Asymmetric Star Polymers Research Articles

Segregation kinetics of miktoarm star polymers: A dissipative particle dynamics study.

We study the phase separation kinetics of miktoarm star polymer (MSP) melts/blends with diverse architectures using dissipative particle dynamics simulation. Our study focuses on symmetric and asymmetric miktoarm star polymer (SMSP/AMSP) mixtures based on arm composition and number. For a fixed MSP chain size, the characteristic microphase-separated domains initially show diffusive growth with a growth exponent ϕ∼1/3 for both melts that gradually crossover to saturation at late times. The simulation results demonstrate that the evolution morphology of SMSP melt exhibits perfect dynamic scaling with varying arm numbers; the timescale follows a power-law decay with an exponent θ≃1 as the number of arms increases. The structural constraints on AMSP melts cause the domain growth rate to decrease as the number of one type of arms increases while their length remains fixed. This increase in the number of arms for AMSP corresponds to increased off-criticality. The saturation length in AMSP follows a power-law increase with an exponent λ≃2/3 as off-criticality decreases. Additionally, macrophase separation kinetics in SMSP/AMSP blends show a transition from viscous (ϕ∼1) to inertial (ϕ∼2/3) hydrodynamic growth regimes at late times; this exhibits the same dynamical universality class as linear polymer blends, with slight deviations at early stages.

The “solvent” effect of short arms on linear and nonlinear shear rheology of entangled asymmetric star polymers

This study examines the influence of the short arms in model asymmetric 3-arm star polymers, in which the short arm is unentangled while the other two long arms are entangled, on linear and nonlinear shear rheological behavior. As increasing the short arm length of the asymmetric star polymers, the linear viscoelastic rubber plateau decreases, indicating the relaxed short arms act as “solvent” that dilute the star polymers. This idea is examined by the relationship between the plateau moduli of polymer solutions GN(φ) and the corresponding polymer melts GN(1) for entangled linear polymers, GN(φ) = GN(1)φ1+α, where φ is the volume fraction of the polymer. The “solvent” effect of the short arms is also supported by the nonlinear rheology results showing weaker damping function and larger peak strain at stress overshoot. With the above clarification of the short-arm contributions, this work provides a guidance of molecular design for tuning linear and nonlinear rheology of star polymers.

Synthesis and microphase separation of dendrimer-like block copolymers by anionic polymerization strategies

Anionic polymerization for the preparation of polystyrene-b-polybutadiene is well-established and leads to thermoplastic elastomers on industrial scale. The classical ABA block copolymer (BCP) architecture and composition usually forms a cylindrical morphology in the bulk state. Their anisotropic mechanical properties are, however, unfavorable for many applications. The gyroid microphase is entirely isotropic, but it is only formed in a narrow compositional area of around 35 vol% of the minority polymer block. In the present study, a second-generation dendrimer-like block copolymer structure ((AB)2B)3 is described. This BCP architecture is expected to show a higher curvature on the microphase boundaries, which leads to a larger morphological range for the gyroid phase. Three compositionally different polymers are synthesized by living anionic polymerization strategies and the resulting morphology is analyzed via transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). The dendrimer-like BCPs are compared to their less branched analogues, namely the asymmetric star polymers and H-shape stars. The expected influence of the dendrimer-like BCP architecture on the microphase separation is investigated paving the way to a promising synthetic platform for interesting mechanical and optical properties.

Facile synthesis of AA'B- and ABC-type polypept(o)ide miktoarm star polymers utilizing polysarcosine end group functionalization for core introduction

Miktoarm star polymers display asymmetric architectures with combinations of multiple polymeric arms of different chemical nature emanating from a shared core. Their unique structure–property relationships in comparison to linear counterparts (with same molecular weight) make these architectures interesting for the design of novel polymeric species and the development of nanosized delivery systems. However, the synthesis of such structures is often demanding. Based on polypept(o)ides, we herein report on the synthesis of AA'B- and ABC-type miktoarm star polymers by introducing a multifunctional lysine end group to a polysarcosine (pSar) chain end, comprising orthogonal amine-protective groups. Therefore, each polymeric arm could be synthesized separately by living ring-opening polymerization (ROP) of respective N-carboxyanhydrides (NCAs), offering high reaction control and a resulting structure completely based on amino acids. We demonstrate the utility and versatility of this approach by designing a small, asymmetric and big AA'B miktoarm star polymer comprising two pSar arms with chain lengths of ∼50 or ∼150 in different combinations and a poly(Nε-trifluoroacetate-lysine) (pLys(TFA)) arm, as well as an ABC architecture by introducing a poly(γ-benzyl-glutamate) (pGlu(OBn)). 1H NMR, including 1H DOSY experiments, as well as size-exclusion chromatography (SEC) proof the successful and controlled synthesis of asymmetric miktoarm star polymers with precise control over degree of polymerization of the individual arms with narrow molecular weight distributions.

