溶胶—凝胶法制备PLA基杂化复合薄膜及性能研究
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摘要
随着石油基非可再生资源的巨大消耗和白色污染的日益严重，制备新型的可生物降解包装材料成为研究的热点。聚乳酸(PLA)是一种新型可生物降解的环境友好型脂肪族聚酯高分子材料，在环境中能被微生物完全分解成二氧化碳和水。但是，氧气、二氧化碳、水蒸气和有机小分子等物质易透过PLA薄膜，从而限制了PLA膜作为包装材料的应用范围。
因此，为了提高可生物降解PLA薄膜的阻隔性，本文采用溶胶-凝胶法，以正硅酸乙酯(TEOS)为前驱体、γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)为偶联剂、无水乙醇为共溶剂、盐酸为催化剂，制备SiO_2复合薄膜，再以羟丙基甲基纤维素(HPMC)和硬脂酸(STA)为有机相组分，分别制备了HPMC/SiO_2杂化PLA复合薄膜和STA/HPMC/SiO_2杂化PLA复合薄膜。最终，制备了三种PLA基阻隔性复合膜，通过表征和测试结果如下：
在SiO_2复合膜中，通过正交实验及单因素实验，得出最佳制备SiO_2复合膜的摩尔配比为：(TEOS+KH560):H_2O:EtOH:HCl=1:3:3:0.3，TEOS:KH560=3:2。此时， SiO_2复合薄膜的氧气阻隔性是PLA基膜的9.6倍；水蒸气阻隔性是PLA基膜的1.7倍；拉伸强度是PLA基膜的1.08倍，具有良好的透明性。
在HPMC/SiO_2杂化PLA复合薄膜中，HPMC与SiO_2以Si-O-C共价键和C=O键相结合，形成了致密的杂化网络结构。随HPMC含量的增加，杂化复合薄膜的阻隔性能先提高后下降，当HPMC体积分数为6%时，氧气阻隔性能比未经碱处理的PLA基膜提高了近36倍；水蒸气阻隔性能提高了近3倍；拉伸强度是PLA基膜的1.13倍；具有良好的透明性。
在STA/HPMC/SiO_2杂化PLA复合薄膜中，有机相与无机相相容性较好，无分相现象，杂化层与PLA基膜附着紧密。随STA量的增多，杂化膜的氧气阻隔性能先增加后减少，水蒸气阻隔性持续增加。当STA体积分数为5%时，其氧气阻隔性能比未经碱处理的PLA基膜提高了80.6倍；水蒸气阻隔性提高了7.3倍；拉伸强度为PLA基膜的1.16倍；透光率仍大于90%具有良好的透明性。
With oil and non-renewable resource consuming and white pollution increasingly serious,the preparation of a new type of biodegradable packaging materials has become a research hotspot. Polylactic acid (PLA) is a kind of biodegradable and environment-friendly aliphaticpolymer materials, in the environment can be completely decomposed into carbon dioxide andwater by the microbe. However, oxygen, water vapor, carbon dioxide and small organicmolecules and so on can easily through the PLA film, which limit the application of PLA as apackaging material.
Therefore, In our work, in order to improve the barrier property of PLA film. Via sol-gelprocess was used in SiO_2coating on PLA film. Tertaethoxysilane(TEOS) was used as theprecursor. The KH560was used as a coupling agent. Besides, absolute alcohol was used as thecosolvent and hydrochloric acid was used the catalyst. Then, Hydroxypropyl methylcellulose(HPMC) and stearic acid(STA) were used as the organic compounds to prepare theHPMC/SiO_2hybrid composite film and STA/HPMC/SiO_2hybrid composite film. Finally, threekinds of composite films consisted of PLA film and the coatings were prepared. The structure ofthese films was charactered and properties was measured. The main conclusions are as follows:
For the SiO_2composite films, the optimum experimental conditions of preparation barriercomposite films had been obtained through the orthogonal experiment and single factorexperiment. The molar ratio of (TEOS+KH560): deionized water: absolute alcohol: hydrochloricacid was optimized at1:3:3:0.3, and the molar ratio of TEOS to KH560was3:2. Then, oxygenbarrier properties, water vapor barrier properties and tensile strength of PLA/SiO_2compositefilms was9.6times,1.7times and1.08times that of the bare PLA film. The PSiO_2compositefilms had a good transparency.
For the PLA/HPMC/SiO_2hybrid composite films, HPMC combined with SiO_2by Si-O-Ccovalent bond and C=O bond, which formed a dense organic-inorganic network structure. As increased the HPMC content, the barrier properties of PLA/HPMC/SiO_2hybrid composite filmswas increased firstly and then decreased. As the Volume fraction of HPMC increased to6%, theoxygen barrier properties, water vapor barrier properties and tensile strength ofPLA/HPMC/SiO_2hybrid composite films was36times,3times and1.13times that of the barePLA film. At the same time, The PLA/HPMC/SiO_2hybrid composite films had a goodtransparency.
For the PLA/STA/HPMC/SiO_2hybrid composite films, hybrid composite film and the PLAsubstrate film was closely adhere. No creaking and no phase separation were observed on thesurface of the coating. Along with the increase content of STA, the oxygen barrier properties ofPLA/STA/HPMC/SiO_2hybrid composite films was rised firstly and then reduced, while thewater vapor barrier property of the hybrid composite films continue to rise. As the Volumefraction of STA increased to5%, the oxygen barrier properties, water vapor barrier propertiesand tensile strength of PLA/STA/HPMC/SiO_2hybrid composite films was80.6times,7.3timesand1.16times that of the bare PLA film. At the same time, Because of the light transmission ratewas more than90%, The hybrid composite films of PLA/STA/HPMC/SiO_2still had a goodtransparency.
