Preparation of Fe3O4/poly(styrene-isooctyl acrylate) composite emulsion via miniemulsion polymerization and damping properties of its latex film
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摘要: 用于制备水性阻尼涂层的苯丙乳液需进一步提升阻尼因子并拓宽有效阻尼温域范围。为改进苯丙乳液阻尼性能，本文以油酸(OA)修饰的纳米Fe3O4 (OA-Fe3O4)为被包覆填料，采用细乳液聚合法制备了Fe3O4/聚(苯乙烯-丙烯酸异辛酯) (Fe3O4/P(St-2-EHA))复合乳液，使用FTIR、XRD、TEM、SEM、DLS、TG和DMA等方法对复合乳液及其胶膜进行表征，研究了共聚物组成、纳米Fe3O4表面特性与掺量对乳液及胶膜结构与性能的影响。结果表明，OA-Fe3O4颗粒的直接团聚现象减弱，在复合乳液中的分散性显著改善。单体St与2-EHA质量比为5∶5时，所得P(St-2-EHA)胶膜具有最高的损耗因子(tanδ)峰值1.926。当OA-Fe3O4用量为St、2-EHA 总质量的10wt%时，所得Fe3O4/P(St-2-EHA)复合胶膜的性能最佳，其tanδ峰值和有效阻尼温域分别为2.066和59.2℃，均优于纯P(St-2-EHA)胶膜和共混法制备的复合胶膜；其吸水率比后两者分别降低3.4%和10.4%，且初始热分解温度升高，热稳定性改善。Abstract: The styrene-acrylic emulsion used to prepare waterborne damping coatings needs to further increase the damping factor and broaden the effective damping temperature range. In order to improve the damping performance of styrene-acrylic emulsion, oleic acid (OA) modified nano-Fe3O4 (OA-Fe3O4) was used as the coated filler to prepare Fe3O4/poly(styrene acrylate) (Fe3O4/P(St-2-EHA)) composite damping emulsion via miniemulsion polymerization. The composite emulsion and its latex film were characterized by FTIR, XRD, TEM, SEM, DLS, TG and DMA. The effects of copolymer composition, surface properties and content of nano-Fe3O4 on the structure and performance of the emulsion and latex film were studied. The results show that the direct agglomeration of OA-Fe3O4 nanoparticles is weakened, and its dispersion in the composite emulsion is significantly improved. When the mass ratio of monomer St to 2-EHA is 5∶5, the obtained P(St-2-EHA) latex film has the highest loss factor (tanδ) peak (1.926). When the mass ratio of OA-Fe3O4 to the total mass of St and 2-EHA is 10wt%, the obtained Fe3O4/P(St-2-EHA) composite latex film has the best performance. Its tanδ peak value and effective damping temperature range width are 2.066 and 59.2℃, which are better than pure P(St-2-EHA) latex film and composite latex film prepared by blending method. Its water absorption rate is 3.4% and 10.4% lower than the latter two respectively. And the initial thermal decomposition temperature is higher, with the thermal stability improved.
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Key words:
- Fe3O4 /
- miniemulsion polymerization /
- encapsule /
- damping performance /
- water absorption /
- thermostability
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图 1 纳米Fe3O4 (a)、Fe3O4/聚(苯乙烯-丙烯酸异辛酯) (P(St-2-EHA))复合乳液及其胶膜 (b) 的制备过程示意图
Figure 1. Schematic diagrams of preparation process of Fe3O4 nanoparticles (a), Fe3O4/poly(styrene-isooctyl acrylate) (P(St-2-EHA)) composite latex and its latex films (b)
SDS—Sodium dodecyl sulfate; APS—Ammonium persulfate; OA—Oleic acid
图 2 纯Fe3O4颗粒和OA-Fe3O4的XRD图谱
Figure 2. XRD patterns of pure Fe3O4 particles and OA-Fe3O4
图 3 纯Fe3O4颗粒、OA和OA-Fe3O4的FTIR图谱
Figure 3. FTIR spectra of pure Fe3O4 particles, OA and OA-Fe3O4
图 4 纯Fe3O4 (a) 和OA-Fe3O4 (b) 的TEM图像
Figure 4. TEM images of pure Fe3O4 particles (a) and OA-Fe3O4 particles (b)
图 5 单体质量比对P(St-2-EHA)胶膜损耗因子tanδ的影响
Figure 5. Effect of monomer mass ratio on loss factor tanδ of P(St-2-EHA) film
图 6 单体质量比对P(St-2-EHA)胶膜玻璃化转变温度的影响
Figure 6. Effect of monomer mass ratio on glass transition temperature of P(St-2-EHA) film
图 7 P(St-2-EHA)和Fe3O4/P(St-2-EHA)胶膜FTIR图谱
Figure 7. FTIR spectra of P(St-2-EHA) latex film and Fe3O4/P(St-2-EHA) composite latex film
图 8 P(St-2-EHA)粒子 (a) 和Fe3O4/P(St-2-EHA)复合粒子 (b) 的TEM图像及DLS粒度数据 (c)
Figure 8. TEM images of P(St-2-EHA) latex particles (a) and Fe3O4/P(St-2-EHA) composite latex particles (b), with particle size data obtained by DLS (c)
图 9 不同复合胶膜的SEM图像及元素分布：(a) Fe3O4/P(St-2-EHA)；(b) P(St-2-EHA) blended with Fe3O4
Figure 9. SEM images and element distribution of two latex films under different preparation processes: (a) Fe3O4/P(St-2-EHA); (b) P(St-2-EHA) blended with Fe3O4
图 10 OA-Fe3O4用量对Fe3O4/P(St-2-EHA)胶膜损耗因子的影响
Figure 10. Effect of the amount of OA-Fe3O4 on the loss factor of the Fe3O4/P(St-2-EHA) latex film
图 11 复合工艺对P(St-2-EHA)、Fe3O4/P(St-2-EHA)和共混复合胶膜损耗因子的影响
Figure 11. Effect of composite process on loss factor of P(St-2-EHA), Fe3O4/P(St-2-EHA) and blended composite latex film
图 12 Fe3O4、OA-Fe3O4粒子与P(St-2-EHA)、Fe3O4/P(St-2-EHA)、共混复合胶膜的TGA曲线
Figure 12. TGA curves of Fe3O4, OA-Fe3O4 particles, P(St-2-EHA), Fe3O4/P(St-2-EHA) and blended composite latex film
图 13 P(St-2-EHA)、Fe3O4/P(St-2-EHA)和共混复合胶膜的吸水率
Figure 13. Water absorption of P(St-2-EHA), Fe3O4/P(St-2-EHA) and blended composite latex films
表 1 纯Fe3O4颗粒和OA-Fe3O4的粒度数据
Table 1. Particle size data of pure Fe3O4 particles and OA-Fe3O4
Particle Size/nm PDI Zeta/mV Fe3O4 1796.0 0.929 −11.3 OA-Fe3O4 197.5 0.395 −19.3 Note: PDI—Polydispersion index. 
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