Study on ammonium polyphosphate coated with melamine-epoxy resin and its application in PP

doi:10.11949/0438-1157.20190104

Abstract

Abstract:

For the problem of insufficient water resistance of ammonium polyphosphate (APP) and poor compatibility with polymer materials such as polypropylene(PP), APP (EM-APP) is coated with formaldehyde-melamine (melamine resin) and epoxy resin double layer. The coating effect was characterized by means of FT-IR, SEM, TGA and water solubility test. The effects of coating APP on flame retardant PP were investigated by means of horizontal vertical combustion, oxygen index instrument, cone calorimeter and thermo gravimetric-infrared combination, and the flame retardant mechanism was discussed.The results show that the coating operation not only improves the water resistance of APP effectively, but also introduces the coating layer with charring function to the surface of APP. Compared with APP, the residual carbon content of EM-APP increases by 14.2% at 800℃. When the same mass fraction of flame retardant is added to polypropylene, EM-APP has higher flame retardant efficiency, and its heat release rate, total heat release, smoke release rate and total smoke release were significantly reduced. The compatibility between APP and PP is improved by coating treatment. The coatings play a synergistic role in charring during combustion.

Key words: polymer, melamine resin, epoxy resin, ammonium polyphosphate, pyrolysis, polypropylene, composites

摘要：

针对聚磷酸铵(APP)耐水性不足、与聚丙烯(PP)等高分子材料相容性差等问题，采用甲醛-三聚氰胺(蜜胺树脂)和环氧树脂双层包覆了APP(EM-APP)，采用红外、扫描电镜、热重分析、溶解度测试等方式表征了包覆效果；采用水平垂直燃烧、氧指数仪和锥形量热仪、热重-红外联用等设备考察了包覆APP用于阻燃PP的效果，探讨了阻燃机理。结果表明：包覆操作不但有效提高了APP的耐水性，且将具有成炭功能的包覆层引入到APP表面；EM-APP相较APP，800℃时残炭量提高14.2%，在聚丙烯中加入同样质量份时，前者具有更高的阻燃效率，热释放速率、总热释放量、烟释放速率和总烟释放量都明显降低；包覆改善了APP与PP的相容性；燃烧过程中包覆层起到了协同成炭的作用。

关键词: 聚合物, 蜜胺树脂, 环氧树脂, 聚磷酸铵, 热解, 聚丙烯, 复合材料

CLC Number:

TQ 317.9

Shouwu YU, Shujuan XIAO, Zewen ZHAO, Xiaowen HUO, Junfu WEI. Study on ammonium polyphosphate coated with melamine-epoxy resin and its application in PP[J]. CIESC Journal, 2019, 70(6): 2370-2376.

于守武, 肖淑娟, 赵泽文, 霍晓文, 魏俊富. 蜜胺-环氧树脂双层包覆聚磷酸铵及其阻燃PP的研究[J]. 化工学报, 2019, 70(6): 2370-2376.

Figures/Tables 12

Fig.1 FT-IR spectra of APP and EM-APP

Fig.2 TG curves of APP and EM-APP

Fig.3 SEM images of APP and EM-APP

Table 1 Flame retardancy of PP and flame retardant PP

样品	极限氧指数/%	水平燃烧等级	是否熔滴	t _f/s	垂直燃烧等级
PP	17.5	无等级	是	—	无等级
PP/APP/CFA	27.5	HB	否	8.2	V-0
EMFR-PP	31.5	HB	否	3.0	V-0

Fig.4 HRR curves of PP and EMFR-PP

Fig.5 THR curves of PP and EMFR-PP

Fig.6 SPR curves of PP and EMFR-PP

Fig.7 TSP curves of PP and EMFR-PP

Fig.8 Residue photos of PP and EMFR-PP

Fig.9 FT-IR spectra of pyrolysis gases EM-APP at different temperatures

Fig.10 FT-IR spectra of pyrolysis products of PP and EMFR-PP at maximum thermal weight loss temperature

Fig.11 SEM image of EMFR-PP (impact section)

