含磺酸甜菜碱两性离子共聚物P(AM-co-VPPS)的合成及盐溶液性质

4-乙烯基吡啶(4-VP)与1,3-丙烷磺内酯在80℃下反应20h,合成了4-乙烯基-1-(3-磺丙基)吡啶内嗡盐(4-VPPS);并在水溶液中与丙烯酰胺(AM)单体进行自由基共聚合,获得了同时含正负离子基团的磺酸甜菜碱两性离子共聚物P((AM-co-VPPS));采用红外光谱和1H-NMR对共聚物结构和组成进行了表征;进而考察了单体组成、引发剂用量、单体总浓度及反应温度对两性离子共聚物特性黏数的影响.通过考察单体投料比与共聚物组成的关系,利用Finemann-Ross和Kelen-Tudos方法,获得AM和4-VPPS单体对的竞聚率分别为2.01、8.71和1.99、8.44.共聚物溶液性质研究结果表明,P(AM-co-VPPS)在含NaCl和CaCl2的水溶液中的特性黏数都比纯水中的大,表现出明显的反聚电解质行为.特性黏数增加的程度随共聚物中4-VPPS单元的含量和水中盐浓度增加而增大;当共聚物中4-VPPS摩尔含量为10.2%时,其在1mol/LNaCl、2mol/LNaCl和2mol/LCaCl2水溶液中特性黏数与在纯水中相比,分别增加47.3%、56.7%和56.8%.     

AMPS/DMAM/FA/AM共聚物的合成及溶液性能研究

本文采用氧化还原引发体系合成了AMPS（2-丙烯酰胺基-2-甲基丙烷磺酸钠）／DMAA（N,N-二甲基丙烯酰胺）／FA（富马酸）／AM（丙烯酰胺）共聚物,研究了共聚物的水溶液性能。结果表明,随聚合物浓度的增加,溶液表观粘度急剧增加;无机盐的加入使聚合物溶液的粘度下降,但很快稳定;随老化温度的提高,聚合物溶液的粘度有所增加;共聚物试样在盐水中表现出随剪切速率的增加,表观粘度增加。     

模板聚合法合成P(AM/AA)多嵌段共聚物的溶液性质和自缔合作用

研究了模板法合成多嵌段状丙烯酰胺(AM)和丙烯酸(AA)共聚物(简称模板共聚物TP)在水溶液中的溶液性质和缔合作用.结果表明,模板共聚物具有明显的结构效应.不同于无模板参与聚合的无规共聚物(CP),模板共聚物随着溶液pH的降低或加入多价金属离子容易发生相分离.透射电子显微镜(TEM)表明,加入Ca2+离子后,聚合物形成了大的分子间交联体,且随着Ca2+离子浓度的增加,交联程度增加,致使溶液产生相分离.随着溶液pH的升高,模板共聚物溶液粘度变化与丙烯酸均聚物具有相同的规律,都是先增大后减小,粘度有一个最大值,但模板共聚物溶液粘度升高幅度更大.TEM表明在粘度最大处形成了带状分子间缔合体.     

丙烯酰胺/甲基丙烯酰氧乙基二甲基丙磺酸铵共聚物的合成及其性能

以二甲氨基乙醇和丙烯酰氯为原料,制得丙烯酸二甲胺乙酯（DMAEA）; DMAEA与1,3-丙磺内酯反应制得甜菜碱型乙烯基两性离子单体--甲基丙烯酰氧乙基二甲基丙磺酸铵（MSBM）; MSBM与50%丙烯酰胺水溶液共聚合成了两性聚合物丙烯酰胺/甲基丙烯酰氧乙基二甲基丙磺酸铵(AM/MSBM),其结构经¹H NMR和IR确证。研究了矿化度,剪切作用和温度对AM/MSBM粘度的影响。结果表明：AM/MSBM具有反聚电解质溶液行为。在实验条件（盐水矿化度1 075.9 mg·L^-1,温度45~75 ℃,剪切速率2 000 rpm）下,AM/MSBM的粘度保持率＞90%。模拟驱油实验结果表明,AM/MSBM可提高采收率13.2%。     

亚硫酸酯盐型共聚物的合成及性能研究

以2-(3-甲基丙烯酰胺丙基二甲氨基)乙基亚硫酸内盐(MAPES)和双烯丙基十二烷基苯磺酰胺(DDBSA)为功能单体,在(NH_4)_2S_2O_8-NaHSO_3引发体系下改性部分水解聚丙烯酰胺(HPAM)制备了一种水溶性亚硫酸内盐型两性离子聚合物驱油剂AM/AA/MAPES/DDBSA。通过黏弹性、耐温抗盐抗剪切等流变测试以及室内模拟岩心驱替实验研究了两性离子聚合物提高采收率的能力,结果表明了在同等条件下,0.2 wt%亚硫酸内盐型共聚物溶液比部分水解聚丙烯酰胺(HPAM)具有更好的增黏性(845.3 m Pa.s)、抗剪切性(1000 s~(-1),94.2 m Pa·s)、耐温性(100℃,94.8 m Pa·s),抗老化性(80℃下进行10天的老化性测试,黏度保留率达到25%)以及抗盐性(NaCl:30 g·L~(-1),81.8 m Pa·s;MgCl-2和CaCl_2:3 g·L~(-1),77.4、77.9 m Pa·s)。0.2 wt%共聚物溶液在模拟油藏环境下(地层水矿化度:9374.13 mg·L~(-1),油藏温度75℃),提高采收率(EOR)达到了11.5%。     

