Study On Synthesis Of Novel Functional Derivatives From Modified Rosin

Rosin, a kind of natural and renewable resources, is extremely abundant in China. However, the deep processing ratio of rosin now in China is comparatively low. Therefore, the exploitation of deep processing of rosin to increase its commodity additional value is a significant research project worthy of carrying out deeply. In this paper, four novel functional modified rosin derivatives were synthesized, which aims at the exploitation of novel fine chemical products of rosin and the investigation of a new path for the deep processing of rosin which is extremely abundant in Guangxi, China.Firstly, the intermediate hydrogenated rosin-polyethylene glycol ester and the target product hydrogenated rosin-polyethylene glycol-citric acid ester were synthesized under microwave irradiation using hydrogenated rosin as starting materials. Some synthetic conditions of intermediate and target product were investigated and the optimal conditions of intermediate were found to be as follows: reaction time 90min, reaction temperature 240℃, mole ratio of hydrogenated rosin to glycol-citric acid 1:1.6. Synthetic conditions of target product were investigated and the optimal conditions were found to be as follows: reaction time 60min, reaction temperature 150℃, microwave power 500W. The intermediate and target product were analyzed and identified by IR spectrum. Furthermore, their surface properties were determined.Secondly, the intermediate disproortionated rosin-polyethylene glycol ester and the target product disproortionated rosin-polyethylene malic acid ester were synthesized under microwave irradiation using disproortionated rosin as starting materials. Some synthetic conditions of intermediate and target product were investigated and the optimal conditions of intermediate were found to be as follows: reaction time 90min, reaction temperature 240℃, mole ratio of disproortionated rosin to malic acid 1:1.6. Synthetic conditions of target product were investigated and the optimal conditions were found to be as follows: reaction time 60min, reaction temperature 140℃, microwave power 800W. The intermediate and target product were analyzed and identified by IR and UV spectra. Furthermore, their surface properties were determined.Thirdly, dehydroabietic acid was isolated and purified from dispropportionated rosin. Then, N, N-diethoxyldehydroabietylamide was synthesized through the intermediate of dehydroabietic acid chloride by using the dehydroabietic acid as starting material. Some synthetic conditions were investigated and found to be as follows: reaction time 2 h, reaction temperature 20～30℃, mole ratio of the amine to the chloride 4 : 1 ( amine:chloride ). The conversion rate of dehydroabietic acid chloride amounted to 95.1%. In order to find out the conversion rate of dehydroabietic acid chloride during the reaction, oxygen flask method and complexometric titration method were used to determine the content of Cl in the target products. The experiments showed that it has comparatively higher content of Cl and it is more accurate by oxygen flask method. The target product was analyzed and characterized by IR, UV and MS spectra. Furthermore, surface tension and critical micelle concentration (CMC) of the target product were determined in this paper. The prepared target product is a novel nonionic surfactant which has not been reported in literature so far.Finally , L-ascorbyldehydroabietate was synthesized through the intermediate of dehydroabietic acid chloride by using dehydroabietic acid and L-ascorbic acid as starting materials. Influence factors such as mole ratio of L-ascorbic acid to dehydroabietic acid chloride, reaction temperature, reaction time, volume ratio of the solvents were investigated, and the optimum synthetic conditions were found to be as follows: mole ratio of L-ascorbic acid to acid chloride 1.2:1.0, reaction temperature 40℃, reaction time 12 h, volume-ratio of dichloromethane to DMF0.5:1.0 .The yield of L-ascorbyldehydroabietate amounted to 70.56% under the optimum conditions. The target product was analyzed and characterized by IR, UV and HPLC.The antioxidation activity of the target product showed that L-ascorbyldehydroabietate is a novel fat-soluble antioxidant.