辐射接枝法制备离子交换膜的研究现状

聚合物离子交换膜有多种制备方法，其中高分子材料辐射引发接枝功能性单体是一种文献中屡见报道且简单可行的方法．通过在不同聚合物基体上接枝各种类型的单体，可以改变接枝膜的电化学性能、物理化学等性能．丈中详细介绍了不同的高分子基材辐射接枝各类单体制备聚合物离子交换膜的研究现状．     

含季铵基离子交换纤维的制备研究

以辐射接枝丙烯酸(AA)后的聚丙烯(PP)无纺布(PP-g-AA)为基材,采用紫外引发的方法接枝甲基丙烯酰氧乙基三甲基氯化铵(DMC),建立了一种制备阴离子交换纤维的新方法,得到了PP-g-AA-DMC纤维.研究了丙烯酸接枝率、DMC浓度、溶剂种类、光照时间,浸泡时间等因素对DMC接枝率的影响,结果表明,DMC的接枝率随着丙烯酸接枝率、DMC浓度、光照时间和纤维浸泡时间的增加而增大.接枝前后纤维的红外光谱分析表明,DMC被成功接枝在PP-g-AA基材上.吸附性能测定结果表明,纤维对水中以阴阳离子存在的金属铬均具有较好的吸附性能.     

壳聚糖与N-异丙基丙烯酰胺接枝共聚凝胶的辐射合成及性能研究

采用γ辐射技术引发壳聚糖与N异丙基丙烯酰胺进行接枝共聚,制备了温度及pH敏感水凝胶.研究了单体浓度、辐射剂量等对接枝率和接枝效率的影响,并用13CCPMASNMR和TG表征了接枝物的结构.研究结果表明,用γ射线引发壳聚糖接枝异丙基丙烯酰胺具有较高的接枝率和接枝效率,接枝的聚合物具有明显的温度及pH敏感的特点.     

N,N-二乙基丙烯酰胺与丙烯酸在聚丙烯薄膜表面光接枝制备二元接枝膜及其温度、pH值敏感特性研究

以二苯甲酮为引发剂,聚丙烯薄膜(CPP)为基材,通过紫外光接枝的方法制备了具有温度和pH值双重敏感特性的聚N,N-二乙基丙烯酰胺(PNDEA)与聚丙烯酸(PAA)二元接枝膜.在PNDEA一次接枝膜的制备过程中,引发剂与单体配比相同时,本体接枝方法的接枝速率在反应初期明显高于溶液接枝方法;采用溶液法时,增大引发剂与单体配比等可提高接枝率.用本体法所制得的PNDEA一次膜光活化接枝PAA时接枝速率较溶液法高,并且能够实现较高的PAA接枝率.用红外光谱(FTIR)、X射线光电子能谱化学分析(ESCA)对接枝层组成的表征结果证实了二元接枝层的存在.在不同温度下,PNDEA一次接枝膜的FTIR谱图中酰胺Ⅰ带特征吸收峰发生位移表明它具有温度敏感特性.用扫描电子显微镜(SEM)对PNDEA接枝层表征结果表明,用不同接枝手段所制备的接枝膜具有不同的表面形貌.通过吸水率测定研究了二元接枝膜的温度及pH值敏感特性.     

脂肪酶催化合成纤维素-甲基丙烯酸丁酯接枝聚合吸油材料

以棉浆粕为基材,硝酸铈铵/HNO3为引发剂,甲基丙烯酸丁酯(BMA)为接枝单体,脂肪酶为催化剂,N,N′-亚甲基双丙烯酰胺为交联剂,采用悬浮震荡接枝聚合反应制备了纤维素-BMA接枝聚合吸油材料.采用红外光谱、X射线衍射、扫描电镜、热重、差热等手段对产物结构进行了表征,考察了棉浆粕的引发及其后的接枝聚合反应,得到脂肪酶催...     

