CN111479596B - 封端聚异丁烯聚氨酯 - Google Patents
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Abstract
一种聚合物材料包括聚异丁烯‑聚氨酯嵌段共聚物。聚异丁烯‑聚氨酯嵌段共聚物包括软链段、硬链段和端基。所述软链段包括聚异丁烯二醇残基。所述硬链段包括二异氰酸酯残基。端基通过脲键键合到二异氰酸酯残基的一部分上。端基包括单官能胺的残基。
Description
相关申请的交叉引用
本申请要求于2018年1月17日提交的美国临时申请号62/618,262的优先权,通过整体引用将其并入本文。
技术领域
本公开涉及聚合物材料。更具体地,本公开涉及聚异丁烯-聚氨酯嵌段共聚物、制备聚异丁烯-聚氨酯嵌段共聚物的方法,以及含有聚异丁烯-聚氨酯嵌段共聚物的医疗设备。
背景技术
聚合物材料广泛用于医疗设备领域中。例如,聚合物材料如硅橡胶、聚氨酯和含氟聚合物用作医疗导线、支架、导管和其它设备的涂层和/或绝缘材料。
嵌段共聚物是由聚合单体的交替段制成的聚合物材料。聚异丁烯-聚氨酯嵌段共聚物是具有许多独特物理和机械性质的聚合物材料。在医疗设备领域中可能特别期望的示例性性质包括热稳定性、耐化学性、生物相容性和不透气性等。
将聚合物材料结合到可植入医疗设备中可以通过多种方法来完成,这取决于具体应用。在一些应用中,例如,对于可植入的引线体,可以在足以使嵌段共聚物流动但不足以高到使聚合物材料分解的温度下挤出聚合物材料。也就是说,在挤出和冷却之后形成引线的材料具有与原始聚合物材料基本相同的结构。
在其它应用中,可能需要采用基于溶剂的处理来将聚合物材料结合到可植入医疗设备中。基于溶剂的处理包括电喷雾、电纺、喷涂、浸涂和强力纺丝。对聚合物材料的所有基于溶剂的处理来说,重要的是能够将聚合物材料引入溶液中,同时保持聚合物材料的基本结构。
发明内容
实施例1是一种包括聚异丁烯-聚氨酯嵌段共聚物的聚合物材料。聚异丁烯-聚氨酯嵌段共聚物包括软链段、硬链段和端基。所述软链段包括聚异丁烯二醇残基。所述硬链段包括二异氰酸酯残基。端基通过脲键键合到二异氰酸酯残基的一部分上。端基包括单官能胺的残基。
实施例2是如实施例1所述的聚合物材料,其中所述单官能胺是伯胺或仲胺。
实施例3是如实施例1或2中任一项所述的聚合物材料,其中所述单官能胺包括C3至C30脂族链。
实施例4是如实施例1-3中任一项所述的聚合物材料,其中所述单官能胺是丁胺。
实施例5是如实施例1-4中任一项所述的聚合物材料,其中所述软链段以共聚物的约40重量%至约70重量%的量存在于共聚物中,且所述硬链段以共聚物的约30重量%至约60重量%的量存在于共聚物中。
实施例6是如实施例1-5中任一项所述的聚合物材料,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中任一项所述的聚合物材料,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所述的聚合物材料,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中任一项所述的聚合物材料,其中所述软链段进一步包括聚醚二醇残基、聚酯二醇残基和聚碳酸酯二醇残基中的至少一种。
实施例10是一种医疗设备,其包括如权利要求1-9中任一项所述的聚合物材料。
实施例11是一种制备聚合物材料的方法。所述方法包括:将软链段组分和硬链段组分的混合物加热至高温以形成预聚物,使扩链剂与预聚物反应以形成聚合物,和使封端剂与所述预聚物和所述聚合物中的至少一种反应以形成聚合物材料。所述软链段组分包括聚异丁烯二醇。所述硬链段组分包括二异氰酸酯。所述封端剂包括单官能胺。
