CN1143732C - 纯化有机体生理液的材料的方法、以及生产该材料的方法 - Google Patents
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Abstract
本发明提供了一种纯化有机体生理液的方法,它是这样进行的,将取自病人的具有毒素的生理液通过一种材料,该材料具有选择的尺寸、形状、和结构以从生理液中去除分子量范围300-30000道尔顿的毒性化合物,且所述材料由多孔憎水二乙烯基苯共聚物组成,该共聚物起始具有表面暴露乙烯基,然后这些乙烯基通过化学改性形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
Description
技术领域
本发明涉及一种用于纯化有机体生理液的方法和材料、以及生产该材料的方法。
背景技术
人们熟知,在有机体中毒时,以及在疾病,尤其是肝病和肾病时,有机体生理液,如血液、血浆、腹膜液等可聚集和运输各种毒素。因此可以考虑从生理液中去除毒素以明显改善病人的状况。已经发明了许多方法并将它们用于从血液、血浆和其它生理液中去除毒素。一种最有效的方法是血液透析。但该方法一般局限于去除小毒性分子,而去除属于所谓中号分子(分子量为500-30000道尔顿)的毒素则太慢,即使使用现代“高通量”渗析膜也是如此。据信还可考虑改进已有方法以有效纯化有机体生理液,尤其针对具有较大分子尺寸的毒素,这样可防止疾病传播或治疗该疾病。
按照本发明,如果将常规的血液透析法补充以吸附步骤,应该可从血液或其它生理液中去除较广谱的毒性化合物。后者(吸附步骤)应该可去除扩散通过渗析膜时太慢的较大毒素。
吸附材料应该对中等范围分子量的毒素具有高吸附能力,并与血液或相应的生理液具有足够的相容性。本发明的一个目的是设计出合适的聚合物吸附材料。
大孔苯乙烯-二乙烯基苯共聚物代表最常用的聚合物吸附材料。许多公司都生产这种类型的吸附剂。Amberlite XAD-4(来自Rohm andHaas)可能是最有名的一种。虽然稍被忽略,但同样有价值的是通过二乙烯基苯(DVB)与其它单体,如甲基丙烯酸丁酯、丙烯腈和其它单体的共聚反应而制成的大孔吸附材料。
为了在各种使用条件下保持聚合物颗粒的多孔结构和几乎恒定的体积,这些聚合物的三维网状结构应该具有足够的刚性,即,它必须包含高含量的交联二乙烯基苯。后一产品在纯净态下相当昂贵。更易得到的工业产品包含最高30-40%的乙基乙烯基苯乙烯,因此市售大孔吸附剂应该最好是指DVB、乙基乙烯基苯乙烯和苯乙烯的共聚物。通常,这种单体混合物具有用作稀释剂的有机溶剂,这在聚合反应工艺过程中会引起微相分离,从而形成最终材料的大孔结构。
已经反复表明,自由基聚合物工艺从不消耗参与共聚的DVB中的所有乙烯基。平均来说,约30%的DVB没有用作交联桥,而是仅通过其两个乙烯基中的一个包含在网状结构中。因此,大孔吸附剂的一个显著特征是具有相对较高量的未反应乙烯基。可以预料,这些自由的乙烯基优选暴露于聚合物珠及其大孔的表面上,因此应该容易进行化学改性。
大孔DVB-共聚物表面的化学改性取决于表面暴露的未反应乙烯基的化学反应,目的是将这些基团转化成更亲水的官能团。这种转化可赋予起始憎水吸附材料以血相容性,因为亲水表面吸附血细胞和血浆蛋白质较少,因此不如起始憎水表面那样迅速活化凝固栅状物。
在我们的早期专利申请号08/756445中公开了某些解决方案。
本发明的公开内容
因此,本发明的一个目的是提供一种用于纯化有机体生理液的方法和材料、以及生产该材料的方法,这是以上特定领域中的进一步改进。
按照本发明,纯化有机体生理液的方法包括从病人处取出包含毒素的生理液;将生理液通过多孔憎水二乙烯基苯共聚物,它起始具有表面暴露的乙烯基,然后通过化学改性乙烯基,形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
按照本发明的另一特征,提出了由多孔憎水二乙烯基苯共聚物组成的用于纯化有机体生理液的材料,所述共聚物起始具有表面暴露的乙烯基,然后这些乙烯基通过化学改性,形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
最后,提出了一种用于生产纯化有机体生理液所用材料的方法,按照该方法,一种多孔憎水二乙烯基苯聚合物起始具有表面暴露的乙烯基,然后这些乙烯基通过化学改性,形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
在按照申请人的发明提供用于纯化有机体生理液的方法和材料、以及一种生产该材料的方法时,它们可产生非常有利的结果。
实施本发明的最佳方式
