How different mesophases affect the interactive crystallisation of a block co-oligomer

An effective method for fabrication of long range ordered micro- and nanostructures on surfaces is to control the interactive crystallisation of block copolymers. In this study, the influence of different initial mesophases of a double crystalline polyethylene-block-poly (ethylene oxide) (PE-b-PEO) diblock co-oligomer on the interactive crystallisation process was studied using synchrotron radiation X-ray diffraction (SAXS/WAXD), in situ optical microscopy and differential scanning calorimetric analysis (DSC). According to the applied annealing procedure, different PE-b-PEO initial mesophases, i.e., disordered, cylindrical and spherical, have been induced. In all cases, the subsequent PEO crystallisation disrupted these initial microdomains and transformed them into crystalline lamellar morphologies with the same long periods. However, the different initial mesophases significantly affected the PEO crystallisation kinetics due to different topological confinements. An initial disordered mesophase induced the highest PEO crystallisation rate because PEO nucleation and crystal growth were limited only by chain diffusion. For an initial spherical or cylindrical mesophase, decreased PEO crystallisation rates were observed. Here, the chain diffusion was decreased by the microdomain structure. For an initial cylindrical mesophase, the earlier formed PE crystals act as a template for the subsequent PEO crystallisation and, thus, increased the PEO crystallisation as compared to the spherical mesophase where the PE was amorphous. This study demonstrates that the topological confinement of the block copolymer's initial mesophase strongly influences the crystallisation kinetics and, thus, the structures formed at the surface of drop-casted films.     

Crystallization of double crystalline block copolymer/crystalline homopolymer blends: 1. Crystalline morphology

The crystalline morphology formed in binary blends of poly(ε-caprolactone)- block-polyethylene (PCL-b-PE) copolymers and PCL homopolymers has been examined using synchrotron small-angle X-ray scattering (SR-SAXS) and differential scanning calorimetry (DSC) as a function of the homopolymer fraction in the blend. The PE block crystallized first on quenching from a lamellar microdomain structure to set a hard lamellar morphology (PE lamellar morphology) in the blend, followed by the crystallization of PCL chains (i.e., PCL homopolymers + PCL blocks). Two binary blends were studied by considering the miscible state of PCL homopolymers in the microdomain structure: when the PCL homopolymers were uniformly mixed with PCL blocks, they formed a mixed crystal. When the PCL homopolymers were localized between PCL blocks in the microdomain structure, DSC results suggested the possible formation of separate PCL crystals in the PE lamellar morphology. The effect of the advance crystallization of PE blocks on the subsequent crystallization of PCL chains was discussed as compared with the crystalline morphology formed in PCL-block-polybutadiene copolymer/PCL homopolymer blends, where the crystallization of PCL chains started directly from a microdomain structure without forming the hard lamellar morphology.     

Ionic conductivity in polyethylene-b-poly(ethylene oxide)/lithium perchlorate solid polymer electrolytes

The ionic conductivity and phase arrangement of solid polymeric electrolytes based on the block copolymer polyethylene-b-poly(ethylene oxide) (PE-b-PEO) and LiClO₄ have been investigated. One set of electrolytes was prepared from copolymers with 75% of PEO units and another set was based on a blend of copolymer with 50% PEO units and homopolymers. The differential scanning calorimetry (DSC) results, for electrolytes based on the copolymer with 75% of PEO units, were dominated by the PEO phase. The PEO block crystallinity dropped and the glass transition increased with salt addition due to the coordination of the cation by PEO oxygen. The conductivity for copolymers 75% PEO-based electrolyte with 15 wt% of salt was higher than 10⁻⁵ S/cm at room temperature and reached to 10⁻³ S/cm at 100 °C on a heating measurement. The blend of PE-b-PEO (50% PEO)/PEO/PE showed a complex thermal behavior with decoupled melting of the blocks and the homopolymers. Upon salt addition the endotherms associated with PEO domains disappeared and the PE crystals remained untouched. The conductivity results were limited at 100 °C to values close to 10⁻⁴ S/cm and at room temperature values close to 3 × 10⁻⁶ S/cm were obtained for the 15 wt% salt electrolyte. Raman study showed that the ionic association of the highly concentrated blend electrolytes at room temperature is not significant. Therefore, the lower values of conductivity in the case of the blend with 50% PEO can be assigned to the higher content of PE domains leading to a morphology with lower connectivity for ionic conduction both in the crystalline and melted state of the PE domains.     

