超大孔P(AA-co-AM)/PVA水凝胶的制备及吸附性能研究

采用泡沫分散聚合法,以饱和Na2CO3水溶液为发泡剂,过硫酸铵(APS)及NaHSO3为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,聚(氧化乙烯/氧化丙烯)(PF127)为泡沫稳定剂,丙烯酸(AA)和丙烯酰胺(AM)为单体,聚乙烯醇(PVA)为第二网络,制备超大孔半互穿水凝胶P(AA-co-AM)/PVA,并研究其对阳离子兰染料的吸附性能。研究表明,P(AA-co-AM)/PVA具有相互贯穿的超大孔结构;当n(AM):n(AA)=1.5:1,w(PVA)=1.6%时凝胶的平衡溶胀度达186.56g/g;凝胶具有很好的离子响应性,在蒸馏水中的平衡溶胀度为129.16g/g时,在0.1mol/L NaCl溶液中只有31.07g/g;对阳离子兰染料溶液的脱色率达92.17%,吸附容量达17.16mg/g。     

DSC研究高吸水树脂吸水性能与分子结构的关系

以丙烯酸(AA)、丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为共聚单体合成了聚丙烯酸-丙烯酰胺-2-丙烯酰胺基-2-甲基丙磺酸(PAA-AM-AMPS)三元共聚物高吸水树脂.利用茶叶袋法测定了其最大吸水倍率,通过差示扫描量热仪(DSC)测定并比较了含水量为50%,75%和91%的各种水凝胶的自由水和结合水含量.结果表明在蒸馏水和生理盐水中高吸水树脂的最大吸水倍率分别为1900g/g和185g/g,共聚物的结合水含量随着AMPS和AA含量增加及AM含量的减少而增大;在0.9%生理盐水中,结合水含量随着AMPS和AM含量增加及AA含量的减少而增大,共聚物和均聚物高吸水树脂的最大吸水倍率呈现出与结合水含量相同的变化规律.     

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.     

聚丙烯酰胺-埃洛石复合型高吸水性树脂的制备及其吸水性能

以丙烯酰胺(AM),丙烯酸(AA)和埃洛石(AL)为原料,环己烷(CYH)为油相,Span 60为分散剂,过硫酸铵(APS)为引发剂,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,经反相悬浮聚合法制备了聚丙烯酰胺-埃洛石复合型高吸水性树脂(1ηγ-ALTa),其结构经SEM表征。考察了单体质量比η[m(AM)∶m(AA)],油水体积比γ[V(油)∶V(水)],MBA用量和ALTa用量[T为煅烧温度,a为酸化浓度]对1ηγ-ALTa吸水性能的影响。在最佳反应条件[Span 60 1.2 g,CYH 154 m L,MBA 12 mg,AM 5.0 g,η=0.5,γ=3.5,AL90015225 mg,APS 0.12 g,于70℃反应3 h]下制备的10.53.5-AL90010吸水性能最好,吸水倍率,吸盐水倍率和溶胀速率分别为1 740.34 g·g-1,246.36 g·g-1和29.0 g·min-1。     

一步乳液聚合法制备高溶解性导电聚苯胺

报道了一种高溶解性导电聚苯胺(PANI)的制备方法,以聚2-丙烯酰胺-2-甲基丙磺酸(PAMPS)作为掺杂酸和乳化剂,利用其特有的长链、亲水性及强酸性基团效应,通过乳液聚合法一步合成出具有较高溶解性的导电聚苯胺。利用核磁共振光谱仪(NMR)、傅里叶红外光谱仪(FT-IR)和扫描电子显微镜(SEM)等技术手段对产物结构和性能进行了表征分析。结果表明,在m(苯胺)∶m(AMPS)∶m(APS)=1∶2∶1.5;AMPS质量分数为20%;APS质量分数为30%;反应时间为5 h;反应温度为5℃的条件下,聚苯胺的产率高达86%,在有机溶剂二甲基甲酰胺(DMF)中的溶解度可达0.3814 g/g,在水中的溶解度可达0.2123 g/g,电导率达5.9 S/cm。     

P(AMPS-co-DMAA)凝胶的制备及对Ag+吸附性能的研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、N,N-二甲基丙烯酰胺(DMAA)为单体,通过水溶液聚合法制备P(AMPS-co-DMAA)凝胶。用红外光谱(FT-IR)和扫描电子显微镜(SEM)等对凝胶的结构进行表征。研究单体配比、交联剂用量、AgNO_3初始浓度对Ag~+吸附性能的影响,结果表明,当n(DMAA):n(AMPS)=4:1,交联剂用量为1.6%,AgNO_3浓度为0.03mol/L时,凝胶最大吸附容量为240mg/g。同时探讨凝胶的吸附动力学,结果表明,准二级动力学模型符合凝胶的吸附动力学,内扩散不是控制吸附过程的唯一步骤。     

泡沫分散聚合法制备超大孔水凝胶及其性能研究

采用泡沫分散聚合法,以自制的4-乙酰基丙烯酰乙酸乙酯(AAEA)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)为单体,制备了具有相互贯穿超大孔结构的快速响应型水凝胶.结果表明,引发剂和交联剂用量分别为2.5%和0.6%时平衡溶胀度最高;当以饱和碳酸钠溶液为发泡剂时制得的凝胶孔洞均匀贯穿;凝胶经无水乙醇处理...     

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。     

新型高吸水聚合物凝胶型屏蔽暂堵剂MTC-1的合成及性能

以丙烯酸（AA）、丙烯酰胺（AM）、2-丙烯酰胺基-2-甲基丙磺酸（AMPS）为原料，蒙脱土（MMT）为改性剂，过硫酸钾和无水亚硫酸氢钠为氧化还原引发体系，六亚甲基四胺（C₆H₁₂N₄）为交联剂，采用水溶液聚合法合成了一种新型高吸水聚合物凝胶型屏蔽暂堵剂（MTC 1），其结构经IR表征。在最优合成条件（AM/AMPS/AA=11/7/1, m/m/m，引发剂加量0.6 wt%，于45 ℃反应2.5 h）下，MTC-1的最大吸水倍率为1006倍。岩心流动实验结果表明：MTC-1的堵水性能较高，封堵效率达到83.72%。     

耐水解高吸水树脂的合成与性能研究

采用2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)、十二烷基苯磺酸钠(LAS)为主要原料,以二乙烯基苯(DVB)为交联剂制备出P(AMPS+AA)高吸水膨胀树脂,考察了AMPS与AA配比、中和度、交联剂种类与用量、LAS加量等合成工艺对吸水树脂性能的影响。研究结果表明,在丙烯酸系吸水树脂中引入AMPS结构单元,有利于提高树脂在盐水中的吸液能力,改善高吸水树脂的耐盐性;在以DVB为交联剂制备P(AMPS+AA)树脂时,LAS加量对树脂性能影响显著,当DVB用量为0.3%-0.45%、十二烷基苯磺酸钠用量0.15%-0.3%时,制备的P(AMPS+AA)树脂具有较高吸水能力,并且其稳定性比N,N’-亚甲基双丙烯酰胺(NMBA)交联的树脂优良,在高温碱性或酸性条件下显示出良好的耐水解性能。     

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.     

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%).     

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.     

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.     

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.     

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.