添加剂对PVDF相转化过程及膜孔结构的影响

研究了PVP、PEG及LiCl 3种成孔添加剂下PVDF DMAc H2 O 添加剂体系的成膜机理 .无论那种添加剂的铸膜液相转换成膜过程中都存在凝胶分相和液液分相两种相变方式 ,在 30～ 6 0℃时凝胶分相在较低的非溶剂浓度下先于液液分相发生 ,LiCl作为添加剂较PEG、PVP对铸膜液有较强的致凝胶作用 ,成膜过程中凝胶分相段时间依PVP、PEG、LiCl的顺序延长 ,导致液液分相初始分相点处聚合物浓度增大 ,阻止了大孔结构的充分发展 .制得的膜依PVP、PEG、LiCl的顺序有效孔隙率和通量降低 ,结晶度升高 .以LiCl为添加剂制得的膜几乎不改变PVDF膜的疏水性 ,而以PVP或PEG为添加剂的膜隔水压差降低约 2 0kPa .     

聚醚砜溶液流变性的研究

研究了聚醚砜（PES）/二甲基亚砜（DMSO）体系中PES的质量分数、原液温度对流变性的影响和原液中PES的质量分数对粘流活化能的影响,从而得出PES/DMSO体系属于切力变稀流体,非牛顿指数随着PES质量分数的增加而不断减小,随着溶液温度的升高而不断增大.     

干／湿相转换法制备聚芳醚砜致密皮层不对称膜

以聚芳醚砜为膜材料，采用干／湿相转换法．在非挥发性溶剂－挥发性添加剂以及挥发性溶剂／共溶剂－弱挥发性添加剂两种溶剂体系中研究了致密皮层不对称膜的制备和形成条件，并对它们的结构及氮、氢气体透过性能进行了测试。结果表明，采用前一种溶剂体系。虽然可以在一定范围内控制膜平均孔径的变化，却难以得到致密皮层不对称膜。而后一种溶剂体系，在控制铸膜液组成、适当的制膜条件下可以得到具有海绵状支撑结构的不对称气体分离膜。     

PEU/PES共混膜的制备工艺条件研究

利用L-S相转化法将聚醚型聚氨酯（PEU）和聚醚砜（PES）共混,以聚乙二醇（PEG）为添加剂,制备PEU/PES共混膜,并通过测定比较共混膜的结构与性能.结果表明：聚合物浓度、共混组成比、添加剂种类与浓度是影响PEU/PES共混膜性能的主要因素.     

填充液压力对聚醚砜中空纤维膜微结构和性能的影响

研究了聚醚砜／二甲基亚砜(PEs／DMS0)体系中填充液压力的变化对PES中空纤维结构及性能的影响。结果表明,随着填充液压力的增大,中空纤维膜的水通量增大,轴向取向度下降。为纺制具有合适性能的中空纤维膜提供参考。     

酚酞型聚醚砜（PES—C）超滤膜的制备及性能

以聚乙烯吡咯烷酮（PVP）和乙醇（EtOH）为添加剂,采用相转化法制得了酚酞型聚醚砜（PES-C）超滤膜。结果表明：当以乙醇为添加剂时,随着乙醇含量的增加,膜上表面变为致密结构,下表面呈多孔结构,水通量先上升后减小;当以PVP为添加剂时,随着PVP含量增加,PES—C膜的指状孔得到发展,膜通量和截留率都上升,当PVP的质量含量为10％时,PES—C膜的通量达到134．3L／（m^2·h）,对牛血清蛋白的截留率达85．1％。     

循环电位沉积Yb-Bi薄膜

利用循环电位沉积法从非水体系中制备了Yb-Bi薄膜。在这一沉积过程中，基体电位是在两个电位之间连续循环的。研究了沉积电位、沉积时间和扫描速率对沉积膜中Yb含量以及表面形态的影响。实验结果表明，在0．10mol．L^-1Ybcl3 0．10mol．L^-1Bi(N03)3 0．10mol．L^-1LiCl DMSO体系中，当控制恰当的沉积条件，可得到表面黑色、均匀、有金属光泽和附着力强的非晶态Yb-Bi薄膜，其中Yb的质量分数可达21．04％～36．36％(质量分数)，所得到的沉积膜通过SEM，EDS和XRD进行了表征。     

