光辅助引发制备聚甲基丙烯酰氧乙基三甲基氯化铵

在紫外灯照射和引发剂作用下,通过水溶液聚合法制备聚甲基丙烯酰氧乙基三甲基氯化铵(PDMC).考察了氧化-还原引发体系、氧化-还原和偶氮类引发剂用量、单体浓度、溶液pH、引发温度和络合荆用量等因素对产物特性黏数的影响,并与无光照条件下的聚合结果进行了对比.用红外光谱对所得产物进行了表征.结果表明:光辅助引发可以显著促进DMC的聚合反应.采用硫酸亚铁-过硫酸铵引发剂体系,在引发剂质量分数为0.002 0%,单体质量分数为75%,pH=4,引发温度为10℃,络合剂质量分数为0.003 0%时,所得聚合物的特性黏数达8.4 dL/g以上.     

咪唑型阳离子聚丙烯酰胺P(AM/MAPD)的合成

以丙烯酰胺(AM)、自制的1-(2-甲基丙烯酰氧丙基)-3-癸基咪唑盐酸盐(MAPD-Cl)为原料,通过自由基共聚合,得到了咪唑型阳离子聚丙烯酰胺P(AM/MAPD)。 红外光谱表征结果证明其为目标产物。 采用单因素考察和响应面分析法相结合,对聚合工艺条件进行了优化。 优化聚合条件为：单体总质量分数25.41%,反应温度26 ℃,引发剂(NaHSO3-(NH4)2S2O4)质量分数0.03%,反应时间10 h。 所得聚合物的特性粘数可达到12.56 dL/g。     

胺甲基化聚丙烯酰胺稀溶液行为的研究——pH值对粘性行为及其絮凝作用的影响

pH值对胺甲基化聚丙烯酰胺(CPAM)稀溶液粘性行为的研究表明:不同的CPAM-H_2O溶液体系(胺化度28.8～38mol％,外加盐浓度0～0.2M)的粘性行为,特性粘数[η]和Huggins常数k′随溶液pH值变化分别是现极大值和极小值;CPAM对有机污泥脱水絮凝作用随溶液pH值变化存在极大值。本文从CPAM电荷的形成、电荷密度的增加以及屏蔽出发讨论了上述两种极限现象。     

阳离子聚丙烯酰胺合成工艺条件及絮凝性能的研究

以丙烯酰胺(AM)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)为共聚单体,采用氧化还原/偶氮化合物复合引发剂体系在水溶液中进行自由基聚合,合成了阳离子型聚丙烯酰胺聚合物(CPAM)。系统研究了反应条件对反应产物的影响,用红外光谱对CPAM的结构进行了表征。结果表明,制备较高分子量CPAM的优化工艺参数为:单体总质量分数35%(AM∶DMC=3∶1),氧化还原引发剂质量分数0.06%((NH_4)_2S_2O_8∶NaHSO_3=1∶1),偶氮类引发剂质量分数0.09%,助溶剂质量分数1.5%,络合剂质量分数1.5%。在此优化条件下,所得CPAM的分子量达1.2×10~6,对蒙脱土模拟废水的絮凝效果良好,经其处理后的模拟废水透光率达到99.3%。     

利用造纸污泥制备木素基阳离子絮凝剂及其性能的研究

以造纸污泥中提取的木质素为原料,合成了木素基阳离子絮凝剂。研究了催化剂种类、反应物配料比、反应温度、反应时间等对合成产物脱色性能的影响,确定了较佳合成工艺条件为:引发剂K2S2O8用量为木质素磺酸钠质量的0.7%,活化时间1.5 min,木质素磺酸钠与单体质量比为1∶1.5,反应温度为70℃,反应时间1.5 h,采用红外光谱对产物结构进行了表征。产物对几种模拟染料废水具有良好的脱色性能,在酸性(pH1～2)条件下,脱色率均达84.4%以上。通过比较木质素与接枝产物的絮凝效果以及絮体的微观形貌,对其絮凝机理进行了初步探讨。     

超高分子量高阳离子度AM-DMC-DAC三元共聚物的合成及其絮凝性能

在较高阳离子含量下,合成了丙烯酰胺(AM)-甲基丙烯酰氧乙基三甲基氯化铵(DMC)-丙烯酰氧乙基三甲基氯化铵(DAC)三元共聚物.考察了引发剂浓度、单体浓度、反应体系pH及链转移剂对聚合反应产物黏度的影响.结果表明:该三元共聚物的特性黏度可以达到36 dL/g,溶解性能良好,阳离子度高,絮凝性能优良.     

聚己内酯大分子单体接枝丙烯酰胺共聚物的合成与表征

首次制备了末端为双键的功能化聚己内酯(PCL)大分子单体(AECL);AECL与丙烯酰胺(AM)在过硫酸钾引发剂作用下进行水溶液自由基聚合反应,合成了接枝PCL侧链的水溶性新型聚丙烯酰胺共聚物(PAM-g-PCL),其结构经1H NMR,IR和元素分析表征.PAM-g-PCL的特性粘数为3.4 dL·g-1～5.3 dL·g1-.     

反相乳液聚合法制备PDA及其性能

用水溶性的氧化还原引发剂引发,通过反相乳液聚合制备了二甲基二烯丙基氯化铵（DMDAAC）-丙烯酰胺（AM）共聚物（PDA）,聚合反应中水／油体积比为1．0／1．2,单体质量分数ω=0．33,阳离子单体DMDAAC与AM的摩尔比为1／9。研究了温度和引发剂浓度对聚合动力学的影响,结果表明聚合温度40℃、mt（引发剂）／mM（单体）=0．5／100．0是最佳反应条件。探讨了PDA在不同浓度KBr溶液和不同种类小分子电解质溶液中的粘度特性,随小分子电解质浓度的增大和小分子电解质阴离子半径的增加,比浓粘度和特性粘数减小。当PDA与明矾复配用于絮凝时,明矾的最佳投料量为25mg／L、PDA投料量为4．16mg／L,且该体系的pH适用范围较广。     

PAM-Fe(OH)3有机-无机杂化型高分子絮凝剂的合成及表征

在水溶液中以过硫酸铵((NH4)2S2O8)和亚硫酸氢钠(NaHSO3)为引发体系,利用原位聚合法合成了聚丙烯酰胺(PAM)-氢氧化铁(Fe(OH)3)有机-无机杂化型高分子絮凝剂.通过正交实验得到合成杂化絮凝剂的最佳条件为:反应温度40℃,引发剂质量分数0.5%,丙烯酰胺质量分数30%,反应时间7 h.FT-IR、T...     

阴离子型聚电解质P（AM-co-AAK）的制备和性能

以丙烯酰胺（AM）、丙烯酸钾（AAK）为单体,采用反相乳液聚合法合成了阴离子型聚电解质P（AM-co-AAK）,并对产物的结构、形貌等进行了表征。研究了产物的抗盐性,考察了产物特性黏数、用量和体系pH对w=0.1%的高岭土悬浮液模拟废水的絮凝性能的影响。结果表明：产物具有较好的抗盐性;当其特性黏数为6.6dL/g,絮凝剂的最佳用量为3mg/L时,絮凝性能最好,透过率达到最高值（54.43%）,并且产物在碱性条件下的絮凝性能明显优于在酸性条件下的。     

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.     

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.     

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.     

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.     

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.     

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.     

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.