CN114367311B - 一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法及应用 - Google Patents
一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法及应用 Download PDFInfo
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Abstract
本发明公开了一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法及应用。本发明通过悬浮聚合的方法，采用廉价、绿色的水溶液作为聚合反应体系，以明胶为分散剂，亚甲基蓝为助分散剂，以偶氮二异丁腈为引发剂，两种聚合物单体在引发剂、分散剂的存在下，以水相为连续相进行加热聚合交联，得到了微米级单分散的聚合物微球，将该微球与杂多酸进行离子交换后得到了固体酸催化剂，然后用于醋酸丙酸纤维素酯的催化合成。催化反应结束后，固体酸催化剂微球可通过简单的化工分离过程与产品分离，进行回收，实现催化剂的循环利用；所制得的醋酸丙酸纤维素酯分子量大，粘度高。
Description
技术领域
本发明属于纤维素混合酯合成技术领域，尤其涉及一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法及应用。
背景技术
木浆粕中纤维素含量丰富，是一类成熟且低廉的纤维素制品的原料，适用于纤维素衍生物的合成制备。木浆粕主要以乔木类树木经过物理化学加工提取而来的植物纤维，这类天然纤维素具有高度结晶性，难以溶解，这就导致了纤维素的衍生化反应在初始阶段多是非均相反应。首先酯化反应只能发生在纤维素的表面，只有当纤维素表面的羟基被酯基所取代，生成可溶性的产物，次外层才会裸露出来，被反应试剂所触及并进一步反应，最终形成高粘度的反应体系。
在纤维素酯化反应过程中，催化剂是影响产品结构和性能的关键因素之一，多酸能够可控制备纤维素酯产品，并且在90℃以下不会发生纤维素降解，所以采用多酸代替浓H2SO4可避免浓H2SO4催化纤维素带来的纤维素降解问题和冗杂且不可控的水解步骤。但是多酸本身存在比表面积小、在水中溶解度大、易流失等问题，将其固载到载体上是一种有效的解决策略。高分子微球作为催化剂载体有得天独厚的优势，良好的化学稳定性、热稳定性和机械稳定性使其在催化反应中有着广泛的应用。高分子微球负载的催化剂不仅保持了原催化剂的催化活性，而且可以通过化工过程中简单的过滤回收，不污染产品，可重复使用，因此高分子微球负载催化剂是实现绿色催化的重要途径之一。
发明内容
本发明的目的是针对以木浆粕为纤维素原料的纤维素酯化过程中高粘度的反应体系催化剂易流失、难回收的难题，通过悬浮聚合的方法，采用廉价、绿色的水溶液作为聚合反应体系，以明胶为分散剂，亚甲基蓝为助分散剂，以偶氮二异丁腈为引发剂，两种聚合物单体在引发剂、分散剂的存在下，以水相为连续相进行加热聚合交联，得到了微米级单分散的聚合物微球，将该微球与杂多酸进行离子交换后得到了固体酸催化剂，然后用于醋酸丙酸纤维素酯的合成。
本发明所述的悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法为：先在30-70℃温度下将明胶溶解在水中，加入二乙烯基苯、1-(4-乙烯基苄基)-3-甲基咪唑、偶氮二异丁腈和亚甲基蓝，然后在75-95℃聚合反应1-5h，搅拌速度为100-350r/min；过滤得到的高分子微球用乙醇、水洗涤后加入到乙醇中，然后加入杂多酸，在30-80℃下搅拌反应12-24h，过滤，用无水乙醇洗涤后干燥，即得到高分子微球负载杂多酸催化剂。
所述明胶的质量浓度为0.5-5％。所述二乙烯基苯的质量浓度为0.5-1％。所述1-(4-乙烯基苄基)-3-甲基咪唑的质量浓度为3-10％。所述偶氮二异丁腈的质量为二乙烯基苯和1-(4-乙烯基苄基)-3-甲基咪唑质量和的0.5-1％。所述亚甲基蓝的质量浓度为0.05-0.1％。
所述高分子微球的质量是杂多酸质量的2-20倍。
所述杂多酸为磷钨酸、硅钨酸或磷钼酸。
一种醋酸丙酸纤维素酯的制备方法为：(1)将木浆粕进行机械破碎预处理，然后喷淋有机酸并于室温下活化0.5-6h；(2)活化后的木浆粕中加入液体酸催化剂、高分子微球负载杂多酸催化剂和有机酸酐酯化剂，在30-60℃下反应0.5-6h；(3)将反应液分离回收高分子微球负载杂多酸催化剂，回收后的高分子微球负载杂多酸催化剂经洗涤后可重复使用，滤液中加入5-10倍量的水，搅拌后层析，洗涤后干燥，得到醋酸丙酸纤维素酯。
所述的有机酸为醋酸和/或丙酸。有机酸的喷淋量为木浆粕质量的5-11倍。
所述的有机酸酐酯化剂为醋酸酐、丙酸酐的混合液。有机酸酐酯化剂的质量为木浆粕质量的1-5倍。
所述的液体酸催化剂和高分子微球负载杂多酸催化剂的总用量为反应液质量的0.005-5％。