Asymmetric Miktoarm Star Polymers as Polyester Thermoplastic Elastomers

Asymmetric Miktoarm Star Polymers as Polyester Thermoplastic Elastomers

Convergent Synthesis of Branched Metathesis Polymers with Enyne Reagents.

Branched polymers have found utility in an array of fields due to the high density of functional groups combined with unique physical properties. Despite the abundant methods reported to synthesize various branched structures, controlling parameters such as the location of branch points and molecular weight distribution still remains a challenge. This report explores the ability of enyne-containing branching agents to synthesize star and miktoarm star polymers through a convergent synthesis pathway using ring-opening metathesis polymerization (ROMP). The branching agents contain an enyne metathesis terminator covalently linked to a norbornene monomer. When these agents are introduced into a living ROMP, macromonomers are generated in situ that continue to propagate via a grafting-through process with the remaining living chains. This strategy permits control over the degree of polymerization of the star arms, control of the number of star arms, and chain-extension with additional monomer to produce functional asymmetric miktoarm star polymers.

Primitive Chain Network Simulations of Entangled Melts of Symmetric and Asymmetric Star Polymers in Uniaxial Elongational Flows

Ianniruberto and Marrucci developed a theory whereby entangled branched polymers behave like linear ones in fast elongational flows. In order to test such prediction, Huang et al. performed elongational measurements on star polymer melts, indeed revealing that, in fast flows, the elongational viscosity is insensitive to the molecular structure, provided the molecular weight of the backbone is the same. Inspired by these studies, we here report on results obtained with multi-chain slip-link simulations for symmetric and asymmetric star polymer melts, as well as calculations of the Rouse time of the examined branched structures. The simulations semi-quantitatively reproduce the experimental data if the Kuhn-segment orientation-induced reduction of friction (SORF) is accounted for. The observed insensitivity of the nonlinear elongational viscosity to the molecular structure for the same span molar mass may be due to several factors. In the symmetric case, the calculated Rouse time of the star marginally differs from that of the linear molecule, so that possible differences in the observed stress fall within the experimental uncertainty. Secondly, it is possible that the flow-induced formation of hooked star pairs makes the effective Rouse time of the aggregate even closer to that of the linear polymer because the friction center moves towards the branchpoint of the star molecule. In the asymmetric case, it is shown that the stress contributed by the short arms is negligible with respect to that of the long ones. However, such stress-reduction is balanced by a dilution effect whereby the unstretched arms reduce SORF as they decrease the Kuhn-segment order parameter of the system. As a result of that dilution, the stress contributed by the backbone is larger. The two effects compensate one another so that the overall stress is virtually the same as the other architectures.

Synthesis and Self-Assembly of ABn Miktoarm Star Polymers

The stability of tetrahedrally close-packed (TCP) phases in block copolymer melts is predicted by theory to depend on molecular architecture, yet no experimental studies to date have probed its effect. Motivated by this open question, here we report an efficient synthesis of asymmetric ABn miktoarm star polymers using functionalized sugars as cores for orthogonal grafting-from block copolymerizations. A combination of ring-opening and atom transfer radical polymerization produced model low dispersity materials comprising a single A = poly(lactide) (L) and multiple B = poly(dodecyl acrylate) (D) arms that amplify "conformational asymmetry" through two concerted effects: the mikto architecture and disparate block statistical segment lengths. Analyzing the self-assembly of LD2 and LD3 samples resulted in the discovery of two TCP phases, σ and A15, that remained stable to significantly higher A-block volume fractions as the number of B arms increased. These results experimentally establish the importance of conformational asymmetry and molecular architecture as powerful design tools for the self-assembly of block copolymers into nonclassical phases.

