CN110475602B - 含有高分子量亲水性添加剂的均孔自组装嵌段共聚物膜及其制备方法 - Google Patents
含有高分子量亲水性添加剂的均孔自组装嵌段共聚物膜及其制备方法 Download PDFInfo
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- CN110475602B CN110475602B CN201780077997.2A CN201780077997A CN110475602B CN 110475602 B CN110475602 B CN 110475602B CN 201780077997 A CN201780077997 A CN 201780077997A CN 110475602 B CN110475602 B CN 110475602B
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Abstract
本发明提供了通过在浇铸粘稠物制剂中添加高分子量亲水性添加剂来显著改善均孔嵌段共聚物(BCP)膜的抗压实性的体系和方法。所公开的体系和方法还公开了对膜特性的若干其他多功能的增强,包括:低污染倾向、改善的渗透率、改善的干燥时的渗透率保持率以及调节这些新BCP膜的子结构和孔尺寸的能力。这些多孔BCP膜可用于过滤应用和分离应用中,并且适合于标准制造实践。
Description
技术领域
本发明涉及均孔嵌段共聚物(“BCP”)膜(film)以及制造其的方法。
背景技术
膜片(membrane)污染和膜片压实是膜片过滤过程中通量劣化的两个主要原因。膜片污染是公知的对膜片性能的阻碍。它在使用期间当溶液或颗粒物质沉积在膜片上时发生。膜片污染导致膜片性能的劣化。膜片污染机制是众所周知的并且由污染引起的通量劣化可以通过设计耐污染性膜片、过程改善和原位清洗技术而在许多过滤应用中完全恢复。
与在许多应用中可逆的膜片污染不同,膜片压实导致不可逆的通量劣化和膜片的多孔子结构的不可逆变化。膜片压实由此影响过滤选择性。膜片压实是由使用期间的跨膜压差引起的膜片的变形。当膜片暴露于高压差时,水和溶解的组分通过膜片的通量随时间而减小。为了保持通量,必须施加更大的压差,导致多孔区域中甚至更高的应力,这可能导致聚合物的结构重组,使材料的密度增加。另外,物理压实使膜片的总孔隙率减小,并因此可能加剧膜片污染。膜片压实是一个难以克服的问题,因为施加的进料压力需要随时间而增加以保持相同的通过量。由于更高的能量需求和膜片的使用寿命的缩短,所有这些都导致企业增加的资本支出与运营开支(“CAPEX/OPEX”),从而削减了利润。
先前存在的膜片技术利用基于这样的三嵌段聚合物例如聚(异戊二烯-b-苯乙烯-b-4-乙烯基-吡啶)(“ISV”)的嵌段共聚物(BCP)膜片。这样的BCP膜片公开在WO 2012/151482 A3中,WO 2012/151482 A3描述了通过受控溶剂蒸发和公知的浸没沉淀过程的组合制造这样的膜片。然而,类似于由常规聚合物制造的膜片,由纯ISV聚合物生产的BCP膜片也易受物理压实。
