聚碳酸酯的绿色合成工艺研究进展

综述了采用环境友好方法合成聚碳酸酯的工艺,并与光气法进行了对比分析.新方法以二氧化碳为原料,通过系列反应可以依次制得碳酸乙烯酯(EC)、碳酸二甲酯(DMC)、碳酸二苯酯(DPC),最后得到高纯度、高性能的聚碳酸酯(PC).其中,在得到的碳酸酯系列产品中,EC的收率为98%,选择性为100%;DMC的收率和选择性均可达到99.5%;DPC在出料口流出液中的含量可达92.6%,选择性为98%.     

氧化羰化法直接合成双酚A型聚碳酸酯

使用Pd系氧化还原催化体系氧化羰化双酚A和CO直接合成了聚碳酸酯。在PdCl20．016mmol,n(Pd)：n(Cu)：n(对苯醌)：n(四丁基溴化铵)=1：4：40：40,双酚A22mmol,CH2Cl250mL。4A分子筛4g,CO5．5MPa,O2O．5MPa,反应温度100℃,搅拌速度800rpm的条件下反应12h,得到的聚碳酸酯重均分子量M。为2450。探索了杂多酸和杂多酸的四丁基铵盐对氧化羰化双酚A直接合成聚碳酸酯的促进作用。使用Pd-Mn-(TBA)8SiW12O42啦催化剂体系,在上述相同的实验条件下反应8h,得到的聚碳酸酯重均分子量Mw为2225,好于Pd-Cu-苯醌催化体系的结果(Mw=1720)。对合成得到的聚碳酸酯进行了IR光谱分析,并通过与相同条件下得到的商品聚碳酸酯(Mw=22000)的IR光谱对照,对实验结果进行了确认。     

咔唑-磷酸酯阻燃剂的合成及阻燃聚碳酸酯应用

聚碳酸酯作为一种重要的有机高分子材料,被广泛应用于汽车装饰、电子电器和生活日用品生产中,由于聚碳酸酯自身阻燃性能级别低,因此在实际应用中必须进行阻燃处理。本文针对聚碳酸酯的阻燃需求,设计合成了结构新颖的咔唑-磷酸酯阻燃剂,测试结果显示该阻燃剂具有良好的阻燃性能,能够作为聚碳酸酯阻燃材料使用。     

二氧化碳与环氧化合物直接制备聚碳酸酯

综述了近几年来发展的用于二氧化碳与环氧化合物直接催化合成聚碳酸酯的各类催化剂,并详细讨论了其催化反应机理.利用二氧化碳与环氧化合物来合成聚碳酸酯,对于高分子合成化学、碳资源利用和环境保护都具有重大意义.它是发展聚碳酸酯生产的一个具有很大潜力的方面.     

二氧化碳与环氧化物的共聚反应

自1969年Inoue用ZnEt₂/H₂O的混合物作催化剂由二氧化碳与环氧化物合成聚碳酸酯以来，化学家们在催化剂体系的设计与合成方面进行了大量研究。目前，这条合成聚碳酸酯的绿色合成路线已日渐成熟。本文综述了近5年来环氧化物与二氧化碳反应合成聚碳酸酯的研究成果，主要考察催化剂的催化活性对共聚反应的影响以及反应机理研究。     

20世纪中国聚碳酸酯的发展(1949—2000)

聚碳酸酯是一种工程塑料,具有优良的综合性能。新中国成立以来,聚碳酸酯被广泛用于电气、机械、航空、汽车、仪表等领域,对国防、经济建设以及尖端技术产生重大影响。考察了20世纪我国聚碳酸酯的发展历程并将其分为3阶段：第一阶段是1949—1970年,参考国外成果进行试制,自主建立起百吨至千吨级生产装置,解决聚碳酸酯从无到有的问题;第二阶段是1970—1978年,自主开展聚碳酸酯质量与技术攻关会战,解决产品质量不佳与技术改造升级的问题;第三阶段是1978—2000年,自主开展新技术开发并扩大产能,加快核心生产技术突破与产业规模化的问题。根据考察结果从工业化和技术、技术创新以及化学史和化学教育角度做了讨论。     

脂肪族聚碳酸酯共聚物的研究进展

脂肪族聚碳酸酯共聚物是一类可完全生物降解的新型材料,自1969年井上祥平等首次通过二氧化碳与环氧化合物反应合成脂肪族聚碳酸酯以来,人们在将二氧化碳固定为全降解聚合物这一研究领域取得了大量研究成果.本文综述了用于二氧化碳和环氧化合物共聚合成脂肪族聚碳酸酯的各类催化剂及反应机理,讨论了脂肪族聚碳酸酯结构/性能关系,并简要介绍了其在不同领域的应用.     

CO2与环氧化合物聚合反应的金属卟啉催化体系研究

作为金属卟啉催化作用的新研究领域,金属卟啉作为催化剂催化CO2与环氧化合物合成具有生物降解性能的聚碳酸酯,具有良好的应用前景,在碳资源利用、环境保护和高分子合成化学方面具有重大意义.自从1978年Inoue首次采用金属卟啉催化剂由CO2与环氧化物合成聚碳酸酯以来,化学家们在金属卟啉催化剂体系的设计与合成方面进行了大量研究.在此基础上,本文对金属卟啉作为催化剂应用于CO2与各种环氧化合物的聚合反应、偶联反应及其反应机理研究加以综述;并展望了其应用前景.     

脂肪族聚碳酸酯及其在医学中的应用

脂肪族聚碳酸酯具有优良的生物降解性、生物相容性和可功能化性等特点,近十几年来在生物医学领域得到了迅速发展。结合本实验室对生物可降解脂肪族聚碳酸酯的研究工作以及国内外研究现状,根据高分子链的几何形状对脂肪族聚碳酸酯进行了分类介绍,综述了它们的合成方法及其在生物医学领域中的应用,同时展望了脂肪族聚碳酸酯的未来发展趋势。     

新型芳香型超支化聚酯的合成与应用研究

以酯 3,5－二羟基苯甲酸（DBA）为原料,通过酯化反应及酯化产物与氯乙醇的反应合成了单体酯 3,5－二羟乙氧基苯甲酸丙酯（PDEB）;通过PDEB的熔融缩聚,合成了具有芳脂型结构的超支化合物PPDEB,并对其进行了表征;研究了PPDEB对聚碳酸酯（PC）的流变改性作用。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.