微孔PI气体分离膜的研究进展

自具微孔材料(PIMs)由于自身刚性分子链的扭曲折叠等会产生高比表面积的微孔结构,相应的膜材料具有优异的气体分离性能。将刚性扭曲的结构单元引入到聚酰亚胺(PI)主链中就得到自具微孔PI。微孔型PI是近年来发展的一种新型PI,其微孔结构使得PI膜的气体分离性能得到很大提升,其中气体渗透系数的提升尤为显著,且保持了传统PI良好的热稳定性、化学稳定性及高力学强度等性质。本文重点介绍了微孔PI以及基于微孔PI复合膜的最新研究进展,并对其未来发展趋势进行了展望。     

共轭微孔聚合物膜的制备策略及其分离应用

降低工业分离过程的能耗为缓解全球能源紧缺问题提供了有效途径. 相比传统工业分离技术, 膜分离技术能耗低、经济效益高, 开发高效的膜材料是提升膜分离性能的重要手段. 共轭微孔聚合物(CMP)膜具有刚性永久超微孔道、高孔隙率、孔结构及化学环境可调控、交联骨架稳定性好等优势, 在分离领域具有良好的应用前景. 概述了近年来CMP膜的制备方法并简要对比了其优缺点, 阐述了CMP膜在气体分离、有机溶剂纳滤、离子筛分和手性分离等领域的分离机理和研究进展, 为开发新型具有良好分离性能的CMP膜材料提供研究思路.     

钴掺杂二氧化硅膜的制备、表征及氢气分离性能

采用正硅酸乙酯(TEOS)和Co(NO3)2.6H2O为前驱体通过溶胶-凝胶法制备掺钴微孔二氧化硅膜,研究钴在二氧化硅膜材料中的存在状态、膜材料孔结构以及膜材料的气体渗透和分离性能。结果表明钴元素以Si-O-Co的形式存在于SiO2骨架之中,掺杂Co 10%的微孔SiO2膜具有典型的微孔结构,其孔体积为0.119 cm3·g-1,平均孔径在0.52 nm左右且孔径主要分布在0.4～0.55 nm之间。氢气在膜材料中的输运低温下遵循Knudsen扩散机理,高于100℃时遵循活化扩散机理,300℃时膜材料的H2渗透率达到6.41×10-7 mol.m-2.s-1.Pa-1,H2/CO2分离系数达到6.61,高于Knudsen扩散的理想分离系数。     

有机微孔聚合物研究进展

有机微孔聚合物(MOPs)是一类新型的多孔材料,具有合成方法多样、化学和物理性质稳定、孔尺寸可调控、表面可修饰等优点。近年来,MOPs在物理吸附储存气体方面表现出巨大潜力,从而在储氢和温室气体封存方面成为研究的热点之一。本文首先介绍了MOPs的结构类型及特点,分别介绍了自具微孔聚合物、超交联聚合物、共价有机网络以及共轭微孔聚合物的最新进展,分析结构与性能间的关系,并对其在催化、分离和气体储存方面的应用做了简单总结。最后对MOPs未来的研究进行了展望。     

敏感性高分子功能膜的研究进展

某些高分子凝胶膜、膜表面或微孔内接枝改性膜、液晶膜具有化学阀的功能,其膜的通透性随外界环境条件变化而改变。详细介绍了ＰＨ、温度、电场等外界环境条件变化对此三类膜的敏感性及通透性的影响,以及敏感性功能膜在物质的分析与检测,混合物的分离与纯化过程中的应用前景。     

氯化锂为添加剂制得的疏水聚偏氟乙烯不对称微孔膜的形态结构及其膜蒸馏性能

结合膜的形态结构研究了以 LiCl为添加剂制得的疏水 PVDF膜的膜蒸馏性能。与来用水溶液高分子添加剂制得的PVDF微孔膜相比,膜蒸馏性能有了较大提高,尤其具有更高的截留率。制得的微孔膜的蒸馏通量已接近商品膜的膜蒸馏通量,表明以LiCl为添加剂制得的PVDF疏水微孔膜是一种适用于膜蒸馏的较理想的疏水微孔膜。     

热致相分离法制备聚烯烃微孔膜研究进展

非极性及弱极性的结晶高聚物常温下无合适的良溶剂,所以无法使用传统的非溶剂致相分离法制取微孔膜,而近年来发展的热致相分离法解决了这一问题。研究发现聚乙烯、聚丙烯、乙烯．乙烯醇共聚物、乙烯．丙烯酸共聚物、聚(4-甲基-1-戊烯)等聚烯烃是可采用热致相分离法制备微孔膜的材料。本文综述了近年来在热致相分离法制备聚烯烃微孔膜方面的研究进展,重点介绍各种制膜材料(聚合物、稀释剂、萃取剂和助剂)与各种制膜工艺对制得的聚烯烃微孔膜孔径、膜通量和非对称结构等的影响。     

