Solvent-free Synthesis, Crystal Structure and Thermal Stability of Ionic Liquid 1-Hexadecyl-3-methylimidazolium Bromide

Ionic liquid 1-hexadecyl-3-methylimidazolium bromide [C16mim]Br was synthesized by solvent-free alkylation of N-methylimidzole with hexadecyl bromide. A large transparent single crystal of 1-hexadecyl-3-methylimidazolium bromide monohydrate （[C16mim]Br·H2O）, 4 mm in length, was firstly obtained in the water-trichloromethane-toluene growth system （Vwater＇Vtrichloromethane＇Vtoluene = 0.1：1：2）. The crystal structure was determined by single-crystal X-ray diffraction method. It crystallizes in the triclinic system, space group P1, with a = 5.4962（15）, b = 7.839（2）, c = 27.279（8） A, α = 94.375, β = 91.500, γ = 101.999°, Z = 2, V = 1145.2（5） A3, C20H41BrN2O, Mr = 405.46, Dc = 1.176 Mg/m3, μ = 1.804 mm^-1, F（000） = 436, the final R = 0.0523 and wR = 0.1345. The 3D supramolecular structure is constructed through weak interactions between imidazolium cations, Br- anions and lattice water molecules. The long alkyl chain to the imidazolium ring and lattice water molecules play an important role in the self-assembly process. Moreover, it is proposed that [C16mim]Br in water has aggregation behavior and the possible self-assembled structure is the interdigitated pattern. Finally, thermal stability of [C16mim][Br]·H2O was also studied by DSC and TGA analysis.     

主链型热致性液晶高分子芳香共聚酯的红外光谱研究

本文用傅里叶红外光谱法结合变温方法和偏振技术研究了主链型芳香共聚酯热致性高分子液晶。测定了光谱的变温性质以及液晶的有序度参数。结果表明分子链中液晶基元上苯环之间的相互作用在液晶相形成过程中起重要作用。液晶有序度参数与Roca和Yoon的理论值相一致。     

聚苯撑苯并二噻唑(PBT)的耐热性和液晶性研究

PBT溶于甲基磺酸(MSA)和多聚磷酸(PPA)等强酸溶剂中时能形成液晶。用TGA法测定了PBT在氮气和空气中的热分解温度,分别高达690℃和585℃。计算了PBT在氮气中的分解活化能为161 kJ/mol。测定了PBT-MSA体系液晶的退偏振光强度-温度谱和浓度-温度二元液晶区域相图,并发现8％的PBT-PPA体系表现出特殊的退偏光强度-温度特性。液晶和PBT固体的X-衍射图表明液晶状态下沉积的薄膜保持了液晶态的结构,固体小角光散射的H_v图表明非液晶态下沉积的PBT薄膜有球晶结构。     

Thermal characterization of natural and modified cyclodextrins using TG-MS combined technique

Summary Thermoanalytical techniques (TG, DSC) are frequently used in the investigation of the thermal properties of cyclodextrins and their inclusion complexes. However, the above techniques do not provide information on the chemical composition of the evolved fragments upon the thermal decomposition. In this study &agr;-, &bgr;- and &ggr;-cyclodextrins and 4 methylated and 3 ethylated &bgr;-CD derivatives were investigated with a TG-MS combined thermoanalytical technique in order to get information about their fragmentation behaviour. By comparison of the TG/DTA curves, a different thermal behaviour was found for each of the native and the chemically modified cyclodextrins. Except for the water loss profiles and the solid-solid phase transformations, the thermal behaviour of the (investigated) native CDs do not show remarkable differences. However, the chemical modification of the native &bgr;-CD resulting in a new compound may change the strength of interactions between host and guest causing differences in the thermal stabilities of the derivatives. The mass spectrometry results supported the observed thermal differences and showed significant alterations in the fragmentation of ethylated and methylated compounds. The investigated natural CDs possess a very similar fragmentation profile, due to the common &agr;-D-glucopyranose building units. In the case of modified CDs characteristic signals of the substituents are present.     

离子液体增塑生物基聚丁内酰胺的热分解机理

采用疏水性1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF₆)和亲水性1-丁基-3-甲基咪唑四氟硼酸盐 ([BMIM]BF₄)两种咪唑类离子液体(IL)增塑聚丁内酰胺(PBL), 探讨了IL对PBL结晶性能及热性能的影响. 研究发现, 两种IL都会削弱PBL分子间氢键, 并抑制PBL晶体在(200)晶面的生长, 降低PBL结晶度. 当IL添加质量分数为5%时, 增塑膜熔点下降7~8 ℃. 与纯PBL膜相比, [BMIM]BF₄增塑PBL膜热稳定性下降, 而[BMIM]PF₆增塑PBL膜的热稳定性提高. [BMIM]PF₆增塑PBL膜热分解过程的热动力学分析结果表明, 其热分解反应活化能为46.68 kJ/mol, 反应级数为1, 热分解最概然机理函数模型符合Mampel单行法则(一级), 即PBL受到热刺激后, 在聚合物和分解产物界面无规律成核, 反应核心具备反应活性, 随后反应逐步扩大, 直至结束.     