实施例12是如实施例11所述的方法,其中所述单官能胺是伯胺或仲胺。
实施例13是如实施例11或12中任一项所述的方法,其中所述单官能胺包括C3至C30脂族链。
实施例14是如实施例11-13中任一项所述的方法,其中所述单官能胺是丁胺。
实施例15是如实施例11-14中任一项所述的方法,其中所述二异氰酸酯相对于聚异丁烯二醇和扩链剂是化学计量过量的,且所述单官能胺相对于二异氰酸酯是至少等摩尔量的。
实施例16是一种包括聚异丁烯-聚氨酯嵌段共聚物的聚合物材料。聚异丁烯-聚氨酯嵌段共聚物包括软链段、硬链段和端基。所述软链段包括聚异丁烯二醇残基。所述硬链段包括二异氰酸酯残基。端基通过脲键键合到二异氰酸酯残基的一部分上。所述端基包括单官能胺的残基,所述单官能胺包括C3至C30脂族链。
实施例17是如实施例16所述的聚合物材料,其中所述单官能胺是伯胺或仲胺。
实施例18是如实施例16或17中任一项的实施例所述的聚合物材料,其中所述单官能胺是丁胺。
实施例19是如实施例16-18中任一项所述的聚合物材料,其中所述软链段以共聚物的约40重量%至约70重量%的量存在于共聚物中,且所述硬链段以共聚物的约30重量%至约60重量%的量存在于共聚物中。
实施例20是如实施例16-19中任一项所述的聚合物材料,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21是如实施例16-19中任一项所述的聚合物材料,其中所述硬链段进一步包括扩链剂残基。
实施例22是如实施例21所述的聚合物材料,其中所述扩链剂残基是1,4-丁二醇残基。
实施例23是如实施例16-22中任一项所述的聚合物材料,其中所述软链段进一步包括聚醚二醇残基、聚酯二醇残基和聚碳酸酯二醇残基中的至少一种。
实施例24是一种包括聚合物材料的医疗设备。所述聚合物材料包括聚异丁烯-聚氨酯嵌段共聚物。聚异丁烯-聚氨酯嵌段共聚物包括软链段、硬链段和端基。所述软链段包括聚异丁烯二醇残基。所述硬链段包括二异氰酸酯残基。端基通过脲键键合到二异氰酸酯残基的一部分上。所述端基包括单官能胺的残基,所述单官能胺包括C3至C30脂族链。
实施例25是如实施例24所述的医疗设备,其中所述单官能胺是伯胺或仲胺。
实施例26是如实施例24或25中任一项所述的医疗设备,其中所述单官能胺是丁胺。
实施例27是如实施例24-26中任一项所述的医疗设备,其中所述软链段以共聚物的约40重量%至约70重量%的量存在于共聚物中,且所述硬链段以共聚物的约30重量%至约60重量%的量存在于共聚物中。
实施例28是如实施例24-27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29是一种制备聚合物材料的方法。所述方法包括:将软链段组分和硬链段组分的混合物加热至高温以形成预聚物,使扩链剂与预聚物反应以形成聚合物,和使封端剂与所述预聚物和所述聚合物中的至少一种反应以形成聚合物材料。所述软链段组分包括聚异丁烯二醇。所述硬链段组分包括二异氰酸酯。所述封端剂包括单官能胺,所述单官能胺包括C3至C30脂族链。
实施例30是如实施例29所述的方法,其中所述单官能胺是伯胺或仲胺。
实施例31是如实施例29或30中任一项所述的方法,其中所述单官能胺是丁胺。
实施例32是如实施例29-31中任一项所述的方法,其中所述二异氰酸酯相对于聚异丁烯二醇和扩链剂是化学计量过量的,且所述单官能胺相对于二异氰酸酯是至少等摩尔量的。
实施例33是如实施例29-32中任一项所述的方法,其进一步包括使扩链剂与加热后的混合物和叔胺催化剂反应。
