甲基丙烯酸酯的基团转移嵌段共聚研究

甲基丙烯酸酯的基团转移嵌段共聚研究戴李宗邹友思陈良坦潘容华（厦门大学化学系厦门３６１００５）关键词基团转移聚合，甲基丙烯酸酯，嵌段共聚物，结构表征基团转移聚合［１］（ＧｒｏｕｐＴｒａｎｓｆｅｒＰｏｌｙｍｅｒｉｚａｔｉｏｎ，ＧＴＰ）具有活性聚合的特点...     

Perspective on metal-mediated polar monomer/alkene copolymerization

A major unsolved problem in polymer synthesis is the design of efficient metal-mediated systems for the copolymerization of alkenes with polar vinyl monomers, such as acrylates and methacrylates. There are several reasons for the absence of efficient transition metal-based insertion copolymerization catalysts. First, following insertion, the ester group of the acrylate coordinates to the metal thereby hindering subsequent monomer coordination. A second reason stems from the preferred 2,1-insertion of acrylates into metal-carbon bonds resulting in the placement of the ester group on the α-carbon. This makes the metal-alkyl species particularly prone to homolysis because of the enhanced stability of the resultant alkyl radical, one that is essentially the same as the propagating species in radical-initiated acrylate polymerization. In this perspective we focus on this issue of facile metal-carbon bond homolysis, especially following acrylate insertion, using examples from our own work. We suggest ways to circumvent these issues, for example forcing 1,2-insertion by imposing steric crowding at the metal. Finally, we discuss the danger of relying on radical traps as probes for polymerization mechanism. Radical traps can react with metal-hydrides and attenuate metal-centered nonradical reactions. However, even when radical traps fail to stop an observed polymerization, it may be wrong to conclude that a nonradical mechanism is at work since the traps can be destroyed under certain reaction conditions.     

单一化学交联与物理化学复合交联高吸油树脂的比较

提出在单一化学交联吸油树脂中引入物理交联的设想，并采用悬浮聚合法了单一化学交联和物理－化学复合交联的聚丙烯酸酯系高吸油树脂，对两种不同树脂的吸油速率，低亲油性单体树脂的吸油性能，最佳单体配比以及化学交联剂含量的影响进行了比较，结果表明物理交联的引入加快了树脂的吸油速率，提高低亲油性单体树脂的吸油能力，并且还使最佳单体配比中低亲油性单体含量增加，同时表明部分物理交联吸油树脂有一最佳化学交联剂含量区。     

Structure-activity relationship of some pentacoordinated Tributyltin(IV) complexes derived from sterically hindered Schiff bases of heterocyclic β-diketones

Some pentacoordinated tributyltin(IV) complexes of sterically hindered Schiff bases of heterocyclic β-diketones having the general formula Bu₃SnL (where LH = RC:NZC:C(OH)N(C₆H₅)N:CCH₃ where R = –CH₃, –C₆H₅, –C₆H₄Cl (p) and Z = –C₆H₄Cl(m), –C₆H₄Cl(p) and –C₆H₄Cl(p)] were screened for their antimicrobial activity against the bacterial strain (Bacillus subtillis) and fungal strains (Candida albicans and Aspergillas niger). These monomeric pentacoordinated tributyltin(IV) complexes possess six membered ring which provide stability to the complexes. These complexes possess Sn←N bond scaffold which impart biological activity in tributyltin(IV) complexes. Antimicrobial bioassay results reveal that these tributyltin(IV) complexes derived from sterically hindered Schiff bases of heterocyclic β-diketones were possess more inhibition potential than their respective parent ligands. These pentacoordinated tributyltin(IV) complexes may used as antibiotic drug in future.     

Novel methacrylate copolymers with fluorine containing: Synthesis, characterization, reactivity ratios, thermal properties and biological activity

New methacrylate based monomers 2-(4-benzoylphenoxy)-2-oxoethyl-2-methylacrylate (BOEMA), 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate (AOEMA), and 2-[(4-fluorophenyl)amino]-2-oxoethyl-2-methylacrylate (FPAMA), were synthesized first time. The free-radical-initiated copolymerization of AOEMA and BOEMA with FPAMA were carried out in 1,4-dioxane solution at 65 °C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomers and copolymers were characterized by FTIR, ¹H NMR and ¹³C NMR spectral studies. The copolymer compositions were evaluated by nitrogen content in polymers. The reactivity ratios of the monomers were determined by the application of Fineman-Ross and Kelen-Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPAMA, and copolymers formed are statistically in nature. The molecular weights ( and ) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPAMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPAMA in the copolymers. The prepared homo and copolymers were tested for their antimicrobial activity against bacteria, fungi and yeast.     