Sr^2＋对Li0.2375＋xLa0.5875-xSrxTiO3^-LaPO4体系的性能的影响

利用循环电位沉积法从非水体系中制备了Yb-Bi薄膜。在这一沉积过程中，基体电位是在两个电位之间连续循环的。研究了沉积电位、沉积时间和扫描速率对沉积膜中Yb含量以及表面形态的影响。实验结果表明，在0．10mol．L^-1Ybcl3 0．10mol．L^-1Bi(N03)3 0．10mol．L^-1LiCl DMSO体系中，当控制恰当的沉积条件，可得到表面黑色、均匀、有金属光泽和附着力强的非晶态Yb-Bi薄膜，其中Yb的质量分数可达21．04％～36．36％(质量分数)，所得到的沉积膜通过SEM，EDS和XRD进行了表征。     

成膜条件对聚醚砜超滤膜性能和结构的影响

以聚醚砜(PES)为膜材,聚乙二醇600(PEG600)为添加剂,N,N-二甲基甲酰胺(DMF)为溶剂,纯水为凝固浴,用相转化法制备聚醚砜超滤膜.详细探讨了PES浓度、添加剂含量、凝固浴温度对膜性能和结构的影响规律,确定了制备高水通量、高截留率聚醚砜超滤膜的最佳工艺条件.     

聚乙二醇对聚醚砜微孔膜致孔作用的研究

以聚醚砜聚乙二醇溶剂为铸膜液体系、采用干湿相转化法制备微孔滤膜,研究了各种制膜条件对膜孔径结构的影响.实验发现聚乙二醇在体系中起到分散稳定的作用,只有到浓度大于70%时,才会对铸膜液的粘度产生明显影响,聚合物在铸膜液中的溶解状态也随之改变,进而影响膜的结构.不同溶剂NMP、DMF、DMAc、DMSO等极性溶剂或固体溶剂己内酰胺均可制得开孔率较高的微孔膜,但对膜的结构和性能影响差别不大.在本研究体系中,膜的结构取决于聚乙二醇、溶剂的浓度比例关系.     

Ab initio study of the unimolecular decomposition of 2‐butenenitrile: Molecular elimination channels

Ab initio molecular orbital calculations have been performed for the unimolecular decomposition of 2‐butenenitrile (CH₃CH?CHCN), especially for HCN and H₂ molecular elimination channels. Structures and energies of the reactants, products, and relevant species in the individual reaction pathways were determined by MP2 gradient optimization and MP4 CCSD(T) single‐point energy calculations. Direct 1,1 and 1,2 molecular eliminations and H or CN migration followed by elimination channels were identified. Dissociation rates for the individual reaction pathways were calculated from vibrational frequencies at the ab initio transition state geometries by employing Rice–Ramsperger–Kassel–Marcus theory, from which channel branching ratios were determined. It was concluded that the most important reaction channel should be the direct 1,1 three‐center molecular elimination of HCN. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Thermal elimination of isobutene from meta and para tert-di-butyl pyromellitic acid

An investigation of the kinetics of the thermal elimination of isobutene from the meta and para isomers of the tert-butyl diesters of pyromellitic acid has been carried out using Fourier transform-Raman spectroscopy and mass spectroscopy. These studies indicate that the elimination of the tert-butyl group occurs at a temperature 26°C lower for the meta isomer than for the para isomer; the maximum rate of elimination occurs at 184°C for the former and at 210°C for the latter. Analysis of the Raman spectra of the compounds indicates that this effect results from the better packing arrangement in the para monomer compared with the meta monomer. Formation of pyromellitic dianhydride in the tert-butyl diesters of pyromellitic acid occurred only after formation of the pyromellitic acid; thus it occurred at lower temperatures for the meta isomer. When the meta and para tert-butyl diesters of pyromellitic acid are dissolved at 1% concentration in poly (vinyl acetate), the elimination of isobutene occurs at 173°C for both isomers, indicating that it is the differences in crystal packing which give rise to the 26°C difference in the solid-state samples. For the meta, para, and 50/50 mixed isomers of the tert-butyl esters of oxydianiline/pyromellitic dianhydride polyamic acid, the elimination of the tert-butyl group occurs at the same temperature (177°C). This result indicates that the packing arrangement of the tert-butyl group is disrupted in the polymer chain, so that intermolecular bonding does not hinder thermal deprotection of the tert-butyl group from the polymer. © 1992 John Wiley & Sons, Inc.     