实施例34是如实施例29所述的方法,其中所述二异氰酸酯包括4,4'-亚甲基二苯基二异氰酸酯。
实施例35是如实施例29-34中任一项所述的方法,其中所述软链段组分进一步包括:聚四氢呋喃二醇,所述二异氰酸酯相对于聚异丁烯二醇、扩链剂和聚四氢呋喃二醇是化学计量过量的,且所述单官能胺相对于二异氰酸酯是至少等摩尔量的。
虽然公开了多个实施例,但是根据示出和描述说明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是说明性的而非限制性的。
附图说明
图1是示出根据本公开的一些实施方案生产聚异丁烯-聚氨酯的方法的第一步骤的示意图。
图2是示出根据本公开的一些实施方案生产聚异丁烯-聚氨酯的方法的第二步骤的示意图。
图3是示出根据本公开的一些实施方案生产聚异丁烯-聚氨酯的另一种方法的示意图。
图4是根据本公开的一些实施方案的聚异丁烯-聚氨酯溶液的动态粘度作为浓度的函数的图。
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
根据本公开的各个方面,公开了聚异丁烯-聚氨酯嵌段共聚物(本文也统称为“PIB-PUR”)及其制备方法。还公开了可植入或可插入患者体内并且包含聚异丁烯氨基甲酸酯共聚物的医疗设备。PIB-PUR是含有硬链段和软链段的热塑性聚氨酯(TPU)。PIB-PUR可用于许多应用,包括用于插入或植入患者的医疗设备,因为它们是水解稳定的并具有良好的氧化稳定性。
聚氨酯是一类由多官能异氰酸酯(例如二异氰酸酯,包括脂族二异氰酸酯和芳族二异氰酸酯)和多元醇(例如巨二醇(macroglycol))合成的共聚物。通常使用的巨二醇包括聚酯二醇、聚醚二醇和聚碳酸酯二醇。巨二醇可形成聚氨酯的聚合物链段。脂族二醇或芳族二醇也可用作扩链剂,例如,以赋予聚氨酯改进的物理性能。
在一些实施方案中,聚异丁烯氨基甲酸酯共聚物包括一个或多个聚异丁烯链段、包括一个或多个二异氰酸酯残基的一个或多个链段、任选地一个或多个另外的聚合物链段(除了聚异丁烯链段)和任选地一种或多种扩链剂。
如本文所用,“聚合物链段”或“链段”是聚合物的一部分。聚异丁烯氨基甲酸酯共聚物的聚异丁烯链段通常被认为构成软链段,而含有二异氰酸酯残基的链段通常被认为构成硬链段。附加的聚合物链段可以包括软聚合物链段或硬聚合物链段。如本文所用,软链段和硬链段是描述含有这样的链段的聚合物材料的性质的相对术语。不限制前述内容,软链段可显示低于体温的玻璃化转变温度(Tg),更典型地为35℃至20℃至0℃至-25℃至-50℃或更低。硬链段可以显示高于体温的Tg,更典型地为40℃至50℃至75℃至100℃或更高。Tg可以通过差示扫描量热法(DSC)、动态力学分析(DMA)和/或热机械分析(TMA)来测量。
在各种实施方案的聚异丁烯氨基甲酸酯共聚物中,软链段与硬链段的重量比可以变化,以获得宽范围的物理和机械性质,并获得一系列期望的功能性能。例如,聚合物中软链段与硬链段的重量比可以在99:1至95:5至90:10至75:25至50:50至25:75至10:90至5:95至1:99,更特别地95:5至90:10至80:20至70:30至65:35至60:40至50:50,和甚至更特别地约80:20至约50:50的范围内变化。在一些实施方案中,软链段组分可以是共聚物的约40重量%至约70重量%,且硬链段组分可以是共聚物的约30重量%至约60重量%。
