CN101406853B - 一种附聚型强酸性阳离子色谱柱用填料的合成方法及产品 - Google Patents

一种附聚型强酸性阳离子色谱柱用填料的合成方法及产品 Download PDF

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CN101406853B
CN101406853B CN2008101597014A CN200810159701A CN101406853B CN 101406853 B CN101406853 B CN 101406853B CN 2008101597014 A CN2008101597014 A CN 2008101597014A CN 200810159701 A CN200810159701 A CN 200810159701A CN 101406853 B CN101406853 B CN 101406853B
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崔成来
王金平
荆建增
王群
朱新勇
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QINGDAO SHENGHAN CHROMATOGRAPHY TECHNOLOGY Co Ltd
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Abstract

一种附聚型强酸性阳离子色谱柱用填料的合成方法,将表面氯甲基化、季胺化、转型的合成体型交联芳香烯烃有机共聚物基球与磺化、转型的合成体型交联芳香烯烃有机共聚物乳胶附聚,然后装柱,表面采用浓盐酸和甲醛进行氯甲基化、有碱性阴离子交换基团的体型交联芳香烯烃有机共聚物作为基球,表面有酸性阳离子交换基团的体型交联芳香烯烃有机共聚物作为乳胶。基球采用浓盐酸和甲醛进行氯甲基化,避免了采用氯甲基醚和二氯甲基醚进行氯甲基化对人体的毒害。采用多价盐的形态附聚,电荷密度高,附聚反应更迅速、更完全。浓硫酸、二甲基乙醇胺或三乙醇胺毒性较小。悬浮聚合法制作基球反应块,周期短。用本发明合成方法生产产品更环保、安全。

