软管内壁构筑多层微凝胶薄膜及净化染料污水的研究

为了解决染料污水处理问题，本文通过LbL技术，利用聚丙烯胺盐酸盐与葡聚糖交联得到的微凝胶和聚4-苯乙烯磺酸钠的静电自组装，将多层膜沉积在了模拟排污管(聚乙烯软管)内壁，并利用多层膜的高效负载能力对流经软管的模拟染料污水(甲基橙水溶液)进行净化，测定了最佳净化流速。采用极少量一定pH值的水溶液对染料分子进行完全脱附后，多层膜能够循环利用，这大大降低了使用成本，其在环境治理领域具有重要的意义。     

带羧基乳胶颗粒的制备、聚焦以及与重氮树脂的自组装

从苯乙烯、丙烯酸丁酯和丙烯酸制备了表面带－COOH的不同粒径的乳胶颗粒（－100－400nm）。研究了因水分挥发由毛细管力引起的乳胶颗粒的聚集，以及这些乳胶颗粒和含－N2^ 的高分子（重氮树脂，Mn-2500g/mol）的自组装，结合紫外光照，制备了高分子与乳胶粒交替的三明治（sandwich）结构的超薄膜，结果表明，层与层间的光反应是高分子与乳胶粒成功组装的关键。由于光照中，层与层间的离子键已转变为共价键，这种超薄膜对极性溶剂和盐水溶液非常稳定，在DMF、c(NaCl)=0.1mol/L的水溶液中，室温下（－20℃）分别浸泡24h，组装膜仍完好无损。     

1-甲氧基-9，10-二苯基葸的制备及在农业上的应用

以蒽醌、溴苯等为主要起始原料，通过蒽的1位及9、10位取代，合成了1-甲氧基-9，10-二苯基蒽（MDPA）。改进和优化了各步合成工艺条件：在汞盐催化下，当反应温度为130℃，发烟硫酸浓度为20％-25％，反应时间为1．5h时，中间体蒽醌-1-硫酸钾收率为53．7％；采用苯基锂与1．甲氧基蒽醌加成后，直接用SnCl2的乙酸水溶液还原，产品收率为68．9％。测试了MDPA在PE农膜中的转光性质。结果表明，将MDPA掺入PE树脂中而形成的蓝光膜能在波长438nm处光致发光，该波长与植物光合作用所需的蓝光区相吻合；与普通农膜相比，蓝光膜可促进作物生长，使白菜、茼蒿、莴笋等蔬菜产量增加20％左右。     

聚(乙烯-alt-马来酸)的R-1-4-甲氧基苯乙胺衍生物合成及自组装

本实验合成了光学活性聚电解质聚(乙烯-alt-马来酸)的R-1-4-甲氧基苯乙胺衍生物(PEMA-PMEA),并与聚烯丙基胺盐酸盐(PAH)进行自组装,构筑了具有光学活性的多层膜。研究了多层膜的增长模式,并对不同膜层的旋光和表面形态进行表征。该功能性多层膜的开发,对聚电解质多层膜的应用研究具有指导作用。     

1，1，3-三甲基-3-苯基茚满的催化合成木

本文研究了在酸性离子液体的催化作用下α-甲基苯乙烯二聚合成1,1,3-三甲基-3-苯基茚满。实验结果表明,在无溶剂的条件下室温离子液体（CH3CH2）3NHCl-AlCl3对该反应具有很高的催化活性和目标产物的选择性,反应进行到5min即可达到100%的α-甲基苯乙烯转化率和97%的环状二聚物1,1,3-三甲基-3-苯基茚满的选择性。     

4-二甲胺基吡啶合成新工艺研究

4-二甲氨基吡啶（简称DMAP）是一种应用广泛的催化剂,被广泛的应用于多种有机反应当中,被称为超级催化剂。论文研究以4-氰基吡啶和苯乙烯为原料制备DMAP新工艺。优化得到反应条件为4-氰基吡啶与苯乙烯摩尔比为1:1.2,使用40 %氢氧化钠水溶液回流2h裂解中间体,并回收了苯乙烯,反应产率达73.8 %。产品通过核磁、红外和元素分析等确认产品结构。     

通过环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物与亚硫酸氢钠的开环反应制备磺化离聚体

用环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物（ESBS）在相转移催化剂、开环催化剂存在下与亚硫酸氢钠的水溶液进行开环反应制备了SBS磺化离聚体,用傅里叶变换红外光谱法对产物进行了表征。研究表明,当环氧基转化率达90％时,反应条件为ESBS的质量浓度0．12g／mL。NaHSO3／环氧基（摩尔比）1．8,促进剂／NaHSO3（质量比）0．36。四乙基澳化铵／ESBS（质量比）0．05,二甲基苯胺／ESBS（质量比）0．05,60℃,7h。     

