固态后缩聚方法合成高分子量的含磷热致性液晶共聚酯

为了获得较高分子量的具有高阻燃性的热致性液晶高分子,通过固态聚合方法合成了一种基于对羟基苯甲酸、对苯二甲酸、乙二醇和含磷菲环取代二酚的高热稳定性、较低相转变温度和宽的液晶相转变温度范围的含磷液晶共聚酯(BDQTEP),并对该含磷液晶共聚酯预聚物(pre-BDQTE)在不同固态聚合条件下获得的聚合物热性能和液晶性进行了研究.对其固态反应速率控制进行了初步的探讨,当反应温度为235℃时,固态聚合反应较为理想.在聚合的初始阶段,共聚酯特性黏数[η]、黏流温度Tf和羧基浓度[COOH]均随聚合时间而明显变化,但在6 h后变化较小,几乎不变.通过固态后缩聚,将熔融聚合获得的特性黏数[η]=0.44 dL/g的含磷液晶共聚酯BDQTE的特性黏数提高了近两倍.     

固态缩聚尼龙66的熔化行为

固态缩聚尼龙６６的熔化行为沈百拴，张喜亮，李新法（郑州大学材料工程系郑州４５００５２）关键词尼龙６６，固态缩聚物，熔化行为，差示扫描量热注关于固态缩聚反应的研究国内外已有报道［１～４］，叵未见固态缩聚尼龙６６（ＳＳＰＰＡ６６）熔化行为的报道。本文用Ｄ...     

4,4′-二羟基二苯砜二钾盐与4,4′-二氯二苯砜的溶液缩聚

对4,4′-二羟基二苯砜二钾盐与4,4′-二氯二苯砜的溶液缩聚,进行了较系统的研究:选择了环丁砜为聚合介质,二甲苯作带水剂;研究了缩聚温度,时间及固含量的影响;讨论了单体配比及碱用量对双酚S配比变化对聚合物分子量的影响,在成盐时添加K_2CO_3可减少产物分子量的波动范围。讨论了影响聚芳砜在加工温度下的热稳定性的因素,并建议了控制后处理过程的方法,最后列出了全对位聚芳砜的主要性能。     

固态缩聚尼龙1010的熔化行为

本工作借助示差扫描量热法和X-射线衍射分析法(WAXD)首次研究了固态缩聚反应所得初生态尼龙1010的结晶特征和熔化行为。实验结果表明:固态缩聚反应的温度和时间以及产物分子量对初生态尼龙1010的熔化行为有着明显的影响。初生态尼龙1010结晶熔融双峰的显隐与其X-射线衍射峰特征没有明显的依赖关系,但随着尼龙大分子结晶的完善化而出现表观体积收缩观象。     

新型含硅聚芳醚酮的合成与表征

对FeBr3／Me6TREN催化的反向原子转移自由基聚合进行了研究。在不同的催化剂、引发剂的配比、聚合温度和配体用量等条件下，该催化体系催化的MMA聚合反应动力学为一级反应。聚合物分子量可控，分子量分布很窄，说明该体系催化的聚合反应为活性可控聚合，通过实验计算了反应的活化能，并利用UV光谱对催化剂进行了研究。     

Ziegler-Natta催化体系中影响聚丙烯分子量分布的因素研究进展

分子量分布是聚丙烯产品的一个重要参数,直接影响材料的使用和应用,关于聚丙烯分子量和分子量分布的控制和影响因素的研究对于工业界和学术研究都有十分重要的意义。本文主要从催化剂组成、聚合条件等方面对Ziegler-Natta催化体系中影响聚丙烯分子量分布的因素进行了详细的综述。在催化剂组成方面,主要讨论了内给电子体、外给电子体及给电子体复合技术对聚丙烯分子量分布的影响;在聚合条件方面,主要讨论了聚合时间、聚合温度、助催化剂、聚合工艺对聚丙烯分子量分布的影响。     

用反应挤出法制备尼龙6塑料

利用双螺杆挤出机进行了尼龙６阴离子开环聚合反应的研究，通过改变引发剂及活化剂的浓度、螺杆转速、机筒的温度分布以及螺杆元件构型的排布等，研究这些工艺参数对尼龙６反应挤出产物性能的影响。结果表明，反应挤出的尼龙６综合机械性能比水解缩聚法生产，且具有较高的性能价格比。     

丁二酸酐与SnCl2·2H2O共催化含水乳酸缩聚制备高分子量聚乳酸

用丁二酸酐与SnCl2.2H2O共催化含水乳酸本体缩聚,合成黏均分子量为6×104的聚乳酸.合成反应时间短,聚乳酸产率高、纯度好.单体为含水10%～15%的乳酸.聚合方法环境友好,不使用任何共沸溶剂.讨论了催化剂用量、反应温度、聚合时间等对聚合反应的影响,并用红外光谱和核磁共振光谱对合成的聚乳酸进行了表征.     

茂基二价钐配合物高效催化己内酯开环聚合

研究了二茂基二价钐配合物(C5H5)2Sm(THF)作为单组分催化剂催化己内脂开环聚合反应,考察了催化剂用量、聚合反应时间、聚合反应温度对己内酯聚合反应的影响。结果表明,配合物(C5H5)2Sm(THF)对己内酯聚合有极高的催化活性且产物的数均分子量较高,当催化剂与单体摩尔比为1：5000时,聚合产率仍可达50.3%,数均分子量可高达32.4万;温度升高,聚合反应的转化率增加,聚合产物数均分子量降低;催化剂用量增加,聚合转化率增加,聚合产物分子量降低;聚合产物的分子量分布较窄;通过凝胶色谱法对聚合产物的分子量及分子量分布进行了表征。     

甲基丙烯酸长链烷基酯的基团转移聚合研究

进行了甲基丙烯酸长链烷基酯（庚、辛、壬酯的混合物）的基团转移聚合．得到了具有较高分子量和转化率．分子量分布较窄的聚合产物．研究了聚合条件对产物的分子量及分布，转化率，聚合速率的影响．探讨了聚合反应动力学．认为聚合体系的非极性不利于催化剂的离解，单体较大的空间障碍使扩散困难．均是表观活化能升高和转化难以完全的原因．发现此类单体的基团转移聚合对温度的依赖性极大，本体聚合无自加速现象，容易得到较高的分子量．     

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.