CN116903916A - 一种多孔聚合物毫米球及其制备方法 - Google Patents
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Abstract
本发明具体涉及一种多孔聚合物毫米球及其制备方法，该制备方法包括步骤：将含有表面活性剂的水相预热至70~90°C；将聚苯乙烯、苯乙烯、二乙烯基苯、引发剂搅拌至均相，在机械搅拌下逐滴加入预热后的含有表面活性剂的水相，聚合反应3~5 h；然后经过滤、用水洗涤、用溶剂抽提、烘干，得球型聚合物；将球型聚合物在二氯乙烷中溶胀，加入二甲氧基甲烷和路易斯酸催化剂，在室温下反应，所得产物过滤后在盐酸中浸泡，再过滤，用水、二氯乙烷依次洗涤，烘干后获得多孔聚合物毫米球。本发明多孔聚合物毫米球的制备方法提升了球型聚合物颗粒的比表面积，增加了颗粒整体微孔吸附容量，对小分子具有强吸附能力。
Description
技术领域
本发明属于聚合物功能材料领域，具体涉及一种多孔聚合物毫米球及其制备方法。
背景技术
工业生产中产生的有机废气排放入空气中将会对大气产生污染，并对周边人或动物的健康造成损伤，例如致癌、致畸作用。然而在工业化的大型生产设备中，对有机废气有最佳吸附效率的多孔聚合物吸附材料一般都以纳米尺寸粉体的形式存在，导致其在使用过程中需要设计吸附床以便收集和再生。而大尺寸的沸石分子筛一般又因亲水性较好，对有机废气的吸附效果不理想。因此毫米粒径球形聚合物吸附材料在有机废气处理过程中有着很高的实用价值。
常规通过悬浮聚合合成的交联聚苯乙烯白球可以达到毫米级球形颗粒，但其内部几乎无孔，比表面积较小。高比表面积的多孔聚合物材料一般都处于微米至纳米级的尺度，不适用于大型工业设备。
发明内容
为了解决现有技术中存在的上述问题，本发明提供了一种多孔聚合物毫米球及其制备方法。本发明要解决的技术问题通过以下技术方案实现：
一种多孔聚合物毫米球的制备方法，包括如下步骤：
步骤一：将含有表面活性剂的水相预热至70~90°C；
步骤二：将聚苯乙烯、苯乙烯、二乙烯基苯、引发剂搅拌至均相，在机械搅拌下逐滴加入预热后的含有表面活性剂的水相，聚合反应3~5 h；
步骤三：将步骤二所获得的产物经过滤、用水洗涤、用溶剂抽提、烘干，得球型聚合物；
步骤四：将步骤三所获得的球型聚合物在二氯乙烷中溶胀，加入二甲氧基甲烷和路易斯酸催化剂，在室温下反应，所得产物过滤后在盐酸中浸泡，再过滤，用水、二氯乙烷依次洗涤，烘干后获得多孔聚合物毫米球。
进一步地，上述聚苯乙烯的制备方法为：将苯乙烯、过硫酸铵、十二烷基硫酸钠加入去离子水中，60~80°C聚合反应3~5 h，50~60°C烘干后研碎。
进一步地，上述步骤一中表面活性剂选自聚乙烯醇，十二烷基硫酸钠、十六烷基三甲基溴化铵中的至少一种，含有表面活性剂的水相浓度为0.1%~1.5%。
进一步地，上述步骤二中苯乙烯与二乙烯苯的体积比为3:1~39:1，聚苯乙烯的质量与苯乙烯、二乙烯苯体积和的比例为1g:4mL~3g:4mL，苯乙烯、二乙烯苯体积和与水相体积的比例为4%。
进一步地，上述步骤二中引发剂选自偶氮二异丁腈或过氧化苯甲酰，所述步骤二中机械搅拌转速为200 rpm~400 rpm。
进一步地，上述步骤三中使用的溶剂选自二氯甲烷或四氢呋喃，烘干温度为50~55°C。
进一步地，上述步骤四中路易斯酸催化剂选自无水三氯化铝或无水三氯化铁。
进一步地，上述步骤四中反应时间为18~24h，浸泡时间为1~3h，烘干温度为50~55°C。
一种多孔聚合物毫米球，采取上述的一种多孔聚合物毫米球的制备方法制得。
进一步地，上述多孔聚合物毫米球的平均粒径为2mm。
与现有技术相比，本发明的有益效果：
