三种松香季铵盐的合成及抑木腐菌性能研究
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摘要
木材是一种天然的可再生生物材料,其开发和利用符合环保的要求,但是它的主要缺点之一是容易受到微生物等的侵害而腐朽,从而影响其使用。随着木材的需求量日益增加,木材防腐产业成为了节约森林资源的重要途径。
本文以松香为原料合成了几种具有抑菌活性和表面活性的松香基季铵盐。松香基季铵盐的合成,一方面充分利用了松香这一可再生资源,大大提高了它的附加值,另一方面为合成价格低廉、高活性、无毒、环保、易生物降解的木材防腐剂提供新的种类。
以松香为原料,合成了N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵,首先松香与环氧氯丙烷进行反应,反应物的摩尔比为n(松香)：n(环氧氯丙烷)=1：2,在90℃下反应时间为3.5 h,将产物与二甲胺以摩尔比1：2在80℃下反应2.5h,生成N-(3-松香酰氧-2-羟)丙基-N,N-二.甲基氯,最后再与环氧氯丙烷在90℃下反应3h,反应摩尔比为1：1得到季铵盐的得率为72.8%。因原料松香中含有很多杂质,故以脱氢松香为原料用同一方法合成了N-(3-脱氢松香酰氧-2-羟)丙基-N,N-二甲基氯化铵,通过对其结构的表征来证明目标产物N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵的结构,利用FTIR、HPLC、1H-NMR对N-(3-脱氢松香酰氧-2-羟)丙基-N,N-二甲基氯化铵的结构进行了确证。测定了N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵对四种木材腐朽菌黑曲霉(Aspergillus niger)、宛氏拟青霉(Paecilomyces variot Bainier)、彩绒革盖菌(Coriolus versicolor)、密黏摺菌(Gloeophyllum trabeum)的抑菌性能,发现对四种木腐菌均有抑制效果,尤其是对密黏摺菌的抑制效果最好。选择N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵浓度为16 mg/mL、32 mg/mL、64 mg/mL,浸泡试材木块,进行木块微生物培养实验,’用失重法检测松香基酰胺对木材的防腐性能,结果显示松香基酰胺的浓度在64mg/mL时对彩绒革盖菌和密粘褶菌获得了Ⅰ级防腐。
以松香为原料,与丙烯酸反应后,经环氧氯丙烷改性,再与二甲胺反应,得到的产物再与环氧氯丙烷在80℃下反应4.5h,反应的摩尔比为1：3得到双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲基氯化铵。利用FTIR、HPLC、1H-NMR对其官能团及结构进行了表征,季铵盐得率为92.8%。用双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵对绵腐卧孔菌(Postia placenta),彩绒革盖菌(Coriolus versicolor)、密粘褶菌(Gloeophyllum trabeum)、乳白耙菌(Irpex lacteas)四种菌进行了抑菌试验,发现对四种菌均有较好的抑制效果,尤其是绵腐卧孔菌和乳白耙菌。选择双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵浓度为16 mg/mL、32 mg/mL、64 mg/mL,浸泡试材木块,进行木块防腐实验,用失重法评价了双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵对木材的防腐性能,结果显示双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵浓度在64 mg/mL时对彩绒革盖菌、密粘褶菌都是获得了Ⅰ级防腐。通过测定表面张力手段研究了双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵的表面活性,其临界胶束浓度(CMC)为8×10-3mol/L,表面张力(γCMC)为39.38mN/m,乳化力为56min,泡沫力为250mm,泡沫稳定性为200 mm。
以松香为原料与丙烯酸反应生成改性松香,再将改性松香与三乙胺与环氧氯丙烷进行反应所生成的季铵盐中间体环氧丙基三乙基氯化铵进行反应,生成产物双N-(3-松香酰氧基-2-羟)丙基-N,N-三乙基氯化铵,并通过重量法得出季铵盐产率为87.7%。分别利用了FTIR、HPLC对产物的结构进行了表征,结果证明已合成目标产物。利用菌丝倒扣法测定了双N-(3-松香酰氧基-2-羟)丙基-N,N-三乙基氯化铵对绵腐卧孔菌(Postia placenta),彩绒革盖菌(Coriolus versicolor)、密粘褶菌(Gloeophyllum trabeum)、乳白耙菌(Irpex lacteas)四种菌进行了抑菌试验,当浓度为0.5 mg/mL时,对于彩绒革盖菌、密粘褶菌及绵腐卧孔菌均有明显的抑制效果,当浓度为1 mg/mL时才对乳白耙菌有明显抑制效果。
Wood is a kind of nature renewable resource. The exploration and the use of wood are environmentally safe, however, wood is low decay resistance. With the need of wood increasing, wood protection becomes an important way of saving the forest resources.
