壳聚糖/阳离子聚丙烯酰胺水分散体系的研究
|
摘要
阳离子聚丙烯酰胺因含有阳离子基团而具有特殊功效,是目前功能高分子研究领域的热点之一。水分散聚合技术具有反应过程简单,不使用有机溶剂等优点,是制备聚丙烯酰胺的一种环境友好型新技术。水分散聚合体系中的分散稳定剂是影响分散聚合过程的关键因素,对分散聚合有着重要的影响,而目前水分散聚合应用的分散剂大多集中在人工合成的均聚物或共聚物,对天然高分子聚合物的应用鲜见报道。本论文将天然高分子聚合物——壳聚糖作为新型分散剂引入到阳离子聚丙烯酰胺水分散体系中,对该环境友好型水分散阳离子聚丙烯酰胺的制备规律进行了细致的研究,通过多种表征方法详细表征了聚合物的结构,并且探讨了壳聚糖/阳离子聚丙烯酰胺产品的絮凝性能。
1.以壳聚糖(Cts)为分散剂,丙烯酰胺(AM)和阳离子共聚单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)为主要单体原料,选择水溶性偶氮化合物(V50)为引发剂,在氯化钠的弱酸溶液中采用水分散聚合制备了稳定的Cts/CPAM聚合物。
2.在弱酸条件下(pH = 5.5)系统考察了单体用量、单体配比AM/DMC(质量比)、分散剂用量、无机盐用量、引发剂用量、反应温度等因素对水分散聚合反应、产品特性(分子量)和体系稳定性的影响。
3.通过正交试验法确定了较佳的合成工艺条件:分散剂用量为1.50 %,无机盐的用量为17.50 %,引发剂用量为0.042‰,反应温度为60.0℃。
4.利用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、热失重(TGA)等分析方法对聚合物产品进行了表征,从微观角度对产品的结构性质进行了细致的研究。结合前面单因素实验分析,可以推测壳聚糖作为分散剂时,在AM与DMC聚合的过程中,壳聚糖也接枝到聚合物分子中,使体系产生了一种自稳定的分散作用。该方法制备的聚合物颗粒细小、分布均匀,热性稳定性能较高。
5.以质量分数为1‰的高岭土模拟废水进行絮凝实验,系统考察了水分散型Cts/CPAM的投加量、温度等因素对絮凝性能的影响。实验表明:该聚合物具有投加量少、絮凝性能良好的特点,而且聚合物的絮凝效果受pH变化的影响较小,对温度不敏感,因此该聚合物具有较广的使用范围。
6.通过分析絮体的结构特征,探讨了聚合物的絮凝机理。实验结果表明:聚合物处理高岭土模拟废水所产生的絮体具有较明显的分形特征,微絮体与絮凝聚集体之间的吸附架桥现象明显。
Cationic polyacrylamide with cation group could prove significant special effects, so it had been one of the hot researchs in the main researeh areas of functional polymers. Aqueous dispersion polymerization was a new excellent method which had many advantages such as simplicity in process, solvent-free and so on. The stabilizer was important to the aqueous dispersion polymerization as the key factor in the system, the most commonly used stabilizers were synthetic copolymers and homopolymers; but the natural polymers was not reported. In the thesis, chitosan(Cts) was introduced into aqueous dispersion polymerization of cation polyacrylamide as new dispersant. The preparation of environment-friendly aqueous dispersion of cationic polyacrylamide were detailedly investigated. The structure of copolymer was characterized by various methods. Meanwhile, the performances of the coagulation-flocculation were discussed.
1. This research selected chitosan as dispersant stabilizer, acrylamide(AM) and cationic monomer dimethylaminoethyl methacrylate methyl chloride (DMC) as main raw materials, and azo-compounds(V50) as initiator, the cationic polyelectrolyte of Cts/CPAM was synthesized by aqueous dispersion polymerization in the sodium chloride solution with weak acid.
2. The effects of varying factors on the polymerization, the product character (i.e. molecular weight) and the stability of the system were investigated including the dosage of monomers, dispersant, sodium chloride and the dosage of initiator, the mass ratios of AM/DMC, the reaction temperature and so on.
3. By the orthogonal experiment, the optimum conditions of synthesis were determined as follows, the dosage of dispersant 1.50 %, the concentration of inorganic salt 17.50 %, the concentration of initiator 0.042‰and the react temperature 60.0℃.
4. The dispersion copolymers were characterized with Fourier Transform Infra-Red (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetry analysis (TGA). The property of the copolymer was researched with microscopic viewpoint. Combined with previous discussion of the single factor experiment, it was speculated that Cts was grafed to the copolymer of AM and DMC in the reaction process, making the system generated self-stabilization. And the copolymer particles were smaller and homogeneous, its thermal stability was good.
5. The high molecular weight Cts/CPAM was used as flocculant to treat kaolin waste water. The influences of the concentration of the copolymer, the temperature and stirring rate etc. on the flocculation efficiency were investigated. It was found that the dosage was few, but the flocculating effect was good. In addition, the flocculating property had the advantages, such as small pH effeet and wide temperature range.
6. The flocculating mechanism of the copolymer was discussed based on the floc form. The results illustrated that the flocs of kaolin treated by the coplymer had obviously features of fractal, and the performance of absorbing and bridging was well between microflocs and flocculated aggregates.