PBT-b-PEO-b-PBT triblock copolymers: Synthesis,characterization and double-crystalline properties

We demonstrated here a facile method to synthesize novel double crystalline poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(butylene terephthalate) (PBT-b-PEO-b-PBT) triblock copolymers by solution ring-opening polymerization (ROP) of cyclic oligo(butylene terephthalate)s (COBTs) using poly(ethylene glycol) (PEG) as macroinitiator and titanium isopropyloxide as catalyst. The structure of copolymers was well characterized by ¹H NMR and GPC. TGA results revealed that the decomposition temperature of PEO in triblock copolymers increased about 30 °C to the same as PBT copolymers, after being end-capped with PBT polymers. These triblock copolymers showed double crystalline properties from PBT and PEO blocks, observed from DSC and WAXD measurements. The melting and crystallization peak temperatures corresponding to PBT blocks increased with PBT content. The crystallization of PBT blocks showed the strong confinement effects on PEO blocks due to covalent linking of PBT blocks with PEO blocks, where the melting and crystallization temperatures and crystallinity corresponding to PEO blocks decreased significantly with increment of PBT content. The confinement effect was also observed by SAXS experiments, where the long distance order between lamella crystals decreases with increasing PBT length. For the triblock copolymer with highest PBT content (PBT₅₄-b-PEO₂₂₇-b-PBT₅₄), this effect shows a 30 °C depression on PEO crystals' melting temperature and 77% on enthalpy, respectively, compared to corresponding PEO homopolymer. The crystal morphology was observed by POM, and amorphous-like spherulites were observed during PBT crystallization.     

Grafting of poly(ethylene-block-ethylene oxide) onto a vapor grown carbon fiber surface by γ-ray radiation grafting

To modify the surface of vapor grown carbon fiber (VGCF), poly(ethylene-block-ethylene oxide) (PE-b-PEO, M_n=1400, PEO content=50 wt%) was successfully grafted onto the surface by using γ-ray irradiation of the PE-b-PEO-adsorbed VGCF in solvent-free system. It is found that the percentage of polymer grafting reached 15.0% when the PE-b-PEO-adsorbed VGCF was irradiated by γ-ray over 40 kGy dose at 110 °C, but at the lower irradiation temperature of 75 °C, the grafting reaction scarcely proceeded. This indicates that polymer radicals formed by γ-ray irradiation were successfully trapped by VGCF surface above melting point of PE-b-PEO. On the other hand, when the dispersion of VGCF in THF solution of PE-b-PEO was irradiated, the percentage of PE-b-PEO grafting was less than 4.0%. It was confirmed by a field-emission scanning electron microscope (FE-SEM) that the surface of the VGCF was uniformly covered by grafted PE-b-PEO. In addition, the surface free energy of ungrafted and PE-b-PEO-grafted VGCF was determined.     

Morphology of melt-quenched poly(ε-caprolactone)-block-polyethylene copolymers

The morphology of a melt-quenched crystalline-crystalline diblock copolymer, poly(ε-caprolactone)-block-polyethylene (PCL-b-PE), was studied by small-angle X-ray scattering and transmission electron microscopy. The melting behavior of PCL-b-PE was also investigated by differential scanning calorimetry. The melting temperature of PCL blocks, T_m,PCL, was ca. 55 °C and that of PE blocks was ca. 96 °C. Therefore, the PE block always crystallized first during quenching from the microphase-separated melt into various temperatures T_c below T_m,PCL to yield an alternating structure composed of PE lamellae and amorphous layers (PE lamellar morphology), and subsequently the crystallization of PCL blocks started at T_c after some induction period. The PE lamellar morphology was preserved after the crystallization of PCL blocks at low crystallization temperatures (T_c<30 °C), that is, the PCL block crystallized within the PE lamellar morphology. At high crystallization temperatures (45 °C>T_c>30 °C), on the other hand, the crystallization of PCL blocks destroyed the PE lamellar morphology to result in a new lamellar morphology mainly consisting of PCL lamellae and amorphous layers (PCL lamellar morphology). The PE crystals were fragmentarily dispersed in the PCL lamellar morphology.     

