疏水缔合聚丙烯酰胺在表面活性单体胶束溶液中的制备及其流变特性

配制了表面活性单体2-丙烯酰胺基十二烷磺酸钠(NaAMC12S)与十二烷基硫酸钠(SDS)的胶束溶液,分别测定了强疏水单体N-正十二烷基丙烯酰胺(C12AM)在两种胶束溶液中的增溶性能;在此基础上,于两种胶束溶液中分别进行了丙烯酰胺(AM)与C12AM的胶束共聚合,制备了疏水缔合聚丙烯酰胺(HAPAM),它们分别为二元共聚物C12AM/AM与三元共聚物C12AM/NaAMC12S/AM;测定了两种共聚物的红外光谱;采用荧光探针法与表观粘度法重点研究了它们的疏水缔合性与流变性能.结果表明,在表面活性单体NaAMC12S的胶束溶液中,可顺利地实现AM与疏水单体的胶束共聚合,由于表面活性单体也参与了共聚合,故制得的产物为三元共聚物C12AM/NaAMC12S/AM;与在SDS胶束溶液中制备的二元共聚物C12AM/AM相比,前者的疏水缔合性更强,其强疏水缔合性以强疏水单体C12AM的贡献为主,以表面活性单体NaAMC12S的贡献为辅.     

用超临界CO2制备疏水改性聚丙烯酸

用超临界CO2制备疏水改性聚丙烯酸;丙烯酸十八酯;超临界二氧化碳;疏水缔合     

水溶性疏水缔合型聚(丙烯酰胺-丙烯酸十六酯)溶液性质的研究

采用沉淀聚合法制备水溶性的丙烯酰胺－丙烯酸十六疏水缔合型共聚物,研究了共聚物水溶液的性质及其影响因素。随着疏水基团含量增加,共聚物在纯水中及NaCl溶液中的特性粘数[η]均减小,疏水基团临界缔合浓度降低。共聚物溶液浓度高于监界缔合浓度时,溶液表现粘度急剧增加,表明溶液中分子间缔合大量形成。     

粘度法研究疏水改性聚丙烯酸与Np7.5的相互作用

研究了氟基团改性和氟碳、碳氢基团同时改性的聚丙烯酸（HM－PAA）以及参与聚合物（PAA）与非离子表面活性剂Np7.5分别在稀溶液和亚浓溶液下的相互作用对特性粘数和Brookfield表观粘度的影响。结果表明,PAA与Np7.5无明显作用,而M－PAA在Np7.5达到一定浓度后,由于Np7.5参与了疏水缔合,特性粘数和表观粘度发生了明显变化。稀溶液中,氟碳基团较多的聚合物出现了链构象的伸展。亚浓溶液中,疏水改性聚合物的粘度都有先上升后下降的变化,但氟碳含量较多的变化更强烈。     

疏水缔合水溶性聚合物溶液性能研究进展

本文针对疏水缔合水溶性聚合物的稀溶液和半浓溶液两种情况，综述了最近十多年来溶液的性能的研究进展。文中讨论了表征分子量和疏水相互作用的特性粘数与Huggins常数。分别介绍了聚合物浓度、分子量、疏水基类型、含量、长短及序列分布、离子基团的种类和位置、剪切速率、温度以及化学相互作用对溶液性能的影响。     

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.     

荧光探针法研究疏水改性聚丙烯酰胺溶液的疏水缔合行为

采用胶束共聚 共水解方法合成疏水改性水溶性聚合物聚(丙烯酰胺/丙烯酸钠/N 辛基丙烯酰胺)[P(AM/NaAA/C8AM)],并以芘为荧光探针,应用稳态荧光光谱法研究了它的疏水缔合行为。结果表明,随聚合物浓度、疏水单体摩尔分数、疏水侧链长和温度的增加,疏水缔合作用增强;不同疏水单体含量的P(AM/NaAA/C8AM)的临界缔合浓度为1.5~3.0 g/L;表面活性剂十二烷基硫酸钠(SDS)与P(AM/NaAA/C8AM)发生了强烈的疏水相互作用,形成混合胶束,得到SDS的临界胶束浓度(CMC)为8×10-3 mol/L;由于聚合物链上羧基的存在,使其具有良好的 pH敏感性,随 pH值的增大,P(AM/NaAA/C8AM)的疏水缔合作用呈现先减弱后恒定再增强的变化。     

