疏水缔合聚丙烯酰胺的合成及溶液性能研究

水溶性疏水缔合聚合物是在聚合物亲水主链上引入极少量疏水基团(一般小于2ｍｏｌ%)而形成的一种新型水溶性聚合物[1]。由于这类聚合物具有独特的流变性能,因而备受学术界和工业界关注。目前已作为涂料增稠剂[2]和流变改性剂[3]得到了应用,而通过在部分水解聚丙烯酰胺(ＨＰＡＭ)的亲水主链上引入少量疏水单体而形成的疏水缔合聚丙烯酰胺(ＨＡＰＡＭ)则可望克服ＨＰＡＭ耐温、耐盐性差的缺陷[4]而作为新一代水溶性聚合物材料用于油气开采作业[5,6]。由于亲水单体和疏水单体的不相容性,通常通过在反应溶液中加入表面活性剂使亲水单体和疏水单体…     

改性聚丙烯酰胺水溶液的疏水缔合性质

合成了一种疏水缔合水溶性聚丙烯酰胺共聚物,使用荧光光谱法并结合紫外及流变性实验,对制备的疏水缔合水溶性聚丙烯酰胺共聚物在水溶液中形成疏水微区、超分子聚集体及空间网络结构进行了研究,并用扫描电子显微镜证实了溶液中网络结构的存在.     

疏水缔合聚丙烯酰胺的合成和表征的研究进展

论文综述了疏水缔合聚丙烯酰胺(HAPAM)的合成方法,包括共聚合法和化学改性法。共聚法主要包括非均相共聚法,均相共聚法,反相(微)乳液聚合法,胶束共聚合法,模板聚合法,无皂乳液聚合法,活性阴离子聚合法,超临界CO2介质法。此外,论文还对HAPAM的表征方法进行了综述,并对HAPAM的合成和表征方面的发展前景进行了展望。     

含氟疏水缔合聚丙烯酰胺的制备及溶液性质研究

以异佛尔酮二异氰酸酯(IPDI)、四氟丙醇(FOH)和烯丙基聚乙二醇(APEG1200)为原料合成了含氟表面活性单体(FSM),并以FSM为疏水单体,在它的胶束溶液中实现了其与丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)的水溶液共聚合,制备出含氟疏水缔合聚丙烯酰胺(FAPAM)。采用流变仪研究了FAPAM水溶液的疏水缔合性能,并考察了盐、剪切率和温度对FAPAM缔合性能的影响。结果表明,FAPAM水溶液的疏水缔合性能受FSM含量的影响,具有一定的耐盐性。FAPAM属于假塑性体系,表现出较强的抗剪切性能。适当升高温度对FAPAM水溶液的疏水缔合有一定的促进作用。     

一种水溶性疏水缔合聚合物二临界缔合行为研究

对三元共聚疏水缔合聚合物（丙烯酰胺／十八烷基二甲基烯丙基氯化铵／苯乙烯）的临界缔合浓度进行研究,发现其具有二临界缔合现象以及其在二临界缔合浓度附近不同的耐温抗盐的流变行为。研究结果表明,该疏水缔合聚合物的第一临界缔合浓度（C1^＊）为500mg／L,第二临界缔合浓度（C2^＊）为2400mg／L;C2^＊附近聚合物溶液的耐温性能较差;抗盐性能表现出三种不同的情况：随着盐质量浓度的增加,C〈C1^＊时,溶液粘度下降;C1^＊〈C〈C2^＊时,溶液粘度先增加后下降;C〉C2^＊时,溶液粘度先快速增加,后缓慢增加,最后下降。     

水溶性疏水缔合型聚(丙烯酰胺-丙烯酸十六酯)溶液性质的研究

采用沉淀聚合法制备水溶性的丙烯酰胺－丙烯酸十六疏水缔合型共聚物,研究了共聚物水溶液的性质及其影响因素。随着疏水基团含量增加,共聚物在纯水中及NaCl溶液中的特性粘数[η]均减小,疏水基团临界缔合浓度降低。共聚物溶液浓度高于监界缔合浓度时,溶液表现粘度急剧增加,表明溶液中分子间缔合大量形成。     

环糊精功能化疏水缔合丙烯酰胺聚合物的制备与性能评价

以十六烷基二甲基烯丙基氯化铵(C₁₆DMAAC)为疏水单体、烯丙基环糊精(A-CD)为环糊精功能化单体,与丙烯酰胺(AM)通过自由基共聚作用制备了环糊精功能化疏水缔合丙烯酰胺聚合物P(AM/A-CD/C₁₆DMAAC)。采用红外光谱和电子扫描电镜对P(AM/A-CD/C₁₆DMAAC)的结构进行表征。并考察了聚合物的水溶性、粘浓性质、特性粘数和粘均分子量。发现聚合物具有良好的空间结构和溶解特性,临界缔合浓度为1600mg/L,粘均分子量达5.5×10⁶g/mol,聚合物具备作为三次采油的应用潜能。     

