Synthesis and refractive‐index control of fluoropolymers by the polyaddition of bis(epoxide)s and triazine di(aryl ether)s

The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (T_g's) and refractive‐indices (n_D's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of T_g's and n_D's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007     

Alternating copolymerization of carbon dioxide and epoxide by manganese porphyrin: The first example of polycarbonate synthesis from 1-atm carbon dioxide

The first successful example of the formation of polycarbonate from 1-atm carbon dioxide and epoxide was demonstrated by the alternating copolymerization of carbon dioxide and epoxide with manganese porphyrin as a catalyst. The copolymerization of carbon dioxide and cyclohexene oxide with (porphinato)manganese acetate proceeded under the 1-atm pressure of carbon dioxide to give a copolymer with an alternating sequence. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3549–3555, 2003     

Novel platinum-containing initiators for ring-opening polymerizations

A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species.     

胍催化邻苯二甲酰亚胺对环氧化合物的开环反应

作为有机强碱,胍类化合物可用于催化多种反应[1 5],并且反应可以在均相、无水条件下进行,不需要相转移催化剂。本文探讨用胍催化邻苯二甲酰亚胺对环氧化合物进行开环。用三光气将二乙胺转变为四乙基脲1,后者用五氯化磷和叔丁胺处理得到1,1,3,3 四乙基 2 叔丁基胍2。用2催化邻苯二甲酰亚胺与末端环氧化合物的反应,实现了环氧化合物的区域选择性开环。合成路线如下:1　实验部分1 1仪器与试剂WC 1型显微熔点仪(四川大学科仪厂),温度计未校正;Carlo ErbaModel1110自动元素分析仪,Varian400MHz核磁共振仪。溶剂和试剂经干燥、重蒸后使用…     

Synthesis and cationic photopolymerization of electroactive monomers containing functional groups

The synthesis and cationic photopolymerization of different cationically polymerizable monomers containing electroactive groups are reviewed with 98 references. The preparation of various compounds containing electron‐donor or electron‐acceptor moieties and photopolymerizable functional groups is described. After a short discussion of basic principles of cationic polymerization, photoinduced cationic polymerizations of various cationically polymerizable monomers containing both electron‐donor or electron‐acceptor chromophores and the functional groups such as epoxy, vinyl, thiiranyl, oxetanyl and others are reviewed. Copyright © 2005 John Wiley & Sons, Ltd.     

SYNTHESIS, CHARACTERIZATION, METAL-UPTAKE BEHAVIOR OF BIS（BENZIMIDAZOLE） RESIN SUPPORTED ON EPOXIDE POLYMER

The new chelate resins, abbreviated as PNBMZs and PBBMZs based on epoxide polymer, were synthesized by polycondensation of N,N-diglycidyl-4-glycidyloxyaniline or 1,4-bis（2,3-epoxypropyl）benzene with the primary amine group of 1,3-bis（benzimidazol-2yl）propylamine （BBPAH）. The ion exchangers contain 2.71-3.23 mmol of the ligand contents per gram of the resin. Batch extraction capacities were determined for the metal chloride salts in buffer solutions in the pH range from -1 to 6.0. The chelate resins were very selective for Cu^2＋, Zn^2＋, Cd^2＋ in the presence of other divalent transition metal ions. The maximum uptake capacities of PNBMZ （synthetic molar ratio = 1：1.5） under non-competitive condition were found to be 0.94 mmol/g for Cu^2＋ at pH = 2, 1.3 mmol/g for Cd^2＋ at pH = 1 and 1.75 mmol/g for Zn^2＋ at pH = -1 respectively. While in the case of PBBMZ, it was 1.39 mmol/g for Cd〉 at pH = 1. The metal-uptake behaviors for both of them showed strong pH dependence, and their extraction capacities increase with decreasing pH. The uptake of Cu^2＋ by the resin PNBMZs at pH = 1 was found to be rather fast with t1/2 = 18 min. Metal-uptake experiments under competitive conditions also confirm that the chelate resins have a high selectivity for Cu^2＋, Zn^2＋, Cd^2＋ and the contrary pH dependence.     

氯化锌催化硒酚对环氧化合物开环反应合成β-羟基硒醚

 研究了在室温下ZnCl2催化硒酚对环氧化合物开环反应合成β-羟基硒醚. 通过这一简单、有效和原子经济性的反应,高收率和高选择性地合成了几种β-羟基硒醚. 从环氧化合物3-邻甲苯氧基-1,2-环氧丙烷出发,经一锅三步反应,合成了相应的1,3-恶唑-2-酮.     

~(13)C NMR法研究环氧戊烯醛的热异构化

本文利用~(13)C NMR方法研究顺式环氧戊烯醛(1)的热异构化。测定了1在受热前后的~(13)CNMR谱,标识了它和它的热异构化产物的~(13)C NMR谱线;通过对异构化过程的动力学考察,表明1的热转化遵从一级反应规律,分别求出了80,100,120和140℃下的反应速度常数,并估算了活化能;同时也监测了异构化产物的变化过程。     

溴化锌-季(鎓)三溴盐催化二氧化碳和环氧化合物偶联反应

研究了溴化锌-季鎓三溴盐催化二氧化碳和环氧化合物偶联反应,考察了反应温度、压力和不同金属盐对反应的影响以及催化剂的循环使用性能.结果表明,在413 K和1.0 MPa条件下,以溴化锌为催化剂,苯基三甲基三溴化铵为共催化剂,无需加入任何溶剂就可以使二氧化碳和环氧化合物发生偶联反应,并以很高的收率得到环碳酸酯.     

A palladium-catalyzed synthetic approach to new Huperzine A analogues modified at the pyridone ring

The synthesis of two new Huperzine A analogues is reported. Both products present an amino substituted benzo-fused system in place of the pyridone ring of the natural alkaloid. The synthetic strategy to the two analogues is based on three different key palladium-catalyzed steps, namely a carbonylation reaction, an epoxide isomerization and a bicycloannulation reaction.