1,3—戊二烯／苯乙烯阳离子共聚合反应

本文研究了以甲苯为溶剂,ＡｌＣｌ３和ＢＦ３·ＯＥｔ２为引发剂,１,３－戊二烯（ＰＤ）与苯乙烯（Ｓｔ）的阳离子共聚合反应,并用红外光谱测定聚合物的微观结构。由共聚单体ＰＤ和Ｓｔ加入顺序的不同可生成无规共聚物Ｐ（ＰＤ－ｃｏ－Ｓｔ）和接枝共聚物Ｐ（ＰＤ－ｇ－Ｓｔ）和Ｐ（Ｓｔ－ｇ－ＰＤ）。无论是由ＡｌＣｌ３引发聚合反应,还是由ＢＦ３·ＯＥｔ２引发聚合反应,Ｓｔ上的碳阳离子的活性都高于ＰＤ上碳阳离子的活性。由ＡｌＣｌ３首先引发ＰＤ进行聚合反应,结束后再引入Ｓｔ时,聚合体系不能引发Ｓｔ聚合反应;相反ＡｌＣｌ３首先引发Ｓｔ聚合后的体系能继续引发ＰＤ的聚合反应。ＢＦ３·ＯＥｔ２无论先引发Ｓｔ或是ＰＤ,都能在聚合反应完成后接着引发另一单体而生成接枝共聚物Ｐ（ＰＤ－ｇ－Ｓｔ）和Ｐ（Ｓｔ－ｇ－ＰＤ）。二苯醚与烯丙基氯的加入,提高了碳阳离子的稳定性,增加了聚合物的分子量,但降低了碳阳离子的活性,使得聚合反应的产率降低,同时对Ｓｔ和ＰＤ碳阳离子的活性次序无明显影响     

胶束体系中光敏聚合的研究 Ⅶ．微泡水溶液体系中光聚合的研究

研究了在双十六烷基二甲基溴化铵（ＤＣＤＡＢ）形成的微泡溶液中，二苯酮（ＢＰ）／三乙胺（ＴＥＡ）体系的光化学初级反应和引发ＭＭＡ光聚合反应．动力学实验结果表明，ＤＣＤＡＢ微泡对聚合反应有显著的催化作用，使聚合速度提高近４倍左右，其效果和离子型胶束的催化作用结果相近．由ＤＣＤＡＢ微泡中光聚合得到的产物ＰＭＭＡ，具有较高的结构规整性，它的间同和全同结构可达７０％左右．     

樟脑酮/过氧化物复合体系引发丙烯酸酯可见光聚合反应

采用差热扫描方法（ＤＳＣ）研究了樟脑酮（ＣＱ）／过氧化物（ＰＯ）复合体系引发三缩乙二醇双甲基丙烯酸酯（ＴＥＧＤＭ）的可见光聚合．与ＣＱ单一引发体系相比,ＣＱ和ＰＯ组成的复合体系更为有效．实验结果指出,加入过氧化物,如ＤＣＰＯ和ＤＢＰＯ,使聚合速率显著增加,最大速率到达时间明显缩短,然而它们对应的过氧化氢化合物,如ＴＢＨＰ、ＣＭＨＰ却效果不佳,复合体系的增效作用表明,激发态ＣＱ通过能量传递机制,使过氧化物发生有效的光解生成活性自由基,同时发现在含氧的条件下聚合反应速率得到增加．     

新型高活性催化剂乙烯气相聚合的研究（I）：气相均聚和共聚…

研究了新型高活性乙烯气相聚合催化剂ＴｉＣｌ４／ＭｇＣｌ２／ＺｎＣｌ２／ＳｉＣｌ４／醇／Ａｌ（ｉ－Ｂｕ）３体系中钛和醇组分含量对聚合反应和产物颗粒形态的影响。测定了乙烯气相聚合反应动力学曲线，确定了聚合动力学方程。用ＳＥＭ，ＤＳＣ，ＷＡＸＤ，＾１＾３ＣＮＭＲ对催化剂及聚合物的形态，结构和性能进行了分析和表征。     