1.以壳聚糖(Cts)为分散剂,丙烯酰胺(AM)和阳离子共聚单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)为主要单体原料,选择水溶性偶氮化合物(V50)为引发剂,在氯化钠的弱酸溶液中采用水分散聚合制备了稳定的Cts/CPAM聚合物。
2.在弱酸条件下(pH = 5.5)系统考察了单体用量、单体配比AM/DMC(质量比)、分散剂用量、无机盐用量、引发剂用量、反应温度等因素对水分散聚合反应、产品特性(分子量)和体系稳定性的影响。
3.通过正交试验法确定了较佳的合成工艺条件:分散剂用量为1.50 %,无机盐的用量为17.50 %,引发剂用量为0.042‰,反应温度为60.0℃。
4.利用红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、热失重(TGA)等分析方法对聚合物产品进行了表征,从微观角度对产品的结构性质进行了细致的研究。结合前面单因素实验分析,可以推测壳聚糖作为分散剂时,在AM与DMC聚合的过程中,壳聚糖也接枝到聚合物分子中,使体系产生了一种自稳定的分散作用。该方法制备的聚合物颗粒细小、分布均匀,热性稳定性能较高。
5.以质量分数为1‰的高岭土模拟废水进行絮凝实验,系统考察了水分散型Cts/CPAM的投加量、温度等因素对絮凝性能的影响。实验表明:该聚合物具有投加量少、絮凝性能良好的特点,而且聚合物的絮凝效果受pH变化的影响较小,对温度不敏感,因此该聚合物具有较广的使用范围。
6.通过分析絮体的结构特征,探讨了聚合物的絮凝机理。实验结果表明:聚合物处理高岭土模拟废水所产生的絮体具有较明显的分形特征,微絮体与絮凝聚集体之间的吸附架桥现象明显。
Cationic polyacrylamide with cation group could prove significant special effects, so it had been one of the hot researchs in the main researeh areas of functional polymers. Aqueous dispersion polymerization was a new excellent method which had many advantages such as simplicity in process, solvent-free and so on. The stabilizer was important to the aqueous dispersion polymerization as the key factor in the system, the most commonly used stabilizers were synthetic copolymers and homopolymers; but the natural polymers was not reported. In the thesis, chitosan(Cts) was introduced into aqueous dispersion polymerization of cation polyacrylamide as new dispersant. The preparation of environment-friendly aqueous dispersion of cationic polyacrylamide were detailedly investigated. The structure of copolymer was characterized by various methods. Meanwhile, the performances of the coagulation-flocculation were discussed.
1. This research selected chitosan as dispersant stabilizer, acrylamide(AM) and cationic monomer dimethylaminoethyl methacrylate methyl chloride (DMC) as main raw materials, and azo-compounds(V50) as initiator, the cationic polyelectrolyte of Cts/CPAM was synthesized by aqueous dispersion polymerization in the sodium chloride solution with weak acid.
2. The effects of varying factors on the polymerization, the product character (i.e. molecular weight) and the stability of the system were investigated including the dosage of monomers, dispersant, sodium chloride and the dosage of initiator, the mass ratios of AM/DMC, the reaction temperature and so on.
3. By the orthogonal experiment, the optimum conditions of synthesis were determined as follows, the dosage of dispersant 1.50 %, the concentration of inorganic salt 17.50 %, the concentration of initiator 0.042‰and the react temperature 60.0℃.
4. The dispersion copolymers were characterized with Fourier Transform Infra-Red (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetry analysis (TGA). The property of the copolymer was researched with microscopic viewpoint. Combined with previous discussion of the single factor experiment, it was speculated that Cts was grafed to the copolymer of AM and DMC in the reaction process, making the system generated self-stabilization. And the copolymer particles were smaller and homogeneous, its thermal stability was good.
5. The high molecular weight Cts/CPAM was used as flocculant to treat kaolin waste water. The influences of the concentration of the copolymer, the temperature and stirring rate etc. on the flocculation efficiency were investigated. It was found that the dosage was few, but the flocculating effect was good. In addition, the flocculating property had the advantages, such as small pH effeet and wide temperature range.
6. The flocculating mechanism of the copolymer was discussed based on the floc form. The results illustrated that the flocs of kaolin treated by the coplymer had obviously features of fractal, and the performance of absorbing and bridging was well between microflocs and flocculated aggregates.
引文
[1]夏军,刘春蓁,任国玉.气候变化对我国水资源影响研究面临的机遇与挑战[J].地球科学进展, 2011,26(1): 1-12.
[2] Lee K E, Morad N, Poh B T, et al. Comparative study on the effectiveness of hydrophobically modified cationic polyacrylamide groups in the flocculation of kaolin[J]. Desalination, 2011,270(1/2/3): 206-213.
[3] Tekin N, Din er A, Demirbas, et al. Adsorption of cationic polyacrylamide (C-PAM) on expanded perlite[J]. Applied Clay Science, 2010,50(1): 125-129
[4] Wu Y, Wang C, Xu J. Aqueous dispersion polymerization of amphoteric polyacrylamide[J]. Journal of applied polymer science, 2010,115(2): 1131-1137.
[5] Wu Y, Zhang N. Aqueous photo-polymerization of cationic polyacrylamide with hybrid photo-initiators[J]. Journal of Polymer Research, 2009,16(6): 647-653.
[6] Xu J, Wu Y, Wang C, et al. Dispersion polymerization of acrylamide with 2-acrylamide-2-methyl-1-propane sulfonate in aqueous solution of sodium sulfate[J]. J Polym Res, 2009,16(5): 569-575.
[7]陈庆芬,武玉民,毕建美,等.水分散型阳离子聚丙烯酰胺的合成与应用[J].高分子材料科学与工程, 2008,24(3): 75-78.
[8]蒋挺大.壳聚糖[M].北京:化学工业出版社, 2007.
[9] Chen CH, Wang FY, Mao CF, et al. Studies of chitosan. I. Preparation and characterization of chitosan/poly (vinyl alcohol) blend films[J]. Journal of applied polymer science, 2007,105(3): 1086-1092.
[10] Alt?n?s?k A, Seki Y, Yurdako K. Preparation and characterization of chitosan/KSF biocomposite film[J]. Polymer Composites, 2009,30(8): 1035-1042.
[11] Lee E J, Shin D S, Kim H E, et al. Membrane of hybrid chitosan-silica xerogel for guided bone regeneration[J]. Biomaterials, 2009,30(5): 743-750.
[12]王军,周本权,杨许召,等.低聚壳聚糖的制备及应用研究进展[J].日用化学工业, 2010,40(2): 124-128.
