摘要
减阻聚合物微胶囊化是指在减阻聚合物颗粒的表面,利用物理法、化学法或机械法包覆一层其他材料,以避免减阻聚合物颗粒易粘接的缺点,制备出常温条件下能够储存的颗粒,或分散成浆液后可长期储存。减阻聚合物微胶囊化属于胶体化学的范畴,涉及到颗粒的表面性质,颗粒和液体的界面作用;同时,实施微胶囊化还需要运用高分子化学、高分子物理等学科的相关理论作为指导;此外,开发减阻聚合物微胶囊化的工业应用,还需运用化工工程的相关理论来设计工艺流程,优化工艺路线。鉴于石油减阻聚合物在石油运输行业中的重要性,以及石油减阻聚合物在生产、储存、运输等方面存在的问题,对减阻聚合物颗粒表面进行改性具有重要的现实意义。
研究分析了减阻聚合物颗粒的化学结构及其表面的主要性质,指出减阻聚合物颗粒为疏松多孔的粘弹性固体颗粒,其分子具有长链多支链的分子结构,这是减阻聚合物颗粒易粘结的主要原因;分析了可用于减阻聚合物微胶囊化的壁材及方法。
以聚氨酯为壁材,对高分子聚α-烯烃粘弹性聚合物颗粒表面进行了微胶囊包覆制备技术与工艺的研究。采用分子动力学模拟方法讨论了相关的分子设计,以丙三醇和甲苯-2,4二异氰酸酯(TDI)为聚合活性单体,采用界面聚合法制备了性能稳定的聚氨酯微胶囊。研究了合成聚α-烯烃微胶囊壁材的单体种类、配比、粒度和壁材用量对包覆性能的影响,对聚α-烯烃微胶囊的表面性状、油溶性、耐热性和抗压性做了测试及分析,同时采用油品减阻剂室内模拟环道评价系统对减阻增输效果的影响进行了评价。研究结果表明,在包覆壁材分子设计中应对支链的长度和支链数目有具体的要求;确定了在水溶液体系中,异氰酸酯基(—NCO)与羟基(—OH)摩尔比为1:1,聚α-烃颗粒粒度为60~80目(250~180um),聚氨酯壁材用量占聚α-烯烃颗粒质量的0.5%,表面活性剂用量为聚α-烯烃质量的0.1%;常压25℃为聚氨酯包覆聚α-烯烃制备微胶囊的合理工艺条件;制备的聚α-烯烃微胶囊具有良好的表观形貌性状、较快的释放速度,制备的微胶囊不影响原有减阻效果、并具有优良的耐热性和抗压性。同时聚α-烯烃微胶囊在常温下以粉末状固体形式储存,具有现场使用时直接分散到注入溶剂中形成油品减阻剂的特点,解决了工业应用中的分散技术难题。
将一步法进行工业放大,成功得到了减阻聚合物微胶囊的初级工业品。产品质量符合设计要求。微胶囊化产品可以长期储存而不粘结。将脲醛树脂制备的微胶囊产品制备成醇基和水基浆液,并与未包覆颗粒制备的浆液进行比较,发现用微胶囊制备的醇基和水基浆液在热稳定性上远远优于未包覆颗粒制备的浆液。
Drag reducing polymer microencapsulation are drag reducing polymer particles on the surface of which there is a layer material by physical, chemical or mechanical methods. The aim of microencapsulation is that avoiding the adhesion of particles and producing particles which can be stably stored in room temperature or when the particles are scattered as slurry. The drag reducing polymer microencapsulation belongs to the domain of Gel chemistry, and it involves the surface characters of particles, the surface interaction between particle and liquid; and the same time, microencapsulating needs the theory guidance of high molecular chemistry and physics and so on; In addition, with the industrial application of drag reducing polymer microencapsulation, technological process must be designed and it must be optimized flowed by the theory of chemical engineering. Because of the importance of drag reducing agent (DRA) in oil transportation industry and the problems in producing, storage and transportation of DRA, it is imperative that enforcing surface modification of drag reducing polymer particles.
It analyzed the surface characters and chemical structure of drag reducing polymer particles; It pointed out the porous characters and molecular structure of long chain with multiple branched chains, this was the main reason that caused the adhesion of drag reducing polymer particles; It analyzed the wall materials and methods of drag reducing polymer microencapsulation.
With polyurethane as wall material, the preparation technology and process of microcapsule coating were studied on the surface of poly-α-olefin viscoelastic polymer particles. Molecular dynamics simulation methods were used to discuss the relevant molecular designs, and stable performance polyurethane microcapsules were produced by the method of interfacial polymerization, with toluene 2,4-diisocyanate (TDI) and glycerol as active monomers. We researched the influence on coating in monomer type, ratio, particle size and amount of wall material, tested and analyzed the surface morphology, oil solubility, heat and pressure resistance of poly-α-olefin microcapsules, and evaluated the influences of drag reduction effect by the indoor simulative loop evaluation system for oil drag reduction agent. The results show that the length and number of branched chains had specific requirements in the design of coated wall material moleculars. The reasonable process conditions of polyurethane-coated poly-a-olefin microcapsules were as follows:the system was aqueous solution, the molar ratio of isocyanate group (-NCO) and hydroxyl (-OH) was 1:1, the mesh number of poly-a-olefin particle size was 60~80 (250~180um), the weight of wall material accounted for 0.5% of poly-α-olefin particles, the weight of surfactant accounted for 0.1% of poly-a-olefin particles, the temperature was 25℃under atmospheric pressure. The producing poly-a-olefin microcapsule had good surface morphology, faster release speed, no effect on the original drag reduction, excellent heat and pressure resistance. Moreover, poly-a-olefin microcapsules which were stored in powder-like solid at room temperature can be made into oil drag reduction agent easily at the time of on-site using by being dispersed into the solvent directly and solved the technical problem of dispersion in industrial applications.
One-step method was used for industrial scaling-up, and the elementary industry product of drag reducing polymer microcapsules was obtained. The quality of this product met the design requirements. The microcapsules production could be stored for long time. The microcapsules produced by urea-formaldehyde polymerizing method were prepared into alcohol-based and water-based slurries. The slurries were contrasted with slurry which was prepared with drag reducing polymer particles that were not coated, and the themo-stability of the former are better than that of the latter.
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