绿色阻垢剂聚环氧磺羧酸的合成及其性能评定
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摘要
目前由于磷系水处理剂的广泛使用，已对环境造成了损害。出于环境保护的目的，环保法规日益严格，磷系水处理剂的使用必将受到严格限制，因此开发对环境无污染的绿色水处理剂必将是21世纪水处理行业的发展方向。聚环氧琥珀酸（PESA）不仅对碳酸钙、硫酸钙具有良好的阻垢分散性能，还兼有一定的缓蚀作用，且可生物降解，有很好的应用前景，已成为国外水处理剂研究的热点，国内在这方面的研究刚刚起步。
本文首先在催化剂钨酸钠的存在下，用过氧化氢在醇-水体系中氧化马来酸酐制得了环氧琥珀酸氢钠，在75%的乙醇水溶液中获得的环氧琥珀酸氢钠晶体直接析出率为93.4%，并对其结构进行了表征。采用单体直接聚合的方法使环氧琥珀酸钠盐在引发剂氢氧化钙的作用下开环聚合得到聚环氧琥珀酸（PESA），对其结构进行了表征，并对其聚合条件进行了一些摸索，结果表明：环氧琥珀酸氢钠与引发剂用量在10:1～10:2左右、聚合时间在2h左右、聚合温度在95℃制得的PESA静态阻碳酸钙垢性能较好。采用静态阻垢法对不同条件下合成的三种PESA抑制碳酸钙、硫酸钙、磷酸钙垢沉积，稳定锌盐和分散氧化铁的性能进行了评定，结果表明：（1）PESA对碳酸钙有比较好的阻垢性能，其阻碳酸钙垢的能力随用量的增加而增加，当使用浓度超过15 mg .L-1后，其阻垢率不再明显增加，其中PESA1在用量为7 mg .L-1时，其阻垢率达到79.6%；（2）PESA阻硫酸钙垢的性能比较理想，在质量浓度为2mg .L-1时，其阻垢率在85%以上，5 mg .L-1时达90%以上；（3）PESA抑制磷酸钙沉积、稳定锌盐和分散氧化铁的能力不佳；（4）不同聚合条件下得到的PESA，其阻垢性能有差异。
鉴于共聚物中磺酸基团的引入可改善其对磷酸钙、锌垢的抑制能力及对金属离子的稳定作用，本文通过环氧氯丙烷与亚硫酸氢钠反应合成得到3-氯-2-羟基丙磺酸钠，然后将3-氯-2-羟基丙磺酸钠与氢氧化钠作用生成了2,3-环氧丙磺酸钠，进一步与环氧琥珀酸钠盐在引发剂氢氧化钙的作用下发生共聚制得了聚环氧磺羧酸（PECS），用红外光谱和核磁共振对PECS及其中间体的结构进行了表征，
表明得到环氧琥珀酸——环氧丙磺酸共聚物PECS。并对不同条件下聚合得到的PECS的阻垢分散性能及缓蚀性能进行了评定，结果表明：（1）PECS阻碳酸钙垢的性能与PESA相比，没有提高，反而下降，在20 mg .L-1时，所合成的PECS1～PECS6对碳酸钙的阻垢率分别为：66.2%，84.1%，87.7%，61.3%，78.7%， 80.7%。（2） PECS阻硫酸钙垢的性能比较理想，当用量在7 mg .L-1时，所合成的PECS1～PECS6对硫酸钙的阻垢率分别为：93.7%，93.8%，94.6%，90.6%，92.0%和94.3%。（3）在目前共聚条件下，PECS抑制磷酸钙沉积、稳定锌盐及分散氧化铁的能力与PESA相比均有不同程度的改善。此外，极化曲线实验和旋转挂片缓蚀实验的研究表明：PESA和PECS均是阳极抑制型缓蚀剂，它们在两倍自来水介质中的浓度为50 mg .L-1时，对碳钢的缓蚀效果比较理想，其缓蚀率分别在98%以上和90%以上。对PECS这一新型绿色阻垢剂值得进一步深入研究
At present, in domestic and international markets, the staple scale inhibitors for water treatment are phosphorous compounds that have already given rise to the pollution of the environment. Their production and usage must be strictly controlled according to the environmental protection laws. The research and development of non-phosphorous and environmentally friendly water treatment agents must be one important trend in twenty-first century. Polyepoxysuccinic acid is a novel green water treatment agent developed abroad in recent years. It is reported that it has become the new hot point of water treatment agent industry for its excellent scale inhibition, dispersion, corrosion inhibition and biodegradability. Its research work just began in China.