美国专利申请2010/0224555 A1(“Hoek等”)公开了设计成抵抗压实的其他膜片。该申请教导了可以通过在聚合物基体中并入纳米颗粒来改善膜片压实。该参考文献公开了这些纳米颗粒的包含改善了膜片材料的刚性和韧性,并因此改善了其保持其多孔结构和抵抗物理压实的能力。然而,将纳米颗粒并入膜片的嵌段共聚物基体中倾向于破坏微相分离区域的有序自组装。此外,向浇铸粘稠物制剂中添加任何外来添加剂(例如纳米颗粒、成孔剂)以制造BCP膜片是复杂的,而不像由常规聚合物生产的膜片那样简单。ISV聚合物的独特优点之一是它们自组装并在浇铸溶液中形成尺寸均匀的胶束的能力,这又在膜片的表面上提供了高度有序的均孔结构。高度有序的尺寸均匀的孔给出了非常明确的截留分子量,并且为分离不同尺寸的分子提供了优异的选择性。鉴于此,保留膜片的自组装结构是极重要的。因此,Hoek等的公开内容并未解决本领域中存在的膜片压实问题。
为了解决本领域中的那些和另一些缺陷,本发明旨在这样的BCP膜片:其在分离分子时在保持高水平选择性的同时抗压实。还公开了用于制造这样的膜片的方法。
附图说明
当结合附图考虑时,通过参照以下详细描述,由于其变得更好理解,将容易获得本发明的更完整的理解及其许多伴随的优点,其中:
图1示出了仅用ISV29形成的BCP膜与用ISV29和5%PVP-K90形成的BCP膜的粘度比较;
图2A和2B示出了并入和没有并入高分子量添加剂聚乙二醇(PEG-150K)的BCP膜片的显微镜扫描;
图3示出了有和没有高分子量添加剂的ISV BCP膜在不同溶剂体系中的顶表面;
图4示出了由本发明公开的ISV膜与纯ISV聚合物膜相比的通量下降;
图5示出了体现本发明的BCP膜的通量下降百分比的表;
图6示出了对于并入聚(乙烯基吡咯烷酮)(PVP-K90)或低分子量聚乙二醇(PEG400)的四个ISV22 BCP膜,在70分钟时间间隔内的通量的图;
图7A示出了纯聚合物膜与并入PVP-K90的ISV29BCP膜的吸附相比的蛋白质吸附;
图7B示出了并入PVP-K90的BCP膜在7nm与20nm之间的膜选择性的图;箭头表示数据点对应的轴;
图7C是示出了本发明的BCP膜的通量性能再现性的图;以及
图7D示出了溶剂体系对并入PVP-K90的BCP膜的渗透率的影响;
图8是对于有(白色圆圈)或没有(+符号)PVP-K90高分子量添加剂的两个ISV43BCP膜,在270分钟(4.5小时)时间间隔内保持的通量(J/Jo)的图。
图9是示出了由没有(左)PVP-K90或有(右)PVP-K90高分子量添加剂的各BCPISV43浇铸的六个膜的平均纯水渗透率(PWP)的图。
具体实施方式
在描述附图中示例的本发明的一个优选实施方案时,为了清楚起见,将采用特定术语。然而,本发明并不旨在限于如此选择的特定术语,并且应理解,每个特定术语包括以类似方式操作以实现类似目的的所有技术等同物。出于说明的目的对本发明的若干优选实施方案进行了描述,应理解,本发明可以以未在附图中具体示出的其他形式实施。在一些实施方案中,膜(flim)是膜片(membrane),其是膜的子集。在本发明的上下文中,“高分子量”限定为等于或大于包含本发明材料的大多数嵌段共聚物的分子量的50%。膜具有限定为约1nm至200nm的中孔。在本发明的上下文中,均孔意指具有基本上窄的孔径分布。膜是对称的或不对称的。
在由常规聚合物制造的膜中,向膜浇铸溶液中添加不同分子量的聚(乙烯基吡咯烷酮)(PVP)以改善水通量、亲水性,调节孔尺寸以及调节浇铸溶液的粘度。如本文中所公开的,发明人已经发现向膜的制剂中添加高分子量PVP改善了其抗压实性。与由纯ISV聚合物生产的膜相比,在浇铸溶液中添加少量(0.1重量%至15重量%)高分子量(360,000Da)聚(乙烯基吡咯烷酮)(PVP-K90)(相对于BCP)显著改善了BCP膜的抗压实性。