微藻油脂制备生物基多元醇理化性能分析与结构表征  

Physicochemical property analysis and structural characterization of bio-based polyol prepared form microalgae oil

作　　者：杨晓琴 喻艳华 谢东 Petrovic Zoran S 洪健 万显美 Yang Xiaoqin;Yu Yanhua;Xie Dong;Petrovic Zoran S.;Hong Jian;Wan Xianmei(Key Laboratory of Forest Resources Conservation and Utilization in the Southwest Mountains of China,Ministry of Education,Key Laboratory of State Forestry Administration on Highly-Efficient Utilization of Forestry Biomass Resources in Southwest China,College of Chemical Engineering,Southwest Forestry University,Kunming 650224,China;Kansas Polymer Research Center,KS 66762,US)

机构地区：[1]西南山地森林资源保育与利用教育部重点实验室,西南地区林业生物质资源高效利用国家林业与草原局重点实验室,西南林业大学化学工程学院,昆明650224 [2]美国匹兹堡州立大学堪萨斯聚合物研究中心,堪萨斯66762

出　　处：《农业工程学报》2020年第7期248-255,共8页Transactions of the Chinese Society of Agricultural Engineering

基　　金：云南省应用基础研究计划项目农业联合面目项目[2017FG01(-022)]。

摘　　要：为了实现有效高值利用非食用、不占耕地的绿色可再生油脂资源,该研究以微藻油脂为原料,采用环氧化-开环法和氢甲酰化-加氢还原法制备了2种生物基多元醇,通过主要理化指标碘值、酸值、环氧基含量、羟值的测定,重要理论理化指标理论双键含量、理论环氧基含量、理论羟值、转化率和选择性的计算,结合气质联用、凝胶渗透色谱、红外光谱、核磁共振等仪器分析手段,对原料和产物的理化性能和结构进行分析与表征。结果表明,微藻油脂的主要脂肪酸是油酸,质量分数为91.10%,碘值为88.46 g/100 g,理论双键含量0.34 mol/100 g,环氧-开环法得到的多元醇碘值降至0.62 g/100 g,羟值为150.35 mg/g,原料转化率和目标产物选择性分别为99.30%和86.74%,结构中引入仲羟基,通过及时除去环氧反应过程中生成的水、开环反应选择适宜的醇用量可提升产品质量。氢甲酰化-加氢还原法得到的多元醇碘值降至2.12 g/100 g,羟值为166.29 mg/g,原料转化率和目标产物选择性分别为97.60%和95.83%,结构中引入伯羟基,该法为非均相反应,催化剂过滤可除,副反应少,溶剂廉价可回收,产品易分离且质量容易控制。2种方法的原料利用率都很高,目标产物选择性好,产品性能可通过简单易行的理化指标测定和理论计算方法进行有效评价,并可利用仪器分析手段快速监测反应进程、保证产品质量、查找质量问题、拓宽应用范围,具有很好的经济性和工业应用前景,研究结果为油脂为原料的生物基多元醇深入研究和工业应用提供了科学可靠的数据基础和技术支持。In order to cope with the resource crisis and environmental pollution that caused by the rapidly depletion of non-renewable petroleum resources,as well as to achieve the efficient and high value utilization of inedible green renewable oils were investigated.Bio-based polyols with different structures were prepared from microalgae oil,and the methods of epoxidation-ring opening and hydroformylation-hydroreduction were used to obtain the goal products.Physical and chemical properties of the raw materials and the resulted products were analyzed by determining the critical indexes including iodine value,acid value,oxirane oxygen content and hydroxyl value,and theoretical double bond content,theoretical oxirane oxygen content,theoretical hydroxyl value,conversion rate and selectivity.Structure of the raw material and the resulted products were characterized by gas chromatography-mass spectrometry,gel permeation chromatography,Fourier transform inferred spectrometry,and nuclear paramagnetic resonance.Results of the physical and chemical analysis and the structure characterization demonstrated that the main fatty acid composition of microalgae oil was oleic acid with high content of 91.10%,the iodine value of microalgae oil was 88.46 g/100g,and the theoretical double bond content of microalgae oil was 0.34 mol/100g.The iodine value of polyols obtained via epoxidation-ring opening method decreased to 0.62 g/100 g,the hydroxyl value was 150.35 mg/g,the conversion rate of microalgae oil was 99.30%,the selectivity of resulted target polyol was 86.74%,and the secondary hydroxyl group was introduced into the double bonds of triacylglycerol in microalgae oil.In addition,the goal polyol quality can be effectively promoted by immediately removing the water that generated in the epoxy reaction process and selecting the appropriate amount of alcohol in the ring opening reaction process.The iodine value of polyols obtained via hydroformylation-hydroreduction method decreased to 2.12 g/100g,the hydroxyl value was 166.29 mg/g,the con

关 键 词：理化性能 结构表征 微藻油脂 多元醇 环氧化 氢甲酰化 

分 类 号：TQ645[化学工程—精细化工] TQ644.2