不同結(jié)構(gòu)疏水締合聚合物復(fù)合體系溶液性質(zhì)研究
發(fā)布時(shí)間：2019-07-02 13:25
【摘要】：疏水締合聚合物與普通部分水解聚丙烯酰胺聚合物相比較,其能夠表現(xiàn)出更好的溶液性能和特殊的流變性,從而在提高采收率領(lǐng)域有著廣泛的應(yīng)用。但是對(duì)于那些特殊的復(fù)雜油藏,單一的疏水締合聚合物依舊不能滿足其高效增粘、耐高礦化度、耐高溫、抗剪切的苛刻要求。鑒于此,人們開始探索將不同單一聚合物復(fù)配形成高分子復(fù)合物來提高單一聚合物性能的研究思路,一些研究表明,與單一聚合物相比,復(fù)合體系性能通常情況下確實(shí)能得到很大的提高,能夠更好地符合應(yīng)用要求。然而,當(dāng)將兩種帶相反電荷的疏水締合聚合物進(jìn)行混合形成復(fù)合體系后,其溶液性能會(huì)發(fā)生怎樣的變化?哪些結(jié)構(gòu)參數(shù)會(huì)是性能變化的主導(dǎo)因素?針對(duì)這些問題,本文進(jìn)行了如下研究：1.采用穩(wěn)態(tài)熒光猝滅法獲得了在AM存在條件下,陽離子型疏水單體十六烷基二甲基烯丙基氯化銨(C16DMAAC)的膠束聚集數(shù)Nagg和微嵌段長(zhǎng)度NH隨正戊醇加量的變化曲線,并以此為依據(jù)合成了不同NH的陽離子型疏水締合聚合物PN系列；以AM和2-丙烯酰胺基十四烷基磺酸鈉(NaAMC14S)為共聚單體,純水和乙醇／水(質(zhì)量比為1：3)混合溶液分別作溶劑,調(diào)整光引發(fā)劑的加量,通過光引發(fā)聚合合成了不同分子量的陰離子型疏水締合聚合物PM系列；綜合各種表征結(jié)果,證實(shí)PN系列聚合物除了NH存在差異外,其他結(jié)構(gòu)參數(shù)都一致,分子量是PM系列聚合物最主要的差異。2.流變性測(cè)試獲得的PN系列聚合物粘濃曲線結(jié)果表明,同一濃度下,NH越長(zhǎng),分子間締合程度越大,對(duì)聚合物粘度貢獻(xiàn)越大；將不同NH的疏水締合聚合物PN系列與PM-h進(jìn)行復(fù)配,考察了NH、復(fù)配比、聚合物濃度對(duì)PN系列/PM-h復(fù)合體系溶液性能的影響,流變測(cè)試結(jié)果表明當(dāng)復(fù)合體系的總濃度一定時(shí),PN系列NH越長(zhǎng),復(fù)合體系的零剪切粘度(η0)越大,即PN-15/PM-hPN-7/PM-h PN-4/PM-h; NH一定時(shí),復(fù)合體系的總濃度越高,η0越大,即3000mg/L1500mg/L700mg/L; PN系列：PM-h=4：6(3：7)時(shí),復(fù)合體系粘度最大；熒光光譜實(shí)驗(yàn)中,隨NH和濃度的增加,單一組分聚合物和復(fù)合體系的13/11值隨之增大,隨PN系列在復(fù)合體系中質(zhì)量分?jǐn)?shù)的增加,13/11值呈現(xiàn)先增大后減小的趨勢(shì)。3.將PN-15與不同分子量疏水締合聚合物PM系列進(jìn)行復(fù)配,流變實(shí)驗(yàn)表明PN-15/PM-t體系的粘度主要源于PN-15聚合物粘度的貢獻(xiàn)；熒光實(shí)驗(yàn)也表明PN-15/PM-t體系的非極性主要源于PN-15聚合物分子間締合作用的貢獻(xiàn),體系的13/I1值始終小于純的PN-15；當(dāng)固定PN-15的濃度,向其中逐漸加入PM系列聚合物時(shí),混合后體系的粘度和13/11隨PM系列聚合物濃度的增加而增加。4.分別將不同水解度的HPN-15和HPM-h、HPM-t進(jìn)行混合,流變實(shí)驗(yàn)表明對(duì)于HPN-15/HPM-h體系,隨著水解度的增加,組分聚合物之間的相互作用越來越弱,復(fù)合程度逐漸減小,體系的粘度增長(zhǎng)幅度越來越小；對(duì)于HPN-15/HPM-t體系,與未水解體系類似,體系的η0仍是源于HPN-15的貢獻(xiàn)；熒光實(shí)驗(yàn)表明,隨水解度的增加,HPN-15/HPM-h體系和HPN-15/HPM-t體系的13/11值都會(huì)下降。5.通過考察上述三種因素對(duì)疏水締合聚合物復(fù)合體系溶液性能的影響,得到了如下規(guī)律性認(rèn)識(shí)：復(fù)合體系中某一組分的微嵌段長(zhǎng)度越長(zhǎng),則體系的增粘性越好；分子量相當(dāng)(處在同一數(shù)量級(jí))的帶相反電荷的兩組分進(jìn)行混合,體系的粘度會(huì)急劇增加,而水解度增加,二者的相互作用程度會(huì)減小,粘度也會(huì)隨之減��；分子量相差一個(gè)數(shù)量級(jí)以上的兩組分組成的復(fù)合體系,無論是否水解,體系的粘度都主要源于分子量較高的組分的貢獻(xiàn)。這些認(rèn)識(shí)能夠?yàn)橥ㄟ^調(diào)節(jié)分子結(jié)構(gòu)參數(shù)來改善聚合物復(fù)合體系的應(yīng)用性能打下夯實(shí)基礎(chǔ)和提供有利參考依據(jù)。
[Abstract]:The hydrophobic association polymer can exhibit better solution performance and special rheological property compared with the conventional partially hydrolyzed polyetheramine polymer, thereby having wide application in the field of enhanced oil recovery. However, for those special complex reservoirs, the single hydrophobic association polymer can not meet the severe requirements of high efficiency, high salinity, high temperature resistance and shear resistance. in that light of this, people have begun to explore the idea of combining different single polymers to form a polymer complex to improve the performance of a single polymer, some of which show that the performance of the composite system can be greatly improved when compared to a single polymer, And the application requirements can be better met. However, how can the solution performance change after the two oppositely charged hydrophobic association polymers are mixed to form a composite system? What structural parameters are the dominant factors for performance change? In view of these problems, the following research has been carried out:1. A steady-state fluorescence quenching method is adopted to obtain the change curve of the micelle aggregation number of the cationic hydrophobic monomer hexadecyl dimethylallyl chloride (C16DAAC) and the amount of the n-pentanol in the presence of the AM. The cation-type hydrophobic association polymer (PN) series with different NH groups was synthesized by using AM and 2-tetradecylamine-based sodium tetradecyl sulfonate (NaAMC14S) as co-monomer, and the mixed solution of pure water and ethanol/ water (mass ratio of 