Functional Thermoplastic Polyurethane Elastomers with α, ω-Hydroxyl End-Functionalized Polyacrylates.

Thermoplastic polyurethane (TPU) is an essential class of materials for demanding applications, from soft robotics and electronics to medical devices and batteries. However, traditional TPU development is primarily relied on specific soft segments, such as polyether, polyester, and polycarbonate polyols. Here, a novel method is introduced for developing TPU elastomers with enhanced performance and superior functionalities compared to conventional TPUs, achieved through the use of α,ω-hydroxyl end-functionalized polyacrylates.

End Group Functionality of 95-99%: Epoxide Functionalization of Polystyryl-Lithium Evaluated via Solvent Gradient Interaction Chromatography.

End group functionality is a key parameter of functional polymer chains. The end-capping efficiency of living polystyryl lithium with various epoxides, namely ethylene oxide (EO), ethoxy ethyl glycidyl ether (EEGE) and isopropylidene glyceryl glycidyl ether (IGG), is investigated with solvent gradient interaction chromatography (SGIC). Generally, end-capping efficiencies >95% are observed.

Nonlinear rheometry of entangled polymeric rings and ring-linear blends.

We present a comprehensive experimental rheological dataset for purified entangled ring polystyrenes and their blends with linear chains in nonlinear shear and elongation. In particular, data for shear stress growth coefficient, steady-state shear viscosity, and first and second normal stress differences are obtained and discussed as functions of shear rate as well as molecular parameters (molar mass, blend composition and decreasing molar mass of linear component in blend). Over the extended parameter range investigated, rings do not exhibit clear transient undershoot in shear, in contrast to their linear counterparts and ring-linear blends.

Molecular Weight Distribution of Two Types of Living Chains Formed during Nitroxide-Mediated Polymerization of Styrene.

Different types of polymer chains generated during the nitroxide-mediated polymerization of styrene are separated for the first time, and their molecular weight distribution (MWD) is investigated. Living and dead chains are monitored during the reaction; specifically, two types of living chains derived from the initiation of the alkoxyamine (RT) and the self-initiation of styrene and dead chains present in the as-prepared polystyrene (PS). To distinguish between each polymer species, different numbers of hydroxyl groups are introduced onto the T and R groups of the alkoxyamine (one and two groups, respectively).

Stress relaxation in symmetric ring-linear polymer blends at low ring fractions.

We combine linear viscoelastic measurements and modelling in order to explore the dynamics of blends of the same-molecular-weight ring and linear polymers in the regime of the low volume fraction (0.3 or lower) of the ring component. The stress relaxation modulus is affected by the constraint release (CR) of both rings and linear components due to the motion of linear chains.

Threading-Unthreading Transition of Linear-Ring Polymer Blends in Extensional Flow.

Adding small amounts of ring polymers to a matrix of their linear counterparts is known to increase the zero-shear-rate viscosity because of linear-ring threading. Uniaxial extensional rheology measurements show that, unlike its pure linear and ring constituents, the blend exhibits an overshoot in the stress growth coefficient. By combining these measurements with ex-situ small-angle neutron scattering and nonequilibrium molecular dynamics simulations, this overshoot is shown to be driven by a transient threading-unthreading transition of rings embedded within the linear entanglement network.

Two-Dimensional Liquid Chromatography Analysis of Polystyrene/Polybutadiene Block Copolymers.

A detailed characterization of a commercial polystyrene/polybutadiene block copolymer material (Styrolux) was carried out using two-dimensional liquid chromatography (2D-LC). The Styrolux is prepared by statistical linking reaction of two different polystyrene- block-polybutadienyl anion precursors with a multivalent linking agent. Therefore, it is a mixture of a number of branched block copolymers different in molecular weight, composition, and chain architecture.

Molecular Weight Distribution of Living Chains in Polystyrene Prepared by Atom Transfer Radical Polymerization.

Living and dead chains of a polystyrene synthesized by atom transfer radical polymerization were separated and characterized by high performance liquid chromatography (HPLC), size exclusion chromatography (SEC), NMR, and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The bromine end group in the living chain was quantitatively converted to a hydroxyl end group via first azidation and subsequent copper-catalyzed azide-alkyne cycloaddition (CuAAC) click reaction with propargyl alcohol. The living chains bearing a polar end group are fully resolved from the unmodified dead chains by HPLC separation using a bare silica stationary phase.

Influence of the Solvent Quality on Ring Polymer Dimensions.

