CN109647296A - 一种多孔中空微球及其制备方法和应用 - Google Patents
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Abstract
本发明涉及一种多孔中空微球及其制备方法和应用。该微球初制备液组分包括:聚砜、致孔剂、表面活性剂、第一有机溶剂和第二有机溶剂。该方法包括:将各组分混合,得到的溶液采用注射泵推注挤出通过聚四氟软管进入凝固浴中,利用剪切场将软管端口处流出溶液剪切分散,搅拌,离心,洗涤,烘干。该微球物理稳定性和化学稳定性好,机械强度较高,具有较好的抗破坏性能和较长的使用寿命。
Description
技术领域
本发明属于有机微球及其制备和应用领域,特别涉及一种多孔中空微球及其制备方法和应用。
背景技术
聚砜(PSU)是一种热塑性工程塑料,其主链上含有芳环和砜基,从分子链结构上看,硫原子处于最高氧化状态,而砜基的两边都有苯环,可以形成共轭结构。因此,对于这类树脂来说具有非常优异的力学性能,如耐磨性和高强度等性能。在宽广的温度范围内又有优良的化学稳定性和电性能,除浓硫酸、浓硝酸、卤代烷外,能耐一般的盐、碱、酸。在微滤、超滤、气体分离、反渗透、固定化载体等方面得到广泛的应用。
由于聚砜膜材料具有疏水性,在膜分离过程中易与物料中的微粒、胶体粒子或溶质大分子发生吸附作用,利用聚砜制备的超滤膜可以用作超纯水的制备,废弃溶剂与油料的回收以及生物药剂的分离提纯和浓缩。同样也可以用来制备催化剂的载体与微吸附的载体。申请号为200310110855.1的中国专利公开了一种聚砜多孔微球和膜以及制造方法和用途,多孔微球的配方按重量计为:聚砜分子量20000~50000 5~25份,溶剂75~95份,添加剂0~5份。该方法制备聚砜微球制备过程复杂,孔隙度差,微球尺寸无法控制,无法满足在化学与医学上控制释放、催化降解、吸附提取的应用。
发明内容
本发明所要解决的技术问题是提供一种多孔中空微球及其制备方法和应用,以克服现有技术中制孔效果较差,形貌尺寸难以控制、孔隙度低的问题,提高在控制释放、催化降解、吸附提取等领域的运用。
本发明的一种多孔中空微球,所述微球初制备液组分包括:质量比为1.0-1.5:0.8-0.85:0.8-0.85:7-10的聚砜、致孔剂、表面活性剂和第一有机溶剂,以及第二有机溶剂;其中第一有机溶剂与第二有机溶剂的体积比为0.9-1.2:5-6。
所述微球制备过程中将初制备液利用剪切场剪切分散。
所述微球直径为50-100μm,孔壁厚度为5-20μm,平均孔径为1-8μm。
所述聚砜的分子量为50K-100K;致孔剂选自Mw为200-2000的聚乙二醇、羟丙基纤维素、聚维酮等。
所述致孔剂选自Mw为200、600、1000或2000的聚乙二醇、羟丙基纤维素、聚维酮等。
所述表面活性剂为聚乙烯吡咯烷酮、司班-80、吐温20、吐温80、油酸、聚乙烯醇中的至少一种。
所述第一有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜中的一种。
所述第二有机溶剂为二氯甲烷、三氯甲烷、二氯乙烷、石油醚中的一种。
本发明的一种多孔中空微球的制备方法,包括:
(1)将聚砜、致孔剂、表面活性剂混合,加入第一有机溶剂搅拌,待聚砜完全溶解再加入第二有机溶剂搅拌,超声,得到混合溶液,其中聚砜、致孔剂、表面活性剂和第一有机溶剂的质量比为1.0-1.5:0.8-0.85:0.8-0.85:7-10,第一有机溶剂与第二有机溶剂的体积比为0.9-1.2:5-6;
(2)将步骤(1)中混合溶液采用注射泵推注挤出通过聚四氟软管进入凝固浴中,利用剪切场将软管端口处流出溶液剪切分散,并搅拌充分分散,待第二有机溶剂挥发后离心,洗涤,烘干,得到多孔中空微球。
所述步骤(1)中聚砜混合前干燥除去水分。
所述步骤(1)中聚砜的分子量为50K-100K;致孔剂选自Mw为200-2000的聚乙二醇、羟丙基纤维素、聚维酮等。
所述步骤(1)中表面活性剂为聚乙烯吡咯烷酮、司班-80、吐温20、吐温80、油酸、聚乙烯醇中的至少一种。
所述步骤(1)中第一有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜中的一种。
