诺卜二烯的合成反应研究及其光固化应用探索
摘要
松节油作为一种天然可再生资源,它的深加工利用越来越受到国内外研究者的重视。诺卜二烯是松节油深加工衍生产物,广泛用于香料化学、手性合成及各种配方的有效成分等。本文详细研究了以诺卜醇直接脱水制备诺卜二烯的反应,优化了工艺技术条件,改进并优化了诺卜醇对甲苯磺酸酯消去制备诺卜二烯的传统方法。探索了诺卜二烯的紫外光固化反应特性及其固化产物性能。本研究为萜烯类化合物及其结构类似物在光固化材料中的应用创造了基础。
对比研究了以10 %硫酸、对甲苯磺酸、硫酸氢钾、硫酸铜、硅胶、硫酸铜-硅胶复合催化剂和硅胶负载硫酸铜作脱水剂或催化剂时诺卜醇脱水制备诺卜二烯的反应效果。结果发现,以硅胶负载硫酸铜作脱水剂反应效果最好,且后处理简单,催化剂可以重复回收利用。当以硅胶负载硫酸铜做脱水剂时,以甲苯做带水剂反应效果最佳,以二甲苯和乙酸戊酯作带水剂虽然脱水在较短时间完成,但异构体含量较高。
以硅胶负载硫酸铜作脱水剂,甲苯作带水剂时,优化实验的结果表明:脱水剂中硅胶与硫酸铜的质量比为4∶1时的脱水效果最佳;脱水剂用量在一定范围内产品收率呈先增大后减小的趋势,用量以硫酸铜计与诺卜醇的物质的量之比为1∶4时产品收率最大;甲苯作溶剂兼带水剂最佳用量为70 mL(诺卜醇为5.0 g时);反应时间在1.0～8.0 h内产品收率呈先增大后减小的趋势,在4.0 h时产品收率达到最大值。在较佳反应条件下诺卜二烯的产率为83.0 %,纯度91.0 %。该方法比较适合于较大规模制备诺卜二烯,具有工业化开发应用的前景。
分别采用三种方法合成了诺卜醇对甲苯磺酸酯,这其中以三乙胺做溶剂和催化剂产率最高,达96.7 %,且后处理简单,去除三乙胺后以正己烷重结晶即得产品。诺卜醇对甲苯磺酸酯在氢氧化钾、乙醇钠、乙酸钾、碳酸钾四种碱性试剂作用下发生消去反应时,诺卜二烯产率递减。以氢氧化钾做碱性试剂,偶极溶剂二甲亚砜做溶剂时,诺卜醇对甲苯磺酸酯反应效果最佳,以消去产物最主,诺卜二烯产率达72.9 %,纯度95.2 %。该方法比较适合于制备纯度要求较高的诺卜二烯。
探索研究了诺卜二烯的UV光聚合反应特性,引发剂Irgacure 6512和Darocure 1173用量分别为诺卜二烯质量的8.0 %和7.0 %,乙烯基双键转化率分别为91.5 %和90.7%,固化产物数均分子量分别达到1 286和941道尔顿,平均聚合度分别为约9和6,虽然聚合度不高,但均匀性较好。固化产物性能测试结果表明,涂膜具有较好的柔韧性、附着力、耐酸、耐碱、耐水性等。
Turpentine, as a kind of renewable resources, its deep process and ulitilation are paid more and more attention. Nopadiene is a kind of turpentine deratives, which is wildly used in perfume chemistry, chiral synthesis, and it is also an important effective ingredient in a number of formulas. In this paper, the direct dehydration of nopol was studied to prepare nopadiene with a process optimization, and the elimination of nopol tosylate was improved and optimized to prepare nopadiene as a traditional method. The UV curing reaction of nopadiene and the properties of the cured product were also studied. This work will provie a reference for the application of terpenoid and its analogus as UV curing materials.
Sulfuric acid (10 %), p-toluenesulfonic acid, potassium hydrogen sulfate, copper sulfate, silica-gel,copper sulfate-silica gel composite as well as silica-gel supported copper sulfate were compared as catalysts or dehydrating agents for the dehydration to prepare nopadiene. The result showed that the silica-gel supported copper sulfate was the best dehydration agent, with easy after-treatment and recovery. When the silica-gel supported copper sulfate was used as a dehydration agent, toluene was the best carrying-water agent, although xylene or amyl acetate made faster dehydration with more isomerization.
