Synthesis And Characterization Of Several Anti-fungal Rosin Derivatives

Abundant pine oleoresin resources are available in China. The yield of gum rosin is more than 500,000t in China. However, the task of synthesizing fine products is at the start stage. The raw material is exported to foreign countries and then deep processing rosin is sold back to our country. It results in enormous economic losses for our country. Therefore, it is very important to start the research of modified rosin and exploit products of deep processing rosin that comply with the requirements of our country's market. It's not only significant for the reasonable development of our country's forestry exploration and utilization, but also for the protection of environment.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.Rosin was used as raw material to prepare a rosin amide derivative. First, rosin was modified by acryl acid. Then the modified rosin reacted with diethyltriamine and the rosin amide derivative was produced under the following conditions:modified rosin and diethyltriamine mole ratio of 1:3, dimethylbenzene as water carrying agent, reaction temperature of 142℃and reaction time of 8 h; the yield of product is 98.72%.The chemical structure of the product as a rosin amide derivative was identified by Fourier transform infrared spectroscopy, electrospray ionization-mass spectrometry, and 1H nuclear magnetic resonance analysis.The anti fungal activity of a rosin amide derivative was determined in vitro with wood decay fungi such as Coriolus versicolor, Gloeophyllum trabeum and wood stain fungi such as Aspergillus niger and Paecilomyces variot Bainier. The anti-fungal experiment results signified that a rosin amide derivative was active to these fungi, especially to Paecilomyces variot Bainier. The concentrations of the rosin amide are 32 mg/mL,64 mg/mL and 128 mg/mL. The test blocks were soacked in solutions and decay chambers were prepared with corn powder and sand culture. The weight-loss method was used to detect the performance of rosin amide on wood protection. The result show that when the concentration of rosin amide is 64 mg/mL, the resistence to Coriolus versicolor are on the first grade of the wood protection; when the concentration of rosin amide is 32 mg/mL, the resistence to Gloeophyllum trabeum are on the first grade of the wood protection. A rosin amide derivative has a critical micellar concentration (CMC) of 8.0×10-4 mol/L, a surface tension of 39.161mN/m, an emulsification activity of 1320 s, a height of foam of 135 mm, and a foam stability of 125 mm.BisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine 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. Finally, bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine was produced at the conditions as follows:the intermediate and dimethylamine mole ratio of 1:2, reaction temperature of 78℃and reaction time of 2.5 h. The chemical structure of the product was identified by FTIR. The anti fungal activity of a bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N,N dimethylamine was determined in vitro with wood decay fungi such as Coriolus versicolor, Gloeophyllum trabeum and wood stain fungi such as Aspergillus niger and Paecilomyces variot Bainier. The anti-fungal experiment results signified that bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N,N dimethylamine was active to these fungi, especially to Coriolus versicolor and Gloeophyllum trabeum. The concentrations of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine are 8 mg/mL,16 mg/mL and 32 mg/mL. The test blocks were soacked in solutions and decay chambers were prepared with corn powder and sand culture. The weight-loss method was used to detect the performance of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N, N dimethylamine on wood protection,and when the concentration of bisN-(3-rosin acyloxy-2-hydroxyl) propyl-N,N dimethylamine is 32 mg/mL, the coriolus versicolor and the gloeophyllum trabeum are on the first grade of the wood protection.Rosin was used as raw material to prepare N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N diethanol amine. First, rosin was modified by epoxy chloropropane. Then the modified rosin reacted with diethanol amine and N-(3-rosin acyloxy-2-hydroxyl) propyl-N, N diethanol amine was produced under the following conditions:modified rosin and diethanol amine mole ratio of 1:2, reaction temperature of 78℃, and reaction time of 2.5 h. The chemical structure of the product as a rosin amide derivative was identified by Fourier transform infrared spectroscopy, liquid chromatography-mass spectrography and 1H nuclear magnetic resonance analysis. The anti fungal activity of a N-(3-rosin acyloxy-2-hydroxyl) propyl-N,N diethanol amine was determined in vitro with wood decay fungi such as Coriolus versicolor, Gloeophyllum.trabeum and wood stain fungi such as Aspergillus niger and Paecilomyces variot Bainier. The anti-fungal experiment results signified that N-(3-rosin acyloxy-2-hydroxyl) propyl-N,N diethanol amine was active to these fungi, at a certain concentration, so it is not suitable for the use of wood preservative.The optimal reaction conditions of a rosin amine salt was modified rosin and dimethylamine mole ratio of 1:2, reaction temperature of 78℃and reaction time of 2 h.The yield is 79.1%. The chemical structure of the product was identified by Fourier transform infrared spectroscopy, electrospray ionization-mass spectrometry and 1H nuclear magnetic resonance analysis. The anti fungal activity of a rosin amine salt was determined in vitro with wood decay fungi such as Coriolus versicolor, Gloeophyllum trabeum and wood stain fungi such as Aspergillus niger and Paecilomyces variot Bainier. The anti-fungal experiment results signified that a rosin amine salt was no active to these fungi.Rosin amine salt has a critical micellar concentration (CMC) of 8.0×10-3mol/L, a surface tension of 43.663 mN/m, an emulsification activity of 300 s, a height of foam of 165 mm, and a foam stability of 143 mm.