References 30

1	Feng C M , Li Z W , Liang M Y , et al . Preparation and characterization of a novel oligomeric charring agent and its application in halogen-free flame retardant polypropylene[J]. Journal of Analytical & Applied Pyrolysis, 2015, 111: 238-246.
2	Huang G B , Wang S Q , Song P A , et al . Combination effect of carbon nanotubes with graphene on intumescent flame-retardant polypropylene nanocomposites[J]. Composites Part A Applied Science and Manufacturing, 2014, 59(2):18–25.
3	Wang L L ， Zhang M L ， Zhou B B . Thermal stability, combustion behavior, and mechanical property in a flame-retardant polypropylene system[J]. Applied Sciences, 2017, 7(1): 55.
4	Xiao D ， Li Z ， de Juan S ，et al . Preparation, fire behavior and thermal stability of a novel flame retardant polypropylene system[J]. Journal of Thermal Analysis & Calorimetry, 2016, 125(1): 321-329.
5	Lu L G , Nan G , Qian X D , et al . Thermal degradation and combustion behavior of intumescent flame-retardant polypropylene with novel phosphorus-based flame retardants[J]. Journal of Applied Polymer Science, 2018: 45962.
6	Zhu C J , He M S , Yu L , et al . Synthesis and application of a mono-component intumescent flame retardant for polypropylene[J]. Polymer Degradation & Stability, 2018, 151: 144-151.
7	Gao S , Liu G S . Synthesis of amino trimethylene phosphonic acid melamine salt and its application in flame‐retarded polypropylene[J]. Journal of Applied Polymer Science, 2018, 135(22): 46274.
8	RibeiroSP D S , Cescon L D S , Landesmann A , et al . Effect of clay minerals structure on the polymer flame retardancy intumescent process[J]. Applied Clay Science, 2018, 161: 301-309.
9	Werner P , Horst S , Georg E . Method for the preparation of hydrolysis-stable finely divided flame retardants based on ammonium polyphosphate: EP0180795[P]. 1986-05-14.
10	Ni J X ， Tai Q L ， Lu H D ，et al . Microencapsulated ammonium polyphosphate with polyurethane shell: preparation, characterization, and its flame retardance in polyurethane[J]. Polymers for Advanced Technologies, 2010, 21(6): 392-400.
11	Wu K , Song L , Wang Z Z , et al . Microencapsulation of ammonium polyphosphate with PVA-melamine-formaldehyde resin and its flame retardance in polypropylene[J]. Polymers for Advanced Technologies, 2008, (19): 1914-1921.
12	张延奎，吴昆，张卡，等 . 双层包裹聚磷酸铵微胶囊合成及其在环氧树脂中阻燃研究[J]. 高分子学报, 2012, (7): 759-765.
	Zhang Y K , Wu K , Zhang K , et al . Synthesis of double-coated ammonium polyphosphate microcapsules and their flame retardancy in epoxy resin[J]. Acta Polymerica Sinica, 2012, (7): 759-765.
13	Kun W ， Lei S ， Wang Z Z ，et al . Preparation and characterization of double shell microencapsulated ammonium polyphosphate and its flame retardance in polypropylene[J]. Journal of Polymer Research, 2009, 16(3): 283-294.
14	Gao W Y ， Qian X D ， Wang S J . Preparation of hybrid silicon materials microcapsulated ammonium polyphosphate and its application in thermoplastic polyurethane[J]. Journal of Applied Polymer Science, 2018, 135(4): 45742.
15	Chen Y J ， Li L S ， Xu L F ，et al . Phosphorus‐containing silica gel‐coated ammonium polyphosphate: preparation, characterization, and its effect on the flame retardancy of rigid polyurethane foam[J]. Journal of Applied Polymer Science, 2018, 135(22): 46334.
