Tensile Mechanical Properties of Hydrophobic Association Hydrogels: Effect of Crosslinking Method,Synthesis Temperature,Mineral Salt and Swelling

Hydrophobic association hydrogels (HA-gels) were prepared through micellar copolymerization of acrylamide (AM) and a small amount of octylphenol polyoxyethylene acrylate (OP-10-AC) in an aqueous solution containing sodium dodecyl sulfate (SDS). For the P(AM/OP-10-AC) HA-gels, the effect of crosslinking method, synthesis temperature, mineral salt (NaCl) and swelling on their tensile mechanical properties was investigated in detail. The experimental results show that crosslinking method, synthesis temperature, NaCl and swelling powerfully influenced tensile mechanical properties of the P(AM/OP-10-AC) HA-gels. In addition, according to the tensile experimental results of the P(AM/OP-10-AC) HA-gels swollen, an effective crosslinking density change model is proposed. The effect of swelling on tensile mechanical properties of the P(AM/OP-10-AC) HA-gels was discussed on the basis of the model.     

Synthesis,Characterization, and Property Evaluation of a Hydrophobically Modified Polyacrylamide as Enhanced Oil Recovery Chemical

A novel hydrophobically modified polyacrylamide p(AM/NaA/OP-10-AC/BOAM) was successfully synthesized via an aqueous micellar copolymerization method from acrylamide (AM), sodium acrylate (NaA), octylphenol polyoxyethylene acrylate (OP-10-AC), and small amounts of N-benzyl-N-octylacrylamide (BOAM), with the aim of investigating the copolymer's rheological behaviors under various conditions such as polymer concentration, shearing, temperature, and salinity. The copolymer was characterized by infrared spectroscopy, scanning electron microscopy, and atomic force microscope. Scanning electron micrographs show large aggregates in solution formed by the association from the hydrophobic groups of the copolymer. Compared with partially hydrolyzed polyacryamide (HPAM), the copolymer shows a much higher thickening capability and a much greater ability to resist shearing, heat, and salts. This good property of the copolymer is attributed to its three-dimensional dimensional network structure. According to the core flooding test, it can be obtained that oil recovery is enhanced about 4.3% by the copolymer flooding contrasted to the HPAM flooding in mid-low permeability cores under conditions of 1500 mg/L of polymers and 45°C. All the results prove that the copolymer has the capability of increasing oil recovery by improving waterflood sweep efficiency in high-salinity reservoirs.     

十二烷基磺酸钠对丙烯酰胺－烯丙基磺酸钠共聚物溶液粘度的影响

丙烯酞胺-烯丙基磺酸钠共聚物(PASA)优良的絮凝性能已在前文^[1]中报道.本文主要考察阴离子表面活性剂R₁₂SO₃Na对其溶液粘度的影响,并与PAM做了对照.     

新型疏水缔合聚合物P(AM/POEA)与表面活性剂的相互作用

采用粘度法、荧光探针和透射电镜研究了新型疏水缔合聚合物P(AM/POEA)和表面活性剂SDS和CTAB在水溶液中的相互作用. 聚合物P(AM/POEA)结构中, 疏水体(2-苯氧乙基丙烯酸酯)呈嵌段状无序地分布在聚丙烯酰胺主链上. 这类聚合物很容易和表面活性剂相互作用, 通过疏水缔合, 形成混合胶束状聚集体, 导致溶液粘度剧增. 随聚合物溶液中SDS的加入, 溶液粘度发生大幅度起伏变化, 出现最大值. 粘度最大值对应的表面活性剂浓度c_S,max位于表面活性剂CMC附近, 并发现它的位置不随聚合物微结构而变化. 然而它们缔合作用的增粘程度却与聚合物疏水体含量X_H及疏水嵌段尺寸N_H有关. 在实验浓度范围内, X_H和N_H愈大, 溶液的粘度越高. 此外用透射电镜直接观察到聚合物/表面活性剂体系中聚集体的交联结构形貌.     

中低渗透高温高盐油藏驱油共聚物P(AM/AMPSNa/AANa)的合成及性能

在中低渗透高温高盐油藏聚合物驱技术中, 超高相对分子质量聚丙烯酰胺(HPAM)存在不易注入、剪切降粘显著和耐温抗盐性能差等问题。 本文以丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体, 采用过硫酸胺(NH₄)₂S₂O₈和甲基丙烯酸N, N-二甲氨基乙酯(DMAEMA)作为支化结构复合引发体系, 通过共聚后水解工艺, 合成含支化结构耐温抗盐驱油共聚物P(AM/AMPSNa/AANa)。 研究了引发温度、链转移剂用量、引发剂用量对共聚物特性黏数的影响, 并通过红外光谱(IR)和¹³C NMR表征了产物结构。 筛选特性黏数1915 mL/g左右的共聚物, 进行性能评价。 实验结果表明, 共聚物具有优异的耐温抗盐性能、抗剪切性能、抗老化性、注入性和驱油性能, 可应用在中低渗透高温高盐油藏三次采油中。     