Lewis酸催化1,4-脱水-2,3-二-氧-(对迭氮基苯甲基)-α-D-核糖的选择性开环聚合反应

在低温下用三氟化硼乙醚催化１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－核糖（ＡＤＡＢＲ）的阳离子选择性开环聚合反应，首次合成了具有１，５－开环α－结构的聚合物。单体ＡＤＡＢＲ由１，４－脱水－α－Ｄ－核糖在ＤＭＦ溶剂中与对溴甲基迭氮基苯反应获得。聚合物的结构由比旋光度、１Ｈ－ＮＭＲ和１３Ｃ－ＮＭＲ及ＩＲ谱确认。用五氟化锑为催化剂则得到了同时含有α－呋喃单元和β－吡喃单元混合结构的聚合物。研究了催化剂及其用量、聚合反应时间对聚合反应的影响，讨论了聚合反应机理。为研究１，４－脱水－２，３－二－氧－（对迭氮基苯甲基）－α－Ｄ－吡喃核糖的聚合活性以及便于测试迭氮基的含量对聚合物光刻性能的影响，还初步研究了单体ＡＤＡＢＲ与１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖（ＡＤＢＲ）的共聚反应。从共聚物的结构分析可以认定共聚物具有１，５－α－结构，并且单体１，４－脱水－２，３－二－氧－苯甲基－α－Ｄ－吡喃核糖在实验条件下具有较高的活性。     

甲基丙烯酸甲酯、丁酯在钕盐催化体系中聚合动力学和机理研究

采用Ｎｄ（Ｐ５０７）３－Ａｌ（ｉ－ＢＵ）３聚合体系催化甲基丙烯酸甲酯（ＭＭＡ）和甲基丙烯酸丁酯（ＢＭＡ）聚合．发现介质对聚合反应速率影响甚大．在石油醚中聚合反应速率与单体（ＭＭＡ、ＢＭＡ）、钕盐的浓度分别呈一级关系．ＭＭＡ．ＢＭＡ聚合的表现活化能分别为３３ｋＪ．ｍｏｌ－１和２４ｋＪ．ｍｏｌ－１．ＰＭＭＡ的间同含量达７０％左右．聚合反应属配位自由基机理．     

含时间变量的凝胶溶胶分配方程及其应用

在Ａａ－Ｂｂ型综聚反应的凝胶溶胶分配（ＧＳＤ）方程中引入相应的聚合反应动力学方程．模拟计算的溶胶分数（Ｓ）对反应程度（Ｐ_Ｂ，Ｐ_Ｂ＇）的关系曲线与实验结果基本吻合．利用含时间的ＧＳＤ方程，解决了非线型缩聚反应交联网络的模拟计算，给出了交联度随时间的变化曲线，也为凝胶点的计算提供了一种方法．     

AlCl_3／SbCl_3引发α－蒎烯阳离子聚合反应──引发活性种本质研究

考察了复合催化剂ＡｌＣｌ_３／ＳｂＣｌ_３的不同配制方法和质子捕捉剂２，６－二异丁基－４－甲基吡啶（ＤＴＢＭＰ）对α－蒎烯阳离子聚合反应的影响。结果表明，ＡｌＣｌ_３和ＳｂＣｌ_３加热熔融复合比简单复合的引发聚合活性更高；ＤＴＢＭＰ对该复合催化剂的聚合反应速率及其产物分子量分布均无明显影响，证明该复合催化剂形成的活性种本质上与质子Ｈ活性种不同，是新型活性种。根据２７ＡｌＮＭＲ对该体系活性种分析结果，认为引发阳离子是［Ｓｂ（Ｖ）Ｃｌ_４］，抗衡阴离子是［Ａｌ_２Ｃｌ_７］     

不等活性缩聚反应动力学及其分子量分布Monte Carlo模拟

将缩聚产物分子量分布（ＭＷＤ）的ＭｏｎｔｅＣａｒｌｏ方法和聚合反应动力学的ＭｏｎｔｅＣａｒｌｏ方法结合起来，可在研究聚合反应动力学的同时获得ＭＷＤ随时间的变化．将该方法用于研究非等活性的ＡＢ—ＡＡ型缩聚反应的动力学与实验结果十分一致．通过考察高活性ＡＡ单体加入后对其动力学行为和相应的ＭＷＤ的影响，作者提出了对聚苯撑醚砜的ＡＢ型缩聚合成中加快其反应速度和改进ＭＷＤ的实用方法．     

2-(N,N-二乙基二硫代氨基甲酰氧基)乙酸苄酯存在下苯乙烯光聚合

研究了２ Ｎ, Ｎ 二乙基二硫代氨基甲酰氧基乙酸苄酯（ Ｂｚ Ｄ Ｃ Ａ） 引发的苯乙烯光聚合反应,发现单体转化率和数均分子量（ Ｍｎ） 都随反应时间而增加,在反应时间相同时随着 Ｂｚ Ｄ Ｃ Ａ 浓度的增加单体转化率升高而 Ｍｎ 降低．聚苯乙烯（ Ｐ Ｓ） 的 Ｍｎ 同单体转化率成线性关系并同理论计算值符合得较好．以２ 甲基 ２ 亚硝基丙烷（ Ｍ Ｎ Ｐ） 为捕捉剂用（ Ｅ Ｐ Ｒ） 技术对聚合反应机理进行了研究．认为 Ｂｚ Ｄ Ｃ Ａ 引发的 Ｓｔ 光聚合是一个“活性”聚合过程     

