Liquid Crystalline Block Copolymers Research Articles

Fabrication of Hierarchical Nanostructures Featuring Amplified Asymmetry Through Co‐Assembly of Liquid Crystalline Block Copolymer and Chiral Amphiphiles

AbstractThe widespread presence of hierarchical asymmetric structures in nature has sparked considerable interest because of their unique functionalities. These ingenious structures across multiple scales often emerge from the transfer and amplification of asymmetry from chiral molecules under various synergistic effects. However, constructing artificial chiral asymmetric structures, particularly in developing hierarchical multicomponent structures analogous to those formed in nature through synergistic non‐covalent interactions, still presents tremendous challenges. Herein, we propose a co‐assembly strategy to fabricate hierarchical chiral mesostructures by combining a liquid crystalline block copolymer (LC‐BCP) with a small molecular amphiphile containing chiral alanine or phenylalanine as a linker. Through a classic solvent‐exchange process, chiral amphiphiles embedded within LC‐BCP finely regulate the LC ordering effect and facilitate transfer and amplification of asymmetry. Consequently, various co‐assembled structures with significant hierarchical chirality features are obtained through synergetic effects. Remarkably, subtle alterations to the side groups of amino acids in the amphiphiles effectively adjust the hierarchical morphology transition. Moreover, the covalent bonding sequence of amino acids in the amphiphiles emerges as a critical factor governing the formation of hierarchical nanofibers and multilayered vesicles exhibiting a superhelical sense.

Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture.

Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units. The molecular architecture of the host polymers and the morphological pattern formed by the complexes can affect orientational behavior of Azo groups under irradiation with linearly polarized light. Photoorientation of hydrogen-bonded Azo groups is accompanied by the cooperative orientation of non-photochromic PhM units, which form individual microphases and stabilize the orientation of Azo groups. This effect is specific for block copolymer complexes and it is absent for random copolymer complex, which is used as a reference sample. Optical anisotropy induced in films of the block copolymer complexes can be amplified by heating above the glass transition temperature and subsequent rinsing with diethyl ether allows colorless birefringent polymer films to be prepared.

Fabrication of Hierarchical Nanostructures Featuring Amplified Asymmetry Through Co-Assembly of Liquid Crystalline Block Copolymer and Chiral Amphiphiles.

The widespread presence of hierarchical asymmetric structures in nature has sparked considerable interest because of their unique functionalities. These ingenious structures across multiple scales often emerge from the transfer and amplification of asymmetry from chiral molecules under various synergistic effects. However, constructing artificial chiral asymmetric structures, particularly in developing hierarchical multicomponent structures analogous to those formed in nature through synergistic non-covalent interactions, still presents tremendous challenges. Herein, we propose a co-assembly strategy to fabricate hierarchical chiral mesostructures by combining a liquid crystalline block copolymer (LC-BCP) with a small molecular amphiphile containing chiral alanine or phenylalanine as a linker. Through a classic solvent-exchange process, chiral amphiphiles embedded within LC-BCP finely regulate the LC ordering effect and facilitate transfer and amplification of asymmetry. Consequently, various co-assembled structures with significant hierarchical chirality features are obtained through synergetic effects. Remarkably, subtle alterations to the side groups of amino acids in the amphiphiles effectively adjust the hierarchical morphology transition. Moreover, the covalent bonding sequence of amino acids in the amphiphiles emerges as a critical factor governing the formation of hierarchical nanofibers and multilayered vesicles exhibiting a superhelical sense.

Self-assembly and energy storage potentials of biphasic phase change azobenzene liquid crystalline block copolymers

Flexible polymeric materials with potentials in energy storage have attracted extensive attention in today's sustainable society. Here, we reported a series of crystalline-liquid crystalline biphasic phase change block copolymers, poly(ethylene oxide)-b-poly(11-(4-(4-cyanophenylazo)phenoxy)undecane methacrylate) (PEO-b-PMAAzo), and studied the UV and Li+ ions coordination-mediated self-assembly for the potentials in phase change energy storage and solid electrolytes. The PEO-b-PMAAzo BCPs possess both the solid-liquid phase transition of PEO and the photo-chemical-thermal energy transition of PMAAzo block. Meanwhile, PEO has the capability to coordinate with the Li+ for the ionic conductivity. We explored the binary phase change behaviors and thermal energy density of the BCPs with different lithium ion concentrations before and after UV irradiation. The addition of LiTFSI salts increases the interaction parameters (χ) of the BCPs leading to phase transition of the self-assembled nanostructures. The phase diagram covering LAM, HEX, GYR, Fddd and HPL nanostructures facilitating ion transport was demonstrated. The PMAAzo block enabled the solid feature of the BCPs and ensured the high energy density and high conductivity. This work demonstrates that the combination of the functional polymers in one BCP not only provides multiple morphology tunabilities but also enables multiple functionalities from energy conversation and storage to ionic conductive electrolytes.