While silica-gel supported copper sulfate was used as dehydrating agent and toluene was used as water-carrying agent, the optimizing experiment showed that the mass ratio of silica- gel and copper sulfate was 4:1; the yield of nopadiene increased at first and then declined with the increase of dehydration agent and reaction time (range of 1.0 h～8.0 h, suitable time is 4 h). Nopadiene was prepared in yield of 83.0 % with purity of 91.0 %(GC) when 5.0 g nopol was dehydrate in 70 mL toluene under the optimized conditions. This method may be suitable for a larger-scale preparation of nopadiene with the prospect of industrial development and application.
Nopyl tosylate was prepared in triethyl amine (TEA) as both catalyst and solvent in a yield of 96.7 % because of its easy after-treatment compared with other two methods. When elimination reaction of nopol tosylate occurred under the of, Hereafter, nopadiene was prepared with the elimination of nopol tosylate in a yield decreasing by a sequence of potassium hydroxide, sodium ethoxide, potassium acetate and potassium carbonate. And nopadiene yielded in a yield of 72.9 % with a purity of 95.2% by potassium hydroxide as alkaline reagent and the dipole solvent DMSO as a solvent. This method may be suitable for preparation of nopadiene with higher purity.
The UV curing reactivity of nopadiene has been also investigated in this paper, and it was found that conversion rates of vinylic double bond were 91.5 % and 90.7 % by using photoinitiators in dosages of 8.0 % Irgacure 6512 and 7.0 % Darocure 1173 based to the mass of nopadiene, respectively. The cured product photoinitiated by Irgacure 6512 and Darocure 1173 gave number average molecular weights of 1 286 daltons and 941 daltons with polymerization degrees of 9 and 6, respectively, and the uniformity was good. The obtained coating represented superior properties such as hardness, flexibility, mechanical, impact and acid resistance, alkali resistance.
对比研究了以10 %硫酸、对甲苯磺酸、硫酸氢钾、硫酸铜、硅胶、硫酸铜-硅胶复合催化剂和硅胶负载硫酸铜作脱水剂或催化剂时诺卜醇脱水制备诺卜二烯的反应效果。结果发现,以硅胶负载硫酸铜作脱水剂反应效果最好,且后处理简单,催化剂可以重复回收利用。当以硅胶负载硫酸铜做脱水剂时,以甲苯做带水剂反应效果最佳,以二甲苯和乙酸戊酯作带水剂虽然脱水在较短时间完成,但异构体含量较高。
以硅胶负载硫酸铜作脱水剂,甲苯作带水剂时,优化实验的结果表明:脱水剂中硅胶与硫酸铜的质量比为4∶1时的脱水效果最佳;脱水剂用量在一定范围内产品收率呈先增大后减小的趋势,用量以硫酸铜计与诺卜醇的物质的量之比为1∶4时产品收率最大;甲苯作溶剂兼带水剂最佳用量为70 mL(诺卜醇为5.0 g时);反应时间在1.0～8.0 h内产品收率呈先增大后减小的趋势,在4.0 h时产品收率达到最大值。在较佳反应条件下诺卜二烯的产率为83.0 %,纯度91.0 %。该方法比较适合于较大规模制备诺卜二烯,具有工业化开发应用的前景。
分别采用三种方法合成了诺卜醇对甲苯磺酸酯,这其中以三乙胺做溶剂和催化剂产率最高,达96.7 %,且后处理简单,去除三乙胺后以正己烷重结晶即得产品。诺卜醇对甲苯磺酸酯在氢氧化钾、乙醇钠、乙酸钾、碳酸钾四种碱性试剂作用下发生消去反应时,诺卜二烯产率递减。以氢氧化钾做碱性试剂,偶极溶剂二甲亚砜做溶剂时,诺卜醇对甲苯磺酸酯反应效果最佳,以消去产物最主,诺卜二烯产率达72.9 %,纯度95.2 %。该方法比较适合于制备纯度要求较高的诺卜二烯。
探索研究了诺卜二烯的UV光聚合反应特性,引发剂Irgacure 6512和Darocure 1173用量分别为诺卜二烯质量的8.0 %和7.0 %,乙烯基双键转化率分别为91.5 %和90.7%,固化产物数均分子量分别达到1 286和941道尔顿,平均聚合度分别为约9和6,虽然聚合度不高,但均匀性较好。固化产物性能测试结果表明,涂膜具有较好的柔韧性、附着力、耐酸、耐碱、耐水性等。
Turpentine, as a kind of renewable resources, its deep process and ulitilation are paid more and more attention. Nopadiene is a kind of turpentine deratives, which is wildly used in perfume chemistry, chiral synthesis, and it is also an important effective ingredient in a number of formulas. In this paper, the direct dehydration of nopol was studied to prepare nopadiene with a process optimization, and the elimination of nopol tosylate was improved and optimized to prepare nopadiene as a traditional method. The UV curing reaction of nopadiene and the properties of the cured product were also studied. This work will provie a reference for the application of terpenoid and its analogus as UV curing materials.
