有机改性蒙脱土对聚乳酸-聚丁二酸丁二醇酯合金的增容效应

吕若昀; 田瑶; 张杰; 彭亚; 唐逸铭; 余鹏

doi:10.13801/j.cnki.fhclxb.20211129.002

有机改性蒙脱土对聚乳酸-聚丁二酸丁二醇酯合金的增容效应

doi: 10.13801/j.cnki.fhclxb.20211129.002

湖北工业大学　材料与化学工程学院，湖北工业大学绿色轻工材料湖北省重点实验室，湖北工业大学绿色轻质材料与加工协同创新中心，武汉 430068

基金项目: 大学生创新创业训练计划项目(201910500003)

详细信息

通讯作者:
余鹏，博士，副教授，硕士生导师，研究方向为生物可降解材料　 E-mail: yupeng@mail.hbut.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-09-22
- 修回日期: 2021-11-14
- 录用日期: 2021-11-19
- 网络出版日期: 2021-11-30
- 刊出日期: 2022-12-01

Compatibilization of poly(lactic acid)-poly(butylene succinate) blends by using organic modified montmorillonite as a compatibilizer

School of Materials and Chemical Engineering, Hubei Provincial Key Laboratory of Green Materials for Light Industry, Collaborative Innovation Center of Green Light-weight Materials and Processing, Hubei University of Technology, Wuhan 430068, China

摘要

摘要: 为了获得综合性能优良的聚乳酸基生物可降解复合材料，利用二甲基双十八烷基氯化铵有机改性蒙脱土(OMMT)作为非反应型增容剂，通过直接熔融共混法制备了有机改性蒙脱土/聚乳酸-聚丁二酸丁二醇酯(OMMT/PLA-PBS)复合材料，研究了OMMT含量对PLA-PBS共混体系的增容效果及其对力学性能的影响规律。微观结构表明，OMMT能够显著降低分散相PBS的粒径和均匀粒径分布，分布在PLA与PBS相界面处的OMMT，起到了类似嵌段共聚物的增容作用，增加了PLA与PBS之间的黏结力。动态流变结果表明，当OMMT含量为3wt%时，OMMT在PLA-PBS共混物中形成三维网络结构。动态热机械性能结果显示，添加OMMT后，OMMT/PLA-PBS复合材料中PLA相与PBS相对应的玻璃化转变温度相互靠拢，当OMMT含量为1wt%时，PLA与PBS的玻璃化转变温度相互靠拢的幅度最大，增容效果最好。热性能数据表明，加入OMMT后，复合材料中PLA的结晶度出现先增加后降低的变化趋势，在OMMT含量为1wt%时，PLA结晶度达到最大值12.7%。力学性能结果表明，当OMMT含量为1wt%时，OMMT/PLA-PBS复合材料的综合力学性能达到最佳，拉伸强度和冲击强度分别为62.5 MPa和12.6 kJ/m²，较PLA-PBS共混物分别提高了32.1%和80%。
- 聚乳酸 /
- 聚丁二酸丁二醇酯 /
- 有机改性蒙脱土 /
- 增容 /
- 力学性能
Abstract: In order to obtain excellent properties of poly (lactic acid) based biodegradable composite, organic modified montmorillonite (OMMT) with dimethyl dioctadecyl ammonium chloride was used as a non-reactive compatibilizer. The organic modified montmorillonite/poly(lactic acid)-poly(butylene succinate) (OMMT/PLA-PBS) composites were prepared by direct melt blending method. The effect of OMMT contents on compatibility between PLA and PBS, and mechanical properties of the composites were investigated in this work. Morphological analyses reveal that OMMT can significantly reduce the particle size and result in uniform distribution of the dispersed phase PBS. The OMMT distributes in the interface between PLA and PBS can act as compatibilizer similar to block copolymer and increases interface adhesion between PLA and PBS. The dynamic rheological results indicate that OMMT forms a three-dimensional network structure at 3wt% OMMT. From dynamic thermo-mechanical analysis, glass transition temperatures of PLA and PBS in the composites get closer with the addition of OMMT. At 1wt%, the degree of glass transition temperature convergence is maximum, corresponding to the best compatibilization. Thermal data show that the crystallinity of PLA in composites first increases and then decreases by addition of OMMT. The crystallinity of PLA reaches maximum of 12.7% at 1wt%. The results of mechanical properties show that the comprehensive mechanical properties of OMMT/PLA-PBS composites reach the best when the OMMT content is 1wt%. The tensile strength and impact strength are 62.5 MPa and 12.6 kJ/m², respectively, which are 32.1% and 80% higher than those of the PLA-PBS blend.
- poly(lactic acid) /
- poly(butylene succinate) /
- organic modified montmorillonite /
- compatibilization /
- mechanical property

