阳离子聚丙烯酰胺乳液的制备及其絮凝性能研究
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摘要
随着我国对水污染治理力度加大,聚丙烯酰胺类药剂消耗量迅速增长。阳离子絮凝剂以其优良的处理效果而被广泛应用。本论文在综合相关文献基础上,以丙烯酰胺(AM)与阳离子单体(2一甲基丙烯酰氧乙基)三甲基氯化铵(DMC)为反应单体,分别以聚(2一甲基丙烯酰氧乙基)三甲基氯化铵(PDMC)、甲基丙烯酰氧乙基二甲基苄基氯化铵与丙烯酰胺的共聚物为分散稳定剂,在硫酸铵和叔丁醇(TBA)的水溶液中制备了稳定的AM/DMC共聚物乳液。通过单因素实验考察了单体浓度、单体配比、分相介质浓度、引发剂浓度、聚合温度对共聚物分子量和分散相颗粒大小的影响,实验得到的较佳反应条件为:单体浓度8%～15%,阳离子度10%～20%,硫酸铵浓度15%～30%,稳定剂浓度1.5%～3.0%(单体),稳定剂分子量3×10~5～10×10~5,反应温度为18℃-50℃。所得乳液粘度小、稳定性好,单体最终转化率可达到99%以上,共聚物分子量达到320万。利用红外光谱(IR)对所得聚合物的结构进行了表征,表明产物是AM/DMC的共聚产物。用溴化法测定聚合体系反应转化率,通过扫描电镜(SEM)测定考察反应时间
对聚合程中聚合物粒径的影响。沉降实验评价絮凝剂絮凝效果。通过测定透光率和沉淀速率来考察pH值、阳离子絮凝剂浓度、阳离子度及絮凝剂分子量等对絮凝效果影响。
With strength increase on waste water treatment , wastage of cationic polymerflocculants(CPF)increases rapidly.The perfect performance of CPF is used widely in the waste water fields.On the basis of the relevant literatures, copolymerization of acrylamide(AM)and dimethacrylatoethyl trimethyl ammonium chloride(DMC)was carried out using poly(dimethyla- minoethyl methacrylate methyl chloride)(PDMC) and poly(dimethylamino- ethyl methacrylate benzyl chloride?acrylamide)(PDMB?AM) as the steric stabilizer , and in ammonium sulfate(AS) and uncle butanol aqueous solution aqueous solution. The effects of varying factors,i.e.the total concentration of monomers and the molar ratios of DMC:AM,the initiator concentration,the temperature,the concentration of ammonium sulfate and the stabilizer on the monomer conversion,the initial copolymerization rate,the molecular weight of copolymer and the Z.average particle size were systematically investigated.By the single.Factor experiments .the optimum conditions for the performance ofAM/DMC Were determined to be as follows:8%～1 5%for monomer,10%～20%for the cationic monomer, 1.5%～3.O%for PDMC,0.003%～0.009%for V-44,the molecular weight of PDMC 3.0x 10~5～10.0x 10~5 and 18℃～50℃for the temperature.The structure of the copolymer was charactered by FTIR.The spectra results revealed that the main chain units ofAM、DMC were showed in the figures,The obtained system had lower visieosity and good stability after a long period of storage.The final monomer conversion exceeded 99%and the molecular weight of the copolymer Was more than 32 million.
The effect of monomer,initiators,temperture and dispersants on the reaction speed is studied by the test of bromize method.IR spectrogram confirms the structure of P(AM-DAC). Optics microscope and SEM reviews the change of grain size under the different period.And study the flocculation effect through settlement experimental and measuring light transmittance by cationic flocculant concentration, cationic degrees and molecular weight of flocculants .