1:3) was used as a solvent to adjust the amount of the photoinitiator. The PM series of anion-type hydrophobically associating polymer with different molecular weights was synthesized by photo-initiated polymerization. The results of various characterization showed that, in addition to the difference of NH, the other structural parameters were the same, and the molecular weight was the main difference of the PM-series polymer. The results show that the longer the NH, the greater the degree of association between the molecules, the greater the contribution to the viscosity of the polymer under the same concentration, the higher the degree of association between the molecules and the greater the degree of association between the molecules, and the combination of the N series of the hydrophobic association polymer of different NH and the PM-h, and the compound ratio of NH, The effect of polymer concentration on the performance of PN series/ PM-h composite system has been studied. The results show that when the total concentration of the composite system is constant, the longer the PN series NH, the larger the zero shear viscosity of the composite system, i.e. the higher the PN-15/ PM-hPN-7/ PM-h PN-4/ PM-h, the higher the total concentration of the composite system, The larger the viscosity, that is,3000 mg/ L 1500mg/ L 700mg/ L, PN series: PM-h = 4:6 (3:7), the viscosity of the composite system is the most; in the fluorescence spectrum experiment, the 13/11 value of the single component polymer and the composite system increases with the increase of NH and concentration. With the increase of the mass fraction of the PN series in the composite system, the 13/11 value presents a tendency to decrease. The results show that the viscosity of the PN-15/ PM-t system is mainly due to the contribution of the viscosity of the PN-15 polymer. The fluorescence experiment also shows that the non-polar of the PN-15/ PM-t system is mainly due to the contribution of the association between the PN-15 polymer molecules. The 13/ I1 value of the system is always less than pure PN-15; when the concentration of PN-15 is fixed, the viscosity of the post-mixing system and 13/11 increase as the concentration of the PM-series polymer increases as the concentration of the fixed PN-15 is gradually added to the PM-series polymer. HPN-15 and HPM-h and HPM-t of different degrees of hydrolysis were mixed with HPM-t respectively. The rheological experiments show that with the increase of the degree of hydrolysis, the interaction between the components of the HPN-15/ HPM-h system is more and more weak, the composite degree is gradually reduced, and the viscosity of the system is increasing and smaller; for the HPN-15/ HPM-t system, Similar to the unhydrolyzed system, the HPN-15/ HPM-h system and the HPN-15/ HPM-t system of HPN-15/ HPM-t system will decrease with the increase of the degree of hydrolysis. The effect of the above three factors on the performance of the solution of the hydrophobic association polymer composite system was investigated. The following regularity was obtained: the longer the microblock length of a certain component in the composite system, the better the viscosity of the system; The viscosity of the system can be increased sharply, and the degree of hydrolysis is reduced, and the viscosity can be reduced as the degree of hydrolysis is increased, and the degree of hydrolysis is increased. The composite system, which is composed of two components with a molecular weight different from one order of magnitude, is mainly due to the contribution of the components with higher molecular weight, whether or not to be hydrolyzed or not. These understandings can provide a solid foundation for improving the application performance of the polymer composite system by adjusting the molecular structure parameters and providing an advantageous reference basis.
