CN106947009B - 一种开孔型有机泡沫材料的制备方法 - Google Patents

一种开孔型有机泡沫材料的制备方法 Download PDF

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CN106947009B
CN106947009B CN201710172523.8A CN201710172523A CN106947009B CN 106947009 B CN106947009 B CN 106947009B CN 201710172523 A CN201710172523 A CN 201710172523A CN 106947009 B CN106947009 B CN 106947009B
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张晨
林世航
杜中杰
邹威
王洪
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Beijing University of Chemical Technology
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Abstract

本发明涉及多孔泡沫材料领域，特别涉及一种开孔型有机泡沫材料的制备方法。一种开孔型有机泡沫材料的制备方法，包括以下步骤：将表面活性剂、引发剂、发泡剂分别加入到单体中，搅拌均匀，得到油相溶液；于搅拌条件下将水滴加到所述油相溶液中，继续搅拌，得到浓乳液；将所述浓乳液倒入到模具中，于50～90℃进行聚合反应后，于60～90℃干燥使水相挥发，形成孔洞，得到开孔型有机泡沫基材；将所述开孔型有机泡沫基材于93～300℃进行二次发泡处理，得到开孔型有机泡沫材料。本发明的有益效果在于：所述开孔型有机泡沫材料开孔率更高、通孔更多、BET比表面积更高，并能通过改变发泡剂和发泡诱导剂的添加量改变孔直径的范围。

Description

一种开孔型有机泡沫材料的制备方法
技术领域
本发明涉及多孔泡沫材料领域，特别涉及一种开孔型有机泡沫材料的制备方法。
背景技术
多孔材料是一种由相互贯通或封闭的孔洞构成网络结构的材料，孔洞的边界或表面由支柱或平板构成。典型的孔结构有：一种是由大量多边形孔在平面上聚集形成的二维结构，由于其形状类似于蜂房的六边形而被称为“蜂窝”材料；更为普遍的是由大量多面体形状的孔洞在空间聚集形成的三维结构，通常称之为“泡沫”材料。如果构成的孔洞的固体只存在于边界(即孔洞之间是相通的)，则称为开孔，如果孔洞表面也是实心的，即每个孔洞与周围孔洞完全隔开，则称为闭孔；而有些孔洞则是半开孔半闭孔的，由于多孔材料具有相对密度低，比强度高，重量轻，隔音，隔热，渗透性好等优点，其应用范围远远超过单一功能的材料。
超浓乳液又称高内相比乳液，凝胶乳液，烃类胶质。它的外观似胶冻，结构象液-液泡沫，分散相体积分率超过74％，甚至高达99％。此时，分散相的液滴不再是球形，而是变形为被含有表面活性剂的连续相薄液膜隔离的液胞，液胞表面吸附的表面活性剂产生双层静电斥力，保证超浓乳液有足够的稳定性。与传统乳液一样，超浓乳液也有O/W型和W/O型.前者以疏水性物质为分散相，水或水溶性物质的水溶液为连续相；后者以水溶性物质为分散相，有机溶剂或疏水性物质作连续相。
但浓乳液模板法制得的多孔泡沫材料开孔率低，连接大孔之间的通孔少而且BET比表面积低。本发明在浓乳液的基础上添加入发泡剂以及发泡诱导剂，然后在一定环境中进行发泡处理，得到的多孔材料开孔率更高，BET比表面积更高。
发明内容
本发明的目的是提供一种开孔型有机泡沫材料的制备方法，在浓乳液聚合的基础上，通过加入发泡剂和发泡诱导剂使得制备的泡沫材料开孔率更高、通孔更多、BET比表面积更高，通过改变发泡剂和发泡诱导剂的添加量改变孔直径的范围，并能够通过控制发泡剂的种类以及发泡诱导剂的种类来控制有机泡沫材料的孔形态、孔形貌、开孔率以及BET比表面积等，经济有效的解决现有技术中存在的问题。
本发明具体技术方案如下：
一种开孔型有机泡沫材料的制备方法，包括以下步骤：
将表面活性剂、引发剂、发泡剂分别加入到单体中，搅拌均匀，得到油相溶液；
于搅拌条件下将水滴加到所述油相溶液中，继续搅拌，得到浓乳液；
