Bottlebrush Block Copolymers at the Interface of Immiscible Liquids: Adsorption and Lateral Packing.

Amphiphilic bottlebrush block copolymers (BBCPs), having a hydrophilic bottlebrush polymer (BP) linked covalently to a hydrophobic BP, were found to segregate to liquid-liquid interfaces to minimize the free energy of the system. The key parameter influencing the outcome of the experiments is the ratio between the degree of polymerization of the backbone (NBB) and that of the side-chain brushes (NSC). Specifically, a spherical, star-like configuration results when NBB < NSC, while a cylindrical, bottlebrush-like shape is preferred when NBB > NSC. Dynamic interfacial tension (γ) and fluorescence recovery after photobleaching (FRAP) measurements show that the BBCP configuration influences the areal density and in-plane diffusion at the fluid interface. The characteristic relaxation times associated with BBCP adsorption (τA) and reorganization (τR) were determined by fitting time-dependent interfacial tension measurements to a sum of two exponential relaxation functions. Both τA and τR initially increased with NBB up to 92 repeat units, due to the larger hydrodynamic radius in solution and slower in-plane diffusivity, attributed to a shorter cross-sectional diameter of the side-chains near the block junction. This trend reversed at NBB = 190, with shorter τA and τR attributed to increased segregation strength and exposure of the bare water/toluene interface due to tilting and/or wiggling of the backbone chains, respectively. The adsorption energy barrier decreased with higher NBB, due to a reduced BBCP packing density at the fluid interface. This study provides fundamental insights into macromolecular assembly at fluid interfaces, as it pertains to unique bottlebrush block architectures.

3D Printing of Aqueous Two-Phase Systems with Linear and Bottlebrush Polyelectrolytes.

We formed core-shell-like polyelectrolyte complexes (PECs) from an anionic bottlebrush polymer with poly (acrylic acid) side chains with a cationic linear poly (allylamine hydrochloride). By varying the pH, the number of side chains of the polyanionic BB polymers (Nbb), the charge density of the polyelectrolytes, and the salt concentration, the phase separation behavior and salt resistance of the complexes could be tuned by the conformation of the BBs. By combining the linear/bottlebrush polyelectrolyte complexation with all-liquid 3D printing, flow-through tubular constructs were produced that showed selective transport across the PEC membrane comprising the walls of the tubules. These tubular constructs afford a new platform for flow-through delivery systems.

Janus bottlebrush compatibilizers.

Bottlebrush random copolymers (BRCPs), consisting of a random distribution of two homopolymer chains along a backbone, can segregate to the interface between two immiscible homopolymers. BRCPs undergo a reconfiguration, where each block segregates to one of the homopolymer phases, adopting a Janus-type structure, reducing the interfacial tension and promoting adhesion between the two homopolymers, thereby serving as a Janus bottlebrush copolymer (JBCP) compatibilizer. We synthesized a series of JBCPs by copolymerizing deuterated or hydrogenated polystyrene (DPS/PS) and poly(tert-butyl acrylate) (PtBA) macromonomers using ruthenium benzylidene-initiated ring-opening metathesis polymerization (ROMP). Subsequent acid-catalyzed hydrolysis converted the PtBA brushes to poly(acrylic acid) (PAA). The JBCPs were then placed at the interface between DPS/PS homopolymers and poly(2-vinyl pyridine) (P2VP) homopolymers, where the degree of polymerization of the backbone (NBB) and the grafting density (GD) of the JBCPs were varied. Neutron reflectivity (NR) was used to determine the interfacial width and segmental density distributions (including PS homopolymer, PS block, PAA block and P2VP homopolymer) across the polymer-polymer interface. Our findings indicate that the star-like JBCP with NBB = 6 produces the largest interfacial broadening. Increasing NBB to 100 (rod-like shape) and 250 (worm-like shape) reduced the interfacial broadening due to a decrease in the interactions between blocks and homopolymers by stretching of blocks. Decreasing the GD from 100% to 80% at NBB = 100 caused an increase the interfacial width, yet further decreasing the GD to 50% and 20% reduced the interfacial width, as 80% of GD may efficiently increase the flexibility of blocks and promote interactions between homopolymers, while maintaining relatively high number of blocks attached to one molecule. The interfacial conformation of JBCPs was further translated into compatibilization efficiency. Thin film morphology studies showed that only the lower NBB values (NBB = 6 and NBB = 24) and the 80% GD of NBB = 100 had bicontinuous morphologies, due to a sufficient binding energy that arrested phase separation, supported by mechanical testing using asymmetric double cantilever beam (ADCB) tests. These provide fundamental insights into the assembly behavior of JBCPs compatibilizers at homopolymer interfaces, opening strategies for the design of new BCP compatibilizers.

