CN1262960A - 不透射线的聚合物涂料 - Google Patents
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Abstract
一种装置和生产不透射线的医疗植入物的方法。形成一种不透射线的溴化聚氨基甲酸酯涂料和聚氨基甲酸酯管芯的组合。在一个实施方案中,聚氨基甲酸酯涂料包括二异氰酸酯和溴浓度为30%或更多的溴化二醇。将涂料施加在弹性的聚氨基甲酸酯管芯表面上。医疗植入物利用溴化不透射线的聚氨基甲酸酯及弹性热塑性聚氨基甲酸酯管芯而不降低这些需要的特性。
Description
本发明总体涉及医疗植入物,具体涉及包括用于导管、斯坦特固定模(stents)和其它装置的手术用管子或套管的医疗植入物。
在某些医疗过程中,把医疗植入物放入体内。这些植入物包括插入身体孔道、血管或腔洞的导管,用于输送流体、排泄流体、进行检查等。斯坦特固定模是医疗植入物的第二种形式,用于皮肤多植时保持身体孔口或腔洞,或提供管状结构的支撑,例如在吻合手术的过程之中或之后。
通常要求医疗植入物如导管和斯坦特固定模应该是射线透不过的,以使其在宿主体内(host body)的精确定位能够用X射线检查探测到。此外,有利的是,这类医疗植入物是光学透明,使得可以观察到其中流体的流动。
许多管状医疗植入物,如导管和斯坦特固定模,是用聚合物基质制造的。选择那些能够形成管形的聚合物,特别是在导管的情况下,具有足够的的挠曲性以迂回或蜿蜒前进至体内位置的聚合物。在末梢插入中心导管(peripherally insertedcentral catheter)(PICC)的情况中,例如,导管的管子是迂回或蜿蜒前进的,在某种情况下通过病人手臂或颈部静脉到达病人心脏的上腔静脉。管子必须有足够的挠曲性,可在此方式下迂回前进而不致引起病人的创伤。选择作为医疗植入物的聚合物在形成管子后应有足够的强度,使得空腔在通道或孔口不至于瓦解。而且,管子应该耐卷曲或扭结以确保连续的通路。热塑性聚氨基甲酸酯(polyurethane)为基质的聚合物是医疗植入物聚合物的常用选择。
一般,聚氨基甲酸酯是二异氰酸酯(含有两个官能度的异氰酸酯化合物)与软嵌段多元醇(soft-block polyols)之间反应的缩合产物。通常,聚氨基甲酸酯结合低分子量的脂族或芳族二醇或二胺作为链增长剂,而得到挠曲性、强度和耐扭结的有用的弹性体性质。低分子量二醇包括丁二醇、戊二醇、己二醇、庚二醇、苯二甲醇、氢醌二乙醇和乙二醇。二胺包括乙二胺、丁二胺、丙二胺及戊二胺。以二胺为基质的化合物通常形成一类称为聚氨酯脲(polyurethaneureas)的聚氨基甲酸酯。用二醇或二氨链增长剂制成的这些聚氨基甲酸酯的另一个特点是由这些材料制成的导管、斯坦特固定模或血管移植物通常是光学透明的,使得这些聚合物基质成为用作医疗植入物的极好的化合物。然而,遗憾的是这些聚氨基甲酸酯一般不是射线透不过的。
包括不透射线聚氨基甲酸酯的不透射线医疗植入物,如导管,已经开发出来。这些不透射线聚合物结构一般是两种形式。第一种形式的不透射线聚合物掺混有不透射线填料或颜料。典型的填料包括硫酸钡(BaSO4)、碱式碳酸铋或某些金属如钨(W)。另外一些不透射线填料是用来掺混在聚合物管子中的颜料,包括氯氧化铋和其它铋盐,如硝酸氧铋和氧化铋(见美国专利No.3,618,614)。掺混有填料的聚合物的缺点是,虽然这样的聚合物是射线透不过的,但是填料容易使得聚合物不透明。
可用于医疗植入物的第二种形式的不透射线聚合物在聚合物中掺混一种卤化链增长剂。这类聚合物的例子叙述于美国专利No.4,722,344、No.5,177,170和No.5,346,981中。在这些专利中优选的卤素是溴(Br)。在聚合物基质中掺混溴化链增长剂的聚合物通常生产出一种不透射线的和光学透明的管子。
