醚化稻草改性机理的光谱研究
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摘要
本研究利用醚化反应对稻草进行化学改性,使其转化为具有一定热塑性的高分子材料。以NaOH作润胀剂及催化剂,环氧氯丙烷和苄基氯作醚化剂,十六烷基溴化铵作相转移催化剂(只用于苄基化改性),甲苯作溶剂,对稻草进行了醚化改性后,其微观结构有了很大改变,部分消除了稻草的极性。
本研究采用增重率、红外光谱、固体CP/MAS 13C NMR光谱和X射线衍射相结合的方法,对环氧氯丙烷改性稻草和苄基氯改性稻草的改性过程和反应机理进行分析和研究。
对于环氧氯丙烷改性稻草,研究了改性时间为1-8h的改性稻草增重率,结果表明,增重率随改性时间的增加而增加,改性稻草在前5h内的增重率稳步增加至90.12%,5h后增重率基本稳定在93.00%左右。对比改性前后红外光谱图和固体13C核磁共振光谱图,以及不同改性时间的红外光谱图,推断出环氧氯丙烷醚化稻草的改性反应过程主要分为两步：第一步是断C-Cl键取代纤维素上一个-OH的H；第二步是被取代到纤维素上的环氧环被打开,与纤维素分子上另外一个-OH反应。最后,用X射线衍射分析稻草在改性前后的结晶度变化,改性后稻草秸秆的结晶度降低。
对于苄基氯改性稻草,研究了改性时间为1-10h的增重率变化趋势和红外光谱图,分析改性时间和改性效果的关系。结果表明,改性1-2h时,增重率基本为0.00%；改性3-8h时,增重率随改性时间的增加而增加,在8h时增重率达到最高,为61.37%；改性时间为9-10h时,增重率反而下降。在红外光谱图中观察到了相一致的结果。反应2h苄基化样品的红外光谱图中没有苄基化官能团的特征吸收峰出现,从4h样品的红外光谱图中开始出现苄基化官能团的特征吸收峰,8h样品的苄基化特征吸收峰最多,其峰值也最强。
In this study, etherification reaction was applied to modify rice straw into a thermoplastic material. Etherification of rice straw was carried out with NaOH as swelling agent and catalyst, epichlorohydrin and benzyl chloride as etherifying agent, hexadecyl trimethyl ammonium bromide as phase transfer catalyst (only for benzylated straw) and toluene as solvent. The microstructure of rice straw changed greatly and the polarity was erased partly after modification.
Weight percent gain (WPG), infrared spectrum (IR spectrum), CP/MAS 13C NMR spectrum and X-ray diffraction (XRD) were used to study the reaction progress and mechanism of modification.
According to WPG of epichlorohydrin-modified rice straw(1-8h), it was found that WPG increased as modification time increased. WPG of epichlorohydrin-modified rice straw increased to 90.12% within 5h in steps, but it kept steadily about 93.00% after 5h. From the IR spectra and 13C NMR spectra of epichlorohydrin-modified rice straw, it was suggested that epichlorohydrin-modified reaction of rice straw could be devided into two steps. Firstly, C-Cl bond of epichlorohydrin broke and repalaced an H of-OH in cellulose. Secondly, epoxy ring of epichlorohydrin which was replaced on cellulose opened and reacted with another-OH of cellulose. Finally, XRD was used to analyse the crystallinity of rice straw before and after modification. It indicated that the crystallinity of rice straw reduce after modification.
According to WPG of benzylated straw(1～10h), WPG was about 0.00%within 2h. WPG increasd as modification times increased between 3-8h and achieved the highest of 61.37%. But WPG fell down after 8h. This was approved by IR spectra. There were no benzyl functional group absorption peaks in the IR spectrum of benzylated straw with 2h. The absorption peaks appeared in the IR spectrum when reaction time was longer than 4h. The number of absorption peaks and peak values got maxium at 8h.
