CN115417940A - 一种聚合物多孔微球及其制备方法 - Google Patents
一种聚合物多孔微球及其制备方法 Download PDFInfo
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- CN115417940A CN115417940A CN202211032331.4A CN202211032331A CN115417940A CN 115417940 A CN115417940 A CN 115417940A CN 202211032331 A CN202211032331 A CN 202211032331A CN 115417940 A CN115417940 A CN 115417940A
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Classifications
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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Abstract
本发明公开了一种聚合物多孔微球,所述聚合物多孔微球以光聚合材料经光固化形成的聚合物为基体,所述聚合物多孔微球的粒径分布为500nm~200μm,孔径分布为2~150nm,比表面积为5~300m2/g;所述光聚合材料包括可光聚合物质、光引发剂、有机溶剂组成;可光聚合物质与有机溶剂的质量比为1:20~4:1,光引发剂用量为可光聚合物质的1.0~5.0wt%。本发明聚合物多孔微球通过乳液法结合光聚合技术制得,制备方法简单快速,高效节能,具有良好的适用性;该聚合物多孔微球的孔结构具有可调性,可应用于涂层、化妆品、药物控释、催化剂载体、吸附分离等领域。
Description
技术领域
本发明涉及多孔材料技术领域,尤其是涉及一种聚合物多孔微球及其制备方法
背景技术
聚合物多孔微球是一种通过活性单体聚合反应形成或以高分子聚合物为基体的具有高交联度和多孔结构的聚合物球形颗粒。将其与传统的实心微球相比,实心微球的密度取决于基材本身的密度,且比表面积随着微球粒径的增加而降低,这极大地限制了传统微球的可用性。而多孔微球则不同,低密度和大比表面积是其固有特性,同时孔结构带来的特殊的吸收与释放行为使其在药物控释、催化剂载体、组织再生支架、微反应器等领域表现出广阔的应用前景。
研究至今,学者们已经开发出众多可用于制备多孔微球的方法。根据致孔物质的不同,可大体将致孔剂分为液体致孔剂、固体致孔剂和气体致孔剂三种。液体类致孔剂主要包括溶剂、聚合物/单体以及乳液滴。而固体致孔剂则主要为聚合物粒子和无机固体颗粒。而常见的气体类致孔剂则是以氧气、氮气为主。其中,采用溶剂致孔是目前最为常用,研究最广的致孔方法,由此延伸出的制备方法也包括悬浮聚合法、沉淀聚合法、种子溶胀法、溶剂挥发法和模板法等。然而,采用上述方法进行多孔微球的制备往往是通过热聚合的方式,制备时间较长,体系组分较为复杂,流程相对繁琐。
近年来,紫外光聚合技术凭借节能高效、经济环保等特点备受关注。而将光聚合技术引入到聚合物多孔微球制备中,丰富制备方法,提高制备效率同样具有吸引力。目前,已有部分生产工艺实现了基于紫外光聚合技术的聚合物多孔微球的制备,而相对较长的紫外光辐照时间导致了制备效率的下降,同时受限的可光聚合组分和孔结构调节方法限制了光聚合技术在多孔微球制备领域的进一步发展。
因此如何能够在较短时间内快速高效地制备聚合物多孔微球,拓宽可用材料范围,增强多孔微球的可设计性仍是需要研究的方向。
发明内容
