一锅法合成野豌豆淀粉基高吸水树脂

doi:10.3969/j.issn.0253-2417.2017.04.017

摘要/Abstract

摘要： 为有效利用野生淀粉资源，利用过硫酸铵（APS）引发丙烯酸（AA）和野豌豆淀粉的接枝聚合反应，采用静态一锅法制备了凝胶型淀粉基高吸水性树脂（VS-SAP）。研究了不同反应条件对产物吸水性能的影响，并探讨了起泡剂用量和加入时间对产物平衡和实时吸水性能的影响，结果表明：较佳制备条件为淀粉0.3 g，纯水24 mL，NaOH 0.80 g，APS 30 mg，N，N'-亚甲基双丙烯酰胺（MBA）6 mg，AA 3.6 mL，在65℃反应30 min后添加NaHCO₃ 0.5 g/g （以淀粉质量计），继续反应4.5 h，在此条件下合成的VS-SAP得率为95.7%，其对纯水、自来水、生理盐水和人工尿液的吸液率分别为2 589、604、101和104 g/g，浸泡1 h吸自来水可达257 g/g。傅里叶变换红外光谱（FT-IR）结果显示丙烯酸成功地接枝到淀粉分子链上；碘显色试验结果显示产物仍然保留了淀粉的部分分子链结构；热重和扫描电镜结果显示起泡剂NaHCO₃的加入使产物热稳定性提高，形貌更加疏松、粗糙。

关键词: 接枝共聚, 水凝胶, 交联, 野豌豆, 淀粉

Abstract: The transparent gel-like super absorbent polymers (SAP) were synthesized to utilize wild starch resources effectively. The VS-SAP were prepared by the static one-pot method through the graft copolymerization between acrylic acid (AA) and vetch starch(VS) initiated by ammonium persulfate. The reaction conditions, the foaming agent amount and added time that affect the equilibrium and real-time swelling capacity in running water were further investigated. The optimal conditions were that starch 0.3 g, water 24mL, NaOH 0.80g, APS 30mg, bisacrylamide(MBA)6mg, AA 3.6mL, respectively, including reaction at 65℃ for 30 min, then adding 0.5 g/g NaHCO₃ (based on the starch mass) and keeping for 4.5 h reaction. Under the optimum conditions, the yield of the synthesized VS-SAP was 95.7% and the VS-SAP could absorb 2 589, 604, 101 and 104 g/g water, in distilled water, running water, normal saline and artificial urine, respectively. The water absorption capacity in running water at 1 h was 257 g/g. The Fourier translation infrared spectroscopy (FT-IR) indicated that acrylic was successfully grafted onto the starch molecule chain. The iodine staining results showed that VS-SAP still retained the main molecular chains' structure of starch. The TG results indicated that the VS-SAP samples had a stronger thermal stability than original starch and poly(acrylic acid) (PAA). The SEM results showed that the surface structures were more coarse and loose after reaction.

Key words: graft copolymerization, hydrogel, cross-linking, vetch, starch

中图分类号:

TQ91
O636.1

刘廷国, 钱立武, 黄志良, 吴小说, 郭军, 刘天宝. 一锅法合成野豌豆淀粉基高吸水树脂[J]. 林产化学与工业, 2017, 37(4): 115-122.

LIU Tingguo, QIAN Liwu, HUANG Zhiliang, WU Xiaoshuo, GUO Jun, LIU Tianbao. Vetch Starch Based Superabsorbent Polymers Synthesized by One-pot Method[J]. Chemistry and Industry of Forest Products, 2017, 37(4): 115-122.