Crystallization behavior of poly(β-propiolactone)-block-polyethylene copolymers with varying polyethylene crystallinities

The crystallization behavior of poly(β-propiolactone)-block-polyethylene (PPL-b-PE) copolymers with high PE crystallinities χ_PE (>0.30) has been examined using time-resolved synchrotron small-angle X-ray scattering and Fourier transform infrared spectroscopy, where the PE block crystallized first and subsequently the PPL block crystallized on quenching from a strongly segregated melt. The crystallization of PE blocks destroyed the lamellar microdomain structure (LMS) existing in the melt to form the crystalline lamellar morphology (CLM), and then PPL blocks crystallized within CLM. This morphology formation was compared to our previous results for the crystallization of PPL-b-PE copolymers with low χ_PE (0.12 < χ_PE < 0.26), where the crystallizability of PE blocks was not sufficiently large to destroy LMS. As a result, PE blocks crystallized promptly within LMS to reinforce and stabilize it against the subsequent crystallization of PPL blocks, yielding the confined crystallization of both blocks within LMS. We summarize these results including the case of χ_PE = 0, and propose three mechanisms of morphology formation occurring in PPL-b-PE copolymers according to χ_PE (i.e., high, low, or zero).     

Comparison of crystallization kinetics in various nanoconfined geometries

Phase morphological effect on crystallization kinetics in various nanoconfined spaces in a polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer with a PEO volume fraction of 37 vol% was investigated. The phase morphology was characterized by small-angle X-ray scattering and transmission electron microscopy techniques. When the sample was cast from chloroform solution and annealed at 150 °C, a double gyroid (DG) phase was obtained. After it was subjected to a large-amplitude reciprocating shear, the sample transformed to an oriented hexagonal cylinder (Hex) phase. To obtain a lamellar confined geometry, lamellar single crystals were grown from dilute solutions. The crystallization in the lamellar (Lam) phase was one-dimensionally (1D) confined, while it was two-dimensionally (2D) confined in the DG and Hex phases, although they had different structures. Differential scanning calorimetry (DSC) was employed to study the crystallization kinetics using the Avrami analysis for these three nanoconfined geometries. Heterogeneous nucleation was found in all three samples in the crystallization temperature (T_c) regions studied. DSC results indicated that the crystallization kinetics in the Lam phase was the fastest, and the PEO crystals possessed higher thermodynamic stability than in the DG and Hex phases. For the crystallization kinetics in two 2D-confined phases, at low T_c (<35 °C) the PEO crystallization rates in the DG and Hex phases were similar, while at high T_c (>35 °C) the PEO crystallization was slower in the DG phase than in the Hex phase. The Avrami exponent n-values for the DG and the Hex samples were similar (∼1.8), yet the values of lnK in the DG phase were smaller than those in the Hex phase. This suggested that the linear growth rate was slower in the DG phase than in the Hex phase due to continuous curved channels in the DG phase.     

