Synthesis of Phosphorus-Nitrogen Synergistic Flame-Retardant Compounds with Imide Structure and Their Flame Retardant Effect on Epoxy Resin

doi:10.11944/j.issn.1000-0518.2020.02.190213

Chinese Journal of Applied Chemistry ›› 2020, Vol. 37 ›› Issue (2): 144-154.DOI: 10.11944/j.issn.1000-0518.2020.02.190213

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Synthesis of Phosphorus-Nitrogen Synergistic Flame-Retardant Compounds with Imide Structure and Their Flame Retardant Effect on Epoxy Resin

YOU Geyun(),FENG Bin,FAN Fangfang,YANG Changjie,LIANG Cong

Key Laboratory of Regional Ecological Environment Analysis and Pollution Control of West Guangxi,College of Chemistry and Environment Engineering,Baise University,Baise,Guangxi 533000,China

Received:2019-08-01 Accepted:2019-10-28 Published:2020-02-01 Online:2020-02-06
Contact: YOU Geyun
Supported by:
Supported by the Natural Science Foundation of Guangxi Province(No.2016GXNSFBA380072), the Middle-Aged and Young Teachers' Basic Ability Promotion Project of Guangxi(No.2017KY0713), and the Science Research Foundation of Baise University(No.2015KAN05)

Abstract

Abstract:

Two novel phosphate-imine bifunctional flame-retardant compounds (FR:N¹,N⁴-bis{[4-(5,5-dimethyl-2-oxide-1,3,2-dioxaphosphinan-2-yl)oxy]benzylidene}benzene-1,4-diamine(PNB); N¹,N²-bis{[4-(5,5-dimethyl-2-oxide-1,3,2-dioxaphosphinan-2-yl)oxy]benzylidene}ethane-1,2-diamine(PNE)) were synthesized via aldehyde amine condensation reaction using 4-(5,5-dimethyl-1,3-dioxygen heterocyclic phosphoryl) benzaldehyde (PCHO), p-phenylene diamine and ethylenediamine as raw materials, respectively. FRs were applied on a bisphenol-A diglycidyl ether type epoxy resin (DGEBA) cured by 4,4'-diaminodiphenylsulfone (DDS) and the flame retarded mechanism was studied. The results showed that the introduction of FR greatly improved the char residues (R_c) of DGEBA/DDS at 700 ℃ and enhanced the flame retardant properties of epoxy resin systems. PNE with ethylene diamine unit presented a better flame retardant performance than PNB with p-phenylene diamine unit. With 1.5% phosphorus content, PNE-1.5/DGEBA/DDS could obtain R_c of 35.1% in nitrogen atmosphere and 14.4 % in air, respectively, and a limiting oxygen index(LOI) value of 33.2%, reaching UL-94 V-0 grade. At the same time, PNE-1.5/DGEBA/DDS maintained the bending strength and more than 76% of the impact strength compared to DGEBA/DDS, which is significantly superior to PNB-1.5/DGEBA/DDS. Analysis of flame retardant results showed that FR presented a comprehensive mechanism of condensed phase, gas phase and phosphorus-nitrogen synergistic effect in DGEBA/DDS system. In conclusion, phosphate-imine bifunctional compounds FR have excellent flame retardancy for epoxy resin systems and have potential applications.

Key words: imide, phosphorus-nitrogen synergy, flame retardant, epoxy resin

YOU Geyun, FENG Bin, FAN Fangfang, YANG Changjie, LIANG Cong. Synthesis of Phosphorus-Nitrogen Synergistic Flame-Retardant Compounds with Imide Structure and Their Flame Retardant Effect on Epoxy Resin[J]. Chinese Journal of Applied Chemistry, 2020, 37(2): 144-154.

