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[1]涂伟强,张 旗*.磷-氮有机盐改性聚氨酯弹性体的制备与性能[J].武汉工程大学学报,2024,46(01):43-49.[doi:10.19843/j.cnki.CN42-1779/TQ.202212022]
　TU Weiqiang,ZHANG Qi*.Preparation and properties of polyurethane elastomers modified byphosphorus-nitrogen organic salts[J].Journal of Wuhan Institute of Technology,2024,46(01):43-49.[doi:10.19843/j.cnki.CN42-1779/TQ.202212022]
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磷-氮有机盐改性聚氨酯弹性体的制备与性能(/HTML)
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《武汉工程大学学报》[ISSN:1674-2869/CN:42-1779/TQ]

卷:
46
期数:
2024年01期
页码:
43-49
栏目:
材料科学与工程
出版日期:
2024-03-12

文章信息/Info

Title:
Preparation and properties of polyurethane elastomers modified by
phosphorus-nitrogen organic salts
文章编号:
1674 - 2869（2024）01 - 0043 - 07
作者:
涂伟强; 张 旗*
武汉工程大学材料科学与工程学院，湖北 武汉 430205
Author(s):
TU Weiqiang; ZHANG Qi*
School of Materials Science and Engineering，Wuhan Institute of Technology，Wuhan 430205，China
关键词:
热塑性聚氨酯弹性体; 依替膦酸; 糠胺; 阻燃性能
Keywords:
thermoplastic polyurethane elastomer;  etidronic acid;  2-furfurylamine;  flame retardancy
分类号:
TQ323.8
DOI:
10.19843/j.cnki.CN42-1779/TQ.202212022
文献标志码:
A
摘要:
以依替膦酸和糠胺为原料合成了一种新型磷-氮阻燃剂（EAFOS），并采用熔融共混法将EAFOS添加至热塑性聚氨酯弹性体（TPU）中制备改性TPU（TPU/EAFOS）。通过红外光谱和核磁共振氢谱对EAFOS的化学结构进行了表征。通过极限氧指数（LOI）、垂直燃烧等级（UL-94）测试、热重分析、马弗炉热解测试、炭层拉曼测试以及拉伸测试研究了TPU/EAFOS的阻燃性能、热稳定性以及力学性能。结果发现：EAFOS的加入可明显提升TPU的阻燃性能并抑制TPU燃烧过程中的融滴现象。与纯TPU相比，仅添加1%质量分数EAFOS的样品的LOI（30.5%）提升了40.0%，并且通过了UL-94 V-0评级。EAFOS受热分解催化TPU燃烧时成炭，形成石墨化程度更高更致密的炭层来抑制TPU燃烧过程中的热量与氧气的交换从而提升TPU的阻燃性能。另外，EAFOS的加入会降低TPU的力学性能，其原因可能是EAFOS破坏了TPU分子链间的氢键。

Abstract:
A novel phosphorus-nitrogen flame retardant （etidronic acid 2-furfurylamine organic salt,EAFOS） was synthesized with etidronic acid and 2-furfurylamine as starting materials，and it was added to thermoplastic polyurethane elastomer （TPU） by melt blending method to fabricate modified TPU （TPU/EAFOS）. The chemical structure of EAFOS was characterized by infrared spectroscopy and nuclear magnetic resonance spectroscopy. The flame retardancy， thermal stability and mechanical properties of TPU/EAFOS were investigated by limiting oxygen index （LOI），underwriters laboratory-94 （UL-94），thermogravimetric analysis，muffle pyrolysis，Raman and tensile test. The results reveal that the addition of EAFOS significantly improves the flame retardancy of TPU and inhibits the melt-drop phenomenon during the combustion. The sample with only 1% mass fraction of EAFOS shows an increase of 40% in LOI value （30.5%） compared with the pure TPU，and it can pass the V-0 rating for UL-94. The thermal decomposition of EAFOS catalyzes the formation of char during combustion，forming a higher degree of graphitization and denser char layer to inhibit the exchange of heat and oxygen during the combustion of TPU，which improves the flame retardancy of TPU. In addition， the mechanical properties of TPU decrease after the addition of EAFOS. The likely cause of this problem is that the hydrogen bonds between the TPU molecular chains are broken by EAFOS.

参考文献/References:

［1］ 张尧，陈露，黄小冬，等. 阻燃聚氨酯的研究及应用进展［J］. 塑料助剂，2020（1）：1-10.