发明人假定这些有益效果可能是由于PVP在分离层中不仅停留表面上,而且还停留在子结构中并且充当改善膜的刚性并因此改善其抗压实性的增强剂。另一种可能性是PVP的存在导致在浸没沉淀过程期间延迟的混合,从而抑制大孔的形成并形成具有密实分离层的海绵状子结构。更值得注意地,PVP的添加保持了支撑在织造/非织造织物上的下部具有开放的大孔结构的膜的高度有序自组装选择性分离层。该结果与本领域的常规知识相反,并因此是出乎意料的结果,因为理论上,如果添加剂的分子量基本上高于前体聚合物的分子量,则自组装被破坏的可能性较高。另一个出乎意料的结果是,与文献中记载的相反,高分子量PVP的添加倾向于有利地降低浇铸溶液的粘度。如图1中所示,相同ISV聚合物重量%下的溶液的粘度显示出随着5%PVP-K90的添加,粘度降低了接近20%。具体地,在室温和类似的剪切条件下进行的测量显示出没有添加剂的ISV溶液测量为1473cP,而向溶液中添加5%PVP-K90使粘度降低至1180cP。如本文中所公开的,根据溶剂体系的类型,由纯ISV聚合物(即没有PVP的ISV聚合物)浇铸的膜的通量下降(作为时间的函数的%损失)在60%至70%的范围内,而由包含高分子量添加剂的浇铸溶液生产的膜的通量下降为5%至30%。具有PVP的膜的蛋白质吸附与来自纯ISV聚合物的膜相比低约35%。这可能是由于较高分子量的添加剂被夹裹在聚合物基体中并赋予膜亲水特性。这些膜对尺寸相差约3倍的蛋白质具有优异的选择性。例如,仅56%的牛血清白蛋白(7nm)被所公开的新膜截留,相比之下甲状腺球蛋白(20nm)为96%。另外,可以通过改变溶剂体系来调节BCP膜的孔尺寸。例如,并入5%PVP-K90的ISV聚合物膜在二烷/四氢呋喃溶剂体系中显示出渗透率增加47%,而在类似的浇铸条件下相同的膜在二烷/丙酮溶剂体系中显示出渗透率降低60%。参见以下进一步详细讨论的图7D。用于形成均孔嵌段共聚物(BCP)膜的方法包括以下步骤:通过将至少一种嵌段共聚物与至少一种溶剂和至少一种高分子量亲水性聚合物混合来配制聚合物溶液;使聚合物溶液形成为膜;使一部分溶剂蒸发;将膜浸没在凝固浴中;以及任选地,用水漂洗BCP膜。用于聚合物溶液的溶剂BCP膜浇铸溶液溶剂包括以下中的至少一种:乙醛、乙酸、丙酮、乙腈、苯、氯仿、环己烷、二氯甲烷、二甲氧基乙烷、二甲基亚砜、二甲基乙酰胺、二甲基甲酰胺、1,4-二烷、乙醇、乙酸乙酯、甲酸、己烷、甲醇、N-甲基-2-吡咯烷酮、丙醇、吡啶、环丁砜、四氢呋喃或甲苯。
前述方法的一个实施方案可以如下进行。该过程的第一步是复合结构的创建。该过程包括将聚合物溶液配制到织造/非织造微孔基底(例如聚酯)上,从而将高度多孔的织物埋置在液体溶液中,所述聚合物溶液包含:(1)嵌段共聚物,例如聚(异戊二烯-b-苯乙烯-b-4-乙烯基-吡啶)(ISV)(摩尔质量50kg/mol至500kg/mol);(2)溶剂,例如1,4-二烷和任选的四氢呋喃(THF)或丙酮。对本领域普通技术人员显而易见的是,其他已知的嵌段共聚物可以替代本文中公开的ISV聚合物。本文中描述的ISV的分子量如下:ISV22:94,000Da;ISV28:124,000Da;ISV29:91,000Da;ISV43:53,000Da。
该步骤之后使挤出的BCP膜中的溶剂蒸发(持续60秒至160秒)。然后将BCP膜浸没在凝固水浴中,优选在5℃至45℃的温度下。该溶液通过公知的浸没沉淀过程凝固并形成固体分离层。所得的多孔复合材料表现出存在于多孔子结构上方的薄的自组装均孔顶层(其中孔尺寸在约5nm至50nm范围内)。形成的多孔复合材料产生超滤尺寸(约5nm至25nm)的孔。
