基于超支化聚合物两性水凝胶的制备及性能

通过N-丙烯酰-1,2-乙二胺盐酸盐(ADE)的Michael加成反应制备阳离子超支化低聚物聚N-丙烯酰-1,2-乙二胺盐酸盐(HADE),以HADE为大分子单体,以丙烯酰胺(AAm)和丙烯酸(AAc)为单体,在无需外加有机交联剂的条件下制备具有高机械强度的两性聚电解质水凝胶(HAH凝胶).结果表明,HAH凝胶可以被压缩超过99%的形变而不断裂,压缩强度高达61.2 MPa;HAH凝胶的断裂伸长率和断裂强度分别达到1700%和70.2 k Pa.由于HADE末端伯胺基与强氧化引发剂通过氧化还原反应生成胺自由基和自身结构中的双键同时参与聚合反应,因而为凝胶网络形成提供了必要的化学交联作用.同时HADE结构中胺基正电荷与AAc的羧基负电荷之间的离子交联也为凝胶网络提供了物理交联作用.2种交联作用的协同作用是HAH凝胶具有良好机械性能的根本原因.     

丙烯酰乙二胺盐酸盐的合成

丙烯酰氯与Boc单保护的乙二胺反应,合成了功能单体--丙烯酰乙二胺盐酸盐,总收率65%,其结构经1H NMR和IR表征.     

一锅法制备pH响应性聚丙烯酰基乙二胺盐酸盐-卟啉/芴荧光聚合物

采用可逆加成-断裂链转移聚合法(RAFT)制备了含有双硫酯片段的聚N-叔丁基氧羰基-丙烯酰基乙二胺(PBAEN).利用一锅法制备出含卟啉(EPT)或芴(DEPF)单元的PBAEN.经脱保护反应得到水溶性聚丙烯酰基乙二胺盐酸盐-卟啉(PAEN-EPT)和聚丙烯酰基乙二胺盐酸盐-芴(PAEN-DEPF).PAEN-EPT和PAENDEPF具有良好的水溶性,其中PAEN-EPT的荧光量子产率达0.097.当溶液pH≥7时,PAEN-EPT和PAEN-DEPF均出现荧光猝灭现象.PAEN-EPT和PAEN-DEPF的pH响应行为使得该类聚合物在水溶性荧光探针领域具有潜在的应用前景.     

N-(2-乙烯氧乙基)-1,8-萘二甲酰亚胺聚合物与共聚物的荧光行为

<正> 我们曾报道过一系列含有给电子生色基团的丙烯酰类单体如甲基丙烯酸二甲氨基苄酯、N-(N′,N′-二甲氨基苯基)丙烯酰胺类、8-丙烯酰氧喹啉类、N-丙烯酰-N′-苯基哌嗪类、N-丙烯酰-N′-嘧啶哌嗪类、N-甲基丙烯酰氧乙基-N-甲基代苯胺等的合成、聚合、引发行为以及它们的聚合物的荧光行为。这些单体结构的共同点在于其双键为缺电子性而生色基团为给电子性,因而在荧光行为上,由于生成激基复合物或电荷转移而发生荧光     

N-甲基丙烯酰-N′-嘧啶基哌嗪及其聚合物敏化的丙烯腈光聚合

我们曾报道过同一分子中含有给电子生色基团和电子受体基团的一类功能性单体,如甲基丙烯酸-4-N,N-二甲氨基苄酯(DMABMA),N-(4-N′,N′-二甲氨基苯基代丙烯酰胺,N-(4-N′、N′)-二甲氨基苯基代甲基丙烯酰胺(DMAPMA),8-丙烯酰氧喹啉(AQ),N-丙烯酰-N′-苯基哌嗪(APP)的合成、聚合以及单独或与过氧化二酰构成氧化还原体系以引发烯类单体的聚合研究。N-甲基丙烯酰-N′-嘧啶基哌嗪(MPMP)     

聚丙烯酸修饰咔唑的电化学聚合及表征

合成了侧链带有咔唑的N-丙烯酰氧己基咔唑(MACZ),通过自由基聚合得到聚N-丙烯酰氧己基咔唑(PMACZ),在四氢呋喃含10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中,直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧己基咔唑)(PPMACZ)薄膜.PPMACZ薄膜具有良好的氧化还原性和热稳定性,电导率为1.34×10-5S·cm-1.1HNMR和红外光谱表明PMACZ二次聚合反应发生在咔唑单元的3,6位上,荧光光谱表明PPMACZ薄膜是一种良好的蓝色发光材料.     

烷基步长对聚丙烯酸修饰咔唑电聚合的影响

合成了含有不同烷基链取代的N-丙烯酰氧癸基咔唑(MACZ10)和N-丙烯酰氧十二烷基咔唑(MACZ12), 通过自由基聚合得到聚N-丙烯酰氧烷基咔唑(PMACZ). 分子量分析表明, 随着烷基链长度的增加, 聚合物分子量减小, 分布变宽. 荧光光谱表明, 随着烷基链长度的增加, 聚合物在353 nm处的发射峰逐渐减弱. 在四氢呋喃和体积分数为10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中, 直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧烷基咔唑)(PPMACZ)薄膜. PPMACZ薄膜具有良好的氧化还原活性、热稳定性和蓝色发光性能, 聚合物氧化还原可逆性随着烷基链长的增加而增加, 且发射峰变宽.     

