2,3-丁二醇分离纯化中反应精馏工艺

乙醛-环己烷反应萃取体系能够有效分离发酵液中的2,3-丁二醇。文章重点研究了2,3-丁二醇-乙醛反应萃取液的连续水解精馏工艺,为工业化生产提供理论基础。水解精馏使用阳离子交换树脂HZ732为水解催化剂,以2,4,5-三甲基-1,3-二氧戊环(2,3-丁二醇-乙醛缩醛)水解率为指标,考察了反应段温度、反应段级数、进料速度、进料油水比(2,4,5-三甲基-1,3-二氧戊环和水摩尔比)和回流比的影响。通过实验得到优化水解精馏工艺条件为:反应段平均温度90℃,反应段理论板数为20,进料油水比为0.6,进料速度0.2 h-1。在该条件下2,4,5-三甲基-1,3-二氧戊环水解率为73%,未水解2,4,5-三甲基-1,3-二氧戊环被回收。水解液经精馏得到2,3-丁二醇产品,纯度(质量分数)>96%,总收率≥93%。开发了连续水解精馏工艺,为整个工艺工业化实践提供了参考。     

阳离子易染涤纶细旦丝的染色性能研究

本文应用了阳离子染料在ECDP纤维上进行了一系列的染色性能试验,着重从热力学、动力学角度对染色机理、染色性能、工艺条件进行了探讨.为选择合适的ECDP纤维的染整加工条件提供了一定的理论依据.     

Epoxy‐Based Azopolymers with Enhanced Photoresponsive Properties Obtained by Cationic Homopolymerization

Azopolymers are highly versatile materials due to their unique photoresponsive properties. In this contribution, a novel azo‐modified epoxy network is synthesized by cationic homopolymerization with boron trifluoride monoethylamine (BF₃.MEA) complex as initiator. The effect of the addition of a fixed content of amino‐functionalized azo chromophore, Disperse Orange 3, into the polymer matrix is studied in detail. First of all, the thermal curing cycle is optimized by means of differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) measurements. Then, the resulting bulk azo‐modified epoxy networks are characterized by means of thermogravimetric analysis (TGA), FTIR, DSC, UV–vis spectroscopy, and rheological measurements. Finally, the optical response of thin films of these materials is determined. The results evidence that azo‐modified epoxy networks obtained by cationic polymerization with optimized curing cycle display high T _g values, high maximum photoinduced birefringence, fast writing speed, and exceptionally high remnant anisotropy. Therefore, this material is a promising candidate to be used for optical storage applications.     

2-Methoxypyridine as a Thymidine Mimic in Watson–Crick Base Pairs of DNA and PNA: Synthesis,Thermal Stability,and NMR Structural Studies

The development of nucleic acid base-pair analogues that use new modes of molecular recognition is important both for fundamental research and practical applications. The goal of this study was to evaluate 2-methoxypyridine as a cationic thymidine mimic in the A–T base pair. The hypothesis was that including protonation in the Watson–Crick base pairing scheme would enhance the thermal stability of the DNA double helix without compromising the sequence selectivity. DNA and peptide nucleic acid (PNA) sequences containing the new 2-methoxypyridine nucleobase (P) were synthesized and studied by using UV thermal melting and NMR spectroscopy. Introduction of P nucleobase caused a loss of thermal stability of ≈10 °C in DNA–DNA duplexes and ≈20 °C in PNA–DNA duplexes over a range of mildly acidic to neutral pH. Despite the decrease in thermal stability, the NMR structural studies showed that P–A formed the expected protonated base pair at pH 4.3. Our study demonstrates the feasibility of cationic unnatural base pairs; however, future optimization of such analogues will be required.     

The intramolecular capture of thermally generated merocyanine dyes derived from naphthopyrans: Photochromism of 5-(diarylhydroxymethyl)-2H-naphtho[1,2-b]pyrans

A series of 2H-naphtho[1,2-b]pyrans bearing a diarylmethanol unit at C-5 have been synthesised by the addition of an excess of an aryllithium reagent to alkyl 2H-naphtho[1,2-b]pyran-5-carboxylate precursors. These naphthopyrans show photochromism when exposed to ultraviolet irradiation and also generate intense colours at low pH through triarylmethine cation generation. However, photochromism of the triarylmethine cation derived from the naphthopyran unit could not be detected. An irreversible cascade process initiated by the thermally-induced ring-opening of the diarylmethanol substituted 2H-naphtho[1,2-b]pyrans in the presence of an acid catalyst afforded novel benzopentalenonaphthalenone dyes.     

