疏水缔合丙烯酰胺共聚物浓度对其在水溶液中聚集态的影响

通过荧光探针研究了丙烯酰胺(AM)-苯乙烯衍生物(STD)-2-甲基-2-丙烯酰胺基丙磺酸钠(NaAMPS)共聚物(PASA)在溶液中的疏水缔合作用。结果表明．PASA在淡水和盐水中均具有强的疏水缔合效应,盐的加入使疏水缔合结构更紧密。0．3g／dL PASA在淡水和盐水中的I1/I3值分别为1.23和1．05。环境扫描电镜(ESEM)的研究结果表明,0．05g／dL PASA在淡水中已形成了连续的物理交联网络,使其具有优异的增粘能力。盐的加入破坏了交联网络结构,形成紧密的球形、椭球形和棒状聚集体,使溶液粘度下降。     

AM-STD-NaAMPS三元疏水缔合共聚物的表征及耐热性能

以自制的疏水单体苯乙烯衍生物(STD)和丙烯酰胺(AM)、2-甲基-2-丙烯酰胺基丙磺酸钠(NaAMPS)为原料,合成了三元疏水缔合水溶液共聚物PASA。用红外光谱、核磁共振1H谱和DSC分析证实了共聚物的结构,采用元素分析测定了聚合物的组成,通过原子力显微镜对聚合物溶液形态的表征,证实了PASA水溶液疏水微区的存在。TG分析显示PASA具有优良的耐热性能,其分解温度高达312℃。PASA浓度为0.1g/dL时,表观粘度达208mPa.s,表明了其聚合物具有优良的增粘能力。     

梳型丙烯酰胺共聚物在水溶液中的缔合结构

采用荧光探针研究了丙烯酰胺(AM)/4-乙烯苄基辛烷基酚聚氧乙烯(10)醚(VBPOE)/2-丙烯酰胺基-2-甲基丙磺酸钠(NaAMPS)梳型共聚物(PAVA)在水溶液中的疏水缔合微结构。结果发现,在纯水和盐水溶液中,随聚合物浓度的增大,疏水微区的数量和非极性明显增加,但当PAVA浓度高于0.20 g/dL时,疏水微区的非极性趋于恒定,而且0.5 g/dLNaCl的加入对I1/I3值(I1/I3的变化可以表征疏水微区是否形成以及监测疏水缔合微区的变化)的影响极小,这证实了分子链在盐水中的构象仍然较伸展,使得PAVA在盐水中也能形成连续的缔合结构,从而赋予聚合物良好的抗盐和增粘性能。随着盐浓度的增加,缔合微结构的非极性变化不大,但其紧密度和数量增加,Ie/Im值持续增大。     

含大单体四元共聚物的盐诱导增粘和缔合行为EI北大核心CSCD

针对驱油聚合物难以应用于高盐油藏的难题,合成了新型大单体烯丙基辛基酚聚氧乙烯(20)醚(APE),将其与丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸钠(NaAMPS)和4-乙烯基联苯(VP)共聚,获得了抗盐共聚物PSA。PSA显示了优异的由盐诱导的增粘性能,在70.00g/L NaCl中的临界缔合浓度只有0.3g/L;当NaCl浓度高于40.0g/L后,溶液黏度反而比纯水中的黏度高得多,且随着NaCl浓度的增加急剧上升。探针分析以及原子力显微镜结果显示,PSA分子链在纯水中的构象伸展,通过分子间疏水缔合作用形成了分子链束,高盐的加入使缔合作用显著加强,溶液黏度急剧上升。     

