Multicomponent Polymer Systems Research Articles

Molecular dynamics simulations of thermomechanical properties of silicone-modified phenolic polymer

The silicone-phenolic multicomponent polymers are typically employed as the matrix of fiber-reinforced nanocomposites developed for reentry vehicles due to their excellent thermal and mechanical properties. The thermomechanical properties of the silicone-phenolic multicomponent polymer system, which are greatly related to the processing and microstructures, were studied using molecular dynamics (MD) simulations combined with experiments. A multistep dynamic polymerization approach was utilized to form the crosslinked polymer model, which was also validated in terms of both microstructures and properties. The thermomechanical properties of the crosslinked polymer system were established as a function of crosslinking degree, component ratio, temperature, strain rate, and cooling rate, and the influence mechanisms of the processing parameters were revealed. The crosslinking degree can greatly influence the glass transition temperature and volumetric coefficient of thermal expansion, which is attributed to the constrained chain mobility. The crosslinking degree and the component ratio have a significant effect on the morphologies and vibrational density of states of the polymer system, respectively, which in turn affects the thermal conductivity. The failure mode during uniaxial tensile was investigated in terms of the atomic energy distribution through MD simulations. The elastic and plastic deformation stages are dominated by intermolecular non-bonding interactions, but less contributed by the bonding interactions. This work can guide the design of polymeric nanocomposites by establishing the relationship of processing-microstructure-thermomechanical properties.

Exact analytical solution of the Flory-Huggins model and extensions to multicomponent systems.

The Flory-Huggins theory describes the phase separation of solutions containing polymers. Although it finds widespread application from polymer physics to materials science to biology, the concentrations that coexist in separate phases at equilibrium have not been determined analytically, and numerical techniques are required that restrict the theory's ease of application. In this work, we derive an implicit analytical solution to the Flory-Huggins theory of one polymer in a solvent by applying a procedure that we call the implicit substitution method. While the solutions are implicit and in the form of composite variables, they can be mapped explicitly to a phase diagram in composition space. We apply the same formalism to multicomponent polymeric systems, where we find analytical solutions for polydisperse mixtures of polymers of one type. Finally, while complete analytical solutions are not possible for arbitrary mixtures, we propose computationally efficient strategies to map out coexistence curves for systems with many components of different polymer types.

Effect of blend ratio on the phase structure and ozone aging resistance of ethylene-propylene-diene, butyl, and chlorobutyl rubber blends

ABSTRACT In the present study, the effect of elastomer ratios in solution-based mixtures on the formation of the phase structure and properties of compositions based on butyl rubber, chlorobutyl rubber, and ethylene-propylene-diene rubber was investigated. This work determined the influence of the elastomer ratios in uncured blends and their impact on the patterns of phase structure formation in multicomponent polymer systems, alterations in molecular mobility, and their influence on ozone resistance. Attenuated total reflectance – Fourier transform infrared spectroscopy was employed to analyze the chemical structure of the polymer surfaces. The influence of blend ratio (mass percentage ratios of 100/0, 80/20, 60/40, 50/50, 40/60, 20/80, and 0/100) on the phase structure and surface ozone oxidation was studied. The green strengths of the blends of ethylene-propylene-diene rubber and butyl/chlorobutyl rubbers were studied over a wide range of blend ratios.

Reversibly Interlocking of Immiscible Covalent Adaptive Networks in Solid State: A Paradigm for Enhancing Interfacial Interaction of Multicomponent Polymer Systems

Reversibly Interlocking of Immiscible Covalent Adaptive Networks in Solid State: A Paradigm for Enhancing Interfacial Interaction of Multicomponent Polymer Systems

Polyurethane toughened covalent adaptive networks epoxy composite based on thermoreversible Diels‐Alder reaction: Self‐healable, shape memory, and recyclable