We present a systematic investigation of well-characterized, experimentally pure polystyrene (PS) rings with molar mass of 161 000 g/mol in dilute solutions. We measure the ring form factor at - and good-solvent conditions as well as in a polymeric solvent (linear PS of roughly comparable molar mass) by means of small-angle neutron scattering (SANS). Additional dynamic light scattering (DLS) measurements support the SANS data and help elucidate the role of solvent quality and solution preparation.

Comprehensive two-dimensional liquid chromatographic analysis of poloxamers.

Poloxamers are low molar mass triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), having number of applications as non-ionic surfactants. Comprehensive one and two-dimensional liquid chromatographic (LC) analysis of these materials is proposed in this study. The separation of oligomers of both types (PEO and PPO) is demonstrated for several commercial poloxamers.

Structural characterization of telechelic polyisobutylene diol.

The chemical homogeneity of telechelic polyisobutylene diol (PIB-diol), prepared by hydroboration-oxidation of allyl telechelic PIB obtained by reacting living PIB with allyltrimethylsilane, was investigated by liquid chromatography at critical conditions (LCCC) and HPLC coupled with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). A normal phase gradient HPLC method was developed that was able to separate the as-synthesized PIB-diol into three components; PIB-diol, PIB-monool and PIB without any OH functionality. These were analyzed by MALDI-TOF MS, which suggested that the reaction of living PIB with allyltrimethylsilane was incomplete.

Characterization of polylactides with different stereoregularity using electrospray ionization ion mobility mass spectrometry.

We investigated the effect of stereoregularity on the gas-phase conformations of linear and cyclic polylactides (PLA) using electrospray ionization ion mobility mass spectrometry (ESI-IM-MS) combined with molecular dynamics simulations. IM-MS analysis of PLA ions shows intriguing difference between the collision cross section (ΩD) value of poly-L-lactide (PLLA) and poly-LD-lactide (PLDLA) ions with respect to their chain architecture and stereoregularity. In the singly sodiated linear PLA (l-PLA∙Na(+)) case, both l-PLLA and l-PLDLA up to 11mer have very similar ΩD values, but the ΩD values of l-PLLA are greater than that of l-PLDLA ions for larger ions.

Strain hardening in startup shear of long-chain branched polymer solutions.

We show for the first time that entangled polymeric liquids containing long-chain branching can exhibit strain hardening upon startup shear. As the significant long-chain branching impedes chain disentanglement, Gaussian coils between entanglements can deform to reach the finite extensibility limit where the intrachain retraction force exceeds the value expected from the usual conformational entropy loss evaluated based on Gaussian chain statistics. The phenomenon is expected to lead to further theoretical understanding.

Viscosity of ring polymer melts.

We have measured the linear rheology of critically purified ring polyisoprenes, polystyrenes and polyethyleneoxides of different molar masses. The ratio of the zero-shear viscosities of linear polymer melts to their ring counterparts at isofrictional conditions is discussed as function of the number of entanglements . In the unentangled regime is virtually constant, consistent with the earlier data, atomistic simulations, and the theoretical expectation .

Elution behavior of shortened multiwalled carbon nanotubes in size exclusion chromatography.

We present a rigorous investigation on elution behaviors of ultrasonically shortened multiwalled carbon nanotubes in size-exclusion chromatography. The size separation of five carbon nanotube samples that underwent ultrasonic shortening for varying lengths of time revealed the existence of three kinds of carbon species: large nanotubes, small nanotubes, and amorphous carbon species. Separation of the three different carbon species was confirmed by SEM analyses on the fractionated eluates and also by light scattering/UV absorbance double detection.

Model Branched Polymers: Synthesis and Characterization of Asymmetric H-Shaped Polybutadienes.

A new type of model branched polymer, asymmetric H-shaped polybutadienes, consisting of central crossbars having various combinations of short and long arms attached to the ends of the crossbars, was synthesized using living anionic polymerization and chlorosilane linking chemistry. The linking agent 4-(dichloromethylsilyl)diphenylethylene provides selective reactivity to attach short or long arms on one side or both sides as desired. The samples were characterized thoroughly by size exclusion chromatography with light scattering detection (SEC-LS) and found to exhibit controlled molecular weights, as well as narrow polydispersity indices (PDIs of 1.

In Silico Molecular Design, Synthesis, Characterization, and Rheology of Dendritically Branched Polymers: Closing the Design Loop.