图1示出了仅用ISV29形成的BCP膜与用ISV29和5%PVP-K90形成的BCP膜的粘度的比较。粘度以厘泊(cP)计算,并且在类似的剪切条件下在室温下进行测量。如图1中所示,一般的ISV29膜表现出1473cP的粘度,而具有5%PVP-K90的ISV29膜显示出1180cP的粘度,低约20%。这种因PVP-K90添加的粘度降低是出乎意料的有利结果,其影响本发明的膜的抗压实性改善。
图2A和2B示出了对在BCP膜的浇铸中使用高分子量添加剂的初步研究。除了使用如随后的附图和相关公开内容中公开的PVP-K90之外,还对在纯ISV29BCP膜中使用30%PEG-150K(平均分子量为150,000Da的聚乙二醇)进行了测试。如图2A中所示,PEG-150K的使用虽然由于可能的溶解性问题而在膜中引入缺陷,但是成功地显示了膜的自组装不受添加剂引入的影响。更值得注意地,如图2B中所示,30%PEG-150K ISV29 BCP膜的显微镜分析显示出在形成的膜的子结构中存在大孔,这是在没有添加剂的ISV29BCP膜中不存在的有利特征。
图3示出了在不同溶剂体系中有和没有高分子量添加剂的ISV BCP膜的顶表面的显微镜扫描。图像显示出出乎意料的结果,即在添加5%PVP K90之后,在DOX/THF和DOX/Ace溶剂溶液二者中,ISV BCP膜的自组装均未被破坏。因为膜的自组装未被破坏,所以膜在浇铸溶液中形成尺寸均匀的胶束,这又在膜表面上提供了高度有序的均孔结构。高度有序的尺寸均匀的孔给出非常明确的截留分子量,并且为分离不同尺寸的分子提供了优异的选择性。
图4示出了由本发明公开的膜与一般的BCP膜相比的性能。特别地,图4对本领域先前已知的“纯”ISV聚合物膜相对于包含聚(乙烯基吡咯烷酮)(“PVP”)和聚(乙二醇)(“PEG”)的新ISV聚合物膜的性能进行了比较。在所示的图中,对四个膜的通量下降进行了比较。通量下降用于测量膜的性能,因为性能更好的膜将显示出随时间更小的通量下降。在图4中,通量(纯水渗透率)测量为[(升/m2/小时)/巴g],通常注释为LMH/巴。所测试的膜的这种通量度量在图的y轴上示出。x轴为时间的度量,以分钟计。因此,图4示出了膜的通量随时间如何变化。所测试的第一个膜为本领域先前已知的没有并入任何PVP的ISV28,聚(异戊二烯-b-苯乙烯-b-4-乙烯基-吡啶)膜(“纯”ISV聚合物膜)。所测试的第二个膜为具有1.3%PVP360K-1(平均分子量为360,000Da的聚(乙烯基吡咯烷酮))的ISV28膜。所测试的第三个膜是具有1.3%PVP360K-2(平均分子量为360,000Da的聚(乙烯基吡咯烷酮))的ISV28膜。所测试的第四个膜是具有1%PEG58K(平均分子量为58,000Da的聚乙二醇)的ISV29膜。然后在250分钟内测量通量。
一般的ISV膜(ISV28BCP膜)最初表现出约650LMH/巴的通量。然而,在250分钟的时间段内,ISV28膜表现出通量下降至低于300LMH/巴。这种通量下降主要是由于随着溶液通过而产生的膜压实,并且建立了可以对新制造的膜的性能进行比较的基线。所测试的第二个膜和第三个膜代表并入有高分子量PVP的ISV BCP膜。与ISV28BCP膜不同,在整个250分钟时间间隔内,具有1.3%PVP360K-1的ISV28膜保持约300LMH/巴的通量,同时具有1.3%PVP360K-2的ISV28膜保持约200LMH/巴的通量。相对于ISV28膜,所测试的第四个膜(具有1%PEG58K的ISV29膜)表现出减小的随时间的通量下降,即在250分钟之后从约480LMH/巴的初始通量下降至约300LMH/巴。图4是两点的证明。第一,高分子量PVP的并入产生在保护ISV膜免受由压实引起的通量下降方面的出乎意料的改善。第二,图4示出了与替代的高分子量添加剂PEG相比,在高分子量PVP的情况下这些出乎意料的效果特别地显著。
