Hydrothermal processing of polyamide 6 (PA6) with the presence of lanthanum chloride (LaCl₃) was studied in the temperature region from 160 °C to 250 °C. PA6 will be dissolved in the superheated water when temperature is above 160 °C. And as PA6 is dissolved, hydrolysis will happen, which makes PA6 chains degrade. By adding LaCl₃ in the hydrothermal environment, the PA6 hydrolysis will intensify, especially when the hydrothermal temperature is higher than 200 °C. When the hydrothermal system cools down, the hydrolyzed PA6 segments will crystallize from the solution or remain dissolved in the solution depending on molecular weight. In addition, the hydrolyzed compound of LaCl₃ would affect the crystallization of PA6 segments with proper size, and γ phase would be presented.

Two novel decyloxyphenylquinoxaline-based donor-acceptor (D-A) electroactive monomers bearing dialkoxythiophene as the donor unit are synthesized using Stille coupling reaction. The corresponding polymers, poly[2,3- bis(4-decyloxyphenyl)-5,8-bis(3,4-dimethoxylthiophen-2-yl)quinoxaline] (P1) and poly[2,3-bis(4-decyloxyphenyl)-5,8- bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)quinoxaline] (P2), are directly deposited onto the working electrode surface by electropolymerization. All materials were characterized by nuclear magnetic resonance (NMR), mass spectrometry (MS), scanning electron microscopy (SEM), cyclic voltammetry (CV), ultraviolet-visible absorption spectrometry (UV-Vis) and spectro-electrochemical measurements. Electrochemical studies demonstrate that both polymers are capable of showing both reasonable n- and p-doping processes, and advanced long-term switching stabilities. 3,4-Ethylenedioxythiophene substituted for 3,4-dimethoxythiophene as a donor unit, which enhances the conjugated double-bond character of the conducting polymer, thus leading to a lower electronic band-gap. Likewise, the neutral state color of the synthesized polymer tuned from blue to blue-green corresponding to the red shift of the maximum absorption wavelengths in the visible region. In addition, kinetics study of P1 revealed 42% (595 nm), 30% (839 nm) and 69% (1500 nm) transmittance changes (ΔT%), while P2 exhibited 32% (740 nm), 71% (2000 nm) at the dominant wavelengths. It was also observed that both films could switch quickly between the neutral state and oxidation state, with the response time less than 1 s both in visible and near infrared regions.

The aggregation behavior of cyclic rod-coil (RC) diblock copolymers in dilute solutions is investigated through dissipative particle dynamics simulation. By varying the rod length and coil length, cyclic RC copolymers in selective solvents exhibit various morphologies, including spherical micelle, vesicle, bilayer disc, and ribbon bundle structure. Compared with the equivalent linear RC copolymer, only spherical micelle and barrel bundle phase are observed. Rod length is the major factor that controls the liquid-crystalline behavior of RC copolymer systems, while the coil length has a secondary effect on the aggregate morphology. The size of rod bundle varies with the coil length, especially for the end-toend ribbon bundle and side-by-side barrel bundle, which are assembled by cyclic and linear RC copolymer solutions. This finding indicates that the ribbon bundle or nanofiber-like structure in cyclic RC copolymers can be obtained by controlling the rod length and coil length, and thus the optical and electrical properties of RC copolymer would be further controlled and optimized. Results illustrate that cyclization of a linear RC copolymer induces remarkable differences in the rod arrangement and aggregation behavior, thereby indicating the competition between interfacial energy, rod orientational entropy, coil stretching entropy, and packing constraints.

Reactivity ratio is a traditional parameter quantifying the reaction kinetics in copolymerization, which is important for potentially controlling microstructures of polymers and guiding the copolymerization process. Our recent experiments using tube-NMR technique enable us to in situ monitor the concentration profiles of the co-monomers during the anionic copolymerization process. This motivates us to revisit the Mayo-Lewis (ML) equation, which is the basis for derivation of reactivity ratio and has been extensively utilized in addition copolymerization. We found that although an explicit ML expression is desirable for ease of calculation and correlation with experimental data, it fails in our anionic copolymerization experiment as well as some data available in the literature. The origin is ascribed to the validity of the steady state assumption which is essential in the ML equation. This assumption can be released in anionic copolymerization and replaced by the fact that the overall concentration of the living chain ends keeps constant throughout the copolymerization. Alternative numerical method has been utilized to obtain the rate constants and consequently the reactivity ratios. Our work suggests that the ML equation should be applied with caution.

