微波协同强酸性阳离子交换树脂催化湿地松香异构化反应

研究以乙醇为溶剂,在不同加热方式下强酸性阳离子交换树脂对湿地松香的催化异构化反应.结果表明,在普通回流加热方式下,强酸性阳离子交换树脂催化湿地松香的异构化反应主要表现为酸催化作用;微波辐照加热能大大加快强酸性阳离子交换树脂的催化异构化反应,反应2 h后,枞酸型树脂酸的异构化反应已达到平衡,枞酸和异海松酸成为异构平衡溶液的主要树脂酸,在过滤回收催化剂后,通过枞酸十二胺盐结晶法分离提纯.     

丙烯海松酸的合成研究

通过松香与丙烯酸的Diels-Alder加成反应制备了丙烯海松酸,考察了原料摩尔比对反应的影响。实验结果表明,随着丙烯酸用量的增加,产物的酸值和软化点逐步升高至不变;紫外光谱研究发现,随着丙烯酸用量的增长,枞酸型树脂酸相对含量下降,而海松酸型树脂酸的含量未见显著变化;气相色谱-质谱联用分析显示,在松香树脂酸与丙烯酸的加成反应中,树脂酸中的海松酸、异海松酸、脱氢枞酸等不参与反应,而长叶松酸、枞酸和新枞酸异构化为左旋海松酸,与丙烯酸发生加成反应;即使丙烯酸过量,长叶松酸和枞酸转化率最高也只可以达到91%和86%;研究还发现,加成产物丙烯海松酸有二种构造异构体,分别占丙烯海松酸量的20%和80%。     

改变树脂酸异构物的数目和含量降低松香结晶趋势的研究

在松脂加工成松香的过程中,松脂中含有不同数量的各种树脂酸,经热异构化反应,树脂酸的组成在不断地变化,而树脂酸的组分比例则同松香的结晶趋势又有直接的联系。按照我省现有松香加工的工艺技术条件,松香成品的树脂酸组分,经气相色谱分析发现:在热异构过程中,起异构化反应的主要是带有两个双键的枞酸型树脂酸,而海松酸型的树脂酸则变化不大。而在枞酸型的树脂酸中,左旋海松酸最为敏感,它在松脂加工成松     

印尼松香的化学组成特征

利用GC-MS联用仪和GC对印尼松香进行了定性和定量分析,鉴定出7个组分,占总量的97. 11%,其中海松酸型,枞酸型树脂酸及二元羧酸分别占23. 57%,64. 68%,8. 86%。主要成分为山达海松酸,异海松酸,长叶松酸,枞酸和南亚松酸,含量分别为9. 03%,14. 54%,22. 17%,32. 60%,8. 86%。结果表明,印尼松香成分类似我国海南南亚松松香,确定该松香原料来自南亚松。     

浮油松香中树脂酸的毛细管气相色谱—质谱

用开管毛细管柱的气相色谱和质谱法研究芬兰浮油松香中树脂酸的组成。在一个涂有1.4—丁二酸丁二醇酯的柱子上,浮油松香样品中已知的16个树脂酸都能得到很好的分离,并且能用质谱加以记录。气相色谱—质谱法证实了所有的树脂酸都是海松酸型和枞酸型的。在相应的粗浮油中有8个酸没有被检出,很明显它们是在蒸馏工艺过程中形成的。8,15—海松二烯—18—酸和8,15—异海松二烯—18—酸在松香中是存在的,而不存在于粗浮油中,这就表明在浮油蒸馏过程中海松酸型酸也发生了多样的异构作用。另外,在蒸馏过程中形成了三个二氢枞酸和具有同一质谱峰的两个酸,据推测是7,9(11)—枞二烯—18—酸的立体异构体。     

树脂酸组成与松香结晶

松香主要由各种树脂酸组成,约占80～85%,其它还有一些脂肪酸、中性物质和少量的高沸点萜烯化合物。天然马尾松松脂的树脂酸部分中主要含有海松酸型酸:海松酸、异海松酸,枞酸型酸:枞酸、左旋海松酸、长叶松酸、去氢枞酸等。在松脂加工成松香的过程中,具有两个双键系统的枞酸型酸:枞酸、左旋海松酸、长叶松酸、新枞酸在加热的条件下发生同分异构化作用,而使松香成为主要由各种同分异构的树脂酸组成的熔合物。     

