CN109593159A - 一种基于多孔材料为模板制备分子印记聚合物的方法 - Google Patents

一种基于多孔材料为模板制备分子印记聚合物的方法 Download PDF

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CN109593159A
CN109593159A CN201811388147.7A CN201811388147A CN109593159A CN 109593159 A CN109593159 A CN 109593159A CN 201811388147 A CN201811388147 A CN 201811388147A CN 109593159 A CN109593159 A CN 109593159A
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章圣苗
张茂林
王彦华
朱芸
朱文潇
周策
张晓宇
王梦洁
刘晓
朱汉颍
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East China University of Science and Technology
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Abstract

本发明公开了一种以可逆加成‑断裂链转移聚合所得多孔材料为模板制备分子印记聚合物的制备方法。以可逆加成‑断裂链转移聚合高内相乳液制备的多孔材料为模板，再与功能单体、交联剂、模板分子相互反应，制得最终产物。步骤如下：以苯乙烯和二乙烯基苯做油相，水做水相，搅拌成乳液。以可逆加成‑断裂链转移聚合的方式制备多孔材料。再将制备出的多孔材料作为模板制备分子印迹聚合物，经测试该方法制备出的分子印迹聚合物其物质吸收率较其他方法有一定程度的提升，且不用繁琐复杂的后处理，在药物提取，环境治理等方面有很大的潜在应用价值。

