High Molecular Weight Polymers Research Articles

Rheological behavior and fiber spinning of polyacrylonitrile (PAN)/Carbon nanotube (CNT) dispersions at high CNT loading

Rheological studies play an important role in polymer processing including fiber spinning. In the current work, rheological behavior has been studied for polyacrylonitrile (PAN)/carbon nanotube (CNT) dispersions in dimethyl formamide (DMF), where CNT loading is as high as 15 wt% of the total solids (polymer + CNT). The presence of CNTs increased the elastic-like and shear thinning behavior of the dispersions. The terminal slope of the log G′ versus log G″ curve, which was used to characterize the homogeneity of solution or dispersion, is dependent on the CNT concentration but independent of temperature between 0 and 60 °C. PAN/CNT-10 (90 wt% PAN +10 wt% CNT) and PAN/CNT-15 were gel spun at different conditions, with small diameter capillary at high shear rate and large diameter capillary at relatively low shear rate. For PAN/CNT-10, fiber spinning with lower molecular weight polymer showed increased continuous jetting time when compared to spinning with higher molecular weight polymer. In addition, the rheological behavior of PAN/cellulose nanocrystal (CNC) dispersion with 20–60 wt% CNC was also compared to that of the PAN/CNT dispersions. PAN/CNC and PAN/CNT share similarities in both rheological behavior and fiber spinning at high filler loading.

Partially bio‐based furyl‐functionalized organosoluble poly(ether ether ketone)s

AbstractA new series of partially bio‐based (co)poly(ether ether ketone)s bearing pendent furyl groups was synthesized by nucleophilic aromatic substitution polycondensation of varying molar proportions of 4,4′‐(furan‐2‐ylmethylene)bis(2‐methoxyphenol) and bisphenol‐A with 4,4′‐difluorobenzophenone. The chemical structures, compositions and random nature of (co)poly(ether ether ketone)s were confirmed by NMR spectroscopy. Inherent viscosities and number‐average molecular weights of the (co)poly(ether ether ketone)s were in the range 0.74–2.90 dL g−1 and 33 500–46 300 g mol−1, respectively, indicating the formation of reasonably high molecular weight polymers. (Co)poly(ether ether ketone)s were readily soluble in common organic solvents and could be cast into tough, transparent and flexible films from chloroform solutions. (Co)poly(ether ether ketone)s exhibited 10% weight loss and glass transition temperatures in the range 429–464 and 152–156 °C, respectively. A representative copoly(ether ether ketone) was crosslinked with 1,1′‐(methylenedi‐1,4‐phenylene)bismaleimide via Diels–Alder reaction to form a crosslinked polymer which showed improved mechanical properties and was recycled twice without significant loss of mechanical properties. Diels–Alder/retro Diels–Alder reaction was demonstrated by studies of sol–gel transformation, solubility tests, DSC and stress–strain measurements. © 2020 Society of Chemical Industry

Poly(acrylic acid) nanocomposites: Design of advanced materials

Poly(acrylic acid) is a synthetic polymer that is polymerized from acrylic acid monomers. Poly (acrylic acid) is a high molecular weight polymer having good water solubility. Poly(acrylic acid) also exists in the cross-linked forms. Poly(acrylic acid) is an important polymer for making polymeric blends and nanocomposites. This state-of-the-art review is an endeavour to define the unique capabilities of poly (acrylic acid) to form high performance nanocomposites. The nanofiller nanomaterials including carbon nanotube, graphene, nanodiamond, and inorganic nanoparticles are promising nanofillers for a poly(acrylic acid) matrix. Consequently, the article discusses the following categories: poly(acrylic acid)/carbon nanotube, poly(acrylic acid)/graphene, poly(acrylic acid)/nanodiamond, and poly(acrylic acid)/inorganic nanoparticle nanocomposites. The nanocomposite characteristics are significantly enhanced with the added nanoparticles. Especially, the nanoparticles influenced the electrical conductivity, thermal stability, strength, biocompatibility, adsorption, and anti-bacterial features of the poly(acrylic acid) nanocomposites. Their high performance was related to the interface interactions between the matrix and the nanofillers. The poly (acrylic acid) derived nanocomposites have been used to form advanced hybrid materials for batteries, sensors, antibacterial, and water filters.

