PEO Block Research Articles

Effect of Pyrrolidinium Formate Ionic Liquid on Micellization of Direct and Reverse Pluronics in Aqueous Solutions.

The behavior of direct and reverse Pluronic, copolymer nonionic surfactants, poly(ethylene oxide) PEO, and poly(propylene oxide) PPO copolymers, in aqueous solution and in the pyrrolidinium formate ([pyrr][F]) ionic liquid, was investigated using Fourier transform infrared spectroscopy (FTIR spectroscopy). The study was performed for a fixed Pluronic concentration at room temperature. We showed that in aqueous solution, the spectra associated with the direct and reverse Pluronics are similar irrespective of the difference in length of the various PPO and PEO blocks, their positions and the PPO:PEO ratio. The study of those same Pluronics dissolved in a pure pyrrolidinium formate solution showed that the Pluronic types were soluble and that the micellization process can take place at room temperature. The interaction between the Pluronic 10R5 aqueous solutions and the [pyrr][F] for various ionic liquid volumes is reported.

Characterization and application of mixed micellar assemblies of PEO-PPO star block copolymers for solubilization of hydrophobic anticancer drug and in vitro release

Over the past few decades, polymeric micelles have attracted enormous attention due to their beneficial properties such as (i) core-shell structure, capable to accommodate hydrophobic drugs, boosting the overall solubility in aqueous medium; (ii) appropriate size which favors accumulation within the tumor, displaying improved permeability and retention (EPR) effect and (iii) unimers that tune the activity of efflux pumps engaged in multidrug resistance (MDR). Taking this into consideration, the present study aims the optimization and application of mixed copolymeric system of polyethylene oxide-polypropylene oxide (PEO-PPO) star block copolymers, Tetronics® 901 and 904 (hereafter written as T901 and T904), with almost same molecular weight of PPO blocks but distinct PEO block lengths, for the solubilization and in vitro release of hydrophobic anticancer drug, curcumin (CN). The copolymer T901 being incorporated with a long PPO block (10% PEO, M. Wt. 4700) is highly unstable and has poor water solubility at ambient temperature. Thus, undergoes phase separation at temperatures below 25 °C. Tetronic® T904 (40% PEO, M. Wt. 6700) with relatively longer PEO blocks forms stable core-shell micelles (hydrodynamic diameter, Dh ~ 12.0 nm and aggregation number, Nagg ~ 24) in water. The inclusion of copolymer T901 in the micellar system of T904 is mutually beneficial for both the copolymers as the insertion of T901 in T904 extends its PPO core and consequently improves its drug solubilizing capacity. On the other hand, the solubility of T901, which otherwise remains insoluble in water (at ambient temperature) is increased. Hence, the assemblies so formed are more efficient for drug delivery and improve the carrier properties of both the copolymers. The solubility and release profiles of drug was also checked in the presence of commonly used pharmaceutical excipients viz. sodium chloride (NaCl) and glucose in isotonic conditions and it was witnessed that the presence of both the excipients promoted micellization and augmented the solubilization capacity of the mixed assemblies many folds. The in-vitro release profiles suggested release of drug through diffusion from the mixed assemblies.

High-Molecular-Weight PLA-b-PEO-b-PLA Triblock Copolymer Templated Large Mesoporous Carbons for Supercapacitors and CO2 Capture

High-molecular-weight PLA440-b-PEO454-b-PLA440 (LEL) triblock copolymer was synthesized through simple ring-opening polymerization (ROP) by using the commercial homopolymer HO-PEO454-OH as the macro-initiator. The material acted as a single template to prepare the large mesoporous carbons by using resol-type phenolic resin as a carbon source. Self-assembled structures of phenolic/LEL blends mediated by hydrogen bonding interaction were determined by FTIR and SAXS analyses. Through thermal curing and carbonization procedures, large mesoporous carbons (>50 nm) with a cylindrical structure and high surface area (>600 m2/g) were obtained because the OH units of phenolics prefer to interact with PEO block rather than PLA block, as determined by FTIR spectroscopy. Furthermore, higher CO2 capture and good energy storage performance were observed for this large mesoporous carbon, confirming that the proposed approach provides an easy method for the preparation of large mesoporous materials.