Convoluted micellar morphological transitions driven by tailorable mesogenic ordering effect from discotic mesogen-containing block copolymer

Solution-state self-assemblies of block copolymers to form nanostructures are tremendously attractive for their tailorable morphologies and functionalities. While incorporating moieties with strong ordering effects may introduce highly orientational control over the molecular packing and dictate assembly behaviors, subtle and delicate driving forces can yield slower kinetics to reveal manifold metastable morphologies. Herein, we report the unusually convoluted self-assembly behaviors of a liquid crystalline block copolymer bearing triphenylene discotic mesogens. They undergo unusual multiple morphological transitions spontaneously, driven by their intrinsic subtle liquid crystalline ordering effect. Meanwhile, liquid crystalline orderedness can also be built very quickly by doping the mesogens with small-molecule dopants, and the morphological transitions are dramatically accelerated and various exotic micelles are produced. Surprisingly, with high doping levels, the self-assembly mechanism of this block copolymer is completely changed from intramolecular chain shuffling and rearrangement to nucleation-growth mode, based on which self-seeding experiments can be conducted to produce highly uniform fibrils.

Mesogenic Ordering-Driven Self-Assembly of Liquid Crystalline Block Copolymers in Solution.

With the development of nanotechnology, the preparation of polymeric nanoparticles with nicely defined structures has been well-developed, and the functionalization and subsequent applications of the resultant nanostructures are becoming increasingly important. Particularly, by introducing mesogenic ordering as the driving force for the solution-state self-assembly of liquid crystalline (LC) block copolymers (BCPs), micellar nanostructures with different morphologies, especially anisotropic morphologies, can be easily prepared. This review summarizes the recent progress in the solution-state self-assembly of LC BCPs and is mostly focused on four main related aspects, including an in-depth understanding of the mesogenic ordering-driven self-assembly, precise assembly methods, utilization of these methods to fabricate hierarchical structures, and the potential applications of these well-defined nanostructures. We hope not only to make a systematic summary of previous studies but also to provide some useful thinking for the future development of this field.

Synthesis and Characterization of Side-Chain Liquid-Crystalline Block Copolymers Containing Cyano-Terminated Phenyl Benzoate Moieties

Block copolymers, known for their capacity to undergo microphase separation, spontaneously yield various periodic nanostructures. These precisely controlled nanostructures have attracted considerable interest due to their potential applications in microfabrication templates, conducting films, filter membranes, and other areas. However, it is crucial to acknowledge that microphase-separated structures typically exhibit random alignment, making alignment control a pivotal factor in functional material development. To address this challenge, researchers have explored the use of block copolymers containing liquid-crystalline (LC) polymers, which offer a promising technique for alignment control. The molecular structure and LC behavior of these polymers significantly impact the morphology and alignment of microphase-separated structures. In this study, we synthesized LC diblock copolymers with cyano-terminated phenyl benzoate moieties and evaluated the microphase-separated structures and molecular alignment behaviors. The LC diblock copolymers with a narrow molecular weight distribution were synthesized by atom transfer radical polymerization. Small angle X-ray scattering measurements revealed that the block copolymers exhibit smectic LC phases and form cylinder structures with a lattice period of about 18 nm by microphase separation. The examination of block copolymer films using polarized optical microscopy and polarized UV-visible absorption spectroscopy corroborated that the LC moieties were uniaxially aligned along the alignment treatment direction.

Controllable One-Step Assembly of Uniform Liquid Crystalline Block Copolymer Cylindrical Micelles by a Tailored Nucleation-Growth Process and Their Application as Tougheners.

