Yixian Wu

ABA type liquid crystalline triblock copolymers by combination of living cationic polymerizaition and ATRP: synthesis and self-assembly

Lamellar and hexagonal-coil-cylinder self-assembled structures of ABA type triblock copolymers containing mesogen-jacketed liquid crystalline polymer (MJLCP) as the rod block, and polyisobutylene (PIB) as the coil middle block were discovered. PIB was synthesized by living cationic polymerization of isobutylene initiated by 1,4-bis(2-chloro-2-propyl)benzene (p-DCC), and then a small amount of styrene was introduced at the end of the PIB chains to form the difunctional PIB macroinitiator with -CH2CH(C6H5)Cl end groups for further atom transfer radical polymerization (ATRP). 2,5-Bis[(4-methoxyphenyl)oxycarbonyl]styrene (MPCS) was block-copolymerized from the difunctional PIB macroinitiators at 110 °C. The molecular characterization of the triblock copolymers was performed with 1H NMR, 13C NMR, gel permeation chromatography (GPC), and thermogravimetric analysis (TGA). Their phase structures and transitions were investigated by differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), and polarized optical microscopy experiments. It was demonstrated that the triblock copolymers formed lamellar structures at moderate rod fractions and hexagonal coil cylinders in the rod matrix at high rod fractions. The d-spacing of the microphase-separated structures was influenced by the liquid crystalline phase of rod-like PMPCS blocks.

Cross-Linked Quaternized Poly(styrene-b-(ethylene-co-butylene)-b-styrene) for Anion Exchange Membrane: Synthesis, Characterization and Properties

Poly(styrene-b-(ethylene-co-butylene)-b-styrene) triblock copolymer (SEBS) was selected for functionalization and cross-linking reaction to prepare the anion exchange membrane. The cross-linked quaternized SEBS (QSEBS-Cn) membranes were synthesized by simultaneous of quaternization and cross-linking of chloromethylated SEBS with α,ω-difunctional tertiary amines. The spacer groups of (-CH2-)n in diamines did affect the functionalization, micromorphology and properties of the resulting QSEBS-Cn membranes. The ionic conductivity of QSEBS-Cn membranes greatly increased and methanol resistance slightly decreased with increasing the length of spacer groups in the cross-linked structures from -(CH2)- to -(CH2)6-. Compared to the un-cross-linked QSEBS, the QSEBS-Cn membranes behaved much higher mechanical property, service temperature, chemical stability and thermal stability. Moreover, the hybrid composite membrane of QSEBS-C6 with 0.5% of graphene oxide could also be in situ prepared. This hybrid membrane had both relatively high ionic conductivity of 2.0 × 10(-2) S·cm(-1) and high selectivity of 7.6 × 10(4) S·s·cm(-3) at 60 °C due to its low methanol permeability.

Development of a cross-linked quaternized poly(styrene-b-isobutylene-b-styrene)/graphene oxide composite anion exchange membrane for direct alkaline methanol fuel cell application

A cross-linked quaternized poly(styrene-b-isobutylene-b-styrene)/graphene oxide composite anion exchange membrane has been prepared via intercalation of organo-modified graphene oxide (GOA), and characterized as a promising anion exchange membrane for direct alkaline methanol fuel cell application. In order to further increase the ionic conductivity of the composite membrane, quaternized GOA (GOAN) was introduced into QSIBS. Compared with the Nafion® membrane, the new anion exchange membranes show a comparable ionic conductivity (1.95 × 10−2 S cm−1) but much lower methanol permeability (1.7 × 10−7 cm2 s−1). The QSIBS/0047OAN-0.50 wt% composite membrane has the highest selectivity, which is about 12 times higher than that of the Nafion 115 membrane. The promising performance is attributed to two factors: one is the barrier effect of the quaternized octadecylamine-functionalized graphene oxide sheets, which is unfavourable for methanol crossover; and the other is the presence of interconnected ionic transportation channels between the incorporated modified graphene oxide and polymer, which is favourable for ionic transport.

