CN108070068A - 一种低成本高抗菌性能聚氨酯弹性体的制备方法 - Google Patents

一种低成本高抗菌性能聚氨酯弹性体的制备方法 Download PDF

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CN108070068A
CN108070068A CN201611002674.0A CN201611002674A CN108070068A CN 108070068 A CN108070068 A CN 108070068A CN 201611002674 A CN201611002674 A CN 201611002674A CN 108070068 A CN108070068 A CN 108070068A
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quaternary ammonium
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万晓波
裴丹凤
穆有炳
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Abstract

本发明涉及一种低成本高抗菌性能聚氨酯弹性体的制备方法,利用反应型高分子季铵盐抗菌剂,使其参与聚氨酯(PU)的形成反应,键合成为PU结构一部分。主要特征为:于反应釜中加入聚醚二元醇和高分子双羟基季铵盐抗菌剂的混合多元醇,经脱水后加入异氰酸酯和扩链剂,50‑80℃反应,降至室温,即制得抗菌聚氨酯。其优点在于:1)合成方法简捷高效,成本低,易于工业化生产;2)抗菌剂键合为PU结构的一部分,不会游离释放出来,可达到高效、长期、安全的效果。该弹性体具有优异的机械性能和抗菌性能,可作为一种优异的抗菌材料,应用前景广阔。