AbstractCovalent adaptive networks (CANs) epoxy based on the Diels‐Alder (DA) reaction usually are commonly used for self‐healing materials. However, poor toughness greatly limits its application in innovative materials. Herein, based on retaining the excellent dynamic characteristics of DA reactive CANs, we introduced thermoplastic polyurethane (TPU) in situ during crosslinking, improving the composite material's strength and toughness. A multicomponent polymeric system with advanced performance can be produced by the individual components on the condition of the synergistic hybrid effects. Molecular‐level interlocking polymer networks between the chain entanglement of TPU and the reversible covalent crosslink of DFB were formed by the topological reorganization of these two immiscible polymers. As the gelation proceeds, a homogenous structure instead of conventional phase separation is formed. When the mixing ratio of DFB and TPU is 1:1, the tensile strength of the prepared sample reaches 35 MPa, and the elongation at break reaches 110%. At the same time, the composites possess good thermal stability and solvent resistance due to the presence of interlocking polymer networks. Furthermore, these DFB‐TPU composites show excellent shape memory, self‐healing, and closed‐loop recycling properties.

Diblock Copolymer Melt in an Electric Field: Stability of the Homogeneous State in the Random Phase Approximation

The contribution of I.Ya. Erukhimovich (1947–2022) to the creation of the theory of microphase separation in di- and triblock copolymers has been briefly analyzed. His matrix method of calculating correlation functions for multicomponent polymer systems has been applied to find the spinodal of a diblock copolymer melt in a static electric field. It has been strictly shown that for a linear dependence of local dielectric constant of the copolymer on the order parameter the spinodal condition remains the same as in the absence of the electric field. The correction to the critical value of the Flory‒Huggins parameter has been calculated for more general case of the quadratic dependence.

Zn-based Metal-Organic Frameworks (MOFs) Incorporated into Collagen-Polysaccharide-based Composite Hydrogels for Their Use in Wound Healing

Based on the physicochemical properties of metal-organic frameworks (MOFs), and the need of having an anti-inflammatory and antibacterial effect at the same time in a material for wound healing applications, a multicomponent polymer system was synthesized. Zn-based MOFs having different amino acids acting as ligands (L-tryptophan (Trp), L-phenylalanine (Phe), and L-histidine (His)) in their coordination sphere were successfully prepared and validated by FTIR and XRD. Each MOF was incorporate d into a semi-interpenetrated polymeric network (semi-IPN) based on collagen (C)-guar gum (GG)-polyurethane (PU), given composite hydrogels as end products. The physicochemical properties of these novel composite hydrogels, their in vitro biocompatibility, and their use as cell carriers were studied. The maximum swelling capacity was shown by CGG-Zn(Trp) while the crosslinking index was higher for CGG-Zn(Phe) and CGG-Zn(His), indicating that the chemical structure of the amino acid of the Zn-based MOF tailors these physicochemical properties. All composite hydrogels were resistant to a hydrolysis degradation process (at pH=5 and 7.4) being not entirely degraded after 14 days and having residual masses above 57%. The incorporation of Zn-based MOFs increased the biocompatibility in terms of metabolic activity and proliferation of porcine fibroblast in contact with the composite hydrogels. The low release capacity of fibroblast encapsula ted inside hydrogels evaluated for 10 days indicated the non-efficient capacity of these matrixes as cell carriers, regardless of the structure of the Zn-based MOF. The strong adhesion of porcine fibroblast to the composite hydrogels is related to improving metabolic activity al lowing its proliferation, making these multicomponent polymeric systems useful as efficient materials in biomedical applications such as wound dressing and tissue engineering.

Electrospinning vs. Electro-Assisted Solution Blow Spinning for Fabrication of Fibrous Scaffolds for Tissue Engineering

Biodegradable polymeric fibrous non-woven materials are widely used type of scaffolds for tissue engineering. Their morphology and properties could be controlled by composition and fabrication technology. This work is aimed at development of fibrous scaffolds from a multicomponent polymeric system containing biodegradable synthetic (polylactide, polycaprolactone) and natural (gelatin, chitosan) components using different methods of non-woven mats fabrication: electrospinning and electro-assisted solution blow spinning. The effect of the fabrication technique of the fibrous materials onto their morphology and properties, including the ability to support adhesion and growth of cells, was evaluated. The mats fabricated using electrospinning technology consist of randomly oriented monofilament fibers, while application of solution blow spinning gave a rise to chaotically arranged multifilament fibers. Cytocompatibility of all fabricated fibrous mats was confirmed using in vitro analysis of metabolic activity, proliferative capacity and morphology of NIH 3T3 cell line. Live/Dead assay revealed the formation of the highest number of cell-cell contacts in the case of multifilament sample formed by electro-assisted solution blow spinning technology.