对聚合程中聚合物粒径的影响。沉降实验评价絮凝剂絮凝效果。通过测定透光率和沉淀速率来考察pH值、阳离子絮凝剂浓度、阳离子度及絮凝剂分子量等对絮凝效果影响。
With strength increase on waste water treatment , wastage of cationic polymerflocculants(CPF)increases rapidly.The perfect performance of CPF is used widely in the waste water fields.On the basis of the relevant literatures, copolymerization of acrylamide(AM)and dimethacrylatoethyl trimethyl ammonium chloride(DMC)was carried out using poly(dimethyla- minoethyl methacrylate methyl chloride)(PDMC) and poly(dimethylamino- ethyl methacrylate benzyl chloride?acrylamide)(PDMB?AM) as the steric stabilizer , and in ammonium sulfate(AS) and uncle butanol aqueous solution aqueous solution. The effects of varying factors,i.e.the total concentration of monomers and the molar ratios of DMC:AM,the initiator concentration,the temperature,the concentration of ammonium sulfate and the stabilizer on the monomer conversion,the initial copolymerization rate,the molecular weight of copolymer and the Z.average particle size were systematically investigated.By the single.Factor experiments .the optimum conditions for the performance ofAM/DMC Were determined to be as follows:8%～1 5%for monomer,10%～20%for the cationic monomer, 1.5%～3.O%for PDMC,0.003%～0.009%for V-44,the molecular weight of PDMC 3.0x 10~5～10.0x 10~5 and 18℃～50℃for the temperature.The structure of the copolymer was charactered by FTIR.The spectra results revealed that the main chain units ofAM、DMC were showed in the figures,The obtained system had lower visieosity and good stability after a long period of storage.The final monomer conversion exceeded 99%and the molecular weight of the copolymer Was more than 32 million.
The effect of monomer,initiators,temperture and dispersants on the reaction speed is studied by the test of bromize method.IR spectrogram confirms the structure of P(AM-DAC). Optics microscope and SEM reviews the change of grain size under the different period.And study the flocculation effect through settlement experimental and measuring light transmittance by cationic flocculant concentration, cationic degrees and molecular weight of flocculants .
引文
[1]吴少杰,苗利.当前我国城市污水资源化存在的问题与对策[J].环境保护,2003,5(2):50-54
[2]国家环保总局.环境保护[N]. 2002年中国环境状况公报, 2003-7-3(13)
[3]刘明华,邓贇.稀土对生态环境的影响.环境与健康杂志, 1999, 16(5): 316~318
[4]唐受印,汪大翠等编.废水处理工程.北京:化学工业出版社, 1998
[5]严瑞瑄.水处理剂应用手册.北京:化学工业出版社, 2001
[6]何铁林.水处理化学品手册.北京:化学工业出版社, 2000
[7]汤鸿霄.无机高分子絮凝剂的几点新认识.工业水处理, 1997, 17(4): 1~5
[8]冉千平.两性高分子絮凝剂的合成及絮凝性能与机理研究:[学位论文].成都:四川大学,2000
[9]朱羡著.高分子化学及物理.北京:中国轻工业出版社,1996
[10]李群,王槐三著.高分子化学.成都科技大学出版社,1991
[11]林保平.丙烯酰胺水溶液聚合反应的研究.现代化工,199(l)l
[12]王善奇主编.高分子化学原理.北京航空航天大学出版社,1992
[13]刘明华.有机高分子絮凝剂的制备及应用.北京:北京化工出版社2006.3
[14]周军贤,一种丙烯酰胺凝胶的新型光聚合法,生物化学与生物物理进展, 1998,25(2):167一170
[15]徐初阳,聂容春,张明旭,光引发合成聚丙烯酰胺在选煤厂的应用,选煤技术, 2 0 0 3 , ( 5 ) : 1 1一1 3