针对现有技术存在的上述问题,本发明提供了一种聚合物多孔微球及其制备方法。本发明通过乳液法结合光聚合技术进行聚合物多孔微球的制备,可以在几十秒至几分钟内完成聚合反应,且不需加热,实现快速高效的制备过程。且该方法简单高效节能,具有良好的适用性,可选择的光聚合物质范围较广,所制备的微球孔结构具有可调性。
本发明的技术方案如下:
一种聚合物多孔微球,所述聚合物多孔微球以光聚合材料经光固化形成的聚合物为基体,所述聚合物多孔微球的粒径分布为500nm~200μm,孔径分布为2~150nm,比表面积为5~300m2/g;
所述聚合物多孔微球的内部和外表面均具有孔结构,其外表面孔结构为开放式孔结构,内部孔结构为开放式和闭合式孔结构。
所述光聚合材料由可光聚合物质、光引发剂、有机溶剂组成;可光聚合物质与有机溶剂的质量比为1:20~4:1,光引发剂用量为可光聚合物质的1.0~5.0wt%。
优选方案,所述可光聚合物质为光敏单体、光敏预聚物中的一种或多种。
所述光敏单体为单官丙烯酸酯类单体、双官丙烯酸酯类单体、多官丙烯酸酯类单体中的一种或多种。
所述光敏单体为多官能度(官能度大于等于三)的化合物或其两种和两种以上的混合物,或是单官能度或二官能度的化合物与多官能度化合物的混合物。
更进一步,所述单官丙烯酸酯类单体为(甲基)丙烯酸二甲氨基乙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸硬脂酸酯、(甲基)丙烯酸月桂酯、丙氧化壬基丙烯酸酯、双环戊烯基、乙氧基化(甲基)丙烯酸酯、2-苯氧基乙基甲基丙烯酸酯、四氢化糠基甲基丙烯酸酯、(甲基)丙烯酸缩水甘油醚、异冰片基(甲基)丙烯酸酯、甲基丙烯酸环己酯、苄基(甲基)丙烯酸酯、甲基丙烯酸2-乙基己酯、乙氧基乙氧基乙基丙烯酸酯、甲氧基聚乙二醇丙烯酸酯中的一种或多种;
所述双官丙烯酸酯类单体为(乙氧化)1,6-己二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇(200、300、400、600)二(甲基)丙烯酸酯、乙氧化双酚A二(甲基)丙烯酸酯、(乙氧化)2-甲基-1,3-丙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯中的一种或多种;
所述多官丙烯酸酯类单体包括季戊四醇三丙烯酸酯、(乙氧基化、丙氧基化)三羟甲基丙烷三丙烯酸酯、(乙氧基化、丙氧基化)三羟甲基丙烷三甲基丙烯酸酯、(乙氧化、丙氧化)季戊四醇四丙烯酸酯、双三羟甲基丙烷四丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或多种;
优选方案,所述光敏预聚物为聚氨酯丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯中的一种或多种。
所述光敏预聚物为二官能度或多官能度(理论官能度大于等于二)的预聚物或其两种和两种以上的混合物,或是二官能度光敏预聚物与多官能度光敏预聚物的混合物。
更进一步,可光聚合物质组成为光敏单体和光敏预聚物的混合物。
优选方案,所述光引发剂为2-羟基-甲基苯基丙烷-1-酮、1-羟基环己基苯基甲酮、2-甲基-1-(2-甲硫基苯基)-2-吗啉基-1-丙酮、安息香双甲醚、2,4,6-三甲基苯甲酰基二苯基氧化膦、异丙基硫杂蒽酮、2,4-二乙基硫杂蒽酮、4-(N,N-二甲氨基)苯甲酸乙酯、二苯甲酮、4-氯二苯甲酮、邻苯甲酰苯甲酸甲酯、二苯基碘鎓盐六氟磷酸盐、N,N-二甲氨基苯甲酸异辛酯、4-甲基二苯甲酮、邻苯甲酰基苯甲酸甲酯、4-苯基二苯甲酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种或多种。
优选方案,所述有机溶剂为甲苯、二甲苯中的一种或多种。
所述有机溶剂对光敏单体、光敏预聚物和光引发剂都有良好的溶解性,且本发明申请中的有机溶剂作为致孔剂,勿需额外加入致孔剂。
