CN106000349A - 一种乙酰化聚乙烯醇整体柱的制备方法 - Google Patents

一种乙酰化聚乙烯醇整体柱的制备方法 Download PDF

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CN106000349A
CN106000349A CN201610298055.4A CN201610298055A CN106000349A CN 106000349 A CN106000349 A CN 106000349A CN 201610298055 A CN201610298055 A CN 201610298055A CN 106000349 A CN106000349 A CN 106000349A
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孙晓霞
王新厚
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Donghua University
National Dong Hwa University
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Abstract

本发明涉及一种乙酰化聚乙烯醇整体柱的制备方法，包括：将乙酰化聚乙烯醇粉末在80～95℃溶于水中，得到乙酰化聚乙烯醇溶液；将乙酰化聚乙烯醇溶液降温至40～55℃，滴加贫溶剂，‑196～30℃静置1～36h，溶剂置换，干燥，得到乙酰化聚乙烯醇整体柱。本发明的方法简单易行，制备得到的乙酰化聚乙烯醇整体柱具有连通的大孔结构，且具有较大的比表面积；可以作为固定酶反应器或者重金属吸附材料进行应用。

Description

一种乙酰化聚乙烯醇整体柱的制备方法
技术领域
本发明属于聚合物整体柱的制备领域，特别涉及一种乙酰化聚乙烯醇整体柱的制备方法。
背景技术
聚合物整体柱是一种具有三维连通孔隙结构的多孔材料。它具有优异的渗透性、快速传质性能、很好的稳定性并且容易进行化学修饰。因此可用于色层分析、除油、生物分子固定、控制药物释放和作为催化剂载体。目前制作聚合物整体柱的方法包括热诱导自由基聚合法、通过γ射线或电子束等高能射线进行的辐射诱导法、活性聚合法和缩聚法等。专利CN201510063386.5公开了一种利用热诱导自由基聚合法制备了亲水性甲基丙烯酰胺聚合物整体柱，该方法需要大量单体进行聚合物。CN101845430A公开了一种利用溶胶凝胶法发明了一种有机-无机杂化整体柱材料的新方法，然而该方法涉及到多种前体分子、螯合剂、模板分子、催化剂等，过程复杂，制备过程需要精确控制。上述方法均以单体聚合为基础，制备过程复杂。
贫溶剂诱导相分离法制备聚合物整体柱是Hiroshi Uyama教授小组于2011年首次提出的一种可控制备聚合物整体柱的方法(Xin Y,Fujimoto T,Uyama H.Polymer,2012,53,2847-2853)。该方法摒弃了传统的基于单体聚合反应的聚合物整体柱的制备方法，具有聚合物适用性广、工艺条件简单、易于实现工业化等显著优点。
发明内容
本发明所要解决的技术问题是提供一种乙酰化聚乙烯醇整体柱的制备方法，该方法简单易行，得到的整体柱具有三维连通的大孔结构和较大的比表面积；修饰后可以作为重金属吸附剂用于污水处理；也可应用于固定化酶反应器。
本发明的一种乙酰化聚乙烯醇整体柱的制备方法，包括：
(1)将乙酰化聚乙烯醇粉末在80～95℃溶于水中，得到乙酰化聚乙烯醇溶液；
(2)将步骤(1)中的乙酰化聚乙烯醇溶液降温至40～55℃，滴加贫溶剂，-196～30℃静置1～36h，溶剂置换，干燥，得到乙酰化聚乙烯醇整体柱。
所述步骤(1)中乙酰化聚乙烯醇溶液的浓度为13wt％～30wt％。
所述步骤(1)中乙酰化聚乙烯醇由日本合成化学公司赠送，分子量为28900～10400，乙酰化程度为1.8mol％～5.5mol％，醇解度为97.5％～99％。
所述步骤(2)中贫溶剂为丙酮。
所述步骤(2)中溶剂置换为：用丙酮(或乙醇、甲醇等)置换3次，每次12h。溶剂置换的作为用将体系中的溶剂置换出来，放置干燥过程中整体柱的孔径结构发生坍塌。溶剂置换时所使用的溶剂需要与水有较强的互溶作用，并且乙酰化聚乙烯醇不溶于该溶剂。
所述步骤(2)中贫溶剂的加入量为1.8mL～2mL(每2ml乙酰化聚乙烯醇溶液)。
所述步骤(2)中乙酰化聚乙烯醇整体柱作为重金属吸附剂用于污水处理或者应用于固定化酶反应器。
本发明中利用贫溶剂诱导相分离的方法，将乙酰化聚乙烯醇粉末在高温下溶于水中，制备得到透明均匀的乙酰化聚乙烯醇溶液，接着将溶液降温至55℃，将贫溶剂逐滴加入乙酰化聚乙烯醇溶液中，滴加完毕后将溶液系统置于20℃条件下。24h后进行溶剂置换和干燥，最终制得乙酰化聚乙烯醇整体柱。
本发明中贫溶剂诱导相分离法制备乙酰化聚乙烯醇整体柱，通过向乙酰化聚乙烯醇溶液中滴加贫溶剂，使溶液系统转化成聚合物聚集相和溶剂聚集相，并进一步发生液液相分离，形成三维具有连续贯通孔径结构的整体材料。该方法需要在溶液加热条件下进行贫溶剂的滴加。对于某些聚合物溶液来说，在常温下的溶液黏度很大，不利于贫溶剂的均匀分散，因此该方法对滴加贫溶剂前的聚合物溶液系统有加热步骤，从而使得聚合物溶液的黏度降低，更利于贫溶剂的分散。另外，通过该方法制备的乙酰化聚乙烯醇整体柱同时具有大孔和介孔的双孔径结构。
有益效果
(1)本发明利用贫溶剂诱导相分离法，通过聚合物溶液直接制备聚合物整体柱，具有操作简单、易于控制、节能环保等优点；
(2)本发明制备的聚合物整体柱，具有高孔隙率、较大的比表面积、连续贯通的大孔结构、低背压等优点；
(3)本发明制备的聚合物整体柱，可以通过进一步修饰和改性应用于多个领域，如固定酶反应器、重金属吸附材料等，具有很好的应用前景。
附图说明
图1为实施例1中乙酰化聚乙烯醇整体柱(a)及干燥后的乙酰化聚乙烯醇整体柱(b)；
图2为实施例2中乙酰化聚乙烯醇整体柱内部结构的扫描电镜图(3000倍)；
图3为实施例3中乙酰化聚乙烯醇聚合物整体柱吸附铜离子过程示意图；(a)吸附前；(b)吸附后；
图4为实施例4中乙酰化聚乙烯醇聚合物整体柱固定化酶反应器制备过程示意图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
将468mg乙酰化聚乙烯醇粉末在90℃溶于2mL的水中4h，得到透明均匀的乙酰乙酰基聚乙烯醇溶液。将溶液降温至55℃，将1.9mL的丙酮逐滴加入溶液中，然后将系统在20℃的环境中静置24h。之后，将整体柱用丙酮置换3次，每次12h，最后进行真空干燥得到乙酰乙酰基聚乙烯醇整体柱，如图1所示。
实施例2
将585mg乙酰化聚乙烯醇粉末在90℃溶于2mL的水中4h，得到透明均匀的乙酰乙酰基聚乙烯醇溶液。将溶液降温至55℃，将1.9mL的丙酮逐滴加入溶液中，然后将系统在20℃的环境中静置24h。之后，将整体柱用丙酮置换3次，每次12h，最后进行真空干燥得到乙酰乙酰基聚乙烯醇整体柱；所得乙酰化聚乙烯醇整体柱内部结构图如图2所示。
实施例3
室温下，乙酰化聚乙烯醇整体柱(实施例2中得到的)浸泡于10mL的聚乙酰亚胺的乙醇溶液中24h。聚乙酰亚胺的乙醇溶液的浓度为40mg/mL，聚乙酰亚胺的平均分子量为10000。接着，反应后的乙酰化聚乙烯醇整体柱用乙醇清洗3次，每次12h。清洗后的整体柱真空干燥24h。将修饰后的乙酰化聚乙烯醇整体柱置于20mg/mL的氯化铜溶液中6h，即可实现乙酰化聚乙烯醇整体柱对铜离子的吸附，效果图如图3。
实施例4
室温下，乙酰化聚乙烯醇整体柱(实施例1中得到的)浸泡于10mL的聚乙酰亚胺的乙醇溶液中24h。聚乙酰亚胺的乙醇溶液的浓度为40mg/mL，聚乙酰亚胺的平均分子量为10000。接着，反应后的乙酰化聚乙烯醇整体柱用乙醇清洗3次，每次12h。清洗后的整体柱真空干燥24h。之后，在40℃下，聚乙酰亚胺修饰后的乙酰化聚乙烯醇整体柱浸泡在戊二醛水溶液中1h。戊二醛水溶液的浓度为1wt％，pH 8。然后反应后的整体柱用水清洗，然后冻结干燥。20mg脂肪酶溶于50mM磷酸盐缓冲液(pH7)，得到脂肪酶溶液。然后在4℃下，将20mg修饰后的带有醛基的整体柱浸入1mL酶溶液中，放置24h，利用整体柱的醛基将酶固定在整体柱的表面。之后用同样的磷酸盐缓冲液清洗未反应的酶，即得到整体柱固定化酶反应器(图4)。