Modulation of protein release from penta-block copolymer microspheres

Releasing a protein according to a zero-order profile without protein denaturation during the polymeric microparticle degradation process is very challenging. The aim of the current study was to develop protein-loaded microspheres with new PLGA based penta-block copolymers for a linear sustained protein release. Lysozyme was chosen as model protein and 40 µm microspheres were prepared using the solid-in-oil-in-water solvent extraction/evaporation process. Two types of PLGA-P188-PLGA penta-block copolymers were synthetized with two PLGA-segments molecular weight (20 kDa or 40 kDa). The resulting microspheres (50P20-MS and 50P40-MS) had the same size, an encapsulation efficiency around 50–60% but different porosities. Their protein release profiles were complementary: linear but non complete for 50P40-MS, non linear but complete for 50P20-MS. Two strategies, polymer blending and microsphere mixing, were considered to match the release to the desired profile. The (1:1) microsphere mixture was successful. It induced a bi-phasic release with a moderate initial burst (around 13%) followed by a nearly complete linear release for 8 weeks. This study highlighted the potential of this penta-block polymer where the PEO block mass ratio influence clearly the Tg and consequently the microsphere structure and the release behavior at 37 °C. The (1:1) mixture was a starting point but could be finely tuned to control the protein release.

A Global View on Block Copolymers.

In this systematic review, a total of 45,143 publications on block copolymers, issued between 1952 and 2019, are analyzed in terms of number, source, language, institution, country, keywords, and block copolymer type, to find out their evolution and predict research trends. The number of publications devoted to block copolymers has been growing for over six decades, maintaining a consistent level throughout the last few years. In their majority, documents came out of the United States, although more recently, Chinese institutions are those displaying the largest production. Keywords analysis indicated that one-third of the publications concerned synthesis, around 20% explored self-assembly and morphological aspects, and another 20% referred to block copolymer applications in solution. In particular, 2019 confirmed the expansion of studies related to drug delivery, and in minor extent, to a deeper view of self-assembling. Styrene–butadiene–styrene block copolymer was the most popular in studies covering both basic and industrially oriented aspects. Other highly investigated copolymers are PEO-b–PPO-b–PEO (Pluronic©) and amphiphilic block copolymers based on polycaprolactone or poly(lactic acid), which owed their success to their potential as delivery vehicles. Future trending topics will concern nanomedicine challenges and technology-related applications, with a special attention toward the orientation and ordering of mesophase-separated morphologies.

Spatial Distribution of PEO-PPO-PEO Block Copolymer and PEO Homopolymer in Lipid Bilayers.

Maintaining the integrity of cell membranes is indispensable for cellular viability. Poloxamer 188 (P188), a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer with a number-average molecular weight of 8700 g/mol and containing 80% by mass PEO, protects cell membranes from various external injuries and has the potential to be used as a therapeutic agent in diverse applications. The membrane protection mechanism associated with P188 is intimately connected with how this block copolymer interacts with the lipid bilayer, the main component of a cell membrane. Here, we report the distribution of P188 in a model lipid bilayer comprising 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC) using neutron reflectivity (NR) and atomic force microscopy (AFM). We also investigated the association of a PEO homopolymer (PEO8.4K; Mn = 8400 g/mol) that does not protect living cell membranes. These experiments were conducted following incubation of a 4.5 mmol/L polymer solution in a buffer that mimics physiological conditions with supported POPC bilayer membranes followed by washing with the aqueous medium. In contrast to previous reports, which dealt with P188 and PEO in salt-free solutions, both P188 and PEO8.4K penetrate into the inner portion of the lipid bilayer as revealed by NR, with approximately 30% by volume occupancy across the membrane without loss of bilayer structural integrity. These results indicate that PEO is the chemical moiety that principally drives P188 binding to bilayer membranes. No defects or phase-separated domains were observed in either P188- or PEO8.4K-incubated lipid bilayers when examined by AFM, indicating that polymer chains mingle homogeneously with lipid molecules in the bilayer. Remarkably, the breakthrough force required for penetration of the AFM tip through the bilayer membrane is unaffected by the presence of the large amount of P188 and PEO8.4K.