将所述浓乳液倒入到模具中，于50～90℃进行聚合反应后，于60～90℃干燥使水相挥发，形成孔洞，得到开孔型有机泡沫基材；
将所述开孔型有机泡沫基材于93～300℃进行二次发泡处理，得到开孔型有机泡沫材料。
进一步地，所述油相溶液中还包括发泡诱导剂，所述发泡诱导剂为甲苯、丁酮、二氯乙烷、环己烷、环己酮、乙酸乙酯、环己醇或异丁醇中的一种。
进一步地，所述单体为甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯、丁二烯、丙烯酰胺或丙烯酸丁酯中的一种或几种。
进一步地，所述发泡剂为碳酸氢钠、碳酸铵、亚硝酸铵、偶氮二甲酰胺、对甲苯磺酰肼或偶氮二碳酸二异丙酯中的一种。
进一步地，所述引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈、偶氮二环己基甲腈或偶氮二异丁酸二甲酯中的一种。
进一步地，所述表面活性剂为司盘85(山梨醇酐三油酸酯，C60H108O8)、司盘80(失水山梨糖醇脂肪酸酯，C24H44O6)、司盘40(山梨醇酐单棕榈酸酯，C22H42O6)、司盘20(单十二酸脱水山梨醇酯，C18H34O6)、吐温60(聚氧乙烯山梨醇酐单硬脂酸酯，C64H126O26)、吐温40(聚氧乙烯山梨糖醇酐单棕榈酸酯，C62H122O26)或吐温20(聚氧乙烯失水山梨醇单月桂酸酯，C58H114O26)中的一种。
进一步地，所述表面活性剂添加量以质量百分比计，为所述单体质量的2～20％。
进一步地，所述引发剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
进一步地，所述发泡剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
进一步地，所述发泡诱导剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
本发明与现有技术相比，具有以下有益效果：
将浓乳液聚合与化学发泡技术结合，浓乳液聚合过程中，聚合反应的温度控制在50～90℃，干燥的温度控制在60～90℃，聚合反应温度过高会直接破坏乳液，而干燥温度过高时，会使得材料软化，导致孔消失，因此聚合温度和干燥温度不宜过高。由此得到的开孔型有机泡沫基材，由于干燥过程中，水相蒸发，在壁上形成孔洞；
将所述开孔型有机泡沫基材于93～300℃条件下进行二次发泡，由于浓乳液聚合过程中添加了发泡剂与发泡诱导剂，而所述浓乳液聚合过程中，温度低于所述发泡剂的发泡温度，所以发泡剂并未发生分解反应；当温度升高，达到所述发泡剂的发泡温度时，在所述开孔型有机泡沫基材孔洞的孔壁上再次进行发泡，使得孔壁上出现连接大孔的通孔，得到BET比表面积更大的开孔型有机泡沫材料。
本发明是制备开孔型有机泡沫材料的一种新方法，制备的有机泡沫材料是一种介孔材料，具有有序的结构，运用在污水处理等领域会有很大的潜力，将能与金属发生螯合作用的基团嵌入介孔材料骨架，得到具有良好重金属吸附性能的功能材料，该方法得到的材料有很多连接大孔的通孔即有很高的开孔率，因此该材料有很高的重复利用率；该方法能够通过控制发泡剂的种类、发泡剂的用量以及发泡剂的诱导剂来控制有机泡沫材料的孔形态、孔形貌、开孔率及BET比表面积等。
附图说明
图1为本发明实施例1的扫面电镜图；
图2为本发明实施例2的扫面电镜图；
图3为本发明实施例3的扫面电镜图；
图4为本发明实施例4的扫面电镜图；
图5为本发明对比例的扫面电镜图。
具体实施方式
下面将结合实施例对本发明的具体实施方式进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
一种开孔型有机泡沫材料的制备方法，包括以下步骤：
将表面活性剂、引发剂、发泡剂分别加入到单体中，搅拌均匀，得到油相溶液；
于搅拌条件下将水滴加到所述油相溶液中，水的添加量以体积百分数计，为74～99％，继续搅拌10～60min，得到浓乳液；
将所述浓乳液倒入到模具中，于50～90℃密封24～48h进行聚合反应后，于60～90℃干燥24～48h，使水相挥发，形成孔洞，得到开孔型有机泡沫基材；在聚合和干燥过程中温度不能过高，聚合温度过高会直接破坏乳液，干燥温度过高材料软化导致孔消失，因此聚合温度和干燥温度不宜过高；
将所述开孔型有机泡沫基材于93～300℃进行二次发泡处理1～60min，得到开孔型有机泡沫材料；
