以聚偏氟乙烯为基底的高渗透选择性聚酰胺/酯纳滤膜的制备与表征

以亲水性聚(N-羟乙基丙烯酰胺)(PHEAA)、疏水性聚甲基丙烯酸甲酯(PMMA)为链段的两亲性三嵌段共聚物PHEAA-b-PMMA-b-PHEAA(PHMH)为改性剂,以聚偏氟乙烯(PVDF)为基底膜材料,利用非溶剂诱导相分离法制备了PVDF/PHMH基底.与未改性PVDF基底相比,PVDF/PHMH基底表面孔径变小,孔隙率和亲水性增加;与PVDF基底纳滤膜N0相比,通过界面聚合制备的PVDF/PHMH基底纳滤膜N1表面粗糙度大、亲水性强、截留分子量小,N1纳滤膜对Na₂SO₄的截留率为96.0%,水渗透通量高达304 L·m^-2·h^-1·MPa^-1,优于商业化纳滤膜的渗透选择性.     

熔融纺丝-拉伸法制备PVDF中空纤维膜及其油-水分离性能

以聚偏氟乙烯(PVDF)为成膜聚合物, 聚全氟乙丙烯(FEP)为添加剂, 聚乙二醇(PEG)和氯化钙(CaCl₂)为复合成孔剂, 采用熔融纺丝-拉伸法制备了PVDF中空纤维膜. 在制膜过程中未使用其它溶剂和稀释剂, 实现了制膜过程的相对绿色化. 分析和讨论了拉伸比对PVDF中空纤维膜结构与性能的影响, 测试了纤维膜的孔径分布、 力学性能和油-水分离性能等. 结果表明, 进行拉伸后处理的膜的孔径分布较窄, 在油包水乳液分离测试中, 分离效率均在97%以上, 表现出良好的油-水分离效果.     

PVDF亲水复合膜的制备及表征

聚偏氟乙烯(PVDF)膜材料存在强疏水性的缺陷,亲水化改性是解决该问题的主要途径。以PVDF为基膜材料、聚乙烯醇(PVA)为共混材料、N,N-二甲基乙酰胺(DMAc)为溶剂,采用相转化法制备PVDF/PVA复合膜。考察了复合膜的PVDF/PVA共混比、固含量、低分子化合物添加剂、聚合物添加剂等非溶剂添加剂对复合膜接触角的影响。结果表明,当PVDF/PVA共混比为7/3,固含量为13%时,制备的复合膜接触角为22.92°;当添加剂为无水氯化锂、纳米二氧化硅、聚乙烯吡咯烷酮(PVP)时,复合膜接触角分别从53.12°、30.51°和41.89°都降低到了0°,亲水性提高,其中纳米二氧化硅作为添加剂时复合膜亲水性最好;当添加剂为丙三醇、PMMA、PEG时,复合膜接触角都增大,亲水性变差。     

多孔碳基复合膜的真空冷冻干燥制备及高效太阳能水蒸发性能

以多壁碳纳米管(CNTs)和聚偏氟乙烯(PVDF)为原料, 通过相转化法形成均匀共混的胶体, 利用真空冷冻干燥(冻干)技术使胶体固化, 并在真空状态下使部分溶剂挥发, 制备了具有多孔结构的CNTs/PVDF复合膜. 实验结果表明, 冻干CNTs/PVDF复合膜具有优异的光吸收能力、 极佳的表面亲水性能. 在1 kW/m²光照强度下, 其水蒸发速率可达1.95 kg·m^-2·h^-1、 光热转化效率为92.9%. 搭载了冻干CNTs/PVDF复合膜的蒸发器在处理模拟海水和染料废水时, 均表现出良好的抗盐污染性、 显著的稳定性和优异的太阳能蒸发性能.     

基于点击化学反应的织物超疏水改性研究

基于巯基烯的点击化学反应,成功将γ-巯丙基三乙氧基硅烷(KH-580)与乙烯基封端的聚二甲基硅氧烷(vinyl-PDMS)接枝到织物上,制备出具有优异油水分离效果的超疏水织物。利用红外光谱、扫描电子显微镜、X-射线光电子能谱等对改性织物进行表征,并考察了其表面疏水性及油水分离性能。结果表明,得到的超疏水织物表面具有沟壑和条纹结构,接触角最高可达156°,滚动角最高可达2°。超疏水织物的油水分离效率最高为99.8%,并且在连续进行20次油水分离之后,依然保持99%的分离效率。     

树莓状超疏水多孔复合棉纤维的制备及油水分离性能

基于聚多巴胺（PDA）的化学性质和树莓状纳米粒子的粗糙结构,以聚多巴胺包覆的棉纤维为基底,制备了具有多重粗糙度的树莓状超疏水多孔复合棉纤维材料.通过扫描电子显微镜观察树莓状超疏水多孔复合棉纤维表面的微观形貌,PDA-SiO₂纳米粒子稳定地固定在聚多巴胺涂覆的棉纤维表面.经过氟化改性的树莓状超疏水多孔复合棉纤维具有超疏水性,水接触角为158.2°,油接触角为0°.油/水分离实验结果表明,树莓状超疏水多孔复合棉纤维对己烷/水混合物的分离效率可达99.4%以上,使用20次后仍维持较高的分离效率.同时,其具有较高的溶剂吸附能力（13~34 g/g）、重复使用性及机械稳定性,吸油能力可与硅气凝胶相媲美.     