[13]周景润,辛梅华,李明春.壳聚糖季铵盐的制备及其应用研究进展[J].化工进展, 2008,27(5): 679-686.
[14]程德书,李明春,辛梅华.壳聚糖及其衍生物固载环糊精的制备及应用研究进展[J].化工进展, 2008,27(6): 819-824.
[15]陶凤,席隆一,邓胜伟,等.叶酸接枝聚乙二醇化壳聚糖衍生物的合成[J].化学研究与应用, 2010,22(2): 182-185.
[16]谢英,李明春,辛梅华,等.烷基化改性壳聚糖制备条件对酚类化合物吸附的影响[J].应用化学, 2008,25(10): 1201-1204.
[17]车小琼,孙庆申,赵凯.甲壳素和壳聚糖作为天然生物高分子材料的研究进展[J].高分子通报, 2008,(2): 45-49.
[18]邬思辉,苏政权.壳聚糖及其衍生物作为药物载体研究进展[J].现代生物医学进展, 2008,8(8): 1588-1591.
[19]杨靖先,贺大庆,吴军,等.在铈盐引发下甲壳质膜与甲基丙烯酸甲酯的接枝聚合反应[J].中国海洋大学学报(自然科学版), 1984,14(4): 58-62.
[20]张光华,谢曙辉,郭炎,等.一类新型壳聚糖改性聚合物絮凝剂的制备与性能[J].西安交通大学学报, 2002,36(5): 541-544.
[21]唐星华,舒红英,吴再国. CTS―AM―DMC强阳离子型天然高分子絮凝剂的合成[J].水处理技术, 2005,31(9): 52-55.
[22]方道斌,郭睿威,哈润华,等.丙烯酰胺聚合物[M].北京:化学工业出版社, 2006.
[23]王允雨,聂容春,申秀梅,等.两性离子型聚丙烯酰胺的研究进展[J].安徽化工, 2010,36(6): 12-15.
[24]陈密峰,杨健茂,张秀娟,等.二甲基二烯丙基氯化铵(DMDAAC)及其聚合物研究新进展[J].化学世界, 2003,44(9): 496-499.
[25]张凯,雷毅,王宇光,等.单分散聚苯乙烯微球的制备及影响因素研究[J].功能高分子学报, 2002,15(2): 189-193.
[26]邓敏,扈蓉,何培新.水溶性单体分散聚合的研究进展[J].胶体与聚合物, 2005,23(4): 35-40.
[27]王淑霞.疏水缔合型两性聚丙烯酰胺絮凝剂[J].中华纸业, 2009,(22): 106-106.
[28]温会涛.聚丙烯酰胺的合成及其在水处理中的应用进展[A].2008年中国精细化工协会水处理化学品行业年会论文集[C]. 2008.
[29]尚宏周,刘建平,郑玉斌,等.阳离子聚丙烯酰胺类高聚物的研究进展[J].现代化工, 2007,27(z1): 118-121.
[30]隋智慧,刘安军,赵欣.阳离子高分子絮凝剂处理造纸废水的研究[J].中国造纸学报, 2007,22(3): 52-56.
[31] Zeng X, Wei W, Li X, et al. Direct electrochemistry and electrocatalysis of hemoglobin entrapped in semi-interpenetrating polymer network hydrogel based on polyacrylamide and chitosan[J]. Bioelectrochemistry, 2007,71(2): 135-141.
[32]孙德君,匡洞庭.驱油用超高分子量聚丙烯酰胺的合成[J].精细石油化工, 2001,(5): 13-15.
[33]刘志良,齐宁,李晓军,等.丙烯酰胺的分散聚合研究进展及在油田中应用[J].大庆石油地质与开发, 2009,28(6): 218-222.
[34] You L, Lu F, Li D, et al. Preparation and flocculation properties of cationic starch/chitosan crosslinking-copolymer[J]. Journal of hazardous materials, 2009,172(1): 38-45.
[35]高景恒,裴宁,楚学慧.医用聚丙烯酰胺水凝胶临床应用的国内外进展[J].实用美容整形外科杂志, 2003,14(4).
[36]员学锋,吴普特.聚丙烯酰胺(PAM)的改土及增产效应[J].水土保持研究, 2002,9(2): 55-58.
[37]张学佳,纪巍,康志军,等.聚丙烯酰胺应用进展[J].化工中间体, 2008,(5): 34-39.
[38]程丽鸿.国内聚丙烯酰胺市场研究[J].精细与专用化学品, 2009,(7): 29-30.
[39] Hong J, Hong CK, Shim SE. Synthesis of polystyrene microspheres by dispersion polymerization using poly (vinyl alcohol) as a steric stabilizer in aqueous alcohol media[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007,302(1/2/3): 225-233.
[40]罗正平,张秋禹.分散聚合研究[J].高分子通报, 2002,(5): 35-40.
[41] Yokota S, Ohta T, Kitaoka T, et al. Preparation and characteristics of anionic polyacrylamides containing direct dye with a high affinity for cellulose[J]. BioResources, 2009,4(2): 497-508.
[42] Zhang J, Li A, Wang A. Study on superabsorbent composite. VI. Preparation, characterization and swelling behaviors of starch phosphate-graft-acrylamide/attapulgite superabsorbent composite[J]. Carbohydrate Polymers, 2006,65(2): 150-158.
[43] Ceska G. The effect of carboxylic monomers on surfactant-free emulsion copolymerization[J]. Journal of applied polymer science, 1974,18(2): 427-437.
[44] AraújoP.H.H, Pinto J. Mathematical modeling of dispersion polymerizations study of the styrene polymerization in ethanol[J]. Brazilian Journal of Chemical Engineering, 2000,17(4/5/6/7): 383-394.
[45] PaineA.J. Journal of Colloid and Interface Science, 1990,(138): 157-169.
