de Britto Douglas, de Assis Odilio B G
Embrapa Instrumentação Agropecuária, Rua XV de Novembro, 1452, CP 741, 13560-970 São Carlos, Brazil.
Int J Biol Macromol. 2007 Jul 1;41(2):198-203. doi: 10.1016/j.ijbiomac.2007.02.005. Epub 2007 Feb 16.
A novel method is described to synthesize quaternary salts of chitosan with dimethylsulfate and subsequently cast films. In an attempt to improve both mechanical and hydrophobic characteristics, the chitosan was previously modified by N-alkylation, introducing 4, 8 and 12 carbons moieties into the polymeric chain. Analysis by FTIR and solid-state CP-MAS (13)C NMR spectroscopy confirmed the success of both alkylation and quaternization processes. The average degree of quaternization of these N-methylated derivatives was calculated to be 35%. DMA measurements indicated that chitosan and its derivative films are typically brittle materials, exhibiting similar non-linear viscoelastic behaviors. The films of unmodified chitosan have a very small strain (approximately 2.8%), though they were the most resistant films (Young's modulus=2283 MPa; tensile strength >44.0 MPa). In general, the alkyl-chitosan derivatives appear to be more plastic than chitosan films but less resistant, e.g., for butyl chitosan: maximum strain=13.1%; tensile strength=13.4 MPa and Young's modulus=171 MPa. Conversely the quaternization reaction increased the hardness of the parent sample, viz. for quaternary salt of dodecyl chitosan: maximum strain=2.6%; tensile strength=38.3 MPa and Young's modulus=1792 MPa.
本文描述了一种用硫酸二甲酯合成壳聚糖季铵盐并随后流延成膜的新方法。为了同时改善其机械性能和疏水特性,壳聚糖预先经过N-烷基化改性,将含有4个、8个和12个碳的部分引入到聚合物链中。通过傅里叶变换红外光谱(FTIR)和固态交叉极化魔角旋转(13)C核磁共振光谱分析证实了烷基化和季铵化过程均取得成功。这些N-甲基化衍生物的平均季铵化度经计算为35%。动态热机械分析(DMA)测量表明,壳聚糖及其衍生物薄膜通常是脆性材料,表现出相似的非线性粘弹性行为。未改性壳聚糖薄膜的应变非常小(约2.8%),不过它们是最坚韧的薄膜(杨氏模量=2283兆帕;拉伸强度>44.0兆帕)。一般来说,烷基壳聚糖衍生物似乎比壳聚糖薄膜更具塑性,但韧性较差,例如,对于丁基壳聚糖:最大应变=13.1%;拉伸强度=13.4兆帕,杨氏模量=171兆帕。相反,季铵化反应提高了母体样品的硬度,即对于十二烷基壳聚糖季铵盐:最大应变=2.6%;拉伸强度=38.3兆帕,杨氏模量=1792兆帕。