疏水聚合物Mannich碱的合成及溶液性能

将增黏用碳五石油树脂(C_5)作为疏水单体,与丙烯酰胺(AM)聚合反应得到AM/C_5二元共聚物,通过胺甲基化反应制得疏水聚合物Mannich碱。考察了单体质量比、引发剂用量、反应温度以及pH对聚合反应的影响;讨论了反应时间、反应温度以及溶液pH对Mannich碱溶液表观黏度的影响。采用FTIR、~1HNMR对产品进行结构表征,并对产品性能进行分析。结果表明,最佳聚合条件为:反应温度40℃,pH=8,引发剂用量为0.5%(以单体质量计),丙烯酰胺与碳五石油树脂的质量比为15∶1。当反应时间为5 h,温度60~70℃,pH=9,丙烯酰胺、甲醛、二甲胺的物质的量比为1∶1.1∶1.5,Mannich碱溶液黏度达到最佳(418 m Pa·s)。温度为90℃时,Mannich碱的黏度保留率为43.3%;当加入的NaCl、CaCl_2的质量浓度均为2 000 mg/L时,其黏度保留率分别为32.8%、21.7%。该Mannich碱具有较好的增黏、耐温及耐盐性。     

驱油用超支化聚合物的合成及性能

以聚环糊精(HCD)为母核,丙烯酰胺(AM)及甲基丙烯酰乙基磺基甜菜碱(BTAM)为接枝单体,在硝酸铈铵引发下,通过水相自由基聚合,制备了一种具有球形母核及两性离子功能链段的超支化聚合物(HCD-HPAM-BTAM)。考察了聚合时间、引发剂用量、HCD用量、水解烘干温度、BTAM用量对聚合物溶液黏度的影响。采用FTIR和1HNMR对聚合物结构进行了表征,并对其溶解、增黏、抗剪切、抗盐及抗老化性能进行了评价。得到的最佳聚合条件为:聚合时间5.5 h、引发剂60 mg、HCD 20~30 mg、烘干温度120℃、BTAM200 mg。在总矿化度为9374.13 mg/L的矿化水中,聚合物HCD-HPAM-BTAM溶解时间基本小于50 min。2000 mg/L的聚合物溶液黏度可达31.2 mPa?s,3500 r/min剪切20 s后黏度保留率高达80%,老化90 d黏度保留率为63%,均优于未改性的部分水解聚丙烯酰胺(HPAM)。     

丙烯酰胺黄原胶接枝共聚物水溶液粘性行为研究

以丙烯酰胺（AM）、黄原胶（XG）为主要原料,硝酸铈铵（CAN）为引发剂,合成了丙烯酰胺黄原胶接枝共聚物（XGA）,研究了无机盐（NaCl、CaCl2、MgCl2）浓度、温度、老化时间和剪切速率等因素对XGA溶液黏性行为的影响。结果表明,XGA具有与XG相同的优良的耐盐性能,XGA溶液的黏度在高温（85℃）下具有更好的时间稳定性;XG和XGA溶液的流变曲线均表现为宾汉流体的流变行为,当剪切速率由最大值逐渐减小时,溶液黏度逐渐恢复,但与初始黏度相比存在滞后现象。     

一种水溶性P(AM-NaAA-NIDA)的合成及溶液性能

以丙烯酰胺(AM)、丙烯酸钠(Na AA)、1-(2-N-丙烯酰基氨乙基)-2-油酸基咪唑啉(NIDA)为单体,在氧化还原体系下进行自由基胶束共聚合成了一种水溶性三元共聚物P(AM-Na AA-NIDA),并通过FTIR、1HNMR对聚合物进行了结构表征和性能评价。结果发现,2 000 mg/L的聚合物溶液具有较好的流变性能(120℃:黏度保留率为21.18%;1 000 s-1:黏度保留率为17.22%)及抗盐性能(12 000 mg/L Na Cl溶液:黏度保留率为20.33%)。相比30℃,该聚合物在120℃的黏度保留率为21.18%;在室内模拟岩芯驱替实验中,该聚合物提高采收率达17.68%。     