图5示出了对体现本发明的多种制造的膜的通量下降百分比进行计算的另外的数据。在所有测试的膜中,使用ISV BCP来形成膜。然后多个实施方案并入0.5重量%至5重量%的PVP-K90(平均分子量为360,000Da的高分子量PVP)。在实施方案中使用多种溶剂体系,如图3中所公开的,包括二烷和丙酮(DOX/Ace)的70:30混合物以及二烷和四氢呋喃(DOX/THF)的70:30混合物。
在图6中,将图5中公开的一些实施方案以及具有低分子量PEG400添加剂的ISVBCP的通量下降模式制成图。然后,如下计算表明膜的抗压实性的百分比通量下降:(1-最后4个数据点的平均值/前四个数据点的平均值)*100。图6示出了除了其高分子量PVP K90或低分子量PEG400的并入之外均相同的四个ISV22BCP膜(膜ID:L160520和L160422)在70分钟时间间隔内的通量下降。并入PVP-K90的膜表现出显著低于具有小分子量PEG400的膜的通量下降。
在图6中,并入PVP-K90的膜显示出明显大于并入PEG400的那些的抗压实性。并入PEG400和PEG400的膜分别以约750LMH/巴和690LMH/巴的初始通量开始。70分钟之后,它们的通量分别明显降低至约450LMH/巴和350LMH/巴,或降低40%和49%。这种通量的下降表明有限的抗压实性。因此,并入PEG的ISV BCP膜的膜通量的下降与本领域先前已知的ISVBCP膜的那些高度相似。相比之下,并入PVP-K90的ISV BCP膜显示出在测量的时间间隔内强的抗压实性。并入1A-PVP-K90的膜在整个70分钟的时间间隔保持约500LMH/巴的通量,同时并入3B-PVP-K90的膜在该时间间隔的持续时间保持其约480LMH/巴的通量,证明PVP-K90的并入对ISV BCP膜的抗压实性具有明显地积极作用。图5和6一起显示,当PVP-K90以0.5重量%至5重量%并入时,在ISV BCP膜中并入PVP-K90的出乎意料的抗压实性特别显著。
所公开的新膜的有利特性不限于抗压实性。如图7A至7D中所示,所公开的新膜表现出较小程度的污染,并且在制造时显示出高水平的再现性,使得可以基于所使用的溶剂体系调节膜的渗透率以调节膜的孔尺寸。图7A显示出在本发明的新膜中发生的较小程度的膜污染。将纯聚合物膜ISV29的蛋白质吸附与本发明的一个实施方案的还并入PVP-K90的ISV29 BCP膜(膜ID L160729JS-2B)进行比较。在ISV29膜中,在该时间间隔内以261ug/cm2的量收集IgG抗体,而在并入PVP-K90的膜上在相同的时间间隔内仅以171ug/cm2的量收集,因此显示出低约35%的吸附(和膜污染)。
图7B显示出在本发明的新膜中对颗粒物质的渗透的高水平选择性。对同样制造的膜(并入1.3%PVP-K90的ISV28BCP膜)测试对BSA(约7nm)和甲状腺球蛋白(约20nm)的渗透率(LMH/巴)。使用该渗透率计算对BSA和甲状腺球蛋白的截留百分比。首先用BSA对膜进行测试,用0.1N NaOH清洗,在去离子水中浸泡超过48小时,然后用甲状腺球蛋白进行测试。如图7B中所示,该膜显示出对BSA的157LMH/巴的渗透率和56%的截留百分比。然而,在更大的粒径下,该膜显示出对甲状腺球蛋白的仅95LMH/巴的渗透率和96%的截留百分比。
