Phase behavior, crystallization, and hierarchical nanostructures in self-organized thermoset blends of epoxy resin and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) triblock copolymers

Nanostructured thermoset blends of bisphenol A-type epoxy resin (ER) and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers were successfully prepared. Two samples of PEO-PPO-PEO triblock copolymer with different ethylene oxide (EO) contents, denoted as EO30 with 30 wt % EO content and EO80 with 80 wt % EO content, were used to form the self-organized thermoset blends of varying compositions using 4,4'-methylenedianiline (MDA) as curing agent. The phase behavior, crystallization, and morphology were investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS). It was found that macroscopic phase separation took place in the MDA-cured ER/EO30 blends containing 60-80 wt % EO30 triblock copolymer. The MDA-cured ER/EO30 blends with EO30 content up to 50 wt % do not show macroscopic phase separation but exhibit nanostructures on the order of 10-30 nm as revealed by both the TEM and SAXS studies. The AFM study further shows that the ER/EO30 blend at some composition displays structural inhomogeneity at two different nanoscales and is hierarchically nanostructured. The spherical PPO domains with an average size of about 10 nm are uniformly dispersed in the 80/20 ER/EO30 blend; meanwhile, a structural inhomogeneity on the order of 50-200 nm is observed. The ER/EO80 blends are not macroscopically phase-separated over the entire composition range because of the much higher PEO content of the EO80 triblock copolymer. However, the ER/EO80 blends show composition-dependent nanostructures on the order of 10-100 nm. The 80/20 ER/EO80 blend displays hierarchical structures at two different nanoscales, i.e., a bicontinuous microphase structure on the order of about 100 nm and spherical domains of 10-20 nm in diameter uniformly dispersed in both the continuous microphases. The blends with 60 wt % and higher EO80 content are completely volume-filled with spherulites. Bundles of PEO lamellae with spacing of 20-30 nm interwoven with a microphase structure on the order of about 100 nm are revealed by AFM study for the 30/70 ER/EO80 blend.

Synthesis and Characterization of Coil-Rod-Coil Triblock Copolymers Comprising Fluorene-Based Mesogenic Monodisperse Conjugated Rod and Poly(ethylene oxide) Coil

A series of coil-rod-coil triblock copolymers (i.e., F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125) with a mesogenic monodisperse conjugated oligomer comprising 3 fluorene, 8 thiophene, and 2 phenyl units as the rod and poly(ethylene oxide) (PEO) as the coil were synthesized. A reference compound, that is F3T8ME2, with the identical rod but without PEO was also prepared for comparison. The volume fraction of PEO (f(PEO)) was 0, 0.16, 0.28, 0.50, and 0.73 for F3T8ME2, F3T8EO8, F3T8EO17, F3T8EO45, and F3T8EO125, respectively. It was found that the introduction of PEO into the triblock copolymers encouraged the formation of H-type aggregation and f(PEO)-dependent highly ordered mesophases while f(PEO) < 0.73. For F3T8ME2, only nematic mesophase was observed. In contrast, F3T8EO8 and F3T8EO17, with f(PEO) of 0.16 and 0.28, respectively, are smectic A (SA) mesomorphism.

Tethered diblock copolymer chains on platelets prepared by semicrystalline ABC triblock copolymers in toluene with trace amounts of water

Lamellar platelets of triblock copolymers grown in dilute toluene solution with trace amounts of water can be used as templates for tethered diblock copolymer chain preparation and analysis. Polystyrene-bpoly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two different block fractions were used as model templates to generate tethered P2VP-b-PS chains on the platelet basal surfaces. In toluene solution the aggregation states of PS-b-P2VP-b-PEO were sensitive to the water content in the solution. For toluene with trace amount of water, spherical micelles were formed in the early stage and large square platelets would gradually grow from these spherical micelles. The hydrogen bonding between water and EO units was responsible for the formation of micelles and subsequent square platelets in the solution. Tethered P2VP-b-PS chains on basal surface of PEO platelets could be regarded as diblock copolymer brushes and the density (or: 0.086-0.36) and height (d: 3.5-14.3 nm) of these tethered chains could be easily modulated by changing the crystallization condition and/ or the molecular weight of each block. The tethered P2VP-b-PS chains were responsive to different solvent vapor.