疏水缔合两性聚丙烯酰胺的合成与性能研究

利用疏水单体苯乙烯能够提高分子链刚性,可以与丙烯酰胺进行共聚,并且苯乙烯与丙烯酰胺共聚物在水溶液中存在疏水缔合作用的特性,将苯乙烯、丙烯酰胺和3-[2-(N-甲基丙烯酰胺基)-乙基二甲基铵基]丙基磺酸盐采用反相乳液聚合的方式进行聚合反应得到一种疏水缔合的两性聚丙烯酰胺。聚合物结构经过核磁和红外验证,并对其耐盐性能进行验证,着重研究了其耐温性能,该种聚合物耐温性能有显著提高。该聚合物经100℃老化48h后剪切黏度保留率达到63%,而80℃老化48 h后剪切黏度保留率则高达87%。     

疏水缔合型丙烯酰胺共聚物P(AA-AM-TP)的制备及溶液性质

疏水缔合型聚合物(HAPAM)具有优异的增黏能力,因此被认为是一种潜在的用于条件苛刻油田的驱油剂。本文以丙烯酰胺、丙烯酸、三苯基-1-戊烯为原料使用胶束共聚法成功制备出一种新型聚合物。研究了聚合物浓度、盐度、温度对溶液黏度的影响。结果表明,当浓度超过1500mg/L时,黏度大幅增高;三元共聚物具有一定的抗温耐盐性质。并使用红外光谱表征了聚合物的结构。     

两性疏水缔合聚丙烯酰胺的室内性能研究

以丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和一种疏水长链烷基烯丙基氯化铵(M-18A)为单体,以溶剂油为油相,采用反相乳液聚合法合成一种两性疏水缔合聚丙烯酰胺增稠剂(AP-AM18)。在最佳合成条件下,利用核磁共振氢谱(¹H NMR)、红外光谱(FTIR)、X-射线衍射(XRD)和热重分析仪(TGA)对AP-AM18进行了表征。红外光谱结果表明,单体发生聚合;XRD图显示其具有非晶体结构;对聚合物AP-AM18的热稳定性分析发现,分解温度超过500℃后,样品质量基本不变,表明聚合物具有良好的耐温性;对AP-AM18进行增稠、耐盐性能测试发现,随着浓度的升高,表观黏度逐渐上升,当浓度为2%时,聚合物AP-AM18在清水中的表观黏度达到893 m Pa·s,在5×101H NMR)、红外光谱(FTIR)、X-射线衍射(XRD)和热重分析仪(TGA)对AP-AM18进行了表征。红外光谱结果表明,单体发生聚合;XRD图显示其具有非晶体结构;对聚合物AP-AM18的热稳定性分析发现,分解温度超过500℃后,样品质量基本不变,表明聚合物具有良好的耐温性;对AP-AM18进行增稠、耐盐性能测试发现,随着浓度的升高,表观黏度逐渐上升,当浓度为2%时,聚合物AP-AM18在清水中的表观黏度达到893 m Pa·s,在5×10⁴mg/L矿化水中,表观黏度达到391 m Pa·s,表明其具有较好的增稠、耐盐性能。     

盐对聚丙烯酰胺黏度的影响评价

聚丙烯酰胺的抗盐、抗剪切性能较差,且有一定的化学降解性能,因此,聚合物(PAM)驱油剂的耐盐、增黏问题已经成为三次采油技术中极具挑战性的研究课题。影响溶液黏度的因素较多,本文主要研究几种离子对聚丙烯酰胺黏度的影响。以分子量500～700万的聚丙烯酰胺为原料,在一定温度下,探究不同的放置时间及不同的离子浓度下所形成的聚丙烯酰胺水溶液的黏度,通过测量其不同情况下的黏度,研究离子对聚丙烯酰胺的降黏效果。实验结果表明,聚合物的浓度越高,聚丙烯酰胺水溶液的黏度越大;聚合物浓度一定时,加入一定的盐,水溶液体系的黏度降低,且随着盐浓度的增加,体系黏度减小得更为明显。当盐的量达到某一程度,体系的黏度不再减小。此类盐的离子中,钙、镁、钡等二价离子的降黏效果较为明显,对聚丙烯酰胺水溶液黏度的影响依次为Ca~(2+)Mg~(2+)Ba~(2+)K~+Na~+。     

