新型有机硅聚合物冠醚的合成及其络合性能研究

通过双羟甲基 - 18-冠 - 6与烯丙基氯反应得到双烯丙氧甲基 - 18-冠 - 6,以之为原料 ,与不同量的含氢硅油加成制备出 5种新型有机硅聚合物冠醚 ,同时测试了它们对K+和Na+的络合容量。     

^29SiNMR测定含氢硅油中Si—H键含量

聚二甲基甲基氢化硅氧烷(简称含氢硅油)是一类反应性有机硅聚合物。这类聚合物中含有的si—H键十分活泼,其化学性质在有机硅工业中十分有用,如合成不同类型的硅油、有机硅树脂、硅橡胶、改性有机硅表面活性剂等。     

高含氢聚甲基硅氧烷改性聚丙烯酸酯乳液的结构与涂层性能

高含氢聚甲基硅氧烷改性聚丙烯酸酯乳液的结构与涂层性能;高含氢聚甲基硅氧烷; 改性聚丙烯酸酯乳液; 核壳型共聚乳胶; 涂层剂     

机械力化学法疏水改性高岭土

以含氢硅油为表面改性剂,用机械力化学法改性高岭土.研究了影响高岭土疏水改性效果的相关因素,并对改性后高岭土进行了IR,BET,TEM和接触角等表征.结果表明,含氢硅油改性剂的加入量对高岭土疏水性能影响很大,存在一个最佳值.当油料比为1:30时,改性高岭土粉体粒度较小,分散均匀,改性后高岭土对水的接触角可达155.98 °.此接触角数值远超过改性剂含氢硅油本身和水的接触角,对这一现象进行了深入讨论.     

不同厚度三倍频SiO2增透膜的设计、制备与改性

本文通过光学计算设计了具有不同厚度的三倍频增透膜。以氨水为催化剂、正硅酸乙酯(TEOS)为前驱体,通过溶胶-凝胶(Sol-Gel)技术制得SiO2溶胶;采用浸渍提拉法镀膜得到符合设计要求的三倍频增透膜。研究结果表明,增透膜的耐磨擦性能随着膜层厚度的增大而增大,本文制得的厚度达到200 nm以上的三倍频增透膜耐磨擦性能显著优于传统的1/4波长三倍频增透膜。此外,本文以甲基含氢硅油为膜表面修饰剂,提出一种全新的超快的表面疏水性改性的方法。经该方法处理后,增透膜由亲水膜转变为疏水膜,对水的接触角从23.4°增大至95°,增透膜的耐环境性显著提高。     

反应加工体系PVC/PHMS的转矩流变性能研究(Ⅰ)

含氢聚甲基硅氧烷;聚氯乙烯;反应加工体系PVC/PHMS的转矩流变性能研究(Ⅰ)     

含氢硅油表面接枝改性PET织物的拒水性能

通过接枝率、接触角、透水时间、拉伸应力应变、ＥＳＣＡ的测定以及不冲击实验研究了在ＤＣＰ和ＢＰ等存在下电晕放电引发含氢硅油接枝ＰＥＴ织物及其拒水性能,实验结果表明：电晕放电能有效引发含氢硅油在ＰＥＴ织物表面的接枝共聚反应,随电晕放电处理时间的延长,ＰＥＴ织物表面接枝率增大;接枝后ＰＥＴ织物拒水效果明显增强;电晕放电引发接枝改性后ＰＥＴ织物无损伤,力学性能基本保持不变。     

从含氢硅油制取水性氟硅聚合物

在无溶剂的条件下, 通过硅氢加成法将烯丙基聚氧乙烯聚氧丙烯醚, 氟化丙烯酸烷基酯接枝共聚到甲基含氢硅油侧链, 成功地合成了一系列有机氟硅聚合物. 通过高速剪切乳化法可制得不同质量投料比时的水性氟硅聚合物水分散物. 采用FTIR, ¹H NMR和TEM对有关产物和乳液进行了结构分析, 并进一步系统研究了水分散物表面张力, 流变性等性能, 结果表明: 质量分数为2.0%的水性氟硅聚合物水分散物的表面张力降低至22.00～26.00 N/m, 其黏度随着剪切速率的增大有剪切变稠现象发生, 且不同质量投料比时, 其粒子粒径大小及形状也有较大差别.     

含氢硅油-三氯化钌催化酰胺的还原反应研究

以原位形成的膦钌络合物为催化剂,研究了含氢硅油对酰胺的还原反应,考察了酰胺的结构、反应溶剂、配体等条件对催化反应的催化效率及产物结构的影响.仲胺基及伯胺的酰胺化合物被还原成相应的叔胺及仲胺;丙烯酰胺与含氢硅油反应时,选择性较差,得到丙烯腈、丙腈及与硅烷基相连的聚丙烯酰胺与聚丙烯腈.     

含氢聚甲基硅氧烷/丙烯酸丁酯/羟甲基丙烯酰胺复合乳液的制备方法对乳液性质的影响

采用自由基引发剂用３种不同的聚合方法制备了新型的含氢聚甲基硅氧烷（ＰＨＭＳ）／丙烯酸丁酯（ＢＡ）／羟甲基丙烯酰胺（ＮＭＡ）复合聚合物乳液。详细讨论了不同聚合方法对乳液稳定性和乳胶粒子的影响，同时对聚合反应的机理、产物的结构作了考察．结果表明：通过乳液聚合，得到了ＰＨＭＳ／ＢＡ／ＮＭＡ共聚物；单体乳液滴加法所得乳液粒径较小，乳液性能稳定，是制备ＰＨＭＳ／ＢＡ／ＮＭＡ复合聚合物乳液较适宜的方法．     

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.