[46] Liu X, Chen D, Yue Y, et al. Dispersion copolymerization of acrylamide with acrylic acid in an aqueous solution of ammonium sulfate: Synthesis and characterization[J]. Journal of applied polymer science, 2006,102(4): 3685-3690.
[47] Chen D, Liu X, Yue Y, et al. Dispersion copolymerization of acrylamide with quaternary ammonium cationic monomer in aqueous salts solution[J]. European polymer journal, 2006,42(6): 1284-1297.
[48]张凯,曾敏,雷毅,等.分散聚合反应[J].化学通报, 2002,65(w85): 1-5.
[49]曹同玉,戴兵.分散聚合稳定机理及动力学研究[J].高分子材料科学与工程, 1998,14(1): 31-34.
[50] Tuncel A., Kahtaman R., Piskin E. Journal of applied polymer science, 1994,51: 1485–1498.
[51] Lok.K.P, Ober.C.K. Canadian Journal of Chemistry, 1985,63: 209-216.
[52]叶强,张志成,葛学武.分散聚合的研究进展――(Ⅰ)各种单体的分散均聚合研究概述[J].高分子材料科学与工程, 2004,20(3): 5-8.
[53]王梓,徐冉,李风亭,等.分散聚合法合成阳离子聚丙烯酰胺研究进展及应用[J].工业用水与废水, 2010,41(1): 10-13.
[54]张彦昌,王冬梅,赵献增,等.“水包水”型阳离子聚丙烯酰胺乳液的合成[J].化学研究与应用, 2010,22(4): 519-520.
[55]陈庆芬,许军,王传兴,等.水分散聚合法制备DMDAAC/AM共聚物[J].高校化学工程学报, 2007,21(4): 705-709.
[56] Wu Y, Chen Q, Xu J, et al. Aqueous dispersion polymerization of acrylamide with quaternary ammonium cationic comonomer[J]. Journal of applied polymer science, 2008,108(1): 134-139.
[57]王玉峰,胡惠仁.阳离子聚丙烯酰胺水包水乳液的分散聚合及其应用[J].中国造纸, 2009,28(2): 26-31.
[58]陈菊勤,关一峰,顾文忠.胺甲基聚丙烯酰胺的合成及其絮凝作用考察[J].工业水处理, 1993,13(5): 23-26.
[59]马喜平,邵定波.阳离子化聚丙烯酰胺的合成及絮凝性能研究[J].油田化学, 1999,16(1): 37-40.
[60]李卓美.一种新型阳离子聚丙烯酰胺[J].广州化工, 1995,23(4): 60-63.
[61]黄祥虎.粉状阳离子聚丙烯酰胺的研制[J].高分子材料科学与工程, 1992,4: 120-122.
[62]杨旭,赵立志.阳离子絮凝剂研制[J].重庆环境科学, 1995,17(5): 17-19.
[63] Yang Z, Gao B, Li C, et al. Synthesis and characterization of hydrophobically associating cationic polyacrylamide[J]. Chem Eng J, 2010,161(1/2/3): 27-33.
[64] Wang L J, Wang J P, Zhang S J, et al. A water-soluble cationic flocculant synthesized by dispersion polymerization in aqueous salts solution[J]. Separation and Purification Technology, 2009,67(3): 331-335.
[65]孙艳霞,车吉泰.高分子量丙烯酰胺-DAC共聚物的研制[J].精细石油化工进展, 2003,4(9): 44-45.
[66]徐雄立,郦华兴.天然高分子化合物改性聚丙烯酰胺[J].合成材料老化与应用, 2001,(1): 20-23.
[67] Singh V, Tiwari A, Tripathi D, et al. Microwave enhanced synthesis of chitosan-graft-polyacrylamide[J]. Polymer, 2006,47(1): 254-260.
[68]张文轩,尚亚波,袁博,等.壳聚糖改性絮凝剂絮凝性能的研究[J].高分子通报, 2010,(4): 49-54.
[69]刘志良,齐宁,李晓军,等.丙烯酰胺的分散聚合研究进展及在油田中应用[J].大庆石油地质与开发, 2009,28(6): 218-222.
[70]张春芳,沈一丁.阳离子型聚丙烯酰胺在造纸工业中的应用[J].西北轻工业学院学报, 2001,19(4): 75-77.
[71] Kawaguchi S, Ito K. Dispersion polymerization[J]. Polymer Particles, 2005,175: 299-328.
[72] Song B, Cho M, Yoon K, et al. Dispersion polymerization of acrylamide with quaternary ammonium cationic comonomer in aqueous solution[J]. Journal of applied polymer science, 2003,87(7): 1101-1108.
[73] Liu X, Chen Q, Xu K, et al. Preparation of polyacrylamide aqueous dispersions using poly (sodium acrylic acid) as stabilizer[J]. Journal of applied polymer science, 2009,113(4): 2693-2701.
[74] Yuan B, Shang Y, Lu Y B, et al. The flocculating properties of chitosan-graft-polyacrylamide flocculants (I)—effect of the grafting ratio[J]. Journal of applied polymer science, 2010,117(4): 1876-1882.
[75] GB12005.10-92.聚丙烯酰胺分子量测定方法[S].
[76] Wang X, Yue Q, Gao B, et al. Dispersion copolymerization of acrylamide and dimethyl diallyl ammonium chloride in ethanol-water solution[J]. Journal of Applied Polymer Science, 2011,120(3): 1496-1502.
[77] Ye Q, Zhang Z, Ge X. Highly efficient flocculant synthesized through the dispersion copolymerization of water-soluble monomers induced byγ-ray irradiation: Synthesis and polymerization kinetics[J]. Journal of Applied Polymer Science, 2003,89(8): 2108-2115.
[78] Xu J, Wu Y, Wang C, et al. Dispersion polymerization of acrylamide with 2-acrylamide-2-methyl-1-propane sulfonate in aqueous solution of sodium sulfate[J]. Journal of Polymer Research, 2009,16(5): 569-575.
