CN106674580A - 一种聚砜类纳米多孔聚合物的制备方法 - Google Patents
一种聚砜类纳米多孔聚合物的制备方法 Download PDFInfo
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Abstract
本发明涉及一种聚砜类纳米多孔聚合物的制备方法,包括:将聚砜类聚合物与极性聚合物的共聚物浸没于复合溶胀剂中,在室温以上保持至少1min;所述的复合溶胀剂是由溶剂A和溶剂B混配组成的“溶剂对”;所述的溶剂A与聚砜类聚合物有高亲和性;所述的溶剂B与极性聚合物有高亲和性;将处理后的共聚物从复合溶胀剂中取出,干燥脱除溶剂,即得到所述的聚砜类纳米多孔聚合物。本发明所述的方法得到的聚合物孔道均匀,孔径分布在10‑100nm范围内,且相互连通,孔道结构的热、机械稳定性高,孔壁为极性聚合物分子链所覆盖而高度亲水,而且本发明的方法适用于不同尺寸形态的共聚物,操作简便,易于规模化实施。
Description
技术领域
本发明涉及一种多孔聚合物的制备方法,尤其涉及一种纳米多孔聚合物的制备方法。
背景技术
纳米多孔聚合物由于孔道细小、孔隙率高、比表面大、比强度大等特点,而在分离、催化、组织工程、生物医药等领域具有广阔的应用前景。在这些应用过程中,多孔聚合物的孔道大小、孔径分布和孔壁表面性质决定着性能的优劣。但是,由于成孔方法的限制,纳米多孔聚合物还普遍存在孔径分布宽、孔径难于减小到100纳米以下、制备工序复杂难于规模化制备以及成本较高等问题。
目前的制备纳米多孔聚合物的方法,主要有相转化(溶剂或温度诱导)、发泡、模板法以及选择性剔除分相嵌段共聚物中一些组分等方法。这些方法在一些特定领域得到了应用,但还存在不足之处,或只是在某个或某些方面具有优势。如广泛使用的聚合物发泡法,很难获得孔径在100nm以下的孔道,且多为闭孔结构,表面还会产生致密皮层,因而由发泡得到的多孔聚合物不具备通透性,孔道不能容纳、传递物质,故较难应用于涉及到流体传输的分离、催化、药物释放等领域。
此外,聚砜类聚合物分子链中含有砜基、芳环和醚键,具有优良的物理和化学性能,在医疗器械、生物分子检测和诊断、电子电器、航空航天、交通运输、膜制品和中空纤维领域有广泛地应用。但由于其玻璃化转变温度较高以及分子结构化学稳定性高难于在温和条件下进行化学反应等性质,聚砜类聚合物在制备纳米多孔材料时难度更高,采用现有的方法很难获得均匀、稳定、连通性好的纳米多孔材料。
因此,急需发展兼顾高稳定性、孔道均匀细小、连通性好、孔径分布窄、宜于规模化制备等特点的,适用于聚砜类聚合物的纳米多孔聚合物的制备方法。
发明内容
本发明的目的在于:提供一种以聚砜类聚合物为主体的纳米多孔聚合物的制备方法。
本发明的技术方案为:一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚砜类聚合物与极性聚合物的共聚物浸没于复合溶胀剂中,在室温以上保持至少1min;所述的复合溶胀剂是由溶剂A和溶剂B混配组成的“溶剂对”;所述的溶剂A与聚砜类聚合物有高亲和性;所述的溶剂B与极性聚合物有高亲和性;
2)将步骤1)处理后的共聚物从复合溶胀剂中取出,干燥脱除溶剂,即得到所述的聚砜类纳米多孔聚合物。
本发明所述的制备方法中,步骤1)所述的聚砜类聚合物与极性聚合物的共聚物可以是由聚砜类聚合物与多种极性聚合物通过多种共聚方法得到的多种产品。所述的聚砜类聚合物是指分子结构中含有砜基的聚合物,常用的有聚砜、聚醚砜、聚苯硫醚等。所述的极性聚合物可以是水溶性聚合物、醇溶性聚合物等;所述的共聚方法可以是无规、接枝或者嵌段共聚。本发明优选的方案中,所述共聚物是聚砜类聚合物与水溶性聚合物的共聚物;进一步优选的方案中,所述的水溶性聚合物可以选自聚乙二醇、聚乙二醇单甲醚、聚丙二醇或聚乙烯吡咯烷酮;最优选聚乙二醇。