参考文献

[1] 谢华飞,贾振宇,尹国强,等. 合成系绿色高吸水树脂研究进展[J]. 材料导报,2011(3):79-82. XIE H F, JIA Z Y, YIN G Q, et al. Research progress in synthetic green superabsorbent polymer materials[J]. Material Review,2011(3):79-82.
[2] 崔英德,黎新明,尹国强. 绿色高吸水树脂[M]. 北京:化学工业出版社,2008. CUI Y D, LI X M, YIN G Q. Green Superabsorbent Polymers[M]. Beijing:Chemical Industry Press,2008.
[3] 余响林,饶聪,秦天,等. 反相悬浮聚合法制备高吸水树脂研究进展[J]. 化工新型材料,2014,42(10):20-22. YU X L, RAO C, QIN T, et al. Research progress of superabsorbent polymer by inverse suspension polymerization[J]. New Chemical Material,2014,42(10):20-22.
[4] 陆爱霞,罗扬,严勇. 微波催化玉米淀粉基高吸水树脂制备工艺的研究[J]. 食品与机械,2010,26(5):33-35. LU A X, LUO Y, YAN Y. Preparation of superabsorbent based on maize starch by microwave irradiation[J]. Food & Machinery,2010,26(5):33-35.
[5] 罗志河,杨万泰,杨正根. 紫外光引发制备高吸水树脂研究进展[J]. 高分子通报,2010(5):12-16. LUO Z H, YANG W T, YANG Z G. Advances of preparation of super-absorbent resin by UV initiation[J]. Polymer Bulletin,2010(5):12-16.
[6] 张素芬,汪海燕,戚文元,等. 淀粉接枝聚丙烯酸钠高吸水树脂的电子束法制备及结构表征[J]. 核农学报,2015,29(3):462-471. ZHANG S F, WANG H Y, QI W Y, et al.Preparation and characterization of starch grafting acrylic acid superabsorbent via 10 MeV electron-beam irradiation[J]. Journal of Nuclear Agricultural Sciences,2015,29(3):462-471.
[7] ZOU W, YU L, LIU X X, et al. Effects of amylose/amylopectin ratio on starch-based superabsorbent polymers[J]. Carbohydrate Polymers,2012,87(2):1583-1588.
[8] ZHANG Y N, CUI J Y, XU S A. Effects of chain structures of corn starches on starch-based superabsorbent polymers[J]. Starch/Stärke,2015,67:1-9.
[9] 赵琦,王文国. 我国淀粉植物的地理分布特征分析[J]. 四川农业大学学报,2013,31(2):176-181. ZHAO Q, WANG W G. Geographic distribution characteristics of the starch plants in China[J]. Journal of Sichuan Agricultural University,2013,31(2):176-181.
[10] 徐晓俞,李爱萍,康智明,等. 野豌豆属植物化学成分及其药理活性研究进展[J]. 中国农学通报,2015,31(31):74-80. XU X Y, LI A P, KANG Z M, et al. Research progress of chemical constituents and pharmacological activities of Vicia genus[J]. Chinese Agricultural Science Bulletin,2015,31(31):74-80.
[11] 杨晓玲,郭彦东. 野豌豆花色素的体外抗氧化性及抑菌性[J]. 食品科学,2012,33(23):129-132. YANG X L, GUO Y D. In vitro antioxidant and antibacterial activity of pigments from flowers of Vicia sepium[J]. Food Science,2012,33(23):129-132.
[12] 肖家军,郝培应,程滨,等. 野豌豆不同提取物抑菌活性比较[J]. 生物学杂志,2010,27(1):97-99. XIAO J J, HAO P Y, CHENG B, et al. Comparison of antibacterial activity from different parts of Vicia sepium[J]. Journal of Biology,2010,27(1):97-99.
[13] ARABESTANI A, KADIVAR M, AMORESANO A, et al. Bitter vetch (Vicia ervilia) seed protein concentrate as possible source for production of bilayered films and biodegradable containers[J]. Food Hydrocolloids,2016,60:232-242.
[14] 赵梅. 红小豆淀粉提取工艺研究[J]. 粮食与油脂,2013,26(5):23-24. ZHAO M. Study on extraction technology of adzuki beans starch[J]. Cereals & Oils,2013,26(5):23-24.
[15] 王丹,商士斌,宋湛谦,等. 羧甲基纤维素改性高吸水树脂合成及性能研究[J]. 林产化学与工业,2007,27(5):6-10. WANG D, SHANG S B, SONG Z Q, et al. Synthesis and property of superabsorbent polymers modified by carboxymethyl cellulose[J]. Chemistry and Industry of Forest Products,2007,27(5):6-10.
[16] 刘廷国,李斌,朱坤坤,等. 均相条件下甲壳素基高吸水树脂的制备及性能研究[J]. 高分子学报,2013,(7):915-921. LIU T G, LI B, ZHU K K, et al. Preparation and properties of chitin-based superabsorbent polymers under homogeneous conditions[J]. Acta Polymerica Sinica,2013(7):915-921.
[17] 刘廷国,叶洋,吴小说,等. 微波辅助合成壳聚糖基高吸水性树脂[J]. 核农学报,2012,26(3):527-534. LIU T G, YE Y, WU X S, et al.Microwave assisted synthesis of chitosan-g-poly(acrylic acid) superabsorbent polymers[J]. Journal of Nudear Agricultural Sciences, 2012,26(3):527-534.
[18] 董彬,目仁更,温国华,等. 淀粉糊化用水量对高吸水树脂吸水性能影响的研究[J]. 功能材料,2011,42(增刊1):79-81. DONG B, MU R G, WEN G H, et al. A review on the influence of starch gelatinization water-consumption to the water absorbability of SAP[J]. Journal of Functional Materials,2011,42(S1):79-81.
[19] 林真,彭少贤,赵西坡,等. 多孔高吸水性树脂制备方法及应用研究进展[J]. 化工新型材料,2013,41(2):160-162. LIN Z, PENG S X, ZHAO X P, et al.Research progress on forming method and application of porous superabsorbent resin[J]. New Chemical Materials, 2013, 41(2):160-162.
[20] LIU T G, WANG YT, GUO J, et al. One-step synthesis of corn starch urea based acrylate superabsorbents[J]. Journal of Applied Polymer Science, 2017, 134(32):45175.