Copolymers In Aqueous Solution Research Articles

Superabsorbent polymer with enhanced gel strength and heat resistance using itaconic acid‐based oligomer

AbstractThe preparation of an itaconic acid‐based oligomer and its polymerization with acrylic acid via aqueous solution copolymerization are described herein for application as novel superabsorbent polymers (SAPs). The structure of the SAP is characterized using Fourier transform infrared (FT‐IR) spectroscopy. In addition, the absorption properties of the SAPs with various oligomer contents and degrees of monomer neutralization are evaluated by measuring the free absorbency, centrifuge retention capacity (CRC), and absorbency under load (AUL) in 0.9 wt% saline solution. Further, the gel strengths and thermal stabilities are examined via rheological thermo gravimetric analyses. The results demonstrate that the introduction of the IA‐based oligomer into the SAP network is improves the AUL, gel strength, and thermal stability of the SAP. We found the best performance of an SAP using IA‐based oligomer with a CRC of 36.7 and AUL of 22.7 g/g.

Using the SAFT-γ-Mie to Generate Coarse-Grained Force Fields Useable in Molecular Dynamics Simulations: Describing the Micellar Phases of Polyalkylglycols in Aqueous Solutions

In this work, we showcase the potential of the SAFT-γ-Mie equation of state to obtain, in a top-down approach, coarse-grained molecular models capable of describing micellization phenomena. For this purpose, we selected polyethylene oxide (PEO)/polypropylene oxide (PPO) triblock copolymers in aqueous solutions as a case study. The model was fitted to reproduce the thermophysical properties─liquid densities and vapor pressures─of small PEO/PPO oligomers as well as the activity coefficients or liquid–liquid phase diagrams of their binary mixtures with water. At low concentrations, the MD simulations show the formation of spherical micelles of morphology comparable to experiments, with the characteristic star-shaped or flower-shaped morphology depending on the polymer block sequence. The local structure and molecular conformations were analyzed, showing distinctions between the two types of aggregates. At higher concentrations, depending on the co-polymer sequence, the molecules form larger micelles or coalesce into larger aggregates when signs of phase separation are observed, as expected.

Unexpected influence of acrylamide on clouding behavior of PEO-PPO-PEO triblock copolymers in aqueous solution

Unexpected influence of acrylamide on clouding behavior of PEO-PPO-PEO triblock copolymers in aqueous solution

Double Stimuli-Responsive di- and Triblock Copolymers of Poly(N-isopropylacrylamide) and Poly(1-vinylimidazole): Synthesis and Self-Assembly.

For the first time, double stimuli-responsive properties of poly(N-isopropylacrylamide) (PNIPA) and poly(1-vinylimidazole) (PVIM) block copolymers in aqueous solutions were studied. The synthesis of PNIPA60-b-PVIM90 and PNIPA28-b-PVIM62-b-PNIPA29 was performed using reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by size exclusion chromatography and 1H NMR spectroscopy. The conformational behavior of the polymers was studied using dynamic light scattering (DLS) and fluorescence spectroscopy (FS). It was found that PNIPA and block copolymers conformation and ability for self-assembly in aqueous medium below and above cloud point temperature depend on the locus of hydrophobic groups derived from the RAFT agent within the chain. Additionally, the length of PVIM block, its locus in the chain and charge perform an important role in the stabilization of macromolecular micelles and aggregates below and above cloud point temperature. At 25 °C the average hydrodynamic radius (Rh) of the block copolymer particles at pH 3 is lower than at pH 9 implying the self-assembling of macromolecules in the latter case. Cloud points of PNIPA60-b-PVIM90 are ~43 °C and ~37 °C at a pH of 3 and 9 and of PNIPA28-b-PVIM62-b-PNIPA29 they are ~35 °C and 31 °C at a pH of 3 and 9. Around cloud point independently of pH, the Rh value for triblock copolymer rises sharply, achieves the maximum value, then falls and reaches the constant value, while for diblock copolymer, it steadily grows after reaching cloud point. The information about polarity of microenvironment around polymer obtained by FS accords with DLS data.

