CN110997746B - 用于增强的耐久性的光交联聚合物 - Google Patents

用于增强的耐久性的光交联聚合物 Download PDF

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CN110997746B
CN110997746B CN201880052503.XA CN201880052503A CN110997746B CN 110997746 B CN110997746 B CN 110997746B CN 201880052503 A CN201880052503 A CN 201880052503A CN 110997746 B CN110997746 B CN 110997746B
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约瑟夫·T·小德兰尼
大卫·R·伍尔夫曼
帕特里克·威洛比
安德鲁·J·罗
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Abstract

一种嵌段共聚物，其包括：多个聚合链和将所述多个聚合链连在一起的多个交联化合物残基。所述多个聚合链形成多个硬域和多个软域。每个聚合链包括多个软链段和多个硬链段。所述多个软链段包括聚异丁烯二醇或二胺残基。所述多个软链段形成所述多个软域。所述多个硬链段包括二异氰酸酯残基。所述多个硬链段形成所述多个硬域。所述交联化合物残基将所述多个聚合链的硬链段连在一起。

Description

用于增强的耐久性的光交联聚合物
相关申请的交叉引用
本申请要求于2017年8月17日提交的美国临时申请号62/547,059的优先权，通过引用将其整体并入本文。
技术领域
本公开涉及嵌段共聚物。更具体地，本公开涉及交联的基于聚异丁烯的聚氨酯、制备交联的基于聚异丁烯的聚氨酯的方法和含有交联的基于聚异丁烯的聚氨酯的医疗设备。
背景技术
聚合材料广泛用于可植入医疗设备领域中。例如，聚合材料如硅橡胶、聚氨酯和含氟聚合物用作医疗导线、支架和其它设备的涂层和/或绝缘材料。聚合材料也可以用于置换心脏瓣膜的小叶。
嵌段共聚物是由聚合单体的交替段制成的聚合材料。聚异丁烯-聚氨酯嵌段共聚物是可以具有许多期望的物理和机械特性包括热稳定性、耐化学性、生物相容性和不透气性等的聚合材料。
发明内容
实施例1是一种嵌段共聚物，其包括：多个聚合链和将所述多个聚合链连在一起的多个交联化合物残基。所述多个聚合链形成多个硬域和多个软域。每个聚合链包括多个软链段和多个硬链段。所述多个软链段包括聚异丁烯二醇或二胺残基。所述多个软链段形成所述多个软域。所述多个硬链段包括二异氰酸酯残基。所述多个硬链段形成所述多个硬域。所述交联化合物残基将所述多个聚合链的硬链段连在一起。
实施例2是如实施例1所述的嵌段共聚物，其中所述交联化合物残基是多官能二苯甲酮的残基。
实施例3是如实施例2所述的嵌段共聚物，其中所述多官能二苯甲酮具有大于2且小于7的二苯甲酮官能度。
实施例4是如实施例1-3中任一项所述的嵌段共聚物，其中所述共聚物包括第一部分和第二部分，所述多个交联化合物残基设置在第一部分的硬域中，第二部分不含所述多个交联化合物残基。
实施例5是如实施例4所述的嵌段共聚物，其中所述共聚物进一步包括交联化合物，其中所述交联化合物是所述多个交联化合物残基的前体，所述交联化合物设置在第二部分的硬域中。
实施例6是如实施例1-5中任一项所述的嵌段共聚物，其中所述二异氰酸酯残基包括4,4’-亚甲基二苯基二异氰酸酯残基。
实施例7是如实施例1-6中任一项所述的嵌段共聚物，其中所述硬链段进一步包括扩链剂残基。
实施例8是如实施例7所述的嵌段共聚物，其中所述扩链剂残基是1,4-丁二醇残基。
