Page 199 - 《精细化工》2021年第9期

第 38 卷第 9 期 精 细 化 工 Vol.38, No.9
202 1 年 9 月 FINE CHEMICALS Sept. 2021

橡塑助剂
低聚羟丙基磷酸乙酯阻燃剂的合成及应用

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张 继，边金彩，何珍妮，周可杰，职慧珍 ，黄小冬 ，杨锦飞
（南京师范大学 化学与材料科学学院，江苏 南京 210023）

摘要：以五氧化二磷、环氧丙烷为主要原料合成了低聚羟丙基磷酸乙酯阻燃剂。考察了环氧丙烷的滴加温度及
用量、反应温度、反应时间、反应体系压力对其酸值的影响。得到的最优工艺条件为环氧丙烷与中间体Ⅱ的质
量比为 0.67∶1.0、环氧丙烷滴加温度为 15 ℃、反应体系压力为 0.5 MPa、反应温度为 70 ℃、反应时间为 1.5 h，
在该条件下产品酸值可达 0.6 mg KOH/g。利用 FTIR、GPC、TGA、化学滴定法等对其结构及性能进行了表征。
用低聚羟丙基磷酸乙酯阻燃剂对聚氨酯硬泡（RPUF）进行阻燃改性得到阻燃聚氨酯硬泡。TGA 数据表明，当
阻燃剂添加量为 10%（以聚醚多元醇质量计，下同）时，900 ℃的残炭量由未改性前的 7.9%提升到 20.7%；其
阻燃性能测试数据表明，当阻燃剂添加量为 30%时，制备的聚氨酯硬泡的极限氧指数值（LOI）可达 27.1%，通
过垂直燃烧（UL-94）V-0 级，且保留了泡沫基本的机械性能。
关键词：五氧化二磷；低聚羟丙基磷酸乙酯；阻燃剂；聚氨酯硬泡；阻燃性能；橡塑助剂
中图分类号：TQ314.24 文献标识码：A 文章编号：1003-5214 (2021) 09-1913-08

Synthesis and application of oligohydroxypropyl ethyl
phosphate flame retardant

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ZHANG Ji, BIAN Jincai, HE Zhenni, ZHOU Kejie, ZHI Huizhen ,
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HUANG Xiaodong , YANG Jinfei
（School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China）

Abstract: Oligohydroxypropyl ethyl phosphate flame retardant was synthesized by using phosphorus
pentoxide and propylene oxide as main raw materials. The effects of dropping temperature and dosage of
propylene oxide, reaction temperature, reaction time and reaction system pressure on the acid value of
target product were investigated. The results showed that under the optimum conditions of mass ratio of
propylene oxide to intermediate Ⅱ 0.67∶1.0, dropping temperature of propylene oxide 15 ℃, reaction
system pressure was 0.5 MPa, reaction temperature 70 ℃, reaction time 1.5 h, the acid value of target
product reached 0.6 mg KOH/g. The structure and properties were characterized by FTIR, GPC, TGA and
chemical titration. Subsequently, the synthesized flame retardant was used to modify polyurethane rigid
foam (RPUF). TGA data showed when the addition amount of flame retardant was 10% (based on the mass
of polyether polyol, the same below), the carbon residue rate of the modify polyurethane rigid foam at 900
℃ increased from 7.9% (without modification) to 20.7%. The flame retardant performance test data
showed the polyurethane rigid foam with an addition amount of 30% flame retardant achieved a limit
oxygen index value (LOI) value of 27.1% and could pass the UL-94 V-0 rating test, and retained the basic
mechanical properties of RPUF.
Key words: phosphorus pentoxide; oligohydroxypropyl ethyl phosphate; flame retardants; polyurethane
rigid foam; flame retardancy; rubber and plastics auxiliaries

随着住宅、商业及工业领域对能源消耗日益增 加，国际社会对节能减排愈加重视 [1-2] ，而绝缘隔热

收稿日期：2021-03-17; 定用日期：2021-06-15; DOI: 10.13550/j.jxhg.20210277
作者简介：张 继（1995—），女，硕士生。联系人：职慧珍（1974—），女，副教授，E-mail：zhihuizhen@163.com；黄小冬（1978—），
男，讲师，E-mail：06209@njnu.edu.cn。