PNIPA和PDEA在水-甲醇混合溶剂中性质的研究

分别研究了聚N-异丙基丙烯酰胺（PNIPA）和聚N,N-二乙基丙烯酰胺（PDEA）在水-甲醇混合溶剂中的溶液性质.结果表明,在PDEA和PNIPA体系中均存在水和甲醇分子之间的复合.由于PDEA比PNIPA的亲脂性强,在水-甲醇混合溶剂中,水与甲醇分子形成的复合物对PDEA和PNIPA的溶剂化作用不同,导致随着体系中甲醇体积分数（φ）的增大,PNIPA体系的低临界溶解温度（TLCS）发生了再进入相转变,而PDEA体系的TLCS则逐渐升高.     

P(DEAM-co-MAA)在稀水溶液中构象行为的荧光探针研究

利用UV透光率测定,荧光探针技术等研究了N,N-二乙基丙烯酰胺(DEAM)与甲基丙烯酸(MAA)的共聚物P(DEAM-co-MAA) 在稀水溶液中的构象行为.结果表明，当共聚物中DEAM含量小于8.00％(molar fraction),溶液的pH < 6时,P(DEAM-co-MAA)在稀水溶液中的构象行为与聚甲基丙烯酸(PMAA)相似,共聚物可形成疏水微区,表现为一种较为高度压缩的线团构象;当共聚物中DEAM含量大于8.00％(molar fraction)时,由于高分子的稀释效应,P(DEAM-co-MAA)在pH 2～10范围内表现为较为松散的伸展构象.P(DEAM-co-MAA)构象随其组成和pH变化的这种性质有可能在新型敏感性凝胶的合成设计上获得应用.     

聚N,N-二乙基丙烯酰胺低聚物水溶液的分子动力学研究

对50个单元构成的聚N,N-二乙基丙烯酰胺(PDEA)低聚物的水溶液体系进行了分子动力学的研究,分别模拟了300 K时的伸展链、310 K时的伸展链以及紧缩链与水构成的体系,对溶液中PDEA周围溶剂水分子的分布情况以及水分子形成氢键的情况进行了统计,结果表明在PDEA周围的水产生了比本体水更有序的结构,形成了更多的氢键,这种有序结构维持到第二水合层甚至更远.发生相分离后,PDEA与水分子形成的氢键大部分未被破坏,水合层中每个水分子形成的氢键数也没有明显变化,但水合层(形成有序结构的水分子)内水分子数目的减少使得总的氢键数目减少,从而造成体系能量增加及熵增加.同时还研究了聚合物及水分子的自扩散系数,表明PDEA影响周围水分子结构的同时,对水的动力学性质也产生了很大影响.     

聚N,N-二乙基丙烯酰胺溶液粘度的温度依赖性

通过自由基聚合,合成了线型聚N,N-二乙基丙烯酰胺（PDEA）,用乌氏粘度计测定并考察了该聚合物在四氢呋喃（THF）、H2O以及THF-H2O混合溶剂中粘度的温度依赖性.实验结果表明,PDEA 在上述三种溶剂中粘度的温度依赖性不同，PDEA-THF体系的相对粘度随温度升高而增大；PDEA-H2O体系以及PDEA-THF-H2O体系的相对粘度随温度升高而减小,且THF体积分数φTHF < 0.7时具有透明-白浊转变现象；对PDEA-THF-H2O体系,φTHF增加,透明-白浊转变温度升高,而当φTHF=0.7时,则观察不到透明-白浊转变现象.     

疏水缔合水溶性聚合物P(AM/NaAA/DiAC16)的合成与性能

以双烯丙基胺和1-溴代十六烷为原料合成了疏水单体N,N-双烯丙基十六胺,采取前加碱二元胶束共聚-后水解法合成了三元疏水缔合水溶性聚合物聚(丙烯酰胺/丙烯酸钠/N,N-双烯丙基十六胺)[P(AM/NaAA/DiAC16)],用FTIR、1H-NMR进行了结构表征;以芘为荧光探针,利用稳态荧光光谱法、粘度法研究了P(AM/NaAA/DiAC16)在水溶液的缔合行为.当x(DiAC16)=0.10～0.40 %时,在30℃、1mol·L-1NaCl溶液中,其Huggins常数KH小于0.80(144～0.294),表明稀溶液中缔合作用较弱.随聚合物浓度、疏水单体用量的增加,P(AM/NaAA/DiAC16)在二次蒸馏水中、1.000 mol·L-1 NaCl水溶液中,I1/I3值减少;在矿化度为19 334 μg/g盐水溶液中,水溶液的表观粘度增加、临界缔合浓度降低.结果表明,P(AM/NaAA/DiAC16)缔合行为取决于聚合物浓度、疏水单体用量及介质的极性.     

