Dilute solutions and phase behavior of polydisperse A-b-(A-co-B) diblock copolymers

The effect of polydispersity on dilute solution properties and microphase separation of polydisperse high-molecular-weight (M_w > 10⁵ g mol⁻¹) polystyrene-block-poly(styrene-co-acrylonitrile) diblock copolymers, PS-block-P(S-co-AN), was studied in this work. For experiments, a series of diblock copolymers with variable weight fractions of acrylonitrile units (w_AN = 0.08-0.29) and length of block P(S-co-AN) was synthesized using nitroxide-mediated radical polymerization (NMP) technique, namely, by chain extension of nitroxide-terminated polystyrene (PS-TEMPO). According to light scattering and viscometry measurements in dilute tetrahydrofuran (THF) solutions the studied diblock copolymers assumed random coil conformation with the values of characteristic structure factor R_g/R_h = 1.50-1.76. It was found that polydisperse diblock copolymers being in strong segregation limit (SSL) self-assembled into microphase-separated ordered morphologies at ordinary temperature. The long periods of lamellar microdomains were larger compared to theoretical predictions for hypothetical monodisperse diblock copolymers. It was demonstrated by means of SAXS and TEM that a transition from a lamellar (LAM) to irregular face-centered-cubic (FCC) morphology occurred with increasing volume fraction of P(S-co-AN) block.     

Crystallization of double crystalline symmetric diblock copolymers

We report dynamic Monte Carlo simulation results on the crystallization of double crystalline symmetric A-B diblock copolymer, wherein the melting temperature of A-block is higher than B-block. Crystallization of A-block precedes the crystallization of B-block upon cooling from a homogeneous melt. The morphological development is controlled by the interplay between crystallization and microphase separation. With increasing segregation strength, we observe a gradual decrease in crystallinity accompanying with smaller and thinner crystals. During crystallization, A-block crystallizes first and creates confinement for the crystallization of B-block. Thus, crystallization of B-block slows down influencing the overall crystal morphology. At higher segregation strength, due to the repulsive interaction between blocks, block junction is stretched out, which is reflected in the increased value of mean square radius of gyration. As a result, a large number of smaller size crystals form with less crystallinity. The onset of microphase separation shifts towards higher temperature with increasing segregation strength. Isothermal crystallization reveals that the transition pathways strongly depend on segregation strength. The value of Avrami index shows the formation of two dimensional lamellar crystals of both the blocks. Two-step (sequential), compared to one-step (coincident) isothermal crystallization, produces higher crystallinity in A-block, however, the crystallinity of B-block is almost identical in both the cases.     

Microphase separation and crystallization in mixtures of polystyrene-poly(methyl methacrylate) diblock copolymer and poly(vinylidene fluoride)

This study examined the microdomain structures and the crystallization behavior in binary blends consisting of an asymmetric block copolymer and a homopolymer using small-angle X-ray scattering, optical microscopy and differential scanning calorimetry. A polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) was mixed with a low molecular weight poly(vinylidene fluoride) (PVDF), where the PS-b-PMMA had a 0.30 wt fraction of the PMMA block. At a PVDF concentration of <13.0 wt%, the PVDF was completely miscible with the PMMA microdomains, and the blends had a cylindrical structure. The addition of PVDF altered the morphology from a PMMA-cylindrical structure to a lamellar structure and finally to a PS-cylindrical structure. When the PVDF concentration was <23.0 wt%, the PVDF was distributed uniformly within the PMMA microdomains. After adding more PVDF, some of the PVDF was locally dissolved in the middle of the PMMA microdomains. The addition of PVDF also affected the ordered microstructure in the blends, leading to a well-defined microdomain structure. However, PVDF crystallization significantly disturbed the pre-existing microdomain structure, resulting in a poorly ordered morphology. In the blends, PVDF had unique crystallization behavior as a result of the space constraints imposed by the microdomains.     