基于DFT密度泛函理论的聚酯热降解反应机理研究

本文应用密度泛函理论（DFT）研究钛系催化剂催化聚酯热降解的反应机理。分别以Ti(OEt)4化合物以及Ti(OEt)3 阳离子化合物为催化剂,探讨了二苯甲酸乙二酯（EDB）解聚反应的Lewis酸催化热降解反应机理（M1机理）和烷氧基配位催化热降解反应机理（M2机理）。结果表明,Lewis酸催化热降解反应机理在两种催化剂下的解聚反应能垒与无催化剂反应非常相似,未表现出明显促进作用;Ti(OEt)3 催化剂在M2机理中明显降低了解聚反应能垒,是聚酯热降解反应的催化活性中心。经轨道相互作用分析发现,阳离子催化剂和反应物EDB之间存在较为明显的轨道相互作用。     

红外光谱法热分析液晶相变过程

液晶物质在升温过程中会发生多个相转变过程 ,DSC热分析可测量这些相转变的能量变化 ,但却不能提供变化的微观原因和细节 .而温度升高对液晶样品的红外光谱图强度、峰形和吸收频率都有显著影响 .引起这样变化的原因一是热膨胀改变了分子内部化学键的力常数和相互作用 ,从而改变了分子振动偶极矩的性质 ;二是分子中有红外吸收的基团浓度随温度升高而改变 .红外光谱可以给出样品能量变化过程中分子结构变化的细节 ,通过计算还可获得分子结构变化的表观焓变 .前人做过的探索性工作 [1～ 3]都集中在一个或几个功能团的变化上 .在能量变化上仅…     

Thermal Conductivity and Thermal Diffusivity Anisotropy in a Liquid Crystal

Thermal conductivity (k) and thermal diffusivity (D) of the 9CB liquid crystal have been simultaneously determined by a photopyroelectric (PPE) technique in the temperature range from 308 K to 332 K where two different phase transitions occur. The measurements have been performed on oriented samples and the k and D anisotropy has been studied. The behaviour of the macroscopic order parameter vs. temperature has been determined and the order of the phase transitions checked. This revised version was published online in July 2006 with corrections to the Cover Date.     

两个有机锡对碘苯甲酸酯的合成、结构、热稳定性和除草活性

在乙醇-苯溶剂中,对碘苯甲酸分别与三苯基氢氧化锡、二丁基氧化锡反应,合成了2个有机锡对碘苯甲酸酯,Ph3Sn(p-IC6H4O2)(1)和{[n-Bu2Sn(p-I-C6H4O2)]2O}2(2)。经IR、1H NMR、元素分析和X射线单晶衍射对配合物进行了表征。配合物1属三斜晶系,空间群为P1,中心锡原子与苯基碳原子、羧基氧原子构成畸型四面体,并且分子间通过氢键和C-I…π共同作用形成二聚体结构;配合物2属单斜晶系,空间群为C2/c,配合物是以Sn2O2构成的平面四元环为中心的二聚体结构,并且分子间通过I…I共同作用形成了一维链状结构。热重分析表明,配合物1和2在230℃以下具有良好的热稳定性。配合物1、2对杂草刺苋(Amaranthus spinosus)、马齿苋(Portulaca oleracea)的抑制活性大于对农作物绿豆的影响,且配合物1的抑制活性高于配合物2的抑制活性,为刺苋、马齿苋除草剂研究提供了一种方法。     

两个有机锡对碘苯甲酸酯的合成、结构、热稳定性和除草活性

在乙醇-苯溶剂中,对碘苯甲酸分别与三苯基氢氧化锡、二丁基氧化锡反应,合成了2个有机锡对碘苯甲酸酯,Ph₃Sn(p-I-C₆H₄O₂) (1)和{[n-Bu₂Sn(p-I-C₆H₄O₂)]₂O}₂ (2).经IR、¹H NMR、元素分析和X射线单晶衍射对配合物进行了表征.配合物1属三斜晶系,空间群为P1,中心锡原子与苯基碳原子、羧基氧原子构成畸型四面体,并且分子间通过氢键和C-I…π共同作用形成二聚体结构;配合物2属单斜晶系,空间群为C2/c,配合物是以Sn₂O₂构成的平面四元环为中心的二聚体结构,并且分子间通过I…I共同作用形成了一维链状结构.热重分析表明,配合物1和2在230 ℃以下具有良好的热稳定性.配合物1、2对杂草刺苋(Amaranthus spinosus)、马齿苋(Portulaca oleracea)的抑制活性大于对农作物绿豆的影响,且配合物1的抑制活性高于配合物2的抑制活性,为刺苋、马齿苋除草剂研究提供了一种方法.     

