氨基膦酸螯合树脂的合成与应用研究
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摘要
工业的发展,环境污染的加剧,人类赖以生存的食品,饮用水中过多的重金属对人类的伤害越来越明显。本文提出从苯乙烯系树脂出发,制备螯合树脂去除重金属离子的方法,该法具有设备简单、占地面积小、可富集金属使水得到重复循环利用,不产生二次污染的优点。
本文通过Friedel-Crafts反应,以苯乙烯—二乙烯苯聚合物为载体自制乙酰化交联聚苯乙烯微球,再经Mannich反应法,制备了新型胺基树脂,避免了氯甲基化法使用氯甲醚等致癌物质带来的弊端。再由胺基树脂出发,制备出氨基膦酸型螯合树脂,并对重金属离子铅进行静态吸附,测定研究树脂的吸附性能、再生效果。
文中讨论了反应温度和时间、物料比等因素对各部反应的影响并对机理进行探讨。在自制乙酰化交联聚苯乙烯微球过程中,当反应时间为3小时,三氯化铝与苯乙烯树脂的摩尔比为2.5,乙酸酐与苯乙烯树脂质量比2时,产物乙酰基团的取代度可到65%左右。同时对产物乙酰化程度进行红外定量分析方法研究。
乙酰化交联聚苯乙烯微球胺化反应中,当胺和乙酰基的摩尔比例为:10:1,胺和多聚甲醛摩尔比为:1:1,胺和盐酸的摩尔比例为:4:1,反应时间9h,反应温度60℃时,产物的增重率可达80%左右。对数据作出回归分析得出方程,以便给所需要的特定胺化率树脂设定反应条件。
氨基膦酸树脂的制备中,当亚磷酸与NH2摩尔比8:1,甲醛与NH2摩尔比8:1,盐酸与NH2摩尔比2:1,反应温度为70℃,反应时间为10h时,产物的氨基转化率达到90%左右。对各反应参数的数据分析,找到了一些重要的影响条件及其与产物氨基转化率之间线性关系。
通过螯合树脂对重金属铅的吸附及解吸,看出树脂对浓度在0~1mg/L范围内铅的吸附不容易进行。功能基含量为1.64mmol/ g的树脂对铅的静态饱和吸附后,功能基与铅的摩尔比为1:0.009,近似于100:1。但树脂解吸效果很好,用0.3mol/l盐酸做洗脱剂,最大洗脱率可达99%左右。
With industrial developing and the worsening environmental pollution, the heavy metals in foods and the drinking water which people feed on have injured the health more obviously. The article gives the preparation of chelating resin which is from acetylated polystyrene micro-beads.The chelating resin can reduce the quantities of heavy metals.The method is of simple equipment, small occupy area and also make water be used repeatly by metal enrichment with no second pollution.
In this paper, the new amino resin was prepared from acetylated polystyrene micro-beads, formaldehyde and tetraethylene pentamine by Mannich reaction, which can substitute anion-exchange resin prepared from chloromethyl polystyrene resin which used chloromethyl methylether as reactant, that is strong carcinogen due to methylene bridge exists in the chloromethyl polystyrene. Then the amino methylene phosphonic acid resin was prepared from the new amino resin. The static adsorption and the regeneration character of the resin for Pb2+ were preliminary studied.
Influencing factors were discussed such as time and temperature of the reaction, molar ratio of materials and so on. Their mechanism was also discussed in the paper. In the process of preparing acetylated polystyrene micro-beads, the optimum experimental conditions were as follows: AlCl3 : polystyrene(molar ratio)=2.5:1, acetic anhydride : polystyrene(mass ratio) =2:1, reaction time=3 hours. The maximum loading of the acetyl polystyrene could be about 65%. Substituted PS was quantified by infrared spectrum analysis from which we got absorbance of several characteristic peaks.
After the new amino resin was prepared, the mass-gain rate of products may reach at 80% in the following reaction conditions. Amine: formaldehyde: hydrochloride: Acetyl=10:10:2.5:1, reaction temperature=60℃and reaction time=9 hours. The certain equation was provided by the regression analyzed data. So we can get the resin which has the given rate of amination by the equation in the future.
In the process of preparing amino methylene phosphonic acid resin, the amino-transferring of products may reach at 90% in the following conditions, such as phosphorous acid: formaldehyde: hydrochloride: amino=8:8:2:1, reaction temperature =70℃and reaction time=10 hours. The data of each reaction condition have been analysed and we found more important influence conditions and the linear relationship between conditions and amino-transferring of products.
