ABC Star Terpolymers Research Articles

Design of Linear Block Copolymers and ABC Star Terpolymers That Produce Two Length Scales at Phase Separation.

Quasicrystals (materials with long-range order but without the usual spatial periodicity of crystals) were discovered in several soft matter systems in the last 20 years. The stability of quasicrystals has been attributed to the presence of two prominent length scales in a specific ratio, which is 1.93 for the 12-fold quasicrystals most commonly found in soft matter. We propose design criteria for block copolymers such that quasicrystal-friendly length scales emerge at the point of phase separation from a melt, basing our calculations on the Random Phase Approximation. We consider two block copolymer families: linear chains containing two different monomer types in blocks of different lengths, and ABC star terpolymers. In all examples, we are able to identify parameter windows with the two length scales having a ratio of 1.93. The models that we consider that are simplest for polymer synthesis are, first, a monodisperse ALBASB melt and, second, a model based on random reactions from a mixture of AL, AS, and B chains: both feature the length scale ratio of 1.93 and should be relatively easy to synthesize.

Formation of Perpendicular Three-Dimensional Network Nanostructures in ABC-Star Copolymers.

Perpendicular arrangements in hierarchical nanostructures show superior mechanical properties and provide great opportunities for the development of advanced membranes because different channels are connected by the perpendicular blocks. To obtain these perpendicular hierarchical nanostructures, we use a simple ABC-star terpolymer because of the existence of a conjunction point by using the A block as a polymer network template, which guides the BC phase separation accordingly. When χBC is 10, the formed phase and the corresponding phase diagram of ABC-star are similar to those of the AB2 triblock because of the mixture between the B and C blocks. Interestingly, at increased χBC, the B and C blocks phase separate, leading to the formation of a series of perpendicular nanostructures, including perpendicular lamellae-in-lamellae (L⊥), perpendicular lamellae-in-cylinder (C⊥), and even perpendicular three-dimensional polymer networks (G⊥). The corresponding stability regime of each phase is identified through the dedicated comparison of free energy, which can well explain the missing phases in Monte Carlo simulations. Our proposed design route according to the target structures and the calculated phase diagram can provide useful guidance for the experimental observation of these perpendicular nanostructures.

A simulation study of the self-assembly of ABC star terpolymers confined between two parallel surfaces.

The phase behavior of ABC star terpolymers confined between two identical parallel surfaces is systematically studied using a simulated annealing method. Several phase diagrams are constructed for systems with different bulk phases or with different interfacial interaction strength ratios in the space of surface distance (D) and surface preference for different arms, or in the space of D and the arm-length ratio x. Phases, including tiling patterns [6.6.6], [8.8.4], [8.6.6; 8.6.4], [8.6.6; 8.6.4; 10.6.6; 10.6.4] and hierarchical lamellar structures of lamella + cylinders and lamella + rods, are identified both in the bulk and in the films. Our results suggest that the self-assembled structure of a phase is largely controlled by x, while an increase of the interfacial interaction strength ratio shifts the x-window for each phase to the smaller x side. The orientation of a confined phase depends on the "effective surface preference" which is a combined effect of the interfacial interaction strength ratio, the surface preference, and the entropic preference. In the case of neutral or weak "effective surface preference", phases with a perpendicular orientation are usually observed, while in the case of strong "effective surface preference" phases with a perpendicular orientation or also with outermost wetting-layers can be frequently observed under some circumstances.

Synthesis and Star/Linear Topology Transformation of a Mechanically Linked ABC Terpolymer.

The synthesis of an ABC star terpolymer containing one polymer chain connected mechanically through a rotaxane linkage and its topology transformation to a linear structure are reported. Pseudo[2]rotaxane, which was designed as the key trifunctional species for the star polymer synthesis, comprised a sec-ammonium axle with ethynyl and hydroxy groups and a crown ether wheel with a trithiocarbonate group. Stepwise polymer connections to the pseudo[2]rotaxane using the three groups afforded a rotaxane-linked ABC star terpolymer. The topology transformation from star to linear by the removal of the attractive interaction between the axle and wheel components yielded a linear ABC terpolymer via the wheel shifting to the axle end. The spectroscopic and solution property changes clearly indicated the occurrence of the polymer topology change.