Description

一种附聚型强酸性阳离子色谱柱用填料的合成方法及产品
技术领域
本发明涉及阳离子色谱柱填料,具体的讲是一种附聚型强酸性阳离子色谱柱用填料的合成方法及产品。
背景技术
中国发明专利申请号01141658.0《表面附聚薄壳型高效阳离子色谱柱填料的新制备方法》提供了一种在表面季胺化的聚苯乙烯-二乙烯基苯的基球表面直接通过静电作用附聚磺酸化的阳离子乳胶的制备方法,该制备方法采用常规方法对单分散聚苯乙烯-二乙烯基苯微球氯甲基化,常规氯甲基化使用氯甲基醚(其中有少量二氯甲基醚)在无水三氯化铝或无水氯化锌的催化作用下进行反应,毒性很大的氯甲基醚和二氯甲基醚是强致癌物质。另外,季胺化的聚苯乙烯-二乙烯基苯基球和磺酸化的聚苯乙烯-二乙烯基苯乳胶表面都是一价离子,电荷密度不高,吸引力弱。
发明内容
针对上述制备方法的缺点,本方法提供一种制作过程中毒性较小的附聚型强酸性阳离子色谱柱用填料的合成方法及产品。
为了实现上述发明目的,本发明采取的技术方案是:一种附聚型强酸性阳离子色谱柱用填料的合成方法,包括将表面氯甲基化、季胺化、转型的合成体型交联芳香烯烃有机共聚物基球与磺化、转型的合成体型交联芳香烯烃有机共聚物乳胶附聚,然后装柱,其特征在于表面采用浓盐酸和甲醛进行氯甲基化、有碱性阴离子交换基团的体型交联芳香烯烃有机共聚物作为基球,表面有酸性阳离子交换基团的体型交联芳香烯烃有机共聚物作为乳胶。
基球采用浓盐酸和甲醛进行氯甲基化,避免了采用氯甲基醚和二氯甲基醚进行氯甲基化对人体的毒害。
基球氯甲基化还要搅拌并加入无水氯化铝,反应温度40-80℃。
基球采用二甲基乙醇胺或三乙醇胺进行季胺化,反应保持温度30-70℃。避免了采用易挥发、气味重的三甲胺进行季胺化对人体的毒害。
基球表面有至少二价强碱性阴离子交换基团,乳胶表面有至少二价强酸性阳离子交换基团。基球和乳胶表面离子电荷密度大,两者吸引力大,附聚反应的更完全。
基球的强碱性阴离子交换基团是二价-NR3OH或-NR3HCO3,乳胶的强酸性阳离子交换基团是二价-SO3H或-SO3Na。
乳胶采用浓硫酸进行磺化,磺化反应升温保持在50-100℃。避免了采用二氯乙烷和氯磺酸时磺酸化反应控制比较困难、氯磺酸易挥发对人的呼吸道有较大的刺激的缺点。
基球和乳胶的的体型是球形。
基球和乳胶是苯乙烯-二乙烯苯共聚物。
基球采用悬浮聚合法制作。悬浮聚合法反应块,周期短。
一种附聚型强酸性阳离子色谱柱用填料,其特征在于所述的附聚型强酸性阳离子色谱柱用填料是采用上述任意一种合成方法制造的。
本发明的优点是基球采用浓盐酸和甲醛进行氯甲基化,避免了采用氯甲基醚和二氯甲基醚进行氯甲基化对人体的毒害。采用多价盐的形态附聚,电荷密度高,附聚反应更迅速、更完全。浓硫酸、二甲基乙醇胺或三乙醇胺毒性较小。悬浮聚合法制作基球反应块,周期短。用本发明合成方法生产产品更环保、安全。
附图说明:
实施例一的色谱柱性能测试曲线。
具体实施方式
实施例一
1、悬浮聚合法合成粒径为10-30μm,交联度10%的苯乙烯-二乙烯苯聚合物小球并经过分级备用。
2、氯甲基化、季胺化、转型
在配有搅拌器、回流冷凝器和温度计的500ml三颈瓶中加入浓盐酸200ml和多聚甲醛30g,并加入上述制得的苯乙烯-二乙烯苯聚合物小球10g,维持慢速搅拌。无水氯化铝40g分3次加入上述混合物中,维持60℃保温反应2小时。取出上述反应后的物料倒入大量去离子水中,以溶解过量的催化剂和稀释未反应的原料,自然沉降后抽滤,用去离子水将抽滤后的基料洗涤三次,60℃真空干燥。将氯甲基化的基球置已经装配好温度计,回流冷凝器和搅拌器的250ml三颈瓶中,在30分钟内滴加30%的二甲基乙醇胺水溶液50ml,保温45℃,慢速搅拌反应1小时,反应完成后用去离子水洗涤3次,加入1M的碳酸钠溶液转型为CO3 2-型,洗涤干净过量的碳酸钠备用。
3、采用乳液聚合法合成粒径为20-60μm的苯乙烯-二乙烯苯乳液并磺化、转型
在装配好搅拌器、回流冷凝器和温度计的250ml三颈烧瓶中,加入120ml去离子水、十二烷基苯磺酸钠1g和饱和肥皂液5ml,升温至30℃保温至十二烷基苯磺酸钠完全溶解,然后加入经过减压蒸馏过的苯乙烯30ml和二乙烯苯10ml,通氮气15分钟,升温到60℃,加入过硫酸钾溶液15ml(过硫酸钾0.5g事先用去离子水30ml溶解)保温反应4小时,加入过硫酸钾溶液15ml,再保温反应4小时,结束后冷却至室温。将上述反应物加入饱和氯化钠溶液10ml以破乳,将沉淀物用去离子水洗涤后60℃真空干燥。在配好搅拌器,回流冷凝器以及温度计的三颈烧瓶中,加入干燥后的固体10g,并加入去离子水9ml,在室温下搅拌1小时使之成为均匀的浆状悬浮液。加入浓硫酸100ml,升温至90℃保温反应1小时。反应结束后取出用大量去离子水稀释并过滤得到的反应物。加入1M碳酸钠溶液中和并转型为Na型配制成固体含量为1%的溶液备用。
4、附聚
取上述第二步已经制好并转型的苯乙烯和二乙烯苯基球树脂3g,用1M碳酸钠溶液配置成1%固体含量的均匀悬浊液;取第三步制得并转型的磺化苯乙烯和二乙烯苯乳胶30ml,在不断搅拌下将悬浊液滴加到乳胶中,滴加完毕,继续搅拌30分钟使反应完成。慢速离心分离,倾倒上层乳浊液并多次用去离子水洗涤和慢速离心。匀浆后于200kgf/cm2下装柱。
5、色谱柱性能测试
称取上述制得的附聚型强酸性阳离子色谱柱用去离子水冲洗1小时,流速1.4ml/min,配置4mM硝酸为淋洗液,冲洗3小时,流速1.4ml/min。配制Li+、Na+、NH4 +、K+标准样品,浓度分别为:0.5、2.5、2.5、5.0mg/L进样测试分离性能。谱图见附图。
实施例二
合成过程与实施例一的区别是在基球季胺化步骤中将氯甲基化的基球置已经装配好温度计,回流冷凝器和搅拌器的250ml三颈瓶中,在30分钟内滴加30%的三乙醇胺水溶液50ml,保温45℃,慢速搅拌反应1小时,反应完成后用去离子水洗涤3次,加入0.1M的NaHCO3溶液,转型为HCO3碳酸氢根,洗涤干净过量的NaHCO3备用;在乳胶磺化步骤中加入浓硫酸100ml反应结束取出用大量去离子水稀释并过滤得到的反应物后,加入1M NaOH溶液中和并转型为Na型,配制成固体含量为1%的溶液备用。
实施例三
合成过程与实施例一的区别是在基球氯甲基化步骤中无水氯化铝40g分3次加入上述混合物后,维持40℃保温反应6小时;在基球季胺化步骤中当30分钟内滴加30%的二甲基乙醇胺水溶液50ml,保温30℃,慢速搅拌反应3小时;在乳胶磺化步骤中加入浓硫酸100ml后,升温至50℃保温反应5小时。
实施例四
合成过程与实施例一的区别是在基球氯甲基化步骤中无水氯化铝40g分3次加入上述混合物后,维持80℃保温反应1.5小时;在基球季胺化步骤中当30分钟内滴加30%的二甲基乙醇胺水溶液50ml,保温70℃,慢速搅拌反应1小时;在乳胶磺化步骤中加入浓硫酸100ml后,升温至100℃保温反应30分钟。

