Degree of crosslinking and mechanical properties of crosslinked poly(vinyl alcohol) beads for use in solid-phase organic synthesis

The limited swellability in polar media of the commonly used polystyrene/divinylbenzene (PS-DVB) support materials for solid-phase organic synthesis has led to the development of novel, highly swellable hydrophilic gels designed for use in aqueous or polar media. Poly(vinyl alcohol) beads crosslinked with epichlorohydrin (PVA-EP) were prepared by a two-step inverse-suspension polymerization method. While it is known that the morphology of the resulting beads can be controlled by the ratio of EP versus PVA as well as by the pre-crosslinking time, the actual degree of crosslinking of the beads and their mechanical properties remain unknown. It is therefore the purpose of this study to evaluate the actual degree of crosslinking of beads prepared with different quantities of crosslinker in the feed by spectroscopic (Raman, nuclear magnetic resonance) and chemical (functional group loading) methods. The mechanical properties of these swollen PVA-EP beads will be evaluated by single-bead unconfined compression in solvents such as water, N,N-dimethylformamide (DMF), and tetrahydrofuran (THF) and compared to model PS-DVB beads commonly used for solid phase synthesis.     

Transitions of saturated monoacid triglycerides: Modeling conformational change at glycerol during α→β′→β transformation

The glycerol region geometry of modeled saturated monoacid triglycerides was altered by bond rotations and minor angle distortions to convert theoretical α-forms into bent β′- and β-forms. Direct α to β conversion involves lateral disruption of fatty chain packing to generate side-chain character typical of the β-form. Such disruption, which could contribute to fat bloom, allows additional molecular movement and shifts in molecular mechanics energy (MME) that may approximate thermal changes observed by differential scanning calorimetry during α to β transformations. Energy calculations at 100 points throughout each transformation identified plausible conversion routes. A two-stage conversion, α to either of two stereospecific β′-forms bent at glycerol followed by subsequent conversion to β, showed less chain movement and more favorable MME than direct α to β conversion. The preferred path, based on energy profiles of each conversion, involves a β′-D form and rotation of carbonyl to α-carbon bonds in chain #2 and a side chain (chain #3).     

PMMA‐modified divinylester/styrene resins: Phase diagrams and morphologies

Binary and ternary experimental cloud‐point curves (CPCs) for systems formulated with a low molar mass synthesized divinylester (DVE) resin, styrene (St), and poly(methyl methacrylate) (PMMA) were determined. The CPCs results were analyzed with the Flory–Huggins (F‐H) thermodynamic model taking into account the polydispersity of the DVE and PMMA components, to calculate the different binary interaction parameters and their temperature dependences. The St‐DVE system is miscible in all the composition range and down to the crystallization temperature of the St; therefore, the interaction parameter expression reported for a higher molar mass DVE was adapted. The interaction parameters obtained were used to calculate the phase diagrams of the St‐PMMA and the DVE‐PMMA binary systems and that of the St‐DVE‐PMMA ternary system at three different temperatures. Quasiternary phase diagrams show liquid–liquid partial miscibility of the St‐PMMA and DVE‐PMMA pairs. At room temperature, the St‐DVE‐PMMA system is miscible at all compositions. Final morphologies of PMMA‐modified cured St‐DVE materials were generated by polymerization‐induced phase separation (PIPS) mechanism from initial homogeneous mixtures. SEM and TEM micrographs were obtained to analyze the generated final morphologies, which showed a direct correlation with the initial miscibility of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4539–4549, 2006     

相转移催化法合成多聚乙二醇二环氧甘油醚

以多聚乙二醇和环氧氯丙烷为原料合成了多聚乙二醇二环氧甘油醚。NaOH为催化剂,季铵盐为相转移催化剂。结论为:作为催化剂NaOH固体效果优于NaOH溶液;四正丁基硫酸氢铵(TBAS)催化醚化反应效果最佳,GC监测表明,二醚的选择性达98％以上;n(多聚乙二醇):n(环氧氯丙烷):n(NaOH):n(TBAS)= 1:10:7:0．08;反应温度55-60℃;反应时间1．5 h;产率83％。     

纤维素衍生物液晶相转变和织态结构

本文综述了纤维素衍生物液晶态相转变和织态结构。描述了纤维素衍生物从各向同性态向液晶态的转变过程和液晶态的织构特征。讨论了溶液浓度和温度对液晶相织构的影响。探讨了各种因素,如溶剂、取代基含量、外加力场和外加磁场等对液晶相的形成及织态结构的影响。     

相空间重构在语音情感识别中的研究

为了更为全面地表征语音情感状态,弥补线性情感特征参数在刻画不同情感类型上的不足,将相空间重构理论引入语音情感识别中来,通过分析不同情感状态下的混沌特征,提取Kolmogorov熵和关联维作为新的情感特征参数,并结合传统语音特征使用支持向量机（SVM）进行语音情感识别。实验结果表明,通过引入混沌参数,与传统物理特征进行识别的方案相比,准确率有了一定的提高,为语音情感的识别提供了一个新的研究途径。     

美国能源部的浆态床F－T合成技术

浆态床Ｆ－Ｔ合成技术是美国能源部Ｆ－Ｔ合成技术的主要开发项目。本文就浆态相Ｆ－Ｔ合成催化剂的开发、中试示范实验和浆态反应器的化工基础研究作一扼要的介绍。     

Liquid-phase stereoselective thymol hydrogenation over supported nickel catalysts

The stereoselective hydrogenation of thymol was studied in liquid phase over several nickel catalysts, modified by coimpregnation of inorganic compounds containing chlorine. The total activity of all catalysts studied was decreased and was on the same order of magnitude, indicating that chlorine even after reduction remains on the surface and is responsible for the poisoning effects. Such blocking of accessible sites results in similar reaction rates for the catalysts studied. Selectivity and stereoselectivity to menthols and menthones changed significantly. The modifiers could influence the rate of keto-enol transformations, which is thought to be the key selectivity and stereoselectivity governing step.     

Preparations and properties of thermosensitive terpolymers of N‐isopropylacrylamide,sodium 2‐acrylamido‐2‐methyl‐propanesuphonate,and N‐tert‐butylacrylamide

Terpolymers based on N‐isopropylacrylamide, sodium 2‐acrylamido‐2‐methyl‐propanesulfonate, and N‐tert‐butylacrylamide were synthesized by free‐radical copolymerization with 2,2′‐azobisisobutyronitrile as an initiator. The lower critical solution temperatures (LCSTs) of the linear polymer aqueous solutions were determined by the measurement of the transmittance on UV at different temperatures. The influence of the polymer concentration, polymer composition, and ionic strength on the LCSTs of the linear polymers was investigated. The LCST decreased with increases in the hydrophobic monomer N‐tert‐butylacrylamide, polymer concentration, and ionic strength. The phase transition became sharp when the polymer concentration and ionic strength increased. Meanwhile, the crosslinked hydrogels were prepared with the same recipe used for the linear terpolymers, but a crosslinker was added to the reaction system. The swelling ratios of the hydrogels at various temperatures and salt solutions were determined. The hydrogels possessed both high swelling ratios and thermosensitivity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007