合成丁苯嵌段共聚物的影响因素

采用负离子溶液聚合方法制备了丁苯嵌段共聚物，研究了引发剂、活化剂、偶合剂、终止剂对聚合产物性能的影响。     

高分子表面活性剂对超声辐照下苯乙烯乳液聚合的影响

在超声辐照引发苯乙烯乳液聚合中加入一种新型的以羧甲基纤维素为基础的高分子表面活性剂(CMC—A9)，讨论了高分子表面活性剂对反应动力学的影响。实验表明，超声辐照下初级自由基并非由通常认为的高分子表面活性剂产生，而是十二烷基硫酸钠在超声辐照下断裂，产生自由基。通过对反应动力学的研究，发现超声辐照下乳液聚合机理不同于常规乳液聚合，聚合反应过程只有两个阶段，即加速期和减速期，不存在恒速期。加入CMC—A9高分子表面活性剂，可以在较短的时间内和较低的超声功率下达到较高的单体转化率。     

十二酰胺丙基二甲基羟乙基氯化铵与十二烷基硫酸钠水溶液的表面吸附和胶束形成

利用十二酰胺丙基二甲胺和氯乙醇反应 ,合成了十二酰胺丙基二甲基羟乙基氯化铵 (DDHA)阳离子表面活性剂 ,将其与十二烷基硫酸钠 (SDS)以不同摩尔比进行混合 ,测定了混合系统的表面张力 ,计算了单一系统和混合系统的饱和吸附量、分子最小截面积 ,表面层和胶束中 DDHA的摩尔分率及分子间相互作用参数 ,目视观察了混合系统的浑浊情况。结果表明 :在降低γcmc和 cmc方面 ,DDHA SDS混合系统有协同效应 ,表面层和胶束的组成与二组分配比有关 ,但是非对称的 ,等物质的量混合物中 ,DDHA在胶束和表面层中具有较大的摩尔分数。DDHA与 SDS在实验测定的各混合系统中都不出现混浊     

CuMgAl类水滑石的制备和表征

用盐-碱制备法合成了CuMgAl三元类水滑石化合物。探讨了原料配比、合成方式、水热处理温度和时间对合成过程的影响,筛选出合成HTLcs的适宜条件,并对HTLcs结构的热稳定性进行初步研究。结果表明,制备HTLcs主要取决于pH值,同时由于Cu2+的姜-太勒效应,合成结构单一的CuMgAl类水滑石要求原料配比中n(Cu)∶n(Mg)不得超过1.0,CuMgAl-HTLcs热稳定性较差,300℃焙烧2h结构破坏,600℃开始烧结,在300~500℃之间,随焙烧温度提高所得复合氧化物比表面积增大,最高可达200 m2/g。     

Preparation of BaMgAl10O17∶Eu2+ and Its Phase Behavior in Microemulsion System

BaMgAl10O17∶Eu2 (BAM) was prepared in the microemulsion system and its phase behavior was studied. There exists a small region in the reverse microemulsion system where the dispersed particles are of spherical form. In this way, BAM blue phosphor with good dispersion can be synthesized. The microemulsion phase diagrams of the pseudo-ternary system (Triton X-100/cosurfactant-oil-BAM brine) were first established intuitively by the dilution method. The microstructure of microemulsions was determined through eyeballing, conductance technique, and polar optical microscopy. Its phase behavior is affected by various factors, such as temperature (room temperature, 30, 40 ℃), oil, surfactants, and cosurfactants in microemulsions. According to the phase diagrams, the microemulsion system of Triton X-100/1-hexanol-hexane-BAM brine was chosen to prepare the precursor. The BAM phosphor can be obtained via sintering the precursor at a comparatively low temperature. The phosphors were characterized by XRD and vacuum ultraviolet (VUV) spectra.     

Effect of surfactants and liquid hydrocarbons on gas hydrate formation rate and storage capacity

Hydrate formation rate plays an important role in making hydrates for the storage and transport of natural gas. Micellar surfactant solutions were found to increase gas hydrate formation rate and storage capacity. With the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation reduced. Surfactants (an anionic surfactant, a non‐ionic surfactant and their mixtures) and liquid hydrocarbons (cyclopentane and methylcyclohexane) were used to improve hydrate formation. The experiments of hydrate formation were carried out in the pressure range 3.69–6.82 MPa and the temperature range 274.05–277.55 K. The experimental pressures were kept constant during hydrate formation in each experimental run. The effect of anionic surfactant (sodium dodecyl sulphate (SDS)) on natural gas storage in hydrates is more pronounced compared to a non‐ionic surfactant (dodecyl polysaccharide glycoside (DPG)). The induction time of hydrate formation was reduced with the presence of cyclopentane (CP). Cyclopentane and methylcyclohexane (MCH) could increase hydrate formation rate, but reduced hydrate storage capacity The higher methylcyclohexane concentration, the lower the hydrate storage capacity. Copyright © 2003 John Wiley & Sons, Ltd.     

苯并口恶嗪-环氧化合物-胺类催化剂体系开环聚合反应的研究

采用TLC，GPC，1H－NMR及IR等分析方法，对苯并恶嗪－环氧化合物－胺类催化剂体系的聚合反应进行了研究，表征了产物结构，并探讨了聚合反应机理，结果表明，苯并恶唪－环氧化合物体系在胺类催化剂如苄胺，咪唑的作用下，能发生开环聚合反应，生成低分子量的聚合物。     

甲基丙烯酸三氟乙酰氧乙酯的聚合

对甲基丙烯酸三氟乙酰氧乙酯(TFAOEMA)的阴离子聚合及原予转移自由基聚合进行了研究。常用的阴离于引发剂如丁基锂、1，1-二苯基已基锂等很难引发TFAOEMA的阴离子聚合，而碱性较弱的引发剂如三乙基铝却容易引发，且产率较高。以氯化亚铜、五甲基二乙基三胺、溴代丙酸乙酯为引发体系的TFAOEMA的本体原子转移自由基聚合符合活性聚合特征。但在四氢呋喃为溶剂的原子转移自由基聚合中却存在活性中心失活现象。以末端含卤素的聚甲基丙烯酸甲酯为大分子引发剂，引发TFAOEMA的原子转移自由基聚合，得到了含氟双嵌段聚合物。     

Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.     

Micellar polymerisation of ionic surfactants studied by conductimetry

The micellar polymerisation of ionic surfactants such as allyldodecyl-dimethylammonium bromide and 3-dodecyl-1-vinyl imidazolium iodide has been studied by conductimetry in aqueous solution. The polymerisation was carried out using two different sources of γ rays directed into solutions of surfactant above the critical micellar concentration. Conductimetry is shown to be a very good physicochemical method for analysis of these solutions. The results showed different behaviour for the two surfactants, which has highlighted a change in the structure of their aggregates which led to the assumption of an interaction between the polymers of high mass and different products of the polymerisation (oligomers, products of degradation, monomers etc.). Ultrafiltration experiments coupled with ¹H-NMR and conductivity analysis confirm these assumptions.