芴酮引发光接枝改性LDPE膜的研究

采用紫外光引发接枝表面改性的方法,以芴酮(FL)为引发剂,在低密度聚乙烯(LDPE)薄膜表面上接枝丙烯酸(AA)、甲基丙烯酸(MAA)、丙烯酸甲酯(MA)、甲基丙烯酸甲酯(MMA)、丙烯酰胺(AM)等单体,以赋予薄膜表面新的化学性质.考察了引发剂浓度、紫外光的辐照时间、辐照强度、单体种类对LDPE薄膜接枝程度的影响.结果表明,在一定范围内,增加芴酮浓度,可以提高单体的接枝率,但当芴酮浓度达到5%时,接枝率反而下降.延长辐照时间至4 min和提高紫外光的辐照强度达100 W/m2,均有利于接枝反应的进行.不同单体在LDPE膜上的接枝能力与单体的活性、单体与基材的相容性等因素有关.接枝后,LDPE与水的接触角下降程度不仅与单体在膜上的接枝量有关,还与接枝单体的亲水性能密切相关.     

羧甲基香菇多糖表面修饰的聚乳酸材料的表面性能研究

制备了香菇多糖羧甲基衍生物,再通过化学接枝方法利用共价键将羧甲基香菇多糖固定在氨基化聚乳酸基材表面,得到羧甲基香菇多糖化学接枝修饰的聚乳酸材料.此外,通过在氨基化聚乳酸基材表面进行羧甲基香菇多糖与壳聚糖的层层自组装,得到生物多糖层层自组装修饰的聚乳酸材料.采用扫描电子显微镜、水接触角测量仪、抗菌活性测试、溶血试验和血栓试验等方法对被修饰聚乳酸材料的表面性能和生物性能进行了分析和比较.结果表明采用2种表面修饰方法得到的羧甲基香菇多糖修饰的聚乳酸材料的亲水性、血液相容性以及对大肠杆菌抗菌活性得到改善.与化学接枝方法相比,经过羧甲基香菇多糖与壳聚糖层层自组装修饰的聚乳酸材料具有更好的亲水性、血液相容性和抗菌活性.     

等离子体辐照的聚乙烯表面接枝交联共聚合

聚合物利用低温等离子体预辐照进行表面接枝共聚合已有报道.此方法的优点是接枝层被限制在聚合物表面,辐照过程对基材本体性质无影响,且整个过程对环境无污染. 用等离子体使聚合物表面产生自由基,不需要表面具有不饱和键或特殊官能团,因而适用于任何聚合物,甚至于一些无机物如玻璃等.利用等离子辐照后暴露于空气的聚合物表面上生成的过氧自由基或过氧化物进行接枝反应,一般接枝量不大.本工作中,我们自己设计了反应器,以超高分子量聚乙烯(UHMWPE)为基材,以甲基丙烯酸甲酯(MMA)为接枝单体,在无氧条件下利用等离子体辐照产生的表面自由基进行了接枝聚合,产物接枝量高达10％.还用顺磁共振技术对表面自由基性质及其在接枝过程中的行为进行了跟踪研究.     

辐射接枝共聚合反应及其在有机生物医用材料制备中的应用

γ-射线辐射高分子材料表面接枝共聚合是一种绿色的、重要的有机生物材料合成制备方法. 综述了γ-射线辐射接枝共聚反应的原理、特点, 阐述了预辐射接枝共聚和共辐射接枝共聚的方法, 介绍了当前γ-射线辐射接枝共聚反应在改善有机生物医用材料的表面亲水性、生物相容性等方面的应用. 对辐射接枝共聚合制备功能药物载体研究进行了简要介绍.     

亚麻等麻类纤维与乙烯基类单体接枝共聚反应的研究进展

近年来,乙烯基类单体与亚麻、大麻、苧麻等麻类纤维的接枝共聚反应已得到关注。本文着重总结接枝的引发方法,包括:1.辐射引发接枝;2.光引发接枝;3.Ce(Ⅳ)离子引发接枝;4.锰盐引发接枝;5.V(Ⅴ)离子引发接枝;6.Fenton's 试剂(Fe~(2+)-H_2O_2)引发接枝;7.过硫酸盐氧化还原引发体系接枝。上述各类引发体系及接枝纤维的结构与性能表征均在本文中作了述评。     

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%.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.