PLLA/SA共混材料的制备及性能表征
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摘要
为了降低聚乳酸(PLA)材料的生产加工成本,改善其柔韧性,扩大PLA基塑料的应用范围,本工作以L-型聚乳酸(PLLA)和醋酸酯淀粉(SA)为主要原料,钛酸四丁酯(Ti(OBU)4)为增容剂,柠檬酸三乙酯(TEC)为增塑剂,首次采用熔融共混挤出技术制备了一系列的PLLA/SA共混材料。考察了SA、增容剂和增塑剂等对共混材料的力学性能、动态热机械性能、结构与形态、耐热性、熔体流动速率、耐水性和生物降解性等方面的影响。研究发现：
1.增容剂的加入使PLLA/SA共混材料中PLLA和SA的相容性得到了一定程度的改善。
2.SA含量及增容剂与增塑剂含量对共混体系的力学性能有显著的影响,适量的增容剂可以很好地改善PLLA/SA共混体系的相容性,同时适量增塑剂可以提高共混材料的柔韧性。在SA含量为25%,增容剂含量为8%,增塑剂含量为10%时,与原料PLLA相比,共混材料的强度和刚度有所下降,但柔韧性得到了明显改善。
3.动态热力学性能分析表明,在2.00～33.30Hz的频率范围内,SA含量、增容剂含量及增塑剂对材料的储能模量有较大的影响,随着增容剂含量的增加,储能模量降低,Tanδ峰值温度逐渐向低温方向移动；而随着SA含量的增加,共混材料储能模量增加,Tanδ峰值温度移向高温方向,但当SA含量增加到25%以上时,Tanδ峰值温度基本保持恒定；增塑剂的加入大大降低了材料的储能模量,提高了Tanδ峰值。
4.热重分析表明,增塑剂的含量、增容剂的含量和SA含量对共混材料的热分解有影响。增塑剂降低了材料的耐热性；增容剂可以提高共混材料的耐热性；SA含量增加导致共混材料的耐热性小幅下降。共混材料的热降解温度范围较原料PLLA宽,在360℃左右趋于完全降解。
5.SA、增容剂和增塑剂的含量对PLLA/SA共混体系的MFR产生了一定的影响。增容后的不含增塑剂的简单共混体系的MFR均高于未增容体系,且随着SA含量的增加有所增大；在增容剂含量一定(2%)时,增塑后共混体系的MFR高于未增塑体系；SA含量和增塑剂含量一定的情况下,共混体系的MFR随着增容剂含量的增加呈先减小后增大的趋势,且在增容剂含量为8%时达到最小,为3.62g/10min,但仍高于原料PLLA的MFR(2.04g/10min),说明共混材料的流动性较原料PLLA的好,更适合塑料成型加工的要求。
6.SEM分析表明,添加适量的增容剂能有效地改善PLLA/SA共混体系的相容性。随着SA含量的增加,共混体系的相容性变差。
7.耐水性研究发现,随着SA含量的增加,共混材料的吸水率逐渐增大,耐水性降低；随着增容剂含量的增加共混材料的吸水率稍有提高。在增容剂含量较低(2%)时,SA含量为25%的共混材料吸水后的拉伸强度与吸水前相比略有降低,其他SA含量的共混材料吸水后的拉伸强度均有提高；而在SA含量一定时,随着增容剂含量的增加,共混材料吸水后的拉伸强度均下降,但在增容剂含量为8%时下降的程度很小。
8.生物降解性实验表明,SA和增塑剂的加入均使原料PLLA的生物降解性有所提高,但是并未随着他们二者的含量变化呈规律性变化。
In order to reduce the cost of the polylactic acid (PLLA) material and improve its flexibility to expand the application of PLA-based plastic,we used PLLA and starch acetate (SA) as the main raw material, tetrabutyl titanate (Ti(OBU)4) as compatibilizer, and triethyl citrate (TEC) as plasticizer,to prepare a series of PLLA/ SA blends by melt mixing firstly.It was investigated the effect of the content of SA,the compatibilizer and its content, the plasticizer and its content on the mechanical properties,dynamic mechanical properties,structure and morphologies, heat-resistant performance,melt flow rate and water-resistant performance and other implications of blends. The results of research show that:
The compatibility of PLLA and SA of the blends was improved to some extent after adding the compatibilizer.