PH-sensitive packaging of cationic particles by an anionic block copolymer shell

Cationic non-viral vectors show great potential to introduce genetic material into cells, due to their ability to transport large amounts of genetic material and their high synthetic versatility. However, designing materials that are effective without showing toxic effects or undergoing non-specific interactions when applied systemically remains a challenge. The introduction of shielding polymers such as polyethylene glycol (PEG) can enhance biocompatibility and circulation time, however, often impairs transfection efficiency. Herein, a multicomponent polymer system is introduced, based on cationic and hydrophobic particles (P(nBMA46-co-MMA47-co-DMAEMA90), (PBMD)) with high delivery performance and a pH-responsive block copolymer (poly((N-acryloylmorpholine)-b-(2-(carboxy)ethyl acrylamide)) (P(NAM72-b-CEAm74), PNC)) as shielding system, with PNAM as alternative to PEG. The pH-sensitive polymer design promotes biocompatibility and excellent stability at extracellular conditions (pH 7.4) and also allows endosomal escape and thus high transfection efficiency under acidic conditions. PNC shielded particles are below 200 nm in diameter and showed stable pDNA complexation. Further, interaction with human erythrocytes at extracellular conditions (pH 7.4) was prevented, while acidic conditions (pH 6) enabled membrane leakage. The particles demonstrate transfection in adherent (HEK293T) as well as difficult-to-transfect suspension cells (K-562), with comparable or superior efficiency compared to commercial linear poly(ethylenimine) (LPEI). Besides, the toxicity of PNC-shielded particles was significantly minimized, in particular in K-562 cells and erythrocytes. In addition, a pilot in vivo experiment on bone marrow blood cells of mice that were injected with PNC-shielded particles, revealed slightly enhanced cell transfection in comparison to naked pDNA. This study demonstrates the applicability of cationic hydrophobic polymers for transfection of adherent and suspension cells in culture as well as in vivo by co-formulation with pH-responsive shielding polymers, without substantially compromising transfection performance.Graphical

Effect of Tm of blend components on the isothermal melt-crystallization process of PHB/PLLA blends investigated using spectroscopic imaging and DSC

The understanding of morphology and crystallization in biopolymer blends offers the ability to tune these properties for specific uses. In this study, the isothermal melt-crystallization process of poly (3-hydroxybutyrate) (PHB)/poly ( l -lactic acid) (PLLA) blends with different weight loadings and molecular weights was investigated using in-situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopic imaging and differential scanning calorimetry (DSC). When the isothermal crystallization temperature is constant, increasing the fraction of blend component with a lower T m results in the decreasing T m of both blend components, which is indicated in DSC thermograms. The reduced T m delays the crystallization of both blend components and then the restrained crystallization leads to a greater extent of phase separation, which is shown in ATR-FTIR spectroscopic images. Likewise, at a constant isothermal crystallization temperature, with the decreasing molecular weights of blend components, the miscibility of polymer blend should be enhanced because of the shift of the phase boundary in phase diagram to lower temperatures. However, the decreasing overall crystallization rate and the delay of crystallization indicated in the integrated absorbance profiles and the decreasing T m indicated in the DSC thermograms can be used to explain the greater extent of phase separation in the PHB/PLLA blend shown in the spectroscopic images. A phase diagram was prepared to show the effect of polymer molecular weight on the miscibility of PHB/PLLA blends. Thus, increasing the fraction of the blend component with a higher T m , choosing polymers with a higher molecular weight and decreasing the isothermal crystallization temperature have been demonstrated to be effective methods to promote the miscibility of upper critical solution temperature (UCST) crystallizable polymer blends. Moreover, it was concluded that in-situ ATR-FTIR spectroscopic imaging can be combined with integrated absorbance profiles and DSC thermograms to deepen the understanding of multicomponent polymer systems. • A phase diagram was prepared to show the effect of M w on the miscibility of PHB/PLLA blends. • Effective methods are found to promote the miscibility of UCST polymer blends during isothermal crystallization process. • Spectroscopic imaging can be combined with DSC thermograms to deepen the understanding of multicomponent polymer systems.

