粉煤灰复合聚丙烯酸钠凝胶的制备及其溶胀性能

doi:10.11944/j.issn.1000-0518.2016.04.150196

摘要/Abstract

摘要：

粉煤灰(CFA)存在的情况下,采用自由基溶液聚合法,以过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了粉煤灰复合聚丙烯酸钠凝胶(CFAPAANa)。以丙烯酸单体质量为基准,当交联剂用量为0.08%,引发剂用量为0.4%,粉煤灰用量为3%,丙烯酸中和度为70%,聚合温度为70 ℃时,所合成的粉煤灰复合聚丙烯酸钠凝胶在蒸馏水和生理盐水中平衡溶胀比最高,分别为1556(g/g)和168(g/g)。考察了复合凝胶在不同介质溶液中的溶胀动力学,保水性能以及在土壤中的降解行为。溶胀动力学研究表明,蒸馏水中溶胀初期复合凝胶聚合物链段的扩散运动能够调控凝胶溶胀的快慢及程度,而生理盐水中水分子的平移和对流运动在凝胶的溶胀过程中起着关键性作用。保水和降解实验结果表明,25 ℃时,50 h凝胶保水率为64%,土壤中50 d时降解率达60%。相比于聚丙烯酸钠凝胶,粉煤灰复合凝胶保水率提高了8%。

关键词: 粉煤灰, 聚丙烯酸, 耐盐性, 保水性, 降解

Abstract:

Coal fly ash composited sodium polyacrylate superabsorbent polymer hydrogel(CFAPAANa) was prepared by free radical solution polymerization of acrylic acid(AA) using potassium persulfate(KPS) as an initiator and N,N'-methylene-bis-acrylamide(NNMBA) as a crosslinker in the presence of coal fly ash(CFA). The CFAPAANa gel has the highest equilibrium swelling degree of 1556 g/g and 168 g/g in distilled water and physiological saline, respectively, when the mass ratio of cross linker to AA is 0.08%, initiator to AA is 0.4%, fly ash to AA is 3%, the neutralization degree of acrylic acid is 70% and polymerization temperature is 70 ℃. The swelling kinetics of gel in different media solution, the water retention properties and degradation behavior in soil were also studied, respectively. Results of the swelling kinetics show that the water absorbent capacity and rate are limited by the expanding polymer segment in distilled water, but the translation and convective diffusion of water play an important role during the swelling process in saline. The results obtained from tests of water retention and degradation show that water retention ratio of hydrogel is 65% after 50 h at 25 ℃, and the degradation percent is about 60% after 50 days in soil. Water retention ratio increases by 8% compared with that of PAANa hydrogel.

Key words: fly ash, poly(acrylic acid), salt resistance, water retention, degradation

张军旗, 金淑萍, 韩玉琦, 禹兴海, 岳国仁. 粉煤灰复合聚丙烯酸钠凝胶的制备及其溶胀性能[J]. 应用化学, 2016, 33(4): 419-429.

ZHANG Junqi, JIN Shuping, HAN Yuqi, YU Xinghai, YUE Guoren. Preparation and Swelling Properties of Coal Fly Ash Composited Sodium Polyacrylate Hydrogel[J]. Chinese Journal of Applied Chemistry, 2016, 33(4): 419-429.