在一些实施方案中,共聚物可以包括量为软链段的约60重量%至约100重量%的聚异丁烯和量为软链段的约0重量%至约40重量%的聚醚、聚酯或聚碳酸酯。例如,共聚物可以包括量为共聚物的约40重量%至约70重量%的软链段,其中聚异丁烯以软链段的约60重量%至约100重量%的量存在,且聚醚以软链段的约0重量%至约40重量%的量存在。在另一个实施方案中,共聚物可以包括量为共聚物的约40重量%至约70重量%的软链段,其中聚异丁烯(例如,聚异丁烯二醇残基)以软链段的约70重量%至约95重量%的量存在,且聚醚(例如,聚四氢呋喃二醇残基)以软链段的约5重量%至约40重量%的量存在。
用于形成各种实施方案的PIB-PUR的二异氰酸酯包括芳族和非芳族(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,聚醚二醇如聚四氢呋喃二醇(PTMO二醇)、聚环氧己烷二醇(PHMO二醇)、聚环氧辛烷二醇或聚环氧癸烷二醇,可以与聚异丁烯二醇和二异氰酸酯结合形成聚异丁烯聚氨酯共聚物。在一些实施方案中,PIB-PUR可以具有通常均匀分布的聚氨酯硬链段、聚异丁烯链段和聚醚链段,以在聚合物中实现有利的微相分离。在一些实施方案中,聚醚链段可以改善关键机械性质,例如肖氏硬度、拉伸强度、拉伸模量、挠曲模量、伸长撕裂强度、挠曲疲劳、拉伸蠕变和/或磨损性能等。
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。
根据各个实施方案的PIB-PUR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。扩链剂也可以选自基于硬聚合物链段和软聚合物链段(更通常地软聚合物链段)的短链二醇聚合物(例如,具有小于或等于1000的分子量的α,ω-二羟基封端的聚合物)中的合适成员,例如上述那些,包括短链聚异丁烯二醇,短链聚醚多元醇如聚四氢呋喃二醇,短链聚硅氧烷二醇如聚二甲基硅氧烷二醇,短链聚碳酸酯二醇如聚六亚甲基碳酸酯二醇,短链聚(氟化醚)二醇,短链聚酯二醇,短链聚丙烯酸酯二醇,短链聚甲基丙烯酸酯二醇,和短链聚(乙烯基芳族)二醇。扩链剂还可以选自合适的二醇,如丙二醇、二丙二醇,和三丙二醇。
如上所述,可能需要采用基于溶剂的处理来将聚合物材料如PIB-PUR结合到可植入医疗设备中。在一些实施方案中,可以合成PIB-PUR并储存一段时间,直到将其引入溶剂处理中。例如,PIB-PUR可以储存数天、数周或数月的时间。对于溶剂处理,将PIB-PUR溶解在溶剂中,例如2,6-二甲基吡啶或四氢呋喃(THF),以得到所需浓度和/或粘度的所得PIB-PUR溶液。然后,通过电喷雾、静电纺丝、喷涂、浸涂或强力纺丝,可将PIB-PUR溶液沉积在基材如医疗设备上。
已经发现,当PIB-PUR储存延长的时间时,在数周和数月的数量级上,PIB-PUR的分子量(重均分子量(Mw)和数均分子量(Mn))可以在储存期间增加。在一些情况下,储存的PIB-PUR形成凝胶。这样的凝胶不再易溶于2,6-二甲基吡啶或THF,因此不再适于基于溶剂的处理。
已经发现,在一些实施方案中,封端剂为单官能胺可以减轻由于延长的储存时间而导致的分子量增加。此外,已经发现,在一些实施方案中,将这样的封端剂加入到已经储存了较长时间的PIB-PUR中可以逆转PIB-PUR分子量的增加。此外,已经发现,即使在PIB-PUR胶凝并且不再溶于2,6-二甲基吡啶或THF中后加入这样的封端剂,也可破坏凝胶中的交联,使得PIB-PUR溶于2,6-二甲基吡啶或THF中。凝胶定义为基本上稀释的交联体系,其在稳态时表现为不流动。
单官能胺可包括C3至C30脂族链,其可为直链或支链的、饱和或不饱和的伯胺或仲胺。例如,在一些实施方案中,单官能胺可以是丁胺或丁胺醚,如2-甲氧基乙胺。
