苯乙烯-马来酸酐共聚物对PLA/PBAT共混物的相形态及其性能的影响

莫智翔; 刘小超; 刘跃军; 毛旭升; 郑伟

doi:10.13801/j.cnki.fhclxb.20220630.001

苯乙烯-马来酸酐共聚物对PLA/PBAT共混物的相形态及其性能的影响

doi: 10.13801/j.cnki.fhclxb.20220630.001

1.
湖南工业大学　包装与材料工程学院，株洲 412000
2.
厦门长塑实业有限公司，厦门 361000

基金项目: 国家自然科学基金(11872179)；湖南省自然科学基金(2020JJ5137)；湖南省教育厅科学研究项目(19A138；19B152)

详细信息

通讯作者:
刘小超，博士，讲师，硕士生导师，研究方向为高分子材料加工工程、先进包装材料与技术　E-mail: xcliu_2014@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2022-04-18
- 修回日期: 2022-05-23
- 录用日期: 2022-06-10
- 网络出版日期: 2022-07-01
- 刊出日期: 2023-04-15

Effect of styrene-maleic anhydride on phase morphology and properties of PLA/PBAT blends

1.
School of Packaging and Materials Engineering, Hunan University of Technology, Zhuzhou 412000, China
2.
Xiamen Changsu Industrial CO., LTD., Xiamen 361000, China

Funds: National Natural Science Foundation of China (11872179); Natural Science Foundation of Hunan Province (2020JJ5137); Scientific Research Project of Education Department of Hunan Province (19A138; 19B152)

摘要

摘要: 聚己二酸-对苯二甲酸丁二酯(PBAT)具有很好的延展性，但其强度较低，而聚乳酸(PLA)高模量可以解决PBAT的缺陷。以苯乙烯-马来酸酐共聚物(SMA)为增容剂，通过双螺杆挤出机制备了PLA/ PBAT共混物，研究了不同含量的SMA对PLA/PBAT共混物的结晶性能、热性能、流变行为及拉伸性能的影响。结果表明：SMA能显著降低分散相PLA的粒径大小，在SMA含量为1.5wt%时变化最明显，PLA的粒径从1.75 μm降低到0.60 μm；SMA能促进PBAT的结晶，随着SMA含量增加，PBAT的结晶度呈现先增大后降低的趋势，当SMA含量为2wt%时，PBAT的结晶度达到最大为9.22%；通过Han曲线发现，在SMA含量较低时，共混物更接近均质物，随着SMA含量提高，共混物的弹性行为增强；SMA能够提高PLA/PBAT共混物的拉伸性能，随着SMA含量增加，拉伸强度与断裂伸长率都呈现先增大后减小的趋势，但总体高于未加SMA时的拉伸强度与断裂伸长率，SMA含量为1.5wt%时，拉伸强度相对于未添加SMA时，从18.1 MPa增加到21.8 MPa，提高了21%，断裂伸长率在SMA含量为1wt%时达到最大，为433.7%，相对未添加SMA时提高了25%。
- 聚己二酸-对苯二甲酸丁二酯 /
- 聚乳酸 /
- 相容性 /
- 旋转流变 /
- 毛细管流变 /
- 生物可降解材料
Abstract: Poly(butylene adipate-terephthalate) (PBAT) has outstanding ductility, but its strength is low, then, high modulus of polylactic acid (PLA) can solve the defects of PBAT. The styrene-maleic anhydride (SMA) was used as compatibilizer to prepare poly(lactic acid)/poly(butylene adipate-co-butylene terephthalate) (PLA/PBAT) blends. The effect of the content of SMA on the crystallization performance, thermal performance, rheological behavior and tensile properties of the blends were investigated. The results show that the SMA can significantly reduce the particle size of PLA, and the size of the dispersed PLA phase decreases from 1.75 μm to 0.60 μm when the content of SMA is 1.5wt%. The SMA can increase the crystallinity of PBAT, and as the SMA is added up to 2wt%, the crystallinity reaches up to the maximum value of 9.22%. It is found by the Han curves that low content of the SMA can give rise to closely homogeneous blends, and the elasticity of PLA/PBAT melt increase gradually with the increase in amount of SMA content. Moreover, the SMA enhance the tensile properties of PLA/PBAT blends. As the addition of SMA, the tensile strength and elongation at break both increase first and then decrease. The tensile strength of the composite with 1.5wt% SMA is 21.8 MPa, which is 21% higher than that of the counterpart without SMA (18.1 MPa). The elongation at break reaches the maximum value of 433.7% when SMA content is 1wt%, which is 25% higher than that of the composite without SMA.
- poly(butylene adipate-co-butylene terephthalate) /
- polylactic acid /
- compatibility /
- rotational rheology /
- capillary rheology /
- biodegradable material