含大单体四元共聚物的盐诱导增粘和缔合行为

针对驱油聚合物难以应用于高盐油藏的难题,合成了新型大单体烯丙基辛基酚聚氧乙烯(20)醚(APE),将其与丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸钠(NaAMPS)和4-乙烯基联苯(VP)共聚,获得了抗盐共聚物PSA。PSA显示了优异的由盐诱导的增粘性能,在70.00g/L NaCl中的临界缔合浓度只有0.3g/L;当NaCl浓度高于40.0g/L后,溶液黏度反而比纯水中的黏度高得多,且随着NaCl浓度的增加急剧上升。探针分析以及原子力显微镜结果显示,PSA分子链在纯水中的构象伸展,通过分子间疏水缔合作用形成了分子链束,高盐的加入使缔合作用显著加强,溶液黏度急剧上升。     

新型缔合聚合物P(AM/POEA)溶液的流变性质

应用黏度法和动态模量研究了新型缔合聚合物P(AM／POEA)的溶液流变性质。该聚合物由丙烯酰胺(AM)和少量2-苯氧乙基丙烯酸酯(POEA)(n(POEA)≤1．0％)组成。结果表明,共聚物的微结构对其溶液的流变性能有重要影响。嵌段共聚物(BP系列)具有显著的增黏能力,而无规共聚物(RP系列)则没有这种作用。这种由分子间的疏水缔合作用而产生的疏水缔合增黏能力与疏水嵌段的数量和长度密切相关．同时进一步研究了聚合物浓度、盐浓度、温度和剪切速率对溶液黏度的影响。动态模量测试表明,该聚合物缔合体系在实验浓度范围内黏性响应占有优势。     

阴离子长链疏水缔合水溶性聚合物的合成及溶液性能

利用溶液聚合制备了离子型疏水缔合水溶性共聚物P(AM/AMPS/C11AM),在共聚物结构中引入了既带有疏水长链又带有可离子化的基团,红外光谱确认了所合成的共聚物为目标共聚物;P(AM/AMPS/C11AM)系列共聚物溶液的表观黏度与共聚物浓度有很大关系,即使在极低的共聚物溶液浓度下也具有很好的增粘效果;在一定温度,一定pH值和表面活性剂的条件下,研究了系列共聚物溶液行为,结果与接枝疏水单体改性的丙烯酰胺是不同的。荧光光谱研究证实了共聚物在水溶液中的缔合行为。     

一种疏水缔合丙烯酰胺共聚物的合成及流变性能评价

采用自由基胶束共聚法以丙烯酰胺(AM)和N-苄基-N-辛基丙烯酰胺(BOAM)为原料,合成了疏水缔合共聚物(AM-NaA-BOAM),并用红外光谱(FT-IR)和核磁共振(1H-NMR)表征了共聚物的结构.溶液的流变性实验表明,当共聚物浓度大于600 mg/L时,表现黏度显著增大,表现出疏水缔合行为,溶液的储能模量(G...     

聚合物P(NaAMPS-VCL-DVB)分子结构对其温敏缔合行为的影响

采用可见分光光度计、变温核磁共振氢谱、流变仪等,从浊点和黏度变化方面研究了2-甲基-2-丙烯酰胺基丙磺酸钠(NaAMPS)/N-乙烯基己内酰胺(VCL)/二乙烯苯(DVB)聚合物PAVD在水溶液中的温敏缔合作用,揭示了PAVD分子结构对其温敏缔合作用的影响规律。可见分光光度计和变温核磁共振氢谱对PAVD水溶液相变过程的跟踪研究表明,聚合物分子中VCL含量越高,浊点越低,且变温核磁共振氢谱测试表明,PAVD分子VCL侧链上亚甲基链段会随着温度的升高而变为疏水性,进而产生疏水缔合作用;流变测试表明,只有当聚合物分子中VCL含量处于一定范围内时,其溶液会出现明显的温敏增稠现象,且VCL含量越高,临界增稠温度越低,温敏增稠现象越显著。最后基于临界增稠温度和浊点的对比分析,对聚合物水溶液的温敏缔合过程进行探讨。     