SA content, addition of compatibilizer and its content, addition of plasticizer and its content, all of them affect the mechanical properties greatly.The appropriate content of the compatibilizer can improve the compatibility of PLLA/SA blends effectively, while the flexibility of the blends can be improved by adding the plasticizer.When the content of the SA is 25%, the content of compatibilizer is 8%, and the the content of plasticizer is 10%, the stiffness and the strength of the blends declined, while the flexibility is improved greatly as compared with pure PLLA material,
The results of dynamic mechanical analysis showed that the varying trend of the tanδpeak temperature and the storage modulus with increasing temperature is similar under different frequency.It illustrates that the change of the frequency has little influence on the storage modulus and the internal friction.But the content of SA and the content of the compatibilizer have greater impact on the storage modulus.As the content of the compatibilizer increases, the tanδpeak temperature moves to a lower temperature, and the storage modulus of the blends decreases.With increasing the content of SA in the blends, the tanδpeak temperature moved to a higher temperature, and the storage of the blends increases. But, when the content of SA is increased over 25%, Tanδpeak temperature and the storage modulus.keep constant. The storage modulus of the blends decreases greatly after adding the plasticizer, Tanδpeak temperature is enhanced.
Thermogravimetric analysis showed that the compatibilizer and the plasticizer also have the effect on the heat-resistant of the blends, and the blend without the compatibilizer has worse heat resistance.When the content of the plasticizer is definite, the material heat resistance is improved with the increase of compatibilizer's content compared to the blends without the compatibilizer. Compared with PLLA raw material, the range of the thermal degradation temperature is wider. The blends degrade almost completely when the temperature rises to 360℃.
SA content, the addition of compatibilizer and plasticizer and their contents have a certain effect on MFR of PLLA/SA blends.The MFR of blends compatibilized without plasticizer is higher than the system without compatibilizer, and it increases with SA content inceased. With the fixed content of compatibilizer(2%), the MFR of the blends with plasticizer is higher than the blends without plasticizer;When SA content and plasticizer content are certain, the MFR of the blends increases first and then decreases with the increase of the compatibilizer content. When the compatibilizer content is 8%, the MFR reach the minimum and is 3.62g/10min, but is still higher than that of pure PLLA (MFR 2.04g/10min), which shows that the blends have better mobility than PLA, and are more suitable for the requirements of the plastic molding.
SEM analysis shows that the appropriate amount of the compatibilizer could improve the compatibility of the PLLA/SA blends effectivelly, and the system's compatibility gets worse with the content of SA increasing.
Through inverstigating the water resistance, we find that the water absorption gradually increases with the SA's content incrasing.The blends'water absorption is' enhanced after the addition of the compatibilizer. When the copatibilizer content is lower(2%),except 25% content of SA the other blends'tensile strengths after water absorption are improved. When the content of SA is fixed(25%), by increasing the content of compatibilizer, the tensile strengths after water absorption decrease, and the extent is not great when the content of compatibilizer is 8%.
The addition of SA and the plasticizer improves the biodegradability of PLLA, but no regularity is found between the enhancment and the content of both.
1.增容剂的加入使PLLA/SA共混材料中PLLA和SA的相容性得到了一定程度的改善。
2.SA含量及增容剂与增塑剂含量对共混体系的力学性能有显著的影响,适量的增容剂可以很好地改善PLLA/SA共混体系的相容性,同时适量增塑剂可以提高共混材料的柔韧性。在SA含量为25%,增容剂含量为8%,增塑剂含量为10%时,与原料PLLA相比,共混材料的强度和刚度有所下降,但柔韧性得到了明显改善。
3.动态热力学性能分析表明,在2.00～33.30Hz的频率范围内,SA含量、增容剂含量及增塑剂对材料的储能模量有较大的影响,随着增容剂含量的增加,储能模量降低,Tanδ峰值温度逐渐向低温方向移动；而随着SA含量的增加,共混材料储能模量增加,Tanδ峰值温度移向高温方向,但当SA含量增加到25%以上时,Tanδ峰值温度基本保持恒定；增塑剂的加入大大降低了材料的储能模量,提高了Tanδ峰值。
4.热重分析表明,增塑剂的含量、增容剂的含量和SA含量对共混材料的热分解有影响。增塑剂降低了材料的耐热性；增容剂可以提高共混材料的耐热性；SA含量增加导致共混材料的耐热性小幅下降。共混材料的热降解温度范围较原料PLLA宽,在360℃左右趋于完全降解。
5.SA、增容剂和增塑剂的含量对PLLA/SA共混体系的MFR产生了一定的影响。增容后的不含增塑剂的简单共混体系的MFR均高于未增容体系,且随着SA含量的增加有所增大；在增容剂含量一定(2%)时,增塑后共混体系的MFR高于未增塑体系；SA含量和增塑剂含量一定的情况下,共混体系的MFR随着增容剂含量的增加呈先减小后增大的趋势,且在增容剂含量为8%时达到最小,为3.62g/10min,但仍高于原料PLLA的MFR(2.04g/10min),说明共混材料的流动性较原料PLLA的好,更适合塑料成型加工的要求。
6.SEM分析表明,添加适量的增容剂能有效地改善PLLA/SA共混体系的相容性。随着SA含量的增加,共混体系的相容性变差。
7.耐水性研究发现,随着SA含量的增加,共混材料的吸水率逐渐增大,耐水性降低；随着增容剂含量的增加共混材料的吸水率稍有提高。在增容剂含量较低(2%)时,SA含量为25%的共混材料吸水后的拉伸强度与吸水前相比略有降低,其他SA含量的共混材料吸水后的拉伸强度均有提高；而在SA含量一定时,随着增容剂含量的增加,共混材料吸水后的拉伸强度均下降,但在增容剂含量为8%时下降的程度很小。