为了赋予有用的射线不透性,卤化链增长化的聚合物,如溴链增长化聚合物,必须含有最小量的卤素(即溴)以赋予聚合物射线不透性。试验研究指出,该最小量的溴,例如在作为导管使用的聚氨基甲酸酯为基质的聚合物中,约为15%。小于这个量容易使管难于用X射线检测。
卤化链增长化的聚合物的第二个问题是,能掺混到聚合物的卤素的最大量受到限制。试验研究显示,例如含溴浓度超过30%的聚合物对于用作医疗植入物,如导管,则太硬。因此,管子的射线不透性受限于可掺混入聚合物基质而不降低由这种聚合物制成的管子性质的溴含量。
如上所述,某些卤化链增长化的聚合物能同时提供射线不透性和光学透明性两者。但是,为了保持无卤化链增长剂的惯用热塑性聚氨基甲酸酯显示出的优异弹性体性质,必须严格限制卤素量。在某些情况中,希望有这样的含射线不透性的卤七链增长化的聚合物,它不受限于掺混入聚合物基质中溴的量。所需要的组合为,能使植入物的射线不透性最大化,而又不使聚合物中卤素浓度超过将会对医疗植入物的物理性质产生负面影响的浓度。
有鉴于此,本发明提供改善射线不透性而又保持光学透明性的一种方法和装置。在一个实施方案中,所述管子具有聚氨基甲酸酯第一层及结合在第一层上的溴化聚氨基甲酸酯第二层。
图1、2和3是本发明的三种等效的实施方案的横截面图。
在生产医疗植入物时,由溴化作用赋予不透射线性质的聚合物材料的射线不透性是受到溴含量限制的,溴可被包括于其中但不改变聚合物性质。可以保持和利用聚合物的挠曲性及完整性,同时提高溴的浓度及由此而来的射线不透性的装置或方法,具有重要的用途。
本发明涉及一种不透射线的装置以及生产这种装置的方法,在本发明的一个实施方案中,医疗植入物,如导管的管子或斯坦特固定模,是由以聚合物为基质的管芯及聚合物涂层制成。聚合物芯包含二异氰酸酯、多元醇和链增长剂,它任选可含至多10%的溴浓度,但是,在另一个实施方案中,没有使用溴浓度。在一个实施方案中,聚合物涂层的溴浓度超过30%重量。在一个实施方案中,聚合物涂层含有二异氰酸酯及溴化共聚单体。在另一个实施方案中,聚合物涂层可以包括化学上可忽略量的多元醇。
图1表示聚合物涂料10施加到管芯20外表面上的一种管子的横断面。(参考数字30代表管子孔道)。图2也表示一种管子的横断面,显示施加聚合物涂料到形成确定孔道30的管壁的管芯20的内表面10上。图3显示聚合物涂料10涂覆在内外表面上的管芯20的横断面。
在一个实施方案中,聚合物芯是采用聚合物涂料涂覆导管管子的形式。聚合物芯的涂覆方法取决于实施方案。在一个实施方案中,聚合物涂料是分别形成后溶解在溶剂中,然后施加在聚合物芯上。溶解聚合物的溶剂在本领域是熟知的,包括四氢呋喃、丙酮、二甲基甲酰胺、二甲基乙酰胺、甲基乙基酮和环己酮。涂覆后,将溶剂除去,在一个实施方案中是用蒸发法留下聚合物涂料粘附在管芯上。在一个实施方案中,可以选择溶剂以温和地作用在管芯表面上,使管芯和涂覆聚合物之间充分地粘合。
在一个实施方案中,管芯是基于它的物理和化学性质选择的聚合物。在管芯是聚氨基甲酸酯的情况下,管芯可包含二异氰酸酯、多元醇及链增长剂。聚合和生产这样的聚氨基甲酸酯的方法和步骤公开于美国专利No.4,722,344、No.5,177,170和No.5,346,981中。这种技术在本领域中是公知的。链增长剂例如是低分子量的二醇,包括但不限于乙二醇、丙二醇、氢醌双羟基乙基醚、丁二醇、戊二醇、己二醇、庚二醇及苯二甲醇及其异构物。链增长剂也可以是二胺,包括但不限于乙二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺。聚氨基甲酸酯的多元醇化合物为例如聚四氢呋喃、聚乙二醇、乙二醇-b-丙二醇-b-乙二醇、聚酯二醇及聚酯碳酸酯二醇(polyestercarbonate diol)。