本发明通过在聚合过程中加入线型高分子聚合物为模板合成交联聚苯乙烯毫米尺度多孔微球，线型高分子聚合物不仅调整了聚合单体的粘度，有利于形成稳定的毫米级球型颗粒，同时，线型聚合物充当致孔剂，通过后期的抽提工艺制孔，提高了毫米级球型聚合物颗粒的孔容，最后通过后交联溶剂编织法进一步提升球型聚合物颗粒的比表面积，增加颗粒整体微孔吸附容量，以获得对小分子的强吸附能力。
附图说明
图1是实施例1未经抽提产物剖面的扫描电镜图。
图2是实施例1经过抽提后产物剖面的扫描电镜图。
图3是实施例1抽提后产物与后交联得到产物的红外光谱图。
图4是实施例1抽提前后产物与后交联得到产物的氮气等温吸附线。
图5是实施例1多孔聚合物毫米球的光学照片。
实施方式
下面结合具体实施例对本发明做进一步详细的描述，但本发明的实施方式不限于此。
本发明提供了一种多孔聚合物毫米球的制备方法，该制备方法包括如下步骤：
步骤一：将含有表面活性剂的水相预热至70~90°C，其中，表面活性剂选自聚乙烯醇，十二烷基硫酸钠、十六烷基三甲基溴化铵中的至少一种，含有表面活性剂的水相浓度为0.1%~1.5%。
步骤二：将聚苯乙烯、苯乙烯、二乙烯基苯、引发剂搅拌至均相，在机械搅拌下逐滴加入预热后的含有表面活性剂的水相，聚合反应3~5 h；其中，苯乙烯与二乙烯苯的体积比为3:1~39:1，聚苯乙烯的质量与苯乙烯、二乙烯苯体积和的比例为1g:4mL~3g:4mL，苯乙烯、二乙烯苯体积和与水相体积的比例为4%；引发剂选自偶氮二异丁腈或过氧化苯甲酰，机械搅拌转速为200 rpm~400 rpm。
步骤三：将步骤二所获得的产物经过滤、用水洗涤、用溶剂抽提、烘干，得球型聚合物，使用的溶剂选自二氯甲烷或四氢呋喃，烘干温度为50~55°C。经抽提后比表面积可提升至5-50 m2/g。
步骤四：将步骤三所获得的球型聚合物在二氯乙烷中溶胀，加入二甲氧基甲烷和路易斯酸催化剂，在室温下反应，所得产物过滤后在盐酸中浸泡，再过滤，用水、二氯乙烷依次洗涤，烘干后获得多孔聚合物毫米球；其中，路易斯酸催化剂选自无水三氯化铝或无水三氯化铁，反应时间为18~24h，浸泡时间为1~3h，烘干温度为50~55°C。 经后交联后比表面积可提升至80-120 m2/g。
本发明聚苯乙烯的制备方法为：将苯乙烯、过硫酸铵、十二烷基硫酸钠加入去离子水中，60~80°C聚合反应3~5 h，50~60°C烘干后研碎。
本发明还提供了一种多孔聚合物毫米球，该多孔聚合物毫米球采用本发明的一种多孔聚合物毫米球的制备方法制得。该多孔聚合物毫米球的平均粒径为2 mm。
实施例1：
将100 mL 0.1 %质量分数的十二烷基硫酸钠溶液预热至80°C，将1.5 g聚苯乙烯、0.05 g偶氮二异丁腈溶解于3 mL苯乙烯、1 mL二乙烯基苯中搅拌至均相透明，在250 rpm机械搅拌下将上述溶液逐滴加入预热的十二烷基硫酸钠溶液中，在80℃反应4 h。待反应结束后将产物过滤，用水洗涤，在索氏抽提装置中使用溶剂四氢呋喃充分抽提产物24 h，在55°C下烘干；取0.2g球型聚合物装有25 mL二氯乙烷中，加入0.3 g无水三氯化铝，0.1 mL二甲醇缩甲醛进行后交联处理，室温反应24h，过滤后在盐酸中浸泡1h，再过滤，用水、二氯乙烷依次洗涤，55°C烘干后获得多孔聚合物毫米球。
本实施例的聚苯乙烯的制备方法：将25 mL苯乙烯，1 g 过硫酸铵，1.5 g十二烷基硫酸钠加入500 mL去离子水中，70°C聚合反应4 h，60°C烘干后研碎。
本实施例未经抽提产物剖面的扫描电镜图如图1，从图1可以看出未经抽提产物有致密的结构。本实施例经过抽提后产物剖面的扫描电镜图如图2，从图2可以看出线型聚合物被抽提后留下明显孔隙，且经抽提后比表面积提升至50 m2/g。抽提后产物与后交联得到产物的红外光谱图如图3所示。抽提前后产物与后交联得到产物的氮气等温吸附线如图4所示，从图4可以看出抽提后和交联后比表面积有所提升，本实施例经后交联后比表面积可提升至120 m2/g。图5为本实施例的多孔聚合物毫米球的光学照片。