含氟丙烯酰胺共聚物的合成及性能

为制备性能较好的疏水缔合聚合物,以1H,1H,2H,2H-十七氟癸烷丙烯酸酯(HFA)为疏水单体,以丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为水溶性单体,采用胶束聚合法合成了含氟丙烯酰胺共聚物(FPAM)。使用红外、荧光、扫描电镜等方法对FPAM结构进行表征,研究了FPAM的耐温、抗盐及抗剪切性能。结果表明,聚合产物结构与疏水单体加量有关,在聚合体系中加入含氟疏水单体后,聚合产物的相对分子质量降低;FPAM中HFA单体结构单元含量先随HFA加量的增加而增大,由于含氟疏水单体的空间位阻效应,当HFA质量分数大于0.4%之后变化趋势变缓。FPAM聚合物中含有HFA强疏水性单体结构单元,在水溶液中会发生疏水缔合作用,到达一定浓度后会形成超分子聚集体,FPAM的临界缔合浓度为300~400mg/L,与相对分子质量较高的丙烯酰胺-2-丙烯酰胺基-2-甲基丙磺酸共聚物相比,含氟疏水缔合聚合物FPAM具有更强的增黏能力和更好的耐温、抗盐及抗剪切性能,可望用于油气开采领域。     

Properties and influence of hydrophobically associating polyacrylamide modified with 2-phenoxylethylacrylate

The properties of hydrophobically associating copolymer P(acrylamide (AM)/2-phenoxylethylacrylate (POEA)), composed of acrylamide and a small amount of POEA (≤ 1.0 mol.%) as hydrophobe, were investigated in aqueous solution under various conditions. The results showed that the solution properties were strongly affected by the microstructure of copolymer. The copolymers (BP series) with hydrophobic microblocky structure exhibited large viscosity enhancement due to the inter-molecular hydrophobic association, while that did not occur for the random copolymers (RP series). The hydrophobic association thickening behaviors were also remarkably dependent on the number and length of the hydrophobic block in polymer chain. Nonlinear viscosity relationship was found as increasing hydrophobe content and SMR (surfactant/hydrophobic monomer molar ratio), and a maximum appeared at the middle position as a result of the competitive effect between inter- and intra- molecular hydrophobic associations. Solution properties were further studied as a function of the polymer concentration, salinity, temperature and shear rate. The block copolymers show high salt tolerance and shear thinning as well as recovery after shear.     

Properties and influence of hydrophobically associating polyacrylamide modified with 2-phenoxylethylacrylate

The properties of hydrophobically associating copolymer P(acrylamide (AM)/2-phenoxylethylacrylate (POEA)), composed of acrylamide and a small amount of POEA (⩽1.0 mol.%) as hydrophobe, were investigated in aqueous solution under various conditions. The results showed that the solution properties were strongly affected by the microstructure of copolymer. The copolymers (BP series) with hydrophobic microblocky structure exhibited large viscosity enhancement due to the intermolecular hydrophobic association, while that did not occur for the random copolymers (RP series). The hydrophobic association thickening behaviors were also remarkably dependent on the number and length of the hydrophobic block in polymer chain. Nonlinear viscosity relationship was found as increasing hydrophobe content and SMR (surfactant/hydrophobic monomer molar ratio), and a maximum appeared at the middle position as a result of the competitive effect between inter- and intra- molecular hydrophobic associations. Solution properties were further studied as a function of the polymer concentration, salinity, temperature and shear rate. The block copolymers show high salt tolerance and shear thinning as well as recovery after shear.     