Description

一种基于多孔材料为模板制备分子印记聚合物的方法
技术领域
本发明属于材料领域，具体涉及以可逆加成-断裂链转移聚合高内相乳液所得的多孔材料为模板，在此模板基础上，继续采用可逆加成-断裂链转移聚合方式进行分子印记聚合物合成的方法。
背景技术
分子印迹聚合物是一种人工合成的具有分子识别能力的新型高分子材料，其最大特点是对目标分子具有预定的选择性。在药物识别顺反异构体，处理水污染等其他方面有着巨大的潜在应用。但常规方法制备的分子印记聚合物后处理繁琐复杂，例如本体聚合而成的分子印记聚合物其印迹分子被包覆其中需经粉碎，过筛，洗脱之后才可以使用。
高内相乳液即分散相体积百分数大于等于74. 05%的乳液。这一乳液自从二十世纪六十年首次报道以来，作为模板来制备开孔聚合物材料，已经有众多的文献报道，如道化学公司于2000年申请的美国专利(US Pat 6, 147, 131)及卡梅隆、比斯麦和章圣苗等于聚合物杂志上发表的一系列文章等。
本发明采用高内相乳液模板法得到的聚合物多孔材料当模板制备多孔材料，此方法可利用多孔材料表面积大的特性，增多其识别位点。可逆加成-断裂链转移聚合方式可使得印迹位点在材料表面，更有利于物质识别和吸附，也免去了后处理复杂的弊端。
本发明涉及一种以多孔材料为模板制备分子印记聚合物的制备方法，具体涉及以乳液模板法制备出的多孔材料为模板，再与其他分子印记聚合物所需的物质放置于烧瓶中，搅拌静置一段时间使印迹分子和功能单体进行自组装，再用双排管进行除氧充氮处理，再在65摄氏度下进行反应，将得到的聚合物块状材料移到淋洗溶剂中淋洗2~3天，平均每24小时换一次淋洗溶剂，最后冷冻干燥得到干燥的具有有识别效果的多孔材料。
发明内容
本发明需要解决的技术问题是公开一种以多孔材料为模板进行分子印记聚合物制备的制备方法。
本发明所述的以多孔材料为模板进行分子印记聚合物制备的制备方法，包括如下步骤：
以苯乙烯和二乙烯基苯为外相，一定浓度的氯化钠溶液为内相，再向内加入链转移剂，引发剂，乳化剂，真空条件下在磁力转子搅拌条件下来制备乳液体系。设置温度65摄氏度，采用可逆加成-断裂链转移聚合的方法引发外相聚合。将制备的聚合物在淋洗溶剂中除去未反应的物质和乳化剂。以此为模板与制备分子印记聚合物的物质进行混合，除氧加热反应，反应得到的固体用适当的溶剂除去未反应的物质，最后冷冻干燥得到干燥的具有识别效果的多孔材料。
所说的一定浓度的氯化钠溶液浓度为0.02摩尔每升；
所说的乳液体系为高内相乳液；
所说的链转移剂为2-氰丙基-2-基苯并二硫；
所说的乳化剂为司班80；
所说的淋洗溶剂是乙醇、水或乙醇和水的混合物。
采用扫描电镜(SEM)S-3400(日本JEOL公司)观测第一步所得块状聚合物开孔材料的内外形貌，再用红外测得可逆加成-断裂链转移实际特征峰来证明该聚合物中有链转移剂。采用UV-500s（上海精密仪器仪表有限公司）测定特定双酚A溶液的浓度，将制得的材料放入上述溶液中24小时，之后再检测其溶液浓度，看其吸附量。
具体实施方式
实施例1
以0.967克苯乙烯，0.411克二乙烯基苯作油相，以7.5毫升0.02 摩尔每升的氯化钠溶液作为水相，0.207克的司盘80做乳化剂，0.015克2-氰丙基-2-基苯并二硫作链转移剂，0.011克偶氮二异丁氰作引发剂。在双排管真空条件下，通过磁力搅拌的作用，将氯化钠溶液滴入油相中。乳液稳定后，让装置置于65摄氏度油浴锅中反应24小时得到粉红色块状固体，将得到的聚合物块状材料移到无水乙醇中浸泡2-3天，平均每12小时换一次酒精，以去除未反应的单体和乳化剂。最后冷冻干燥得到具有活性种的多孔材料。再以该多孔材料为模板，以6毫升乙腈作溶剂，依次向里面加入0.0256克双酚A，0.0473克四乙烯基吡啶，0.255毫升二甲基丙烯酸乙二醇酯。超声分散10分钟，静止一小时让其进行自组装，再向内加入0.003克偶氮二异丁氰作引发剂，在氮气保护，65度油浴环境下反应24小时，将得到的固体用甲醇/乙酸（9:1,甲醇体积/乙酸体积）进行索氏提取48小时去除未反应的物质。选取0.05摩尔每升的双酚A乙腈溶液，将所得分子印记聚合物浸入上述液体24小时，已知双酚A的乙腈溶液在紫外分光光度计300纳米波段有吸收峰，因此可以通过200纳米-1000纳米的波长的光谱扫描，判断吸收峰的高低来确认双酚A被识别和吸附量的多少。经24小时静止后与实验前波峰高度比较，结果表明该分子印记聚合物对印迹分子的吸附量为17.6毫克每克。
实施例2
以0.967克苯乙烯，0.411克二乙烯基苯作油相，以7.5毫升 0.02摩尔每升的氯化钠溶液作为水相，0.207克的司盘80做乳化剂，0.015克2-氰丙基-2-基苯并二硫作链转移剂，0.011克偶氮二异丁腈作引发剂。在双排管真空条件下，通过磁力搅拌的作用，将氯化钠溶液滴入油相中。待乳液稳定，让装置置于65摄氏度油浴锅中反应24小时得到粉红色块状固体，将得到的聚合物块状材料移到无水乙醇中浸泡2-3天，平均每12小时换一次酒精，以去除未反应的单体和乳化剂。最后冷冻干燥得到具有活性种的多孔材料。再以该多孔材料为模板，以70 毫升乙腈作溶剂，一次向内加入2毫摩尔对甲氧基苯胺，8毫摩尔四乙烯基吡啶，20毫摩尔乙-醇二甲基丙烯酸酯，超声分散10分钟，静止一小时让其进行自组装，再向内加入50毫克偶氮二异丁氰作引发剂，在氮气保护，65摄氏度油浴环境下反应24小时，将得到的固体用甲醇/乙酸（9:1,甲醇体积/乙酸体积）进行索氏提取48小时去除未反应的物质。选取10毫克每升的对甲基苯胺乙腈溶液，将所得固体浸入上述液体24小时，已知对甲基苯胺的乙腈溶液在紫外分光光度计300纳米波段有吸收峰，因此可以通过200纳米-1000纳米的波长的光谱扫描，判断吸收峰的高低来确认对甲基苯胺被识别和吸附量的多少。经24小时静止后与实验前波峰高度比较，结果表明该分子印记聚合物对对甲基苯胺的吸附量为20.7毫克每克。
实施例3
以0.967克苯乙烯，0.411克二乙烯基苯作油相，以7.5毫升0.02摩尔每升的氯化钠溶液作为水相，0.207克的司盘80做乳化剂，0.015克2-氰丙基-2-基苯并二硫作链转移剂，0.011克偶氮二异丁腈作引发剂。在双排管真空条件下，通过磁力搅拌的作用，将氯化钠溶液滴入油相中。让装置置于65摄氏度油浴锅中反应24小时得到粉红色块状固体，将得到的聚合物块状材料移到无水乙醇中浸泡2-3天，平均每12小时换一次酒精，以去除未反应的单体和乳化剂。最后冷冻干燥得到具有活性种的多孔材料。再以该多孔材料为模板，以10毫升乙腈作溶剂，依次向内加入2毫摩尔三氯生，8 毫摩尔四乙烯基吡啶，40 毫摩尔二甲基丙烯酸乙二醇酯，超声分散10分钟，静止一小时让其进行自组装，再向内加入50毫克偶氮二异丁氰作引发剂，在氮气保护，65度油浴环境下反应24小时，将得到的固体用甲醇/乙酸（9:1,甲醇体积/乙酸体积）进行索氏提取48小时去除未反应的物质。选取10毫克每升的三氯生乙腈溶液，将所得固体浸入上述液体24小时，已知三氯生的乙腈溶液在紫外分光光度计280纳米波段有吸收峰，因此可以通过200纳米-1000纳米的波长的光谱扫描，判断吸收峰的高低来确认对甲基苯胺被识别和吸附量的多少。经24小时静止后与实验前波峰高度比较，结果表明该分子印记聚合物对对甲基苯胺的吸附量为27.5毫克每克。

