典型聚醚的封端研究

【作者】 张盛军；

【导师】 辛寅昌；

【作者基本信息】 山东师范大学 ， 物理化学， 2008， 硕士

【摘要】 本文所说的典型聚醚是指由活泼氢引发的分子链末端带有活性基团的聚氧链烯基共聚物,这类带有活性基团的未封端的聚醚,由于活性基团的存在,其耐酸碱性、耐盐性和耐温性受到一定限制,而封端聚醚由于链末端羟基被取代,具有较高的化学稳定性,而且此类封端聚醚还具有浊点下降、发泡能力降低、去油性能力增强、临界胶束浓度下降和化学性质更为稳定等特点,适用于不同pH值下、高温长时间使用,由此拓宽了聚醚使用范围。聚醚的封端方法主要可分为醚化封端、酯化封端和交联封端,是指聚醚上的羟基通过各种有机小分子化合物进行醚化、酯化或者交联反应,羟基上的活泼氢被各种短链的烷基、芳烷基、酯基或其它基团取代。封端后,改变了其物理化学性质,增加了某些新的功能。本文对典型聚醚的封端合成技术及典型封端聚醚的性能进行了系统的研究,并将合成的典型封端聚醚进行了原油的降摩阻性能的应用研究。另外一类含有不饱和键的聚醚因为具有反应性,一般把其视为非典型聚醚,由于羟基的存在影响不饱和键与环境体系的反应。链末端羟基必须封端改性,而这一类封端聚醚由于具有特殊的化学稳定性和可反应的性质,所以本文就该类活性聚醚的封端也进行了部分研究。石油作为工业的血脉,随着“能源危机”时代的到来,石油的开采和输运日益得到人们的广泛重视,尤其是高粘稠油的开采显得尤为重要,但是解决高粘稠油的开采输送是全世界石油行业的最大难题。但是关于原油降摩阻的机理不论是从经典的学术著作还是近年来发表的学术论文,都认为其机理复杂,很难表述清楚。原油的降摩阻与降粘和流动改进的机理既有类同之处,又有本质的不同。乳化降粘需要至少20%以上的水才能形成O/W,而流动改进剂仅对不含水原油有效,如果原油含水,流动改进剂效果反而不好。实验中笔者曾发现双环咪唑啉衍生物封端聚醚对原油具有降摩阻作用,特别是在含水量较大的原油中,能减小原油的流动阻力。本文研究中发现,利用合成的典型双环咪唑啉衍生物封端聚醚与活性高聚物复配制备的复合降摩阻剂,拓宽了含水原油的使用范围,由原来对含水10%以上原油能有效降低流动阻力,拓宽到对原油含水5%以上也可有效降摩阻。就此问题,笔者在典型封端聚醚的研究基础上,我们重点研究了这种复合降摩剂的降摩阻机理。关于降摩阻剂的降摩阻机理比较复杂,它涉及到流变学、流体动力学、摩擦学、聚合物的物理化学等学科,降摩阻剂的相关机理有很多不同的说。我们主要从界面化学、微观动力学及微观状态的角度研究了降摩阻剂的降摩阻机理。我们在通过此种复合降摩阻剂与一般降粘剂和单一双环咪唑啉衍生物封端聚醚进行性能对比的基础上,我们得出了原油微观状态的改变可能是导致原油流动阻力大大下降的原因,复合降摩阻剂的加入使原油的微观流动状态由原来的平动转化为“轴动”状态,而这种轴动状态无论是从摩擦学还是动力学角度,都可以很好的减小原油与介质以及原油本体之间的相互作用力。实验证明我们发现了一种更有效的降低原油流动阻力的石油降摩阻剂。本文研究的主要工作和贡献如下:(1)介绍了国内外聚醚型表面活性剂的研究进展及应用。(2)介绍了典型封端聚醚的合成技术。(3)合成典型双环咪唑啉衍生物封端聚醚,并与活性高聚物复配制备了一种复合原油降摩阻剂。(4)该复合降摩阻剂在高粘稠油开采和输送中具有很好的降摩阻降粘效果。(5)从界面化学、微观动力学的角度以及流变学的角度入手,研究了加入复合降摩阻剂前后原油流动阻力的变化、原油粘度、原油表面张力、吸附力以及原油微观形态的变化。(6)初步认为原油复合降摩阻剂的降摩阻机理为原油的微观状态发生了改变,导致原油流动状态由平动转变为“轴动”,进而大大降低了其在流动过程中的流动阻力。更多还原

