含磷聚合物型阻燃剂<strong>(PMP)</strong>对乙烯基酯树脂<strong>(VER)</strong>的阻燃改性

doi:10.11901/1005.3093.2021.217

材料研究学报

2021, Vol. 35

Issue (11): 843-849 DOI: 10.11901/1005.3093.2021.217

研究论文

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含磷聚合物型阻燃剂(PMP)对乙烯基酯树脂(VER)的阻燃改性

徐春萍¹^,², 陈春悦¹^,², 张永航¹, 龚维², 班大明¹^,²(

)

^1.贵州师范大学化学与材料科学学院贵阳 550001
^2.贵州省功能高分子材料科技创新人才团队贵阳 550025

Flame Retard Modification of Vinyl Ester Resin with Phosphorous Polymer Type Flame Retardant

XU Chunping¹^,², CHEN chunyue¹^,², ZHANG yonghang¹, Gong wei², BAN daming¹^,²(

)

^1.School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001 China
^2.Guizhou Functional Polymer Materials Science and Technology Innovation Talent Team, Guiyang 550025, China

引用本文:

徐春萍, 陈春悦, 张永航, 龚维, 班大明. 含磷聚合物型阻燃剂(PMP)对乙烯基酯树脂(VER)的阻燃改性[J]. 材料研究学报, 2021, 35(11): 843-849.
Chunping XU, chunyue CHEN, yonghang ZHANG, wei Gong, daming BAN. Flame Retard Modification of Vinyl Ester Resin with Phosphorous Polymer Type Flame Retardant[J]. Chinese Journal of Materials Research, 2021, 35(11): 843-849.

全文: PDF(2939 KB) HTML

摘要:

使三氯氧磷与4-甲氧基苯酚发生反应制备阻燃剂聚对甲氧基苯氧基磷酸-4,4’-二羟基联苯酯(PMP)，用傅里叶变换红外光谱(FTIR)和核磁共振(¹H-NMR,¹³C-NMR,³¹P-NMR)等手段表征其结构，并测试其煅烧后残炭的X射线光电子谱(XPS)。用阻燃剂PMP复配聚磷酸铵(APP) 改性乙烯基酯树脂(VER)，制备出PMP/APP/VER复合材料。用热失重分析(TGA)、极限氧指数(LOI)和垂直燃烧(UL-94)等手段研究了这种材料的阻燃性能和热稳定性能。结果表明，阻燃剂PMP/APP添加量为15%的PMP/APP/VER复合材料其UL-94测试等级达到V-1级；PMP/APP添加量为20%时LOI值达到25.0%，在温度为700℃时的残炭量为34.6%，是纯VER的3.72倍。这表明，PMP/APP能显著提高VER基体的阻燃性能和热稳定性。

关键词 ：功能高分子材料, 乙烯基酯树脂, 聚磷酸铵, 阻燃性能, 热稳定性能

Abstract：

The flame retardant poly (p-methoxy phenoxy phosphate) -4,4 '-dihydroxy biphenyl ester (PMP) was prepared by reaction process with 4-methoxy phenol and phosphorus trichloride as raw materials and its structure was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹H-NMR,¹³C-NMR,³¹P-NMR). Its carbon residue after calcination was measured by X-ray photoelectron spectroscopy (XPS). Further, the composite of PMP/APP/VER was fabricated with vinyl ester resin (VER) as raw material and the compound of ammonium polyphosphate (APP) and flame retardant PMP as modifier. The flame retardancy and thermal stability of the prepared composite was investigated by means of thermogravimetric analysis (TGA), limiting oxygen index (LOI) and vertical combustion (UL-94). The results show that the PMP/APP/VER composite with 15% PMP/APP could be rated as grade V-1 corresponding to the UL-94 test. When the composite with 20% PMP/APP, its LOI value reached 25.0%, and carbon residue was 34.6% after calcined at 700℃, which was 3.72 times that of the bare VER. These results demonstrate that PMP/APP can significantly improve the flame retardant performance and thermal stability of VER matrix.

Key words： functional polymer material VER APP flame retardancy thermal stability

收稿日期: 2021-04-06

ZTFLH:

O623.4

基金资助:国家自然科学基金(51763005);贵州省科技计划(黔科合平台人才［2017］5726号)

作者简介: 徐春萍，女，1996年生，硕士生

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表1 PMP/VER和PMP/APP/VER复合材料的配方、氧指数和垂直燃烧等级