Synthesis and characterization of diblock copolymers based on crystallizable poly(ε-caprolactone) and mesogen-jacketed liquid crystalline polymer block

Diblock copolymers comprising crystallizable poly(ε-caprolactone) and poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) were synthesized by ring-opening polymerization of ε-caprolactone and subsequent atom transfer radical polymerization (ATRP) of MPCS. The molecular structure of the copolymers was confirmed by ¹H NMR spectroscopy and GPC. Kinetic study of ATRP showed that the polymerization proceeded in a controlled way up to high conversions. Three series of diblock copolymers were obtained with relatively narrow polydispersity indices (PDI≤1.11) and PCL blocks of 8000, 12,900, and 22,800 molecular weights, respectively. The existence of microphase separation was identified by differential scanning calorimetry (DSC) and directly observed through transmission electron microscopy (TEM). The melting behavior of PCL block was significantly affected by the length of PCL block and composition of PMPCS. The thermotropic liquid crystalline behavior was examined by polarized optical microscopy (POM) and DSC. The result showed that the diblock copolymer exhibited liquid crystalline behavior when the degree of polymerization (DP) of PMPCS block was not less than 44.     

Functionalized organic nanoparticles from core-crosslinked poly(4-vinylbenzocyclobutene-b-butadiene) diblock copolymer micelles

Surface-functionalized polymeric nanoparticles were prepared by: a) self-assembly of poly(4-vinylbenzocyclobutene-b-butadiene) diblock copolymer (PVBCB-b-PB) to form spherical micelles (diameter: 15-48 nm) in decane, a selective solvent for PB, b) crosslinking of the PVBCB core through thermal dimerization at 200-240 °C, and c) cleavage of the PB corona via ozonolysis and addition of dimethyl sulfide to afford aldehyde-functionalized nanoparticles (diameter: ∼16-20 nm), along with agglomerated nanoparticles ranging from ∼30 to ∼100 nm in diameter. The characterization of the diblock copolymer precursors, the intermediate micelles and the final surface-functionalized crosslinked nanoparticles was carried out by a combination of size exclusion chromatography, static and dynamic light scattering, viscometry, thermogravimetric analysis, ¹H NMR and FTIR spectroscopy and transmission electron microscopy.     

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.     

Photocontrolled microphase separation in a nematic liquid-crystalline diblock copolymer

Using a bromo-terminated poly(ethylene oxide) as a macroinitiator, an amphiphilic liquid-crystalline (LC) diblock copolymer with an azobenzene moiety as a nematic mesogen was prepared by an atom transfer radical polymerization process. In thin films of the well-defined diblock copolymer with the mesogenic block as a continuous phase upon microphase separation, the influence of supramolecular cooperative motion on the microphase-separated nanocylinders was systematically studied. Although the major phase of the hydrophobic nematic LC block showed only one-dimensional order, it could endow the separated minor phase of the hydrophilic PEO nanocylinders with three-dimensionally ordered structures. Both out-of-plane perpendicular and in-plane parallel patternings of the regularly ordered nanocylinder arrays were successfully fabricated on macroscopic scales by thermal annealing and photoalignment, respectively. The microphase-separated nanostructures with high regularity showed excellent reproducibility and mass production, which might guarantee nanotemplated fabrication processes and would lead to novel industrial applications in macromolecular engineering.     

(Polystyrene-g-polyisoprene)-b-polystyrene comb-coil block copolymer in selective solvent

Comb-coil block copolymers consisting of two components polystyrene (PS) and polyisoprene (PI) were synthesized through combining TEMPO living free radical polymerization (LFRP) and anionic polymerization using “grafting-onto” strategy. Two typical samples with the same backbone but grafted with different numbers and lengths of branches, forming lamellar and cylinder phases, respectively, were investigated. As the selective solvent was added into these block polymers, the micro-structures transformed from disordered or weakly ordered structure into well-organized lamellar structure in the intermediate polymer concentration. The power law behavior of the lamellae space with respect to polymer concentration indicates that the two samples form the well-organized structure through different paths. The sample with longer branch length thus less branch points forms lamellae phase with smaller lamellae space. This difference at lamellae spacing is attributed to the two different ways that the chain assembles.     