Sulfuric acid (10 %), p-toluenesulfonic acid, potassium hydrogen sulfate, copper sulfate, silica-gel,copper sulfate-silica gel composite as well as silica-gel supported copper sulfate were compared as catalysts or dehydrating agents for the dehydration to prepare nopadiene. The result showed that the silica-gel supported copper sulfate was the best dehydration agent, with easy after-treatment and recovery. When the silica-gel supported copper sulfate was used as a dehydration agent, toluene was the best carrying-water agent, although xylene or amyl acetate made faster dehydration with more isomerization.
While silica-gel supported copper sulfate was used as dehydrating agent and toluene was used as water-carrying agent, the optimizing experiment showed that the mass ratio of silica- gel and copper sulfate was 4:1; the yield of nopadiene increased at first and then declined with the increase of dehydration agent and reaction time (range of 1.0 h～8.0 h, suitable time is 4 h). Nopadiene was prepared in yield of 83.0 % with purity of 91.0 %(GC) when 5.0 g nopol was dehydrate in 70 mL toluene under the optimized conditions. This method may be suitable for a larger-scale preparation of nopadiene with the prospect of industrial development and application.
Nopyl tosylate was prepared in triethyl amine (TEA) as both catalyst and solvent in a yield of 96.7 % because of its easy after-treatment compared with other two methods. When elimination reaction of nopol tosylate occurred under the of, Hereafter, nopadiene was prepared with the elimination of nopol tosylate in a yield decreasing by a sequence of potassium hydroxide, sodium ethoxide, potassium acetate and potassium carbonate. And nopadiene yielded in a yield of 72.9 % with a purity of 95.2% by potassium hydroxide as alkaline reagent and the dipole solvent DMSO as a solvent. This method may be suitable for preparation of nopadiene with higher purity.
The UV curing reactivity of nopadiene has been also investigated in this paper, and it was found that conversion rates of vinylic double bond were 91.5 % and 90.7 % by using photoinitiators in dosages of 8.0 % Irgacure 6512 and 7.0 % Darocure 1173 based to the mass of nopadiene, respectively. The cured product photoinitiated by Irgacure 6512 and Darocure 1173 gave number average molecular weights of 1 286 daltons and 941 daltons with polymerization degrees of 9 and 6, respectively, and the uniformity was good. The obtained coating represented superior properties such as hardness, flexibility, mechanical, impact and acid resistance, alkali resistance.
引文
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[3] Conrad J, Bruns K ,Upadek H. 4(5)-Acetyl-9,9-dimethyltricyclo-[4.4.0.18,10]-undec-1-ene, its preparation and use in perfumery compositions as an odorant: US, 4322559[P]. 1982-03-30.
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[5] Lange W. Silvichemicals from coniferous wood. Part 2: on some diene-adducts of nopadiene [J]. Holz als Roh- und Werkstoff , 1976, 34(3): 101-105.
[6] James S T, Kenneth F, Stiah, et al. Heat transfer fluid compositions for low temperature applications: EP, 947572[P]. 2003-11-26.
[7] Kemp J A. Improvements in or relating to the stability of films of vinyl halide polymers: GB, 881534[P]. 1959-01-19.
[8] Jansen B R, Sears S E. Heat exchange cleaning process: US, 6936112[P]. 2005-10-30.
[9] Ashkenazi P, Benn R, Grinsburg D. The reaction of nopadiene with 4-substituted 1,2,4-triazoline-3,5- diones [J]. Helvetica Chimica Acta, 1984, 67(2): 583-585.
[10] Minuti L, Taticchi A, Marrocchi A, et al. Synthesis of optically active polycyclic compounds by Diels-Alder reactions of nopadiene[J]. Tetrahedron∶Asymmetry, 2004, 15(20): 3245-3248.
[11] Minuti L, Taticchi A, Marrocchi A, et al. High pressure Diels–Alder reactions of (+)-nopadiene with cycloalkenones [J]. Tetrahedron: Asymmetry, 2004, 15: 1187-1192.
[12] Tanasri B. Novel synthesis of chiral 1,2-aminophosphine ligands and their applications in asymmetric catalysis[D]. Ludwig-Maximilians-Universit?t München, 2003.
[13] Wojciechowska J K, Markowicz W S. Crystal and molecular of a sesquiterpene lactone with pinane skeleton [J]. Journal of Crystallographic and Spectrosopic Research, 1993, 23(1): 33-36.
[14] Szymoniak J, Felix D, Besancon J, et al. A simple and practical synthesis of 3,10-disubstitutedβ-pinene derivatives [J]. Tetrahedron, 1996, 52(12): 4377-4382.
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