Synthesis and properties of bromide‐ functionalized poly(isobutylene‐co‐p‐ methylstyrene) random copolymer

Poly(isobutylene‐co‐p‐methylstyrene) (IB/p‐MS) random copolymer is a new generation of polyisobutylene‐based elastomers. The cationic copolymerization of IB with p‐MS was thoroughly examined by using 2‐chloro‐2,4,4‐trimethylpentane/ethylaluminiumsesquichloride/electron donor as initiating system. IB/p‐MS random copolymers with high molecular weight were obtained at elevated temperature through the addition of ethyl acetate; the reaction proceeded in a mildly exothermic manner. Although the reactivity ratios of comonomer pairs differ by close to an order of magnitude, p‐MS was uniformly distributed in the chains. IB/p‐MS random copolymer can be brominated by adding molecular bromine into the copolymer solution, thereby yielding a completely saturated polymer backbone with a chemically reactive site. The types and selection of appropriate vulcanization systems for bromide‐functionalized IB/p‐MS random copolymers are also discussed. © 2016 Society of Chemical Industry     

Self‐Assembly Behaviors of Anionic–Cationic Binary Surfactant Systems in Poly(ethylene glycol) 200

The self‐assembly behaviors of mixtures of sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) and didodecyl dimethylammonium bromide (DDAB) in polyethylene glycol 200 (PEG 200) and in water were investigated by surface tension, conductivity, steady‐state fluorescence and dynamic light scattering (DLS) methods. The results show that the oppositely charged binary surfactant system can form micelles in PEG 200; the critical micellization concentration (CMC) decreases for the binary system versus those of either surfactant alone. Although there is no charge screening in the PEG 200 system, the CMC values significantly increase and the system does not precipitate or show turbidity at any proportion of AOT to DDAB, while a multiphase composition gap exists in water due to the strong electrostatic attraction. It is speculated that the weak polarity of PEG 200, the decreased solvophobic interaction between the alkyl chain and PEG 200, and the loose structure of the resulting micelles might explain the experimental phenomena. Observed from the values of the interaction parameter, it is found that there are a strong attractive interaction and a synergistic effect between AOT and DDAB in aqueous solution, in comparison, the synergy between them in PEG 200 is very weak.     

非离子表面活性剂对阳离子复合杀菌剂杀菌性能的影响

在棕榈油乙氧基化物(NOE-Pn)(n=3,6,9,12和14)质量浓度为50 mg/L的条件下,通过研究其EO加合数(n)对由双癸基二甲基甲酸铵(DDAF)、双烷基(碳数8~10)二甲基氯化铵(D8-10)、聚六亚甲基双胍盐酸盐(IB)、双癸基甲基羟乙基氯化铵(DEQ)和十二烷基二甲基苄基氯化铵(1227)5种阳离子表面活性剂复合组成的杀菌剂(阳离子复合杀菌剂,总质量浓度为140 mg/L,其中m(DDAF)∶m(D8-10)∶m(IB)∶m(DEQ)∶m(1227)=3∶2∶3∶3∶3)杀菌性能的影响,结果发现杀菌时间为20 min的条件下在n=9时(NOE-P9),对阳离子复合杀菌剂的影响最小,与脂肪醇聚氧乙烯(9)醚(AEO9)基本一致。在阳离子复合杀菌剂中引入非离子表面活性剂NOE-P9、AEO9和烷基糖苷(APG0810)以及阴-非离子表面活性剂脂肪醇聚氧乙烯(9)醚羧酸(AE9C),发现其对白色念珠菌的影响较大。在此基础上,对比了提高杀菌剂的总质量浓度至180 mg/L和延长杀菌时间至1 h的杀菌效果。结果发现浓度的提高使得杀菌性能略有增强;延长杀菌时间可以明显提升复合体系的杀菌效果,尤其是非离子表面活性剂质量浓度较低时,对金黄色葡萄球菌和大肠杆菌的杀灭对数值均大于6。     

疏水缔合型阳离子聚丙烯酰胺的合成及絮凝性能

以甲基丙烯酸三氟乙酯(TFEMA)为疏水单体、丙烯酰胺(AM)为主单体、甲基丙烯酰氧乙基三甲基氯化铵(DMC)为阳离子单体,以过硫酸铵和亚硫酸氢钠为复合引发剂,采用自由基胶束聚合法合成了共聚物P(AM-DMC-TFEMA)。分别考察了反应温度、引发剂用量、单体总质量分数及反应时间对P(AM-DMC-TFEMA)的产率及阳离子度的影响。确定较佳工艺条件为:反应温度65℃,引发剂用量占单体总质量的2%,单体总质量分数26%,反应时间3 h。采用红外光谱(FT-IR)、核磁共振氢谱(~1H NMR)和环境扫描电镜(ESEM)对其结构进行了表征。同时考察了P(AM-DMCTFEMA)对硅藻土悬浮液的絮凝效果,结果表明,其对硅藻土具有良好的絮凝效果,絮凝时间仅为20 s,合成的共聚物上清液透过率为97.31%。     

油水界面上阴/阳离子型复配表面活性剂体系的分子动力学模拟

采油过程中阴/阳离子型表面活性剂复配使用可显著增强驱油效果,对其微观机理的深入研究有助于驱油用表面活性剂的结构优化设计及使用。采用分子动力学方法研究了不同摩尔比的阴离子表面活性剂聚醚羧酸钠(PECNa)和阳离子表面活性剂十八烷基三甲基氯化铵(OTAC)复配体系在油水界面上的分子行为和物理性质。结果表明,复配体系比单种表面活性剂体系更有利于降低油水界面张力。不同复配比体系中,两种表面活性剂头基相反电荷间的吸引作用使表面活性剂之间对各自反离子的静电吸引作用减弱,且等摩尔比体系尤为明显。阴离子表面活性剂的亲水头基对阳离子表面活性剂亲水头基形成的水化层内水分子的结构取向无显著影响,反之亦然。通过调节两种离子型表面活性剂的复配比例,可调整油水界面吸附层微观结构,有望降低油水界面张力,提高采收率。