The vesicle formation in a binary amphiphilic diblock copolymer/homopolymer solution

The formation of vesicles in a binary blend of an amphiphilic diblock copolymer AB/homopolymer C was studied in a dilute solution using the real space two-dimensional self-consistent field theory (SCFT). Special attention was played to the role played by the homopolymer C in controlling the vesicle formation. In the simulations, it was found that as the averaged volume fraction of homopolymer C was decreased while keeping the total averaged volume fraction of block copolymer AB and homopolymer C unchanged, there was a morphological transition from the bilayer vesicles to rod-like/circle-like micelles. The compound vesicle structure was observed in the simulations. When the averaged volume fraction of block copolymer AB was further increased while the total averaged volume fraction of AB and C remained unchanged, the compound vesicle structure became less favored entropically than the unilamellar vesicle structure. The effect of the degree of polymerization of the homopolymer C on the vesicle formation of the amphiphilic system was examined. By reducing the degree of polymerization of the homopolymer C to unity, the component C became a small solvent molecule immiscible with the bulk solvent. It was found that the small solvent C exerted no influence on the morphological stability of the vesicles.     

Effect of interfacial tension on micellization of a polystyrene-poly(ethylene oxide) diblock copolymer in a mixed solvent system

The micellization of a polystyrene-poly(ethylene oxide) (PS-PEO) diblock copolymer in a mixed solvent of water and tetrahydrofuran (THF) was studied in terms of an aggregation number as measured by laser light scattering. The results show the aggregation number (f) of the micelle decreases monotonically as the amount of THF is increased. These experimental results are compared with a theoretical model that includes the variations in the interfacial tension. Experimentally, the interfacial tension is adjusted with the addition of relatively low levels of THF. The theory indicates that the aggregation number decreases as the interfacial tension is decreased. The theoretical prediction is in very good agreement with the experimental results. The main conclusion of this study is that the interfacial tension is the key factor in determining the aggregation number of the diblock copolymer micelle in a water-THF solvent system.     

Fluorescence studies of pyrene-labelled, pH-responsive diblock copolymer micelles in aqueous solution

Fluorescence spectroscopic techniques, and time-resolved anisotropy measurements (TRAMS) in particular, have provided valuable information regarding micelle formation in luminescently labelled pH-responsive diblock copolymers of 2-(diethylamino)ethyl methacrylate (DEA) and 2-(dimethylamino)ethyl methacrylate (DMA). A pyrenyl derivative, located at the DEA block, allowed motion of this site to be monitored via TRAMS in aqueous solution: a significant reduction in the mobility of this label was apparent at concentrations in excess of the critical micelle concentration, CMC, of the diblock copolymer. This is consistent with the labelled DEA block being located in the core of the micelles. At concentrations below the CMC, unimers were detected in solution. The micelle size estimated from TRAMS is approximately half of that determined from dynamic light scattering measurements. This suggests that the chain ends of the block copolymer are not “frozen” into position but that limited motion may occur due to fluidity within the micelle core. This is reasonable given the low T_g of the DEA block. Alternatively, a model is proposed which suggests that the interior of the micelle is a hard sphere, surrounded by flexible, fast-moving corona, which imparts little viscous drag on the core.     

The nature of phase transitions of symmetric diblock copolymer melts under confinement

The effects of confinement, both the structure frustration and the surface field, on phase transitions of symmetric diblock copolymer melts are investigated within several theoretical methods on the mean-field level. Confinements are applied by restricting polymer chains in the finite spaces of slabs. The surface can be neutral or preferential depending on the strength of the surface field. Within the one-dimensional self-consistent mean-field theory, for the neutral surface case, an oscillative behavior is observed for the size dependence of the order-disorder transition (ODT) point (χN)_t due to the structure frustration. The spinodal (χN)_s for this corresponding confined system is also calculated using the Gaussian fluctuation theory and the Landau-Brazovskii theory, and (χN)_s coincides exactly with (χN)_t. On the other hand, the surface effect plays the role to decrease (χN)_t due to the surface-induced spatial oscillation for the preferential surface case. In all confined systems considered, the ODT for symmetric diblock copolymer melts is a continuous second-order phase transition in the present mean-field calculation.     