实施例9是如实施例1-8中任一项所述的嵌段共聚物，其中所述聚异丁烯二醇或二胺残基是5-叔丁基-1,3-双(1-甲氧基-1-甲基乙基)苯。
实施例10是如实施例1-9中任一项所述的嵌段共聚物，其中所述多个交联化合物通过共价键将所述多个聚合链的硬链段的至少一部分连在一起。
实施例11是一种医疗设备，其包括如权利要求1-10中任一项所述的嵌段共聚物。
实施例12是如实施例11所述的医疗设备，其中所述医疗设备是心脏瓣膜。
实施例13是一种制备嵌段共聚物的方法。所述方法包括将包括软链段组分和硬链段组分的混合物加热至高温。所述软链段组分包括至少一种聚异丁烯二醇或二胺。所述硬链段组分包括至少一种二异氰酸酯。所述方法进一步包括将所述加热的混合物保持足以使所述软链段组分和所述硬链段组分形成包括软链段和硬链段的多个聚合链的时间。所述聚合链形成软域和硬域的聚合物基体，所述软域包括聚合链的软链段，所述硬域包括聚合链的硬链段。所述方法进一步包括将交联化合物加入到所述聚合物基体中，所述交联化合物集中在所述硬域中。所述方法进一步包括将所述聚合物基体的至少一部分暴露于辐射以活化所述交联化合物。活化的交联化合物键合至暴露部分中的聚合链。所述键合集中在硬域中以形成嵌段共聚物。
实施例14是如实施例13所述的方法，其中所述交联化合物是多官能二苯甲酮。
实施例15是如实施例13或14中任一项所述的方法，其中将整个聚合物基体暴露至辐射。
实施例16是一种嵌段共聚物，其包括：多个聚合链和将所述多个聚合链连在一起的多个交联化合物残基。所述多个聚合链形成多个硬域和多个软域。每个聚合链包括多个软链段和多个硬链段。所述多个软链段包括聚异丁烯二醇或二胺残基。所述多个软链段形成所述多个软域。所述多个硬链段包括二异氰酸酯残基。所述多个硬链段形成所述多个硬域。所述交联化合物残基通过共价键将所述多个聚合链的硬链段连在一起。
实施例17是如实施例16所述的嵌段共聚物，其中所述交联化合物残基是多官能二苯甲酮的残基。
实施例18是如实施例17所述的嵌段共聚物，其中所述多官能二苯甲酮具有大于2且小于7的二苯甲酮官能度。
实施例19是如实施例16-18中任一项所述的嵌段共聚物，其中所述共聚物包括第一部分和第二部分，所述多个交联化合物残基设置在第一部分的硬域中，第二部分不含所述多个交联化合物残基。
实施例20是如实施例19所述的嵌段共聚物，其中所述共聚物进一步包括交联化合物，其中所述交联化合物是所述多个交联化合物残基的前体，所述交联化合物设置在第二部分的硬域中。
实施例21是如实施例16-20中任一项所述的嵌段共聚物，其中所述二异氰酸酯残基包括4,4’-亚甲基二苯基二异氰酸酯残基。
实施例22是如实施例16所述的嵌段共聚物，其中所述硬链段进一步包括扩链剂残基。
实施例23是如实施例22所述的嵌段共聚物，其中所述扩链剂残基是1,4-丁二醇残基。
实施例24是一种包括嵌段共聚物的医疗设备。所述嵌段共聚物包括多个聚合链和将所述多个聚合链连在一起的多个交联化合物残基。所述多个聚合链形成多个硬域和多个软域。每个聚合链包括多个软链段和多个硬链段。所述多个软链段包括聚异丁烯二醇或二胺残基。所述多个软链段形成所述多个软域。所述多个硬链段包括二异氰酸酯残基。所述多个硬链段形成所述多个硬域。所述交联化合物残基通过共价键将所述多个聚合链的硬链段连在一起。
实施例25是如实施例24所述的医疗设备，其中所述交联化合物残基是多官能二苯甲酮的残基。
实施例26是如实施例25所述的医疗设备，其中所述多官能二苯甲酮具有大于2且小于7的二苯甲酮官能度。
实施例27是如实施例24-26中任一项所述的医疗设备，其中所述共聚物包括第一部分和第二部分，所述多个交联化合物残基设置在第一部分的硬域中，第二部分不含所述多个交联化合物残基。
实施例28是如实施例27所述的医疗设备，其中所述共聚物进一步包括交联化合物，其中所述交联化合物是所述多个交联化合物残基的前体，所述交联化合物设置在第二部分的硬域中。
