疏水缔合聚丙烯酰胺和三元共聚阳离子聚丙烯酰胺的合成及性能评价
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摘要
聚丙烯酰胺(PAM)是一种线型水溶性高分子,是水溶性高分子化合物中应用最为广泛的品种之一,广泛应用于石油、化工、水处理等领域。
石油作为重要的能源和化工原料,是一种有限的不可再生资源,其储量正在不断地减少。为保证石油长期稳定供应,满足人类的需求,必须研究和发展新的石油采收技术。目前,国内使用的部分水解聚丙烯酰胺由于抗温抗盐抗剪切性能较差,应用受到很大的限制。因此,为了提高采油助剂的耐温、耐盐和耐剪切性能,开展了疏水缔合型聚丙烯酰胺的研究。
本文以丙烯酰胺为亲水单体,2-乙烯基吡啶为疏水单体,过硫酸钾和偶氮化合物AM-01为复合引发体系,通过水溶液自由基共聚后水解的方法,合成了一种新的疏水缔合型聚丙烯酰胺。
研究了单体浓度、引发温度、引发剂种类及用量、pH值、疏水单体含量及添加剂等聚合反应条件对聚合物相对分子质量的影响,确定了最佳合成条件:单体质量分数30%,引发温度12℃,pH值为5.0,疏水单体摩尔分数0.4%,引发剂AM-01和K_2S_2O_8的浓度分别为0.025%和0.0025%,添加剂尿素加量为5%。用黏度法测定了聚合物的分子量,运用红外光谱和核磁共振对聚合物结构进行表征。考察了聚合物溶液的浓度、温度、盐浓度及剪切速率对聚合物溶液性质的影响。疏水缔合型聚丙烯酰胺水溶液的表观粘度随其浓度的增加,出现了一个临界缔合浓度(CAC)。与部分水解的聚丙烯酰胺产品相比,疏水缔合型聚丙烯酰胺具有更好的耐温、耐盐和耐剪切性能。并且当剪切应力消失后,疏水缔合聚丙烯酰胺溶液的表观粘度逐渐恢复,表现出剪切作用的可逆性,对实际应用有重要的意义。
同时,随着淡水资源的日益匮乏和人们对环境保护的日渐重视,水处理用絮凝剂的研制受到越来越多的关注。水溶性阳离子型聚丙烯酰胺作为一种有效的絮凝剂,广泛应用于生活污水以及石油、造纸和冶矿等领域。目前国内阳离子聚丙烯酰胺絮凝剂的生产技术水平还落后于国外,急需生产出一种低成本、高性能的产品。
因此,本文以丙烯酰胺(AM)为分子骨架,丙烯酰氧乙基三甲基氯化铵(DAC)和二烯丙基二甲基氯化铵(DMDAAC)为阳离子单体,通过水溶液共聚合的方法,合成了一种阳离子型聚丙烯酰胺絮凝剂P(AM-DAC-DMDAAC)。确定了反应的最佳合成条件:单体质量分数30%,引发温度12℃,pH值为5.0,阳离子单体含量25%,引发剂AM-01和K_2S_2O_8的浓度分别为0.03%和0.003%。用黏度法测定了聚合物的相对分子质量,运用红外光谱和核磁共振对聚合物结构进行分析,并用合成的絮凝剂对城市生活污水进行絮凝试验,测定其絮凝性能。
Polyacrylamide is one kind of linear water-soluble macromolecule with the most extensive use,which is applied in the field of petroleum,chemical engineering and water treatment extensively.
As an important energy and chemical material,oil is a limited and non-renewable resource.Therefore,we must research and develop the new oil recovery technologies in order to ensure the long-term and stable supply of oil.At present,because of bad tolerance of salt,shear rate and temperature,the application of partially hydrolyzed polyacrylamide which used in China is greatly limited.So the study of hydrophobically associating polyacrylamide was carried out to rasie the salt, shear rate and temperature resistance of oil recovery additive.
In this article,the hydrophobically associating polyacrylamide was synthesized by the aqueous solution polymerization and following hydrolysis,selecting acrylamide as hydrophilic monomer,2-Vinylpyridine as hydrophobic monomer, potassium persulfate and azo-compound AM-01 as the complex initiator.
