水葫芦基保水剂的制备

利用水葫芦中的纤维素,以过硫酸钾为引发剂,N,N-亚甲基双丙烯酰胺为交联剂,采用复合引发剂体系制备出土壤改良用途的水葫芦基保水剂。考察了单体用量、引发剂用量和交联剂用量对保水剂的吸水吸盐性能的影响。结果表明,以水葫芦为原料,与单体AA进行接枝共聚制备水葫芦基保水剂的最优单体与纤维素的质量比为12∶1,最优引发剂KPS用量为单体质量的0.6%,最优交联剂NMBA用量为单体质量的0.12%,制得的树脂吸水吸盐性能最优。     

速溶型高吸水性树脂的制备及性能研究

以丙烯酸为单体，Ｋ＿２Ｓ＿２Ｏ＿８为引发剂，Ｎ，Ｎ’－亚甲基双内烯酰胺为交联剂，进行反相乳液聚合，制得内交联高吸水性树脂。研究了聚合物吸水性能与内烯酸浓度，丙烯酸中和度，引发剂用量，交联剂用过的关系。考察了该树脂的吸水速率，保水性，在不同电解质溶液中的吸水速度及水饱和树脂在盐水中的失水率。     

碳纳米管复合聚丙烯酸钠的制备及吸水性能

以过硫酸铵(APS)为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,采用水溶液聚合法制备了碳纳米管/聚丙烯酸钠高吸水树脂。系统考察了碳纳米管质量分数、引发剂、交联剂和聚合温度对树脂吸水性能的影响。结果表明,以单体丙烯酸质量为基准,当交联剂,引发剂和碳纳米管质量分数分别为0.04%、0.3%和0.3%,聚合温度75℃时,所合成树脂的吸水性能最佳。添加碳纳米管后树脂表面粗糙和形成孔结构导致了其吸水性能的变化,使得碳纳米管/聚丙烯酸钠的吸水量和吸水速率明显提高,其吸去离子水和生理盐水能力分别达到1423和104g/g。该树脂重复吸水5次后,其吸水能力为1081.5g/g,达到最大吸水倍数的76.0%。     

粉煤灰复合聚丙烯酸钠凝胶的制备及其溶胀性能

粉煤灰(CFA)存在的情况下,采用自由基溶液聚合法,以过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了粉煤灰复合聚丙烯酸钠凝胶(CFAPAANa)。 以丙烯酸单体质量为基准,当交联剂用量为0.08%,引发剂用量为0.4%,粉煤灰用量为3%,丙烯酸中和度为70%,聚合温度为70 ℃时,所合成的粉煤灰复合聚丙烯酸钠凝胶在蒸馏水和生理盐水中平衡溶胀比最高,分别为1556(g/g)和168(g/g)。 考察了复合凝胶在不同介质溶液中的溶胀动力学,保水性能以及在土壤中的降解行为。 溶胀动力学研究表明,蒸馏水中溶胀初期复合凝胶聚合物链段的扩散运动能够调控凝胶溶胀的快慢及程度,而生理盐水中水分子的平移和对流运动在凝胶的溶胀过程中起着关键性作用。 保水和降解实验结果表明,25 ℃时,50 h凝胶保水率为64%,土壤中50 d时降解率达60%。 相比于聚丙烯酸钠凝胶,粉煤灰复合凝胶保水率提高了8%。     

淀粉接枝丙烯酸/醋酸乙烯酯高吸水性树脂的制备

以过硫酸铵为引发剂,N,N-亚甲基双丙烯酰胺为交联剂,淀粉与丙烯酸/醋酸乙烯酯混合单体通过接枝共聚,制备了吸水及耐盐性能均较好的淀粉接枝丙烯酸/醋酸乙烯酯高吸水性树脂(CGAV)。最佳工艺条件为:淀粉10.0 g,m(混合单体)∶m(淀粉)=4∶1,w(引发剂)=0.3%,w(交联剂)=0.05%,于45℃反应2h~3 h。在最佳工艺条件下制得的CGAV吸去离子水率760 g.g-1,吸0.9%NaC l水溶液率68 g.g-1。     