低温非水环境中疏水缔合聚丙烯酸钠与两性离子表面活性剂的相互作用

疏水缔合聚合物和表面活性剂是构建黏弹性流体的重要物质, 二者的相互作用对流体性质具有显著影响, 一直是该领域的研究热点, 但此前的研究仅聚焦于水溶液中室温及以上温度范围, 而零下极端低温环境中的相互作用尚未涉及. 本文以疏水缔合聚丙烯酸钠(HMPA)为模型聚合物, 研究了低温(-20~20 ℃)环境中其与两性离子表面活性剂N-(顺-二十二碳-13-烯酸酰胺基丙基)-N,N-二甲基羧酸甜菜碱(EDAB)在乙二醇/水混合溶剂中的相互作用及混合体系的流变性质. 先后考察了HMPA溶解于纯水和乙二醇/水混合溶剂时的流变行为和HMPA-EDAB在乙二醇/水混合溶剂中的流变行为及自组装结构形貌. 研究发现, 加入50%(体积分数)的乙二醇会阻碍HMPA疏水支链形成缔合结构, 减弱其增黏性能, 但同时也会大幅降低体系的冰点. 在HMPA- EDAB混合体系中, HMPA疏水支链会进入EDAB胶束内核自组装形成混合胶束. 混合胶束的形貌取决于 HMPA和EDAB的浓度及环境温度, 进而影响体系的流变行为. 零下的低温有助于EDAB形成蠕虫状胶束, 因此HMPA与EDAB表现出更强的协同增效作用.     

疏水缔合水溶性聚合物AO的溶液粘度行为研究

研究了稀溶液中疏水链链长、无机电解质NaCl和CaCl2对疏水缔合水溶性丙烯酰胺／甲基丙烯酰氨乙基-二甲基烷基溴化铵／丙烯酸钠共聚物(AO)在水溶液中的特性粘数和Huggins常数的影响，以及聚合物AO-8的特性粘数和Huggins常数随温度的变化。结果表明：在稀溶液中，无机电解质离子强度增大，共聚物AO在NaCl和CaCl2溶液中的特性粘数减小，Huggins常数增大。在亚浓溶液范围对聚合物质量分数、温度、剪切速率及NaCl含量对聚合物的水溶液表现粘度的影响进行了研究，观察到疏水缔合聚合物盐水溶液在NaCl含量提高的情况下，出现的增粘现象。     

微嵌段疏水缔合聚合物/十二烷基硫酸钠溶液体系的流变特性

研究了疏水微嵌段长度和阴离子表面活性剂十二烷基硫酸钠(SDS)对聚/表体系的流变性的影响。研究表明,微嵌段长度对疏水缔合聚合物溶液的粘性有较大影响,嵌段越长聚合物越容易发生分子间缔合其溶液粘度越大。随着SDS的加入,各聚/表体系粘度短期内出现一个极值,然后降至一个稳定值,嵌段长度越长,其极值点越大。聚合物与SDS体系表现出的剪切增稠和粘弹性特征也随嵌段长度增加而增大。通过研究不同体系平台区模量(G0)和特征松弛时间(TR)的变化规律,发现嵌段长度和SDS含量对聚/表体系物理交联缔合点的密度有较大影响,对缔合点强度影响较小。本文有助于更好地解释微嵌段疏水缔合聚合物与表面活性剂相互作用的内在因素。     

Swelling of hydrophobically modified poly(acrylamide) and poly(acrylamide)-co-(acrylic acid) gels in surfactant solutions

A series of hydrophobically modified polyacrylamide and polyacrylamide-co-poly(acrylic acid) gels with systematically varying hydrophobicity were prepared by free-radical polymerization of acrylamide, n-alkylacrylamides (n = 10, 12, and 14), and acrylic acid. The swelling of these gels was examined in water and in both anionic and cationic surfactant solutions. It was found that the gels which incorporated acrylic acid showed extremely high swelling in water. Maximum swelling was observed in gels which incorporated 10 mol% acrylic acid. The swelling of these gels was much less in solutions of both anionic and cationic surfactants than in water. The gels which did not incorporate acrylic acid demonstrated little swelling in water, but showed increased swelling in both anionic and cationic surfactant solutions with increased hydrophobicity of the gel. Received: 1 February 1999 Accepted in revised form: 5 March 1999     

Dynamics and energetics of the self-assembly of a hydrophobically modified polyelectrolyte: Naphthalene-labeled poly(acrylic acid)