Claims (1)

1.一种以可逆加成-断裂链转移所得多孔材料为模板制备分子印记聚合物的制备方法，其特征在于适用广泛，后处理简单，单位表面积上的识别位点远多于本体聚合的分子印迹聚合物，主要包括如下步骤：
将少量无机盐溶解在蒸馏水中作为水相，将乳化剂、引发剂、可逆加成-断裂链转移试剂溶于有机试剂中作为油相；分别进行除氧操作，控制不同的水油比例制备高内相乳液；在磁力搅拌条件下，形成稳定的乳液，在一定温度下反应24小时，用淋洗溶剂进行淋洗去除各种未反应的物质和乳化剂；将所制得的多孔材料切成小块，与制备分子印记聚合物所需要的材料放置在一个烧瓶中，进行除氧操作，在65摄氏度反应24 小时再用特定淋洗溶剂去除印迹分子；根据印迹分子的不同采取不同溶质的溶剂进行吸收测试，用紫外分光光度计测试其性能；
所说的少量无机盐为氯化钠，浓度为0.02 摩尔每升；
所说的有机溶剂是苯乙烯和二乙烯基苯的混合物；
所说的乳化剂、引发剂、可逆加成-断裂链转移试剂分别指司班80、偶氮二异丁氰、2-氰丙基-2-基苯并二硫；
所说的淋洗溶剂是指甲醇/乙酸（9:1，甲醇体积/乙酸体积）。
CN201811388147.7A 2018-11-21 2018-11-21 一种基于多孔材料为模板制备分子印记聚合物的方法 Pending CN109593159A (zh)

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