Asymmetric epoxidation, Michael addition, and triple cascade reaction using polymer-supported prolinol-based auxiliaries

The applicability of polymer-supported diphenylprolinol derivatives in directing either asymmetric epoxidation or Michael addition of suitable α,β-unsaturated substrates has been assessed. Epoxidation of cinnamaldehyde in the solid state give poorer yields and stereoselectivities than in the solution-phase systems. In contrast Michael additions of several aldehyde enolates to 2-nitro-1-arylalkenes gave results that approached or surpassed those in solution, and could be extended successfully to a three-component Michael/Michael/aldol cascade process. Comparisons of the results of pendant- versus crosslinked functionalized resins in these applications were revealing of the benefits and limitations of each, as were attempts to reuse the polymer-bound auxiliaries.     

Crosslinking poly[1-(trimethylsilyl)-1-propyne] and its effect on physical stability

Poly[1-(trimethylsilyl)-1-propyne] (PTMSP) has been crosslinked using 3,3′-diazidodiphenylsulfone to improve its solvent resistance and physical stability. This study reports the influence of crosslinking on N₂, O₂ and CH₄ gas permeabilities and fractional free volume (FFV) as a function of time. Crosslinking PTMSP renders it insoluble even in excellent solvents for the uncrosslinked polymer. The gas permeability and FFV of uncrosslinked and crosslinked PTMSP decreased over time, so crosslinking PTMSP does not arrest physical aging. The addition of 10 wt.% polysiloxysilsesquioxanes (POSS) nanoparticles decreased the permeability of PTMSP by 55%, and the permeability and FFV values were stable over time for PTMSP films containing 10 wt.% POSS nanoparticles. The permeability of PTMSP at a given FFV was greater than that of other substituted polyacetylenes, polysulfones or polycarbonates, which is consistent with differences in the arrangement of free volume in these polymers, as probed by positron annihilation lifetime spectroscopy (PALS). Ellipsometry was used to characterize physical aging of thin (400 nm) uncrosslinked and crosslinked PTMSP films supported on silicon wafers. The ellipsometry results showed that crosslinking does not markedly slow physical aging of thin PTMSP films.     

Improving anion exchange membranes for DMAFCs by inter-crosslinking CPPO/BPPO blends

New anion exchange membranes are prepared by heat-treating the blend base membranes of chloroacetylated poly(2,6-dimethyl-1,4-phenyleneoxide)(CPPO)/bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO). A partially inter-crosslinked structure can be formed therein via a Friedel–Crafts reaction without adding any crosslinking reagent or catalyst. FT-IR and NMR analyses are used to confirm this inter-crosslinking structure and quantify the crosslinking distribution. Physical properties, such as toughness and thermal stability, are enhanced remarkably due to this heat treatment. Furthermore, the final membranes exhibit a high hydroxyl conductivity (up to 0.032 S cm⁻¹ at 25 °C) and extremely low methanol permeability (1.26–1.04 × 10⁻⁷ cm² s⁻¹), which match the requirements for application in low temperature direct methanol alkaline fuel cells (DMAFCs).     

Poly(Ethylene Piperidinium)s for Anion Exchange Membranes

The lack of anion exchange membranes (AEMs) that possess both high hydroxide conductivity and stable mechanical and chemical properties poses a major challenge to the development of high-performance fuel cells. Improving one side of the balance between conductivity and stability usually means sacrificing the other. Herein, we used facile, high-yield chemical reactions to design and synthesize a piperidinium polymer with a polyethylene backbone for AEM fuel cell applications. To improve the performance, we introduced ionic crosslinking into high-cationic-ratio AEMs to suppress high water uptake and swelling while further improving the hydroxide conductivity. Remarkably, PEP80-20PS achieved a hydroxide conductivity of 354.3 mS cm⁻¹ at 80 °C while remaining mechanically stable. Compared with the base polymer PEP80, the water uptake of PEP80-20PS decreased by 69 % from 813 % to 350 %, and the swelling decreased substantially by 85 % from 350.0 % to 50.2 % at 80 °C. PEP80-20PS also showed excellent alkaline stability, 84.7 % remained after 35 days of treatment with an aqueous KOH solution. The chemical design in this study represents a significant advancement toward the development of simultaneously highly stable and conductive AEMs for fuel cell applications.     

Size-Selective Ionic Crosslinking Provides Stretchable Mixed Ionic–Electronic Conductors

Mechanically compliant conductors are of utmost importance for the emerging fields of soft electronics and robotics. However, the development of intrinsically deformable organic conductors remains a challenge due to the trade-off between mechanical performance and charge mobility. In this study, we report a solution to this issue based on size-selective ionic crosslinking. This rationally designed crosslinking mediated by length-regulated oligo(ethylene glycol) pendant groups and metal ions simultaneously improved the softness and toughness and ensured excellent mixed ionic–electronic conductivity in poly(3,4-ethylenedioxythiophene):polystyrene sulfonate composite materials. Moreover, the added ions remarkably promoted accumulation of charge carriers in response to temperature gradient, thus offering a viable approach to stretchable thermoelectric generators with enhanced stability against humidity.     

Synthesis and characterization of crosslinkable polyimides

A series of copolyimides were prepared from benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA) and various aromatic diamines which contain a fluorenyl group and/or alkyl substituents in ortho position to the amine groups. The effect of the chemical composition on the glass transition temperature (T_g), thermal stability as well as on the dielectric constant of these polymers was studied. High T_g polymers (T_g ranging from 260 °C to 370 °C), withstanding temperatures as high as 400 °C for 10 h and having a low dielectric constant (from 2.6 to 3.1) were successfully synthesized. All these polymers were able to crosslink under UV or thermal treatments.     