A study of the versatile micropatterns of diblock copolymer micelles: the effect of copolymer concentration, substrate, film thickness and micelles morphology

We report the novel use of polystyrene-block-poly(acrylic acid) (PS-b-PAA) diblock copolymer micelles as the nano-building blocks in fabricating orderly aligned three-dimensional micropatterns with high regularity through a one-step evaporation-induced cracking process. Crack patterns of square, rectangular, stripe-like and mesh-like structures in micron scale were obtained. The effect of the concentration of diblock copolymer, the properties of the substrates, the thickness of the drying layer, and the morphology of the micelles on the regularity of the crack patterns was studied. By regulating the above factors, we achieved micropatterns of various structures. We further developed a cheap, fast, and simple method for fabricating micromolded structures using the crack patterns as templates.     

One-pot synthesis of poly(methacrylic acid)-b-poly(2,2,2-trifluoroethyl methacrylate) diblock copolymers via RAFT polymerization

In this work, the reversible addition-fragmentation chain transfer (RAFT) polymerization was utilized to synthesize the amphiphilic diblock copolymers of poly(methacrylic acid)-b-poly(2,2,2-trifluoroethyl methacrylate) (PMAA-b-PTFEMA) via one-pot two-step reaction protocol. The controlled radical polymerization of MAA monomer was first carried out in pure water by using 4-cyanopentanoic acid dithiobenzoate (CADB) as chain transfer agent. Subsequently, the as-synthesized PMAA homopolymers with dithiobenzoate end-groups were employed as macro-CTA and chain-extended in situ with the hydrophobic TFEMA monomer. The reactions were carried out in 1,4-dioxane/water medium. Both the polymerization of PMAA and PTFEMA blocks showed the well controllability on the molecular weighs and distributions. It was found that the amphiphilic diblock copolymers formed the stable spherical particles via the polymerization-induced self-assembly. Meanwhile, the effect of various parameters, such as the concentration ratio of TFEMA monomer over PMAA macro-CTA, the solvent condition (different ratio of 1,4-dixane/water), and the pH, on the RAFT polymerization of TFEMA monomer were investigated in detail. Their kinetic results suggested that the propagation of TFEMA monomer on the macro-CTA was performed at the particle/water interfaces. The concentration of chain transfer agents at the interfaces determined the polymerization rate. Finally, the stability of the fluorinated polymer dispersions was also evaluated in this work.     

Excluded volume effect on the self-assembly of amphiphilic AB diblock copolymer in dilute solution

The self-assembly of amphiphilic AB diblock copolymer in solution with different molecular size was investigated by using the self-consistent field theory (SCFT). By continuously varying the solvent size and the polymer concentration, the phase diagram is constructed. The aggregate concentration of the amphiphilic AB diblock copolymer decreases in solution with larger solvent size. The phase will transit in solution with different solvent size due to the excluded volume interaction effect. This widely existing excluded volume effect is very useful for the separation of polymers and helpful for understanding the crowding effect in bio-molecules.     

羟乙基纤维素-聚N-异丙基丙烯酰胺嵌段共聚物的制备与表征

通过羟乙基纤维素与氨基封端的聚N-异丙基丙烯酰胺进行还原性氨化反应合成了温敏性羟乙基纤维素-聚N-异丙基丙烯酰胺嵌段共聚物。利用凝胶渗透色谱、傅立叶红外光谱和固态核磁共振谱对共聚物的结构进行了表征。利用紫外分光光度计研究了共聚物水溶液的透光率随温度的变化。研究表明共聚物的低临界溶解温度为33℃,当高于33℃后,共聚物聚集形成平均长度为100 nm的类似棒状的胶束。     

Synthesis and characterization of phenylene-thiophene all-conjugated diblock copolymers