实施例29是如实施例24-28中任一项所述的医疗设备，其中所述二异氰酸酯残基包括4,4’-亚甲基二苯基二异氰酸酯残基。
实施例30是如实施例24-29中任一项所述的医疗设备，其中所述硬链段进一步包括扩链剂残基。
实施例31是如实施例30所述的医疗设备，其中所述扩链剂残基是1,4-丁二醇残基。
实施例32是如实施例24-31中任一项所述的医疗设备，其中所述医疗设备是心脏瓣膜。
实施例33是一种制备嵌段共聚物的方法。所述方法包括将包括软链段组分和硬链段组分的混合物加热至高温。所述软链段组分包括至少一种聚异丁烯二醇或二胺。所述硬链段组分包括至少一种二异氰酸酯。所述方法进一步包括将所述加热的混合物保持足以使所述软链段组分和所述硬链段组分形成包括软链段和硬链段的多个聚合链的时间。所述聚合链形成软域和硬域的聚合物基体，所述软域包括聚合链的软链段，所述硬域包括聚合链的硬链段。所述方法进一步包括将交联化合物加入到所述聚合物基体中，所述交联化合物集中在所述硬域中。所述方法进一步包括将所述聚合物基体的至少一部分暴露于辐射以活化所述交联化合物。活化的交联化合物共价键合至暴露部分中的聚合链。所述键合集中在硬域中以形成嵌段共聚物。
实施例34是如实施例33所述的方法，其中所述交联化合物是多官能二苯甲酮。
实施例35是如实施例33或34中任一项所述的方法，其中将整个聚合物基体暴露于辐射。
虽然公开了多个实施例，但是根据示出和描述示例性实施方案的以下详细描述，根据本公开的其他实施例对于本领域技术人员将变得显而易见。因此，附图和详细描述应被认为实质上是示例性的而非限制性的。
附图说明
图1是根据本公开的实施方案的心脏瓣膜的透视图。
图2-4是根据本公开的实施方案的PIB-PUR嵌段共聚物的构造的示意图。
图5是根据本公开的实施方案的PIB-PUR嵌段共聚物的另一个实施方案的示意图。
图6-9是示出根据本公开的实施方案的适合于形成PIB-PUR嵌段共聚物的多官能二苯甲酮的实施例的化学图。
虽然本公开可修改为各种修改和供选择的形式，但具体实施方案已通过附图中的实施例示出，并且在下面详细描述。然而，本发明不是要将本公开限制于所描述的特定实施方案。相反，本公开旨在覆盖落入由所附权利要求限定的本公开的范围内的所有修改、等同方案和替代方案。
具体实施方式
医疗设备可以包括代替天然组织的合成聚合物。例如，在一些置换心脏瓣膜中，合成聚合物可以替代形成瓣膜小叶的天然组织。天然组织包括胶原蛋白和弹性蛋白。不希望受任何理论的束缚，据信胶原蛋白和弹性蛋白的组合允许瓣叶在低应力下容易地移动，然后当达到较高应力时显著地硬化。这种非线性“应变硬化”提供了一种天然心脏瓣膜，其柔软、有效并且能够在低应力水平下以很小的应力移动，但是在较高应力水平下硬化以减少蠕变引起的损伤。
聚异丁烯聚氨酯(PIB-PUR)嵌段共聚物是适用于多种医疗应用的耐久的、生物相容性聚合物。PIB-PUR嵌段共聚物由包括硬链段和软链段的聚合链组成。构成硬链段的组分比构成软链段的组分极性更大。当形成PIB-PUR嵌段共聚物时，在硬链段组分和软链段组分之间存在由缔合的氢键和由硬链段组分的极性引起的分子间力驱动的自然相分离。此自组织行为可以提供本体材料的物理交联，这可以提供PIB-PUR嵌段共聚物的一些有利特性。
在热塑性PIB-PUR嵌段共聚物中，氢键和分子间力起作用以将聚合链组织到聚合物基体中，使得相邻聚合链的硬链段组分键合在一起以形成硬域，留下软链段组分以形成软域。在硬域中将聚合链键合在一起的氢键的强度和分子间力较弱，这使得聚合链在施加热或应力时彼此分离，然后当热或应力去除时重新连接。由热塑性PIB-PUR嵌段共聚物形成的瓣膜小叶可以是软的并且由于弱的键合而可以在应力下有效地移动。然而，由于弱键合，，随着弱键的断裂和重新形成使聚合物基体变形，热塑性PIB-PUR嵌段共聚物可以在应力下蠕变，导致蠕变引起的小叶损伤。在一些情况下，蠕变引起的损伤可使小叶变形到足以导致瓣膜泄漏。