两性疏水缔合聚丙烯酰胺的室内性能研究

以丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和一种疏水长链烷基烯丙基氯化铵(M-18A)为单体,以溶剂油为油相,采用反相乳液聚合法合成一种两性疏水缔合聚丙烯酰胺增稠剂(AP-AM18)。在最佳合成条件下,利用核磁共振氢谱(~1H NMR)、红外光谱(FTIR)、X-射线衍射(XRD)和热重分析仪(TGA)对AP-AM18进行了表征。红外光谱结果表明,单体发生聚合;XRD图显示其具有非晶体结构;对聚合物AP-AM18的热稳定性分析发现,分解温度超过500℃后,样品质量基本不变,表明聚合物具有良好的耐温性;对AP-AM18进行增稠、耐盐性能测试发现,随着浓度的升高,表观黏度逐渐上升,当浓度为2%时,聚合物AP-AM18在清水中的表观黏度达到893 m Pa·s,在5×10~4mg/L矿化水中,表观黏度达到391 m Pa·s,表明其具有较好的增稠、耐盐性能。     

一种疏水缔合聚合物的合成及溶液性能

将十八烷基-二甲基甲代烯丙基氯化铵(C18DMMAAC)作为疏水单体,与丙烯酸(AA)、丙烯酰胺(AM)在水溶液中通过自由基聚合得到疏水缔合聚合物HAPAM-18,通过1HNMR和红外光谱对其结构进行了表征。最佳的聚合反应条件为:n(AM)∶n(AA)∶n(C18DMMAAC)=74.94∶25∶0.06,AA的摩尔中和度为95%,单体总质量分数为20%,引发剂质量分数为0.05%(以单体总质量计),温度45℃,反应时间12 h。研究表明,聚合物溶液的临界缔合质量浓度为2 g/L;聚合物溶液对温度较为敏感,80℃时黏度保留率为70.93%;聚合物溶液仍为剪切变稀的假塑性流体,但表现出良好的抗剪切性能,剪切1 h后黏度保留率达115%;由于设计为含较多阴离子的聚合物,该聚合物的抗盐性较差。     

Preparation and performance study of functional polymer with self demulsifying

In polymer flooding, the residual polymer in the produced fluid can increase the stability of crude oil emulsion, thereby negatively affecting the demulsification process. Therefore, a polymer that has no effect on the stability of crude oil emulsion is required. Herein, a polymerizable monomer with a demulsification function (MD) was synthesized and then copolymerized with acrylamide, acrylic acid, and 2-acrylamide-2-methylpropane sulfonic acid to prepare a novel copolymer (self-demulsifying polymer, PDM). The dissolution time, solution viscosity, shear resistance, static adsorption on quartz sand, and the effect on the crude oil emulsion stability of PDM were compared with those of regular polyacrylamide (PAM). Experimental results showed that owing to the steric hindrance effect of MD, the molecular weight of PDM was lower than that of PAM. Both polymers exhibited satisfactory solubility, solution viscosity, shear resistance, and static adsorption, which can meet the requirements of polymer for use in oil displacement. However, in contrast to PAM, PDM had no negative effect on the crude oil emulsion stability. This study provides a new solution to the problem of increased crude oil emulsion stability in polymer flooding.     

脂肪醇嵌段聚醚丙烯酸酯与丙烯酰胺共聚物及其水溶液特性的研究

本文合成了脂肪醇嵌段聚醚丙烯酸酯单体 ,并与丙烯酰胺共聚 ,得到共聚物PEPO PAM。芘荧光光谱分析表明 ,该聚合物在水溶液中依靠分子链上的疏水基团形成一定的缔合作用。PEPO PAM相对于部分水解聚丙烯酰胺 (HPAM )具有更好的增粘性。通过调整分子的组成 ,可使该聚合物不仅具有较强的增粘性 ,同时具有良好的水溶性。     