图7C提供了所公开的方法和新BCP膜的再现性的汇总。PVP-K90作为添加剂显著改善了由ISV聚合物浇铸的膜的再现性,没有添加剂的ISV膜表现出218±195LMH/巴的纯水渗透率(对五个分离膜求平均值),以及具有5%PVP-K90的ISV膜表现出451±24LMH/巴的纯水渗透率(对八个膜求平均值)。因此,图7C证明了本发明的BCP膜中的再现性与不含有高分子量添加剂的那些相比是优异的。
图7D示出了并入PVP-K90的新膜如何受到过滤期间所使用的溶剂体系变化的影响。将纯ISV28BCP膜与并入5%PVP-K90的ISV28BCP膜进行比较。在DOX/THF(70/30)和DOX/Ace(70/30)溶剂环境中测试膜的渗透率。ISV28BCP膜显示出渗透率的微小变化,从445LMH/巴增加至537.5LMH/巴,而并入5%PVP-K90的ISV28BCP膜表现出渗透率的明显降低,从658LMH/巴至217LMH/巴。因为渗透率与孔尺寸成比例,所以可以基于所使用的溶剂体系利用那些渗透率测量结果结合例如图7B中所公开的已知数据用于调节并入PVP-K90的膜的孔尺寸。
在图8中,并入相对于BCP的5%(质量)的PVP-K90的膜显示出明显大于没有PVP-K90的那些的抗压实性。没有PVP-K90的ISV43膜的初始通量为约202LMH/巴。270分钟之后,其通量显著降低至约135LMH/巴,下降33%。这种通量的下降表明显著的压实。相比之下,并入PVP-K90的ISV43BCP膜在测量的时间间隔内显示出强的抗压实性。并入PVP-K90的膜在整个270分钟的时间间隔内保持约267LMH/巴的通量,下降仅6%。PVP-K90的并入对ISV BCP膜的抗压实性具有明显地积极作用。
图9是显示出通过在ISV43BCP膜中包含PVP-K90,膜的通量增加的图。没有高分子量添加剂的六个ISV43膜的平均通量为203±16 LMH/巴。具有相对于BCP的5%(质量)的PVP-K90的六个ISV43膜的平均通量为355±59 LMH/巴,与没有PVP-K90的膜相比增加82%。
在干燥时将膜/膜片暴露于甘油溶液以防止孔瓦解(并因此损失通量)是本领域公知的。与没有PVP-K90的ISV43膜相比,具有PVP-K90的ISV43膜在暴露于1:1(质量)甘油:水之后在干燥时保持更多它们的通量。两个未干燥的没有PVP-K90的ISV43膜的平均通量为199LMH/巴的平均通量;在暴露于1:1甘油:水之后干燥的没有PVP-K90的四个ISV43膜的平均通量为168LMH/巴,通量保持率为85%。两个未干燥的具有PVP-K90的ISV43膜的平均通量为279LMH/巴的平均通量;在暴露于1:1甘油:水之后干燥的具有PVP-K90的四个ISV43膜的平均通量为268LMH/巴,通量保持率为96%。该结果显示,亲水性高分子量聚合物的包含增加了在暴露于甘油溶液之后在干燥时的通量保持率。这种效果可能是由于添加剂的亲水性,其可能有助于甘油的保持。这种效果以及通量增加和抗压实性证明了在均孔BCP膜中包含高分子量亲水性聚合物添加剂的意想不到的益处。
在一些实施方案中,所述膜用于分离应用或过滤应用。
