文献类型：期刊文献

中文题名：腰果酚基乙酸酯增塑剂的合成及其增塑聚氯乙烯性能

英文题名：Synthesis and application performance of environmentally-friendly plasticizer cardanol acetate for PVC

作者：陈洁[1,2] 李小英[2] 王义刚[2] 黄金瑞[2] 李科[2] 聂小安[1,2] 蒋剑春[1,2]

第一作者：陈洁

通信作者：Nie, Xiaoan|[a0005997aa787f4d4afa0]聂小安;

机构：[1]中国林业科学研究院林业新技术研究所,北京100091;[2]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业局林产化学工程重点开放性实验室,南京210042

年份：2015

卷号：31

期号：14

起止页码：303-308

中文期刊名：农业工程学报

外文期刊名：Transactions of the Chinese Society of Agricultural Engineering

收录：CSTPCD;;EI(收录号：20153301178198);Scopus(收录号：2-s2.0-84939197203);北大核心:【北大核心2014】；CSCD:【CSCD2015_2016】；

基金：中央级公益性科研院所基本科研业务费专项基金(CAFINT2014C12);国家“十二五”科技支撑计划(2014BAD02B02);国家“十二五”科技支撑计划(2015BAD15B08)

语种：中文

中文关键词：共混;性能;近红外光谱;环保增塑剂;腰果酚;聚氯乙烯

外文关键词：blending;stability;infrared spectroscopy;enviromental plasticizer;cardanol;polyvinyl chloride

分类号：TQ322.3

摘要：为了进一步利用农林剩余物资源替代石化原料,该研究以腰果酚为原料,通过对其酚羟基进行酯化改性,制备腰果酚基乙酸酯(cardanol acetate,CA)增塑剂。采用核磁共振氢谱(1H nuclear magnetic resonance,1H NMR)和核磁共振碳谱(13C nuclear magnetic resonance,13C NMR)对产物的结构进行表征。通过动态力学性能(dynamic thermo mechanical analysis,DMA),拉伸性能测试,热重分析(thermogravimetric analysis,TGA),以及与聚氯乙烯(polyvinyl chloride,PVC)共混样品的傅里叶红外分析(fourier transform infrared spectroscopy,FT-IR)等方法,评价腰果酚基乙酸酯作为辅助增塑剂应用于软质聚氯乙烯的增塑效果,并与商业增塑剂对苯二甲二辛酯(bis(2-ethylhexyl)benzene-1,4-dicarboxylate,DOTP)进行对比。研究结果表明,m(DOTP)∶m(CA)=4∶6为较佳配伍比例,共混体系的玻璃化转变温度由41.52℃降低至35.93℃,断裂伸长率由244.75%增加到了302.13%,热稳定性及相容性均得到有效改善,因此腰果酚基乙酸酯可用作聚氯乙烯的优良辅助增塑剂。研究结果为腰果酚在增塑剂领域的应用提供了参考。
As the plastic industry and the environmental awareness continuously grow, there is an urgent unmet need to develop new natural plasticizers with improved properties and cost competitiveness. Natural plasticizers from vegetable origin, such as modified or epoxidized vegetable oil, epoxidized fatty acid methyl eater and glycerin acetates, are alternatives for phthalate. Numerous raw materials have been used, like soybean, corn, sunflower, palm, flaxseed. As one of the most commonly used renewable raw material, cardanol, and its derivatives, have important applications in developing new eco-friendly materials. In this work, the cardanol-based polyvinyl chloride （PVC） plasticizer, cardanol acetate （CA） was prepared by the reaction of cardanol with acetic anhydride using potassium carbonate as a catalyst. 1H nuclear magnetic resonance （1H NMR） and13C nuclear magnetic resonance （13C NMR） analyses were used to characterize the structure of the product. The results showed that the CA was obtained. The plasticizing effects of the obtained plasticizer onPVC formula were also investigated. The commercial phthalate plasticizer bis （2-ethylhexyl） benzene-1, 4-dicarboxylate （DOTP） was used as the control. Dynamic thermal mechanical properties, mechanical properties, thermal stability and compatibility were assessed by means of dynamic thermo mechanical analysis （DMA）, tensile analysis, thermogravimetric analysis （TGA） and Fourier transform infrared spectroscopy （FT-IR）, respectively. The results indicated that the glass-transition temperature of the plasticized PVC samples decreased from 41.52 to 36.35＆#176;C, reflecting a good compatibility of the CA with polyvinyl chloride resin. The reasons for this performance were that the plasticizers mixed with CA had higher ability to lubricate by incorporating itself among the polymer chains, and therefore reduced PVC-PVC interactions due to the replacing partly by plasticizer-PVC interactions. From the characteristic temperatures in TGA curves, it could be observed that the degradation of all the films consisted of 3 steps of weight loss. The degradation at the first stage was at around 80-220℃, which could be attributed to the evaporation of water and small molecules. The second stage at around 220-400℃ was fast and due to dechlorination of the PVC, with the formation and evolution of HCl and a few chlorinated hydrocarbons. The third mass-loss step above 450℃, was corresponding to the degradation and decomposition of the complex structures resulting from aromatization. Furthermore, the mass of residual char of the PVC samples at 600℃ was significantly increased with the adding of the CA. The results of tensile analysis suggested that the elongation at break increased with the CA content increasing, indicating the increase of flexibility and toughness for all the samples. And the tensile strength and elastic modulus were decreased in the same trend. These results were consistent with the DMA results, indicating that the CA had a significant effect on the flexibility property and exhibited the best toughness. FT-IR spectra of the PVC film samples were obtained. The results indicated that the mixed plasticizers of the CA and DOTP could interact with the PVC by hydrogen bonds between the polar parts of the CA （benzene ring, ester group） and the PVC （carbon-chloride bond）. So, it can be concluded that this cardanol-derived plasticizer shows promise as a secondary plasticizer for soft PVC, as well as an alternative to partially replace petroleum-based plasticizers. Furthermore, more new type of PVC plasticizer based on cardanol might be developed on the basis of this study.