聚磷酸铵和微囊化聚磷酸铵对NR/BR复合材料的性能影响

doi:10.3976/j.issn.1002-4026.20240072

摘要/Abstract

摘要：

聚磷酸铵(APP)作为常见的阻燃剂,可显著改善橡胶阻燃性,但APP分子结构中含有大量的磷铵基团,容易吸水受潮。基于APP受潮问题,采用密胺树脂将APP微囊包覆,得到微囊化聚磷酸铵(MF201),虽然MF201可解决受潮问题,但微囊化外壳的存在可能对橡胶性能产生影响。为研究两种阻燃剂的差距,分别将APP和MF201引入到天然橡胶/顺丁橡胶(NR/BR)复合材料,研究其对NR/BR复合材料的硬度、阻燃性、耐磨性和其他物理机械性能影响。结果表明,APP和MF201的添加,使NR/BR复合材料的硬度增加、阻燃性提高、耐磨性降低、力学性能降低。APP和MF201对NR/BR复合材料的耐磨性降低相同以及阻燃性提升相同,45 phr APP和MF201使NR/BR复合材料的极限氧指数(LOI)提高到25.5%,UL-94燃烧等级达到HB。此外,添加MF201的NR/BR复合材料硬度较低、断裂伸长率较高。综上,微囊化外壳没有改变APP对NR/BR复合材料阻燃性和耐磨性,但提高了断裂伸长率,降低了硬度。

关键词: 磷系阻燃剂, 阻燃性, 磨损, 天然橡胶, 顺丁橡胶

Abstract:

As a common flame retardant, ammonium polyphosphate (APP) can considerably improve the flame retardancy of rubber, but the molecular structure of APP shows that it contains a large number of ammonium phosphate groups, rendering it highly hygroscopic. To address this hygroscopic issue of APP, microencapsulated APP (MF201) was obtained by coating APP microcapsules with melamine resin. Although MF201 can solve the hygroscopic issue of APP, the presence of microencapsulated shells may affect the properties of rubber. To study the difference between the two flame retardants, APP and MF201 were introduced into a natural rubber/butadiene rubber (NR/BR) composite to investigate their impacts on the hardness, flame retardancy, wear resistance, and other physical and mechanical properties of NR/BR composites. The results show that the addition of APP and MF201 can improve the flame retardancy, hardness, mechanical properties, and wear resistance of NR/BR composites. Due to the plasticizing effect of the melamine resin shell, the hardness of NR/BR composites decreases slightly when MF201 is added. Furthermore, APP and MF201 improve the flame retardancy of NR/BR composites to the same extend. For example, 45 phr APP and MF201 increase the limiting oxygen index of NR/BR composites to 25.5% and their UL-94 combustion rating to HB. In addition, the effects of APP and MF201 on wear resistance are basically the same. The NR/BR composites with MF201 added have lower hardness and higher elongation at break. Therefore, the microencapsulated shell did not change the flame retardant and wear resistance of APP to NR/BR composites, but increased the elongation at break and reduced the hardness.

Key words: phosphorous flame retardant, flame retardancy, wear, natural rubber, butadiene rubber

中图分类号:

TQ330.7

徐立杰, 张旭, 徐瑞龙, 郑佳旺, 姜怡婷, 赵帅, 李琳. 聚磷酸铵和微囊化聚磷酸铵对NR/BR复合材料的性能影响[J]. 山东科学, 2025, 38(4): 86-94.

XU Lijie, ZHANG Xu, XU Ruilong, ZHENG Jiawang, JIANG Yiting, ZHAO Shuai, LI Lin. Effects of ammonium polyphosphate and microencapsulated ammonium polyphosphate on NR/BR composite properties[J]. Shandong Science, 2025, 38(4): 86-94.

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样品	t₁₀ /min	t₉₀ /min	M_L /(dN·m)	M_H/(dN·m)	门尼黏度(ML(1+4) 100 ℃)
REF	4.2	8.0	1.5	17.5	44.9
A-35	3.8	7.5	1.9	21.9	49.2
A-40	3.7	7.4	1.9	22.8	49.8
A-45	3.6	7.0	1.8	23.4	47.8
M-35	4.3	8.1	1.9	22.0	50.2
M-40	4.3	8.0	1.9	22.2	48.2
M-45	4.2	7.7	2.0	23.1	49.2

样品	密度/(g·cm^-3)	邵氏硬度A	回弹性/%
REF	1.09	59	64
A-35	1.19	64	60
A-40	1.20	65	59
A-45	1.21	66	57
M-35	1.18	63	61
M-40	1.20	64	60
M-45	1.21	65	59

性能	REF	A-35	A-40	A-45	M-35	M-40	M-45
LOI /%	22.1	25.0	25.0	25.5	25.0	25.0	25.5
UL-94	NR			HB			HB