CN86107568A - 聚合物表面改性及其实施方法 - Google Patents
聚合物表面改性及其实施方法 Download PDFInfo
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- CN86107568A CN86107568A CN86107568.4A CN86107568A CN86107568A CN 86107568 A CN86107568 A CN 86107568A CN 86107568 A CN86107568 A CN 86107568A CN 86107568 A CN86107568 A CN 86107568A
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Abstract
本发明阐明了一种为各种聚合物支撑表面进行改性的方法。预先选定的改性用聚合物,不可逆地被吸附在对于改性用聚合物有附着性质的,支撑聚合物的几乎整个表面。被选用的改性用聚合物可以赋予被改性聚合物表面所希望的特性。
Description
本发明从广义而言为各种聚合物支撑表面提供一种表面改性的方法。主要是通过将一种适宜作改性用的聚合物不可逆地吸附到几乎整个支撑膜表面,以便改善膜性能,从而得到新的改性膜。
以前膜改性的操作方法是通过溶剂蒸发,在膜上沉积一层涂层材料。在这些方法中,要在膜上用改性用材料溶液,然后从膜上除去过量溶剂,最后再将膜干燥以除去残存溶剂。在某些情况下,为了使作改性的材料分布更均匀,可以加入表面活性剂,这样改性剂复盖在膜上,它的厚度可通过膜上保留的溶液量及改性剂溶液的浓度来确定。为了使涂层稳定,可使改性用材料在干燥期间交联。这些方法固有的局限性是配制作改性用的材料以获得足够薄且在膜上均匀分散的聚合物,此改性用材料又经常要在膜表面上浓缩。
图1表示实施例4结合在苯丙酰基葡聚糖上的细胞色素C改性的聚砜膜。
图2表示实施例14改性膜的结构。
图3表示聚砜支撑膜溶解后,所得的“简缩”结构(short structure)。
本发明广义而言是为各种聚合物支撑表面提供一种表面改性的方法,它是通过将可作改性用的聚合物不可逆地吸附到支撑表面上,该聚合物应具有合乎要求的化学性能。例如,用象尼龙一类聚合物材料组成的织物,经表面改性可增加其吸湿能力,用这种改性织物所做的衣服穿起来更舒适。采用本方法可进行表面改性,使本来常用疏水性聚合物材料制成的各种实验室及医用器件具有明显的亲水性,而疏水性聚合物材料对蛋白质类物质活性是不符要求的。表面改性还可用交联的方法使它进一步稳定。
为了简要说明本发明,下面将首先说明半透膜的表面改性,它是通过在半透膜内,整个疏水支撑膜不可逆地吸附一种适当的聚合物材料,在膜的所有表面,而这种聚合物材料具有明显亲水性和/或其他所要求的化学性能。结果得到的超滤膜或微量过滤膜,既具有疏水性支撑膜的力学强度,又具有作表面改性用的亲水性聚合物的表面特性。当然后面述及的参数可用于非膜聚合物表面改性。
那些熟悉该技术的人员公认需要表面改性膜。实际上,某种亲水性改性用聚合物对于特殊过滤应用具有所要求的化学性能,却不具备制成有用膜的必要特性。例如,葡聚糖是亲水的,且与蛋白质结合能力差,但未能制成具有一定强度的膜。相反,某一聚合物用于制膜可能是优良材料,可是在某些过滤应用中,它却具有某些不合要求的表面相互作用。例如,聚砜膜可高压减菌,而且具有强度,可是它是疏水的,且有与蛋白质在其表面上结合的趋势。这样,本发明提供的膜表面改性,目的是为了生成一个亲水表面和/或在一个强度好的疏水膜上形成无蛋白结合表面;将反应活性基团引入到一个活性较差的膜上;以膜的形式形成离子交换膜,反相或亲合型支撑物。先前表面涂膜法是与支撑膜的取向有关,而本方法导致与环境溶液相接触的几乎整个表面的改性,涂上一层基本上为单分子层的改性用聚合物。
支撑膜基本上由任何一种疏水性聚合物材料制成,这种材料能制成强度较好的膜,尤其用不可逆吸收进行表面改性的支撑膜,可以由许多疏水聚合物制成,例如,聚砜、聚醚砜、聚2,6-二甲基-4-苯醚、以及它们的衍生物,聚酰胺、聚酰亚胺、聚醚酰亚胺、聚丙烯、聚乙烯、聚偏氟乙烯等等。当然合适的支撑聚合物可能包括上述聚合物混合物和共混物,以及其他疏水性聚合物,尤其适用于做支撑膜的聚合物为聚砜,聚醚砜和聚丙烯。这些膜至少一面应该是多孔的,这样改性同聚合物可以扩散通过表面孔隙,以达到处理膜内部之目的。支撑膜可以含有大空隙,也可以不含大孔隙,所谓“不含大孔隙”意思是膜不含有比直接与膜相接触部分的孔隙大20倍左右的孔。用疏水聚合物制造多孔膜的许多方法为那些膜生产技术人员所熟知,这些方法包括用非溶剂或温度换相,以及拉伸微晶膜。用非溶剂换相即将聚合物溶解于某一溶剂中,通过冲膜挤出形成膜片或管膜,然后将挤出的聚合物溶液与一个液体接触,该液体对于聚合物为非溶剂,而与溶剂是可混溶的,当溶剂被抽提出去后,聚合物溶液胶凝,同时留下多孔结构。并于某些聚合物在多种溶剂中都不溶(例如聚丙烯),那么可以用一种成孔材料,当它与聚合物在熔融态混合时,便形成单相溶液,而在较低温度下,它不能与聚合物混溶。这样,一个含有聚合物与成孔剂的混合熔体,在换相温度以上的某一温度,通过冲模将其挤出,挤出物冷却至低于换相温度,溶液便胶凝,接着再用蒸发或洗涤将成孔剂除去。当聚合物能够形成微晶时,制作多孔膜的另一种方法为,将聚合物熔体在可诱发形成微晶区的条件下挤出,然后拉伸结晶膜,使其在晶区之间产生许多孔隙。这些技术在《合成聚合物膜:结构透视图》一书中更详细的说明(“Synthetic Polymeric Membranes:Astructural Perspectiv”)该书,作者,罗伯特E凯斯廷(Robert E Kesting),第二版,由威廉-因特赛恩斯(Wiley-Interscience)公司出版(纽约,1985)。