Iron-Based Catalytically Active Complexes in Preparation of Functional Materials

Iron complexes are particularly interesting as catalyst systems over the other transition metals (including noble metals) due to iron’s high natural abundance and mediation in important biological processes, therefore making them non-toxic, cost-effective, and biocompatible. Both homogeneous and heterogeneous catalysis mediated by iron as a transition metal have found applications in many industries, including oxidation, C-C bond formation, hydrocarboxylation and dehydration, hydrogenation and reduction reactions of low molecular weight molecules. These processes provided substrates for industrial-scale use, e.g., switchable materials, sustainable and scalable energy storage technologies, drugs for the treatment of cancer, and high molecular weight polymer materials with a predetermined structure through controlled radical polymerization techniques. This review provides a detailed statement of the utilization of homogeneous and heterogeneous iron-based catalysts for the synthesis of both low and high molecular weight molecules with versatile use, focusing on receiving functional materials with high potential for industrial application.

Investigation of soft and living matter using a micro-extensional rheometer

Rheological properties of a material often require to be probed under extensional deformation. Examples include fibrous materials such as spider-silk, high-molecular weight polymer melts, and the contractile response of living cells. Such materials have strong molecular-level anisotropies which are either inherent or are induced by an imposed extension. However, unlike shear rheology, which is well-established, techniques to perform extensional rheology are currently under development and setups are often custom-designed for the problem under study. In this article, we present a versatile device that can be used to conduct extensional deformation studies of samples at microscopic scales with simultaneous imaging. We discuss the operational features of this device and present a number of applications.

Sugar‐Based Polymers from d‐Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release

AbstractEnyne monomers derived from D‐xylose underwent living cascade polymerizations to prepare new polymers with a ring‐opened sugar and degradable linkage incorporated into every repeat unit of the backbone. Polymerizations were well‐controlled and had living character, which enabled the preparation of high molecular weight polymers with narrow molecular weight dispersity values and a block copolymer. By tuning the type of acid‐sensitive linkage (hemi‐aminal ether, acetal, or ether functional groups), we could change the degradation profile of the polymer and the identity of the resulting degradation products. For instance, the large difference in degradation rates between hemi‐aminal ether and ether‐based polymers enabled the sequential degradation of a block copolymer. Furthermore, we exploited the generation of furan‐based degradation products, from an acetal‐based polymer, to achieve the release of covalently bound reporter molecules upon degradation.

Sugar-Based Polymers from d-Xylose: Living Cascade Polymerization, Tunable Degradation, and Small Molecule Release.

Enyne monomers derived from D-xylose underwent living cascade polymerizations to prepare new polymers with a ring-opened sugar and degradable linkage incorporated into every repeat unit of the backbone. Polymerizations were well-controlled and had living character, which enabled the preparation of high molecular weight polymers with narrow molecular weight dispersity values and a block copolymer. By tuning the type of acid-sensitive linkage (hemi-aminal ether, acetal, or ether functional groups), we could change the degradation profile of the polymer and the identity of the resulting degradation products. For instance, the large difference in degradation rates between hemi-aminal ether and ether-based polymers enabled the sequential degradation of a block copolymer. Furthermore, we exploited the generation of furan-based degradation products, from an acetal-based polymer, to achieve the release of covalently bound reporter molecules upon degradation.

Selective Synthesis of Single‐Handed Helical Polymers from Achiral Monomer and a Mechanism Study on Helix‐Sense‐Selective Polymerization

AbstractInspired by the exquisite helices in Nature, fabrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis of single left‐ and right‐handed helical polyisocyanides through living polymerization of achiral monomers using chiral palladium catalysts under helix‐sense‐selective manner. Mechanism study revealed that the yielded helices with opposite handedness showed different activity of the living chain end. The helix with unfavored handedness was self‐terminated, while the one with favored handedness showed high activity and could undergo chain propagation to form a high molecular weight polymer with maintained single‐handed helicity.

Selective Synthesis of Single-Handed Helical Polymers from Achiral Monomer and a Mechanism Study on Helix-Sense-Selective Polymerization.

Inspired by the exquisite helices in Nature, fabrication of helical materials with controlled handedness has attracted considerable attention. Herein, we report on precis synthesis of single left- and right-handed helical polyisocyanides through living polymerization of achiral monomers using chiral palladium catalysts under helix-sense-selective manner. Mechanism study revealed that the yielded helices with opposite handedness showed different activity of the living chain end. The helix with unfavored handedness was self-terminated, while the one with favored handedness showed high activity and could undergo chain propagation to form a high molecular weight polymer with maintained single-handed helicity.

