含烯丙基硅氧烷的合成与表征

以含氯烃基的硅氧烷同邻烯丙基苯酚进行威廉逊反应,制得了几种含烯丙基的硅氧烷。在浓硫酸催化下,1,3-双氯甲基-四甲基二硅氧烷(Ⅰ)同八甲基环四硅氧烷反应得到α,ω-双氯甲基-二甲基硅氧烷低聚物(Ⅱ);将Ⅰ或Ⅱ同过量的邻烯丙基苯酚在乙醇中回流反应8 h,分别得到1,3-双(邻烯丙基苯氧甲基)-1,1,3,3-四甲基二硅氧烷和α,ω-双(邻烯丙基苯氧甲基)-二甲基硅氧烷低聚物;室温下,γ-氯丙基甲基二甲氧基硅烷(Ⅲ)水解得到γ-氯丙基甲基硅氧烷低聚物(Ⅳ),Ⅲ同氯甲基二甲基氯硅烷共水解得到氯甲基封端的γ-氯丙基甲基硅氧烷低聚物(Ⅴ);在氢氧化钾作用下,用四丁基溴化铵为催化剂,将Ⅳ或Ⅴ同邻烯丙基苯酚在二甲基甲酰胺中回流反应16 h,分别得到γ-(邻烯丙基苯氧基)丙基甲基硅氧烷低聚物和α,ω-双(邻烯丙基苯氧甲基)-γ-(邻烯丙基苯氧基)丙基甲基硅氧烷低聚物。用1H NMR和IR等方法对产物的结构进行了表征。     

透明成核剂1,3-2,4-二(对甲基亚苄基)-1-烯丙基山梨醇的合成

以HBr醇水溶液为溶剂,用金属催化葡萄糖烯丙基化,合成了中间产物1-烯丙基山梨醇,再与对甲基苯甲醛经醇醛缩聚合制备了1,3-2,4-二(对甲基亚苄基)-1-烯丙基山梨醇,分别考察了金属催化剂种类、HBr醇水溶液浓度、乙醇用量、反应温度以及反应时间等对产物收率的影响,并对产物结构进行了表征。结果表明:以Sn粉为催化剂,HBr醇水溶液浓度为0.5 mol/L,乙醇体积分数为10%,室温条件下反应48 h,产物收率最高可达55.4%;所得产物的熔点为275.00~278.00℃。     

五味子挥发油成分气相色谱-质谱分析

采用水蒸气蒸馏法提取五味子中的挥发油并用气相色谱-质谱法对提取物进行分析。按峰面积归一化法求出挥发性化学成分的相对含量。在提取物中,总共鉴定了23个挥发性化合物,占总色谱流出峰面积的88.33%。其主要化合物有:2,4a,5,6,7,8-六氢-3,5,5,9-四甲基-(R)-1H-苯并环庚烯(35.06%),2,6,6,9-四甲基-三环[5.4.0.02,8]十一-9-烯(6.69%),1,2,4a,5,6,8a-六氢-4,7-二甲基-1-(1-甲乙基)-(1à,4aà,8aà)-萘(6.09%),(4a S-顺)-2,4a,5,6,7,8,9,9a-八氢-3,5,5-三甲基-9-甲烯基-,1H-苯并环庚烯(5.49%),长松叶烯-(V4)(3.73%),土青木香烯(3.55%),6-(1,3-二甲基-丁基-1,3-二胺基)-1,5,5-三甲基-7-氧化-双环[4.1.0]庚-2-烯(3.38%),4,4,11,11-四甲基-7-四环[6.2.1.0(3.8)0(3.9)]十一-醇(3.21%),4,5,5a,6,6a,6b-六氢-4,4,6b-四甲基-2-(1-异丙烯基)-2H-环丙基苯基呋喃(3.21%)。     