选择改性用的聚合物材料,应考虑到它具有所需要的化学性能,而且将不可逆地吸附到支撑膜上。用“不可逆吸收”这个词意思是指当在溶液中某一高分子量的聚合物与表面接触时,聚合物就结合到表面上去,接着开始洗去过量的改性用聚合物,在与吸收条件相似的条件下,已被吸附的聚合物基本上不会脱附。在选择或合成不可逆吸收的改性用聚合物时,应考虑到以下因素:1)要求在表面与每个聚合物分子之间有相当多的结合位置;2)聚合物分子量越大,它具有的结合位置数目就越多,因此它的不可逆结合能力比分子量小的聚合物更强;3)在与开始那步不可逆结合条件完全不同的情况下,结合也可能是可逆的,这样通过寻找一种顶替剂(displacing agent)便可以除去聚合物;4)如果分子量不同的两种聚合物都可渗入基质内,那么用分子量大的聚合物而不用分子量小的聚合物。
适于改性用聚合物应是非蛋白质的,其分子量应大于10,000,这样才能满足不可逆吸附条件。以实用观点来看,人们已经发现,经洗涤2-4天后,仍检测不出脱附下来的聚合物信号,则这种聚合物便可用于这里所述的表面改性。如果改性用表面不是经交联稳定的,那么改性用聚合物分子量应比与被改性表面相接触的材料的分子量大,以使不致被顶替掉(其他因素相同)。改性用聚合物应主要由分子基团组成,希望这些基团被安在支撑表面上以获得例如增加亲水性。而为了不可逆吸收,它还必须包含足够数目的基团,能够与支撑表面相互作用。结合基团应从能与膜相互作用的分子中选取。在某些情况下,合乎要求的表面基团和结合基团可能是相同的,例如,人们已发现包含大量羟基的分子不能满意地从水中吸附到聚砜上。对于聚砜羟基不是好的结合基团,因为水不能湿润聚砜。羟乙基、羟丙基或苯甲酰基则是良好结合基团,因为含有这些基团的小分子是可湿润,在某些情况下,能增塑或溶解聚砜。至于聚四氟乙烯膜,带有碳氟型侧基的葡聚糖应该是一种适宜的亲水性表面改性剂。在结合基团和应用于本发明的疏水性支撑聚合物之间的疏水结合,有许多优点超过了先前提出的方法,这对那些熟悉该技术的人员将是明显的。技术上讲授的离子键相互作用,对PH和离子强度的变化更敏感,而这种PH和离子强度变化在生物分离过程中经常发生。
要求的结合基团数目取决于其与支撑膜的结合强度,如果一个聚合物含有N个结合基团,每个结合基团的结合常数为K,那么聚合物的结合常数为KN。若KN大于10,000,则过程一般被认为是不可逆的,而结合常数小于10,000,某些支撑物与改性用材料的结合则可是不可逆吸收。然而,得到的结合常数大大地大于10,000,一般这是合乎要求的,而且也是可能的。
为了确定预定结合基团的取代程度是否足以导致不可逆吸收到疏水支撑膜上,我们必须估计该结合基团的结合能。典型的结合能数据在C.坦福德,约翰 威廉编写的题目为《疏水效应》一书中给出(“The Hydrophobic Effect”by C.Tanford John Wiley(1980))。
结合能也可以用“兰格缪尔结合试验”(Langmuir binding experiment)对准备用的结合基团从实验上进行估测。用该法选择的结合基团在化学性能上大致与准备用的结合基团相同,例如,未离子化的苯甲酸可认为与葡聚糖上的苯甲酰基非常类似。然而,对于同一基团在离子化条件下(如在高PH下),是否正确,这是值得怀疑的。于是结合能是通过测量结合到支撑膜上结合基团的量(是浓度的函数)来测定的,其他参数如温度、PH或体系中加入的第三组分也可以研究。这些数据将决定个别结合基团的结合强度,同时可以用来确定上述适宜的改性同聚合物的特定组成。
例如,如果我们选了一个分子量为40,000的葡聚糖,它的每个分子包含有224个葡萄糖单元,每隔十个葡萄糖单元带有一个苯丙酰基,那么改性剂聚合物可能总共有22个苯丙酰基。根据苯丙氨基酸的R-基团已报导的数值(-2.5千卡,C.Tanford著The Hydrophobic Effect”)可以对疏水表面的单个苯丙酰基的结合能进行估算。在25℃对于每个苯丙酰基的结合常数为e×p(4.16)=64。5,因此对于每个聚合物分子的结合常数为64。522=1040。这个数值比上述规定的10,000这个结合常数限定值要大得多。结合常数大表明如果结合基团可以分配到疏水支撑材料中去,则该聚合物应是适宜的改性用聚合物。用“分配”(Partitioning)的意思是指结合基团从本体相移到支撑膜上或支撑膜内。在某些情况下,由于支撑材料的聚合物键迁移能力增加(如提高温度),结合基团的分配作用也可能随之增强。吸收到结晶支撑聚合物(如聚丙烯)的吸收作用应只与表面性质及无定形区有关,除非在低于支撑聚合物熔点温度,那时结合基团可以插到晶体结构中去。
可供选择的结合基团包括那些对支撑膜聚合物有增塑作用的小分子,增塑剂就是能降低聚合物玻璃化温度(Tg)的试剂。Tg的测定见下述文献,村山(Takayuki Murayama),Polymer Engineering and Science,1982年8月,第22卷,NO.12,788-791页。简单地说,对于无定形聚合物的玻璃化转变温度是通过热膨胀系数发生实质性变化和/或突变来确定的,该变化发生的温度即为聚合物的Tg。