A Generalized Mechano-statistical Transient Network Model for Unravelling the Network Topology and Elasticity of Hydrophobically Associating Multiblock Copolymers in Aqueous Solutions

In this contribution, we unravel the transient network topology and elasticity of micellar networks formed by hydrophobically associating multiblock copolymers in aqueous solutions. Unlike studies on conventional triblock copolymers bearing hydrophobic blocks as end groups, our research focuses on alternating poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) multiblock copolymers having multiple hydrophobic PPO blocks along the chain. We adopt a combinatorics approach to extend and generalize the mechano-statistical transient network model developed by Annable et al. for telechelic triblock copolymers [ Journal of Rheology, 1993, 37, 695] to multiblock copolymers. The model allows one to predict the concentration dependent elasticity of networks formed by multiblock copolymers with known molecular characteristics by using knowledge of the micellar network microstructure. The spatial distribution of the hydrophobic nodes is inferred from Small-Angle X-ray Scattering (SAXS) by converting the structure factor to the radial distribution function. The number of closely neighboring micellar cores between which an elastic bridge can be formed (nm) is calculated by spherical integration of the radial distribution function up to a distance of the radius of gyration of an intermediate soluble PEO block. Using the evolution of nm with concentration as an input for the model, the predictions show good agreement with experimental elasticity data, as inferred from the plateau modulus in linear shear rheology. The network evolves from loop-dominated, poorly elastic with cross-linking nodes with low functionality at low concentrations to bridge-dominated, highly elastic with higher node functionalities at more elevated concentrations. It is anticipated that our generalized mechano-statistical transient network model can also be used for equally spaced, multisticker associating polymers forming networks by multifunctional interactions other than micellar aggregation.

PH-Responsive, Thermo-Resistant Poly(Acrylic Acid)-g-Poly(boc-L-Lysine) Hydrogel with Shear-Induced Injectability.

In this study we report the rheological behavior of aqueous solutions of an amphiphilic graft copolymer constituting a polyacrylic acid (PAA) grafted by poly(boc-L-lysine), P(b-LL). Due to the highly hydrophobic nature of the grafted chains, the copolymer self-assembles spontaneously in aqueous media forming three-dimensional (3D) finite size networks (microgels). The rheological analysis demonstrated that the copolymer behaves as a strong elastic hydrogel, showing characteristics of a "frozen" network. Moreover, it is noteworthy that the formulation shows the above-described characteristics in very small concentrations (0.25-1.20 wt%) compared to other naturally cross-linked hydrogels that have been studied so far. Concentration significantly affects the rheological properties of the hydrogel, showing considerable increase in elastic modulus, following the scaling law G'~C1.93. At the same time, the hydrogels can be described as intelligent stimuli-responsive systems, showing pH and shear responsiveness as well as stability with temperature changes. Thanks to the pH dependance of the degree of ionization of the weak polyelectrolyte PAA backbone, stiffness and swelling of the hydrogels can be tuned effectively by adjusting the pH conditions. Simulating conditions such as those of injection through a 28-gauge syringe needle, the gel demonstrates excellent response to shear, due to its remarkable shear thinning behavior. The combination of pH-sensitivity and shear responsiveness leads to excellent injectability and self-healing properties, given that it flows easily upon applying a low stress and recovers instantly in the site of injection. Therefore, the physically cross-linked PAA-g-P(b-LL) hydrogel exhibits remarkable features, namely biocompatibility, biodegradability of cross-links, pH responsiveness, shear-induced injectability and instantaneous self-healing, making it a potential candidate for various biomedical applications.

Loose Semirigid Aromatic Polyester Bottle Brushes at Poly(2-isopropyl-2-oxazoline) Side Chains of Various Lengths: Behavior in Solutions and Thermoresponsiveness.