In this paper, rosin is used as raw material to synthesize some kinds of rosin derivatives which have anti-fungal activity and surface activity. Synthesis based on rosin not only can make full use of this renewable resource and can increase greatly its additional value but also can prompt the industry of deep processing development of rosin. Wood preservatives from rosin are renewable, active and environment-friendly.
i.Rosin was used as raw material to prepare N-(3- rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride. Firstly, the rosin was esterified by epoxy chloropropane with the mole ratio of 1:2, the reaction time of 3.5h at 90℃. The intermediate was 3-rosin acyloxy-2-hydroxypropyl chlorine. Then, the intermediate reacted with demethylamine to produce N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine at the following conditions:their mole ratio of 1:2, reaction temperature of 80℃and reaction time of 2.5h. Finally, the N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine was quaternized by epoxy chloropropane with the mole ratio of 1:1, the reaction time of 3h at 90℃. The content of the product was characterized by gravimetric analysis with sodium tetraphenylborate as its precipitation reagent and the yield was 72.8%. There are many impurities in the rosin, so N-(3-dehydrogenated rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride was synthesized in the same mechanism used to characterize the structure of N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride. The chemical structure of the product was identified by FTIR、HPLC、1H-NMR.
The antifungal activity of the product was determined by paper-disc method with wood decay fungi such as Trametes versicolor, Gloeophyllum trabeum and wood stain fungi such as Aspergillus niger and Paecilomyces variot Bainier. The anti-fungal experiment results signified that the N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride, is active to these fungi, especially Gloeophyllum trabeum.. The concentrations of the product are 16 mg/mL,32 mg/mL and 64 mg/mL. The weight-loss method was used to detect the performance of N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride on wood protection. The result show that when the concentration of N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride is 64 mg/mL, the resistence to Trametes versicolor, Gloeophyllum trabeum is on the first grade of the wood protection.
2. Rosin was used as material to prepare bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride firstly, the rosin was modified by acrylic acid and a carboxylic acid group was introduced to the rosin. Secondly, the modified rosin reacted with the epoxy chloropropane, the intermediate I was obtained by the way. Thirdly, the intermediate reacted with dimethylamine. By this way the intermediateⅡwas synthesized. Finally the intermediate II reacted with the epoxy chloropropane in the mole ratio of 1:3, the reaction time of 4.5h at 80℃. The content of the product was characterized by gravimetric analysis with sodium tetraphenylborate as its precipitation reagent and the yield was 92.8%. The chemical structure of the product was identified by FTIR、HPLC、1H-NMR. The antifungal activity of the product was determined by paper-disc method with wood decay fungi such as Coriolus versicolor Gloeophyllum trabeum Irpex lacteas and Postia placenta. The anti-fungal experiment results signified that the bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride, is active to these fungi, especially Irpex lacteas and Postia placenta. The concentrations of the product are 16 mg/mL,32 mg/mL and 64 mg/mL. The weight-loss method was used to detect the performance of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride on wood protection. The result show that when the concentration of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride is 64 mg/mL, the resistence to Trametes versicolor, Gloeophyllum trabeum is on the first grade of the wood protection. BisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride has a critical micellar concentration (CMC) of 8×10-3mol/L, a surface tension of 39.381mN/m, an emulsification activity of 56min, a height of foam of 250 mm, and a foam stability of 200 mm.
BisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N triethylamine was synthsised by three steps. Firstly, the modified rosin was synthesised by the reaction of rosin and acryl acid. Secondly, the modified rosin was esterified with epoxy chloropropane with the mole ratio of 1:3, the product was 3-rosin acyloxy-2-hydroxypropyl chlorine. Finally, the intermediate reacted with epoxy propyl triethyl ammonium chloride to produce bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N triethylamine. The content of the product was characterized by gravimetric analysis with sodium tetraphenylborate as its precipitation reagent and the yield was 87.7%. The chemical structure of the product was identified by FTIR、HPLC. Antifungal assays of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N trimethylamine chloride were performed based on the method of Chang et al. (1999) with slight modifications with wood decay fungi such as Coriolus versicolor Gloeophyllum trabeum Irpex lacteas and Postia placenta. The anti-fungal experiment results signified that the bisN-(3- rosin acyloxy-2-hydroxyl) propyl-N, N trimethylamine chloride is active to these fungi, when the concentration of the product is 0.5 mg/mL, the resistence to Coriolus versicolor Gloeophyllum trabeum and Postia placenta was obvious, when the concentration of the product is 1.0 mg/mL, the resistence to Irpex lacteas was obvious.
本文以松香为原料合成了几种具有抑菌活性和表面活性的松香基季铵盐。松香基季铵盐的合成,一方面充分利用了松香这一可再生资源,大大提高了它的附加值,另一方面为合成价格低廉、高活性、无毒、环保、易生物降解的木材防腐剂提供新的种类。
以松香为原料,合成了N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵,首先松香与环氧氯丙烷进行反应,反应物的摩尔比为n(松香)：n(环氧氯丙烷)=1：2,在90℃下反应时间为3.5 h,将产物与二甲胺以摩尔比1：2在80℃下反应2.5h,生成N-(3-松香酰氧-2-羟)丙基-N,N-二.甲基氯,最后再与环氧氯丙烷在90℃下反应3h,反应摩尔比为1：1得到季铵盐的得率为72.8%。因原料松香中含有很多杂质,故以脱氢松香为原料用同一方法合成了N-(3-脱氢松香酰氧-2-羟)丙基-N,N-二甲基氯化铵,通过对其结构的表征来证明目标产物N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵的结构,利用FTIR、HPLC、1H-NMR对N-(3-脱氢松香酰氧-2-羟)丙基-N,N-二甲基氯化铵的结构进行了确证。测定了N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵对四种木材腐朽菌黑曲霉(Aspergillus niger)、宛氏拟青霉(Paecilomyces variot Bainier)、彩绒革盖菌(Coriolus versicolor)、密黏摺菌(Gloeophyllum trabeum)的抑菌性能,发现对四种木腐菌均有抑制效果,尤其是对密黏摺菌的抑制效果最好。选择N-(3-松香酰氧-2-羟)丙基-N,N-二甲基氯化铵浓度为16 mg/mL、32 mg/mL、64 mg/mL,浸泡试材木块,进行木块微生物培养实验,’用失重法检测松香基酰胺对木材的防腐性能,结果显示松香基酰胺的浓度在64mg/mL时对彩绒革盖菌和密粘褶菌获得了Ⅰ级防腐。
以松香为原料,与丙烯酸反应后,经环氧氯丙烷改性,再与二甲胺反应,得到的产物再与环氧氯丙烷在80℃下反应4.5h,反应的摩尔比为1：3得到双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲基氯化铵。利用FTIR、HPLC、1H-NMR对其官能团及结构进行了表征,季铵盐得率为92.8%。用双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵对绵腐卧孔菌(Postia placenta),彩绒革盖菌(Coriolus versicolor)、密粘褶菌(Gloeophyllum trabeum)、乳白耙菌(Irpex lacteas)四种菌进行了抑菌试验,发现对四种菌均有较好的抑制效果,尤其是绵腐卧孔菌和乳白耙菌。选择双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵浓度为16 mg/mL、32 mg/mL、64 mg/mL,浸泡试材木块,进行木块防腐实验,用失重法评价了双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵对木材的防腐性能,结果显示双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵浓度在64 mg/mL时对彩绒革盖菌、密粘褶菌都是获得了Ⅰ级防腐。通过测定表面张力手段研究了双N-(3-松香酰氧基-2-羟)丙基-N,N-二甲胺基氯化铵的表面活性,其临界胶束浓度(CMC)为8×10-3mol/L,表面张力(γCMC)为39.38mN/m,乳化力为56min,泡沫力为250mm,泡沫稳定性为200 mm。
以松香为原料与丙烯酸反应生成改性松香,再将改性松香与三乙胺与环氧氯丙烷进行反应所生成的季铵盐中间体环氧丙基三乙基氯化铵进行反应,生成产物双N-(3-松香酰氧基-2-羟)丙基-N,N-三乙基氯化铵,并通过重量法得出季铵盐产率为87.7%。分别利用了FTIR、HPLC对产物的结构进行了表征,结果证明已合成目标产物。利用菌丝倒扣法测定了双N-(3-松香酰氧基-2-羟)丙基-N,N-三乙基氯化铵对绵腐卧孔菌(Postia placenta),彩绒革盖菌(Coriolus versicolor)、密粘褶菌(Gloeophyllum trabeum)、乳白耙菌(Irpex lacteas)四种菌进行了抑菌试验,当浓度为0.5 mg/mL时,对于彩绒革盖菌、密粘褶菌及绵腐卧孔菌均有明显的抑制效果,当浓度为1 mg/mL时才对乳白耙菌有明显抑制效果。
Wood is a kind of nature renewable resource. The exploration and the use of wood are environmentally safe, however, wood is low decay resistance. With the need of wood increasing, wood protection becomes an important way of saving the forest resources.