The static adsorption and the regeneration character of the resin for Pb2+ was studied. It shows that when the low concentration of Pb2+ varies from 0 to 1mg/L, the adsorption is difficult. When amino phosphonic acid chelating resin loading 1.64mmo1/g of phosphorous acid groups adsorbs Pb2+ in a saturated adsorption state, the ratio between functional groups and Pb2+ is 1:0.009 near 100:1.
But the desorption is more effective, especially using hydrochloric acid (the concentration is 0.3mol/l) as the stripping agent. Its stripping ratio is about 99%.
本文通过Friedel-Crafts反应,以苯乙烯—二乙烯苯聚合物为载体自制乙酰化交联聚苯乙烯微球,再经Mannich反应法,制备了新型胺基树脂,避免了氯甲基化法使用氯甲醚等致癌物质带来的弊端。再由胺基树脂出发,制备出氨基膦酸型螯合树脂,并对重金属离子铅进行静态吸附,测定研究树脂的吸附性能、再生效果。
文中讨论了反应温度和时间、物料比等因素对各部反应的影响并对机理进行探讨。在自制乙酰化交联聚苯乙烯微球过程中,当反应时间为3小时,三氯化铝与苯乙烯树脂的摩尔比为2.5,乙酸酐与苯乙烯树脂质量比2时,产物乙酰基团的取代度可到65%左右。同时对产物乙酰化程度进行红外定量分析方法研究。
乙酰化交联聚苯乙烯微球胺化反应中,当胺和乙酰基的摩尔比例为:10:1,胺和多聚甲醛摩尔比为:1:1,胺和盐酸的摩尔比例为:4:1,反应时间9h,反应温度60℃时,产物的增重率可达80%左右。对数据作出回归分析得出方程,以便给所需要的特定胺化率树脂设定反应条件。
氨基膦酸树脂的制备中,当亚磷酸与NH2摩尔比8:1,甲醛与NH2摩尔比8:1,盐酸与NH2摩尔比2:1,反应温度为70℃,反应时间为10h时,产物的氨基转化率达到90%左右。对各反应参数的数据分析,找到了一些重要的影响条件及其与产物氨基转化率之间线性关系。
通过螯合树脂对重金属铅的吸附及解吸,看出树脂对浓度在0~1mg/L范围内铅的吸附不容易进行。功能基含量为1.64mmol/ g的树脂对铅的静态饱和吸附后,功能基与铅的摩尔比为1:0.009,近似于100:1。但树脂解吸效果很好,用0.3mol/l盐酸做洗脱剂,最大洗脱率可达99%左右。
With industrial developing and the worsening environmental pollution, the heavy metals in foods and the drinking water which people feed on have injured the health more obviously. The article gives the preparation of chelating resin which is from acetylated polystyrene micro-beads.The chelating resin can reduce the quantities of heavy metals.The method is of simple equipment, small occupy area and also make water be used repeatly by metal enrichment with no second pollution.
In this paper, the new amino resin was prepared from acetylated polystyrene micro-beads, formaldehyde and tetraethylene pentamine by Mannich reaction, which can substitute anion-exchange resin prepared from chloromethyl polystyrene resin which used chloromethyl methylether as reactant, that is strong carcinogen due to methylene bridge exists in the chloromethyl polystyrene. Then the amino methylene phosphonic acid resin was prepared from the new amino resin. The static adsorption and the regeneration character of the resin for Pb2+ were preliminary studied.
Influencing factors were discussed such as time and temperature of the reaction, molar ratio of materials and so on. Their mechanism was also discussed in the paper. In the process of preparing acetylated polystyrene micro-beads, the optimum experimental conditions were as follows: AlCl3 : polystyrene(molar ratio)=2.5:1, acetic anhydride : polystyrene(mass ratio) =2:1, reaction time=3 hours. The maximum loading of the acetyl polystyrene could be about 65%. Substituted PS was quantified by infrared spectrum analysis from which we got absorbance of several characteristic peaks.
After the new amino resin was prepared, the mass-gain rate of products may reach at 80% in the following reaction conditions. Amine: formaldehyde: hydrochloride: Acetyl=10:10:2.5:1, reaction temperature=60℃and reaction time=9 hours. The certain equation was provided by the regression analyzed data. So we can get the resin which has the given rate of amination by the equation in the future.