当分子吸附到膜的显露表面时,还应考虑到另外一个因素,即改性用聚合物大小与膜孔径大小的关系。显然,把一个分子量为100,000的膜切割段放到分子量为100,000的改性用聚合物中,可能导致膜基本上完全被盖堵。还应考虑的一个因素,即象改性葡聚糖这样的无规线团分子,当它吸附到某一表面上后,可能被“压偏”了(flatten out),因此它在表面上的尺寸要比在溶液时的尺寸小。于是需要对具有某一孔径膜使用的聚合物最大分子量进行近似估算。从经验来看,我们已经发现,如果对于纯水,膜的渗透性没有明显下降(也即<30%),那么无规线团分子的流体力学半径小于或等于1/5的膜孔径,则可用于改性过程。更大的分子也可用于改性,然而少量结合上的聚合物会大大降低膜的渗透性(即与未改性膜相比,减少40%或更多)。这种情况在有些特殊应用中或许是合乎需要的,辟如要求一个比较厚的改性表面,或者非特定的蛋白质吸收到未改性的疏水支撑膜上,这样可能使渗透性减少的程度比改性剂更显著。这些观察到的现象连同用电子显微镜检测以下不同分子量聚合物改性的膜,可得到如下结果,改性用层的厚度基本上与改性用聚合物的大小为同一数量级(例如,对分子量为40,000至4,000,000的葡聚糖,厚度为10-100毫微米)。
人们已发现经改性处理整个膜壁是均匀的,而且改性用聚合物基本上以单分子层沉积在整个待冷膜的表面上,且已有文献报导是只作膜的外表面处理,(Ind.Eng.Chem.Prod.Res.Dev.‘19’573-580(1980))。这很容易得到证明,经交联(这在以后会讲到)后,用适当的溶剂溶解支撑膜,为的是以“蛇皮”(snake skin)或“空胞”(ghost)形式保留改性用材料,空胞结构的显微镜检测表明,它与原膜一样,同时它还包含支撑膜内部及表面的特性。
虽然极大多数可溶性聚合物当与一表面接触时,表现出某种“非特定结合”(nonspecific binding),但是这种结合不都足以交联。充分结合以使交联,通常可以用下列一般规则得到,这些规则为疏水的,离子交换,反相,共价色谱和亲合色谱所遵循。例如一个疏水聚合物与疏水膜相结合要比亲水聚合物强;在亲水聚合物上的疏水基团将有利于与疏水表面相互作用,如兰葡聚糖(疏水基∶亲水基为1∶57),或苯丙酰基葡聚糖(比为1∶10)与聚砜膜的作用。从亲合色谱知道,“链索”(leash)或“间隔基臂”(Spacer arm)对于加强改性用聚合物上的结合基与膜之间相互作用或许是必要的。
结合到膜上的活性基团可以进一步用于表面改性反应,应用对纤维素树脂建立起来的标准化学方法,可将含有羟基聚合物改性的膜进一步转变为离子交换膜。例如,氯乙酸可以在碱性条件下加到改性膜中,以获得阳离子交换膜。用同样化学方法将胺基结合到改性剂上以形成交联改性层。例如,丙二胺的一个氨基将与乙二醇二环氧甘油醚(EDGE)反应,留下的一个自由伯胺连到改性剂上以备后用。最后,使生物活性材料(例如,蛋白质,亲合配位体,酶)固定到葡聚糖,琼脂糖和其他胶型支撑物上所采用的化学方法,也能用于适宜的表面改性膜。主要考虑是与表面改性剂一致的试剂和反应条件必须不与形态学相矛盾,或者不降低支撑膜的关键渗透性。对于用兰葡聚糖(分子量为2-3×106的葡聚糖,每57个葡聚糖重复单元便有大约一个汽巴克龙(cibacron)兰色染料分子)涂层的聚砜和/或聚丙烯膜作进一步改性,适用的化合物有溴化氰,双环氧乙烷,高碘酸氧化,碳化二亚胺(carbodiimide),羟基丁二酰亚胺,氯甲酸酯(只适于聚丙烯)。另外,表面改性用的聚合物,包括在涂布支撑膜以前,只要存在反应基团,那么所要求的反应基团不会影响改性用聚合物的结合基团分配到支撑膜内或膜上。
对于某一支撑膜,一旦改性用聚合物被确定,那么为了从本方法获得最佳结果,当支撑膜受到改性用聚合物作用时,其作用条件是十分重要的。一个重要参数是在溶液中与支撑膜相接触的改性用聚合物的浓度。随着改性溶液中聚合物浓度的增加,沉积到膜上的聚合物量也增加,一直至达到某一平稳值为止,通常对于分子量为40,000的改性葡聚糖该值约为10%重量体积比(W/V),对于分子量为3,000,000的改性葡聚糖为5%W/V。这样,用于该膜的改性用聚合物量是可以控制的。所用聚合物量越少导致膜物理性质变化也越小。尤其,我们发现膜的纯水渗透性减少与结合材料的量,在结合曲线的起始部分呈线性关系。然而,那些熟悉该技术的人员将会看到,形成膜的所有物理参数所受影响的程度是不同的,同时吸附到表面的改性用聚合物适宜量将取决于膜的最终应用。例如,我们已发现用于阻止蛋白质与聚砜结合所要求的改性用聚合物羟丙基纤维素用量,比欲生成迅速再润湿膜要求的量少得多。
本发明提供的方法,在表面改性用聚合物存在下,支撑膜不必干燥,此外,由于采用不可逆吸收促使改性用聚合物的均匀沉积。用“均匀”这个词意思是改性用聚合物基本上以单分子层沉积在与它相接触的支撑膜几乎整个表面。均匀程度可由显微镜法和/或化学法来测定。常常由纺丝过程(将膜浸在甘油中,干燥同时适当地再吸水),所得到的疏水膜是完全水合的。于是将疏水膜浸在一个改性用聚合物的水溶液中,该溶液的重量体积比最好为0.1-10%(M/V)左右。其浓度将取决于所用改性用聚合物及膜的孔隙度,吸收时间应足以达到平稳。亲水性膜可直接放入改性剂溶液或在涂布前再进行水合。
有时候采用加热以利于改性用聚合物与支撑膜结合。在这些情况下,将膜和改性用聚合物溶液加热到大约40℃至100℃之间的某一温度会有助于此种结合,最好是加热的温度范围为60℃至80℃左右。另外也可以通过基质物的脱气来增强改性用聚合物的结合,基质膜脱气只需将膜经真空处理即可很易完成,此真空要足以促使截留气脱去。我们认为在极大多数情况下,真空度大约为26-28英吋汞高,在室温下约用2至4小时,基质膜脱气就足够了。如果减少真空(即低于26英吋汞高),那么必须延长时间。提高温度可以加速脱气过程,但要求在此温度下对膜无损害。