[79] Rabiee A. Acrylamide-based anionic polyelectrolytes and their applications: A survey[J]. Journal of Vinyl and Additive Technology, 2010,16(2): 111-119.
[80] Lu J, Peng B, Li M, et al. Dispersion polymerization of anionic polyacrylamide in an aqueous salt medium[J]. Petroleum Science, 2010,7(3): 410-415.
[81]梁升,纪欢欢,李露,等.氨基酸离子液体对壳聚糖溶解性能的影响[J].高分子材料科学与工程, 2010,(2): 70-72.
[82]潘祖仁.高分子化学[M].化学工业出版社, 2007.
[83] Singh V, Sharma A, Sanghi R. Poly (acrylamide) functionalized chitosan: An efficient adsorbent for azo dyes from aqueous solutions[J]. J Hazard Mater, 2009,166(1): 327-335.
[84] Elizalde-Pe?a E, Flores-Ramirez N, Luna-Barcenas G, et al. Synthesis and characterization of chitosan-g-glycidyl methacrylate with methyl methacrylate[J]. Eur Polym J, 2007,43(9): 3963-3969.
[85] Tiwari A, Singh V. Synthesis and characterization of electrical conducting chitosan-graft-polyaniline[J]. eXPRESS Polymer Letters, 2007,1(5): 308-317.
[86] Li Y, Liu J, Du G, et al. Reversible heat-set organogel based on supramolecular interactions ofβ-cyclodextrin in N, N-dimethylformamide[J]. J Phys Chem B, 2010,114(32): 10321-10326.
[87] Yamada Y, Sakamoto T, Gu S, et al. Soap-free synthesis for producing highly monodisperse, micrometer-sized polystyrene particles up to 6μm[J]. J Colloid Interface Sci, 2005,281(1): 249-252.
[88] Erbil H. Surface chemistry of solid and liquid interfaces[M]. India: Wiley-Blackwell, 2006.
[89] Duan W, Chen C, Jiang L, et al. Preparation and characterization of the graft copolymer of chitosan with poly [rosin-(2-acryloyloxy) ethyl ester][J]. Carbohydr Polym, 2008,73(4): 582-586.
[90]徐晓军.化学絮凝剂作用原理[M].北京:科学出版社, 2005.
[91]刘明华.有机高分子絮凝剂的制备及应用[M].北京:化学工业出版社, 2006.
[92] Tian D, Wu X, Liu C, et al. Synthesis and flocculation behavior of cationic konjac glucomannan containing quaternary ammonium substituents[J]. Journal of applied polymer science, 2010,115(4): 2368-2374.
[93] Zhang Z, Xia S, Zhao J, et al. Characterization and flocculation mechanism of high efficiency microbial flocculant TJ-F1 from Proteus mirabilis[J]. Colloids and Surfaces B: Biointerfaces, 2010,75(1): 247-251.
[94] Ho Y, Norli I, Alkarkhi A F M, et al. Characterization of biopolymeric flocculant (pectin) and organic synthetic flocculant (PAM): A comparative study on treatment andoptimization in kaolin suspension[J]. Bioresource technology, 2010,101(4): 1166-1174.
[95] Yang Z H, Huang J, Zeng G M, et al. Optimization of flocculation conditions for kaolin suspension using the composite flocculant of MBFGA1 and PAC by response surface methodology[J]. Bioresource technology, 2009,100(18): 4233-4239.
[96]吕广明,贺新.高分子聚合物在絮凝过程中作用及机理探讨[J].辽宁化工, 1998,27(6): 304-306.
[97]王峰,李义久,倪亚明.丙烯酰胺接枝共聚壳聚糖絮凝剂的合成及絮凝性能研究[J].工业水处理, 2003,23(12): 45-47.
[98] Krishnamoorthi S, Adhikary P, Mal D, et al. Novel polymeric flocculants based on polyacrylamide grafted dextran in kaolin suspension[J]. Journal of applied polymer science, 2010,118: 3539–3544.
[99] Lee K E, Morad N, Poh B T, et al. Comparative study on the effectiveness of hydrophobically modified cationic polyacrylamide groups in the flocculation of kaolin[J]. Desalination, 2011,270: 206-213.
[100]褚衍洋,孙晓杰.丙烯酰胺改性壳聚糖絮凝剂处理焦化废水[J].污染防治技术, 2007,20(2): 6-8.
[101]钟润生,张锡辉,肖峰,等.絮体分形结构对沉淀速度影响研究[J].环境科学, 2009,30(8): 2353-2357.
[102] Verney R, Lafite R, Brun-Cottan J C. Flocculation potential of estuarine particles: the importance of environmental factors and of the spatial and seasonal variability of suspended particulate matter[J]. Estuaries and Coasts, 2009,32(4): 678-693.
[103] Son M, Hsu T J. Flocculation model of cohesive sediment using variable fractal dimension[J]. Environmental Fluid Mechanics, 2008,8(1): 55-71.
[2] Lee K E, Morad N, Poh B T, et al. Comparative study on the effectiveness of hydrophobically modified cationic polyacrylamide groups in the flocculation of kaolin[J]. Desalination, 2011,270(1/2/3): 206-213.
[3] Tekin N, Din er A, Demirbas, et al. Adsorption of cationic polyacrylamide (C-PAM) on expanded perlite[J]. Applied Clay Science, 2010,50(1): 125-129
[4] Wu Y, Wang C, Xu J. Aqueous dispersion polymerization of amphoteric polyacrylamide[J]. Journal of applied polymer science, 2010,115(2): 1131-1137.
[5] Wu Y, Zhang N. Aqueous photo-polymerization of cationic polyacrylamide with hybrid photo-initiators[J]. Journal of Polymer Research, 2009,16(6): 647-653.
[6] Xu J, Wu Y, Wang C, et al. Dispersion polymerization of acrylamide with 2-acrylamide-2-methyl-1-propane sulfonate in aqueous solution of sodium sulfate[J]. J Polym Res, 2009,16(5): 569-575.