文献《无机吸热型发泡剂碳酸氢钠的改性研究》、《发泡剂分解温度的研究》、《液体发泡剂偶氮二碳酸二异丙酯简介》、《亚硝酸铵溶液的分解速度》中分别记载了碳酸氢钠、碳酸铵、偶氮二甲酰胺、对甲苯磺酰肼、偶氮二碳酸二异丙酯和亚硝酸铵的发泡分解温度，本发明所述的发泡剂，其分解温度均高于93℃，防止所述发泡剂在乳液聚合阶段发泡，导致乳液成分破坏。
本发明所述的，水为蒸馏水、去离子水、反渗透水或超纯水，本发明以去离子水为例进行举例说明。
本发明所述的，油相溶液中还包括发泡诱导剂，所述发泡诱导剂为甲苯、丁酮、二氯乙烷、环己烷、环己酮、乙酸乙酯、环己醇或异丁醇中的一种。
本发明所述的，单体为甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯、丁二烯、丙烯酰胺或丙烯酸丁酯中的一种或几种。
本发明所述的，发泡剂为碳酸氢钠、碳酸铵、亚硝酸铵、偶氮二甲酰胺、对甲苯磺酰肼或偶氮二碳酸二异丙酯中的一种。
本发明所述的，引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈、偶氮二环己基甲腈或偶氮二异丁酸二甲酯中的一种。
本发明所述的，表面活性剂为司盘85、司盘80、司盘40、司盘20、吐温60、吐温40或吐温20中的一种。
本发明所述的，表面活性剂添加量以质量百分比计，为所述单体质量的2～20％。
本发明所述的，引发剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
本发明所述的，发泡剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
本发明所述的，发泡诱导剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
实施例1
称取5.0g甲基丙烯酸甲酯作为单体，将0.1g吐温20、0.005g偶氮二异庚腈和0.005g碳酸氢钠加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将15g去离子水滴加至所述油相溶液中，继续搅拌30min，得到浓乳液；
将所述浓乳液倒入到模具中，50℃密封进行聚合反应24h，并于60℃干燥24h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于93℃进行二次发泡处理30min，冷却至室温，得到开孔型有机泡沫材料。
实施例2
称取5.0g甲基丙烯酸甲酯作为单体，将0.1g吐温20、0.005g偶氮二异庚腈、0.005g碳酸氢钠和0.005g甲苯加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将15g去离子水滴加至所述油相溶液中，继续搅拌30min，得到浓乳液；
将所述浓乳液倒入到模具中，50℃密封进行聚合反应24h，并于60℃干燥24h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于93℃进行二次发泡处理30min，冷却至室温，得到开孔型有机泡沫材料。
实施例3
称取4.5g苯乙烯和0.5g丁二烯混合均匀，作为单体，将0.25g司盘80、0.25g偶氮二异丁腈和0.25g偶氮二甲酰胺加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将15g去离子水滴加至所述油相溶液中，继续搅拌30min，得到浓乳液；
将所述浓乳液倒入到模具中，70℃密封进行聚合反应30h，并于60℃干燥24h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于150℃进行二次发泡处理30min，冷却至室温，得到开孔型有机泡沫材料。
实施例4
称取4.5g苯乙烯和0.5g丁二烯混合均匀，作为单体，将0.25g司盘80、0.25g偶氮二异丁腈、0.25g偶氮二甲酰胺和0.25g异丁醇加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将15g去离子水滴加至所述油相溶液中，继续搅拌30min，得到浓乳液；
