One-pot polyvinyl chloride preparation utilizing polyacrylate latex with tertiary amine groups for improved thermal stability,toughness, and reduced reactor scaling

In this paper, crosslinked polyacrylate latex with tertiary amine groups (ACLN) and base latex without tertiary amine groups (ACL) were prepared by emulsion polymerization using butyl acrylate as the monomer and 1,4-butanediol dimethacrylate as the crosslinker. Composite resins of polyvinyl chloride (PVC), ACL/PVC and ACLN/PVC, were prepared by suspension polymerization of vinyl chloride in a 20 L high-pressure reactor by adding ACL and ACLN as modifiers. The inner pressure of the reactor and initiator concentration as a function of reaction time during suspension polymerization were studied. Morphology of resin particles, processing properties, thermal stability and mechanical properties of ACL/PVC and ACLN/PVC products were investigated. A commercial PVC product named PVC-SG5 was used as the control sample for comparison. It was found that compared with typical PVC-SG5 preparation, ACL/PVC fabrication took less time while initiator concentrations needed to be increased to 2400 ppm in ACLN/PVC preparation in order to complete the polymerization within the same time. Reactor scaling occurred during ACL/PVC preparation, but could be avoided in ACLN/PVC preparation owing to the hydrophilicity of ACLN. The morphology of ACL/PVC and ACLN/PVC particles was smooth microspheres and mosaic particle shapes, respectively, the diameter of which were all smaller than PVC-SG5 particles. The covalent-bonding existing in ACL/PVC and ACLN/PVC, and ionic-bond formation of quaternary ammonium in ACLN/PVC composite resins, between tertiary amine groups in ACLN and chlorine atoms in PVC, contributed to the dramatic increase in thermal stability. ACLN/PVC exhibited the shortest plasticizing time and the longest elongation at break, followed by ACL/PVC. The toughness of both ACL/PVC and ACLN/PVC were greatly enhanced without affecting the tensile strength and softening temperature of the resin. Thus, three issues, namely, low thermal stability, low toughness and reactor scaling during polymerization of PVC have been comprehensively solved by introducing ACLN to PVC through a one-pot method.     

pH and thermo responsive aliphatic tertiary amine chromophore hyperbranched poly(amino ether ester)s from oxa-Michael addition polymerization

In this research, we developed a novel and facile strategy to prepare aliphatic tertiary amine chromophore hyperbranched poly(amino ether ester)s with pH and thermo responsiveness via phosphazene base (t-BuP₂) catalyzed oxa-Michael addition polymerization of triethanolamine with ethylene glycol diacrylate at room temperature. UV–vis and fluorescence analyses results showed that the tertiary amine at branching point for hyperbranched poly(amino ether ester)s is very important to retain strong blue fluorescence of tertiary amine chromophore. Moreover, the hyperbranched poly(amino ether ester)s exhibit an aggregation caused quenching (ACQ) fluorescence, solvent induced red-shifted emission, molecular weight, and temperature dependent emission characters. More interestingly, the hyperbranched poly(amino ether ester)s show extreme acid induced quenching fluorescence phenomenon, and also display good water solubility, specific recognition of Fe³⁺ ion, low cytotoxicity, and bright cell imaging, which could serve as a microenvironment-responding fluorescent probe for application in chemical sensing, cell imaging, drug delivery, or disease diagnostics. This research provides a versatile method for the preparation of stimuli-responsive aliphatic tertiary amine chromophore polymers, and supplies ideas for researchers to explore other unconventional fluorescent polymers for application.     

Synthesis of Enantioenriched Vicinal Tertiary and Quaternary Carbon Stereogenic Centers within an Acyclic Chain

Overcoming the inherent difficulty to prepare quaternary carbon stereogenic centers, the diastereo‐ and enantioselective preparation of acyclic carbon backbones possessing vicinal quaternary and tertiary stereogenic centers (i.e. in a 1,2‐relationship) causes distorted geometries and represents a very acute problem in organic synthesis. Several approaches are discussed in this minireview underlining the challenges illustrated by the rather limited number of approaches available to practitioners.     

Collision‐induced loss of AgH from Ag+ adducts of alkylamines,aminocarboxylic acids and alkyl benzyl ethers leads exclusively to thermodynamically favored product ions

The loss of AgH from [M + Ag]⁺ precursor ions of tertiary amines, aminocarboxylic acids and aryl alkyl ethers is examined by deuterium labeling combined with collision activation (CA) dissociation experiments. It was possible to demonstrate that the AgH loss process is highly selective toward the hydride abstraction. For tertiary amines and aminocarboxylic acids, hydrogen originates from the α‐methylene group carrying the nitrogen function (formation of an immonium ion). In all cases examined, the most stable, i.e. the thermodynamically favored product ion is formed. In the AgH loss process, a large isotope effect operates discriminating against the loss of D. The [M + Ag]⁺ ion of benzyl methyl ether loses a hydride ion exclusively from the benzylic methylene group supporting the experimental finding that the AgH loss reaction selectively cleaves the weakest C? H bond available. Copyright © 2008 John Wiley & Sons, Ltd.     