Enhanced Anti‐Bacterial Activity of Non‐Antibacterial Drug Candesartan Cilexetil by Delivery through Polymeric Micelles

AbstractCandesartan Cilexetil (CC) is a prodrug of candesartan and an angiotensin II receptor antagonist. It is used as a drug for different diseases like myocardial infarction, hypertension, and heart failure. The applicability of CC is impeded due to its poor water solubility, low permeability, and low bioavailability. This study is targeted to improve the efficacy and bioavailability of CC by its delivery through MeO‐PEO5K‐PCL micelles. The effect of length of hydrophobic block (PCL) on size of the micelles, drug encapsulation efficiency, and drug release behavior is evaluated. MeO‐PEO5K‐PCL based micelles were prepared by solvent evaporation method. The size of PMs was determined by dynamic light scattering, morphology by atomic force microscopy, and critical micelles concentration by fluorescence method. Encapsulation efficiency and drug release behaviors of MeO‐PEO5K‐PCL based PMs were evaluated by UV‐visible spectroscopy and dispersion method, respectively. The size of micelles increased and drug release rate decreased with increase in the length of PCL block. Maximum encapsulation efficiency of 96.42 % for CC is achieved with ABCs having equal PEO and PCL block lengths. A comparison of antibacterial activity of CC in pure form and encapsulated in PMs against MRSA is conducted. The MIC50 for CC loaded PMs has decreased to more than half in comparison to pure drug. AFM based morphological analysis also confirmed the decrease in MIC50 by delivery through PMs.

Dehydrating Heavy Crude Oils with New Amphoteric Block Bipolymers

A series of new amphoteric block bipolymers were prepared by the functionalization of PEO–PPO–PEO block bipolymers with a terminal tertiary amine and subsequently, with acrylic acid derivatives by ...

Pharmaceutical excipient salts effect on micellization and drug solubilization of PEO-PPO-ph-PPO-PEO block copolymer

Hydrophobic modification PEO-PPO copolymer BP123 was synthesized, with two aromatic rings in the centre linked to PEO-PPO blocks, and the identical PEO and PPO block numbers were possessed with commercial copolymer P123. The influence of three common pharmaceutical excipient salts sodium chloride (NaCl), sodium citrate (NaCA) and sodium benzoate (NaBZ) on self-assembly behaviors of BP123 and P123 was investigated via cloud point, surface tension, pyrene fluorescence and dynamic light scattering. Solubilization for hydrophobic drug simvastatin (SV) and in vitro drug release behavior were assessed accordingly. In the presence of NaCl or NaCA, cloud point and critical micellization concentration (CMC) decreased, micelles became more hydrophobic, micellar size and drug solubilization increased, drug release rate slowed, and the impact of NaCA was more significant than NaCl. Oppositely, cloud point and CMC increased with the addition of NaBZ. NaBZ could participate in the formation of micelles by hydrophobic aromatic ring, which greatly raised solubilization of SV. Moreover, a different performance occurred when NaBZ was added to BP123 or P123, due to the hydrophobic benzene rings in BP123, which prominently enhanced the interaction with hydrophobic drug, leading to obvious delay of drug release for BP123. This work is conducive to turning copolymer property in diverse pharmaceutical applications and in drug delivery systems as drug carriers.

Formation of well-organized, concentric-ringed spherulites of four-arm star symmetric PEO-b-PCL via confined evaporative crystallization

Toluene solvent-assisted topology confinement facilitates PCL block templated rhythmic crystallization into concentric-ringed spherulites of star symmetric P(EO2.5k-b-CL2.7k)4.

