不同结构疏水缔合聚合物复合体系溶液性质研究
发布时间：2019-07-02 13:25
【摘要】：疏水缔合聚合物与普通部分水解聚丙烯酰胺聚合物相比较,其能够表现出更好的溶液性能和特殊的流变性,从而在提高采收率领域有着广泛的应用。但是对于那些特殊的复杂油藏,单一的疏水缔合聚合物依旧不能满足其高效增粘、耐高矿化度、耐高温、抗剪切的苛刻要求。鉴于此,人们开始探索将不同单一聚合物复配形成高分子复合物来提高单一聚合物性能的研究思路,一些研究表明,与单一聚合物相比,复合体系性能通常情况下确实能得到很大的提高,能够更好地符合应用要求。然而,当将两种带相反电荷的疏水缔合聚合物进行混合形成复合体系后,其溶液性能会发生怎样的变化?哪些结构参数会是性能变化的主导因素?针对这些问题,本文进行了如下研究：1.采用稳态荧光猝灭法获得了在AM存在条件下,阳离子型疏水单体十六烷基二甲基烯丙基氯化铵(C16DMAAC)的胶束聚集数Nagg和微嵌段长度NH随正戊醇加量的变化曲线,并以此为依据合成了不同NH的阳离子型疏水缔合聚合物PN系列；以AM和2-丙烯酰胺基十四烷基磺酸钠(NaAMC14S)为共聚单体,纯水和乙醇／水(质量比为1：3)混合溶液分别作溶剂,调整光引发剂的加量,通过光引发聚合合成了不同分子量的阴离子型疏水缔合聚合物PM系列；综合各种表征结果,证实PN系列聚合物除了NH存在差异外,其他结构参数都一致,分子量是PM系列聚合物最主要的差异。2.流变性测试获得的PN系列聚合物粘浓曲线结果表明,同一浓度下,NH越长,分子间缔合程度越大,对聚合物粘度贡献越大；将不同NH的疏水缔合聚合物PN系列与PM-h进行复配,考察了NH、复配比、聚合物浓度对PN系列/PM-h复合体系溶液性能的影响,流变测试结果表明当复合体系的总浓度一定时,PN系列NH越长,复合体系的零剪切粘度(η0)越大,即PN-15/PM-hPN-7/PM-h PN-4/PM-h; NH一定时,复合体系的总浓度越高,η0越大,即3000mg/L1500mg/L700mg/L; PN系列：PM-h=4：6(3：7)时,复合体系粘度最大；荧光光谱实验中,随NH和浓度的增加,单一组分聚合物和复合体系的13/11值随之增大,随PN系列在复合体系中质量分数的增加,13/11值呈现先增大后减小的趋势。3.将PN-15与不同分子量疏水缔合聚合物PM系列进行复配,流变实验表明PN-15/PM-t体系的粘度主要源于PN-15聚合物粘度的贡献；荧光实验也表明PN-15/PM-t体系的非极性主要源于PN-15聚合物分子间缔合作用的贡献,体系的13/I1值始终小于纯的PN-15；当固定PN-15的浓度,向其中逐渐加入PM系列聚合物时,混合后体系的粘度和13/11随PM系列聚合物浓度的增加而增加。4.分别将不同水解度的HPN-15和HPM-h、HPM-t进行混合,流变实验表明对于HPN-15/HPM-h体系,随着水解度的增加,组分聚合物之间的相互作用越来越弱,复合程度逐渐减小,体系的粘度增长幅度越来越小；对于HPN-15/HPM-t体系,与未水解体系类似,体系的η0仍是源于HPN-15的贡献；荧光实验表明,随水解度的增加,HPN-15/HPM-h体系和HPN-15/HPM-t体系的13/11值都会下降。5.通过考察上述三种因素对疏水缔合聚合物复合体系溶液性能的影响,得到了如下规律性认识：复合体系中某一组分的微嵌段长度越长,则体系的增粘性越好；分子量相当(处在同一数量级)的带相反电荷的两组分进行混合,体系的粘度会急剧增加,而水解度增加,二者的相互作用程度会减小,粘度也会随之减小；分子量相差一个数量级以上的两组分组成的复合体系,无论是否水解,体系的粘度都主要源于分子量较高的组分的贡献。这些认识能够为通过调节分子结构参数来改善聚合物复合体系的应用性能打下夯实基础和提供有利参考依据。
[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.
【学位授予单位】：西南石油大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.2
本文编号：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.
【学位授予单位】：西南石油大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.2
【参考文献】
相关期刊论文 前10条
1 徐辉;;超高分子缔合聚合物溶液特性及驱油性能研究[J];石油与天然气化工;2014年01期
2 冯茹森;嵇薇;郭拥军;孙建辉;唐昊;宋汝彤;;疏水缔合聚合物重均分子量的测定[J];高分子学报;2014年01期
3 杨志钢;;三次采油技术及进展[J];化工进展;2011年S1期
4 安会勇;陈强;宋春雷;;离子型疏水缔合水溶性聚合物的研究进展[J];科技导报;2011年15期
5 李春;陈庆柏;李万捷;;光敏引发合成聚丙烯酰胺[J];功能高分子学报;2010年02期
6 吕挺;单国荣;;黏度法研究聚丙烯酰胺与聚乙二醇在水中的相互作用[J];高分子学报;2010年02期
7 钟传蓉;邓俊;罗平亚;刘文祥;;离子型疏水缔合共聚物的分子复合[J];石油学报(石油加工);2009年01期
8 耿同谋;;疏水缔合水溶性聚合物——P(AM-NaAA-DiAC_8)的合成及其缔合性能[J];合成化学;2009年01期
9 江立鼎;高保娇;孔德轮;;丙烯酰胺型阴离子表面活性单体与丙烯酰胺共聚物水溶液的流变特性[J];高分子学报;2007年04期
10 戴玉华;吴飞鹏;李妙贞;王尔擰;;荧光淬灭法研究疏水缔合共聚物(PAM-b-PPOEA)_n自组装聚集数[J];高分子学报;2006年03期
相关硕士学位论文 前2条
1 杨化彪;季铵型疏水缔合聚丙烯酰胺的合成及性质研究[D];山东大学;2012年
2 张玲;溶液中不同的醇及不同水解度聚丙烯酰胺与瓜尔胶高分子之间的相互作用研究[D];中国科学技术大学;2010年
，本文编号：2508967
本文链接：https://www.wllwen.com/kejilunwen/huaxue/2508967.html
教材专著