The fabrication of uniform cylindrical nanoobjects from soft materials has attracted tremendous research attention from both fundamental research and practical application points of view but has also posed outstanding challenges in terms of their preparation. Herein, we report a one-step method to assemble cylindrical micelles (CMs) with highly controllable lengths from a single liquid crystalline block copolymer by an in situ nucleation-growth strategy. By adjusting the assembly conditions, the lengths of the CMs are controlled from hundreds of nanometers to micrometers. Several influencing factors are systematically investigated to comprehensively understand the process. Particularly, the solvent quality is found determinative in either enhancing or suppressing the nucleation process to produce shorter and longer CMs, respectively. Taking advantage of this strategy, the lengths of CMs can be nicely controlled over a wide concentration range of four orders of magnitude. Lastly, CMs are produced on decent scales and applied as additives to dramatically toughen glassy plastic matrix, revealing an unprecedented length-dependent toughening effect.

Controllable One‐Step Assembly of Uniform Liquid Crystalline Block Copolymer Cylindrical Micelles by a Tailored Nucleation‐Growth Process and Their Application as Tougheners

AbstractThe fabrication of uniform cylindrical nanoobjects from soft materials has attracted tremendous research attention from both fundamental research and practical application points of view but has also posed outstanding challenges in terms of their preparation. Herein, we report a one‐step method to assemble cylindrical micelles (CMs) with highly controllable lengths from a single liquid crystalline block copolymer by an in situ nucleation‐growth strategy. By adjusting the assembly conditions, the lengths of the CMs are controlled from hundreds of nanometers to micrometers. Several influencing factors are systematically investigated to comprehensively understand the process. Particularly, the solvent quality is found determinative in either enhancing or suppressing the nucleation process to produce shorter and longer CMs, respectively. Taking advantage of this strategy, the lengths of CMs can be nicely controlled over a wide concentration range of four orders of magnitude. Lastly, CMs are produced on decent scales and applied as additives to dramatically toughen glassy plastic matrix, revealing an unprecedented length‐dependent toughening effect.

Synergetic Self-Assembly of Liquid Crystalline Block Copolymer with Amphiphiles for Fabrication of Hierarchical Assemblies.

Novel functions and advanced structure, where each single component could not be produced individually, can exhibit from the collective and synergistic behavior of component systems. This synergetic strategy has been successfully demonstrated for co-assembly of polymer-polymer to construct hierarchical nanomaterials. However, differences in the natures of polymer and small molecules impose challenges in the construction of sophisticated co-assemblies with geometrical and compositional control. Herein, a synergetic self-assembly strategy is proposed to prepare organic-organic hybrid colloidal mesostructures by blending a liquid crystalline block copolymer (LC-BCP) with small molecular amphiphiles. Through a classic solvent-exchange process, amphiphiles embedded with LC-BCP realize multi-component nucleation and hierarchical assembly driven by anisotropic interaction from the LC ordering alignment of the core-forming block. 1D nanofibers with a periodic striped structure are formed by further LC component fusion and refinement. In addition, LC ordering effect of LC-BCP can be regulated by selecting appropriate solvents and leads to the formation of vesicular co-micelles. By means of the thermal-responsive behavior of amphiphiles, hexagonal pore arrays are finally generated on the surface of those vesicles.

In situ Nucleation-Growth Strategy for Controllable Heterogeneous Supramolecular Polymerization of Liquid Crystalline Block Copolymers and Their Hierarchical Assembly.

The self-assembly morphologies of subunits are largely governed by thermodynamics, which plays a less important role in dimensional control. Particularly for one-dimensional assemblies from block copolymers (BCPs), the negligible energy difference between short and long ones imposes great challenges in length control. Herein, we report that by incorporating additional polymers to induce in situ nucleation and trigger the subsequent growth, controllable supramolecular polymerization driven by mesogenic ordering effect could be realized from liquid crystalline BCPs. The length of the resultant fibrillar supramolecular polymers (SP) is controlled by tuning the ratio between nucleating and growing components. Depending on the choice of BCPs, the SPs can be homopolymer-like, heterogeneous triblock, and even pentablock copolymer-like. More interestingly, with insoluble BCP as a nucleating component, amphiphilic SPs are fabricated, which can undergo spontaneous hierarchical assembly.