Crystal orientation of poly(?-caprolactone) blocks confined in crystallized polyethylene lamellar morphology of poly(?-caprolactone)-block-polyethylene copolymers

The crystal orientation of poly(?-caprolactone) (PCL) blocks in PCL-block-polyethylene (PE) copolymers has been investigated using two-dimensional small-angle X-ray scattering (2D-SAXS) and 2D wide-angle X-ray diffraction (2D-WAXD) as a function of crystallization temperature T_c and thickness of PCL layers d_PCL. The PCL blocks were spatially confined in the solid lamellar morphology formed by the crystallization of PE blocks (PE lamellar morphology), an alternating structure of crystallized PE lamellae and amorphous PCL layers. This confinement is expected to be intermediate between hard confinement by glassy lamellar microdomains and soft confinement by rubbery ones, because the crystallized PE lamellae consist of hard PE crystals covered with amorphous (or soft) PE blocks. The 2D-SAXS results showed uniaxial orientation of the PE lamellar morphology after applying the rotational shear to the sample. Therefore, it was possible to investigate crystal orientation of PCL blocks within the oriented PE lamellar morphology. The 2D-WAXD results revealed that the c axis of PCL crystals (i.e., stem direction of PCL chains) was parallel to the lamellar surface normal irrespective of T_c when 16.5 nm ≥ d_PCL ≥ 10.7 nm. However, it changed significantly with changing T_c when d_PCL = 8.8 nm; the c axis was perpendicular to the lamellar surface normal at 45 °C ≥ T_c ≥ 25 °C while it was almost random at 20 °C ≥ T_c ≥ 0 °C. These results suggest that the PE lamellar morphology plays a similar role to glassy lamellar microdomains regarding spatial confinement against subsequent PCL crystallization.     

Morphology of an asymmetric ethyleneoxide-butadiene di-block copolymer in bulk and thin films

We present experiments on the melt and crystal morphology of a asymmetric semi-crystalline poly(ethylene/butylene-b-ethyleneoxide) diblock copolymer (PB_h-b-PEO) in bulk as well as in thin films. Simultaneous small- and wide-angle X-ray scattering combined with AFM and TEM images reveal in the melt a bulk morphology of hexagonally packed cylinders of PEO in a PB_h matrix, that transforms into a hexagonal perforated lamellar phase upon crystallization. X-ray reflectivity of thin films of PB_h-b-PEO in the melt indicates wetting layers at the top and bottom interfaces, which force the cylinders in the interior to orient parallel to the substrate. Crystallization of the PEO block leads to roughening of the air/film interface and causes lateral structuring coexisting with planar lamellar layers in thinner films.     

Composition dependence of crystallized lamellar morphology formed in crystalline-crystalline diblock copolymers

We have investigated the crystallized morphology formed at each temperature T_c (20 °C ≤ T_c ≤ 45 °C) in double crystalline poly(?-caprolactone)-block-polyethylene (PCL-b-PE) copolymers as a function of composition (or volume fraction of PE blocks ?_PE) by employing small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) techniques. When PCL-b-PE with ?_PE ≤ 0.58 was quenched from a microphase-separated melt into T_c, the crystallization of PE blocks occurred first to yield an alternating structure consisting of thin PE crystals and amorphous PE + PCL layers (PE lamellar morphology) followed by the crystallization of PCL blocks, where we can expect a competition between the stability of the PE lamellar morphology (depending on ?_PE) and PCL crystallization (on T_c). Two different morphologies were formed in the system judging from a long period. That is, the PCL block crystallized within the existing PE lamellar morphology at lower T_c (<30 °C) to yield a double crystallized alternating structure while it crystallized by deforming or partially destroying the PE lamellar morphology at higher T_c (>35 °C) to result in a significant increase of the long period. However, the temperature at which the morphology changed was almost independent of ?_PE. For PCL-b-PE with ?_PE ≥ 0.73, on the other hand, the morphology after the crystallization of PE blocks was preserved at every T_c investigated.     

