氟碳疏水缔合型阳离子胍胶的制备及其性能研究

发布时间：2018-01-21 02:50

本文关键词： 含氟单异氰酸酯疏水缔合阳离子胍胶溶液性能压裂液性能　出处：《陕西科技大学》2015年硕士论文　论文类型：学位论文

【摘要】：氟碳疏水缔合型阳离子胍胶(FCGG)是指在胍胶的亲水性大分子链上通过化学反应接入少量氟碳疏水基团而制备的水溶性高分子聚合物,因其克服了普通胍胶在增稠、耐温、耐剪切及破胶性能上的不足而有望成为新一代广泛应用于石油工业的水溶性聚合物材料,特别适合于应用在二次、三次压裂采油领域中。本文以六氟丁醇(FOH)和异佛尔酮二异氰酸酯(IPDI)为原料合成出中间体含氟单异氰酸酯(FSM),再以FSM和阳离子胍胶(CGG)为原料合成了氟碳疏水缔合型阳离子胍胶(FCGG),通过检测异氰酸根的含量确定了合成的最佳反应条件,利用红外光谱(FT-IR)、核磁共振氟谱(19F-NMR)和X射线衍射(XRD)对FCGG进行了检测表征。利用流变仪、荧光光谱、紫外光谱和动态激光光散射技术(DLS)研究了FCGG溶液的疏水缔合性能及疏水缔合对FCGG粘度、耐温、耐剪切、模量等性能的影响。同时将FCGG与有机硼交联剂(JL)复配形成冻胶,考察了FCGG冻胶的耐剪切性、耐温性、冻胶模量和破胶性能。研究结果表明,采用n(IPDI):n(FOH)=1:1、丙酮为溶剂、二月桂酸二丁基锡(T-12)为催化剂,且催化剂添加量为0.015-0.02wt%,反应温度为80℃,反应4h时后反应生成中间体FSM。以n(CGG):n(FSM)=1:1,T-12添加量为0.02-0.025wt%,70℃下反应6h时可成功制备出FCGG。FCGG溶液随着取代度(DS)的变化而呈现出明显变化。随着DS增加,FCGG的疏水缔合作用越明显。这是因为随着DS增大,亲水大分子中的活性羟基被氟碳疏水基团取代程度越高,疏水基团由于疏水作用而相互缔合形成了更多的疏水微区,所产生的缔合作用也更加明显。通过表观粘度测试证实,随着FCGG浓度的增大,溶液表观粘度呈现上升趋势,而且存在粘度快速上升过程。荧光光谱测试表明随着FCGG浓度增加,氟碳链迅速增加而形成更多的疏水微区,FCGG分子间疏水缔合作用增强,溶液极性减弱。模量测试和幂律模型表明DS的含量越高,FCGG产生更多的物理交联结构,溶液的粘弹性增强,形成冻胶状液体,证明含氟疏水基团自组装行为使大分子交联网状结构增强,表观粘度增加。耐温耐剪切测试证明,随着剪切速率的增大和温度的升高,FCGG表现出特殊的粘度变化趋势,粘度均上升到一定程度后下降。并且随着DS增大,粘度上升幅度越明显。紫外光谱和紫外光散射测试表明,相比于CGG,FCGG溶液中疏水基团形成了较多的疏水微区且紫外吸收增强;DLS则通过测试FCGG的粒径分布表明FCGG聚集体尺寸分布变宽,且更加分散,反映出其具有较强的疏水缔合性能。FCGG与JL复配交联形成大分子网状结构,表观上表现为具有粘弹性的胶冻。结果表明:相比于GG和CGG,FCGG冻胶在耐剪切性和耐温性方面均有很大提升,FCGG冻胶在170s-1、50℃下剪切约60min时粘度仍大于100m Pa·s,而此时GG和CGG粘度均下降到50m Pa·s。随着温度的升高,FCGG粘度下降缓慢,在85℃时才会发生突降,与GG和CGG冻胶相比,FCGG的耐温性得到了提高。破胶结果显示,FCGG滤液的水-空气界面张力、水-油界面张力均小于GG和CGG,流体摩擦阻力明显减少,降低水锁对地层的伤害,而残渣量也明显低于GG。
[Abstract]:Fluorocarbon Hydrophobically Associating Cationic Guar Gum (FCGG) refers to the preparation of water soluble polymers by chemical reaction to access small hydrophobic groups in the hydrophilic fluorocarbon macromolecular chain guar gum, because it overcomes the defects of guar gum in thickening, temperature resistance, resistance to shear and lack of gel breaking performance of the is expected to become a new generation is widely used in oil industry of water soluble polymer materials, especially suitable for application in two times, three times of fracturing oil fields. This paper takes six fluorine butyl alcohol (FOH) and isophorone diisocyanate (IPDI) was synthesized by intermediates of fluorine - containing isocyanate (FSM), and then to FSM and cationic guar gum (CGG) synthesis of fluorocarbon Hydrophobically Associating Cationic Guar Gum (FCGG) as raw materials, the optimum reaction conditions were determined by the synthesis of isocyanate content detection, using infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (19F-NMR) fluoride and X ray diffraction (XRD) of FCG G were detected respectively. Using rheometer, fluorescence spectroscopy, UV spectroscopy and dynamic light scattering technique (DLS) of FCGG solution of hydrophobically associating properties and hydrophobic association of FCGG viscosity, temperature resistance, shear resistance, impact modulus and other properties. At the same time, FCGG and organic boron crosslinker (JL) compound formation the effects of FCGG gel, gel shear resistance, temperature resistance, gel modulus and gel breaking performance. The results show that using n (IPDI): n (FOH) =1:1, acetone as solvent, two lauric acid two butyl tin (T-12) as catalyst, and the catalyst amount was 0.015-0.02wt% the reaction temperature is 80 DEG C, the reaction time is 4h after the reaction of intermediate FSM. n (CGG): n (FSM) =1:1, T-12 dosage 0.02-0.025wt%, reaction 6h at 70 DEG C can be successfully prepared FCGG.FCGG solution with the degree of substitution (DS) changes and showing a significant change. With the increase of DS, hydrophobic association of FCGG is more obvious. This is because with the increase of DS, the activity of hydroxyl hydrophilic macromolecule in the fluorocarbon hydrophobic substitution degree is higher, the hydrophobic group due to hydrophobic interaction and mutual association formed a more hydrophobic region, the association is more obvious. The apparent viscosity test confirmed that, with the increase of FCGG concentration, the apparent solution the viscosity increased, and there is viscosity rise fast. The fluorescence spectra show that with the increase of FCGG concentration increased rapidly and the formation of fluorocarbon chain more hydrophobic microdomains, FCGG enhanced hydrophobic interaction, the polarity of the solution decreased. Modulus test and power-law model showed that higher levels of DS, FCGG physical crosslinking structure more, the viscoelastic solution increased, forming the jelly like liquid, that fluorinated hydrophobic groups the self-assembly behavior of the macromolecule cross-linked structure increased, the apparent viscosity increased. Nevinne shear The test proved that increased with the increase of shear rate and temperature, FCGG showed the viscosity variation tendency of the viscosity rises to a certain extent. And then decreased with the increase of DS, the viscosity increase is more obvious. The ultraviolet spectrum and ultraviolet light scattering tests show that, compared to CGG, FCGG solution of hydrophobic groups in the formation of the absorption enhancement the more hydrophobic region and UV; DLS by testing the particle size distribution of FCGG FCGG showed that the aggregate size distribution becomes wider, and more dispersed, reflecting its strong hydrophobic properties of.FCGG and JL was cross-linked macromolecular network structure, the apparent performance of viscoelastic gel. The results showed that: compared to GG and CGG, FCGG gel has greatly improved in the shear resistance and temperature resistance, FCGG gel at 170s-1,50 deg. shear at about 60min Pa s viscosity was higher than 100m, while the GG and CGG viscosity decreased 50m Pa to S. with the increase of temperature, the viscosity of FCGG decreased slowly, will occur suddenly at 85 DEG C, compared with GG and CGG gel, FCGG temperature resistance is improved. The gel breaking results show that FCGG filtrate water air interface tension, water oil interfacial tension was less than GG and CGG flow, friction resistance decreased, water lock of formation damage is reduced, and the residue was also lower than GG.

【学位授予单位】：陕西科技大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O631;TE357.12

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