16	Li J Z ， Wang W ， Zhang W ，et al . Preparation and characterization of microencapsulated ammonium polyphosphate with UMF and its application in WPCs[J]. Construction and Building Materials, 2014, 65: 151-158.
17	Zhang P K ， Fan H J ， Hu K ，et al . Solvent-free two-component polyurethane conjugated with crosslinkable hydroxyl-functionalized ammonium polyphosphate: curing behaviors, flammability and mechanical properties[J]. Progress in Organic Coatings, 2018, 120: 88-99.
18	Sun L Si ， Qu Y T ， Li S X . Co-microencapsulate of ammonium polyphosphate and pentaerythritol in intumescent flame-retardant coatings[J]. Journal of Thermal Analysis and Calorimetry, 2013, 111(2): 1099-1106.
19	Jiang Z W ， Liu G S . Microencapsulation of ammonium polyphosphate with melamine-formaldehyde-tris(2-hydroxyethyl)isocyanurate resin and its flame retardancy in polypropylene[J]. RSC Advances, 2015, 5(107): 88445-88455.
20	Zheng Z H ， Sun H M ， Li W J ，et al . Co-microencapsulation of ammonium polyphosphate and aluminum hydroxide in halogen-free and intumescent flame retarding polypropylene[J]. Polymer Composites, 2014, 35(4): 715-729.
21	Yang L ， Cheng W L ， Zhou J ，et al . Effects of microencapsulated APP-II on the mcrostructure and flame retardancy of PP/APP–II/PER composites[J]. Polymer Degradation and Stability, 2014, 105: 150-159.
22	Ye X M ， Wang Y H ， Zhao Z L ，et al . A novel hyperbranched poly(phosphorodiamidate) with high expansion degree and carbonization efficiency used for improving flame retardancy of APP/PP composites[J]. Polymer Degradation & Stability, 2017, 142: 29-41.
23	Yan Z ， Han P Y ， Fang Z P . Synthesis of phospholipidated β-cyclodextrin and its application for flame-retardant poly(lactic acid) with ammonium polyphosphate[J]. Journal of Applied Polymer Science, 2017, 135(13), 46054.
24	Lai X J , Zeng X R , Li H Q , et al . Preparation and properties of flame retardant polypropylene with an intumescent system encapsulated by thermoplastic polyurethane[J]. Journal of Macromolecular Science, Part B, 2012, 51(1): 35-47.
25	Ren Y , Yuan D D , Li W M , et al . Flame retardant efficiency of KH-550 modified urea-formaldehyde resin cooperating with ammonium polyphosphate on polypropylene[J]. Polymer Degradation and Stability, 2018, 151: 160-171.
26	Wu K , Zhang Y K , Zhang K , et al . Effect of microencapsulation on thermal properties and flammability performance of epoxy composite[J]. Journal of Analytical and Applied Pyrolysis, 2012, 94: 196-201.
27	Zhao Z L , Jin Q , Zhang N E , et al . Preparation of a novel polysiloxane and its synergistic effect with ammonium polyphosphate on the flame retardancy of polypropylene[J]. Polymer Degradation & Stability, 2018, 150: 73-85.
28	Lai X J ， Tang S ， Li H Q ，et al . Flame-retardant mechanism of a novel polymeric intumescent flame retardant containing caged bicyclic phosphate for polypropylene[J]. Polymer Degradation & Stability, 2015, 113: 22-31.
29	Nguyen T H , Hoang D Q , Kim J . Effect of ammonium polyphosphate and melamine pyrophosphate on fire behavior and thermal stability of unsaturated polyester synthesized from poly(ethylene terephthalate) waste[J]. Macromolecular Research, 2018, 26(1): 22-28.
30	Lai X J , Zeng X R , Li H Q , et al . Effect of polyborosiloxane on the flame retardancy and thermal degradation of intumescent flame retardant polypropylene[J]. Journal of Macromolecular Science, Part B, 2014, 53(4):721-734.