Obtaining and studying the structure and properties of nanocomposites based on polyolefi ns and mineral fi llers: state of the art

The literature data on the problems of obtaining and studying polymer composite materials, nanocomposites, dynamically vulcanized elastoplasts are presented. Phase transformations and their infl uence on the structure and properties of multicomponent polymer systems are considered.

FEATURES OF IN SITU FORMATION OF MIXTURES OF LINEAR POLYMERS

This article is devoted to the analysis of the results of the investigation of the process of forming mixtures of linear polymers formed simultaneously in situ according to different mechanisms. The first mechanism is polyaddition, the second mechanism is radical polymerization. This is one of the possible ways to obtain multicomponent polymer systems. The kinetics of chemical reactions of the formation of components and the phase separation which accompanies these reactions were studied for mixtures of poly(methyl methacrylate) (PMMA) with two polyurethanes (PU) of different chemical nature of both flexible and rigid blocks. PU-1 was synthesized from macrodiisocyanate based on oligo(tetramethylene glycol) with molecular mass 1000 g·mol–1 and hexamethylene diisocyanate taken in the molar ratio 1 : 2 using diethylene glycol as a chain extender. PU-2 was synthesized from macrodiisocyanate based on olygo(propylene glycol) with molecular mass 1000 g·mol–1 and toluylene diisocyanate taken in the molar ratio 1 : 2 using butanediol as a chain extender. The mixture of polystyrene (PS) with PU-2 was studied too. It is established that regardless of the chemical nature of the components, the process of in situ mixture formation is subject to general laws. In particular, the change in the chemical nature of the component formed by the mechanism of polyaddition (mixtures PMMA/PU-1 and PMMA/PU-2) or of the component formed by radical polymerization (mixtures PMMA/PU-2 and PS/PU-2) does not affect the nature of the dependence of the conversion degree of components and the fraction of formed polymers at the beginning of the phase separation on the composition of the initial reaction mixtures. Only the absolute values of these parameters change due to different reactivity and different thermodynamic compatibility of the mixed components.

Spatial distribution of silica fillers in phase‐separated rubber blends investigated by three‐dimensional elemental mapping

AbstractThe distribution of nano‐sized silica in binary rubber blends is characterized by scanning transmission electron microscopy (STEM) tomography combined with energy dispersive X‐ray spectrometry (EDX). 3D distribution of silica is visualized by STEM‐EDX tomography with the tilt‐series of silicon elemental maps, while the phase‐separated morphologies of polyisoprene rubber (IR) and styrene‐butadiene rubber (SBR) are visualized by STEM‐tomography in high‐angle‐annular‐dark field (HAADF) mode. The combination of STEM‐EDX and STEM‐HAADF tomography enables us to determine the distribution of silica between the two rubber phases quantitatively even with high contents of silica up to 70 phr (weight parts per hundred rubber). It is found that silica is preferentially distributed in the SBR phase, but it is also distributed in the IR phase when the IR fraction in the total rubber components is higher than 40 wt%. The preferential distribution of silica in the SBR phase improves the dispersion of the IR domains. This is the first use of this technique for a multicomponent polymer system, showing the advantage to characterize the complicated multicomponent polymer composite morphologies.

Visualization of Inter- and Intramolecular Interactions in Poly(3-hydroxybutyrate)/Poly(L-lactic acid) (PHB/PLLA) Blends During Isothermal Melt Crystallization Using Attenuated Total Reflection Fourier Transform infrared (ATR FT-IR) Spectroscopic Imaging.