P(NIPAm-AABC-NMA)温敏微凝胶自组装膜及其重金属离子选择性

以N-异丙基丙烯酰胺（NIPAm）为单体，丙烯酸（AA）和N-羟甲基丙烯酰胺（NMA）为功能单体，通过自由基乳液聚合制备P(NIPAm-AA-NMA)微凝胶，利用N-(3-二甲基氨基丙基)-N''-乙基-碳二亚胺盐酸盐（EDC）的耦合作用，实现4''-氨基苯并-18-冠醚-6(ABC)对微凝胶的修饰，合成P（NIPAm-AABC-NMA）微凝胶；进一步，通过溶剂挥发制备微凝胶自组装膜。采用FTIR、SEM和DLS表征微凝胶及其自组装膜的微观结构；采用UV-Vis研究自组装膜的温敏性及其对金属离子的选择响应性能。结果表明，ABC修饰前、后微凝胶粒径分别为240和300nm左右，随环境温度或离子浓度变化，自组装膜中微凝胶粒径随之变化，自组装膜对入射光的衍射发生显著变化，而呈现不同的结构色。特别是，当Pb2+浓度在0~120μmol/L之间变化时，自组装膜衍射峰红移60nm左右。     

中间体2-氨基-4-二甲氨基-6-三氟乙氧基均三嗪的合成

以三聚氯氰为原料，分别与氨水、二甲胺及三氟乙醇反应，合成2-氨基-4-二甲氨基-6-三氟乙氧基均三嗪。考察了原料配比，溶剂选择，反应时间，反应温度等因素对产品产率的影响，并通过试验得到了该反应的优化了工艺条件。胺化条件：n（三聚氯氰）：n（氨水）：n（二甲胺）=1：2：1．8～1．9，反应时间30min；醚化条件：n（2-氨基-4-二甲氨基-6-氯均三嗪）：n（氢氧化钾）：n（三氟乙醇）=1：1：1．1，反应时间2h。在此条件下，收率达到88．7％。     

聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子的制备及性能

由种子乳液聚合法制备了聚苯乙烯-聚甲基丙烯酸甲酯核-壳粒子。以过硫酸钾（KPS）为引发剂，分别以非离子型辛基酚聚氧乙烯醚（OP—10）和复合十二烷基硫酸钠（SDS）／OP—10（质量比为1：4）为乳化剂，合成了聚苯乙烯种子核。连续滴加甲基丙烯酸甲酯（MMA），以OP—10乳化的种子乳液可以制备粒径范围在0．16～0．67μm的核-壳粒子，当单体苯乙烯与甲基丙烯酸甲酯（St／MMA）的质量比为3：7时，所得粒径为0．18μm，粒径分散系数为0．012。而以OP-10／SDS质量比为4：1制备的种子乳液所得核壳粒子直径在毫米级。差示扫描量热研究显示，以OP-10乳化所得种子乳液制衢的复合粒子的玻璃化转变温度为97．2℃，峰形单一，表现山良好的热性能。     

带羧基乳胶颗粒的制备、聚集以及与重氮树脂的自组装

从苯乙烯、丙烯酸丁酯和丙烯酸制备了表面带COOH的不同粒径的乳胶颗粒 (～ 10 0～40 0nm)。研究了因水分挥发由毛细管力引起的乳胶颗粒的聚集 ,以及这些乳胶颗粒和含N2 + 的高分子 (重氮树脂 ,Mn～ 2 5 0 0g/mol)的自组装 ,结合紫外光照 ,制备了高分子与乳胶粒交替的三明治 (sandwich)结构的超薄膜 ,结果表明 ,层与层间的光反应是高分子与乳胶粒成功组装的关键。由于光照中 ,层与层间的离子键已转变为共价键 ,这种超薄膜对极性溶剂和盐水溶液非常稳定 ,在DMF、c(NaCl) =0 1mol/L的水溶液中 ,室温下 (～ 2 0℃ )分别浸泡 2 4h ,组装膜仍完好无损。     

硅溶胶/苯乙烯-丙烯酸酯共聚物无机-有机杂化水分散液的制备和表征

A stable silica sol with 3-5 nm in diameter, which can form homogeneous film without crack, was prepared and characterized. Then, the inorganic-organic hybrid aqueous dispersion composed of such a silica sol and an emulsion of styrene （St） and acrylate （Ac） copolymer was prepared and the hybrid effect between the silica sol and poly（St-co-Ac） was observed by Fourier transform infra-red （FT-IR） spectroscope. The toughness of the film prepared by this kind of hybrid aqueous dispersion was excellent, as it was enhanced appreciably by commixing with a small amount of poly（St-co-Ac） emulsion. Some amino-polysiloxane modified hybrid aqueous dispersions were also prepared and the properties of the modified dispersions and their films were investigated. The experimental results showed that the film prepared with such an amino-polysiloxane modified hybrid dispersion exhibited excellent hydrophobicity and low surface energy after heat treatment for 1.5 h, during which the formation of the graft copolymer was observed. The surface energy of this film decreases as a result of the enrichment of siloxane segments on the film surface.     