然后将所得的改性膜用过量溶剂(即改性用溶液减去改性用聚合物)洗涤,为了除去过量未发生相互作用的聚合物,最好洗大约5-24小时。最后产物是由支撑聚合物组成的膜,整个膜表面吸收了一层非常薄而且甚至从分子数量级来看也相信是均一的改性用聚合物。如果由于某种原因,吸附的聚合物量不够,则膜还可以用更高浓度的改性用聚合物溶液进行处理;相反如果吸附的聚合物太多,则可用顶替剂(参看实施例14)除去多余的改性用聚合物,并将膜进行重新处理。
聚合物和膜的等温吸附线可以表明单层还是多层结合,也可以用来测定膜表面上改性用聚合物分子的密度。该方法也可用来测定各种物理参数的作用(即改性用聚合物浓度、离子强度、PH、介电常数等等),这些参数又可以用来改变被吸附的改性用聚合物表面密度。用这种方式改性的支撑膜可以吸附具有改性用聚合物特性的表面,例如用兰葡聚糖改性的疏水聚砜膜可成为亲水的。这已由下述事实说明,即它们可被再润湿及可通过一个按布罗克(Brock)在“膜过滤:使用者指南和参考方法”所精心设计的“泡点试验(bubble point test)(见“Membrane Filtration:User′s Guide and Reference Manual”Science Tech,Inc(1983))。用聚乙烯醇改性的疏水聚丙烯支撑膜变成亲水性的,表现出对蛋白质的结合减弱,不然蛋白质会强烈地与未改性聚丙烯膜结合;用含有表面羟基的兰葡聚糖改性的聚丙烯膜,可用于交联及其他化学反应,而未改性的聚丙烯膜却没有这些特性。
用这种方式改性的膜可以放置几个月仍保持稳定,然而改性用聚合物在适当条件下可予以除去(例如在0.5%十二烷基硫酸钠洗涤剂中,煮沸兰葡聚糖改性的聚砜,便可除去改性用聚合物)。对于本发明的许多具体说明,最好是将改性用聚合物交联成稳定的改性表面。在极大多数情况下,宁可用化学交联剂,那么熟悉本技术的人员认为交联还可通过其他方法来完成,如辐射和加热,这要取决于改性用聚合物的化学组分。对于水溶性、含羟基改性用聚合物,适宜的交联条件为用环氧氯丙烷或乙二醇二环氧甘油醚(EGDE)浓度分别为1-3%及1-10%体积比(V/V)的1N NaOH溶液。由于EGDE能在较高溶液浓度(至少10%V/V)促使交联,而不被不溶的交联剂所损害疏水的聚合物膜,是优于其他交联剂的。交联后,在能除去未交联改性剂的条件下,表面改性剂是稳定的,除非该条件促使改性用聚合物化学降解或发生交联反应。为了得到稳定的交联,吸附用聚合物必须以足够高的密度存在,为的是使在膜上毗邻的聚合物分子间相接触。
若改性膜将在有强顶替剂的条件下使用时,交联之后的膜应该用这些试剂洗涤,以除去未交联的聚合物。这种情况,在亲合性膜的应用中很可能遇到。
测定交联程度,可以采用除去未交联的表面改性用聚合物的方法(如热洗涤剂)或者采用将膜溶解于支撑材料的良好溶剂中的方法。在这些条件下,已交联的改性用聚合物应该是稳定的。否则,应继续进行交联反应直到获得理想的产物。例如,将经交联的羟丙基纤维改性的聚砜膜溶于氯仿,氯仿不溶解的部分就形成了“蛇皮”或“空胞”结构,而生成改性的表面。用显微镜测定这些结构,结果表明,“空胞”与原有膜的整个表面结构是一模一样的,包括所有可以接触到改性用聚合物溶液的内表面。见实施例14。
通过表面改性得到的膜有多种用途。经改性后具有亲水性,非离子性表面的膜呈现出低的吸收蛋白质能力。这种膜的用途之一,是用于以空心丝作基础的哺乳动物细胞培养反应器的开发研究。在这种情况下,蛋白质吸收将导致降低膜的性能,同时也损失由哺乳动物细胞产生的蛋白质产物。亲水性聚合物改性膜的另一用途是制备一种亲水膜。市上出售的许多用于水体系的疏水膜,是用一种聚合物湿润剂浸润的,在使用之前,必须将其洗掉。在洗掉湿润剂之后,膜不能再被干燥和再湿润,从这个意义上来说,被不可逆结合的改性用聚合物就象一种“永久的湿润剂”一样,因为它不会从膜上被洗脱,因而膜是可以被干燥和多次再润湿的。低蛋白质结合膜在那些必须过滤蛋白质溶液的生物学研究中有许多用处。过去,解决蛋白质结合的问题的办法之一是使用保护剂(blocking agent)(例如:白蛋白或低分子量聚乙二醇)。用该方法存在的问题是,保护剂不稳定,而且会给过滤物带入污染物质。(见Millipore Technical Brief#TB004)从这个意义上来说,若经过设计或选择,使被结合的聚合物不会脱落,而且不会污染过滤物,那么,被不可逆结合的聚合物又象一种“永久保护剂”。如同本发明所描述的,离子交换膜也可以经表面改性制备。这种膜允许带有相反电荷的物质通过,因而可以从溶液中选择性地除去某些离子型物质。这种膜在使用粒子俘获吸收方法的过滤操作中将是有用的。
亲合性膜也可以通过表面改性制备。这种膜适用于有高选择性和快速再生时间(regeneration tim es)的间歇式分离。我们制备的亲合性膜,在选择性和再生时间方面可与HPLC型树脂体系相媲美。
下面是本发明一些较好的应用实例。应当明确的是,它们仅仅是用来说明本发明的,并不限制本发明的范围。
下列列子,通常用于制备表面改性膜的方法是,先将膜放入0.1-10%(W/V)的改性用聚合物溶液中,浸渍5-24小时。如果将改性用聚合物溶液经过支撑膜过滤,也可缩短浸渍时间。吸附到膜上的聚合物量根据改性用聚合溶液的浓度加以控制。然后,用与配制改性用聚合物溶液的同一溶液洗膜。洗涤,直进行到在洗涤溶液中没有聚合物被检验出为止。即使当膜被浸渍几天后,其洗涤液中也应没有聚合物被检出。之后,膜或是准备使用,或是通过交联反应进一步作稳定处理。交联反应条件和开始提到的吸收条件是相似的。以便在反应期间,使改性聚合物不发生被明显的顶替。