聚阳离子三甲基烯丙基氯化铵-丙烯酰胺共聚物的溶液性质研究

按实用要求对不同阳离子度及分子量的三甲基烯丙基氯化铵 丙烯酰胺共聚物Ｐ（ＴＭ ｃｏ ＡＡＭ）分别在水、水 甲醇、水 乙酸，不同浓度的ＮａＣｌ、ＫＣｌ、ＫＢｒ及Ｎａ２ＳＯ４水溶液中的溶液粘度行为进行了探讨，考察了低阳离子度的Ｐ（ＴＭ ｃｏ ＡＡＭ）的聚电解质行为及其大分子链在溶液中的分子链运动形态．     

激光光散射研究丙烯酰胺丙烯酸共聚物的溶液行为

用激光光散射技术研究了丙烯酰胺 丙烯酸共聚物 (简称P(AM AA) )的溶液行为 .结果表明 ,纯水中P(AM AA)分子的流体力学半径Rh的分布存在 10 0～ 5 0 0nm的范围 ,与溶液中的网状结构对应 .当加入NaCl后 ,Rh 分布变窄 ,集中在 10 0nm以下的范围内 ,10 0～ 5 0 0nm这一范围消失 ,说明P(AM AA)在纯水溶液中主要以网状结构存在 ,小分子盐如NaCl的加入会破坏这种网状结构 .网状结构的破坏导致溶液稳定性下降 ,在0 1mol LNaCl溶液中 ,当c c 时 ,放置一段时间后 ,溶液中出现白色絮状沉淀 .     

PABA疏水缔合水溶性共聚物溶液的合成与性能研究

本文根据高分子的分子设计原理，合成了带苯基的疏水单体N－苯基对正丁基丙烯酰胺（BBAM）。采用自由基胶束共聚的方法制备了水溶性丙烯胺／N－苯基对正丁基丙烯酰胺（BBAM）疏水缔合型共聚物（PABA）。研究了共聚物溶液的性能及影响因素。结果表明，随共聚物溶液浓度的增加，在临界缔合浓度以上，分子间缔合大量形成，水溶液表现粘度迅速增加，表现出明显的疏水缔合行为，与HPAM相比有优异的抗盐性。     

Mechanical Properties and Network Structure of Hydrophobic Association Hydrogels Prepared from Octylphenol Polyoxyethylene(7) Acrylate and Sodium Dodecyl Sulfate

Hydrophobic association hydrogels(HA-gels) with high mechanical strength were prepared by free radical micellar copolymerization in aqueous solutions of acrylamide(AM), anion surfactant sodium dodecyl sulfate(SDS) and a small amount of hydrophobic monomer octylphenol polyoxyethylene(7) acrylate(OP-7-AC). We found that the molar ratio of SDS to OP-7-AC has a great effect on the tensile strength and other mechanical property parameters. The best ratio point R' was determined. On the basis of Mooney theory and statistical theory, the critical tensile ratios and critical tensile strengths of the hydrogels were obtained, elastic parameters C₁ and C₂ were calculated via uniaxial tensile equation and structural parameters, such as the effective network chain density and the averaged molecular weight of the chain between cross-linking points of all the hydrogels were evaluated. The results indicate that the variation of mechanical property parameters depends on the number of effective cross-linking points and the match degree of long and short chains.     

新一族疏水缔合聚丙烯酰胺NaAMC14S/AM与Gemini表面活性剂之间的相互作用

在水溶液中进行了表面活性单体丙烯酰胺基十四烷基磺酸钠(NaAMC14S)与丙烯酰胺(AM)的均相共聚合, 制备了具有微嵌段结构的疏水缔合聚丙烯酰胺NaAMC14S/AM, 合成了阳离子型Gemini表面活性剂二溴化-N,N′-二(二甲基十二烷基)己二铵(C12C6C12Br2), 采用表观粘度法和荧光探针法研究了共聚物NaAMC14S/AM与Gemini表面活性剂C12C6C12Br2的相互作用. 研究结果表明, 疏水缔合聚丙烯酰胺NaAMC14S/AM与Gemini表面活性剂C12C6C12Br2之间存在着很强的相互作用, 既存在静电相互作用, 又存在强烈的疏水相互作用, 表现在以下几方面: C12C6C12Br2的加入, 使共聚物NaAMC14S/AM在浓度小于其临界缔合浓度(cac)时即发生分子间的缔合; C12C6C12Br2在低于其临界胶束浓度时, 就与共聚物NaAMC14S/AM形成混合胶束; 当共聚物的浓度为0.30%(w)时, 随着C12C6C12Br2加入量的增多, 共聚物水溶液的粘度会发生大幅度的增加, 在最大值处粘度竟提高了3个数量级. 研究还发现, 共聚物NaAMC14S/AM与C12C6C12Br2之间的相互作用还与共聚物分子链中的疏水微嵌段含量有关, 疏水微嵌段含量越多, NaAMC14S/AM与C12C6C12Br2之间的相互作用越强, 溶液粘度增加的程度越大.     