In the process of preparing amino methylene phosphonic acid resin, the amino-transferring of products may reach at 90% in the following conditions, such as phosphorous acid: formaldehyde: hydrochloride: amino=8:8:2:1, reaction temperature =70℃and reaction time=10 hours. The data of each reaction condition have been analysed and we found more important influence conditions and the linear relationship between conditions and amino-transferring of products.
The static adsorption and the regeneration character of the resin for Pb2+ was studied. It shows that when the low concentration of Pb2+ varies from 0 to 1mg/L, the adsorption is difficult. When amino phosphonic acid chelating resin loading 1.64mmo1/g of phosphorous acid groups adsorbs Pb2+ in a saturated adsorption state, the ratio between functional groups and Pb2+ is 1:0.009 near 100:1.
But the desorption is more effective, especially using hydrochloric acid (the concentration is 0.3mol/l) as the stripping agent. Its stripping ratio is about 99%.
引文
[1]孔维,周慧,王立平等.重氮法固定化糖化酶活力和稳定性[J].高等学校化学学报,1994(05):681-684
[2]葛玉斌,王立平,孔维等.葡萄糖异构酶的固定化及其性质研究[J].高等学校化学学报,1996(05):735-738
[3]曾清如,廖柏寒,杨仁斌.EDTA溶液萃取污染土壤中的重金属及其回收技术[J].中国环境科学,2003(06):38-42
[4]蒋建国,王伟,赵翔龙等.重金属螯合剂在废水治理中的应用研究[J].环境科学,1999,20(1):65-67
[5] Carey W S, et al. Polymeric dithiocarbamate acid salt compositions and method of use [P].US 5371726,1994
[6]杨通在,刘亦农.阳离子型改性高分子絮凝剂对轻工废水的处理[J].工业水处理,1998,18(3):27-29
[7]马彦峰,吴韶华.沉淀法处理含重金属污水的研究[J].环境保护学,1998,24(3):1-3
[8]陈玉成,熊双莲,熊治廷.基于表面活性剂的重金属去除技术[J].环境科学与技术,2004,27(4):162-165
[9]梅建庭.离子交换纤维对水中Cr(Ⅵ)的吸附与解吸[J].材料保护,1996 ,29 (11) :26-28.
[10]何炳林,黄文强.离子交换与吸附树脂[M].上海:上海科技教育出版社,1995.20-23
[11] Moffat A. S. Plants proving their worth in toxic metal cleanup[J]. Science, 1995 (269) :302-303
[12]王榕树,李海明.活性氧化铝/硅胶吸附剂对环境水体的脱氟行为研究及应用初探[J].环境科学学报,1992,30(9):333-340
[13]孙楠,薛健.中药中重金属测定的研究进展[J].中草药,2005,36(12):1907-1999
[14]陈世忠.氢化物发生电感耦合等离子体原子发射光谱法测定黄姜中的砷锑和铋[J].微量元素与健康研究,2003,20(3):34-36
[15]何炳林、黄文强.离子交换与吸附树脂[M]上海:上海科技教育出版社,1995:63
[16]向万宏.螯合树脂的合成及应用研究新进展[J].化工技术与开发,2003,32(2):16-23
[17] Bozena N. Kolarza, Dorota Jermakow icz-Bartkow iaka, et al. Influence of the structure of chelating resins with guanidyl groups on gold sorption [J]. Reactive and FunctionalPolymers, 1999, 42 (3): 213-222
[18]朱端卫,刘义新,程东升.8-羟基喹啉螯合树脂与重金属作用研究[J].华中农业大学学报,2000,19(1):15-17
[19] M. C. Yebra, R. M. Cespón. Indirect automatic determination of iodide by flame atomic absorption spectrometry[J]. Analytical Acta, 2000, 405(1):191-196.