Steady-state and time-resolved fluorescence studies were performed on aqueous solutions of poly(acrylic acid) hydrophobically modified with two very different levels of naphthalene (Np). It is demonstrated that unique information on association phenomena involving hydrophobe-modifed polymers can be obtained from an extended fluorescence study by using data for a less-modified polymer as a reference. For the more highly modified polymer, the presence of excited-state (as well as ground-state) dimers in addition to monomer emission due to locally excited naphthalene gives evidence for hydrophobic association between naphthalene groups. This association becomes, as expected, much less important at higher pH due to the electrostatic repulsion between different chain segments. However, it is noted that even at high pH there is a significant self-association. The coexistence of static and dynamic quenching phenomena of the Np monomer label was also revealed in the time-resolved fluorescence data. The data are compatible with the existence of two types of monomers and one excimer and suggest that the essential contribution to the monomer emission comes from isolated chromophores, whereas excimer formation arises from both a dynamic route (excited Np chromophores able to produce a dynamic excimer) and a static route (excitation of ground-state Np dimers). At room temperature, the dissociative reaction, excimer-to-monomer, can be neglected, and thus the rate constant for excimer formation and decay could be obtained with and without considering the influence of preformed dimers. Temperature has shown to induce different behavior in the polymer photophysics. In the case of the less-labeled polymer, the decays were found to be single-exponential with the fluorescence lifetime decreasing with increasing temperature. From the temperature dependence of the steady-state fluorescence data, the activation energy for excimer formation and the binding energy of the excimer were evaluated at different pH values, through the Stevens-Ban-type plots of the excimer-to-monomer intensity ratio. With the time-resolved data, measured in the temperature range of 5-60 degrees C, it was possible to extract the intrinsic activation energies for excimer formation. The thermodynamic driving force for the intrapolymeric association was found to be dependent on a balance between hydrophobic and electrostatic interactions, which are dependent on the pH, temperature, and hydrophobic content of the polymer.     

Rheology of hydrophobically modified polyacrylamide-co-poly(acrylic acid) on addition of surfactant and variation of solution pH

Constant shear and shear dependent viscosity measurements are reported in aqueous systems of co- and terpolymers of acrylamide (AM), N-n-alkylacrylamide (C10, C12, and C14 alkyl groups), and acrylic acid (AA) with added anionic surfactant sodium dodecyl sulfate (SDS). The results are presented as three-dimensional plots of viscosity vs surfactant concentration and pH at constant shear rate or viscosity vs shear rate and surfactant concentration at constant pH. For terpolymers incorporating AA, a strong viscosity maximum is observed at intermediate pH values (pH 4-6) where the AA groups are partially ionized and at SDS concentrations close to the critical micelle concentration. At high pH, all AA incorporating terpolymer solutions with SDS are strongly shear thinning, but at pH 3-4 the systems of terpolymers with SDS are strongly shear thickening at low shear, followed by a shear-thinning region at high shear. These results are explained in terms of surfactant-mediated network formation with polymer coil expansion and hydrogen bonding between partially ionized AA groups as additional factors.     

Solubilization of phosphatidylcholine vesicles by hydrophobically modified poly(acrylamide)-co-(acrylic acid): effects of acrylic acid fraction and polymer concentration

The interaction of hydrophobically modified copolymers of acrylamide and acrylic acid, designated as PAM-C12-AA (X%) (X% indicates the percentage of acrylic acid unit and X = 5, 10, 20), with dimyristoylphosphatidylcholine (DMPC) vesicles has been studied. Complementary techniques including isothermal titration microcalorimetry (ITC), differential scanning calorimetry (DSC), turbidity measurement, calcein leakage measurement, dynamic light scattering (DLS), and transmission electron microscopy (TEM) were used to get comprehensive information. The results show that PAM-C12-AA leads to solubilization of DMPC vesicles. There is a critical concentration (C(s)) for PAM-C12-AA to induce obvious vesicle disruption. This concentration is very close to the critical aggregation concentration (CAC) for the polymer self-aggregation. The Cs values are found to be similar for the three polymers. However, the disruption of DMPC vesicles induced by the polymers increases to a greater degree at higher AA fraction, owing to the increasing strength of interaction between the polymer and the lipid bilayer.     

Hydrophobicity of fluoro‐containing physical crosslinkage domains in hydrophobically modified poly(acrylic acid) gels

A series of hydrophobically modified poly(acrylic acid) gels were prepared by the radical copolymerization of acrylic acid and small amounts of hydrophobic comonomers, 2‐(N‐ethylperfluorooctane‐sulfoamido)ethyl methacrylate and lauryl acrylate, in tert‐butanol. The effects of the fractions and species of hydrophobes on hydrophobic association were determined. The hydrophobic association within the hydrophobically modified gels was proven with measurements of swelling and fluorescence as well as Fourier transform infrared spectroscopy. Fluorocarbon‐modified hydrogels showed stronger hydrophobicity than hydrocarbon‐modified hydrogels. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1236–1244, 2002     

Self-aggregates of hydrophobically modified poly(2-hydroxyethyl aspartamide) in aqueous solution