内部振动对30m望远镜三镜的影响

利用数值方法得到任意形式振动下30m望远镜三镜的光学传递函数,并分析其数值精度.在光学传递函数的基础上引入标准化点源敏感性来表征振动对系统光线中继功能的影响.为了验证理论分析,对于某大口径设备进行实验,采用多个加速度计共同采集数据并合成信号的方法来实现镜面运动信息的解耦与测量误差抑制.结果表明:在内部振源工作的情况下,设备点源敏感性从0.999 96下降到0.999 92;使用二阶巴特沃兹带通滤波器后,对于外部的力输出为0.075N.     

Preparation of cruciferous phytoalexin related metabolites, (−)-dioxibrassinin and (−)-3-cyanomethyl-3-hydroxyoxindole, and determination of their absolute configurations by vibrational circular dichroism (VCD)

Cruciferous phytoalexin related metabolites, (−)-dioxibrassinin (1) and (−)-3-cyanomethyl-3-hydroxyoxindole (2) were prepared from isatin as racemates and were resolved by chiral HPLC. Their absolute configurations were determined by the new chiroptical technique, vibrational circular dichroism (VCD), as well as by the conventional electronic circular dichroism (ECD). It is concluded that the absolute configurations of the naturally occurring (−)-1 and (−)-2 are both S.     

含叔胺结构高光响应性香豆素衍生物的设计合成

以环氧氯丙烷为桥接, 将具有较强给电子能力的芳叔胺(ATA)结构引入香豆素衍生物C分子中, 通过芳叔胺结构的光化学促进作用加速香豆素基元的光二聚反应. 用紫外(UV)和荧光(FL)光谱等手段对该香豆素衍生物进行表征. 结果表明, 芳叔胺结构的引入可有效增强香豆素基元在260-400 nm之间的吸收. 紫外点光源光二聚反应实验表明, 芳叔胺结构的引入使香豆素基元的光响应性能得以大幅增强, 在相同光照条件下, 其在匀速反应区间内对光照时间的依赖性的斜率高达6.47, 光二聚反应程度达到80%时所需光照时间仅为29 s.     

Tertiary amine-functionalized polymers by atom transfer radical polymerization

The quantitative synthesis of tertiary amine-functionalized polymers by atom transfer radical polymerization is reported. Tertiary amine-functionalized polystyrene was prepared with the adduct of 1-(bromoethyl)benzene with 1-(4-dimethyl-aminophenyl)-1-phenylethylene as an initiator in the atom transfer radical polymerization of styrene in the presence of a copper (I) bromide/2,2′-bipyridyl catalyst system. The polymerization proceeded via a controlled free-radical polymerization process to afford quantitative yields of the corresponding tertiary amine-functionalized polystyrene with predictable number-average molecular weights (1600–4400), narrow molecular weight distributions (1.09–1.31), and an initiator efficiency of 0.95. The polymerization process was monitored by gas chromatographic analysis. The tertiary amine-functionalized polymers were characterized by thin-layer chromatography, size exclusion chromatography, potentiometry, and spectroscopy. All experimental evidence was consistent with quantitative functionalization via the 1,1-diphenylethylene derivative. Polymerization kinetic measurements showed that the polymerization reaction followed first-order-rate kinetics with respect to monomer consumption and that the number-average molecular weight increased linearly with monomer conversion. © 2001 John Wiley & Sons, Inc. J Polym Sci A Part A: Polym Chem 39: 2058–2067, 2001     

苯二胺和联苯二胺类叔芳胺的合成及发光性能的研究

N,N′-二苯基-1,4-苯二胺和N⁴,N^4'-二苯基-4,4'-联苯二胺分别与芳基溴在Pd(OAc)₂/P(t-Bu)₃催化下于120 ℃邻二甲苯溶液中反应生成苯二胺和联苯二胺类叔芳胺有机电致发光材料, 这些化合物的熔点都在300 ℃以上. 产物的结构经¹H NMR, ¹³C NMR, ¹³C (DEPT), MS (HREI和EI)表征. 用UV-Vis, PL, DSC测定了苯二胺和联苯二胺类叔芳胺化合物的发光性能.