聚丙烯酰胺的水解

本文报告聚丙烯酰胺的硷性水解及酸性水解。用浓酸或浓硷处理,都可接近完全水解,用稀酸或稀硷水解则不完全。在0.6～3.3N氢氧化钠及100°时,水解程度为65—70％,Van Slyke法可用以测定丙烯腈与丙烯酰胺共聚物中酰胺基量。用X-射线衍射法测定聚丙烯酰胺长链的等同周期为5.2A。硷性水解之不完全,主要是由于邻近羧基的负电场对羟基向酰胺基进攻时的屏蔽作用所致。合成丙烯酰胺分别与丙烯酸、丙烯醇、或乙酸乙烯酯的共聚物,从而研究其硷性水解,前者的水解限度为75％,后二者可以接近完全,直接证明邻近非负性基团不能产生负电场因而没有屏蔽作用,故水解接近完全。研究若干N取代聚丙烯酰胺及共聚物的水解,在一定条件下它们的水解程度按下列次序递减:聚丙烯酰胺>聚N-甲基丙烯酰胺>聚N,N-二甲基丙烯酰胺>聚N,N-二乙基丙烯酰胺。除了邻近负电场的屏蔽作用外,N及N,N-取代基在长链中有不容忽视的空间阻碍。     

Fenton试剂氧化处理模拟含聚丙烯酰胺污水的研究北大核心CSCD

主要研究了利用Fenton试剂氧化法处理模拟含部分水解聚丙烯酰胺的污水,考察了H2O2浓度、Fe2+浓度、温度、反应时间、pH值等因素对Fenton试剂氧化降解模拟含部分水解聚丙烯酰胺污水的影响。结果表明:H2O2浓度为5.3mmol.L-1、Fe2+浓度为1.44mmol.L-1、温度30℃、反应时间15min、pH值范围3～4时,聚丙烯酰胺的氧化降解效果最好,且在最佳条件下,聚丙烯酰胺和CODCr的去除率分别达到87.61%和82.60%。通过对Fenton氧化降解前后的聚丙烯酰胺样品的红外谱图对比,可以推断出Fenton试剂将侧链的酰胺基氧化成羧基。     

部分水解聚丙烯酰胺/Cr(Ⅲ)交联作用的研究方法

部分水解聚丙烯酰胺（HPAM）／Cr(Ⅲ）凝胶已在油田广泛应用，是一类有效的调剖堵水剂，对于调整吸水剖面和提高原油采收率起到重要作用。本文简要概述HPAM/Cr(Ⅲ）交联反应机理的研究方法，如粘度法，紫外－可见吸光光度法，原子力显微镜（AFM），激光光散央求地，原子吸收法等，并对流变学法的应用进行了重点介绍。     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基两酸）大分子单体，用端基滴定法和１Ｈ—ＮＭＲ法测定了大分子单体的分子量，用１３Ｃ—ＮＭＲ和氢氧化钠水解法测定了支化度．在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酸胺、丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）接枝共聚物．用１Ｈ—ＮＭＲ和滴定法测定了接枝共聚物的组成．溶液性质的数据表明，与部分水解聚丙烯酰胶相比，聚（β－胺基丙酸）含量较高的接枝共聚物具有较好的耐盐性和优异的贮存稳定性．     

三羟甲基苯酚与部分水解聚丙烯酰胺成胶机理研究

采用13C固体核磁共振技术、X-射线电子能谱及红外光谱技术对部分水解聚丙烯酰胺(HPAM)与三羟甲基苯酚交联前后的结构进行了表征,发现体系中生成仲胺基团的同时伯胺基团有所减少;进一步采用两种表征手段对一系列交联样品进行了测试,定量地计算了仲胺基团含量的增加和伯胺基团含量的减少,得到一致的结果;在此基础上提出了水溶性酚醛交联剂与HPAM的交联机理.     

