CN112831013A - 一种功能化聚氨酯及其制备方法和应用 - Google Patents
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Abstract
本发明提供了一种功能化聚氨酯,由聚碳酸酯二元醇和聚异丁烯二元醇构成的柔性链段,与二异氰酸酯和扩链剂构成的刚性链段共聚得到;所述扩链剂包括组分A和组分B;所述组分A为含有4‑苯并环丁烯基结构的二元醇;所述组分B为其它低分子二元醇和/或低分子二元胺。本发明提供的功能化的聚氨酯软段中聚碳酸酯结构具有耐水解功能、聚异丁烯结构具有耐氧化功能,和刚性链段扩链剂中4‑苯并环丁烯基结构可以在升高的温度(优选高于190℃)发生自交联反应。因此该功能化聚氨酯具有良好的耐水解、耐氧化、抗蠕变性能,可实现医用聚氨酯体内服役的持久性并用于制作长期植入体内的人工心脏瓣膜、人工血管、介入类医用导管等器械。
Description
技术领域
本发明涉及医用材料技术领域,尤其涉及一种功能化聚氨酯及其制备方法和应用。
背景技术
医用聚氨酯弹性体是由聚醚、聚酯二元醇等为软段、二异氰酸酯为硬段所组成,软段的柔韧性赋予聚氨酯良好的弹性,硬段的刚性形成结晶区,软段和硬段属热力学不相容体系,存在极性差异,可引起微相分离。通过调节软硬段的比例、结构、分子分布等方法,使聚氨酯材料获得适宜的力学强度、耐磨性、回弹性、生物相容性、抗凝血性等特点。医用聚氨酯可以用在植介入医疗器械,如中心静脉导管、外周静脉导管、动脉导管鞘、球囊扩张导管、腹膜透析导管、球囊导管、输液港、心脏瓣膜、人工血管等。聚氨酯由于有酯基、氨基甲酸酯基和脲基的存在,在人体复杂环境下,水会导致聚氨酯分子链水解;巨噬细胞所释放的物质引包括H+、酶以及体内自由基等氧化介质易造成聚氨酯氧化降解,上述的水解和氧化反应造成的聚氨酯分子链降解导致其力学性能降低,很难应用到长期植/介入人体环境的器械。另外聚氨酯材料及制品如应用在长期植入器械中会由承受长期的疲劳应力而导致蠕变,也会限制其进一步应用。因此,制备出具有耐氧化、耐水解和抗蠕变性能的医用聚氨酯弹性体成为业内广泛关注的研究热点。
发明内容
有鉴于此,本发明要解决的技术问题在于提供一种功能化聚氨酯及其制备方法和应用,制备的功能化聚氨酯具有耐水解、耐氧化和抗蠕变性能。
为达到上述目的,本发明提供了一种功能化聚氨酯,由聚碳酸酯二元醇和聚异丁烯二元醇构成的柔性链段,与二异氰酸酯和扩链剂构成的刚性链段共聚得到;
所述扩链剂包括组分A和组分B;
所述组分A为含有4-苯并环丁烯基结构的二元醇;所述组分B为其它低分子二元醇和/或低分子二元胺。
本发明优选的,所述聚碳酸酯二元醇为具有耐水解功能的聚碳酸酯二元醇。
本发明优选的,所述聚异丁烯二元醇为具有耐氧化功能的聚异丁烯二元醇。
本发明优选的,所述聚碳酸酯二元醇的分子量优选为400~8000,更优选为500~5000。
本发明优选的,所述聚碳酸酯二元醇为含有1,6-己二醇的聚碳酸醇,和/或含有1,4-环己烷二甲醇的聚碳酸醇。
在本发明的一些具体实施例中,所述聚碳酸酯二元醇选自日本宇部含有1,6-己二醇的聚碳酸醇UH-CARB50(分子量500)、UH-CARB100(分子量1000)、UH-CARB200(分子量2000)和含1,4-环己烷二甲醇的聚碳酸醇UC-CARB100(分子量1000)中的一种或多种。
本发明优选的,所述聚异丁烯二元醇中含有式Ⅱ所示结构:
n为聚合度1-70,更优选为2-50;
本发明对所述聚异丁烯二元醇的来源并无特殊限定,可以为一般市售,或按照本领域技术人员熟知的方法制备。
