Swelling–shrinking behavior of hydrated noncross‐linked copolymer films in response to photoreversible isomerizaton and metal complexation of spiropyran units of the copolymers

The copolymer of hydroxypropyl methacrylate (HPMA) and photochromic spiropyran methacrylate (SPMA) has been synthesized. The films of the copolymer (P(HPMA‐SPMA)) in a hydrated state showed reversible swelling–shrinking behavior in response to photoreversible isomerization and metal complexation of SPMA units in spite of covalently noncross‐linked copolymers. In addition, the protonated open form of the SPMA units of the copolymer was possibly stabilized thermodynamically by the HPMA units from ultraviolet–visible absorption measurement of the hydrated P(HPMA‐SPMA) film. On the other hand, the difference in color of the hydrated films between P(HPMA‐AABMA) and P(NIPMA‐AABMA), which was a copolymer of N‐isopropyl methacryl amide (NIPMA) and azobenzene methacrylate (AABMA) as a pH indicator, was suggestive of the interference of the proximal hydroxyl groups of the immobilized HPMA units with protonation of the AABMA units. The HPMA units of the copolymers also contributed to improvement of thermodynamic stability of the metal complexes with the SPMA units. Copyright © 2013 John Wiley & Sons, Ltd.     

Photo-alignment Property of Azobenzene-containing Polyimide Films Swollen by Alkyl-amine

Photo-alignment efficiency of polyimide containing azobenzene in the backbone structure (Azo-PI) is significantly enhanced by exposing the precursor (polyamic acid: Azo-PAA) film to alkyl-amine vapor prior to photo-alignment. In this study, we have investigated the relationships between the alkyl-amine vapor treatment time, the swelling ratio of Azo-PAA films, and the photo-induced in-plane anisotropy. We found that: the Azo-PAA film swells on exposure to alkyl-amine vapor, and the swelling finally saturates; and the photo-induced in-plane anisotropy is correlated very closely with the swelling ratio. In addition, we pointed out the importance of the process order of alkyl-amine vapor treatment and photo-alignment.     

Effect of shell thickness on the temperature-sensitive property of core-shell composite polymer particles

Core-shell composite polymer particles having temperature-sensitive shell were prepared by seeded emulsion copolymerization of dimethylaminoethyl methacrylate and ethylene glycol dimethacrylate (EGDM) with 0.14 μ-sized polystyrene seed particles according to our previous article. In this article, the effects of crosslinking density and thickness of the shell on the temperature-sensitive property were studied. Two series of composite particles, one with various EGDM contents in the shell and the other with various shell contents, were prepared for this study. The composite particles at the EGDM content of 3 wt % with the shell content of 47 wt %, showed the maximum swelling and deswelling phenomena at temperatures, respectively, below and above the lower critical solution temperature. The adsorption and desorption behaviors of low molecular weight cationic emulsifier and bio-molecules were dependent on the shell content. In almost all cases, the adsorption/desorption behavior reached to the maximum variations at the shell content of 17 wt %. © 1996 John Wiley & Sons, Inc.     

考虑膨胀力的非饱和介质热-水-应力耦合二维有限元分析

从建立应力平衡方程、水连续性方程、能量守恒方程和弹塑性矩阵入手,使用Galerk in方法,将各控制方程分别在空间域和时间域进行离散,开发出了一个可考虑膨胀力的用于分析非饱和介质中热-水-应力耦合弹塑性问题的二维有限元程序.通过对一个假定的核废料地下处置库的热-水-应力耦合问题的数值计算,比较了无、有膨胀力时的情况,在定性上验证了该程序的正确性.     

EQUILIBRIUM SWELLING AND MUTUAL ENTANGLEMENTS IN POLY(VINYL ACETATE)/POLY(METHYL ACRYLATE) IPNS

Based on Thiele-Cohen model, a swelling equation was derived by introducing the interaction parameters of a three-component system of polymer Ⅰ-polymer Ⅱ-solvent, which is a reasonable representation of the swelling behavior of general homogeneous IPNs. The degrees of equilibrium swelling of polyvinyl acetate/polymethyl actylate (PVAc/PMA) IPNs were compared between the theoretical and experimental values. The obvious effects of mutual entanglements were observed.     

疏水改性pH响应型智能水凝胶P(HEMA-NaAA-DiAC16)的制备及其溶胀性能

以二烯丙基胺和1-溴代十六烷为原料合成了疏水单体N,N-二烯丙基正十六烷胺(DiAC16),用FTIR、1H NMR 和元素分析对其进行了表征。 以2-羟基甲基丙烯酸乙酯(HEMA)、丙烯酸(AA)和N,N-二烯丙基正十六烷胺为共聚单体,N,N′-亚甲基双丙烯酰胺(BIS)为交联剂,十二烷基硫酸钠(SDS)为表面活性剂,过硫酸铵-四甲基乙二胺(TMEDA)为引发体系,制得的疏水改性智能水凝胶P(HEMA-NaAA-DiAC16)具有pH敏感特性。 研究了DiAC16、NaAA、BIS用量及pH值和离子强度等因素对水凝胶P(HEMA-NaAA-DiAC16)溶胀性能的影响。 结果表明,凝胶在水中的平衡溶胀率(为78.9～163.91),随DiAC16、BIS用量的增加和NaAA用量的减少而减少,n值(一般在0.5~1.0之间)随DiAC16、NaAA和BIS用量的增加而增加,为非Fickian扩散。 水凝胶的吸水溶胀是放热过程,ΔHm在-2.09～-3.64 kJ/mol,ΔHm的绝对值随DiAC16用量的减少、NaAA用量和BIS用量的增加而增大,聚合物与水的亲和力逐渐增强。 随离子强度的增强,平衡溶胀率下降。     