本研究采用增重率、红外光谱、固体CP/MAS 13C NMR光谱和X射线衍射相结合的方法,对环氧氯丙烷改性稻草和苄基氯改性稻草的改性过程和反应机理进行分析和研究。
对于环氧氯丙烷改性稻草,研究了改性时间为1-8h的改性稻草增重率,结果表明,增重率随改性时间的增加而增加,改性稻草在前5h内的增重率稳步增加至90.12%,5h后增重率基本稳定在93.00%左右。对比改性前后红外光谱图和固体13C核磁共振光谱图,以及不同改性时间的红外光谱图,推断出环氧氯丙烷醚化稻草的改性反应过程主要分为两步：第一步是断C-Cl键取代纤维素上一个-OH的H；第二步是被取代到纤维素上的环氧环被打开,与纤维素分子上另外一个-OH反应。最后,用X射线衍射分析稻草在改性前后的结晶度变化,改性后稻草秸秆的结晶度降低。
对于苄基氯改性稻草,研究了改性时间为1-10h的增重率变化趋势和红外光谱图,分析改性时间和改性效果的关系。结果表明,改性1-2h时,增重率基本为0.00%；改性3-8h时,增重率随改性时间的增加而增加,在8h时增重率达到最高,为61.37%；改性时间为9-10h时,增重率反而下降。在红外光谱图中观察到了相一致的结果。反应2h苄基化样品的红外光谱图中没有苄基化官能团的特征吸收峰出现,从4h样品的红外光谱图中开始出现苄基化官能团的特征吸收峰,8h样品的苄基化特征吸收峰最多,其峰值也最强。
In this study, etherification reaction was applied to modify rice straw into a thermoplastic material. Etherification of rice straw was carried out with NaOH as swelling agent and catalyst, epichlorohydrin and benzyl chloride as etherifying agent, hexadecyl trimethyl ammonium bromide as phase transfer catalyst (only for benzylated straw) and toluene as solvent. The microstructure of rice straw changed greatly and the polarity was erased partly after modification.
Weight percent gain (WPG), infrared spectrum (IR spectrum), CP/MAS 13C NMR spectrum and X-ray diffraction (XRD) were used to study the reaction progress and mechanism of modification.
According to WPG of epichlorohydrin-modified rice straw(1-8h), it was found that WPG increased as modification time increased. WPG of epichlorohydrin-modified rice straw increased to 90.12% within 5h in steps, but it kept steadily about 93.00% after 5h. From the IR spectra and 13C NMR spectra of epichlorohydrin-modified rice straw, it was suggested that epichlorohydrin-modified reaction of rice straw could be devided into two steps. Firstly, C-Cl bond of epichlorohydrin broke and repalaced an H of-OH in cellulose. Secondly, epoxy ring of epichlorohydrin which was replaced on cellulose opened and reacted with another-OH of cellulose. Finally, XRD was used to analyse the crystallinity of rice straw before and after modification. It indicated that the crystallinity of rice straw reduce after modification.
According to WPG of benzylated straw(1～10h), WPG was about 0.00%within 2h. WPG increasd as modification times increased between 3-8h and achieved the highest of 61.37%. But WPG fell down after 8h. This was approved by IR spectra. There were no benzyl functional group absorption peaks in the IR spectrum of benzylated straw with 2h. The absorption peaks appeared in the IR spectrum when reaction time was longer than 4h. The number of absorption peaks and peak values got maxium at 8h.
引文
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7. Ye D Y, Montane D, Farriol X. Preparation and Characterization of Methylcellulose from Annual Cardoon and Jurenile Eucalyptus[J].Carbohydr. Polym.,2005,61(4):446-454.
8. Ye D Y, Montane D, Farriol X. Preparation and Characterization of Methylcellulose from Miscanthus Sinensis[J].Carbohydr. Polym.,2005,62(3):258-266.
9. Sun R C, Sun X F. Structural and Thermal Characterization of Acetylated Rice, Wheat, Rye, and Barley Straws and Poplar Wood Fibre[J].Industrial Crops and Products,2002, 16(3):225-235.
10.许凤,孙润仓.化学改性秸杆原料作高效吸油剂[J].纤维素科学与技术,2003,11(2)：51-56.
11.Liu C F, Ren J L, Sun R C, et al. Isolation and Characterization of Cellulose Obtained from Ultrasonic Irradiated Sugarcane Bagasse[J].J. Agric. Food Chem.,2006,54(16): 5742-5748.
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14. Liu C F, Ren J L, Sun R C, et al. Homogeneous Modification of Sugarcane Bagasse Cellulose with Succinic Anhydride using an Ionic Liquid as Reaction Medium[J]. Carbohydr. Res.,2007,342 (7):919-926.
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