ОЧИЩЕННЯ АКРИЛАМІДУ ВІД ІНГІБІТОРІВ ПОЛІМЕРИЗАЦІЇ ДЛЯ ВИГОТОВЛЕННЯ ВИСОКОЯКІСНИХ ФЛОКУЛЯНТІВ НА ОСНОВІ ПОЛІАКРИЛАМІДУ

Polyacrylamide and its copolymers are widely used as flocculating agents for the separation of industrial suspensions. The formation of high molecular weight polymers depends on the content of various impurities present in the monomer. The article presents the scientific and practical information on the production of acrylamide by sulfuric acid method of hydration of nitrile acrylic acid in the form of an aqueous solution of different concentrations and a more modern heterogeneously catalytic method of hydration of acrylonitrile using as catalysts with variable valence. Ways to get different impurities in the stages of production of acrylamide with the purpose of applying appropriate methods for its purification. Laboratory studies of the purification of an aqueous solution of acrylamide from iron ions were carried out as an element of inhibition of the premature polymerization process.

Optimization of Conditions of Polymer Separation by Hydrodynamic Chromatography

For the well-known theoretical model of hydrodynamic chromatography, which relates the relative retention of an analyte and the separation efficiency to the characteristic parameter of a system, expressions are proposed that make it possible to find the optimal conditions for analysis. The theoretical model well predicts the relative retention of analytes but greatly overestimates the separation efficiency, especially for high molecular weight polymers. The observed discrepancy is due to the impossibility within one separation to create optimal conditions for all components of the sample and/or the influence of the polydispersity of the studied polymer samples on the separation efficiency.

Towards High Molecular Weight Furan-Based Polyesters: Solid State Polymerization Study of Bio-Based Poly(Propylene Furanoate) and Poly(Butylene Furanoate).

In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV and end groups concentration during SSP.

Neutral Nickel(II) Catalysts: From Hyperbranched Oligomers to Nanocrystal-Based Materials

ConspectusPlastics materials are a vital component of modern technologies. They are applied, e.g., in construction, transportation, communication, water supply, or health care. Consequently, polyolefins-the most important plastics by scale-are produced in vast amounts by catalytic polymerization. Effective and selective as the catalysts used may be, their high sensitivity toward any polar compounds limits these methods to hydrocarbon reaction media and monomers like ethylene and propylene, respectively. This can be overcome by less oxophilic late transition metal catalysts, and here particularly neutral nickel(II) catalysts have seen major advances in the past few years. They stand out due to being capable of aqueous catalytic polymerizations. Aqueous polymerizations are benign processes that advantageously yield polymers in the form of particles. Moreover, these catalysts can incorporate polar monomers like acrylates, a realm previously restricted to noble metal catalysts. The introduction of polar moieties can induce properties like compatibility with metals or fibers in high performance composite materials or a desirable degradability.This Account provides a personal account of developments in the past decade. Prior findings are outlined briefly as a background. Aqueous polymerizations afford unique polyethylene morphologies as a result of the unusual underlying particle growth mechanism. Polymer single crystals are formed, which can be composed of a single ultrahigh molecular weight chain. This represents a completely disentangled state of such extremely long polymer chains, which has been long sought-after in order to overcome the difficult processing of high performance ultrahigh molecular weight materials. A key prerequisite for this approach and utilization of these catalysts, in general, is control of polymer branching and molecular weight. This is achieved via remote substituents on the Ni(II)-chelating ligand. Despite their distal position to the active site, weak secondary interactions control whether branching and chain transfer pathways compete very effectively with chain growth or are suppressed entirely. This provides access to hyperbranched oligomers, on the one hand, and enables living polymerizations to strictly linear high molecular weight polymer, on the other hand. Other advanced catalysts provide linear copolymers with in-chain polar monomer repeat units for the first time with non-noble metal active sites. Mechanistic studies further revealed that for copolymerizations with polar vinyl monomers the decisive limiting factor is irreversible termination reactions with neutral Ni(II) catalysts, rather than the well-recognized reversible blocking of coordination sites by the polar functional groups found for other types of catalysts. The mechanistic picture also implies the possibility of free-radical pathways, and their role in the formation of desirable polymer end groups and polymer blends is now being recognized. The area of neutral Ni(II) catalysts has progressed significantly in the entire range from fundamental mechanistic understanding, catalyst performance, and previously inaccessible polymer microstructures, and it is moving forward to materials through unique concepts. The unprecedented ability to incorporate functional groups into linear crystalline polyethylene also provides perspectives for much needed polyolefin materials that will not persist in the natural environment for several decades but that can be degraded by virtue of low levels of functional groups.