本发明优选的方案中,所述的聚砜类聚合物与极性聚合物的共聚物中,极性聚合物的体积组成占整个共聚物的5-40%。
本发明所述的制备方法中,步骤1)所述共聚物的形态没有特别限制,可以是块体、薄膜、纤维、颗粒及粉末等。
本发明所述的制备方法中,步骤1)复合溶胀剂中所述的溶剂A可以选自现有的多种与聚砜类聚合物有高亲和性的溶剂,包括但不限于乙酸、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、丙酮、丁酮或乙腈中的任意一种,或它们中任意两种以上的混合物;步骤1)复合溶胀剂中所述的溶剂B可以选自现有的多种与极性聚合物有高亲和性的溶剂,包括但不限于水、分子链中含1至8个碳的醇类或酯类液体有机溶剂,具体例如甲醇、乙醇、异丙醇、正己醇、甲酸甲酯中的任意一种,或它们中任意两种以上的混合物。本发明优选的方案中,所述的溶剂A为乙酸、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)或丙酮中的任意一种,最优选丙酮或乙酸;所述的溶剂B为水、乙醇、异丙醇或正己醇中的任意一种,最优选乙醇。
本发明所述的方法中,调节步骤1)所述复合溶胀剂中的溶剂A、B体积比可以使产品获得不同的致孔效果,本发明优选的方案中,溶剂A、B体积比优选控制在5:95-95:5之间;更优选控制在5:95-25:75之间。
本发明所述的制备方法中,最优选的“溶剂对”包括:丙酮和乙醇以20:80的体积比、DMF和水以10:90的体积比、乙酸和异丙醇以15:85的体积比、DMSO和正己醇以10:90的体积比、或者DMAc和乙醇以5:95的体积比混配组成的“溶剂对”。
本发明所述的制备方法中,可以通过调节步骤1)所述的浸没温度和/或浸没时间来调节所得多孔聚合物的孔道大小及分布状态;本发明优选的方案中,步骤1)所述的温度优选控制在30-80℃之间;所述的时间优选控制在1分钟至24小时,更优选控制在0.1-12小时。
本发明优选的方案中,优选在步骤2)所述的干燥之前先将复合溶胀剂中取出的共聚物在低沸点溶剂中置换,将残存于共聚物中的溶剂进一步脱除。
本发明优选的方案中,步骤2)所述的干燥的温度控制在30-80℃。
本发明是基于聚砜类聚合物与极性聚合物(如聚乙二醇、聚乙烯吡咯烷酮等)的强烈相互排斥的作用而发生微观相分离,再经过使用复合溶剂调控两相的溶胀程度以产生纳米孔道的机理。聚砜类聚合物分子中富含苯环,为刚性分子结构,高度疏水;而聚乙二醇等极性聚合物是柔性分子,与水具有高度的亲和性。由于在化学结构和物化性质上的巨大差异,二者通过化学键连接而得到的共聚物有强烈的趋势会发生分相,共聚产物中极性聚合物链段形成的微区分散于聚砜类聚合物的连续相之中。本发明人在对致孔所用溶剂的研究中发现,应从聚砜和极性聚合物的自身物理化学性质出发,选择对共聚物中某一种链段具有高度亲和性而同时对另一种链段亲和性弱的溶剂进行处理;同时发现,单独使用任意一种性质的溶剂进行处理的效果很不理想,均不能使聚砜共聚物获得开孔的效果。单独使用亲聚砜的溶剂时,由于聚砜共聚物在该类溶剂中发生胶束化作用,而整体结构会被破坏;而单独使用亲极性聚合物的溶剂时,由于聚砜本体相的链段缺乏足够的运动能力,聚乙二醇微区的溶胀被抑制,不能形成孔道。本发明人经大量试验验证,必须选择亲聚砜的溶剂和亲聚乙二醇等极性聚合物的溶剂混配组合,以特定比例形成“溶剂对”,才能够获得聚砜类共聚物的最佳致孔效果。本发明的方法中,步骤1)复合溶胀剂中的溶剂A属于亲聚砜的溶剂,对聚砜类聚合物有中等到强烈溶胀作用;而溶剂B属于亲极性聚合物的溶剂,对极性聚合物(例如,聚乙二醇、聚丙二醇等)有强烈溶胀作用,但对聚砜类聚合物的溶胀作用较弱。在用所述溶剂A和溶剂B组成的“溶剂对”处理共聚物时,溶剂B在聚乙二醇等极性聚合物微区中不断富集,产生渗透压。溶剂A对聚砜本体相产生增塑作用,聚砜分子链的活动能力得到提高,在极性聚合物微区中积累的渗透压作用下,聚砜本体相发生局部的挤压变形。在脱除溶剂后,极性聚合物分子链坍塌,从而产生孔道。孔道的大小由溶剂处理前的极性聚合物微区的尺寸决定,一般在10-100nm,可通过改变共聚物的组成、溶剂对的组成和处理时间和温度调节。