SYNTHESIS OF POLYISOBUTYLENE WITH SEC-ARYLAMINO TERMINAL GROUP BY COMBINATION OF CATIONIC POLYMERIZATION WITH ALKYLATION

The highly reactive polyisobutylenes (PIBs) with α-double bonds (87.5 mol%) or tert-chloro (tert-Cl) groups (95 mol%) could be prepared via the cationic polymerization of isobutylene (IB) coinitiated by BF3 or TiCl4 respectively. The Friedel-Crafts alkylation of diphenylamine (DPA) with the highly reactive PIB with α-double bonds was further conducted under different conditions, such as at different alkylation temperature, in the mixed solvents of CH2Cl2/n-hexane with different solvent polarity and at DPA concentration ([DPA]). The resultant PIBs with sec-arylamino terminal groups were characterized by GPC with RI/UV dual detectors and 1H-NMR spectrum. The experimental results indicated that alkylation efficiency increased with increases in reaction temperature, solvent polarity and [DPA]. The 77 mol% of sec-arylamino terminated PIBs could be obtained in 10/90 (V/V) mixture of nHex/CH2Cl2 with [DPA]/[PIB] of 3.0 at 60°C for 45 h. Moreover, the alkylation of DPA with highly reactive PIBs with mainly tert-C...

SYNTHESIS OF POLY(GLUTAMIC ACID- co -ASPARTIC ACID) VIA COMBINATION OF N -CARBOXYANHYDRIDE RING OPENING POLYMERIZATION WITH DEBENZYLATION

The random copolymers of glutamic acid (LG) and aspartic acid (ASP), poly(LG-co-ASP), with designed compositions could be successfully synthesized via combination of N-carboxyanhydride ring opening copolymerization with debenzylation. Ring opening copolymerizations of β-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) and -benzyl-Laspartate N-carboxyanhydride (BLA-NCA) were carried out by using different amines including triethylamine (TEA), diethylamine, n-hexylamine (NHA), triphenylamine, diphenylamine or aniline as initiators. All the 6 amines were highly efficient to get well-defined poly(BLG-co-BLA) copolymers with designed compositions although the polymerizations proceeded via different mechanisms (normal amine mechanism or/and activated monomer mechanism), which are based on chemical structure of amines. The molecular weights of poly(BLG-co-BLA) copolymers could be mediated by both TEA concentration and polymerization time. Then, debenzylation of poly(BLG-co-BLA) copolymers was conducted to prepare the corresponding hydrophilic random copolymers of poly(LG-co-ASP) with α-subunit structure in ASP structural units. The contents of LG structural units in poly(LG-co-ASP) copolymers matched with those of BLG-NCA in NCA-monomer feeds in ring opening copolymerizations initiated by NHA or TEA and were closed to the theoretical line. The diblock copolymer of poly(BLG-b-BLA) could also be synthesized via living NCA ring opening copolymerization by sequential addition of BLGNCA and BLA-NCA.

Real-time Monitoring of Living Cationic Ring-opening Polymerization of THF and Direct Prediction of Equilibrium Molecular Weight of PolyTHF

A convenient real-time monitoring of monomer concentration during living cationic ring-opening polymerizations of tetrahydrofuran (THF) initiated with methyl triflate (MeOTf) has been developed for kinetic investigation and determination of equilibrium monomer concentration ([M]e) via in situ FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance (ATR) immersion probe. The polymerization rate was first order with respect to monomer concentration and initiator concentration from the linear slope of ln([M]0-[M]e)/([M]-[M]e) versus polymerization time at different temperatures in various solvents. [M]e decreased linearly with initial monomer concentration while increased exponentially with increasing polymerization temperature. The equilibrium also strongly depends on solvent polarity and its interaction with monomer. The equilibrium polymerization time (te) decreased with increasing solvent polarity and decreased linearly with increasing [M]0 in three solvents with different slopes to the same point of bulk polymerization in the absence of solvent. Equation of Mn,e = 72.1/(0.14-0.04[M]e) has been established to provide a simple and effective approach for the prediction for the number-average molecular weight of polyTHFs at equilibrium state (Mn,e) in the equilibrium living cationic ring-opening polymerization of THF at 0 °C.

