Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties

A new kind of nanocomposite (NC) hydrogel with Na‐montmorillonite (MMT) is presented in this article. The NC hydrogels were synthesized by free radical copolymerization of acrylamide and (3‐acrylamidopropyl) trimethylammonium chloride (ATC) in the presence of MMT and N,N′‐methylene‐bis‐acrylamide used as chemical cross‐linker. Due to the cation‐exchange reaction between MMT and ATC (cationic monomer) during the synthesis of NC hydrogels, MMT platelets were considered chemical “plane” cross‐linkers, different from “point” cross‐linkers. With increasing amount of MMT, the crosslinking degree enhanced, causing a decrease of the swelling degree at equilibrium. Investigations of mechanical properties indicated that NC hydrogels exhibited enhanced strength and toughness, which resulted from chemical interaction between exfoliated MMT platelets and polymer chains in hydrogels. Dynamic shear measurements showed that both storage modulus and loss modulus increased with increasing MMT content. The idea described here provided a new route to prepare hydrogels with high mechanical properties by using alternative natural Na‐MMT. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1020–1026     

基于一维数据逐段均匀条件下的参考分布研究

聚类分析中一个重要的问题是估计聚类数,GS方法通过参考分布对聚类数进行合理的估计,解决了其他聚类方法无法对应分为一类的数据进行分类的问题,具有更好的分类效果;目前已通过理论证明得出,在分布为对数凹且一维情况下,GS方法的参考分布为均匀分布,而有关其在其他条件下的参考分布研究较少;针对这一情况,提出解决一维且逐段均匀条件下GS方法的参考分布问题,以类内平方和为评价标准,通过拉格朗日乘数法求解与问题等价的优化问题,理论证出条件下总体均匀分布是类内平方和最大的情况,进而得出对于一维数据,逐段均匀条件下的参考分布仍为均匀分布的结论。     

Formation of porous polymer morphology by microsyneresis during divinylbenzene polymerization

This article describes the investigation of the importance of various reaction conditions on microsyneretic pore formation during polymerization of divinylbenzene (DVB) under so‐called “solvothermal” conditions. To induce microsyneretic pore formation, the most important parameter is an unusually high dilution of monomers with a “good” porogen solvating the polymer chains. High dilution and solvation of the growing poly(DVB) chains promote the prolongation of the polymer chains rather than their interconnection by crosslinking. Consequently, when the polymer gel density reaches the point where syneresis starts, the polymer network is geometrically too extensive to be broken up into precipitating entities and, instead, porogen droplets are formed within the continuous polymer gel. The pore geometry created by microsyneresis offers high surface area in wide mesopores and hence, high capacity for supporting functional groups or reactions with much better accessibility than narrow pores between polymer microspheres produced by macrosyneresis in conventional styrenic polymer supports. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 774–781     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry

Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO₂/N₂ selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557     

Thermally Crosslinkable and Chemically Modifiable Aromatic Polyesters Possessing Pendant Propargyloxy Groups

New aromatic (co)polyesters containing pendant propargyloxy groups were synthesized by phase transfer‐catalyzed interfacial polycondensation of 5‐(propargyloxy)isophthaloyl chloride (P‐IPC) and various compositions of P‐IPC and isophthaloyl chloride with bisphenol A. FTIR and NMR spectroscopic data, respectively, revealed successful incorporation of pendant propargyloxy groups into (co)polyesters and formation of (co)polyesters with desired compositions. (Co)polyesters exhibited good solubility in common organic solvents such as chloroform, dichloromethane, and tetrahydrofuran and could be cast into transparent, flexible, and tough films from chloroform solution. Inherent viscosities and number average molecular weights of (co)polyesters were in the range 0.77–1.33 dL/g and 43,600–118,000 g/mol, respectively, indicating the achievement of reasonably high‐molecular weights. The 10% weight loss temperatures of (co)polyesters were in the range 390–420 °C, demonstrating their good thermal stability. (Co)polyesters exhibited T_g in the range 146–170 °C and T_g values decreased with increase in mol % incorporation of P‐IPC. The study of non‐isothermal curing by DSC indicated thermal crosslinking of (co)polyesters via propargyloxy groups. The utility of pendant propargyloxy group was demonstrated by post‐modification of the selected copolyester with 1‐(4‐azidobutyl)pyrene, 9‐(azidomethyl)anthracene, and azido‐terminated poly(ethyleneglycol) monomethyl ether via copper(I)‐catalyzed Huisgen 1,3‐dipolar cycloaddition reaction. FTIR and ¹H NMR spectra confirmed that click reaction was quantitative. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 588–597     

Crosslinking network of bio‐based bis‐functional epoxides derived from trans‐limonene oxide

The thiol‐ene reaction between trans‐limonene oxide (trans‐LO) and ethane‐1,2‐dithiol in the presence of triethylborane affords a bio‐based bis‐functional epoxide (bis‐trans‐LO). The crosslinking reaction of bis‐trans‐LO with branched polyethyleneimine (BPEI; M_n = 600; BPEI₆₀₀) at a feed ratio of bis‐trans‐LO/BPEI₆₀₀ = 57/43 (wt/wt) yields the corresponding network polymer with T_d10 (10% thermal decomposition temperature) of 304.7 °C in 98% yield. In contrast, negligible amounts of network polymer are obtained by the reaction of bis‐LO (bis‐functional epoxide derived from cis and trans‐LO) and BPEI₆₀₀ regardless of the feed ratio. The mechanical strengths as measured by direct tensile tests of the network polymers derived from bis‐trans‐LO and BPEI_600,1800 (M_n = 600 and 1800) were approximately 16 and 11 times higher than that of bis‐LO and BPEI₁₈₀₀, respectively. The tensile shear strengths of the metal‐to‐metal adhesive bonds induced by bis‐trans‐LO and BPEI_600,1800 were 9.5 and 14.1 MPa, respectively. DMA revealed that the storage modulus of the network polymer derived from bis‐trans‐LO and BPEI₁₈₀₀ in the rubber region was higher than that of the material prepared from bis‐LO and BPEI₁₈₀₀, indicating higher crosslink density of the bis‐trans‐LO/BPEI₁₈₀₀ system. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2466–2473     

Diastereoselective Cyclobutenol Synthesis: A Heterogeneous Palladium-Catalyzed Oxidative Carbocyclization-Borylation of Enallenols

A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.     

Computation of limit periodic continued fractions. A survey

Over the last 20 years a large number of algorithms has been published to improve the speed and domain of convergence of continued fractions. In this survey we show that these algorithms are strongly related. Actually, they essentially boil down to two main principles.We also prove some results on asymptotic expansions of tail values of limit periodic continued fractions.Dedicated to Luigi Gatteschi on his seventieth birthdayThis research was partially supported by The Norwegian Research Council and by the HMC project ROLLS, under contract CHRX-CT93-0416.     

HF-Ⅰ新型改性酚醛树脂研制及性能评价

以苯酚、甲醛、环氧树脂、聚乙烯醇等为原料在酸性催化条件下 ,研制成一种新型环氧改性酚醛树脂 ,通过性能评价并从砂轮、切割片的应用表明。该粘合剂粘结性能、强度、韧性均达到国内同类产品先进水平 ,制做的砂轮、切割片性能优良。