在一些实施方案中,所述膜被包装为注射器过滤器、囊状物、滤筒、平片材、螺旋缠绕式或中空纤维。
在一些实施方案中,嵌段共聚物包含复杂的构造。复杂的构造定义为:具有非线性嵌段的排列,即在至少一个嵌段中或临近的至少一个嵌段具有多于一种化学性质/配置/结构的构造。
虽然已经结合本发明的特定形式和实施方案对本发明进行了描述,但是应理解,在不脱离本发明的精神或范围的情况下,可以采用除了以上所讨论的那些之外的多种修改。例如,其他高分子量添加剂可以包括聚(丙烯酸酯)、聚(甲基丙烯酸酯)、聚(丙烯酸)、聚(丙烯酰胺)、聚(乙烯基吡啶)、聚(乙烯醇)、聚(乙烯基吡咯烷酮)、天然来源的聚合物(包括但不限于纤维素、壳聚糖、复合碳水化合物)、聚(醚)、聚(马来酸酐)、聚(苯乙烯磺酸盐)、聚(烯丙胺盐酸盐)、聚(砜)、聚(醚砜)、聚(乙二醇)、或上述的替代等同物。高分子量添加剂的分子量可以为至少50%嵌段共聚物分子量。此外,其他要素可以替代具体示出和描述的那些,某些特征可以独立于其他特征使用,并且在某些情况下,要素的特定位置可以颠倒或插入,所有这些都不脱离如所附权利要求中限定的本发明的精神或范围。
Claims (20)
1.一种嵌段共聚物BCP膜,包含:
至少一种嵌段共聚物和至少一种高分子量亲水性聚合物;
其中至少一部分孔为均孔且中孔的;
其中所述高分子量亲水性聚合物的分子量等于或大于所述至少一种嵌段共聚物的分子量的50%;以及
其中相对于所述BCP,所述高分子量亲水性聚合物以0.1重量%至15重量%的范围存在。
2.根据权利要求1所述的BCP膜,其中所述至少一种嵌段共聚物包含至少一种亲水性嵌段。
3.根据权利要求1所述的BCP膜,其中所述至少一种嵌段共聚物以5重量%至25重量%的范围存在。
4.根据权利要求1所述的BCP膜,其中所述膜为对称的或不对称的。
5.根据权利要求1所述的BCP膜,其中所述膜表现出减小的随时间的通量下降。
6.根据权利要求1所述的BCP膜,其中所述至少一种高分子量亲水性聚合物包括:聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸、聚丙烯酰胺、聚乙烯基吡啶、聚乙烯基吡咯烷酮、聚乙烯醇、天然来源的聚合物、聚醚、聚马来酸酐、聚苯乙烯磺酸盐、聚烯丙胺盐酸盐、聚砜、聚醚砜、或聚乙二醇。
7.根据权利要求6所述的BCP膜,其中所述高分子量亲水性聚合物为聚乙烯基吡咯烷酮,并且所述聚乙烯基吡咯烷酮的平均分子量为360,000Da。
8.根据权利要求1所述的BCP膜,其中至少一种BCP为AB或ABC三嵌段共聚物。
9.根据权利要求1所述的BCP膜,其中均孔BCP膜表现出减少的蛋白质吸附。
10.根据权利要求1所述的BCP膜,其中所述膜在暴露于保湿剂溶液之后在干燥时表现出增加的通量保持率。
11.一种分离或过滤装置,包含根据权利要求1至10中任一项所述的BCP膜。
12.根据权利要求11所述的分离或过滤装置,其中所述装置被包装为注射器过滤器、囊状物、滤筒、平片材、螺旋卷绕材料、或中空纤维中的任一者。
13.一种用于形成其中至少一部分孔为均孔且中孔的均孔中孔嵌段共聚物BCP膜的方法,包括以下步骤:
(a)通过将至少一种嵌段共聚物与至少一种溶剂和至少一种高分子量亲水性聚合物混合来配制聚合物溶液;
(b)使所述聚合物溶液形成为膜;
(c)使一部分所述至少一种溶剂蒸发;
(d)将所述膜浸没在凝固浴中;以及
(e)任选地,用水漂洗所述膜;
其中所述高分子量亲水性聚合物的分子量等于或大于所述至少一种嵌段共聚物的分子量的50%;以及