新型环氧丙烯酸树脂增韧剂的合成

用马来酸酐和聚乙二醇1000合成具有反应活性端基的聚乙二醇,用红外与核磁共振进行了表征,并用其对环氧丙烯酸树脂进行改性;研究反应温度、反应时间对反应及产物性能的影响;用红外对反应性聚乙二醇和环氧丙烯酸树脂的固化物进行分析.结果表明,反应性聚乙二醇参与了环氧丙烯酸树脂的固化反应,可在交联网络中构成不同长度的柔性链段,显著地提高了环氧丙烯酸树脂的冲击强度.     

Intermediate detection in real time using reactive surface desorption dielectric‐barrier discharge ionization mass spectrometry

Reactive intermediates play key roles for reaction mechanism elucidation. A suitable tool for identifying the key intermediates is crucial and highly desirable. In this study, surface desorption dielectric‐barrier discharge ionization (reactive SDDBDI) was developed for characterization of the reactive intermediates. In reactive SDDBDI, the plasma is doped with a reagent before the plasma ions are directed at a cover slip surface bearing another analyte. Different from SDDBDI, reactive SDDBDI can be used both as an ambient ionization source and as a means to produce reagent ions for ambient ion/molecule reactions. The online derivation of 4‐aminophenol with trifluoroacetic anhydride demonstrated that reactive SDDBDI can be used for chemical analysis where improved specificity or sensitivity is required. The utility of this approach for real‐time detection of reactive intermediate was demonstrated by the Schiff‐base and Eberlin reactions. The formed intermediates and products could be readily detected and identified by tandem mass spectrometry. These results indicate that reactive SDDBDI can be used to generate reagent ions that undergo ion/molecule reactions in the open air with an analyte at condensed phase on a surface. Reactive SDDBDI has high‐efficiency ion transmission and high MS sensitivity. It is thus a potential tool to perform ambient ion/molecule reactions and detect reactive intermediates.     

A biosorption isotherm model for the removal of reactive azo dyes by inactivated mycelia of Cunninghamella elegans UCP542

The biosorption of three reactive azo dyes (red, black and orange II) found in textile effluents by inactive mycelium of Cunninghamella elegans has been investigated. It was found that after 120 hours of contact the adsorption led to 70%, 85%, 93% and 88% removal of reactive orange II, reactive black, reactive red and a mixture of them, respectively. The mycelium surface was found to be selective towards the azo dyes in the following order: reactive red > reactive black > orange II. Dye removal from a mixture solution resulted in 48.4 mg/g retention by mycelium and indicated a competition amongst the dyes for the cellular surface. A Freundlich adsorption isotherm model exhibited a better fit, thus suggesting the presence of heterogeneous binding sites. Electrondense deposits observed on the mycelium ultrastructure suggest that the dyes are mainly retained under the cellular surface of the inactive biomass of C. elegans.     

Influence of in situ reactive interphase with graft copolymer on shear and extensional rheology in a model bilayered polymer system

Influence of an in situ reactive interphase composed of graft copolymer on the melt shear and extensional rheology was systematically studied with a model bilayer of polyamide-6 (PA6)/maleic anhydride grafted poly(vinylidene fluoride) (PVDF-g-MAH). Firstly, small-amplitude oscillatory shear was used in situ to probe the development of reactive interphase from the interfacial reactions by tracking the changes of viscoelastic responses. Secondly, shear (start-up shear, shear stress relaxation) and extensional rheology was comparatively performed on the healed bilayers to evaluate the effects of reactive interphase. Interestingly, shear stress relaxation and especially extensional rheology were pretty sensitive to the presence of reactive interphase, whereas start-up shear showed negligible sensitivity. Specifically, the reactive interphase retarded the stress relaxation of healed bilayers subjected to step strains. Particularly, extensional rheology provided a more direct and quantitative view of the contribution of reactive interphase to melt rheology in both linear and nonlinear regimes. The remarkable increase in transient extensional viscosity and enhanced strain hardening resulting from the interfacial reaction in bilayer were demonstrated in terms of the interfacial stress. Besides, effect of reaction extent on extensional rheology was further examined, where it was found that interfacial stress increased with reaction time. The observed changes in rheology were attributed to the in situ formed interphase with graft copolymers and the resulting increased entanglements between neighboring layers. This study highlights the remarkable sensitivity of shear stress relaxation and especially extensional rheology to a reactive interphase.     

