聚丙烯酰胺类疏水缔合聚合物的合成与表征

发布时间：2018-07-28 10:16

【摘要】：聚丙烯酰胺(PAM)是一种水溶性聚合物,在油田上的应用十分广泛。其中疏水缔合水溶性聚丙烯酰胺是目前聚丙烯酰胺类聚合物的主要发展趋势。本文同时考虑两性单体和疏水单体对聚合物的影响,将丙烯酰胺分别与两性单体和疏水单体进行共聚,合成了三类新型丙烯酰胺类疏水缔合水溶性聚合物,并主要研究不同因素对聚合物溶液聚集行为的影响及其应用性能。1、采用胶束聚合法,以丙烯酰胺(AM)、两性单体甲基丙烯酰氧乙基-N,N-二甲基丙磺酸盐(DMCPS)及疏水单体甲基苯乙烯(α-MSt)为原料,以十二烷基硫酸钠(SDS)为乳化剂,制备一系列两性疏水改性水溶性共聚物PADM,并利用红外光谱、核磁共振、元素分析、静态光散射进行了结构分析。通过表面张力、荧光光谱、共振散射法、动态光散射法手段对PADM溶液的聚集行为进行了深入研究,并重点探究了浓度、温度、无机盐种类及浓度对PADM分子在溶液中的聚集行为的影响。实验结果表明：PADM具有较好的水溶解性、表面活性,同时具有良好的疏水缔合能力,且其临界缔合浓度为0.lmg·mL-1,温度、外加盐均会对其聚集行为产生影响。由于PADM结构中存在苯环结构,因此无需外加探针便可通过荧光光谱法分析PADM在水溶液中的聚集行为,使得测试更加便捷。此外PADM在高剪切速率和高温下仍具有较好的粘度保留率,测试表明两性单体DMCPS以及具有刚性结构的α-MSt单体的加入使得PADM具有良好的耐温抗盐性能。2、采用无皂乳液聚合法,以丙烯酰胺(AM)、两性单体甲基丙烯酰氧乙基-N,N-二甲基丙磺酸盐(DMCPS)与带有PEO长链的二十二烷基封端的丙烯酸酯新型大分子单体二十二烷基聚氧乙烯醚甲基丙烯酸酯(BEM)为原料,在KPS/ NaHSO3/AIBA-2HC1组成的混合型引发剂作用下共聚,制备一系列具有超长疏水长链的两性水溶性聚合物PADB。利用FT-IR、1H-NMR、元素分析、静态光散射对其结构进行了分析,并通过表／界面张力、紫外光谱、荧光光谱、共振散射法、动态光散射法手段对PADB的溶液聚集行为进行了深入研究。最后重点研究了PADB的乳化能力、润湿性以及稠油乳化降粘性质。实验结果表明：PADB结构中含有较长的疏水长链,本身可以形成单分子胶束,降低表面张力和界面张力的水平有限。由于单体BEM具有碳22长链,因此PADB在水溶液中具有较强的分子内疏水缔合作用,同时由于单体DMCPS带有相反电荷,PADB在外加盐的作用下,分子间相互作用由分子内缔合转变为分子间缔合。此外应用性能方面的测试表明当PADB浓度达到1.5 g/L以上时,原油乳状液为水包油型,PADB具有较好的原油润湿性,并可以起到很好的稠油乳化降粘的效果。3、通过无皂乳液聚合法,以丙烯酰胺(AM)、丙烯酸钠(NaAA)以及具有表面活性的疏水单体BEM为原料,共聚合成一系列新型的具有超长链的疏水改性部分水解聚丙烯酰胺共聚物PAAB.通过红外光谱、核磁共振等表征了其结构,并通过动态光散射、共振光散射手段深入研究了RAAB在水溶液和盐水中微观聚集形态。此外还通过乳化降粘性质的研究拓宽了其应用价值。结果表明：由于长链疏水单体BEM的引入,部分水解的RAAB耐温性能增强,同时RAAB可在水溶液中发生疏水缔合作用。此类疏水改性的部分水解聚丙烯酰胺PAAB具有较好的稠油乳化性能,并能起到很好稠油降粘的效果,因此其具有良好的应用前景。
[Abstract]:Polyacrylamide (PAM) is a water-soluble polymer and is widely used in oil fields. Hydrophobically associating water-soluble polyacrylamide is the main development trend of polyacrylamide polymers at present. In this paper, the effects of amphoteric and hydrophobic monomers on polymers are considered, and acrylamide is respectively with amphoteric monomer and hydrophobic monomers. Three new types of hydrophobically associating water-soluble acrylamide type polymers were synthesized by copolymerization. The effects of different factors on the aggregation behavior of polymer solution and their application performance.1 were mainly studied. By micellar polymerization, acrylamide (AM), amphoteric methyl acryl oxoethyl -N, N- two methyl propyl sulfonate (DMCPS) and hydrophobic monomer armor were used. A series of amphoteric hydrophobically modified water-soluble copolymer PADM was prepared with styrene (alpha -MSt) as raw material and twelve alkyl sodium sulfate (SDS) as emulsifier. The structure was analyzed by infrared spectroscopy, nuclear magnetic resonance, elemental analysis and static light scattering. The solution of PADM solution by surface tension, fluorescence spectra, resonance scattering, and dynamic light scattering. The effect of concentration, temperature, inorganic salt type and concentration on the aggregation behavior of PADM molecules in the solution is investigated. The experimental results show that PADM has good solubility in water, surface activity, and good hydrophobic association energy, and its critical association concentration is 0.lmg. ML-1, temperature, and outside. Adding salt can affect the aggregation behavior. Because of the existence of