反相微乳液中疏水缔合型聚丙烯酰胺的合成及其性能研究

在反相微乳液体系中合成了疏水缔合型聚丙烯酰胺 (HAPAM ) ,用Brookfield旋转粘度计测定了其水溶液性能 ,并与传统胶束聚合法制备的HAPAM作了比较 .结果显示 ,前者有更优越的耐盐和抗剪切性能 ,这主要是因为前者的大分子链上疏水共聚单体呈无规分布而后者呈嵌段分布 ,其疏水分子链以分子间而不是分子内缔合为主     

疏水缔合聚丙烯酰胺在表面活性单体胶束溶液中的制备及其流变特性

配制了表面活性单体2-丙烯酰胺基十二烷磺酸钠(NaAMC12S)与十二烷基硫酸钠(SDS)的胶束溶液,分别测定了强疏水单体N-正十二烷基丙烯酰胺(C12AM)在两种胶束溶液中的增溶性能;在此基础上,于两种胶束溶液中分别进行了丙烯酰胺(AM)与C12AM的胶束共聚合,制备了疏水缔合聚丙烯酰胺(HAPAM),它们分别为二元共聚物C12AM/AM与三元共聚物C12AM/NaAMC12S/AM;测定了两种共聚物的红外光谱;采用荧光探针法与表观粘度法重点研究了它们的疏水缔合性与流变性能.结果表明,在表面活性单体NaAMC12S的胶束溶液中,可顺利地实现AM与疏水单体的胶束共聚合,由于表面活性单体也参与了共聚合,故制得的产物为三元共聚物C12AM/NaAMC12S/AM;与在SDS胶束溶液中制备的二元共聚物C12AM/AM相比,前者的疏水缔合性更强,其强疏水缔合性以强疏水单体C12AM的贡献为主,以表面活性单体NaAMC12S的贡献为辅.     

疏水缔合聚丙烯酰胺与阳离子双子表面活性剂的相互作用

通过表面张力法和电导率法分别考察了阳离子双子表面活性剂(12-2-12)与非离子疏水缔合聚丙烯酰胺(HMPAM)和普通聚丙烯酰胺(PAM),传统表面活性剂十二烷基三甲基溴化铵(DTAB)与HMPAM和PAM之间的相互作用。结果表明,12-2-12 HMPAM复合体系与12-2-12水溶液体系相比,在w(聚合物含量)CMC时,复合体系的电导率(κ)具有下降的趋势,且κ随着w的增大下降的趋势越明显,说明12-2-12与HMPAM之间存在相互作用。     

荧光法研究含长链烷基聚丙烯酰胺的疏水微区结构

荧光法研究含长链烷基聚丙烯酰胺的疏水微区结构邱星屏，张雪蓉，丁马太（厦门大学化学系，厦门，３６１００５）关键词萘酚，聚丙烯酰胺，疏水微区聚丙烯酰胺作为增粘剂和絮凝剂，已用于石油开采、水处理等领域［１］．在聚丙烯酰胺链上引进少量疏水侧基，可显著地改变其...     

Solution Association Characterization of Hydrophobically Associating Polyacrylamide Obtained from Produced Fluids

The hydrophobically associating polyacrylamide (HAPAM) obtained from produced fluids with compositional homogeneity was systematically investigated by zero-shear viscosity, fluorescence, sand-pipes experiment and adsorption behavior. The results showed that HAPAM obtained from produced solution through porous media has been possession in hydrophobic association character. The critical association concentration (CAC) determined by viscosity method, fluorescence spectroscopy method and micro-pore method have no obvious change compared with the original polymer. The hydrophobic associative capability of HAPAM obtained from produced fluids was smaller than that of original HAPAM. Compared to original PAM and PAM obtained from produced fluids, HAPAM obtained from produced fluids still exhibits promising applied potential. It reveals the possibility that HAPAM obtained from produced could be re-used for enhance oil recovery.     

Influence of Hydrophobically Associating Polyacrylamide on Dispersion Property of Water-Soluble Phenol-For-maldehyde Resin

To improve dispersion stability of water soluble phenol-fomaldehyde resin (PFR) in relatively low salinity water, the effect of hydrophobically associating polymer (HAP) on the dispersion property of PFR in NaCl solution was studied by the measurement of the size and zeta potential of PFR, HAP, and PFR/HAP molecule aggregates in NaCl solution, and the turbidity of PFR and PFR/HAP dispersions. The results show that due to the hydrophobically group on HAP molecule has similar structure as molecular structure of PFR and stronger hydrophobically association of HAP molecules in NaCl solution, HAP, and PFR molecules can form complex molecule aggregates together. The formation of the complex molecule aggregates enhanced the stability of PFR dispersion in NaCl solution.     

