CN109456507B - 一种高外表面磁性多孔树脂球及制备方法 - Google Patents

一种高外表面磁性多孔树脂球及制备方法 Download PDF

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CN109456507B
CN109456507B CN201811305354.1A CN201811305354A CN109456507B CN 109456507 B CN109456507 B CN 109456507B CN 201811305354 A CN201811305354 A CN 201811305354A CN 109456507 B CN109456507 B CN 109456507B
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porous resin
resin ball
magnetic
magnetic porous
silicone oil
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张宝亮
王继启
寇晓康
张秋禹
刘琼
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Sunresin New Materials Co ltd Xi'an
Northwestern Polytechnical University
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Northwestern Polytechnical University
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Abstract

本发明涉及一种高外表面磁性多孔树脂球及制备方法，将疏水性磁性粒子分散配比合理的油相中作为分散相，加入到高稳定性的水相中，搅拌获得分散相液滴，热引发聚合将磁性粒子包裹其中，得到表面具有褶皱形貌的磁性多孔树脂球，表面褶皱的形貌主要由聚合物组分、致孔剂组分的合理搭配导致，聚合物成分为P(GMA‑St‑DVB)。多孔树脂球外表面呈现褶皱形貌，内部含有丰富的孔道，表面带有大量的环氧官能团，可以在磁场下快速分离富集，有利于接触吸附和分离再生。本方法基于悬浮聚合体系，因此易于工业化放大，外表面的增大，有利于提高吸附量和吸附速度，这种复合微球有望在开放式水体处理、发酵物分离等领域有着潜在应用价值。