In this paper, rosin is used as raw material to synthesize some kinds of rosin derivatives which have anti-fungal activity and surface activity. Synthesis based on rosin not only can make full use of this renewable resource and can increase greatly its additional value but also can prompt the industry of deep processing development of rosin. Wood preservatives from rosin are renewable, active and environment-friendly.
i.Rosin was used as raw material to prepare N-(3- rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride. Firstly, the rosin was esterified by epoxy chloropropane with the mole ratio of 1:2, the reaction time of 3.5h at 90℃. The intermediate was 3-rosin acyloxy-2-hydroxypropyl chlorine. Then, the intermediate reacted with demethylamine to produce N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine at the following conditions:their mole ratio of 1:2, reaction temperature of 80℃and reaction time of 2.5h. Finally, the N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine was quaternized by epoxy chloropropane with the mole ratio of 1:1, the reaction time of 3h at 90℃. The content of the product was characterized by gravimetric analysis with sodium tetraphenylborate as its precipitation reagent and the yield was 72.8%. There are many impurities in the rosin, so N-(3-dehydrogenated rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride was synthesized in the same mechanism used to characterize the structure of N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride. The chemical structure of the product was identified by FTIR、HPLC、1H-NMR.
The antifungal activity of the product was determined by paper-disc method with wood decay fungi such as Trametes versicolor, Gloeophyllum trabeum and wood stain fungi such as Aspergillus niger and Paecilomyces variot Bainier. The anti-fungal experiment results signified that the N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride, is active to these fungi, especially Gloeophyllum trabeum.. The concentrations of the product are 16 mg/mL,32 mg/mL and 64 mg/mL. The weight-loss method was used to detect the performance of N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride on wood protection. The result show that when the concentration of N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride is 64 mg/mL, the resistence to Trametes versicolor, Gloeophyllum trabeum is on the first grade of the wood protection.
2. Rosin was used as material to prepare bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride firstly, the rosin was modified by acrylic acid and a carboxylic acid group was introduced to the rosin. Secondly, the modified rosin reacted with the epoxy chloropropane, the intermediate I was obtained by the way. Thirdly, the intermediate reacted with dimethylamine. By this way the intermediateⅡwas synthesized. Finally the intermediate II reacted with the epoxy chloropropane in the mole ratio of 1:3, the reaction time of 4.5h at 80℃. The content of the product was characterized by gravimetric analysis with sodium tetraphenylborate as its precipitation reagent and the yield was 92.8%. The chemical structure of the product was identified by FTIR、HPLC、1H-NMR. The antifungal activity of the product was determined by paper-disc method with wood decay fungi such as Coriolus versicolor Gloeophyllum trabeum Irpex lacteas and Postia placenta. The anti-fungal experiment results signified that the bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride, is active to these fungi, especially Irpex lacteas and Postia placenta. The concentrations of the product are 16 mg/mL,32 mg/mL and 64 mg/mL. The weight-loss method was used to detect the performance of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride on wood protection. The result show that when the concentration of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride is 64 mg/mL, the resistence to Trametes versicolor, Gloeophyllum trabeum is on the first grade of the wood protection. BisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine chloride has a critical micellar concentration (CMC) of 8×10-3mol/L, a surface tension of 39.381mN/m, an emulsification activity of 56min, a height of foam of 250 mm, and a foam stability of 200 mm.
BisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N triethylamine was synthsised by three steps. Firstly, the modified rosin was synthesised by the reaction of rosin and acryl acid. Secondly, the modified rosin was esterified with epoxy chloropropane with the mole ratio of 1:3, the product was 3-rosin acyloxy-2-hydroxypropyl chlorine. Finally, the intermediate reacted with epoxy propyl triethyl ammonium chloride to produce bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N triethylamine. The content of the product was characterized by gravimetric analysis with sodium tetraphenylborate as its precipitation reagent and the yield was 87.7%. The chemical structure of the product was identified by FTIR、HPLC. Antifungal assays of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N trimethylamine chloride were performed based on the method of Chang et al. (1999) with slight modifications with wood decay fungi such as Coriolus versicolor Gloeophyllum trabeum Irpex lacteas and Postia placenta. The anti-fungal experiment results signified that the bisN-(3- rosin acyloxy-2-hydroxyl) propyl-N, N trimethylamine chloride is active to these fungi, when the concentration of the product is 0.5 mg/mL, the resistence to Coriolus versicolor Gloeophyllum trabeum and Postia placenta was obvious, when the concentration of the product is 1.0 mg/mL, the resistence to Irpex lacteas was obvious.
引文
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[12]任世学.季按盐类木材防腐剂的应用研究[D].东北林业大学,S782.33
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[15]朱昆新型木材防腐剂DCP的开发[D]南京林业大学2010.6.
[16]黄永平.把松脂加工办成广西大产业[J].广西林业,1998,(1)：7-8.
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[21]丁霞.松香衍生物的合成、结构表征及生物活性的研究.南京林业大学[D].2006.6.
[22]任天瑞,李永红.松香化学及其应用1M].北京化学工业出版社,2005
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[24]陈贻炽.松香及其化工应用[M].北京化工学院,1993
[25]张慧.松香基季按盐的合成及其抑菌活性初探[D]南京理工大学硕士论文.2008.6
[26]粟子安.树脂酸聚合反应过程的研究[J].林产化学与工业,1985,5(3)：1-22
[27]Jong song Lee. Synthesis of acrylic rosin derivatives and application as negative photoresist [J]. European Polymer Journal 2002,38:387-392
[28]Ayman M. Atta. New vinyl ester resins based on rosin for coating applications[J]. Reactive & Functional Polymers,2006,66:1596-1608
[29]魏晓惠,廖世珍.松香基双季铵盐阳离子表面活性剂的合成与性能[J].精细化工.2003.20(9)：557-560
[30]祝远姣,陈小鹏.氢化松香的制备与应用[J].化工时刊,2006,20(10)：71-74
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[32]黎永刚.自制皂化松香胶在废纸浆施胶中的应用[J]Paper Science&Technology,2004, 23(5):23-25
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[35]曹铸.松香酸钠胶囊的研制及治疗银屑病临床疗效观察[J].中华医学实践杂志.2004.4(5)：458-459
[36]王金源,王洪军.高效肥皂的无污染加工方法[P].CN：1279277,2001
[37]Fei Wang,Takuya Kitaoka,Hiroo Tanaka.Supramolecular structure and sizing performance of rosin based emulsion size microparticles [J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2003,221:19-28
[38]Yu Caili, Zhang faai. Preparation and characterization of rosin glycerin ester and itsbromide[J]. Front. Chem. China,2006,2:158-160
[39]周文富,赖文忠,陈芳琴等.丙烯酸松香聚氧乙烯蔗糖酯的合成与结构表征[J]。精细化工,2000,17(2)：704-707
[40]周文富,赖文忠,陈芳琴等.一种新型的松香聚氧乙烯蔗糖酯的合成与性能研究[J].日用化学工业,2001,31(3)：66-68
[41]Paul H.Aldrich. Aqueous dispersions of rosin anhydride and their use as sizing agent for paper [P].US:3582464,1971
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[46]饶小平松香树脂酸衍生物的合成、表征及生物活性研究中国林业科学研究院2007年6月
[47]LegrouyelleeA,Use of abietic acid as a film-forming Produetto be used on wounds and burns[P].FR 8400611A
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[49]NobuyukiT.,TeruoK.,Tsuyoshi.G..,et al.,Abietic acid activates peroxisome proliferato-aetivated receptor-Q(PPARQ) inRAW 264.7 maerophages and 3T3-L1 adipocytes to regulategene expression involved in infianllnation and lipid Metabolism[J].FEBS Letters,2003,550:190-194.