Microphase separated structures in the solid and molten states of double-crystal graft copolymers of polyethylene and poly(ethylene oxide)

Transitions from one microphase separated structure in the solid state to a different one in the molten state in polyethylene-graft-poly(ethylene oxide) copolymers, PE-g-PEO, were investigated by variable temperature X-ray scattering measurements and thermal analyses. Small-angle X-ray scattering patterns from polymers with PEO grafts with 25, 50 and 100 ethylene oxide (EO) units show that the polymer passes through three distinct structures at ～10 nm length scales with increase in temperature (T): lamellar structures of PE and PEO at T < T_m^PEO, PE lamellae surrounded by molten PEO at T_m^PEO < T < T_m^PE, and microphase separated structures at T > T_m^PE when both PE and PEO are molten (T_m refers to the melting temperature). These phase transformations also occur during cooling but with hysteresis. Crystalline phases of PEO side chains and PE main chains could be identified in the wide-angle X-ray diffraction profiles indicating that the PE backbone and PEO grafts crystallize into separate domains, especially with longer grafted chains (50 and 100 units). At EO segment lengths > 50, PEO shows the expected increase in melting and crystallization temperatures with the increase in the grafted chain length. PE does not affect T_m^PEO but does decrease the onset of crystallization upon cooling. PEO grafts result in fractionation of PE, decrease the melting point of PE and increase the undercooling for the onset of crystallization of PE.     

On the structure of holographic polymer-dispersed polyethylene glycol

Holographic polymerization (H-P) has been used to fabricate polymer-dispersed liquid crystals and pattern inert nanoparticles. In this article, one-dimensional grating structures of Norland resin and polyethylene glycol (PEG) were achieved using the H-P technique. Both reflection and transmission grating structures were fabricated. The optical properties of the reflection grating structures (also known as Bragg reflectors, BRs) are thermosensitive, which is attributed to the formation and crystallization of PEG crystals. The thermal switching temperature of the BR can be tuned by using different molecular weight PEG samples. The hierarchical structure and morphology of the BR were studied using synchrotron X-ray, polarized light microscopy and transmission electron microscopy. PEG crystals were found to be confined in ∼60 nm thick layers in the BR. Upon crystallization, the PEG lamellae were parallel to the BR surfaces and PEG chains were parallel to the BR normal, resembling the confined crystallization behavior of polyethylene oxide (PEO) in PEO-block-polystyrene (PEO-b-PS) block copolymers. This observation suggests that the tethering effect in the block copolymer systems does not play a major role in PEG chain orientation in the confined nanoenvironment.     

Dynamically confined crystallization in a soft lamellar space constituted by alternating polymer co-brushes

Crystallization kinetics and behavior of PCL side chains in polymer co-brushes constituted with PCL and PEO side chains alternatively attached on poly(styrene-alt-maleimide) backbones have been determined using in-situ FT-IR and DSC methods. Avrami analysis shows the exponent n increasing from one at 10 °C to two at 30 °C, demonstrating confined crystallization of PCL side chains through homogeneous or heterogeneous nucleation. PLM morphological characterization displays typical spherulites of which size is dependent on the crystallization temperature and further AFM visualization shows typical PCL lamellae at 30 °C and broken lamellae at 10 °C embedded within PEO + backbone matrix inside of spherulites. Such lamellar structure explains the confined crystallization with Avrami exponent n ≤ 2. Formation of the broken lamellae can further clarify the reason why Avrami exponent decreases to n ≈ 1 at 10 °C, that is, homogeneous nucleation in the isolated crystals. Dynamically confined crystallization has been proposed based on their special molecular architecture. Comparing to statically confined crystallization, the construction of confined space and the crystallization process were almost synchronous. The formation of spherulites mesoscopically reveals the entire molecule motion and assembly through a pathway of conventional crystalline polymers and the crystallization of PCL side chains in a space constituted by stiff backbones of poly(styrene-alt-maleimide) plus soft PEO layer microscopically reflects a confined character which has been observed in some conventional block copolymers.     