Claims (7)

1.一种附聚型强酸性阳离子色谱柱用填料的合成方法,包括将表面氯甲基化、季胺化、转型的合成体型交联芳香烯烃有机共聚物基球与磺化、转型的合成体型交联芳香烯烃有机共聚物乳胶附聚,然后装柱,其特征在于表面采用浓盐酸和甲醛进行氯甲基化、有碱性阴离子交换基团的体型交联芳香烯烃有机共聚物作为基球,表面有酸性阳离子交换基团的体型交联芳香烯烃有机共聚物作为乳胶。
2.根据权利要求1所述的一种附聚型强酸性阳离子色谱柱用填料的合成方法,其特征在于基球氯甲基化还要搅拌并加入无水氯化铝,反应温度40-80℃。
3.根据权利要求1所述的一种附聚型强酸性阳离子色谱柱用填料的合成方法,其特征在于基球采用二甲基乙醇胺或三乙醇胺进行季胺化,反应保持温度30-70℃。
4.根据权利要求1所述的一种附聚型强酸性阳离子色谱柱用填料的合成方法,其特征在于乳胶采用浓硫酸进行磺化,磺化反应升温保持在50-100℃。
5.根据权利要求1所述的一种附聚型强酸性阳离子色谱柱用填料的合成方法,其特征在于基球和乳胶的的体型是球形。
6.根据权利要求1或5所述的一种附聚型强酸性阳离子色谱柱用填料的合成方法,其特征在于基球和乳胶是苯乙烯-二乙烯苯共聚物。
7.根据权利要求1所述的一种附聚型强酸性阳离子色谱柱用填料的合成方法,其特征在于基球采用悬浮聚合法制作。
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