Effect of commonly used EOR polymers on low concentration surfactant phase behaviors

High molecular weight polymers are required for the purpose of mobility and conformance control during surfactant chemical flooding. However, they are usually not incorporated in the process of phase behavior tests to screen surfactant formulations. Literature review shows some particular polymers have a boosting effect on surfactant solubilization efficiency. To gain more insight into this subject, we performed phase behavior tests in the presence of four commonly used EOR polymers for low concentration surfactant systems (0.3%). They were two partially hydrolyzed polyacrylamides (HPAM) with different molecular weights, one xanthan gum, and one hydrophobically associating polymer (HAP). Their influence on the optimal salinity, solubilization ratio, quickness of phase equilibration, and middle phase rheological behavior was assessed. The results showed: (1) a decrease of surfactant solubilization efficiency and the optimal salinity was observed with HPAM polymers. This trend became more pronounced as increase of polymer concentration and molecular weight; (2) xanthan seemed to slightly increase the optimal salinity without significantly affecting middle phase volume; (3) both HPAM and xanthan did not delay or quicken the equilibration of various phases compared to the zero polymer case. The analysis of the oil/water solubilization ratios showed HPAM tended to drag water out of the middle phase, while the presence of xanthan increased the water solubilization in the middle phase; (4) the viscosity and rheology of the middle phase microemulsions were very similar for systems containing HPAM, xanthan, and zero polymer. This confirmed the partitioning of polymer molecules in the middle phase was negligible; (5) the association of HAP with surfactants thickened the surfactant-rich phase, which made the phase separation dramatically slow. These phenomena could be explained well by the nature of their molecular structures. For both water-soluble HPAM and xanthan gum, unlike the reported diblock copolymers, they lack the amphiphilic features, which prevents them from adsorbing in the surfactant film. Conversely, the introduction of hydrophobic group into the backbone renders associating polymers some surfactant-like attributes, enabling them to associate with surfactant molecules and affect the surfactant-rich phase behaviors.

Photoinitiated polymerization of methacrylates comprising phenyl moieties

AbstractInvestigation of photopolymerization kinetics of 4‐(4‐methacryloyloxyphenyl)‐butan‐2‐one (1) in comparison with 2‐phenoxyethyl methacrylate (2) and phenyl methacrylate (3) using a UV‐LED emitting at 395 nm shows significantly faster polymerization of 1 compared to both 2 and 3 at 40°C. Vitrification affects photopolymerization kinetics of all methacrylates under investigation. Interestingly, quantitative final conversion is observed during photoinitiated polymerization of 1 and 2 whereas 3 shows limited conversion at about 80%. Furthermore, higher degree of polymerization is obtained by photoinitiated polymerization of 1 compared to 2 and 3. This shows that the 3‐oxobutyl substituent at the phenyl ring of 1 significantly affects both polymerization kinetics and final conversion of the photoinitiated polymerization. Moreover, an additional higher molecular weight fraction is observed in case of polymerization of 1 at 85°C that is above the glass transition temperature of the polymer formed during photoinitiated polymerization. As a thermal polymerization at 85°C in the absence of light results in a high molecular weight polymer as well, an additional thermal process may be discussed as reason for the higher molecular weight polymer fraction in case of the photopolymer made at 85°C.

Influence of Polymer Reagents in the Drilling Fluids on the Efficiency of Deviated and Horizontal Wells Drilling

Improving the efficiency of well drilling process in a reservoir is directly related to subsequent well flow rates. Drilling of deviated and horizontal wells is often accompanied by an increase in pressure losses due to flow resistance caused by small size of the annular space. An important role in such conditions is played by the quality of borehole cleaning and transport capacity of drilling fluid, which is directly related to the rheological parameters of the drilling fluid. The main viscosifiers in modern drilling fluids are polymer reagents. They can be of various origin and structure, which determines their features. This work presents investigations that assess the effect of various polymers on the rheological parameters of drilling fluids. Obtained data are evaluated taking into account the main rheological models of fluid flow. However, process of fluid motion during drilling cannot be described by only one flow model. Paper shows experimentally obtained data of such indicators as plastic viscosity, dynamic shear stress, non-linearity index and consistency coefficient. Study has shown that high molecular weight polymer reagents (e.g., xanthan gum) can give drilling fluid more pronounced pseudoplastic properties, and combining them with a linear high molecular weight polymer (e.g., polyacrylamide) can reduce the value of the dynamic shear stress. Results of the work show the necessity of using combinations of different types of polymer reagents, which can lead to a synergetic effect. In addition to assessing the effect of various polymer reagents, the paper presents study on the development of a drilling fluid composition for specific conditions of an oil field.