聚丙烯酰胺稀溶液的粘度与剪切速率的关系的研究

聚丙烯酰胺稀溶液的粘度与剪切速率的关系的研究陈九顺，刘忠义，刘波，张艳红（黑龙江大学化学系，哈尔滨，１５００８０）关键词聚丙烯酰胺，部分水解聚丙烯酰胺，粘度，剪切速率水溶性高聚物聚丙烯酰胺（ＰＡＭ）和部分水解聚丙烯酰胺（ＰＨＰ）的水溶液是一种假塑性流...     

聚丙烯酰胺和部分水介聚丙烯酰胺溶液粘度及分子量

丙烯酰胺自1954年由美国氰胺公司实现工业化生产以来,日益受到重视,应用日广,其聚合体聚丙烯酰胺(简称PAM)因其具有某些优异性能而在石油开采、造纸、食品、印染、医药、水质处理等部门得到了广泛的应用。近年来,国内的使用量也急速增加。聚丙烯酰胺除了直接使用外,相当一部分是使用其部分水介产物,即部分水解聚丙烯酰胺(简称HPAM)。聚丙烯酰胺在碱性(或酸性)情况下,发生水介,部分酰胺基反应而变成羧基,其反应式如下:     

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.     

水溶性聚合物和两亲聚合物：聚（丙烯酰胺－co－丙烯酸钠）－g－聚（β－胺基丙酸）接枝共聚物

合成了端丙烯酰胺基聚（β－胺基丙酸）大分子单体，用端基滴定法和１Ｈ－ＮＭＲ法测定了大分子单体的分子量，用＾１＾３Ｃ－ＭＮＲ和氢氧化钠水解法测定了支化度，在水溶液中用硫酸亚铁／异丙苯过氧化氢氧化还原引发体系引发丙烯酰胺，丙烯酸钠与聚（β－胺基丙酸）大分子单体的共聚反应，合成了聚（丙烯酰胺－ｃｏ－丙烯酸钠）－ｇ－聚（β－胺基丙酸）用１Ｈ－ＮＭＲ和滴定法测定了接枝共聚物的组成。溶液性质的数据表明，与部分     

聚丙烯酰胺与Cr(Ⅲ)低聚物交联机理的研究

采用分离Cr(Ⅲ )低聚物 ,分别考察其与聚丙烯酰胺反应活性的方法 ,研究了Cr(Ⅲ )低聚物与部分水解的聚丙烯酰胺交联机理 .用离子交换色谱法分离Cr(Ⅲ )低聚物得到纯的单体、二聚体和三聚体 ,经紫外、氧化还原滴定和离子色谱法确定了它们的结构 ,分别用它们与部分水解的聚丙烯酰胺交联反应 .在pH =6～ 12 ,聚合物浓度在 30 0～ 10 0 0mg L ,交联剂Cr(Ⅲ )浓度在 2～ 2 5mg L的范围 ,对成胶因素进行对比研究 .实验结果发现二聚体成胶的pH范围宽 ,用量少 ,三聚体次之 ,单体最差 .说明Cr(Ⅲ )低聚物是成胶反应的决定步骤 ,二聚体的反应活性最高 .从而完善地阐述了Cr(Ⅲ )离子与聚丙烯酰胺交联反应的机理     

聚丙烯酰胺水溶液粘度依时性及其稳定剂

本文对常用的粘度法测定聚丙烯酰胺分子量体系ＰＡＭ－１ｍｏｌ／ＬＮａＮＯ３、ＰＡＭ－０．１ｍｏｌ／ＬＮａ２ＳＯ４和ＰＡＭ－０．５ｍｏｌ／ＮａＣｌ的粘度进行了稳定性考察，并对上述体系加入少量不同种类的稳定剂，考察其粘度对时间的依赖性，确定了粘度法测定ＰＡＭ分子量的适宜溶液体系。     

腐植酸钠/聚丙烯酰胺/粘土杂化水凝胶的研究

以过硫酸钾为引发剂、N,N′-亚甲基双丙烯酰胺为交联剂、丙烯酰胺单体和腐植酸钠、Laponite RD粘土为原料,用溶液聚合交联法合成了腐植酸钠/聚丙烯酰胺/粘土(SH-PAM-Clay)系列水凝胶.用场发射扫描电镜对其表面形貌进行了研究,并对水凝胶的吸水性和流变性能进行了测试和研究.结果表明这系列水凝胶都具有致密的网络结构和优良的吸水性能.     