按照本发明,提出通过去除毒素来纯化有机体的生理液。将病人的血液从动脉血循环入口取出,将其通过能去除毒素的本发明材料,然后由静脉入口再注入病人。该材料具有选择的尺寸、形状、和结构,以从生理液中去除分子量范围300-30000道尔顿的毒性化合物。
按照本发明的材料可用于本发明方法以纯化有机体生理液,而且可按照本发明的生产方法来生产,它是一种起始具有表面暴露乙烯基的多孔憎水二乙烯基苯共聚物,然后这些乙烯基通过化学改性,形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
按照本发明,表面乙烯基的改性是按照以下三个基本原则,在水性介质或含水有机介质中进行的:
·通过甲基丙烯酸2-羟乙基酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、或其它水溶性单体的自由基聚合反应,将亲水聚合物链进行接枝,
·将乙烯基氧化成环氧基,随后将环氧基与水、乙二醇、胺或2-氨基乙醇(2-amonoethanol)分子进行反应,和
·将高分子量血相容性聚合物,尤其是聚(三氟乙氧基)膦嗪(poly(trifluorethoxy)phosphazene)沉积在聚合物珠的表面上。
在任何情况下,都可通过干燥的改性材料易于用水润湿看出如此改性的表面的亲水性,而起始干燥的未改性吸附剂在与水直接接触时则不能被润湿。
在以下实施例中,将中孔二乙烯基苯-乙基苯乙烯-苯乙烯共聚物(一种典型的聚苯乙烯-型吸附材料)、以及具有表面暴露双键的DVB与甲基丙烯酸丁酯的共聚物用于改性。
表面改性材料显示出良好的血相容性,即,它们不会明显改变血液的凝固时间,不造成溶血且未表现出细胞毒性效应。在与血浆或全血接触时,这些材料可有效地消除中号分子,这可容易地通过常规的分光光度测量来了解。
中孔二乙烯基苯共聚物的制备
实施例1
将130克对-乙基苯乙烯、132克二乙烯基苯(对位和间位-异构体的约1∶1混合物)和2.62克过氧化苯甲酰在150毫升甲苯和100毫升异戊醇中的溶液悬浮在包含1%纤维素稳定剂的4升纯水中。在室温搅拌39分钟之后,将该混合物在40℃加热1小时,60℃2小时,80℃5小时,以及90℃2小时。将该混合物冷却至室温,然后过滤所得材料的珠,并用热水、甲醇和水洗涤。将该聚合物在80℃炉中干燥一天。
实施例2
室温下,将75克丙烯酸丁酯、51克二乙烯基苯(对位和间位-异构体的约1∶1混合物)和1克苯甲酰在250毫升甲苯中的溶液悬浮在包含15克纤维素稳定剂的2.4升纯水中。搅拌30分钟之后,将该混合物在60、80和95℃下加热,每个温度加热3小时。冷却至室温,然后过滤所得珠,并用热水、甲醇和水洗涤。将珠在80℃炉中干燥7小时。
将亲水聚合物链接枝到表面暴露的乙烯基上
实施例3
用乙醇洗涤实施例1制备的聚合物,然后用水漂洗,得到一种用水完全润湿的材料,其中所有的孔都填充有水。该材料包含40%聚合物和60%水。向如此用水润湿的1克聚合物中,加入1毫升3%甲基丙烯酸2-羟乙基酯(HEMA)水溶液和0.1毫升10%过硫酸铵水溶液,然后在用磁力搅拌器恒定搅拌该混合物的情况下,加入亚硫酸钠水溶液(2摩尔/摩尔过硫酸盐)。在40℃下慢慢混合该混合物2小时或在10℃下10小时。过滤该聚合物,水洗,然后在80℃以下干燥。
实施例4
向1克实施例1制备的干燥聚合物中,加入3.5毫升乙醇,然后加入1.6毫升6%HEMA水溶液、0.3毫升10%过硫酸铵水溶液,最后加入0.3毫升1M亚硫酸钠水溶液(或0.3毫升0.5M抗坏血酸溶液)。将该混合物在10℃下搅拌10小时。过滤该聚合物,水洗,然后在70℃干燥。
按照几乎相同的方式,用HEMA接枝在实施例2中制备的二乙烯基苯与甲基丙烯酸丁酯的共聚物。
实施例5
向1克实施例1中制备的水润湿聚合物中,加入1.0毫升6%N-乙烯基吡咯烷酮水溶液、和0.2毫升10%过硫酸铵水溶液,然后将该混合物在40℃下搅拌2小时。过滤该聚合物,水洗并干燥。
实施例6
向1克实施例1中制备的水润湿聚合物中,加入2.0毫升3%N-乙烯基吡咯烷酮、0.3毫升10%过硫酸钠水溶液和0.3毫升亚硫酸钠水溶液,然后将该混合物在25℃下搅拌2小时。过滤该聚合物并如上处理。
在表面暴露双键上的聚合物类似反应
实施例7
向1克实施例2中制备的水润湿聚合物中,加入2.0毫升3%N-丙烯酰胺、0.3毫升10%过硫酸钠水溶液和0.3毫升1M亚硫酸钠水溶液,然后将该混合物在25℃下搅拌2小时。过滤该聚合物并如上处理。
实施例8
向实施例1中制备的6克干燥聚合物中,加入25毫升乙酸酐,将该混合物冷却至0℃,慢慢加入2毫升40%过氧化氢水溶液,然后在10-15℃下搅拌8小时。过滤该聚合物,用冰醋酸洗涤,得到含环氧基的材料。
向用冰醋酸涨大的2克以上环氧基改性聚合物中,加入10-15毫升水和2滴浓硫酸,然后在50-70℃下搅拌加热3-5小时,这样可将环氧基转化成二醇基团。过滤该聚合物,仔细水洗并干燥。