在热固性PIB-PUR嵌段共聚物中，聚合链通过共价键彼此交联。共价键可以一直沿着聚合链在软域以及硬域中形成，从而产生刚性聚合物基体。共价键的强度比通过氢键和分子间力形成的键的强度大大约三个数量级。结果，由热固性PIB-PUR嵌段共聚物形成的瓣膜小叶可能不在应力下蠕变。然而，热固性PIB-PUR嵌段共聚物是刚性的，并且在应力下可能不容易移动，因此由热固性PIB-PUR嵌段共聚物制成的瓣膜小叶由于需要更多能量来起作用而可能较低效。因此，热塑性PIB-PUR嵌段共聚物和热固性PIB-PUR嵌段共聚物都不表现出在一些天然组织如心脏瓣膜小叶中发现的所需非线性应变硬化。
本发明的实施方案包括PIB-PUR嵌段共聚物，其是软的并且容易在低应力下移动，并且当达到较高应力时显著硬化。这样的PIB-PUR嵌段共聚物可表现出在一些天然组织中发现的非线性应变硬化，并且可用于例如置换心脏瓣膜的小叶中，以提供与其他合成聚合物相比更有效且更耐久的心脏瓣膜。
图1是根据本公开的实施方案的心脏瓣膜10的透视图。如图1中所示，心脏瓣膜10是包括连接至外壳14的三个瓣膜小叶12的三叶心脏瓣膜。外壳14包括三个支柱16，当安装在患者心脏中(未示出)时，支柱16从支架结构18沿下游方向延伸。支架结构18可以是被配置为植入患者心脏内的圆环。三个瓣膜小叶12的每一个连接到三个支柱16中的两个和支架结构18。在一些实施方案中，根据下面描述的实施方案，三个瓣膜小叶12和外壳14可以由PIB-PUR嵌段共聚物一体形成。在这样的实施方案中，外壳14可以含有由比嵌段共聚物更刚性的材料形成的内部骨架(未示出)，并且瓣膜小叶12和外壳14的聚合物部分可以围绕内部骨架一体形成。在其他实施方案中，三个瓣膜小叶12可以由根据实施方案的PIB-PUR嵌段共聚物形成，然后附接至外壳14。在这样的实施方案中，外壳14可以由除嵌段共聚物以外的材料形成。
在使用中，心脏瓣膜10可具有如图1所示的闭合位置和打开配置(未示出)。在闭合配置中，三个瓣膜小叶12中的每一个具有凹曲度并且彼此接触，但不彼此附接。当下游侧(与支柱16相同的一侧)的血压大于上游侧(与下游侧相对)的血压时，三个瓣膜小叶12被施加在瓣膜小叶12的凹曲度上的血压推到一起，以密封心脏瓣膜10并防止血液在上游方向流动。当上游侧的血压大于下游侧的血压时，瓣膜小叶12被强制分开，形成打开配置以允许血液从上游侧流到下游侧。由于PIB-PUR嵌段共聚物的柔软性质，三个瓣膜小叶12在打开配置和闭合配置之间容易且有效地移动。但是当经受较高应力时，其可能扭曲瓣膜小叶12的形状，PIB-PUR嵌段共聚物硬化，这保护三个瓣膜小叶12不受蠕变引起的损伤。
尽管上述实施方案包括结合到心脏瓣膜10中的根据下述实施方案的PIB-PUR嵌段共聚物，但是应理解，根据下述实施方案的PIB-PUR嵌段共聚物可以结合到可以植入或嵌入患者体内并且经受显著量的动态应力的各种医疗设备中的任一种中。实施例医疗设备可以包括但不限于：用于节律管理设备的电导线和电缆、人工心包、主动脉袖带和导管，如胆汁引流导管。
图2-4是根据本公开的实施方案的PIB-PUR嵌段共聚物的构造的示意图。图2示出了包括形成多个硬域24和多个软域26的多个聚合链22的PIB-PUR嵌段共聚物基体20。聚合链22的每个可以包括一个或多个软链段28和一个或多个硬链段30。硬链段30的氢键和分子间力起作用以将多种聚合链22组织到PIB-PUR嵌段共聚物基体20中，以使得相邻聚合链22的硬链段30键合在一起以形成多个硬域24，留下软链段28以形成多个软域26。