Bottlebrush Polymers at Liquid Interfaces: Assembly Dynamics, Mechanical Properties, and All-Liquid Printed Constructs.

Bottlebrush polymer surfactants (BPSs), formed by the interfacial interactions between bottlebrush polymers (BPs) with poly(acrylic acid) side chains dissolved in an aqueous phase and amine-functionalized ligands dissolved in the oil phase, assemble and bind strongly to the fluid-fluid interface. The ratio between NBB (backbone degree of polymerization) and NSC (side chain degree of polymerization) defines the initial assembly kinetics, interface packing efficiency, and stress relaxation. The equilibrium interfacial tension (γ) increases when NBB < NSC, but decreases when NBB ≫ NSC, correlating to a pronounced change in the effective shape of the BPs from being spherical to worm-like structures. The apparent surface coverage (ASC), i.e., the interfacial packing efficiency, decreases as NBB increases. The dripping-to-jetting transition of an injected polymer solution, as well as fluorescence recovery after photobleaching experiments, revealed faster initial assembly kinetics for BPs with higher NBB. Euler buckling of BPS assemblies with different NBB values was used to characterize the stress relaxation behavior and bending modulus. The stress relaxation behavior was directly related to the ASC, reflecting the strong influence of macromolecular shape on packing efficiency. The bending modulus of BPSs decreases for NBB < NSC, but increased when NBB ≫ NSC, showing the effect of molecular architecture and multisite anchoring. All-liquid printed constructs with lower NBB BPs yielded more stable structured liquids, underscoring the importance of macromolecular packing efficiency at fluid interfaces. Overall, this work elucidates fundamental relationships between nanoscopic structures and macroscopic properties associated with various bottlebrush polymer architectures, which translate to the stabilization of all-fluidic printed constructs.

In Situ Hydrolysis of Block Copolymers at the Water-Oil Interface.

In situ manipulation of the chemical composition of block copolymers at the fluid interfaces affords a route by which the interfacial tension, the packing of the copolymers, and the penetration of the blocks into the two liquids can be controlled. Here, a series of linear block copolymers of poly(solketal methacrylate-b-styrene) (PSM-b-PS) are used, converting hydrophobic PSM block into a hydrophilic glycerol monomethacrylate (GM) block, that results in a marked decrease in the liquid-liquid interfacial tension. The kinetics of the first-order hydrolysis reaction was analyzed by monitoring the time-dependent interfacial tension as a function of pH, polymer concentration, molecular weight, and composition. Fluorescence recovery after photobleaching (FRAP) was used to measure the in-plane dynamics of the copolymers before and after hydrolysis. This work provides insights into a quantitative pathway by which in situ interfacial reactions may be performed and monitored in real time, completely changing the interfacial activity of the molecule.

Reconfiguration and Reorganization of Bottlebrush Polymer Surfactants.

Bottlebrush random copolymers (BRCPs), having randomly distributed hydrophilic and hydrophobic side chains, are shown to reconfigure into hydrophilic-rich and hydrophobic-rich conformations at liquid-liquid interfaces to reduce interfacial energy. Both the degree of polymerization (NBB ) and extent of grafting in these BRCPs were found to impact surface coverage and assembly kinetics. The time-dependence of the interfacial tension is described as the sum of two exponential relaxation functions characterizing BRCP diffusion, interfacial adsorption, and reorganization. Interfacial tension (γ) and fluorescence recovery after photobleaching (FRAP) results showed that higher molecular weight BRCPs require longer time to adsorb to the water-oil interface, but less time for interfacial reorganization. Overall, this work describes fundamental principles of BRCP assembly at liquid-liquid interfaces, with implications pertaining to polymer design with enhanced understanding of emulsification, adhesion, and related properties in fluids and at interfaces.

Zwitterionic Ammonium Sulfonate Polymers: Synthesis and Properties in Fluids.

Polymer zwitterions continue to emerge as useful materials for numerous applications, ranging from hydrophilic and antifouling coatings to electronic materials interfaces. While several polymer zwitterion compositions are now well established, interest in this field of soft materials science has grown rapidly in recent years due to the introduction of new structures that diversify their chemistry and architecture. Nonetheless, at present, the variation of the chemical composition of the anionic and cationic components of zwitterionic structures remains relatively limited to a few primary examples. In this article, the versatility of 4-vinylbenzyl sultone as a precursor to ammonium sulfonate zwitterionic monomers, which are then used in controlled free radical polymerization chemistry to afford "inverted sulfobetaine" polymer zwitterions, is highlighted. An evaluation of the solubility, interfacial activity, and solution configuration of the resultant polymers reveals the dependence of properties on the selection of tertiary amines used for nucleophilic ring-opening of the sultone precursor, as well as useful properties comparisons across different zwitterionic compositions.