如上所述的聚氨基甲酸酯通常是光学透明的,但是,该聚氨基甲酸酯有优越的物理性质,包括挠曲性和耐扭结性,使其成为医疗植入物如导管管子的普遍选择。在一个实施方案中,管芯,如所述的聚氨基甲酸酯,也含有少量的卤化链增长剂,特别是溴化链增长剂。在一个实施方案中,管芯是溴化链增长剂的含量少于10重量%的聚氨基甲酸酯。
限制管芯中溴化链增长剂含量的一个原因是保持所需的管芯的物理性质,特别是管芯挠曲性和弹性。大量的溴化链增长剂容易使聚氨基甲酸酯挠曲性降低,因而较不适合例如作导管管子之用。
在一个实施方案中,聚合物涂料是含有二异氰酸酯和溴浓度超过约30重量%的溴化共聚单体的聚氨基甲酸酯。在现有技术的组合物中,由于溴的这种浓度对聚合物性质有潜在影响以及化学计量限制过量的溴结合到聚合物上,所以在聚合物中,溴的浓度是少于聚合物的约30重量%。但是,本发明的聚合物涂料采用溴浓度大于聚合物涂料的约30重量%的共聚单体施加于聚合物管子表面上。
适用于聚氨基甲酸酯为基质的聚合物涂料、可与共聚单体聚合以保持溴浓度大于聚合物涂料的30重量%的合适的二异氰酸酯包括1,3-二异氰酸酯基丙烷、1,4-二异氰酸酯基丁烷、1,6-二异氰酸酯基己烷、环己基二异氰酸酯、1,4-苯二异氰酸酯、甲苯二异氰酸酯、异佛尔酮二异氰酸酯、三甲基-1,6-二异氰酸酯基己烷、1,3-双(异氰酸酯基甲基)苯、1,3-双(异氰酸酯基甲基)环己烷、亚甲基-双二苯基二异氰酸酯及亚甲基-双二环己烷二异氰酸酯。本发明的合适的溴共聚单体包括但不限于溴化双酚A-二乙醇、溴化氢醌二乙醇、溴化苯二甲醇及溴化二苯氧基二乙醇。
一般,聚合物涂料施加在管芯上的量约为装置(管芯及涂层)的10-50重量%。在以聚氨基甲酸酯为基质的管芯和以聚氨基甲酸酯为基质的涂料的实施方案中,在聚合物涂料中的分布在管芯表面的高浓度的溴粘附在管芯且增加装置的射线不透性。虽然表面涂层的溴含量只有整个装置(管芯和涂层)重量的10-15%,其在涂料中的浓度超过30%,显著大于先前工艺中公开的用于射线不透性的聚合物中的溴浓度。并且,达到这样的百分比不会显著地降低聚合物管子的弹性和挠曲性,因为在管的组合物中不需有卤素链增长剂。
在一个实施方案中,管装置由本领域熟知的热挤塑法形成。将芯聚合并挤塑成例如管芯。根据已知技术,制备聚合物涂料是在合适的溶剂中溶解聚合后的聚氨基甲酸酯均聚物组合物,或是在溶剂中分别加入聚氨基甲酸酯成份(例如溴化的共聚单体和二异氰酸酯),并引发聚合作用,然后将聚合物涂料施加于管芯。
一个制备一定量的涂料组合物或溶液中的聚合物涂料的实例是,将63.2g(0.1mole)的四溴双酚A-二乙醇加入到453ml经分子筛干燥约等份的丙酮和甲基乙基酮的混合物中,在此混合物中加入0.02g的辛酸亚锡,然后将混合物加热至50℃并搅拌,当二醇溶解后,将16.8g(0.1mole)的1,6-己烷二异氰酸酯逐滴加入到混合物中,同时温度保持在50-55℃之间。加入二异氰酸酯后,混合物回流8小时后完成反应,这种具体制剂在涂料组合物或溶液中含有约为15重量%的聚氨基甲酸酯均聚物。均聚物组合物或溶液的溴浓度约为6重量%的溴。
下表表示用在本发明的各种其它均聚物及分别采用四溴苯-1,4-二甲醇和四溴双酚A-乙二醇的相应溴浓度。
二异氰酸酯 四溴苯-1,4-二甲醇 四溴双酚A-乙二醇
重量%溴 重量%溴1,3-二异氰酸酯基丙烷 55.14 41.691,4-二异氰酸酯基丁烷 53.84 40.931,6-二异氰酸酯基己烷 51.42 39.50环己烷二异氰酸酯 51.58 39.901,4-苯二异氰酸酯 52.08 39.90甲苯二异氰酸酯 50.92 39.20异佛尔酮二异氰酸酯 47.29 36.99三甲基-1,6-二异氰酸酯基己烷 48.19 37.961,3-双(异氰酸酯基甲基)苯 49.81 38.981,3-双(异氰酸酯基甲基)环己烷 49.50 38.79亚甲基-双二苯基二异氰酸酯 45.42 35.83亚甲基-双二环己烷二异氰酸酯 44.66 35.34