[7]陈庆芬,武玉民,毕建美,等.水分散型阳离子聚丙烯酰胺的合成与应用[J].高分子材料科学与工程, 2008,24(3): 75-78.
[8]蒋挺大.壳聚糖[M].北京:化学工业出版社, 2007.
[9] Chen CH, Wang FY, Mao CF, et al. Studies of chitosan. I. Preparation and characterization of chitosan/poly (vinyl alcohol) blend films[J]. Journal of applied polymer science, 2007,105(3): 1086-1092.
[10] Alt?n?s?k A, Seki Y, Yurdako K. Preparation and characterization of chitosan/KSF biocomposite film[J]. Polymer Composites, 2009,30(8): 1035-1042.
[11] Lee E J, Shin D S, Kim H E, et al. Membrane of hybrid chitosan-silica xerogel for guided bone regeneration[J]. Biomaterials, 2009,30(5): 743-750.
[12]王军,周本权,杨许召,等.低聚壳聚糖的制备及应用研究进展[J].日用化学工业, 2010,40(2): 124-128.
[13]周景润,辛梅华,李明春.壳聚糖季铵盐的制备及其应用研究进展[J].化工进展, 2008,27(5): 679-686.
[14]程德书,李明春,辛梅华.壳聚糖及其衍生物固载环糊精的制备及应用研究进展[J].化工进展, 2008,27(6): 819-824.
[15]陶凤,席隆一,邓胜伟,等.叶酸接枝聚乙二醇化壳聚糖衍生物的合成[J].化学研究与应用, 2010,22(2): 182-185.
[16]谢英,李明春,辛梅华,等.烷基化改性壳聚糖制备条件对酚类化合物吸附的影响[J].应用化学, 2008,25(10): 1201-1204.
[17]车小琼,孙庆申,赵凯.甲壳素和壳聚糖作为天然生物高分子材料的研究进展[J].高分子通报, 2008,(2): 45-49.
[18]邬思辉,苏政权.壳聚糖及其衍生物作为药物载体研究进展[J].现代生物医学进展, 2008,8(8): 1588-1591.
[19]杨靖先,贺大庆,吴军,等.在铈盐引发下甲壳质膜与甲基丙烯酸甲酯的接枝聚合反应[J].中国海洋大学学报(自然科学版), 1984,14(4): 58-62.
[20]张光华,谢曙辉,郭炎,等.一类新型壳聚糖改性聚合物絮凝剂的制备与性能[J].西安交通大学学报, 2002,36(5): 541-544.
[21]唐星华,舒红英,吴再国. CTS―AM―DMC强阳离子型天然高分子絮凝剂的合成[J].水处理技术, 2005,31(9): 52-55.
[22]方道斌,郭睿威,哈润华,等.丙烯酰胺聚合物[M].北京:化学工业出版社, 2006.
[23]王允雨,聂容春,申秀梅,等.两性离子型聚丙烯酰胺的研究进展[J].安徽化工, 2010,36(6): 12-15.
[24]陈密峰,杨健茂,张秀娟,等.二甲基二烯丙基氯化铵(DMDAAC)及其聚合物研究新进展[J].化学世界, 2003,44(9): 496-499.
[25]张凯,雷毅,王宇光,等.单分散聚苯乙烯微球的制备及影响因素研究[J].功能高分子学报, 2002,15(2): 189-193.
[26]邓敏,扈蓉,何培新.水溶性单体分散聚合的研究进展[J].胶体与聚合物, 2005,23(4): 35-40.
[27]王淑霞.疏水缔合型两性聚丙烯酰胺絮凝剂[J].中华纸业, 2009,(22): 106-106.
[28]温会涛.聚丙烯酰胺的合成及其在水处理中的应用进展[A].2008年中国精细化工协会水处理化学品行业年会论文集[C]. 2008.
[29]尚宏周,刘建平,郑玉斌,等.阳离子聚丙烯酰胺类高聚物的研究进展[J].现代化工, 2007,27(z1): 118-121.
[30]隋智慧,刘安军,赵欣.阳离子高分子絮凝剂处理造纸废水的研究[J].中国造纸学报, 2007,22(3): 52-56.
[31] Zeng X, Wei W, Li X, et al. Direct electrochemistry and electrocatalysis of hemoglobin entrapped in semi-interpenetrating polymer network hydrogel based on polyacrylamide and chitosan[J]. Bioelectrochemistry, 2007,71(2): 135-141.
[32]孙德君,匡洞庭.驱油用超高分子量聚丙烯酰胺的合成[J].精细石油化工, 2001,(5): 13-15.
[33]刘志良,齐宁,李晓军,等.丙烯酰胺的分散聚合研究进展及在油田中应用[J].大庆石油地质与开发, 2009,28(6): 218-222.
[34] You L, Lu F, Li D, et al. Preparation and flocculation properties of cationic starch/chitosan crosslinking-copolymer[J]. Journal of hazardous materials, 2009,172(1): 38-45.
[35]高景恒,裴宁,楚学慧.医用聚丙烯酰胺水凝胶临床应用的国内外进展[J].实用美容整形外科杂志, 2003,14(4).
[36]员学锋,吴普特.聚丙烯酰胺(PAM)的改土及增产效应[J].水土保持研究, 2002,9(2): 55-58.
[37]张学佳,纪巍,康志军,等.聚丙烯酰胺应用进展[J].化工中间体, 2008,(5): 34-39.
[38]程丽鸿.国内聚丙烯酰胺市场研究[J].精细与专用化学品, 2009,(7): 29-30.
[39] Hong J, Hong CK, Shim SE. Synthesis of polystyrene microspheres by dispersion polymerization using poly (vinyl alcohol) as a steric stabilizer in aqueous alcohol media[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007,302(1/2/3): 225-233.
[40]罗正平,张秋禹.分散聚合研究[J].高分子通报, 2002,(5): 35-40.