Hierarchical self-assembly of a striped gyroid formed by threaded chiral mesoscale networks.

Numerical simulations reveal a family of hierarchical and chiral multicontinuous network structures self-assembled from a melt blend of Y-shaped ABC and ABD three-miktoarm star terpolymers, constrained to have equal-sized A/B and C/D chains, respectively. The C and D majority domains within these patterns form a pair of chiral enantiomeric gyroid labyrinths (srs nets) over a broad range of compositions. The minority A and B components together define a hyperbolic film whose midsurface follows the gyroid minimal surface. A second level of assembly is found within the film, with the minority components also forming labyrinthine domains whose geometry and topology changes systematically as a function of composition. These smaller labyrinths are well described by a family of patterns that tile the hyperbolic plane by regular degree-three trees mapped onto the gyroid. The labyrinths within the gyroid film are densely packed and contain either graphitic hcb nets (chicken wire) or srs nets, forming convoluted intergrowths of multiple nets. Furthermore, each net is ideally a single chiral enantiomer, induced by the gyroid architecture. However, the numerical simulations result in defect-ridden achiral patterns, containing domains of either hand, due to the achiral terpolymeric starting molecules. These mesostructures are among the most topologically complex morphologies identified to date and represent an example of hierarchical ordering within a hyperbolic pattern, a unique mode of soft-matter self-assembly.

Insights into ordered microstructures and ordering mechanisms of ABC star terpolymers by integrating dynamic self-consistent field theory and variable cell shape methods

A theoretical approach coupling dynamic self-consistent field (SCF) theory for inhomogeneous polymeric fluids and variable cell shape (VCS) method for automatically adjusting cell shape and size is developed to investigate ordered microstructures and the ordering mechanisms of block copolymer melts. Using this simulation method, we first re-examined the microphase separation of the simplest AB diblock copolymers, and tested the validity and efficiency of the novel method by comparing the results with those obtained from the dynamic SCF theory. An appropriate relaxation parameter of the VCS method effectively accelerates the system towards a stable morphology without distortions or defects. The dynamic SCF/VCS method is then applied to identify the richness morphologies of ABC star terpolymers and explore the ordering mechanisms of star terpolymer melts quenched from homogenous states. A diverse range of ordered microstructures, including two-dimensional tiling patterns, hierarchical structures and ordinary microstructures, are predicted. Three types of ordering mechanisms, namely, one-step, quick-slow and step-wise procedures, are discovered in the disorder-to-order transition of ABC star terpolymers. The procedures of microphase separation in the ABC star terpolymer melts are remarkably affected by the composition of star terpolymers and the strength of interaction parameters.

Synthesis and Bulk Self-Assembly of ABC Star Terpolymers with a Polyferrocenylsilane Metalloblock

The synthesis, characterization, and self-assembly of a range of ABC star polymers with arms of polyisoprene, poly(ferrocenylethylmethylsilane), and polystyrene is reported. A library of azide-functionalized polyisoprene and poly(ferrocenylethylmethylsilane) homopolymers were prepared by living anionic polymerization. Polystyrene was synthesized by living anionic polymerization and quenched with 3-triisopropylsilylethynyl-5-trimethylsilylethynylbenzaldehyde, yielding “core-functionalized” polystyrene with two different alkyne units. The azide-functionalized monomers were sequentially attached to core-functionalized polystyrene via copper(I)-catalyzed azide–alkyne cycloaddition reactions, giving polystyrene–polyisoprene–poly(ferrocenylethylmethylsilane) ABC star terpolymers with different compositions and narrow dispersities. Additionally, a chlorosilane route was employed as an alternative means of synthesis. Bulk films of each star terpolymer were prepared, and their self-assembly was analyzed by transmi...

ChemInform Abstract: Why Are Quasicrystals Quasiperiodic?

AbstractReview: 60 refs.