Dehydrocholic acid (DHA) grafted poly(2-hydroxyethyl aspartamide) (PHEA)s were successfully synthesized and their self-aggregates in aqueous solution were characterized by fluorescence spectra and light scattering. PHEA was obtained by a simple reaction of ethanolamine with synthesized poly(succinimide) (PSI), and then PHEA-g-DHA was synthesized through an ester linkage between DHA and PHEA. The degree of substitution (DS) of DHA groups, defined by grafted mole%, was determined from both ¹H-NMR and elemental analysis. The grafting reaction of DHA was retarded up to almost 10 mole% feed ratio of DHA/PHEA, but increased linearly above the threshold ratio. Nano-size self-aggregates in aqueous solution were examined with four DSs less than 10. As DS increased, the critical aggregation concentrations (CAC) of polymers were continuously reduced and the size of primary aggregates reduced to as small as 40 nm in diameter. When stored, the sonicated aggregates of high DS were destabilized, apparently forming large aggregates with small curvatures. The formation of irreversible interfused secondary structures would be induced by the curvature change or aggregation of primary particles. A simple calculation indicates that a small change of separation between grafted DHA groups may induce the large curvature shift, in fact, sphere-to-planar surface transition.     

Hydrophobically modified polyelectrolytes I. Dilute solution properties of fluorocarbon-containing poly (acrylic acid)

Dilute solution viscosity of fluorocarbon‐containing hydrophobically modified poly (acrylic add) was measured in aqueous solutions of various NaCl concentrations. The intrinsic viscosity ([η]) and Huggins coefficient (k_H) were evaluated using Huggins equations. It is found that, at low Nacl concentration, the modified polymers exhibit values of intrinsic viscosity ([η]) and Huggins coefficient (k_H) similar to those of unmodified polymers. For both of the modified and unmodified polymers, the intrinsic viscosity decreases with increase of NaCl concentration, while the Huggins coefficient increases upon addition of NaCl. But the variation of [η] and k_H is more significant for the modified polymers, which reflects the enhanced intra‐ and intermolecular hydrophobic association at higher Nacl concentration.     

Adsorption of hydrophobically modified poly(acrylamide)-co-(acrylic acid) on an amino-functionalized surface and its response to the external solvent environment

The adsorption of hydrophobically modified poly(acrylamide)-co-(acrylic acid), designated as PAM-C14-AA (x%) (x = 5, 10, 20, representing the mole percent of acrylic acid units), at an amino-functionalized silicon surface was studied. The effect of polymer charge density was determined by varying the acrylic acid content of the copolymer. Characteristics of the adsorbed layer were evaluated by atomic force microscopy, water contact angle measurements, and X-ray photoelectron spectroscopy. The results showed that the adsorption behavior of PAM-C14-AA (x%) is influenced by the balance among the electrostatic, hydrogen-bonding, and hydrophobic interactions. Adjusting the solution pH and polymer charge density significantly affects the morphology and thickness of the adsorbed film. Furthermore, it was found that the adsorbed PAM-C14-AA undergoes conformational rearrangements when the surface is wetted by selected organic solvents. The resultant morphology and wettability of the films indicated that the different affinities of the solvents for different segments of PAM-C14-AA (x%) can be considered to be the possible cause of the conformational rearrangements of adsorbed polymer.     

Fluorocarbon- containing hydrophobically modified poly(N-isopropylacrylamide)

A fluorocarbon-modified poly(N-isopropylacrylamide) has been synthesized by copolymerization of N-isopropyl acrylamide with a small amount of acrylate or methacrylate containing a perfluoroalkyl group. It was found that the hydrophilicity of macromolecular backbone is an important factor to the solution properties of the copolymers and that hydrophobic association between fluorocarbon groups is stronger than that between the corresponding hydrocarbon analogies. The viscosity of some of the copolymer solutions was very sensitive to temperature. It was dilatant at higher fluorocarbon comonomer content ( > 0.20-1.0 mol%) and was Newtonian at very low fluorocarbon comonomer content (0.03-0.2 mol% ) . Evidence for hydrophobic association of the fluorocarbon groups was obtained from the effects of adding Nad and surfactants on the solution viscosity. The LC-ST properties of these copolymers were studied by DSC method and this was also found to be consistent with hydrophobic association between the fluorocarbo     

Calorimetric investigation of poly(methacrylic acid) and poly(acrylic acid) in aqueous solution

The enthalpy of dissociation of poly(acrylic acid) and of poly(methacrylic acid) in water and in 0.5N NaCl at 25°C has been measured over a wide range of degrees of neutralization of the polyelectrolytes. In the case of poly(methacrylic acid) the calorimetric data permit the direct evaluation of the enthalpy of conformational transition of the polymer. For this transition, with the aid of standard free energy data derived from potentiometric titrations, the change in entropy was also estimated. The relative accuracy of the thermodynamic data, and the possibility of deriving therefrom information on the mechanism of transitions of the type, globular coils → expanded coils for partially hydrophobic synthetic polyelectrolytes in aqueous solution are discussed.