分散聚合技术及其研究进展

介绍了分散聚合体系中各组分及反应条件对反应过程和最终产物性能的影响,简要归纳了分散聚合成核机理、稳定机理及其反应动力学,并着重阐述了近年来分散聚合发展的新技术以及制备的功能微球在各领域的应用等方面的研究进展.分散聚合与其它非均相聚合方法相比,是制备粒径范围在1-10μm且单分散性较好的聚合物微球的有效方法.最近,许多新思路不断引入分散聚合体系,如采用水和超临界CO2作为分散介质,尝试微波和辐射引发聚合以及按照活性聚合机理进行反应等.     

分散聚合研究

介绍了分散聚合制备聚合物微球的研究进展，对分散聚合的成核与稳定机理、聚合过程、动力学、反应参数对聚合物微球粒径及分散性的影响以及运用分散聚合制备功能性聚合物微球及聚合物－－磁性材料复合微球的研究现状进行了回顾。     

流动注射化学发光法测定针剂中的头孢唑啉钠

在多聚磷酸介质中,用KMnO4氧化头孢唑啉钠能产生强化学发光,据此本文建立了一种流动注射化学发光测定头孢唑啉钠的新方法.化学发光信号ICL与头孢唑啉钠质量浓度ρ在0～350 mg/L范围内呈良好线性关系,回归方程为ICL=1.415＋0.959ρ（r=0.9999,n=11）,方法的检出限为1.6 mg/L,相对标准偏差为0.6%（n=11,ρ=50.0 mg/L）.用本法对针剂中头孢唑啉钠进行测定.并初步探讨了该化学发光反应的发光机理.     

乙酸乙酯/乙醇混合溶液中分散聚合制备单分散亚微米级聚丙烯酰胺微球

以乙酸乙酯/乙醇混合溶液为分散介质, PVP为分散剂, 通过分散聚合法合成了单分散亚微米级PAM微球. 在反应初期, 自动加速现象明显. 由于凝胶效应的影响, 分子量随着单体转化率的提高而逐渐增大. 考察了分散剂浓度对最终产物增率的影响, 并用IR光谱对产物的结构进行了表征, 证明分散聚合体系中吸附稳定机理和接枝稳定机理同时存在, 且以后者为主. 同时还研究了混合溶剂比例、分散剂浓度、初始单体浓度和引发剂浓度对微球粒径及粒径分布的影响. 结果表明, 乙酸乙酯/乙醇体积比在5∶5-7∶3范围内, 可得到粒径在200 nm左右, 且分布较窄的PAM微球; 分散剂浓度增大, 粒径减小; 引发剂浓度增加, 粒径增大; 初始单体浓度较高或较低时, 都得不到单分散性微球.     

纳米铬粉的制备研

以ＣrＣ１３为原料,三乙基硼氢化钠为还原剂,聚乙烯吡咯烷酮为分散剂,ＰdＣ１２为成核剂,于甲苯溶剂中制备出平均粒径约５０ｎｍ的铬粉,反应温度、反应物浓度、分散剂与成核剂的添加是影响粒径的主要因素。同时探讨了反应的机理与铬粉的热稳定性。     

Ru/氧化物催化剂在甲苯部分加氢反应中的载体效应

采用浸渍-化学还原法制备了一系列负载型Ru催化剂,考察了一些常见的氧化物载体（SiO₂、m-ZrO₂、t-ZrO₂、γ-Al₂O₃和P25）对甲苯部分加氢制甲基环己烯催化性能的影响。采用N₂物理吸附、X射线粉末衍射（XRD）、透射电子显微镜（TEM）和X射线光电子能谱（XPS）等手段对催化剂进行了系统的表征。研究表明,载体通过影响Ru的粒径,进而影响甲苯部分加氢催化性能。当Ru纳米粒子的粒径由2.6 nm增大到17.3 nm时,甲苯的转换频率（TOF）以及甲基环己烯初始选择性（S₀）先增加,然后降低,呈火山型变化趋势,二者的最大值均在Ru粒径为3.0 nm时出现。在催化性能最优的Ru/P25催化剂上,进一步考察了修饰剂的种类和浓度、反应温度、反应压力等条件的影响。当反应温度为423 K、H₂压力为5.0 MPa,以0.25 g七水合硫酸锌为修饰剂时,Ru/P25催化剂上的初始加氢速率（r₀）为26 mmol·g^-1·min^-1,S₀为57%,甲基环己烯得率可达36%。     

单分散,大为闰径聚苯乙烯微球的制备

以聚乙烯基吡咯酮为人发散剂，偶氮二异丁腈为引发剂、醇／水浊给物为分散介质进行了苯乙烯的分散聚合，讨论了初始单体浓度，分散剂量用、引发剂浓度、分散介质组成和反应温度等反应条件对所得聚合物颗粒直径和直和戏分布的影响。     

单分散、大粒径聚苯乙烯微球的制备

以聚乙烯基吡咯烷酮为分散剂、偶氮二异丁腈为引发剂、醇／水混合物为分散介质进行了苯乙烯的分散聚合，讨论了初始单体浓度、分散剂用量、引发剂浓度、分散介质组成和反应温度等反应条件对所得聚合物颗粒直径和直径分布的影响．通过大量的试验，筛选出了较为理想的分散聚合的条件及配方，制备出了粒径为４８μｍ的单分散聚苯乙烯微球．然后，以分散聚合所制得的聚合物颗粒为种子，用动力学溶胀法制成了粒径增大近四倍的单分散、大粒径聚苯乙烯微球，并讨论了滴水速度和补加分散剂对溶胀的影响     

二亚(3,4-二甲基)苄基山梨糖醇的合成与表征

山梨糖醇与3,4-二甲基苯甲醛在酸催化下缩合成聚丙烯透明成核剂——二亚（3,4-二甲基）苄基山梨糖醇。实验结果表明,在3,4-二甲基苯甲醛66mmol,n（醇）：n（醛）=1．0：2．0,ω（催化剂）=0．6％-1.2％（以反应单体的质量计算）,ω（促进剂）=15％～18％（以反应物的总质量计算）,回流反应5h的最佳反应条件下,收率在96.5％以上。     

水溶性钯膦络合物催化1-辛烯的氢羧基化反应

利用水溶性配体TPPTS与Pd（OAc）2在水相中催化1-辛烯的氢羧基化反应,能实现有机相产物与水相催化剂的清洁分离和催化剂的循环利用．分别考察了钯浓度、表面活性剂（CTAB）、酸助剂、反应时间、CO压力以及温度对该反应的影响．在H2O=16mL,C（Pd）=2．0mmol／L,C（TPTS）／c（Pd）=25,C（p...     

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.