[20]董先明,胡艾希,符若文.Friedel-Crafts酰基化反应研究进展[J].合成化学,2001(06): 495-498
[21]卞国建.乙酰化PS载体的制备及其应用的研究[D]:[硕士学位论文].南京:南京工业大学生物工程学院,2004
[22]刘杨,邸进申.Friedel-Crafts反应催化剂的研究进展[J].精细石油化工,2001(06):19-22
[23] Leslied Roland, John R Millar. The Long Tragedy of CME[J]. Chemistry & industry. 1993(04): 10-13
[24] James H. Barret, Cornwells Heights, Method of preparing anion exchange resins with sulfuryl chloride[P]. US 3812061, 1974-5-21
[25]陈义镛,许承威,刘同保等,氯化硫酰-甲缩醛法合成强碱型阴离子交换树脂[J].高分子通讯,1980(04):254-256
[26]张政朴,钱庭宝.交联苯乙烯-二乙烯苯共聚物的氯甲基化反应[J].离子交换与吸附, 1987,3(5):70-78
[27] Warshawsky A, Deshe A. Halomethyl octyl Ethers: Convenient Halomethylation Reagents[J].J Polym Sci: Poym Chem Ed. 1985(23):1839-1841
[28]张效田,孙树玉,杨师鞠等.交联聚苯乙烯酰胺甲基化反应[J].北学通报,1979(1):43-45
[29] Glavis F L ,Clemens D H.Preparation, polymerization, and use of new bis-vinylbenzyl nitrogenous monomers[P]. US 4137264.1979-01-30
[30]许辉,胡喜章.Friedel-Crafts酰基化法制备聚苯乙烯阴离子交换树脂[J].功能高分子学报,1998,11(4):513-520
[31]汪众钢.亲核加成反应[M].北京:高等教育出版社,1994.29-46
[32]万道正.曼尼希反应和曼尼希碱化学[M].北京:北京科学出版社.1986,347-366
[33] Bayer. E., X.N.Liu, U. Tallarek, et al., Polystyrene-immobilized Poly(ethylene imine) Chains-a New Class of Graft Copolymers[J]. Polym. Bull.1996(37):565-572
[34]曾佑林,徐满才,黄明刚.一种新型亲水性胺基羧酸树脂的合成及其性能研究[J].离子交换与吸附,2002,18(3):272-276
[35]何炳林,程晓辉,阎虎生等,亲水性亚胺二乙酸基螯合树脂合成与性能的研究[J].离子交换与吸附,1992,8(2):159-163
[36] M.Nicolalla,C.Rosina.N.Toussetb,Y.Nicolai.Trace metals analysis inestuarine and seawater by ICP-MS using online preconcentration and matrixe limination with chelating resin[J]. Talanta. 1999, 50(2):433-44
[37] Rivas B L, Maturana H A, Hauser P. Adsorption behavior and separation of Vanadium(V), Molybdenum(VI) and Rhenium(VII) ions on crosslinked polymers containing acrylic acid derivative moieties[J]. Joumal of Applied Polymer Science.19 99,(73) : 369-373
[38]范云鸽,史作清. 8-羟基喹啉螯合树脂的制备及应用研究进展[J].离子交换与吸附.2001,17(3):281-288
[39]李彦锋,马应霞,周林成.糠醛系氮配位螯合树脂对贵金属元素的吸附性能[J].功能高分子学报,2001,1(2):221-225
[40]李贺先,张政朴,张华等.D412螯合树脂用于离子膜法制烧碱精制二次盐水的研究[J].离子交换与吸附,1997,13(2):195-202
[41]宋宽秀,李晓云,颜秀茹等.氨基膦酸螯合树脂吸附Ce(Ⅳ)的性能及机理研究[J].高分子材料科学与工程.2001,17(5):121一124