[1]	Lei WU, Jiao LIU, Changcong LI, Jun ZHOU, Gan YE, Tiantian LIU, Ruiyu ZHU, Qiuli ZHANG, Yonghui SONG. Catalytic microwave pyrolysis of low-rank pulverized coal for preparation of high value-added modified bluecoke powders containing carbon nanotubes [J]. CIESC Journal, 2023, 74(9): 3956-3967.
[2]	Xingzhi HU, Haoyan ZHANG, Jingkun ZHUANG, Yuqing FAN, Kaiyin ZHANG, Jun XIANG. Preparation and microwave absorption properties of carbon nanofibers embedded with ultra-small CeO₂ nanoparticles [J]. CIESC Journal, 2023, 74(8): 3584-3596.
[3]	Ao ZHANG, Yingwu LUO. Low modulus, high elasticity and high peel adhesion acrylate pressure sensitive adhesives [J]. CIESC Journal, 2023, 74(7): 3079-3092.
[4]	Jie WANG, Xiaolin QIU, Ye ZHAO, Xinyang LIU, Zhongqiang HAN, Yong XU, Wenhan JIANG. Preparation and properties of polyelectrolyte electrostatic deposition modified PHBV antioxidant films [J]. CIESC Journal, 2023, 74(7): 3068-3078.
[5]	Jing ZHAO, Chengwen GU, Xigao JIAN, Zhihuan WENG. Preparation and performance evaluation of magnolol-based epoxy resin anti-corrosion coatings [J]. CIESC Journal, 2023, 74(7): 3010-3017.
[6]	Jie LIU, Lisheng WU, Jinjin LI, Zhenghong LUO, Yinning ZHOU. Preparation and properties of polyether-based vinylogous urethane reversible crosslinked polymers [J]. CIESC Journal, 2023, 74(7): 3051-3057.
[7]	Zhenghao YANG, Zhen HE, Yulong CHANG, Ziheng JIN, Xia JIANG. Research progress in downer fluidized bed reactor for biomass fast pyrolysis [J]. CIESC Journal, 2023, 74(6): 2249-2263.
[8]	Bin CAI, Xiaolin ZHANG, Qian LUO, Jiangtao DANG, Liyuan ZUO, Xinmei LIU. Research progress of conductive thin film materials [J]. CIESC Journal, 2023, 74(6): 2308-2321.
[9]	Zhen LONG, Jinhang WANG, Junjie REN, Yong HE, Xuebing ZHOU, Deqing LIANG. Experimental study on inhibition effect of natural gas hydrate formation by mixing ionic liquid with PVCap [J]. CIESC Journal, 2023, 74(6): 2639-2646.
[10]	Qin YANG, Chuanjian QIN, Mingzi LI, Wenjing YANG, Weijie ZHAO, Hu LIU. Fabrication and properties of dual shape memory MXene based hydrogels for flexible sensor [J]. CIESC Journal, 2023, 74(6): 2699-2707.
[11]	Jialin DAI, Weidong BI, Yumei YONG, Wenqiang CHEN, Hanyang MO, Bing SUN, Chao YANG. Effect of thermophysical properties on the heat transfer characteristics of solid-liquid phase change for composite PCMs [J]. CIESC Journal, 2023, 74(5): 1914-1927.
[12]	Shaoyun CHEN, Dong XU, Long CHEN, Yu ZHANG, Yuanfang ZHANG, Qingliang YOU, Chenglong HU, Jian CHEN. Preparation and adsorption properties of monolayer polyaniline microsphere arrays [J]. CIESC Journal, 2023, 74(5): 2228-2238.
[13]	Jianhua ZHANG, Mengmeng CHEN, Yawen SUN, Yongzhen PENG. Efficient nitrogen and phosphorus removal from domestic wastewater via simultaneous partial nitritation and phosphorus removal combined Anammox [J]. CIESC Journal, 2023, 74(5): 2147-2156.
[14]	Zhen LONG, Jinhang WANG, Yong HE, Deqing LIANG. Characteristics study on hydrates formation from gas mixture under ionic liquid together with kinetic hydrate inhibitors [J]. CIESC Journal, 2023, 74(4): 1703-1711.
[15]	Xuehong WU, Linlin LUAN, Yanan CHEN, Min ZHAO, Cai LYU, Yong LIU. Preparation and thermal properties of degradable flexible phase change films [J]. CIESC Journal, 2023, 74(4): 1818-1826.