本文關(guān)鍵詞： 含氟單異氰酸酯 疏水締合 陽(yáng)離子胍膠 溶液性能 壓裂液性能　出處：《陜西科技大學(xué)》2015年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：氟碳疏水締合型陽(yáng)離子胍膠(FCGG)是指在胍膠的親水性大分子鏈上通過(guò)化學(xué)反應(yīng)接入少量氟碳疏水基團(tuán)而制備的水溶性高分子聚合物,因其克服了普通胍膠在增稠、耐溫、耐剪切及破膠性能上的不足而有望成為新一代廣泛應(yīng)用于石油工業(yè)的水溶性聚合物材料,特別適合于應(yīng)用在二次、三次壓裂采油領(lǐng)域中。本文以六氟丁醇(FOH)和異佛爾酮二異氰酸酯(IPDI)為原料合成出中間體含氟單異氰酸酯(FSM),再以FSM和陽(yáng)離子胍膠(CGG)為原料合成了氟碳疏水締合型陽(yáng)離子胍膠(FCGG),通過(guò)檢測(cè)異氰酸根的含量確定了合成的最佳反應(yīng)條件,利用紅外光譜(FT-IR)、核磁共振氟譜(19F-NMR)和X射線衍射(XRD)對(duì)FCGG進(jìn)行了檢測(cè)表征。利用流變儀、熒光光譜、紫外光譜和動(dòng)態(tài)激光光散射技術(shù)(DLS)研究了FCGG溶液的疏水締合性能及疏水締合對(duì)FCGG粘度、耐溫、耐剪切、模量等性能的影響。同時(shí)將FCGG與有機(jī)硼交聯(lián)劑(JL)復(fù)配形成凍膠,考察了FCGG凍膠的耐剪切性、耐溫性、凍膠模量和破膠性能。研究結(jié)果表明,采用n(IPDI):n(FOH)=1:1、丙酮為溶劑、二月桂酸二丁基錫(T-12)為催化劑,且催化劑添加量為0.015-0.02wt%,反應(yīng)溫度為80℃,反應(yīng)4h時(shí)后反應(yīng)生成中間體FSM。以n(CGG):n(FSM)=1:1,T-12添加量為0.02-0.025wt%,70℃下反應(yīng)6h時(shí)可成功制備出FCGG。FCGG溶液隨著取代度(DS)的變化而呈現(xiàn)出明顯變化。隨著DS增加,FCGG的疏水締合作用越明顯。這是因?yàn)殡S著DS增大,親水大分子中的活性羥基被氟碳疏水基團(tuán)取代程度越高,疏水基團(tuán)由于疏水作用而相互締合形成了更多的疏水微區(qū),所產(chǎn)生的締合作用也更加明顯。通過(guò)表觀粘度測(cè)試證實(shí),隨著FCGG濃度的增大,溶液表觀粘度呈現(xiàn)上升趨勢(shì),而且存在粘度快速上升過(guò)程。熒光光譜測(cè)試表明隨著FCGG濃度增加,氟碳鏈迅速增加而形成更多的疏水微區(qū),FCGG分子間疏水締合作用增強(qiáng),溶液極性減弱。模量測(cè)試和冪律模型表明DS的含量越高,FCGG產(chǎn)生更多的物理交聯(lián)結(jié)構(gòu),溶液的粘彈性增強(qiáng),形成凍膠狀液體,證明含氟疏水基團(tuán)自組裝行為使大分子交聯(lián)網(wǎng)狀結(jié)構(gòu)增強(qiáng),表觀粘度增加。耐溫耐剪切測(cè)試證明,隨著剪切速率的增大和溫度的升高,FCGG表現(xiàn)出特殊的粘度變化趨勢(shì),粘度均上升到一定程度后下降。并且隨著DS增大,粘度上升幅度越明顯。紫外光譜和紫外光散射測(cè)試表明,相比于CGG,FCGG溶液中疏水基團(tuán)形成了較多的疏水微區(qū)且紫外吸收增強(qiáng);DLS則通過(guò)測(cè)試FCGG的粒徑分布表明FCGG聚集體尺寸分布變寬,且更加分散,反映出其具有較強(qiáng)的疏水締合性能。FCGG與JL復(fù)配交聯(lián)形成大分子網(wǎng)狀結(jié)構(gòu),表觀上表現(xiàn)為具有粘彈性的膠凍。結(jié)果表明:相比于GG和CGG,FCGG凍膠在耐剪切性和耐溫性方面均有很大提升,FCGG凍膠在170s-1、50℃下剪切約60min時(shí)粘度仍大于100m Pa·s,而此時(shí)GG和CGG粘度均下降到50m Pa·s。隨著溫度的升高,FCGG粘度下降緩慢,在85℃時(shí)才會(huì)發(fā)生突降,與GG和CGG凍膠相比,FCGG的耐溫性得到了提高。破膠結(jié)果顯示,FCGG濾液的水-空氣界面張力、水-油界面張力均小于GG和CGG,流體摩擦阻力明顯減少,降低水鎖對(duì)地層的傷害,而殘?jiān)恳裁黠@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.

【學(xué)位授予單位】：陜西科技大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：O631;TE357.12

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本文編號(hào)：1450234