Efficient Synthesis of Asymmetric Miktoarm Star Polymers.

Asymmetric miktoarm star polymers comprising an unequal number of chemically-distinct blocks connected at a common junction produce unique material properties, yet existing synthetic strategies are beleaguered by complicated reaction schemes that are restricted in both monomer scope and yield. Here, we introduce a new synthetic approach coined "μSTAR" - Miktoarm Synthesis by Termination After Ring-opening metathesis polymerization - that circumvents these traditional synthetic limitations by constructing the block-block junction in a scalable, one-pot process involving (1) grafting-through polymerization of a macromonomer followed by (2) in-situ enyne-mediated termination to install a single mikto-arm with exceptional efficiency. This modular μSTAR platform cleanly generates AB n and A(BA') n miktoarm star polymers with unprecedented versatility in the selection of A and B chemistries as demonstrated using many common polymer building blocks: poly(siloxane), poly(acrylate), poly(methacrylate), poly(ether), poly(ester), and poly(styrene). The average number of B or BA' arms (n) is easily controlled by the molar equivalents of macromonomer relative to Grubbs catalyst in the initial ring-opening metathesis polymerization step. While these materials are characterized by dispersity in n that arises from polymerization statistics, they self-assemble into mesophases that are identical to those predicted for precise miktoarm stars as evidenced by small-angle X-ray scattering experiments and self-consistent field theory simulations. In summary, the μSTAR technique provides a significant boost in design flexibility and synthetic simplicity while retaining the salient phase behavior of precise miktoarm star materials.

Dynamics of asymmetric star polymers under coarse grain simulations

AbstractThe asymmetric star polymers are studied by coarse grain simulations. Each polymer chain is represented by number of consecutive soft blobs and additional uncrossability constraints are added to prevent chain crossings. In this work two types of asymmetric star polymers with different backbone lengths are structured. Their dynamical properties are discussed by comparisons with corresponding linear chains, the one covers chain length along with the asymmetric arm through the branch point to one of the symmetric arm, or the backbone chain between two symmetric arm ends, or the largest linear possesses the same molecular weight of the entire star. To reveal the influence of the asymmetric arm length on their relaxation decay times, the autocorrelation function of the vectors from each branching point to corresponding asymmetric arm end are calculated, results are compared with the symmetric star having the same backbone chain.

Photo-controlled one-pot strategy for the synthesis of asymmetric three-arm star polymers

A one-pot tandem strategy for the synthesis of asymmetric star polymers was developed. Two wavelengths of light were used to provide spatial and temporal control for the reactions. A series of stars were synthesised using this procedure giving well-defined structures.

Probing relationship between structure and viscosity of unentangled polymers in steady shear flow

Structural responses of unentangled polymers of various architectures, including linear, ring, star, asymmetric star, and H-shaped polymers, in steady shear flow are investigated via nonequilibrium molecular dynamics simulations. As observed in our previous simulations, these polymers, when having an identical equilibrium mean-square radius of gyration exhibit the same viscosity curve in both the linear and nonlinear regimes. In this article, the polymer orientation and deformation and the rate of deformation are calculated as a function of shear rate. The differences between different architectures in most of these properties are found to be related to the polymer extensibility, the number of free ends and the ability of folding. The unique architecture-independent quantity is the gradient component of the radius of gyration tensor. We find that a simple relation η=C η (3 / )3/2 gives a near-perfect fit to shear viscosity η data, where C η is a constant. The results suggest that this relation between chain thickness and viscosity is universal for unentangled polymers of various architectures.

Synthesis of pyridoxine‐based eagle‐shaped asymmetric star polymers through seATRP

The vitamin B6‐based macroinitiator was prepared for the first time by the transesterification reaction of pyridoxine with 2‐bromoisobutyryl bromide. A pyridoxine‐based star‐shaped block copolymer with a hydrophilic pyridoxine core and a dual hydrophilic poly(2‐(dimethylamino)ethyl methacrylate)‐block‐poly(N‐isopropylacrylamide) arms was synthesized for the first time via a simplified electrochemically mediated atom transfer radical polymerization, utilizing only 20 ppm of catalyst complex. The rate of the polymerizations was controlled by applying appropriate potential/current values during electrolysis to prevent the possibility of intermolecular coupling of the polymer stars. The asymmetric star polymers showed narrow molecular weight distribution (Đ = 1.09–1.13). 1H NMR spectral results confirm the formation of star‐like block (co)polymers. These new vitamin B6‐based eagle‐shaped star (co)polymers may find biomedical and biosensor applications as pH‐sensitive and thermo‐sensitive drug delivery systems. Copyright © 2017 John Wiley & Sons, Ltd.

