PLA大分子单体接枝NVP共聚物的合成与性能

制备了末端为双键的功能化聚乳酸大分子单体(PLA-HEMA),并以此大分子单体与N-乙烯基吡咯烷酮(NVP)进行自由基溶液共聚,合成了具有亲水性PVP-PHEMA主链和疏水性PLA支链的接枝共聚物。用FT-IR1、H-NMR、GPC、DSC、表面接触角测定研究了共聚物的结构与性能。结果表明:共聚物为非晶聚合物;NVP的摩尔投料量对共聚物的性能有显著影响,随NVP投料量增大,共聚物的分子量有所下降,玻璃化转变温度(Tg)增大;由于亲水性PVP和PHEMA链段的引入,共聚物的亲水性优于相应的线型聚乳酸材料。     

聚苯乙烯大分子单体与醋酸乙烯酯接枝共聚物的合成及表征

<正> 用大分子单体与小分子单体共聚是七十年代初才出现的合成接枝共聚物的一种新方法。通过共聚合反应而不是接枝反应同时形成主干及支链。这种接枝共聚物由于形成支链的大分子单体是预先合成的,其分子量分布较窄,又可调节控制,所以合成的接枝共聚物支链长短比较均一,副反应较少,链结构比较明确,因此也易于表征。     

亲水梳状环氧聚合物载体柔性固定化脂肪酶

以氯乙酰化聚苯乙烯微球载体为大分子引发剂,以甲基丙烯酸缩水甘油酯和亲水性丙烯酰胺为共聚接枝单体,以氯化亚铜及2,2'-联吡啶为催化体系,采用原子转移自由基聚合法接枝合成了具有柔性链的亲水梳状环氧聚合物载体PS-acyl-P(AM-co-GMA),并将其用于耐有机溶剂YCJ01脂肪酶的共价柔性固定化.结果表明,固定化酶催...     

以聚苯乙烯为把的聚四氢呋喃(PTHF)梳型聚合物的制备

高分子的自组装已成为当今高分子科学的热门研究课题之一[1] .开展该研究工作 ,首先要获得特定结构的聚合物 .我们设计合成如图 1所示的梳型聚合物 ,调节制备Ａ ,Ｂ ,Ｃ三链段所用的单体和它们的聚合度等参数 ,并进一步进行自组装研究 .若Ａ段是结晶聚合物 ,且熔融温度低于Ｃ段的玻璃化转变温度 ,则在定型储能材料等方面具有应用前景 .合成梳型嵌段聚合物有三个方法 ,即发散 (Ｇｒａｆｔｆｒｏｍ) ,收敛 (Ｇｒａｆｔｔｏ)和大分子方法 .采用大分子技术 ,每个梳型链长及支化密度可控 ,一直是人们青睐的方法[2 ] .一般采用与普通烯类单体共聚…     

用NMR分析可生物降解的两亲性嵌段共聚物的相对分子质量和组成

凝胶渗透色谱(GPC)法是根据聚合物分子链流体力学体积大小的比较来测定聚合物相对分子质量(以下简称分子量)的,测得的聚合物分子量与聚合物分子链在溶剂中的构象有关[1]。两亲性嵌段共聚物分子链中亲水链段和亲油链段的极性差异很大,几乎在任何溶剂中它们的构象都不相同,因此可     

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…     

RAFT法合成两亲性嵌段共聚物PSt-b-PAA-b-PSt及其在离子液体[BMIM][PF_6]中的自组装

用三硫代碳酸二(α,α′-二甲基-α-乙酸)酯(BDATC)作为链转移剂,苯乙烯St作为第一单体,通过可逆加成-断裂链转移聚合(RAFT)方法合成出大分子链转移剂PSt-CTA,以丙烯酸AA作为第二共聚单体合成出3个不同嵌段比的两亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸-b-聚苯乙烯(PSt-b-PAA-b-PSt).通过傅里叶变换红外光谱(FTIR)和核磁共振氢谱(1H-NMR)确定了PSt-b-PAA-b-PSt结构,使用凝胶渗透色谱(GPC)测定了大分子引发剂PSt-CTA和嵌段共聚物PSt-b-PAA-b-PSt的分子量及分子量分布.将这3个不同嵌段比的两亲性嵌段共聚物在离子液体1-丁基-3-甲基咪唑六氟磷酸盐[BMIM][PF6]中进行自组装,用透射电子显微镜(TEM)观察聚合物在离子液体中自组装结构.研究发现,当PSt的链段长度固定时,胶束的自组装形态主要依赖于PAA链的长度.当PAA链段较长时,胶束呈球形;PAA链段变得较短时,胶束的形态则由球形转变为核壳结构,并且胶束形态在25℃至100℃之间不受温度影响.     

对-氯甲基苯乙烯共聚物引发合成接枝共聚物

接枝共聚物含有性质差别很大的主链和支链,具有许多特殊的性质,因而一直是人们感兴趣的研究课题之一^[1～5].原子转移自由基聚合(ATRP)^[6,7]的问世,为接枝共聚物的合成提供了一条新的途径.本文用对-氯甲基苯乙烯和其它乙烯基单体自由基共聚.     

β-蒎烯嵌段、接枝共聚物的合成

分别使用苯乙烯 HCl加成物 (a)和 2 氯乙基乙烯基醚 HCl加成物 (b)作为引发剂 ,TiCl4 Ti(OiPr) 4(3∶1mol mol)为活化剂 ,在nBu4NCl存在下 ,- 40℃、CH2 Cl2 中 ,通过顺序活性阳离子聚合 ,合成了 β 蒎烯与苯乙烯、对甲基苯乙烯的嵌段共聚物 .又用带丙烯酰氧功能基的引发剂c [CH3CH (OCH2 CH2 X )Cl,X =OCOC(CH3)CH2 ]引发 β 蒎烯活性阳离子聚合 ,合成了 β 蒎烯大分子单体 .该大分子单体在AIBN引发下与甲基丙烯酸甲酯进行自由基共聚 ,获得主链为聚甲基丙烯酸甲酯、侧链为聚 β 蒎烯的接枝共聚物     

β-蒎烯嵌段、接枝共聚物的合成

分别使用苯乙烯 HCl加成物 (a)和 2 氯乙基乙烯基醚 HCl加成物 (b)作为引发剂 ,TiCl4 Ti(OiPr) 4(3∶1mol mol)为活化剂 ,在nBu4NCl存在下 ,- 40℃、CH2 Cl2 中 ,通过顺序活性阳离子聚合 ,合成了 β 蒎烯与苯乙烯、对甲基苯乙烯的嵌段共聚物 .又用带丙烯酰氧功能基的引发剂c [CH3CH (OCH2 CH2 X )Cl,X =OCOC(CH3)CH2 ]引发 β 蒎烯活性阳离子聚合 ,合成了 β 蒎烯大分子单体 .该大分子单体在AIBN引发下与甲基丙烯酸甲酯进行自由基共聚 ,获得主链为聚甲基丙烯酸甲酯、侧链为聚 β 蒎烯的接枝共聚物     

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%.     

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.     

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.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

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.