双重响应性核交联星型聚合物的合成及其性能研究

通过"臂优先"的途径和可逆加成-断裂转移(RAFT)自由基聚合制备了以p H响应性聚(3-丙烯酰胺基苯硼酸-co-丙烯酰胺)(PAA-DMP)为线性外臂,温敏性聚(N-异丙基丙烯酰胺-co-苯乙烯-co-N,N-亚甲基双丙烯酰胺)(PNSB)为核的核交联星型聚合物(PNSB@PAA-DMP).采用傅里叶红外光谱(FTIR)、核磁氢谱(1H-NMR)和凝胶渗透色谱(GPC)对产物进行了表征.粒径和形貌也分别通过动态光散射(DLS)和透射电子显微镜(TEM)做了表征.采用紫外可见光谱(UV-Vis)和动态光散射(DLS)考察了聚合物在水中的相变行为.结果表明,所制备的核交联星型聚合物具有p H和温度双重响应,其低临界溶解温度(LCST)可以通过改变核内聚苯乙烯的量来进行调节.除此之外,在高浓度(20 mg/m L)下,还可以通过控制温度和p H实现聚合物溶液溶胶-凝胶(sol-gel)的转化.     

激光光散射测量荧光/磷光体系溶液结构的原理和方法

通过对商业化激光光散射谱仪改造升级,以4种不同波长的激光785、632.8、532和457 nm作为独立光源,可以根据不同的荧光体系选择不同的入射激光,有效避免荧光、磷光对散射光信号的干扰,从而使激光光散射谱仪能用于荧光/磷光等吸光材料溶液结构的测定.非荧光和荧光聚苯乙烯小球标准样品的测定都验证了改造后仪器测量结果的准确性和精确性.实验结果表明,当荧光体系对入射光有吸收时,动态光散射的相关函数与静态光散射得到的均方回转半径都不能反映荧光样品的真实溶液结构,此时的结果只能作为定性参考,只有选择样品无吸收的入射光波长,符合(准)弹性散射时,所测结果才能反映样品的真实结构.单分子荧光谱仪的对照实验证实了改造光散射谱仪的正确性与必要性.     

星型三杂臂共聚物的合成及其自组装性能研究

通过将点击化学,原子转移自由基聚合与阳离子开环聚合相结合,合成了一种含亲水性聚乙二醇(PEG),疏水性聚四氢呋喃(PTHF)和环境响应性聚甲基丙烯酸N,N-二甲氨基乙酯(PDMA)的ABC星型杂臂聚合物MPEG-PTHF(-PDMA).通过FTIR、1H-NMR和凝胶渗透色谱/多角度激光光散射联用(SEC/MALLS)对其结构进行了表征.通过激光粒度仪和透射电子显微镜测试,并研究其在溶液中的自组装行为,分别在pH为5.0、7.4和9.5的缓冲溶液中测试了这种星型三元共聚物自组装性能,其可表现出温度响应性.     

激光光散射表征寡链聚苯乙烯微胶乳粒子的方法

本文阐述了利用激光光散射表征寡链（ｐａｕｃｉ－ｃｈａｉｎ）聚苯乙烯微胶乳的方法。在静态光散射中，可测得微胶乳粒子的重均摩尔质量，结合粒子内所含高分子链的重均分子量，进而计算出每个微胶乳粒子内高分子链的平均数目；在动态光散射中，通过对时间相关光谱的拉普拉斯反演求出粒子的平动扩散系数分布Ｇ（Ｄ），进而得到流体力学半径（Ｒｈ）及分子量的分布。通过综合分析静态与动态光散射的结果，建立了计算球形粒子密度的光散射方法，并发现，寡链聚苯乙烯微胶乳的密度低于通常的胶乳粒子以及本体聚苯乙烯的密度     

建筑用梳形共聚物分散剂溶液行为的光散射研究

采用激光光散射研究了一种主链为聚丙烯酸侧链为聚乙二醇的梳形共聚物分散剂的一些溶液行为.从静态光散射得出了较为合理的表观重均分子量、均方旋转半径等参数.动态光散射给出了流体力学半径分布及其角度和浓度依赖性.结合静态和动态光散射,上述梳形共聚物分散剂在溶液中的构象也得到初步的表征.通过与描述梳形聚合物的Gay-Raphae模型进行比较表明,这类梳形共聚物溶液在低盐离子和低pH值条件下存在聚集行为,形成以PAA主链为核PEG为壳层的类胶束聚集.     