参考文献

[1]	ZHANG Xiaohong,CUI Yingde. Study on the Properties and Structure of Sodium Alginate Superabsorbent[J]. Polym Mater Sci Eng,2006,22(4):91-94(in Chinese). 张小红,崔英德. 可生物降解海藻酸钠高吸水性树脂的性能与结构[J]. 高分子材料科学与工程,2006,22(4):91-94.
[2]	van der Merwea E M,Prinsloob L C,Mathebulaa C L,et al. Surface and Bulk Characterization of an Ultrafine South African Coal Fly Ash with Reference to Polymer Applications[J]. Appl Surf Sci,2014,317(10):73-83.
[3]	Kruger R A. Fly Ash Beneficiation in South Africa:Creating New Opportunities in the Market-place[J]. Fuel,1997,76(8):777-779.
[4]	Joshi R C,Lothia R P. Fly Ash in Concrete: Production, Properties and Uses[M]. Advances in Concrete Technology,vol. 2. New York: Gordon and Breach Science Publishers,1997.
[5]	BAI Guanghui,XU Peng,TENG Wei,et al.Preparation 4A-Molecular Sieve with Sulfate Residue from Fly Ash Extraction of Aluminum[J]. Coal Convers,2009,32(2):81-82(in Chinese). 白光辉,徐鹏,腾玮,等. 粉煤灰提取硫酸铝的残渣制备4A分子[J]. 煤炭转化,2009,32(2):81-82.
[6]	Skorina T,Tikhomirova I. Flue Gas Desulfurization Gypsum and Coal Fly Ash as Basic Components of Prefabricated Building Materials[J]. Waste Manage,2013,33(3):628-633.
[7]	Gonzalez A,Moreno N,Navia R,et al.Development of a Non-conventional Sorbent From Fly Ash and Its Potential Use in Acid Wastewater Neutralization and Heavy Metal Removal[J]. Chem Eng J,2011,166(3):896-905.
[8]	Qiu Q,Hlavacek V. Energy Estimation on CRN Process of Fly Ash as a Slow Release Nitrogen Fertilizer[J]. Ind Eng Chem Res,2010,49(12):5939-5944.
[9]	Liu P,Zhong W. Novel Magnetic Crosslinked Composites with Fly Ash as Filler via Facile “one-pot” in-situ Radical Bulk Polymerization[J]. J Taiwan Inst Chem Eng,2014,45(9):1098-1104.
[10]	LIU Yongjuan,ZHANG Zhihong. A Research of Technological Conditions on Modified Fla Ash Filled Sodium Polyacrylate Superabsorbent Polymer[J]. Energy Environ Prot,2011,25(4):29-32(in Chinese). 刘永娟,张治红. 改性粉煤灰填充聚丙烯酸钠高吸水性凝胶合成工艺研究[J]. 能源环境保护,2011,25(4):29-32.
[11]	Ahmaruzzaman M. A Review on the Utilization of Fly Ash[J]. Prog Energy Combust Sci,2000,36(3):327-363.
[12]	GENG Pengfei,GAO Shuai,CHU Fengge. Comprehensive Utilization of Fly Ash[J]. Clean Coal Technol,2012,18(2):102-104(in Chinese). 耿朋飞,高帅,楚风格. 粉煤灰的综合利用[J]. 洁净煤技术,2012,18(2):102-104.
[13]	SHEN Junfeng. Study on Lean Soil Improvement for Planting in Baotou Trialarea,Inner Mongolia, China, by Adding Coal Ash, Reservoir Sediments and Sewage Sludge[D]. Beijing:China University of Geosciences,2002(in Chinese). 申俊峰. 粉煤灰水库淤积物和污水沉淀物改良砂质贫瘠土壤植树种草的研究—以内蒙古包头试验区为例[D]. 北京:中国地质大学,2002.
[14]	LING Hui,SHEN Shangyue,FAN Liren,et al.Preparation for Fly Ash/Sodium Polyacrylate Super Absorbent Polymer Composite Material[J]. Funct Mater,2006,11(37):1812-1815(in Chinese). 凌辉,沈上越,范力仁,等. 粉煤灰/聚丙烯酸钠高吸水复合材料的研制[J]. 功能材料,2006,11(37):1812-1815.
