多乙烯基硅油改性丙烯酸酯乳液的合成及性能

以自制阳离子型乳化剂H、多乙烯基硅油和丙烯酸类单体为主要原料,采用一步法和半连续种子乳液聚合法合成有机硅改性丙烯酸酯乳液。研究了不同聚合方法、不同有机硅含量对硅丙乳液乳胶膜的吸水率、疏水性能的影响,通过纳米粒度-Zeta电位分析仪、接触角仪、红外光谱、透射电镜对乳液及聚合物结构进行了表征。结果表明有机硅单体参与了聚合,乳液稳定性好、平均粒径小。采用半连续种子乳液聚合法合成乳液,有机硅最大添加量为40%(占壳层单体总量),乳胶膜的吸水率只有3.2%,对水的接触角达到105.2o。     

含氟丙烯酸酯-苯乙烯共聚物的制备及其表面性能的研究

研究了聚合工艺、含氟丙烯酸酯类单体种类和用量、苯乙烯和自由基引发剂用量及硅烷偶联剂、催化剂等因素对含氟丙烯酸酯-乙烯共聚物表面性能的影响。结果表明：聚合工艺、含氟丙烯酸酯类单体种类和用量对共聚物表面的憎水性能有显著的影响;采用延时滴加含氟丙烯酸酯类单体可提高共聚物膜表面的憎水性;随含氟丙烯酸酯类单体侧链含氟烷基的链长和氟原子数及含氟单体用量的增加,共聚物水接触角增大,吸水率下降;共聚物薄膜的硬度则与含氟丙烯酸酯类单体中α-取代基、侧链含氟烷基的链长和用量、苯乙烯用量、引发剂浓度等相关;硅烷偶联剂和催化交联剂的加入可提高共聚物薄膜的强度。     

含短碳氟链聚合物处理的织物表面疏水/疏油-亲水转换特性的研究

采用半连续加入乳液聚合的方法合成了含不同长度氟碳链的丙烯酸酯-丙烯酸共聚物。通过傅里叶变换红外光谱(FT-IR)和热重分析(TGA)对聚合物的组成、热稳定性等性质进行了表征,详细考察了不同氟碳链对聚合物性质的影响。经聚合物乳液整理后织物的水接触角和二碘甲烷接触角显示出织物表面具有良好的疏水疏油性,与长氟烷基链聚合物相比有相同的特性;此外,接触角、荧光显微镜以及元素面分布结果表明,整理后的织物具有疏水/疏油-亲水性转换功能,这对于织物的抗污及清洗具有良好的作用。     

含氟硅丙烯酸酯乳液超疏水膜中疏水基团的梯度分布与表面微观结构研究

利用含氟疏水基团的梯度分布,结合草莓形纳米SiO2粒子提供的双重粗糙表面,制备了具有类"荷叶效应"的超疏水涂膜,水接触角达(174.2±2)°,滞后角几乎接近0°.通过原子力显微镜、扫描电镜和水接触角的测试对膜表面形貌及疏水性能进行了表征;探讨了其表面微观结构与表面疏水性能的关系.草莓形复合粒子在膜表面的无规则排列赋予涂膜表面不同等级的粗糙度,使水滴与涂膜表面接触时能够形成高的空气捕捉率,这种微观结构与疏水基团的梯度分布相结合,赋予了含氟硅丙烯酸酯乳液涂膜表面超疏水性能.     

直链型与支链型疏水缔合水凝胶的机械性能与溶胀行为

以丙烯酰胺(AM)为亲水单体,脂肪醇聚氧乙烯醚丙烯酸酯(AEO-AC-n-m,n为疏水端烷基链碳的数目,m为亲水端PEG链的长度,n,m=13,5;10,5;13,10)为疏水单体,十二烷基硫酸钠(SDS)为表面活性剂,过硫酸钾(KPS)为引发剂,通过胶束聚合制备了3种聚丙烯酰胺-co-脂肪醇聚氧乙烯醚丙烯酸酯(AM-co-AEO-AC)疏水缔合水凝胶.以疏水烷基链为直链的疏水单体AEO-AC-13-5合成的直链型水凝胶的网络结构均匀且强度高,其形态在水中可维持180 d.而以疏水烷基链为支链的疏水单体AEO-AC-10-5与AEO-AC-13-10合成的支链型水凝胶的机械性能较弱,60 d内即溶解于水中.在相同条件下,直链型水凝胶断裂时的最大应力是支链型水凝胶的4~5倍.利用弹性橡胶理论中的新胡克方程计算了直链型和支链型水凝胶的有效交联密度ν0和有效交联点间的分子量Mc.     