【學(xué)位授予單位】：西南石油大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O631.2
本文編號(hào)：2508967
[Abstract]:The hydrophobic association polymer can exhibit better solution performance and special rheological property compared with the conventional partially hydrolyzed polyetheramine polymer, thereby having wide application in the field of enhanced oil recovery. However, for those special complex reservoirs, the single hydrophobic association polymer can not meet the severe requirements of high efficiency, high salinity, high temperature resistance and shear resistance. in that light of this, people have begun to explore the idea of combining different single polymers to form a polymer complex to improve the performance of a single polymer, some of which show that the performance of the composite system can be greatly improved when compared to a single polymer, And the application requirements can be better met. However, how can the solution performance change after the two oppositely charged hydrophobic association polymers are mixed to form a composite system? What structural parameters are the dominant factors for performance change? In view of these problems, the following research has been carried out:1. A steady-state fluorescence quenching method is adopted to obtain the change curve of the micelle aggregation number of the cationic hydrophobic monomer hexadecyl dimethylallyl chloride (C16DAAC) and the amount of the n-pentanol in the presence of the AM. The cation-type hydrophobic association polymer (PN) series with different NH groups was synthesized by using AM and 2-tetradecylamine-based sodium tetradecyl sulfonate (NaAMC14S) as co-monomer, and the mixed solution of pure water and ethanol/ water (mass ratio of 1:3) was used as a solvent to adjust the amount of the photoinitiator. The PM series of anion-type hydrophobically associating polymer with different molecular weights was synthesized by photo-initiated polymerization. The results of various characterization showed that, in addition to the difference of NH, the other structural parameters were the same, and the molecular weight was the main difference of the PM-series polymer. The results show that the longer the NH, the greater the degree of association between the molecules, the greater the contribution to the viscosity of the polymer under the same concentration, the higher the degree of association between the molecules and the greater the degree of association between the molecules, and the combination of the N series of the hydrophobic association polymer of different NH and the PM-h, and the compound ratio of NH, The effect of polymer concentration on the performance of PN series/ PM-h composite system has been studied. The results show that when the total concentration of the composite system is constant, the longer the PN series NH, the larger the zero shear viscosity of the composite system, i.e. the higher the PN-15/ PM-hPN-7/ PM-h PN-4/ PM-h, the higher the total concentration of the composite system, The larger the viscosity, that is,3000 mg/ L 1500mg/ L 700mg/ L, PN series: PM-h = 4:6 (3:7), the viscosity of the composite system is the most; in the fluorescence spectrum experiment, the 13/11 value of the single component polymer and the composite system increases with the increase of NH and concentration. With the increase of the mass fraction of the PN series in the composite system, the 13/11 value presents a tendency to decrease. The results show that the viscosity of the PN-15/ PM-t system is mainly due to the contribution of the viscosity of the PN-15 polymer. The fluorescence experiment also shows that the non-polar of the PN-15/ PM-t system is mainly due to the contribution of the association between the PN-15 polymer molecules. The 13/ I1 value of the system is always less than pure PN-15; when the concentration of PN-15 is fixed, the viscosity of the post-mixing system and 13/11 increase as the concentration of the PM-series polymer increases as the concentration of the fixed PN-15 is gradually added to the PM-series polymer. HPN-15 and HPM-h and HPM-t of different degrees of hydrolysis were mixed with HPM-t respectively. The rheological experiments show that with the increase of the degree of hydrolysis, the interaction between the components of the HPN-15/ HPM-h system is more and more weak, the composite degree is gradually reduced, and the viscosity of the system is increasing and smaller; for the HPN-15/ HPM-t system, Similar to the unhydrolyzed system, the HPN-15/ HPM-h system and the HPN-15/ HPM-t system of HPN-15/ HPM-t system will decrease with the increase of the degree of hydrolysis. The effect of the above three factors on the performance of the solution of the hydrophobic association polymer composite system was investigated. The following regularity was obtained: the longer the microblock length of a certain component in the composite system, the better the viscosity of the system; The viscosity of the system can be increased sharply, and the degree of hydrolysis is reduced, and the viscosity can be reduced as the degree of hydrolysis is increased, and the degree of hydrolysis is increased. The composite system, which is composed of two components with a molecular weight different from one order of magnitude, is mainly due to the contribution of the components with higher molecular weight, whether or not to be hydrolyzed or not. These understandings can provide a solid foundation for improving the application performance of the polymer composite system by adjusting the molecular structure parameters and providing an advantageous reference basis.
【學(xué)位授予單位】：西南石油大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O631.2
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