强阴离子型丙烯酰胺共聚物P(AM-co-NaAMPS)的结构与性能

在水介质中实施了丙烯酰胺 (AM)与 2 丙烯酰胺基 2 甲基丙磺酸钠 (NaAMPS)的溶液共聚合 ,制备了组成系列变化的强阴离子型共聚物P(AM co NaAMPS) ;通过红外光谱法与元素分析法对共聚物的组成进行了表征 ;稀释外推粘度法测定了共聚物的特性粘数及Huggins常数 ;测定了共聚物纯水溶液及盐水溶液的表观粘度及高温下共聚物盐水溶液的粘度保持率 ;重点考察了共聚物的结构与组成对其各种性能的影响规律 .实验结果表明 ,在聚丙烯酰胺 (PAM)分子主链上引入NaAMPS链节后 ,磺酸根的强阴离子性与庞大侧基的位阻效应 ,赋于共聚物P(AM co NaAMPS)以优良的溶解、增稠、耐温与抗盐性能 ,且这些性能随共聚物的结构与组成的改变发生规律性的变化 .     

疏水基改性聚丙烯酰胺的合成及溶液性质

利用自由基胶束聚合法,由丙烯酰胺和甲基丙烯酸十八酯共聚合成了疏水缔合型水溶性聚合物.通过红外光谱表征了共聚物的结构,考察了共聚物浓度、盐浓度、剪切速率以及温度对共聚物溶液性能的影响.试验结果表明,聚合物质量分数大于临界缔合浓度(2%)时,溶液的粘度急剧增大;疏水缔合聚合物溶液的表观粘度随着溶液中NaCl质量分数的增加而增大.     

疏水化修饰的聚N-异丙基丙烯酰胺高分子的水溶液性质研究

为了研究不同疏水化修饰的聚Ｎ 异丙基丙烯酰胺（ＰＮＩＰＡＭ）高分子的水溶液性质,合成了一系列Ｎ 异丙基丙烯酰胺（ＮＩＰＡＭ）和长链丙烯酸酯及丙烯酸胆固醇酯的共聚物．利用表面张力法证实了该类共聚物在室温下都具有良好的表面活性,在水溶液中能够形成胶束．利用荧光探针法,研究了共聚物的低温临界溶液温度（ＬｏｗｅｒＣｒｉｔｉｃａｌＳｏｌｕｔｉｏｎＴｅｍｐｅｒａｔｕｒｅ,ＬＣＳＴ）,发现,随着丙烯酸酯碳链及其配比（摩尔投料比）的变化,共聚物的ＬＣＳＴ变化不明显,但它们都比均聚的ＰＮＩＰＡＭ要低;利用荧光偏振法研究了共聚物在水溶液中的微粘度,发现其微粘度不随共聚物中丙烯酸酯链长和配比的变化而变化,说明了该类共聚物在室温下能够形成相类同的胶束内核．     

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 .     

疏水化两性离子纤维素接枝共聚物/疏水化聚丙烯酰胺复合溶液的粘性行为

疏水缔合作用;羧甲基纤维素;疏水化两性离子纤维素接枝共聚物/疏水化聚丙烯酰胺复合溶液的粘性行为     

Shear rheology of anionic and zwitterionic modified polyacrylamides

Two groups of copolymers were synthesized from high molecular weight polyacrylamides. One group of copolymers consisted of sulfonated, anionic copolymers (PAM-S) of acrylamide with the sodium salt of 2-acryloamido-2-methyl-1-propane sulfonic acid, and the other consisted of zwitterionic copolymers (PAM-Z) of acrylamide with a sulfobetaine methacrylate monomer. The shear rheology of aqueous solutions of the copolymers and their mixtures was studied experimentally. Solutions of both copolymers exhibit shear thinning behavior in the range of concentrations explored. Solutions of mixtures of two copolymers (PAM-Z and PAM-S) exhibited a slight viscosity synergy at high relative contents of PAM-S. Addition of a relatively high concentration of an electrolyte (0.3 M NaCl) induces decreases in viscosity due to coil contraction and eliminates the synergy of the mixtures. Mixtures of the zwitterionic copolymer and a cationic surfactant, cetyl trimethylammonium p-toluene sulfonate (CTAT), were also studied. These solutions exhibit a strong synergistic effect at low-shear rates when the surfactant forms wormlike micelles. In addition, oscillatory shear measurements demonstrate that PAM-Z/CTAT mixtures are significantly more elastic than CTAT solutions, which indicates that PAM-Z is effective in promoting micelle entanglements, as reflected by the increase in relaxation time with PAM-Z content.     

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).     