In this paper, sodium hydrogen epoxysuccinate has been produced by eopoxidizing maleate with hydrogen peroxide in the presence of an epoxidation catalyst-sodium tungstate. The structure of the product has been characterized by IR, 1HNMR and element analysis. The productivity of sodium hydrogen epoxysuccinate was 93.4% in the aqueous solution containing 75% by volume of alcohol. Polyepoxysuccinic acid has also been synthesized by polymerization of epoxysuccinate disodium salt in the presence of the initiator-calcium hydroxide. The polymer's structure has been also characterized by IR and 1HNMR. According to the test results, the optimal polymerization condition was that the molar ratio of the monomer to the initiator was 10:1 to 10:2, the reaction time about 2 hour and the reaction temperature 95℃. Three kinds of polyepoxysuccinic acid were synthesized under different reaction conditions, and the performance of scale inhibition was evaluated by static test. The zinc salt stabilization and the ferric oxide dispersion of the polymer were also evaluated in this paper. The following conclusions can be deduced from the results of the tests. (1) Polyepoxysuccinic acid (PESA) is a good inhibitor on calcium carbonate scale. Its scale inhibition efficiency improved if its
concentration in aqueous system increased. But when its concentration was more than 15 mg .L-1, its calcium carbonate scale inhibition efficiency did not improved evidently. The calcium carbonate scale inhibition efficiency of PESA1 was 79.6% when its concentration in aqueous system was 7 mg .L-1. (2) Polyepoxysuccinic acid has good capacity of calcium sulfate scale inhibition. The calcium sulfate scale inhibition efficiency of PESA was more than 85% when its concentration in aqueous system was 2 mg .L-1, and the scale inhibition efficiency was more than 90% when the concentration was 5 mg .L-1. (3) Polyepoxysuccinic acid has poor capacity of calcium phosphate inhibition, zinc salt stabilization and ferric oxide dispersion. (4) The different polyepoxysuccinic acids synthesized under different conditions have different capacities in scale inhibition.
It is reported that polymeric scale inhibitor's capabilities in calcium phosphate scale inhibition, zinc salt scale inhibition and metal ionic dispersion would improved if sulphoacid groups were introduced into the polymer's molecular. In this paper, the sodium 3-chloro-2-hydroxypropylsulfonate has been synthesized by epichlorohydrin react on sodium hydrogen sulfite at first, then sodium 2,3-epoxypropylsulfonate has been produced by sodium 3-chloro-2-hydroxypropylsulfonate react on sodium hydroxide, at last, epoxysuccinate-2,3-epoxypropylsulfonate copolymer (PECS) has been synthesized by copolymerization in the presence of the initiator--calcium hydroxide. The copolymer's structure was confirmed by IR and 1HNMR. A series of PECS was synthesized under different reaction conditions, and their performance of scale inhibition was evaluated by static test. The zinc salt stabilization and the ferric oxide dispersion of PECS were also evaluated in this paper. The following conclusions can be deduced from the results of the tests. (1) The copolymer's capacity in calcium carboate scale inhibition decreased compared with polyepoxysuccinic acid. The calcium
本文首先在催化剂钨酸钠的存在下，用过氧化氢在醇-水体系中氧化马来酸酐制得了环氧琥珀酸氢钠，在75%的乙醇水溶液中获得的环氧琥珀酸氢钠晶体直接析出率为93.4%，并对其结构进行了表征。采用单体直接聚合的方法使环氧琥珀酸钠盐在引发剂氢氧化钙的作用下开环聚合得到聚环氧琥珀酸（PESA），对其结构进行了表征，并对其聚合条件进行了一些摸索，结果表明：环氧琥珀酸氢钠与引发剂用量在10:1～10:2左右、聚合时间在2h左右、聚合温度在95℃制得的PESA静态阻碳酸钙垢性能较好。采用静态阻垢法对不同条件下合成的三种PESA抑制碳酸钙、硫酸钙、磷酸钙垢沉积，稳定锌盐和分散氧化铁的性能进行了评定，结果表明：（1）PESA对碳酸钙有比较好的阻垢性能，其阻碳酸钙垢的能力随用量的增加而增加，当使用浓度超过15 mg .L-1后，其阻垢率不再明显增加，其中PESA1在用量为7 mg .L-1时，其阻垢率达到79.6%；（2）PESA阻硫酸钙垢的性能比较理想，在质量浓度为2mg .L-1时，其阻垢率在85%以上，5 mg .L-1时达90%以上；（3）PESA抑制磷酸钙沉积、稳定锌盐和分散氧化铁的能力不佳；（4）不同聚合条件下得到的PESA，其阻垢性能有差异。
鉴于共聚物中磺酸基团的引入可改善其对磷酸钙、锌垢的抑制能力及对金属离子的稳定作用，本文通过环氧氯丙烷与亚硫酸氢钠反应合成得到3-氯-2-羟基丙磺酸钠，然后将3-氯-2-羟基丙磺酸钠与氢氧化钠作用生成了2,3-环氧丙磺酸钠，进一步与环氧琥珀酸钠盐在引发剂氢氧化钙的作用下发生共聚制得了聚环氧磺羧酸（PECS），用红外光谱和核磁共振对PECS及其中间体的结构进行了表征，
表明得到环氧琥珀酸——环氧丙磺酸共聚物PECS。并对不同条件下聚合得到的PECS的阻垢分散性能及缓蚀性能进行了评定，结果表明：（1）PECS阻碳酸钙垢的性能与PESA相比，没有提高，反而下降，在20 mg .L-1时，所合成的PECS1～PECS6对碳酸钙的阻垢率分别为：66.2%，84.1%，87.7%，61.3%，78.7%， 80.7%。（2） PECS阻硫酸钙垢的性能比较理想，当用量在7 mg .L-1时，所合成的PECS1～PECS6对硫酸钙的阻垢率分别为：93.7%，93.8%，94.6%，90.6%，92.0%和94.3%。（3）在目前共聚条件下，PECS抑制磷酸钙沉积、稳定锌盐及分散氧化铁的能力与PESA相比均有不同程度的改善。此外，极化曲线实验和旋转挂片缓蚀实验的研究表明：PESA和PECS均是阳极抑制型缓蚀剂，它们在两倍自来水介质中的浓度为50 mg .L-1时，对碳钢的缓蚀效果比较理想，其缓蚀率分别在98%以上和90%以上。对PECS这一新型绿色阻垢剂值得进一步深入研究
