CN104084062B - 一种基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法 - Google Patents
一种基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法 Download PDFInfo
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Abstract
本发明公开一种基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法，其步骤为：将端氨丙基聚二甲基硅氧烷、聚氧化丙烯二醇与甲苯‑2,4‑二异氰酸酯混合溶于二甲苯溶剂中，并加入催化剂二月桂酸二丁基锡合成预聚体；然后将二苯基甲烷二胺加入到预聚体中，得到基于端氨丙基聚二甲基硅氧烷聚氨酯铸膜液；再将基于端氨丙基聚二甲基硅氧烷聚氨酯铸膜液进行真空脱泡后在聚四氟乙烯板上流延成膜，常温下自然晾干后，置于真空干燥，即得到基于端氨丙基聚二甲基硅氧烷聚氨酯膜。本发明工艺简单，生产成本低，对低浓度的丙酮/丁醇/水混合溶液具有较好的分离效果。
Description
技术领域
本发明涉及一种用于渗透汽化优先透过有机物的基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法，属于渗透汽化膜分离领域。
背景技术
受能源危机影响，石油价格上涨，作为新型生物能源的丁醇越来越受到重视。生物发酵法制备丁醇（ABE发酵）的产物中主要含丙酮、丁醇和乙醇，受产物丁醇的抑制作用，发酵液中总溶剂浓度只能达到约20gL-1，生产能力较低。为了解决上述问题，科学家尝试将一些分离方法，渗透汽化（PV）、吸附、液液萃取、气提和反渗透等，（Ezeji, T.C., N. Qureshi,
and H.P. Blaschek, Butanol fermentation research: Upstream and downstream
manipulations. Chemical Record. 2004. 4(5): 305-314）直接与发酵过程耦合以实现丁醇的原位分离，减轻丁醇对微生物的抑制作用，提高发酵强度和原料利用率。
众多分离方法中，渗透汽化（pervaporation，PV）能够以低的能耗实现蒸馏、萃取、吸附等传统方法难于完成的分离任务，特别适于分离近沸点、恒沸点混合物及同分异构体的分离，对有机溶剂及混合溶剂中微量水的脱除及废水中少量有机污染物的分离具有明显的技术上和经济上的优势。
目前应用于ABE发酵过程分离研究的渗透汽化膜主要有高分子聚合膜，无机膜以及液体膜。无机膜材料价格昂贵，且易收到微生物污染，液体膜稳定性较差等，相对而言，高分子聚合膜研究较多。主要应用于优先透醇的渗透汽化分离膜材料有有机硅聚合物（PDMS、PTMSP），如含氟类聚合物（PTFE、PVDF）和其他聚合物（PDMS/PVDF、PEBA）等，如Srinivasan用硅脂改性的PVDF膜对7.5wt%的丁醇溶液进行渗透汽化分离，50℃条件下，总通量为3.42 kgm-2h-1，分离因子为4.88（Srinivasan, K., K.
Palanivelu, and A.N. Gopalakrishnan, Recovery of 1-butanol from a model
pharmaceutical aqueous waste by pervaporation. Chemical Engineering Science.
2007. 62(11): 2905-2914）。Liu用PEBA制得厚度100μm的聚合膜对二元体系（丙酮－水、丁醇－水、乙醇－水）的分离效果为：分离因子α 丙酮＝4.2、α 丁醇＝8.2和α 乙醇＝2.4，对应的总渗透通量分别为27.4 gm-2h-1、65.3 gm-2h-1和37.2gm-2h-1（Liu, FF; Liu, L; Feng, XS.