在本发明的一些具体实施例中,所述聚异丁烯二元醇制备方法参照JournalofPolymer Science:Polymer Chemistry Edition,1980,18,3177-3191。
本发明优选的,所述二异氰酸酯为脂肪族二异氰酸酯或芳香族二异氰酸酯。更优选为2,4-甲苯二异氰酸酯(TDI)、4,4'-二苯甲烷二异氰酸酯(MDI)、间苯二甲基异氰酸酯(XDI)、异佛尔酮二异氰酸酯(IPDI)、1,6-已二异氰酸酯(HDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)中的一种或多种。
本发明优选的,所述含有4-苯并环丁烯基结构的二元醇具有式Ⅲ所示结构:
m,y,k优选为0-20;更优选为1~10,进一步优选为1~5。在本发明的一些具体实施例中,m=1,y=1,k=1。
本发明中,上述二元醇结构中含有的4-苯并环丁烯基结构,该结构中存在应变的四元环导致在190℃转化成邻亚二甲基苯,因此苯并环丁烯基团与亲二烯体发生Diels-Alder反应形成六元环,或与自身反应形成八元环。聚氨酯分子量含多个苯并环丁烯基团可以与亲二烯体热交联。。
在本发明的一些具体实施例中,所述含有4-苯并环丁烯基结构的二元醇由如下反应所得到。
其中,m,y,k为0-20;更优选为1~10,进一步优选为1~5。在本发明的一些具体实施例中,m=1,y=1,k=1。
本发明优选的,所述其它低分子二元醇包括乙二醇、丙二醇、丁二醇、戊二醇和己二醇中的一种或多种。
本发明优选的,所述低分子二元胺包括乙二胺、丙二胺、丁二胺、戊二胺和己二胺中的一种或多种。
本发明优选的,所述聚碳酸酯二元醇和聚异丁烯二元醇的总量,和二异氰酸酯、组分A、组分B的质量比为(20~85):(4~40):(0.2~40):(0.5~20)。
本发明提供了上述功能化聚氨酯的制备方法,包括以下步骤:
将聚碳酸酯二元醇和聚异丁烯二元醇、二异氰酸酯、扩链剂按配比用一步法或二步法或半预聚法的本体聚合或溶剂聚合制备得到。
本发明所用的一步法或二步法或半预聚法的本体聚合或溶剂聚合,以及需用的催化剂均在CN1371927A中有详细描述。
本发明提供了上述功能化聚氨酯,或上述制备方法制备的功能化聚氨酯,作为植/介入医疗器械原材料的应用。
所述植介入医疗器械包括但不限于中心静脉导管、外周静脉导管、动脉导管鞘、球囊扩张导管、腹膜透析导管、球囊导管、输液港、人工心脏瓣膜、人工血管等。
与现有技术相比,本发明提供了一种功能化聚氨酯,由聚碳酸酯二元醇和聚异丁烯二元醇构成的柔性链段,与二异氰酸酯和扩链剂构成的刚性链段共聚得到;所述扩链剂包括组分A和组分B;所述组分A为含有4-苯并环丁烯基结构的二元醇;所述组分B为其它低分子二元醇和/或低分子二元胺。本发明提供的功能化的聚氨酯软段中聚碳酸酯二元醇结构具有耐水解功能、聚异丁烯二元醇结构具有耐氧化功能,和刚性链段扩链剂中4-苯并环丁烯基结构可以在升高的温度(优选高于180℃)发生自交联反应。因此该功能化聚氨酯具有良好的耐水解、耐氧化性能,即使在氧化介质和水解介质的侵蚀下变化也不大,同时还具有抗蠕变性能,可实现医用聚氨酯体内服役的持久性并用于制作长期植/介入体内的人工心脏瓣膜、人工血管、介入类医用导管等器械。另外,本发明采用的制备方法除原料单体配方外,其合成工艺方法均为已有的常规方法,方法简单、成熟、易于控制。
试验结果表明,本发明提供的功能化聚氨酯在水解和氧化条件下力学性能变化不大,以及合成的聚氨酯经过热处理自交联后在一定应力作用下,应变量较小,说明该功能化聚氨酯既耐水解又耐氧化,同时又具有较好的耐蠕变性能。
具体实施方式