实施例9
向用冰醋酸涨大的2克环氧基改性(按照实施例7)聚合物中,加入5毫升冰醋酸中的1毫升乙二醇(或5毫升无水乙酸乙酯),加入2滴浓硫酸,然后在50-70℃下搅拌加热5-8小时。该步骤可将乙二醇加成到环氧基官能团上。过滤该聚合物,用水、乙醇、再用水洗涤,然后干燥。
实施例10
使用无水乙酸乙酯仔细洗涤用冰醋酸涨大的2克环氧基改性(按照实施例7)聚合物,然后加入于4毫升乙酸乙酯中的1毫升2-羟乙基胺。将该混合物在40℃下搅拌5小时,以将羟乙基氨基加成到环氧基上。过滤该聚合物,用水、1N HCl、再用水洗涤至中性pH值。
在一个单独的试验中,使用二乙胺替代2-羟乙基胺。如上所述,用水、1N HCl、和水洗涤。
将聚(三氟乙氧基)膦嗪沉积在聚合物(分子量20.106道尔顿)的表面上
实施例11
将实施例9所得产物真空干燥。向3克干燥聚合物中迅速加入0.3毫克聚(三氟乙氧基)膦嗪(分子量20.106)在10毫升乙酸乙酯中的溶液,然后搅拌直到所有溶剂都完全被聚合物珠所吸收。然后将该材料在减压下干燥并用乙醇洗涤。
实施例12
向实施例2中制备的3克干燥未改性聚合物中,迅速加入1毫克聚(三氟乙氧基)膦嗪在10毫升乙酸乙酯中的溶液,然后按照实施例10所述干燥去除溶剂。
可以理解,以上描述的每个要素、或两个或多个的组合,还可用于不同于上述类型的其它种类方法和产品中。
尽管本发明已根据纯化有机体生理液的方法和材料、以及生产该材料的方法加以说明和描述,但它并不局限于所给出的这些具体内容,因为只要不背离本发明的精神,可以进行各种改进和结构变化。
无需进一步分析,前述内容已完全反映了本发明的精神,因此人们可容易通过应用现有知识使其适用于各种应用,而不失去在已有技术看来明显构成本发明一般方面或特定方面的基本特征的特点。
在所附权利要求中,给出了新的且需要专利保护的内容。
Claims (10)
1.一种纯化有机体生理液的方法,包括以下步骤,从病人处取出具有毒素的生理液;将具有毒素的生理液通过一种材料,所述材料具有选择的尺寸、形状、和结构以从生理液中去除分子量范围300-30000道尔顿的毒性化合物,且所述材料由多孔憎水二乙烯基苯共聚物组成,该共聚物起始具有表面暴露乙烯基,然后共聚物中的这些乙烯基通过化学改性形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团;然后将该液体返回病人。
2.一种用于纯化有机体生理液的材料,所述材料具有选择的尺寸、形状、和结构以从生理液中去除分子量范围300-30000道尔顿的毒性化合物,且所述材料由多孔憎水二乙烯基苯共聚物组成,该共聚物起始具有表面暴露乙烯基,然后共聚物中的这些乙烯基通过化学改性形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
3.根据权利要求2所定义的材料,其中所述多孔憎水二乙烯基苯共聚物包括二乙烯基苯与选自苯乙烯、乙基苯乙烯、丙烯腈、甲基丙烯酸丁酯的共聚单体的共聚物。
4.根据权利要求2所定义的材料,其中相对乙烯基具有更高亲水性和更高生理相容性的所述表面暴露官能团是接枝的亲水聚合物链,所述聚合物链选自甲基丙烯酸2-羧乙基酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、N-丙烯酰胺的聚合物。
5.根据权利要求2所定义的材料,其中相对乙烯基具有更高亲水性和更高生物相容性的所述表面暴露官能团是所述乙烯基氧化成环氧基,随后加成极性化合物的产物,所述极性化合物选自水、乙二醇、小的伯或仲胺、2-羟乙基胺。
6.根据权利要求4所定义的材料,其中相对乙烯基具有更高亲水性和更高生物相容性的所述表面暴露官能团是所述乙烯基氧化成环氧基,随后加成小的伯或仲胺或2-羟乙基胺并沉积高分子量聚(三氟乙氧基)膦嗪的结果。
7.一种生产权利要求2的用于纯化有机体生理液的材料的方法,包括提供一种多孔憎水二乙烯苯共聚物,其具有选择的尺寸、形状、和结构以从生理液中去除分子量范围300-30000道尔顿的毒性化合物,且其起始具有表面暴露乙烯基;然后这些乙烯基通过化学改性形成相对这些乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团。
8.根据权利要求7所定义的方法,其中对乙烯基的化学改性导致形成相对乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团,而不明显影响起始二乙烯基苯共聚物的多孔结构和憎水内部,所述化学改性包括,在水性介质或含水有机介质中,接枝聚合选自甲基丙烯酸2-羟乙基酯、N-乙烯基吡咯烷酮、N-乙烯基己内酰胺、N-丙烯酰胺的水溶性单体。