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图 1 反应性熔融共混的分子间反应

Figure 1. Chemical reaction during reactive blending

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图 2 不同苯乙烯-马来酸酐共聚物(SMA)含量的PLA/PBAT共混物的FTIR图谱

Figure 2. FTIR spectra of PLA/PBAT blends with different SMA contents

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图 3 PLA/PBAT共混物的脆断截面SEM图像及PLA的粒径分布直方图：(a) PLA/PBAT；(b) PLA/PBAT-0.5wt%SMA；(c) PLA/PBAT-1wt%SMA；(d) PLA/PBAT-1.5wt%SMA；(e) PLA/PBAT-2wt%SMA；(f) PLA/PBAT-3wt%SMA

Figure 3. SEM images showing fracture surface of PLA/PBAT blends and particle size distribution histogram: (a) PLA/PBAT; (b) PLA/PBAT-0.5wt%SMA; (c) PLA/PBAT-1wt%SMA; (d) PLA/PBAT-1.5wt%SMA; (e) PLA/PBAT-2wt%SMA; (f) PLA/PBAT-3wt%SMA

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图 4 不同SMA含量的PLA/PBAT共混物的DSC曲线：(a) 第二次升温曲线；(b) 降温曲线

Figure 4. DSC curves of PLA/PBAT blends with different SMA contents: (a) Second heating procedure; (b) Cooling

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图 5 不同SMA含量的PLA/PBAT共混物的XRD图谱

Figure 5. XRD spectra of PLA/PBAT blends with different SMA contents

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图 6 不同SMA含量的PLA/PBAT共混物的TGA曲线

Figure 6. TGA curves of PLA/PBAT blends with different SMA contents

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图 7 PLA/PBAT共混物的表观黏度与剪切速率关系：(a) 不同SMA含量(温度T=190℃)；(b) 不同温度T (PLA/PBAT-1.5wt%SMA)

Figure 7. Apparent viscosity versus shear rate curves of PLA/PBAT blends: (a) Different SMA contents (temperature T=190℃); (b) Different temperatures T (PLA/PBAT-1.5wt%SMA)

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图 8 PLA/PBAT共混物的剪切应力与剪切速率的关系(T=190℃)

Figure 8. Shear stress versus shear rate curves of PLA/PBAT blends (T=190℃)

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图 9 不同SMA含量PLA/PBAT共混物的动态频率扫描曲线：(a) 储能模量G'；(b) 损耗模量G''；(c) 复数黏度η*

Figure 9. Curves of dynamic frequency sweep for PLA/PBAT blends with different SMA contents: (a) Storage modulus G'; (b) Loss modulus G''; (c) Complex viscosity η*

ω—Angular frequency

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图 10 不同SMA含量的PLA/PBAT共混物的Han曲线

Figure 10. Han plots of PLA/PBAT blends with different SMA contents

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图 11 不同SMA含量PLA/PBAT共混物的损耗因子(tanδ)与角频率(ω)的关系

Figure 11. Loss factor (tanδ) versus angle frequency (ω) curves of PLA/PBAT blends with different SMA contents

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图 12 不同SMA含量PLA/PBAT共混物的拉伸强度与断裂伸长率 (a) 和拉伸应力-应变曲线 (b)

Figure 12. Tensile strength and elongation at break (a) and tensile stress-strain curves (b) of PLA/PBAT blends with different SMA contents