具有pH和还原双重敏感性壳聚糖纳米微凝胶的制备及其控释性能

以含双硫键的N,N-二(3-羧基丙烯酰)胱胺(BCCy)为交联剂,在1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐/N-羟基琥珀酰亚胺(EDC/NHS)的催化下将壳聚糖(CS)交联,在水溶液中制备了纳米微凝胶。通过红外、元素分析、纳米粒度仪和扫描电镜等对其结构和形貌进行了表征,考察了pH和还原性环境对粒径的影响。对抗癌药物喜树碱(CPT)进行了负载,考察了载药粒子在还原性环境中对药物的控释性能。结果表明:随交联剂用量的增加,纳米微凝胶的粒径减小。该纳米微凝胶具有较好的生物相容性、较显著的pH和还原敏感性。     

亲电硫试剂参与的2-芳基-3-硫代-2,3-二氢喹啉-4(1H)-酮的合成

以(E)-1-(2-对甲苯磺酰胺基)-3-芳基丙-2-烯-1-酮(1)为底物与N-硫代丁二酰亚胺(2)通过亲电环化反应合成了2-芳基-3-硫代-2,3-二氢喹啉-4(1H)-酮类化合物。以三氟化硼乙醚(20(mol)%)为催化剂、1,2-二氯乙烷为溶剂、60℃下反应,可以60%～92%的收率得到一系列2-芳基-3-硫代-4(1H)-喹啉酮衍生物。化合物3a～3l未见文献报道,其结构均经1H NMR、13C NMR以及高分辨质谱进行确定。     

1,2-二甲基咪唑啉的合成及表征

对1,2-二甲基咪唑啉的合成进行了详细研究. 以甲胺水溶液和2-溴乙胺氢溴酸盐(1)为原料进行反应, 在两种原料物质的量之比为5∶1, 缓缓回流12 h的条件下, 得到N-甲基乙二胺(2), N-甲基乙二胺经过乙酸化得到N-甲基-N,N′-二乙酰基乙二胺(3), 然后, N-甲基-N,N′-二乙酰基乙二胺和氧化钙在高温下关环得到1,2-二甲基咪唑啉(4). 并对所得到的产物1,2-二甲基咪唑啉经元素分析, 1H NMR, IR和GC-MS得到了表征.     

<Emphasis Type="Italic">N</Emphasis>-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/<Emphasis Type="Italic">γ</Emphasis>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

A simple method for N-alkylation of 1,2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/γ-Al₂O₃ as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of 1,2-diaminoethane with both primary and secondary alcohols. Mono-N-alkylation of 1,2-diaminoethane with low-carbon alcohols resulted in high yields; the yields of tetra-N-alkylation of 1,2-diaminoethane with low-carbon alcohols declined markedly with the increase of the molecular volume of alcohols.     

Characterization and demulsification of produced liquid from weak base ASP flooding

Weak base alkali-surfactant-polymer (ASP) flooding technology has been applied in Daqing oilfield to enhance oil recovery. The effects of ASP on the characteristics of oil droplets in produced liquid were investigated. Surfactant can decrease interfacial tension (IFT) and zeta potential, making main contribution to the stability of oil droplets. Weak alkali (Na₂CO₃) can decrease IFT and polymer can decrease zeta potential, resulting in stable oil droplets in produced liquid. The produced liquid from weak base ASP flooding is easier to treat than that from strong base ASP flooding. A mixed demulsifier GFD410-8 was prepared and used to enhance oil–water separation in produced liquid. When the demulsifier dose of 50 mg/kg was used to demulsify the simulated produced liquid with the concentrations of alkali 2000 mg/kg, surfactant 600 mg/kg and polymer 600 mg/kg, water volume and water content after 30 min settling were less than 30% and 1000 mg/L, respectively. The demulsifier also greatly decreased water content in oil phase and oil concentration in water phase for actual produced liquid from oil well. The demulsification mechanism was also investigated in terms of IFT and zeta potential.     

Synthesis of nitrogen containing heterocycles over copper chromite

The reactions of 1,2-diaminopropane, 1-amino-2-propanol, 1-amino-2-ethanol and N-(-aminoethyl)-1,2-diaminoethane in the gas phase over copper chromite have been investigated with the objective of synthesising nitrogen containing heterocycles. At 240–360°C 1,2-diaminopropane gave principally methyl- and 2,5-dimethylpyrazine, whereas the basic reaction for 1-amino-2-propanol was dehydration to give 1-aminoethyl-2-methylaziridine (with a selectivity of up to 78%). The main cyclic product from the dehydration of 1-amino-2-ethanol was pyrazine, while piperazine was farmed together with pyrazine from N-(-amonoethyl)-1-2-diaminoethane.Latvian Institute of Organic Synthesis, Riga, LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 950–957, July, 1994.     