At present, in domestic and international markets, the staple scale inhibitors for water treatment are phosphorous compounds that have already given rise to the pollution of the environment. Their production and usage must be strictly controlled according to the environmental protection laws. The research and development of non-phosphorous and environmentally friendly water treatment agents must be one important trend in twenty-first century. Polyepoxysuccinic acid is a novel green water treatment agent developed abroad in recent years. It is reported that it has become the new hot point of water treatment agent industry for its excellent scale inhibition, dispersion, corrosion inhibition and biodegradability. Its research work just began in China.
In this paper, sodium hydrogen epoxysuccinate has been produced by eopoxidizing maleate with hydrogen peroxide in the presence of an epoxidation catalyst-sodium tungstate. The structure of the product has been characterized by IR, 1HNMR and element analysis. The productivity of sodium hydrogen epoxysuccinate was 93.4% in the aqueous solution containing 75% by volume of alcohol. Polyepoxysuccinic acid has also been synthesized by polymerization of epoxysuccinate disodium salt in the presence of the initiator-calcium hydroxide. The polymer's structure has been also characterized by IR and 1HNMR. According to the test results, the optimal polymerization condition was that the molar ratio of the monomer to the initiator was 10:1 to 10:2, the reaction time about 2 hour and the reaction temperature 95℃. Three kinds of polyepoxysuccinic acid were synthesized under different reaction conditions, and the performance of scale inhibition was evaluated by static test. The zinc salt stabilization and the ferric oxide dispersion of the polymer were also evaluated in this paper. The following conclusions can be deduced from the results of the tests. (1) Polyepoxysuccinic acid (PESA) is a good inhibitor on calcium carbonate scale. Its scale inhibition efficiency improved if its
concentration in aqueous system increased. But when its concentration was more than 15 mg .L-1, its calcium carbonate scale inhibition efficiency did not improved evidently. The calcium carbonate scale inhibition efficiency of PESA1 was 79.6% when its concentration in aqueous system was 7 mg .L-1. (2) Polyepoxysuccinic acid has good capacity of calcium sulfate scale inhibition. The calcium sulfate scale inhibition efficiency of PESA was more than 85% when its concentration in aqueous system was 2 mg .L-1, and the scale inhibition efficiency was more than 90% when the concentration was 5 mg .L-1. (3) Polyepoxysuccinic acid has poor capacity of calcium phosphate inhibition, zinc salt stabilization and ferric oxide dispersion. (4) The different polyepoxysuccinic acids synthesized under different conditions have different capacities in scale inhibition.
It is reported that polymeric scale inhibitor's capabilities in calcium phosphate scale inhibition, zinc salt scale inhibition and metal ionic dispersion would improved if sulphoacid groups were introduced into the polymer's molecular. In this paper, the sodium 3-chloro-2-hydroxypropylsulfonate has been synthesized by epichlorohydrin react on sodium hydrogen sulfite at first, then sodium 2,3-epoxypropylsulfonate has been produced by sodium 3-chloro-2-hydroxypropylsulfonate react on sodium hydroxide, at last, epoxysuccinate-2,3-epoxypropylsulfonate copolymer (PECS) has been synthesized by copolymerization in the presence of the initiator--calcium hydroxide. The copolymer's structure was confirmed by IR and 1HNMR. A series of PECS was synthesized under different reaction conditions, and their performance of scale inhibition was evaluated by static test. The zinc salt stabilization and the ferric oxide dispersion of PECS were also evaluated in this paper. The following conclusions can be deduced from the results of the tests. (1) The copolymer's capacity in calcium carboate scale inhibition decreased compared with polyepoxysuccinic acid. The calcium
引文
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