共查询到20条相似文献,搜索用时 93 毫秒
1.
对甲基酚醛树脂热裂解产物的固体~(13)CNMR谢德民,张建国,王存国,王荣顺(东北师范大学化学系,长春,130024)关键词对甲基酚醛树脂,裂解,固体~(13)C,NMR酚醛树脂经热裂解制备的聚并苯导电材料在空气中稳定,由裂解温度可控制碳化程度,其本... 相似文献
2.
3.
甲苯热解机理的AM1研究(Ⅰ)热力学分析 总被引:2,自引:0,他引:2
在实验的基础上,本文用Gaussian98程序包中AM1法UHF计算,对碳材料用碳前驱体甲苯的热裂解反应机理进行了研究。在对反应物,产物自由基的结构进行能量梯度法全优化的同时,计算了不同温度下的标准热力学参数(298-1073K)。热力学计算结果表明:(1)当甲苯的热裂解温度相对较低时(773K左右),热力学计算结果首先支持苯环上甲基C-H键的断裂生成苯基自由基并继而生成联二甲苯的反应;随着温度的提高(达1073K时),生成苯自由基和甲基自由基的反应比例将大生成苄基自由基的比例;该反应机理与实验结果基本一致。(2)采用Gaussian98程序包中AM1法中的UHF计算,较适合低级芳香烃热裂解反应机理的理论研究。 相似文献
4.
采用裂解气相色谱-质谱法(Py-GC-MS)研究了香叶醇热裂解性质。以氦气为载气,将香叶醇样品分别在不同温度(300,400,500,600,650,700,800℃)下进行热裂解,将热解产物直接引入气相色谱-质谱仪进行定性和半定量分析。结果表明:在700℃时香叶醇完全裂解,裂解产物可达87种。根据主要的裂解产物和其相对含量的变化对香叶醇裂解机理进行初步探讨,为香叶醇在卷烟中的作用评价提供重要的理论依据。 相似文献
5.
6.
7.
正癸烷与二甲苯在超临界压力下的热裂解 总被引:1,自引:0,他引:1
采用连续流动装置对正癸烷和二甲苯在超临界压力下的热裂解对比研究. 用气相色谱和色质联用仪对其气相产物和液相产物进行分析, 计算气相产物产率和裂解转化率, 并运用计算化学方法获得正癸烷和二甲苯不同化学键的键能, 从实验和理论上分析其裂解反应的难易程度和裂解规律. 实验结果表明, 在4 MPa和650、700、750 ℃条件下, 正癸烷比二甲苯更容易裂解, 正癸烷裂解产物以C1-C3小分子的烃类和氢气为主, 而二甲苯裂解产物主要为乙苯、甲苯和其它芳香类化合物; 键能计算结果表明, 正癸烷碳链骨架的C-C键能和C-H键能均较小, 裂解反应的诱发步骤应该是C-C键断裂, 而二甲苯苯环上C-C和C-H键能均较大, 裂解诱发步骤应该是侧链甲基脱氢反应. 因此正癸烷裂解反应以C-C键断裂和脱氢反应为主, 二甲苯裂解主要发生侧链甲基C-C键断裂和脱氢反应, 而芳环则比较稳定, 理论计算键能分析与裂解实验结果一致. 相似文献
8.
9.
不同氛围下烟草的热裂解行为研究 总被引:2,自引:0,他引:2
烟丝分别在He和空气环境中于600、700、800、900、1 000 ℃下进行热裂解,裂解产物用GC-MS进行在线检测,研究了烟丝样品分别在惰性和有氧氛围中不同温度下的热裂解行为.数据表明,烟丝在He气和空气中热裂解时的产物有较大差异,He气下的裂解产物以烯烃、苯和苯系物为主;在空气下裂解的主要产物为酮、醛、醇、酸和酯等羰基化合物.有氧氛围有益于异戊二烯和1,3-丁二烯的生成,但在一定程度上抑制了酚类物质的产生.在惰性和有氧氛围下,随着温度的升高,多环芳烃化合物的产生量均进一步增加.He氛围下得到的裂解产物类型接近卷烟燃烧时的热解区,而空气氛围下得到的裂解产物类型接近燃烧区. 相似文献
10.
11.