A polycondensation aromatic polyester with an oxygen spacer was synthesized and used as a macroinitiator for the grafting of linear poly(2-isopropyl-2-oxazoline) (PiPrOx) by the cationic polymerization method. The length of the thermosensitive side chains was varied by the initiator:monomer ratio. Using methods of molecular hydrodynamics, light scattering and turbidimetry, the copolymers were studied in organic solvents and in water. The molecular characteristics of the main chain and graft copolymers, the polymerization degree of side chains and their grafting density have been determined. The equilibrium rigidity of the macroinitiator and the conformations of grafted macromolecules were evaluated. In selective solvents, they take on a star-like conformation or aggregate depending on the degree of shielding of the main chain by side chains. The thermoresponsiveness of graft copolymers in aqueous solutions was studied, and their LCST were estimated. The results are compared with data for graft copolymers composed of PiPrOx side chains and flexible or rigid chain backbones of aromatic polyester type.

Structure and Dynamics of Inhomogeneities in Aqueous Solutions of Graft Copolymers of N-Isopropylacrylamide with Lactide (P(NIPAM-graft-PLA)) by Spin Probe EPR Spectroscopy.

Coil-to-globule transition and dynamics of inhomogeneities in aqueous solutions of graft copolymers of NIPAM with different content of oligolactide groups were studied using spin probe continuous wave EPR spectroscopy. The technique of the suppressing of TEMPO as spin probe by spin exchange with Cu2+ ions was applied. This approach allowed us to detect individual EPR spectra of the probe in collapsed globules and estimate its magnetic and dynamic parameters reliably. The formation of inhomogeneities at temperatures lower than the volume phase transition temperature measured via transmission, and differential scanning calorimetry was fixed. An increase in oligolactide content in copolymers leads to the formation of looser globules, allowing for the exchange of the probe molecules between the globules and the external solution.

Biocidal Coatings from Complexes of Carboxylated Latex Particles and a Linear Cationic Polymer.

A linear polycation, poly(diallyldimethylammonium chloride), electrostatically interacts with anionic latex particles from a carboxylated butadiene-styrene copolymer in aqueous solution thus forming an interpolyelectrolyte complex. A mutual neutralization of oppositely charged latex and polycation groups occurs at W = latex/polycation = 50 w/w ratio. At W = 27, an ultimate polycation adsorption is reached, resulting in the formation of positive polycomplex particles, while at W ˂ 27, two-component systems are formed composed of positive polycomplex particles and free polycation. A film created from the W = 12 formulation shows a high toxicity to Gram-positive and Gram-negative bacteria and yeast. Repeated washing the film leads to partial removal of polycation and a 50% decrease in the activity of the film only towards Gram-negative Pseudomonas aeruginosa. The results indicate the potential for use of the mixed polymer formulations for the fabrication of antimicrobial films and coatings.

Synthesis of an optically transparent poly(N-isopropylacrylamide)-based thermally gelling material

Restrictive barriers and efficient clearance mechanisms make delivery of therapeutics to the back of the eye particularly challenging. An optically transparent, thermally gelling copolymer scaffold that can simply be mixed with an active pharmaceutical ingredient of choice and injected directly into the vitreous chamber has been designed. The poly( N-isopropylacrylamide) (PNIPAAm)-based copolymer possesses a lower critical solution temperature near body temperature. Incorporating acrylic acid and poly(ethylene glycol) methacrylate into the polymer at optimized ratios modulates the lower critical solution temperature to transition the aqueous copolymer solution into a volume-consistent gel, which does not expel water, a common challenge with PNIPAAm-based materials. The addition of acryloyloxy dimethyl-γ-butyrolactone to the copolymer enables the polymer to slowly degrade and be cleared from the body. Herein, the synthesis and characterization of the novel copolymer scaffolds are described. A detailed report is provided on the intraocular biocompatibility profile as assessed via in vivo imaging techniques, histology, and immunostaining. Overall, the scaffolds were well tolerated in the rodent eye for the duration of the 17-day experiment.

