互穿网络结构高吸水树脂的合成与性能
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摘要
本文以过硫酸钾(KPS)为引发剂，N,N'-亚甲基双丙烯酰胺(MBA)为交联剂，以丙烯酸羟丙酯(HPA)与2-丙烯酰胺-2-甲基丙磺酸(AMPS)的共聚物(P(HPA/AMPS))为互穿聚合物，采用溶液聚合，合成了一种具有互穿网络结构的新型高性能聚丙烯酸钠高吸水树脂(PSA-IP-P(HPA/AMPS))。讨论了引发剂用量、交联剂用量、反应温度、单体中和度、互穿聚合物的组成及用量对高吸水树脂PSA-IP-P(HPA/AMPS)性能的影响。比较了PSA-IP-P(HPA/AMPS)与聚丙烯酸钠高吸水树脂(PSA)的吸液性能。研究了其红外光谱特性和热性能。
红外光谱研究表明，PSA-IP-P(HPA/AMPS)树脂吸水前后在1290cm~(-1)处出现了明显的-S=O伸缩振动吸收峰，PSA树脂则无此吸收峰出现。热重分析表明，PSA-IP-P(HPA/AMPS)和PSA的失重趋势很相似，但在400℃附近，相对PSA，前者出现了较明显的失重。结合红外光谱和热分析结果，认为P(HPA/AMPS)和PSA形成了互穿网络结构。
对高吸水树脂吸液性能的研究表明，PSA-IP-P(HPA/AMPS)吸去离子水和生理盐水的能力和PSA相比有较大幅度的提高。也优于相同单体用量的丙烯酸(AA)、HPA、AMPS交联共聚的高吸水树脂。当引发剂用量为单体用量的0.1％，交联剂用量为单体用量的0.02％，反应温度为70℃，单体中和度为70％，互穿聚合物的重均分子量为220万、HPA和AMPS的质量比为0.5、用量为2.4％时，合成的PSA-IP-P(HPA/AMPS)高吸水树脂具有最佳的吸水能力。其吸去离子水量为2075ml/g，吸生理盐水量为115ml/g，分别比PSA高36.1％和35.3％。
本文研究了影响PSA-IP-P(HPA/AMPS)树脂吸水能力的各因素。结果表明：
盐对树脂的吸水能力影响较大，随着盐浓度的增加，树脂的吸水能力急剧下降，
但当盐浓度大于0.5%以后下降趋于平稳。盐的种类及金属离子的价态不同对树
脂吸水能力的影响程度也不同(Na+ 水的能力不同，当pH为6时，其吸收能力达到最佳，但pH在5一9之间树脂的
吸水量均大于1000ml/g。树脂的吸水能力几乎不受水温的影响。
文中还研究了该树脂的其他性能如吸水速度、保水能力、稳定性等。结果
表明，树脂的吸水速度受粒径影响较大，其大小顺序为20目<20一60目<60一120
目。在一10℃下经过5次反复冷冻一解冻过程，其性能基本不变。在不同温度下
加热处理1小时，在100℃以前树脂的吸水能力变化不大;100℃下经过5小时
的处理，吸水率仅下降约10%。研究结果还表明，树脂的自然保水性、热保水
性、加压保水性均较好。
As a new superabsorbent with high performance, the sample of interpenetrating polymer network, i.e., PSA-IP-P(PHA/AMPS), coming from poly(sodium acrylate) (PSA) and the copolymer of hydroxypropyl acrylate (HPA) and 2-acrylamido-2-methy propone sulfonate (AMPS) was prepared by aqueous solution polymerization, in which potassium persulfate (KPS) was used as initiator and N,N'-methylene bis-acrylamid (MBA) as cross-linking agent. The factors influencing the water absorption capacities of the superabsorbent such as the amount of initiator, crossing agent and P(HPA/AMPS), the polymerizing temperature, the neutralizing degree of AA, and the component of P(HPA/AMPS) were discussed. The water absorption capacities of PSA-IP-P(PHA/AMPS) and poly(sodium acrylate) (PSA) were compared, and their infrared spectra and thermal degradation behaviors were characterized.