Hierarchical Branched Mesoporous TiO2-SnO2 Nanocomposites with Well-Defined n-n Heterojunctions for Highly Efficient Ethanol Sensing.

The direct assembly of functional nanoparticles into a highly crystalline mesoporous semiconductor with oriented configurations is challenging but of significance. Herein, an evaporation induced oriented co‐assembly strategy is reported to incorporate SnO2 nanocrystals (NCs) into a 3D branched mesoporous TiO2 framework by using poly(ethylene oxide)‐block‐polystyrene (PEO‐b‐PS) as the template, SnO2 NCs as the direct tin source, and titanium butoxide (TBOT) as the titania precursor. Owing to the combined properties of ultrasmall particle size (3–5 nm), excellent dispersibility and presence of abundant hydroxyl groups, SnO2 NCs can easily interact with PEO block of the template through hydrogen bonding and co‐assemble with hydrolyzed TBOT to form a novel hierarchical branched mesoporous structure (SHMT). After calcination, the obtained composites exhibit a unique 3D flower‐like structure, which consists of numerous mesoporous rutile TiO2 branches with uniform cylindrical mesopores (≈9 nm). More importantly, the SnO2 NCs are homogeneously distributed in the mesoporous TiO2 matrix, forming numerous n–n heterojunctions. Due to the unique textual structures, the SHMT‐based gas sensors show excellent gas sensing performance with fast response/recovery dynamics, high sensitivity, and selectivity toward ethanol.

Iodine‐transfer polymerization and CuAAC “click” chemistry: A versatile approach toward poly(vinylidene fluoride)‐based amphiphilic triblock terpolymers

ABSTRACTThis study presents the synthesis and properties of linear PVDF‐based amphiphilic triblock terpolymers with PS and PEO, [PVDF‐b‐PS‐b‐PEO], by adopting a procedure that involves: (a) iodine‐transfer polymerization (ITP) of VDF with 1‐iodoperfluorohexane (C6F13I) serving as chain‐transfer agent (CTA) to afford C6F13‐PVDF‐I, (b) ITP of styrene with the C6F13‐PVDF‐I macromolecular‐CTA to obtain C6F13‐PVDF‐b‐PS‐I diblock copolymer, (c) end‐group exchange from iodo‐ to azido‐group by nucleophilic substitution reaction with NaN3, and (d) copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) with alkyne‐terminated PEO to achieve C6F13‐PVDF‐b‐PS‐b‐PEO triblock terpolymers. The 1H and 19F NMR spectroscopy confirmed the presence of all blocks, while gel permeation chromatography traces showed the living nature of ITP technique. The self‐assembly of these terpolymers was investigated in films (atomic force microscopy and DSC), as well as in aqueous and organic solvents (DLS). The analysis of crystalline phases based on the FTIR spectroscopy indicated the conversion of PVDF α‐phase into α + β‐phases and β + γ‐phases upon the incorporation of PS and PEO blocks, respectively. The synthesized amphiphilic copolymers were evaluated (fluorescence spectroscopy) as carriers of small hydrophobic molecules in water. © 2019 Wiley Periodicals, Inc. J. Polym. Sci. 2020, 58, 163–171

The Impact of Selectively Plasticized Poly (ethylene oxide) (PEO) Block in Nanostructured Polystyrene−PEO−Polystyrene Triblock Copolymer Electrolytes