软链段28可以由聚异丁烯二醇或二胺形成，因此包括聚异丁烯二醇或二胺的残基。例如，聚异丁烯二醇可以是以双官能引发剂化合物如5-叔丁基-1,3-双(1-甲氧基-1-甲基乙基)苯(受阻二枯基醚)开始通过碳阳离子聚合形成的远螯聚异丁烯二醇。所得化合物可以是根据分子式I的聚异丁烯二醇：
分子式I：
Figure BDA0002383335850000091
任选地，在一些实施方案中，软链段可另外由一种或多种聚醚二醇形成，因此包括一种或多种聚醚二醇的残基。合适的任选聚醚二醇可以包括聚四亚甲基氧化物二醇(PTMO二醇)、聚六亚甲基氧化物二醇(PHMO二醇)、聚亚辛基氧化物二醇和聚亚癸基氧化物二醇。
硬链段30可以由多官能异氰酸酯如二异氰酸酯包括脂族和芳族二异氰酸酯形成，因此包括二异氰酸酯残基。用于形成PIB-PUR嵌段共聚物基体20的二异氰酸酯可以包括芳族和非芳族(例如脂族)二异氰酸酯。芳族二异氰酸酯可以选自下列适当成分：4,4’-亚甲基二苯基二异氰酸酯(MDI)、2,4’-亚甲基二苯基二异氰酸酯(2,4-MDI)、2,4-和/或2,6-甲苯二异氰酸酯(TDI)、1,5-萘二异氰酸酯(NDI)、对苯二异氰酸酯、3,3’-亚甲苯-4,4’-二异氰酸酯和3,3’-二甲基-二苯基甲烷-4,4’-二异氰酸酯。非芳族二异氰酸酯可以选自下列适当成分：1,6-六亚甲基二异氰酸酯(HDI)、4,4’-二环己基甲烷二异氰酸酯(H12-MDI)、3-异氰酸根合甲基-3,5,5-三甲基环己基异氰酸酯(异佛尔酮二异氰酸酯或IPDI)、环己基二异氰酸酯和2,2,4-三甲基-1,6-六亚甲基二异氰酸酯(TMDI)。
在一些实施方案中，硬链段30可以进一步包括一种或多种任选的扩链剂残基。扩链剂可以增加硬链段长度，这进而可以导致具有更高拉伸模量、更低断裂伸长率和/或增加的强度的共聚物。扩链剂可以由脂族或芳族二醇形成，在这种情况下，尿烷键在与异氰酸酯基反应时形成。扩链剂可以选自下列适当成分：1,4-环己烷二甲醇、α,ω-链烷二醇，如乙二醇(1,2-乙二醇)、1,4-丁二醇(BDO)和1,6-己二醇。
图3示出了PIB-PUR嵌段共聚物基体32。PIB-PUR嵌段共聚物基体32除了包括交联化合物34以外与图2的PIB-PUR嵌段共聚物基体20相同。交联化合物34是多官能化合物以使其能够键合至至少两个不同的聚合链22以使聚合链22交联。交联化合物34比构成软链段28的组分极性更大，并且对硬链段30的亲和力比对软链段28的亲和力大。交联化合物34对硬链段30的更大的亲和力驱使交联化合物34在当交联化合物34扩散通过PIB-PUR嵌段共聚物基体32时置于硬链段30附近和之中的硬域24中。因此，交联化合物34将集中于硬域24中，如图3中所示。
图4示出了PIB-PUR嵌段共聚物基体36。除了PIB-PUR嵌段共聚物基体36已经暴露于辐射以活化交联化合物34(图3)之外，PIB-PUR嵌段共聚物基体36可以与图3的PIB-PUR嵌段共聚物基体32相同。辐射通过形成容易与聚合链22上最近的碳-氢键形成共价键的基团来活化交联化合物34。由于交联化合物34对硬链段30的亲和力，最近的碳-氢键将最可能在硬链段30之一中。由于交联化合物34是多官能的，交联化合物34可共价键合到多个聚合链22以形成将聚合链22连在一起的交联化合物残基38。因此，交联化合物34是交联化合物残基38的前体。如图4中所示，PIB-PUR嵌段共聚物基体36包括将多个聚合链22连在一起的多个交联化合物残基38。所述交联化合物残基38将多个聚合链22的硬链段30连在一起以形成PIB-PUR嵌段共聚物基体36。
具有图4中所示的PIB-PUR嵌段共聚物基体36的PIB-PUR嵌段共聚物可以是软的，并且由于未交联的多个软域26而在低应力下容易移动。当由于软域26达到其弹性程度而达到较高应力时，共价交联的多个硬域24由于将聚合链22保持在一起可使PIB-PUR嵌段共聚物基体36显著硬化。共价交联的硬域24的强度可以降低或防止蠕变引起的损伤。因此，PIB-PUR嵌段共聚物基体36可表现出在一些天然组织中发现的非线性应变硬化，并且可用于例如心脏瓣膜10中的心脏瓣膜小叶12中，以提供与其他合成聚合物相比更有效且更耐久的心脏瓣膜10。