Synthesis of polystyrene-based Y-shaped asymmetric star by the combination of ATRP/RAFT and its thermal and rheological properties

A2A′-type asymmetric stars and A2B-type miktoarm star polymers were prepared by the combination of atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer polymerization (RAFT) using the designed initiator.

Asymmetric AB3 Miktoarm Star Polymers: Synthesis, Self-Assembly, and Study of Micelle Stability Using AF4 for Efficient Drug Delivery.

A simple and versatile methodology, which employs a combination of ring-opening polymerization and alkyne-azide click chemistry to synthesize amphiphilic AB3 miktoarm stars, is reported. Their aqueous self-assembly behavior was studied using dynamic light scattering, fluorescence, and asymmetrical flow field-flow fractionation (AF4). AB3 miktoarm stars form micelles which incorporate curcumin with high efficiency, and significantly reduce the viability of glioblastoma cells in spheroids. We demonstrate that AF4 is an effective technique to determine the size distribution of self-assembled structures exposed to a biological medium. The ease, with which asymmetric AB3 miktoarm polymers are constructed, provides a platform that can be widely employed to deliver a variety of lipophilic drugs.

Synthesis and Characterization of ABC-Type Asymmetric Star Polymers Comprised of Poly(3-hexylthiophene), Polystyrene, and Poly(2-vinylpyridine) Segments

ABC-type asymmetric star polymers containing a P3HT segment were successfully synthesized by polymer coupling/linking reactions by combining the Kumada catalyst-transfer polymerization and living anionic polymerization for the first time. The synthetic methodology involves the following three stage reactions: (a) the anionic linking reaction between ω-chain-end-functionalized P3HT with a bromobutyl moiety (P3HT-C4-Br) and living anionic PS end-capped with 1-(3-tert-butyldimethylsilyloxymethylphenyl)-1-phenylethylene (1), (b) the transformation reaction of the 3-tert-butyldimethylsilyloxymethylphenyl (TBDMS) moiety at the junction between the P3HT and PS segments into the α-phenyl acrylate (PA) moiety through the hydroxymethylphenyl moiety, and (c) the anionic linking reaction between PA-in-chain-functionalized P3HT-b-PS and living anionic P2VP. Indeed, the well-defined ABC star polymers in which A, B and C are poly(3-hexylthiophene) (P3HT), polystyrene (PS), and poly(2-vinylpyridine) (P2VP), respectively,...

Synthesis of AB3‐type miktoarm star polymers with steroid core via a combination of “Click” chemistry and ring opening polymerization techniques

ABSTRACTWell‐defined AB3‐type miktoarm star‐shaped polymers with cholic acid (CA) core were fabricated with a combination of “click” chemistry and ring opening polymerization (ROP) methods. Firstly, azide end‐functional poly(ethylene glycol) (mPEG), poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(ε‐caprolactone) (PCL) polymers were prepared via controlled polymerization and chemical modification methods. Then, CA moieties containing three OH groups were introduced to these polymers as the end groups via Cu(I)‐catalyzed click reaction between azide end‐functional groups of the polymers (mPEG‐N3, PMMA‐N3, PS‐N3, and PCL‐N3) and ethynyl‐functional CA under ambient conditions, yielding CA end‐functional polymers (mPEG‐Cholic, PMMA‐Cholic, PS‐Cholic, and PCL‐Cholic). Finally, the obtained CA end‐capped polymers were employed as the macroinitiators in the ROP of ε‐caprolactone (ε‐CL) yielding AB3‐type miktoarm star polymers (mPEG‐Cholic‐PCL3, PMMA‐Cholic‐PCL3, and PS‐Cholic‐PCL3) and asymmetric star polymer [Cholic‐(PCL)4]. The chemical structures of the obtained intermediates and polymers were confirmed via Fourier transform infrared and 1H nuclear magnetic resonance spectroscopic techniques. Thermal decomposition behaviors and phase transitions were studied in detail using thermogravimetric analysis and differential scanning calorimetry experiments. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3390–3399

Complex Self-Assembled Morphologies of Thin Films of an Asymmetric A3B3C3 Star Polymer.