[16]周应才,汪秀英,王永芝,等.可控分子量聚丙烯酰胺的辐射聚合,高分子材料科学与工程,1997,13(4):137一139
[17]李万捷,阮路,微波场中PAM合成及其在洗煤废水中的应用,煤炭转化, 1999,22(4):87一89
[18]张卫华,援晓淮,等离子体引发丙烯酰胺水溶液聚合,高分子学报,200,0 (5):577一579
[19]田华,微乳阳离子聚丙烯酰胺絮凝剂的研制,化工科技,2000(:2)35一36
[20]程原,杜栓丽,丙烯酰胺反相乳液聚合的研究,华北工学院学报,1999.20(l):79一82
[21]刘莲英,韩淑珍,金关泰,反相悬浮法碱水解合成阴离子型聚丙烯酰胺,北京化工大学学报,2000,27(4):36一38
[22] HuangS丫RosatiL,KozakiewiczJJ,AqueousdisPersions,US6702946, 2004
[23] CroucherMD,WinnikMA,NA丁0ASIseries(FuutreDirPolymColloid), 1987,137一209
[24] BarrettKEJ, DisPersion Polymerrizationin Ogranic Media, New York, Interscience ,1975
[25] TsengCM,LaY丫EI一AtlsserMS,VanderhoffJW,JPolymSci,Part一A, Polym ChemEd ,1985 ,24:2995
[26]曹同玉,戴兵,戴俊燕等,分散聚台稳定机理及动力学研究,高分子材料科学与工程,1998,14(l):31一34
[27] ConnorsEJ,CotterML,ChenF ,Processofrthe PreParation of aqueous Dispersion Polymers,US5707533,1998
[28]曹同玉,戴兵,戴俊燕等,分散聚台稳定机理及动力学研究,高分子材料科学与工程,1998,14(l):31一34
[29]崔正刚,殷福珊编.微乳化技术及应用.北京:中国轻工业出版社,1999.357~365
[30]加藤忠哉監修.水溶性·水分散型高分子材料最新技术动向及工业应用.东京:日本化学情报(株),2001.280～282,453～466,602
[31]福嶋礼造.化学装置,1998,8:63～68
[32] CroucherMD,WinnikMA,NA丁0ASIseries(FuutreDirPolymColloid), 1987,137一209
[33] HuangS丫KozakiewiczJJ,RosatiL,AqueousdisPersions,US6262168, 200 [34 Huriock J R ,Proces sofr PreParinghydro Philicdis Persion Polymersofr Treating wastewate,r US6025426,2000 [35 RameshM,CrammJR,W亡gresDL,HydroPhobicallyassociatingdisPersants Usedinofmring Polymerdis Persions,US 5597858 ,1997 [36 TakedaH,KawanoM,ProcessofrProductionofwater一solublePolymer Dis Persion,US5006590 ,1991
[37] TakedaH,ProcessofrPreParationofdisPersionofwater一solublecationic PolymerthedisPersionProducedtherebyanditsuse,US5587415,1996
[38] NzudieD,TVanhoyeD,ConcentratedaqueousdisPersionsofwater一soluble Polymers,US6174950, 2001
[39]孙艳萍.超高相对分子质量阳离子聚丙烯酰胺絮凝剂的合成研究:[硕士学位论文].大庆:大庆石油学院,2004
[40]韩磊,宁荣昌.分散聚合法制备聚丙烯酰胺水包水乳液[J].功能高分子学报,2004,1 7(3):493—496
[41] Wang Z.Synthesis and characterization of PAA-g-NPEO copolymers and evaluation asdispersants in dispersion polymerization of acrylamide.Poly Materials Sci andE,2005,2 1(3):89.95
[42] 22.崔玉,张书香.分散聚合法制备高分子量聚丙烯酰胺[J].济南大学学报,2002,1 6(4):327-329
[43] Guha,Ray B.Anomalous solubility of polyacrylamide prepared by dispersion (precipitation) polymerization in aqueous tertbutyl alcoh01.Journal of Polymer Science,Part A:Poly Chem,2001,39(1 9):3434-3437
[44]汪多仁,聚丙烯酰胺的合成进展与应用,造纸化学品,1998,10(2):13一巧[45 Mallo,wetal,Cationicwater一soluble Polyme rPreciPitation in saltsolutions,US 6013708, 2000
[46]姚重华.混凝与絮凝剂.北京:中国环境科学出版社,1991:536
[2]国家环保总局.环境保护[N]. 2002年中国环境状况公报, 2003-7-3(13)
[3]刘明华,邓贇.稀土对生态环境的影响.环境与健康杂志, 1999, 16(5): 316~318
[4]唐受印,汪大翠等编.废水处理工程.北京:化学工业出版社, 1998
[5]严瑞瑄.水处理剂应用手册.北京:化学工业出版社, 2001
[6]何铁林.水处理化学品手册.北京:化学工业出版社, 2000
[7]汤鸿霄.无机高分子絮凝剂的几点新认识.工业水处理, 1997, 17(4): 1~5
[8]冉千平.两性高分子絮凝剂的合成及絮凝性能与机理研究:[学位论文].成都:四川大学,2000