Water-Soluble Random and Graft Copolymers for Utilization in Enhanced Oil Recovery

Copolymer structure has a marked effect on solution properties and thus behavioral characteristics of water-soluble copolymers utilized in enhanced oil recovery. The ability of random and graft copolymers to maintain large hydrodynamic volumes in dilute solutions in the presence of mono- and divalent electrolytes is critical for mobility control. The differences in viscosity behavior are described for a series of random and graft copolymers of acryl-amide with sodium-2-acrylamido-2-methylpropane sulfonate (NaAMPS), diacetone acrylamide (DAAM), and sodium acrylate (NaA) as a function of polymer microstructure, temperature, concentration, and added electrolytes. Copolymers of AM-NaAMPS show enhanced salt tolerance and phase stability over their AM-NaA counterparts with similar compositions and molecular weights. The AM-DAAM copolymers show unusual solution behavior with increases in viscosity in the presence of added salt.     

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。     

NaCMC与甲基丙烯酰氧乙基二甲基辛基溴化铵及AM接枝共聚物的性能

水溶性增粘剂;增粘性能;协同增效作用;疏水缔合作用;剪切作用;NaCMC与甲基丙烯酰氧乙基二甲基辛基溴化铵及AM接枝共聚物的性能     

Studies on rheological behaviour of hydrophobically associating polyacrylamide with strong positive salinity sensitivity

Hydrophobically associating polymer has been obtained by homogeneous copolymerization of acrylamide and an anionic surface-active monomers (surfmer) of acrylamide-type, sodium 2-acrylamido-tetradecane sulfonate (NaAMC₁₄S) in aqueous solution, and under different concentration conditions of NaAMC₁₄S above its critical micellar concentration (CMC) and below CMC, two structure types of copolymers P (AM–NaAMC₁₄S) were prepared in which main chains NaAMC₁₄S were distributed in microblock and in random manner, respectively. The hydrophobically associating property and rheological behaviour of the copolymers were studied with viscosimetry and then by fluorescence probe method. It was found that the apparent viscosity of the aqueous solution of the copolymers with microblock structures exhibits strong positive salinity sensitivity, whereas the positive salinity sensitivity of the apparent viscosity of the aqueous solution of the copolymers with random structure only appears generally and the apparent viscosity was diminutively increased because of salinity-promoting hydrophobic association. For those copolymers with microblock structures, the apparent viscosities of their brine solution are much higher than that of their pure water solution. In CaCl₂ solution (2 wt%), as the copolymer concentration attains 0.2 wt%, the apparent viscosity enhances dramatically with the increase in concentrations, and as the copolymer concentration was 0.3 wt%, the apparent viscosity can enhance by almost two orders of magnitude (from 32 to 1,000 mPa·s) as compared with in pure water solution. Thus, for copolymer P (AM–NaAMC₁₄S) with microblock structure, the peculiar positive salinity sensitivity, i.e. salinity thickening, is displayed distinctly. The unusual positive salinity sensitivity of copolymers P (AM–NaAMC₁₄S) with microblock structure was also revealed by fluorescence probe method, and the value I ₁/I ₃ of pyrene in the brine solution of the copolymers was smaller than that in pure water solution of the copolymers. This unique salinity sensitivity is a reflection of the unusual microstructure of the copolymers. The experiment results are interpreted in terms of the effects of the surfmer distribution manner in the copolymer main chain and bonding way of the ionic surfmer to the copolymer main chain on the forming intermolecular association.     

丙烯酰胺-苯乙烯双亲嵌段共聚物水溶液的粘度性能

通过改变丙烯酰胺 (AM)与苯乙烯 (St)两单体的投料比 ,在微乳液介质中制备了分子组成系列变化的丙烯酰胺 苯乙烯双亲嵌段共聚物 (PAM b PSt) ,使用旋转粘度计测定了共聚物水溶液的表观粘度 ,详细考察了共聚物浓度、共聚物链结构、剪切速率、盐度及温度等因素对共聚物水溶液表观粘度的影响规律 .研究结果表明 ,由于PAM b PSt分子链中的PSt疏水嵌段链段之间具有强的疏水缔合作用 ,导致其具有独特的流变性能 .当共聚物水溶液的浓度高于某一临界值后 ,疏水缔合作用以分子间的缔合为主 ,大分子链之间会形成动态物理交联网络 ,增大了流体力学体积 ,使PAM b PSt水溶液可产生良好的增稠性能 ;疏水缔合作用是一吸热过程 ,升高温度有利于分子间的缔合 ,因此PAM b PSt水溶液具有良好的耐温性 ;聚合物水溶液中盐类物质的存在 ,会增强溶剂的极性 ,有利于分子间的缔合 ,使PAM b PSt水溶液具有良好的耐盐性 .     

丙烯酰胺/2-丙烯酰胺基十六烷磺酸铵无规共聚物的形态结构研究

本工作应用透射电子显微镜研究了丙烯酰胺/2-丙烯酰胺基十六烷磺酸铵无规共聚物(AM/AMC_(16)SNH_4)的形态结构.给出共聚物在水溶液中具有伸展网状结构,并存在一定程度的疏水基因间的缔合作用.是一种在耐盐性和储存稳定性方面有明显改善的新型改性聚丙烯酰胺.