黏度法研究非离子型高分子对盐水溶液中油酸钾聚集行为的影响

测定了在不同浓度聚丙二醇(PPG)、聚乙二醇(PEG)和聚乙烯基吡咯烷酮(PVP)存在条件下油酸钾盐水溶液的黏度,研究了非离子型高分子对盐水溶液中油酸钾表面活性剂聚集行为的影响,结果表明,随着非离子型高分子的加入,油酸钾盐水溶液的黏度迅速下降,但是程度显著不同,不仅如此,加入更加疏水的聚丙二醇以后,油酸钾盐水溶液黏度下降的程度最低。由此可见,非离子型高分子疏水程度不是导致表面活性剂盐水溶液黏度下降的唯一因素,高分子与表面活性剂疏水和亲水基团之间的相互作用,以及由此形成的高分子/表面活性剂聚集体的形态,是决定表面活性剂盐水溶液黏度下降最主要的原因。     

Thermorheologic Properties of Aqueous Solutions and Gels of Poloxamer 407

A Theological study of poloxamer 407 aqueous solution of 10-25% (w/w) concentrations was carried out at temperatures ranging from 27°C to 45°C and at various shear rates. An exponential relationship was found between viscosity and temperature, with curve slopes dependant upon poloxamer concentration. The viscosity of 25% poloxamer 407 aqueous solution showed a Newtonian fluid at 4°C and linearly increased on increasing temperature. The viscosity of 25 % poloxamer 407 aqueous solution was sharply increased at about 12°C and maintained highly constant. During such a desolvation process, the closer approach of polymer chains, which gave rise to an increase in the number of interactions among the chains, gave an increase in the solution viscosity with temperature. The gelling concentration was examined using an interfacial tensiometer. The results showed that the first inflection point appeared at the 0.003% (w/w) concentration and the second point appeared at the 17.5% (w/w) concentration. It implied that poloxamer solutions formed monomolecular micelles at low concentration; as the concentration was increased, multimolecular aggregates were formed.     

AM-AMPS-DMDA水溶性疏水两性共聚物溶液性能的研究

采用自由基共聚合反应制备了水溶性丙烯酰胺（ＡＭ）／２－丙烯酰胺基－２－甲基丙磺酸钠（ＮａＡＭＰＳ）／２－甲基丙烯酰氧乙基－二甲基十二烷基溴化铵（ＤＭＤＡ）疏水两性共聚物。对共聚物稀溶液性质及聚合物组成、聚合物浓度、电解质浓度、温度、剪切速率等因素对共聚物溶液性能的影响进行了研究。结果表明，由于在同一聚合物中引入了疏水结构及两性离子结构，这类疏水两性聚合物表现出较好的耐温抗盐等性能。     

两亲性超支化聚(酰胺-酯)对染料相转移行为的研究

利用苯甲酰氯对超支化聚(酰胺-酯)端羟基修饰,合成了一种新型的以超支化聚(酰胺-酯)为亲水核,苯环为疏水壳的两亲性超支化聚(酰胺-酯)。此两亲性超支化聚合物在0.125～0.5g/L的浓度范围内能够以单分子胶束形式将甲基橙(MO)从水相转移到二氯甲烷相,转移是个动态平衡过程,呈现前快后慢的趋势,22h后转移量达到95%,转移后的甲基橙也可以被可逆释放到二氯甲烷相。此外,对甲基橙和甲基蓝(MB)的双染料转移,表明少量甲基蓝分子的存在可以使甲基橙的转移量大大增加,起到了协同转移作用。     

不同中和度聚丙烯酸水溶液的黏度行为

测定了不同中和度聚丙烯酸水溶液的黏度,结果表明,在中和度为0.25时聚丙烯酸水溶液比浓黏度出现最大值。进一步测定了中和程度分别为0.04和0.09、以及没有经过中和的聚丙烯酸水溶液比浓黏度的浓度依赖性,发现存在着两个特征的浓度C1和C2。当溶液的浓度小于C1时,高分子溶液的比浓黏度保持恒定;当溶液的浓度大于C1时,高分子溶液的比浓黏度随着浓度的增加而增加。当溶液浓度达到C2时高分子溶液比浓黏度对浓度作图再次出现转折,此时进一步增加溶液的浓度,高分子溶液比浓黏度虽然继续增加,但是增加的梯度有所下降。高分子溶液比浓黏度的浓度依赖性与溶液中高分子内和高分子之间相互作用密切相关。