实施例2：
将100 mL 0.1 %质量分数的聚乙烯醇溶液预热至70°C，将1.5 g聚苯乙烯、0.1 g过氧化苯甲酰溶解于6mL苯乙烯、1 mL二乙烯基苯中搅拌至均相透明，在200 rpm机械搅拌下将上述溶液逐滴加入预热的聚乙烯醇溶液中，在70℃反应5 h。待反应结束后将产物过滤，用水洗涤，在索氏抽提装置中使用溶剂四氢呋喃充分抽提产物24 h，在50°C下烘干；取0.2g球型聚合物装有25 mL四氢呋喃中，加入0.3 g无水三氯化铁，0.1 mL二甲醇缩甲醛进行后交联处理，室温反应24h，过滤后在盐酸中浸泡3h，再过滤，用水、二氯乙烷依次洗涤，53°C烘干后获得多孔聚合物毫米球。
本实施例经抽提后比表面积可提升至30 m2/g。经后交联后比表面积可提升至105m2/g。
本实施例的聚苯乙烯的制备方法：将25 mL苯乙烯，1 g 过硫酸铵，1.5 g十二烷基硫酸钠加入500 mL去离子水中，70°C聚合反应4 h，60°C烘干后研碎。
实施例3：
将100 mL 0.1 %质量分数的十六烷基三甲基溴化铵溶液预热至90°C，将1.5 g聚苯乙烯、0.1 g偶氮二异丁腈溶解于6mL苯乙烯、1 mL二乙烯基苯中搅拌至均相透明，在400rpm机械搅拌下将上述溶液逐滴加入预热的十六烷基三甲基溴化铵溶液中，在90℃反应3h。待反应结束后将产物过滤，用水洗涤，在索氏抽提装置中使用溶剂二氯甲烷充分抽提产物24 h，在55°C下烘干；取0.2g球型聚合物装有25 mL四氢呋喃中，加入0.3 g无水三氯化铁，0.1 mL二甲醇缩甲醛进行后交联处理，室温反应18h，过滤后在盐酸中浸泡2h，再过滤，用水、二氯乙烷依次洗涤，50°C烘干后获得多孔聚合物毫米球。
本实施例经抽提后比表面积可提升至25 m2/g。经后交联后比表面积可提升至110m2/g。
本实施例的聚苯乙烯的制备方法：将25 mL苯乙烯，1 g 过硫酸铵，1.5 g十二烷基硫酸钠加入500 mL去离子水中，70°C聚合反应4 h，60°C烘干后研碎。
实施例4：
将100 mL 0.1 %质量分数的十二烷基硫酸钠溶液预热至80°C，将1.5 g聚苯乙烯、0.05 g偶氮二异丁腈溶解于3 mL苯乙烯、1 mL二乙烯基苯中搅拌至均相透明，在250 rpm机械搅拌下将上述溶液逐滴加入预热的十二烷基硫酸钠溶液中，在80℃反应4 h。待反应结束后将产物过滤，用水洗涤，在索氏抽提装置中使用溶剂二氯甲烷充分抽提产物18 h，在55°C下烘干；取0.2g球型聚合物装有30 mL二氯乙烷中，加入0.5g无水三氯化铁，0.1 mL二甲醇缩甲醛进行后交联处理，室温反应24h，过滤后在盐酸中浸泡1h，再过滤，用水、二氯乙烷依次洗涤，55°C烘干后获得多孔聚合物毫米球。
本实施例经抽提后比表面积可提升至20 m2/g。经后交联后比表面积可提升至115m2/g。
本实施例的聚苯乙烯的制备方法：将25 mL苯乙烯，1 g 过硫酸铵，1.5 g十二烷基硫酸钠加入500 mL去离子水中，70°C聚合反应4 h，60°C烘干后研碎。
本发明通过在聚合过程中加入线型高分子聚合物为模板合成交联聚苯乙烯毫米尺度多孔微球，线型高分子聚合物不仅调整了聚合单体的粘度，有利于形成稳定的毫米级球型颗粒，同时，线型聚合物充当致孔剂，通过后期的抽提工艺制孔，提高了毫米级球型聚合物颗粒的孔容，最后通过后交联溶剂编织法进一步提升球型聚合物颗粒的比表面积，增加颗粒整体微孔吸附容量，以获得对小分子的强吸附能力。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。