将所述浓乳液倒入到模具中，70℃密封进行聚合反应30h，并于60℃干燥24h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于150℃进行二次发泡处理30min，冷却至室温，得到开孔型有机泡沫材料。
实施例5
称取5.0g甲基丙烯酸丁酯作为单体，将0.8g司盘40、0.3g偶氮二异庚腈、0.01g对甲苯磺酰肼加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将30g去离子水滴加至所述油相溶液中，继续搅拌10min，得到浓乳液；
将所述浓乳液倒入到模具中，65℃密封进行聚合反应25h，并于70℃干燥30h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于180℃进行二次发泡处理15min，冷却至室温，得到开孔型有机泡沫材料。
实施例6
称取1.0g丙烯酸丁酯和4.0g丙烯酰胺混合均匀，作为单体，将0.5g吐温40、0.05g偶氮二异丁酸二甲酯、0.45g碳酸铵、0.05g丁酮加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将50g去离子水滴加至所述油相溶液中，继续搅拌25min，得到浓乳液；
将所述浓乳液倒入到模具中，85℃密封进行聚合反应32h，并于90℃干燥32h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于120℃进行发泡处理8min，冷却至室温，得到开孔型有机泡沫材料。
实施例7
称取5.0g甲基丙烯酸乙酯作为单体，将0.6g司盘40、偶氮二异戊腈0.2和0.1g对甲苯磺酰肼加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将15g去离子水滴加至所述油相溶液中，继续搅拌40min，得到浓乳液；
将所述浓乳液倒入到模具中，55℃密封进行聚合反应40h，并于65℃干燥28h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于93℃进行发泡处理25min，冷却至室温，得到开孔型有机泡沫材料。
实施例8
称取3.0g苯乙烯、1.0g甲基丙烯酸乙酯和1.0g丁二烯混合均匀作为单体，将0.3g吐温20、0.1g偶氮二环己基甲腈、0.3g亚硝酸铵和0.35g环己酮加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将200g去离子水滴加至所述油相溶液中，继续搅拌40min，得到浓乳液；
将所述浓乳液倒入到模具中，55℃密封进行聚合反应40h，并于65℃干燥28h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于93℃进行发泡处理25min，冷却至室温，得到开孔型有机泡沫材料。
实施例9
称取4.0g丙烯酸丁酯和1g丙烯酸胺混合均匀，作为单体，将0.75g司盘85、0.35g偶氮二异丁酸二甲酯、0.35g偶氮二甲酰胺加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将16g去离子水滴加至所述油相溶液中，继续搅拌35min，得到浓乳液；
将所述浓乳液倒入到模具中，80℃密封进行聚合反应35h，并于80℃干燥35h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于200℃进行发泡处理30min，冷却至室温，得到开孔型有机泡沫材料。
实施例10
称取5.0g丙烯酰胺作为单体，将1g司盘20、0.5g偶氮二环己基甲腈、0.5g碳酸氢钠、0.5g乙酸乙酯加入到单体中，混合搅拌至均匀，得到油相溶液；
于搅拌条件下将50g去离子水滴加至所述油相溶液中，继续搅拌35min，得到浓乳液；
将所述浓乳液倒入到模具中，90℃密封进行聚合反应48h，并于90℃干燥48h，水相挥发后形成孔洞，得到开孔型有机泡沫基材；
以所述开孔型有机泡沫基材为二次发泡基体，利用其中所述发泡剂和所述发泡诱导剂，于300℃进行发泡处理1min，冷却至室温，得到开孔型有机泡沫材料。
对比例
称取5.0g甲基丙烯酸丁酯为单体，将0.25g Span-80、0.25g偶氮二异丁腈加入到单体中，混合搅拌至均匀，得到油相溶液；将15g去离子水在搅拌条件下滴加到所述油相溶液中，滴加后搅拌30分钟，得到浓乳液。将所述浓乳液倒入到模具中，放入70℃的环境中反应30h；放入70℃的环境中干燥30h；放入100℃环境中30min，冷却至室温，得到有机泡沫材料。