[41] Yokota S, Ohta T, Kitaoka T, et al. Preparation and characteristics of anionic polyacrylamides containing direct dye with a high affinity for cellulose[J]. BioResources, 2009,4(2): 497-508.
[42] Zhang J, Li A, Wang A. Study on superabsorbent composite. VI. Preparation, characterization and swelling behaviors of starch phosphate-graft-acrylamide/attapulgite superabsorbent composite[J]. Carbohydrate Polymers, 2006,65(2): 150-158.
[43] Ceska G. The effect of carboxylic monomers on surfactant-free emulsion copolymerization[J]. Journal of applied polymer science, 1974,18(2): 427-437.
[44] AraújoP.H.H, Pinto J. Mathematical modeling of dispersion polymerizations study of the styrene polymerization in ethanol[J]. Brazilian Journal of Chemical Engineering, 2000,17(4/5/6/7): 383-394.
[45] PaineA.J. Journal of Colloid and Interface Science, 1990,(138): 157-169.
[46] Liu X, Chen D, Yue Y, et al. Dispersion copolymerization of acrylamide with acrylic acid in an aqueous solution of ammonium sulfate: Synthesis and characterization[J]. Journal of applied polymer science, 2006,102(4): 3685-3690.
[47] Chen D, Liu X, Yue Y, et al. Dispersion copolymerization of acrylamide with quaternary ammonium cationic monomer in aqueous salts solution[J]. European polymer journal, 2006,42(6): 1284-1297.
[48]张凯,曾敏,雷毅,等.分散聚合反应[J].化学通报, 2002,65(w85): 1-5.
[49]曹同玉,戴兵.分散聚合稳定机理及动力学研究[J].高分子材料科学与工程, 1998,14(1): 31-34.
[50] Tuncel A., Kahtaman R., Piskin E. Journal of applied polymer science, 1994,51: 1485–1498.
[51] Lok.K.P, Ober.C.K. Canadian Journal of Chemistry, 1985,63: 209-216.
[52]叶强,张志成,葛学武.分散聚合的研究进展――(Ⅰ)各种单体的分散均聚合研究概述[J].高分子材料科学与工程, 2004,20(3): 5-8.
[53]王梓,徐冉,李风亭,等.分散聚合法合成阳离子聚丙烯酰胺研究进展及应用[J].工业用水与废水, 2010,41(1): 10-13.
[54]张彦昌,王冬梅,赵献增,等.“水包水”型阳离子聚丙烯酰胺乳液的合成[J].化学研究与应用, 2010,22(4): 519-520.
[55]陈庆芬,许军,王传兴,等.水分散聚合法制备DMDAAC/AM共聚物[J].高校化学工程学报, 2007,21(4): 705-709.
[56] Wu Y, Chen Q, Xu J, et al. Aqueous dispersion polymerization of acrylamide with quaternary ammonium cationic comonomer[J]. Journal of applied polymer science, 2008,108(1): 134-139.
[57]王玉峰,胡惠仁.阳离子聚丙烯酰胺水包水乳液的分散聚合及其应用[J].中国造纸, 2009,28(2): 26-31.
[58]陈菊勤,关一峰,顾文忠.胺甲基聚丙烯酰胺的合成及其絮凝作用考察[J].工业水处理, 1993,13(5): 23-26.
[59]马喜平,邵定波.阳离子化聚丙烯酰胺的合成及絮凝性能研究[J].油田化学, 1999,16(1): 37-40.
[60]李卓美.一种新型阳离子聚丙烯酰胺[J].广州化工, 1995,23(4): 60-63.
[61]黄祥虎.粉状阳离子聚丙烯酰胺的研制[J].高分子材料科学与工程, 1992,4: 120-122.
[62]杨旭,赵立志.阳离子絮凝剂研制[J].重庆环境科学, 1995,17(5): 17-19.
[63] Yang Z, Gao B, Li C, et al. Synthesis and characterization of hydrophobically associating cationic polyacrylamide[J]. Chem Eng J, 2010,161(1/2/3): 27-33.
[64] Wang L J, Wang J P, Zhang S J, et al. A water-soluble cationic flocculant synthesized by dispersion polymerization in aqueous salts solution[J]. Separation and Purification Technology, 2009,67(3): 331-335.
[65]孙艳霞,车吉泰.高分子量丙烯酰胺-DAC共聚物的研制[J].精细石油化工进展, 2003,4(9): 44-45.
[66]徐雄立,郦华兴.天然高分子化合物改性聚丙烯酰胺[J].合成材料老化与应用, 2001,(1): 20-23.
[67] Singh V, Tiwari A, Tripathi D, et al. Microwave enhanced synthesis of chitosan-graft-polyacrylamide[J]. Polymer, 2006,47(1): 254-260.
[68]张文轩,尚亚波,袁博,等.壳聚糖改性絮凝剂絮凝性能的研究[J].高分子通报, 2010,(4): 49-54.
[69]刘志良,齐宁,李晓军,等.丙烯酰胺的分散聚合研究进展及在油田中应用[J].大庆石油地质与开发, 2009,28(6): 218-222.
[70]张春芳,沈一丁.阳离子型聚丙烯酰胺在造纸工业中的应用[J].西北轻工业学院学报, 2001,19(4): 75-77.
[71] Kawaguchi S, Ito K. Dispersion polymerization[J]. Polymer Particles, 2005,175: 299-328.
[72] Song B, Cho M, Yoon K, et al. Dispersion polymerization of acrylamide with quaternary ammonium cationic comonomer in aqueous solution[J]. Journal of applied polymer science, 2003,87(7): 1101-1108.
[73] Liu X, Chen Q, Xu K, et al. Preparation of polyacrylamide aqueous dispersions using poly (sodium acrylic acid) as stabilizer[J]. Journal of applied polymer science, 2009,113(4): 2693-2701.