兼具有强阴离子性与疏水缔合性的丙烯酰胺三元共聚物

在微乳液介质中实施了丙烯酰胺 (AM)、苯乙烯 (St)、2 丙烯酰胺基 2 甲基丙磺酸钠 (NaAMPS)的共聚合 ,制备了既含有强阴离子性基团 (—SO3Na)又含有疏水基团 (St)的丙烯酰胺三元共聚物AM NaAMPS St;通过红外光谱法、紫外分光光度法及元素分析法对共聚物的结构及组成进行了表征 ;稀释外推粘度法测定了共聚物的特性粘数 ;测定了共聚物纯水溶液及盐水溶液的表观粘度 ;荧光探针法考察了三元共聚物的疏水缔合性以及离子基团对疏水缔合性的影响规律 .实验结果表明 ,在聚丙烯酰胺 (PAM )分子主链上同时引入强阴离子性基团与疏水基团后 ,阴离子的电粘效应与疏水基团的疏水缔合作用相互协同 ,会使共聚物水溶液的黏度显著提高 ;盐溶液对疏水缔合作用的增强效应与强阴离子基团对盐的较大容忍度相互结合 ,会使共聚物水溶液的抗盐性能明显得以提高 ;大分子链上的强阴离子基团磺酸根的存在 ,在一定程度上会削弱疏水基团之间的疏水缔合作用 ,即对疏水基团的疏水缔合行为会产生一定的负性影响 .     

高分子表面活性剂P(AM-co-OPMA)的合成与表征

辛基酚聚氧乙烯醚(10)(OP-10)与马来酸酐在95℃下反应,合成了辛基酚聚氧乙烯醚马来酸单酯(OPMA);并在水溶液中与丙烯酰胺(AM)单体进行共聚合,获得了高分子表面活性剂P(AM-co-OPMA);考察了引发剂用量、单体组成、单体总浓度及反应温度对共聚物特性粘数与阴离子度的影响.通过红外光谱、紫外光谱、荧光发射光谱和电导滴定对共聚物结构和组成进行了表征;利用视频光学接触角测量仪分别测定了共聚物表面和界面张力.结果表明,在聚丙烯酰胺分子主链上引入OPMA链节后,不仅保持了PAM优良的增稠能力(特性粘数达764.31 mL/g),且赋予了共聚物较高的表面活性(浓度为1.5 g/L共聚物水溶液的表面和界面张力分别可达53.94 mN/m和5.41 mN/m).     

Effects of nonionic surfactant and associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions

The effect of a low molecular weight nonionic surfactant and an acrylic associative thickener on the rheology of polyacrylamide in aqueous glycerol solutions under steady shear was experimentally investigated. The nonionic surfactant (Tween20), associative thickener (Acrysol TT935) and polyacrylamide (Separan AP30) underwent complex molecular interactions in solution as reflected by rheological measurements. The surfactant also interacted with the glycerol solvent. The addition of surfactant in aqueous glycerol solutions reduced the surface tension, as well as the solution viscosity, at low surfactant concentration. The solution viscosity went through a minimum at certain surfactant concentration, depending on the composition of glycerol/water mixture, before increasing again. Similar behavior was found when the surfactant was added to the polyacrylamide solution, except there was an initial increase in the viscosity before the reduction. The associative thickener, Acrysol TT935 (an anionic acrylic emulsion copolymer) exhibited a strong affinity with polyacrylamide in solution, as indicated by a sharp increase in the solution viscosity. The dilute polyacrylamide solution became highly elastic in the presence of either the nonionic surfactant on the associative thickener. A threestage model was proposed to describe the surfactant/thickener/polymer interactions.     