交联网络和浓溶液中高分子链运动的NMR研究 Ⅱ质子自旋-自旋弛豫与凝胶和浓溶液体系中高分子链段运动

用自旋－自旋弛豫时间考察了线型聚苯乙烯溶液与溶胀交联聚丙烯酰胺－丙烯酸凝胶的质子弛豫行为。发现在溶胀交联体系中，不论交联度高低，聚丙烯酰胺－丙烯酸质子的弛豫时间弛豫都呈现出双指数衰减特征；而在线型溶液体系中，聚苯乙烯质子的弛豫时间弛豫符合单指数衰减特征。说明在线性聚苯乙烯溶液中，高分子的链段运动是一种均匀行为，而在溶胀交联聚丙烯酰胺－丙烯酸体系中，不论交联度高低，高分子链段运动始终存在快慢不同的两部分。     

凝胶化反应全过程的激光光散射跟踪研究

在苯乙烯（Ｓｔ） 二乙烯苯（ＤＶＢ）自由基共聚的凝胶化反应过程中定时取样，得到凝胶化点前后及至终点的一系列样品，然后用激光光散射技术，包括研究散射光强及其角度依赖性的静态光散射（ＳＬＳ）和研究散射光频移的动态光散射（ＤＬＳ），表征了这系列样品的重均分子量Ｍｗ、均方旋转半径Ｒｇ、第二维利系数Ａ２及流体力学半径Ｒｈ等静、动态参量及这些参量的变化规律，定量地描述了凝胶化反应全过程     

多检测GPC/SEC技术在高分子表征中的应用Ⅳ.氘化高分子的溶液性质

采用体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测联用技术表征了氘化聚苯乙烯、聚苯乙烯和氘化聚苯乙烯－ 聚异戊二烯。结果表明,在θ条件下,虽然氘化聚苯乙烯的化学依赖性常数υＴ,ＤＰＳ比聚苯乙烯的化学依赖性常数υＴ,ＰＳ大,但２５ ℃时在四氢呋喃中,氘化聚苯乙烯的分子尺寸仍小于聚苯乙烯的分子尺寸。由于嵌段共聚物的淋洗体积随组成变化,所以用传统的ＳＥＣ／ＲＩ得不到准确的分子量。经比较膜渗透、小角激光光散射和基质辅助激光脱吸与离子化时间飞行质谱等的实验结果,证明体积排斥色谱法／ 示差折光指数／ 直角激光光散射／ 示差粘度三检测技术能准确地得到氘化二嵌段共聚物的分子量以及其它重要信息。     

聚丙烯酰胺凝胶结构非均匀性的动态光散射研究

利用动态光散射技术研究了聚丙烯酰胺 (PAAm)凝胶结构的非均匀性 ,分析了PAAm凝胶结构非均匀性的形成原因及凝胶动态光散射的数据处理方法和分析结果的物理意义 .研究结果表明 ,PAAm凝胶中含有动态相关长度 (LC)不同的两相 ,其中 ,LC 为 10～ 2 0nm的区域是聚合物稀疏相 ,LC 为 85nm左右的区域是聚合物密集相 ,两相的不均匀分布形成了PAAm凝胶结构的非均匀性 .分析表明 ,PAAm凝胶存在两相主要是由于单体和交联剂的溶解度存在差异所致 .随交联度增大 ,PAAm凝胶结构的非均匀性显著增强     

无皂高分子胶乳粒子的组成、单分散性和稳定性

分别用控压微波辐照法、常压微波辐照法和常压水浴合成法制备出无皂聚苯乙烯胶乳粒子.运用静态激光光散射和动态激光光散射对粒子的表观分子量及其粒径大小与分布进行了表征.结果表明,微波辐照加热法对于形成小尺寸、单分散的胶乳粒子起着很重要的作用.通过凝胶渗透色谱仪（GPC）测定聚合产物的分子量,并结合Zimm作图法,计算出胶乳粒子所含高分子链的数目.发现由控压微波辐照法所得到的聚苯乙烯胶乳粒子的表观分子量最大,而且粒子的分散性并不是由聚合物高分子链的分散性直接决定的.在微波辐照下的无皂乳液聚合,虽然聚合物的高分子链大小不一,但它们在乳液中缠结在一起而形成的胶乳粒子却具有单分散性.通过对均聚和共聚乳液进行静置考察,发现无皂高分子胶乳粒子的稳定性与制备方法、共聚单体的结构及性质有着密切的关系.     