图1是示出根据本公开的一些实施方案生产聚异丁烯-聚氨酯的方法的第一步骤的示意图。根据本公开的实施方案的包括PIB-PUR的聚合物材料可通过以下来制备:将包括聚异丁烯二醇12和任选的聚醚二醇14(示出PTMO)的软链段组分10和包括二异氰酸酯18(示出MDI)的硬链段组分16混合在一起,并在催化剂20存在下加热该混合物至高温以形成预聚物22。
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。催化剂可以是任何合适的催化剂,例如有机金属催化剂,例如2-乙基己酸锡(II)(辛酸亚锡),或叔胺催化剂,例如2,6-二甲基吡啶、1-环己基-N,N-二甲基甲胺、N,N,N',N',N”-五甲基二亚乙基三胺,或4-甲基吗啉、1-甲基咪唑。
第二步骤示于图2中。在高温下,在催化剂20存在下,使扩链剂24(示出BDO)与预聚物22以及单官能胺26(示出丁胺)反应,以形成PIB-PUR 28。如图2中所示,单官能胺26给PIB-PUR 28封端,与二异氰酸酯18反应以防止进一步的链增长。单官能胺26也可与过量的二异氰酸酯18反应并减少不需要的副反应。在一些实施方案中,单官能胺26可与增链剂24同时加入预聚物22中。在其他实施方案中,可以在扩链剂24已经至少部分地与预聚物22反应形成聚合物之后加入单官能胺26。在一些实施方案中,单官能胺26可与扩链剂24同时且在扩链剂24至少部分与预聚物22反应形成聚合物之后加入到预聚物22中。
二异氰酸酯18可以相对于聚异丁烯二醇12、任选的聚醚二醇14和扩链剂24化学计量过量。二异氰酸酯18可以过量以解决二异氰酸酯与残余水反应损失的问题。例如,在一些实施方案中,二异氰酸酯18相对于聚异丁烯二醇12、任选的聚醚14和扩链剂24过量少至0.5摩尔%(mol%)、1mol%、1.5mol%或2mol%,或多至2.5mol%、3mol%、4mol%,或5mol%,或在任何两个前述值之间的任何值。例如在一些实施方案中,二异氰酸酯18相对于聚异丁烯二醇12、任选的聚醚14和扩链剂24过量0.5mol%至5mol%、1mol%至4mol%、1.5mol%至3mol%、2mol%至2.5mol%,或0.5mol%至2.5mol%。
在一些实施方案中,单官能胺26可以以相对于二异氰酸酯18至少等摩尔量加入。在一些实施方案中,可以加入过量的单官能胺26。如果需要,一些过量的单官能胺26可通过加热到高于单官能胺26的沸点而除去。例如,过量的丁胺可以通过加热到高于丁胺的沸点约78℃而除去。
因此,图2所示的PIB-PUR 28是至少包括含有聚异丁烯二醇12的残基的软链段、至少含有二异氰酸酯18的残基的硬链段和通过脲键键合到一些二异氰酸酯残基上的端基的聚合物材料。端基是单官能胺26的残基。图2所示实施方案的硬链段还包括扩链剂24的残基。图2所示实施方案的软链段还进一步包括聚醚二醇14的残基。在一些实施方案中,软链段可以替代地或另外地包括聚碳酸酯二醇和/或聚酯二醇的残基。
图3是示出根据本公开的一些实施方案生产聚异丁烯-聚氨酯的另一种方法的示意图。在图3所示的实施方案中,单官能胺26(示出丁胺)在聚合反应至少基本完成后加入。当聚异丁烯-聚氨酯的粘度在数小时的时间内没有显著增加时,聚合反应至少基本上完成。图3显示PIB-PUR链30和键合到PIB-PUR30的氨基甲酸酯键上形成脲基甲酸酯34的二异氰酸酯残基32。在一些实施方案中,可以制备PIB-PUR 30,并用单官能胺封端,如上述PIB-PUR28。在其他实施方案中,当最初合成时,PIB-PUR 30可以不用单官能胺封端。二异氰酸酯残基32可以是如上所述用于制备PIB-PUR 30的过量二异氰酸酯的结果。
