超临界CO2发泡PBAT/PLA复合材料及其形状记忆性能

doi:10.11949/0438-1157.20241003

摘要/Abstract

摘要：

采用超临界CO₂辅助制备生物可降解聚己二酸对苯二甲酸丁二醇酯（PBAT）/聚乳酸（PLA）形状记忆发泡材料，研究了PLA含量对PBAT/PLA复合材料中CO₂溶解扩散行为、熔融结晶、流变行为及发泡行为的影响，考察了PLA含量对PBAT/PLA发泡材料的形状记忆性能和力学性能的影响。结果表明，PBAT有利于PLA分子链段局部运动，促进了PLA的冷结晶过程；在低频剪切作用下，随着PLA含量的增加，PBAT/PLA的复数黏度增加；PLA降低了CO₂在PBAT/PLA复合材料中的解吸扩散系数，提高了发泡材料的刚性，起到稳定泡孔形貌和抗收缩的作用；PLA质量分数20%时，复合材料获得最大稳定发泡倍率20.5倍，PBAT/PLA发泡材料（发泡倍率7.5）形状固定率为86.8%，形状恢复率为94.3%，综合性能最佳。PLA有利于提高PBAT/PLA发泡材料的形状固定率，但不利于其形状恢复率。同时，PLA质量分数低于20%时，PLA的引入提高了PBAT/PLA发泡材料的拉伸/压缩模量和强度。

关键词: 超临界二氧化碳, 聚合物加工, 泡沫, 生物可降解, 形状记忆性能

Abstract:

Supercritical CO₂was used to assist the preparation of biodegradable poly (butylene adipate terephthalate) (PBAT)/polylactic acid (PLA) shape memory foaming materials. The impacts of PLA content on CO₂ solubility and desorption behavior, melting and crystallization, rheological behavior, and foaming behavior of PBAT/PLA composites were studied. The impacts of PLA content on shape memory properties and mechanical properties of PBAT/PLA foams were also studied. The results show that PBAT is conducive to the local movement of PLA molecular segments and promotes the cold crystallization process of PLA. Under low-frequency shear, as PLA content increased, the complex viscosity of PBAT/PLA increased. The diffusion coefficient of CO₂ was fitted from Fick diffusion law. PLA reduced the diffusion coefficient of CO₂ in PBAT/PLA composites during the desorption process, improved the rigidity of the foams and played an anti-shrinkage role. At the PLA content of 20% (mass), PBAT/PLA composite obtained a maximum stabilized expansion ratio of 20.5. PLA was crucial for enhancing the shape fixing ratio of PBAT/PLA foams, while it was unfavorable to the shape recovery ratio. When PLA content was 20% (mass), PBAT/PLA foam had the great comprehensive performance with an expansion ratio of 7.5, a shape fixing ratio of 86.8% and a shape recovery ratio of 94.3%. Additionally, when PLA content was below 20% (mass), the tensile/compressive modulus and strength of PBAT/PLA foams increased with the increase of PLA content.

Key words: supercritical carbon dioxide, polymer processing, foam, biodegradability, shape memory properties

中图分类号:

TQ 317.9

宫政, 高秀鲁, 赵玲, 胡冬冬. 超临界CO₂发泡PBAT/PLA复合材料及其形状记忆性能[J]. 化工学报, 2025, 76(2): 888-896.

Zheng GONG, Xiulu GAO, Ling ZHAO, Dongdong HU. Preparation and shape memory properties of PBAT/PLA foams by supercritical CO₂[J]. CIESC Journal, 2025, 76(2): 888-896.

图/表 12

表1 PBAT/PLA共混配方

Table 1 PBAT/PLA blending formulations

样品	PBAT/%	PLA/%	抗氧剂1010/%
PBAT	99.8	0	0.2
PBAT/PLA10	89.8	10	0.2
PBAT/PLA20	79.8	20	0.2
PBAT/PLA30	69.8	30	0.2

图1 PBAT/PLA复合材料的熔融结晶曲线

Fig.1 Melt crystallization curves of PBAT/PLA composites

表2 PBAT/PLA复合材料的DSC数据

Table 2 DSC data of PBAT/PLA composites

样品	T_{g, PLA}/℃	T_{c, PBAT}/℃	T_{cc, PLA}/℃	T_{m, PBAT}/℃	T_{m, PLA}/℃
PBAT	—	71.7	—	120.7	—
PLA	62.2	—	136.0	—	167.1
PBAT/PLA10	61.5	71.9	103.6	122.4	168.6
PBAT/PLA20	61.3	72.1	105.6	123.6	169.2
PBAT/PLA30	61.2	73.1	106.8	125.0	169.5

图2 PBAT/PLA复合材料的剪切流变行为

Fig.2 Shear rheological properties of PBAT/PLA composites

图3 PBAT/PLA复合材料的解吸曲线

Fig.3 Desorption curves of PBAT/PLA composites

表3 CO2在PBAT/PLA复合材料中的溶解度和解吸扩散系数

Table 3 Solubility and desorption coefficients of CO2 in PBAT/PLA composites

样品	M₀/g	D_d/(10^-11 m²·s^-1)
PBAT	17.1	6.5
PBAT/PLA10	14.7	6.3
PBAT/PLA20	13.4	5.7
PBAT/PLA30	12.1	5.1

图4 PBAT/PLA发泡材料的泡孔形貌

Fig.4 Cell morphologies of PBAT/PLA foams

图5 PBAT/PLA发泡材料的泡孔结构参数

Fig.5 Quantitative cell structure information of PBAT/PLA foams

图6 PBAT/PLA发泡材料的初始发泡倍率、平衡发泡倍率及收缩率

Fig.6 Initial expansion ratio, balanced expansion ratio and shrinkage ratio of PBAT/PLA foams

图7 具有相同发泡倍率的PBAT/PLA发泡材料的形状记忆性能

Fig.7 Shape memory properties of PBAT/PLA foams with similar expansion ratios

图8 具有不同发泡倍率的PBAT/PLA20发泡材料的形状记忆性能

Fig.8 Shape memory properties of PBAT/PLA20 foams with different expansion ratios

图9 具有相同发泡倍率的PBAT/PLA发泡材料的力学性能

Fig.9 Mechanical properties of PBAT/PLA foams at similar expansion ratios

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超临界CO₂发泡PBAT/PLA复合材料及其形状记忆性能

Preparation and shape memory properties of PBAT/PLA foams by supercritical CO₂

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