Formation of intra- and interparticle polyelectrolyte complexes between cationic nanogel and strong polyanion

Polyelectrolyte complex formation of a strong polyanion, potassium poly(vinyl alcohol) sulfate (KPVS), with positively charged nanogels was studied at 25 degrees C in aqueous solutions with different KCl concentrations (C(s)) as a function of the polyion-nanogel mixing ratio based on moles of anions versus cations. Used as the gel sample was a polyampholytic nanogel consisting of lightly cross-linked terpolymer chains of N-isopropylacrylamide, acrylic acid, and 1-vinylimidazole; thus, the complexation was performed at pH 3 at which the imidazole groups are fully protonated to generate positive charges. Turbidimetric titration was employed to vary the mixing ratio. Also employed for studies of the resulting complexes at different stages of the titration were dynamic light scattering (DLS) and static light scattering (SLS) techniques. It was found from the titration as well as DLS and SLS that there is a critical mixing ratio (cmr) at which both the size and molar mass of the complexed gel particles abruptly increase. The value of the cmr at C(s) = 0 or 0.01 M (mol/L) was observed at approximately 1:1 mixing ratio of anions versus cations but at lower mixing ratios than the 1:1 ratio under conditions of C(s) = 0.05 and 0.1 M. At the mixing ratios less than the cmr, the molar mass of the complex agrees with that of one gel particle with the calculated amount of the bound KPVS ions, indicating the formation of an "intraparticle" KPVS-nanogel complex, by the aggregation of which an "interparticle" complex is formed at the cmr. During the process of the intraparticle complex formation, both the hydrodynamic radius by DLS and the radius gyration by SLS decreased with increasing mixing ratio, demonstrating the gel collapse due to the complexation. At C(s) = 0 or 0.01 M and under conditions where the amount of KPVS bindings was less than half of the nanogel cations, however, the decrease of the hydrodynamic radius was very small, while the radius gyration fell monotonically. These results were discussed in connection with a collapse of dangling chains attached to the nanogel surface by the binding of KPVS.     

Gelation mechanism of poly(N-isopropylacrylamide)-clay nanocomposite hydrogels synthesized by photopolymerization

The gelation process of poly-(N-isopropylacrylamide)-clay nanocomposite hydrogels (PNIPAAm-clay NC gels) was investigated by dynamic and static light scattering (DLS and SLS), as well as by fluorescence correlation spectroscopy (FCS). The photopolymerization method chosen for the radical polymerizing system ensured that, when the irradiation is removed, the reaction stopped immediately. Experiments showed that shortly before the gelation threshold is reached, no changes in the DLS autocorrelation functions appear, while the monomer conversion can be observed by 1H NMR spectroscopy. These results correspond to the formation of microparticles, in which the PNIPAAm chains are closely attached to the clay platelets. During the further polymerization process, clay clusters are developed before the sol-gel threshold is reached. FCS measurements were performed to obtain information on the motion of the clay platelets inside the NC gel. The DLS method gives only an average of the motions in the gel. In a time window between 10 micros and 1 s, the clay sheets labeled with Rhodamine B show no characteristic motions.     

Temperature-induced association and gelation of aqueous solutions of pectin. A dynamic light scattering study

Dynamic light scattering (DLS) measurements were carried out on aqueous solutions of low-methoxyl pectin at different temperatures and polymer concentration. Low temperature and increased polymer concentration promote the formation of multichain aggregates. The time correlation data obtained from the DLS experiments revealed, for all polymer solutions, the existence of two relaxation modes, one single exponential at short times followed by a stretched exponential at longer times. In the semidilute regime, a temperature reduction induced enhanced chain associations in the solutions with high values of the slow relaxation time and a strong wave vector dependence of the slow mode. These features could be rationalized in the framework of the coupling model of Ngai. At low temperatures (10 °C), gelation occurs in the semidilute regime and a transparent gel is formed. In this state, the profile of the correlation function changes and nonergodic signs are observed. The conjecture is that the association complexes and the gel network are stabilized through intermolecular hydrogen bonds, which are broken-up at higher temperatures. The hydrogen-bonded structures are formed in a process where the polymer chains have been “zipped” together in a cooperative manner.     