交联的检验,是通过除去未交联的表面改性用聚合物的方法(如热洗涤剂),或是通过将膜溶解于支撑聚合物的良溶剂中的方法。
由给定的膜测定显示出的非特定的蛋白质结合度,将空心丝膜剪成五段1厘米长的段,加入到2-4毫升蛋白质溶液中。进行此类研究最常用的蛋白质是细胞色素C。这种蛋白质对于疏水性膜具有相对高的亲合力。由于它的红颜色,可以目测观察到结合的情况。被浸入蛋白质溶液之前,膜总是完全水合的。选择蛋白质溶液的浓度,以使得蛋白质结合量处于从零到完全饱和的范围。结合到膜上的蛋白质的量由下述方法度量:计算加入膜之前的起始蛋白质溶液的浓度;将加入膜的蛋白质溶液在室温放置16小时,使其达到平衡,再计算此时溶液的浓度;蛋白质结合量即是两种溶液浓度之差。蛋白质浓度由分光光度分析法测定。必要时,应该考虑到被截留在空心丝膜中的溶液对蛋白质溶液的稀释作用。典型的结合曲线见图1。在另一种情况中,可以目测用细胞色素C使膜着色达饱和程度(即1-2毫克/毫升)的相对颜色,并将其与按上述结合实验所得膜的颜色作比较,进行估计蛋白质结合量的减少。
在某些情况中,结合于膜的蛋白质量可以用碱性磷酸酶进行测量。用这种方法测定蛋白质结合膜的量,是将对硝基苯基磷酸酯的比色物溶液通过膜进行过滤。结合于膜的蛋白质的量与滤液显示出的颜色有关。
膜的亲水特性实验是首先要进行一个泡点试验,保证膜没有缺陷,并且在泡点压力以下不允许气体通过膜。然后,在80℃将膜进行加热干燥,或是在室温将膜放入干燥的氮气流中进行几小时干燥。干膜与湿膜相比,前者在比泡点压力数值低的压力下,可允许气体自由地通过。当干燥的疏水膜浸入水中后,就会显示出这种性质。然而,将干燥的亲水膜浸入水中后,它就会重新获得干燥前的特征。相似的试验可用蒸馏水同样进行。这时,水可以自由地通过亲水膜。但是,直到到达水的浸入压力前是不能通过疏水膜的。
实施例1
将孔径大小为0.1微米的,商业上的“含有大空隙”的聚砜膜,浸入1.0%(W/V)羟丙基纤维素的无离子水溶液,保持16小时。然后,在搅动下用无离子水洗膜16小时。表面改性膜是亲水的,与未经处理的膜相比,结合细胞色素C的能力降低10倍。经6个月的实验周期观察,没有发现细胞色素C顶替羟丙基纤维素的现象。存在于支撑膜上的聚合物改性剂用名称为“Bial′S”的薄层色谱试剂进行测定。将膜浸入该试剂中30秒,然后放入78-80℃的烘箱中保持15-30分钟。未经处理的膜呈现出灰色,经处理的膜显兰色,颜色的强弱与结合改性用聚合物的量成正比。用分子量100,000和300,000的羟丙基纤维素聚合物可以获得相似的结果。
实施例2
用聚砜作支撑膜,“兰葡聚糖”作改性用聚合物(兰葡聚糖是分子量为2-3百万的葡聚糖的普通名称,每57个葡聚糖重复单元约有一个汽巴克龙Cibacron兰色染料分子)。操作同实施例1。表面改性膜是亲水的,经目测检验测定是无限期稳定的。检验方法如下:在膜与水溶液接触时,膜转变成兰色,颜色的强弱保持不变,且在水溶液中没有观察到兰葡聚糖。与未改性的膜比较,改性膜的水渗透率降低约34%。虽然,在80℃干燥24小时后,改性膜可以重新获得其初始水流量(water flux)的70%,而未经改性的膜经干燥后,则不能再获得任何可以测量的水流量。
实施例3
用聚砜作支撑膜,苯甲酰基葡聚糖作改性用聚合物,除温度为80℃外,其余操作同实施例1。苯甲酰基葡聚糖分子量70,000,每10个葡聚糖聚合物重复单元约有一个苯甲酰基。制备上述聚合物的方法是,在室温下,用10%W/V的葡聚糖的1N NaOH溶液与苯甲酰氯反应。表面改性膜用前述方法测定是亲水的,存在于膜上的葡聚糖由Bial′s试剂检验,说明可以稳定几天。将不经过改性的葡聚糖处理的膜(室温或80℃),或者是在室温,将苯甲酰基葡聚糖处理的膜,经去离子水洗6小时后,经再湿润和Bial′S试剂检验表明,全部失掉了葡聚糖。
实施例4
除了使用苯丙酰氯使葡聚糖带上苯丙酰基结合基团外,实验操作同实施例3。在上述条件下,不可逆的结合反应于室温进行迅速。表面改性膜是亲水的,Bial′S试剂试验检测存在于膜上的葡聚糖,并证实它是稳定的。用分子量40,000和500,000的葡聚糖可以获得相似的结果。用分子量40,000的聚合物没有测量到水流量(water flux)的下降,而用分子量500,000的聚合物,水流量下降10%。据吸附细胞色素C的实验证明,与未改性的膜对比,蛋白质吸收减少了至少1/10。图1是用分子量500,000的苯丙酰基葡聚糖改性膜测得的。
实施例5
改用0.2微米的尼龙6,6膜,操作同实施例2。通过目测膜的兰颜色证明,表面改性膜是稳定的。放有膜的溶液经80℃24小时,然后室温放置11个月没有发现兰颜色。增加一块未处理的尼龙6,6膜(0.2微米)到同一溶液中,也没有观察到兰颜色,这表明兰葡聚糖,不会从一块膜移动到另一块对于改性用聚合物有相同亲合力的膜上。
实施例6
用尼龙无纺布(Spun bonded nylon fabric)(即Monsanto′s Cerex材料)作支撑材料,其操作同实施例5。用水连续浸渍后,目测布的兰颜色,证明体系是稳定的。与未处理的无纺布相比,处理过的布具有更高的亲水性。这通过下述水珠实验验证。将一滴去离子水珠滴在未处理材料表面,它被吸收进入纤维需要几分钟,而滴在经处理的纤维表面则立即被水吸收。
实施例7
用0.2微米的聚丙烯膜作支撑材料,操作同实施例2。据以上描述的实验测定,不亲水的改性膜是是无期限稳定的。表面改性用聚合物的羟基可以进一步反应,制备各种离子交换膜和亲和性膜。
实施例8
用10微米孔经大小的聚乙烯作支撑材料,操作同实施例2。目测兰颜色证明,经处理的材料是稳定的。