Study on the Nucleophilic Addition to (η4-Cis-1-Methoxy-1,3-Butadiene)Iron Tricarbonyl Complex

Reaction of the reactive carbanion with (η⁴-cis-l-methoxy-1,3-butadiene)Fe(CO)3, followed by acid quenching, generates the C-1 substitution product (27%) together with the regular C-2 adduct (71%). A very stable ferracyclopentanone was isolated and its x-ray diffraction analysis determined.     

The synthesis of chiral functionalised morpholine N-oxides using a tandem Cope elimination/reverse-Cope elimination protocol

Hydroxylamine derivatives of (S)-prolinol have been generated using a Cope elimination. These undergo reverse-Cope elimination onto a pendant double bond to give morpholine N-oxides containing three contiguous chiral centres.     

羰基钴催化烯烃醛化反应中RCOCo(H)2(CO)3还原消去关键步骤的理论研究

在其催化循环过程中,RCOCo(CO)_3与H2_氧化加成生成RCOCO(H)_2(CO)_3,此中间体进一步还原消去生成醛是涉及氢在整个醛化反应催化循环中活化作用的关键步骤,文献[2]认为它是整个循环的控制步骤,由于反应的各中间物光谱无法准确测定,无法分别考察这两个步     

Unclicking of thioureas: Base catalyzed elimination of anilines and isothiocyanates from thioureas

Bisaromatic thioureas are widely used in e.g. asymmetric organocatalysis and considered to be robust compounds. Herein we show, in strong contrast to common notion, that thioureas dissociate to amines and isothiocyanates in a base catalyzed reaction under mild conditions. This ‘unclicking’ process can occur in the presence of weak organic bases even at moderate temperatures. The influence of the substituents at the aromatic rings of the thiourea on the regioselectivity of this unclicking process is also shown.     

SBS单组分橡胶防水涂料的消泡研究

研制了一种高强度、高延伸率的SBS单组分橡胶防水涂料,针对该涂料在日晒下施工时起泡的原因,研究了有效的消泡措施,改进了技术路线及配方,实际施工效果满意。     

Dynamics of Atomic and Molecular Hydrogen Elimination from Hydrocarbons at VUV Excitation

Elimination of atomic hydrogen (H) and molecular hydrogen (H₂) are important elementary chemical processes in photochemistry and combustion chemistry. Recently, unique and sensitive detection techniques for atomic and molecular hydrogen detection were developed in our laboratory. Using the advanced molecular beam methods, we have studied the photodissociation of a few typical hydrocarbons at 157 nm excitation, especially their atomic and molecular hydrogen elimination processes. In this report, we will briefly describe the results from photodissociation of propane, ethylene, propyne and methanol at 157 nm excitation. These molecules represent different classes of hydrocarbons such as alkane, alkene, alkyne and alcohol. Through careful studies on differently deuterated compounds, clear pictures of selective atomic and molecular hydrogen elimination processes can be constructed for all of the above compounds. These results will help us to understand the dissociation dynamics of the small hydrocarbon molecules.     

ω-甲亚砜基苯乙酮阴离子与对硝基苄基衍生物的反应

Russell 等于六十年代曾用 ESR 的方法和化学方法证实某些脂肪族和芳香族硝基化合物与各种阴离子之间发生单电子转移,时-硝基苄基衍生物也可以与许多阴离子反应。我们则进一步研究对-硝基苄基衍生物(1～4)与ω-     

Unusual Hofmann elimination at low temperature. Reaction of 3-hydroxymethylpyrrolidines withp-toluensulfonyl chloride

Summary Trans-2-aryl-3-hydroxymethyl-1-methylpyrrolidines suffer an unusual Hofmann elimination when treated withp-toluensulfonyl chloride in basic medium at room temperature.

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Ungewöhnliche Hofmann-Eliminierung bei niederer Temperatur. Die Reaktion von 3-Hydroxymethylpyrrolidinen mitp-Toluolsulfonylchlorid (Kurze Mitt.)

Zusammenfassung Trans-3-hydroxymethylpyrrolidine erleiden in basischem Medium bei Behandlung mitp-Toluolsulfonylchlorid eine ungewöhnliche Hofmann-Eliminierung.