三嵌段共聚物EO20PO70EO20相分离行为的耗散粒子动力学模拟

采用耗散粒子动力学(DPD)方法研究了嵌段共聚物EO₂₀PO₇₀EO₂₀(P123)在水、乙醇/水溶液及二氧化硅溶胶体系中的相分离行为. 不同质量分数的P123在水溶液中共形成4种相分离状态: 球状胶束(10%); 椭球胶束(20%)、棒状胶束(30%)和三维立方胶束(50%). 在模板剂质量分数为10%的乙醇/水溶液中, 模板剂胶束稳定性随着乙醇含量的增加而变差. 在二氧化硅溶胶体系中, 模板剂质量分数低于5%时无胶束形成; 模板剂质量分数增至10%时, P123发生相分离形成三维球状胶束; 随着模板剂质量分数的进一步增加, 模板剂分子夹含着水分子形成三维椭球状结构(20%)、三维立方结构(40%)和层状结构(60%). 模拟结果与实验结果一致, 说明DPD模拟可以从计算角度推测模板剂对介孔材料结构的影响.     

疏水缔合水溶性聚合物——P(AM-NaAA-DiAC_8)的合成及其缔合性能

以双烯丙基胺和1-溴代辛烷为原料,合成了疏水单体N,N-双烯丙基辛胺(DiAC8).采取前加碱二元胶束共聚-共水解法合成了三元疏水缔合水溶性聚合物--聚(丙烯酰胺-丙烯酸钠-N,N-双烯丙基辛胺)[P(AM-NaAA-DiAC8)]. DiAC8和P(AM-NaAA-DiAC8)的结构经1H NMR和FT-IR表征.以芘为荧光探针,利用稳态荧光光谱法研究了P(AM-NaAA-DiAC8)在水溶液中的缔合行为,结果表明当r(DiAC8)=0.1%～1.4%时,随聚合物浓度、疏水单体用量的增加,P(AM-NaAA-DiAC8)在二次蒸馏水和1 mol·L-1NaCl水溶液中的Ⅰ1/Ⅰ3值减少.表明P(AM-NaAA-DiAC8)缔合行为取决于聚合物浓度、疏水单体用量及介质的极性.     

聚N-异丙基丙烯酰胺在十二烷基硫酸钠水溶液中的线团球体转变

高分子链在溶液中,当溶剂由良变劣时,将发生线团-球体转变,而同时由于链间聚集造成的相分离,使得很难真正观察到热力学意义上稳定的高分子单链紧缩球体。表面活性剂的加入有助于阻止高分子链间发生聚集,在不同的外部条件下,表面活性剂同高分子链将形成形态迥异且又复杂有趣的复合结构。本文主要讨论了聚N-异丙基丙烯酰胺在十二烷基硫酸钠水溶液体系中的线团-球体转变行为,以及聚N-异丙基丙烯酰胺与十二烷基硫酸钠分子间的相互作用及结构模型。     

核壳结构葡萄糖敏感微凝胶的制备

用先合成聚N-异丙基丙烯酰胺(PNIPAM)微凝胶核再包一层N-异丙基丙烯酰胺/丙烯酸共聚物(P(NIPAM-co-AA))壳的办法合成了一系列核壳结构微凝胶.微凝胶壳层厚度随投入的壳储备溶液的增加而增加.研究了pH=3.5时核壳微凝胶的温敏体积相转变行为.由于PNIPAM核和P(NIPAM-co-AA)壳的相转变温度很接近,因此只观察到一个相转变.在EDC催化下使3-氨基苯硼酸与壳层中的羧基反应,将苯硼酸基(PBA)引入微凝胶,得到核为PNIPAM、壳为P(NIPAM-co-AMPBA)的核壳结构微凝胶.改性后的微凝胶表现出3个体积相转变过程.其中第一个对应于P(NIPAM-co-AMPBA)壳层的体积相转变.第二和第三个则是PNIPAM核的相转变过程.由于在沉淀聚合时交联剂BIS反应性更大,PNIPAM核结构不均一,形成BIS含量高的"核"和BIS含量低的"壳".BIS含量低的"壳"被一层疏水的P(NIPAM-co-AMPBA)壳包裹,拉大了其与"核"的相转变温度的差别,因此随着温度升高表现出两个相转变过程.PBA改性的微凝胶同样表现出葡萄糖敏感性,但在葡萄糖存在下溶胀度的改变较小.     