Preparation of Copolymer of Dihydroxy Monomer and Acrylamide and Its Solution Properties with Polyphenylboronic Acid Compounds

: The construction of composite flooding system based on dynamic covalent bonds is one of the effective methods to improve the salt and temperature resistance of polymer flooding agents. The polymers used in most composite systems are xanthan gum and guar gum. In this paper, a novel multi-hydroxyl polymer was synthesized, and a new composite system was constructed based on the dynamic boronic ester bonds. Firstly, the multi-hydroxyl polymer P(AM-DPMOH2) was prepared by aqueous solution copolymerization of acrylamide (AM) and a dihydroxy monomer 2,3-dihydroxy-N-(3-methacrylamidopropyl)-N,N-dimethylpropan-1-aminium (DPMOH2), which was obtained by quaternization reaction between 3-chloro-1,2-propanediol and N-(3-dimethylaminopropyl). Then, the composite system was prepared by the P(AM-DPMOH2) solution and polyboronic acid compound (BPEI). The effects of DPMOH2 content in P(AM-DPMOH2), molecular weight of P(AM-DPMOH2), molecular weight of BPEI, phenylboronic acid groups content in BPEI and pH on the formation of thickening composite system were investigated. The results showed that when the content of DPMOH2 in P(AM-DPMOH2) exceeded 40 wt%, viscosity average molecular weight of P(AM-DPMOH2) was higher than 5.0×105 g/mol, the molecular weight of PEI in BPEI was larger than 3000 g/mol, the content of phenylboronic acid groups in BPEI was more than 39.3 %, and pH was in the range of 8–9, the thickening composite system can be formed by P(AM-DPMOH2) and BPEI. In addition, both the temperature and salt resistance of the composite system formed by 3000 mg/L P(AM-DPMOH2) and 2000 mg/L BPEI was much better than that of 3000 mg/L P(AM-DPMOH2). The results of this paper provide a new finding of how to construct a composite flooding system with dynamic covalent bonds.

Hierarchical Self-Assembly of Triphilic Main-Chain-Type Semifluorinated Alternating Graft Copolymers in Aqueous Solution.

Fluorinated copolymers can self-assemble in solution and form micelles with rare properties due to the peculiar behavior of fluorinated groups. However, the process description of the self-assembly is still largely phenomenological and difficult to explain due to the tendency of the fluorinated segments to segregate from both the hydrophilic and lipophilic segments, which can result in various morphologies. Herein, the controlled formation of ellipsoidal micelles, disklike micelles, and sheets by hierarchical self-assembly of triphilic main-chain-type semifluorinated alternating graft copolymers (AB)n A-g-mOEG is presented (where A represents unit of α,ω-diiodoperfluoroalkane, B represents the unit of α,ω-unconjugated diene, and mOEG represents methoxy oligo(ethylene glycol)), which are synthesized by step transfer-addition and radical-termination (START) polymerization and azide-alkyne click chemistry. Furthermore, the possible self-assembly mechanism of these micron-level aggregates is proposed, which is ascribed to the hierarchical self-assembly, crowding effect of hydrophilic chains and the interfacial tension between the fluoroalkane and alkane segments. This study can provide a facile and highly efficient approach to the synthesis of main-chain-type fluorinated graft copolymers and expand the research field for the solution self-assembly of fluorinated copolymers.

Computational Approach to the Surface-Crosslinking Process of Superabsorbent Polymer via Central Composite Design.

The improvement of gel strength and absorption properties through the surface-crosslinking of superabsorbent polymers (SAPs) is essential for sanitary industry applications. We prepared core-SAP via aqueous solution copolymerization, and then surface-crosslinked the core-SAP under various conditions. The structure of the SAP was characterized using Fourier transform infrared (FT-IR) spectroscopy. Central composite design (CCD) of response surface methodology (RSM) has been applied to determine the optimum surface-crosslinking conditions such as surface-crosslinker content, reaction temperature, and reaction time. The optimal surface-crosslinking conditions were identified at a surface-crosslinker content of 2.22 mol%, reaction temperature of 160 °C, and reaction time of 8.7 min. The surface-crosslinked SAP showed excellent absorbency under load of 50 g/g with a permeability of 50 s. Other absorption properties were also evaluated by measuring the free absorbency and centrifuge retention capacity in saline solution.

Redox-Responsive Polymersomes as Smart Doxorubicin Delivery Systems.

