微晶纤维素的改性及其在热塑性淀粉复合材料中的应用
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摘要
微晶纤维素具有成本低、密度小、模量高、可再生、可降解、来源广泛等优点，可以作为复合材料的增强剂改善材料的性能。热塑性淀粉由于具有成本低、可生物降解等优点，是最有发展前景的生物降解材料之一。然而，热塑性淀粉耐水性差，力学性能随环境湿度变化较大等缺点限制了它的应用。用微晶纤维素作为增强剂，制备热塑性淀粉复合材料，可以有效改善热塑性淀粉的性能。但是，微晶纤维素表面存在大量的羟基，易于团聚，不利于其均匀分散在淀粉基体中，从而影响微晶纤维素增强热塑性淀粉复合材料力学性能、耐水性能以及透湿性能的改善。
本论文对微晶纤维素进行机械微细化和酸解处理，减小微晶纤维素的尺寸；并以大豆油为酯化剂，对微晶纤维素、机械微细化处理的微晶纤维素和酸解处理的微晶纤维素进行酯化改性，降低微晶纤维素的极性并提高其疏水性。通过考查反应时间、大豆油浓度等因素的影响，调节和控制微晶纤维素的酯化改性程度；最后用上述三种酯化改性的微晶纤维素作为增强剂，制备热塑性淀粉复合膜，考查微晶纤维素的添加量、表面性质、以及尺寸对热塑性淀粉复合膜力学性能、亲/疏水性和透湿性能的影响，探索通过控制微晶纤维素尺寸、酯化改性程度以及添加量，调节控制微晶纤维素增强热塑性淀粉复合材料力学性能、亲/疏水性和透湿性能的技术方法。
通过激光粒度仪对微晶纤维素的粒径进行了表征。结果显示，机械微细化和酸解的方法都可以减小微晶纤维素的粒径，微晶纤维素的粒径随剪切乳化机转速的增加或机械微细化时间的延长而减小。但当处理时间超过60min后，微晶纤维素的粒径不再随机械微细化时间的延长而发生明显变化。
通过红外光谱对酯化改性微晶纤维素进行了表征。结果表明，三种微晶纤维素均可以和大豆油发生酯化反应。在温度为110oC时，反应时间和大豆油溶液浓度对微晶纤维素酯化程度的影响不明显。当酯化条件相同时，机械微细化处理的微晶纤维素更易于和大豆油发生酯化反应。水煮实验表明，制备微晶纤维素/热塑性淀粉复合膜的过程不会破坏对微晶纤维素的酯化改性。
通过X-射线衍射对微晶纤维素的结晶结构进行了表征。结果表明，酸解和机械微细化处理没有破坏微晶纤维素的结晶结构。用大豆油对微晶纤维素进行的酯化改性并没有破坏微晶纤维素的结晶结构，说明酯化反应只发生在微晶纤维素表面。
通过润湿性实验对微晶纤维素表面极性进行了表征。结果表明，酯化改性影响微晶纤维素的润湿性。当酯化条件相同时，酯化改性机械微细化微晶纤维素更易于被极性低的溶剂润湿。酯化时间越长，酯化改性机械微细化微晶纤维素的酯化程度越高，并能在极性越低的溶剂中稳定分散。
通过拉伸试验、吸（透）湿性试验和接触角测量对微晶纤维素增强热塑性淀粉复合膜的力学性能、亲/疏水性和透湿性进行了表征。结果表明，随着添加量的增加，微晶纤维素增强热塑性淀粉复合膜的拉伸强度和弹性模量不断增大，断裂伸长率不断减小；随着添加量的增加，酯化改性微晶纤维素增强热塑性淀粉复合膜的拉伸强度先增大后减少，弹性模量不断增大，断裂伸长率不断减小。热塑性淀粉复合膜的弹性模量只随着微晶纤维素含量的增加而增大，而受微晶纤维素酯化改性地影响不明显。微晶纤维素增强热塑性淀粉复合膜的吸湿率随微晶纤维素添加量的增加不断减小。当添加量相同时，酯化改性微晶纤维素对减小热塑性淀粉复合膜的吸湿率更有效。微晶纤维素增强热塑性淀粉复合膜的透湿性随微晶纤维素添加量的增加不断减小。当添加量相同时，酯化改性微晶纤维素能够更好地阻止水分透过复合膜。添加微晶纤维素，对热塑性淀粉复合膜表面与水的接触角影响不明显。在所考查的微晶纤维素含量范围内，微晶纤维素的尺寸对热塑性淀粉复合膜的弹性模量和透湿性有显著影响。
Microcrystalline cellulose（MCC）has advantages of low cost，low density，high elasticrenewable and biodegradable，it can be used as a reinforcement to prepare composites.Thermoplastic starch（TPS），as a renewable，inexpensive and biodegradable natural polymer，is one of the most promising biodegradable materials. But the mechanical properties of TPS issensitive to the humidity of environment，which limits its applications. When MCC was usedas a reinforcement，the properties of MCC/TPS composite can be improved. However，MCCtends to self-aggregate due to the hydrogen bonding ineraction from the surface carryinghydroxyl groups，which causes uniformly dispersion of MCC in TPS matrix and hinders theimprovements of mechanical properties，water resistance and water barrier properties ofMCC/TPS composites.
In this study，MCC was treated by mechanical ultrafine processing and sulfuric acidhydrolysis， and modified with soybean oil through esterification to improve thehydrophobicity. The effects of reaction time，soybean oil concentration were investigated inorder to control the degree of the modification. The modified MCC was used to prepare MCCreinforced TPS composites. The effects of particle loading， particle size and surfacemodification on the mechanical properties and water barrier properties were investigated. Thechanges of mechanical properties and water barrier properties to the content and size of MCCwere obtained to provide some essential scientific date for applications.