聚氨酯类反应型高分子表面活性剂的研究进展

反应型高分子表面活性剂兼有反应型表面活性剂可以以牢固的共价键键合到聚合物粒子上,有效避免了表面活性剂在聚合物膜中迁移的优点和高分子表面活性剂性质稳定、耐水性好、低毒或无毒的优点,是一种备受关注的新型表面活性剂,其中含有双键的聚氨酯类可聚合型高分子表面活性剂因其软硬度可调、反应活性高等优点而成为此类研究的一个新热点。本文综述了国内外聚氨酯类反应型高分子表面活性剂最新研究概况,简述了其合成路线和应用性能,并对未来的研究方向进行了预测。     

"Reactive filtration": use of functionalized porous polymer monoliths as scavengers in solution-phase synthesis

[reaction: see text] Solid functionalized porous monolithic disks with reactive polymer chains grafted to their inner pore surface have been developed for scavenging excess reagents from reaction mixtures. A poly(chloromethylstyrene-co-divinylbenzene) monolith was cut into disks and activated by graft polymerizing 4-vinyl-2,2-dimethylazlactone to its pore surface. In contrast to the direct copolymerization of reactive monomers, grafting increases the accessibility of the reactive groups. Application of the reactive disks is demonstrated in the scavenging of excess amines from reaction mixtures in different solvents.     

连续流微通道反应技术在合成黄酮类天然产物中的应用研究

本文采用连续流微通道反应技术,通过碘介导的二氢黄酮的氧化反应对黄酮类化合物半合成工艺进行了研究。首先选择黄酮类代表药物地奥司明为研究对象,通过连续流微通道反应器分别考察了在常压和背压条件下不同反应条件的影响,实现橙皮苷转化率98%,产品地奥司明收率90%。然后,采用连续流微通道反应完成了多种黄酮、黄酮醇和异黄酮类天然产物的合成。本文研究的黄酮类天然产物的连续流微通道反应工艺,不仅实现了与传统工艺相当的转化率和收率,而且反应时间从传统工艺的8~20小时缩短到2~3 min,反应过程更加安全、高效和快捷,同时拓展了连续流微通道反应技术在药物合成领域的应用范围。     

氧对n-BuLi/THF引发丁二烯苯乙烯共聚合的影响

研究了氧分子与活性种快速失活的定量关系 ,二代杂质对活性种及聚合物微观结构的影响 .从聚合动力学及聚合物相对分子质量等方面来测定氧分子快速杀死活性种数 ,并考察了体系中氧产生的偶联反应及其对丁苯共聚物物理机械性能、动态力学性能及耐磨性能的影响 .结果表明 :氧对n BuLi THF体系丁苯共聚合有不利影响 .     

H2O2/TiO2超声协同光降解活性艳橙的研究

以活性艳橙溶液为模拟废水,通过H₂O₂/TiO₂超声(US)协同作用光降解活性艳橙溶液,探讨了TiO₂催化剂用量、H₂O₂用量、活性艳橙溶液的初始浓度、pH值、TiO₂催化剂锻烧温度等对活性艳橙溶液降解率的影响,并比较了几种不同作用方式对活性艳橙溶液的降解效果.结果表明:UV/H₂O₂/TiO₂/US协同作用降解活性艳橙溶液的效果最好;当活性艳橙溶液的初始浓度为20 mg·L^-1,pH＝5,TiO₂用量为0.4 g·L^-1,H₂O₂用量为0.4 ml·L^-1时,降解率可达92.06%.     

Reactive blending of poly(ethylene terephthalate) with ethylene-propylene rubber

A gram-scale miniature reactor designed for reactive blendind was introduced. A brief review was given on the light scattering method for morphology characterization and the ellipsometric analysis on polymer-polymer interface. These methods were applied for the reactive blending of poly(ethylene terephthalate) with ethylene-propylene rubber (70/30 PET/EPR). Compared with non-reactive system, the reactive one yielded finer dispersion of rubber particles. It showed better stability of particle dispersion during static annealing. The reactive system with thick interface showed higher impact strength than the non-reactive one having same particle size but thinner interface, suggesting that the thick interface may be a prerequisite to the rubber toughening.