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图 1 不同OMMT含量的OMMT/PLA-PBS复合材料在不同放大倍率下的SEM图像和对应的PBS分散相粒径分布图

Figure 1. SEM images at different magnifications of OMMT/PLA-PBS composites with different OMMT contents and corresponding particle size distribution of PBS dispersed phase

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图 2 不同OMMT含量的OMMT/PLA-PBS复合材料TEM图像

Figure 2. TEM images of OMMT/PLA-PBS composites with different OMMT contents

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图 3 分散在界面处的OMMT增容PLA与PBS的示意图

Figure 3. Schematic illustration of compatibilization effect of OMMT located at interface between PLA and PBS

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图 4 OMMT及不同OMMT含量的OMMT/PLA-PBS复合材料的XRD图谱

Figure 4. XRD patterns of OMMT and OMMT/PLA-PBS composites with different OMMT contents

d₀₀₁—Interlamellar spacing

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图 5 OMMT/PLA-PBS复合材料的动态流变性能曲线

Figure 5. Dynamic rheological property curves of OMMT/PLA-PBS composites

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图 6 OMMT/PLA-PBS复合材料的动态热机械性能曲线

Figure 6. Dynamic thermo-mechanical property curves of OMMT/PLA-PBS composites

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图 7 OMMT/PLA-PBS复合材料的DSC热流曲线

Figure 7. DSC heat flow curves of OMMT/PLA-PBS composites

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图 8 OMMT/PLA-PBS复合材料的拉伸性能

Figure 8. Tensile properties of OMMT/PLA-PBS composites

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图 9 OMMT/PLA-PBS复合材料的冲击强度

Figure 9. Impact strength of OMMT/PLA-PBS composites

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表 1 有机改性蒙脱土/聚乳酸-聚丁二酸丁二醇酯(OMMT/PLA-PBS)复合材料组成配比

Table 1. Formulation of organic modified montmorillonite/poly(lactic acid)-poly(butylene succinate) (OMMT/PLA-PBS) composites wt%

Samples	Mass fraction of PLA	Mass fraction of PBS	Mass fraction of OMMT
PLA-PBS	80	20	0
0.5wt%OMMT/PLA-PBS	80	20	0.5
1wt%OMMT/PLA-PBS	80	20	1
2wt%OMMT/PLA-PBS	80	20	2
3wt%OMMT/PLA-PBS	80	20	3

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表 2 从损耗模量和力学损耗角正切得到PLA、PBS和OMMT/PLA-PBS复合材料的玻璃化转变温度

Table 2. Glass transition temperature of PLA, PBS and OMMT/PLA-PBS composites obtained from loss modulus and loss tangent

Sample	Loss modulus G''		Loss tangent tanδ
Sample	T_{g, PBS}/℃	T_{g, PLA}/℃	T_{g, PBS}/℃	T_{g, PLA}/℃
PLA	—	61.0	—	67.3
PLA-PBS	−22.5	60.5	−17.6	66.9
0.5wt%OMMT/PLA-PBS	−21.7	60.4	−17.5	66.5
1wt%OMMT/PLA-PBS	−18.4	58.5	−16.1	64.4
2wt%OMMT/PLA-PBS	−18.4	59.6	−16.3	65.8
3wt%OMMT/PLA-PBS	−19.4	60.1	−17.8	65.7
PBS	−22.4	—	−17.8	—
Notes: T_{g, PBS}—Glass transition temperature of PBS phase; T_{g, PLA}—Glass transition temperature of PLA phase.

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表 3 从DSC热流曲线得到的OMMT/PLA-PBS复合材料的热性能参数

Table 3. Thermal data obtained from the DSC heat flow curves of OMMT/PLA-PBS composites

Sample	T_{g, PLA}/°C	T_{cc, PLA}/°C	T_{m, PBS}/°C	T_{m, PLA}/°C	X_{c ,PLA}/%
PLA-PBS	59.3	117.7	111.9	151.2	1.2
0.5wt%OMMT/PLA-PBS	60.1	117.0	114.3	149.9/155.4	7.1
1wt%OMMT/PLA-PBS	62.8	116.7	114.1	149.5/154.9	12.7
2wt%OMMT/PLA-PBS	59.8	117.1	114.1	149.7/154.9	8.8
3wt%OMMT/PLA-PBS	59.3	116.5	114.2	149.5/155.6	7.0
Notes: T_g—Glass transition temperature; T_cc—Cold crystallization temperature; T_m—Melting temperature; X_c—Degree of crystallinity.

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