Separation of acetone–butanol–ethanol (ABE) from dilute
aqueous solution by pervaporation[J]. Sep. Purif. Technol. 2005, 42(3):
273-282）。有机硅聚合物虽分离效果较好，但自身成膜性、机械性能差，含氟类聚合物虽然因含氟原子而具有良好的憎水性，但选择性不好，且成本过高，复合膜制备工艺相对复杂。本发明采用的聚氨酯（PU）是一种重要的高分子材料，具有优良的机械强度，经过简单的改性即可提高其对有机物的选择性，成本低，工业化应用价值高，前景广阔。
发明内容
本发明的目的在于针对上述关键技术问题，提供一种优先通过丙酮/丁醇的基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法。
为实现上述目的，本发明所采取的技术方案是：该基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法包括以下步骤：
A. 在装有氮气保护、机械搅拌和冷凝回流的反应器中加入二甲苯作为溶剂，将端氨丙基聚二甲基硅氧烷、聚氧化丙烯二醇与甲苯-2,4-二异氰酸酯混合成混合体，后溶于二甲苯溶剂中，并加入催化剂二月桂酸二丁基锡，搅拌均匀， 75～80℃下反应2～3h后冷却至室温，合成预聚体；所述的端氨丙基聚二甲基硅氧烷平均分子量为2200～2700；所述的聚氧化丙烯二醇与端氨丙基聚二甲基硅氧烷摩尔比为0.5～1:1；所述的甲苯-2,4-二异氰酸酯与端氨丙基聚二甲基硅氧烷摩尔比为4～10:1；所述的混合体与二甲苯溶剂的质量比为1:0.5～4；所述的二月桂酸二丁基锡与端氨丙基聚二甲基硅氧烷的质量比为0.0005～0.001:1；
B.按照端氨丙基聚二甲基硅氧烷与二苯基甲烷二胺摩尔比1:1～2.5称取二苯基甲烷二胺，并逐滴加入到预聚体中，升温至50～55℃反应1h，即得基于端氨丙基聚二甲基硅氧烷聚氨酯铸膜液；
C.将基于端氨丙基聚二甲基硅氧烷聚氨酯铸膜液进行真空脱泡，后将该铸膜液在聚四氟乙烯板上流延成膜，常温下自然晾干后，置于50～90℃真空烘箱中真空干燥8～12h，得到基于端氨丙基聚二甲基硅氧烷聚氨酯膜。
与现有技术相比，本发明制备的聚氨酯膜以适量的端氨丙基聚二甲基硅氧烷为软段，对聚氨酯本身的力学性能影响较小，保证了膜的机械性能强，同时，有机硅良好的疏水性、耐高低温性，保证了膜对有机物选择性，不受发酵料液污染。本发明制备工艺简单、操作方便，原料成分低廉，应用前景广阔。
具体实施方式
以下结合具体实例对本发明的技术方案做进一步的说明。
实施例1：
A.在装有氮气保护、机械搅拌和冷凝回流的反应器中加入二甲苯作为溶剂，将端氨丙基聚二甲基硅氧烷、聚氧化丙烯二醇与甲苯-2,4-二异氰酸酯混合成混合体，后溶于二甲苯溶剂中，并加入催化剂二月桂酸二丁基锡，搅拌均匀，75℃下反应3h后冷却至室温，合成预聚体；其中端氨丙基聚二甲基硅氧烷平均分子量为2500；聚氧化丙烯二醇与端氨丙基聚二甲基硅氧烷摩尔比为0.5:1；甲苯-2,4-二异氰酸酯与端氨丙基聚二甲基硅氧烷摩尔比为4:1；混合体与二甲苯溶剂的质量比为1:0.5；二月桂酸二丁基锡与端氨丙基聚二甲基硅氧烷的质量比为0.0005:1；
B.按照端氨丙基聚二甲基硅氧烷与二苯基甲烷二胺摩尔比1:1称取二苯基甲烷二胺，并逐滴加入到预聚体中，升温至50℃反应1h，得聚氨酯铸膜液；
C.将聚氨酯铸膜液真空脱泡后将该铸膜液在聚四氟乙烯板上流延成膜，常温下自然晾干后，置于50℃真空烘箱中真空干燥12h，得到基于端氨丙基聚二甲基硅氧烷聚氨酯膜。