所述步骤(1)中第二有机溶剂为二氯甲烷、三氯甲烷、二氯乙烷、石油醚中的一种。
所述步骤(2)中推注速度为0.8-1.2ml/min;搅拌速度为300-500rpm。
所述步骤(2)中凝固浴包括体积比为0.8-1.2:15-30的有机溶剂与0.5%聚乙烯醇水溶液,其中有机溶剂与步骤(1)中第二有机溶剂相同。
本发明的一种多孔中空微球的应用。
本发明与申请号为200310110855.1的中国专利的具体区别:
1.制备方法
本发明所用制备方法为程控推注,流体剪切溶剂挥发相转化法,该方法利用流体剪切使得铸膜液充分分散,再利用第二溶剂挥发使得铸膜液与凝固浴接触发生相转化固化成型的机理,利用推注泵推注控制径流量,剪切力分散、防止铸膜液发生聚集固化并在凝固浴中充分分散成单一液滴,且由于表面活性剂加入乳液液滴,液滴自发乳化形成水核油壳的液滴,移除溶剂得到中空结构,最终制备成型多孔中空微球。
2.形貌结构
本发明所制备多孔中空微球,多孔提供物质交换通道,空心结构具有低密度,高比表面积的特点,其内部可以容纳大量客体分子或大尺寸的客体,可以产生类似于微观包裹的特性,而表面多孔结构提供大尺寸分子运动通道有助于物质的交换、吸附与催化降解。本发明与申请号为200310110855.1的专利相比中空结构密度更低,比表面积更大且根据卡西润湿理论有更加优秀的疏水性能,可以在多种领域运用。
有益效果
(1)本发明的多孔中空微球物理稳定性和化学稳定性好,机械强度较高,具有较好的抗破坏性能并可多次重复利用;
(2)本发明的方法可以制备出不同分子量,不同孔径大小,且比表面积较大的多孔中空聚砜微球,具有显著吸附效果。
附图说明
图1为本发明实施例1中多孔中空微球SEM图。
图2为本发明实施例2中微球破碎后的中空微球SEM图。
图3为实施例1中多孔微球经2M HCl浸泡3h后微球形貌SEM图。
图4为实施例1中多孔微球经0.1mol/L NaOH浸泡3h后微球形貌SEM图。
图5为本发明实施例2中多孔中空微球SEM图。
图6为本发明实施例3中多孔中空微球SEM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。
试剂来源为:聚砜(PSF),山东浩然;聚乙烯吡咯烷酮(PVP),沃凯试剂;羟丙基纤维素、聚维酮、聚乙烯醇124,司班-80、国药试剂;聚乙二醇(PEG),麦克林试剂;二甲基甲酰胺,国药试剂;二甲基乙酰胺,国药试剂;甲基吡咯烷酮,国药试剂;吐温-20/80,国药试剂;司班-80,国药试剂;油酸,国药试剂;二氯甲烷/三氯甲烷、二氯乙烷、石油醚,国药试剂。
实施例1
(1)按下列组分和组成配料(按照质量分数):聚砜10%;聚乙烯吡咯烷酮7.5%;聚乙二醇7.5%,第一有机溶剂90%,将聚砜(Mw=80000)、聚乙烯吡咯烷酮、聚乙二醇(Mw=600)加入溶解釜内,先在室温下加入第一有机溶剂(NMP)搅拌0.5小时,待得溶解完全,加入体积是第一有机溶剂5倍的第二有机溶剂(三氯甲烷)继续在室温下搅拌0.5h后进行超声分散。
(2)制备过程是采用注射泵推注挤出,经聚四氟软管进入凝固浴中,于软管端口剪切分散完全后移除第二溶剂固化成型,采用10ml针管推注速度选择1ml/min,凝固浴搅拌速度为400rpm,将铸溶液缓慢滴加入凝固浴(体积比为1:20的三氯甲烷与0.5%聚乙烯醇水溶液)中经搅拌充分分散,待三氯甲烷充分挥发后取溶液离心移除上层清液后得到产物后经乙醇与水反复洗涤2次后,烘干即可得到目标多孔中空微球。所制备的微球材料性能如表1。
本实施例所制备出的多孔中空微球平均孔隙度经计算为67.2%,尺寸分布在90-110μm,孔径分布在1-8μm,对其进行耐酸碱测试,结果如图3、4所示,将所制备微球分别在2MHCl、0.1mol/L NaOH中浸泡3h后取出,微球形貌并无变化。利用本实施例所制备微球进行相关污染物与药物吸附实验结果如表2所示。
表1微球材料性能
表2聚砜多孔中空微球清除吸附效果
移除物质中文名称 | 移除物质英文缩写 | 吸附率(mg/g) |
夫地西酸 | FA | 50-80 |
利褔平 | RIF | 30-60 |
联苯 | BP | 35-55 |
双酚A | BPA | 10.5-20 |
二苯呋喃 | DBF | 40-60 |
实施例2