［2］ 朱青美，张妍婧，付慧莉，等. 木质素/聚氨酯复合膜的制备与表征［J］. 武汉工程大学学报，2022，44（4）：403-407.
［3］ CHEN X L， JIANG Y F， LIU J B， et al. Smoke suppression properties of fumed silica on flame-retardant thermoplastic polyurethane based on ammonium polyphosphate［J］. Journal of Thermal Analysis and Calorimetry，2015，120（3）：1493-1501.
［4］ WANG J L，ZHANG D C，ZHANG Y，et al. Construction of multifunctional boron nitride nanosheet towards reducing toxic volatiles （CO and HCN） generation and fire hazard of thermoplastic polyurethane［J］. Journal of Hazardous Materials，2019，362：482-494.
［5］ 郭嘉昒，马慧，李为民，等. 阻燃聚氨酯材料的研究现状［J］. 上海化工，2018，43（9）：35-37.
［6］ HOFFMANN T， FRIEDEL P， HARNISCH C， et al. Investigation of thermal decomposition of phosphonic acids［J］. Journal of Analytical and Applied Pyrolysis，2012，96：43-53.
［7］ 金芳芳，丁逸飞，夏寅，等. 羟基乙叉二膦酸三聚氰胺盐的合成及膨胀阻燃应用［J］. 高分子材料科学与工程，2015，31（7）：22-27，33.
［8］ XIA Y， MAO Z W， JIN F F， et al. Synthesis of 1-hydroxy ethylidene-1,1-diphosphonic ammonium and the promise of this ammonium salt as an intumescent flame retardant in polystyrene［J］. Polymer Degradation and Stability，2014，102：186-194.
［9］ SUN J H， LI L，LI J. Effects of furan-phosphamide derivative on flame retardancy and crystallization behaviors of poly(lactic acid)［J］. Chemical Engineering Journal，2019，369：150-160.
［10］ SHEN X B， DAI J Y，LIU Y， et al. Synthesis of high performance polybenzoxazine networks from bio-based furfurylamine：furan vs benzene ring［J］. Polymer，2017，122：258-269.
［11］ YE G F， HUO S Q， WANG C， et al. One-step and green synthesis of a bio-based high-efficiency flame retardant for poly(lactic acid)［J］. Polymer Degradation and Stability，2021，192：109696.
［12］ LU Y，JIA Y L，ZHOU Y，et al. Straightforward one-step solvent-free synthesis of the flame retardant for cotton with excellent efficiency and durability［J］. Carbohydrate Polymers，2018，201：438-445.
［13］ HU W J，LI Y M，PANG Y Y，et al. The preparation of phosphorus and nitrogen-containing structure towards the enhancement of flame retardancy for thermoplastic polyurethane elastomer［J］. Colloids and Surfaces A：Physicochemical and Engineering Aspects，2023，656（Part A）：130375.
［14］ ZHU Z M，SHANG K，WANG L X，et al. Synthesis of an effective bio-based flame-retardant curing agent and its application in epoxy resin：curing behavior，thermal stability and flame retardancy［J］. Polymer Degradation and Stability，2019，167：179-188.
［15］ LIU Y L，CHOU C I. High performance benzoxazine monomers and polymers containing furan groups［J］. Journal of Polymer Science Part A：Polymer Chemistry，2005，43（21）：5267-5282.
［16］ SHI J P， ZENG W， YANG Z W， et al. Effect of particle size on flame retardancy and mechanical properties of hydroxyethyl diphosphate modified aluminum hydroxide intrinsic polyethylene terephthalate ［J］. Journal of Applied Polymer Science，2021，138（21）：50500.
［17］ ZHU Z M，WANG L X， LIN X B，et al. Synthesis of a novel phosphorus-nitrogen flame retardant and its application in epoxy resin［J］. Polymer Degradation and Stability，2019，169：108981.
［18］ DING S，FENG J，HAO J W，et al. A study on the fire resistance performance and thermal degradation behavior of a new intumescent flame retardant fluoroelastomer［J］. Journal of Fire Sciences，2014，32（4）：362-373.
［19］ LIU W，WANG Y X，REN J Y，et al. Flame retardant thermoplastic polyurethane based on a combination of chitosan and phosphotungstic acid［J］. Journal of Thermal Analysis and Calorimetry，2022，147（22）：12791-12803.
［20］ XU W Z，XU B L，LI A J，et al. Flame retardancy and smoke suppression of MgAl layered double hydroxides containing P and Si in polyurethane elastomer［J］. Industrial & Engineering Chemistry Research，2016，55（42）：11175-11185.
［21］ AI L H，CHEN S S，YANG L，et al. Synergistic flame retardant effect of organic boron flame retardant and aluminum hydroxide on polyethylene［J］. Fibers and Polymers，2021，22（2）：354-365.
［22］ LIU J，QI P，MENG D，et al. Eco-friendly flame retardant and smoke suppression coating containing boron compounds and phytic acids for nylon/cotton blend fabrics［J］. Industrial Crops and Products，2022，186：115239.
［23］ 赵海珠，周易，彭治汉. 一种三聚氰胺多膦酸盐阻燃剂在聚丙烯中的应用研究［J］. 塑料工业，2015，43（3）：111-114.
［24］ SAMI S， YILDIRIM E， YURTSEVER M， et al. Understanding the influence of hydrogen bonding and diisocyanate symmetry on the morphology and properties of segmented polyurethanes and polyureas：computational and experimental study［J］. Polymer，2014，55（18）：4563-4576.
［25］ LIU L B，XU Y，HE Y T，et al. An effective mono-component intumescent flame retardant for the enhancement of water resistance and fire safety of thermoplastic polyurethane composites［J］. Polymer Degradation and Stability，2019，167：146-156.
［26］ TORRESI S，CALVO-CORREAS T，BASASORO S，et al. Furan-containing biobased polyurethane nanofibers：a new versatile and green support clickable via Diels-Alder reaction［J］. Reactive and Functional Polymers，2022，178：105353.
［27］ KIM J M，KIM J H，AHN J H，et al. Synthesis of nanoparticle-enhanced polyurethane foams and evaluation of mechanical characteristics［J］.Composites Part B：Engineering，2018，136：28-38.

相似文献/References:

备注/Memo

备注/Memo:
收稿日期：2022-12-22
基金项目：武汉工程大学科学研究基金（20QD26）
作者简介：涂伟强，硕士研究生。Email：894060987@qq.com
*通信作者：张 旗，博士，副教授。Email：whzq_2014@163.com
引文格式：涂伟强，张旗. 磷-氮有机盐改性聚氨酯弹性体的制备与性能［J］. 武汉工程大学学报，2024，46（1）：43-49.
更新日期/Last Update: 2024-03-01