References

[1]	Ren H,Sun J Z,Wu B J,et al. Synthesis and Properties of a Phosphorus-Containing Flame Retardant Epoxy Resin Based on Bis-phenoxy(3-hydroxy) Phenyl Phosphine Oxide[J]. Polym Degrad Stabil,2007,92(6):956-961.
[2]	PEI Zhanyu,ZHU Jing,DONG Zhenhua.Research Rrogress of Reactive Phosphorus-Containing Flame-Retardant Epoxy Resins[J]. New Chem Mater,2009,37(9):30-32(in Chinese). 裴占宇,朱靖,董振华. 反应型含磷阻燃环氧树脂的研究进展[J]. 化工新型材料,2009,37(9):30-32.
[3]	Yurddaskal M,Celik E.Effect of Halogen-Free Nanoparticles on the Mechanical, Structural, Thermal and Flame Retardant Properties of Polymer Matrix Composite[J]. Compos Struct,2018,183:381-388.
[4]	Long J P,Li S X,Liang B.Synthesis and Properties of a New Halogen-Free Flame Retardant for Polyethylene[J]. Pigm Resin Technol,2018,47(3):208-215.
[5]	LI Pei,FU Hai,ZHAO Ou,et al. Influence of Polyphosphate Flame Retardant Couple with Ammonium Polyphosphate on Epoxy Resin[J]. Chem J Chinese Univ,2017,38(2):294-302(in Chinese). 李霈,付海,赵欧,等. 聚磷酸酯阻燃剂复配聚磷酸铵对环氧树脂阻燃性能的影响[J]. 高等学校化学学报,2017,38(2):294-302.
[6]	Wang C,Wu Y C,Li Y C,et al. Flame-Retardant Rigid Polyurethane Foam with a Phosphorus-Nitrogen Single Intumescent Flame Retardant[J]. Polym Adv Technol,2018,29(1):668-676.
[7]	Gaan S,Sun G,Hutches K,et al. Effect of Nitrogen Additives on Flame Retardant Action of Tributyl Phosphate: Phosphorus-Nitrogen Synergism[J]. Polym Degrad Stabil,2008,93(1):99-108.
[8]	Levchik G F,Grigoriev Y V,Balabanovich A I,et al. Phosphorus-Nitrogen Containing Fire Retardants for Poly(butylene terephthalate)[J]. Polym Int,2000,49(10):1095-1100.
[9]	HE Hongwu,YOU Geyun,PENG Hao,The Preparation and Application of Phosphaphenanthrene-Based Compounds: CN108864193A[P].2018-11-23(in Chinese). 贺红武,游歌云,彭浩. 磷杂菲类化合物及其制备方法和用途:中国,CN108864193A[P].2018-11-23.
[10]	You G Y,Cheng Z Q,Peng H,et al. The Synthesis and Characterization of a Novel Phosphorus-Nitrogen Containing Flame Retardant and Its Application in Epoxy Resins[J]. J Appl Polym Sci,2014,131(22):1-8.
[11]	You G Y,Cheng Z Q,Tang Y Y,et al. Functional Group Effect on Char Formation, Flame Retardancy and Mechanical Properties of Phosphonate-Triazine-Based Compound as Flame Retardant in Epoxy Resin[J]. Ind Eng Chem Res,2015,54(30):7309-7319.
[12]	Zhan J,Song L,Nie S B,et al. Combustion Properties and Thermal Degradation Behavior of Polylactide with an Effective Intumescent Flame Retardant[J]. Polym Degrad Stabil,2009,94(3):291-296.
[13]	Zang L,Wagner S,Ciesielski M,et al. Novel Star-Shaped and Hyperbranched Phosphorus-Containing Flame Retardants in Epoxy Resins[J]. Polym Adv Technol,2011,22(7):1182-1191.
[14]	Qian L J,Qiu Y,Sun N,et al. Pyrolysis Route of a Novel Flame Retardant Constructed by Phosphaphenanthrene and Triazine-Trione Groups and Its Flame-Retardant Effect on Epoxy Resin[J]. Polym Degrad Stabil,2014,107:98-105.
[15]	Chen L J,Song L,Lv P,et al. A New Intumescent Flame Retardant Containing Phosphorus and Nitrogen: Preparation, Thermal Properties and Application to UV Curable Coating[J]. Prog Org Coat,2011,70(1):59-66.
[16]	You G Y,Cheng Z Q,Peng H,et al. The Synthesis and Characterization of a Novel Phosphorus-Nitrogen Containing Flame Retardant and Its Application in Epoxy Resins[J]. J Appl Polym Sci,2014,131(22):1-8.
[17]	You G Y,Cheng Z Q,Peng H,et al. Synthesis and Performance of a Novel Nitrogen-Containing Cyclic Phosphate for Intumescent Flame Retardant and Its Application in Epoxy Resin[J]. J Appl Polym Sci,2015,132(16):1-9.
[18]	LI Zhengqiu.Synthesis and Properties of Phosphate Esters and Phosphoryl Thiourea Compounds[D]. Wuhan:Central China Normal University,2007(in Chinese). 李正球. 磷酸酯类化合物及磷酰基硫脲类化合物的合成及其性质研究[D]. 武汉:华中师范大学,2007.
[19]	Hoang D Q,Kim J,Jang B N.Synthesis and Performance of Cyclic Phosphorus-Containing Flame Retardants[J]. Polym Degrad Stabil,2008,93:2042-2047.
[20]	Wang P,Cai Z.Highly Efficient Flame-Retardant Epoxy Resin with a Novel DOPO-Based Triazole Compound:Thermal Stability, Flame Retardancy and Mechanism[J]. Polym Degrad Stabil,2017,137:138-150.
[21]	Sun D C,Yao Y W.Synthesis of Three Novel Phosphorus-Containing Flame Retardants and Their Application in Epoxy Resins[J]. Polym Degrad Stabil,2011,96(10):1720-1724.
[22]	Ma C,Yu B,Hong N,et al. Facile Synthesis of a Highly Efficient, Halogen-Free, and Intumescent Flame Retardant for Epoxy Resins:Thermal Properties, Combustion Behaviors, and Flame-Retardant Mechanisms[J]. Ind Eng Chem Res,2016,55(41):10868-10879.
[23]	Zhang T, Cai Q, Wu D Z,et al. Phosphazene Cyclomatrix Network Polymers:Some Aspects of the Synthesis, Characterization, and Flame-Retardant Mechanisms of Polymer[J]. J Appl Polym Sci,2005,95(4):880-889.
[24]	Perret B,Schartel B,St K,et al. Novel DOPO-Based Flame Retardants in High-Performance Carbon Fibre Epoxy Composites for Aviation[J]. Eur Polym J,2011,47(5):1081-1089.
[25]	Chen K,Xu Z J.Synthesis and Characterizations of Novel Phosphorous-Nitrogen Containing Poly(ether sulfone)s[J]. Polym Degrad Stabil,2011,96(2):197-203.
[26]	Liang B,Cao J,Hong X D,et al. Synthesis and Properties of a Novel Phosphorous-Containing Flame-Retardant Hardener for Epoxy Resin[J]. J Appl Polym Sci,2013,128(5):2759-2765.

Synthesis of Phosphorus-Nitrogen Synergistic Flame-Retardant Compounds with Imide Structure and Their Flame Retardant Effect on Epoxy Resin

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