An asymmetric nine-arm star polymer, (polystyrene)3-(poly(4-methoxystyrene))3-(polyisoprene)3 (PS3-PMOS3-PI3) was synthesized, and the details of the structures of its thin films were successfully investigated for the first time by using in situ grazing incidence X-ray scattering (GIXS) with a synchrotron radiation source. Our quantitative GIXS analysis showed that thin films of the star polymer molecules have very complex but highly ordered and preferentially in-plane oriented hexagonal (HEX) structures consisting of truncated PS cylinders and PMOS triangular prisms in a PI matrix. This HEX structure undergoes a partial rotational transformation process at temperatures above 190 °C that produces a 30°-rotated HEX structure; this structural isomer forms with a volume fraction of 23% during heating up to 220 °C and persists during subsequent cooling. These interesting and complex self-assembled nanostructures are discussed in terms of phase separation, arm number, volume ratio, and confinement effects.

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the “macromonomer” approach

We describe herein the synthesis and characterisation of a series of asymmetric three arm polystyrene stars via the “macromonomer” approach. The stars have been designed as model polymers to probe branched polymer dynamics and in particular to establish the chain-length of side-arm which precipitates a change in the rheological properties of the resulting polymers from “linear-like” to “star-like”. Thus, a homologous series of three arm stars have been prepared in which the molar mass of two (long) arms are fixed at 90,000gmol−1 and the molar mass of the remaining (short) arm is varied from below the entanglement molecular weight (Me) to above Me. The arms were prepared by living anionic polymerisation, resulting in well-defined chain lengths with narrow molecular weight distribution. In contrast to the usual chlorosilane coupling approach, the macromonomer approach involves the introduction of reactive chain-end functionalities on each of the arms, either through the use of a functionalised (protected) initiator or a functional end-capping agent, which allows the stars to be constructed by a simple condensation coupling reaction. In this study we will compare the relative efficiency of a Williamson and ‘click’ coupling reaction in producing the stars. Most significantly, although this approach maybe a little more time-consuming than the more common silane coupling reaction, in the present study the “long” arm may be produced in sufficient quantity such that all of the asymmetric stars are produced with long arms of identical molecular weight – the only remaining variable being the molecular weight of the short arm. This will allow for a far more robust interpretation of the resulting characterisation of the dynamic properties. Temperature gradient interaction chromatography was used alongside size exclusion chromatography to characterise the structural dispersity of the resulting stars and establish the degree of structural homogeneity.

Primitive chain network simulations for asymmetric star polymers

For branched polymers, the curvilinear motion of the branch point along the backbone is a significant relaxation source but details of this motion have not been well understood. This study conducts multi-chain sliplink simulations to examine effects of the spatial fluctuation and curvilinear hopping of the branch point on the viscoelastic relaxation. The simulation is based on the primitive chain network model that allows the spatial fluctuations of sliplink and branch point and the chain sliding along the backbone according to the subchain tension, chemical potential gradients, drag force against medium, and random force. The sliplinks are created and∕or disrupted through the motion of chain ends. The curvilinear hopping of the branch point along the backbone is allowed to occur when all sliplinks on a branched arm are lost. The simulations considering the fluctuation and the hopping of the branch point described well the viscoelastic data for symmetric and asymmetric star polymers with a parameter set common to the linear polymer. On the other hand, the simulations without the branch point motion predicted unreasonably slow relaxation for asymmetric star polymers. For asymmetric star polymers, further tests with and without the branch point hopping revealed that the hopping is much less important compared to the branch point fluctuation when the lengths of the short and long backbone arms are not very different and the waiting time for the branch point hopping (time for removal of all sliplinks on the short arm) is larger than the backbone relaxation time. Although this waiting time changes with the hopping condition, the above results suggest a significance of the branch point fluctuation in the actual relaxation of branch polymers.