壳聚糖固定化总状毛霉MR137-3蛋白酶的性质

以壳聚糖为载体,戊二醛作交联剂,将总状毛霉MR137—3蛋白酶固定在壳聚糖上。研究了戊二醛浓度,给酶量,处理时间对MR137—3蛋白酶固定化的影响。同时对固定化酶与游离酶的热稳定性、最适pH、最适温度以及脲、有机溶剂、金属离子的影响等理化性质进行了探讨。     

Dehydration of 1,4-dioxane by pervaporation using filled and crosslinked polyvinyl alcohol membrane

Polyvinyl alcohol (PVOH) membrane, was modified both physically and chemically by incorporation of inorganic filler, sodium aluminosilicate and chemical crosslinking with maleic acid and glutaraldehyde. The change of morphology and crystallinity of PVOH by this physical and chemical modification was studied by FTIR, DSC, TGA, SEM and XRD. These membranes were evaluated in terms of its potential for dehydration of dioxane by preferential sorption and permeation using pervaporation (PV) technique. These membranes were cast in the laboratory by solution casting from the polymer and other additives. The performance of the unfilled (containing no filler) glutaraldehyde (GA) crosslinked PVOH-1 and maleic acid (MA) crosslinked PVOH-2 membranes were compared with filled (containing aluminosilicate filler) but GA crosslinked PVOH-3 and filled but MA crosslinked PVOH-4 membranes. The filled membranes were found to show higher flux and water selectivity. Among all the four used membranes, the MA crosslinked filled PVOH-4 membrane was found to show best results in terms of both water selectivity and flux.     

Synthesis and properties of porous polyvinylamine microspheres from acrylonitrile

A novel route to synthesize crosslinked porous polyvinylamine (PVAm) microspheres from acrylonitrile (AN) was developed. In the first step, crosslinked porous polyacrylonitrile (PAN) spheres were prepared by copolymerization of AN and divinylbenzene (DVB). Then they were hydrolyzed to form polyacrylamide (PAM) spheres. And lastly, the porous PVAm spheres were successfully obtained via Hofmann degradation of PAM spheres. Scanning electron microscope (SEM) indicated that these PVAm microspheres have rough surfaces and porous interior structure. The pore size, the amino content, and the content of equilibrium water were also investigated. The pore size of these PVAm microspheres increased with the hydrolytic process. The contents of equilibrium water was changed from 49.6 to 96.5% depending on the different crosslinking degrees, and the amino contents were varied between 9.60 and 15.30 mmol/g depending on the different molar ratio of n(NaClO)/n(NaOH). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1674–1682, 2008     

Synthesis and Characterization of Biosuperabsorbent Based on Ovalbumin Protein

A biosuperabsorbent (Bio-SAP) hydrogel from ovalbumin (egg protein) was synthesized via modification with an acylating reagent and a bifunctional crosslinker, and its swelling behavior was investigated. The protein was acylated using ethylenediaminetetraacetic dianhydride (EDTAD), and then crosslinked by glutaraldehyde and dried. Bio-SAP provided through this method includes modification of lysyl residues in the unfolded protein by adding one or more hydrophilic carboxyl groups to increase the hydrophilicity of protein. The water binding capacity was measured in deionized water, 0.9% NaCl solution and synthetic urine, which under the best conditions were 296, 64 and 56 g/g after 24 h, respectively. In addition, the effects of EDTAD/protein ratio on the chemical modification of the protein, the various chemical neutralization agents, pH sensitivity and ionic strength, as well as temperature and particle size on the water absorption capacity with and without load and its kinetic were also investigated.     