气相色谱用马尾松松香标准样品的定值

系统地介绍了气相色谱用马尾松松香标准样品的定值方法。采用单一方法通过6家实验室联合定值,得到标准样品中7种树脂酸的GC含量(%)的特性值和扩展不确定度:海松酸8.2683±0.3203;山达海松酸:1.7433±0.3199;异海松酸:0.7652±0.3118;长叶松酸:30.8201±1.3668;去氢枞酸:3.2731±0.8693;枞酸:34.9275±1.2664;新枞酸:18.7469±1.8494。     

提高歧化松香中去氢枞酸含量

日本公开昭63-81181提出,通过加入烯烃和Pa/C催化剂来提高去氢枞酸(Ⅰ)产量。如脂松香(酸价168.5,枞酸型树脂酸79.4,海松酸型树脂酸10.7,中性物99%)与1:1的1-十八烯-1-十六烯在180℃下加热,然后加入5%钯/碳     

混合松香试验报告

我国马尾松脂松香含枞酸型树脂酸较多(约占树脂酸总量的73%),形成松香结晶的主要成份是长叶松酸和枞酸。在热异构化进程中,此二酸达到适宜比值范围(长叶松酸∶枞酸=1∶1.4～1.8),结晶可能性较少。马尾松脂热异构规律表明,长叶松酸、枞酸在松脂中的含量并不太大,松脂中主要成份是左旋海松酸,由于左旋海松酸较容易异构,松脂加工成松香时,基本异构完全,其异构产物主要是长叶松酸和枞酸。新枞酸虽     

Pd/C上松香催化歧化反应集总动力学

以松香为原料、改性Pd/C为催化剂、200#油为溶剂及N2为保护气，进行松香催化歧化反应集总动力学的研究。在消除内外扩散影响的条件下，在线跟踪48315～53315 K的反应产物并用毛细管柱气相色谱法测定反应体系组成随时间的变化关系。根据松香歧化反应机理和特点，借鉴集总思想和方法，按结构族组成和动力学相近原则划分该复杂反应体系的集总组分，构建了Pd/C上松香歧化集总反应网络，建立了枞酸型树脂酸、海松酸型树脂酸、氢化枞酸型树脂酸、氢化海松酸型树脂酸和脱氢枞酸五集总动力学模型；采用Levenberg-Marquart法，以Matlab编程和SPSS数理统计软件估算了模型参数，得到枞酸型树脂酸脱氢、加氢，海松酸型树脂酸加氢反应过程的活化能分别为11139 kJ·mol-1、10876 kJ·mol-1、9735 kJ·mol-1，结果表明，所建动力学模型与实验数据吻合良好，并能预测反应在54315 K的集总组分浓度分布。     

Capillary gas chromatography-mass spectrometry of resin acids in tall oil rosin

The resin acid composition of Finnish tall oil rosin was investigated by gas chromatography and mass spectrometry employing open tubular capillary columns. On a column coated with 1,4-butanediol succinate, 16 resin acids found in tall oil rosin samples were well resolved, and mass spectra could be recorded. All resin acids were confirmed to be of the pimaric and abietic types by gas chromatographymass spectrometry. Eight of the acids were not detected in the corresponding crude tall oils and evidently had been formed during the technical distillation process. The presence of 8,15-pimaradien-18-oic and 8,15-isopimaradien-18-oic acids in the rosin, but not in the crude tall oil, indicates that the pimaric type acids also undergo extensive isomerization during tall oil distillation. Additionally, three dihydroabietic acids and two acids with identical mass spectra, tentatively stereoisomers of 7,9(11)-abietadien-18-oic acid, were formed during the distillation process.     

Fatty and resin acids of spanishpinus pinaster Ait. Subspecies

The qualitative and quantitative composition of the acid fraction of wood extractives from three SpanishPinus pinaster Ait. subspecies (Atlantic, mountain Mediterranean and plain Mediterranean) were studied. Seven samples of each subspecies were prepared according to Technical Association of Pulp and Paper Standards, extracted with petroleum ether (b.p. 40–60°C) in a Soxhlet apparatus and saponified with ethanolic 0.4N potassium hydroxide. The acid fraction was methylated with diazomethane and studied by combined gas chromatography/mass spectrometry. The major constituents found were palmitic, oleic and linoleic among the fatty acids and pimaric, sandaracopimaric, levopimaric, isopimaric, abietic and dehydroabietic among the resin acids. Neoabietic and palustric acids were not found. Variations in the quantitative composition of the acid fraction enable us to distinguish the three subspecies. Main quantitative differences are found between the Atlantic subspecies and the two Mediterranean subspecies.     