In situ Nucleation‐Growth Strategy for Controllable Heterogeneous Supramolecular Polymerization of Liquid Crystalline Block Copolymers and Their Hierarchical Assembly

AbstractThe self‐assembly morphologies of subunits are largely governed by thermodynamics, which plays a less important role in dimensional control. Particularly for one‐dimensional assemblies from block copolymers (BCPs), the negligible energy difference between short and long ones imposes great challenges in length control. Herein, we report that by incorporating additional polymers to induce in situ nucleation and trigger the subsequent growth, controllable supramolecular polymerization driven by mesogenic ordering effect could be realized from liquid crystalline BCPs. The length of the resultant fibrillar supramolecular polymers (SP) is controlled by tuning the ratio between nucleating and growing components. Depending on the choice of BCPs, the SPs can be homopolymer‐like, heterogeneous triblock, and even pentablock copolymer‐like. More interestingly, with insoluble BCP as a nucleating component, amphiphilic SPs are fabricated, which can undergo spontaneous hierarchical assembly.

Self‐assembly of side‐chain liquid crystalline block copolymers to anisotropic polymeric nanoparticles

AbstractAnisotropic polymeric nanoparticles (NPs) have attracted considerable attention due to their morphology‐dependent applications in the fields of nanocatalysts, drug delivery and sensors. By introducing liquid crystalline (LC) driving force into NPs, the region of non‐spherical shapes in phase diagrams can be broadened effectively, which attracts great interest of many researchers. LC mesogens can be easily introduced to monomers, such as acrylates and methacrylates, as side groups connected by spacers with tunable length, and then side‐chain LC polymers can be acquired after polymerization accordingly. Among these polymers, amphiphilic block copolymers (BCPs) have been widely studied, attributed to their property of spontaneous assembly into NPs under appropriate conditions. In this review, based on traditional solution self‐assembly and polymerization‐induced self‐assembly, the recent research into side‐chain LC BCP NPs is elaborated in terms of the aspects of the types of LC mesogens, LC phases, morphologies and functionalities. Finally, we summarize recent progress, and prospect the development trend in the future. © 2023 Society of Industrial Chemistry.

Synthesis and Self-Assembly of Silicon-Containing Azobenzene Liquid Crystalline Block Copolymers

The synthesis and self-assembly of a high interaction parameter silicon-containing liquid crystalline block copolymer (Si-LCBCP) are reported, containing thermally and photo-responsive azobenzene mesogens in the side chains which undergo molecular structural transitions, influencing phase transitions and orientation in the block copolymer. A series of the azobenzene-containing Si-LCBCPs, poly{dimethylsiloxane-b-11-[4-(4-cyanophenylazo)phenoxy]undecane methacrylate}, were synthesized through atom transfer radical polymerization, and the bulk self-assembly as well as the influence of the liquid-crystalline (LC) phase transition of the LC block on the microphase-separated nanostructure of the BCPs is described. As the volume fraction of the PMAAzo block (fPMAAzo) changes from 41 to 71%, lamellar, double gyroid (GYR), orthorhombic Fddd network, hexagonally packed cylindrical (HEX), and body centered cubic nanostructures were obtained. When fPMAAzo = 55–57%, a thermally reversible HEX-GYR-Fddd phase transition induced by the temperature change and LC phase transition was observed. Bulk morphologies are compared with thin-film self-assembly, and pattern transfer into silica nanostructures is demonstrated.

Photocontrollable liquid-crystalline block copolymers: design, photo-directed self-assembly and applications

Recent progress in various photocontrollable liquid-crystalline block copolymers, including their photoresponsive mechanisms, alignment techniques of microphase-separated nanodomains, outstanding properties and applications is shown.

High Mechanical Strength and Multifunctional Microphase-Separated Supramolecular Hydrogels Fabricated by Liquid-Crystalline Block Copolymer.

The development of multifunctional supramolecular hydrogels with high mechanical strength and multifunction is in high demand. In this work, the diblock copolymer poly(acrylamide-co-1-benzyl-3-vinylimidazolium bromide)-block-polyAzobenzene is synthesized through reversible addition-fragmentation chain transfer polymerization. The dynamic host-guest interactions between the host molecule cucurbit[8] uril and guest units are used to fabricate a 3D network of supramolecular hydrogels. Investigations on the properties of the supramolecular hydrogels show that the tensile stress of the sample is 1.46MPa, eight times higher than that of hydrogel without liquid-crystalline block copolymer, and the self-healing efficiency of the supramolecular hydrogels at room temperature is 88.3% (fracture stress) and 100% (fracture strain) after 24h. Results show that microphase-separated structure plays a key role in the high-strength hydrogel, whereas the host-guest interaction endows the hydrogel with self-healing properties. The supramolecular hydrogels with high mechanical strength, photo-responsivity, injectability, and biocompatibility can be used in various potential applications.