Description

一种高外表面磁性多孔树脂球及制备方法
技术领域
本发明属于多孔吸附分离材料领域，涉及一种高外表面磁性多孔树脂球及制备方法。
背景技术
磁性树脂微球作为一类非常重要的吸附分离材料已在工业上得到应用，典型的工业化产品是澳大利亚ORICA公司开发的MIEX磁性离子交换树脂，主要被用在去除水中难以降解的有机污染物，国内也有不少模仿MIEX树脂的磁性多孔树脂材料。可以发现，可真正实现工业化应用的磁性多孔树脂必须具备几个特点：(1)原料易得，生产工艺简单，易于工业化生产；(2)孔道丰富，大孔、小孔并存，有利于传质，处理速度快；(3)比表面积大，吸附量大；(4)便于再生，使用成本低；(5)磁响应性高，便于分离富集；(6)合适的密度，可以悬浮在液体环境(多数为水)中。不难看出，树脂物性方面主要强调和要求的是孔性能。悬浮聚合目前仍是工业规模生产磁性多孔树脂的最重要和最有效的方法。但由于悬浮聚合为非均相体系，含有磁性粒子致孔剂的油相以液滴的形式悬浮在含有稳定剂的水相当中，热引发聚合得到磁性多孔树脂微球，基于张力越低越稳定的原因，得到的树脂球均具有光滑表面。在应用过程中起到吸附作用的是聚合物表面，所以光滑表面是降低了树脂球的外表面积。目前，尚未见到利用悬浮聚合制备表面褶皱状磁性多孔树脂微球的报道。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种高外表面磁性多孔树脂球及制备方法。
技术方案
一种高外表面磁性多孔树脂球，其特征在于：外表面采用有机组分为甲基丙烯酸缩水甘油酯GMA、苯乙烯St、二丙烯酸乙二醇酯EGDA三种单体共聚得到的多孔材料P(GMA-St-EGDA)，表面带有环氧官能团，呈现褶皱形貌；树脂球内部包裹的无机组分为磁性纳米粒子；所述GMA∶St∶EGDA∶磁性纳米粒子四种组分的质量比10～15∶30～40∶20～30∶1～3。多孔树脂球外表面呈现褶皱形貌，内部含有丰富的孔道，表面带有大量的环氧官能团，可以在磁场下快速分离富集，有利于接触吸附和分离再生。
所述磁性纳米粒子为表面疏水性处理具有磁性的铁、钴、镍的纳米尺度单质或氧化物或合金。
一种所述高外表面磁性多孔树脂球的制备方法，其特征在于步骤如下：
步骤1：配置含质量浓度为1.5～1.75％的明胶、0.5～0.1％的聚乙烯醇和1.0～2.0％的氯化钠的水溶液作为水相；
步骤2：将过氧化苯甲酰、甲基丙烯酸缩水甘油酯GMA、苯乙烯St、二丙烯酸乙二醇酯EGDA、甲苯、硅油、磁性纳米粒子按照质量比1∶10～15∶30～40∶20～30∶35～45∶5～10∶1～3充分溶解、混匀，作为油相；
步骤3：将油相加入到水相中，静止5min，开启搅拌，搅拌速度为400～550rpm，其中油相与水相的质量比为1∶4～6；
步骤4：搅拌30min后，将体系升温到85～90℃，恒温反应6～10h；
步骤5：反应结束后，依次经过磁分离、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球。
所述聚乙烯醇参数为醇解度为80～88％，聚合度为1000～2000。
所述硅油为粘度在50-200间的甲基硅油、乙基硅油或甲基苯基硅油，条件为25℃,cps。
有益效果
本发明提出的一种高外表面磁性多孔树脂球及制备方法，将疏水性磁性粒子分散配比合理的油相中作为分散相，加入到高稳定性的水相中，搅拌获得分散相液滴，热引发聚合将磁性粒子包裹其中，得到表面具有褶皱形貌的磁性多孔树脂球，表面褶皱的形貌主要由聚合物组分、致孔剂组分的合理搭配导致，聚合物成分为P(GMA-St-DVB)。多孔树脂球外表面呈现褶皱形貌，内部含有丰富的孔道，表面带有大量的环氧官能团，可以在磁场下快速分离富集，有利于接触吸附和分离再生。本方法基于悬浮聚合体系，因此易于工业化放大，外表面的增大，有利于提高吸附量和吸附速度，这种复合微球有望在开放式水体处理、发酵物分离等领域有着潜在应用价值。
本发明制备的表面具有褶皱形貌的磁性多孔树脂球，表面褶皱的形貌主要由聚合物组分、致孔剂组分的合理搭配导致，聚合物成分为P(GMA-St-DVB)，磁性纳米粒子为表面疏水性修饰的铁、钴、镍单质、氧化物或合金，可以与油相具有很好的相容性，可以简单的分散在油相中通过聚合实现复合。本合成方法基于悬浮聚合体系，因此易于工业化放大，外表面的增大，有利于提高吸附量和吸附速度。
附图说明
图1是高外表面磁性多孔树脂球的SEM照片
图2是高外表面磁性多孔树脂球的累计比表面积曲线
图3是高外表面磁性多孔树脂球的孔径分布曲线
图4是高外表面磁性多孔树脂球的磁响应性曲线
具体实施方式
现结合实施例、附图对本发明作进一步描述：
实施例1：高外表面磁性多孔树脂球的制备
称取含质量浓度为1.5％的明胶、0.5％的聚乙烯醇(醇解度80％，聚合度1000)和1.5％的氯化钠的水溶液400g，加入配有搅拌和冷凝的三口瓶中；称取过氧化苯甲酰0.80g、甲基丙烯酸缩水甘油酯8.20g、苯乙烯29.20g、二丙烯酸乙二醇酯20.80g、甲苯33.25g、硅油5.80g(25℃，100cps，甲基硅油)、疏水Fe3O4纳米粒子1.69g，充分溶解、混匀后加入到三口瓶内，静止5min，开启搅拌，搅拌速度为450rpm，搅拌30min后，将体系升温到85℃，恒温反应7h；反应结束后，依次经过离心、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球P(GMA-St-DVB)/Fe3O4。
实施例2：高外表面磁性多孔树脂球的制备
称取含质量浓度为1.6％的明胶、0.5％的聚乙烯醇(醇解度88％，聚合度1200)和1.7％的氯化钠的水溶液400g，加入配有搅拌和冷凝的三口瓶中；称取过氧化苯甲酰0.83g、甲基丙烯酸缩水甘油酯9.17g、苯乙烯25.83g、二丙烯酸乙二醇酯17.50g、甲苯29.17g、硅油5.83g(25℃，100cps，乙基硅油)、疏水Co3O4纳米粒子1.67g，充分溶解、混匀后加入到三口瓶内，静止5min，开启搅拌，搅拌速度为480rpm，搅拌30min后，将体系升温到90℃，恒温反应8h；反应结束后，依次经过离心、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球P(GMA-St-DVB)/Co3O4。
实施例3：高外表面磁性多孔树脂球的制备
称取含质量浓度为1.7％的明胶、0.6％的聚乙烯醇(醇解度85％，聚合度2000)和1.8％的氯化钠的水溶液400g，加入配有搅拌和冷凝的三口瓶中；称取过氧化苯甲酰0.70g、甲基丙烯酸缩水甘油酯7.94g、苯乙烯24.50g、二丙烯酸乙二醇酯16.33g、甲苯29.72g、硅油5.30g(25℃，50cps，乙基硅油)、疏水Fe纳米粒子1.41g，充分溶解、混匀后加入到三口瓶内，静止5min，开启搅拌，搅拌速度为500rpm，搅拌30min后，将体系升温到85℃，恒温反应10h；反应结束后，依次经过离心、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球P(GMA-St-DVB)/Fe。
实施例4：高外表面磁性多孔树脂球的制备
称取含质量浓度为1.6％的明胶、0.7％的聚乙烯醇(醇解度88％，聚合度1300)和1.8％的氯化钠的水溶液900g，加入配有搅拌和冷凝的三口瓶中；称取过氧化苯甲酰1.40g、甲基丙烯酸缩水甘油酯18.20g、苯乙烯51.80g、二丙烯酸乙二醇酯36.40g、甲苯56.00g、硅油11.20g(25℃，200cps，甲基硅油)、疏水Ni纳米粒子4.20g，充分溶解、混匀后加入到三口瓶内，静止5min，开启搅拌，搅拌速度为500rpm，搅拌30min后，将体系升温到90℃，恒温反应8h；反应结束后，依次经过离心、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球P(GMA-St-DVB)/Ni。
实施例5：高外表面磁性多孔树脂球的制备
称取含质量浓度为1.5％的明胶、0.8％的聚乙烯醇(醇解度86％，聚合度1000)和1.7％的氯化钠的水溶液900g，加入配有搅拌和冷凝的三口瓶中；称取过氧化苯甲酰1.68g、甲基丙烯酸缩水甘油酯20.16g、苯乙烯60.48g、二丙烯酸乙二醇酯40.32g、甲苯65.52g、硅油10.08g(25℃，80cps，甲基硅油)、疏水Fe3O4纳米粒子1.76g，充分溶解、混匀后加入到三口瓶内，静止5min，开启搅拌，搅拌速度为480rpm，搅拌30min后，将体系升温到80℃，恒温反应10h；反应结束后，依次经过离心、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球P(GMA-St-DVB)/Fe3O4。
实施例6：高外表面磁性多孔树脂球的制备
称取含质量浓度为1.7％的明胶、0.9％的聚乙烯醇(醇解度88％，聚合度1500)和1.7％的氯化钠的水溶液900g，加入配有搅拌和冷凝的三口瓶中；称取过氧化苯甲酰1.30g、甲基丙烯酸缩水甘油酯16.11g、苯乙烯43.40g、二丙烯酸乙二醇酯34.71g、甲苯45.95g、硅油6.50g(25℃，100cps，甲基硅油)、疏水NiO纳米粒子2.50g，充分溶解、混匀后加入到三口瓶内，静止5min，开启搅拌，搅拌速度为500rpm，搅拌30min后，将体系升温到90℃，恒温反应9h；反应结束后，依次经过离心、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球P(GMA-St-DVB)/NiO。

