Page 230 - 《精细化工》2020年第4期

·864· 精细化工 FINE CHEMICALS 第 37 卷

从正交实验结果可以看出，以上四因素对反应 军), et al. Synthesis and application of N-alkylacrylamide in oilfield
的影响水平从大到小依次为 A＞B＞C＞D，即莰烯 chemicals [J]. Oilfield Chemistry (油田化学), 2015, 32(2): 296-300.
[3] XUE W, HAMLEY I W, CASTELLETTO V, et al. Synthesis and
与丙烯腈物质的量之比＞催化剂用量＞反应时间＞ characterization of hydrophobically modified polyacrylamides and
反 应温度 。同 时，也 可得 出最佳 反应 条件 为 some observations on rheological properties[J]. European Polymer
Journal, 2004, 40(1): 47-56.
A 3 B 3 C 3 D 3 ，即莰烯与丙烯腈物质的量之比为 1∶4， [4] ALEXANDER A, KHAN J, SARAF S, et al. Polyethylene glycol
FeCl 3 含量为 12%，反应时间 15 h，反应温度为 (PEG)–poly (N-isopropylacrylamide) (PNIPAAm) based thermosensitive
130 ℃。 injectable hydrogels for biomedical applications[J]. European Journal
of Pharmaceutics and Biopharmaceutics, 2014, 88(3): 575-585.
将正交实验优化的条件进行重复性实验，结果 [5] AMINABHAVI T M, NADAGOUDA M N, MORE U A, et al.
如表 3 所示。 Controlled release of therapeutics using interpenetrating polymeric
networks[J]. Expert Opinion on Drug Delivery, 2015, 12(4):
表 3 稳定性实验结果 669-688.
Table 3 Results of repeat experiment [6] LE P N, NGUYEN N H, NGUYEN C K, et al. Smart dendrimer-
based nanogel for enhancing 5-fluorouracil loading efficiency against
实验号 条件 得率/% 选择性/% MCF7 cancer cell growth[J]. Bulletin of Materials Science, 2016,
1 A 3B 3C 3D 3 92.8 93.6 39(6): 1493-1500.
2 A 3B 3C 3D 3 93.6 95.7 [7] Davoodi S, Soleimanian A, Ramazani S A A, et al. Application of a
novel acrylamide copolymer containing highly hydrophobic
3 A 3B 3C 3D 3 93.3 94.1
comonomer as filtration control and rheology modifier additive in
water-based drilling mud[J]. Journal of Petroleum Science and
由上表可以看出，在此反应条件下进行 3 次重 Engineering, 2019, 180: 747-755.
复性实验，NIBAM 的平均得率为 93.2%，选择性为 [8] SASMAL D, MAITY J, KOLYA H, et al. Study of congo red dye
removal from its aqueous solution using sulfated acrylamide and N,
94.5% 。而单因 素实 验 分 析 得 到 的 最 佳 条件是
N-dimethyl acrylamide grafted amylopectin[J]. Journal of water
A 2B 2C 2D 2 ，即莰烯与丙烯腈物质的量之比为 1∶3， process engineering, 2017, 18: 7-19.
FeCl 3 含量为 10%，反应时间 12 h，反应温度为 [9] TOURRETTE A, DE GEYTER N, JOCIC D, et al. Incorporation of
poly (N-isopropylacrylamide)/chitosan microgel onto plasma
120 ℃。该条件下 NIBAM 得率为 90.3%，选择性为 functionalized cotton fibre surface[J]. Colloids and surfaces A:
97.6%，两者相差不大，从节约成本考虑，最终选用 Physicochemical and engineering aspects, 2009, 352(1/2/3): 126-135.
单因素实验分析得到的条件作为最终工艺条件。 [10] JOCIC D, TOURRETTE A, GLAMPEDAKI P, et al. Application of
temperature and pH responsive microhydrogels for functional
finishing of cotton fabric[J]. Materials technology, 2009, 24(1): 14-23.
3 结论 [11] WENG Yuhui (翁玉辉), XIAO Zhuanquan (肖转泉), CHEN Jinzhu
( 陈金 珠 ), et al. Research progress on synthesis of camphene
使 用路易 斯酸 催化 剂 FeCl 3 完成了莰 烯到 derivatives [J]. Guangzhou Chemical Industry (广州化工), 2015,
43(21): 16-21.
NIBAM 的转化。通过对莰烯与丙烯腈和水的物质的
[12] CARVALHO A M S, HEIMFARTH L, SANTOS K A, et al. Terpenes
量之比、催化剂 FeCl 3 用量、反应时间以及反应温 as possible drugs for the mitigation of arthritic symptoms—A
度对产物得率与反应选择性的影响进行分析，确定 systematic review[J]. Phytomedicine, 2019, 57: 137-147.
[13] MEWALAL R, RAI D K, KAINER D, et al. Plant-derived terpenes:
出正交实验的各因素和水平。综合考虑得到了最佳 A feedstock for specialty biofuels[J]. Trends in biotechnology, 2017,
反应条件：莰烯与丙烯腈和水物质的量之比为 1∶ 35(3): 227-240.
3∶1、催化剂 FeCl 3 含量为 10%、反应时间 12 h、 [14] HE X, XU R, ZHANG L, et al. Alkoxylation of camphene catalyzed
by cation exchange resins[J]. Chemical Engineering Research and
反应温度 120 ℃。在此条件下，NIBAM 的产率和选 Design, 2016, 114: 60-68.
择性分别为 90.3%和 97.6%。该体系工艺简单、反 [15] TIWARI M, KAKKAR P. Plant derived antioxidants-geraniol and
camphene protect rat alveolar macrophages against t-BHP induced
应时间短、催化剂价格低廉，为 NIBAM 的生产提 oxidative stress[J]. Toxicology in Vitro, 2009, 23(2): 295-301.
供了一种新的方法。 [16] GU Yuncui (谷运璀), CAO Jinrong (曹进荣), WU Zhengbing (吴征
本 文只研 究了 均相催 化剂 FeCl 3 催化 合成 兵), et al. Main factors affecting the esterification of camphene with
lower aliphatic acid and synthesis of isobornyl carboxylate [J].
NIBAM 的工艺条件，接下来的研究可以考虑将其单 Flavour Fragrance Cosmetics (香料香精化妆品), 2007, (6): 6-9.
独或与其他路易斯酸一起负载化，制备非均相催化 [17] CHEN Y, ZHANG G, ZHANG H. Copolymerization of methyl
methacrylate and N-alkyl methacrylamide[J]. Journal of applied
剂，从而实现催化剂的循环利用。
polymer science, 2001, 82(2): 400-405.
[18] KARTASHOV V R, ARKHIPOVA A V, MALKOVA K V, et al.
参考文献： Synthesis of N-substituted amides by the Ritter reaction with
[1] ZHANG Haibo (张海波), CHEN Lanlan (陈岚岚), YANG Yanping heteropoly acids as catalysts[J]. Cheminform, 2006, 37(46): 387-389.
( 杨艳平 ), et al. Progress in synthesis and application of [19] XU Xiaowei (徐晓维), XU Xu (徐徐), WANG Shifa (王石发), et al.
polyacrylamide [J]. Polymer Materials Science and Engineering (高 Synthesis and properties of isobornyl methacrylate [J]. Chemistry
分子材料科学与工程), 2016, 32(8): 177-181. and Industry of Forest Products (林产化学与工业), 2013, 33(3):
[2] KONG Yong (孔勇), YANG Xiaohua (杨小华), LI Zhoujun (李舟 100-104.