本发明的优势在于：
(1)采用悬浮聚合法，以水/明胶为反应体系，体系粘度低，易传热和控温，聚合过程易于控制，后处理简单，生产成本较低，三废较少；
(2)所制备的高分子微球负载杂多酸固体酸催化剂为微米级，分散良好的球状，粒径分布均匀，具有优异的机械性能和化学稳定性；
(3)反应结束后，固体酸催化剂微球可通过简单的化工分离过程与产品分离，进行回收，实现催化剂的循环利用；
(4)所制得的醋酸丙酸纤维素酯分子量大，粘度高。
附图说明
图1.为实施例1制备的高分子微球负载杂多酸催化剂的产品实物图及光学显微镜照片。
图2.为应用例1合成的醋酸丙酸纤维素液体核磁氢谱，由此计算得到取代度。
图3.为应用例1合成的醋酸丙酸纤维素的凝胶色谱图。
具体实施方式
本发明用以下实施例说明，但本发明并不限于下述实施例，在不脱离前后所述宗旨的范围下，变化实施均包括在本发明的技术范围内。
实施例1
在带有机械搅拌的500ml三口烧瓶中加入350ml水，加入明胶的质量为水质量的2％，明胶的溶解温度为50℃，待明胶溶解，水溶液变为澄清透明状后，加入二乙烯基苯的质量为水质量的0.5％，1-(4-乙烯基苄基)-3-甲基咪唑的质量为水质量的4％，偶氮二异丁腈的质量为二乙烯基苯和1-(4-乙烯基苄基)-3-甲基咪唑质量和的0.5％，亚甲基蓝的质量为水的0.05％，聚合温度为80℃，反应时间为4h，搅拌速度为150r/min，过滤得到的高分子微球用乙醇、水洗涤。将5g高分子微球加入到100ml乙醇溶液中，向其中加入1.0g磷钨酸，温度为50℃，搅拌20h，过滤，用无水乙醇洗涤后干燥，即得到高分子微球负载杂多酸催化剂。经测试得到催化剂的物理参数如表1所示。
表1
实施例2
在带有机械搅拌的20L聚合反应釜中加入11L水，加入明胶的质量为水质量的5％，明胶的溶解温度为70℃，待明胶溶解，水溶液变为澄清透明状后，加入二乙烯基苯的质量为水质量的1％，1-(4-乙烯基苄基)-3-甲基咪唑的质量为水质量的9％，偶氮二异丁腈的质量为二乙烯基苯和1-(4-乙烯基苄基)-3-甲基咪唑质量和的1％，亚甲基蓝的质量为水的0.1％，聚合温度为95℃，反应时间为2h，搅拌速度为300r/min，过滤得到的高分子微球用乙醇、水洗涤。将1000g高分子微球加入到12L乙醇溶液中，向其中加入200g磷钨酸，温度为70℃，搅拌20h，过滤，用无水乙醇洗涤后干燥，即得到高分子微球负载杂多酸催化剂。
应用例1
将10g木浆粕进行机械破碎预处理，喷淋25ml醋酸、29.4ml丙酸并于室温下活化3h；活化后的木浆粕加入19.2ml醋酸酐，23.6ml丙酸酐，50μl浓硫酸和1.37g实施例1制备的高分子微球负载杂多酸催化剂，在45℃下反应3小时，过滤，层析，洗涤，干燥后得到的醋酸丙酸纤维素酯总取代度～2.9，乙酰基含量为26～28％，丙酰基含量为17～19％，产物重均分子量为～158000，粘度为～330mpa·s。
Claims (3)
1.一种悬浮聚合法制备微米级单分散高分子微球负载杂多酸催化剂的方法，其特征在于，所述方法的具体步骤为：先在30-70℃温度下将明胶溶解在水中，加入二乙烯基苯、1-(4-乙烯基苄基)-3-甲基咪唑、偶氮二异丁腈和亚甲基蓝，然后在75-95℃聚合反应1-5h，搅拌速度为100-350r/min；过滤得到的高分子微球用乙醇、水洗涤后加入到乙醇中，然后加入杂多酸，在30-80℃下搅拌反应12-24h，过滤，用无水乙醇洗涤后干燥，即得到高分子微球负载杂多酸催化剂；
其中，所述二乙烯基苯的质量浓度为0.5-1％；所述1-(4-乙烯基苄基)-3-甲基咪唑的质量浓度为3-10％；
所述明胶的质量浓度为0.5-5％；
所述偶氮二异丁腈的质量为二乙烯基苯和1-(4-乙烯基苄基)-3-甲基咪唑质量和的0.5-1％；所述亚甲基蓝的质量浓度为0.05-0.1％；
所述高分子微球的质量是杂多酸质量的2-20倍；
所述杂多酸为磷钨酸、硅钨酸或磷钼酸。
2.一种醋酸丙酸纤维素酯的制备方法，其特征在于，所述制备方法的具体步骤为：(1)将木浆粕进行机械破碎预处理，然后喷淋有机酸并于室温下活化0.5-6h；(2)活化后的木浆粕中加入液体酸催化剂、根据权利要求1所述的方法制备的高分子微球负载杂多酸催化剂和有机酸酐酯化剂，在30-60℃下反应0.5-6h；(3)将反应液分离回收高分子微球负载杂多酸催化剂，回收后的高分子微球负载杂多酸催化剂经洗涤后可重复使用，滤液中加入5-10倍量的水，搅拌后层析，洗涤后干燥，得到醋酸丙酸纤维素酯；
其中，所述的有机酸为醋酸和/或丙酸，有机酸的喷淋量为木浆粕质量的5-11倍；
所述的有机酸酐酯化剂为醋酸酐、丙酸酐的混合液，有机酸酐酯化剂的质量为木浆粕质量的1-5倍。
3.根据权利要求2所述的制备方法，其特征在于，所述的液体酸催化剂和高分子微球负载杂多酸催化剂的总用量为反应液质量的0.005-5％。
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