Inter- and intramolecular interactions in multicomponent polymer systems influence their physical and chemical properties significantly and thus have implications on their synthesis and processing. In the present study, chemical images were obtained by plotting the peak position of a spectral band from the data sets generated using in situ attenuated total reflection Fourier transform infrared (ATR FT-IR) spectroscopic imaging. This approach was successfully used to visualize changes in intra- and intermolecular interactions in poly(3-hydroxybutyrate)/poly(L-lactic acid) (PHB/PLLA) blends during the isothermal melt crystallization. The peak position of ν(C＝O) band, which reflects the nature of the intermolecular interaction, shows that the intermolecular interactions between PHB and PLLA in the miscible state (1733 cm−1) changes to the inter- and intramolecular interaction (CH3⋯O=C, 1720 cm−1) within PHB crystal during the isothermal melt crystallization. Compared with spectroscopic images obtained by plotting the distribution of absorbance of spectral bands, which reveals the spatial distribution of blend components, the approach of plotting the peak position of a spectral band reflects the spatial distribution of different intra- and intermolecular interactions. With the process of isothermal melt-crystallization, the disappearance of the intermolecular interaction between PHB and PLLA and the appearance of the inter- and intramolecular interactions within the PHB crystal were both visualized through the images based on the observation of the band position. This work shows the potential of using in-situ ATR FT-IR spectroscopic imaging to visualize different types of inter- or intramolecular interactions between polymer molecules or between polymer and other additives in various types of multicomponent polymer systems.

Nanomechanical and Chemical Mapping of the Structure and Interfacial Properties in Immiscible Ternary Polymer Systems

It is a challenge to identify each phase in a multi-component polymer system and uniquely determine the interfacial properties between the different phases. Using atomic force microscopy nanomechanical mapping (AFM-NM) and AFM-based infrared spectroscopy (AFM-IR), we identify each phase, visualize structural developments, and determine the interfacial properties in a blend of three polymers: high-density polyethylene (HDPE), polyamide (PA6) and poly(styrene-b-ethylene-co-butylene-b-styrene) (SEBS). Each phase can be identified from the Young’s modulus, along with the structural development within the phases before and after compatibilization. The interfacial widths between HDPE/PA6, HDPE/SEBS and SEBS/PA6 were determined independently in one measurement from a Young’s modulus map. The structural, mechanical property development and identity of the phases were determined by AFM-NM, while AFM-IR, providing complementary chemical information, identified interfacial reactions, showed the chemical affinity of a compatibilizer with the component phases, and mapped the distribution of the compatibilizer in the ternary polymer blends. The chemical, structural and interfacial information obtained by these measurements provide information that is essential for producing mechanically robust materials from incompatible mixtures of polymers.

A practical method to account for random phase approximation effects on the dynamic scattering of multi-component polymer systems.

Investigations of polymer systems that rely on the interpretation of dynamical scattering results as, e.g., the structure factor S(Q, t) of single chains or chain sections may require the inclusion of effects, as described within the framework of the random phase approximation (RPA) for polymers. To do this in practice for the dynamic part of S(Q, t) beyond the initial slope is a challenge. Here, we present a method (and software) that allows a straightforward assessment of dynamical RPA effects and inclusion of these in the process/procedures of model fitting. Examples of applications to the interpretation of neutron spin-echo data multi-component polymer melts are shown.

A Facile Preparation of Mussel-Inspired Poly(dopamine phosphonate-co-PEGMA)s via a One-Pot Multicomponent Polymerization System.