Crystallization, melting, and morphology of a poly(ethylene oxide) diblock copolymer containing a tablet-like block of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene}

A poly(ethylene oxide) diblock copolymer containing a short block of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PEO-b-PMPCS) has been successfully synthesized via atom transfer radical polymerization (ATRP) method. The number average molecular weights (M_n) of the PEO and PMPCS blocks are 5300 and 2100 g/mol, respectively. Combining the techniques of differential scanning calorimetry (DSC), optical microscopy (OM), wide angle X-ray diffraction (WAXD), and small angle X-ray scattering (SAXS), we have found that the PMPCS blocks, which are tablet-like, can significantly affect the crystallization and melting of the diblock copolymer. The sample studied can form the crystals with a monoclinic crystal structure identical to that of the homo-PEO. The melting temperature (T_m) of the diblock copolymer increases monotonically with crystallization temperature (T_c), which is remarkably similar to the behavior of long period. On the basis of Gibbs-Thomson relationship, the equilibrium T_m of the diblock copolymer is estimated to be 65.4 °C. In a wide undercooling (ΔT) range (14 °C<ΔT<30 °C), the isothermal crystallization leads to square-shaped crystals. The PEO-b-PMPCS crystallization exhibits a regime I→II transition at ΔT of 19 °C. The PEO blocks are non-integral folded (NIF) in the crystals, and the PMPCS blocks rejected to lamellar fold surfaces prevent the NIF PEO crystals from transforming to integral folded (IF) ones. Furthermore, the PMPCS tablets may adjust their neighboring positions up or down with respect to the lamellar surface normal, forming more than one PMPCS layer to accompany the increase in the PEO fold length with increasing T_c.     

Morphologies and structures in poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide-<Emphasis Type="Italic">b</Emphasis>-ethylene oxide) copolymers determined by crystallization,microphase separation,and vitrification

Morphologies and structures determined by crystallization of the blocks, microphase separation of the copolymers, and vitrification of PLLA block in poly(l-lactide-b-ethylene oxide) (PLLA-b-PEO) copolymers were investigated using microscopic techniques and synchrotron small angle X-ray scattering. The PLLA-b-PEO copolymer films were crystallized from two different annealing processes: melt crystallization (process A) or crystallized from glass state of PLLA block after quenching from melt state (process B). The relationship between the crystalline morphology and microstructure of the copolymers were explored using SAXS. The morphology and phase structure are predominated by crystallization of PLLA block, and greatly influenced by microphase separation of the copolymers. In process B, lozenge-shape and truncated lozenge-shaped PLLA crystals of nanometer scale can be observed. The crystalline morphology is markedly affected by the microstructure formed during the annealing process. Star-shaped morphologies stacked with PLLA single crystals were observed.     

Crystallization behavior of poly(ε-caprolactone) blocks starting from polyethylene lamellar morphology in poly(ε-caprolactone)-block-polyethylene copolymers

The crystallization behavior of poly(ε-caprolactone) (PCL) blocks starting from a solid lamellar morphology formed in advance by the crystallization of polyethylene (PE) blocks (PE lamellar morphology) in a PCL-b-PE diblock copolymer was investigated by differential scanning calorimetry (DSC), small-angle X-ray scattering with synchrotron radiation (SR-SAXS), and polarized optical microscope (POM). The crystallization behavior was quantitatively compared with that of a PCL-block-polybutadiene copolymer, where the crystallization of PCL blocks started from a rubbery lamellar microdomain. DSC and SR-SAXS results revealed that the crystallization rate of PCL blocks in PCL-b-PE increased drastically with decreasing crystallization temperature T_c and the Avrami exponent depended significantly on T_c. SR-SAXS curves during the crystallization of PCL blocks at high T_c showed a bimodal scattering character, that is, the peak position moved discontinuously with crystallization time. At low T_c, on the other hand, no shift of the SAXS peak position was observed. The macroscopic change in morphology was detected only at high T_c by POM observations. These experimental results for the crystallization behavior of PCL blocks in PCL-b-PE all support our previous conclusions obtained by static measurements; the crystallization mechanism at low T_c is completely different from that at high T_c, that is, the PCL blocks crystallize within the PE lamellar morphology at low T_c while the crystallization of PCL blocks at high T_c yields a morphological transition from the PE lamellar morphology into a new solid morphology.     