GAP黏合剂体系交联网络结构研究

为改善聚叠氮缩水甘油醚(GAP)黏合剂体系的网络结构,分别考察了GAP与二官能度的甲苯二异氰酸酯(TDI)或异佛尔酮二异氰酸酯(IPDI)预聚、缩二脲多异氰酸酯(N-100)与二官能度固化剂的种类和配比对GAP弹性体力学性能、网络结构参数、网络结构完整性以及拉伸断面形貌的影响.结果表明,将GAP与TDI预聚可提高体系交联网络结构的完整性,同时提高弹性体的断裂延伸率和最大拉伸强度.适量加入二官能度异氰酸酯能改善体系的网络结构完整性,由于预聚体中TDI与IPDI结构和反应活性的差别,GAP/TDI/N-100弹性体在N-100与TDI质量比为7∶3时体系网络结构最完整,而GAP/IPDI/N-100弹性体在N-100与IPDI质量比为5∶5时体系网络结构最完整;在相同的N-100含量下GAP/IPDI/N-100体系比GAP/TDI/N-100体系强度高,延伸率略低.随着N-100含量的减少,GAP/TDI/N-100体系最大拉伸强度(δ_m)从0.66 MPa降低到0.32 MPa,断裂延伸率(ε_b)从104.6%提高到506.3%;GAP/IPDI/N-100体系强度在W(N-100)∶W(IPDI)=7∶3时达到最大值0.69 MPa,断裂延伸率从103.2%提高到391.4%.扫描电镜(SEM)结果表明,弹性体的拉伸断面形貌与弹性体的网络结构完整性和力学性能具有良好的对应关系.     

分散聚合制备羧基化单分散聚苯乙烯交联微球

以苯乙烯(St)、丙烯酸(AA)为单体,二乙烯基苯(DVB)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用分散聚合和交联剂后滴加法合成了单分散羧基化交联聚苯乙烯微球。通过傅立叶红外光谱(FT-TR),扫描电子显微镜(SEM),激光粒度及Zeta电位分析仪等对微球结构进行了表征。结果表明,引发剂、分散剂用量和交联剂的加入方式对微球粒径及单分散性影响显著,当St用量为15%(wt)、DVB用量为1%(wt)、AA用量为1%(wt)、AIBN用量为2%(wt)、PVP用量为6%(wt)时所制备的微球具有良好的单分散性和球形形貌,粒径达到4μm,且微球表面带负电荷。     

Accelerated water tree aging of crosslinked polyethylene with different degrees of crosslinking

The effect of crosslinking degree on accelerated water tree aging in crosslinked polyethylene (XLPE) was investigated. The peroxide-crosslinking process was adopted to make XLPE specimens with different degrees of crosslinking by controlling the doping content of dicumyl peroxide (DCP) in low-density polyethylene (LDPE). The water blade electrode method was applied to accelerate water-tree aging of LDPE and XLPE specimens (hereafter referred to as the specimens), and their morphologies were observed using an optical microscope. The variation of crystalline morphology and anti-cracking performance of the amorphous region in the specimens were analyzed by differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and an electronic universal testing machine. Based on the experimental results, it was found that XLPE has great anti-water-treeing performance compared to LDPE. In addition, the higher the crosslinking degree, the better the anti-water-treeing performance. Although crystal growth is inhibited due to the crosslinking reaction, the density of tie molecular chains greatly increases in the amorphous region and exhibits significantly tighter lamellar stacking, which is the reason that water tree growth is restrained with increasing crosslinking degree.     

Thermal properties of poly(methyl methacrylate-co-butyl acrylate-co-acrylic acid) modified with divinyl benzene and vinyltrimethoxysilane

The effect of butyl acrylate (BA), divinyl benzene (DVB) and vinyltrimethoxysilane (TMVS) on the thermal properties of poly(methyl methacrylate-co-butyl acrylate-co-acrylic acid) was investigated. Glass transition temperature (T_g), melting temperature (T_m) and specific heat capacity of the copolymers were investigated using Differential Scanning Calorimetry. Thermal stability of the copolymers which is associated with the degradation temperature (T_d) was studied by Thermogravimetric Analysis. Polyacrylates with T_g ranges between -19°Cand 19°C were obtained. With the incorporation of >7 wt% of DVB, the T_g of the copolymer increases from about ?17°C to ?10°C even though they have not undergone UV irradiation. Gel content results prove that crosslinking has occurred in the copolymers. With increasing amount of TMVS from 0 wt% to 7 wt%, the T_m of the copolymers prepared at acidic pH is about 40-60°C higher than that at the alkaline pH. However, the addition of TMVS gives no significant effect to the T_g and T_d of the copolymer films. The thermal stability of the copolymer has improved with increasing amount of BA and DVB, with DVB being more effective. The highest T_d of 425°C with 8% of DVB has been obtained. Consequently, a polyacrylate copolymer with a T_g of about ?13°C, a T_m of 170 °C and a T_d of about 424°C has been successfully synthesized. Hence, the soft polyacrylate with its relatively high T_m and T_d could serve as a superb material especially to be applied in the areas that require high melting temperature and good thermal stability.