高分子共聚物P（DMDAAC/AM）的合成及在制糖中的应用
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摘要
随着我国制糖企业的发展和产品质量的要求,食品加工使用添加剂的安全毒性问题越来越受到重视。制糖生产中大量使用聚丙烯酰胺产生的残留毒性问题的确立,使人们对高效、无毒型阳离子型高分子絮凝剂的需求增长迅速。而二甲基二烯丙基氯化铵和丙烯酰胺的共聚物有着高效低耗、安全无害、无二次污染方向的特点正好满足了制糖澄清的需要。因此,本文对二甲基二烯丙基氯化铵和丙烯酰胺共聚物的合成及应用进行了较为深入的研究。
本文着重研究了二甲基二烯丙基氯化铵和丙烯酰胺单体的配比、引发剂加入量、反应时间、反应温度及聚合pH值等因素对聚合反应的影响。用水溶液自由基聚合的方法,通过一系列的实验,确定了二甲基二烯丙基氯化铵和丙烯酰胺共聚物的最佳合成条件为:聚合反应温度为80℃;二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)单体质量比为6:1;(NH_4)_2S_2O_8加入量为0.90g/100g溶液,Na_2SO_3加入量为0.3g/100g溶液,Ce~(4+)加入量为0.45mL/100g溶液;聚合反应的中和pH值为7.0;聚合反应时间为6.6h。
从应用的角度研究了高分子二甲基二烯丙基氯化铵和丙烯酰胺的聚合物对含赤砂糖糖汁的处理效果,并着重研究了聚合反应温度、DMDAAC和AM单体质量比、(NH_4)_2S_2O_8加入量、Na_2SO_3加入量、Ce~(4+)加入量、pH值、聚合反应时间等因素对澄清脱色的影响,得出了符合回溶赤砂糖汁澄清脱色的产品的最佳工艺条件。
通过与市售聚二甲基二烯丙基氯化铵进行比较,本实验合成的高分子共聚物处理糖汁的色值、浊度、简纯度三项指标均高于市售聚二甲基二烯丙基氯化铵。综合研究结果表明,二烯丙基氯化铵和丙烯酰胺共聚物(P(DMDAAC/AM))是一种有效的糖用高分子絮凝剂。
As China's sugar-scale enterprises and the development of the continuous expansion of the toxic polyacrylamide established, efficient, non-toxic type cationic polymer flocculant rapid growth in demand. And dimethy ammonium chloride and acrylamide acrylamide polymer has a low-efficient, safe, and no secondary pollution is the direction of the characteristics of the sugar to meet the needs of clarification process. Therefore, this paper to clarify the process used in the sugar dimethyl ammonium chloride and acrylamide acrylamide polymer cationic organic polymer flocculant Preparation and application of a more in-depth study.
The article focuses on the ratio of DMDAAC and AM, the amount of initiator, polymerization time, the polymerization temperature and polymerization factors such as pH of the polymerization reaction. Aqueous solution by free radical polymerization method and through a series of experiments to determine the organic polymer flocculant dimethyl ammonium chloride and acrylamide acrylamide polymer synthesis conditions for the best: polymerization temperature is 80℃; propylene dimethyl ammonium chloride (DMDAAC) and acrylamide (AM) is 6: 1; the addition of (NH_4)_2S_2O_8 is 0.90g/100g, the addition of Na_2SO_3 is 0.30g/100g, the addition of Ce~(4+) is 0.45ml/100g; polymerization reaction in the pH is 7.0 ; polymerization reaction time is 6.6 h.
With the market-dimethyldiallylammonium chloride comparison, the experimental synthetic copolymer handle the color, turbidity and simple purity were higher than the market-dimethyl The allyl chloride. Study results showed that the two allyl chloride and acrylamide (P (DMDAAC / AM)) is an effective sugar polymer flocculant.