[50]崔秀君,程立方,刘青,等.侧柏中活性成分异海松酸的分离、鉴定与高效液相色谱定量[J].时珍国医国药,2004,15(2)：78-79
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[53]胡旭.新型松香衍生物双子表面活性剂的合成与性能[D].东北林业大学.2007.
[54]韩世岩.松香基季铵盐双子表面活性剂的合成及分析[J].林业科技.2009.34(4)：61-64.
[55]薛元英等.正负离子表面活性剂混合体系中季铵盐的测定[J].延安大学学报.1997,16(1),44-48.
[56]余蜀宜.丙烯酸改性松香聚氧乙烯醚磺酸钠的合成[J].精细与专用化学品,1999,13(4)：4-7.
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[58]李双月.几种抑木腐菌活性松香衍生物的合成与表征[D].东北林业大学.2010.
[2]苏文强树木提取物的功能性合成及其在木材防腐中的应用[D]东北林业大学2008.12
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[7]陈人望,金重为,施振华.我国木材防护工业现状和今后发展建议[J].林产工业,2003,30(5)：3-5.[8].
[8]周明.美国的木材防腐[J].木材工业,1988,2(3)：34-37
[9]孙念超.关于铁路木材防腐工业技术发展及环境保护措施的研究[J].工作研究,2000,18(3)：9-11.
[10]刘磊,苏海涛,张燕君等.我国木材防腐技术发展现状与存在问题[J].中国木材,2006,18(3)：20-22
[11]邓腊云,陈泽君,胡伟.我国木材防腐工业的现状及建议[J].湖南林业科技,2006,33(5)：52-53
[12]任世学.季按盐类木材防腐剂的应用研究[D].东北林业大学,S782.33
[13]姜卸宏,曹金珍.新型木材防腐剂的开发和利用[J].林产工业.2008.35(2)：10-12
[14]曹金珍.国外木材防腐技术和研究现状.林业科技[J].2006.42(7)：120-125
[15]朱昆新型木材防腐剂DCP的开发[D]南京林业大学2010.6.
[16]黄永平.把松脂加工办成广西大产业[J].广西林业,1998,(1)：7-8.
[17]宋湛谦.松香的精细化工利用(Ⅰ)[J].林产化工通讯,2002,36(4)：29-33.
[18]宋湛谦.我国松香松节油行业前景分析[J].精细与专用化学品,2000,(15)：3-4,14.
[19]王延,宋湛谦.松香表面活性剂的开发与应用[J].表面活性剂工业,1994,(2)：7-17.
[20]曾华辉.松香基季铵盐Gemini表面活性剂的合成与应用[D].广西大学.2008.6.
[21]丁霞.松香衍生物的合成、结构表征及生物活性的研究.南京林业大学[D].2006.6.
[22]任天瑞,李永红.松香化学及其应用1M].北京化学工业出版社,2005
[23]杨海东编译.松香再加工及利用[M].北京：中国林业出版社,1984
[24]陈贻炽.松香及其化工应用[M].北京化工学院,1993
[25]张慧.松香基季按盐的合成及其抑菌活性初探[D]南京理工大学硕士论文.2008.6
[26]粟子安.树脂酸聚合反应过程的研究[J].林产化学与工业,1985,5(3)：1-22
[27]Jong song Lee. Synthesis of acrylic rosin derivatives and application as negative photoresist [J]. European Polymer Journal 2002,38:387-392
[28]Ayman M. Atta. New vinyl ester resins based on rosin for coating applications[J]. Reactive & Functional Polymers,2006,66:1596-1608
[29]魏晓惠,廖世珍.松香基双季铵盐阳离子表面活性剂的合成与性能[J].精细化工.2003.20(9)：557-560
[30]祝远姣,陈小鹏.氢化松香的制备与应用[J].化工时刊,2006,20(10)：71-74
[31]Mayer M J J, Meuldijk J.Thoenes D.Influence of dispropotionated rosin acid soap on the emulsion polymerization kinetics of styrene [J].Journal of applied polymer science, 1995,56:119-126.