the benzene ring structure in the PADM structure, the aggregation behavior of PADM in aqueous solution can be analyzed without an additional probe, which makes the test more convenient. In addition, PADM still has a better viscosity retention rate at high shear rate and high temperature, and the test indicates that the amphoteric monomer DMC is found. PS and the addition of a -MSt monomer with rigid structure make PADM good temperature resistance and salt resistance.2, using soap free emulsion polymerization, acrylamide (AM), amphoteric monomer methylacroleoxy ethyl -N, N- two methyl propanosulfonate (DMCPS) and twenty-two alkyl terminated acrylate macromonomer twenty with PEO long chain. Two alkyl polyoxyethylene ether methacrylate (BEM) was used as raw material and copolymerized under the action of KPS/ NaHSO3/AIBA-2HC1 mixed type initiator. A series of amphoteric water-soluble polymers with long hydrophobic long chains were prepared, and PADB. was analyzed by FT-IR, 1H-NMR, elemental analysis and static scattering. UV spectra, fluorescence spectra, resonance scattering and dynamic light scattering methods have been used to study the solution aggregation behavior of PADB. Finally, the emulsification, wettability and viscosity reduction of PADB are studied. The experimental results show that the long hydrophobic long chain in the PADB structure can form a single molecule micelle itself. The level of surface tension and interfacial tension is limited. Since the monomer BEM has a carbon 22 long chain, PADB has a strong intramolecular hydrophobicity Association in aqueous solution. At the same time, the intermolecular interaction is transformed from intramolecular association to intermolecular association because of the opposite charge of the monomer DMCPS with the addition of salt. In addition, the application properties of PADB are also applied. The test shows that when the concentration of PADB is above 1.5 g/L, the emulsion of crude oil is water oil, PADB has good wettability of crude oil, and it can be a good effect of emulsification and viscosity reduction of heavy oil.3. Through soap free emulsion polymerization, acrylamide (AM), sodium acrylate (NaAA) and hydrophobic monomer BEM with surface activity are used as raw materials. A series of new hydrophobic modified partially hydrolyzed polyacrylamide copolymer (PAAB.) copolymers with super long chains were characterized by IR, NMR and so on. The microstructure of RAAB in aqueous solution and brine was investigated by means of dynamic light scattering and resonance light scattering. The results show that the temperature resistance of partial hydrolyzed RAAB is enhanced because of the introduction of long chain hydrophobic monomer BEM, and the hydrophobicity Association of RAAB can occur in aqueous solution. This hydrophobically modified partially hydrolyzed polyacrylamide PAAB has good emulsifying properties of heavy oil, and it can play a good effect on viscosity reduction of heavy oil. Therefore, it has a good prospect of application.
【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TE39;TQ317

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