[9]朱羡著.高分子化学及物理.北京:中国轻工业出版社,1996
[10]李群,王槐三著.高分子化学.成都科技大学出版社,1991
[11]林保平.丙烯酰胺水溶液聚合反应的研究.现代化工,199(l)l
[12]王善奇主编.高分子化学原理.北京航空航天大学出版社,1992
[13]刘明华.有机高分子絮凝剂的制备及应用.北京:北京化工出版社2006.3
[14]周军贤,一种丙烯酰胺凝胶的新型光聚合法,生物化学与生物物理进展, 1998,25(2):167一170
[15]徐初阳,聂容春,张明旭,光引发合成聚丙烯酰胺在选煤厂的应用,选煤技术, 2 0 0 3 , ( 5 ) : 1 1一1 3
[16]周应才,汪秀英,王永芝,等.可控分子量聚丙烯酰胺的辐射聚合,高分子材料科学与工程,1997,13(4):137一139
[17]李万捷,阮路,微波场中PAM合成及其在洗煤废水中的应用,煤炭转化, 1999,22(4):87一89
[18]张卫华,援晓淮,等离子体引发丙烯酰胺水溶液聚合,高分子学报,200,0 (5):577一579
[19]田华,微乳阳离子聚丙烯酰胺絮凝剂的研制,化工科技,2000(:2)35一36
[20]程原,杜栓丽,丙烯酰胺反相乳液聚合的研究,华北工学院学报,1999.20(l):79一82
[21]刘莲英,韩淑珍,金关泰,反相悬浮法碱水解合成阴离子型聚丙烯酰胺,北京化工大学学报,2000,27(4):36一38
[22] HuangS丫RosatiL,KozakiewiczJJ,AqueousdisPersions,US6702946, 2004
[23] CroucherMD,WinnikMA,NA丁0ASIseries(FuutreDirPolymColloid), 1987,137一209
[24] BarrettKEJ, DisPersion Polymerrizationin Ogranic Media, New York, Interscience ,1975
[25] TsengCM,LaY丫EI一AtlsserMS,VanderhoffJW,JPolymSci,Part一A, Polym ChemEd ,1985 ,24:2995
[26]曹同玉,戴兵,戴俊燕等,分散聚台稳定机理及动力学研究,高分子材料科学与工程,1998,14(l):31一34
[27] ConnorsEJ,CotterML,ChenF ,Processofrthe PreParation of aqueous Dispersion Polymers,US5707533,1998
[28]曹同玉,戴兵,戴俊燕等,分散聚台稳定机理及动力学研究,高分子材料科学与工程,1998,14(l):31一34
[29]崔正刚,殷福珊编.微乳化技术及应用.北京:中国轻工业出版社,1999.357~365
[30]加藤忠哉監修.水溶性·水分散型高分子材料最新技术动向及工业应用.东京:日本化学情报(株),2001.280～282,453～466,602
[31]福嶋礼造.化学装置,1998,8:63～68
[32] CroucherMD,WinnikMA,NA丁0ASIseries(FuutreDirPolymColloid), 1987,137一209
[33] HuangS丫KozakiewiczJJ,RosatiL,AqueousdisPersions,US6262168, 200 [34 Huriock J R ,Proces sofr PreParinghydro Philicdis Persion Polymersofr Treating wastewate,r US6025426,2000 [35 RameshM,CrammJR,W亡gresDL,HydroPhobicallyassociatingdisPersants Usedinofmring Polymerdis Persions,US 5597858 ,1997 [36 TakedaH,KawanoM,ProcessofrProductionofwater一solublePolymer Dis Persion,US5006590 ,1991
[37] TakedaH,ProcessofrPreParationofdisPersionofwater一solublecationic PolymerthedisPersionProducedtherebyanditsuse,US5587415,1996
[38] NzudieD,TVanhoyeD,ConcentratedaqueousdisPersionsofwater一soluble Polymers,US6174950, 2001
[39]孙艳萍.超高相对分子质量阳离子聚丙烯酰胺絮凝剂的合成研究:[硕士学位论文].大庆:大庆石油学院,2004
[40]韩磊,宁荣昌.分散聚合法制备聚丙烯酰胺水包水乳液[J].功能高分子学报,2004,1 7(3):493—496
[41] Wang Z.Synthesis and characterization of PAA-g-NPEO copolymers and evaluation asdispersants in dispersion polymerization of acrylamide.Poly Materials Sci andE,2005,2 1(3):89.95
[42] 22.崔玉,张书香.分散聚合法制备高分子量聚丙烯酰胺[J].济南大学学报,2002,1 6(4):327-329
[43] Guha,Ray B.Anomalous solubility of polyacrylamide prepared by dispersion (precipitation) polymerization in aqueous tertbutyl alcoh01.Journal of Polymer Science,Part A:Poly Chem,2001,39(1 9):3434-3437
[44]汪多仁,聚丙烯酰胺的合成进展与应用,造纸化学品,1998,10(2):13一巧[45 Mallo,wetal,Cationicwater一soluble Polyme rPreciPitation in saltsolutions,US 6013708, 2000
[46]姚重华.混凝与絮凝剂.北京:中国环境科学出版社,1991:536