将本实施例所得的改性聚氨酯膜对丙酮/水、丁醇/水混合溶液进行渗透汽化分离实验，性能如表1所示：
表1
实施例2：
A.在装有氮气保护、机械搅拌和冷凝回流的反应器中加入二甲苯作为溶剂，将端氨丙基聚二甲基硅氧烷、聚氧化丙烯二醇与甲苯-2,4-二异氰酸酯混合成混合体，后溶于二甲苯溶剂中，并加入催化剂二月桂酸二丁基锡，搅拌均匀，80℃下反应2h后冷却至室温，合成预聚体；其中端氨丙基聚二甲基硅氧烷平均分子量为2500；聚氧化丙烯二醇与端氨丙基聚二甲基硅氧烷摩尔比为0.7:1；甲苯-2,4-二异氰酸酯与端氨丙基聚二甲基硅氧烷摩尔比为8:1；混合体与二甲苯溶剂的质量比为1:1；二月桂酸二丁基锡与端氨丙基聚二甲基硅氧烷的质量比为0.0005:1；
B.按照端氨丙基聚二甲基硅氧烷与二苯基甲烷二胺摩尔比1:2称取二苯基甲烷二胺，并逐滴加入到预聚体中，升温至50℃反应1h，得聚氨酯铸膜液；
C.将聚氨酯铸膜液真空脱泡后将该铸膜液在聚四氟乙烯板上流延成膜，常温下自然晾干后，置于60℃真空烘箱中真空干燥11h，得到基于端氨丙基聚二甲基硅氧烷聚氨酯膜。
将本实施例所得的改性聚氨酯膜对丙酮/水、丁醇/水混合溶液进行渗透汽化分离实验，性能如表2所示：
表2
实施例3：
A.在装有氮气保护、机械搅拌和冷凝回流的反应器中加入二甲苯作为溶剂，将端氨丙基聚二甲基硅氧烷、聚氧化丙烯二醇与甲苯-2,4-二异氰酸酯混合成混合体，后溶于二甲苯溶剂中，并加入催化剂二月桂酸二丁基锡，搅拌均匀，75℃下反应3h后冷却至室温，合成预聚体；其中端氨丙基聚二甲基硅氧烷平均分子量为2700；聚氧化丙烯二醇与端氨丙基聚二甲基硅氧烷摩尔比为1:1；甲苯-2,4-二异氰酸酯与端氨丙基聚二甲基硅氧烷摩尔比为10:1；混合体与二甲苯溶剂的质量比为1:4；二月桂酸二丁基锡与端氨丙基聚二甲基硅氧烷的质量比为0.001:1；
B.按照端氨丙基聚二甲基硅氧烷与二苯基甲烷二胺摩尔比1:2.5称取二苯基甲烷二胺，并逐滴加入到预聚体中，升温至55℃反应1h，得聚氨酯铸膜液；
C.将聚氨酯铸膜液真空脱泡后将该铸膜液在聚四氟乙烯板上流延成膜，常温下自然晾干后，置于90℃真空烘箱中真空干燥8h，得到基于端氨丙基聚二甲基硅氧烷聚氨酯膜。
将本实施例所得的改性聚氨酯膜对丙酮/水、丁醇/水混合溶液进行渗透汽化分离实验，性能如表3所示：
表3
。
Claims (1)
1.一种基于端氨丙基聚二甲基硅氧烷聚氨酯膜的制备方法，其特征在于该方法包括以下步骤：
A. 在装有氮气保护、机械搅拌和冷凝回流的反应器中加入二甲苯作为溶剂，将端氨丙基聚二甲基硅氧烷、聚氧化丙烯二醇与甲苯-2,4-二异氰酸酯混合成混合体，后溶于二甲苯溶剂中，并加入催化剂二月桂酸二丁基锡，搅拌均匀， 75～80℃下反应2～3h后冷却至室温，合成预聚体；所述的端氨丙基聚二甲基硅氧烷平均分子量为2200～2700；所述的聚氧化丙烯二醇与端氨丙基聚二甲基硅氧烷摩尔比为0.5～1:1；所述的甲苯-2,4-二异氰酸酯与端氨丙基聚二甲基硅氧烷摩尔比为4～10:1；所述的混合体与二甲苯溶剂的质量比为1:0.5～4；所述的二月桂酸二丁基锡与端氨丙基聚二甲基硅氧烷的质量比为0.0005～0.001:1；
B.按照端氨丙基聚二甲基硅氧烷与二苯基甲烷二胺摩尔比1:1～2.5称取二苯基甲烷二胺，并逐滴加入到预聚体中，升温至50～55℃反应1h，即得基于端氨丙基聚二甲基硅氧烷聚氨酯铸膜液；
C.将基于端氨丙基聚二甲基硅氧烷聚氨酯铸膜液进行真空脱泡，后将该铸膜液在聚四氟乙烯板上流延成膜，常温下自然晾干后，置于50～90℃真空烘箱中真空干燥8～12h，得到基于端氨丙基聚二甲基硅氧烷聚氨酯膜。
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