9.根据权利要求7所定义的方法,其中对乙烯基的化学改性导致形成相对乙烯基具有更高亲水性和更高生物相容性的不同的表面暴露官能团,而不明显影响起始二乙烯基苯共聚物的多孔结构,所述化学改性包括,将所述乙烯基氧化成环氧基,随后将极性化合物加成到环氧基上,所述极性化合物选自水、乙二醇、小的伯或仲胺、2-羟乙基胺。
10.根据权利要求7所定义的方法,其中在将所述乙烯基氧化成环氧基之后,将小的伯或仲胺、2-羟乙基胺加成到环氧基上,然后通过下述聚膦嗪与表面暴露氨基的配合,将高分子量聚(三氟乙氧基)膦嗪从其在有机溶剂的溶液中沉积出来。
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-
1998
- 1998-02-06 US US09/019,583 patent/US6114466A/en not_active Expired - Lifetime
- 1998-11-02 US US09/184,685 patent/US6133393A/en not_active Expired - Lifetime
- 1998-12-14 US US09/210,689 patent/US6087300A/en not_active Expired - Lifetime
- 1998-12-14 US US09/210,675 patent/US6153707A/en not_active Expired - Lifetime
- 1998-12-30 JP JP54042799A patent/JP2001524878A/ja not_active Ceased
- 1998-12-30 EP EP98964992A patent/EP0998350A1/en not_active Withdrawn
- 1998-12-30 EA EA199900797A patent/EA001871B1/ru not_active IP Right Cessation
- 1998-12-30 CN CNB988043998A patent/CN1143732C/zh not_active Expired - Lifetime
- 1998-12-30 WO PCT/US1998/027739 patent/WO1999039823A1/en not_active Application Discontinuation
- 1998-12-30 CA CA002285942A patent/CA2285942C/en not_active Expired - Lifetime
- 1998-12-30 UA UA99105411A patent/UA63943C2/uk unknown
-
1999
- 1999-08-02 US US09/366,047 patent/US6156851A/en not_active Expired - Fee Related
- 1999-12-13 US US09/459,612 patent/US6303702B1/en not_active Expired - Lifetime
-
2001
- 2001-12-31 US US10/029,867 patent/US20030057139A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US6153707A (en) | 2000-11-28 |
US6303702B1 (en) | 2001-10-16 |
US20030057139A1 (en) | 2003-03-27 |
CN1252739A (zh) | 2000-05-10 |
CA2285942C (en) | 2007-07-03 |
US6114466A (en) | 2000-09-05 |
US6156851A (en) | 2000-12-05 |
WO1999039823A1 (en) | 1999-08-12 |
UA63943C2 (uk) | 2004-02-16 |
EA001871B1 (ru) | 2001-10-22 |
CA2285942A1 (en) | 1999-08-12 |
EA199900797A1 (ru) | 2000-06-26 |
US6087300A (en) | 2000-07-11 |
JP2001524878A (ja) | 2001-12-04 |
US6133393A (en) | 2000-10-17 |
EP0998350A1 (en) | 2000-05-10 |
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