Gelation kinetics of PAM/PEI system

Excess water production in oil and gas wells causes serious productivity and environmental problems in the oilfield. A mixture composed of a polymer, cross-linker, and water is usually injected into the reservoir to block unwanted water by forming a three-dimensional structure. This transition process from solution to gel is a function of temperature, time, salinity of mixing water, and concentration of the various components. The gelling solution was prepared by mixing polyacrylamide (PAM) with distilled water, and then polyethylenimine (PEI) was added as a cross-linker. The injection process was simulated and investigated by differential scanning calorimeter (DSC) over the temperature range of 80–120 °C. The DSC dynamic scan showed two consecutive peaks. An endothermic peak was observed at low temperature due to PAM alkaline hydrolysis which ends at around 60 °C. Another exotherm was observed at ~70 °C which corresponds to the onset of cross-linking of PAM and PEI. It was found that high temperatures lead to high release of heat due to gelation. The effect of salts on the cross-linking was also examined. More delay in cross-linking was observed in the case of NH₄Cl compared to NaCl. The gelation kinetics was modeled using a rate process model that relates fractional gelation with time. Further, Avrami model, usually used to study crystallization kinetics, was also used to model the gelation process. Kinetic parameters were obtained from the two different models, and the results showed good agreement with experimental data. The presence of salts in seawater leads to a drop of 60–80 % in the rate constant without influencing the order of the gelation reaction.     

Selective retention of some polyaromatic hydrocarbons by highly crosslinked polymer networks

Highly crosslinked polymer networks were characterized in terms of structural differences based on the crosslinked network structures with their chromatographic molecular retentivity for some polyaromatic hydrocarbons (PAHs). Because PAHs and some sterically bulky solutes were used in the chromatographic characterization, tiny differences in the crosslinked polymer networks were observed in terms of the chromatographic molecular retentivity. Ethylene dimethacrylate afforded molecular retentivity for anthracene, and this recognition ability changed with the polymerization time. In addition, 1,4‐butanediol dimethacrylate afforded molecular retentivity for pyrene, and this retentivity was larger than that for anthracene. The polymerization methods also affected the resulting polymer networks drastically. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2556–2566, 2005     

mPAM/mCMC双极膜电解槽中MnO2电催化氧化制备甘油醛

分别以FeCl3和戊二醛等对羧甲基纤维素(CMC)和聚丙烯酰胺(PAM)进行改性, 制备了mPAM/mCMC双极膜. 测定了PAM、CMC胶体的电荷密度, mPAM/mCMC双极膜离子交换能力、I-V工作曲线等参数. 用扫描电镜和红外光谱对膜形貌与成分作表征, 膜厚≈260 μm, 中间界面层厚为纳米级. 热重分析表明膜具有较好的热稳定性. 以mPAM/mCMC双极膜为电解槽的隔膜, 间接电氧化甘油为甘油醛. 在电场的作用下, 双极膜中间层中的水离解产生H＋和OH−, OH−及时地传输入阳极室, 中和了电生成甘油醛时生成的H＋, 促进了正向反应的进行. 槽电压稳定, 产率达91.6%, 电流效率为65.5%.     

Direct astatination of a tumour-binding protein, human epidermal growth factor, using nido-carborane as a prosthetic group

We have investigated a method for direct astatine labeling of proteins. Binding sites for astatine were created by coupling of a nido-carborane derivative to a protein, the human epidermal growth factor (hEGF), using two different conjugation methods - by glutaraldehyde cross-linking or by introduction of sulfohydryl groups by Traut's reagent with subsequent linking of ANC-1 with m-maleimidobenzoyl-N-hydroxysulfosuccinimide ester. The conjugates were astatinated using the Chloramine-T method in high yield. The best labeling was obtained by the glutaraldehyde conjugate with an average yield of 68±9%. In vitro stability tests indicated that the glutaraldehyde conjugated label was as stable as hEGF labeled with astatobenzoate.