【Abstract】 The typical polyether in this paper refers initiation molecular chain terminal has the active group to gather the oxygen alkene base copolymer caused by reactive hydrogen.This kind of polyether without sealed end which has the hydroxyl, as a result of existence of the active hydroxyl, its acidproof alkalinity, the salt endurance and the heat resistance was limited.Moreover, if the initiator includes unsaturated linkage polyether and other active group reaction, the existence of hydroxyl can influence the response between unsaturated linkage and system.The closure-linked polyether as the end of hydroxy be replaced, has a high chemical stability, but such letters have also polyether-cloud point decline in the ability to reduce foam, to enhance the capacity of oil, critical micelle concentration dropped and chemical More stable nature of the characteristics apply to different pH value, high-temperature prolonged use, which widened the scope of the use of polyether.Polyether-way closure can be divided into ether-capped, esterification and cross-linked closed-end closure, polyether is on the hydroxyl molecules through a variety of small organic compounds ether, esterification or cross-linking reaction, Hydroxy hydrogen was lively on the various short-chain alkyl, Fong alkyl, ester-based or other groups to replace.Terminated, has changed its physical and chemical properties, an increase of some new features. In this paper, the closure of the typical polyether-synthesis technology and the performance of typical capped polyether are researched, and the terminal polyether is applied in research of crude oil down the friction.As“the energy crisis”the time coming, the petroleum takes the industry blood vessels, petroleum mining and the transportation attracts people’s widely day by day, particularly viscous crude oil mining appears high especially important, but how to the problem of viscous crude oil the mining and transportation is the biggest difficult problem in the petroleum profession world. At present,domestic and foreign generally add high polymer surface active agent or the viscosity reducer to reduce the flowing resistance in the mining and the transportation process of crude oil,in order to enhancing the transportation efficiency.In view of some questions that the rude oil reduction agent and the thinner exists in thick oil mining and the transportation, and caused the crude oil resistance primary cause in the crude oil flowing process, this article mainly conducts the research to a kind of sealed end polyether synthesis and the performance, the experiment has discovered one kind of the bicycloimidazoline derivative sealed end polyether. The research discovered that this kind of sealed end polyether duplicate matches with one kind of active high polymer as the crude oil frictional resistance reducer, can reduce the crude oil flow resistance effectively, and this kind compound frictional resistance reducer expand the applicable scope of crude oil that contain water ,from contain water 10% above the crude oil expanded to contains water 5% above the crude oil also fall the frictional resistance effectively.We mainly studied from the interfacial and surface chemistry angle to explain the mechanism of frictional resistance.In library using had the oxygen nitrogen structure alkene base imidazoline derivatives terminated linear polyurethane,synthesized bicyloimidazoline derivatices polyesters. Using the bicycloimidazoline derivative sealed end polyether to match the active polymer, prepared the frictional resistance reducer. Carring on the laboratory appraisal, and Discovered that the compound frictional resistance reducer compare to the bicyloimidazoline derivatives teriminated polyesters, the compound frictional resistance reducer can wide the using scope of crude oil water contenting . and it can strengthen the ability of reducing the crude oil the flow resistance. Moreover, using micro-photography method, discovered that, when adding the compound frictional resistance reducer into the different water contents oil, the flow resistance of the crude oil greatly drops, and the microscopic shape of the crude oil has the characteristic change. The experiment proved that we had discovered one kind more effective the frictional resistance reducer .The article includes five aspects as following:(1) Introduced development and the application of polyether surfactants research about the domestic and foreign.(2) Introduced the typical sealed end polyether synthesis technology(3)Using the bicycloimidazoline derivative sealed end polyether to match the active polymer, prepared the frictional resistance reducer.(4) This frictional resistance reducer has the very good effect of reducing the crude oil flowing resistance in mining and transportation process.(5) From the contact surfaces interface collides and rheology study the flowing resistance, surface tension and superficial adsorptive viscosity changes of crude oil before and after adding frictional reducer.(6) using micro-photography method, discovered that, when adding the compound frictional resistance reducer into the different water contents oil, the flow resistance of the crude oil greatly drops, and the microscopic shape of the crude oil has the characteristic change.更多还原