聚对苯二甲酸乙二酯／聚苯膦酸二苯砜酯体系的性能研究

混合热计算和ＦＴＩＲ分析表明，聚对苯二甲酸乙二酯（ＰＥＴ）与聚苯膦酸二苯砜酯（ＰＳＰＰＰ）具有一定的相容性，不同ＰＳＰＰＰ含量的ＰＥＴ均具有较高的热稳定性，ＰＥＴ／ＰＳＰＰＰ体系的阻燃性随阻燃剂ＰＳＰＰＰ含量的增加而提高，ＰＳＰＰＰ重量百分含量５％（下同）的阻燃ＰＥＴ体系的ＬＯＩ值可达到３０．１，由不同分子量的ＰＳＰＰＰ构成的各种配比的ＰＥＴ体系，其表现粘度随切变速率的增大而降低，ＰＳＰＰＰ的分子     

聚丁二酸丁二酯的无卤阻燃性能的研究

本文研究了聚苯基膦酸二苯砜酯(PSPPP)对聚丁二酸丁二酯(PBS)的阻燃作用。研究发现,在PBS中仅添加4wt%的PSPPP,其垂直燃烧就可以达到UL-94 V-0级,极限氧指数达到34,PSPPP对PBS表现出高效阻燃作用。然而,PSPPP对PBS有促进降解的作用,破坏了PBS的力学性能。通过在PBS/PSPPP体系中添加0.5wt%氧化锌后,有效抑制了PBS的降解,力学性能得到改善。     

聚苯基膦酸二苯砜酯对PET凝聚相阻燃作用的研究

采用热重分析、Ｘ－射线光电子能谱和红外光谱分析等手段，研究了含聚苯基膦酸二苯砜酯（ＰＳＰＰＰ）的聚对苯二甲酸乙二酯（ＰＥＴ）阻燃体系的热化学，探讨了ＰＳＰＰＰ对ＰＥＴ的阻燃机理．ＰＳＰＰＰ的加入，明显改变了ＰＥＴ的热分解行为：ＰＳＰＰＰ拓宽了ＰＥＴ的分解温度范围，降低了ＰＥＴ在可燃温度范围内的分解产物的量；在ＰＥＴ的点燃温度以下，ＰＳＰＰＰ对ＰＥＴ的降解起到一定的促进作用，而在点燃温度以上，产生的降解产物有利于促进炭化．４００℃以上，ＰＥＴ和ＰＳＰＰＰ的结构发生了明显的变化，所产生的结构有利于ＰＥＴ的降解，使ＰＥＴ的分子量急剧减小，粘度下降，易于形成熔滴，有利于促使着火部分离开火源，增加燃烧的ＰＥＴ表面的物质损耗和热损耗，起到阻燃作用．     

聚醚酯嵌段共聚物熔体的流变性能

采用毛细管流变仪测定了组成比、聚醚分子量、熔融时间和熔融温度对嵌段聚醚酯熔体表观粘度的影响．结果发现在所研究的温度和切变速率范围内,该结构聚醚酯熔体为假塑性非牛顿流体,其粘度随聚酯段含量的增加而增加,随熔融时间增加而降低,随聚醚分子量的增大而增大．聚醚酯的零切粘度可由Ｓｐｅｎｃｅｒ Ｄｉｌｌｏｎ 公式外推得到,零切粘度对温度的依赖关系服从Ａｎｄｒａｄｅ 公式．     

纤维素芳族酯热致液晶对PET结晶成核作用的研究

用自制的热致液晶性纤维素芳族酯(CAE)作聚对苯二甲酸乙二醇酯(PET)的成核剂,研究了PET/CAE体系(CAE含量≤1%)在110～200℃温度范围内的等温结晶动力学特性.结果表明,CAE能显著加快PET结晶速率(Z),Z随结晶温度和CAE含量变化均有极大值Z_max(T_C)和Z_max(W_CAE),Z_max(T_C)对应的温度T_max随CAE含量增加而降低,CAE促进PET结晶的作用机理与普通成核剂不同.     