A series of predominately hydroxyl-ended polyesters were made from tridecanedioic acid derived from crambe oil. Comparison materials with sebacic and adipic acids were also prepared. Suitable polyesters were converted into polyurethane elastomers by chain extension and cross-linking with a diisocyanate and further diol. Polyesters based on ethandiol were unsuitable for the production of flexible urethanes as a slow crystallization occurred on standing; this did not happen when mixed ethane- and propan-diols were employed in polyesterification. Polyurethanes based on diphenylmethane diisocyanate are stronger than those made with the mixed isomers of toluene diisocyanate. Polyurethane networks based on brassylic acid have a lower 相似文献
12.
F. Gaboriaud J. P. Vantelon 《Journal of polymer science. Part A, Polymer chemistry》1981,19(1):139-150
A polyurethane based on diphenyl methane diisocyanate (MDI) and propoxylated trimethylol propane was thermally degraded by using the techniques of pyrolysis and thermogravimetric analysis (TGA) in an inert atmosphere. Identification of pyrolysis gaseous products at 600°C showed that the first degradation step consists of a reversal of the polycondensation process, i.e., dissociation into starting polyol and diisocyanate, followed by the polyol degradation and a probable diisocyanate polymerization. Kinetic parameters were determined using dynamic and isothermal TGA curves. It is shown that the degradation can be closely compared with a random chain scission process. 相似文献
13.
《液相色谱法及相关技术杂志》2012,35(15):3347-3356
Abstract A gel permeation chromatographic method was developed for the quantitative analysis of toluene diisocyanate and diphenylmethane diisocyanate in polyurethane polymers. Standard curves were linear over the range of concentrations 2–35 μg/mL and a good correlation was established between the amount of diisocyanate injected and the peak height. In addition to rapid quantitation of diisocyanate monomers, the method developed also separates the polyurethane prepolymers and diisocyanate dimers and trimers, allowing analysis of components of commercial samples in a single step. 相似文献
14.
Karoly Vkey Jzsef Tams Arpd Somogyi Antonella Bertazzo Carlo Costa Graziella Allegri Roberta Seraglia Piero Traldi 《Journal of mass spectrometry : JMS》1992,27(11):1216-1219
Structural studies of a synthetic melanin, obtained by means of performic acid oxidation of tryptophan, were carried out by pyrolysis gas chromatography/mass Spectrometry (Py-GC/MS). To identify the best pyrolysis conditions, both Curie-point pyrolysis and filament pyrolysis were employed and the effects of pyrolysis temperatures and times were studied. Using the first approach, various compounds were identified: toluene, ethylbenzene, styrene, indole, methylindole, ethylindole, phenol, cresol and ethylphenol. Using filament pyrolysis some interesting differences could be observed. Whereas toluene, ethylbenzene, phenol, cresol and methylindole were found, neither indole nor ethylindole was detected. Instead, new pyrolysis products were evident, such as methylpyrrole and indolin-2-one. Hence filament pyrolysis seems to activate different thermal decomposition pathways of the melanin under study. It is suggested that tryptophan melanin is a polymer containing indole and hydroxyindole derivatives as subunits. 相似文献
15.
环氧乙烷-四氢呋喃共聚醚基热塑性聚氨酯弹性体氢键体系的定量研究 总被引:1,自引:0,他引:1
氢键为热塑性聚氨酯弹性体内的重要键合力特征。该文基于氢键所引起基团的频移,以FTIR为主要的研究手段,并结合通过动态力学性能(DMA)研究所建立的评估硬段与软段之间混溶的定量方程,对所合成的以环氧乙烷-四氢呋喃无规共聚醚、2,4-甲苯二异氰酸酯以及1,4-丁二醇为原料的热塑性聚醚聚氨酯弹性体的氢键体系进行了定量化研究。结果表明,大约有30%的硬段混溶进入炊段相对软段的醚氧产生氢键作用,主要的氢键包括硬段羰基与硬段氨基之间的氢键以及硬段烷氧与硬段氨基之间的氢键,仍发生在硬段岛区内。 相似文献
16.
