辉光放电电解等离子体引发合成聚丙烯酸钠/腐植酸复合高吸水性树脂

以丙烯酸和腐植酸为原料,N,N-亚甲基双丙烯酰胺为交联剂,在水溶液中采用辉光放电电解等离子体引发聚合反应制备聚丙烯酸钠/腐植酸复合高吸水性树脂。 考察了放电电压、交联剂、丙烯酸中和度、后聚合温度、腐植酸钠和丙烯酸的含量对树脂吸水率的影响,讨论了树脂在0.9%氯化钠溶液中的溶胀速率和不同pH值溶液中的溶胀行为。 用红外光谱和热重分析分别对产物进行了结构表征和稳定性测试,结果表明,最佳的合成条件为：放电电压470 V、交联剂质量分数为0.6%、腐植酸钠质量分数为4%、丙烯酸质量分数为10%、中和度60%、后聚合温度70 ℃。 所得复合树脂对蒸馏水的吸水率为1152 g/g,对0.9%NaCl溶液的吸水率为89 g/g,800 ℃后复合树脂残留率为44.3%。     

表面交联的三元共聚高吸水树脂的合成及其性能研究

以丙烯酸、丙烯酰胺及丙烯磺酸钠为单体,采用水溶液聚合法制得三元共聚高吸水树脂(SAP1),用乙二醇二环氧甘油醚与氯化铝作交联剂,对SAP1进行表面交联处理得高吸水树脂SAP2。SAP2在加压下吸盐水率高,凝胶颗粒表面干爽且易分散。考察了引发温度、丙烯酸中和度、交联剂、引发剂、丙烯酰胺及丙烯磺酸钠的用量对常压下吸盐水率的影响。同时还考察了乙二醇二环氧甘油醚与无机盐用量对常压及加压下吸盐水率的影响。     

丙烯酸-淀粉-硅藻土复合耐盐性高吸水树脂的紫外光引发合成及其性能

以丙烯酸、淀粉和硅藻土为原料,使用自制的紫外光聚合装置合成了复合耐盐性高吸水树脂。研究了丙烯酸中和度、硅藻土和淀粉用量、辐照时间等因素对树脂的吸液性能的影响,及pH、盐溶液浓度对树脂吸水率的影响,并用红外光谱和扫描电镜对产物进行了表征。在最佳试验条件下合成的高吸水树脂的吸去离子水率为3 665 g/g,吸生理盐水率(w=0.9%的NaCl水溶液)为280 g/g。     

辉光放电电解等离子体引发合成高吸水性树脂

以淀粉、丙烯酸和腐殖酸钠为原料,以N,N-亚甲基双丙烯酰胺为交联剂,采用辉光放电电解等离子体在水溶液中引发聚合制备淀粉-聚丙烯酸/腐殖酸钠复合高吸水树脂。考察了放电电压、放电时间,单体与淀粉质量比、腐殖酸钠含量、交联剂、温度及中和度对树脂吸水率的影响。用红外光谱和热重分析分别对树脂进行了结构表征和稳定性测试,结果表明,在优化合成条件下,所得的复合树脂具有较高的吸水性和耐盐性,常温下对蒸馏水吸收量为862g/g,对0.9%NaCl溶液的吸收量为69g/g。     

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%。     

3种丙烯酸系列高吸水树脂的吸水性能

采用反相悬浮聚合法合成了3种聚丙烯酸系列吸水树脂：聚丙烯酸钠(PAA)、丙烯酸-丙烯酰胺共聚物(P(AA/AM))和丙烯酸-马来酸酐共聚物(P(AA/MA))。 对3种树脂的吸水性、保水性、耐候性和耐电解质等性能进行测试比较。 结果表明,P(AA/MA)的吸水性能最优异,10 min内吸蒸馏水量可达3578.4 g/g;在一定的温度或压力范围内,3种树脂均有良好的保水性能,在不同温度下储存均能保持各自的吸水性;P(AA/MA)的耐电解质性能较为突出,吸生理盐水量可达107.2 g/g,其综合性能最好。     

AA/AMPS共聚型吸水树脂反相悬浮合成工艺研究

以过硫酸铵－亚酸钠为引发剂，用反相悬浮法合成丙烯酸／2－丙烯酰胺基－2－甲基丙烷磺酸共聚型吸水树脂，最佳工艺条件为：N，N－亚基双丙烯酰胺浓度＝1．082mmol.L^-1，丙烯酸中和度为80％，2－丙烯酰胺基－2－甲基丙烷磺酸的质量分数w=0.30,OP4-PEG的质量分数w=0.003，双组分引发剂浓度＝22．64mmol.L^-1，反应温度50摄氏度，共聚物吸液率（水及生理盐水）A为：AH2O=1070mL.g^-1,Anormal aaline=220mL.g^-1，抗电解质能力高于聚丙烯酸钠或丙烯酸钠与丙烯酰胺的共聚物（反相悬浮法合成），140℃以上热稳定性低于聚丙烯酸钠，保水性与其相当。     

高耐盐性吸水树脂的紫外光引发合成及其性能

采用紫外光引发聚合法合成了聚乙烯醇与丙烯酸钠高耐盐性吸水树脂.用红外光谱和热重分析法对产物进行了表征,测定了该树脂的溶胀动力学、可逆性能及温度、pH、离子浓度和有机溶剂等因素对树脂吸附率的影响.结果表明:该树脂在蒸馏水中的吸水率为4 100 g/g,在w=0.9%的NaCl水溶液中的吸盐水率为405 g/g;树脂的吸液率与阳离子的价态有关,其吸液率大小顺序为NaCl＞CaCl2＞FeCl3;其溶胀动力学扩散过程中的膨胀指数0.5＜n＜1,属于non-Fickon扩散.     

均相条件下甲壳素基高吸水树脂的制备及性能研究

利用冻融循环处理破坏甲壳素致密的晶体结构和氢键相互作用,使甲壳素溶解在8 wt%NaOH/4wt%urea水溶液中,制备了碱-甲壳素均相溶液.采用静态溶液聚合法,以过硫酸铵(APS)为引发剂、甲叉双丙烯酰胺(MBA)为交联剂,在均相条件下制备了甲壳素接枝聚丙烯酸钠高吸水树脂.研究了丙烯酸、NaOH、MBA和APS用量以及反应温度和时间对产物吸水性能和得率的影响.在最优化条件下制备的树脂的最大吸蒸馏水、自来水、生理盐水和人工尿液倍率分别可达1251,455,84和77 g.g-1.采用FTIR和XRD对合成的树脂进行初步结构表征,证明反应过程中甲壳素与丙烯酸发生了接枝共聚反应,而不是甲壳素与聚丙烯酸钠的简单物理共混.     

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.     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.