聚合物光接枝表面改性研究与应用

主要考察了近年来利用紫外光（ＵＶ）对聚合物进行表面接枝改性研究与应用的最新进展情况，从接枝实验体系与条件、接枝影响因素以及聚合物表面接枝改性的应用等几个方面对其进行了总结和介绍。     

PP熔融接枝改性研究进展

聚丙烯作为一种非极性聚合物,其亲水性、染色性、粘结性及与其它极性聚合物和无机填料的相容性都很差,这大大限制了它的应用。因此,往往采用官能化的方法赋予聚丙烯以极性、反应活性和功能性。通过熔融接枝的方法,在聚丙烯链段上接枝极性单体,可以显著提高聚丙烯的极性,改善表面亲水性及染色性等。本文简要介绍了聚丙烯熔融接枝改性及其影响因素,并按接枝单体分类,综述了熔融接枝聚丙烯的研究进展、性能与应用,展望了其发展趋势。     

PP固相接枝改性研究进展

聚丙烯(PP)是一种具有优异性能且价格低廉的通用高分子材料,但由于聚丙烯为非极性聚合物,其染色性、亲水性、粘结性等均较差,且与其它材料的相容性也很差,这些缺点限制了聚丙烯的应用。通过固相接枝法改性聚丙烯,不仅可以在保持聚丙烯原有优异性能的情况下引入极性官能团,而且具有低温、低压、低成本、较高的接枝率和无需溶剂回收等优点。本文简要介绍了PP固相接枝反应机理,从接枝单体角度综述了近几年PP固相接枝改性的研究进展,并讨论了反应工艺对接枝产物的接枝率、接枝效率和性能的影响。     

氯化原位接枝过程与聚合物高性能化

氯化原位接枝过程是一种基于自由基反应的改性聚合物新方法,经该方法改性的聚合物性能显著改变,充分展现了弱影响、强响应的特征。本文简述了氯化原位接枝反应过程、机理,剖析了氯化原位接枝产物的结构特征,并对各类接枝共聚产物结构与性能关系进行了归纳和总结。详细介绍了各类接枝产物的不同用途,例如用于热塑性弹性体、木板粘合剂、增韧改性剂、成膜涂料等。最后对氯化原位接枝过程更广泛的应用及今后的发展趋势进行了展望。     

等离子体辐照的聚乙烯表面接枝交联共聚合

聚合物利用低温等离子体预辐照进行表面接枝共聚合已有报道.此方法的优点是接枝层被限制在聚合物表面,辐照过程对基材本体性质无影响,且整个过程对环境无污染. 用等离子体使聚合物表面产生自由基,不需要表面具有不饱和键或特殊官能团,因而适用于任何聚合物,甚至于一些无机物如玻璃等.利用等离子辐照后暴露于空气的聚合物表面上生成的过氧自由基或过氧化物进行接枝反应,一般接枝量不大.本工作中,我们自己设计了反应器,以超高分子量聚乙烯(UHMWPE)为基材,以甲基丙烯酸甲酯(MMA)为接枝单体,在无氧条件下利用等离子体辐照产生的表面自由基进行了接枝聚合,产物接枝量高达10％.还用顺磁共振技术对表面自由基性质及其在接枝过程中的行为进行了跟踪研究.     

表面引发接枝聚合法制备高接枝度的接枝微粒SiO2-g-PMAA

将偶联剂γ-氨丙基三甲氧基硅烷(AMPS)键合在硅胶微粒表面,得到改性微粒AMPS-SiO2;使改性微粒表面的氨基与溶液中的过硫酸铵构成氧化-还原引发体系,实现了甲基丙烯酸(MAA)在硅胶微粒的表面引发接枝聚合,制得了高接枝度(0.30 g/g)的接枝微粒SiO2-g-PMAA;研究了影响表面引发接枝聚合的主要因素。 结果表明,适宜的温度为40 ℃。 已接枝到硅胶表面的聚合物层对后续的接枝聚合产生阻隔作用。 适宜的引发剂用量为单体质量的1.1%,适宜的单体质量分数为5%左右。     

在超临界CO_2中进行的PP固相接枝改性研究进展

由于性价比高,聚丙烯(PP)成为增长最快的通用塑料,在汽车工业、家用电器和管材方面得到了广泛地应用。然而由于聚丙烯自身的非极性限制了其在某些领域的应用,向聚丙烯主链上接枝极性单体是改善其极性的有效方法。常用的接枝改性方法有:溶液接枝、熔融接枝、等离子体处理、表面可控活性聚合以及超临界CO2状态下接枝等。其中超临界CO2由于溶解单体能力强,对聚合物基体也有很好的溶胀能力,且阻燃性好、无毒以及价格相对低廉,克服了传统接枝方法存在的操作工艺复杂,溶剂不易回收等缺点,得到了广泛研究。本文从超临界CO2协助固相接枝改性机理、接枝单体的选择、影响过程的因素以及超临界CO2协助固相接枝的应用等方面出发,系统阐述了超临界CO2协助PP固相接枝改性近些年来的研究概况。     

阴离子聚合制备聚乙烯-g-聚氧化乙烯接枝共聚物

聚烯烃 (聚乙烯 ,聚丙烯等 )的化学改性一直是科学研究和实际生产的一个热点 ,改性过的聚烯烃可以广泛应用到高分子共混物和复合材料中 .在众多聚烯烃中 ,聚乙烯产量最大 ,但因其惰性也最难于化学改性 .我们采取的改性方法是在聚合物中引入反应性基团 ,可以在温和条件下进行有选择的而且高效的化学改性 .由于两亲性共聚物可用作乳液聚合和悬浮聚合中的表面活性剂及稳定剂 ,塑料的表面改良剂和聚合物的共混相容剂等[1,2 ] ,因此人们对该共聚物的研究越来越多 .过去 ,多数两亲性共聚物的研究局限于聚苯乙烯 (ＰＳ)和聚氧化乙烯 (ＰＥＯ)接枝共…     

表面接枝聚合物刷与仿生水润滑研究进展

动物关节的超低摩擦系数和长耐磨寿命主要归功于关节软骨表层以及关节滑液中呈“刷”型结构的生物大分子.人工仿制的表而接枝聚合物刷可以对关节润滑进行功能模拟,本文简要综述了近年来表面接枝聚合物刷的水润滑研究进展.重点讨论了不同类型聚合物刷(天然生物大分子、聚电解质刷、两性离子聚合物刷和中性聚合物刷等)的水润滑机理,最后讨论了目前仿生水润滑研究存在的问题以及未来的发展趋势及应用前景.     

等离子体引发HEMA的RAFT接枝聚合改性聚丙烯多孔膜

采用等离子体引发的可逆加成-断裂链转移(RAFT)接枝聚合法,以甲基丙烯酸羟乙酯(HEMA)为单体,对聚丙烯(PP)多孔膜表面作了亲水改性.研究了接枝聚合动力学,并以FT-IR、SEM、压汞、水通量等方法研究了改性膜的表面结构形态及孔结构.结果表明,等离子体引发的RAFT接枝聚合速率显著低于普通等离子体引发的接枝聚合速率.表面接枝率随着接枝聚合时间的延长呈线性增长趋势,同时改性膜的孔径和水通量随之减小.     

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.