固态枞酸和松香氧化过程及其过氧化物生成研究  

Oxidation process and peroxide formation of solid abietic acid and rosin

作　　者：周晓迪 刘雄民[1] 张强[1] 张闻扬 江艳艳 赖福兵 ZHOU Xiao-di;LIU Xiong-min;ZHANG Qiang;ZHANG Wen-yang;JIANG Yan-yan;LAI Fu-bing(College of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,China)

机构地区：[1]广西大学化学化工学院,广西南宁530004

出　　处：《应用化工》2018年第8期1616-1621,共6页Applied Chemical Industry

基　　金：国家自然科学基金地区科学基金项目(11762003);广西科技重大专项(AA17204065-20)

摘　　要：采用碘量法和紫外分光光度法(UV)研究枞酸和松香的氧化反应。通过碘量法测定过氧化值变化,考察固态枞酸和松香在加压氧气和空气中的过氧化物生成规律。利用UV测定枞酸共轭双键变化,探讨枞酸和松香在较低温度下的氧化特性。结果表明,经改良的碘量法测量枞酸和松香的过氧化值具有精密度高、稳定性好的特点。利用该方法跟踪枞酸的氧化反应,温度30~60℃范围内较容易发生氧化反应,过氧化值随氧化温度升高、反应时间增加而增加,在0.5 MPa氧气、60℃的温度中反应8 h,过氧化值达到最大值285 mmol/kg。枞酸固态下的氧化动力学呈现表观一级反应,反应活化能为49.76 k J/mol。松香的氧化反应规律类似于枞酸氧化规律,在50℃中反应6 h,过氧化值达到最大值161 mmol/kg。The oxidation processes of abietic acid and rosin were investigated by iodimetry method and ultraviolet spectrophotometry(UV).The modified iodimetry method for the quantification analysis of peroxide formed in abietic acid and rosin was established.The peroxide formation of solid abietic acid and rosin in high oxygen atmosphere and air were investigated respectively.The behaviors of conjugated double bond of abietic acid and rosin were determined by ultraviolet spectrophotometry(UV)for the investigation of abietic acid and rosin oxidation properties at low temperatures.Results showed that the modified iodimetry method applied to measure the peroxide concentration of abietic acid and rosin had the characteristics of high precision and good stability.Abietic acid was prone to be oxidized at 30~60℃and the peroxide concentration increased as oxidation temperature and time increasing.Moreover,in a 0.5 MPa oxygen atmosphere,the maximum of peroxide concentration formed in abietic acid oxidation process was 285 mmol/kg at 60℃for 8 h.Additionally,the solid state oxidation of abietic followed a pseudo-first-order reaction,the equation as ln(c t/c 0)=-kt+b,where k and b were constant parameters related with temperature.The activation energy of abietic acid oxidation was 49.76 kJ/mol.The oxidation characteristic of rosin was similar to that of abietic acid in high oxygen atmosphere and air.The maximum of peroxide concentration formed in rosin oxidation process was 161 mmol/kg at 50℃for 6 h.

关 键 词：枞酸 松香 氧化反应 过氧化值 动力学 

分 类 号：TQ041.7[化学工程] ST9