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:
苯丙乳液的胶膜由于具有良好的附着力、硬度、耐候性以及可控的成本等优点被广泛用作水性阻尼涂料的基础乳液。如何在常规苯丙乳液所得胶膜的基础上有效提升其损耗因子(tanδ)、拓宽其有效阻尼温域(tanδ≥0.3时对应的温度范围)一直是相关研究者的关注热点。除了调节共聚物单体组成、侧链结构和交联密度之外，合理使用填料也可以增加胶膜的损耗能力，提升阻尼效果。一般情况下，常将膨胀珍珠岩粉、石墨、碳酸钙等微米级无机物作为填料使用。而纳米级填料由于具有极大的比表面积，可大幅增加材料内部界面摩擦，应在提升胶膜阻尼性能方面较微米级填料有更优异表现。将聚合物乳液与填料进行复合的最常见方式是直接共混，而直接共混易造成纳米级填料在聚合物基体中的团聚，难以发挥纳米材料高比表面积的优势，甚至会形成缺陷，影响材料整体性能。本文通过细乳液聚合法将油酸(OA)修饰的纳米Fe3O4包覆在聚(苯乙烯‑丙烯酸异辛酯)(P(St‑2‑EHA))乳胶粒内部得到Fe3O4/P(St‑2‑EHA)复合乳液。由这种复合乳液制备胶膜可克服共混法易产生的纳米填料在聚合物基体中团聚的问题，使纳米填料在胶膜中良好分散，显著增加有机无机界面区域。在外力作用下，界面处发生微观剪切摩擦，提升内耗而增大阻尼效果。结果显示，当St与2‑EHA质量比为5:5、交联剂二乙烯基苯(DVB)用量和OA‑Fe3O4用量分别为St、2-EHA总质量的2wt%和10wt%时，制得的Fe3O4/P(St‑2‑EHA)复合胶膜tanδ峰值和有效阻尼温域分别达到2.066和59.2℃，比纯P(St‑2‑EHA)胶膜分别提升了7.26%和19.87%，比共混法得到的复合胶膜分别提升了28.80%和17.28%。此外，Fe3O4/P(St‑2‑EHA)复合胶膜还较后两者具有了更低的吸水率和更优的热稳定性。 OA‑Fe3O4用量(a)和制备工艺(b)对复合胶膜损耗因子的影响 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 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, 2-EHA is 10wt%, the performance of 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.-
Key words:
- Fe3O4 /
- miniemulsion polymerization /
- encapsule /
- damping performance /
- water absorption /
- thermostability
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图 1 纳米Fe3O4(a)、Fe3O4/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/P(St-2-EHA) composite latex and its latex films(b)
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谱图
Figure 3. FTIR spectra of pure Fe3O4 particles, OA and OA-Fe3O4
图 4 纯Fe3O4(a)和OA-Fe3O4(b)的TEM照片
Figure 4. TEM pictures of pure Fe3O4 particles (a) and OA-Fe3O4 particles (b)
图 5 单体比例对P(St-2-EHA)胶膜损耗因子的影响
Figure 5. Effect of monomer ratio on loss factor of P(St-2-EHA) film
图 6 单体比例对P(St-2-EHA)胶膜玻璃化转变温度的影响
Figure 6. Effect of monomer 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谱图
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照片及DLS粒度数据(c)
Figure 8. TEM pictures of P(St-2-EHA) latex particles (a) and OA-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及元素分布图：(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. The effect of the amount of OA-Fe3O4 on the loss factor of the Fe3O4/P(St-2-EHA) film
图 11 复合工艺对P(St-2-EHA), Fe3O4/P(St-2-EHA)和共混复合胶膜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 particles, OA-Fe3O4 particles, P(St-2-EHA) latex film, Fe3O4/P(St-2-EHA) latex film 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 curves 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 Notes: OA–Oleic acid 
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