Effect of nano-calcium carbonate modified by lactic acid oligomers on the properties of polylactic acid
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摘要: 采用直接缩聚法制备了乳酸低聚物，用该物质对纳米碳酸钙(CaCO3)进行改性，得到改性纳米碳酸钙(g-CaCO3)。将g-CaCO3与聚乳酸(PLA)通过溶液共混制备了g-CaCO3/PLA复合材料。通过FTIR、吸油值等对g-CaCO3进行了表征，并采用SEM、DSC、万能试验机、流变测试仪、透湿仪、紫外-可见-近红外(UV-Vis-AIR)分光光度计研究了g-CaCO3对PLA结构和性能的影响。结果表明，乳酸低聚物的改性降低了CaCO3的吸油值，改善了CaCO3与PLA的界面相容性，促进了CaCO3在PLA基体中的分散；同时，g-CaCO3在PLA基体中起到成核剂的作用，改善了PLA材料的结晶能力；随着g-CaCO3添加量的增加，g-CaCO3/PLA复合材料的拉伸强度和断裂延伸率呈先上升后下降的趋势，当添加5wt%的g-CaCO3时，拉伸强度比5%CaCO3/PLA复合材料高50%，比纯PLA高20%，当添加量达到10wt%时，拉伸强度仍比纯PLA高出13%；加入g-CaCO3能够提高复合材料的储能模量和复数黏度；此外，g-CaCO3的加入，提高了PLA材料对紫外可见光和水蒸气的阻隔性能。Abstract: Lactic acid oligomer was prepared by direct condensation method and used as modifier of nano-calcium carbonate (CaCO3) to developed modified nano-calcium carbonate (g-CaCO3). g-CaCO3 was blended with polylactic acid (PLA) by solution blending to prepare g-CaCO3/PLA composites. The g-CaCO3 was characterized by FTIR and oil absorption value etc. SEM, DSC, universal testing machine, rheometer, water vapor transmission tester and UV-Vis-AIR spectrophotometer were used to study the g-CaCO3 on the structure and performances of the PLA. The results show that the modification of lactic acid oligomer reduces the absorption value of CaCO3, promotes compatibility between CaCO3 and PLA and improves the dispersion of CaCO3 in PLA matrix. At the same time, the g-CaCO3 acts as nucleating agent in PLA matrix, improving the crystallization ability of the PLA. The tensile strength and strain at break of the g-CaCO3/PLA composites first rise and then fall as the g-CaCO3 content increasing. When the g-CaCO3 content is 5wt%, the tensile strength is 50% higher than that of 5%CaCO3/PLA composite. When the addition amount of g-CaCO3 reaches 10wt%, the tensile strength is still 13% higher than that of pure PLA. The storage modulus and complex viscosity of the composites are improved by adding g-CaCO3. In addition, the addition of g-CaCO3 enhances the barrier property of PLA to ultraviolet visible light and water vapor.
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Key words:
- lactic acid oligomer /
- nano-calcium carbonate /
- modification /
- PLA /
- composite /
- mechanical property
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图 1 乳酸低聚物改性纳米碳酸钙(g-CaCO3)洗涤残液的FTIR图谱
Figure 1. FTIR spectra of washing liquor of lactic acid oligomer modified nano-calcium carbonate (g-CaCO3)
图 2 乳酸低聚物的合成及其在纳米碳酸钙(CaCO3)表面的接枝
Figure 2. Synthesis of lactic acid oligomers and its graft on the surface of CaCO3
图 3 CaCO3、g-CaCO3和乳酸低聚物的FTIR图谱
Figure 3. FTIR spectra of CaCO3, g-CaCO3 and lactic acid oligomer
图 5 CaCO3和g-CaCO3在二氯甲烷中的分散性
Figure 5. Dispersion of CaCO3 and g-CaCO3 in dichloromethane
图 6 CaCO3和g-CaCO3对PLA复合材料断面形貌的影响
Figure 6. Influence of CaCO3 and g-CaCO3 on the fracture appearance of PLA
图 7 纯PLA及g-CaCO3/PLA复合材料的DSC曲线
Figure 7. DSC thermograms of pure PLA and g-CaCO3/PLA composites
图 8 5% CaCO3/PLA、纯PLA和不同填料含量的g-CaCO3/PLA复合材料的拉伸性能
Figure 8. Tensile performance of 5% CaCO3/PLA, pure PLA and g-CaCO3/PLA composites with different filler contents
图 9 纯PLA及g-CaCO3/PLA复合材料的动态频率扫描曲线
Figure 9. Dynamic frequency scanning curves of pure PLA and g-CaCO3/PLA composites
图 10 纯PLA及g-CaCO3/PLA复合材料的外观(a)和透过率(b)曲线
Figure 10. Appearance (a) and transmittance (b) of pure PLA and g-CaCO3/PLA composites
图 11 纯PLA和g-CaCO3/PLA复合材料的水蒸气透过率(RWVT)
Figure 11. Water vapor transmission rate (RWVT) for pure PLA and g-CaCO3/PLA composites
表 1 聚乳酸(PLA)基复合材料的组分
Table 1. Component of polylactic acid (PLA) matrix composites
Sample number Mass fraction/wt% PLA g-CaCO3 CaCO3 5% CaCO3/PLA 95 — 5 Pure PLA 100 0 — 2.5% g-CaCO3/PLA 97.5 2.5 — 5% g-CaCO3/PLA 95 5 — 10% g-CaCO3/PLA 90 10 — 20% g-CaCO3/PLA 80 20 — 30% g-CaCO3/PLA 70 30 — 
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表 2 纯PLA和g-CaCO3/PLA复合材料DSC二次升温曲线对应的数据
Table 2. DSC data of pure PLA and g-CaCO3/PLA composites during the second heating scan
Sample number Tg/℃ Tcc/℃ Tm1/℃ Tm2/℃ ∆Hcc/(J·g-1) ∆Hm/(J·g-1) Xc/% Pure PLA 61.0 122.8 165.3 169.7 35.9 38.5 2.8 2.5% g-CaCO3/PLA 61.2 120.7 163.7 169.7 35.3 38.1 3.1 5% g-CaCO3/PLA 61.4 117.1 163.7 169.6 33.7 37.0 3.7 10% g-CaCO3/PLA 60.9 116.7 162.7 169.1 29.2 33.9 5.6 20% g-CaCO3/PLA 58.7 114.2 162.4 169.1 27.6 32.7 6.9 30% g-CaCO3/PLA 60.7 113.7 161.9 168.8 21.3 26.0 7.2 Notes：Tg is glass transition temperature; Tcc is cold crystallization temperature; Tm1 and Tm2 are the melting temperature; ΔHcc is the enthalpy of cold crystallization; ΔHm is the enthalpy of melting; Xc is the crystallization.
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