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表 1 聚乳酸/聚己二酸-对苯二甲酸丁二酯(PLA/PBAT)共混物的原料配比

Table 1. Compositions of poly(lactic acid)/poly(butylene adipate-co-butylene terephthalate) (PLA/PBAT) blends

Sample	PBAT/wt%	PLA/wt%	SMA/wt%
PBAT	100.0	0	0.0
PLA	0.0	100	0.0
PLA/PBAT	75.0	25	0.0
PLA/PBAT-0.5wt%SMA	74.5	25	0.5
PLA/PBAT-1wt%SMA	74.0	25	1.0
PLA/PBAT-1.5wt%SMA	73.5	25	1.5
PLA/PBAT-2wt%SMA	73.0	25	2.0
PLA/PBAT-3wt%SMA	72.0	25	3.0
Note: SMA—Copolymer of styrene and maleic anhydride.

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表 2 不同SMA含量的PLA/PBAT共混物中分散相PLA的平均粒径

Table 2. Mean diameter of PLA in PLA/PBAT blends with different SMA contents

Sample	PLA/PBAT	PLA/PBAT-0.5wt%SMA	PLA/PBAT-1wt%SMA	PLA/PBAT-1.5wt%SMA	PLA/PBAT-2wt%SMA	PLA/PBAT-3wt%SMA
Mean diameter/μm	1.75	1.43	1.40	0.60	0.66	0.61

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表 3 不同SMA含量的PLA/PBAT共混物的DSC热分析数据

Table 3. DSC thermal analysis data of PLA/PBAT blends with different SMA contents

Sample	T_m/℃		T_c/℃	△H_m/(J·g⁻¹)		X_c/%
Sample	PBAT	PLA	T_c/℃	PBAT	PLA	PBAT	PLA
PBAT	122.98	—	58.58	15.62	—	13.70	—
PLA	—	152.46	—	—	6.12	—	0.61
PLA/PBAT	125.41	151.72	77.83	5.41	2.72	6.32	11.68
PLA/PBAT-0.5wt%SMA	124.43	153.66	77.73	6.27	0.23	7.38	1.01
PLA/PBAT-1wt%SMA	125.69	153.12	77.70	6.53	0.25	7.74	1.06
PLA/PBAT-1.5wt%SMA	125.09	153.93	76.90	6.98	0.19	8.33	0.83
PLA/PBAT-2wt%SMA	124.54	—	73.45	7.68	—	9.22	—
PLA/PBAT-3wt%SMA	124.38	—	71.68	7.12	—	8.68	—
Notes: T_m and T_c—Melting peak temperature and the crystallization peak temperature; △H_m and X_c—Melting enthalpy and crystallinity.

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表 4 不同PLA/PBAT共混物的热稳定性

Table 4. Thermal stability of different PLA/PBAT blends

Sample	T_5wt%/℃	T_50wt%/℃
PBAT	372.3	413.9
PLA	336.7	365.4
PLA/PBAT	347.5	401.2
PLA/PBAT-0.5wt%SMA	349.3	402.1
PLA/PBAT-1wt%SMA	344.5	401.8
PLA/PBAT-1.5wt%SMA	347.1	401.5
PLA/PBAT-2wt%SMA	348.9	402.2
PLA/PBAT-3wt%SMA	348.7	402.0
Notes: T_5wt% and T_50wt%—Temperature when the mass loss of the samples is 5wt% and 50wt%, respectively.

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表 5 不同SMA含量的PLA/PBAT共混物的非牛顿指数${\boldsymbol{n}} $

Table 5. Non-Newtonian index ${\boldsymbol{n}} $ of PLA/PBAT blends with different SMA contents

Sample	n
PLA/PBAT	0.627
PLA/PBAT-0.5wt%SMA	0.638
PLA/PBAT-1wt%SMA	0.611
PLA/PBAT-1.5wt%SMA	0.573
PLA/PBAT-2wt%SMA	0.595
PLA/PBAT-3wt%SMA	0.537
Note: Non-Newtonian index (n) was calculated from the linear fitting of the lnη_a versus ln$ \dot{\gamma } $ curve at high shear rates.

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