Precise Synthesis of ABCDE Star Quintopolymers by Combination of Controlled Polymerization and Azide–Alkyne Cycloaddition Reaction

A facile approach based on integrated utilization of ring-opening polymerization (ROP), reversible addition–fragmentation chain transfer (RAFT) process, and azide–alkyne cycloaddition reaction was efficiently used to construct amphiphilic 5-arm ABCDE star quintopolymers. The miktoarm stars are composed of poly(ethylene glycol) (A), poly(e-caprolactone) (B), polystyrene (C), poly(l-lactide) (D), poly(N,N-dimethylaminoethyl methacrylate) (E1), poly(methyl methacrylate) (E2), and poly(methyl acrylate) (E3). Alkyne-in-chain-functionalized BC and DE diblock copolymers were synthesized by successive ROP and RAFT process. Selective [3 + 2] click reaction between two-azide-end-functionalized PEG and BC copolymer gave azide-core-functionalized ABC star terpolymer, and a subsequent click reaction with DE copolymer afforded well-defined ABCDE stars with well-controlled molecular weight, low polydispersity, and precise composition, as evidenced from 1H NMR, GPC, and GPC-MALLS analyses. DSC analyses revealed part of p...

Why are quasicrystals quasiperiodic?

In the past two decades significant progress has been made in the search for stable quasicrystals, the determination of their structures and the understanding of their physical properties. Now, quasiperiodic ordering states are not only known for intermetallic compounds, but also for mesoscopic systems such as ABC-star terpolymers, liquid crystals or different kinds of colloids. However, in spite of all these achievements fundamental questions concerning quasicrystal formation, growth and stability are still not fully answered. This tutorial review introduces the research in these fields and addresses some of the open questions concerning the origin of quasiperiodicity.

Toward the discovery of new soft quasicrystals: From a numerical study viewpoint

AbstractThis is a progress review of an emerging research front: soft quasicrystals including liquid crystalline dendrons, nanoparticles, mesoporous silica, colloids, ABC star and linear terpolymers, and even water and silicon. As an aid to readers, we explain the basics of quasicrystals developed in solid‐state physics: orders in quasicrystals, higher dimensional crystallography, approximants, phason randomness, and the origin of quasicrystal formation. Then we review some numerical studies from early to recent ones. Our main purpose is to elucidate how to construct quasicrystalline structures: The introduction of additional components or a new length‐scale is the key to discover new quasicrystals. As a case study, we describe our recent studies on ABC star terpolymer systems and present the results of simulations of dodecagonal polymeric quasicrystals. In the case of dodecagonal quasicrystals, one easily finds that the key is to search square‐triangle tiling structures with changing components. Application to photonic quasicrystals is reviewed as well. Our hope is that this review will contribute furthering quasicrystal chemistry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

SCFT Study of Tiling Patterns in ABC Star Terpolymers

Ordered phases of ABC star terpolymer melts are investigated using a generic reciprocal-space implementation of the self-consistent field theory (SCFT) of polymers. The most important feature of ABC star triblock terpolymers is that their three blocks are joined at one junction point. This distinct topology of ABC star terpolymers constraints the junction points in one-dimensional lines in an ordered phase, resulting novel microphase-separated morphologies such as tiling patterns. Two types of star triblock terpolymers, with symmetric and asymmetric interaction parameters, are studied in detail. A variety of tiling patterns in ABC star terpolymers have been predicted from the SCFT calculation and relevant phase diagrams have been constructed. The predicted phase transition sequences from the SCFT calculations are in qualitative agreement with experimental and Monte Carlo simulation results.

Helical Vesicles, Segmented Semivesicles, and Noncircular Bilayer Sheets from Solution-State Self-Assembly of ABC Miktoarm Star Terpolymers

