含磷型聚合甘油脂肪酸酯阻燃增塑剂的制备与应用

doi:10.3969/j.issn.0253-2417.2016.01.011

林产化学与工业 ›› 2016, Vol. 36 ›› Issue (1): 77-84.doi: 10.3969/j.issn.0253-2417.2016.01.011

含磷型聚合甘油脂肪酸酯阻燃增塑剂的制备与应用

冯国东^1,2, 胡云¹, 周永红^1,3, 刘朋¹, 马艳¹

1. 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;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2. 江苏强林生物能源材料有限公司, 江苏溧阳 213364;
3. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2014-12-15 出版日期:2016-02-25 发布日期:2016-03-18
通讯作者: 周永红,研究员,博士生导师,研究领域为生物质化学转化与应用;E-mail:yhzhou777@163.com。 E-mail:yhzhou777@163.com
作者简介:冯国东 (1982-),男,河南新乡人,博士生,从事生物质材料的应用与研究工作;E-mail:fengguodong21@163.com
基金资助:
"十二五"国家科技支撑计划资助(2012BAD32B05);中国林科院林业新技术所基本科研业务费专项资金(CAFINT2013K01)

Preparation and Application of a P-containing Polyglycerol Ester Fire-retardant Plasticizer

FENG Guo-dong^1,2, HU Yun¹, ZHOU Yong-hong^1,3, LIU Peng¹, MA Yan¹

1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab. for Biomass Chemical Utilization;Key and Open Lab. of Forest Chemical Engineering, SFA;Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Jiangsu Qianglin Bio-energy and Bio-materials Co. Ltd., Liyang 213364, China;
3. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2014-12-15 Online:2016-02-25 Published:2016-03-18

摘要/Abstract

摘要： 为了提高油脂增塑剂的阻燃性,开发以生物柴油副产粗甘油为直接原料的高附加值产品,以粗甘油、油酸和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)为主原料,经聚合、酯化、环氧化和开环反应,合成含磷型大分子阻燃增塑剂DOPO-环氧乙酰化聚合甘油脂肪酸酯(DOPO-EAPFAE),并通过红外谱图(FT-IR)和核磁共振(¹H NMR)确认了其结构。研究了DOPO-EAPFAE用量对聚氯乙烯(PVC)体系力学性能的影响;通过对PVC样条的热重分析(TG)、极限氧指数(LOI)测定和垂直燃烧测试等,分析了PVC制品的热稳定性和阻燃性能。结果表明:当DOPO-EAPFAE代替邻苯二甲酸二辛酯(DOP)用量为60%时,PVC样条仍具有良好的力学性能;而LOI从21.3上升到了28.7,阻燃级别达到V0级;说明该阻燃增塑剂可有效地改善PVC增塑体系的阻燃性。与小分子阻燃剂磷酸三(2-氯丙基)酯(TCPP)相比,DOPO-EAPFAE阻燃性不仅优于TCPP,而且具有更好的热稳定性能。

关键词: 聚合甘油, 环氧化, 阻燃增塑剂, PVC, 植物油脂

Abstract: In order to improve the flame retardancy of oil plasticizer and develop high value-added products using crude glycerin from by-product of diesel oil as starting materials, a novel P-containing soybean-oil-based fire-retardant plasticizer(DOPO-EAPFAE) was synthesized using crude glycerin, oleic acid and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as raw material through polymerization, esterification, epoxidation and ring opening reaction.The structure was verified by Fourier transform infrared (FT-IR) spectrometry and nuclear magnetic resonance spectroscopy.Thermo-gravimetric behavior and flame retardant properties were evaluated by thermal gravimetric analysis, oxygen index test and vertical burning test.When the amount 60% of phthalic acid dioctyl ester (DOP) was replaced by DOPO-EAPFAE in PVC blends, PVC blends still has good mechanical properties.The limiting oxygen index (LOI) of the blends increased from 21.3 to 28.7, and flame retardant level reached V0 grade.This indicated that the product can effectively improve the flame retardancy of PVC blends.The plasticity and flammability of DOPO-EAPFAE was better than tris(chlorisopropyl) phosphate(TCPP).Comparing to small molecular flame retardant tris(1-chloro-2-propyl) phosphate(TCPP), flame retardant of DOPO-EAPFAE was not only superior to TCPP, but also exhibited better thermal stability.

Key words: polyglycerol, epoxy, flame retardant plasticizer, PVC, vegetable oil

中图分类号:

TQ35
O627.51

冯国东, 胡云, 周永红, 刘朋, 马艳. 含磷型聚合甘油脂肪酸酯阻燃增塑剂的制备与应用[J]. 林产化学与工业, 2016, 36(1): 77-84.

FENG Guo-dong, HU Yun, ZHOU Yong-hong, LIU Peng, MA Yan. Preparation and Application of a P-containing Polyglycerol Ester Fire-retardant Plasticizer[J]. Chemistry and Industry of Forest Products, 2016, 36(1): 77-84.

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含磷型聚合甘油脂肪酸酯阻燃增塑剂的制备与应用

Preparation and Application of a P-containing Polyglycerol Ester Fire-retardant Plasticizer

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