乙酰基硫代甲酰芳胺合成二氢吡嗪的研究

报道了一种合成乙酰基硫代甲酰芳胺的方法. 合成的乙酰基硫代甲酰芳胺与1,2-乙二胺缩合生成5-(4'-取代苯胺基)-6-甲基-2,3-二氢吡嗪类杂环化合物.     

Electronic properties of n-type carbon nanotubes prepared by CF4 plasma fluorination and amino functionalization

Single-walled carbon nanotubes (SWNTs) have been fluorinated by CF4 plasma exposure and further functionalized with 1,2-diaminoethane. The degree of amino functionalization is dependent on the degree of initial fluorination rather than oxygen or carbon defects. Reaction at both ends of 1,2-diaminoethane was observed to increase with fluorine content. Back-gated SWNT devices have shown p-type semiconducting behavior for CF4-functionalized SWNTs and n-type semiconducting behavior for amino-functionalized SWNTs. The degree of n-type behavior increases with the amount of nitrogen attached to the SWNTs.     

Separation and Determination of Diol Pollutants Come from Demulsifier in the Produced Water of Oil Fields

This paper introduced a novel test method for determination of the main demulsifier‐based pollutants in the produced water of oil wells, before draining to seawater. The type, concentration and distribution of diols depend on the demulsifier of interest; however, the main chemical species are the same. The novelty of this work is selective extraction and preconcentration of low chain diols in the produced water of oil fields. In this extraction method, dispersive solvent (1.2 mL, acetonitrile) containing extraction solvent (10.0 μL, carbon tetrachloride) was rapidly injected into the water sample containing analytes, and a cloudy solution was formed. After centrifugation (2 min at 3,000 rpm), these droplets were sedimented in the bottom of the conical test tube. Then 2.0 mL of sedimented phase containing preconcentrated analytes was injected into the gas chromatograph with flame ionization detector. The parameters affecting the extraction efficiency were evaluated and optimized. Factors such as the kind and volume of both extraction and disperser solvents, extraction and centrifugation times, pH and temperature, and salt effect were studied and optimized. The method exhibited enrichment factors and recoveries ranging from 39.0 to 44.4 and 78.9 to 92.2%, respectively, within very short extraction time. The linearity (and limit of detection) of the method ranged 4.0‐100.0 (2.0) ng/mL for 1,2‐ethandiol, 6.0‐80.0 (4.0) ng/mL for 1,3‐propandiol, 2.0‐90.0 (1.0) ng/mL ng/mL for 1,4‐butanediol, 5.0‐120.0 (2.0) ng/mL for 1,5‐pentandiol. The relative standard deviations (RSD) for the concentration of diols, 5.0 ng/mL in water by using the internal standard were in the range of 1.5–4.5% (n = 5) and without the internal standard was in the range of 2.6–9.0% (n = 5). It is concluded that this method is successful for determination of diols in produced water samples.     

The Application and Research of Dispersing In Situ Nano-SiO2 in Polyether Demulsifier TA1031

In order to enlarge the application range of nanomaterial and improve the demulsification performance of macromolecule polyether demulsifier, the nano-SiO₂ was dispersed in situ in polyether demulsifier TA1031 to form a new high efficiency demulsifier. The new demulsifier was analyzed by FTIR, SEM, rotational viscometer, and interfacial tension meter. The result showed that dispersing nano-SiO₂ in crude oil demulsifier would greatly improve the demulsification performance of the original demulsifier. When the ratio of silicon dioxide and TA1031 is 1:10 (mass ratio), the demulsification performance of the new demulsifier was the best, and the dehydration rate of emulsion increased about by 20%. Also the time of demulification and dehydration would be greatly shortened, and the demusification mechanism was preliminary analyzed.     

N,N'-二(2-羟苄基)取代咪唑烷的合成、表征及抑菌活性

利用生物活性叠加原理,将"邻羟苯基"和"咪唑烷"分子片断有机结合,以水杨醛和乙二胺为起始原料,经缩合、NaBH4还原制得N,N'-二邻羟苄基乙二胺(2),进而与芳醛类化合物缩合关环,合成了8种N,N'-二(2-羟苄基)取代咪唑烷类化合物(3a～3h). 化合物的结构经1H NMR、IR、MS和元素分析等测试技术进行了表征. 结果表明,水杨醛与乙二胺的缩合反应,可专一性地生成对称双缩席夫碱化合物(1);芳醛上的取代基对缩合关环反应有显著影响,邻、对位吸电基可使芳醛的羰基活化,有利于缩合关环反应的进行,邻、对位供电基可使芳醛的羰基钝化,不利于缩合关环反应进行. 抑菌测试结果表明,质量分数为0.1%时,N,N'-二(2-羟苄基)取代咪唑烷化合物对不同菌株的抑菌活性具有明显的特异性,对白色念珠菌、大肠杆菌的抑菌率达100%.