8.生物降解性实验表明,SA和增塑剂的加入均使原料PLLA的生物降解性有所提高,但是并未随着他们二者的含量变化呈规律性变化。
In order to reduce the cost of the polylactic acid (PLLA) material and improve its flexibility to expand the application of PLA-based plastic,we used PLLA and starch acetate (SA) as the main raw material, tetrabutyl titanate (Ti(OBU)4) as compatibilizer, and triethyl citrate (TEC) as plasticizer,to prepare a series of PLLA/ SA blends by melt mixing firstly.It was investigated the effect of the content of SA,the compatibilizer and its content, the plasticizer and its content on the mechanical properties,dynamic mechanical properties,structure and morphologies, heat-resistant performance,melt flow rate and water-resistant performance and other implications of blends. The results of research show that:
The compatibility of PLLA and SA of the blends was improved to some extent after adding the compatibilizer.
SA content, addition of compatibilizer and its content, addition of plasticizer and its content, all of them affect the mechanical properties greatly.The appropriate content of the compatibilizer can improve the compatibility of PLLA/SA blends effectively, while the flexibility of the blends can be improved by adding the plasticizer.When the content of the SA is 25%, the content of compatibilizer is 8%, and the the content of plasticizer is 10%, the stiffness and the strength of the blends declined, while the flexibility is improved greatly as compared with pure PLLA material,
The results of dynamic mechanical analysis showed that the varying trend of the tanδpeak temperature and the storage modulus with increasing temperature is similar under different frequency.It illustrates that the change of the frequency has little influence on the storage modulus and the internal friction.But the content of SA and the content of the compatibilizer have greater impact on the storage modulus.As the content of the compatibilizer increases, the tanδpeak temperature moves to a lower temperature, and the storage modulus of the blends decreases.With increasing the content of SA in the blends, the tanδpeak temperature moved to a higher temperature, and the storage of the blends increases. But, when the content of SA is increased over 25%, Tanδpeak temperature and the storage modulus.keep constant. The storage modulus of the blends decreases greatly after adding the plasticizer, Tanδpeak temperature is enhanced.
Thermogravimetric analysis showed that the compatibilizer and the plasticizer also have the effect on the heat-resistant of the blends, and the blend without the compatibilizer has worse heat resistance.When the content of the plasticizer is definite, the material heat resistance is improved with the increase of compatibilizer's content compared to the blends without the compatibilizer. Compared with PLLA raw material, the range of the thermal degradation temperature is wider. The blends degrade almost completely when the temperature rises to 360℃.
SA content, the addition of compatibilizer and plasticizer and their contents have a certain effect on MFR of PLLA/SA blends.The MFR of blends compatibilized without plasticizer is higher than the system without compatibilizer, and it increases with SA content inceased. With the fixed content of compatibilizer(2%), the MFR of the blends with plasticizer is higher than the blends without plasticizer;When SA content and plasticizer content are certain, the MFR of the blends increases first and then decreases with the increase of the compatibilizer content. When the compatibilizer content is 8%, the MFR reach the minimum and is 3.62g/10min, but is still higher than that of pure PLLA (MFR 2.04g/10min), which shows that the blends have better mobility than PLA, and are more suitable for the requirements of the plastic molding.
SEM analysis shows that the appropriate amount of the compatibilizer could improve the compatibility of the PLLA/SA blends effectivelly, and the system's compatibility gets worse with the content of SA increasing.
Through inverstigating the water resistance, we find that the water absorption gradually increases with the SA's content incrasing.The blends'water absorption is' enhanced after the addition of the compatibilizer. When the copatibilizer content is lower(2%),except 25% content of SA the other blends'tensile strengths after water absorption are improved. When the content of SA is fixed(25%), by increasing the content of compatibilizer, the tensile strengths after water absorption decrease, and the extent is not great when the content of compatibilizer is 8%.
The addition of SA and the plasticizer improves the biodegradability of PLLA, but no regularity is found between the enhancment and the content of both.
引文
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