图5是根据本公开的实施方案的PIB-PUR嵌段共聚物的另一个实施方案的示意图。图5示出了包括第一部分42和第二部分44的PIB-PUR嵌段共聚物基体40。第一部分42已暴露于辐射以活化交联化合物34，以形成将多个聚合链22的硬链段30连在一起的交联化合物残基38。因此，第一部分42基本上类似于PIB-PUR嵌段共聚物基体36(图4)。第二部分44与PIB-PUR嵌段共聚物基体32(图3)基本相似，因为第二部分44未暴露于辐射，因此交联化合物34保留为集中在第二部分44的硬域24中的前体。因此，在图5的实施方案中，仅在第一部分42中选择性地活化了交联化合物34以形成将第一部分42中的多个聚合链22的硬链段30连在一起的交联化合物残基38并且第二部分44不含交联残基38。在其他实施方案中，第二部分44可以由于例如轻微疏忽或背景暴露于辐射而不完全不含交联残基38，但是可以基本上不含交联化合物残基38。基本上不含是指第二部分44中的交联化合物34的小于10％、小于8％、小于6％、小于4％、小于2％、小于1％、小于0.5％或小于0.1％或小于任何两个前述百分比之间的任一百分比已经被活化并形成交联残基38。以此方式，可以改变PIB-PUR嵌段共聚物基体40的刚度以匹配天然组织如心脏瓣膜小叶12(图1)中发现的刚度变化。
多个硬域24可以包括非晶部分和晶体部分。直到被活化，交联化合物34可以通过干扰晶体部分的形成而在硬域24中充当增塑剂。然而，由于其极性，交联化合物34可以不驱使硬链段30分离。一旦被活化，交联化合物34用永久共价键取代多个硬域24中的非永久性氢键。因此，在一些实施方案中，交联化合物34可以充当可交联增塑剂。
在以上参考图3-5描述的实施方案中，所有交联化合物34和/或所有交联化合物残基38被显示为位于硬域24中。然而，应理解实施方案包括如上所述的嵌段共聚物，其中交联化合物34和/或交联化合物残基38基本上位于硬域24中。为了本申请的目的，基本上位于硬域24中是指至少90％、92％、94％、96％、98％、99％、99.5％或99.9％或任意两个前述百分比之间的至少任一百分比位于硬域24中。当一些交联化合物34扩散得不够远以至于到达硬域34时，可形成这些实施方案。在这样的实施方案中，交联化合物34和/或交联化合物残基38可以基本上位于硬域24中，并且剩余的交联化合物34和/或剩余的交联化合物残基38可以位于软域26中。在这样的实施方案中，剩余的交联化合物残基38可以将多个聚合链22的一些软链段连在一起。为了本申请的目的，集中于硬域24可以包括位于硬域24中和/或基本上位于硬域24中。
在一些实施方案中，交联化合物34是多官能二苯甲酮。由于二苯甲酮和配位分子核，多官能二苯甲酮是富芳族的并且极性很大。在一些实施方案中，多官能二苯甲酮可以是官能度为2的二苯酰苯(dibenzophenone)，例如，4,4”-氧基-二苯甲酮(CAS:6966-89-8)。在一些其它实施方案中，多官能二苯甲酮可以具有大于2且小于7的官能度以提高更大的交联。图6-9是示出根据本公开的实施方案的适合于形成PIB-PUR嵌段共聚物的多官能二苯甲酮的实施例的化学图。图6中示出的多官能二苯甲酮是1,3,5-三[3-(4-苯甲酰苯氧基)-2-羟丙基]-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(CAS#917248-81-8)，其官能度为三，因为其包括三个二苯甲酮基团。