The Thermal Degradation Mechanism and Thermal Mechanical Properties of Two High Performance Heterocyclic Polymer Fibers

The thermal mechanical properties and degradation behaviors were studied on fibers prepared from two high-performance, heterocyclic polymers, poly(p-phenylenebenzobisthiazole) (PBZT) and poly(p-phenylenebenzobisoxazole) (PBZO). Our research demonstrated that these two fibers exhibited excellent mechanical properties and outstanding thermal and thermo-oxidative stability. Their long-term mechanical tensile performance at high temperatures was found to be critically associated with the stability of the C—O or C—S linkage at the heterocyclic rings on these polymers' backbones. PBZO fibers with the C—O linkages displayed substantially higher thermal stability compared to PBZT containing C—S linkages. High resolution pyrolysis-gas chromatography/mass spectrometry provided the information of the pyrolyzates' compositions and distributions as well as their relationships with the structures of PBZT and PBZO. Based on the analysis of the compositions and distributions of all pyrolyzates at different temperatures, it was found that the thermal degradation mechanisms for both of these heterocyclic polymers were identical. Kevlar®-49 fibers were also studied under the same experimental conditions in order to make a comparison of thermo-oxidative stability and long-term mechanical performance at high temperatures with PBZO and PBZT fibers. The data of two high-performance aromatic polyimide fibers were also included as references.This revised version was published online in November 2005 with corrections to the Cover Date.     

牡丹花色苷的热稳定性和降解动力学

研究了pH值和温度对牡丹花色苷热稳定性的影响。动力学数据分析表明,牡丹花色苷的热降解符合一级反应动力学模型。在70～90℃条件下,当pH值为2.6、3.0、3.6、4.0和4.6时,牡丹花色苷的半衰期分别为27.0～7.9、32.1～8.5、27.9～8.9、35.9～9.4和27.3～10.7h。提高温度,花色苷降解反应速率增大;降解反应速率常数与温度的关系附合Arrhenius公式,反应活化能为48.4～69.4kJ/mol。牡丹花色苷单体的降解速率依次为矢车菊-3-O-二葡萄糖苷芍药-3-O-葡萄糖苷矢车菊-3,5-O-二葡萄糖苷芍药-3,5-O-二葡萄糖苷。牡丹花色苷降解生成褐色物质,褐变指数随加热时间的延长、加热温度的升高、pH值的增大而增大。     

新型异三聚体超分子的密度泛函计算及其晶体结构、热性能研究

运用密度泛函B3LYP方法,在6-31G^*水平上设计优化了丁二酮肟与苯甲酸通过四重氢键构筑的异三聚体超分子、此异三聚体的总能量比三个单体总能量之和低144．0816kJ／mol,四重氢键的平均键能约为36．0204kJ／mol,属中高强度;298．15K时吉布斯自由能变化△GT=-41．70kJ／mol,显示形成三聚体的反应可自发进行．在此设想指导下,实验合成出相关异三聚体,并得到了晶体结构,与预测的结构极为相似．热性能分析显示,此三聚体不是三个单体的简单叠加,而是一个不同于其单体的全新化合物．理论计算数据与实验结果的一致性,证明了理论计算的预见性．     

奈达铂的新合成方法、晶体结构和热稳定性

本文报道了铂族金属抗癌药物奈达铂的一种新合成方法,产率约65%,精品含量超过99%。采用了元素分析、红外光谱、质谱、差热-热重分析和X射线衍射手段对其结构和组成进行了表征。该配合物的晶体属正交晶系,空间群P2₁2₁2₁。单晶X射线衍射结构分析结果表明铂(Ⅱ)离子与2个氨分子的氮原子以及乙醇酸羟基和羧基的氧原子配位,形成平面正方形结构,乙醇酸的二价阴离子通过羟基和羧基上的氧原子与铂(Ⅱ)离子配位形成五原子的螯合物。经TG-DTA     

乙炔基封端液晶-含硅芳炔共聚树脂的固化机理

将热致性乙炔基封端液晶单体(MPBE)与含硅芳炔树脂(PSA)进行共聚,制得乙炔基封端液晶改性含硅芳炔树脂(PSA-MPBE)。采用FT-IR在线表征了PSA-MPBE树脂固化过程的结构变化,用裂解-气相色谱-质谱联用仪(Py-GC-MS)分析了其高温裂解产物,研究了其固化机理,用偏光显微镜(POM)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)分析了共混树脂的相结构、断裂形貌和微观结构。结果表明:MPBE与PSA发生了共聚反应,使介晶域固定在交联网络中,形成结构均匀的以介晶相为小岛的海岛结构,PSA-MPBE树脂的断裂行为从典型的脆性断裂转变为微塑性断裂。     