Synthesis, characterization and flocculation performance of zwitterionic copolymer of acrylamide and 4-vinylpyridine propylsulfobetaine

A novel zwitterionic polyacrylamide AMVPPS copolymer containing sulfobetaine groups was synthesized by copolymerizing acrylamide (AM) and 4-vinylpyridine propylsulfobetaine (4-VPPS) in 0.5 mol/L NaCl solution with potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as initiator. The structure and composition of AMVPPS copolymer were characterized by FT-IR spectroscopy, ¹H NMR and elemental analyses. Thermal stability and solution properties of AMVPPS copolymer were studied by thermogravimetry analysis (TGA) and viscometry. Anti-polyelectrolyte behavior was observed and was found to be enhanced with increasing 4-VPPS content in copolymer. The flocculation performance for 2.5 g/L kaolin suspension and 2.5 g/L hematite suspension was evaluated by transmittance measurement and phase contrast microscopy. The effects of 4-VPPS content in the copolymer, intrinsic viscosity and the added salt on the flocculation performance were investigated. It was found that AMVPPS copolymer was a good flocculant for both anionic kaolin and cationic hematite suspensions and the flocculation performance of copolymer was much better than that of pure polyacrylamide (PAM). A very wide range of the optimum flocculation concentration, named as “flocculation window”, was found for both suspensions. These flocculation characteristics were mainly dependent on the charge neutralization, the intragroup conformation transition from water to NaCl solution and then the interchain bridging of the zwitterionic AMVPPS copolymer.     

氟碳改性聚丙烯酰胺共聚物的溶液性质

研究了氟碳链改性的聚丙烯酰胺水溶液性质及其对盐浓度的依赖性，重点考察 了氟碳疏水组分含量、盐浓度对特性粘数的影响，以及粘度随剪切速率和温度的变 化关系。结果表明聚合物溶液的粘度随盐的引入而增大，但在两种溶液中最小值对 应的共聚单体含量一致。随温度的增加，共聚物溶液粘度依次出现了最小和最大值 。所有实验结果均归于溶液中存在的疏水和氢键两种相反作用的综合结果。     

改性聚丙烯酰胺水溶液的疏水缔合性质

合成了一种疏水缔合水溶性聚丙烯酰胺共聚物,使用荧光光谱法并结合紫外及流变性实验,对制备的疏水缔合水溶性聚丙烯酰胺共聚物在水溶液中形成疏水微区、超分子聚集体及空间网络结构进行了研究,并用扫描电子显微镜证实了溶液中网络结构的存在.     

高强度疏水缔合水凝胶的交联网络结构形成机理

高强度疏水缔合水凝胶(HA-gels)是丙烯酰胺(AM)和少量的疏水单体辛基酚聚氧乙烯(4)醚丙烯酸酯(OP-4-AC)在十二烷基硫酸钠(SDS)水溶液中采用胶束共聚的方法制备的.采用胶束共聚理论、橡胶弹性统计理论及Mooney-Rivlin理论,并结合单向拉伸实验数据,对HA-gels的交联网络结构的形成机理进行了探...     

Phase separation conditions in systems constituted by a nonionogenic surfactant,water, and sodium carbonate

Dependence of the viscosity of aqueous solutions containing a nonionogenic surfactant, OP-10, and sodium carbonate on temperature and concentrations of OP-10 and sodium carbonate was studied. The phase-separation conditions were found for the systems under study.     

甜菜碱型两性离子聚合物P(AM-DMAPAAS)的盐溶液性质

将丙烯酰胺丙基二甲基胺（DMAPAA）和1,3-丙基磺内酯,在55 ℃下反应20 h,合成了3-（丙烯酰胺丙基二甲胺基）丙磺酸盐（DMAPAAS）,将其在盐溶液中与丙烯酰胺（AM）单体进行自由基共聚合反应,获得净电荷为零的磺基甜菜碱型两性离子共聚物P(AM-DMAPAAS);对该两性离子共聚物进行了表征和溶解性评价。 研究结果表明,共聚物在NaCl溶液中的粘度比在纯水中的大,在Mg2+和Ca2+盐溶液中的粘度更大,且随着溶液浓度的增大而增大,表现出明显的反聚电解质溶液性质。 升高相同温度,两性离子共聚物的粘度保留率是普通聚丙烯酰胺的1.4倍。     

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

以丙烯酰胺型阴离子表面活性单体2-丙烯酰胺基十四烷基磺酸钠(NaAMC14S)为共单体,与丙烯酰胺(AM)的水溶液均相共聚合,使NaAMC14S的浓度分别处于临界胶束浓度上下,分别制备了具有无规结构与微嵌段结构的两类共聚物;用红外光谱法对共聚物的结构进行了表征,使用乌氏粘度法测定了特性粘数,相对表示出了共聚物的分子量;采用荧光探针法与表观粘度法重点研究了两类共聚物的疏水缔合性与水溶液的流变特性.研究结果表明,具有微嵌段结构的共聚物具有很强的疏水缔合性,当其水溶液的浓度达0.2wt%后,表观粘度迅速提高;其水溶液的切力变稀行为具有明显的可逆性,表现出强的抗剪切性能.本研究中特别发现,具有微嵌段结构的共聚物其盐水溶液的表观粘度远高于纯水溶液的表观粘度,当共聚物浓度为0.3wt%、CaCl2浓度为2wt%时,溶液的表观粘度竟然提高了3个数量级,表现出独特的正性盐敏性(即遇盐变稠).