三丁基锡化合物与DNA相互作用的光谱研究

通过紫外(UV)和圆二色(CD)光谱,研究了三丁基锡(TBT)与脱氧核糖核酸(DNA)的相互作用。结果表明,TBT具有双重作用。既作用于DNA的碱基部分,影响DNA双螺旋结构;又作用于DNA的磷酸基团,使构象发生变化。TBT的作用位点随时间也不同。短时间内作用,位点是DNA的碱基,紫外光谱表现为增色效应;长时间作用,位点是DNA的磷酸基团,紫外光谱表现为增色效应减弱。随着TBT浓度的增大,紫外光谱的增色效应增强。磷酸根离子浓度对TBT与DNA相互作用有影响。磷酸根的存在削弱了TBT与DNA间的相互作用,也表明TBT与DNA的作用是双重的。     

三丁基锡(TBT)化合物与牛血清白蛋白(BSA)的相互作用

通过紫外、荧光和圆二色(CD)光谱,研究了船体防污漆的防污成分三丁基锡(TBT)化合物与牛血清白蛋白(BSA)的相互作用,考察了浓度、酸度和有机溶剂等因素的影响。结果表明,TBT与BSA的相互作用是双重的,既有TBT中丁基基团的疏水作用,又有锡离子与BSA的配位作用,使BSA内部的色氨酸和酪氨酸等芳香氨基酸残基裸露,导致BSA二级结构破坏,α-螺旋含量减少和构象改变。     

甲基丙烯酸正丁酯/甲基丙烯酸β羟乙酯共聚吸附功能纤维的制备及表征

以过氧化苯甲酰(BPO)为引发剂, 合成了甲基丙烯酸正丁酯/甲基丙烯酸羟乙酯(BMA/HEMA)二元共聚树脂, 采用冻胶纺丝技术制备了低分子量有机液体吸附功能纤维, 利用傅里叶变换红外光谱(FTIR)和13C核磁共振波谱(NMR)、广角X射线衍射仪(WAXD)和综合热分析仪以及环境扫描电子显微镜(SEM)研究了共聚物的交联结构、纤维的结晶性能以及纤维的表面形貌, 同时研究了共聚合阶段HEMA与BMA投料比对纤维饱和吸附量的影响. 研究结果表明, 树脂大分子间不存在化学交联结构, 大分子内和大分子间存在氢键作用, 有利于物理交联结构的形成; 纤维结晶性能随着HEMA质量分数增加而减弱, 且HEMA质量分数对纤维表面形貌有较大影响; 纤维对甲苯和三氯乙烯的饱和吸附量随着HEMA质量分数增加而增大, HEMA质量分数相同时所得纤维对三氯乙烯的吸附量明显高于对甲苯的吸附量.     

氧负离子聚合在超支化聚合物合成中的应用

近年来,氧负离子聚合得到较快发展,单体种类已经由酯基的β位上含有供电性杂原子的甲基丙烯酸酯类扩展到环氧类、甲基丙烯酸羟酯类单体.氧负离子引发这两类单体聚合,可以得到新型结构的超支化聚合物.对氧负离子引发合成超支化聚合物的机理及其应用进行了综述.     

Analysis of triorganotin compounds in water samples by hydrophilic interaction liquid chromatography–electrospray ionization-mass spectrometry

Hydrophilic interaction liquid chromatography (HILIC)–electrospray ionization-mass spectrometry (ESI-MS) was evaluated for the analysis of tributyltin (TBT) and triphenyltin (TPT) in water samples. Separation was performed in isocratic mode on an Atlantis HILIC silica (2.1 mm × 150 mm, 5 μm) column with a mobile phase of acetonitrile–0.1% aqueous HCOOH (86:14, v/v) at a flow rate of 0.2 mL/min. Under optimum conditions, limits of detection for TBT and TPT were 10 and 20 pg injected onto the column, respectively. The extraction of triorganotin compounds from seawater samples was carried out using a polymer-based solid phase extraction cartridge of mixed modes with reversed-phase and weak anion exchange. Tributyltin-d₂₇ chloride and triphenyltin-d₁₅ chloride were used as internal standards. The relative standard deviations for the analysis were less than 4%. Using the proposed method, it was possible to analyze concentrations of TPT and TBT in seawater at ppt levels.