因此，为了提高可生物降解PLA薄膜的阻隔性，本文采用溶胶-凝胶法，以正硅酸乙酯(TEOS)为前驱体、γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)为偶联剂、无水乙醇为共溶剂、盐酸为催化剂，制备SiO_2复合薄膜，再以羟丙基甲基纤维素(HPMC)和硬脂酸(STA)为有机相组分，分别制备了HPMC/SiO_2杂化PLA复合薄膜和STA/HPMC/SiO_2杂化PLA复合薄膜。最终，制备了三种PLA基阻隔性复合膜，通过表征和测试结果如下：
在SiO_2复合膜中，通过正交实验及单因素实验，得出最佳制备SiO_2复合膜的摩尔配比为：(TEOS+KH560):H_2O:EtOH:HCl=1:3:3:0.3，TEOS:KH560=3:2。此时， SiO_2复合薄膜的氧气阻隔性是PLA基膜的9.6倍；水蒸气阻隔性是PLA基膜的1.7倍；拉伸强度是PLA基膜的1.08倍，具有良好的透明性。
在HPMC/SiO_2杂化PLA复合薄膜中，HPMC与SiO_2以Si-O-C共价键和C=O键相结合，形成了致密的杂化网络结构。随HPMC含量的增加，杂化复合薄膜的阻隔性能先提高后下降，当HPMC体积分数为6%时，氧气阻隔性能比未经碱处理的PLA基膜提高了近36倍；水蒸气阻隔性能提高了近3倍；拉伸强度是PLA基膜的1.13倍；具有良好的透明性。
在STA/HPMC/SiO_2杂化PLA复合薄膜中，有机相与无机相相容性较好，无分相现象，杂化层与PLA基膜附着紧密。随STA量的增多，杂化膜的氧气阻隔性能先增加后减少，水蒸气阻隔性持续增加。当STA体积分数为5%时，其氧气阻隔性能比未经碱处理的PLA基膜提高了80.6倍；水蒸气阻隔性提高了7.3倍；拉伸强度为PLA基膜的1.16倍；透光率仍大于90%具有良好的透明性。
With oil and non-renewable resource consuming and white pollution increasingly serious,the preparation of a new type of biodegradable packaging materials has become a research hotspot. Polylactic acid (PLA) is a kind of biodegradable and environment-friendly aliphaticpolymer materials, in the environment can be completely decomposed into carbon dioxide andwater by the microbe. However, oxygen, water vapor, carbon dioxide and small organicmolecules and so on can easily through the PLA film, which limit the application of PLA as apackaging material.
Therefore, In our work, in order to improve the barrier property of PLA film. Via sol-gelprocess was used in SiO_2coating on PLA film. Tertaethoxysilane(TEOS) was used as theprecursor. The KH560was used as a coupling agent. Besides, absolute alcohol was used as thecosolvent and hydrochloric acid was used the catalyst. Then, Hydroxypropyl methylcellulose(HPMC) and stearic acid(STA) were used as the organic compounds to prepare theHPMC/SiO_2hybrid composite film and STA/HPMC/SiO_2hybrid composite film. Finally, threekinds of composite films consisted of PLA film and the coatings were prepared. The structure ofthese films was charactered and properties was measured. The main conclusions are as follows:
For the SiO_2composite films, the optimum experimental conditions of preparation barriercomposite films had been obtained through the orthogonal experiment and single factorexperiment. The molar ratio of (TEOS+KH560): deionized water: absolute alcohol: hydrochloricacid was optimized at1:3:3:0.3, and the molar ratio of TEOS to KH560was3:2. Then, oxygenbarrier properties, water vapor barrier properties and tensile strength of PLA/SiO_2compositefilms was9.6times,1.7times and1.08times that of the bare PLA film. The PSiO_2compositefilms had a good transparency.
For the PLA/HPMC/SiO_2hybrid composite films, HPMC combined with SiO_2by Si-O-Ccovalent bond and C=O bond, which formed a dense organic-inorganic network structure. As increased the HPMC content, the barrier properties of PLA/HPMC/SiO_2hybrid composite filmswas increased firstly and then decreased. As the Volume fraction of HPMC increased to6%, theoxygen barrier properties, water vapor barrier properties and tensile strength ofPLA/HPMC/SiO_2hybrid composite films was36times,3times and1.13times that of the barePLA film. At the same time, The PLA/HPMC/SiO_2hybrid composite films had a goodtransparency.
For the PLA/STA/HPMC/SiO_2hybrid composite films, hybrid composite film and the PLAsubstrate film was closely adhere. No creaking and no phase separation were observed on thesurface of the coating. Along with the increase content of STA, the oxygen barrier properties ofPLA/STA/HPMC/SiO_2hybrid composite films was rised firstly and then reduced, while thewater vapor barrier property of the hybrid composite films continue to rise. As the Volumefraction of STA increased to5%, the oxygen barrier properties, water vapor barrier propertiesand tensile strength of PLA/STA/HPMC/SiO_2hybrid composite films was80.6times,7.3timesand1.16times that of the bare PLA film. At the same time, Because of the light transmission ratewas more than90%, The hybrid composite films of PLA/STA/HPMC/SiO_2still had a goodtransparency.
引文
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