其中相对于所述BCP,所述高分子量亲水性聚合物以0.1重量%至15重量%的范围存在。
14.根据权利要求13所述的方法,其中所述至少一种嵌段共聚物包含至少一种亲水性嵌段。
15.根据权利要求13所述的方法,其中至少一种嵌段共聚物具有包括以下的至少一个嵌段:聚丁二烯、聚异丁烯、聚异戊二烯、聚乙烯、聚苯乙烯、聚丙烯酸甲酯、聚甲基丙烯酸丁酯、聚醚砜、聚甲基丙烯酸甲酯、聚丙烯酸正丁酯、聚甲基丙烯酸2-羟乙基酯、聚甲基丙烯酸缩水甘油酯、聚丙烯酸、聚丙烯酰胺、聚砜、聚偏二氟乙烯、聚N,N-二甲基丙烯酰胺、聚2-乙烯基吡啶、聚3-乙烯基吡啶、聚4-乙烯基吡啶、聚乙二醇、聚丙二醇、聚氯乙烯、聚四氟乙烯、聚环氧乙烷、聚环氧丙烷、聚N-异丙基丙烯酰胺、聚甲基丙烯酸二甲基氨基乙酯、聚酰胺酸、聚二甲基硅氧烷、聚乳酸、聚异氰酸酯、聚氰基丙烯酸乙酯、聚丙烯腈、聚羟基苯乙烯、聚甲基苯乙烯、聚亚乙基亚胺、聚苯乙烯磺酸盐、聚烯丙胺盐酸盐、聚五氟苯乙烯、或聚2-(全氟己基)乙基甲基丙烯酸酯。
17.根据权利要求13所述的方法,其中将所述膜形成在基底上。
18.根据权利要求13所述的方法,其中所述高分子量亲水性聚合物包括:聚丙烯酸酯、聚甲基丙烯酸酯、聚丙烯酸、聚丙烯酰胺、聚乙烯基吡啶、聚乙烯基吡咯烷酮、聚乙烯醇、天然来源的聚合物、聚醚、聚马来酸酐、聚苯乙烯磺酸盐、聚烯丙胺盐酸盐、聚砜、聚醚砜、或聚乙二醇。
19.根据权利要求18所述的方法,其中所述高分子量亲水性聚合物为聚乙烯基吡咯烷酮,并且所述聚乙烯基吡咯烷酮的平均分子量为360,000Da。
20.根据权利要求13所述的方法,其中所述嵌段共聚物以5重量%至25重量%的范围存在。
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KR20200130840A (ko) | 2018-03-12 | 2020-11-20 | 테라포어 테크놀로지스, 인코포레이티드 | 독립형 주름형성 가능한 블록 코폴리머 재료들 및 이의 제조 방법 |
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WO2018093714A1 (en) | 2018-05-24 |
US11401411B2 (en) | 2022-08-02 |
EP3541500B1 (en) | 2021-12-08 |
EP3541500A4 (en) | 2020-06-24 |
KR102596197B1 (ko) | 2023-11-02 |
EP3541500A1 (en) | 2019-09-25 |
CA3044467A1 (en) | 2018-05-24 |
US20190367723A1 (en) | 2019-12-05 |
US11802200B2 (en) | 2023-10-31 |
CN110475602A (zh) | 2019-11-19 |
JP7104040B2 (ja) | 2022-07-20 |
MX2019005774A (es) | 2020-02-07 |
US20220251366A1 (en) | 2022-08-11 |
JP2019537508A (ja) | 2019-12-26 |
KR20190103153A (ko) | 2019-09-04 |
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