[74] Yuan B, Shang Y, Lu Y B, et al. The flocculating properties of chitosan-graft-polyacrylamide flocculants (I)—effect of the grafting ratio[J]. Journal of applied polymer science, 2010,117(4): 1876-1882.
[75] GB12005.10-92.聚丙烯酰胺分子量测定方法[S].
[76] Wang X, Yue Q, Gao B, et al. Dispersion copolymerization of acrylamide and dimethyl diallyl ammonium chloride in ethanol-water solution[J]. Journal of Applied Polymer Science, 2011,120(3): 1496-1502.
[77] Ye Q, Zhang Z, Ge X. Highly efficient flocculant synthesized through the dispersion copolymerization of water-soluble monomers induced byγ-ray irradiation: Synthesis and polymerization kinetics[J]. Journal of Applied Polymer Science, 2003,89(8): 2108-2115.
[78] Xu J, Wu Y, Wang C, et al. Dispersion polymerization of acrylamide with 2-acrylamide-2-methyl-1-propane sulfonate in aqueous solution of sodium sulfate[J]. Journal of Polymer Research, 2009,16(5): 569-575.
[79] Rabiee A. Acrylamide-based anionic polyelectrolytes and their applications: A survey[J]. Journal of Vinyl and Additive Technology, 2010,16(2): 111-119.
[80] Lu J, Peng B, Li M, et al. Dispersion polymerization of anionic polyacrylamide in an aqueous salt medium[J]. Petroleum Science, 2010,7(3): 410-415.
[81]梁升,纪欢欢,李露,等.氨基酸离子液体对壳聚糖溶解性能的影响[J].高分子材料科学与工程, 2010,(2): 70-72.
[82]潘祖仁.高分子化学[M].化学工业出版社, 2007.
[83] Singh V, Sharma A, Sanghi R. Poly (acrylamide) functionalized chitosan: An efficient adsorbent for azo dyes from aqueous solutions[J]. J Hazard Mater, 2009,166(1): 327-335.
[84] Elizalde-Pe?a E, Flores-Ramirez N, Luna-Barcenas G, et al. Synthesis and characterization of chitosan-g-glycidyl methacrylate with methyl methacrylate[J]. Eur Polym J, 2007,43(9): 3963-3969.
[85] Tiwari A, Singh V. Synthesis and characterization of electrical conducting chitosan-graft-polyaniline[J]. eXPRESS Polymer Letters, 2007,1(5): 308-317.
[86] Li Y, Liu J, Du G, et al. Reversible heat-set organogel based on supramolecular interactions ofβ-cyclodextrin in N, N-dimethylformamide[J]. J Phys Chem B, 2010,114(32): 10321-10326.
[87] Yamada Y, Sakamoto T, Gu S, et al. Soap-free synthesis for producing highly monodisperse, micrometer-sized polystyrene particles up to 6μm[J]. J Colloid Interface Sci, 2005,281(1): 249-252.
[88] Erbil H. Surface chemistry of solid and liquid interfaces[M]. India: Wiley-Blackwell, 2006.
[89] Duan W, Chen C, Jiang L, et al. Preparation and characterization of the graft copolymer of chitosan with poly [rosin-(2-acryloyloxy) ethyl ester][J]. Carbohydr Polym, 2008,73(4): 582-586.
[90]徐晓军.化学絮凝剂作用原理[M].北京:科学出版社, 2005.
[91]刘明华.有机高分子絮凝剂的制备及应用[M].北京:化学工业出版社, 2006.
[92] Tian D, Wu X, Liu C, et al. Synthesis and flocculation behavior of cationic konjac glucomannan containing quaternary ammonium substituents[J]. Journal of applied polymer science, 2010,115(4): 2368-2374.
[93] Zhang Z, Xia S, Zhao J, et al. Characterization and flocculation mechanism of high efficiency microbial flocculant TJ-F1 from Proteus mirabilis[J]. Colloids and Surfaces B: Biointerfaces, 2010,75(1): 247-251.
[94] Ho Y, Norli I, Alkarkhi A F M, et al. Characterization of biopolymeric flocculant (pectin) and organic synthetic flocculant (PAM): A comparative study on treatment andoptimization in kaolin suspension[J]. Bioresource technology, 2010,101(4): 1166-1174.
[95] Yang Z H, Huang J, Zeng G M, et al. Optimization of flocculation conditions for kaolin suspension using the composite flocculant of MBFGA1 and PAC by response surface methodology[J]. Bioresource technology, 2009,100(18): 4233-4239.
[96]吕广明,贺新.高分子聚合物在絮凝过程中作用及机理探讨[J].辽宁化工, 1998,27(6): 304-306.
[97]王峰,李义久,倪亚明.丙烯酰胺接枝共聚壳聚糖絮凝剂的合成及絮凝性能研究[J].工业水处理, 2003,23(12): 45-47.
[98] Krishnamoorthi S, Adhikary P, Mal D, et al. Novel polymeric flocculants based on polyacrylamide grafted dextran in kaolin suspension[J]. Journal of applied polymer science, 2010,118: 3539–3544.
[99] Lee K E, Morad N, Poh B T, et al. Comparative study on the effectiveness of hydrophobically modified cationic polyacrylamide groups in the flocculation of kaolin[J]. Desalination, 2011,270: 206-213.
[100]褚衍洋,孙晓杰.丙烯酰胺改性壳聚糖絮凝剂处理焦化废水[J].污染防治技术, 2007,20(2): 6-8.
[101]钟润生,张锡辉,肖峰,等.絮体分形结构对沉淀速度影响研究[J].环境科学, 2009,30(8): 2353-2357.
[102] Verney R, Lafite R, Brun-Cottan J C. Flocculation potential of estuarine particles: the importance of environmental factors and of the spatial and seasonal variability of suspended particulate matter[J]. Estuaries and Coasts, 2009,32(4): 678-693.
[103] Son M, Hsu T J. Flocculation model of cohesive sediment using variable fractal dimension[J]. Environmental Fluid Mechanics, 2008,8(1): 55-71.