实施例9
用聚醚砜作支撑聚合物,按照实施例2的步骤进行实验。目测兰颜色检验表明,改性材料在水中是稳定的。
实施例10
用聚醚酰亚胺作支撑材料,实验步骤同实施例9。由目测兰颜色检验表明,改性材料在水中是稳定的。
实施例11
用部分水解的聚乙烯醇(分子量≌125,000,聚乙烯醇占重量的88%,聚醋酸乙烯酯占重量的12%)作改性用聚合物,实验操作同实施例1。生成的膜是亲水的,将羟丙基纤维素改性膜与上述膜分别放入约1毫克/毫升的细胞色素C溶液中,进行目测比较,结果是,上述膜吸附细胞色素C的能力减少了约10倍。碘试剂测定表明聚乙烯醇是稳定存在的。(即:聚乙烯醇加由3mM碘、9mM碘化钾和0.2M硼酸配成的琥珀色试剂,转变成兰色)。发现98-99%水解的(即98-99%的醋酸酯基被水解)分子量为115000的聚乙烯醇,不能稳定地吸附于聚砜,并且不减少蛋白质吸收。
实施例12
用羟乙基纤维素作改性用聚合物,实验步骤同实施例1。改性膜是亲水的。经彻底的洗涤和Bial′S试剂实验证明,羟乙基纤维素是被不可逆地结合的,但对细胞色素C的蛋白质结合没有明显地减少。
实施例13
使用0.2微米的聚丙烯膜和98-99%水解的聚丙烯醇(98-99%的醋酸酯基被水解),其分子量为14,000和115,000。操作同实施例1。由洗涤、碘试剂(见实施例11)和上述再湿润试验判断,产生的膜是亲水的,稳定的。据目测观察,产生的膜对于细胞色素C的蛋白质吸附明显减少。由酶催化检验表明,分子量115,000聚乙烯醇改性的膜,在碱性磷酸酶中,结合能力减少24倍。和未经处理的膜比较,当经处理的膜被使用在含有可以结合到膜上的物质的原料流时,具有很好的抗污染能力(fouling resistant)。
实施例14
用1%兰葡聚糖取代羟丙基纤维素,用1N NaOH溶液取代去离子水,实验步骤同实施例1。把膜放入5%(按体积V/V)的乙二醇二环氧甘油醚的1N NaOH溶液中,放置16小时,使吸附的兰葡聚糖交联。然后,用去离子水洗膜,如果必须除去残留的环氧基,应该用NaOH进一步与其反应。生成的膜放入沸腾的1%W/V的Alconox
(纽约Alconox公司,New York),或十二烷基硫酸钠洗涤剂溶液中几小时后,目测观察膜的兰颜色,证实它是亲水和稳定的。(未交联的兰葡聚糖在此条件下,30分钟即被除掉)。根据“空胞”实验,判断表面改性层交联的情况。将膜溶于氯仿,当摇动溶液时,可产生兰色的、稳定的“空胞”。未交联的膜也可形成“空胞”结构,但是,当摇动溶液时,它便破碎了。图2给出了改性膜的一般结构。图3给出的是溶解了聚砜支撑膜后,形成的“空胞”结构。
实施例15
实施例1中所说的膜用下述方法交联:将膜浸入0.5%(W/V)的二羟甲基脲交联剂中,搅动30分钟,然后放入90℃烘箱中约30分钟(见“Klucel著羟丙基纤维素的化学和物理性质”Her-cules化学公司,Wilmington,Delaware,1971)。在40℃的温度下交联状的羟丙基纤维素不会被1%(V/V洗涤剂/水)浓度的非离子性洗涤剂,如TRITON
X-100(Rohm and Hass公司)和NONIDEF
P-40(Shell公司)所顶替。
未交联的改性膜在氯仿中,形成清晰的溶液,因为聚砜和羟丙基纤维素都溶于该溶剂。交联的纤维素形成氯仿不溶解的“空胞”。改性膜是亲水的。对比于原始的聚砜膜,改性膜对细胞色素C的结合力明显减少。
实施例16
将聚丙烯膜浸入3%的兰葡聚糖蒸馏水溶液,放置16小时,再用蒸馏水洗涤16小时。然后,将膜浸入1N NaOH及5%(V/V)的乙二醇二环氧甘油醚中,室温放置16-32小时,以使改性的葡聚糖表面交联。膜经水洗后,用无水丙酮洗。于室温,将膜浸入由95%丙酮,5%吡啶配成的,含有3%(W/V)对硝基苯基氯甲酸酯溶液中,保持30分钟,使葡聚糖表面活化,经再洗涤后,将膜贮存于无水的丙酮中。活化基团用6N NaOH水解,就释放出对硝基苯酚。通过测量释放量,我们发现,每克膜(干重量)可以结合8毫摩尔(mM)的活化基团到改性膜表面。产生的膜可用于固定含有的氨基的分子,即蛋白质。例如,将上述制备的膜用1mM HCl蒸馏水溶液洗2分钟,然后,将含1毫克/毫升的蛋白质A的PH=7,0.05M的磷酸钠缓冲剂,经上述膜循环过滤2小时。蛋白质A被固定在膜上,并且将选择性地从含有蛋白质混合物的血清中选择性结合抗体蛋白质。如果避水保存,活化的膜可以稳定几个月。
实施例17
把由实施例14得到的交联之后的膜,立刻放入50%(V/V)的1.3-丙二胺的0.5N NaOH溶液,在室温反应16小时,将得到的膜用去离子水洗涤。然后,用0.1N NaOH,0.1NHCl交替洗涤5次,每次30分钟。茚三酮反应测定结果,生成的膜每克纤维中有30mM的胺基。
实施例18
将从实施例17得到的膜,于室温下,与0.5M的琥珀酸酐的1M磷酸钾溶液(PH=6.0)反应过夜。反应重复进行,直到纤维的茚三酮实验显负性(即观察不到兰色)。如所预期的,膜具有阳离子交换性质。
实施例19
为了固定蛋白质,将从实施例18得到的膜活化。首先用无水的异丙醇洗5遍,然后,把长19-8厘米的空心丝纤维膜浸入10毫升含有0.115克N-羟基琥珀酰亚胺,0.19克1-乙基-3-(3-二甲基氨丙基)碳化二酰亚胺的异丙醇溶液中,室温放置70分钟。使用前,将所制得的膜贮存于无水的异丙醇中。例如,将20毫升水强制通过空心的丝膜,除去膜上剩余的水。然后,加入含有5毫克蛋白质A的2毫升0.05M磷酸钠溶液PH=6,保持在4℃使其过夜。每克空心纤维(干重)可将13毫克蛋白质A固定于其膜,并且可以从血清蛋白质混合物中选择结合抗体蛋白质。