图1 MPC和 PMP的红外光谱

图2 PMP的 1H-NMR(a)、31P NMR(b)、13C NMR(c)谱

图3 PMP煅烧后残炭的XPS谱

表2 纯VER、PMP/APP/VER 和 PMP/VER复合材料的热降解行为

图4 纯VER和VER复合材料的TGA和DTG曲线

1	Mao W, Li S H, Li M, et al. A novel flame retardant UV-curable vinyl ester resin monomer based on industrial dipentene: Preparation, characterization, and properties [J]. J. Appl. Polym. Sci., 2016, 133(41): 44084
2	Vu C M, Nguyen V H, Van T N, et al. Phenyl/vinyl polysilsesquioxane based ladder polymer as novel additive for vinyl ester resin: Fabrication, mechanical and flame-retardant properties [J]. Polym. Test., 2021, 93:106987
3	Shan P N, Dev S, Lee Y, et al. Processing and mechanical properties of bio-derived vinyl ester resin-based composites [J]. J. Appl. Polym. Sci., 2017, 134(13): 44624
4	Zhang X, Zhang W, Zeng G, et al. The effect of different smoke suppressants with APP for enhancing the flame retardancy and smoke suppression on vinyl ester resin [J]. Polym. Eng. Sci., 2020, 60(2): 314
5	Day P. R.. The use of vinyl resins in appliance finishes [J]. Transactions of the IMF., 2017, 37(1): 65
6	Huo S Q, Wang J, Yang S, et al. Synthesis of a novel phosphorus-nitrogen type flame retardant composed of maleimide, triazine-trione, and phosphaphenanthrene and its flame retardant effect on epoxy resin [J]. Polym. Degrad. Stabil., 2016, 131: 106
7	Kanat M, Eren T. Synthesis of phosphorus-containing flame retardants and investigation of their flame retardant behavior in textile applications [J]. J. Appl. Polym. Sci., 2019, 136(36): 47935
8	Kandola B K, Ebdon J R, Zhou C, et al. Development of vinyl ester resins with improved flame retardant properties for structural marine applications [J]. React. Funct. Polym., 2018, 129 (8): 111
9	Tao X X, Duan H J, Dong W J, et al. Synthesis of an acrylate constructed by phosphaphenanthrene and triazine-trione and its application in intrinsic flame retardant vinyl ester resin [J]. Polym. Degrad. Stabil., 2018, 154: 285
10	Zhang W W, Zhang W C, Qin Z L, et al. Mechanical and flame-retardant properties and thermal decomposition of vinyl ester resin modified by different phenyl silsesquioxanes [J]. Polym. Adv. Technol., 2020, 31(8): 1836
11	Tao X X, Duan H J, Dong W J, et al. Preparation of a novel flame retardant TGICA-DOPO and its effects on the properties of vinyl ester resin [J]. Acta Materiae Compositae Sinica., 2018, 35(7): 1731
11	陶晓晓, 段华军, 董文静等. 新型磷氮阻燃剂TGICA-DOPO的合成及其对乙烯基酯树脂阻燃性能的影响 [J]. 复合材料学报,2018, 35(7): 55
12	Huo S Q, Song P G, Yu B, et al. Phosphorus-containing flame retardant epoxy thermosets: Recent advances and future perspectives [J]. Prog. Polym. Sci.,2021, 114: 101366
13	Huo S Q, Wang J, Yang S, et al. Synthesis of a novel reactive flame retardant containing phosphaphenanthrene and triazine-trione groups and its application in unsaturated polyester resin [J]. Materials Research Express., 2018, 5(3): 035306
14	Ji S, Duan H J, Chen Y S, et al.A novel phosphorus/nitrogen-containing liquid acrylate monomer endowing vinyl ester resin with excellent flame retardancy and smoke suppression [J]. Polymer., 2020, 207: 122917
15	Wagner J, Deglmann P, Fuchs S, et al. A flame retardant synergism of organic disulfides and phosphorous compounds [J]. Polym. Degrad. Stabil., 2016, 129: 63
16	Zhang X, Zhang W, Zhang W, et al. Enhanced mechanical and flame retardancy properties of vinyl ester resin systems with the synthesis of two flame retardants with vinyl group [J]. Polymer International., 2020, 69(12): 1196
17	Duan H J, Ji S, Yin T, et al. Phosphorus-nitrogen-type fire-retardant vinyl ester resin with good comprehensive properties [J]. J.Appl. Polym.Sci., 2019, 136(39): 47997
18	Prabhakar M N, Song J I. Influence of chitosan-centered additives on flammable properties of vinyl ester matrix composites [J]. Cellulose., 2020, 27(4): 8087
19	Zeng G, Zhang W, Zhang X, et al. Study on flame retardancy of APP/PEPA/MoO 3 synergism in vinyl ester resins [J]. J.Appl. Polym. Sci., 2020, (4): 49026
20	Shen H Y, Gou J, Ban D M, et al. Synthesis of three of MOPO derived polymeric flame retardant and its application in EP [J]. New Chemical Materials., 2020, 48(5): 192
20	申慧滢, 苟佳, 付海等. 3种4-甲氧基二氯化磷酸苯酯衍生聚合物型阻燃剂的合成及其对环氧树脂改性探究 [J]. 化工新型材料, 2020, 48(5): 192
21	Wang Z Z, Yang T, Hu L F. Preparation and application for EPS foam of melamine-bis [tetrakis (hydroxymethyl) phosphonium] sulfate flame retardant [J]. Chinese Journal of Materials Research., 2018, 32(08): 584
21	王正洲, 杨婷, 胡立飞. 三聚氰胺四羟甲基硫酸磷阻燃剂的合成及其在EPS泡沫中应用 [J]. 材料研究学报, 2018, 32(08): 584

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