P(DEAM-co-NAS)的合成及其温敏性的环境效应

采用自由基溶液聚合法合成聚(N,N-二乙基丙烯酰胺-co-N-丙烯酸琥珀酰亚胺)(P(DEAM-co-NAS))共聚比为7.9∶1、3.5∶1、2.5∶1、2∶1、1.5∶1的五组共聚物.利用傅里叶变换红外(FTIR)光谱和核磁共振(1HNMR)谱对P(DEAM-co-NAS)结构进行表征.共聚物组成和介质性质对P(DEAM-co-NAS)水溶液温敏性有显著影响.结果表明:随着NAS含量增加,共聚物水溶液的低临界溶解温度(LCST)逐渐升高,温敏性降低;盐的引入使P(DEAM-co-NAS)水溶液的LCST降低,所引入盐的阴离子价数越高,影响程度越大;有机酸的引入使P(DEAM-co-NAS)水溶液的LCST降低;NaOH、乙二胺、丁二胺的引入使P(DEAM-co-NAS)水溶液的LCST升高,二胺对P(DEAM-co-NAS)水溶液温敏性影响程度要大于NaOH.     

Study of the phase transition of poly(N,N‐diethylacrylamide) in water by rheology and dynamic light scattering

Poly(N,N‐diethylacrylamide) (PDEA) possesses a lower critical solution temperature (LCST) in aqueous media. The solution properties of PDEA at various temperatures have been characterized with techniques such as rheology and dynamic light scattering. There is a decrease in the coil size before the phase transition due to a coil‐to‐globule transition. At the LCST, rheological and dynamic light scattering studies have also confirmed an aggregation phenomenon. This aggregation modifies the rheological properties of the polymer solutions. High frequencies hinder the phase‐transition process and reduce the LCST of the polymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1627–1637, 2003     

Phase transition of aqueous solutions of poly(N,N-diethylacrylamide-co-acrylic acid) by differential scanning calorimetric and spectrophotometric methods

 The phase transition of aqueous solutions of poly(N,N-diethylacrylamide-co-acrylic acid) (DEAAm–AA) is studied by differential scanning calorimetry (DSC) and UV–vis spectrophotometry. The copolymer aqueous solutions are shown to have well-defined lower critical solution temperatures (LCSTs). The LCST values obtained from the maximum of the first derivatives of the DSC and optical transition curves agree well. DSC can be used to measure the phase-transition temperature of more dilute polymer solutions. On increasing the AA composition in the copolymers, the LCST values of the copolymer increase, then decrease at higher AA composition. For the aqueous solution of the copolymers, the transition curve obtained by the spectrophotometric method is highly wavelength dependent. The LCST values are found to be concentration-dependent. The changes in the heat of the phase transition of the copolymer solutions measured from DSC are lower than that of the homopolymer PDEAAm solution. This is consistent with the suggestion that the polymer chains of the copolymers collapsed only partially at temperatures above the LCST. The added salt (sodium chloride) decreases the transition temperature of the polymer solution. Received: 14 November 2000 Accepted: 15 January 2001     

温度/pH敏感性P(MAA-g-DEAM)共聚物水溶液的相行为

利用大分子单体技术通过自由基共聚法合成了由甲基丙烯酸(MAA)和N, N-二乙基丙烯酰胺(DEAM)组成的几种不同组成的P(MAA-g-DEAM)接枝共聚物.通过UV-Vis 透光率的测定和荧光探针技术, 对共聚物水溶液的相行为进行了研究. 研究表明, 此接枝共聚物具有相互独立的温度和pH 敏感性；几种组成不同的P(MAA-g-DEAM)接枝共聚物具有基本相同的低临界溶解温度(LCST)；它们的临界相变pH与接枝共聚物的组成有关, 温敏性PDEAM 枝链的接枝率越高, 其临界相变pH 越高. pH > 5.5 时, 接枝共聚物的主链是一种较为松散的线团构象；pH < 5.5 时, 接枝共聚物的主链是一种较为压缩的线团构象. 这种接枝共聚物高分子聚集体在新的纳米复合材料的合成方面有可能获得应用.     