聚丙烯酰胺/聚乙烯吡咯烷酮与表面活性剂十二烷基硫酸钠的相互作用

通过对聚合物聚丙烯酰胺/聚乙烯吡咯烷酮(PAM/PVP)与表面活性剂十二烷基硫酸钠(SDS)混合体系的相对黏度和表面张力研究,证明聚合物PAM/PVP与表面活性剂SDS之间存在着明显的相互作用,通过缔合,形成混合胶束状聚集体,导致溶液黏度剧增。随聚合物溶液中SDS的加入,溶液黏度发生起伏变化,出现最大值(最小值)。而2者的相互作用使体系溶液的表面张力在SDS的临界胶束浓度(CMC)前后呈现先减小后增大,最后趋于平衡的情况。且聚表相互作用使溶液界面的界面张力比纯表面活性剂溶液的界面张力有所升高。     

驱油用磺酸盐型聚丙烯酰胺的合成及性能表征

在水介质中进行了丙烯酰胺(AM)与2-丙烯酰胺基-2-甲基丙磺酸(AMPS)的溶液共聚合,其最佳反应条件为:单体AM浓度10%,AMPS占AM的17.5%(摩尔比),引发剂加量为AM质量的0.05%,反应温度为50℃。考察了共聚物的抗温性能及对不同盐的承受能力,结果表明,磺酸基团的强阴离子性与庞大侧基的位阻效应,赋于磺酸盐型聚丙烯酰胺P(AM/AMPS)优良的耐温与抗盐性能。     

AM/AMPS/DMC聚两性电解质的合成、表征与溶液性能

以丙烯酰胺(AM)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)和甲基丙烯酰氧乙基三甲基氯化铵(DMC)为原料,在0.5 mol/L NaC l溶液中,以2,2-偶氮二[2-(2-咪唑啉-2-代)丙烷]二氢氯化物(VA-044)为引发剂,合成了AM/AMPS/DMC系列聚两性电解质。利用13C NMR对共聚产物结构进行表征,结果表明,在高转化率情况下,共聚物组分与投料比基本一致。考察外加小分子电解质和温度对聚两性电解质溶液性能的影响,结果显示,阴、阳离子数量相近的聚两性电解质溶液的粘度随外加盐浓度增大而增大,在温度升高时,其表观粘度保留率高于聚丙烯酰胺,说明AM/AMPS/DMC系列聚两性电解质具有一定的抗温、耐盐能力。     

Conformation of polyacrylamide in aqueous solution with interactive additives and cosolvents

The viscosity of polyacrylamide (PAM) dilute aqueous solutions with NaCl, glucose, and SDS as additives was measured by Ubbelohde viscometry. There was linear relationship between reduced viscosity vs. PAM concentration in aqueous solutions. The Huggins constant k and intrinsic viscosity [η] were used to study the conformation of the polymer chains and the degree of polymer–solvent interaction. In addition, the viscosity of diluted PAM solutions in water with acetone, ethanol, DMF, and ethylene glycol as cosolvent was measured. It was found that the polymer chain conformation contracted as the acetone, ethanol, and DMF cosolvent composition ratio increased, but there was no distinguishing difference between water–ethylene glycol compositions. The solution properties of PAM were used to estimate the swelling properties of PAM gel in the same external conditions, as gel is formed by crosslinking of linear polymer. In good solvent the polymer chain should be expanded, and gel is expected to have large swelling ratio. In water cosolvent systems, when the linear polymer chain underwent coil–globule transition, PAM gel should have volume phase transition under corresponding external conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3122–3129, 2003     

驱油用超支化抗剪切聚丙烯酰胺的合成及溶液性能

以聚环糊精（HCD）为母核,丙烯酰胺（AM）及甲基丙烯酰乙基磺基甜菜碱（BTAM）为接枝单体,在铈盐-羟基引发体系下,通过水相自由基聚合,制备了一种具有球形母核及两性离子功能链段的超支化聚合物HCD-HPAM-BTAM。考察了聚合时间（T1）、引发剂用量（M[O]）、HCD用量（MHCD）、水解烘干温度（t）、BTAM用量（MBTAM）等对聚合物溶液粘度的影响。采用1HNMR对聚合物进行了结构表征,并对其溶解、增粘、抗剪切、抗盐及抗老化性能进行了评价。结果表明,最佳的聚合条件为：T1=5.5h、M[O]=60mg、MHCD=20-30mg、t=120oC、MBTAM=200mg。在9374.13mg/L的矿化水中,HCD-HPAM-BTAM聚合物基本溶解时间均小于40min,2000mg/L的聚合物溶液粘度可达到31.2 mPa?s,Waring搅拌器1档剪切20s后粘度保留率高达80%,老化90天粘度保留率为63%,均优于未改性HPAM聚合物。     