All polymer electrolytes, including block polymer (BP) electrolytes exhibit low ionic conductivity compared to liquid electrolytes. For homopolymer electrolytes, the ionic conductivity can be increased by incorporating plasticizer into the polymer network. However, the subsequent weakened mechanical structure of the network precludes its use in many practical applications. In this work, we selectively plasticize the PEO block in a polystyrene PS-PEO-PS triblock copolymer electrolyte using a PEO-like plasticizer: tetraethylene glycol dimethyl ether (TEGDME). Unlike its homopolymer (PEO) electrolyte counterpart, the mechanical properties of the PS-PEO-PS triblock copolymer electrolyte are not drastically degraded by this plasticizer because it is immiscible in the nonpolar PS block domains. Polymer electrolyte membranes were cast from lithium trifluoromethanesulfonate (LiTFS) solutions with the corresponding polymers. The molar ratio of ethylene oxide to Li+ is 16 for all electrolytes (nEO:nLi = 16:1). The ionic conductivity of the PS-PEO-PS electrolyte at 80 °C is about one order of magnitude lower than that of the homopolymer (PEO) counterpart at the same temperature. However, the shear modulus (G’) of the PS-PEO-PS electrolyte is about three orders of magnitude higher than the homopolymer, indicating the mechanical properties of the copolymer electrolyte is primarily dominated by the PS phase. The addition of TEGDME plasticizer to the PEO homopolymer electrolyte resulted in a ~10% increase in conductivity. The addition of same amount of TEGDME to the PS-PEO-PS electrolyte resulted in ~100% increase in conductivity. Compared to the dry electrolyte counterpart, the low isothermal frequency (ω = 0.1 rad/s) elastic modulus, G’ of the TEGDME plastized PS-PEO-PS was reduced to half at 80 °C (on the order of 106 Pa). Surprisingly, G’ of the plastized membrane surpassed its dry PS-PEO-PS counterpart at higher frequency values (17 < ω < 100 rad/s). This counter intuitive result is further explored using: 1) Fourier-transform infrared spectroscopy (FTIR) to elucidate the salt solvation and coordination to ether oxygens, and 2) small angle X-ray scattering (SAXS) to decipher the domain spacing of the adjacent copolymer blocks. Acknowledgment This work is supported by Dr. Imre Gyuk, Manager, Energy Storage Program, Office of Electricity Delivery and Reliability, Department of Energy. CC acknowldge partial financial support by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.

Microphase separation of poly(propylene monothiocarbonate)-b-poly(ethylene oxide) block copolymers induced by differential interactions with salt

This work describes the microphase separation behavior of poly(propylene monothiocarbonate)-b-poly(ethylene oxide) (PPMTC-b-PEO) block copolymers (BCPs), a type of new sulfur-containing block copolymer, induced by lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI). PPMTC-b-PEO BCPs with a fixed PEO block length but different PPMTC block lengths were synthesized and doped by LiTFSI. Temperature-variable small-angle X-ray scattering result indicates that microphase separation of the PPMTC-b-PEO BCPs can be induced by differential interactions with LiTFSI. However, the ability of LiTFSI to induce microphase separation in PPMTC-b-PEO BCPs does not monotonically increase with the doping ratio (r = [Li+]/([EO] + [PMTC])). It is observed that stronger microphase separation usually occurs at r = 1/12 and 1/6, but microphase separation is weaker at r = 1/24 and 1/3. In most cases, microphase-separated but disordered structures are obtained. Particularly, ordered lamellar structure is formed at suitable doping ratio and block composition. FTIR result confirms the differential complexation of LiTFSI with PEO and PPMTC. LiTFSI preferentially interacts with PEO at low rs, but also strongly interacts with PPMTC at high rs. This work provides a new method to prepare solid polymer electrolytes with double conductive nano-phases, which may be beneficial to both conducting and mechanical properties.

Self‐Assembly of Polyethylene Glycol Ether Surfactants in Aqueous Solutions: The Effect of Linker between Alkyl and Ethoxylate