This report presents a detailed density functional theory (DFT) study on the difference in regioselectivity for the copolymerization reactions of styrene oxide versus propylene oxide with CO₂ utilizing binary (salen)cobalt(III) catalyst systems. This study focuses on the discrepancy of regioselective ring-opening of two terminal epoxides during the copolymerization with CO₂. It was found that the nucleophilic ring-opening of styrene oxide occurred predominantly at the methine C_a―O bond due to the election delocalization of phenyl group to stabilize the transition state for the methine C―O bond cleavage.

A two-stage transition upon crossing the glass transition of polystyrene with increasing temperature was precisely determined and interpreted by using solid-state nuclear magnetic resonance (SSNMR), ¹H-¹H dipolar couplings based double quantum-filtered (DQF) and dipolar filter (DF) experiments and ¹³C chemical shift anisotropy (CSA) based centerband-only detection of exchange (CODEX) experiment are used to fully characterize the time scale of molecular motions during the glass transition. While differential scanning calorimetry (DSC) and CODEX experiment predicted the first stage of glass transiton, DQF and DF experiments provided the evidence for the second stage transition during which the time scale of molecular motions changed from very slow (t > ms) to very fast (t < μs). The first stage of glass transition begins with the occurrence of remarkable slow re-orientation motions of the polymer backbone segments and ends when the degree of slow motion reaches maximum. The onset and endpoint of the conventional calorimetric glass transition of polystyrene can be quantitatively determined at the molecular level by SSNMR. In the second stage, a subsequent dramatic transition associated with the melting of the glassy components was observed. In this stage liquid-like NMR signals appeared and rapidly increased in intensity after a characteristic temperature T_f (~1.1T_g). The signals associated with the glassy components completely disappeared at another characteristic temperature T_c (~1.2T_g).

The viscoelastic properties of synthetic polyisoprenes (PI) reinforced by white carbon black (WCB) have been investigated and compared with WCB reinforced natural rubber (NR), including cure characteristics, physio-mechanical and dynamic mechanical properties. Compared with NR, PI loaded with the same amount of WCB (PI/WCB) exhibited shorter scorch time and optimal cure time, indicating that WCB fillers are comparatively easier to conjugate with PI. The tensile strength and elongation at break decreased with WCB filling in both PI and NR vulcanizates. The hardness of the rubber vulcanizates increased with the WCB filling in the rubber matrix. PI/WCB blends exhibited smaller hardness data, lower tensile strength, as well as lower elongation at break and tensile stress. Increasing the amount of WCB in rubber matrix induced the Payne effect. However, the Payne effect is much more obvious for the PI/WCB system, and PI/WCB also displayed higher storage modulus whereas lower loss modulus and loss tangent than NR/WCB, which could all be attributed to the poor dispersibilities of WCB in the PI matrix.

Electroactive shape memory composites were synthesized using polybutadiene epoxy (PBEP) and bisphenol A type cyanate ester (BACE) filled with different contents of carbon black (CB). Dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), electrical performance and electroactive shape memory behavior were systematically investigated. It is found that the volume resistivity decreased due to excellent electrical conductivity of CB, in turn resulting in good electroactive shape memory properties. The content of CB and applied voltage had significant influence on electroactive shape memory effect of developed BACE/PBEP/CB composites. Shape recovery can be observed within a few seconds with the CB content of 5 wt% and voltage of 60 V. Shape recovery time decreased with increasing content of CB and voltage. The infrared thermometer revealed that the temperature rises above the glass transition temperature faster with the increase of voltage and the decrease of resistance.

In this work, monodisperse giant polymersomes are fabricated by dewetting of water-in-oil-in-water double emulsion droplets which are assembled by amphiphilic block copolymer molecules in a microfluidic device. The dewetting process can be tuned by solvation between solvent and amphiphilic block copolymer to get polymersomes with controllable morphology. Good solvent (chloroform and toluene) hinders dewetting process of double emulsion droplets and gets acornlike polymersomes or patched polymersomes. On the other hand, poor solvent (hexane) accelerates the dewetting process and achieves complete separation of inner water phase from oil phase to form complete bilayer polymersomes. In addition, twin polymersomes with bilayer membrane structure are formed by this facile method. The formation mechanism for different polymersomes is discussed in detail.