Bicontinuous networks made of polyphosphates and of thermoplastic polymers

Composite films are obtained by casting aqueous dispersions obtained by admixture of PVAc or styrene-acrylic latexes with aluminium or iron polyphosphate powders. Film extraction with solution of aqueous EDTA (a solvent for polyphosphate) yields a dense polymer film, but using a polymer solvent (chloroform) a porous monolithic solid is obtained. Composite and solvent-extracted films were characterized by SEM coupled to energy dispersive X-ray analysis, and by Raman microspectrophotometry. The results from morphological, spectral and gravimetric experiments show that the cast films are bicontinuous, indicating a strong compatibility of the organic and inorganic phases. This is assigned to ionic bonds at the interfaces, in which aluminium ions act as bridging groups. © 1997 Elsevier Science Ltd.     

Thixotropic interparticle interaction between silica and nonionic polymer particles prepared by static dispersion polymerization

Static dispersion polymerization of styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate and benzyl methacrylate, initiated by a lipophilic initiator in an aqueous dispersion with unmodified silica particles was investigated. Polymerization of styrene gave a mixed dispersion of silica and monodisperse polystyrene (PS) particles, which was extremely stable compared with the aqueous dispersion of silica particles. The enhanced dispersion stability is due to a thixotropic effect based on weak attractive interparticle interactions between silica and PS particles in aqueous dispersion. An aggregate in which silica particles are surrounded by the smaller PS particles is formed and inhibits flocculation of silica particles, thus giving enhanced dispersion stability. The results of similar static polymerization reactions with methacrylate analogs indicate that hydrogen bonds between benzene ring and hydroxy groups on the silica surface, and not electrostatic interaction derived from initiator residues, are the origin of weak interaction for thixotropic aggregation.     

热敏乳液薄膜的制备及性能

本文介绍了一种可以通过三步法制得的具有亲油的核和亲水的壳的高分子微胶粒。首先,通过乳液聚合得到甲基丙烯酸正丁酯与甲基丙酸甲酯的共聚物乳液(p-(BMA-MMA));利用(p-(BMA-MMA)乳液作为种子,用一种氧化还原引发体系引发反应,通过控制反应条件,在乳胶粒表面包覆一层均匀的聚甲基丙烯酸缩水甘油酯(p-GMA)外壳,壳层聚合物的含量为5~15wt.%之间;最后,壳层表面的环氧基团与三乙醇胺盐酸盐反应,环氧基团转变为季铵盐,使外壳成为极性的亲水表面。核-壳型固体微胶粒可以在水中较好地分散并形成稳定的乳液。通过旋涂法将固体乳液颗粒和PVA的混合水溶液涂在铝版基上,室温下干燥,可得到乳液薄膜。实验发现,室温下核-壳乳液薄膜与水的接触角在16.1°-27.5°范围内,可经过150℃短时间的烤版处理后,接触角将超过87,°表明乳液薄膜通过加热后完全由亲水性转为亲油性。同时,该乳液薄膜在烤版前很容易用中性水由版基上冲洗掉,但烤版后不再能够被洗掉。当在乳液薄膜中加入一种红外染料(最大吸收波长在830nm)后,该薄膜变得对830nm的LD激光敏感,并通过LD激光曝光和中性水显影后,得到阴图型图像。     

Der Einfluß von Tensiden auf physikalische Eigenschaften von Keratinfasern

Influence of Surfactants on the Physical Properties of Keratin Fibres It could be proved by stress-strain tests that keratin fibres are more easily stretched in aqueous solutions of various ionic surfactants than in pure water. This effect can be further intensified in solutions of acidic and alkaline pH values. The extent of weakening of the fibre is dependent upon the chain length of the surfactant and the degree of adsorption. These effects are fully reversible by rinsing with distilled water. However, a splitting of the cystine bonds occurs in strongly alkaline solutions. The damage on keratin fibres caused by aqueous solutions of ionic surfactants is explained by the opening of hydrophobic bonds.     