AbstractThe aqueous self‐assembly behavior of two homologous series of poly(ethylene oxide) (PEO)‐containing nonionic surfactants based on a C10‐Guerbet hydrophobe is reported. The two families of surfactants, alkyl ethoxylates and alkyl alkoxylates, are commercially available from BASF under the trade name Lutensol® XP‐series and XL‐series, respectively. The latter incorporate propylene oxide (PO) units in the surfactant chain. Dye solubilization was used to determine the critical micellization concentration (CMC) of each surfactant at 22 and 50 °C. The PO‐containing alkyl alkoxylates displayed lower CMC values, which were also more sensitive to temperature. The Gibbs free energy, enthalpy, and entropy of micellization were computed from the CMC data and used to identify the contribution of each surfactant moiety (alkyl chain, PO unit, and PEO block) in controlling the CMC. The micellization properties are compared with compositionally similar surfactants with linear alkyl chains, yielding information about the effects of the Guerbet alkyl chain on micellization. Isothermal titration calorimetry was also used to characterize the CMC and enthalpy of micellization which generally compare well with the dye solubilization results. Cloud point data reveal nonmonotonic relationships for the Lutensol® surfactants with respect to composition, unlike linear alkyl chain surfactants. Finally, dilute solution viscosity measurements performed on some Lutensol® surfactants show a change in the slope, suggesting a structural change that tends to be more pronounced for surfactants with longer PEO blocks. The data presented herein enhance the understanding of surfactant structure–property relationships required for industrial formulation.

Solvent mediated inclusion of metal oxide into block copolymer nanopatterns: Mechanism of oxide formation under UV-Ozone treatment

Uniform, periodic and ordered iron oxide nanopatterns can be generated by selective metal ion inclusion into microphase separated polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin films. After solvent mediated metal ion inclusion into the PEO block, an ultraviolet-ozone (UVO) treatment was used to remove the polymer and oxidize the metallic ions to their oxides. This paper provides an in-depth study of the UVO processing steps as a function of exposure time. Surface wettability, topography, morphology, compositional and interfacial changes were analysed by contact angle measurement, microscopic and spectroscopic techniques through the UVO treatment. It was found that the UVO treatment initially cross-links the polymer network followed by oxidation and removal of the polymer simultaneously. It was also found that if short UVO exposure times are used, a post calcination treatment can be used to generate similar patterns. The iron oxide nanopatterns created due to strong coordination bond between metallic ions and free electron pairs of O atoms in the PEO and these interactions are responsible for the final pattern mimicking the original self-assembled BCP morphology. The film thicknesses, surface roughness, the size/shape of the iron oxides and patterns, the amount of residual polymers were also investigated regarding the UVO exposure time.

Hydrogen bonding induces unusual self-assembled structures from mixtures of two miscible disordered diblock copolymers

We synthesized two miscible disordered diblock copolymers, poly(methyl methacrylate–b–vinylphenol) (PMMA-b-PVPh) and poly(4-vinylpyridine–b–ethylene oxide) (P4VP-b-PEO), through anionic living and reversible addition fragmentation chain transfer polymerizations, respectively; together, these polymers contained one hydrogen bond donor (PVPh) and three hydrogen bond acceptors (P4VP, PEO, PMMA). The inter-association equilibrium constants (KA) for the three different hydrogen bonded pairs followed the order PVPh/P4VP (KA = 1200) > PVPh/PEO (KA = 280) > PVPh/PMMA (KA = 47.1), suggesting that the PVPh units prefer to hydrogen bond with P4VP block, rather than PEO and PMMA blocks. Nevertheless, the excluded PMMA and PEO segments experienced weak intermolecular dipole–dipole interactions, such that the PMMA-b-PVPh/P4VP-b-PEO blends exhibited two-phase behavior, forming miscible PVPh/P4VP and PMMA/PEO phases, as evidenced using transmission electron microscopy.

Morphology Tuning of ZnO/P3HT/P3HT- b-PEO Hybrid Films Deposited via Spray or Spin Coating.