本发明的聚砜类纳米多孔聚合物制备方法是一个直接的溶剂处理过程,与现有技术相比具有以下突出优势:(1)制备工艺极为简便,只需浸泡和干燥两个简单步骤,易于放大和规模化制备;(2)孔径均匀,分布在10-100nm范围,且相互连通,便于流体的交换和输送;(3)成孔过程中,极性聚合物分子链会重新分布到共聚物材料的表面和孔壁,赋予得到的多孔材料高度亲水性,十分有利于在水环境的应用,如水处理和生物医药等;(4)由于聚砜类聚合物的玻璃化转变温度接近200摄氏度,且强度高,由本发明方法制备的多孔聚合物主体材料是聚砜,故产品可保持高热稳定性和机械稳定性;(5)适用于多种形态的聚合物原料:不同初始形态的聚砜类共聚物(包括宏观的块体材料)均可通过本发明所述的方法产生纳米孔道;(6)成孔过程中无需进行化学反应,没有物质损失,故成孔后的共聚物可回收循环使用。
总之,本发明方法与其他制备纳米多孔聚合物的方法相比,在制备工艺、结构调控、产品性能以及普适性等方面具有明显优势。
附图说明
图1是实施例1方法制备的纳米多孔聚砜基共聚物的扫描电子显微镜照片。
图2是实施例2方法制备的纳米多孔聚砜块体材料经溶剂对处理前后的外观形貌对比。
图3是实施例2方法制备的纳米多孔聚砜块体材料内部的的扫描电子显微镜照片。
图4是对比例2方法制备的纳米多孔聚砜块体材料的扫描电子显微镜照片。
具体实施方式
实施例1
一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚乙二醇体积比为20%的聚砜与聚乙二醇的嵌段共聚物薄膜浸入70℃下的乙醇/丙酮溶剂对(丙酮体积含量为20%)中处理5小时;
2)将共聚物薄膜从溶剂中取出,在30℃下干燥6小时,得到纳米多孔聚合物膜。
将本实施例所得的多孔聚合物进行了扫描电子显微镜表征,如图1所示,乙醇/丙酮溶剂对处理前致密的聚合物已转变为高度多孔的结构,孔道相互连通,且孔径小于100nm。同时,共聚物薄膜表面的对水接触角从乙醇处理前的85°,减少至50°,说明得到的纳米多孔材料具有良好的亲水性。
实施例2
一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚乙二醇体积比为35%的聚醚砜与聚乙二醇的接枝共聚物块体浸入60℃下的水/DMF溶剂对(DMF体积比为10%)中处理24小时;
2)将共聚物薄膜从溶剂对中取出,在60℃下干燥2小时,得到纳米多孔聚合物块体材料。
本实施例中,经所述的水/DMF溶剂对处理后,共聚物转变为乳白色,体积有所增大,但初始结构基本得以保持,如图2所示。将溶剂对处理后的块体切开,用扫描电镜仍可观察到连通的纳米孔道,证明了整个块体材料都产生了孔道,如图3所示。
实施例3
一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚乙烯吡咯烷酮体积比为40%的聚砜与聚乙烯吡咯烷酮的无规共聚物颗粒浸入50℃下的异丙醇/乙酸(乙酸体积比为20%)中处理0.1小时;
2)将共聚物颗粒从溶剂中取出,在40℃下干燥10小时,得到纳米多孔聚合物颗粒。
实施例4
一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚乙二醇体积比为5%的聚苯硫醚与聚乙二醇的无规共聚物薄膜浸入80℃下的正己醇/DMSO溶剂对(DMSO体积含量为10%)混合溶剂中处理15小时;
2)将共聚物薄膜从溶剂中取出,再置于室温下的乙醇中清洗5分钟,然后取出在30℃下干燥2小时,得到纳米多孔聚合物薄膜。