香椿挥发性化学成分的研究

用水蒸气蒸馏法提取香椿挥发油,并用气相色谱-质谱联用仪对香椿挥发油的化学成分进行了分离和鉴定,分离并鉴定出53个组分,占峰面积的92.34%,并用峰面积归一化法测定了各成分的质量分数。其主要挥发性成分为:α-荜茄醇(4.89%)、桉叶烯(5.67%)、杜松烯(5.49%)、8-异丙烯基-1,5-二甲基-1,5-环癸二烯(5.37%)、1-异丙基-4,7-二甲基-1,2,3,5,8a-六氢化萘(5.88%)、2,4,4-三甲基-3-甲醇-5-(3-甲基-2-丁烯-1-基)环己烯(5.65%)、橙花叔醇(4.97%)、1-异丙基-4-甲基-7-亚甲基-1,2,3,4,4a,5,6,7-八氢化萘(5.87%)、叶绿醇(4.86%)、2,5,6-三甲基-1,3,6-庚三烯(4.31%)、5,7-二乙基-5,6-癸二烯-3-炔(3.14%)、2-甲基-3-乙基-1-戊烯(2.86%)、4-戊烯-2-醇(2.09%)、2-甲基-2-丁烯(2.83%)、2-甲基-5-己烯-3-醇(2.99%)、β-丙内酯(2.63%)、3-己烯-1-醇(2.41%)、3,4-二甲基-1-戊醇(2.34%)。     

气相色谱-质谱研究独活二氯甲烷提取物化学成分

以二氯甲烷为溶剂,用加速溶剂萃取法提取独活化学成分后,用气相色谱-质谱（GC-MS）联用法分析测定,提出了独活二氯甲烷提取物化学成分的方法。结果表明,共分辨出67个色谱峰,鉴定出48种成分,占独活化学成分总质量的86。27％。主要组分为含氧物质、萜类、酮类和酯类,如4-甲氧基-6丙烯基-1,3苯并二噁茂和1-[3-3-甲氧基-5-羟苯基]-1,2,3,4-四甲基异喹啉。该方法可用于独活的进一步开发和质量控制。     

花椒挥发油成分GC-MS分析

采用GC-MS技术初步分析和鉴定花椒中的挥发油成分。采用水蒸汽蒸馏法提取花椒中的挥发油,气相色谱-质谱联用分离并鉴定化学成分。从花椒中共鉴定出56个化合物,相对含量占挥发油总量的88.375%,。其中主要成分为乙酰丁香酮(12.711%)、(-)-4-萜品醇(11.911%)、4-甲基-1-(1-甲基乙基)-二环[3.1.0]己-2-烯(8.866%)、萜品烯(5.922%)、芳樟醇(5.777%)、桉叶油醇(4.483%)、4,7,7-三甲基二环[4.1.0]庚-4-烯(4.312%)、β-水芹烯.(3.745%)、柠檬烯(3.434%)、α-松油醇(3.349%)、邻-异丙基苯(3.149%)。花椒中鉴定出的挥发油成分比较多,为进一步实验研究提供理论依据。     

竹叶提取物的致香成分分析及其在卷烟中的应用

采用氧化石墨烯(GO)辅助乙醇提取竹叶并进行卷烟加香实验,利用高效液相色谱-二极管阵列检测(HPLC-DAD)和气相色谱-质谱联用(GC-MS)技术分别对提取物及其热裂解产物进行分析。结果表明,GO辅助乙醇提液中的物质种类和竹叶黄酮、酚酸类的含量均多于乙醇提液;GO辅助乙醇提液和乙醇提液热裂解后鉴定出的物质分别为50种和46种,且GO辅助乙醇提液热裂解产物中醇、醛和酯类含量较高。卷烟评吸结果表明,竹叶GO辅助乙醇提液可以降低香烟干燥感和刺激性、增加甜润感,效果优于乙醇提液。     

噻唑偶氮类试剂的合成及对其分析性能的研究

介绍了四种4,5-二甲基噻唑(?)氮类显色剂的合成及其质子化行为与金属离子的生色性能,并利用4-(4,5-二甲基噻唑(?)氮)-1,3-二氨基苯(简称 DMTADAB)拟定了钴、钯连续测定的方法。     

