Preparation of epoxy dimeric acid methyl ester plasiticizer from biodiesel and its application in PVC

doi:10.16085/j.issn.1000-6613.2016.09.040

Abstract

Abstract: With biodiesel as raw material,synthesis of dimers and their epoxidation product using the double bonds existing in biodiesel was obtained. Under the reaction conditions of 240℃/6h,the effects of different catalysts and the content of unsaturated bonds on dimerization were investigated. Moreover,the combustion performance of biodiesel after dimerization was explored. The yield of dimeric acid methyl esters(DAME) reached up to 28%(catalyzed by aluminum silicate). Comparing cetane numbers(CN) of biodiesel before and after the reaction,the CN of unreacted biodiesel was essentially unchanged,which indicated that dimerization had no effect on combustion performance.The application of epoxy dimeric acid methyl ester(EDAME) in polyvinyl chloride(PVC) blending with bis(2-ethylhexyl) benzene-1,4-dicarboxylate(DOTP) was further studied. The mechanical properties thermogravimetric analysis(TGA) and processing rheology of PVC were measured. Results showed that the elongation at break of sample F2 increased by 2.62% when EDAME content increased from 0 to 20%. The initial decomposition temperature(T_i),the 10% weight loss temperature(T₁₀) and the 50% weight loss temperature(T₅₀) increased 6.5℃,9.9℃ and 26.8℃,respectively,when EDAME substituted DOTP totally,and the char yield increased from 8.7% to 11.7%. The dynamic stability time increased,and the equilibrium torque of F2 decreased from 3.8N·m to 3.2N·m compared to that of F0. All of these improved the processability of PVC blends. Therefore,it can be considered that EDAME can be treated as an environmentally-friendly and renewable secondary plasticizer to replace DOTP. Meanwhile,the new technology of the production of biodiesel combined with EDAME can improve the comprehensive economic benefit in the process of biodiesel production which has broad market prospects.

Key words: biodiesel, dimerization, epoxy dimeric acid methyl ester, secondary plasiticizer

摘要： 以生物柴油为原料，利用生物柴油存在双键结构的特点，将部分双键组分进行二聚化及环氧化反应，形成了生物柴油联产环氧二聚酸甲酯（EDAME）新技术。在二聚化反应条件为240℃/6h下，研究了催化剂种类、油脂双键组分含量对二聚化反应程度的影响，探索了二聚化反应对生物柴油燃烧性能的影响。获得了二聚化得率为28%（硅酸铝为催化剂）的较佳结果。通过二聚化反应后生物柴油十六烷值比较，发现：二聚化反应后，未参与反应的生物柴油的十六烷值变化不大，二聚化反应不影响生物柴油燃烧性能。考察了EDAME与对苯二甲酸二辛酯（DOTP）共混对PVC的增塑效果。通过对共混塑化体系进行力学性能、热重和流变性能表征，结果表明，当EDAME的含量为20%时，断裂伸长率提高了2.62%；当EDAME全部替代DOTP时，T_i、^T₁₀和T₅₀分别提高了6.5℃、9.9℃和26.8℃，残炭量由8.7%升高到11.7%；动态热稳定时间增加，相比于单独使用DOTP，EDAME含量为20%时的平衡扭矩由3.8N·m减小到3.2N·m，从而改善了热塑材料的加工性能。由此可见，EDAME可以部分替代DOTP，作为一种环保可再生的优良辅助增塑剂使用。同时，生物柴油联产环氧二聚酸甲酯新技术有助于提高生物柴油生产线综合经济效益，具有广阔的市场推广前景。

关键词: 生物柴油, 二聚化, 环氧二聚酸甲酯, 辅助增塑剂

CLC Number:

TQ645

LI Xiaoying, NIE Xiao'an, CHEN Jie, WANG Yigang. Preparation of epoxy dimeric acid methyl ester plasiticizer from biodiesel and its application in PVC[J]. Chemical Industry and Engineering Progree, 2016, 35(09): 2934-2940.

李小英, 聂小安, 陈洁, 王义刚. 生物柴油联产环氧二聚酸甲酯增塑剂新技术[J]. 化工进展, 2016, 35(09): 2934-2940.

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