Investigation by Combined Solid-State NMR and SAXS Methods of the Morphology and Domain Size in Polystyrene-b-Polyethylene Oxide-b-Polystyrene Triblock Copolymers

The microphase structure of a series of polystyrene-b-polyethylene oxide-b-polystyrene (SEOS) triblock copolymers with different compositions and molecular weights has been studied by solid-state NMR, DSC, wide and small angle X-ray scattering (WAXS and SAXS). WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethyleneoxide (PEO) blocks at room temperature as a function of the copolymer chemical composition. Furthermore, DSC experiments allowed the determination of the melting temperatures of the crystalline part of the PEO blocks. SAXS measurements, performed above and below the melting temperature of the PEO blocks, revealed the formation of periodic structures, but the absence or the weakness of high order reflections peaks did not allow a clear assessment of the morphological structure of the copolymers. This information was inferred by combining the results obtained by SAXS and (1)H NMR spin diffusion experiments, which also provided an estimation of the size of the dispersed phases of the nanostructured copolymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48:55-64,2010

Rigidity effect on phase behavior of symmetric ABA triblock copolymers: A Monte Carlo simulation

The phase behavior of symmetric ABA triblock copolymers containing a semiflexible midblock is studied by lattice Monte Carlo simulation. As the midblock evolves from a fully flexible state to a semiflexible state in terms of increase in its persistence length, different phase behaviors are observed while cooling the system from an infinite high temperature to a temperature below T-ODT (order-disorder transition temperature). Within the midblock flexibility range we studied (l(p)/N-c <= 0.105), a lamellar structure is formed at equilibrium state as the situation for fully flexible chains. The fraction of bridge chain is evaluated for the lamellar structures. We find that the increase in midblock rigidity indeed results in the increase in bridge chain fraction within the range from 44.9% to 51.8%.

Self-assembly of rod-coil-rod ABA-type triblock copolymers

Self-assembled behavior of symmetric ABA rod-coil-rod triblock copolymer melts is studied by applying self-consistent-field lattice techniques in three-dimensional space. The phase diagram is constructed to understand the effects of the chain architecture on the self-assembled behavior. Four stable structures are observed for the ABA rod-coil-rod triblock, i.e., spherelike, lamellar, gyroidlike, and cylindrical structures. Different from AB rod-coil diblock and BAB coil-rod-coil triblock copolymers, the lamellar structure observed in ABA rod-coil-rod triblock copolymer melts is not stable for high volume fraction of the rod component (f(rod)=0.8), which is attributed to the intramolecular interactions between the two rod blocks of the polymer chain.

Simulation Study of Aggregate Morphologies Formed by ABC Linear Triblock Copolymers in a Selective Solvent Through the Self-Consistent Field Theory

The effect of the hydrophobic properties of blocks B and C on the aggregate morphologies formed by ABC linear triblock copolymers in selective solvent was studied through the self-consistent field theory. Five typical micelles, such as core-shell-corona, hamburger-like, segmented-wormlike, were obtained by changing the hydrophobic properties of blocks B and C. The simulation results indicate that the shape and size of micelle are basically controlled by the hydrophobic degree of the middle block B, whereas the type of micelle is mainly determined by the hydrophobic degree of the end block C.

Study of self-assembly of symmetric coil-rod-coil ABA-type triblock copolymers by self-consistent field lattice method

The self-assembly of symmetric coil-rod-coil ABA-type triblock copolymer melts is studied by applying self-consistent field lattice techniques in a three-dimensional space. The self-assembled ordered structures differ significantly with the variation of the volume fraction of the rod component, which include lamellar, wave lamellar, gyroid, perforated lamellar, cylindrical, and spherical-like phases. To understand the physical essence of these phases and the regimes of occurrence, we construct the phase diagram, which matches qualitatively with the existing experimental results. Compared with the coil-rod AB diblock copolymer, our results revealed that the interfacial grafting density of the separating rod and coil segments shows important influence on the self-assembly behaviors of symmetric coil-rod-coil ABA triblock copolymer melts. We found that the order-disorder transition point changes from f(rod)=0.5 for AB diblock copolymers to f(rod)=0.6 for ABA triblock copolymers. Our results also show that the spherical-like and cylindrical phases occupy most of the region in the phase diagram, and the lamellar phase is found stable only at the high volume fraction of the rod.