Mussel-inspired polymers attract much research interest due to their potential as effective adhesives. In this work, a new kind of mussel-inspired polymer, poly(dopamine phosphonate-co-PEGMA), is prepared via a one-pot multicomponent polymerization system. The multicomponent polymerization system refers to a combination of multicomponent Kabachnik-Fields (KF) reaction and reversible addition-fragmentation chain transfer (RAFT) polymerization system. Reactants are converted to dopamine phosphonate monomers in situ through the KF reaction and polymerized simultaneously along with poly(ethylene glycol methyl ether) methacrylate (PEGMA) co-monomers by the RAFT process in a one-pot operation. Target polymers with dopamine phosphonate as side groups and well-defined polymer structures are thus facilely and successfully prepared. Afterwards, a series of polymers with various ratios of dopamine phosphonates as well as the crosslinked polymer analogues are prepared. Benefiting from the dopamine phosphonate side groups, aqueous solutions of those polymers show potential as effective adhesives in both dry and wet conditions, and their adhesive strengths are highly related to ratios of dopamine phosphonates in the polymers. Those polymers are non-cytotoxic and show strong bonding affinities on various substrates including metals, polymers, and bovine bones, suggesting their potential as environmentally friendly general adhesives in broad areas.

High-Throughput Preparation of Antibacterial Polymers from Natural Product Derivatives via the Hantzsch Reaction.

SummaryThe Hantzsch and free-radical polymerization reactions were combined in a one-pot high-throughput (HTP) system to simultaneously prepare 30 unique polymers in parallel. Six aldehydes derived from natural products were used as the starting materials to rapidly prepare the library of 30 poly(1,4-dihydropyridines). From this library, HTP evaluation methods led to the identification of an antibacterial polymer. Mechanistic studies revealed that the dihydropyridine group in the polymer side-chain structure plays an important role in resisting bacterial attachment to the polymer surface, thus leading to the antibacterial function of this polymer. This research demonstrates the value of multicomponent reactions (MCRs) in interdisciplinary fields by discovering functional polymers for possible practical applications. It also provides insights to further developing new functional polymers using MCRs and HTP methods with important implications in organic chemistry, polymer chemistry, and materials science.

Topological rearrangement-derived homogeneous polymer networks capable of reversibly interlocking: From phantom to reality and beyond

The combination of polymers can produce a multicomponent polymeric system, with advanced performance that cannot be achieved by the individual components. An ideal case lies in the creation of all interface materials to maximize the synergistic hybrid effects. Thus far, however, even for the elaborate interpenetrating polymer networks, microheterogeneity is inevitably observed. Herein, we show a conceptual innovative approach to prepare molecular-level interlocking polymer networks by topological reorganization of two immiscible single polymer networks with orthogonal reversible covalent crosslinkages. The conventional phase separation is suppressed as gelation proceeds, and the interlocked networks are further unlocked to a homogenous structure, recovering the original single polymer networks. The resultant interlocking polymer networks show nonlinear improvement in mechanical performance in addition to smart adaptivity like self-healability. An extensible platform technology for bringing in new materials may thus be developed, which is breakthrough in the scope of classic polymer engineering dominated by irreversible covalent chemistry. Furthermore, the long-range interlocked networks themselves are a promising model system for studying soft condensed matter physics.

Structural hierarchy in blends of amphiphilic block copolymers self-assembled at the air-water interface

We present a concurrent self-assembly strategy for patterning hierarchical polymeric surface features by depositing variable-composition blends of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and polybutadiene-block-poly(ethylene oxide) (PB-b-PEO) block copolymers at the air-water interface. Hierarchical strand networks of hydrophobic PS/PB blocks anchored via PEO blocks to the water surface, with an internal phase-separation structure consisting of periodic domains of PS blocks surrounded and connected by a matrix of PB blocks, are generated by the interplay of interfacial amphiphilic block copolymer aggregation and polymer/polymer phase separation. In contrast to the cylinder-in-strand structures previously formed by our group in which interfacial microphase separation between PS and PB blocks was constrained by chemical connectivity between the blocks, in the current system phase separation between PS and PB is not constrained by chemical connectivity and yet is confined laterally within surface features at the air-water interface. Investigations of multi-component polymer systems with different connectivities constraining repulsive and attractive interactions provides routes to new hierarchical surface patterns for a variety of applications, including photolithography masks, display technology, surface-guided cell growth and tissue engineering.