上述实施例所述开孔型有机泡沫材料的制备方法，先发生乳液聚合反应，单体借助表面活性剂和机械搅拌，使单体分散在水相中形成乳液，再利用引发剂引发单体聚合；脂溶性发泡剂均匀分布在固相中，而水溶性发泡剂在聚合物干燥后，水分蒸发，水溶性发泡剂均匀分布于固相上；然后采用化学发泡技术，于孔壁上进行发泡，使得孔壁上出现连接大孔的通孔，得到BET比表面积更大的开孔型有机泡沫材料；
对上述优选的实施例1、2、3、4方法所制得的开孔型有机泡沫材料以及对比例制得的开孔型有机泡沫材料进行BET比表面积检测，结果如表1所示；
表1 BET比表面积检测结果
实施方案 实施例1 实施例2 实施例3 实施例4 对比例
BET 27.33319 32.30743 45.83553 51.13313 16.85167
对比可知，与对比例相比，实施例1、2、3、4方法得到的开孔型有机泡沫材料BET比表面积有了大幅提高，并且加入发泡诱导剂的方法得到的开孔型有机泡沫材料比只加入发泡剂的方法得到的开孔型有机泡沫材料BET比表面积更高。
对上述优选的实施例1、2、3、4方法所制得的开孔型有机泡沫材料进行扫描电镜检测，得到电镜扫描结果如图1、2、3、4所示；将对比例方法制得的有机泡沫材料进行扫描电镜检测，得到电镜扫描结果如图5所示；对比可知，与图5相比，图1、图2、图3、图4中的开孔型有机泡沫材料大孔之间的固体有了连接大孔的通孔，且通孔更多，开孔率更高，BET比表面积更高，效果显著；图1到图4随着发泡剂的增多，通孔的直径和数量都呈现增长趋势。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

1.一种开孔型有机泡沫材料的制备方法，其特征在于，包括以下步骤：
将表面活性剂、引发剂、发泡剂分别加入到单体中，搅拌均匀，得到油相溶液；
于搅拌条件下将水滴加到所述油相溶液中，继续搅拌，得到浓乳液；
将所述浓乳液倒入到模具中，于50～90℃进行聚合反应后，于60～90℃干燥使水相挥发，形成孔洞，得到开孔型有机泡沫基材；
将所述开孔型有机泡沫基材于93～300℃进行二次发泡处理，得到开孔型有机泡沫材料。
2.如权利要求1所述的开孔型有机泡沫材料的制备方法，其特征在于，所述油相溶液中还包括发泡诱导剂，所述发泡诱导剂为甲苯、丁酮、二氯乙烷、环己烷、环己酮、乙酸乙酯、环己醇或异丁醇中的一种。
3.如权利要求2所述的开孔型有机泡沫材料的制备方法，其特征在于，所述单体为甲基丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、苯乙烯、丁二烯、丙烯酰胺或丙烯酸丁酯中的一种或几种。
4.如权利要求3所述的开孔型有机泡沫材料的制备方法，其特征在于，所述发泡剂为碳酸氢钠、碳酸铵、亚硝酸铵、偶氮二甲酰胺、对甲苯磺酰肼或偶氮二碳酸二异丙酯中的一种。
5.如权利要求4所述的开孔型有机泡沫材料的制备方法，其特征在于，所述引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异戊腈、偶氮二环己基甲腈或偶氮二异丁酸二甲酯中的一种。
6.如权利要求5所述的开孔型有机泡沫材料的制备方法，其特征在于，所述表面活性剂为司盘85、司盘80、司盘40、司盘20、吐温60、吐温40或吐温20中的一种。
7.如权利要求6所述的开孔型有机泡沫材料的制备方法，其特征在于，所述表面活性剂添加量以质量百分比计，为所述单体质量的2～20％。
8.如权利要求7所述的开孔型有机泡沫材料的制备方法，其特征在于，所述引发剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
9.如权利要求8所述的开孔型有机泡沫材料的制备方法，其特征在于，所述发泡剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
10.如权利要求9所述的开孔型有机泡沫材料的制备方法，其特征在于，所述发泡诱导剂的添加量以质量百分比计，为所述单体质量的0.1～10％。
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