实施例20
按照实施例1的实验步骤,用“无大空隙”(“macro-voidfree”)聚砜作支撑膜,二乙基胺基乙基葡聚糖(DEAE葡聚糖)作改性用聚合物,1N NaOH水溶液作溶剂。在这些条件下,DEAE侧基是非正电性的,因此是疏水的,可以保证聚砜对于DEAE葡聚糖的不可逆吸附。用1N NaOH洗膜,然后浸入10%的乙二醇二环氧甘油醚的1N NaOH溶液,在室温下过夜,使DEAE葡聚糖交联。得到的膜在沸腾的1%十二烷基硫酸钠中是稳定的。碘铂酸钾和德拉根道夫试剂(Dragendorff′s reagents,从Sigma化学公司,St.Louis,Mo获得)实验结果,证实了DEAE基的存在。另外,膜具有阴离子交换特性。例如,在0.06M,PH=8.6的巴比妥钠缓冲剂中,膜选择性地结合C-藻青素(带负电性),而不结合细胞色素C(带正电性)。用这种膜,采用提高氯化钠浓度的办法,进行选择性洗提,可以从鼠腹水液中提纯单细胞系抗体。
实施例21
实施例20的阴离子交换膜,按下列步骤,以共价键方式固定铁蛋白和C-藻青素蛋白质。将膜浸入10mM,PH=9的含有这些蛋白质的碳酸氢钠溶液中,在4℃下过夜,或者采取死端式(dead end mode)过滤的方法,经30分钟以结合蛋白质。然后,用合适的试剂使蛋白质交联,以共价键方式固定蛋白质吸附层。铁蛋白用1%的乙二醇二环氧甘油醚或1%的乙二醇双(琥珀酸N-羟基琥珀酰亚胺酯)在10mM,PH=9的碳酸氢钠中,于室温过夜进行交联。C-藻青素在相同条件下,用乙二醇二环氧甘油醚交联。上述两种膜,70℃条件下,经1%的十二烷基硫酸钠溶液处理4小时是稳定的,而未交联的蛋白质,经上述处理就会被除掉。70℃用1%的洗涤剂进行处理,未经交联的藻青素有72%被除掉,而交联的藻青素仅被除掉了22%。
实施例22
实施例20的阴离子交换膜,于4℃吸附溶于10mM,碳酸氢钠中的蛋白质A反应过夜,可以制成一种亲合性膜,所得蛋白质复盖的膜用1%的乙二醇二环氧甘油醚,或20mM的乙二醇双(琥珀酸N-羟基琥珀酰亚胺酯),在4℃,使用相同的缓冲剂过夜进行交联。生成的膜,在含10%的鼠腹水5mM的磷酸钾,PH=8.0并加有0.2M氯化钠的溶液中,可以选择性地吸附单细胞系抗体,并且当遇到含有0.1M甘氨酸,0.15M氯化钠,PH=2.6的缓冲剂时,膜可将抗体释放出来。乙二醇二环甘油醚交联膜的结合能力,与乙二醇双(琥珀酸N-羟基琥珀酰亚胺酯)交联膜相比是较低的。因此,在这类应用中,后者是较愿选用的交联剂。
实施例23
用“不含大空隙”聚砜作支撑膜,重复实施例1的实施步骤。将改性膜浸渍在10%的乙二醇二环氧甘油醚的1N氢氧化钠溶液中,在60-80℃,过夜。反复进行交联(一般两次),直到膜能形成氯仿不能溶解的“空胞”。得到的膜经下述方法转变成阳离子交换膜。在室温,将膜浸入0.5M的甲醇钠(Kodark Chemical,Rochester,New York产品)中3小时,然后再浸入1M氯醋酸的叔丁醇溶液中,在室温下过夜。生成的膜,在0.06M,PH=8.6的巴比妥钠缓冲剂中,选择性地结合细胞色素C;而不结合藻青素。因此,具有阳离子交换特性。
Claims (38)
1、一种预先选定的聚合支撑材料的表面改性方法,包括所说的支撑材料的几乎整个表面不可逆地吸附一种改性用聚合物,所说的改性用聚合物,分子量至少10,000,它具有较多数量的分配于支撑材料表面或进入支撑材料内部的结合基团,而使改性用聚合物粘合于支撑材料上。
2、按照权利要求1的方法,其中支撑材料是一种支撑膜。
3、按照权利要求2的方法,其中不可逆吸收是由于用含有所说改性用聚合物溶液浸渍载体膜而发生的。
4、按照权利要求3的方法,其中溶液中改性用聚合物的含量约在0.1-10%(按重量计)之间。
5、按照权利要求2的方法,其中提高支撑材料链的流动性,可以促进改性用聚合物结合基团在支撑膜表面或进入支撑膜中的分配。
6、按照权利要求5的方法,其中采取提高温度的办法,提高链的流动性。
7、按照权利要求6的方法,其中温度在约60-80℃之间。
8、按照权利要求2的方法,将改性用聚合物吸附于支撑膜后,进一步使其交联。
9、按照权利要求2的方法,其中改性用聚合物的流体动力学半径小于或等于支撑膜孔径大小的1/5左右。
10、一种表面改性膜,是聚合物支撑膜和被不可逆地吸附在其表面上的改性用聚合物。改性用聚合物分子量至少为10,000,主要以单分子层的形式,基本上分布在支撑膜的整个表面面积上。
11、按照权利要求10的改性膜,其中改性用聚合物是被交联的。
12、按照权利要求10的膜,其中支撑膜是从聚砜、聚醚砜、聚醚酰亚胺、聚丙烯、聚乙烯和聚1,1-二氟乙烯聚合物中选择的。
13、按照权利要求10的膜,其中膜是由聚砜制备的,改性用聚合物是羟丙基纤维素。
14、按照权利要求13的膜,其中改性用聚合物是被交联的。
15、按照权利要求10的膜,其中支撑膜是由聚砜制备的,改性用聚合物是约88%(按重量计)水解的聚醋酸乙烯酯。
16、按照权利要求15的膜,其中改性用聚合物是被交联的。
17、按照权利要求10的膜,其中支撑膜是由聚乙烯制成的,改性用聚合物是聚乙烯醇。
18、按照权利要求17的膜,其中改性用聚合物是被交联的。
19、按照权利要求10的膜,其中支撑膜是由聚丙烯制备的,改性用聚合物是聚乙烯醇。
20、按照权利要求19的膜,其中改性用聚合物是被交联的。
21、按照权利要求10的膜,其中支撑膜是由聚丙烯制成的,改性用聚合物是具有疏水反应性基团的葡聚糖。
22、按照权利要求21的膜,其中改性用聚合物是被交联的。
