二乙基次磷酸铝/次磷酸铝对天然橡胶/顺丁橡胶复合材料性能的影响

doi:10.3976/j.issn.1002-4026.20230115

摘要/Abstract

摘要：

将二乙基次磷酸铝(ADP)和次磷酸铝(ALHP)两种阻燃剂引入到天然橡胶(NR)/顺丁橡胶(BR)中制备复合材料,比较两种阻燃剂对复合材料加工特性、物理性能、阻燃性、力学性能及耐磨性的影响。结果表明,两种阻燃剂均可延迟复合材料的硫化,提高门尼黏度,其中添加ADP的复合材料提升更为明显。两种阻燃剂均可降低复合材料的回弹性、拉伸强度、拉断伸长率及撕裂强度,但会提高复合材料的硬度。当ADP和ALHP添加量为45份时,复合材料的极限氧指数(LOI)分别从22.1%提升到28.7%和24.5%。两种阻燃剂均对耐磨性产生不利影响,ADP和ALHP用量为45份时,复合材料的磨耗量分别增加100%和85%。石墨烯(GE)作为成炭剂用于含ADP的复合材料时,可提升阻燃性,同时不影响耐磨性。综上,ADP和ALHP不同程度地影响着NR/BR复合材料的性能,由于ADP碳含量高以及受热挥发,极大程度提升NR/BR复合材料阻燃性,但拉伸强度和耐磨性低于含ALHP的复合材料。

关键词: 磷系阻燃剂, 天然橡胶, 顺丁橡胶, 阻燃性, 耐磨性

Abstract:

The flame retardants aluminum diethylphosphinate (ADP) and aluminum hypophosphite (ALHP) were introduced into natural rubber (NR) and butadiene rubber (BR) to prepare the composites. In this study, we compared the effects of the two flame retardants on the processing characteristics, physical properties, flame retardancy, mechanical properties, and abrasion resistance of the composites. Results showed that both flame retardants delayed the vulcanization of the composites, increased the Mooney viscosity. ADP exhibited a more evident increase in Mooney viscosity than ALHP. When ADP and ALHP was added at 45 phr, the limiting oxygen index (LOI) of the composites increased from 22.1% to 28.7% and 24.5%, respectively. The addition of ADP and ALHP reduced the rebound resilience of the composites, but increased hardness of it. The flame retardants reduced the tensile strength, elongation at break, and tear strength of the composites. Both flame retardants had an adverse effect on the abrasion resistance, with the abrasion loss of the composites increasing by 100% and 85% at 45 phr of ADP and ALHP, respectively. When graphene is used as a carbonization agent for ADP-containing composites, it can improve the flame retardancy without affecting the abrasion resistance. ADP and ALHP have different degrees of influence on the properties of NR/BR composites. Due to the high carbon content of ADP and volatilization by heat, the flame retardancy of NR/BR composites is greatly improved. But the tensile strength and abrasion resistance of the composites are lower than that of the ALHP-containing composites.

Key words: phosphorous-based flame retardants, natural rubber, butadiene rubber, flame retardancy, abrasion resistance

中图分类号:

TQ330.7

徐立杰, 李嵩, 李琳. 二乙基次磷酸铝/次磷酸铝对天然橡胶/顺丁橡胶复合材料性能的影响[J]. 山东科学, 2024, 37(3): 66-75.

XU Lijie, LI Song, LI Lin. Effects of aluminum diethylphosphinate/aluminum hypophosphite on the properties of natural rubber/butadiene rubber composites[J]. Shandong Science, 2024, 37(3): 66-75.