Synthesis, rapid responsive thickening, and self-assembly of brush copolymer poly(ethylene oxide)-graft-poly(N,N-dimethylaminoethyl methacrylate) in aqueous solutions

Double hydrophilic brush copolymer poly(ethylene oxide)-graft-poly(N,N-dimethylaminoethyl methacrylate) (PEO-g-PDMAEMA) was successfully prepared via atom transfer radical polymerization (ATRP). We investigated the pH/thermoresponsive behaviors of PEO-g-PDMAEMA brush-shaped copolymer concentrated aqueous solutions by rheology. The observed LCST strongly decreased with increasing pH of the solutions, which was lower than that of linear block copolymer for different pH, indicating rapid thermoresponsiveness of the brush PDMAEMA chains. An unexpected shear thickening behavior was observed and could be tuned by the pH, resulting from the mobile nature and tractive force of the densely grafted hydrophobic chains of PDMAEMA at high pH. Self-assembly of the brush copolymer in a different pH and ionic strength environment was studied by transmission electron microscopy. A wormlike cylinder structure was formed at low pH. Fractals were observed for the brush copolymer aqueous solution in the presence of NaCl. The results showed that by adjusting the pH and NaCl concentration of the dispersions fractal aggregates with different topology were obtained. The observations reported here can supply a better understanding of the molecular self-assembling nature and be used to develop responsive materials with better performance.     

FORMATION OF MESOGLOBULES BY POLY(N,N-DIETHYLACRYLAMIDE) CHAINS IN DILUTE SOLUTIONS

The association of poly(N,N-diethylacrylamide)(PDEA) chains has been investigated by a combination of static and dynamic laser light scattering(LLS).Unlike poly(N-isopropylacrylamide)(PNIPAM),PDEA chains can not form the C=O…H-N hydrogen bonds.Our results demonstrate that a limited number of PDEA chains collapse and associate into metastable globules in dilute solutions.The heating rate has great effect on the mesoglobule size.The formation of such mesoglobules is attributed to the competition between in...     

Phase behavior of aqueous solutions of copolymers of N,N'-diisopropylfumaramide and N-isopropylacrylamide: effect of the density of side chains

This letter describes the phase behavior of aqueous solutions of an N-isopropylacrylamide (NIPAM) homopolymer and copolymers of N,N'-diisopropylfumaramide (DIPFAM) and NIPAM as studied by transmittance measurements, infrared spectroscopy, and differential scanning calorimetry to reveal the effect of the density of N-isopropylamide side chain upon the phase behavior. The clouding-point and clearing-point temperatures decreased with increasing the mole fraction of DIPFAM (x(D)). It was noteworthy that only an extra side chain per ca. 7 NIPAM units had a remarkable effect on the phase behavior; the interactions between side chains were stronger, the intrapolymer contraction was less favorable, and the cooperativity of phase transition was lower at x(D) = 0.15 presumably because of the steric hindrance of dense side chains.     

Adsorption characteristics of zwitterionic diblock copolymers at the silica/aqueous solution interface

The adsorption of a zwitterionic diblock copolymer, poly(2-(diethylamino)ethyl methacrylate)-block-poly(methacrylic acid) (PDEA59-PMAA50), at the silica/aqueous solution interface has been characterised as a function of pH. In acidic solution, this copolymer forms core-shell micelles with the neutral PMAA chains being located in the hydrophobic cores and the protonated PDEA chains forming the cationic micelle coronas. In alkaline solution, the copolymer forms the analogous inverted micelles with anionic PMAA coronas and hydrophobic PDEA cores. The morphology of the adsorbed layer was observed in situ using soft-contact atomic force microscopy (AFM): this technique suggests the formation of a thin adsorbed layer at pH 4 due to the adsorption of individual copolymer chains (unimers) rather than micelle aggregates. This is supported by the remarkably low dissipation values and the relatively low degrees of hydration for the adsorbed layers, as estimated using a combination of quartz crystal microbalance with dissipation monitoring (QCM-D) and optical reflectometry (OR). In alkaline solution, analysis of the adsorption data suggests a conformation for the adsorbed copolymers where one block projects normal to the solid/liquid interface; this layer consists of a hydrophobic PDEA anchor block adsorbed on the silica surface and an anionic PMAA buoy block extending into the solution phase. Tapping mode AFM studies were also carried out on the silica surfaces after removal from the copolymer solutions and subsequent drying. Interestingly, in these cases micelle-like surface aggregates were observed from both acidic and alkaline solutions. The lateral dimension of the aggregates seen is consistent with the corresponding hydrodynamic diameter of the copolymer micelles in bulk solution. The combination of the in situ and ex situ AFM data provides evidence that, for this copolymer, micelle aggregates are only seen in the ex situ dry state as a result of the substrate withdrawal and drying process. It remains unclear whether these aggregates are caused by micelle deposition at the surface during the substrate withdrawal from the solution or as a result of unimer rearrangements at the drying front as the liquid recedes from the surface.