不希望受任何理论的束缚,拒信在长时间储存期间,二异氰酸酯残基32还与其它硬链段组分或软链段组分,包括PIB-PUR 30的其它链(未示出)键合,因此使其它硬链段组分或软链段组分与PIB-PUR 30交联,增加了PIB-PUR 30的分子量,并最终如上所述使PIB-PUR 30胶凝。这些副反应可形成脲基甲酸酯34。其它副反应可形成其它交联结构,例如缩二脲(未示出)。
脲基甲酸酯34是可逆键。如上所述,已经发现即使在PIB-PUR 30已经胶凝之后,单官能胺26的加入也逆转了PIB-PUR 30的胶凝并降低了其分子量。不希望受任何理论的束缚,拒信与脲基甲酸酯34相关的空间位阻使键变弱,导致图3所示的可逆键。据信二异氰酸酯残基32优先与单官能胺26结合,将二异氰酸酯残基32束缚在更稳定的烷基胺36(所示的丁胺)中,如图3所示。将二异氰酸酯残基32连接起来可以防止脲基甲酸酯34的再形成,并减少其它硬链段组分或软链段组分与PIB-PUR 30的交联,破坏PIB-PUR30的胶凝,并降低PIB-PUR 30的分子量。在一些实施方案中,PIB-PUR 30的分子量可以降低到PIB-PUR 30线性链的初始分子量。
与例如类似结构的单官能醇相比,单官能胺26的胺封端被认为非常适合于该应用。已经发现,虽然单官能胺26在逆转PIB-PUR 30的胶凝方面是有效的,但类似结构的单官能醇是无效的。
根据本公开的实施方案的PIB-PUR 26或PIB-PUR 30可以被结合到可以被植入或插入患者体内的医疗设备中。示例性医疗设备可包括但不限于:血管移植物、电引线、导管、无引线心脏起搏器(LCP)、骨盆底修复支撑装置、电击线圈覆盖物、包覆支架、尿道支架、内部饲管/球囊、包括瓣叶的结构心脏应用、缝合套管、乳房植入物、包括眼内透镜和青光眼管的眼科应用,以及椎间盘修复。示例电引线可以包括但不限于可植入电刺激或诊断系统,包括神经刺激系统,例如脊髓刺激(SCS)系统、深部脑刺激(DBS)系统、外周神经刺激(PNS)系统、胃神经刺激系统、耳蜗植入系统和视网膜植入系统等,以及心脏系统,包括可植入心律管理(CRM)系统、可植入复律器-除颤器(ICD’s)和心脏再同步和除颤(CRDT)装置等。
实施例
在以下实施例中更具体地描述本公开,这些实施例仅旨在作为说明,因为在本公开范围内的许多修改和变化对于本领域技术人员将是显而易见的。除非另有说明,以下实施例中报道的所有份数、百分比和比率均基于重量,并且实施例中使用的所有试剂均获自或可获自下述化学品供应商,或者可通过常规技术合成。
实施例1
98天后的PIB-PUR处理
如下制备包括含有聚异丁烯二醇残基的软链段和含有二异氰酸酯残基的硬链段的聚异丁烯-聚氨酯嵌段共聚物(PIB-PUR)。在1升树脂釜中,将106克以5-叔丁基-1,3-二(1-甲氧基-1-甲基乙基)苯开始由碳阳离子聚合反应形成的远螯聚异丁烯二醇、72克4'-亚甲基二苯基二异氰酸酯(MDI)和56克聚四氢呋喃二醇溶解在545克2,6-二甲基吡啶中。1升树脂釜装备有顶置式机械搅拌并用干燥氮气吹扫。聚异丁烯二醇的数均分子量(Mn)为1905克/摩尔,且聚四氢呋喃二醇的Mn为1000克/摩尔。在60℃的温度下,在氮气流下通过顶置式机械搅拌器搅拌溶液,同时反应物反应2小时。2小时后,通过滴加将16克新蒸馏的1,4-丁二醇加入到溶液中,并将溶液保持在70℃的温度,同时反应继续另外2小时。在另外的2小时之后,该溶液是含有PIB-PUR的高粘性溶液。