Delivery of pharmaceuticals and other active ingredients with their crystalline cyclodextrin inclusion compounds

In honor of Prof. Thorsteinn Loftsson's 70th birthday, we offer this personal review of our work using cyclodextrins (CDs) complexed with a variety of active ingredients, including pharmaceuticals, for the purpose of improving their delivery to polymer materials, e.g., fibers, films, hydrogels, etc. Using the affinity of CDs to host and form non-covalent inclusion complexes (ICs) with guest molecules, including a variety of high molecular weight polymers, it is possible to readily deliver these guest molecules into polymer materials via either melt or solution processing of their crystalline or soluble guest molecule-CD-ICs or -rotaxanes. This provides the following advantages: i. CDs are non-toxic, implantable, and biodegradable and have earned the GRAS rating from the FDA. ii. Guest molecules, even those that are neat liquids, can form solid crystalline CD-ICs that are thermally stable to~200°C and above. This approach permits facile melt-processing into polymer materials for delivery without migration, loss, or degradation of the active guest ingredient. iii. For guests harmful and toxic to their users and the environment, delivery in the form of crystalline CD-ICs can limit any contact with and release of the included toxic guests before they function and are used. iv. It has been demonstrated that, by simple precipitation methods, neat as-received CDs that adopt cage crystal structures can be readily transformed to their columnar crystal structures containing only water in their channels, which can be easily displaced by small molecule, as well as polymer guests. v. Guest-CD-rotaxanes are water soluble, they protect the threaded guest from sources of degradation, and the CD hydroxyl groups may be modified to direct the guest-CD-rotaxane to specific substrates. For these reasons, here we summarize our contributions to the study of CD inclusion and delivery of a variety of guest molecules, including antibacterials, spermicides, insecticides, flame retardants, and dyes, that can more usefully functionalize polymer materials.

Ultrasonic Activation of PIM-1 Synthesis and Properties of Polymers Obtained by Precipitation Polyheterocyclization in Dimethyl Sulfoxide

A new method for activating the synthesis of high molecular weight polymer PIM-1 obtained in dimethyl sulfoxide is proposed and studied. A simple and technologically effective process of precipitation polyheterocyclization occurs at 60–80°C for 2–5 h under constant exposure to ultrasound at a frequency of 37 kHz. This method allows one to synthesize the PIM-1 polymer with a molecular weight of up to 121 × 103 and a relatively low polydispersity index of 3.8. In addition to powder materials, microporous nanofibrous materials are obtained by electrospinning from polymer solutions. According to the Brunauer–Emmett–Teller method, the specific surface area of PIM-1 reaches 862 m2/g for powders and 362 m2/g for nanofibers.

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.

Effect of ultrasound assisted treatment and microwave combined with water bath heating on gel properties of surimi-crabmeat mixed gels

Crabmeat from Chinese mitten crab (Eriocheir sinensis) has unique flavor and high nutritional value, which make it a useful ingredient in surimi products. To promote the manufacture of surimi-crabmeat mixed gels, we investigated the effect of ultrasound treatment and microwave heating, combined with water bath heating on gel properties. Replacing the second step with microwave heating, in the traditional two-step heating process, significantly increased the deformation and decreased the breaking force of mixed gels. Additionally, microwave heating promoted the aggregation of myosin heavy chains and the formation of high-molecular weight polymers, and improved water holding capacity. However, owing to rapid heating, microwaving led to moisture loss of mixed gels. Raman spectrum analysis indicated that microwave heating increased the α-helical content and decreased β-sheet content, while ultrasound and the addition of crabmeat had minimal effect on the secondary protein structure. Crabmeat conferred better water holding capacity and higher increment of moisture content to surimi gels but led to coarser surface morphology. Ultrasound improved the increment of moisture content and surface morphology. These results suggested that ultrasound and microwave could be used as efficient ways to improve gel properties of mixed surimi gel products.