Multicompartment micelles, especially nanostructured vesicles, offer tremendous potential as delivery vehicles of therapeutic agents and nanoreactors. Solution-state self-assembly of miktoarm star terpolymers provides a versatile and powerful route to obtain multicompartment micelles. Here we report simulations of solution-state self-assembly of ABC star terpolymers composed of a solvophilic A arm and two solvophobic B and C arms. A variety of multicompartment micelles are predicted from the simulations. Phase diagrams for typical star terpolymers are constructed. It is discovered that the overall micelle morphology is largely controlled by the volume fraction of the solvophilic A arms, whereas the internal compartmented and/or segregated structures depend on the ratio between the volume fractions of the two solvophobic arms. The polymer-solvent and polymer-polymer interactions can be used to tune the effective volume fraction of the A-arm and, thereby, induce morphological transitions. For terpolymers with equal or nearly equal length of B and C arms, several previously unknown structures, including vesicles with novel lateral structures (helices or stacked donuts), segmented semivesicles, and elliptic or triangular bilayer sheets, are discovered. When the lengths of B and C arms are not equal, novel micelles such as multicompartment disks and onions are observed.

Preparation of H‐shaped ABCAB terpolymers by atom transfer radical coupling

AbstractH‐shaped ABCAB terpolymers composed of polystyrene (PS) (A), poly(ethylene oxide) (PEO) (B), and poly(tert‐butyl acrylate) (PtBA) (C) were prepared by atom transfer radical coupling reaction using ABC star terpolymers as precursors, CuBr and N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalysts, and nanosize copper as the reducing agent. The synthesis of 3‐miktoarm star terpolymer PS‐PEO‐(PtBA‐Br) involved following steps: (1) the preparation of PS with an active and an ethoxyethyl‐ptotected hydroxyl group at the same end; (2) the preparation of diblock copolymer PS‐b‐PEO with ethoxyethyl‐protected group at the junction point through the ring‐opening polymerization (ROP) of EO; (3) after de‐protection of ethoxyethyl group and further modification of hydroxyl group, tBA was polymerized by atom transfer radical polymerization using PS‐b‐PEO with 2‐bromoisobutyryl functional group as macroinitiator. The H‐shaped terpolymer could be successfully formed by atom transfer radical coupling reaction in the presence of small quantity of styrene, CuBr/PMDETA, and Cu at 90 °C. The copolymers were characterized by SEC, 1H NMR, and FTIR in detail. The optimized coupling temperature is 90 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 59–68, 2009

An all ATRP route to PMMA–PEO–PS and PMAA–PEO–PS miktoarm ABC star terpolymer

An all Atom Transfer Radical Polymerization (ATRP) route to synthesize miktoarm ABC star terpolymer, μ-(poly(methyl methacrylate)–poly(ethylene oxide)–polystyrene) (μ-(PMMA–PEO–PS)), was demonstrated. Poly(methyl methacrylate) (PMMA) with a halide end group was first prepared by ATRP of MMA. It was then activated under ATRP conditions at 30°C to add a styrenic-terminated PEO macromonomer, resulting in the formation of PMMA-b-PEO. Finally, the active halide at the junction point of the diblock copolymer was used to initiate the ATRP of St at higher temperature. By a similar approach, μ-(poly(phenyl methacrylate)–poly(ethylene oxide)–polystyrene) (μ-(PhMA–PEO–PS)) was synthesized, hydrolysis of which in basic medium gave μ-(PMAA–PEO–PS). The polymers were characterized by 1H NMR spectroscopy and gel permeation chromatography.

Synthesis of ABC 3-Miktoarm Star Terpolymers from a Trifunctional Initiator by Combining Ring-Opening Polymerization, Atom Transfer Radical Polymerization, and Nitroxide-Mediated Radical Polymerization

We report a new method to synthesize ABC 3-miktoarm star terpolymers by combining three different controlled/“living” polymerization techniques: ring-opening polymerization (ROP), atom transfer radical polymerization (ATRP), and nitroxide-mediated radical polymerization (NMRP). A trifunctional initiator bearing a hydroxy group, an ATRP initiator, and a NMRP initiator was designed and synthesized. The structure was confirmed by 1H NMR, 13C NMR, and mass spectroscopy. ABC star terpolymers were then prepared from the trifunctional initiator by sequential ROP of e-caprolactone, ATRP of methyl methacrylate, and NMRP of styrene. GPC and kinetic analysis indicated that the polymerizations were controlled. The 3-miktoarm star structure was further confirmed by cleavage of a star terpolymer.