Thermal Stability Of Folic Acid in the solid-state

This study attempts to identify the degradative process which folic acid undergoes in the solid-state under thermal stress. In order to facilitate the process, the various pieces of the chemical structure, namely, p-amino benzoic acid, pterin and glutamic acid as both its d- and l-isomers were investigated as separate entities. These structured solid-state pieces were then compared to the composite solid state folic acid degradative curves in order to identify the peaks seen and provide direction for the interpolation of the degradative mechanism. It was observed that none of the structural pieces could be superimposed as assumed earlier and hence an attempt was made to identify the decomposition products using various analytical techniques such as infrared spectroscopy, mass spectroscopy and X-ray diffraction which suggested that the glutamic acid fragment is lost first as evidenced by acid loss and amide enhancement in the IR spectra. The vitamin was ultimately degrading to carbon fragments and that further identification was not necessary. This revised version was published online in August 2006 with corrections to the Cover Date.     

4-甲基苯硫乙酸与含氮配体构筑的两个化合物的合成，晶体结构，热稳定性与发光性质的研究

合成了2个配合物[ZnL₂(Him)₂] (1)和[ (Cu₂L₂(phen)₂( μ₂-Cl)₂)·(Cu₂( μ₂-L)₂(phen)₂Cl₂)] (2)(L=4-甲基苯硫乙酸,Him=咪唑,phen=1,10-邻菲咯啉),进行了元素分析、红外、热重等表征,并测定了其晶体结构。配合物1晶体属于单斜晶系,空间群为C2/c。配合物2晶体属于三斜晶系,空间群为P1。配合物1是由N-H…O氢键作用形成的一维带状结构。配合物2的单胞中含有2个分别由氯原子与羧基氧原子桥联的双核独立分子,通过C-H…O,C-H…Cl氢键以及C-H…π作用而构成三维结构。室温固体荧光分析显示配合物1具有较强荧光吸收。     

Thermal Behavior and Primary Degradation Mechanism of Some Aromatic Polyethers with Semi-flexible Chain

The present paper describes a thermogravimetric study combined with mass spectrometry of some aromatic polyethers and copolyethers in order to obtain information on the degradation mechanism. The investigated polymers were synthesized starting from 3,3-bis(chloromethyl) oxetane and various bisphenols: 4,4'-dihydroxyazobenzene, 4,4'-dihydroxydiphenyl, bisphenol A and 4,4'-dihydroxydiphenylether. The presence of an oxetanic spacer in the structure, permitting the opening of the cycle, induces more complications in the characterization procedure. But, due to the possibilities relative to the modification of polymers or cross-linking reactions, the presence of the oxetanic moiety may offer some advantages. Out of all the investigated polymers, those containing azobenzenic moieties have the lower thermostability. If the chain flexibility is augmented, the degradation mechanism is based on chain transfer reactions. All polymers present higher thermostability in an argon atmosphere. Based on mass spectra, a degradation mechanism sustained with the assumption that the oxetanic unit is the most labile was proposed. The opening of the oxetanic cycle begins with the most tensioned bond (-C-CH₂-) and generates across-linking process, which is more evident if the polymer melts below 200°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

一维链状锰配位聚合物的合成、晶体结构及热稳定性研究

A manganese coordination polymer, [Mn(C₇H₂I₃O₂)₂(CH₃OH)₂]_n was synthesized and characterized by the element analysis, IR, TG and single crystal X-ray diffraction structure analysis. The title complex crystallizes in monoclinic system with space group P2₁/c, a=0.461 66(9) nm, b=1.716 6(3) nm, c=1.647 5(3) nm, β=91.84(3)°, and V=1.305 2(4) nm³, Z=2, R=0.026 2, wR=0.063 4. Each manganese(Ⅱ) ion exists in an octahedral geometry with four O atoms from three different triiodobenzoate groups and two O atoms from two methanol molecules. Two adjacent manganese(Ⅱ) atoms are bridged by two triiodobenzoate groups in bis-monodentate mode, constructing a one-dimensional chain structure along a axis, with the adjacent Mn…Mn distance being 0.461 7(5) nm. Moreover, the weak interactions between the iodine atoms lead to a three-dimensional supramolecular network. CCDC: 666558.     

新型含氟聚醚链修饰的咪唑离子液体的合成及其热稳定性

含氟聚醚链修饰的咪唑与碘代烷烃经季铵化反应高产率地制备了4个新型的含氟聚醚链修饰的咪唑碘盐(3a ～3d);通过3的复分解反应合成了一系列新型的含氟聚醚链修饰的咪唑离子液体盐(4a ～4d,5a～5d),其结构经1 H NMR,19F NMR,IR和元素分析确证.热重分析研究表明,4和5具有较高的热稳定性.