图7中示出的多官能二苯甲酮是1,1’-[[2,2-双[4-苯甲酰苯氧基)甲基]-1,3-丙二基]双(氧基-4,1-亚苯基)]双[1-苯基甲酮](CAS#1579231-41-6)，其官能度为四，因为其包括四个二苯甲酮基团。图8中示出的多官能二苯甲酮是1,1’,1”,1”’-[1,2-乙烷二基双(次氮基二-4,1-亚苯基)]四[1-苯基甲酮](CAS#1622264-28-1)，其官能度也为四，因为其包括四个二苯甲酮基团。图9中示出的多官能二苯甲酮是2,2,4,4,6,6-六(4-苯甲酰基苯氧基)-2,2,4,4,6,6-六氢化-1,3,5,2,4,6-三氮杂三磷杂苯(CAS#84039-16-7)，其官能度为六，因为其包括六个二苯甲酮基团。
现有技术引发剂体系可以具有产生自由基的单独的交联引发剂，所述自由基然后必须传播到交联剂以成功交联。这样的系统可以要求维持惰性气氛以防止氧在自由基到达交联剂之前与其反应。在交联化合物34是多官能二苯甲酮的实施方案中，交联化合物34既充当交联引发剂又充当交联剂。对于这样的实施方案，不需要保持惰性气氛，因为不需要由引发剂产生的自由基传播，因为活化的交联化合物34直接键合到聚合链22。
PIB-PUR嵌段共聚物基体20可以通过将包括软链段成分和硬链段成分的混合物加热到高温来制备。所述高温是高于室温的任何温度，如30℃、40℃、50℃、60℃、70℃、80℃、90℃或100℃，或在任何前述温度之间的任何温度。软链段组分可以包括至少一种聚异丁烯二醇或二胺，如根据以上分子式I的聚异丁烯二醇。硬链段组分可以包括至少一种二异氰酸酯，如4,4’-亚甲基二苯基二异氰酸酯。在一些实施方案中，硬链段组分可以进一步包括扩链剂，例如，1,4-丁二醇。将所述加热的混合物保持足以使所述软链段组分和所述硬链段组分形成包括软链段28和硬链段30的多个聚合链22的时间，所述聚合链自组织以形成软域26和硬域24的PIB-PUR嵌段共聚物基体20，所述软域26主要包括聚合链22的软链段28，所述硬域24主要包括聚合链22的硬链段30，如图2所示。
在一些实施方案中，可以向混合物添加催化剂以增加反应速度并显著减少基本完成反应的时间。2-乙基己酸锡(II)和2,6-二甲基吡啶是这样的催化剂的实例。
一旦形成PIB-PUR嵌段共聚物基体20，交联化合物34可以加入到PIB-PUR嵌段共聚物基体20中。交联化合物34例如可以是上述多官能二苯甲酮的任一种。交联化合物34由于其极性而对硬链段30具有亲和力，并且将扩散通过聚合链22并集中在硬域24中以形成如图3中所示的PIB-PUR嵌段共聚物基体32。
在一些实施方案中，至少第一部分42可以暴露于辐射以活化交联化合物34，交联化合物34键合至第一部分42中的聚合链22以形成如图5中所示的PIB-PUR嵌段共聚物基体40。在其他实施方案中，可以将整个PIB-PUR嵌段共聚物基体32暴露于辐射以活化交联化合物34，所述交联化合物34键合至聚合链22。在所有实施方案中，所述键合集中在硬域24中。
在一些实施方案中，将PIB-PUR嵌段共聚物基体32或PIB-PUR嵌段共聚物基体40的第一部分42暴露于辐射以活化交联化合物34可以包括暴露于光化光子、电子束或红外源。在一些实施方案中，光化光子可以来自紫外光源，如果仅第一部分42被暴露，所述紫外光源例如可以是部分掩盖的。在一些其它实施方案中，红外源可以来自红外激光。
在不脱离本公开的范围的情况下，可以对所讨论的实施方案进行各种修改和添加。例如，虽然上述实施方案涉及特定特征，但是本公开的范围还包括具有特征的不同组合的实施方案和不包括所有所述特征的实施方案。因此，本公开的范围旨在涵盖落入权利要求及其所有等同方案的范围内的所有这样的替代、修改和变化。
实施例
光交联的聚异丁烯-聚醚-聚氨酯嵌段共聚物的制备