可加入少量的多元醇软段(polyol soft segment)在上述配方中,且仍然获得溴含量大于35%的共聚物。合适的多元醇包括但不限于聚THF、聚乙二醇、乙二醇-b-丙二醇-b-乙二醇、聚酯二醇和聚酯碳酸酯二醇。
在另一个实施方案中,在管芯上施加涂料可由将管子的内外面暴露在聚合物溶液中来完成。在不同的实施方案中,施加涂料可以按照本领域熟知的施加聚氨基甲酸酯的方法。在另一个实施方案中,例如管芯内部的涂层可由使聚合物涂料溶液流动通过管孔道使其只接触内表面来完成。另一种方法,管芯的外部可以用聚合物涂料溶液喷涂,也可以把管芯浸入聚合物涂料溶液池中,由此涂覆管子的内外两表面。在又一个实施方案中,管芯的外表面可由管芯连续绕圈(continuousspooled looping)循环通过聚合物涂料浴池来涂覆。当施加涂料溶液后,管子装置的干燥可以用空气干燥或烘烤来完成。
上述例子中,涂料在均聚物组合物或溶液(15%均聚物)中含有约为6%重量的溴。因此,为生产其中涂料的溴含量大于涂料重量的30%的一种装置,几种(至少5种)涂料组合物将顺序施加(即涂覆、干燥、涂覆等)。可以制造超过含25重量%聚合物的涂料溶液,其溴浓度为12%或更大。即使粘度很高,仍可采用喷涂方法施加涂料。
在前面的详细说明中,本发明是参考其具体的实施方案描述的。但是很明显,可对其作各种修改和变化而不偏离权利要求中规定的本发明的更广泛的精神和范围。因此,本说明书和附图将视为说明而非限制的意思。
Claims (11)
1.一种装置,包括:
一种聚氨基甲酸酯管芯,和
结合于管芯上的不透射线的溴化聚氨基甲酸酯涂层。
2.根据权利要求1的装置,其中聚氨基甲酸酯管芯含有聚合物链增长剂、二异氰酸酯和多元醇化合物的反应产物。
3.根据权利要求1的装置,其中不透射线的聚氨基甲酸酯涂料含有二异氰酸酯和溴化共聚单体的反应产物。
4.根据权利要求1的装置,其中溴化聚氨基甲酸酯涂料的溴含量至少约为30重量%。
5.根据权利要求1的装置,其中溴化聚氨基甲酸酯涂料的溴含量约为管子涂覆部分重量的10-15%的。
6.一种方法,包括下列步骤:
提供聚氨基甲酸酯的管芯,及
用不透射线的聚合物涂覆管芯。
7.根据权利要求6的方法,其中不透射线的聚合物是溴化聚氨基甲酸酯。
8.根据权利要求6的方法,其中涂覆步骤包括:
将管芯浸入溴化聚氨基甲酸酯浴池中,及
除去溶剂使溴化聚氨基甲酸酯层沉积在管芯上。
9.根据权利要求6的方法,其中涂覆步骤包括:
将管芯在溴化聚氨基甲酸酯浴池中连续循环以接触管子外表面;及
除去溶剂使溴化聚氨基甲酸酯层沉积在管芯外表面上。
10.根据权利要求6的方法,其中涂覆步骤包括:
用不透射线的聚氨基甲酸酯喷涂管芯。
11.根据权利要求6的方法,还包括:
在溶剂中,混合溴化聚氨基甲酸酯,所述溴化聚氨基甲酸酯含有二异氰酸酯化合物及溴含量约为30重量%或更多的异氰酸酯反应性溴化共聚单体化合物。
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US09/224,463 US6623823B1 (en) | 1998-12-31 | 1998-12-31 | Radiopaque polymer coating |
US09/224,463 | 1998-12-31 |
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EP (1) | EP1016424A1 (zh) |
JP (1) | JP2000210379A (zh) |
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CN (1) | CN1262960A (zh) |