<正>A series of stable waterborne polysiloxaneurethane(WPSUR) dispersions were prepared using amino-terminated polydimethylsiloxane(NS),dimethylolpropionic acid(DMPA),castor oil,polypropylene glycol and toluene diisocyanate. Meanwhile,NS with different molecular weights was synthesized and used as the soft co-segment.Effects of types and contents of soft co-segments as well as chain extenders on the thermal degradation and stability for WPSUR films were examined.Results reveal that WPSUR films exhibit excellent water resistance and mechanical properties as compared with pure polyurethane(PU) films,and the NS soft co-segment possesses a remarkable effect on the second stage(stageⅡ),while the content of the hard segment is propitious to the initial stage(stageⅠ).Moreover,the highest temperature of stageⅡ(T_(2m)) for WPSUR films using NS as soft co-segment is 413℃,approximately being 30℃higher than that of those typical PUs using HDA and APDMS as the chain extenders,respectively. 相似文献
17.
A series of polyureas were synthesized through the reaction of aniline trimer with toluene‐diisocyanate, diphenylmethane‐4,4′‐diisocyanate, and hexamethylene‐1,6‐diisocyanate, respectively. The chemical structure of these polyureas was characterized and verified by FT‐IR, 1H NMR, elemental analysis, UV, XRD and CV. The conductivity of these polyureas ranged from 10?7 to 10?6 S/cm measured by four‐point‐probe instrument. Compared to the standalone aniline trimer, the stability (thermal stability and electrochemical stability), response range and sensitivity of these polyureas are enhanced. The sensitivity of these polyureas DMF solution to pH value is superior to that of the standalone aniline trimer. The color of the polyureas DMF solution is greatly depended on pH value and the color change process is reversible, whenever from base to acid or from acid to base. These enhancements may give these polyureas more opportunities in order to be used as sensor materials. 相似文献
18.
Pyrrole and acetonitrile, major pyrolysis products of soil humic substances, vary characteristically in abundance with the degree of humification of the organic matter in the soil. Their origin, however, is uncertain because of the large amount of unidentifiable soil nitrogen. A quantitative relationship between amino acid composition and pyrrole and acetonitrile abundances has been established by Curie-point pyrolysis-gas chromatography of a group of test proteins, using polystyrene as an internal standard. The pyrolysis yields of these products from three humic acids extracted from the surface horizons of Scottish brown forest soils (Cambisols or Ochrepts) were entirely accounted for by the known hydrolysable amino acid content and composition, and the products were related to individual amino acids. The peptide amino acid was also found to be the overall source of the aromatic pyrolysis products toluene, phenol and p-cresol. 相似文献
19.
FTIR STUDIES ON THE MODEL POLYURETHANE HARD SEGMENTS BASED ON A NEW WATERBORNE CHAIN EXTENDER DIMETHYLOL BUTANOIC ACID (DMBA) 总被引:2,自引:0,他引:2
Zhi-yongRen Hai-pingWu Jian-mingMa De-zhuMa 《高分子科学》2004,(3):225-230
Three model polyurethane hard segments based on dimethylol butanoic acid (DMBA) and 1,6-hexane diisocyanate (HDI), toluene diisocyanate (TDI) and 4,4‘-diphenylmethane diisocyanate (MDI) were prepared by the solution method.Fourier Infrared (FTIR) spectroscopy was employed to study the H-bonds in these model polyurethanes. The model polyurethane hard segment prepared from HDI and 1,4-butanodiol (BDO) was used for comparison. It was found that the incorporation of the pendent carboxyl through DMBA into the model hard segments weakens the original NH…O=C H-bond but gives more H-bond patterns based on the two H-bond donors, urethane NH and carboxylic OH. The carboxylic dimer is one of the main H-bond types and is stronger than another main H-bond type NH…O=C. In addition, the H-bond in aromatic model hard segments is stronger than that of aliphatic hard segments. The appearance of the free C:O and the fact that almost all N-H is H-bonded suggest that there possibly exist either the third H-bond acceptor or the H-bond formed by one acceptor with two donors. 相似文献
20.
Meisetsu Kajiwara 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):587-594
The reaction of diaminotetraalkoxycyclotriphosphazene compounds with toluene diisocyanate using the mole ratio 1:1 were carried out in benzene for 24 h. The products having the highest average molecular weight was prepared when dimethylamino-tetraethoxycyclotriphosphazene was reacted with toluene diisocyanate. It was found from H-NMR, infrared absorption spectra, and chemical analysis that the products were cyclolinearphos-phazene oligomers. The products dissolved in DMF were coated on polyvinyl chloride laminate and a test of adhesive bonding strength was made. However, it was difficult to obtain satisfactory results for the adhesives although the products were nonflammable materials. 相似文献