一种所述聚合物多孔微球的制备方法,所述制备方法包括如下步骤:
将光聚合材料作为油相,加入到含有乳化剂的水相中,使用均质机乳化形成稳定的水包油型乳液,经紫外光固化后,抽滤收集微球产物,使用去离子水和乙醇交替洗涤,制得所述聚合物多孔微球;
油相与水相的质量比为1:10~2:1;乳化剂用量为水相的1.0~5.0wt%。
优选地,所述乳化剂为聚乙烯醇、聚乙二醇、十二烷基硫酸钠、十二烷基苯磺酸钠、聚苯乙烯-马来酸酐共聚物、吐温-60、吐温-80、司班-60、司班-80、十六烷基三甲基溴化铵、明胶、阿拉伯胶中的一种或多种。
优选地,所述均质机乳化的条件为转速为5000~25000rpm,乳化时间为1~6min。
优选地,紫外光固化的条件为:紫外光波长为230~450nm,固化时间为1~10min。
所述聚合物多孔微球可以用于各类缓蚀剂、修复剂、药物、香料、催化剂等物质,在防腐蚀填料、自修复材料、药物负载、香料缓释、催化剂载体、微反应器等领域具有广阔的应用前景。
本发明有益的技术效果在于:
本发明通过有机溶剂对紫外光聚合过程中可光聚合物质所形成的聚合物交联网络的溶胀能力的大小从而导致的溶剂相和聚合物相之间的相分离现象进行聚合物多孔微球的制备。当所用有机溶剂为甲苯或者二甲苯时,其对可光聚合物质所形成的聚合物交联网络具有一定的溶胀能力。随着聚合反应的进行,油相液滴中聚合物的网络逐渐形成,并在短期内能够被甲苯/二甲苯所溶胀,体系呈现为均相。而随着交联度的增加,交联反应的速率大于甲苯/二甲苯对交联网络的溶胀速率时,聚合物交联网络已经无法再吸收更多的甲苯/二甲苯,此时便产生了相分离现象。聚合物相构筑形成微球基体,相分离后有机溶剂所占据的体积最终形成了微球结构中的孔隙。由于可光聚合物质种类广泛,光聚合反应速率快等特点,通过该种方法进行聚合物多孔微球的制备具有工艺简单、生产成本低、适用范围广且易于工业化等优点。
本发明采用乳液法结合光聚合技术制备聚合物多孔微球,不仅可以在短时间内快速制备具有丰富孔结构的聚合物微球,且聚合过程中产生相分离现象的快慢和相分离程度的大小与有机溶剂极性和聚合物网络的极性及形成的快慢相关。因此,可以通过原料选择、制备条件的改变可以对聚合物微球的孔结构进行有效调节,并赋予一定程度的功能化。同时,该方法适用范围广,体系的可设计性强,在光固化体系中具有较强的通用性。
本发明聚合物多孔微球可广泛用于各类缓蚀剂、修复剂、药物、香料、催化剂等物质的负载,在防腐蚀填料,自修复材料、药物负载、香料缓释、催化剂载体、微反应器等领域具有广阔的应用前景。
附图说明
图1为本发明通过乳液法结合光聚合技术制备聚合物多孔微球的机理图。
图2为本发明制备所得聚合物多孔微球的结构形貌示意图。
图3为本发明实施例1水包油型乳液的超景深图像以及聚合物多孔微球的电子扫描显微镜图像。
图4为本发明实施例1中以不同光敏单体/有机溶剂比例条件下制备所得聚合物多孔微球的电子扫描显微镜图像。
图5为本发明实施例1中以不同光敏单体/有机溶剂比例条件下制备所得聚合物多孔微球的氮气吸附-解吸附等温线。
图6为本发明实施例1中以不同光敏单体/有机溶剂比例条件下制备所得聚合物多孔微球的孔径分布曲线。
图7为本发明实施例2中所得聚合物多孔微球的电子扫描显微镜图像。
图8为本发明实施例3中所得聚合物多孔微球的的电子扫描显微镜图像。
图9为本发明实施例3中不同光敏预聚物/有机溶剂比例条件下制备所得聚合物多孔微球的电子扫描显微镜图像。
图10为本发明实施例4中所得聚合物多孔微球的电子扫描显微镜图像。
图11为本发明实施例5中所得聚合物多孔微球的电子扫描显微镜图像。
图12为本发明实施例6中分别以不同光敏单体/光敏预聚物比例条件下制备所得聚合物多孔微球的电子扫描显微镜图像。