将PIB-PUR在室温下储存在密封容器中。15天后,通过使用多角度光散射检测器(GPC-MALLS)的凝胶渗透色谱法表征PIB-PUR,以测定数均分子量(Mn)和重均分子量(Mw)。在63天和98天后对PIB-PUR重新表征。结果示于下表1中。如表1所示,分子量增加,特别是在64与98天之间。在98天时,观察到PIB-PUR已经胶凝。发现胶凝的PIB-PUR主要不溶于2,6-二甲基吡啶或THF,这表明发生了PIB-PUR的化学交联(分子量由可溶部分测定)。
通过将2,6-二甲基吡啶和0.5g丁胺加入1g胶凝的PIB-PUR中,用相对于MDI过量等摩尔浓度的丁胺处理胶凝的PIB-PUR,然后在摇床上以225rpm、30℃摇动约12小时。处理过的PIB-PUR再次变粘性液体,这表明无论发生什么化学交联,似乎都随着丁胺的加入而逆转。在24小时和25天后重新表征处理过的PIB-PUR溶液。结果还示于表1中。如表1所示,随着丁胺的加入,处理过的PIB-PUR的分子量显著降低。
表1
实施例2
24天后的PIB-PUR处理
如下制备包括含有聚异丁烯二醇残基的软链段和含有二异氰酸酯残基的硬链段的聚异丁烯-聚氨酯嵌段共聚物(PIB-PUR)。在1升树脂釜中,将105克以5-叔丁基-1,3-二(1-甲氧基-1-甲基乙基)苯开始由碳阳离子聚合反应形成的远螯聚异丁烯二醇、72克4'-亚甲基二苯基二异氰酸酯(MDI)和57克聚四氢呋喃二醇溶解在546克2,6-二甲基吡啶中。1升树脂釜装备有顶置式机械搅拌并用干燥氮气吹扫。聚异丁烯二醇的数均分子量(Mn)为1905克/摩尔,且聚四氢呋喃二醇的Mn为1000克/摩尔。在60℃的温度下,在氮气流下通过顶置式机械搅拌器搅拌溶液,同时反应物反应2小时。2小时后,通过滴加将16克新蒸馏的1,4-丁二醇加入到溶液中,并将溶液保持在70℃的温度,同时反应继续另外2小时。在另外的2小时之后,该溶液是含有PIB-PUR的高粘性溶液。
将PIB-PUR在室温下储存在密封容器中。24天后,通过使用多角度光散射检测器(GPC-MALLS)的凝胶渗透色谱法表征PIB-PUR,以测定数均分子量(Mn)和重均分子量(Mw)。结果示于下表2中。
通过将2,6-二甲基吡啶和0.08g丁胺加入1g PIB-PUR中,用相对于MDI至少等摩尔浓度的丁胺处理PIB-PUR,然后在摇床上以225rpm、30℃摇动约12小时。将处理过的PIB-PUR溶液在室温下储存在密封容器中并在24小时后重新表征。结果还示于表2中。如表2所示,处理过的PIB-PUR的分子量随着丁胺的加入而显著降低,这表明在24天内发生的至少一些化学交联似乎随着丁胺的加入而逆转。
表2
在用丁胺处理40之前和处理42之后24小时,测量不同浓度的实施例2的PIB-PUR在2,6-二甲基吡啶中的动态粘度。通过加入适量的2,6-二甲基吡啶,对于处理40前和处理42后中的每一个,制备三种不同浓度的PIB-PUR溶液。结果示于图4中。如表4所示,动态粘度随丁胺的加入而显著下降,这再次表明在24天内发生的至少一些化学交联似乎随着丁胺的加入而逆转。
实施例3
21天后的PIB-PUR处理
如下制备包括含有聚异丁烯二醇残基的软链段和含有二异氰酸酯残基的硬链段的聚异丁烯-聚氨酯嵌段共聚物(PIB-PUR)。在1升树脂釜中,将13克以5-叔丁基-1,3-二(1-甲氧基-1-甲基乙基)苯开始由碳阳离子聚合反应形成的远螯聚异丁烯二醇、9克4'-亚甲基二苯基二异氰酸酯(MDI)和7克聚四氢呋喃二醇溶解在8克2,6-二甲基吡啶中。1升树脂釜装备有顶置式机械搅拌并用干燥氮气吹扫。聚异丁烯二醇的数均分子量(Mn)为1905克/摩尔,且聚四氢呋喃二醇的Mn为1000克/摩尔。在60℃的温度下,在氮气流下通过顶置式机械搅拌器搅拌溶液,同时反应物反应2小时。2小时后,通过滴加将2克新蒸馏的1,4-丁二醇加入到溶液中,并将溶液保持在70℃的温度,同时反应继续另外2小时。在另外的2小时之后,该溶液是含有PIB-PUR的高粘性溶液。