Claims (4)

1.一种高外表面磁性多孔树脂球的制备方法，其特征在于：所述高外表面磁性多孔树脂球外表面采用有机组分为甲基丙烯酸缩水甘油酯GMA、苯乙烯St、二丙烯酸乙二醇酯EGDA三种单体共聚得到的多孔材料P(GMA-St-EGDA)，表面带有环氧官能团，呈现褶皱形貌；树脂球内部包裹的无机组分为磁性纳米粒子；所述GMA∶St∶EGDA∶磁性纳米粒子四种组分的质量比10～15∶30～40∶20～30∶1～3；
所述方法的具体步骤如下：
步骤1：配置含质量浓度为1.5～1.75％的明胶、0.5～0.1％的聚乙烯醇和1.0～2.0％的氯化钠的水溶液作为水相；
步骤2：将过氧化苯甲酰、甲基丙烯酸缩水甘油酯GMA、苯乙烯St、二丙烯酸乙二醇酯EGDA、甲苯、硅油、磁性纳米粒子按照质量比1∶10～15∶30～40∶20～30∶35～45∶5～10∶1～3充分溶解、混匀，作为油相；
步骤3：将油相加入到水相中，静止5min，开启搅拌，搅拌速度为400～550rpm，其中油相与水相的质量比为1∶4～6；
步骤4：搅拌30min后，将体系升温到85～90℃，恒温反应6～10h；
步骤5：反应结束后，依次经过磁分离、热水洗、冷水洗、丙酮索氏提取、真空干燥处理，即得高外表面磁性多孔树脂球。
2.根据权利要求1所述一种高外表面磁性多孔树脂球的制备方法，其特征在于：所述磁性纳米粒子为表面疏水性处理具有磁性的铁、钴、镍的纳米尺度单质或氧化物或合金。
3.根据权利要求1所述一种高外表面磁性多孔树脂球的制备方法，其特征在于：所述聚乙烯醇参数为醇解度为80～88％，聚合度为1000～2000。
4.根据权利要求1所述一种高外表面磁性多孔树脂球的制备方法，其特征在于：所述硅油为粘度在50-200间的甲基硅油、乙基硅油或甲基苯基硅油，条件为25℃,cps。
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