Correlation between crystallization kinetics and melt phase behavior of crystalline-amorphous block copolymer/homopolymer blends

We show that the phase behavior of the strongly segregated blend consisting of a crystalline-amorphous diblock copolymer (C-b-A) and an amorphous homopolymer (h-A), which depends on the degree of wetting of A blocks by h-A, can be probed by the crystallization kinetics of the C block. A lamellae-forming poly(ethylene oxide)-block-polybutadiene (PEO-b-PB) was blended with PB homopolymers (h-PB) of different molecular weights to yield the blends exhibiting ‘wet brush’, ‘partially dry brush’, and ‘dry brush’ phase behavior in the melt state. The crystallization rate of the PEO blocks upon subsequent cooling, as manifested by the freezing (crystallization) temperature (T_f), was highly sensitive to the morphology and spatial connectivity of the microdomains governed by the degree of wetting of PB blocks. As the weight fraction of h-PB reached 0.48, for instance, T_f experienced an abrupt rise as the system entered from the wet-brush to the dry-brush regime, because the crystallization in the PEO cylindrical domains in the former required very large undercooling due to a homogeneous nucleation-controlled mechanism while the process could occur at the normal undercooling in the latter since PEO domains retained lamellar identity with extended spatial connectivity. Our results demonstrate that as long as the C block is present as the minor constituent the melt phase behavior of C-b-A/h-A blends can also be probed using a simple cooling experiment operated under differential scanning calorimetry (DSC).     

Nanostructured unsaturated polyester modified with poly[(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)] triblock copolymer

Miscibility, crystallization and morphology of unsaturated polyester (UP) matrices, nanostructured with a poly[(ethylene oxide)-b-(propylene oxide)-b-(ethylene oxide)] (PEO-b-PPO-b-PEO) block copolymer (BCP) from 0 to 50 wt% has been investigated. Additionally, the role of each block on miscibility and morphology of cured mixtures was studied. Behaviours of non-reactive mixtures of UP thermosetting precursor with two BCPs composed of similar and strong immiscible central PPO block were compared. It was found that one BCP had PEO blocks with not enough molecular weight to compatibilize the PPO block with the UP thermosetting precursor at room temperature. Transmitted light intensity study of mixtures indicated that during curing at 35 °C no macrophase separation took place, contrary to the systems cured at temperatures equal or higher than 60 °C. Curing mixtures at 35 °C produced nanostructured matrices with almost unchanged transparency. Phase separation and miscibility of BCP with UP matrix were measured by means of DSC and DMA. AFM analysis showed worm-like morphology with diameters from 10 to 20 nm and length that evolved from 50 nm to 1 μm with increase of BCP content.     

Effects of micelle structures formed in selective solvents on crystallization behaviors of poly(ethylene glycol)-b-poly(styrene) copolymers

Well-defined amphiphilic block copolymers, poly(ethylene glycol) methyl ether-b-poly(styrene) (mPEG-b-PS), in which the PS blocks had different molecular weights, were synthesized by atom transfer radical polymerization (ATRP). Through introduction of selective solvents for the blocks, crystalline and amorphous blocks were self-assembled into different micelle structures in solutions. Atomic force microscopy (AFM) was used to characterize the micelle structures. It was observed that spherical micelles were always formed, whereas lamellar aggregates appeared only in the PS-selective solvent when the molecular weight of the PS block in mPEG-b-PS was low. The crystallizable mPEG blocks were self-assembled into either the core or corona of the micelles formed. The effects of the self-assembled structures on the crystallization behavior of mPEG blocks were then investigated with differential scanning calorimeter (DSC). When the PS molecular weight was much larger than that of mPEG, the result showed that the crystallinity of the mPEG block was lower when mPEG blocks crystallized in the corona than that in the core of the micelles. In this case, when mPEG blocks crystallized in micelle coronae, the micelle core formed by insoluble PS blocks was very big, so mPEG chains had to distribute sparsely in the micelle coronae. It was hard for mPEG chains in one micelle or among different micelles to gather together to crystallize. However, when the PS molecular weight was lower than that of mPEG, the crystallinity of mPEG was higher when the mPEG chains crystallized in the micelle corona, as the core formed by insoluble PS was small and the mPEG chains in the corona were easy to aggregate and crystallize.