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

doi:10.7503/cjcu20160599

摘要/Abstract

摘要：

合成了一种9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物——聚苯氧基磷酸-2-10-氢-9-氧杂-磷杂菲基对苯二酚酯(POPP), 以间苯二胺(m-PDA)为固化剂, 环氧树脂(EP)为基料, POPP为阻燃剂, 复配聚磷酸铵(APP), 制备了不同磷含量的阻燃环氧树脂. 利用极限氧指数(LOI)和垂直燃烧(UL94)实验表征了环氧树脂的阻燃性能; 以热重分析、锥型量热和扫描电镜分析了阻燃环氧树脂的热性能和表面形态. 研究结果表明, 阻燃剂总加入量(质量分数)为5%时即可达到UL94 V-0级, 同时LOI值为27.7%; 当总加入量为15%, 即w_POPP=5%, w_APP=10 %时, 其LOI值可达到33.8%. 随着磷含量的增加, 阻燃环氧树脂的初始降解温度略有降低, 但高温下的残炭率明显增加. POPP/APP的加入在很大程度上降低了环氧树脂的热释放速率、有效燃烧热、烟释放量和有毒气体释放量. 阻燃环氧树脂在高温下形成比较稳定的致密膨胀炭层, 为底层的环氧树脂主体隔绝了分解产物及热量和氧气交换, 增强了高温下的热稳定性.

关键词: 环氧树脂, 磷系阻燃剂, 聚磷酸铵, 膨胀型阻燃剂

Abstract:

A novel polyphosphate flame retardant, poly(2-10-hydrogen-9-oxa-phosphaphenanthrene hydroquinone phenyl phosphate)(POPP), aimed at improving the flame retardancy of EP was prepared. POPP and ammonium polyphosphate(APP) at the mass ratio of 1:2 were added into EP to form a series of flame retardant modified epoxy resin(FR-EP). The chemical bond adsorptions of FR-EP were investigated by infrared spectroscopic analysis. The thermal stability was study by thermal gravimetric analysis(TGA). Flame retardant properties as well as burning behavior of epoxy resin composites have been investigated by limited oxygen index(LOI) and vertical burning test(UL-94). Fire properties of modified epoxy resin were test by Cone calorimeter. The morphological characteristics of char residue after Cone test were studied by scanning electron microscope(SEM). The result shows that POPP increase burning behavior at lower adding amount, which help epoxy resin to pass UL-94 V-0 at 5%. But POPP modified epoxy resin gave out only 24.2% of LOI value. POPP/APP flame retardant increase not only UL-94 grade but also much higher LOI value. A UL-94 V-0 grade was obtained when 5% POPP/APP were added into the epoxy matrix and 27.7% LOI value. When adding amount of POPP/APP are increased to 15%, a higher LOI value of 33.8% can be get. Results of TGA test indicate that decomposition temperature of FR-EP decrease along with increase of flame retardant amount. But modified samples give out more char residue. By incorporation of POPP/APP, THR, HRR, EHC, TSR and COP of FR-EP were reduced obviously, and promote char residue dramatically. PkHRR decrease from 831.5 kW/m² to 346.8 kW/m² at 15% of adding amount. Morphology study shows that good flame retardant property of FR-EP is contributed to well-formed char residue structure. These structures of char are net-like and type may prevent little burning product from moving out to the surface of matrix. Moreover, this char residue protects inner material from heat.

Key words: Epoxy resin, Phosphorus, Ammonium polyphospate, Intumescent flame retardant

中图分类号:

O634.5

TrendMD:

李霈, 付海, 赵欧, 来方, 陈仕梅, 梅贵友, 赵伟, 班大明. 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. 高等学校化学学报, 2017, 38(2): 294.

LI Pei, FU Hai, ZHAO Ou, LAI Fang, CHEN Shimei, MEI Guiyou, ZHAO Wei, BAN Daming. Influence of Polyphosphate Flame Retardant Couple with Ammonium Polyphosphate on Epoxy Resin^†. Chem. J. Chinese Universities, 2017, 38(2): 294.

图/表 11

Scheme 1 Synthesis route of POPP

Table 1 Composition, LOI and UL94 vertical burning values of the samples

Sample	w_E-44(%)	w_m-PDA(%)	w_POPP(%)	w_APP(%)	LOI(%)	UL-94 rating	w_P(%)
EP-0	92	8	0	0	20.0	No rating	0
EP-a1	87	8	5	0	24.2	V-0	0.67
EP-a2	82	8	10	0	24.8	V-0	1.35
EP-a3	77	8	15	0	25.5	V-0	2.02
EP-b1	87	8	1.67	3.33	27.7	V-0	1.25
EP-b2	82	8	3.33	6.67	28.9	V-0	1.66
EP-b3	77	8	5	10	33.8	V-0	3.77

Fig.1 FTIR spectra of POPP(A), APP(B) and FR-EP(C) a. EP-0; b. EP-b1; c. EP-b2; d. EP-b3.

Fig.2 TGA(A, C) and DTG(B, D) curves of flame retardant and EP-0 (A, B) a. POPP; b. EP-0. (C, D) a. POPP; b. APP; c. POPP/APP.

Fig.3 TGA(A) and DTG(B) curves of EP-0(a), EP-b1(b), EP-b2(c) and EP-b3(d)

Table 2 Thermal gravimetric data of the EP with different content

Sample	T_5%/℃	T_10%/℃	T_50%/℃	T_max/℃	Residue(%)
POPP	393.23	449.88	567.42	510.94, 557.57	35.30
EP-0	362.76	374.81	411.90	398.44	15.03
EP-b1	328.78	344.83	392.99	388.17	20.55
EP-b2	316.95	334.03	386.93	378.10	22.49
EP-b3	308.82	327.4482	387.50	367.89	23.62

Table 3 Mechanical properties of the EP with different content

Sample	Breaking elongation(%)	Tensile strength/MPa	Elasticity modulus/MPa	Stress_max/MPa
EP-0	6.93	84.89	927.35	1398.73
EP-b1	6.45	76.12	1000.35	1141.82
EP-b2	6.05	64.57	879.90	968.57
EP-b3	4.22	40.30	1058.99	604.49

Fig.4 Cone calorimeter curves of EP-0(a), EP-b1(b) and EP-b3(c) (A) HRR; (B) EHC; (C) THR; (D) SPR; (E) COP; (F) TSR.

Table 4 Cone calorimeter data of EP-0, EP-b1 and EP-b3

Sample	TTI/s	PkHRR/ (kW·m^-2)	THR/ (MJ·m^-2)	Mass loss/g
EP-0	43	831.5	54.0	14.5
EP-b1	41	545.1	50.5	22.1
EP-b3	40	346.8	41.6	23.0

Fig.5 Photos of residues of cured epoxy resin samples after cone calorimeter tests(A) EP-0 in vertical view; (B) EP-b1 in vertical view; (C) EP-b3 in vertical view; (D) EP-b1 in level vision; (E) EP-b3 in level vision.

Fig.6 SEM images of char of EP-0(A), EP-b1(B) and EP-b3(C)

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