The effects of experimental factors such as mass fraction of monomer,initiation temperature,amount of initiator,pH,hydrophobic monomer concentration and additives on the molecular weight of the polymer were studied and then the optimum synthesis conditions were determinded.The obtained optimum reaction conditions were as follows:mass fraction of monomer 30%,initiation temperature 12℃,pH 5.0, hydrophobic monomer 0.4%,initiator AM-01 0.025%and K_2S_2O_8 0.0025%,additive urea 5%.The molecular weights of polymers were measured by the viscosity method, and the structure of the polymers were characterized by the infrared absorption spectrum and nuclear magnetic resonance.It was investigated how the properties of the polymer solution were affected by the polymer concentration,emperature,salinity and shear rate.The critical associating concentration(CAC) apparesd with the increasing of the polymer concentration.Compared with the partially hydrolyzed polyacrylamide,the hydrophobically associating polyacrylamide had better resistance of salinity,shear rate and temperature.And when shear stress disappeared,the apparent viscosity of hydrophobically associating polyacrylamide solution recovered, showing that the shearing action was reversible.It had important significance in practical applications.
At the same time,with the diminution of fresh water resource and focusing on the environmental protection,the flocculants played more and more important roles all over the world.Water-soluble cationic polyacrylamide can be used as efficient flocculants for many disperse systems such as water treatment,paper-making,mineral processing and other fields.It is desirable to synthesize the cationic polyacrylamide with low cost and high performance to improve the flocculating performance of domestic flocculant.
Cationic flocculant P(AM-DAC-DMDAAC) was synthesized by aqueous solution polymerization using acrylamide(AM) as the molecular backbone, acryloyloxyethyl trimethyl ammonium chloride(DAC) and dimethyl diallyl ammonium chloride(DMDAAC) as cation group.The obtained optimum reaction conditions were as follows:mass fraction of monomer 30%,initiator temperature 12℃,pH 5.0,cationic monomer concentration 25%,initiator AM-01 0.03%and K_2S_2O_8 0.003%.The molecular weights of polymers were measured by the viscosity method, and the structure of the polymers were characterized by the infrared absorption spectrum and nuclear magnetic resonance.The polymers' capability of flocculating performance was investigated in waste water.
石油作为重要的能源和化工原料,是一种有限的不可再生资源,其储量正在不断地减少。为保证石油长期稳定供应,满足人类的需求,必须研究和发展新的石油采收技术。目前,国内使用的部分水解聚丙烯酰胺由于抗温抗盐抗剪切性能较差,应用受到很大的限制。因此,为了提高采油助剂的耐温、耐盐和耐剪切性能,开展了疏水缔合型聚丙烯酰胺的研究。
本文以丙烯酰胺为亲水单体,2-乙烯基吡啶为疏水单体,过硫酸钾和偶氮化合物AM-01为复合引发体系,通过水溶液自由基共聚后水解的方法,合成了一种新的疏水缔合型聚丙烯酰胺。
研究了单体浓度、引发温度、引发剂种类及用量、pH值、疏水单体含量及添加剂等聚合反应条件对聚合物相对分子质量的影响,确定了最佳合成条件:单体质量分数30%,引发温度12℃,pH值为5.0,疏水单体摩尔分数0.4%,引发剂AM-01和K_2S_2O_8的浓度分别为0.025%和0.0025%,添加剂尿素加量为5%。用黏度法测定了聚合物的分子量,运用红外光谱和核磁共振对聚合物结构进行表征。考察了聚合物溶液的浓度、温度、盐浓度及剪切速率对聚合物溶液性质的影响。疏水缔合型聚丙烯酰胺水溶液的表观粘度随其浓度的增加,出现了一个临界缔合浓度(CAC)。与部分水解的聚丙烯酰胺产品相比,疏水缔合型聚丙烯酰胺具有更好的耐温、耐盐和耐剪切性能。并且当剪切应力消失后,疏水缔合聚丙烯酰胺溶液的表观粘度逐渐恢复,表现出剪切作用的可逆性,对实际应用有重要的意义。
同时,随着淡水资源的日益匮乏和人们对环境保护的日渐重视,水处理用絮凝剂的研制受到越来越多的关注。水溶性阳离子型聚丙烯酰胺作为一种有效的絮凝剂,广泛应用于生活污水以及石油、造纸和冶矿等领域。目前国内阳离子聚丙烯酰胺絮凝剂的生产技术水平还落后于国外,急需生产出一种低成本、高性能的产品。
因此,本文以丙烯酰胺(AM)为分子骨架,丙烯酰氧乙基三甲基氯化铵(DAC)和二烯丙基二甲基氯化铵(DMDAAC)为阳离子单体,通过水溶液共聚合的方法,合成了一种阳离子型聚丙烯酰胺絮凝剂P(AM-DAC-DMDAAC)。确定了反应的最佳合成条件:单体质量分数30%,引发温度12℃,pH值为5.0,阳离子单体含量25%,引发剂AM-01和K_2S_2O_8的浓度分别为0.03%和0.003%。用黏度法测定了聚合物的相对分子质量,运用红外光谱和核磁共振对聚合物结构进行分析,并用合成的絮凝剂对城市生活污水进行絮凝试验,测定其絮凝性能。
Polyacrylamide is one kind of linear water-soluble macromolecule with the most extensive use,which is applied in the field of petroleum,chemical engineering and water treatment extensively.
