化工学报 ›› 2020, Vol. 71 ›› Issue (4): 1871-1880.doi: 10.11949/0438-1157.20191000

• 材料化学工程与纳米技术 • 上一篇    下一篇

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

李梦迪(),王波,王哲慧,张晔,杨荣,李锦春()   

  1. 常州大学材料科学与工程学院 常州大学材料科学与工程国家级实验教学示范中心，江苏省环境友好高分子材料重点实验室，江苏 常州 213164
  • 收稿日期:2019-09-05 修回日期:2019-12-09 出版日期:2020-04-05 发布日期:2019-12-27
  • 通讯作者: 李锦春 E-mail:874142186@qq.com;lijinchun88@163.com
  • 作者简介:李梦迪（1994—），男，硕士研究生，874142186@qq.com
  • 基金资助:
    国家自然科学基金项目(51473024);江苏省高校自然科学基金项目(19KJB430007)

Synthesis of phosphorus-nitrogen flame retardant based on cyclophosphonate and its application on rigid polyurethane foam

Mengdi LI(),Bo WANG,Zhehui WANG,Ye ZHANG,Rong YANG,Jinchun LI()   

  1. School of Materials Science and Engineering, Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials, Changzhou University, Changzhou 213164, Jiangsu, China
  • Received:2019-09-05 Revised:2019-12-09 Online:2020-04-05 Published:2019-12-27
  • Contact: Jinchun LI E-mail:874142186@qq.com;lijinchun88@163.com

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摘要：

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料，成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP），用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性，氮气气氛下的初始分解温度为191.9℃，700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%，最大热释放速率和总热释放量分别从230 kW/m2和20.1 MJ/m2降低至213 kW/m2和16.6 MJ/m2，总产烟量从10.5 m2下降到5.3 m2。

关键词: 泡沫, 合成, 阻燃, 苹果酸多元醇, 硬质聚氨酯泡沫

Abstract:

Flame retardant hexa (4-anilino-methylenephenoxy-diethyl phosphite) cyclotriphosphazene (HADPPCP) was synthesized with hexachlorocyclotriphosphazene, p-hydroxybenzaldehyde, aniline, diethyl phosphite. Then it was used to prepare flame-retardant polyurethane foam. HADPPCP has good thermal stability and char formation. The initial decomposition temperature in a nitrogen atmosphere is 191.9℃, and the residual carbon content at 700℃ is as high as 46.8%(mass) in nitrogen. The addition of HADPPCP improved the fire safety of polyurethane rigid foams. When adding 25%(mass) HADPPCP, the limiting oxygen index of rigid polyurethane foam increased from 18% to 25%. The peak heat release rate and total heat release of polyurethane foam decreased from 230 kW/m2 and 20.1 MJ/m2 to 213 kW/m2 and 16.6 MJ/m2, respectively. Moreover, the total smoke production decreased from 10.5 m2 to 5.3 m2. It suggested that HADPPCP was an efficient flame retardant for RPUF, which can not only decrease heat release rate, but also suppress the smoke release rate of RPUF during the combustion.

Key words: foam, synthesis, flame retardancy, malic acid based polyols, rigid polyurethane foam

中图分类号: 

  • O 631

图1

HADPPCP的合成步骤"

表1

阻燃聚氨酯泡沫的制备配方"

SamplePU-0%FRPU-15%FRPU-20%FRPU-25%FR
malic acid based polyol100100100100
AK88052222
PC-81111
HCFC-141b20202020
H2O1111
HADPPCP045.364.285.6
PM-200132.7132.7132.7132.7

图2

HADPPCP及中间体的红外光谱"

图3

HADPPCP的核磁氢谱分析谱图"

图4

HADPPCP的核磁磷谱分析谱图"

图5

阻燃聚氨酯泡沫横截面的SEM图"

表2

聚氨酯泡沫的基本性能"

Sample

Density/

(kg/m3)

Compressive strength/

kPa

Thermal conductivity/

(W/(m·K))

PU-0%FR371550.0227
PU-15%FR381220.0232
PU-20%FR411100.0253
PU-25%FR461050.0277

图6

阻燃剂HADPPCP的TG和DTG曲线"

表3

阻燃剂HADPPCP的热重分析结果"

T5%/℃T50% /℃Tmax /℃Residues at 700℃/%(mass)
Step1Step2Step3
191.9515.8210.0292.7466.646.8

图7

阻燃聚氨酯泡沫的TG和DTG曲线"

表4

阻燃苹果酸多元醇基聚氨酯泡沫的热重分析结果"

SampleT5%/℃T50%/℃Tmax/℃Residues at 700℃/%(mass)
Step1Step2Step3
PU-0%FR247.8374.4—292.0414.124.6
PU-15%FR179.4398.0198.5300.8438.731.4 (27.9)①
PU-20%FR177.0402.7199.6295.9438.132.8 (29.0)①
PU-25%FR174.9424.2198.7289.7420.037.5 (30.2)①

表5

阻燃聚氨酯泡沫的极限氧指数（LOI）"

SampleLOI/%Self-extinguishing/s
PU-0%FR186
PU-15%FR2310
PU-20%FR2413
PU-25%FR2511

表6

无卤阻燃苹果酸多元醇基聚氨酯泡沫的锥形量热分析数据"

SampleTTI/sPHRR1/(kW/m2)PHRR2/(kW/m2)TTPHRR/sTHR/(MJ/m2)TSP/m2
PU-0%FR1230683520.110.5
PU-25%FR2213—2016.65.3

图8

PU-0%FR和PU-25%FR的热释放速率曲线"

图9

PU-0%FR和PU-25%FR的总热释放量曲线"

图10

PU-0%FR和PU-25%FR的总产烟量曲线"

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