Claims (6)

1.一种乙酰化聚乙烯醇整体柱的制备方法，包括：
(1)将乙酰化聚乙烯醇粉末在80～95℃溶于水中，得到乙酰化聚乙烯醇溶液；
(2)将步骤(1)中的乙酰化聚乙烯醇溶液降温至40～55℃，滴加贫溶剂，-196～30℃静置1～36h，溶剂置换，干燥，得到乙酰化聚乙烯醇整体柱。
2.根据权利要求1所述的一种乙酰化聚乙烯醇整体柱的制备方法，其特征在于，所述步骤(1)中乙酰化聚乙烯醇溶液的浓度为13wt％～26wt％。
3.根据权利要求1所述的一种乙酰化聚乙烯醇整体柱的制备方法，其特征在于，所述步骤(2)中贫溶剂为丙酮。
4.根据权利要求1所述的一种乙酰化聚乙烯醇整体柱的制备方法，其特征在于，所述步骤(2)中溶剂置换为：用溶剂置换3次，每次12h；其中，溶剂为丙酮、乙醇或甲醇。
5.根据权利要求1所述的一种乙酰化聚乙烯醇整体柱的制备方法，其特征在于，所述步骤(2)中贫溶剂与乙酰化聚乙烯醇溶液的比例为1.8mL～2mL：2mL。
6.根据权利要求1所述的一种乙酰化聚乙烯醇整体柱的制备方法，其特征在于，所述步骤(2)中乙酰化聚乙烯醇整体柱作为重金属吸附剂用于污水处理或者应用于固定化酶反应器。
CN201610298055.4A 2016-05-06 2016-05-06 一种乙酰化聚乙烯醇整体柱的制备方法 Pending CN106000349A (zh)

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Application publication date: 20161012