Laser particle sizer was used to analysis the size and distribution of MCC. The resultsindicated that the mechanical ultrafine processing and sulfuric acid hydrolysis reduced thesize of MCC. The size of MCC decreased with increasing of rotation speed during mechanicalultrafine processing and prolongation of treating time. But after60min treatment，the size ofMCC decreased very slowly.
The esterification mofification of MCC was characterized by FTIR spectroscopy. The results indicated that MCC was modified with soybean oil through esterification. The heatingtime and soybean oil concentration did not have a significant effect on the esterification extentof MCC at110oC. The MCC obtained from mechanical ultrafine processing was easier to beesterified with soybean oil. The washing experiment in boiling water showed that thepreparation of the MCC/TPS composites would not damage the esterification of MCC.
The crystalline structure of MCC was characterized by X-ray diffraction (XRD). Theresults indicated that the mechanical ultrafine processing and sulfuric acid hydrolysis did notdestroy the crystalline structure of MCC. XRD measurements aslo confimed that theesterification modification just occurred on the surface of the MCC，because there was noalteration in crystalline structure of MCC after the modification.
The surface polarity of MCC was characterized by wettability experiments. The resultsindicated that the esterification modification affected the wettability of MCC. Afteresterification，the MCC obtained from mechanical ultrafine processing displayed a higheraffinity for low polar solvent. With increasing of esterification reaction time，the MCCobtained from mechanical ultrafine processing displayed a higher affinity for lower polarsolvents.
The mechanical properties，water absorption behaviour，water barrier properties andwater contact angle of MCC/TPS composites were measured. The results suggested that as thecontent of MCC increasing，the tensile strength and Young’s modulus increaseed and theelongation at break decreased. The modified MCC aslo improved the tensile strength andYoung’s modulus of the composites. For the composites with esterification modified MCC，the tensile strength increased at first and then decreased，the Young’s modulus increased andthe elongation at break decreased as the content of the modified MCC increasing. The resultsshowed that the Young’s modulus was largely dependent on the content of MCC and was notremarkablely influenced by the modification of MCC. Addition of MCC and modified MCCreduced the water absorption of the composites，and the water absorption of the compositesdecreased as the content of MCC increasing. Addition of MCC did not influence the watercontact angle of the composites remarkably. The size of MCC had a significant effect on theYoung’s modulus and water barrier property of the MCC/TPS composites.