It has been a long held ambition of both industry and academia to understand the relationship between the often complex molecular architecture of polymer chains and their melt flow properties, with the goal of building robust theoretical models to predict their rheology. The established key to this is the use of well-defined, model polymers, homogeneous in chain length and architecture. We describe here for the first time, the in silico design, synthesis, and characterization of an architecturally complex, branched polymer with the optimal rheological properties for such structure-property correlation studies.

Programmable bipolar and unipolar nonvolatile memory devices based on poly(2-(N-carbazolyl)ethyl methacrylate) end-capped with fullerene.

A novel polymer, poly(2-(N -carbazolyl)ethyl methacrylate) end-capped with fullerene (PCzMA-C(60) ), has been synthesized via living anionic polymerization. Electrically programmable flash memory devices were easily fabricated with this polymer by using solution coating and metal deposition. This polymer was found in these devices to exhibit bipolar and unipolar switching behaviors with a high ON/OFF current ratio, a long retention time, high reliability, and low power consumption.

2D-LC characterization of comb-shaped polymers using isotope effect.

A rigorous molecular characterization of comb-shaped polystyrene (PS) was carried out taking advantage of its molecular structure, a normal hydrogenous backbone, and deuterated side chains. Normal phase LC (NPLC) can separate the comb PS species well according to their molecular weight. Nonetheless, it cannot distinguish the backbone from the side chains and the differently structured polymers having a similar molecular weight, e.

Development of various PS-b-P4VP micellar morphologies: fabrication of inorganic nanostructures from micellar templates.

We demonstrate a simple route for preparing various micellar nanostructures, like spheres, cylinders, and vesicles, by spin-coating or drop-casting process of polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) copolymer solutions in pure tetrahydrofuran (THF), THF/water, and THF/ethanol mixture. Upon drying, a solvent selectivity plays an important role in determining micellar nanostructures in thin films. In solution, micellar sizes and shapes of these PS-b-P4VP copolymers were investigated by dynamic and static light scattering.

Temperature gradient interaction chromatography of polymers: A molecular statistical model.

A new model describing the retention in temperature gradient interaction chromatography of polymers is developed. The model predicts that polymers might elute in temperature gradient interaction chromatography in either an increasing or decreasing order or even nearly independent of molar mass, depending on the rate of the temperature increase relative to the flow rate. This is in contrast to solvent gradient elution, where polymers elute either in order of increasing molar mass or molar mass independent.

Electrical memory characteristics of a nondoped pi-conjugated polymer bearing carbazole moieties.

Poly[bis(9H-carbazole-9-ethyl)dipropargylmalonate] (PCzDPM) is a novel pi-conjugated polymer bearing carbazole moieties that has been synthesized by polymerization of bis(9H-carbazole-9-ethyl)dipropargylmalonate with the aid of molybdenum chloride solution as the catalyst. This polymer is thermally stable up to 255 degrees C under a nitrogen atmosphere and 230 degrees C in air ambient; its glass-transition temperature is 147 or 128 degrees C, depending on the polymer chain conformation (helical or planar structure). The charge-transport characteristics of PCzDPM in nanometer-scaled thin films were studied as a function of temperature and film thickness.

Self-assembled monolayer as a pre-concentrating receptor for selective serotonin sensing.

We describe a novel medium, a captopril/thiophenol (Capt/TP) mixed self-assembled monolayer (SAM) formed on gold, for selectively pre-concentrating serotonin (5-hydroxytryptamine, 5-HT). The 5-HT molecules were shown to be selectively captured via formation of a strong complex, providing anodic stripping currents upon anodic scan or drastic increases in charge-transfer resistances for a redox probe, Fe(CN)(6)(3-/4-) pair, due to their blocking effects. The 5-HT molecules thus collected were subsequently detected by anodic stripping differential pulse voltammetry (ASDPV) or electrochemical impedance spectroscopy (EIS).

Effect of film thickness on the phase behaviors of diblock copolymer thin film.

A phase diagram was constructed for a polystyrene-block-polyisoprene (PS-b-PI, M(W) = 32 700, f(PI) = 0.670) in thin films on Si wafer as a function of film thickness over the range of 150-2410 nm (7-107L(0) (L(0): domain spacing)). The PS-b-PI exhibits a variety of ordered phases from hexagonally perforated lamellar (HPL) via double gyroid (DG) to hexagonally packed cylinder (HEX) before going to the disordered (DIS) phase upon heating.