图13为本发明对比例1中分别以不同极性有机溶剂为油相组分制备所得聚合物多孔微球的电子扫描显微镜图像。
图14为本发明对比例2中所得聚合物微球的电子扫描显微镜图像。
具体实施方式
下面结合附图和实施例,对本发明进行具体描述。
图1是本发明通过乳液法结合光聚合技术制备聚合物多孔微球的机理图。通过乳化作用所形成的水包油型乳液在未经紫外光辐照时,有机溶剂与可光聚合物质处于互溶状态。而随着光照的进行,油相液滴中聚合物的网络逐渐形成,并在短期内能够被有机溶剂所溶胀,体系呈现为均相。随着交联度的增加,交联反应的速率大于有机溶剂对交联网络的溶胀速率时,此时便产生了相分离现象,有机溶剂占据的体积最终形成了微球结构中的孔隙。去除有机溶剂后即得到聚合物多孔微球。
图2为所得聚合物多孔微球的结构形貌示意图,可以看出其内部和外表面均具有孔结构,其外表面孔结构为开放式孔结构,内部孔结构为开放式和闭合式孔结构。
实施例1
一种聚合物多孔微球的制备方法,包括如下步骤:
称取1.0g三羟甲基丙烷三丙烯酸酯和0.01g 2-羟基-甲基苯基丙烷-1-酮(可反应单体质量的1wt%)添加到1.0g甲苯中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将1.0g聚乙烯醇加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成1wt%的聚乙烯醇水溶液,作为水相;
将油相和水相以1:5的质量比相混合,在均质机作用下乳化3min,乳化转速为12000rpm,以形成稳定的水包油型乳液。随后,将乳液置于365nm波长的紫外光下辐照2min,通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h,即得到聚合物多孔微球。
本实施例水包油型乳液的超景深图像以及聚合物多孔微球的电子扫描显微镜图像如图3所示,由图3可以看出,所得聚合物多孔微球的球形结构完整,粒径较为均一,且含有丰富的孔结构。
改变本实施例光敏单体与有机溶剂的比例,为2:1、1:1、1:2、1:3、1:4、1:9、1:19,分别制得一系列聚合物多孔微球,其电子扫描显微镜图像如图4所示,由图4可以看出,聚合物多孔微球中的孔结构随着光敏单体与有机溶剂比例的不断减小而逐渐明显,孔径明显增加,表明孔结构可以通过光敏单体与有机溶剂的比例不同进行快速调控,且比例的调节范围较为宽泛。
图5为本实施例以不同光敏单体/有机溶剂比例条件下制备所得聚合物多孔微球的氮气吸附-解吸附等温线,由图5可以看出,当以光敏单体与有机溶剂比例为2:1条件下制备所得聚合物多孔微球主要以闭孔结构为主,其比表面积6.58m2/g。而当该比例减小至1:1时,制备所得聚合物多孔微球中的孔结构迅速向开孔结构转变,其氮气吸附-解吸附等温线表现为典型的IV型等温线,比表面积迅速增加至163.52m2/g。随着该比例减小至1:3后,制备所得聚合物多孔微球的孔结构更为明显,比表面积进一步增加。表明孔结构可以通过光敏单体与有机溶剂的比例进行调控,且可以制备出一系列具有不同比表面积的聚合物多孔微球。
图6为本实施例以不同光敏单体/有机溶剂比例条件下制备所得聚合物多孔微球的孔径分布曲线。由图6可以看出,当光敏单体与有机溶剂的比例不断减小,制备所得聚合物多孔微球的孔径分布明显变宽,孔体积逐渐增加。表明其孔径和孔体积均可以通过光敏单体与有机溶剂的比例进行调控。
实施例2
一种聚合物多孔微球的制备方法,包括如下步骤:
称取0.5g季戊四醇四丙烯酸酯和0.025g 1-羟基环己基苯基甲酮(可反应单体质量的5wt%)添加到1.5g二甲苯中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将5.0g聚乙烯醇加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成5wt%的聚乙烯醇水溶液,作为水相;
