Preparation of polyethylene grafted acrylic acid composite membrane by pre-irradiation grafting
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摘要: 通过电子束预辐射接枝技术制备不同接枝率的聚乙烯接枝丙烯酸(PE-g-AAc)复合膜，研究探讨了接枝率对复合膜性能影响。结果表明：PE-g-AAc复合膜随丙烯酸浓度增加，接枝率增加，吸水率也随之增加，当丙烯酸体积分数15vol%时，接枝率最大为263%，吸液率最大为635%。PE-g-AAc复合膜随丙烯酸接枝率增加，面电阻降低，当接枝率为30.4%时，PE-g-AAc复合膜面电阻由接枝前45000 mΩ·cm2降低至870.9 mΩ·cm2，接枝率最高263%时，面电阻最低为70.1 mΩ·cm2。拉伸强度随接枝率增加先降低后升高，接枝率最高263%时，拉伸强度最大45.6 MPa；断裂伸长率随接枝率的增加而降低。接枝率分析表明，一定的吸收剂量和反应条件下，丙烯酸浓度越高，链增长速率与链终止速率比值就越大，丙烯酸聚合度越大。吸水率与面电阻分析表明，丙烯酸有效提高聚乙烯膜表面能，增强亲水性，提高离子传导速率，降低聚乙烯膜面电阻。该研究将对聚乙烯接枝丙烯酸膜用于电池隔膜及离子交换膜的制备提供直接的借鉴价值。Abstract: The polyethylene grafted acrylic acid (PE-g-AAC) composite films with different grafting ratios were prepared by electron beam pre-irradiation. The study explored the effect of grafting ratio on the performance of composite membranes. The results show that the grafting ratio and water absorption ration of PE-g-AAc composite membrane increase with the increase of acrylic acid concentration. When the volume fraction of acrylic acid is 15vol%, the maximum grafting ratio is 263%, and the maximum water absorption ratio is 635%. The area resistance of PE-g-AAc composite membrane decreases with the increase of acrylic acid grafting ratio. When the grafting ratio is 30.4%, the area resistance of PE-g-AAc composite membrane decreases from 45000 mΩ·cm2 (without grafting) to 870.9 mΩ·cm2. When the grafting ratio is 263%, the area resistance is 70.1 mΩ·cm2. The tensile strength first decreases and then increases with the increase of grafting ratio. The maximum tensile strength reaches 45.6 MPa when the grafting ratio is 262%. The elongation at break decreases with the increase of grafting ratio. The grafting ratio result shows that under certain absorbed dose and reaction conditions, the higher the concentration of acrylic acid, the greater the ratio of chain growth rate to chain termination rate, and the greater the degree of acrylic acid polymerization. The results on water absorption and area resistance study show that, acrylic acid can effectively increase the surface energy of the polyethylene film, enhance the hydrophilicity, increase the ion conductivity, and reduce the area resistance of the polyethylene film. This study will provide direct reference value for the preparation of polyethylene grafted acrylic membrane for battery separator and ion exchange membrane.
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Key words:
- pre-irradiation /
- polyethylene /
- acrylic acid /
- grafting /
- area resistance /
- composite membrane
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图 1 电子束辐射下聚乙烯自由基的产生及交联、降解和接枝反应
Figure 1. Generation of free radicals of polyethylene under electron beam and the reaction of crosslinking, degrading and grafting
图 2 不同吸收剂量对PE-g-AAc复合膜接枝率的影响
Figure 2. Effect of different absorbed doses on grafting ratio of PE-g-AAc composite membrane
图 3 丙烯酸体积分数对PE-g-AAc复合膜接枝率的影响
Figure 3. Effect of volume fraction of acrylic acid on grafting ratio of PE-g-AAc composite membrane
图 4 接枝率对PE-g-AAc复合膜吸水率的影响
Figure 4. Effect of grafting ratio on water absorption of PE-g-AAc composite membrane
图 5 接枝率对PE-g-AAc复合膜面电阻的影响
Figure 5. Effect of grafting ratio on area resistance of PE-g-AAc composite membrane
图 6 接枝率对PE-g-AAc复合膜力学性能的影响
Figure 6. Effect of grafting ratio on mechanical properties of PE-g-AAc composite membrane
图 7 不同接枝率的PE-g-AAc复合膜结构的FTIR图谱(PE-g-AAC-1、PE-g-AAC-2分别为接枝率30%和170%)
Figure 7. FTIR spectra of PE-g-AAc composite membranes with different grafting ratios (Grafting ratios of PE-g-AAc-1 and PE-g-AAc-2 are 30% and 170%)
图 8 不同接枝率的PE-g-AAc复合膜的XRD图谱(PE-g-AAC-1、PE-g-AAC-2的接枝率分别为30%和170%)
Figure 8. XRD pattarns of PE-g-AAc composite membranes with different grafting ratios (Grafting ratios of PE-g-AAc-1 and PE-g-AAc-2 are 30% and 170%)
图 9 不同接枝率的PE-g-AAc复合膜的DSC曲线(PE-g-AAC-1、PE-g-AAC-2的接枝率分别为30%和170%)
Figure 9. DSC curves of PE-g-AAc composite membranes with different grafting ratios (Grafting ratios of PE-g-AAc-1 and PE-g-AAc-2 are 30% and 170%)
图 10 不同接枝率的PE-g-AAc复合膜表面形貌的SEM图像((a)~(i)接枝率依次为0、15.7%、30.7%、53.0%、72.4%、131.4%、144.8%、170.3%、263.6%)
Figure 10. SEM images of surface morphologies of PE-g-AAc composite membrane with different grafting ratios (Grafting ratios of (a)-(i) are 0, 15.7%, 30.7%, 53.0%, 72.4%, 131.4%, 144.8%, 170.3%, 263.6%)
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