海南核果木果实脂溶性成分的GC-MS分析

采用溶剂提取法、硅胶柱层析分离,获得海南核果木果实脂溶性提取物Ⅰ和Ⅱ,结合气相色谱-质谱联用对其化学成分进行分离、鉴定及分析。结果发现,海南核果木果实脂溶性提取物Ⅰ中主要为邻苯二甲酸二(2-乙基己基)酯(64.2%)和烷烃类(23.6%);从脂溶性提取物Ⅱ中鉴定出19种成分,主要为烯烃类(1.4%)、烷烃类(22.9%)、酯类(68.0%)以及植物醇(2.8%)等,酯类为饱和脂肪酸酯(35.8%),主要为软脂酸甲酯(29.0%)和十八碳酸甲酯(6.8%),不饱和脂肪酸酯(18.6%),主要为11,14-十八碳二烯酸甲酯(10.1%)和6,11-二十碳二烯酸甲酯(8.5%),另外,还含有邻苯二甲酸二(2-乙基己基)酯(13.6%)。     

固化剂的类型对聚醚型聚氨酯弹性体性能的影响

使用脂肪芳香(?)醇((?)乙基苯酚和(?)甲基苯酚)做链增长剂代替芳香醇可使聚乙醇已二酸酯)和二苯甲烷(?)异氰酸酯合成的聚氨酯弹性体的硬度和伸张应力得到增加。同时强度指标实际上不变,但有时因使用的二醇的类型和数量的关系而稍有降低。作者过去的实验表明,在制备聚四甲撑二醇(聚醚)和2,4-甲苯二异氰酸酯为基础的聚     

In-situ monitoring of the stabilization with hydrogen of free radicals thermally induced from coal using high pressure e.s.r., d.t.a. and p.d.a. equipment

High temperature, high pressure e.s.r. measurements of the hydrogenation reaction of Taiheiyo coal in the presence of catalysts were carried out to understand the stabilization of thermally and/or catalytically induced free radicals. A decrease in free radical concentration with increasing temperature was observed for ZnCl₂ and SnCl₂ · 2H₂O catalysts at 10MPa under hydrogen gas. High pressure modified single-cell d.t.a. and p.d.a. equipment augmented the uniquely designed high temperature, high pressure e.s.r. cell. The hydrogenation reaction was monitored under the same experimental conditions as for e.s.r. From the results of the combination of high temperature, high pressure e.s.r. with high pressure d.t.a. and p.d.a., it was established that H₂ molecules can react efficiently with free radicals from coal molecules created by the presence of ZnCl₂ and SnCl₂ · 2H₂O catalysts.     

Characterisation of separated melamine—formaldehyde adducts (methylolmelamines) and adduct mixtures by h.p.l.c. and by n.m.r. and u.v. spectroscopy

Most of the individual methylolmelamines that occur in melamine–formaldehyde adduct mixtures have been separated by preparative high-performance liquid chromatography (h.p.l.c.) and recovered in amounts sufficient to allow their characterisation by high-field ¹H- and ¹³C-n.m.r. Particular attention has been paid to the chemical shifts of the aromatic azine carbons of the melamine nuclei. These carbon shifts are shown broadly to be in agreement with some values previously published, but additional assignments have been made. It is shown that a satisfactory quantitative analysis of the methylolmelamines in a melamine–formaldehyde adduct mixture can be carried out either by h.p.l.c. or by ¹³C-n.m.r.     

Two-dimensional n.m.r. characterization of cycloaliphatic epoxy resins

The cycloaliphatic epoxy resins were studied by various two-dimensional nuclear magnetic resonance (2D n.m.r.) spectroscopies. The ¹³C n.m.r. spectra of the epoxy resins were assigned by using DEPT and 2D INADEQUATE techniques and the ¹H n.m.r. spectra were assigned by using 2D ¹H---¹H and ¹H---¹³C COSY techniques. Complete characterization of the samples synthesized by the oxidation of cyclohexene derivatives not only revealed the existence of the stereochemical isomers resulting from the structural difference of the oxide rings in the samples but also provided the composition ratio of the isomers.     

