第 46 卷第 2 期 Vol. 46 No. 2 2016 年 4 月 Apr 2016

所属栏目：功能材料 两种小分子有机酸修饰的白泥对丁腈橡胶复合材料力学性能的影响

罗琼林，段锦华，徐蓓玉，曹理朝，苏胜培* （湖南师范大学 化学化工学院 资源精细化与先进材料湖南省高校重点实验室，湖南 长沙 410081）

摘　要：利用草酸、乙酸作为白泥的修饰剂，对白泥进行湿法修饰，而后利用石蜡对白泥进行二次包覆制备了有机修饰白泥，并将其作为橡胶填料填充到丁腈橡胶（NBR）中制备了修饰白泥／NBR（300：100）母胶。将不同份数母胶填充到NBR中制备了不同白泥含量的白泥／NBR复合材料。考察了母胶用量，修饰剂种类及用量对NBR复合材料的硫化性能以及力学性能的影响。实验结果表明：当修饰剂的用量逐步增加（以干白泥质量计算）时，母胶填充的白泥／NBR复合材料的力学性能呈现先增大后减小的趋势。草酸用量为白泥的2%且母胶份数为75 phr时其白泥／NBR复合材料的力学性能达到较佳值：拉伸强度11.0 MPa、扯断伸长率483%、300%定伸应力3.9 MPa，与硬脂酸用量为白泥2%且母胶份数为75 phr时其白泥／NBR复合材料的拉伸强度、扯断伸长率、300%定伸应力进行对比分别提高196%、155%、115%；乙酸用量为白泥的2%且母胶份数为75 phr时其白泥／NBR复合材料的力学性能达到最佳值：拉伸强度10.0MPa、扯断伸长率463%、300%定伸应力3.6 MPa，与硬脂酸用量为白泥2%且母胶份数为75 phr时其白泥／NBR复合材料的拉伸强度、扯断伸长率、300%定伸应力进行对比分别提高179%、150%、106%。样品断面扫描电镜（SEM）分析结果表明，白泥经有机修饰后在丁腈橡胶中分散均匀，与基体橡胶的相容性好。多项实验结果表明：利用草酸、乙酸修饰白泥并制备白泥橡胶母胶可作为白泥综合利用的一种有效方法。

关键词：草酸；乙酸；白泥；白泥／丁腈橡胶复合材料

中图分类号：TQ333　　文献标识码：A　　文章编号：1009-9212（2015）06-0047-07

The Effect of Two Kinds of Small Molecule Organic Modifiers on the Mechanic Properties of Lime Mud /NBR Composites

LUO Qiong-lin, DUAN Jin-hua, XU Bei-yu, CAO Li-chao, SU Sheng-pei* (College of Chemistry and Chemical Engineering, Key Lab of Sustainable Resources Processing and Advanced Materials, Hunan Normal University, Changsha 410081, China)

Abstract：Lime mud was modified by wet method using oxalic acid or acetic acid as modifier, and further coating of the modified lime mud with paraffin was performed to obtain the organically-modified lime mud. The lime mud/NBR(300:100) master-batch prepared using the organically-modified lime mud as rubber filler was used to prepare lime mud/NBR composites at different loading of lime mud. The effect of the modifiers and dosage of the master-batch on the vulcanization characteristics and the performance of the composites was explored. Experimental results showed that organically-modified lime mud using acetic acid or oxalic acid hadmproved the mechanical performance of the composite materials compared to that of stearic acid. With the increasing of the dosage (in terms of quality of dry lime mud) of the modifier, the mechanical performance of the composite materials was improved first and then dropped. The best mechanical performance of the composite materials was achieved when the loading of 2% oxalic acid master-batch was 75 phr: the tensile strength of rubber composite is of 11.0 MPa; the elongation at break is of 483%; the 300% modulus is of 3.9 MPa. For the composite materials, compared to lime mud master-batch modified by stearic acid, lime mud master-batch modified by oxalic acid, the mechanical properties including tensile strength, elongation at break, 300% modulus of the composite materials increased by 196%, 155%; 115% respectively. For the acetic acid modified lime mud, the best mechanical performance of the composite materials was achieved when the acetic acid dosage was 2% of the lime mud master-batch and the master-batch loading was 75 phr, the tensile strength of rubber composite is of 10.0 MPa; the elongation at break is of 463%; the 300% modulus is of 3.6 MPa. For the composite materials, compared to lime mud master-batch modified by stearic acid, lime mud master-batch modified by acetic acid, the mechanical performance, including the tensile strength, elongation at break, 300% modulus of the composite materials increased by 179%, 150%, and 106%,respectively. Experimental results of SEM indicated that the organically-modified lime mud was well-dispersed in the rubber compared to that of unmodified lime mud. The results showed that the mechanical properties of rubber material can be improved greatly by the above organically-modification methods.

Key words：oxalic acid; acetic acid; lime mud; lime mud/NBR composites

基金项目： 湖南省战略科兴产业科技攻关项目（S2014G217K）资助。

作者简介：罗琼林（1988-），女，湖南郴州人，博士研究生，研究方向：高分子复合材料（E-mail：qionglinluo@163.com）。

联 系 人： 苏胜培，教授，博士研究生导师（E-mail：sushengpei@yahoo.corn）。

收稿日期：2016-04-06