[32]黎永刚.自制皂化松香胶在废纸浆施胶中的应用[J]Paper Science&Technology,2004, 23(5):23-25
[33]姚光裕.碱性施胶剂的进展[J].国际造纸,1994,(6)：38-40
[34]米彩峰.一种治疗银屑病的植物药及其原料药松香酸的制备工艺[P].CN：1883519,2006
[35]曹铸.松香酸钠胶囊的研制及治疗银屑病临床疗效观察[J].中华医学实践杂志.2004.4(5)：458-459
[36]王金源,王洪军.高效肥皂的无污染加工方法[P].CN：1279277,2001
[37]Fei Wang,Takuya Kitaoka,Hiroo Tanaka.Supramolecular structure and sizing performance of rosin based emulsion size microparticles [J]. Colloids and Surfaces A:Physicochem. Eng. Aspects,2003,221:19-28
[38]Yu Caili, Zhang faai. Preparation and characterization of rosin glycerin ester and itsbromide[J]. Front. Chem. China,2006,2:158-160
[39]周文富,赖文忠,陈芳琴等.丙烯酸松香聚氧乙烯蔗糖酯的合成与结构表征[J]。精细化工,2000,17(2)：704-707
[40]周文富,赖文忠,陈芳琴等.一种新型的松香聚氧乙烯蔗糖酯的合成与性能研究[J].日用化学工业,2001,31(3)：66-68
[41]Paul H.Aldrich. Aqueous dispersions of rosin anhydride and their use as sizing agent for paper [P].US:3582464,1971
[42]Ulrich Cuntze.Surface active compounds based on nature rosin [P].US:4312631,1982
[43]叶存清.松香腈的生产工艺的研究[[J].福建林学院学报,1999,19(4)：331-333
[44]Gottstein W J, Cheney L C. Dehydroabietyl amine-a new resolving agent[J]. J Org Chem,1965,30 (6):2072-2073
[45]Stewart M.Miller. Dehydroabietylammonium salts of 6-oxo-2-piperidinecarboxylic acid[P]. US:4254261,1981
[46]饶小平松香树脂酸衍生物的合成、表征及生物活性研究中国林业科学研究院2007年6月
[47]LegrouyelleeA,Use of abietic acid as a film-forming Produetto be used on wounds and burns[P].FR 8400611A
[48]FernandezM.A.,TomosM.p.,GareiaM.D.Anti-nflammatory activity of abietie acid,a diterpene isolated from Pimenta raeemosa var.grissea[J]. Journal of Pbarmacy and Pharmaeology,2001,53(6):867 - 872.
[49]NobuyukiT.,TeruoK.,Tsuyoshi.G..,et al.,Abietic acid activates peroxisome proliferato-aetivated receptor-Q(PPARQ) inRAW 264.7 maerophages and 3T3-L1 adipocytes to regulategene expression involved in infianllnation and lipid Metabolism[J].FEBS Letters,2003,550:190-194.
[50]崔秀君,程立方,刘青,等.侧柏中活性成分异海松酸的分离、鉴定与高效液相色谱定量[J].时珍国医国药,2004,15(2)：78-79
[51]董泽华,刘靖.防治硫酸铁还原菌的杀菌剂的合成与性能.日用化学工业.1997.(6)：7-11.
[52]门朋朋.新型双子季按盐表面活性剂的合成及性能研究[D].南京理工大学.2007.6.
[53]胡旭.新型松香衍生物双子表面活性剂的合成与性能[D].东北林业大学.2007.
[54]韩世岩.松香基季铵盐双子表面活性剂的合成及分析[J].林业科技.2009.34(4)：61-64.
[55]薛元英等.正负离子表面活性剂混合体系中季铵盐的测定[J].延安大学学报.1997,16(1),44-48.
[56]余蜀宜.丙烯酸改性松香聚氧乙烯醚磺酸钠的合成[J].精细与专用化学品,1999,13(4)：4-7.
[57]武文洁,赵小华,温佩.丙烯酸改性松香的合成工艺研究[J].林业科技2007,32(1)：59-61.
[58]李双月.几种抑木腐菌活性松香衍生物的合成与表征[D].东北林业大学.2010.