Evaluation of a delayed coking process by H and C n.m.r. spectroscopy: 2. Detailed interpretation of liquid n.m.r. spectra

The ¹H and ¹³C nuclear magnetic resonance (n.m.r.) spectra of a delayed coking feedstock and products, presented in a previous paper, are analysed here in detail by matching results from inspection of both nuclei. The conventional spectra of whole samples are used in combination with elemental analysis data, and substantial agreement is obtained. Differences are explored to yield valuable information. Interpretation of some band assignments is modified to account for new results. This approach results in a detailed quantitative estimation of a few key structures that contain the main functional groups that characterize these petroleum fractions.     

E.s.r. spectra of eastern oil shales

E.s.r. spectra of several oil shales from eastern and western USA have been measured at 9 and 25 GHz. The spectra of the western shales were similar to previously reported spectra and consist of a Mn²⁺ signal and a featureless organic signal. The eastern spectra consist of a V⁴⁺ signal and a complex and unusual organic signal consisting of at least four component signals. The organic signal has been characterized in terms of g factor, line-width and saturation characteristics. The effect of oxygen on the signal has also been examined. Electron nuclear double resonance (ENDOR) signals have been obtained from the organic signals of the eastern oil shales.     

An h.p.l.e. and m.s. analysis of distillate fractions of neutral oil from hydrogenated Akabira coal to elucidate chemical structures

Akabira coal-derived neutral oil was separated into 25 narrow boiling range fractions covering 183–423 °C, and subsequently separated into compound class fractions : alkanes, monoaromatics, naphthalene-type diaromatics, fluorene-type diaromatics and tri- and/or tetraaromatics, by high performance liquid chromatography (h.p.l.c.). The compound type analyses of the distillate/h.p.l.c. fractions were performed using electron impact mass spectroscopy (e.i.m.s.) or field ionization mass spectroscopy (f.i.m.s.). Aromatic/hydroaromatic compound types and the alkyl side-chain carbon distribution of the distillate/h.p.l.c. fractions were clarified, based on the separation behaviour of h.p.l.c. and the type analyses according to Z value by m.s. By the distillation/h.p.l.c./m.s. method, coal-derived oil was characterized in terms of the distribution of the numbers of aromatic rings, naphthenic rings and carbons of alkyl groups attached to these rings. The variations in chemical structure in a compound class with distillation temperature are discussed in terms of these chemical structural factors.     

活性染料SEFR值与中性固色工艺研究

根据活性染料染色特征值S．E．F．R．选择适用于中性固色工艺的活性染料，结果表明，S值高和低的活性染料对碱的浓度和温度敏感，对固色率的影响较为杂乱，但在温度为80℃时，这类染料的固色率均达到峰值：染色特征值在50-60范围内的活性染料适用于中性固色、以甲酸钠为中性固色剂对活性染料进行中性固色实验，其固色率均可达到60%左右．各项牢度均达到标准。最佳工艺条件为：甲酸钠：15g／L；尿素：20g／L；双氰胺10g／L，固色温度85℃：浴比：1：20。     

Structural characterization of Saudi Arabian heavy crude oil by n.m.r. spectroscopy

Saudi Arabian heavy crude oil was separated into six fractions, including five distillate fractions (<93, 93–204, 204–260, 260–343 and 343–454 °C) and a >454 °C distillation residue. Each fraction was analysed by ¹H and ¹³C n.m.r. spectroscopy, and combined gained information from these analyses provided reliable average structural parameters. These included estimation of aliphatic and aromatic content, average paraffinic chain length, and estimation of hydrogen, methyl and alkyl bearing aromatic carbons for each of the six fractions. The extent of branching in paraffinic chains and amount of aromatic bridgehead carbons were also calculated.     

球形壳聚糖固定化糖化酶的研究

研究了以球形壳聚糖作载体固定化糖化酶的方法，探讨了戊二醛用量，酶量，温度，pH值对固定化效果的影响。     

13C n.m.r. study of raw materials for carbon black

¹³C n.m.r. spectroscopy has been applied to investigate a number of coal tar and petroleum-derived carbon black feedstocks. Application of the J-modulated spin echo technique is especially rewarding, as this method renders the quaternary carbons directly detectable. Thus the quality of carbon black feedstocks can additionally be gauged on the basis of the contents of quaternary carbons, which is a direct indication of the carbon yield in the carbon black production process.