溶剂萃取预处理对低阶煤大分子结构的影响

为了研究溶剂预处理对低阶煤的固有大分子结构的影响,本研究对锡林郭勒褐煤（XLL）和神府次烟煤（SFC）分别进行了四氢呋喃（THF）索氏抽提、二硫化碳/N-甲基-2-吡咯烷酮（CS₂/NMP）混合溶剂抽提及热溶处理,并对所得抽余煤进行了傅里叶红外漫反射光谱分析（DRIFT）、热重分析（TGA）、压汞法分析（MI）和溶胀度测定。结果表明,溶剂抽提导致煤大分子结构重排和再缔合。其中,THF索式抽提和CS₂/NMP混合溶剂抽提可以改变非共价键交联作用,特别是氢键作用分布,从而不同程度地松弛煤大分子结构。然而,高温溶剂热溶处理主要促进了煤大分子的共价键交联,尤其是对锡林郭勒褐煤（XLL）。所有抽取煤的溶胀都受Fickian扩散控制,且所有抽取煤的溶胀活化能都低于原煤。     

分子内环化对聚乙烯醇交联体系的影响

以聚乙烯醇(PVA)-戊二醛(GA)体系作为研究对象, 系统地研究了分子内环化对凝胶体系的影响, 为水凝胶体系的网络结构评价奠定了一定的实验基础.     

Thermo‐ and pH‐induced phase transitions and network parameters of poly(N‐isopropylacrylamide‐ co‐2‐acrylamido‐2‐methyl‐propanosulfonic acid) hydrogels

Dual temperature‐ and pH‐sensitive hydrogels composed of N‐isopropylacrylamide (NIPAM) and 2‐acrylamido‐2‐methyl‐propanosulfonic acid (AMPS) were prepared by free‐radical crosslinking copolymerization in aqueous solution at 22 °C. The mole percent of AMPS in the comonomer feed was varied between 0.0 and 7.5, while the crosslinker ratio was fixed at 5.0/100. The effect of AMPS content on thermo‐ and pH‐ induced phase transitions as well as equilibrium swelling/deswelling, interior morphology and network structure was investigated. The volume phase transition temperature (VPT‐T) was determined by both swelling/deswelling measurements and differential scanning calorimetry (DSC) technique. In addition, the volume phase transition pH (VPT‐pH) was detected from the derivative of the curves of the swelling ratio (dQ_v/dpH) versus pH. The polymer‐solvent interaction parameter (χ) and the average molecular mass between crosslinks ( ) of hydrogels were calculated from swelling ratios in buffer solutions at various pHs. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter of hydrogels were also determined by using the modified Flory–Rehner equation. The negative values for ΔH and ΔS indicated that the hydrogels had a negative temperature‐sensitive property in water, that is, swelling at a lower temperature and shrinking at a higher temperature. It was observed that the experimental swelling data of hydrogels at different temperature agreed with the modified Flory‐Rehner approach based on the affine network model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1713–1724, 2008     

功能梯度球形水凝胶的化学力学耦合分析

作为一种新型智能材料,水凝胶具有特殊的化学力学耦合性能.采用功能梯度形式可使得水凝胶具有更好的适应性和可调控性.本研究中假设交联密度沿径向按幂函数规律变化,并基于水凝胶的大变形多场耦合一般理论,采用Flory-Huggins自由能函数,建立了功能梯度球形水凝胶在球对称情形的控制方程,并开展了功能梯度球形水凝胶在给定内压和化学势情行的非均匀大变形溶胀行为的理论研究.计算结果表明,不同梯度指数的球形水凝胶的内压、内孔半径曲线和内压、内表面径向伸长率曲线均呈现出一段稳定区间和另一段不稳定区间,说明内压超出某临界值会发生失稳并导致水凝胶的最终破坏.内压的临界值随梯度指数的增大而增大.研究表明,功能梯度球形水凝胶的材料参数(梯度指数、亲疏水特性、交联密度和溶剂分子的体积)和环境化学势对水凝胶溶胀行为具有重要的影响.在给定内表面压力的情况下,功能梯度球形水凝胶内表面的径向位移随梯度指数的改变接近为线性变化,而随其他参数的影响都呈现出明显的非线性.本研究有助于实现水凝胶智能结构和器件在复杂条件下的精准调控.}