新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

doi:10.16085/j.issn.1000-6613.2018-2035

化工进展 ›› 2019, Vol. 38 ›› Issue (07): 3285-3290.DOI: 10.16085/j.issn.1000-6613.2018-2035

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

周威^1,³(),郑开梅^1,²,周永红^3,⁴,张猛^3,⁴()

1. 中国林业科学研究院林产化学工业研究所，江苏南京 210042
2. 南京林业大学林业资源高效加工利用协同创新中心，江苏南京 210037
3. 江苏省生物质能源与材料重点实验室，江苏南京 210042
4. 国家林业局林产化学工程重点开放性实验室，江苏南京 210042

收稿日期:2018-10-14 出版日期:2019-07-05 发布日期:2019-07-05
通讯作者: 张猛
作者简介:周威（1990—），女，博士研究生，研究方向为生物质的高效利用。E-mail:<email>zhouwei90@foxmail.com</email>。
基金资助:
国家自然科学基金(31670577);国家重点研发计划(2017YFD0601304)

Preparation and characterization of novel phosphorus-containing flame retardant tung oil-based rigid polyurethane foam

Wei ZHOU^1,³(),Kaimei ZHENG^1,²,Yonghong ZHOU^3,⁴,Meng ZHANG^3,⁴()

1. Institute of Chemical Industry of Forestry Products, Chinese Academy of Forestry, Nanjing 210042, Jiangsu, China
2. Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
3. Key Laboratory of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, Jiangsu, China
4. Key Laboratory of Forest Chemical Engineering, State Forestry Administration, Nanjing 210042, Jiangsu, China

Received:2018-10-14 Online:2019-07-05 Published:2019-07-05
Contact: Meng ZHANG

摘要/Abstract

摘要：

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO），GTO经环氧化得到环氧化桐油醇解产物（EGTO），EGTO与9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应，通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大，RPUF的压缩强度、密度、热导率先增大后减小，热稳定性提高，极限氧指数（LOI）由18.1%提高至26.0%，而总放热量先减小后增大，这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。

关键词: 聚氨酯, 桐油, 9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物, 阻燃, 硬泡

Abstract:

The monoglyceride of tung oil (GTO) was prepared by using tung oil as raw material, sodium methoxide as catalyst, through alcoholysis reaction with glycerol, and epoxidized monoglyceride of tung oil (EGTO) synthesized by epoxidation. The novel flame retardant tung oil-based polyol (PTOP) was prepared through the ring opening reaction of EGTO with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Rigid polyurethane foam (RPUF) was formed by one step via the reaction of PTOP, polyether polyol (PPG4110) with PAPI and chemical agents. The mechanical behavior, thermal stability and fire behavior of RPUFs were determined by an universal mechanical tester, thermal analyzer and cone calorimetry, respectively. The results showed that with the increase of the substitution of PPG4110 by PTOP, the compressive strength, density and thermal conductivity of RPUFs were increased then decreased, the thermal stability was elevated, the limiting oxygen index (LOI) of RPUF was raised from 18.1% to 26.0% and the total heat released was decreased and then increased, which was due to the flame retardancy of DOPO in PTOP while the fat chain of monoglyceride of tung oil in PTOP was easy to burn and the heat released was higher. RPUF was prepared by PTOP at different levels with good flame retardancy and excellent thermal stability.

Key words: polyurethane, tung oil, DOPO, flame retardancy, rigid foam

中图分类号:

TQ328.3

周威, 郑开梅, 周永红, 张猛. 新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征[J]. 化工进展, 2019, 38(07): 3285-3290.

Wei ZHOU, Kaimei ZHENG, Yonghong ZHOU, Meng ZHANG. Preparation and characterization of novel phosphorus-containing flame retardant tung oil-based rigid polyurethane foam[J]. Chemical Industry and Engineering Progress, 2019, 38(07): 3285-3290.

图/表 10

参考文献 17

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试样	各组分质量/g
试样	PPG4110	PTOP	AK8804	DBTDL	水	发泡剂	PAPI
RPUF-1	80	20	2.4	1.2	1.2	20	120
RPUF-2	60	40	2.4	1.2	1.2	20	120
RPUF-3	40	60	2.4	1.2	1.2	20	120
RPUF-4	20	80	2.4	1.2	1.2	20	120
RPUF-5	0	100	2.4	1.2	1.2	20	120

试样	各组分质量/g
试样	PPG4110	PTOP	AK8804	DBTDL	水	发泡剂	PAPI
RPUF-1	80	20	2.4	1.2	1.2	20	120
RPUF-2	60	40	2.4	1.2	1.2	20	120
RPUF-3	40	60	2.4	1.2	1.2	20	120
RPUF-4	20	80	2.4	1.2	1.2	20	120
RPUF-5	0	100	2.4	1.2	1.2	20	120

试样	压缩强度/MPa	密度/kg·m^-3	热导率/W·(m·K)^-1
RPUF-1	0.39	78.50	0.035
RPUF-2	0.61	106.13	0.036
RPUF-3	0.82	97.08	0.039
RPUF-4	0.75	89.48	0.038
RPUF-5	0.56	83.35	0.034

试样	压缩强度/MPa	密度/kg·m^-3	热导率/W·(m·K)^-1
RPUF-1	0.39	78.50	0.035
RPUF-2	0.61	106.13	0.036
RPUF-3	0.82	97.08	0.039
RPUF-4	0.75	89.48	0.038
RPUF-5	0.56	83.35	0.034

试样	初始分解温度/℃	最大热失重温度/℃			残渣/%
试样	初始分解温度/℃	阶段Ⅰ	阶段Ⅱ	阶段Ⅲ	残渣/%
RPUF-1	282.6	328.5	418.8	455.9	19.90
RPUF-2	281.4	329.2	415.2	461.2	19.00
RPUF-3	278.2	330.9	408.7	461.4	19.40
RPUF-4	261.8	319.6	402.3	460.6	18.33
RPUF-5	274.7	336.4	401.5	463.5	18.73

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

Preparation and characterization of novel phosphorus-containing flame retardant tung oil-based rigid polyurethane foam

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参考文献 17

相关文章 15

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试样	TTI/s	PHRR/kW·m^-2	THR/MJ·m^-2	LOI/%
RPUF-1	2	221.68	24.0	18.1
RPUF-2	2	269.81	20.5	19.8
RPUF-3	2	266.03	22.8	21.3
RPUF-4	3	259.38	18.4	24.0
RPUF-5	4	273.73	30.4	26.0

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