Poly(methyl methacrylate) (PMMA) based ionomers with different lanthanum (La(III)) contents (PMMA-XLa) synthesized by free radical solution polymerization were applied to poly(vinyl chloride) (PVC) resins as a kind of multifunctional aids, and their performances were evaluated by measuring the static stability time, initial discoloration, transparency, fusion behavior and tensile strength of the modified PVC. The ionomers with proper lanthanum (La(III)) contents show a better thermal stability efficiency in comparison with traditional stabilizer lanthanum stearate. Meantime, they can accelerate PVC plasticization more efficiently than PMMA. The rigid PVC products stabilized with the ionomers present good transparency and enhanced tensile strength.

Novel random copolymers for optimizing the morphology of the active layer for high performance organic photovoltaic devices have been demonstrated. Three ternary random copolymers PTBDTDPPSiCN(3/7), PTBDTDPPSiCN(5/5), PTBDTDPPSiCN(7/3) were prepared by polymerization of electron-donating thienyl-substituted benzodithiophene (TBDT) with 2,5-bis[8-(1,1,3,3,5,5,5-heptamethyltrisiloxane-3-yl)octly]-pyrrolo[3,4-c]pyrrole-1,4-dione (DPPSi) and 2,5-dio[5-(5-cyano-5,5-dimethyl-pentyl)]-3,6-dithiophen-2-yl-pyrrolo[3,4-c]pyrrole-1,4-dione (DPPCN) of different ratios. The DPPCN block can well-tune the light absorption and molecular packing, while the DPPSi block is in favor of enhancing the charge mobility. And the formation of organic Si―O―Si networks is beneficial to stabilize the morphology of the active layer. These new copolymers have narrow bandgaps and broaden visible light absorption from 500 nm to 1000 nm. Careful balance of the contents of the trimethoxysilyl group and the cyano group can well-tune the surface energy and morphology of the copolymers. Incorporation of these novel copolymers as additives into the blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₀-butyric acid methyl ester (PC₆₁BM) is found to effectively broaden the light absorption, improve the compatibility and morphology of the active layer. As a result, some devices with certain ratios of these copolymers as additives achieve the enhanced efficiency compared with the device based on pristine P3HT:PC₆₁BM.

A general pre-processing procedure of the measured SAXS patterns for reducing the effect of beam stop and beam stop holder is described. A proper method for automatically choosing the regularization parameter is implemented. The method works out on the two-dimensional SAXS patterns. After deblurring, the corresponding two-dimensional patterns will be converted into one-dimensional integrated intensity distribution curves. We tested the program using both calculated artificial data and real experimental data such as polystyrene and poly(methyl methacrylate) latices. The deblurred results are satisfactory showing the effectiveness of the method. The deblurring process of a typical two-dimensional SAXS pattern using the Matlab based program can be completed in few seconds on normal personal computers.

Oriented thin films of P3HT were obtained by a friction-transfer technique. The morphology and structure of the film were studied by means of optical microscopy, atomic force microscopy and transmission electron microscopy. Optical microscopy observation indicates that large size well-ordered P3HT thin films can be produced by a friction-transfer technique. Highly ordered lamellae were observed in P3HT friction-transferred films by electron microscopy. Electron diffraction results confirm the existence of high orientation with the a- and c-axes of P3HT crystals aligned in the film plane while the c-axis parallel to the friction-transfer direction. The atomic force microscopy observation of the as-prepared P3HT thin film shows, however, a featureless top surface morphology, indicating the structure inhomogeneity of the obtained film. To get highly oriented P3HT thin films with homogenous structure, high temperature annealing, solvent vapor annealing and self-seeding recrystallization of the friction-transferred film were performed. It is confirmed that solvent vapor annealing and self-seeding recrystallization methods are efficient in improving the surface morphology and structure of the frictiontransferred P3HT thin film. Highly oriented P3HT films with unique structure can be obtained through friction-transfer with subsequent solvent vapor annealing and self-seeding recrystallization.