实施例5
一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚乙二醇体积比为40%的聚醚砜与聚乙二醇的嵌段共聚物纤维浸入30℃下的乙醇/DMAc溶剂对(DMAc体积含量为5%)异丙醇中处理24小时;
2)将共聚物纤维从溶剂中取出,再置于室温下的乙醇中清洗5分钟,然后取出在30℃下干燥2小时,得到纳米多孔聚合物纤维。
对比例1
一种聚砜类纳米多孔聚合物的制备方法,其步骤与实施例1大体相同,区别在于:将实施例1中的乙醇/丙酮溶剂对(丙酮体积含量为20%)改为纯的乙醇,其他操作不变,处理后的共聚物保持致密的初始状态,表面没有产生孔道。
对比例2
一种聚砜类纳米多孔聚合物的制备方法,其步骤与实施例1大体相同,区别在于:将实施例1中的乙醇/丙酮溶剂对(丙酮体积含量为20%)改为纯的丙酮,其他操作不变,处理后的共聚物材料不能保持初始的薄膜状态,也没有出现孔道,而是形成球形胶束,其微观结构如图4所示。
Claims (10)
1.一种聚砜类纳米多孔聚合物的制备方法,其步骤包括:
1)将聚砜类聚合物与极性聚合物的共聚物浸没于复合溶胀剂中,在室温以上保持至少1min;所述的复合溶胀剂是由溶剂A和溶剂B混配组成的“溶剂对”;所述的溶剂A与聚砜类聚合物有高亲和性;所述的溶剂B与极性聚合物有高亲和性;
2)将步骤1)处理后的共聚物从复合溶胀剂中取出,干燥脱除溶剂,即得到所述的聚砜类纳米多孔聚合物。
2.权利要求1所述的制备方法,其特征在于:步骤1)所述的极性聚合物是水溶性或醇溶性聚合物;优选聚乙二醇、聚乙二醇单甲醚、聚丙二醇或聚乙烯吡咯烷酮;最优选聚乙二醇。
3.权利要求1所述的制备方法,其特征在于:步骤1)所述的聚砜类聚合物与极性聚合物的共聚物中,极性聚合物的体积组成占整个共聚物的5-40%。
4.权利要求1所述的制备方法,其特征在于:步骤1)复合溶胀剂中所述的溶剂A选自乙酸、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)、丙酮、丁酮或乙腈中的任意一种或它们中任意两种以上的混合物。
5.权利要求1所述的制备方法,其特征在于:步骤1)复合溶胀剂中所述的溶剂B选自水、甲醇、乙醇、异丙醇、正己醇或甲酸甲酯中的任意一种或它们中任意两种以上的混合物。
6.权利要求1所述的制备方法,其特征在于:步骤1)复合溶胀剂中所述的溶剂A为乙酸、N,N-二甲基乙酰胺(DMAc)、二甲基亚砜(DMSO)或丙酮中的任意一种;且所述的溶剂B为水、乙醇、异丙醇或正己醇中的任意一种。
7.权利要求1所述的制备方法,其特征在于:步骤1)复合溶胀剂中溶剂A、B体积比控制在5:95-95:5之间,更优选控制在5:95-25:75之间。
8.权利要求1所述的制备方法,其特征在于:步骤1)复合溶胀剂是丙酮和乙醇以20:80的体积比混配的溶剂对、DMF和水以10:90的体积比混配的溶剂对、乙酸和异丙醇以15:85的体积比混配的溶剂对、DMSO和正己醇以10:90的体积比混配的溶剂对、或者DMAc和乙醇以5:95的体积比混配的溶剂对。
9.权利要求1所述的制备方法,其特征在于:步骤1)所述的温度控制在30-80℃之间;所述的时间控制在1分钟至24小时,优选控制在0.1-12小时。
10.权利要求1所述的制备方法,其特征在于:在步骤2)所述的干燥之前先将复合溶胀剂中取出的共聚物在低沸点溶剂中置换,将残存于共聚物中的溶剂进一步脱除。
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US10927229B2 (en) | 2021-02-23 |
US20190211175A1 (en) | 2019-07-11 |
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