氢氧化铝包覆改性聚磷酸铵及其在阻燃聚丙烯中的应用研究

doi:10.15541/jim20150243

无机材料学报 ›› 2015, Vol. 30 ›› Issue (12): 1267-1272.DOI: 10.15541/jim20150243 CSTR: 32189.14.10.15541/jim20150243

氢氧化铝包覆改性聚磷酸铵及其在阻燃聚丙烯中的应用研究

秦兆鲁, 李定华, 杨荣杰

(北京理工大学材料学院, 国家阻燃材料工程技术研究中心, 北京100081)

收稿日期:2015-05-21 修回日期:2015-07-03 出版日期:2015-12-20 网络出版日期:2015-11-24
作者简介:秦兆鲁(1988–), 男, 博士研究生. E-mail: qinzhaolu@163.com
基金资助:
国家高技术研究发展计划(863计划) (2013AA032003)

Preparation of Ammonium Polyphosphate Coated with Aluminium Hydroxide and Its Application in Polypropylene as Flame Retardant

QIN Zhao-Lu, LI Ding-Hua, YANG Rong-Jie

(School of Material Science and Engineering, National Engineering Research Center of Flame Retardant Materials, Beijing Institute of Technology, Beijing 100081, China)

Received:2015-05-21 Revised:2015-07-03 Published:2015-12-20 Online:2015-11-24
About author:QIN Zhao-Lu. E-mail: qinzhaolu@163.com

摘要/Abstract

摘要：

针对聚磷酸铵(APP)有一定的水溶解性和阻燃效率不高等问题, 提出了采用氢氧化铝(ATH)包覆改性APP的方法。X射线荧光光谱(XRF)和扫描电镜(SEM)分析结果显示, 在APP颗粒表面实现了ATH的包覆改性。测试表明, ATH包覆改性后的APP溶解度明显下降, 比表面大幅增加。将改性后的APP与双季戊四醇(DPER)复配, 作为膨胀阻燃剂添加到PP中, 阻燃PP的燃烧性能测试结果表明: 阻燃剂总添加量为25%时, 包覆ATH的APP使阻燃PP 3.2 mm样条的垂直燃烧级别从V-1提高到V-0, 氧指数(LOI)从26.6%增加到31.8%, 热释放速率峰值(PHRR)从475 kW/m²下降至308 kW/m², 下降了约35%。对阻燃PP的燃烧残炭研究说明, APP经ATH包覆改性后, 促进了阻燃PP在燃烧时形成更加完整均匀的炭层, 因而改善了阻燃性能。

关键词: 聚磷酸铵, 包覆改性, 阻燃聚丙烯, 氢氧化铝

Abstract:

A new surface-modification method was adopted to decrease water solubility and enhance flame retradancy of ammonium polyphosphate (APP) by means of coating with aluminium hydroxide (ATH). The data of X-Ray Fluorescence Spectrometer (XRF) and scanning electron microscope (SEM) demonstrated that ATH was deposited on the surface of APP particles, and lower water resistance and rougher surface were verified. Furthermore, the modified APP was applied with dipentaerythritol (DPER) to prepare flame retarded polypropylene (FR-PP). The combustion behaviors of FR-PP were studied by limiting oxygen index (LOI), UL 94 vertical burning and cone calorimeter tests. Results show that loading of the coated APP has improved flame retardancy of FR-PP composites remarkably. Compared with unmodified APP, PP/DPER/coated APP can pass V-0 in UL 94 test, LOI value increases from 26.6% to 31.8%, and the peak heat release rate (PHRR) decreases from 475 kW/m² to 308 kW/m². Finally, study on char residues of FR-PP composites indicates that APP coated with ATH makes char layer more complete and more compact, which contributes to the improvement of flame retardancy.

Key words: ammonium polyphosphate, surface modification, polypropylene, aluminium hydroxide

中图分类号:

TB321

秦兆鲁, 李定华, 杨荣杰. 氢氧化铝包覆改性聚磷酸铵及其在阻燃聚丙烯中的应用研究[J]. 无机材料学报, 2015, 30(12): 1267-1272.

QIN Zhao-Lu, LI Ding-Hua, YANG Rong-Jie. Preparation of Ammonium Polyphosphate Coated with Aluminium Hydroxide and Its Application in Polypropylene as Flame Retardant[J]. Journal of Inorganic Materials, 2015, 30(12): 1267-1272.

图/表 9

表1 FR-PP的配方表/wt%

Table 1 Formulation of FR-PP composites /wt%

Samples	PP	APP	APP4#	APP6#	DPER	1010	168
PP/DPER/APP	74.7	17.85	-	-	7.15	0.1	0.2
PP/DPER/APP4#	74.7	-	17.85	-	7.15	0.1	0.2
PP/DPER/APP6#	74.7	-	-	17.85	7.15	0.1	0.2

表2 不同实验条件对改性结果影响

Table 2 Influence of different experimental conditions on the modification results

Sample	A/g	B /℃	C/h	Yield/%	Specific surface area/(m²•g^-1)	Water solubility/(g/100 mL)
APP	-	-	-	-	4.71	1.1035
APP1#	2	40	1	85.32	9.09	0.8650
APP2#	2	50	1	87.73	11.93	0.7535
APP3#	2	60	1	91.45	12.62	0.7455
APP4#	2	60	2	95.43	15.37	0.2920
APP5#	2	60	3	95.77	15.84	0.3320
APP6#	4	60	2	98.21	9.88	0.4270

图 1 ATH含量与Al元素强度的工作曲线

Fig. 1 Calibration curves of ATH content and Al measured intensity

图2 APP、APP4#与APP6#不同放大倍率的SEM照片

Fig. 2 Different magnificent SEM images of APP, APP4# and APP6#. (500× a: APP; b: APP4#; c: APP6#; 5000× d: APP; e: APP4#; f: APP6#)

表3 FR-PP的LOI和L1L 94结果

Table 3 LOI values and UL 94 results of FR-PP composites

Sample	LOI/%	UL 94 (3.2mm)	t₁^a /s	t₂^b/s
PP/DPER/APP	26.6	V-1	0.9	8.7
PP/DPER/APP4#	29.7	V-0	0.8	1.2
PP/DPER/APP6#	31.8	V-0	0.7	3.1

图 3 FR-PP的热释放速率(HRR)曲线

Fig. 3 HRR curves of FR-PP composites

表4 FR-PP的燃烧测试结果

Table 4 Cone Calorimeter parameters of FR-PP composites

Sample	TTI /s	PHRR (kW•m^-2)	avCO /(kg•kg^-1)	avCO₂ /(kg•kg^-1)	THR /(MJ•m^-2)	TSR /(m²•s^-1)	Mass loss /%
PP/DPER/APP	29	475	0.066	2.73	124	1828	84.0
PP/DPER/APP4#	28	323	0.060	2.71	117	1595	82.1
PP/DPER/APP6#	27	308	0.063	2.67	114	1407	79.4

图4 FR-PP经燃烧测试后的残炭照片

Fig. 4 Residue chars of FR-PP composites after cone calorimeter test. Top view (a: PP/DPER/APP; b: PP/DPER/APP4#; c: PP/DPER/ APP6#); Side view (d: PP/DPER/APP; e: PP/DPER/APP4#; f: PP/ DPER/APP6#)

图5 FR-PP淬断面的SEM形貌

Fig. 5 Fracture surface SEM images of FR-PP

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氢氧化铝包覆改性聚磷酸铵及其在阻燃聚丙烯中的应用研究

Preparation of Ammonium Polyphosphate Coated with Aluminium Hydroxide and Its Application in Polypropylene as Flame Retardant

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