Stimuli-responsive polymersomes have emerged as smart drug delivery systems for programmed release of highly cytotoxic anticancer agents such as doxorubicin hydrochloride (Dox·HCl). Recently, a biodegradable redox-responsive triblock copolymer (mPEG–PDH–mPEG) was synthesized with a central hydrophobic block containing disulfide linkages and two hydrophilic segments of poly(ethylene glycol) methyl ether. Taking advantage of the self-assembly of this amphiphilic copolymer in aqueous solution, in the present investigation we introduce a solvent-exchange method that simultaneously achieves polymersome formation and drug loading in phosphate buffer saline (10 mM, pH 7.4). Blank and drug-loaded polymersomes (5 and 10 wt.% feeding ratios) were prepared and characterized for morphology, particle size, surface charge, encapsulation efficiency and drug release behavior. Spherical vesicles of uniform size (120–190 nm) and negative zeta potentials were obtained. Dox·HCl was encapsulated into polymersomes with a remarkably high efficiency (up to 98 wt.%). In vitro drug release studies demonstrated a prolonged and diffusion-driven release at physiological conditions (~34% after 48 h). Cleavage of the disulfide bonds in the presence of 50 mM glutathione (GSH) enhanced drug release (~77%) due to the contribution of the erosion mechanism. Therefore, the designed polymersomes are promising candidates for selective drug release in the reductive environment of cancer cells.

Controlling self-assembly of co-polypeptide by block ratio and block sequence

Block ratio and block sequence of polypeptide influenced the self-assembly of copolymer significantly. Tuning self-assembly to form various nanostructures with different properties through molecular design was a rather feasible strategy. Triblock copolymers based on poly( l -alanine) (PA), poly( l -valine) (PV) and poly (ethylene glycol) (PEG) with various block ratio and block sequence were synthesized. The number of amino acid residues was kept at 10. The sol-gel transition behavior, self-assemble nanostructure, secondary structure of the copolymers in aqueous solution were investigated to reveal that PA block between PEG and PV segment interfered the β-sheet structure, resulting in the reduced or increased sol-gel transition temperature or precipitation depended on the block ratio of PA and PV. Shorter PA or PV block displayed more significant influence on sol-gel transition. Interestingly, PV block between PEG and PA segment induced the formation of more stable β-sheet stacking structures, leading to sol-gel transition at higher temperature. PEG dehydration and the enhancement of ordered structure with temperature rising caused the sol-gel transition of these copolymers. We concluded herein that disordered structure in co-polypeptide can enhance thermo-sensitivity. • Conformation of synthesized non-natural polypeptides based on side-chain design. • Block sequence of non-natural polypeptides affected sol-gel transition. • Shorter peptide block influenced more significantly on sol-gel transition. • Less hydrophobic and weaker steric hindrance block at the tail enhanced the stability of nanostructures. • Disordered structure in co-polypeptide enhanced thermo-sensitivity.

Aggregation Behavior of Nonsymmetrically End-Capped Thermoresponsive Block Copolymers in Aqueous Solutions: Between Polymer Coils and Micellar States

Aggregation Behavior of Nonsymmetrically End-Capped Thermoresponsive Block Copolymers in Aqueous Solutions: Between Polymer Coils and Micellar States

Novel inkjet direct printing technology based on thermosensitive sol–gel transition inks

Biodegradable poly( ε-caprolactone-co-lactide)- b-poly(ethylene glycol)- b-poly( ε-caprolactone- co-lactide) (PCLA-PEG-PCLA) triblock copolymer was developed to prepare thermosensitive inks for digital fiber printing applications. The thermosensitive inks can be printed on any textile or fiber that does not need to go through the pretreatment and soaping procedure like traditional inks. This copolymer aqueous solution has a reversible sol–gel transition property, which can be used to prepare thermosensitive sol–gel inks. PCLA-PEG-PCLA had little effect on the physical properties of the inks, including the average particle size, conductivity, and surface tension at room temperature. However, the viscosity of the thermosensitive inks can increase dramatically under high temperature. This was due to the inks undergoing a sol–gel transition with an increase of temperature. The inks were in the sol state in the printer cartridge at room temperature and when the ink drops fell on the heated fiber or textile, a sol–gel transition occurred and turned them into a gel immediately. The high viscosity prevented the ink from spreading around on the fabrics, thus giving a sharp edge. The study indicated that the line width printed by thermosensitive inks was reduced to 266.35 μm from 464.08 μm in the weft direction (reduced by 43%), and the line width in the warp direction was reduced to 264.35 μm from 385.76 μm (reduced by 32%). The polyester fabric printed by thermosensitive ink has a higher color strength ( K/ S) at 47–50°C with excellent colorfastness. Thermosensitive ink is a type of innovative ink, in line with the concept of green ecological textile manufacturing.

