【摘要】：聚丙烯酰胺(PAM)是一種水溶性聚合物,在油田上的應(yīng)用十分廣泛。其中疏水締合水溶性聚丙烯酰胺是目前聚丙烯酰胺類聚合物的主要發(fā)展趨勢。本文同時考慮兩性單體和疏水單體對聚合物的影響,將丙烯酰胺分別與兩性單體和疏水單體進(jìn)行共聚,合成了三類新型丙烯酰胺類疏水締合水溶性聚合物,并主要研究不同因素對聚合物溶液聚集行為的影響及其應(yīng)用性能。1、采用膠束聚合法,以丙烯酰胺(AM)、兩性單體甲基丙烯酰氧乙基-N,N-二甲基丙磺酸鹽(DMCPS)及疏水單體甲基苯乙烯(α-MSt)為原料,以十二烷基硫酸鈉(SDS)為乳化劑,制備一系列兩性疏水改性水溶性共聚物PADM,并利用紅外光譜、核磁共振、元素分析、靜態(tài)光散射進(jìn)行了結(jié)構(gòu)分析。通過表面張力、熒光光譜、共振散射法、動態(tài)光散射法手段對PADM溶液的聚集行為進(jìn)行了深入研究,并重點探究了濃度、溫度、無機(jī)鹽種類及濃度對PADM分子在溶液中的聚集行為的影響。實驗結(jié)果表明：PADM具有較好的水溶解性、表面活性,同時具有良好的疏水締合能力,且其臨界締合濃度為0.lmg·mL-1,溫度、外加鹽均會對其聚集行為產(chǎn)生影響。由于PADM結(jié)構(gòu)中存在苯環(huán)結(jié)構(gòu),因此無需外加探針便可通過熒光光譜法分析PADM在水溶液中的聚集行為,使得測試更加便捷。此外PADM在高剪切速率和高溫下仍具有較好的粘度保留率,測試表明兩性單體DMCPS以及具有剛性結(jié)構(gòu)的α-MSt單體的加入使得PADM具有良好的耐溫抗鹽性能。2、采用無皂乳液聚合法,以丙烯酰胺(AM)、兩性單體甲基丙烯酰氧乙基-N,N-二甲基丙磺酸鹽(DMCPS)與帶有PEO長鏈的二十二烷基封端的丙烯酸酯新型大分子單體二十二烷基聚氧乙烯醚甲基丙烯酸酯(BEM)為原料,在KPS/ NaHSO3/AIBA-2HC1組成的混合型引發(fā)劑作用下共聚,制備一系列具有超長疏水長鏈的兩性水溶性聚合物PADB。利用FT-IR、1H-NMR、元素分析、靜態(tài)光散射對其結(jié)構(gòu)進(jìn)行了分析,并通過表／界面張力、紫外光譜、熒光光譜、共振散射法、動態(tài)光散射法手段對PADB的溶液聚集行為進(jìn)行了深入研究。最后重點研究了PADB的乳化能力、潤濕性以及稠油乳化降粘性質(zhì)。實驗結(jié)果表明：PADB結(jié)構(gòu)中含有較長的疏水長鏈,本身可以形成單分子膠束,降低表面張力和界面張力的水平有限。由于單體BEM具有碳22長鏈,因此PADB在水溶液中具有較強的分子內(nèi)疏水締合作用,同時由于單體DMCPS帶有相反電荷,PADB在外加鹽的作用下,分子間相互作用由分子內(nèi)締合轉(zhuǎn)變?yōu)榉肿娱g締合。此外應(yīng)用性能方面的測試表明當(dāng)PADB濃度達(dá)到1.5 g/L以上時,原油乳狀液為水包油型,PADB具有較好的原油潤濕性,并可以起到很好的稠油乳化降粘的效果。3、通過無皂乳液聚合法,以丙烯酰胺(AM)、丙烯酸鈉(NaAA)以及具有表面活性的疏水單體BEM為原料,共聚合成一系列新型的具有超長鏈的疏水改性部分水解聚丙烯酰胺共聚物PAAB.通過紅外光譜、核磁共振等表征了其結(jié)構(gòu),并通過動態(tài)光散射、共振光散射手段深入研究了RAAB在水溶液和鹽水中微觀聚集形態(tài)。此外還通過乳化降粘性質(zhì)的研究拓寬了其應(yīng)用價值。結(jié)果表明：由于長鏈?zhǔn)杷畣误wBEM的引入,部分水解的RAAB耐溫性能增強,同時RAAB可在水溶液中發(fā)生疏水締合作用。此類疏水改性的部分水解聚丙烯酰胺PAAB具有較好的稠油乳化性能,并能起到很好稠油降粘的效果,因此其具有良好的應(yīng)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.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TE39;TQ317

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