[15]	XU Jieming,XIE Jimin,Zhu Jianjun. Study on Preparing Nanosized SiO2·xH2O from Fly Ash by Gas-phase Method[J]. Inorg Chem Ind,2006,38(7):54-56 (in Chinese). 徐洁明,谢吉民,朱建军. 粉煤灰气相法制备纳米白炭黑研究[J]. 无机盐工业,2006,38(7):54-56.
[16]	AN Jinpeng,LU Zhongyuan,YAN Yun. Fly Ash Based Geopolymers Solidification Material Modified by Blending with Natural Zeolite[J]. J Nucl Radiochem,2008,30(3):134-141(in Chinese). 安金鹏,卢忠远,严云. 沸石改性粉煤灰地聚物水泥固化材料的研究[J]. 核化学与放射化学,2008,30(3):134-141.
[17]	LIU Shuqiong,LIN Qiuyue. Discussion on Absorbency of the Poly(acrylic acid-acrylamide) Resin[J]. Guangdong Chem Ind,2013,40(24):193-195(in Chinese). 刘淑琼,林秋月. 聚丙烯酸凝胶吸液性能的条件探讨[J]. 广东化工,2013,40(24):193-195.
[18]	ZHANG Xiaohong,CUI Bijiang,CUI Yingde. Synthesis and Characterization of Poly(sodium acrylate)/Kaol in Superabsorbent Composite[J]. Fine Chem,2003,22(6):602-605(in Chinese). 张小红,崔笔江,崔英德. 聚丙烯酸钠/高岭土复合高吸水性凝胶的制备、结构与性能[J]. 精细化工,2003,22(6):602-605.
[19]	JIN Shuping,YUE Guoren,ZHANG Feng,et al.Salt Resistance Improvement of Poly acrylic Acid Gel by Activated Carbon Complexand Its Swelling Mechanism[J]. Chinese J Appl Chem,2012,29(2):166-173(in Chinese). 金淑萍,岳国仁,张锋,等. 活性炭复合改善聚丙烯酸凝胶耐盐性及其溶胀机理[J]. 应用化学,2012,29(2):166-173.
[20]	LI Xiang,LI Xiaoyan. Preparation of Highly Bibulous and Moist-holding Composite Materials and Effects of pH Values on Their Bibulous Properties[J]. Chem Ind Times,2011,25(5):22-24(in Chinese). 李翔,李晓燕. 高吸水保水复合材料的研究及pH值对其吸水性能的影响研究[J]. 化学时刊,2011,25(5):22-24.
[21]	Wdowin M,Franus Ma,Panek R,et al.The Conversion Technology of Fly Ash into Zeolites[J]. Clean Technol Environ Policy,2014,16(1):1217-1223.
[22]	Yung K T. Mri Measurements of T1, T2 and D for Gels Undergoing Volume Phase Transition[J]. Magn Reson Imaging,2003,21(2):135-144.
[23]	Falk B,Garramone S,Shivkumar S. Diffusion Coefficient of Paracetamol in a Chitosan Hydrogel[J]. Mater Lett,2004,58(26):3261-3265.
[24]	Hopkinson I,Jones R A L, Black S,et al. Fickian and Case Ⅱ Diffusion of Water into Amylose:A Stray Field NMR Study[J]. Carbohydr Polym,1997,34(1):39-47.
[25]	Jin S P,Bian F L,Liu M Z,et al.Swelling Mechanism of Porous P(VP-co-MAA)/ PNIPAM Semi-IPN Hydrogels with Various Pore Sizes Prepared by a Freeze Treatment[J]. Polym Int,2009,58(2):142-148.
[26]	TIAN Yilong,FU Guorei. Research on Properties of Superabsorbent Polylmer[J]. New Chem Mater,2003,31(9):22-25(in Chinese). 田义龙,付国瑞. 高吸水性凝胶的性能研究[J]. 化工新型材料,2003,31(9):22-25.
[27]	Jin S P,Wang Y S,He J F,et al.Preparation and Properties of a Degradable Interpenetrating Polymer Networks Based on Starch with Water Retention, Amelioration of Soil, and Slow Release of Nitrogen and Phosphorus Fertilizer[J]. J Appl Polym Sci,2013,128(1):407-415.