1617, which is relatively narrow. When the addition of vinyl groups is 5%, the silicone resin Mn decreases to 18,906 g mol−1 and Mw decreases to 28,641 g mol−1. When the addition of aluminum bond groups is 5%, the silicone resin Mn decreases to 17,497 g mol−1 and Mw decreases to 27,114 g mol−1. The result of thermogravimetric analysis shows that the pyrolysis temperature rises from 265.43°C to 266.17°C after the ethylene is added to the silicon resin, and the index of heat tolerance increases from 179.14°C to 191.38°C. After the addition of aluminum bond groups, the pyrolysis temperature rises from 265.43°C to 309.37°C, and the index of heat tolerance increases from 179.14°C to 193.09°C, meaning the silicone resin has higher thermal stability.

Efficient Design to Monitor the Site‐specific Sustained Release of a Non‐Emissive Anticancer Drug

A pH-responsive smart nanocarrier with significant components was synthesized by conjugating the non-emissive anticancer drug methyl orange and polyethylene glycol derived folate moiety to the backbone of polynorbornene. Complete synthesis procedure and characterization methods of three monomers included in the work: norbornene-derived Chlorambucil (Monomer 1), norbornene grafted with polyethylene glycol, and folic acid (Monomer 2) and norbornene attached methyl orange (Monomer 3) connected to the norbornene backbone through ester linkage were clearly discussed. Finally, the random copolymer CHO PEG FOL METH was synthesized by ring-opening metathesis polymerization (ROMP) using Grubbs' second-generation catalyst. Advanced polymer chromatography (APC) was used to find the final polymer's molecular weight and polydispersity index (PDI). Dynamic light scattering, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were utilized to explore the prodrug's size and morphology. Release experiments of the anticancer drug, Chlorambucil and the coloring agent, methyl orange, were performed at different pH and time. Cell viability assay was carried out for determining the rate of survived cells, followed by the treatment of our final polymer named CHO PEG FOL METH.

Fabrication of Graphene-Coated Silica Particles for Polymer Chromatography to Quantify Chemical Composition Distribution of Polyolefin Materials

Fabrication of Graphene-Coated Silica Particles for Polymer Chromatography to Quantify Chemical Composition Distribution of Polyolefin Materials

1,6-heptadiynes based cyclopolymerization functionalized with mannose by post polymer modification for protein interaction

Carbohydrate functionalized polymers or Glycopolymers have earned a great deal of interest in recent times for their potential biomedical applications. In the present study, a mannose containing glycopolymer was synthesized by cyclopolymerization of malonic acid derivative using second generation Hoveyda Grubbs′ catalyst. Post-polymerization modification was done to install a propargyl moiety. Finally, functionalization of the propargylated polymer with 2-azidoethyl mannoside using azide-alkyne “click chemistry” furnished the target glycopolymer which was successfully characterized using NMR, FT-IR, mass spectroscopy and advanced polymer chromatography. The glycopolymer was found to self-assemble into capsule and spherical shape in water and DMSO respectively and these morphologies were observed through SEM and TEM. Upon interaction with Con A, the mannose containing glycopolymer showed an increment in aggregation induced fluorescence with increasing concentration of the lectin. In vitro cytotoxicity studies on MCF 7 cell line showed 90% cell viability up to glycopolymer concentration of 500 μg/mL.

Direct Determination of Interchain Transfer Constants for Radical Polymerization of Benzyl Acrylate by RAFT Polymerization and Polymer Chromatography

Direct Determination of Interchain Transfer Constants for Radical Polymerization of Benzyl Acrylate by RAFT Polymerization and Polymer Chromatography

Size exclusion chromatography of petroleum samples using amino-bonded silica phase

Amino-bonded silica phase, frequently used in adsorption chromatographic mode for petroleum analysis, was evaluated for the separation of petroleum components based on polymer liquid chromatographic modes (viz. size exclusion, critical condition, and interaction). After verification of the stationary phase for polymer chromatography using polystyrene standards at different compositions of cyclohexane and dichloromethane, a similar approach was attempted for a distilled fraction of a crude oil. The approach was successful in size exclusion chromatographic mode whereas other modes were partially achievable because of the complex nature of petroleum samples. Subsequently, size exclusion mode was applied in crude oils with different American Petroleum Institute (API) gravity values. An inverse linear relationship between the API gravity value and the average molecular weights of the aromatic compounds of crude oils was established. It was found that the weight average molecular weight (Mw) was more sensitive to changes in API gravity values of the crude oils in comparison to number average molecular weight (Mn). Additionally, crude oil with lower API gravity value reflected broader distribution of species. Further studies on crude oils with lower API gravity value (<20°) and of different geographical origins will confirm the universality of the method. This method will provide reliable average molecular weights of the aromatic content for aromatic rich refinery streams to optimize process conditions. Furthermore, the developed method can potentially be extended to a two-dimensional LC method using the same stationary phase with different mobile phase compositions for comprehensive characterization of petroleum samples.

Direct Determination of Interchain Transfer Constants of Benzyl Acrylate to Poly(Ethyl Acrylate) by RAFT Polymerization and Polymer Chromatography

AbstractInterchain transfer is an important side reaction in radical polymerization of acrylates and has significant effects on both reaction kinetics and the resulting polymer microstructures. In this study, an effective method for direct determination of the interchain transfer constant (Ctr) is established via the combination of RAFT polymerization of a monomer in the presence of another prepared polymer and subsequent separation using polymer chromatography. The Ctr of benzyl acrylate (BzA) to poly(ethyl acrylate) (PEA) is determined with benzyl N‐carbazole dithiocarbamate (BCBD) as the RAFT agent and the effects of polymerization recipe, such as BzA/BCBD mole ratios, BzA/PEA mass ratios, and solvent amounts on Ctr determination investigated. The results indicate that interchain transfer reactions show clear short chain radical effects in early stage of RAFT polymerization and the experimental recipes have little influence on the determination. The Ctr values are in the range of 1–2 × 10−4 at 90–120 °C and the activation energy of Ctr at 47.8 kJ mol−1.

Dextran based amphiphilic self-assembled biopolymeric macromolecule synthesized via RAFT polymerization as indomethacin carrier

This work demonstrates a facile pathway to develop a biopolymer based amphiphilic macromolecule through reversible addition–fragmentation chain transfer (RAFT) polymerization, using dextran (a biopolymer) as starting material. Also, a new hydrophobic monomer [2-methyl-acrylic acid 1-benzyl-1H-[1,2,3] triazol-4-ylmethyl ester (MABTE)] has been synthesized using methacrylic acid via “click” approach. The resultant copolymer displays controlled radical polymerization characteristics: narrow polydispersity (Ð) and controlled molecular weight as obtained through advanced polymer chromatography (APC) analysis. In aqueous solution, the copolymer can proficiently be self-assembled to provide micellar structure, which has been evidenced from field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) analyses. The in-vitro cytotoxicity study illustrates the nontoxic nature of the copolymer up to 100 μg/mL polymer concentration. The copolymer has been found to be worthy as an efficient carrier for the sustained release of hydrophobic drug: Indomethacin (IND).