为了进一步说明本发明,下面结合实施例对本发明提供的功能化聚氨酯及其制备方法和应用进行详细描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
实施例1一步法溶剂聚合
在四口瓶中加入400ml的四氢呋喃/N,N-二甲基乙酰胺(体积比1:6)溶剂、30g聚碳酸酯二元醇(日本宇部含有1,6-己二醇的聚碳酸醇UH-CARB50(分子量500))和30g聚异丁烯二元醇(分子量1000),搅拌,升温至70℃;加扩链剂10g乙二醇和10g 4-苯并环丁烯基二元醇(m=1,y=1,k=1),充分搅拌,使反应物完全溶解;然后加入20g的4,4'-二苯甲烷二异氰酸酯(MDI),升温至100℃,反应6小时,停止搅拌、冷却,得到固含量约25%的聚氨酯溶液。
实施例2一步法溶剂聚合
在四口瓶中加入400ml的四氢呋喃/N,N-二甲基乙酰胺(体积比1:6)溶剂、30g聚碳酸酯二元醇(日本宇部含有1,6-己二醇的聚碳酸醇UH-CARB200(分子量2000))和30g聚异丁烯二元醇(分子量2000),搅拌,升温至70℃;加扩链剂10g丁二醇和10g 4-苯并环丁烯基二元醇(m=1,y=1,k=1),充分搅拌,使反应物完全溶解;然后加入20g的4,4'-二苯甲烷二异氰酸酯(MDI),升温至100℃,反应6小时,停止搅拌、冷却,得到固含量约26%的聚氨酯溶液。
实施例3两步法溶剂聚合
在四口瓶中依次加入400mlN,N-二甲基乙酰胺溶剂、30g聚碳酸酯二元醇(日本宇部含有1,6-己二醇的聚碳酸醇UH-CARB100(分子量1000))和30g聚异丁烯二元醇(分子量1000),搅拌,升温至70℃,充分溶解;加入20g的4,4'-二苯甲烷二异氰酸酯(MDI)反应60分钟,反应过程中测定异氰酸根含量,在异氰酸根降至理论量时加入10g乙二醇和10g 4-苯并环丁烯基二元醇(m=1,y=1,k=1),加入扩链剂后再反应5小时,停止搅拌、冷却,既得到固含量约23%的聚氨酯溶液。
实施例4本体聚合
在四口瓶中加入30g聚碳酸酯二元醇(日本宇部含1,4-环己烷二甲醇的聚碳酸醇UC-CARB100(分子量1000))和30g聚异丁烯二元醇(分子量2000),搅拌升温至100℃,并在搅拌下真空脱气30分钟,降温至50℃,并依次加入10g乙二醇和10g 4-苯并环丁烯基二元醇(m=1,y=1,k=1)扩链剂和4,4'-二苯甲烷二异氰酸酯(MDI),搅拌升温至100℃反应20分钟,然后将反应混合物转移至100℃预热的聚四氟乙烯盘中,在110℃烘箱中后熟化5小时,冷却、切粒既得到产品。
对比例1
在四口瓶中加入400ml的四氢呋喃/N,N-二甲基乙酰胺(体积比1:6)溶剂、60g聚碳酸酯二元醇(日本宇部含有1,6-己二醇的聚碳酸醇UH-CARB100(分子量1000)),搅拌,升温至70℃;加扩链剂10g乙二醇和10g 4-苯并环丁烯基二元醇(m=1,y=1,k=1),充分搅拌,使反应物完全溶解;然后加入20g的4,4'-二苯甲烷二异氰酸酯(MDI),升温至100℃,反应6小时,停止搅拌、冷却,得到固含量约24%的聚氨酯溶液。
对比例2
在四口瓶中加入400ml的四氢呋喃/N,N-二甲基乙酰胺(体积比1:6)溶剂、60g聚异丁烯二元醇(分子量1000),搅拌,升温至70℃;加扩链剂10g乙二醇和10g 4-苯并环丁烯基二元醇(m=1,y=1,k=1),充分搅拌,使反应物完全溶解;然后加入20g的4,4'-二苯甲烷二异氰酸酯(MDI),升温至100℃,反应6小时,停止搅拌、冷却,得到固含量约26%的聚氨酯溶液。
对比例3