Structure and dynamics of solutions of a polystyrene–polybutadiene pentablock copolymer in a styrene‐selective solvent

We have examined solutions of a polystyrene–polybutadiene pentablock copolymer in 1,4‐dioxane, a slightly selective solvent for polystyrene and a θ solvent for polybutadiene, with static light scattering (SLS), dynamic light scattering (DLS), and small‐angle neutron scattering (SANS). The SANS data have been analyzed with the Percus–Yevick model to represent the scattering from interacting cores, approximated as hard spheres, and with a Lorentzian function to represent the scattering from unassociated and associated polymer chains. The SANS data at 25 °C clearly reveal interacting domains, approximately 6 nm in radius, formed by the association of the insoluble polybutadiene block in the 20% sample. The 4% sample does not show such domains, whereas the 7% sample represents an intermediate situation, with both unassociated polymer and associated polymer. At higher temperatures, the domains dissolve. The DLS data for samples with concentrations of 2–22% show two diffusive modes: a fast mode corresponding to the cooperative dynamics of concentration fluctuations and a slow mode corresponding to the diffusion of clusters. The large length‐scale heterogeneities, indicated by the strong angular dependence of SLS, implies that the small microdomains of about 10–15 polybutadiene blocks are bridged by the polystyrene chains, forming large aggregates with randomly distributed crosslinks on length scales much larger than the domain size. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2807–2816, 2002     

Structural properties of thermoresponsive poly(N-isopropylacrylamide)-poly(ethyleneglycol) microgels

We present investigations of the structural properties of thermoresponsive poly(N-isopropylacrylamide) (PNiPAM) microgels dispersed in an aqueous solvent. In this particular work poly(ethyleneglycol) (PEG) units flanked with acrylate groups are employed as cross-linkers, providing an architecture designed to resist protein fouling. Dynamic light scattering (DLS), static light scattering (SLS), and small angle neutron scattering (SANS) are employed to study the microgels as a function of temperature over the range 10 °C ≤ T ≤ 40 °C. DLS and SLS measurements are simultaneously performed and, respectively, allow determination of the particle hydrodynamic radius, R(h), and radius of gyration, R(g), at each temperature. The thermal variation of these magnitudes reveals the microgel deswelling at the PNiPAM lower critical solution temperature (LCST). However, the hydrodynamic radius displays a second transition to larger radii at temperatures T ≤ 20 °C. This feature is atypical in standard PNiPAM microgels and suggests a structural reconfiguration within the polymer network at those temperatures. To better understand this behavior we perform neutron scattering measurements at different temperatures. In striking contrast to the scattering profile of soft sphere microgels, the SANS profiles for T ≤ LCST of our PNiPAM-PEG suspensions indicate that the particles exhibit structural properties characteristic of star polymer configurations. The star polymer radius of gyration and correlation length gradually decrease with increasing temperature despite maintenance of the star polymer configuration. At temperatures above the LCST, the scattered SANS intensity is typical of soft sphere systems.     

Characterization of riboflavin-photosensitized changes in aqueous solutions of alginate by dynamic light scattering

The effect of irradiation, in the wavelength range of 310-800 nm, on aqueous solutions (pH = 7.4) of alginate in the presence of the photosensitizer riboflavin (RF) has been investigated with the aid of dynamic light scattering (DLS). Under aerobic conditions light irradiation of RF causes scission of the polymer chains which affects the polymer dynamics. The time correlation data obtained from DLS experiments showed at all conditions the existence of two relaxation modes: one single exponential at short times, followed by a stretched exponential at longer times. The slow relaxation time revealed, over the whole considered concentration range, lower values for the alginate/RF system, whereas no effect of photochemical degradation was observed for the fast relaxation time in the semidilute regime. The results suggest that the photochemically induced fragmentation of alginate affects the slow relaxation mode, associated with disengagement relaxation of individual chains or cluster relaxation, in a similar way as the zero-shear viscosity. These findings provide detailed insight into the dynamics of the polymer matrix, and this knowledge can be useful in the context of controlled-release delivery of drugs. The chemical units of alginate (M = mannuronic acid and G = guluronic acid).     

