Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

doi:10.1016/j.cjche.2021.03.048

中国化学工程学报 ›› 2022, Vol. 44 ›› Issue (4): 41-50.DOI: 10.1016/j.cjche.2021.03.048

Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

Xiaojiang Liang¹, Fengjiao Wu¹, Qinglong Xie¹, Zhenyu Wu¹, Jinjin Cai¹, Congwen Zheng¹, Junhong Fu², Yong Nie¹

1 Biodiesel Engineering Lab of China Petroleum & Chemical Industry Federation, and Zhejiang Province Key Lab of Biofuel, Zhejiang University of Technology, Hangzhou 310014, China;
2 Zhejiang Jiaao Enprotech Stock Co., Ltd, Tongxiang 314000, China

收稿日期:2020-12-02 修回日期:2021-03-25 出版日期:2022-04-28 发布日期:2022-06-18
通讯作者: Yong Nie,E-mail:ny_zjut@zjut.edu.cn
基金资助:
Financial support provided by the National High-tech Research and Development Program of China (2014AA022103) is greatly acknowledged.

Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

Xiaojiang Liang¹, Fengjiao Wu¹, Qinglong Xie¹, Zhenyu Wu¹, Jinjin Cai¹, Congwen Zheng¹, Junhong Fu², Yong Nie¹

1 Biodiesel Engineering Lab of China Petroleum & Chemical Industry Federation, and Zhejiang Province Key Lab of Biofuel, Zhejiang University of Technology, Hangzhou 310014, China;
2 Zhejiang Jiaao Enprotech Stock Co., Ltd, Tongxiang 314000, China

Received:2020-12-02 Revised:2021-03-25 Online:2022-04-28 Published:2022-06-18
Contact: Yong Nie,E-mail:ny_zjut@zjut.edu.cn
Supported by:
Financial support provided by the National High-tech Research and Development Program of China (2014AA022103) is greatly acknowledged.

摘要/Abstract

摘要： Biodiesel was used to prepare epoxidized fatty acid isobutyl esters (Ep-FABEs) as a biobased plasticizer in this work. Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor. The conversion achieved nearly 100% within 5 h under the reaction temperature, the mass ratio of catalyst to fatty acid methyl esters (FAMEs), and isobutanol to FAMEs total molar ratio of 180 ℃, 0.4 %(mass), and 5.4:1, respectively. In addition, kinetic model of the transesterification reaction was developed at 150–190 ℃. The calculated activation energy was 48.93 kJ·mol^-1. Then, the epoxidation of obtained fatty acid isobutyl esters (FABEs) was conducted in the presence of formic acid and hydrogen peroxide. The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate (DOP) and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters (Ep-FAMEs). The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP. In addition, the extraction resistance and migration stability of Ep-FABEs were better than those of Ep-FAMEs. Overall, the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.

关键词: Biodiesel, Transesterification, Isobutyl esters, Epoxidized isobutyl esters, Biobased plasticizer

Abstract: Biodiesel was used to prepare epoxidized fatty acid isobutyl esters (Ep-FABEs) as a biobased plasticizer in this work. Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor. The conversion achieved nearly 100% within 5 h under the reaction temperature, the mass ratio of catalyst to fatty acid methyl esters (FAMEs), and isobutanol to FAMEs total molar ratio of 180 ℃, 0.4 %(mass), and 5.4:1, respectively. In addition, kinetic model of the transesterification reaction was developed at 150–190 ℃. The calculated activation energy was 48.93 kJ·mol^-1. Then, the epoxidation of obtained fatty acid isobutyl esters (FABEs) was conducted in the presence of formic acid and hydrogen peroxide. The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate (DOP) and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters (Ep-FAMEs). The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP. In addition, the extraction resistance and migration stability of Ep-FABEs were better than those of Ep-FAMEs. Overall, the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.

Key words: Biodiesel, Transesterification, Isobutyl esters, Epoxidized isobutyl esters, Biobased plasticizer

Xiaojiang Liang, Fengjiao Wu, Qinglong Xie, Zhenyu Wu, Jinjin Cai, Congwen Zheng, Junhong Fu, Yong Nie. Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer[J]. 中国化学工程学报, 2022, 44(4): 41-50.

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Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

Insights into biobased epoxidized fatty acid isobutyl esters from biodiesel: Preparation and application as plasticizer

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