将PIB-PUR在室温下储存在密封容器中。21天后,通过使用多角度光散射检测器(GPC-MALLS)的凝胶渗透色谱法表征PIB-PUR,以测定数均分子量(Mn)和重均分子量(Mw)。结果示于下表3中。
通过将2,6-二甲基吡啶和0.08g丁胺加入1g PIB-PUR中,用相对于MDI至少等摩尔浓度的丁胺处理PIB-PUR,然后在摇床上以225rpm、30℃摇动约12小时。将处理过的PIB-PUR溶液在室温下储存在密封容器中并在24小时后和17天后重新表征。结果还示于表3中。如表3所示,处理过的PIB-PUR的分子量随着丁胺的加入而显著降低,这表明在21天内发生的至少一些化学交联似乎随着丁胺的加入而逆转。如表3进一步所示,在另外的17天的储存中,交联没有再次出现。
表3
PIB-PUR | Mn | Mw |
21天后 | 71,700 | 184,000 |
丁胺处理后24小时 | 65,970 | 159,000 |
丁胺处理后17天 | 61,970 | 147,800 |
在用丁胺处理44之前和处理46之后24小时,测量不同浓度的实施例2的PIB-PUR在2,6-二甲基吡啶中的动态粘度。通过加入适量的2,6-二甲基吡啶,对于处理40前和处理42后中的每一个,制备三种不同浓度的PIB-PUR溶液。结果示于图4中。如表4所示,动态粘度随丁胺的加入而显著下降,这再次表明在24天内发生的至少一些化学交联似乎随着丁胺的加入而逆转。
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相加。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。
Claims (10)
1.一种聚合物材料,其包含:
聚异丁烯-聚氨酯嵌段共聚物,其包括:
包括聚异丁烯二醇残基的软链段;
包括二异氰酸酯残基的硬链段;和
通过脲键键合到一部分二异氰酸酯残基上的端基,所述端基包括单官能胺的残基,
其中所述单官能胺是丁胺。
2.如权利要求1所述的聚合物材料,其中所述软链段以共聚物的40重量%至70重量%的量存在于共聚物中,且所述硬链段以共聚物的30重量%至60重量%的量存在于共聚物中。
3.如权利要求1或2所述的聚合物材料,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。
4.如权利要求1或2所述的聚合物材料,其中所述硬链段进一步包括扩链剂残基。
5.如权利要求4所述的聚合物材料,其中所述扩链剂残基是1,4-丁二醇残基。
6.如权利要求1或2所述的聚合物材料,其中所述软链段进一步包括聚醚二醇残基和聚酯二醇残基中的至少一种。
7.如权利要求1或2所述的聚合物材料,其中所述软链段进一步包括聚碳酸酯二醇残基。
8.一种医疗设备,其包含如权利要求1-7中任一项所述的聚合物材料。
9.一种制备聚合物材料的方法,所述方法包括:
将软链段组分和硬链段组分的混合物加热至高温以形成预聚物,所述软链段组分包括聚异丁烯二醇,且所述硬链段组分包括二异氰酸酯;
使扩链剂与预聚物反应以形成聚合物;和
使封端剂与所述预聚物和所述聚合物中的至少一种反应以形成聚合物材料;其中所述封端剂包括单官能胺,其中所述单官能胺是丁胺。
10.如权利要求9所述的方法,其中所述二异氰酸酯相对于聚异丁烯二醇和扩链剂是化学计量过量的,且所述丁胺相对于二异氰酸酯是至少等摩尔量的。
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