本文着重研究了二甲基二烯丙基氯化铵和丙烯酰胺单体的配比、引发剂加入量、反应时间、反应温度及聚合pH值等因素对聚合反应的影响。用水溶液自由基聚合的方法,通过一系列的实验,确定了二甲基二烯丙基氯化铵和丙烯酰胺共聚物的最佳合成条件为:聚合反应温度为80℃;二甲基二烯丙基氯化铵(DMDAAC)和丙烯酰胺(AM)单体质量比为6:1;(NH_4)_2S_2O_8加入量为0.90g/100g溶液,Na_2SO_3加入量为0.3g/100g溶液,Ce~(4+)加入量为0.45mL/100g溶液;聚合反应的中和pH值为7.0;聚合反应时间为6.6h。
从应用的角度研究了高分子二甲基二烯丙基氯化铵和丙烯酰胺的聚合物对含赤砂糖糖汁的处理效果,并着重研究了聚合反应温度、DMDAAC和AM单体质量比、(NH_4)_2S_2O_8加入量、Na_2SO_3加入量、Ce~(4+)加入量、pH值、聚合反应时间等因素对澄清脱色的影响,得出了符合回溶赤砂糖汁澄清脱色的产品的最佳工艺条件。
通过与市售聚二甲基二烯丙基氯化铵进行比较,本实验合成的高分子共聚物处理糖汁的色值、浊度、简纯度三项指标均高于市售聚二甲基二烯丙基氯化铵。综合研究结果表明,二烯丙基氯化铵和丙烯酰胺共聚物(P(DMDAAC/AM))是一种有效的糖用高分子絮凝剂。
As China's sugar-scale enterprises and the development of the continuous expansion of the toxic polyacrylamide established, efficient, non-toxic type cationic polymer flocculant rapid growth in demand. And dimethy ammonium chloride and acrylamide acrylamide polymer has a low-efficient, safe, and no secondary pollution is the direction of the characteristics of the sugar to meet the needs of clarification process. Therefore, this paper to clarify the process used in the sugar dimethyl ammonium chloride and acrylamide acrylamide polymer cationic organic polymer flocculant Preparation and application of a more in-depth study.
The article focuses on the ratio of DMDAAC and AM, the amount of initiator, polymerization time, the polymerization temperature and polymerization factors such as pH of the polymerization reaction. Aqueous solution by free radical polymerization method and through a series of experiments to determine the organic polymer flocculant dimethyl ammonium chloride and acrylamide acrylamide polymer synthesis conditions for the best: polymerization temperature is 80℃; propylene dimethyl ammonium chloride (DMDAAC) and acrylamide (AM) is 6: 1; the addition of (NH_4)_2S_2O_8 is 0.90g/100g, the addition of Na_2SO_3 is 0.30g/100g, the addition of Ce~(4+) is 0.45ml/100g; polymerization reaction in the pH is 7.0 ; polymerization reaction time is 6.6 h.
With the market-dimethyldiallylammonium chloride comparison, the experimental synthetic copolymer handle the color, turbidity and simple purity were higher than the market-dimethyl The allyl chloride. Study results showed that the two allyl chloride and acrylamide (P (DMDAAC / AM)) is an effective sugar polymer flocculant.