A band of S=O stretching vibration at 1290cm-1 could be observed in the FTIR spectra of PSA-IP-P(PHA/AMPS) before and after absorbing water, while it didn't appear in that of PSA. The thermogravimetric analysis of PSA-IP-P(PHA/AMPS) and PSA showed that their TG curves were similar. However, near 400℃ the former appeared a obvious weight loss, but not PSA. The FTIR and TG results showed that the interpenetrating network of P(HPA/AMPS) and PSA were formed.
The research results of water absorbency showed that PSA-IP-P(PHA/AMPS) possessed higher water and 0.9% saline absorption capacities than PSA and terpolymer of SA, HPA and AMPS. The superabsorbent with the best water
absorption could be synthesized by the following conditions: the polymerizing temperature was 70℃, the neutralizing degree of AA was 70%, the amount of initiator and cross-linking agent was 0.1% and 0.02% weight of monomers, respectively, and the amount of P(HPA/AMPS) (HPA/AMPS=0.5) was 2.4% weight of monomer, the average molecular weight of P(HPA/AMPS) was 2.2×106. The deion-water and 0.9% saline absorbency of PSA-IP-P(PHA/AMPS) superaborbent were 2075ml/g and 115ml/g, 36.1% and 35.3% higher than that of PSA, respectively.
The factors influencing the water absorbability of PSA-EP-P(HPA/AMPS) were studied. It was shown that the water absorbency of superabsorbent was strongly affected by the concentration of salts. As the concentration of salt increases, the water absorbency of superabsorbent decreases rapidly. When the concentration of salt was higher than 0.5%, the decreasing trend was not so obvious. Different sort of salts and different valence state of ions influenced the water absorbency in different degree (Na+ < Mg2+ < Ca2+). The water absorbency of the superabsorbent was different when the absorbed water has the different pH value. When pH value was 6, its absorbency arrived the highest amount. However, in the region from pH5 to pH9, the water absorption of the superabsorbent was higher than 1000ml/g. The results also showed that the water absorbency of the superabsorbent was hardly affected by the test temperature.
Other properties of the superabsorbent, such as the absorption rate, water-retention and stabilities, were studied. It was shown that the water absorption rate of superabsorbent was influenced by its particle size, in the range of 20-120 mesh, 20<20-60<120. After five frozen-defrozen processes at -10℃, the water absorbency of superabsorbent was no change. The water absorbency of superabsorbent hardly changed after one-hour heat-treatment at 100℃ and decreased 10% after five-hour heat-treatment. It also showed that the water retention of the superabsorbent was very good on the conditions of different temperature and pressure.
红外光谱研究表明，PSA-IP-P(HPA/AMPS)树脂吸水前后在1290cm~(-1)处出现了明显的-S=O伸缩振动吸收峰，PSA树脂则无此吸收峰出现。热重分析表明，PSA-IP-P(HPA/AMPS)和PSA的失重趋势很相似，但在400℃附近，相对PSA，前者出现了较明显的失重。结合红外光谱和热分析结果，认为P(HPA/AMPS)和PSA形成了互穿网络结构。
对高吸水树脂吸液性能的研究表明，PSA-IP-P(HPA/AMPS)吸去离子水和生理盐水的能力和PSA相比有较大幅度的提高。也优于相同单体用量的丙烯酸(AA)、HPA、AMPS交联共聚的高吸水树脂。当引发剂用量为单体用量的0.1％，交联剂用量为单体用量的0.02％，反应温度为70℃，单体中和度为70％，互穿聚合物的重均分子量为220万、HPA和AMPS的质量比为0.5、用量为2.4％时，合成的PSA-IP-P(HPA/AMPS)高吸水树脂具有最佳的吸水能力。其吸去离子水量为2075ml/g，吸生理盐水量为115ml/g，分别比PSA高36.1％和35.3％。
本文研究了影响PSA-IP-P(HPA/AMPS)树脂吸水能力的各因素。结果表明：
盐对树脂的吸水能力影响较大，随着盐浓度的增加，树脂的吸水能力急剧下降，
但当盐浓度大于0.5%以后下降趋于平稳。盐的种类及金属离子的价态不同对树
脂吸水能力的影响程度也不同(Na+
吸水量均大于1000ml/g。树脂的吸水能力几乎不受水温的影响。
文中还研究了该树脂的其他性能如吸水速度、保水能力、稳定性等。结果
表明，树脂的吸水速度受粒径影响较大，其大小顺序为20目<20一60目<60一120
目。在一10℃下经过5次反复冷冻一解冻过程，其性能基本不变。在不同温度下
加热处理1小时，在100℃以前树脂的吸水能力变化不大;100℃下经过5小时
的处理，吸水率仅下降约10%。研究结果还表明，树脂的自然保水性、热保水
性、加压保水性均较好。