Hybrid films of zinc oxide (ZnO) and poly(3-hexylthiophen-2,5-diyl) (P3HT) show promising characteristics for application in hybrid bulk-heterojunction solar cells (HBSCs). However, the incompatibility of ZnO and P3HT may lead to a reduced interface area, thus reducing the probability of exciton separation and consequently lowering solar cell efficiencies. Here, a diblock copolymer P3HT- b-poly(ethylene oxide) (PEO) is introduced to improve the interface between ZnO and P3HT. ZnO is synthesized via a block copolymer assisted sol-gel approach, and the used zinc precursor is directly incorporated into the PEO blocks. Thus, the possibility of aggregation is reduced for both the inorganic and the organic components, and a good intermixing is ascertained. Two deposition methods, namely, spray and spin coating, are compared with respect to the resulting film structure, which is investigated with scanning electron microscopy and time-of-flight grazing-incidence small-angle neutron scattering measurements. Both the surface and inner morphologies reveal that the spin coated samples possess smaller and less diverse domain sizes than the sprayed films. Due to the advantage of spray coating in large-scale production, the morphology of the sprayed samples is tailored more meticulously by changing the weight fraction of ZnO in the films. The sprayed hybrid films show smaller domains and less aggregation with decreasing the amount of ZnO. This reveals that both the deposition method and composition of the ZnO/P3HT/P3HT- b-PEO hybrid films play an important role for tailoring the film morphology and thus for improving the performance of HBSCs in future application.

Evidence of pre-micellar aggregates in aqueous solution of amphiphilic PDMS-PEO block copolymer.

The self-assembly process in a water solution of an amphiphilic polydimethylsiloxane-b-polyethyleneoxide (PDMS-PEO) diblock copolymer was investigated by means of small-angle X-ray scattering (SAXS) experiments in the concentration region below (and near) the critical micellar concentration (c.m.c. = 0.007 g cm-3). In the highly diluted region, at the copolymer concentration of c = 0.002 g cm-3, the early stage of the self-assembly process was characterized by the formation of small (primary) micellar units (with a radius of R = 2.7 nm) with core-shell morphology, which coexisted with larger supramolecular aggregates of entangled micelles (with an average radius of R = 9.5 nm). The increase in the copolymer concentration (to c = 0.005 and c = 0.01 g cm-3) caused increase in the sizes of both the small micelles and supra-micellar aggregates. Interestingly, at the concentration of c = 0.005 g cm-3, both the size and micelle aggregation number (Nagg) were found to increase on increasing the temperature in the range of 10 ≤ T ≤ 55 °C. This phenomenon was characterised by the dehydration process of the ethylene oxide (EO) segments, as evidenced by the calculation of excess water in the hydrophilic shell of the micelles. The more compact (less hydrated) structure of the hydrophilic PEO chains, which strongly influenced the spontaneous curvature of the amphiphile hydrophilic region, turned out to be the driving factor that favoured the increase in the micelle aggregation number with the increase in temperature. The obtained results evidence that the self-assembly process of PDMS-PEO copolymer amphiphiles is a gradual process that is already present at the very low concentration region (far below the macroscopically determined c.m.c.); moreover, it is characterised by a multi-stage organization process, where the primary building blocks self-assemble into more complex secondary structures that encompass multiple length scales.

ARGET ATRP of Triblock Copolymers (PMMA-b-PEO-b-PMMA) and Their Microstructure in Aqueous Solution.

Triblock copolymers poly(methyl methacrylate)-b-poly(ethylene oxide)-b-poly(methyl methacrylate) (PMMA-b-PEO-b-PMMA) with designed molecular weight of PMMA and PEO blocks were synthesized via the activator regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) of MMA. The Br-terminated Br–PEO–Br with the molecular weights of 20k and 100k were used as macroinitiators. ARGET ATRP was performed with ppm level amount CuBr2 as the catalyst and ascorbic acid as the reducing agent to overcome the sensitivity to oxygen in a traditional ATRP. The molecular weight of the PMMA block was manipulated by changing the molar ratio of monomers to the Br–PEO–Br macroinitiators. The synthesis of PMMA-b-PEO-b-PMMA and its structure was confirmed by Fourier transform infrared and 1H NMR, and the molecular weight of the PMMA block was determined by 1H NMR. Aqueous solutions of PMMA-b-PEO-b-PMMA were prepared by solvent-exchange, and their microstructures were examined by tensiometry, static light scattering, and transmission electron microscopy. The effects of molecular weight of the PMMA and PEO blocks on the microstructure were elucidated.