κ-卡拉胶热可逆凝胶的非遍历行为研究

采用散射斑纹(speckle)技术, 即散射光强涨落法, 研究了κ-卡拉胶(KC)热可逆凝胶的非遍历行为. 证明了非遍历性的存在, 并研究了浓度、温度等条件对该非遍历性的影响. 结果表明：该物理凝胶存在非遍历性, 并随KC浓度增加, 凝胶非遍历性增大；随温度升高, 凝胶非遍历性逐渐减小, 直至消失.     

Tracer diffusion of star-branched polystyrenes in poly(vinyl methyl ether) gels

The tracer diffusion of 3-, 4-, and 12-arm polystyrene (PS) stars in poly(vinyl methyl ether) (PVME) gels has been measured by dynamic light scattering (DLS). The intensity correlation functions were analyzed by two methods. One was that employed previously in a DLS study of linear PS diffusion in PVME gels [N. A. Rotstein and T. P. Lodge, Macromolecules, Vol. 24. p. 1316 (1992)], and the other was based on consideration of possible nonergodicity effects [P. N. Pusey and W. van Megen, Physica A, Vol. 157, p. 705 (1990)]. Both methods gave equivalent results, suggesting that nonergodicity plays a small role in this system. This conclusion is not unreasonable, given that the PVME gels are almost isorefractive with the solvent (toluene), and that the signal is dominated by scattering from the PS chains. The resulting star diffusivities are consistently less than or equal to those for linear probes of comparable size, with the difference increasing with molecular weight. The diffusivities are also less than or equal to those obtained for the same stars in PVME solutions. A weak dependence on the number of arms is also observed. Finally, the mobility of a given star in a gel is much more sensitive to variations in the average molecular weight between cross-links than is the mobility of a linear chain. All of these features in the data are broadly consistent with the reptation hypothesis. © 1993 John Wiley & Sons, Inc.     

Dynamic scaling of polymer gels comprising nanoparticles

We present dynamic light scattering (DLS) measurements of soft poly(methyl-methacrylate) (PMMA) and polyacrylamide (PA) polymer gels prepared with trapped bodies (latex spheres or magnetic nanoparticles). We show that the anomalous diffusivity of the trapped particles can be analyzed in terms of a fractal Gaussian network gel model for the entire time range probed by DLS technique. This model is a generalization of the Rouse model for linear chains extended for structures with power law network connectivity scaling, which includes both percolating and uniform bulk gel limits. For a dilute dispersion of strongly scattering particles trapped in a gel, the scattered electric field correlation function at small wavevector ideally probes self-diffusion of gel portions imprisoning the particles. Our results show that the time-dependent diffusion coefficients calculated from the correlation functions change from a free diffusion regime at short times to an anomalous subdiffusive regime at long times (increasingly arrested displacement). The characteristic time of transition between these regimes depends on scattering vector as approximately q(-2), while the time decay power exponent tends to the value expected for a bulk network at small q. The diffusion curves for all scattering vectors and all samples were scaled to a single master curve.     

Quantitative comparison between dynamic structure factors obtained experimentally and those calculated with Doi-Onuki theory

This paper reports results of quantitative comparison between dynamic structure factors obtained experimentally and those calculated by using the Doi and Onuki (DO) theory for semidilute polymer solutions. The authors obtained the dynamic structure factors with dynamic light scattering (DLS) experiment while the dynamic structure factors were calculated by using DO theory with osmotic compressibility, viscoelastic relaxation function, and friction coefficient which are obtained independently of DLS experiment. Calculated dynamic structure factors agree with experimental ones well and can express the q-dependent fast modes and the q-insensitive slow mode which experimental ones show. The authors estimated the characteristic parameters, interdiffusion coefficient and cooperative diffusion coefficient, from experimental and calculated results by using the procedure proposed by Einaga and Fujita [Polymer 40, 565 (1999)]. The estimated parameters for the DLS experiment agree with those for the calculation. These agreements in dynamic structure factors and the parameters indicate that DO theory can describe well the relaxation processes of semidilute polymer solutions.