Regulating Chiral Helical Structures in Liquid-Crystalline Block Copolymers with Chiroptical Response by Synergistic Asymmetric Effects

Regulating Chiral Helical Structures in Liquid-Crystalline Block Copolymers with Chiroptical Response by Synergistic Asymmetric Effects

RAFT polymerization-induced self-assembly of semifluorinated liquid-crystalline block copolymers

Abstract It is a major challenge to prepare commercially viable scale semifluorinated liquid-crystalline block copolymers (SEFL-BCPs) using solution processing techniques. The technology of selectively solvating one block in a suitable solvent to realize self-assembly provides a promising route for the preparation of core-corona block polymer materials with extensive potential applications. However, considerable limitations have been discovered after much practice. BCP assemblies often require a separate synthesis step and are performed at high dilution. Herein, a one-pot approach combining polymerization-induced and crystallization-driven self-assembly (PISA-CDSA) was used to obtain well-defined, precise compositions of SEFL-BCPs. It is first synthesized via reversible addition-fragmentation chain transfer ethanol dispersion polymerization between 1H,1H,2H,2H-heptadecafluorodecyl acrylate and poly(N,N-dimethylacrylamide) at a concentration up to 20% v/v. Various morphologies, including 1D fiber-like micelles, 2D lamellar structures, and fusion structures, were first observed via transmission electron microscopy. This scalable PISA-CDSA strategy is greatly expanding the morphology scope and applicability of the polymer liquid crystal materials science field.

Tunable Thin Film Periodicities by Controlling the Orientation of Cylindrical Domains in Side Chain Liquid Crystalline Block Copolymers

A facile approach to block copolymer (BCP) domain orientation control in thin films has been demonstrated by employing a BCP with liquid crystalline semifluorinated side chains by tuning the composition of the copolymers of the bottom surface layer (BSL). 1H,1H,2H,2H-Perfluorodecanethiol was attached to a precursor polymer, polystyrene-block-poly(glycidyl methacrylate) (PS-b-PGMA), to obtain a novel BCP with a C8F17-containing liquid crystal (LC) side chain (PS-b-P8FMA). Anisotropic hexagonally packed cylinder domains in a bulk state were first characterized by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The observed morphology transition of BCPs with different fluorinated side chain lengths of –CF3, –C4F9, and –C6F13 suggested the decisive effects of LC side chain ordering on the anisotropic nanostructures. In the thin film study, poly(methyl methacrylate-random-2,2,2-trifluoroethyl methacrylate-random-methacrylic acid) (PMMA-ran-PTFEMA-ran-PMAA) solution was used as BSLs for tuning the desired periodicities. The surface free energy (SFE) of BSL was simply tailored by changing the composition of comonomers. In atomic force microscopy (AFM) characterization, long-range ordered perpendicularly oriented BCP domains in a hexagonally packed array or parallel oriented BCP domains as striation patterns were easily fabricated on non-preferential or preferential BSL, respectively. The study presents a novel approach to tunable thin film periodicities without changing or modifying BCPs, which is desired in next-generation BCP lithography.

Tunable Thermal Switch via Order-Order Transition in Liquid Crystalline Block Copolymer.

Organic material-based thermal switch is drawing much attention as one of the key thermal management devices in organic electronic devices. This study aims at tuning the switching temperature (TS) of thermal conductivity by using liquid crystalline block copolymers (BCs) with different order-order transition temperature (Ttr) related to the types of mesogens in the side chain. The BC films with low Ttr of 363 K and high Ttr of 395 K exhibit reversible thermal conductivity switching behaviors at TS of ∼360 K and ∼390 K, respectively. The BC films also exhibit thermal conductivity variation originating from the anisotropy of the internal structures: poly(ethylene oxide) domains and liquid crystals. These results demonstrate that the switching behavior is attributed to an order-order transition between BC films with vertically arranged cylinder domains and the ones with ordered sphere domains. This highlights that BCs become a promising thermal conductivity switching material with tailored TS.