引文
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[30]杨海耀,赖风英,林庆生,等.阳离子表面活性剂糖浆脱色除浊[J].中国甜菜糖业,2003(2):8-10
[31]吴振强,梁世中,姚汝华.甘蔗糖蜜酒精废液色素特性及脱除的研究[J].环境污染与防治,1997,19(1):5-8,43-44
[32]李林.蔗汁美拉德反应及其抑制研究[D]:[硕士学位论文].南宁:广西大学图书馆,2001:6-8
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[34]吴雪辉,郭建军,袁松.阴离子交换树脂对糖液色素脱色规律的研究[J].广西蔗糖,1999(2):36-39
[35]张昌军,杨志孝等.新型絮凝剂的研制与应用,化学世界,2000(4):185
[36]徐寿昌.有机化学[M].高等教育出版社,1993
[37]终曼丽.聚合反应原理[M].成都科技大学出版社,1997
[38]潘祖仁.高分子化学[M].化学工业出版社,1997:41-71
[39]GB12005.1-1989,聚丙烯酰胺特性粘度测定方法[s]
[40]Alonso J.Evaluation of differem types of carbons in the decolourization process in sugar refining[R].Cuban Sugar Research Institute Report,1985:68-73
[41]糖品统一分析方法国际委员会编,王律均等人译.糖品分析--国际统一分析方法[M].轻工业出版社,1982
[42]方开泰,马长兴.正交与均匀试验设计[M].北京:科学出版社,2001
[43]廖森.均匀设计在调优试验设计中的应用[J].广西大学学报,2002,27(4):293-297
[44]罗文利,牛亚斌,欧阳坚,王贵江.二甲基二烯丙基氯化铵与丙烯酰胺水溶液共聚合.油田化学[J],1998,15(3):193-196
[45]Hahn Mathias,Jaeger,Wemer,Wandrey Christine,Ballschuh Detlef.Ger.(East)127729,1977
[46]潘祖仁.高分子化学[M].化学工业出版社,1997:308-352
[47]Malkm R D.Catlonie Water-Souble Precictationin Salt Solution[P].US:6013708,2000-01.11
[48]肖遥,邓皓,陈尚冰.有机高分子絮凝剂的合成及应用[J].工业水处理,1994,14(3):17-19
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[2]肖锦,杞永亮.我国絮凝剂发展的现状与对策[J].现代化工,1997,17(12):6-9
[3]何慧琴,童仕唐.水处理絮凝剂的研究发展[J].四川化工,2001,30(16):14-16
[4]John E,Van Benschoten etal.Water Research,1990,24(12):15-23
[5]舒型武,郑怀礼.阳离子有机絮凝剂的研究进展[J].现代化工,2001,21(10):13-16
[6]董银卯.粱藏洲.新型阳离子有机絮凝剂的研制[I].工业水处理,1996,16(2):20-2
[7]Vyshkina,Tamara V.Mannich base copolynler and method for making it[J].US:574563,1998
[8]甘光奉等.高分子絮凝剂研究的进展[J].工业水处理,1999,19(2):6-7
[9]Lima,Emilia Celma etal.Thermoreversible Gel Formation from Aqueous Aluminium Polyphosphate Solutions[J].Colloid Interface Sei.,1994,16(2):309-315
[10]汤鸿宵.高分子絮凝剂的几点新认识[J].工业水处理,1997,17(4):1-5
[11]张光林等.淀粉改性阳离子型絮凝剂的研究进展[J].化学工程师,2002,88(1):38-39
[12]杨旭,赵立志.阳离子絮凝剂的研制[J].重庆环境科学,1995,17(5):17-19
[13]潘橙汉.黎国康,王真智等.接枝型聚丙烯酰胺高分子絮凝剂结构和性能的研究[J].精细化工,1991.8(3):12-15
[14]Prodrom ou K.P.Paulatou-Ve As.Formation of Alumimium Hydroxide Clay Mine as Influnced by Aluminium Salts and Bases[J].Clays&Clay Mine,1995,43(1):111-115
[15]汤鸿宵.无机高分子复合絮凝剂的研制趋向[J].中国给水排水,1999,15(2):1-4