在四口瓶中加入400ml的四氢呋喃/N,N-二甲基乙酰胺(体积比1:6)溶剂、30g聚碳酸酯二元醇(日本宇部含有1,6-己二醇的聚碳酸醇UH-CARB100(分子量1000))和30g聚异丁烯二元醇(分子量1000),搅拌,升温至70℃;加扩链剂20g乙二醇,充分搅拌,使反应物完全溶解;然后加入20g的4,4'-二苯甲烷二异氰酸酯(MDI),升温至100℃,反应6小时,停止搅拌、冷却,得到固含量约25%的聚氨酯溶液。
测试实验:
将制备的聚氨酯采用10%的溶液浇铸成膜,膜厚约1mm,采用哑铃型标准样刀制成样片。
耐水解性能测试:将样品放于0.1MNaAc/HAc(pH=3.3-3.5)在37℃下水解老化半年,然后测试拉伸性能测试,水解介质每周更换两次。
耐氧化性能测试:将样品放于3%H2O2和0.1MCoCl2氧化介质中在37℃下老化半年,然后测试拉伸性能测试,氧化介质每周更换两次。
拉伸性能测试:老化前后的聚氨酯力学样条拉伸性能测试在Instron-5869型拉力试验机上,拉伸速度为10mm/min,每种样品测试数量10个,结果去平均值。
蠕变实验:将哑铃型样件在180℃老化处理10min,然后利用电磁式疲劳试验***在12MPa应力作用下进行蠕变试验,试验温度在20℃下进行,记录在30000秒时样品的应变量。
对实施例1~4及对比例1~3中,样品经水解、氧化及热处理后进行测试,结果参见表1和表2。
表1实施例及比较例所得材料水解和氧化处理前后力学性能比较
表2实施例及比较例所得材料热处理自交联前后力学性能比较
由表1、表2测试结果可以看出,本发明实施例1~4所得聚氨酯具有较好的耐水解、耐氧化和耐蠕变性能。与对比例1的效果对比证明,本发明引入聚异丁烯二元醇,抗氧化性能较好。与对比例2的效果对比证明,本发明引入聚碳酸酯二元醇,耐水解性能较好。与对比例3的效果对比证明,本发明引入4-苯并环丁烯基二元醇,具有较好的耐蠕变性能。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (10)
1.一种功能化聚氨酯,由聚碳酸酯二元醇和聚异丁烯二元醇构成的柔性链段,与二异氰酸酯和扩链剂构成的刚性链段共聚得到;
所述扩链剂包括组分A和组分B;
所述组分A为含有4-苯并环丁烯基结构的二元醇;所述组分B为其它低分子二元醇和/或低分子二元胺。
2.根据权利要求1所述的功能化聚氨酯,其特征在于,所述聚碳酸酯二元醇为具有耐水解功能的聚碳酸酯二元醇;
所述聚异丁烯二元醇为具有耐氧化功能的聚异丁烯二元醇;
所述二异氰酸酯为脂肪族二异氰酸酯或芳香族二异氰酸酯。
3.根据权利要求1所述的功能化聚氨酯,其特征在于,所述聚碳酸酯二元醇分子量为400~8000。
6.根据权利要求1所述的功能化聚氨酯,其特征在于,所述其它低分子二元醇包括乙二醇、丙二醇、丁二醇、戊二醇和己二醇中的一种或多种。
7.根据权利要求1所述的功能化聚氨酯,其特征在于,所述低分子二元胺包括乙二胺、丙二胺、丁二胺、戊二胺和己二胺中的一种或多种。
8.根据权利要求1所述的功能化聚氨酯,其特征在于,所述聚碳酸酯二元醇和聚异丁烯二元醇的总量,和二异氰酸酯、组分A、组分B的质量比为(20~85):(4~40):(0.2~40):(0.5~20)。
9.权利要求1~8任一项所述的功能化聚氨酯的制备方法,包括以下步骤:
将聚碳酸酯二元醇和聚异丁烯二元醇、二异氰酸酯、扩链剂按配比用一步法或二步法或半预聚法的本体聚合或溶剂聚合制备得到。
10.权利要求1~8任一项所述的功能化聚氨酯,或权利要求9所述的制备方法制备的功能化聚氨酯,作为植/介入医疗器械原材料的应用。
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