[42]蒲巧生,刘鹏,吴雄志等.氨基膦酸螯合树脂的合成及其对痕量镧系稀土富集分离性能的研究[J].兰州大学学报(自然科学版),2002,38(3):68-72
[43]马千里,陆妙龙.珠状酚醛系氨基膦酸螯合树脂的制备及其螯合性能[J].离子交换与吸附,2000,16(3):239-246
[44]徐羽梧,杨亚核,李汉平.硫脲树脂的合成及其吸附性能[J]武汉大学学报(自然科学版).1999,45(2):129-134
[45]李曦,赵雷康,张超灿.巯基胺型树脂的合成及其对贵金属离子吸附性能研究[J].湖北化工,2000(1):13-14
[46]张超灿,庞金兴,李曦.核-壳型巯基胺螯合树脂的制各及其吸附性能[J].武汉人学学报,2001,47(2):189-191
[47] U.V.Trivedi, S.K.Menon, Y.K.Agrawal. Polymer supported calix[6] arene hydroxamic acid, anovel chelating resin[J]. Reactive and Functional Polymers, 2002, 50(3): 205-216
[52]张华.现代有机波谱分析[M].北京:北京化学工业出版社,2005:52-60
[53]吴有炜.试验设计与数据处理[M].苏州:苏州大学出版社,2002:170-187
[54]万霞.两性树脂总交换容量测定[J].广州化学,1998(1):42-46
[55]王叔淳.食品卫生检验技术手册[M].北京:北京化学工业出版社,1994,108-110
[56]杨志洁,郭洁.用二甲酚橙显色快速测定植物叶上的铅含量[J].理化检验-化学分册,2000,36(9):412-414
[2]葛玉斌,王立平,孔维等.葡萄糖异构酶的固定化及其性质研究[J].高等学校化学学报,1996(05):735-738
[3]曾清如,廖柏寒,杨仁斌.EDTA溶液萃取污染土壤中的重金属及其回收技术[J].中国环境科学,2003(06):38-42
[4]蒋建国,王伟,赵翔龙等.重金属螯合剂在废水治理中的应用研究[J].环境科学,1999,20(1):65-67
[5] Carey W S, et al. Polymeric dithiocarbamate acid salt compositions and method of use [P].US 5371726,1994
[6]杨通在,刘亦农.阳离子型改性高分子絮凝剂对轻工废水的处理[J].工业水处理,1998,18(3):27-29
[7]马彦峰,吴韶华.沉淀法处理含重金属污水的研究[J].环境保护学,1998,24(3):1-3
[8]陈玉成,熊双莲,熊治廷.基于表面活性剂的重金属去除技术[J].环境科学与技术,2004,27(4):162-165
[9]梅建庭.离子交换纤维对水中Cr(Ⅵ)的吸附与解吸[J].材料保护,1996 ,29 (11) :26-28.
[10]何炳林,黄文强.离子交换与吸附树脂[M].上海:上海科技教育出版社,1995.20-23
[11] Moffat A. S. Plants proving their worth in toxic metal cleanup[J]. Science, 1995 (269) :302-303
[12]王榕树,李海明.活性氧化铝/硅胶吸附剂对环境水体的脱氟行为研究及应用初探[J].环境科学学报,1992,30(9):333-340
[13]孙楠,薛健.中药中重金属测定的研究进展[J].中草药,2005,36(12):1907-1999
[14]陈世忠.氢化物发生电感耦合等离子体原子发射光谱法测定黄姜中的砷锑和铋[J].微量元素与健康研究,2003,20(3):34-36
[15]何炳林、黄文强.离子交换与吸附树脂[M]上海:上海科技教育出版社,1995:63
[16]向万宏.螯合树脂的合成及应用研究新进展[J].化工技术与开发,2003,32(2):16-23
[17] Bozena N. Kolarza, Dorota Jermakow icz-Bartkow iaka, et al. Influence of the structure of chelating resins with guanidyl groups on gold sorption [J]. Reactive and FunctionalPolymers, 1999, 42 (3): 213-222
[18]朱端卫,刘义新,程东升.8-羟基喹啉螯合树脂与重金属作用研究[J].华中农业大学学报,2000,19(1):15-17
[19] M. C. Yebra, R. M. Cespón. Indirect automatic determination of iodide by flame atomic absorption spectrometry[J]. Analytical Acta, 2000, 405(1):191-196.