Characterization, Solution Behavior, and Microstructure of a Hydrophobically Associating Nonionic Copolymer

To obtain an oil-displacement polymer with good thermal stability and solution properties, self-assembling acrylamide (AM)/4-butylstyrene (BST) copolymers (PSA) were synthesized by the micellar copolymerization technique. The resulting polymer was characterized by elemental analysis and UV and FT-IR spectroscopy. Conventional DSC measurement was used successfully to characterize the hydrophobic microblock structure of PSA, and two glass transition temperatures were found in the polymer: at 203 °C for the AM segments and at 106 °C for the hydrophobic BST segments. The initial decomposition temperature (234 °C) of the polymer is higher than that of polyacrylamide (210 °C). The DSC and TG results suggest that incorporation of BST into PSA enhances the molecular rigidity and thermal stability of the polymer. The apparent viscosity of a PSA solution greatly depends on the amount of BST in the polymer, and the polymer exhibits salt-thickening, temperature-thickening, thixotropy, pseudo-plastic behavior, anti shearing, and good anti-aging properties at 80 °C. In addition, the apparent viscosities of PSA solutions are increased remarkably by the addition of a small amount of surfactant. AFM measurements show that large block-like aggregates and small compact aggregates are formed in aqueous solutions of 0.4 g⋅dL⁻¹ PSA because of strong intermolecular hydrophobic associations, despite the low molecular weight, and their sizes increase upon addition of a small amount of salt.     

疏水缔合水溶性聚合物的合成研究进展

综述了疏水缔合水溶性聚合物的合成的最新研究进展。主要合成方法有非均相共聚、均相共聚、胶束共聚、反相微乳液聚合、无皂乳液聚合、活性阴离子聚合以及超临界二氧化碳介质等。     

孪尾疏水缔合水溶性共聚物聚(丙烯酰胺/丙烯酸钠/N,N-二己基丙烯酰胺)/十二烷基硫酸钠水溶液的粘度行为

水溶性三元共聚物;孪尾疏水缔合水溶性共聚物聚(丙烯酰胺/丙烯酸钠/N;N-二己基丙烯酰胺)/十二烷基硫酸钠水溶液的粘度行为     

Effects of Ethylene Oxide Spacer Length on solution Properties of Water—Soluble Fluorocarbon—Containing Hydrophobically Associating Poly（Acrylic Acid—co—Rf—PEG Macromonomer）

Poly(acrylic acid)s (PAAs) modified with a series of fluorocarbon group (Rf) end-capped Poly(ethylene glycol) (PEG) macromonomers(number of ethylene oxide unit:1,9,23,45) and corresponding copolymers without fluorocarbon end groups were synthesized.It was found that the effect of the hydrophobic association of fluorocarbon groups on the solution viscosity prevailed over that of the hydrogen bond between grafted PEG and the backbone.Rheological measurement on the aqueous solutions of these poly(acrylic acid-co-Rf-PEG macromonomer) s demonstrated that the best thickening performance was shown when the number of ethylene oxide unit (EO number) was 23.     

疏水缔合型增稠剂聚(丙烯酰胺-丙烯酸高级酯)的合成及增稠性能研究

采用沉淀聚合法合成了聚（丙烯酰胺－丙烯酸十四酯），聚（丙烯酰胺－丙烯酸十六酯）和聚（丙烯酰胺－丙烯酸十八酯），重点讨论了共聚物中疏水基团数量及疏水基团链长对增稠性能的影响。采用凯达尔定氮法和动态热分析（DMTA）测定了共聚物的组成及玻璃化温度。     

阴阳离子表面活性剂混合体系对原油的乳化及增粘行为

利用阴阳离子表面活性剂复配技术,实现了高含水量原油体系的乳化及增粘. 通过调整表面活性剂分子结构,解决了阴阳离子表面活性剂复配体系在油田模拟水中的溶解度问题. 确定了相关体系高含水量油包水（W/O）乳状液的表面活性剂浓度,研究了可以产生高含水量油包水乳状液的油水混合体积比范围,并研究了温度、pH值、油水混合比例和离子强度对乳化及增粘作用的影响. 获得了一系列具有优良乳化效果和乳状液稳定性的体系,其中部分体系粘度可增大80倍. 这对于三次采油提高采收率有重要意义.     

水溶液中P(AM-co-PEBA)聚合物对Tb3＋离子荧光增强作用

考察了Tb3＋离子在模板法合成的疏水缔合水溶性聚合物聚丙烯酰胺/4-(ω-丙烯酰氧乙氧基)苯甲酸(P(AM-co-PEBA))溶液中的荧光增强行为. 在溶液中P(AM-co-PEBA)通过羧基的络合作用及疏水缔合作用, 改变了 Tb3＋离子所处微环境, 降低了Tb3＋离子络合水的个数, 提高了Tb3＋离子荧光强度. 聚合物中PEBA含量增加或PEBA以微嵌段结构存在, 这一微环境效应得到增强. 另一方面, 聚合物P(AM-co-PEBA)分子内具有紫外光捕获基团, 可通过“天线效应”与Tb3＋离子进行能量传递, 进一步提高了Tb3＋离子的荧光强度.