抗污染PVA/PVDF电纺纳米纤维复合超滤膜的制备及过滤性能

以聚对苯二甲酸二醇酯(PET)无纺布为基底,聚偏氟乙烯(PVDF)纳米纤维为支撑层,聚乙烯醇(PVA)纳米纤维膜为分离层,采用静电纺丝法制备超滤膜,并用水/丙酮混合溶液对复合纳米纤维膜表面进行溶液处理,再加入戊二醛交联改性得到致密分离层.采用扫描电子显微镜(SEM)和红外光谱(FTIR)表征了复合超滤膜的表面,用水接触角(WCA)表征复合超滤膜的亲水性.在0.02 MPa恒压下死端过滤油/水乳液,测试复合超滤膜的过滤性能.结果表明,最优条件下制备的复合超滤膜死端过滤油/水乳液的通量为(42.50±4.78)L/(m~2·h),截留率达到(95.72±0.33)%;循环使用5次后,依然具有较好的过滤性能,常压下死端过滤复合超滤膜的纯水通量为(3469±28)L/(m~2·h).     

Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能

将Cu-BTC颗粒与聚偏氟乙烯(PVDF)溶液共混,原位掺杂制备了Cu-BTC/PVDF杂化膜,利用扫描电子显微镜(SEM)、X射线衍射仪、热重分析仪和傅里叶变换红外光谱仪等对杂化膜的结构进行了表征,并对杂化膜的亲/疏水性质、膜孔隙率以及膜水通量进行了测定,探讨了Cu-BTC的掺杂量对杂化膜结构和性质的影响.结果表明,Cu-BTC的存在使PVDF薄膜的成核机理发生改变,降低了PVDF膜孔尺寸,提高了膜表面亲水性和水通量.在对刚果红(CR)的吸附实验中,Cu-BTC/PVDF杂化膜表现出显著增强的吸附活性,且随着Cu-BTC掺杂量的增加,Cu-BTC/PVDF对CR的吸附性能逐渐增强.吸附热动力学拟合结果表明,吸附过程以Langmuir单分子层吸附和化学吸附为主要特征.     

高性能锂离子电池隔膜的结构设计及其制备与表征

设计并采用高压静电纺丝法制备了单层结构的聚偏氟乙烯(PVDF)/偏氟乙烯与六氟丙烯的共聚物(PVDF-HFP)纳米纤维膜及三层结构、二层结构的PVDF/PVDF-HFP/Al2O3复合纳米纤维膜.复合膜的表面形貌、热物理性质和电化学性能通过扫描电子显微镜(SEM)、示差扫描量热法(DSC)、高温尺寸收缩率、交流阻抗法进行了表征.单层结构的PVDF/PVDF-HFP纳米纤维膜的纤维表面光滑,平均纤维直径2μm,纤维分布较均匀,而PVDF与Al2O3复合后的纤维表面粗糙,平均纤维直径变小,结晶度降低,吸液率增大.二层结构的PVDF/PVDF-HFP/Al2O3复合隔膜在170℃下受热1 h收缩率为3%.将3种结构的复合膜在1 mol/L Li PF6/(EC+DMC+DEC,1∶1∶1,W/W/W)电解质溶液中活化得到聚合物电解质.25℃时,二层结构的PVDF/PVDF-HFP/Al2O3复合隔膜吸液率高达497 wt%,离子电导率可达5.04×10-3S/cm,电化学稳定窗口达到4.62 V(Li/Li+).组装成Li Fe PO4/Li电池测试其电池性能,结果表明,二层结构的PVDF/PVDF-HFP/Al2O3复合膜朝向锂负极时,电池的循环性能更好,且与锂金属负极具有更好的相容性和界面稳定性.     

催化链转移聚合制备接枝型两亲共聚物及其溶液性质研究

采用大分子单体法制备接枝型两亲共聚物, 通过表面张力仪、偏光显微镜、旋转流变仪和小角X射线衍射研究了两亲共聚物在水溶液中的聚集行为及其相结构. 首先末端带有可聚合双键的聚甲基丙烯酸叔丁酯大分子单体(PtBMA Macromonomer)通过催化链转移聚合法制备, 所用到的催化链转移剂为二水合双(二氟化硼苯二酮肟)合钴(II) (COPhBF). 然后将所得到的大分子单体与丙烯酸正丁酯(BA)进行自由基共聚得到接枝共聚物PBA-g-PtBMA, PBA-g-PtBMA中PtBMA的侧链部分在酸性条件下定量水解成聚甲基丙烯酸(PMAA)并用NaOH中和得到主链疏水侧链亲水的接枝型两亲共聚物PBA-g-P(MAA^－Na^＋). 用Wilhelmy吊片法研究了不同浓度的两亲共聚物水溶液的表面张力, 发现其行为与小分子表面活性剂不同. 同时用动态光散射法测量了两亲共聚物水溶液中聚集体的粒度, 发现在研究的浓度范围内(0.02～10 g/L)聚集体都存在两个粒度分布峰(约30和300 nm). 浓溶液(w＝37.5%)的偏光显微照片呈现层状液晶的特征图案, 而流变研究表明此时体系具有明显的粘弹性, 说明体系形成了层状液晶. 并且用小角度X射线衍射测定了层状液晶的层间距, 约为12.6 nm.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.