一种含氟丙烯酸树脂的制备及其表面疏水性

在聚合反应的后期阶段,向体系中引入含氟丙烯酸酯单体全氟辛基-(N-乙基-N-丙烯酸乙酯基)磺酰胺(QG-F814)共聚改性的方法制备了一种含氟丙烯酸树脂.接触角测定表明,该树脂具有良好的疏水性能.热重分析表明,该树脂在改性前后的耐热稳定性差别不大.     

含氟丙烯酸酯共聚物表面性能的稳定化研究

为提高传统含氟丙烯酸酯乳胶膜表面性能的稳定性,以γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷(MPS)作为可交联单体,采用细乳液聚合法合成了MPS改性的含氟丙烯酸酯共聚物,利用DLS、TEM、IR对聚合物进行表征,研究了MPS对合成乳液的稳定性、涂膜性能和膜表面接触角稳定性的影响。结果表明,细乳液聚合法适合用于对水敏感单体的聚合,合成的纯丙烯酸酯乳胶为球形结构,平均粒径为92 nm,而氟丙乳胶和含3%MPS的含硅氟丙乳胶形成了典型的核壳结构,平均粒径分别增大至107 nm和103 nm,含硅氟丙聚合物中存在Si-O-Si的交联结构。涂膜性能测试表明,MPS的引入增加了共聚物膜的硬度、耐溶剂性和耐水性。接触角测试表明,随MPS用量的增加,乳胶膜对水的初始接触角和动态接触角随时间的降低值均呈先增大后减小的趋势,共聚体系中加入适量MPS,通过含氟链段与MPS链段的协同作用,可显著提高涂膜表面性能的稳定性。     

新型含氟环氧单体的合成及其性能的初步研究

由六氟环氧丙烷二聚体、三聚体分别与4-环己烯-1,2-二甲醇反应合成了2种新型的双全氟烷氧基取代的环氧环己烷衍生物（EFPO1和EFPO2）,其结构经FT-IR和1H NMR确证。 与常见全氟烷基型功能单体不同,此类含氟环氧化合物与环氧树脂预聚物具有良好的相容性并且可改善其疏水性能。 初步考察了上述单体对环氧树脂紫外光固化涂料的改性作用,结果表明,随涂料中含氟单体用量的增加,固化膜的初始水接触角线性增大;其中,EFPO2因其含较长的全氟烷氧基团而具有比EFPO1更好的疏水效果。 如加入1%ＥＦＰＯ２时,固化膜接触角为99°,比未添加含氟单体的固化膜大14°,而相同含量ＥＦＰＯ１固化膜接触角为87°。 当ＥＦＰＯ２含量为5%时,固化膜的疏水性能进一步提高,接触角为113°。 此外,固化膜经加热处理（110 ℃,6 h）后疏水性能明显增强,如ＥＦＰＯ２含量为1%～5%时,固化膜经热处理后,接触角由99°~113°提高至113°~118°,ＥＦＰＯ１固化膜经热处理后接触角也由87°~100°提高至99°~110°。 固化膜疏水性能的提高可能是由于经过加热处理,含氟链段向表面迁移。 由此可见,这类含氟单体可作为表面改性剂应用于涂料、油墨和离型材料。     

腰果酚型聚苯并噁嗪基超疏水涂层的制备及其性能

首先合成了腰果酚型苯并噁嗪单体(C-a),然后采用旋涂和热固化的方法制备了腰果酚型聚苯并噁嗪/SiO_2(PC-a/SiO_2)超疏水涂层。通过傅里叶红外光谱(FT-IR)及核磁共振(NMR)等测试手段对单体结构进行了表征,并对PC-a/SiO_2涂层的超疏水性能进行了研究。结果表明,通过调控SiO_2纳米粒子的掺杂量,可制备水接触角为(166±4)°,滚动角为6°的"荷叶效应"型超疏水涂层和水接触角为(151±3)°的"玫瑰花效应"型超疏水涂层。该PC-a/SiO_2超疏水涂层具有良好的热稳定性和抗紫外性能。     

水热法制备铝合金超疏水表面及电化学性能研究

在金属表面构建超疏水膜层是一种有效的防腐技术,本文采用水热处理和自组装技术在铝合金表面构建了超疏水膜层来提升铝合金的耐蚀性能. 通过对不同水热时间下制备的铝合金超疏水表面的电化学性能以及表面形貌进行测试分析,发现当水热反应时间为6 h时,制备的超疏水铝合金超疏水性和电化学性能达到最佳,接触角能达到155.5^o,在模拟海水溶液中保护效率能达到99.6%.     

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.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

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.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.