本论文对微晶纤维素进行机械微细化和酸解处理，减小微晶纤维素的尺寸；并以大豆油为酯化剂，对微晶纤维素、机械微细化处理的微晶纤维素和酸解处理的微晶纤维素进行酯化改性，降低微晶纤维素的极性并提高其疏水性。通过考查反应时间、大豆油浓度等因素的影响，调节和控制微晶纤维素的酯化改性程度；最后用上述三种酯化改性的微晶纤维素作为增强剂，制备热塑性淀粉复合膜，考查微晶纤维素的添加量、表面性质、以及尺寸对热塑性淀粉复合膜力学性能、亲/疏水性和透湿性能的影响，探索通过控制微晶纤维素尺寸、酯化改性程度以及添加量，调节控制微晶纤维素增强热塑性淀粉复合材料力学性能、亲/疏水性和透湿性能的技术方法。
通过激光粒度仪对微晶纤维素的粒径进行了表征。结果显示，机械微细化和酸解的方法都可以减小微晶纤维素的粒径，微晶纤维素的粒径随剪切乳化机转速的增加或机械微细化时间的延长而减小。但当处理时间超过60min后，微晶纤维素的粒径不再随机械微细化时间的延长而发生明显变化。
通过红外光谱对酯化改性微晶纤维素进行了表征。结果表明，三种微晶纤维素均可以和大豆油发生酯化反应。在温度为110oC时，反应时间和大豆油溶液浓度对微晶纤维素酯化程度的影响不明显。当酯化条件相同时，机械微细化处理的微晶纤维素更易于和大豆油发生酯化反应。水煮实验表明，制备微晶纤维素/热塑性淀粉复合膜的过程不会破坏对微晶纤维素的酯化改性。
通过X-射线衍射对微晶纤维素的结晶结构进行了表征。结果表明，酸解和机械微细化处理没有破坏微晶纤维素的结晶结构。用大豆油对微晶纤维素进行的酯化改性并没有破坏微晶纤维素的结晶结构，说明酯化反应只发生在微晶纤维素表面。
通过润湿性实验对微晶纤维素表面极性进行了表征。结果表明，酯化改性影响微晶纤维素的润湿性。当酯化条件相同时，酯化改性机械微细化微晶纤维素更易于被极性低的溶剂润湿。酯化时间越长，酯化改性机械微细化微晶纤维素的酯化程度越高，并能在极性越低的溶剂中稳定分散。
通过拉伸试验、吸（透）湿性试验和接触角测量对微晶纤维素增强热塑性淀粉复合膜的力学性能、亲/疏水性和透湿性进行了表征。结果表明，随着添加量的增加，微晶纤维素增强热塑性淀粉复合膜的拉伸强度和弹性模量不断增大，断裂伸长率不断减小；随着添加量的增加，酯化改性微晶纤维素增强热塑性淀粉复合膜的拉伸强度先增大后减少，弹性模量不断增大，断裂伸长率不断减小。热塑性淀粉复合膜的弹性模量只随着微晶纤维素含量的增加而增大，而受微晶纤维素酯化改性地影响不明显。微晶纤维素增强热塑性淀粉复合膜的吸湿率随微晶纤维素添加量的增加不断减小。当添加量相同时，酯化改性微晶纤维素对减小热塑性淀粉复合膜的吸湿率更有效。微晶纤维素增强热塑性淀粉复合膜的透湿性随微晶纤维素添加量的增加不断减小。当添加量相同时，酯化改性微晶纤维素能够更好地阻止水分透过复合膜。添加微晶纤维素，对热塑性淀粉复合膜表面与水的接触角影响不明显。在所考查的微晶纤维素含量范围内，微晶纤维素的尺寸对热塑性淀粉复合膜的弹性模量和透湿性有显著影响。
Microcrystalline cellulose（MCC）has advantages of low cost，low density，high elasticrenewable and biodegradable，it can be used as a reinforcement to prepare composites.Thermoplastic starch（TPS），as a renewable，inexpensive and biodegradable natural polymer，is one of the most promising biodegradable materials. But the mechanical properties of TPS issensitive to the humidity of environment，which limits its applications. When MCC was usedas a reinforcement，the properties of MCC/TPS composite can be improved. However，MCCtends to self-aggregate due to the hydrogen bonding ineraction from the surface carryinghydroxyl groups，which causes uniformly dispersion of MCC in TPS matrix and hinders theimprovements of mechanical properties，water resistance and water barrier properties ofMCC/TPS composites.