(1)按下列组分和组成配料(按照质量分数):聚砜10%;司班-80 8%;聚乙二醇7.5%,第一有机溶剂90%,将聚砜(Mw=80000)、司班-80、聚乙二醇(Mw=600)加入溶解釜内,先在室温下加入第一有机溶剂(DMF)搅拌0.5小时,待得溶解完全,加入体积是第一有机溶剂5倍的第二有机溶剂(二氯甲烷)继续在室温下搅拌0.5h后进行超声分散。
(2)制备过程是采用注射泵推注挤出,经聚四氟软管进入凝固浴中,于软管端口剪切分散完全后移除第二溶剂固化成型,采用10ml针管推注速度选择1ml/min,凝固浴搅拌速度为400rpm,将铸溶液缓慢滴加入凝固浴(体积比为1:20的二氯甲烷与0.5%聚乙烯醇水溶液)中经搅拌充分分散,待二氯甲烷充分挥发后取溶液离心移除上层清液后得到产物后经乙醇与水反复洗涤2次后,烘干即可得到目标多孔中空微球。本实施例所制备出的多孔中空微球平均孔隙度经计算为60%,尺寸分布在80-150μm,孔径分布在1-5μm。
实施例3
(1)按下列组分和组成配料(按照质量分数):聚砜10%;油酸7.5%;聚乙二醇7.5%,第一有机溶剂90%,将聚砜(Mw=80000)、油酸、聚乙二醇(Mw=600)加入溶解釜内,先在室温下加入第一有机溶剂(NMP)搅拌0.5小时,待得溶解完全,加入体积是第一有机溶剂5倍的第二有机溶剂(二氯乙烷)继续在室温下搅拌0.5h后进行超声分散。
(2)制备过程是采用注射泵推注挤出,经聚四氟软管进入凝固浴中,于软管端口剪切分散完全后移除第二溶剂固化成型,采用10ml针管推注速度选择1ml/min,凝固浴搅拌速度为400rpm,将铸溶液缓慢滴加入凝固浴(体积比为1:20的二氯乙烷与0.5%聚乙烯醇水溶液)中经搅拌充分分散,待二氯甲烷充分挥发后取溶液离心移除上层清液后得到产物后经乙醇与水反复洗涤2次后,烘干即可得到目标多孔中空微球。本实施例所制备出的多孔中空微球平均孔隙度经计算为62%,尺寸分布在80-130μm,孔径分布在1-5μm。
Claims (10)
1.一种多孔中空微球,其特征在于,所述微球初制备液组分包括:质量比为1.0-1.5:0.8-0.85:0.8-0.85:7-10的聚砜、致孔剂、表面活性剂和第一有机溶剂,以及第二有机溶剂;其中第一有机溶剂与第二有机溶剂的体积比为0.9-1.2:5-6。
2.根据权利要求1所述的微球,其特征在于,所述微球制备过程中将初制备液利用剪切场剪切分散。
3.根据权利要求1所述的微球,其特征在于,所述微球直径为50-100μm,孔壁厚度为5-20μm,平均孔径为1-8μm。
4.根据权利要求1所述的微球,其特征在于,所述聚砜的分子量为50K-100K;致孔剂选自Mw为200-2000的聚乙二醇、羟丙基纤维素、聚维酮中一种。
5.根据权利要求1所述的微球,其特征在于,所述表面活性剂为聚乙烯吡咯烷酮、司班-80、吐温20、吐温80、油酸、聚乙烯醇中的至少一种。
6.根据权利要求1所述的微球,其特征在于,所述第一有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜中的一种;第二有机溶剂为二氯甲烷、三氯甲烷、二氯乙烷、石油醚中的一种。
7.一种多孔中空微球的制备方法,包括:
(1)将聚砜、致孔剂、表面活性剂混合后,加入第一有机溶剂搅拌,待聚砜完全溶解再加入第二有机溶剂搅拌,超声,得到混合溶液,其中聚砜、致孔剂、表面活性剂和第一有机溶剂的质量比为1.0-1.5:0.8-0.85:0.8-0.85:7-10,第一有机溶剂与第二有机溶剂的体积比为0.9-1.2:5-6;
(2)将步骤(1)中混合溶液采用注射泵推注挤出通过聚四氟软管进入凝固浴中,利用剪切场将软管端口处流出溶液剪切分散,并搅拌充分分散,待第二有机溶剂挥发后离心,洗涤,烘干,得到多孔中空微球。
8.根据权利要求7所述的方法,其特征在于,所述步骤(2)中推注速度为0.8-1.2mL/min;搅拌速度为300-500rpm。
9.根据权利要求7所述的方法,其特征在于,所述步骤(2)中凝固浴包括体积比为0.8-1.2:15-30的有机溶剂与0.5%聚乙烯醇水溶液,其中有机溶剂与步骤(1)中第二有机溶剂相同。
10.一种如权利要求1所述的多孔中空微球的应用。
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