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参考文献 23

[1]	MENON A R R. Flame-retardant characteristics of natural rubber modified with a bromo derivative of phosphorylated cashew nut shell liquid[J]. Journal of Fire Sciences, 1997, 15(1): 3-13. DOI: 10.1177/073490419701500101.
[2]	张铎, 晋琦, 李维鸽, 等. 球磨分散和超声分散碳纳米管强化天然橡胶性能对比[J]. 应用化工, 2022, 51(4): 971-975. DOI: 10.3969/j.issn.1671-3206.2022.04.014.
[3]	FU J F, YU W Q, DONG X, et al. Mechanical and tribological properties of natural rubber reinforced with carbon blacks and Al₂O₃ nanoparticles[J]. Materials & Design, 2013, 49: 336-346. DOI: 10.1016/j.matdes.2013.01.033.
[4]	汪光亮, 谢艳霞, 孙桂美, 等. 普通用途钢丝绳芯输送带H型覆盖胶的研制[J]. 橡胶工业, 2013, 60(12): 743-745. DOI: 10.3969/j.issn.1000-890X.2013.12.007.
[5]	ISMAWI D H A, HARPER J F, ANSARIFAR A. Influence of flame retardant additives on the flammability behaviour of natural rubber (NR)[J]. Journal of Rubber Research, 2008, 11(4): 223-236.
[6]	PATARAPAIBOOLCHAI O, CHAIYAPHATE S. Improvements of natural rubber for flame resistance[J]. Songklanakarin Journal of Science and Technology, 2010, 32(3): 299.
[7]	王娜, 张鑫雨, 滕海伟, 等. 卡拉胶-纳米氢氧化铝协同阻燃天然橡胶[J]. 精细化工, 2020, 37(3): 598-603. DOI: 10.13550/j.jxhg.20190722.
[8]	YOTKUNA K, CHOLLAKUP R, IMBOON T, et al. Effect of flame retardant on the physical and mechanical properties of natural rubber and sugarcane bagasse composites[J]. Journal of Polymer Research, 2021, 28(12): 455. DOI: 10.1007/s10965-021-02805-6.
[9]	闫闯, 王晨, 李芮地, 等. 氢氧化镁表面改性研究及其在天然胶中的应用[J]. 青岛科技大学学报(自然科学版), 2020, 41(3): 62-67. DOI: 10.16351/j.1672-6987.2020.03.008.
[10]	RYBIŃSKI P, SYREK B, MASŁOWSKI M, et al. Influence of lignocellulose fillers on properties natural rubber composites[J]. Journal of Polymers and the Environment, 2018, 26(6): 2489-2501. DOI: 10.1007/s10924-017-1144-9.
[11]	QU Q, XU J, WANG H H, et al. Carbon nanotube-based intumescent flame retardants achieve high-efficiency flame retardancy and simultaneously avoid mechanical property loss[J]. Polymers, 2023, 15(6): 1406. DOI: 10.3390/polym15061406.
[12]	WANG N, ZHOU M H, ZHANG J, et al. Modified boron nitride as an efficient synergist to flame retardant natural rubber: preparation and properties[J]. Polymers for Advanced Technologies, 2020, 31(9): 1887-1895. DOI: 10.1002/pat.4833.
[13]	郑德志, 辛梅华, 李明春. 软质聚氨酯泡沫塑料无卤阻燃技术研究进展[J]. 化工进展, 2015, 34(9): 3349-3355. DOI: 10.16085/j.issn.1000-6613.2015.09.022.
[14]	白景瑞, 滕进. 阻燃剂的应用与研究进展[J]. 宇航材料工艺, 2001, 31(2): 10-12. DOI: 10.3969/j.issn.1007-2330.2001.02.003.
[15]	胡肖, 颜龙, 黄傲, 等. 磷系阻燃剂在透明防火涂料中的应用研究进展[J]. 消防科学与技术, 2021, 40(7): 1061-1064. DOI: 10.3969/j.issn.1009-0029.2021.07.025.
[16]	中国石油和化学工业协会. 橡胶燃烧性能的测定: GB/T 10707—2008[S]. 北京: 中国标准出版社, 2008.
[17]	中国石油和化学工业协会. 硫化橡胶或热塑性橡胶拉伸应力应变性能的测定: GB/T 528—2009[S]. 北京: 中国标准出版社, 2009.
[18]	中国石油和化学工业联合会. 化工产品密度、相对密度的测定: GB/T 4472—2011[S]. 北京: 中国标准出版社, 2012.
[19]	中国石油和化学工业协会. 硫化橡胶或热塑性橡胶压入硬度试验方法第1部分:邵氏硬度计法: GB/T 531.1—2008[S]. 北京: 中国标准出版社, 2008.
[20]	中国石油和化学工业协会. 硫化橡胶回弹性的测定: GB/T 1681—2009[S]. 北京: 中国标准出版社, 2009.
[21]	中国石油和化学工业协会. 硫化橡胶或热塑性橡胶耐磨性能的测定: GB/T 9867—2008[S]. 北京: 中国标准出版社, 2008.
[22]	ZHAN Z S, XU M J, LI B. Synergistic effects of sepiolite on the flame retardant properties and thermal degradation behaviors of polyamide 66/aluminum diethylphosphinate composites[J]. Polymer Degradation and Stability, 2015, 117: 66-74. DOI: 10.1016/j.polymdegradstab.2015.03.018.
[23]	王金泳, 王兴旺. 无卤阻燃剂二乙基次磷酸铝的热降解和阻燃机理[J]. 中国塑料, 2019, 33(2): 82-85. DOI: 10.19491/j.issn.1001-9278.2019.02.015.

名称	t₁₀ /min	t₉₀ /min	M_L /(dN·m)	M_H/(dN·m)	门尼黏度
REF	4.2	8.0	1.5	17.5	44.9
AD-35	4.2	9.6	3.1	22.0	68.8
AD-40	4.3	9.9	3.7	23.4	70.8
AD-45	4.4	9.9	3.7	23.4	72.3
AL-35	4.4	9.3	2.3	24.5	57.4
AL-40	4.3	9.1	2.3	23.1	58.0
AL-45	4.1	8.9	2.3	23.2	58.1
ADG	4.3	9.7	3.7	25.1	—
ALG	3.9	9.0	2.6	24.9	—

名称	密度/(g·cm^-3)	邵A硬度/HA	回弹性/%
REF	1.09	59	64
AD-35	1.12	67	53
AD-40	1.13	68	51
AD-45	1.13	69	49
AL-35	1.18	66	61
AL-40	1.20	67	59
AL-45	1.20	68	59
ADG	1.14	70	48
ALG	1.22	69	58