分离液体的膜

本文概述了7种以高分子为膜材料、用于混合液体分离的膜分离过程,即离子交换膜与电渗析、反渗透、超滤、微孔过滤、膜萃取、渗透汽化和膜蒸馏。对其原理、高分子膜材料、应用和发展趋向作了简要介绍;并阐述了我国膜分离发展的现状和展望。     

工艺条件对 LLDPE/POE/CaCO3微孔膜的孔结构及防水透湿性能的影响

用拉伸致孔法制备了 LLDPE/POE/CaCO3防水透湿微孔膜,研究了拉伸倍数及体系组成对微孔膜的微孔结构及防水透湿性能的影响.用 SEM 对微孔膜的微孔结构进行考察,用压汞法对微孔膜的孔径及其分布和微孔的孔隙率进行研究.用静水压法及正杯法分别研究了微孔膜的防水和透湿性能.结果表明:拉伸倍数及 CaCO3用量对微孔膜的孔径、孔隙率及防水透湿性能有明显影响.     

聚酰亚胺微孔膜疏水化用于膜蒸馏

采用聚合物表面涂覆改性的方法，将疏水性聚合物硅橡胶涂覆在聚酰亚胺亲水微孔膜上，制得了具有良好膜蒸馏性能的聚酰亚胺疏水微孔复合膜。研究了涂覆工艺条件对所得聚酰亚胺疏水微孔复合膜的膜蒸馏性能的影响。结果表明，控制适当工艺条件可制得具有高膜蒸馏通量的聚酰亚胺微孔复合膜，其透过系数可达２．１７×１０－３ｋｇ／ｍ２·ｈ·Ｐａ。该改性聚酰亚胺疏水微孔复合膜使用３７ｄ后，截留率仍保持在９９．５％以上，具有较长使用寿命。     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Copper catalyzed/mediated synthetic methodology for ebselen and related isoselenazolones

Scope of the copper catalyzed/mediated selenium-nitrogen coupling reaction has been studied for the synthesis of isoselenazolones. It is noticed that the 2-chloro, 2-bromo-, and 2-iodo-aryl amides substrates can be exploited in the selenium-nitrogen coupling reaction by employing 25-100 mol % of CuI/1,10-phenanthroline (L) and potassium carbonate as a base in DMF. Furthermore, electron rich 2-chloro-arylamides also underwent selenium-nitrogen coupling reaction to give biologically important selenium-nitrogen heterocycles. Also, copper-catalyzed selenium-nitrogen coupling reaction has been meticulously applied for the synthesis of diaryl diselenides having methoxy, amine, and amide functionality from respective aryl iodides in the presence of stoichiometric amount of succinimide as an external Se-N coupling partner.     

Knoevenagel condensation catalyzed by novel Nmm-based ionic liquids in water

A series of novel N-methyl morpholine (Nmm) based ionic liquids with 1,2-propanediol group were synthesized and used as catalysts for Knoevenagel condensation at room temperature in water. Under the effect of the catalyst, various aldehydes or aliphatic ketones could react with a wide range of activated methylene compounds well, including malononitrile, alkyl cyanoacetate, cyanoacetamide, β-diketone, barbituric acid, 2-arylacetonitrile and thiazolidinedione. Furthermore, most of the products could be separated just by filtrating and washing with water. Additionally, the catalyst is recyclable and applicable for the large-scale synthesis.     

Construction of polyheterocyclic spirotetrahydrothiophene derivatives via sulfa-Michael/aldol cascade reaction

A series of polyheterocyclic spirotetrahydrothiophene derivatives were obtained in moderate to excellent yields via a catalyst-free sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 under mild conditions. We also present the first asymmetric sulfa-Michael/aldol cascade reaction of chalcones 1 and commercially available 1,4-dithiane-2,5-diol 2 with moderate to good enantioselectivities catalyzed by readily available chiral phase-transfer catalysts (PTCs).     

Suzuki-Miyaura reactions of the soluble guanylate cyclase inhibitor NS2028: a non-product specific route to C-8 substituted analogues

Both soluble guanylate cyclase (sGC) inhibitors ODQ 1 and NS2028 2 are synthesized via improved protocols. In the former case treating 3,4-dihydroquinoxalin-2(1H)-one oxime 8, which can be prepared in two steps from 1,2-benzenediamine, with 1,1′-carbonyldiimidazole (CDI) gives the dihydro-ODQ 10 that in the presence of KMnO₄ oxidises to give ODQ 1 in an overall yield of 46% starting from 1,2-benzenediamine. In the latter case, the synthesis affords NS2028 2 from 2-amino-4-bromophenol 3 in three steps with an overall yield of 85% and avoids the need for chromatography. Furthermore, Suzuki-Miyaura reaction conditions are described that enable the preparation of 8-aryl and 8-heteroaryl derivatives of NS2028 directly from NS2028 2. Finally, demethylation of the 8-(methoxyphenyl) substituted analogues afforded the 8-(hydroxyphenyl) derivatives 40-42. All new products are fully characterised.