In this study，MCC was treated by mechanical ultrafine processing and sulfuric acidhydrolysis， and modified with soybean oil through esterification to improve thehydrophobicity. The effects of reaction time，soybean oil concentration were investigated inorder to control the degree of the modification. The modified MCC was used to prepare MCCreinforced TPS composites. The effects of particle loading， particle size and surfacemodification on the mechanical properties and water barrier properties were investigated. Thechanges of mechanical properties and water barrier properties to the content and size of MCCwere obtained to provide some essential scientific date for applications.
Laser particle sizer was used to analysis the size and distribution of MCC. The resultsindicated that the mechanical ultrafine processing and sulfuric acid hydrolysis reduced thesize of MCC. The size of MCC decreased with increasing of rotation speed during mechanicalultrafine processing and prolongation of treating time. But after60min treatment，the size ofMCC decreased very slowly.
The esterification mofification of MCC was characterized by FTIR spectroscopy. The results indicated that MCC was modified with soybean oil through esterification. The heatingtime and soybean oil concentration did not have a significant effect on the esterification extentof MCC at110oC. The MCC obtained from mechanical ultrafine processing was easier to beesterified with soybean oil. The washing experiment in boiling water showed that thepreparation of the MCC/TPS composites would not damage the esterification of MCC.
The crystalline structure of MCC was characterized by X-ray diffraction (XRD). Theresults indicated that the mechanical ultrafine processing and sulfuric acid hydrolysis did notdestroy the crystalline structure of MCC. XRD measurements aslo confimed that theesterification modification just occurred on the surface of the MCC，because there was noalteration in crystalline structure of MCC after the modification.
The surface polarity of MCC was characterized by wettability experiments. The resultsindicated that the esterification modification affected the wettability of MCC. Afteresterification，the MCC obtained from mechanical ultrafine processing displayed a higheraffinity for low polar solvent. With increasing of esterification reaction time，the MCCobtained from mechanical ultrafine processing displayed a higher affinity for lower polarsolvents.
The mechanical properties，water absorption behaviour，water barrier properties andwater contact angle of MCC/TPS composites were measured. The results suggested that as thecontent of MCC increasing，the tensile strength and Young’s modulus increaseed and theelongation at break decreased. The modified MCC aslo improved the tensile strength andYoung’s modulus of the composites. For the composites with esterification modified MCC，the tensile strength increased at first and then decreased，the Young’s modulus increased andthe elongation at break decreased as the content of the modified MCC increasing. The resultsshowed that the Young’s modulus was largely dependent on the content of MCC and was notremarkablely influenced by the modification of MCC. Addition of MCC and modified MCCreduced the water absorption of the composites，and the water absorption of the compositesdecreased as the content of MCC increasing. Addition of MCC did not influence the watercontact angle of the composites remarkably. The size of MCC had a significant effect on theYoung’s modulus and water barrier property of the MCC/TPS composites.
引文
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