RAFT聚合法合成PDMAEMA-b-PAAAB嵌段共聚物的研究

以甲基丙烯酸二甲氨基乙酯(DMAEMA)为单体、二硫代苯甲酸异丙苯酯(CDB)为链转移剂、偶氮二异丁腈(AIBN)为引发剂,利用RAFT聚合法合成了聚甲基丙烯酸二甲氨基乙酯(PDMAEMA)。以所得PDMAEMA为大分子链转移剂,丙烯酰胺基偶氮苯(AAAB)为单体,AIBN为引发剂,采用RAFT聚合法合成了PDMAEMA-b-PAAAB共聚物,并考察了AAAB的RAFT聚合反应动力学,利用FT-IR、1 H-NMR、GPC和TG对聚合物的结构和热性能进行了表征。结果表明,PDMAEMA的分子量随聚合反应时间的增加而增加,且分子量分布较窄;PDMAEMA-b-PAAAB嵌段共聚物的分子量随着AAAB单体转化率的升高而线性增加,且分子量分布较窄(PDI1.3),聚合反应动力学曲线呈良好的线性关系,且具有较好的热稳定性。     

聚合方法对一种正离子聚丙烯酰胺结构与性能的影响

对相同进料比下,以过硫酸胺/亚硫酸氢钠为氧化还原引发剂,分别用溶液法和反相微乳液法合成的丙烯酰胺(AM)与2-甲基丙烯酰氧乙基三甲基氯化胺(MADQUAT)的共聚物P(AM-MADQUAT),根据单体竞聚率计算了两种共聚物的序列分布和组成分布.考察了两种聚合物结构对高岭土絮体尺寸、zeta电位降以及絮体压缩屈服应力的影响,初步建立了不同聚合方法合成的阳离子聚丙烯酰胺结构与絮凝性能之间的相关性.     

聚苯乙烯-甲基丙烯酸甲酯接枝共聚物的合成和表征

<正> 聚苯乙烯(PS)和聚甲基丙烯酸甲酯(PMMA)都是研究得十分深入的聚合物。它们的接枝共聚物,虽然在基础研究中是十分有兴趣的对象,但因传统的合成方法不能得到结构确定的产物,同时难于与伴生的均聚物分离,进展不大。近年来随着大分子单体方法和极性单体活性阴离子聚合的发展,具有确定结构的接枝共聚物PS-g-PMMA的合成逐步成为可能。例如:Ishizu采用阴离子聚合合成带乙烯基的PMMA大分子单体,再与苯乙烯自由基共聚的路线,Ballegoole等和Watanable分别采用主干接枝法,即用自     

以聚乙二醇-b-聚四乙烯基吡啶为模板制备聚联苯胺微/纳米颗粒及其电容特性

以两亲性嵌段共聚物聚乙二醇-b-聚四乙烯基吡啶(PEO-b-P4VP)为模板制备聚联苯胺微/纳米颗粒,调节模板剂胶束溶液pH,得到了一系列形貌和尺寸可控的聚联苯胺微/纳米颗粒。利用红外光谱、核磁共振、透射电镜、循环伏安、恒电流放电、交流阻抗等测试对材料的结构和性能进行了表征。模板法合成的聚联苯胺为平均直径小于200nm的亚微米至纳米级棒状颗粒,其直径随着模板剂胶束溶液pH的降低而增加。所得聚联苯胺颗粒均显示了一定的电化学活性,当电流密度为1A/g时,聚联苯胺的比电容量达到306.3F/g,经过长时间的充放电测试,不同条件下合成的聚联苯胺的容量衰减率均很小,表现出良好的循环稳定性且各样品电化学性能呈现出随着直径的减小而增强的趋势。     

苯胺共聚物/环氧共混体系防腐蚀行为的研究

以苯胺与邻甲氧基苯胺为单体,采用水溶液化学氧化聚合法合成了聚苯胺、苯胺共聚物及聚邻甲氧基苯胺,并对其性能与结构进行了测试、表征.实验表明:随着邻甲氧基苯胺含量的增加,聚合物的溶解性能有明显的改善,其氧化程度随之降低;以上三种聚合物均对马口铁表现出良好的防腐蚀性,其防腐蚀能力随氧化程度降低而降低;苯胺共聚物/环氧混合体系对马口铁也表现出优异的抗腐蚀性.     