将油相和水相以1:7的质量比相混合,在均质机作用下乳化3min,乳化转速为10000rpm,以形成稳定的水包油型乳液。随后,将乳液置于365nm波长的紫外光下辐照4min,通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h,即得到聚合物多孔微球。
聚合物多孔微球的电子扫描显微镜图像如图7所示,由图7可以看出,制备所得聚合物微球表面分布着大孔和不规则通孔,表明采用不同官能度的光敏单体为可光聚合物质通过该方法同样能够制备得到具有丰富孔结构的聚合物多孔微球。
实施例3
一种聚合物多孔微球的制备方法,包括如下步骤:
称取1.5g聚氨酯丙烯酸酯(理论官能度为6)和0.045g 2-甲基-1-(2-甲硫基苯基)-2-吗啉基-1-丙酮(可反应单体质量的3wt%)添加到0.5g甲苯中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将3.0g聚乙二醇加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成3wt%的聚乙二醇水溶液,作为水相;
将油相和水相以1:1的质量比相混合,在均质机作用下乳化6min,乳化转速为17500rpm,以形成稳定的水包油型乳液。随后,将乳液置于425nm波长的紫外光下辐照6min,通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h,即得到聚合物多孔微球。
改变本实施例光敏预聚物的理论官能度,为二官聚氨酯丙烯酸酯、四官聚氨酯丙烯酸酯、六官聚氨酯丙烯酸酯,分别制得一系列聚合物多孔微球,其电子扫描显微镜图像如图8所示,由图8可以看出所述聚合物多孔微球中的孔结构随着光敏预聚物官能度提高而增加。
改变本实施例光敏预聚物与有机溶剂的比例,为3:1、2:1、1:1、1:2、1:3,分别制得一系列聚合物多孔微球,其电子扫描显微镜图像如图9所示,由图9可以看出,聚合物多孔微球中的孔结构随着光敏预聚物与有机溶剂比例的不断减小而逐渐明显,孔径增加。
实施例4
一种聚合物多孔微球的制备方法,包括如下步骤:
称取1.0g聚酯丙烯酸酯(理论官能度为2)和0.01g 2-羟基-甲基苯基丙烷-1-酮(可反应单体质量的1wt%)添加到1.0g甲苯中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将1.0g聚乙烯醇加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成1wt%的聚乙烯醇水溶液,作为水相;
将油相和水相以1:10的质量比相混合,在均质机作用下乳化3min,乳化转速为7000rpm,以形成稳定的水包油型乳液。随后,将乳液置于365nm波长的紫外光下辐照2min,通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h,即得到聚合物多孔微球。
所得聚合物多孔微球的电子扫描显微镜图像如图10所示,由图10可以看出,制备所得聚合物多孔微球表面分布着大孔和不规则通孔,表明采用聚酯丙烯酸酯为可光聚合物质通过该方法同样能够制备出具有丰富孔结构的聚合物多孔微球。
实施例5
一种聚合物多孔微球的制备方法,包括如下步骤:
称取1.6g环氧丙烯酸酯(理论官能度为2)和0.032g 2-羟基-甲基苯基丙烷-1-酮(可反应单体质量的2wt%)添加到0.4g甲苯中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将4.0g十二烷基苯磺酸钠加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成4wt%的十二烷基苯磺酸钠水溶液,作为水相;