As an important energy and chemical material,oil is a limited and non-renewable resource.Therefore,we must research and develop the new oil recovery technologies in order to ensure the long-term and stable supply of oil.At present,because of bad tolerance of salt,shear rate and temperature,the application of partially hydrolyzed polyacrylamide which used in China is greatly limited.So the study of hydrophobically associating polyacrylamide was carried out to rasie the salt, shear rate and temperature resistance of oil recovery additive.
In this article,the hydrophobically associating polyacrylamide was synthesized by the aqueous solution polymerization and following hydrolysis,selecting acrylamide as hydrophilic monomer,2-Vinylpyridine as hydrophobic monomer, potassium persulfate and azo-compound AM-01 as the complex initiator.
The effects of experimental factors such as mass fraction of monomer,initiation temperature,amount of initiator,pH,hydrophobic monomer concentration and additives on the molecular weight of the polymer were studied and then the optimum synthesis conditions were determinded.The obtained optimum reaction conditions were as follows:mass fraction of monomer 30%,initiation temperature 12℃,pH 5.0, hydrophobic monomer 0.4%,initiator AM-01 0.025%and K_2S_2O_8 0.0025%,additive urea 5%.The molecular weights of polymers were measured by the viscosity method, and the structure of the polymers were characterized by the infrared absorption spectrum and nuclear magnetic resonance.It was investigated how the properties of the polymer solution were affected by the polymer concentration,emperature,salinity and shear rate.The critical associating concentration(CAC) apparesd with the increasing of the polymer concentration.Compared with the partially hydrolyzed polyacrylamide,the hydrophobically associating polyacrylamide had better resistance of salinity,shear rate and temperature.And when shear stress disappeared,the apparent viscosity of hydrophobically associating polyacrylamide solution recovered, showing that the shearing action was reversible.It had important significance in practical applications.
At the same time,with the diminution of fresh water resource and focusing on the environmental protection,the flocculants played more and more important roles all over the world.Water-soluble cationic polyacrylamide can be used as efficient flocculants for many disperse systems such as water treatment,paper-making,mineral processing and other fields.It is desirable to synthesize the cationic polyacrylamide with low cost and high performance to improve the flocculating performance of domestic flocculant.
Cationic flocculant P(AM-DAC-DMDAAC) was synthesized by aqueous solution polymerization using acrylamide(AM) as the molecular backbone, acryloyloxyethyl trimethyl ammonium chloride(DAC) and dimethyl diallyl ammonium chloride(DMDAAC) as cation group.The obtained optimum reaction conditions were as follows:mass fraction of monomer 30%,initiator temperature 12℃,pH 5.0,cationic monomer concentration 25%,initiator AM-01 0.03%and K_2S_2O_8 0.003%.The molecular weights of polymers were measured by the viscosity method, and the structure of the polymers were characterized by the infrared absorption spectrum and nuclear magnetic resonance.The polymers' capability of flocculating performance was investigated in waste water.
引文
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