Claims (10)
1.一种多孔聚合物毫米球的制备方法，其特征在于，包括如下步骤：
步骤一：将含有表面活性剂的水相预热至70~90°C；
步骤二：将聚苯乙烯、苯乙烯、二乙烯基苯、引发剂搅拌至均相，在机械搅拌下逐滴加入预热后的含有表面活性剂的水相，聚合反应3~5 h；
步骤三：将步骤二所获得的产物经过滤、用水洗涤、用溶剂抽提、烘干，得球型聚合物；
步骤四：将步骤三所获得的球型聚合物在二氯乙烷中溶胀，加入二甲氧基甲烷和路易斯酸催化剂，在室温下反应，所得产物过滤后在盐酸中浸泡，再过滤，用水、二氯乙烷依次洗涤，烘干后获得多孔聚合物毫米球。
2.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤二中聚苯乙烯的制备方法为：将苯乙烯、过硫酸铵、十二烷基硫酸钠加入去离子水中，60~80°C聚合反应3~5 h，50~60°C烘干后研碎。
3.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤一中表面活性剂选自聚乙烯醇，十二烷基硫酸钠、十六烷基三甲基溴化铵中的至少一种，含有表面活性剂的水相浓度为0.1%~1.5%。
4.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤二中苯乙烯与二乙烯苯的体积比为3:1~39:1，聚苯乙烯的质量与苯乙烯、二乙烯苯体积和的比例为1g:4mL~3g:4mL，苯乙烯、二乙烯苯体积和与水相体积的比例为4%。
5.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤二中引发剂选自偶氮二异丁腈或过氧化苯甲酰，所述步骤二中机械搅拌转速为200 rpm~400rpm。
6.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤三中使用的溶剂选自二氯甲烷或四氢呋喃，烘干温度为50~55°C。
7.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤四中路易斯酸催化剂选自无水三氯化铝或无水三氯化铁。
8.根据权利要求1所述的一种多孔聚合物毫米球的制备方法，其特征在于，所述步骤四中反应时间为18~24h，浸泡时间为1~3h，烘干温度为50~55°C。
9.一种多孔聚合物毫米球，其特征在于，采取权利要求1~8任一项所述的一种多孔聚合物毫米球的制备方法制得。
10.根据权利要求9所述的一种多孔聚合物毫米球，其特征在于，所述多孔聚合物毫米球的平均粒径为2 mm。
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| US5130343A (en) * | 1991-03-13 | 1992-07-14 | Cornell Research Foundation, Inc. | Process for producing uniform macroporous polymer beads |
| US20100065500A1 (en) * | 2006-12-01 | 2010-03-18 | Institute of Process Engineering, Chinese Academy of Science | Super-macroporous polymeric microspheres and preparation method thereof |
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