将油相和水相以1:10的质量比相混合,在均质机作用下乳化3min,乳化转速为7000rpm,以形成稳定的水包油型乳液。随后,将乳液置于365nm波长的紫外光下辐照2min,通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h,即得到聚合物多孔微球。
所得聚合物多孔微球的电子扫描显微镜图像如图11所示,由图11可以看出,制备所得聚合物多孔微球表面分布着部分大孔结构,表明采用环氧丙烯酸酯为可光聚合物质通过该方法同样能够制备出聚合物多孔微球。
实施例6
一种聚合物多孔微球的制备方法,包括如下步骤:
称取0.5g三羟甲基丙烷三丙烯酸酯、0.5g聚氨酯丙烯酸酯(理论官能度为6)和0.02g 2,4,6-三甲基苯甲酰基二苯基氧化膦(可反应单体质量的2wt%)添加到1.0g甲苯中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将1.0g十二烷基硫酸钠加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成1wt%的十二烷基硫酸钠水溶液,作为水相;
将油相和水相以1:3的质量比相混合,在均质机作用下乳化3min,乳化转速为10000rpm,以形成稳定的水包油型乳液。随后,将乳液置于380nm波长的紫外光下辐照4min,通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h,即得到聚合物多孔微球。
改变本实施例光敏单体与光敏预聚物的比例,为3:1、1:1、1:3,分别制得一系列聚合物多孔微球,其电子扫描显微镜图像如图12所示,由图12可以看出,在上述光敏单体与光敏预聚物比例条件下进行制备,所得聚合物微球表面均呈现出丰富的通孔结构,表明以光敏单体和光敏预聚物的混合物为可光聚合物质通过该方法同样能够制备出聚合物多孔微球,且光敏单体与光敏预聚物的比例可调范围较大。
对比例1
称取1.0g三羟甲基丙烷三丙烯酸酯和0.01g 2-羟基-甲基苯基丙烷-1-酮(可反应单体质量的1wt%)添加到1.0g环己烷中,通过超声使组分完全溶解,形成澄清透明的溶液,作为油相;
将1.0g聚乙烯醇加入到100mL去离子水中,在搅拌作用下至其溶解完全,配置成1wt%的聚乙烯醇水溶液,作为水相;
将油相和水相以1:5的质量比相混合,在均质机作用下乳化3min,乳化转速为10000rpm,以形成稳定的水包油型乳液。随后,将乳液置于365nm波长的紫外光下辐照2min。通过过滤收集微球产物,使用去离子水和乙醇交替洗涤后置于80℃烘箱中干燥2h。
改变本对比例有机溶剂的种类,为环己烷、二氯甲烷、乙酸乙酯,分别制得一系列聚合物微球,其电子扫描显微镜图像如图13所示。可以看出,以环己烷为有机溶剂制备所得聚合物微球呈现出多核结构,由外部的聚合物壳层和内部的聚合物粒子组成,而采用二氯甲烷和乙酸乙酯制备所得的聚合物微球为实心结构,无法制备得到具有多孔结构的聚合物微球。以上结果说明溶剂的选择对多孔微球的形成具有重要的作用。
对比例2
参考Kaiyun Wu,Ziyue Wei,Yuan Dong et al.One-pot efficient preparationof microcapsules based on photopolymerization for self-healingcoatings.Colloids and Surfaces A:Physicochemical and Engineering Aspects,2022,642:128660.