Synthesis and crystallization behaviors of poly(styrene-b-isoprene-b-epsilon-caprolactone) triblock copolymers

The triblock copolymers, poly(styrene-b-isoprene-b-epsilon-caprolactone)s (PS-b-PI-b-PCL) have been synthesized successfully by combination of anionic polymerization and ring-opening polymerization. Diblock copolymer capped with hydroxyl group, PS-b-PI-OH was synthesized by sequential- anionic polymerization of styrene and isoprene and following end-capping reaction of EO, and then it was used as macro initiator in the ring-opening polymerization of CL. The results of DSC and WAXD show big effect of amorphous PS-b-PI on the thermal behaviors of PCL block in the triblock copolymers and the lower degree of crystalline in the triblock copolymer with higher molecular weight of PS-b-PI was observed. The real-time observation on the polarized optical microscopy shows the spherulite growth rates of PCL27, PCL328 and PS-b-PI-b-PCL344 are 0.71, 0.46 and 0.07 mu m s(-1), respectively. The atomic force microscopy (AFM) images of the PS90-b-PI66-b-PCL-(28) show the columns morphology formed by it's self-assembling.

Self-assembly of polypeptide-containing ABC-type triblock copolymers in aqueous solution and its pH dependence

Self-assembling of novel biodegradable ABC-type triblock copolymer poly(ethylene glycol)-poly(L-lactide)-poly(L-glutamic acid) (PEG-PLLA-PLGA) is studied. In aqueous media, it self-assembles into a spherical micelle with the hydrophobic PLLA segment in the core and the two hydrophilic segments PEG and PLGA in the shell. With the lengths of PEG and PLLA blocks fixed, the diameter of the micelles depends on the length of the PLGA block and on the volume ratio of H2O/dimethylformamide (DMF) in the media. When the PLGA block is long enough, morphology of the self-assembly is pH-dependent. It assembles into the spherical micelle in aqueous media at pH 4.5 and into the connected rod at or below pH 3.2. The critical micelle concentration (cmc) of the copolymer changes accordingly with decreasing solution pH. Both aggregation states can convert to each other at the proper pH value. This reversibility is ascribed to the dissociation and neutralization of the COOH groups in the LGA residues. When the PLGA block is short compared to the PEG or PLLA block, it assembles only into the spherical micelle at various pH values.

Probing the micellization of diblock and triblock copolymers of poly(L-lactide) and poly(ethylene glycol) in aqueous and NaCl salt solutions

The micelle formation of a series of amphiphilic block copolymers in aqueous and NaCl solutions was studied by a fluorescent probe technique using pyrene as a 'model drug'. These copolymers were synthesized from poly (ethylene glycol) (PEG) and L-lactide by a new calcium ammoniate catalyst. They had fixed PEG block lengths (44, 104 or 113 ethylene oxide units) and various poly(L-lactide) (PLLA) block lengths (15-280 lactide units). The critical micelle concentration (cmc) was found to decrease with increasing PLLA content. The distinct dissimilarity of the cmc values of diblock and triblock copolymers based on the same block length of PEG provided evidence for the different configurations of their micelles. It was also observed that the introduction of NaCl salt significantly contributed to a decrease in the cmcs of the copolymers with short PEG and PLLA blocks, while it had less influence on the cmcs of copolymers with long PEG or PLLA blocks. The dependence of partition coefficients ranging from 0.2x10(5) to 1.9x10(5) on the PLLA content in the copolymer and on the micelle configuration was also discussed.

Monte Carlo simulation of the aggregation of rod-flexible triblock copolymers in a thin film

The aggregation of rod-flexible ABA and BAB triblock (A was rod block and repulsive with block B) copolymers in a thin film was studied as a function of varying the rigidity (eta) and the length of the rod block by Monte Carlo simulation. The rigidity of block A was defined as eta = R-c/R-max in this study. R-c, was the end-to-end distance below which the conformation of the block was not allowed, whereas R-max, was the longest end-to-end distance that the block could be. If eta = 0 the block was flexible, whereas if eta = 1 the block was a straight rod. The simulation results showed that the ABA triblock copolymer film were likely to form lamella structure with increasing the rigidity (eta) of block A. The lamellas were parallel each other and perpendicular to the film surface. However, the aggregation of BAB triblock copolymers tended to change from lamella to cylinder structure with increasing the rigidity (eta) of block A. Typical lamella and cylinder co-exist structure was obtained at eta = 0.504 for the BAB copolymer film. On the other hand, the simulation results indicated that the film changed from disorder to order, then to disorder structure with increasing the relative length of B block for both ABA and BAB copolymer films.