分散聚合制备羧基化单分散聚苯乙烯交联微球

以苯乙烯(St)、丙烯酸(AA)为单体,二乙烯基苯(DVB)为交联剂,偶氮二异丁腈(AIBN)为引发剂,采用分散聚合和交联剂后滴加法合成了单分散羧基化交联聚苯乙烯微球。通过傅立叶红外光谱(FT-TR),扫描电子显微镜(SEM),激光粒度及Zeta电位分析仪等对微球结构进行了表征。结果表明,引发剂、分散剂用量和交联剂的加入方式对微球粒径及单分散性影响显著,当St用量为15%(wt)、DVB用量为1%(wt)、AA用量为1%(wt)、AIBN用量为2%(wt)、PVP用量为6%(wt)时所制备的微球具有良好的单分散性和球形形貌,粒径达到4μm,且微球表面带负电荷。     

丙烯酸酯类吸油树脂的合成与性能研究

以丙烯酸酯、甲基丙烯酸酯为主要单体,二丙烯酸丁二醇酯为交联剂,过氧化二苯甲酰为引发剂,采用悬浮聚合方法,合成聚丙烯酸酯类高吸油树脂.研究了分散剂、引发剂、交联剂用量及单体配比等因素对树脂吸油性能的影响.结果表明,分散剂用量为单体质量的0.12%,引发剂用量为1.0%,交联剂用量为1.5%时树脂的吸油能力最佳,吸甲苯倍率可达15倍,吸汽油倍率可达10倍,吸机油倍率可达近9倍.     

丙烯酸盐与丙烯酰胺共聚制备耐盐性高吸水树脂

以N,N-亚甲基双丙烯酰胺为交联剂,过硫酸铵-亚硫酸钠为引发剂,采用水溶液聚合法合成了耐盐性高吸水树脂-聚(丙烯酸钠-co-丙烯酰胺).研究了单体配比、丙烯酸中和度、引发剂及交联剂用量以及反应温度对常压及加压(1.96×103Pa)下吸盐水(wNaCl=0.009)率的影响.并对其结构进行了表征.该耐盐性高吸水树脂常压和加压下吸盐水率分别为50g·g-1和18 g·g-1,且凝胶强度好.     

超高吸水性聚丙烯酸钠的制备

以聚-γ-巯丙基硅氧烷作为引发剂,将丙烯酸和少量交联剂对二乙烯基苯,在四氯化碳和氢氧化钠水溶液中进行共聚,可得到吸水量400倍以上的超高吸水性聚丙烯酸钠。如果同时加入二氧六环,没有交联剂对二乙烯基苯,也可以得到吸水量将近400倍的超高吸水性聚丙烯酸钠。     

P(AMPS-co-HEMA)凝胶的合成与吸银性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和甲基丙烯酸羟乙酯(HEMA)为单体,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,采用自由基水溶液聚合法制备P(AMPS-co-HEMA)共聚凝胶,通过傅里叶红外光谱(FT-IR)对材料结构进行了表征.研究单体配比、交联剂的用量、引发剂的用量对共聚凝胶吸水性能的影响,并在此基础上对凝胶的溶胀、吸银及消溶胀性能进行研究.结果表明,当单体摩尔比n(AMPS)∶n(HEMA)=2∶1,交联剂用量ω(MBA)=0.6％,引发剂用量ω(KPS)=0.8％,所制得的凝胶吸水性能最好;凝胶在蒸馏水中的溶胀过程属于松弛平衡扩散;凝胶在AgNO3溶液中60min左右达到消溶胀平衡,且当AgNO3溶液的浓度为0.05mol/L时,银离子吸附量最大,为0.04g/g,消溶胀速率最快.     

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.