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CA (1) | CA2292183A1 (zh) |
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CN100559983C (zh) * | 2004-07-01 | 2009-11-18 | 蛋白毛发涂料工厂有限公司 | 改进的假发 |
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WO2002078779A1 (fr) * | 2001-03-27 | 2002-10-10 | Zeon Corporation | Fil-guide medical |
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CA2501643C (en) * | 2002-10-11 | 2013-12-31 | University Of Connecticut | Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments |
US7794494B2 (en) | 2002-10-11 | 2010-09-14 | Boston Scientific Scimed, Inc. | Implantable medical devices |
RU2373958C2 (ru) * | 2003-09-25 | 2009-11-27 | Рутгерс, Дзе Стейт Юниверсити | Полимерные по существу рентгеноконтрастные продукты для эмболотерапии |
EP1789097B1 (en) * | 2004-08-13 | 2014-08-13 | Rutgers, The State University | Radiopaque polymeric stents |
US20060034769A1 (en) * | 2004-08-13 | 2006-02-16 | Rutgers, The State University | Radiopaque polymeric stents |
JP4721322B2 (ja) * | 2004-10-18 | 2011-07-13 | 日本シャーウッド株式会社 | カテーテル |
US20060210700A1 (en) * | 2005-03-18 | 2006-09-21 | Lachner Thomas F | Flexible and plastic radiopaque laminate composition |
KR100678435B1 (ko) | 2005-04-13 | 2007-02-02 | 주식회사 에스앤지바이오텍 | 혈관 벽 차폐용 튜브형 스텐트 |
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US20110009961A1 (en) * | 2009-07-13 | 2011-01-13 | Gyrus Ent, L.L.C. | Radiopaque middle ear prosthesis |
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- 1999-12-06 CA CA002292183A patent/CA2292183A1/en not_active Abandoned
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