水分散体系中甲基丙烯酸甲酯和丙烯酸八氟戊酯嵌段共聚物的合成与表征

在聚合物链上引入氟元素可以赋予聚合物很多优异的性能 ,如良好的热稳定性、化学稳定性、生物相容性和憎水憎油性等 .含氟单体与一般单体共聚是合成含氟共聚物的重要途径 .通过原子转移自由基聚合 (ATRP)不仅可以实现多种单体的控制 (共 )聚合 ,而且可以合成出具有预定分子量、窄分子量分布以及结构明晰聚合物[1] ,我们曾报道了溶液体系中用ATRP方法合成含氟嵌段共聚物[2～ 4] .众所周知 ,大多数含氟聚合物都是通过乳液或悬浮聚合反应合成的 .然而 ,普通的乳液或悬浮聚合难以合成结构和组成可控的聚合物 ,如嵌段共聚物 ,所以近年来 ,水…     

苯胺与邻甲氧基苯胺共聚的原位紫外-可见光谱电化学研究

运用循环伏安法(CV)和原位紫外-可见光谱电化学法研究了苯胺(AN)和邻甲氧基苯胺(OMA)单独聚合及二者共聚的电化学过程。在1.0 mol/L HCl溶液中,AN和OMA单独聚合及二者共聚时不同的电化学行为表明AN和OMA之间产生了共聚作用。原位紫外-可见光谱的研究表明,在AN与OMA的共聚过程中,AN和OMA首先分别被氧化生成其阳离子自由基,然后,AN和OMA的阳离子自由基与溶液中的AN和OMA单体发生交互反应产生混合二聚物中间体,在紫外-可见吸收光谱中对应于440 nm处的吸收峰。进一步研究发现,AN和OMA的共聚过程与溶液中各单体的浓度比有关,当混合溶液中OMA的浓度较大时,会对共聚产生抑制作用。采用红外光谱技术对共聚物进行了表征并初步探讨了共聚机制。结果表明,在AN和OMA共聚过程中,OMA分子掺杂进入AN聚合物骨架。     

两亲性树枝状嵌段共聚物刷的合成与构象研究

近期研究发现两亲性嵌段共聚物刷能引发“有序自发乳化”,一步法制备有序多孔光晶微球.上述研究主要基于侧链为线形聚合物的嵌段共聚物刷,而侧链拓扑结构变化对乳液受限自组装的影响尚不明确.本工作中设计合成了亲水和疏水的降冰片烯基楔形单体,并通过顺序开环易位聚合(ROMP)成功合成了一类两亲性树枝状嵌段共聚物刷.通过核磁氢谱(¹H-NMR)清晰表征了产物的化学结构,凝胶渗透色谱(GPC)表明共聚物的分子量呈较窄的单峰分布,聚合反应过程具有较好的可控性.通过改变单体和催化剂的比例获得不同分子量的共聚物刷,利用凝胶渗透色谱联用光散射(GPC-MALS)研究了侧链结构对聚合物溶液构象的影响,结果显示一代树枝状共聚物刷表现为无规线团构象,而二代产物则呈现棒状构象,单个聚合物链的原子力(AFM)表征证实了上述结果.     

一种新型温度响应性聚氨基酸/聚类肽嵌段共聚物的合成与表征

以正己胺为引发剂, 通过γ-炔丙基-L-谷氨酸羧酸酐(PLG-NCA)和N-正辛基甘氨酸羧酸酐(Oct-NNCA)逐步开环聚合和后修饰策略合成了分子量分布较窄的温度响应性两嵌段共聚物寡聚乙二醇单元修饰的聚(γ-炔丙基-L-谷氨酸)-b-聚(N-正辛基甘氨酸)[(PPLG-g-EG₃)-b-PNOG]. 通过示差扫描量热法(DSC)研究了不同比例聚合物的结晶行为; 利用圆二色谱法(CD)研究了聚合物的二级结构, 并研究了聚合物在水溶液中的自组装行为, 采用透射电子显微镜(TEM)观察了组装后的形貌. 结果表明, 该温度响应性聚合物在室温下呈现α-螺旋结构, 随着温度升高, α-螺旋的构象减少. 该聚合物可以在水溶液中自发组装成棒状结构.     

丙烯腈可控/"活性"自由基聚合研究进展

可控/"活性"自由基聚合能有效控制聚合物的分子量及其分布,并且能调控其微观拓扑结构。聚丙烯腈及其共聚物具有良好的成纤成膜性能,是一类应用十分广泛的聚合物。本文综述了可控/"活性"自由基聚合法合成聚丙烯腈及其共聚物的研究现状与进展,从氮氧自由基法(NMP)、引发转移终止剂法(iniferter)、原子转移自由基聚合(ATRP)和可逆加成-断裂链转移(RAFT)聚合等方面对丙烯腈均聚物和共聚物的合成研究作了全面的总结,提出了存在的问题,并且对今后的研究方向作了展望。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.