[16]张昌军,杨志孝等.新型絮凝剂的研制与应用[J].化学世界,2000(4):185
[17]天津化工研究院絮凝剂组.高分子聚丙烯酸钠的研制及其应用[J].工业水处理,1985,5(1):6-9
[18]陆兴章,高华星,程树军等.HC型阳离子高分子絮凝剂的絮凝性能及其应用研究[J].环境污染与防治,1994,16(6):6-10
[19]刘晓洪.淀粉接枝型高分子絮凝剂的合成[J].辽宁化工,1999,28(4),202-203
[20]Jaeger Wemer,Hahn Mathias,Lieske Antje,Zimmermann Arvid,Brand Fabien.Polymerization of water-soluble cationic vinyl monomers.Macromol.Symposia,1996 (111):95-106
[21]赵仕林,朱明,罗娅君.P(DMC-AM)阳离子絮凝剂的絮凝性能研究[J].四川师范大学学报(自然科学版),2002,25(5):503-506
[22]马青山,贾瑟,孙丽琳.絮凝化学与絮凝剂[M].北京:中国环境科学出版社,1995
[23]潘祖仁.高分子化学[M].化学工业出版社,1997:205-206
[24]潘祖仁.高分子化学[M].化学工业出版社,1997:206-207
[25]朱红,施秀屏,欧泽深.新型有机复合阳离子絮凝剂的研究[J].工业水处理,1996.16(1):24-27
[26]潘祖仁.高分子化学[M].化学工业出版社,1997:206-207
[27]潘祖仁.高分子化学[M].化学工业出版社,1997:207-208
[28]Brand Fabien,Dautzenberg Herbert,Jaeger Wemer,Hahn Mathias.Polyelectrolytes with various charge densities.Synthesis and characterization of diallyldimethylamonium chloride-acrylamide copolymers.A ngewandte.Makromol.Chemie.1997(248):41-71
[29]Carpenter F.糖中影响精炼的组分[C].见:李伟强主编.国际甘蔗糖学会第十五届年会论文选集(中译本下集).广州:广东省制糖学会,1986:277-282
[30]杨海耀,赖风英,林庆生,等.阳离子表面活性剂糖浆脱色除浊[J].中国甜菜糖业,2003(2):8-10
[31]吴振强,梁世中,姚汝华.甘蔗糖蜜酒精废液色素特性及脱除的研究[J].环境污染与防治,1997,19(1):5-8,43-44
[32]李林.蔗汁美拉德反应及其抑制研究[D]:[硕士学位论文].南宁:广西大学图书馆,2001:6-8
[33]马青山,贾瑟,孙丽琳.絮凝化学与絮凝剂[M].北京:中国环境科学出版社,1995
[34]吴雪辉,郭建军,袁松.阴离子交换树脂对糖液色素脱色规律的研究[J].广西蔗糖,1999(2):36-39
[35]张昌军,杨志孝等.新型絮凝剂的研制与应用,化学世界,2000(4):185
[36]徐寿昌.有机化学[M].高等教育出版社,1993
[37]终曼丽.聚合反应原理[M].成都科技大学出版社,1997
[38]潘祖仁.高分子化学[M].化学工业出版社,1997:41-71
[39]GB12005.1-1989,聚丙烯酰胺特性粘度测定方法[s]
[40]Alonso J.Evaluation of differem types of carbons in the decolourization process in sugar refining[R].Cuban Sugar Research Institute Report,1985:68-73
[41]糖品统一分析方法国际委员会编,王律均等人译.糖品分析--国际统一分析方法[M].轻工业出版社,1982
[42]方开泰,马长兴.正交与均匀试验设计[M].北京:科学出版社,2001
[43]廖森.均匀设计在调优试验设计中的应用[J].广西大学学报,2002,27(4):293-297
[44]罗文利,牛亚斌,欧阳坚,王贵江.二甲基二烯丙基氯化铵与丙烯酰胺水溶液共聚合.油田化学[J],1998,15(3):193-196
[45]Hahn Mathias,Jaeger,Wemer,Wandrey Christine,Ballschuh Detlef.Ger.(East)127729,1977
[46]潘祖仁.高分子化学[M].化学工业出版社,1997:308-352
[47]Malkm R D.Catlonie Water-Souble Precictationin Salt Solution[P].US:6013708,2000-01.11
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