[20]董先明,胡艾希,符若文.Friedel-Crafts酰基化反应研究进展[J].合成化学,2001(06): 495-498
[21]卞国建.乙酰化PS载体的制备及其应用的研究[D]:[硕士学位论文].南京:南京工业大学生物工程学院,2004
[22]刘杨,邸进申.Friedel-Crafts反应催化剂的研究进展[J].精细石油化工,2001(06):19-22
[23] Leslied Roland, John R Millar. The Long Tragedy of CME[J]. Chemistry & industry. 1993(04): 10-13
[24] James H. Barret, Cornwells Heights, Method of preparing anion exchange resins with sulfuryl chloride[P]. US 3812061, 1974-5-21
[25]陈义镛,许承威,刘同保等,氯化硫酰-甲缩醛法合成强碱型阴离子交换树脂[J].高分子通讯,1980(04):254-256
[26]张政朴,钱庭宝.交联苯乙烯-二乙烯苯共聚物的氯甲基化反应[J].离子交换与吸附, 1987,3(5):70-78
[27] Warshawsky A, Deshe A. Halomethyl octyl Ethers: Convenient Halomethylation Reagents[J].J Polym Sci: Poym Chem Ed. 1985(23):1839-1841
[28]张效田,孙树玉,杨师鞠等.交联聚苯乙烯酰胺甲基化反应[J].北学通报,1979(1):43-45
[29] Glavis F L ,Clemens D H.Preparation, polymerization, and use of new bis-vinylbenzyl nitrogenous monomers[P]. US 4137264.1979-01-30
[30]许辉,胡喜章.Friedel-Crafts酰基化法制备聚苯乙烯阴离子交换树脂[J].功能高分子学报,1998,11(4):513-520
[31]汪众钢.亲核加成反应[M].北京:高等教育出版社,1994.29-46
[32]万道正.曼尼希反应和曼尼希碱化学[M].北京:北京科学出版社.1986,347-366
[33] Bayer. E., X.N.Liu, U. Tallarek, et al., Polystyrene-immobilized Poly(ethylene imine) Chains-a New Class of Graft Copolymers[J]. Polym. Bull.1996(37):565-572
[34]曾佑林,徐满才,黄明刚.一种新型亲水性胺基羧酸树脂的合成及其性能研究[J].离子交换与吸附,2002,18(3):272-276
[35]何炳林,程晓辉,阎虎生等,亲水性亚胺二乙酸基螯合树脂合成与性能的研究[J].离子交换与吸附,1992,8(2):159-163
[36] M.Nicolalla,C.Rosina.N.Toussetb,Y.Nicolai.Trace metals analysis inestuarine and seawater by ICP-MS using online preconcentration and matrixe limination with chelating resin[J]. Talanta. 1999, 50(2):433-44
[37] Rivas B L, Maturana H A, Hauser P. Adsorption behavior and separation of Vanadium(V), Molybdenum(VI) and Rhenium(VII) ions on crosslinked polymers containing acrylic acid derivative moieties[J]. Joumal of Applied Polymer Science.19 99,(73) : 369-373
[38]范云鸽,史作清. 8-羟基喹啉螯合树脂的制备及应用研究进展[J].离子交换与吸附.2001,17(3):281-288
[39]李彦锋,马应霞,周林成.糠醛系氮配位螯合树脂对贵金属元素的吸附性能[J].功能高分子学报,2001,1(2):221-225
[40]李贺先,张政朴,张华等.D412螯合树脂用于离子膜法制烧碱精制二次盐水的研究[J].离子交换与吸附,1997,13(2):195-202
[41]宋宽秀,李晓云,颜秀茹等.氨基膦酸螯合树脂吸附Ce(Ⅳ)的性能及机理研究[J].高分子材料科学与工程.2001,17(5):121一124
[42]蒲巧生,刘鹏,吴雄志等.氨基膦酸螯合树脂的合成及其对痕量镧系稀土富集分离性能的研究[J].兰州大学学报(自然科学版),2002,38(3):68-72
[43]马千里,陆妙龙.珠状酚醛系氨基膦酸螯合树脂的制备及其螯合性能[J].离子交换与吸附,2000,16(3):239-246
[44]徐羽梧,杨亚核,李汉平.硫脲树脂的合成及其吸附性能[J]武汉大学学报(自然科学版).1999,45(2):129-134
[45]李曦,赵雷康,张超灿.巯基胺型树脂的合成及其对贵金属离子吸附性能研究[J].湖北化工,2000(1):13-14
[46]张超灿,庞金兴,李曦.核-壳型巯基胺螯合树脂的制各及其吸附性能[J].武汉人学学报,2001,47(2):189-191
[47] U.V.Trivedi, S.K.Menon, Y.K.Agrawal. Polymer supported calix[6] arene hydroxamic acid, anovel chelating resin[J]. Reactive and Functional Polymers, 2002, 50(3): 205-216
[52]张华.现代有机波谱分析[M].北京:北京化学工业出版社,2005:52-60
[53]吴有炜.试验设计与数据处理[M].苏州:苏州大学出版社,2002:170-187
[54]万霞.两性树脂总交换容量测定[J].广州化学,1998(1):42-46
[55]王叔淳.食品卫生检验技术手册[M].北京:北京化学工业出版社,1994,108-110
[56]杨志洁,郭洁.用二甲酚橙显色快速测定植物叶上的铅含量[J].理化检验-化学分册,2000,36(9):412-414