本实施例中，说明了光交联的聚异丁烯-聚醚-聚氨酯嵌段共聚物的制备。将3g的聚异丁烯-聚醚-聚氨酯嵌段共聚物溶解于27g的四氢呋喃(THF)中。聚异丁烯-聚醚-聚氨酯嵌段共聚物由55wt.％的聚异丁烯二醇残基、10wt.％的聚四亚甲基氧化物二醇残基和35wt.％的化学计量比的4,4’-亚甲基二苯基二异氰酸酯和1,4-丁二醇组成。将10wt.％聚异丁烯-聚醚-聚氨酯嵌段共聚物溶液的10g试样用0.1wt.％1,3,5-三[3-(4-苯甲酰基苯氧基)-2-羟丙基]-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮和0.9wt.％1-羟基环己基苯基酮的异丙醇溶液的1g试样处理。将所得溶液在两个铝盘中流延成膜，并置于在50℃氮气流下的烘箱中直至干燥。然后使用Dymax UV固化室处理其中一层膜4分钟，使其静置1小时，翻转，并以类似方式在另一侧处理1小时以固化或交联聚异丁烯-聚醚-聚氨酯嵌段共聚物。另一层膜没有接受UV处理。
将未处理的膜浸入THF中并溶解。将UV处理的膜也浸入THF中，但没有显示出溶解的迹象，因此表明膜已经成功地共价交联，并证实UV引发的交联已经如预期的那样起作用。

Claims (13)

1.一种嵌段共聚物，其包含：
形成多个硬域和多个软域的多个聚合链，每个聚合链包括：
包括聚异丁烯二醇或二胺残基的多个软链段，所述多个软链段形成所述多个软域；和
包括二异氰酸酯残基的多个硬链段，所述多个硬链段形成所述多个硬域；和
多个交联化合物残基，所述交联化合物残基将所述多个聚合链连在一起，所述交联化合物残基将所述多个聚合链的硬链段连在一起，其中所述交联化合物残基是多官能二苯甲酮的残基。
2.如权利要求1所述的嵌段共聚物，其中所述多官能二苯甲酮具有大于2且小于7的二苯甲酮官能度。
3.如权利要求1或2所述的嵌段共聚物，其中所述共聚物包括第一部分和第二部分，所述多个交联化合物残基设置在第一部分的硬域中，第二部分不含所述多个交联化合物残基。
4.如权利要求3所述的嵌段共聚物，其中所述共聚物进一步包括交联化合物，其中所述交联化合物是所述多个交联化合物残基的前体，所述交联化合物设置在第二部分的硬域中。
5.如权利要求1或2所述的嵌段共聚物，其中所述二异氰酸酯残基包括4,4’-亚甲基二苯基二异氰酸酯残基。
6.如权利要求1或2所述的嵌段共聚物，其中所述硬链段进一步包括扩链剂残基。
7.如权利要求1或2所述的嵌段共聚物，其中所述软链段进一步包括聚醚二醇的残基。
8.如权利要求1或2所述的嵌段共聚物，其中所述聚异丁烯二醇或二胺残基是5-叔丁基-1,3-双(1-甲氧基-1-甲基乙基)苯。
9.如权利要求1或2所述的嵌段共聚物，其中所述多个交联化合物残基通过共价键将所述多个聚合链的硬链段的至少一部分连在一起。
10.一种医疗设备，其包含如权利要求1-9中任一项所述的嵌段共聚物。
11.如权利要求10所述的医疗设备，其中所述医疗设备是心脏瓣膜。
12.一种制备嵌段共聚物的方法，所述方法包含：
将包括软链段组分和硬链段组分的混合物加热至高温，所述软链段组分包括至少一种聚异丁烯二醇或二胺，所述硬链段组分包括至少一种二异氰酸酯；
将所述加热的混合物保持足以使所述软链段组分和所述硬链段组分形成包括软链段和硬链段的多个聚合链的时间，所述聚合链形成软域和硬域的聚合物基体，所述软域包括聚合链的软链段，所述硬域包括聚合链的硬链段；
向所述聚合物基体中加入交联化合物，所述交联化合物集中在所述硬域中；
将所述聚合物基体的至少一部分暴露于辐射以活化所述交联化合物，活化的交联化合物与暴露部分中的聚合链键合，所述键合集中在硬域中以形成嵌段共聚物，其中所述交联化合物是多官能二苯甲酮。
13.如权利要求12所述的方法，其中将整个聚合物基体暴露于辐射。
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