The behavior of resin acids during tall oil distillation

The behavior of resin acids during tall oil distillation was studied by analyzing samples from six industrial-scale processes. The same artifact resin acids were formed in all processes. However, the proportion of artifact resin acids in tall oil rosins varied from 8.3 to 18.3% of the resin acids. The lowest values were found for two processes utilizing thin-film evaporators. The yield of resin acids in the tall oil rosin fraction varied from 62 to 80% of the resin acids in the crude tall oil feeds. Dehydroabietic acid was formed in all processes, the amount in rosin being 14-44% more than in the crude tall oil feed. Of the abietic acid, only 45-82% was recovered in the tall oil rosin fraction. The distribution of various resin acids and their reaction products during distillation was determined. Major resin acid impurities in tall oil fatty acids were 8,15-pimaradien-18-oic acid and 8,15-isoprimaradien-18-oic acid, both formed chiefly during distillation, and two secodehydroabietic acid isomers common in crude tall oils. The reactions of resin acids leading to new isomers or non-acidic products are discussed. Some results of this work were presented at the 173rd American Chemical Society Meeting, New Orleans, March 1977.     

海松酸型树脂酸的分离及应用研究进展

系统地总结了近年来从松香树脂酸中分离制备海松酸型树脂酸的主要方法,包括碱金属盐沉淀分离法、直接铵盐沉淀法、间接分步铵盐沉淀法等,其中铵盐沉淀法比碱金属盐沉淀分离法较为实用。综述了海松酸型树脂酸在生物活性、材料及合成等方面的主要应用状况。     

On the Palladium-On-Charcoal Disproportionate of Rosin

Abstract

Changes in the composition of gum rosin during disproportionate in the presence of 5% palladium-on-charcoal have been determined by gas chromatography. The principal reaction product was dehydro-abietic acid. The exocyclic vinyl group of the pimaric/isopimaric-type resin acids was hydrogenated completely. Only a small amount of dihydroabietic acids was formed. Eight dihydro resin acids were identified. No tetrahydro resin acids were observed.     

松香树脂酸的单离与应用

分别综述了枞酸、左旋海松酸、脱氢枞酸、新枞酸等松香树脂酸在医药、农药、表面活性剂制备以及在其他精细化学品合成中的应用,指出纯粹的松香树脂酸作为绿色化学合成的原料有广阔的工业应用前景。介绍了松香树脂酸单离的胺盐结晶方法,提出对松香树脂酸单离的研究重点是加快胺化反应速度、强化结晶传递过程、采用反应与分离耦舍的方法,以提高松香树脂酸的提取率。     

海松酸型树脂酸资源分布及组成研究

海松酸型树脂酸是重要的二萜树脂酸,由于其C_-13位上同时拥有甲基和乙烯基的特殊结构而具有较强的生物活性,如抗菌、抗炎、抗微生物、杀虫、降胆固醇、抗癌等。海松酸型树脂酸广泛分布于松属植物的树脂之中,更多的是存在于各种来源的松香之中,同时在桧柏类等其他植物之中也有分布。海松酸型树脂酸作为树脂酸的一个重要的资源类型,具有较好的发展趋势和开发应用前景。研究其在自然界的具体分布状况,探索和发现一种能够有效分离和提纯制备海松酸型树脂酸或其单体化合物的行之有效的方法,这是海松酸型树脂酸作为资源进行合理而有效利用的重要基础。     

Spectrophotometric analysis of tall oil rosin acids

Summary About half of the rosin acids in whole and distilled tall oil consist of abietic and neoabietic acids, as distinguished from hydroabietic acids, dehydroabietic acid, and the pimaric acids. In this respect the tall oil rosin acids are similar to those from gum or wood rosin. This was established by spectrophotometric analysis of the rosin acids from whole tall oil, double distilled tall oil, rosin acids crystallized from tall oil, and rosin acids separated from tall oil by fractional distillation. The rosin acids crystallized from tall oil contained the highest percentage of abietic acid, but the sum of abietic and neoabietic acids was only slightly higher. The rosin acids from acid refined tall oil contained appreciably less abietic and neoabietic acid than the others. Before spectrophotometric analysis the rosin acids were isolated from the tall oils in about 95% yield by cyclohexylamine precipitation.