Grignard metathesis (GRIM) polymerization for all-conjugated diblock copolymers comprising poly(2,5-dihexyloxy-1,4-phenylene) (PPP) and poly(3-hexylthiophene) (P3HT) blocks were systematically studied with LiCl as additive and 1,2-bis (diphenylphosphino) ethane nickel dichloride (Ni(dppe)Cl₂) or 1,3-bis(diphenylphosphino) propane nickel dichloride (Ni(dppp)Cl₂) as catalyst. It was found that the addition order of the monomers was crucial for the success of copolymerization. With the monomer addition in the order of phenyl and then thienyl Grignard reagents, all-conjugated PPP-b-P3HT diblock copolymers with different block ratios were successfully synthesized. In contrast, the inverted addition order only afforded a mixture containing both block copolymers and deactivated or end-capped homopolymers. Mass spectroscopic analysis indicates that the effect of the addition order of the monomers on copolymerization is attributed to the low efficiency of intramolecular Ni transfer from thiophene to phenylene units. The resulting PPP-b-P3HT diblock copolymers were characterized by differential scanning calorimetry (DSC) and atomic force microscopy (AFM). It was found that both PPP and P3HT blocks in the copolymers were crystalline, and microphase separation between them took place, as indicated by two endothermal transitions corresponding to the melting of PPP and P3HT blocks, respectively. These unique properties may render PPP-b-P3HT diblock copolymers potential applications in optoelectronics.     

Reaction-induced microphase separation in polybenzoxazine thermosets containing poly(N-vinyl pyrrolidone)-block-polystyrene diblock copolymer

Poly(N-vinyl pyrrolidone)-block-polystyrene diblock copolymer (PVPy-b-PS) was synthesized via sequential reversible radical-fragmentation transfer polymerization with S-1-phenylethyl O-ethylxanthate as a chain transfer agent. The block copolymer was incorporated into polybenzoxazine to access the nanostructures in the thermosets. The nanostructures in the thermosets were investigated by means of transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). It was found that disordered and/or ordered PS nanophases were formed in the PBa thermosets. It is judged that the formation of nanophases followed the mechanism of reaction-induced microphase separation in terms of the miscibility of the subchains of the diblock copolymer (viz. PVPy and PS) with polybenzoxazine after and before curing reaction.     

Synthesis of amphiphilic triblock copolymer of polystyrene and poly(4-vinylbenzyl glucoside) via TEMPO-mediated living radical polymerization

4-Vinylbenzyl glucoside peracetate 1 was polymerized with α,α′-bis(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)-1,4-diethylbenzene 2 in chlorobenzene using (1S)-(+)-10-camphorsulfonic acid anhydrous (CSA) as an accelerator ([1]=0.4 M,[1]/[2]/[CSA]=75/1/1.3) at 125 °C for 5 h. The polymerization afforded poly(4-vinylbenzyl glucoside peracetate) having TEMPO moieties on both sides of the chain ends, 3, with a molecular weight (M_w,SLS) of 8500, a polydispersity index (M_w/M_n) of 1.09, and an average degree of polymerization of the 1 unit (x) of 17. Styrene (St) was polymerized with 3 in chlorobenzene at 125 °C (St/chlorobenzene=1/2, w/w). The polymerization successfully afforded polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 4, when the polymerization time was below about 2 h. Polymer 4 with the M_w,SLS of 12,500, 17,900, and 29,400, the compositions (y-x-y) of 20-17-20, 45-17-45, and 100-17-100, and the M_w/M_n of 1.12, 1.14 and 1.17 were modified by deacetylation using sodium methoxide in dry-THF into polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 5. The solubility of polymer 5 was examined using a good solvent for polystyrene such as toluene and for the saccharide such as H₂O.     

Structure and swelling behaviour of epoxy networks based on α,ω-diamino terminated poly(oxypropylene)-block-poly(oxyethylene)-block-poly(oxypropylene)

Structure and swelling behaviour of hydrophilic epoxy networks prepared from α,ω-diamino terminated poly(oxypropylene)-block-poly(oxyethylene)-block-poly(oxypropylene) and diglycidyl ether of brominated Bisphenol A in dependence on the initial molar ratio of reactive amino and epoxy groups has been investigated by small- and wide-angle X-ray scattering (SAXS and WAXS), differential scanning calorimetry (DSC) and dynamic mechanic analysis (DMA). Anomalous swelling behaviour of the networks in water has been found. The anomaly is attributed to the changing microphase separation in the networks controlled by their composition and crosslinking density, and inhomogeneous swelling on nanometer space scale.