As a new superabsorbent with high performance, the sample of interpenetrating polymer network, i.e., PSA-IP-P(PHA/AMPS), coming from poly(sodium acrylate) (PSA) and the copolymer of hydroxypropyl acrylate (HPA) and 2-acrylamido-2-methy propone sulfonate (AMPS) was prepared by aqueous solution polymerization, in which potassium persulfate (KPS) was used as initiator and N,N'-methylene bis-acrylamid (MBA) as cross-linking agent. The factors influencing the water absorption capacities of the superabsorbent such as the amount of initiator, crossing agent and P(HPA/AMPS), the polymerizing temperature, the neutralizing degree of AA, and the component of P(HPA/AMPS) were discussed. The water absorption capacities of PSA-IP-P(PHA/AMPS) and poly(sodium acrylate) (PSA) were compared, and their infrared spectra and thermal degradation behaviors were characterized.
A band of S=O stretching vibration at 1290cm-1 could be observed in the FTIR spectra of PSA-IP-P(PHA/AMPS) before and after absorbing water, while it didn't appear in that of PSA. The thermogravimetric analysis of PSA-IP-P(PHA/AMPS) and PSA showed that their TG curves were similar. However, near 400℃ the former appeared a obvious weight loss, but not PSA. The FTIR and TG results showed that the interpenetrating network of P(HPA/AMPS) and PSA were formed.
The research results of water absorbency showed that PSA-IP-P(PHA/AMPS) possessed higher water and 0.9% saline absorption capacities than PSA and terpolymer of SA, HPA and AMPS. The superabsorbent with the best water
absorption could be synthesized by the following conditions: the polymerizing temperature was 70℃, the neutralizing degree of AA was 70%, the amount of initiator and cross-linking agent was 0.1% and 0.02% weight of monomers, respectively, and the amount of P(HPA/AMPS) (HPA/AMPS=0.5) was 2.4% weight of monomer, the average molecular weight of P(HPA/AMPS) was 2.2×106. The deion-water and 0.9% saline absorbency of PSA-IP-P(PHA/AMPS) superaborbent were 2075ml/g and 115ml/g, 36.1% and 35.3% higher than that of PSA, respectively.
The factors influencing the water absorbability of PSA-EP-P(HPA/AMPS) were studied. It was shown that the water absorbency of superabsorbent was strongly affected by the concentration of salts. As the concentration of salt increases, the water absorbency of superabsorbent decreases rapidly. When the concentration of salt was higher than 0.5%, the decreasing trend was not so obvious. Different sort of salts and different valence state of ions influenced the water absorbency in different degree (Na+ < Mg2+ < Ca2+). The water absorbency of the superabsorbent was different when the absorbed water has the different pH value. When pH value was 6, its absorbency arrived the highest amount. However, in the region from pH5 to pH9, the water absorption of the superabsorbent was higher than 1000ml/g. The results also showed that the water absorbency of the superabsorbent was hardly affected by the test temperature.
Other properties of the superabsorbent, such as the absorption rate, water-retention and stabilities, were studied. It was shown that the water absorption rate of superabsorbent was influenced by its particle size, in the range of 20-120 mesh, 20<20-60<120. After five frozen-defrozen processes at -10℃, the water absorbency of superabsorbent was no change. The water absorbency of superabsorbent hardly changed after one-hour heat-treatment at 100℃ and decreased 10% after five-hour heat-treatment. It also showed that the water retention of the superabsorbent was very good on the conditions of different temperature and pressure.
引文
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2 Fresric L.Buchholz. Products of chemistry. J. Chem. Edu. 1996.73(6).512～515
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