将1.0g聚氨酯丙烯酸酯(理论官能度为2)、1.0g亚麻籽油和0.02g光引发剂2-羟基-甲基苯基丙烷-1-酮(可反应单体质量的2wt%)加入到2.5g二氯甲烷中混合均匀,形成澄清透明的溶液,作为油相;
将油相倒入20mL的聚乙烯醇水溶液(2wt%)中,在均质机作用下,以10000rpm转速乳化2min,形成水包油型乳液。随后将所得乳液置于80℃条件下搅拌4h来脱除溶剂。然后置于365nm波长的紫外光下辐照10min。通过过滤收集微球产物,用水洗涤并在室温下干燥,即得聚合物微球。所得聚合物微球的电子扫描显微镜图像如图14所示,由图14可以看出,制备所得聚合物微球呈现出核壳结构,而不是多孔结构。这说明制备工艺对多孔微球也具有重要的影响,乳液形成后应迅速进行光固化,避免溶剂在光照之前挥发。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内所做的任何修改、同等替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种聚合物多孔微球,其特征在于,所述聚合物多孔微球以光聚合材料经光固化形成的聚合物为基体,所述聚合物多孔微球的粒径分布为500nm~200μm,孔径分布为2~150nm,比表面积为5~300m2/g;
所述光聚合材料由可光聚合物质、光引发剂、有机溶剂组成;可光聚合物质与有机溶剂的质量比为1:20~4:1,光引发剂用量为可光聚合物质的1.0~5.0wt%。
2.根据权利要求1所述的聚合物多孔微球,其特征在于,所述可光聚合物质为光敏单体、光敏预聚物中的一种或多种。
3.根据权利要求2所述的聚合物多孔微球,其特征在于,所述光敏单体为单官丙烯酸酯类单体、双官丙烯酸酯类单体、多官丙烯酸酯类单体中的一种或多种。
4.根据权利要求2所述的聚合物多孔微球,其特征在于,所述光敏预聚物为聚氨酯丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯中的一种或多种。
5.根据权利要求1所述的聚合物多孔微球,其特征在于,所述光引发剂为2-羟基-甲基苯基丙烷-1-酮、1-羟基环己基苯基甲酮、2-甲基-1-(2-甲硫基苯基)-2-吗啉基-1-丙酮、安息香双甲醚、2,4,6-三甲基苯甲酰基二苯基氧化膦、异丙基硫杂蒽酮、2,4-二乙基硫杂蒽酮、4-(N,N-二甲氨基)苯甲酸乙酯、二苯甲酮、4-氯二苯甲酮、邻苯甲酰苯甲酸甲酯、二苯基碘鎓盐六氟磷酸盐、N,N-二甲氨基苯甲酸异辛酯、4-甲基二苯甲酮、邻苯甲酰基苯甲酸甲酯、4-苯基二苯甲酮、2,4,6-三甲基苯甲酰基-二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯中的一种或多种。
6.根据权利要求1所述的聚合物多孔微球,其特征在于,所述有机溶剂为甲苯、二甲苯中的一种或多种。
7.一种权利要求1所述聚合物多孔微球的制备方法,其特征在于,所述制备方法包括如下步骤:
将光聚合材料作为油相,加入到含有乳化剂的水相中,使用均质机乳化形成稳定的水包油型乳液,经紫外光固化后,抽滤收集微球产物,使用去离子水和乙醇交替洗涤,制得所述聚合物多孔微球;
油相与水相的质量比为1:10~2:1;乳化剂用量为水相的1.0~5.0wt%。
8.根据权利要求7所述的制备方法,其特征在于,所述乳化剂为聚乙烯醇、聚乙二醇、十二烷基硫酸钠、十二烷基苯磺酸钠、聚苯乙烯-马来酸酐共聚物、吐温-60、吐温-80、司班-60、司班-80、十六烷基三甲基溴化铵、明胶、阿拉伯胶中的一种或多种。
9.根据权利要求7所述的制备方法,其特征在于,所述均质机乳化的条件为:转速为5000~25000rpm,乳化时间为1~6min。
10.根据权利要求7所述的制备方法,其特征在于,紫外光固化的条件为:紫外光波长为230~450nm,固化时间为1~10min。
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