Preparation and Emulsification Performance Analysis of Octenyl Succnic Anhydride Modified Strach from Mechanical Activated Sago Strach
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摘要: 采用自制搅拌式球磨机对西米淀粉进行机械活化预处理，以辛烯基琥珀酸酐为酯化剂制备辛烯基琥珀酸西米淀粉酯。探讨活化时间、反应时间、辛烯基琥珀酸酐添加量、反应温度和pH等因素对辛烯基琥珀酸西米淀粉酯取代度的影响。结果表明，机械活化对西米淀粉辛烯基琥珀酸酐酯化反应有明显的增强作用；在相同反应条件下，活化淀粉的取代度和反应效率显著上升；通过正交试验确定了活化1.0 h西米淀粉酯的最佳工艺条件：反应时间为2.0 h，辛烯基琥珀酸酐用量为3%，pH为8.0，反应温度为35 ℃；在此条件下酯化得到的淀粉酯取代度为0.02294，反应效率为98.01%。FTIR、XRD、SEM测试结果表明，西米淀粉经过辛烯基琥珀酸酐处理后，产品的红外光谱在1570 cm−1和1712 cm−1处出现了新的吸收峰，淀粉结晶度下降，淀粉颗粒表面受到破坏，颗粒中间出现较大孔洞，进一步证实西米淀粉发生了酯化反应。取代度为0.02294的辛烯基琥珀酸西米淀粉酯的乳化性为26.43%，乳化稳定性为24.10%，均优于原西米淀粉酯。Abstract: The sago starch was mechanically activated by a stirring-type ball mill as pretreatment, and the octenyl succinic acid starch ester was prepared by the esterification agent octenyl succinic anhydride. By adopting the degree of substitution (DS) as evaluating parameters, activation time, reaction time, the amount of octenyl succinic anhydride, reaction tem-perature, and pH on the esterification of sago starch were investigated respectively. The results indicated that mechanical activation significantly improved the esterification of sago starch octenyl succinic anhydride. Under the same reaction conditions, the degree of substitution and reaction efficiency of activated starch increased significantly. Through the orthogonal test, the optimal conditions for the preparation of activated 1.0 h starch ester could be determined: The reaction time was 2.0 h, the amount of octenyl succinic anhydride was 3%, the pH value was 8.0, and the temperature was 35 ℃. Under such conditions, the degree of substitution of starch ester prepared by esterification was 0.02294, the reaction efficiency was 98.01%. The results of the FTIR, XRD and SEM indicated that the FTIR spectrum of octenyl succinic anhydride sago starch showed new absorption peaks at 1570 cm−1 and 1712 cm−1, the crystallinity of starch decreased, and the surface of starch granules was damaged, with large holes appeared in the middle of starch granules. Thus the esterification reaction of sago starch was further confirmed. The emulsifying property of octenyl succnic anhydride modified strach with substitution degree of 0.02294 was 26.43%, and the emulsifying stability was 24.10%, which were superior to those of the original sago starch ester.
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图 4 辛烯基琥珀酸酐添加量对取代度的影响
Figure 4. Effect of the addition of octenyl succinicanhydride on the degree of substitution
图 6 反应温度对取代度的影响
Figure 6. Effect of the reaction temperature on the degree of substitution
图 7 西米原淀粉及活化1.0 h西米淀粉酯（DS=0.02294）FTIR图
Figure 7. FTIR patterns of sago starch and starch ester with activation time for 1.0 h (DS=0.02294)
图 8 西米原淀粉、活化1.0 h西米淀粉及活化淀粉酯（DS=0.02294）XRD图
Figure 8. XRD patterns of sago starch , sago starch with activation time for 1.0 h and starch ester with activation time for 1.0 h (DS=0.02294)
图 9 西米淀粉、西米淀粉酯扫描电镜图
Figure 9. SEM of sago starch and sago starch ester
注：（a）西米原淀粉；（b）西米原淀粉酯（DS=0.01288）；（c）活化1.0 h西米淀粉；（d）活化1.0 h西米淀粉酯（DS=0.02294）。
图 10 西米淀粉、西米淀粉酯乳化离心后的乳液图
Figure 10. Picture of emulsion after centrifugations of native sago starch and octenyl succinate anhydride modified sago starch
注：（a）西米原淀粉；（b）西米原淀粉酯（DS=0.01288）；（c）活化1.0 h西米淀粉酯（DS=0.02113）；（d）活化1.0 h西米淀粉酯（DS=0.02294）。
表 1 正交实验因素水平设计
Table 1. Design of factors and level of orthogonal experiment
水平 因素 A
辛烯基琥珀酸酐用量（%）B
应时间（h）C
反应温度（℃）D
pH1 2% 1.5 30 7.5 2 3% 2.0 35 8.0 3 4% 2.5 40 8.5 
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表 2 制备辛烯基琥珀酸西米淀粉酯正交试验结果
Table 2. Results of the orthogonal experiment for preparation of octenyl succnic anhydride modified sago strach
试验号 因素 DS A B C D 1 1 1 1 1 0.01483 2 1 2 2 2 0.02233 3 1 3 3 3 0.01708 4 2 1 2 3 0.02290 5 2 2 3 1 0.02135 6 2 3 1 2 0.02173 7 3 1 3 2 0.01503 8 3 2 1 3 0.01334 9 3 3 2 1 0.01740 K1 0.01808 0.01759 0.01633 0.01786 K2 0.02120 0.01901 0.02088 0.01970 K3 0.01492 0.01874 0.01782 0.01777 R 0.00628 0.00142 0.00455 0.00193 因素主次 A>C>D>B 优化水平 A2B2C2D2
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表 3 制备辛烯基琥珀酸西米淀粉酯正交试验方差分析结果
Table 3. Results of variance analysis of the orthogonal experiment for preparation of octenyl succnic anhydride modified sago strach
方差来源 离差平方和 自由度 均方 F值 P值 显著性 A 2.06E-05 2 1.02E-04 7.4835 0.003747 * B 1.02E-05 2 5.12E-06 0.37182 0.694144 C 8.63E-05 2 4..32E-05 3.13399 0.06546 D 3.41E-05 2 1.06E-05 0.77159 0.4755 SSe 1.73E-05 20 1.38E-05 1 注：*表示具有显著性（P<0.05）。
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表 4 西米淀粉及其酯化淀粉的乳化性质
Table 4. Emulsifiability of native sago starch and sago starch ester
样品 取代度 乳化性（%） 乳化稳定性（%） 西米原淀粉 / 6.30±0.21f 8.13±0.58e 西米原淀粉酯 0.00556 10.14±0.64e 12.30±0.57d 西米原淀粉酯 0.01094 12.17±0.37d 10.03±0.43e 西米原淀粉酯 0.01288 13.16±0.38d 15.13±0.34c 活化西米淀粉酯 0.01318 15.22±0.53c 16.23±0.29c 活化西米淀粉酯 0.02113 18.06±0.57b 19.20±0.66b 活化西米淀粉酯 0.02294 26.43±0.83a 24.10±0.63a 注：所有数值均为三次重复试验的平均值，同一列中不同字母表示差异显著（P<0.05）。
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