Effect of cationic surfactant addition on the drag reduction behaviour of anionic polymer solutions

Although extensive research work has been carried out on the drag reduction (DR) behaviour of polymers and surfactants alone, little progress has been made on the synergistic effects of combined polymers and surfactants. In this work, the interactions between drag‐reducing anionic polymer (copolymer of acrylamide and sodium acrylate, referred to as PAM) and drag‐reducing cationic surfactant (octadecyltrimethylammonium chloride, OTAC) are studied. Solutions are prepared using both deionised (DI) water and tap water. The measurement of the physical properties such as electrical conductivity and viscosity are used to determine the surfactant–polymer interactions. The addition of surfactant to the polymer solution has a significant effect on the properties of the system. The critical micelle concentration (CMC) of the mixed surfactant–polymer system is found to be different from that of the surfactant alone. With the addition of surfactant to a polymer solution, a substantial decrease in the viscosity occurs. The observed changes in the viscosity of mixed polymer–surfactant system are explained in terms of the changes in the extension of polymeric chains, resulting from polymer–surfactant interactions. The anionic PAM chains tend to collapse upon the addition of cationic OTAC. The pipeline flow behaviour of PAM/OTAC mixtures is found to be consistent with the bench scale results. The DR ability of PAM is reduced upon the addition of OTAC. At low concentrations of PAM, the effect of OTAC on the DR behaviour is more pronounced. The DR behaviour of polymer solutions is strongly influenced by the nature of water (DI or tap). © 2011 Canadian Society for Chemical Engineering     

联合阴极电Fenton和阳极氧化降解高相对分子质量聚丙烯酰胺

采用浸渍-高温煅烧法制备了Fe3O4/石墨毡复合电极,联合阴极电Fenton和阳极氧化法降解聚丙烯酰胺(PAM)。以CODCr和溶液的相对粘度为指标,分别比较阴极电Fenton法、阳极氧化法及联合法对PAM的降解性能。与单一方法相比,联合法对PAM表现出强化降解效果,降解后溶液的CODCr降低了45.6%,相对粘度由2.19降低到1.04。采用凝胶渗透色谱(GPC)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱分析(XPS)对PAM的降解产物进行表征分析。结果表明,在降解过程中PAM的碳主链缩短,侧链基团大量脱落,并有醚键生成。据此推测PAM在电催化氧化中的降解机理为碳主链的断裂与重新缩合的过程,因此,PAM降解产物中仍存在部分高分子聚合物。所生成的聚合物具有较强的可生化降解性,可被好氧活性污泥进一步降解。     

Synthesis,characterization, and properties of amphiphilic block copolymer of acrylamide‐styrene by self‐emulsifying microemulsion method

The copolymerization system of acrylamide (AM) and styrene (St) was acquired by using amphiphilic block copolymer PAM‐b‐PSt with lower molecular weight as polymeric surfactant, and then the microemulsion phase diagram was drawn. The appropriate copolymerization systems were chosen in the phase diagram, and higher molecular weight amphiphilic block copolymers PAM‐b‐PSt were prepared by self‐emulsifying microemulsion method. The chemical composition and structure of the products were analyzed by FTIR, ¹H‐NMR, ¹³C‐NMR, GPC, and UV; the block structure of products was characterized by DSC, and the hydrophobic association property of the products was studied by the fluorescence probe and rotating viscosity measurement. The results showed that O/W microemulsion was also acquired by using the polymeric surfactant; 3 g polymeric surfactant was only used to disperse 0.25 g St into aqueous solution, which showed higher emulsifying efficiency. At the same time, the use of self‐emulsifying microemulsion copolymerizing system can avoid back treatment of small molecular surfactant and the purified block polymer was prepared in one step; the prepared copolymers have good hydrophobic association properties and their aqueous solution showed evident viscosity increment. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009