SYNTHESIS AND CHARACTERIZATION OF POLY(L-GLUTAMIC ACID-co-L-ASPARTIC ACID)

Poly(amino acid) has been widely utilized in drug delivery, tissue engineering and biomedical materials. The biomaterials based on poly(glutamic acid) are usually modified via copolymerization with other monomers such as L-aspartic acid to improve the uncontrolled degradation rate. The ring-opening homo- and co-polymerization of γ-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) and β-benzyl-L-aspartate N-carboxyanhydride (BLA-NCA) were carried out in solution by using triethylamine (TEA) as initiator. The BLG-NCA homopolymerization could take place even at -30°C and molecular weight of poly(γ-benzyl-L-glutamate) decreased with increasing polymerization temperature. The BLA-NCA polymerization did not occur at -10°C and was needed to be carried out at 25°C to improve the polymerization. Poly(γ-benzyl-L-glutamate) and poly(β-benzyl-L-aspartate) with unimodal molecular weigh distribution and weight average molecular weight (Mw) of 32100 and 4000 could be obtained at 25°C. The copolymers of γ-benzyl L-glutamate and β-benzyl L-aspartate with unimodal molecular weight distribution and Mw ranging from 5600 to 24600 could be prepared. The useful copolymers of poly(L-glutamic acid-co-L-aspartic acid) were further prepared by removal of benzyl groups.

Multicomponent Thermodynamics of Strain-Induced Polymer Crystallization.

We developed a linear combination of two Florys melting-point theories, one for stretched and the other for solution polymers, to predict the melting point of stretched solution polymers. The dependences of the melting strains on varying temperatures, polymer volume fractions, and solvent qualities were verified by the onset strains of crystallization in our dynamic Monte Carlo simulations of stretched solution polymers under a constant strain rate. In addition, owing to phase separation before crystallization in a poor solvent, calibration of polymer concentration to the polymer-rich phase appears necessary for the verification. Our results set up a preliminary thermodynamic background for the investigation of the multicomponent effect on strain-induced crystallization of polymers in rubbers and gels as well as on shear-induced crystallization of polymers in solutions and blends.

Synthesis of high molecular weight polyisobutylene via cationic polymerization at elevated temperatures

A novel simple but effective initiating system of H2O/AlCl3/veratrole (VE) has been developed to synthesize high molecular weight polyisobutylene (PIB) at elevated temperatures via cationic polymerization of isobutylene (IB) in solvent mixture of hexane/methylene dichloride (n-Hex/CH2Cl2 = 2/1, V/V). VE played very important roles in decreasing cationicity of the growing chain ends, suppressing side reactions of chain transfer and termination during polymerization, leading to production of high molecular weight PIBs. PIBs with high yields, having very high weight-average molecular weight (Mw) of 1117000 and 370000 g/mol could be synthesized with H2O/AlCl3/VE initiating system at VE concentration of 5.4 mmol/L at −80 and −60 °C respectively. Molecular weight of PIB increased remarkably with increasing VE concentration. The reaction order with respect to VE concentration was determined to be −3.52 via FTIR spectroscopy in combination with a diamond tipped attenuated total reflectance (ATR) immersion probe. The negative reaction order of VE was consistent with its retarding effect on IB polymerization by interacting with the propagating species. Molecular weight of PIB decreased with increasing polymerization temperature. The activation energy for polymerization degree (EDP) could be determined to be around −23 kJ/mol when VE concentration was 5.4 mmol/L or 6.4 mmol/L.

Graft copolymer of PVAc-g-PIB by cationic polymerization

The cationic grafting polymerization of isobutylene (IB) from a poly(vinyl acetate) (PVAc) backbone was initiated by the combination of PVAc with titanium tetrachloride (TiCl4) in methylene chloride (CH2Cl2) solution at –65°C. A mixture of IB homopolymer and PVAc grafted with approximately 9.5% (mol) PIB copolymer was formed. 1H- and 13C-NMR spectra confirmed that IB was successfully grafted from the PVAc backbone. PVAc exhibits both initiation and modification behavior. PVAc acts as a macro-initiator in the polymerization to form the graft copolymer. It also plays a role in the homopolymerization of IB initiated by the combination of residual water with TiCl4 and the product PIB with a narrow molecular weight distribution.