对-乙酰氧基苯甲酸与聚对苯二甲酸乙二醇酯共缩聚反应及醚键形成的研究

监测了对-乙酰氧基苯甲酸与聚对苯二甲酸乙二醇酯(PET)共缩聚反应过程中1HNMR图谱及特性粘度的变化,对乙酰氧基酯交换反应及乙酰脂肪酯的反应活性进行了研究。并研究了以低分子量PET或对苯二甲酸二乙二醇酯为原料时反应中醚键的形成及其进入共聚酯链的规律性。     

不同羧酯比的聚马来酸十八醇酯齐聚物的镉盐LB膜成膜特性研究

由聚马来酸杆和十八醇合成了一系列不同羧酯比的聚马来酸十八醇酯（PMA），并以其为成膜材料、CdCl2水溶液为亚相制备了一系列聚马来酸十八醇酯镉盐（CdPMA）LB膜．借助小角X射线衍射和红外吸收光谱表征了成膜条件及羧酯比对CdPMA膜有序结构的影响．在较高膜压（30mN／m）和快速提拉（10cm／min）条件下，低羧酯比的CdPMA可得到有序性很高的Y-型LB多层膜；高羧酯比的CdPMA得不到高有序性的LB多层膜．     

四氧化疗染色法在PC／PET共混体研究中的应用

以RuO4为双酚A聚碳酸酯／聚对苯二甲酸乙二酯（PC／PET）共混体系的薰染剂，可成功地用透射电观察其微观形态和相结构，该体系两相微观结构受原料分子量，组成和溶剂的影响。     

植物油酸新戊二醇对苯二甲酸复合酯的合成及性能

用新戊二醇(NPG)和对苯二甲酰氯(TPA)反应生成“低聚物”中间体,当n(NPG)/n(TPA)由2.4增加至3.0时,中间体的聚合度(m)在3.5~1.45之间,收率75.5%。再将中间体与油酸、菜籽油酸进行酯化得到复合酯,收率88.5%。结果表明,复合酯的粘度随着分子量的增大而增大,粘度指数大于125,凝点低于－27℃,氧化稳定性随分子量的增大而提高,生物降解率＞70%,最大无卡咬负荷(PB)为784N,磨斑直径0.41mm,热分解温度＞250 ℃,因此植物油酸新戊二醇对苯二甲酸复合酯是性能良好的绿色润滑剂。     

变温红外法研究聚对苯二甲酸乙二酯分子链的松弛运动及其构象转变

在30～170 ℃范围内逐渐升温过程中,用红外光谱仪原位检测无定形聚对苯二甲酸乙二酯（PET）薄膜红外光谱图的变化情况。通过特征谱带吸光度与温度的变化特点,研究了PET分子链在热变化过程中的松弛运动及冷结晶过程中分子链的构象变化。实验结果表明在冷结晶过程中,随PET结晶的不断完善,对应左右式(gauche)构象的吸收峰减弱,对应反式(trans)构象的吸收峰增强,并计算出CH2面外摇摆振动结晶前和结晶后反式构象和左右式构象的相对百分含量随温度的变化关系,以及玻璃化转变和冷结晶的温区范围。     

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.     

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.     

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.     

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.     

关于"对‘燃料电池物理及化学性能的有限时间热力学分析方法'的讨论”答复

把有限时间热力学理论用于化学过程的研究,将会得到一系列新的结论,开展这方面的研究是很有意义的.文献[1]以燃料电池为例,在同时考虑化学反应及传热不可逆性的情况下,研究了燃料电池的性能界限,文献[2]指出了文献[1]计算化学反应及传热不可逆性而引起系统与有关环境的总熵产生率的错误以及由此而导致的结论所存在的问题,并进行了富有启发性的分析与讨论.但文献[2]对于系统与有关环境的总熵产生率的计算也是不正确的,由此得到的其它结论自然不能成立.本文将就此情况下系统与有关环境的总熵产生率的计算再次进行讨论,并给出电池功率和效率的有限时间热力学性能界限.