23、按照权利要求10的膜,其中支撑膜是由聚砜制备的,改性用聚合物是具有疏水反应性基团的葡聚糖。
24、按照权利要求23的膜,其中改性用聚合物是被交联的。
25、在改性用聚合物上结合一个生物活性材料,使按照权利要求10的膜进行进一步的改性。
26、按照权利要求25的膜,其中改性用聚合物是被交联的。
27、按照权利要求25的膜,其中改性用聚合物是交联的离子型聚合物
28、按照权利要求27的膜,其中生物活性材料是多肽。
29、按照权利要求27的膜,其中离子型聚合物是DEAE葡聚糖。
30、按照权利要求29的膜,其中支撑膜是由聚砜制备的。
31、按照权利要求11的膜,其改性用聚合物是离子型的。
32、按照权利要求11的膜,其中改性用聚合物是DEAE葡聚糖。
33、按照权利要求32的膜,其中支撑膜是聚砜。
34、按照权利要求33的膜,其中聚砜支撑膜主要是不含大空隙的(macro-void free)。
35、按照权利要求32的膜,其中支撑膜是聚醚砜。
36、按照权利要求10的膜,支撑膜是由聚合物制备的,聚合物从聚砜、聚醚砜、聚醚酰亚胺、聚丙烯和聚乙烯中选择。
37、按照权利要求36的膜,其中改性用聚合物是兰葡聚糖。
38、按照权利要求10的膜,其中支撑聚合物主要是不含大空隙的(macro-viod free)。
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- 1986-10-30 EP EP86870160A patent/EP0221046B1/en not_active Expired - Lifetime
- 1986-10-30 AT AT86870160T patent/ATE70733T1/de not_active IP Right Cessation
- 1986-10-30 DE DE8686870160T patent/DE3683127D1/de not_active Expired - Lifetime
- 1986-10-31 IL IL80464A patent/IL80464A/xx not_active IP Right Cessation
- 1986-10-31 CN CN86107568A patent/CN1010317B/zh not_active Expired
- 1986-10-31 AU AU64617/86A patent/AU589701B2/en not_active Expired
- 1986-10-31 NZ NZ218132A patent/NZ218132A/en unknown
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102516577A (zh) * | 2011-12-09 | 2012-06-27 | 清华大学 | 一种干态保存离子交换膜的方法 |
CN102516577B (zh) * | 2011-12-09 | 2013-07-03 | 清华大学 | 一种干态保存离子交换膜的方法 |
CN108744984A (zh) * | 2018-05-16 | 2018-11-06 | 南京帝膜净水材料开发有限公司 | 一种卷式膜元件 |
CN113474078A (zh) * | 2019-02-26 | 2021-10-01 | 富士胶片株式会社 | 亲水性多孔膜及亲水性多孔膜的制造方法 |
CN110449033A (zh) * | 2019-08-27 | 2019-11-15 | 湖北中泉环保技术有限公司 | 超滤膜表面有机沉积物的清洗方法 |
CN110585932A (zh) * | 2019-10-29 | 2019-12-20 | 湖南澳维膜科技有限公司 | 一种聚酰胺复合膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
GR3003883T3 (zh) | 1993-03-16 |
DE3683127D1 (de) | 1992-02-06 |
EP0221046A3 (en) | 1988-10-19 |
ATE70733T1 (de) | 1992-01-15 |
AU6461786A (en) | 1987-05-07 |
IL80464A (en) | 1989-10-31 |
ES2000015A4 (es) | 1987-08-16 |
JPS62176508A (ja) | 1987-08-03 |
US5139881A (en) | 1992-08-18 |
DK521286D0 (da) | 1986-10-31 |
JPH0714469B2 (ja) | 1995-02-22 |
CN1010317B (zh) | 1990-11-07 |
NZ218132A (en) | 1990-01-29 |
CA1283582C (en) | 1991-04-30 |
EP0221046B1 (en) | 1991-12-27 |
ES2000015T3 (es) | 1992-07-16 |
EP0221046A2 (en) | 1987-05-06 |
DK521286A (da) | 1987-05-02 |
IL80464A0 (en) | 1987-01-30 |
US4794002A (en) | 1988-12-27 |
AU589701B2 (en) | 1989-10-19 |
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