Thermo-responsive nonionic amphiphilic copolymers as draw solutes in forward osmosis process for high-salinity water reclamation

Recently, thermo-responsive nonionic amphiphilic copolymers have shown a great potential as forward osmosis (FO) draw solutes for high-salinity water desalination and zero-liquid discharge (ZLD). However, the relationship between the copolymer structural properties and key characteristics as draw solutes, as well as copolymer's chemical stability after regeneration have not been much studied. In this work, we systematically investigated poly (ethylene oxide)-block-poly (propylene oxide)-block-poly (ethylene oxide) (PEO-PPO-PEO) copolymers as draw solute. The results showed that the PEO segments significantly influenced the viscosity, osmotic pressure and lowest phase separation temperature of the copolymer aqueous solutions. Among four commercial copolymers studied, Pluronic® L35 with moderate molecular weight (Mn 1,900 Da), 50% PEO, and relatively high hydrophilic-lipophilic balance (HLB) showed the best draw solution (DS) performance. It also showed great stability in physiochemical properties and draw capacity after more than ten cycles of regeneration. On the other hand, despite the fact that membrane fouling was observed due to the use of copolymer DS, the FO flux (∼1.2 L m‒2 h‒1, as similar with the virgin membrane) was not affected when high-salinity feedwater such as seawater RO brine was applied. Overall, our study has provided a more comprehensive understanding on the characteristics of nonionic amphiphilic copolymer DS and showcased the promise of copolymer-driven FO process in high-salinity water desalination and ZLD.

Impact of Two Water-Miscible Ionic Liquids on the Temperature-Dependent Self-Assembly of the (EO)6-(PO)34-(EO)6 Block Copolymer.

There are many studies on the self-assembly of triblock poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) copolymers in aqueous solution. These polymers display a rich phase diagram as a function of block length, concentration, temperature, and additives. Here, we present a small-angle neutron scattering study of the impact of two water-miscible ionic liquids, 1-butyl-3-methylimidazolium chloride ([C4C1mim][Cl]) and 1-butyl-3-methylpyrrolidinium chloride ([C4C1pyrr][Cl]), on the temperature-dependent self-assembly of (EO)6–(PO)34–(EO)6, also known as L62 Pluronic, in aqueous solution. Both ionic liquids depress the temperatures of the various structural transitions that take place, but ([C4C1pyrr][Cl]) has a stronger effect. The structures that the triblock copolymer self-assembles into do not dramatically change nor do they significantly change the series of structures that the system transitions through as a function of temperature relative to the various transition temperatures.

Synthesis and Phase Behavior of a Linear Amphiphilic Multiblock Copolymer.

Linear amphiphilic multiblock copolymer PPMPEs, obtained through a stepwise method, and linear amphiphilic random copolymer PPMPEs-1, obtained through a one-pot method, were synthesized using poly(propylene glycol) diglycidyl ether (PPGDGE), poly(ethylene glycol) diglycidyl ether (PEGDGE), and monoethanolamine (MEA) as the main raw materials. The structures of PPMPEs and PPMPEs-1 were characterized by FT-IR, 1H NMR, and gel permeation chromatography, which proved that the copolymers were synthesized with different components. Transmittance of the copolymer was tested by UV–vis. By changing the ratio of PEGDGE content and the concentration of the copolymer aqueous solution, the phase behaviors of PPMPEs and PPMPEs-1 were compared and studied in depth. It mainly highlighted the advantages of the stepwise method compared to the one-pot method. The transmittance of the polymer solutions could be improved by lowering the pH value in the acidic solution or increasing the pH value in the alkaline solution. Moreover, as the reaction degree of the PPMPEs hydrophobic chain segment increased, the transmittance decreased.