以低分子量聚乙烯基苯磺酸钠为模板的聚3,4-二氧乙烯噻吩水分散体的制备及性能

通过RAFT聚合,制备了低分子量的聚乙烯基苯磺酸钠（PSS）;其次以低分子量的聚乙烯基苯磺酸钠为模板制备了聚3,4-二氧乙烯噻吩（PEDOT）：聚乙烯基苯磺酸钠（PSS）水分散体,研究了作为模板的聚乙烯基苯磺酸钠的不同分子量对PEDOT：PSS水分散体结构和性能的影响。结果显示：通过核磁氢谱（¹H NMR）表征,证明成功制备了分子量为3900,4900,9600和18300的聚乙烯基苯磺酸钠。用荧光探针法发现低分子量PSS在水中能形成胶束,临界胶束浓度在10^-6g·ml^-1左右。用四探针表面电阻测试发现,低分子量PSS为模板可明显提高PEDOT薄膜的导电性,最大提高了近3倍。用紫外可见分光光度计（UV）研究发现,以低分子量PSS为模板使PEDOT的透明性有一定的下降,这主要是由于RAFT试剂部分和PEDOT：PSS的相分离造成的。热稳定性的测试表明,低分子量PSS为模板对PEDOT的热稳定性没有明显的影响。     

Synthesis of sulfonated rubber ionomers by the ring‐opening reaction of epoxidized styrene–butadiene rubber,their characterization,and their properties

A novel method for the synthesis of the sulfonate ionomer of styrene‐co‐butadiene rubber (SBR) was developed. SBR was first epoxidized by performic acid formed from hydrogen peroxide and formic acid in situ in solution, and this was followed by a ring‐opening reaction with an aqueous solution of NaHSO₃. The optimum conditions for the epoxidation of SBR in the presence of a phase‐transfer catalyst and for the ring‐opening reaction of epoxidized SBR with an aqueous solution of NaHSO₃ were studied. During the epoxidation of SBR, a phase‐transfer catalyst, such as poly(ethylene glycol), could enhance the conversion of double bonds to epoxy groups. During the ring‐opening reaction, both the phase‐transfer catalyst and ring‐opening catalyst were necessary to enhance the conversion of the epoxy groups to ionic groups. The addition of Na₂SO₃ to the reaction mixture was important to obtain 100% conversion. The products were characterized with Fourier transform infrared spectrophotometry, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). DSC showed that the sodium sulfonate SBR ionomer possessed a dissociation temperature of ionic domains at 110°C, which appeared as black spots under TEM, after the sodium ions of the ionomer were substituted by lead ions. Some properties of the sodium ionomer, such as the water absorbency, oil absorbency, and dilute solution behavior, were studied. With increasing ionic groups, the water absorbency of the ionomer increased, whereas the oil absorbency decreased. The dilute solution viscosity of the ionomer increased abruptly with increasing ionic group content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3090–3096, 2006     

Polymeric corrosion inhibitors for aluminium pigment

In aqueous alkaline media (e.g. water-borne metallic paints) aluminium pigments react by the evolution of hydrogen. This corrosion reaction can be inhibited by addition of different water-soluble polymers with carboxyl groups like polyacrylic acids, styrene–maleic acid or styrene–acrylate copolymers. As a rough empirical rule can be stated that the corrosion-inhibiting effect of polymers with carboxyl groups increases with decreasing molecular mass and decreasing acid number. Moreover, the isoelectric point (IEP) of aluminium oxide (pH≈9) seems to be an important factor controlling corrosion inhibition (and adsorption) of polymers with carboxyl groups. Thermosetting phenolic resins (resoles) inhibit the corrosion reaction of aluminium pigment excellently at pH 8 but less effectively at pH 10. The corrosion-inhibiting functional group of resoles seems to be the chelating ortho-hydroxybenzyl alcohol structural part. In contrast, the nonionic water-soluble polymer polyvinyl alcohol does not inhibit the corrosion reaction. So, one may assume that an ionic interaction between aluminium pigment surface and polymer is necessary (but not sufficient) for corrosion inhibition.     

Preparation and reticulation of styrene acrylic/epoxy complex latex

The styrene acrylic/epoxy (SA/EP) complex latex with high content of epoxy resin was successfully prepared through emulsion polymerization initiated by both water-soluble and oil-soluble initiators. The resulting complex latex demonstrated regular spherical morphology with a diameter ranging 150–300 nm and with a narrow size distribution. The compatibility between epoxy and styrene acrylic improved due to the styrene acrylic grafting epoxy formation during grafting copolymerization. The factors influencing the structure and storage time of the complex latex were investigated and the corresponding mechanism was revealed. The SA/EP complex latex can form crosslinking structure with epoxy curing agent at room temperature. The crosslinked complex latex film shows good mechanical properties and excellent chemical resistance. These SA/EP complex latexes show great potential in developing high-performance aqueous paints and adhesive.