Description

一种低成本高抗菌性能聚氨酯弹性体的制备方法
技术领域
本发明涉及一种医用抗菌聚氨酯弹性体的制备方法,尤其涉及一种具有低成本、高机械强度、高抗菌性能的抗菌聚氨酯弹性体的制备方法,可用于医用聚氨酯等相关领域。
背景技术
聚氨酯弹性体(TPU)作为医用材料应用于医学领域的研究已有一定的历史。1967年,Boretos和Pierce首次将聚醚型聚氨酯用于左心辅助循环血泵,此后,聚醚型聚氨酯就成为人工心脏和心室辅助循环***中制造心脏腔体的首选材料。到了80年代初,用聚氨酯弹性体制作人工心脏移植手术获得成功,使聚氨酯材料在生物医学上的应用得到进一步的发展。临床实践证明,聚氨酯弹性体在血液相容性、生物相容性、耐久性等方面均优于其他橡胶,成为国内外研制人工心脏及其辅助装置的首选材料。医用聚氨酯产品包括人工心脏辅助装置、医疗导管、聚氨酯敷料、聚氨酯医用薄膜制品、聚氨酯绷带等。但是TPU本身不具备抗菌性能,在适宜的温度和湿度下很容易滋生细菌,从而在临床应用中引起感染。因此,研制本身具有抗细菌感染能力的TPU材料具有重要的意义。
抗菌TPU的研制核心技术在于抗菌剂的研制和生产。季铵盐类抗菌剂在高分子类抗菌剂中研究和应用最多的,该抗菌剂价格低廉,杀菌速度较快,生物安全性高,不会产生细菌耐药性,因此已成为研究者关注的重点。将高分子季铵盐类抗菌剂用作生物医用材料是制备理想抗菌生物医用材料的一种很好的方案。在聚氨酯弹性制备中引入季铵盐类抗菌剂主要有两种方式:(1)在已制备的聚氨酯分子上预留反应官能团(如氨基、叔胺),通过进一步的化学反应,键合上含季铵盐的分子。(2)将双羟基季铵盐的小分子或高分子,作为扩链剂或多元醇的直接参与聚氨酯弹性体的制备。一般而言,第一种方法,后处理繁琐,弹性体的提纯难度增加,不利于扩大化生产;第二种方式制备方法简单,容易实现工业化生产,但是目前目前所使用的双羟基季铵盐的小分子或高分子成本高,不利于工业化生产。因此,针对目前含季铵盐的抗菌聚氨酯弹性体研究所存在的问题,本发明以双羟基聚环氧氯丙烷的季铵盐作为聚氨酯弹性体制备中的抗菌剂,不仅能赋予相关弹性体材料优异的抗菌性能,而且原料廉价易得,合成工艺简单,与其它高分子季铵盐抗菌剂更具规模化生产的优势。
发明内容
本发明的目的在于提供低成本、高机械强度、高抗菌性能的抗菌聚氨酯弹性体的制备方法,以解决现有医用抗菌聚氨酯弹性体成本高难于工业化大规模应用的问题。
为实现上述目的,本发明开发了一种低成本、高机械强度、高抗菌性能的抗菌聚氨酯弹性体,其制备方法为:
于反应釜中加入聚醚二元醇和高分子双羟基季铵盐抗菌剂的混合多元醇,经脱水后加入异氰酸酯和小分子二元醇扩链剂,100-120℃反应3- 10h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
其中,所用聚醚二元醇为聚乙二醇、聚丙二醇或聚四氢呋喃二醇,高分子双羟基季铵盐为双羟基聚环氧氯丙烷季铵盐,双羟基聚环氧氯丙烷季铵盐用量为聚醚二元醇用量的1~10wt%,异氰酸酯的加入量以保证混合多元醇中羟基完全反应为基准,优选异氰酸酯基团与羟基的摩尔比为1:1~1:0.95。小分子二元醇扩链剂用量为聚醚二元醇用量的5~30wt%。
所述聚乙二醇分子量为1000-10000,聚丙二醇的分子量为1000-10000,聚四氢呋喃二醇的分子量为1000-3000。
所述双羟基聚环氧氯丙烷季铵盐的分子量为500-3000,季铵化百分数为10%-70%。
所述异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯、奈二异氰酸酯、苯二亚甲基二异氰酸酯、氢化苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种混合物。
所述扩链剂为乙二醇、1,4-丁二醇、1,4-环己烷二甲醇,1,4- 双(2-羟乙氧基)苯中的一种或几种混合物。
与现有技术相比,本发明有如下优点:
本发明所开发抗菌剂较已有的高分子季铵盐类抗菌剂的成本低,合成方法简单,易于实现工业化生产。
本发明采用一步法即可合成抗菌聚氨酯弹性体,简捷高效,工艺简单;所用原料廉价易得,成本低,易于操作过程的放大以及实现工业化生产。本发明无需加入溶剂反应,绿色环保,无“三废”排放。
本发明所合成的抗菌聚氨酯弹性体性能优良:1)优良的力学性能。采用聚环氧氯丙烷季铵盐类抗菌剂,通过改变抗菌剂的分子量和季铵化程度,可以有效调节聚氨酯弹性体分子间的极性互作用,在保证具有较高拉伸强度的同时,赋予材料优异的断裂伸长率(薄膜拉伸强度大于20MPa,断裂伸长率大于600%)。2)优异的抗菌性能。 抗菌剂键合为PU结构的一部分,因此不会游离释放出来,所以能达到高效、长期、安全的效果。该抗菌聚氨酯弹性体可作为一种优异的抗菌材料,应用前景广阔。
具体实施方式
通过下述实施例将有助于理解本发明,但不限制本发明的内容。
实施例1:
于反应瓶中加入20g 聚丙二醇(Mn=1000),0.2g聚环氧氯丙烷季铵盐(Mn=3000),120℃真空脱水2h,加入甲苯二异氰酸酯5.3g,1,4-丁二醇1.0g,120℃反应3h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
实施例2:
于反应瓶中加入20g 聚丙二醇(Mn=10000),2.0g聚环氧氯丙烷季铵盐(Mn=3000),120℃真空脱水2h,降温至100℃,加入氢化苯二亚甲基二异氰酸酯17.6g,加入1,4-丁二醇6.0g,100℃反应10h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
实施例3:
于反应瓶中加入20g 聚乙二醇(Mn=1000),1.6g聚环氧氯丙烷季铵盐(Mn=500),120℃真空脱水2h,降温至110℃,加入氢化苯二亚甲基二异氰酸酯13.3g,加入1,4-环己烷二甲醇4.6g,110℃反应6h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
实施例4:
于反应瓶中加入20g 聚四氢呋喃二醇(Mn=1000),1.0g聚环氧氯丙烷季铵盐(Mn=1000),120℃真空脱水2h,降温至110℃,加入六亚甲基二异氰酸8.8g,加入1,4-丁二醇3.0g,110℃反应8h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
实施例5:
于反应瓶中加入20g 聚四氢呋喃二醇(Mn=3000),2.0g聚环氧氯丙烷季铵盐(Mn=1000),120℃真空脱水2h,降温至110℃,加入氢化苯二亚甲基二异氰酸酯6.7g,加入1,4-丁二醇1.7g,110℃反应6h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
实施例6:
于反应瓶中加入20g 聚丙二醇(Mn=6000),1.6g聚环氧氯丙烷季铵盐(Mn=3000),120℃真空脱水2h,降温至100℃,加入氢化苯二亚甲基二异氰酸酯9.6g,加入1,4-丁二醇3.0g,100℃反应10h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
实施例7:
于反应瓶中加入20g 聚乙二醇(Mn=10000),2.0g聚环氧氯丙烷季铵盐(Mn=1000),120℃真空脱水2h,加入氢化苯二亚甲基二异氰酸酯9.0g,加入1,4-环己烷二甲醇4.6g,120℃反应4h,降至室温,即制得抗菌聚氨酯弹性体。产品经破碎机粉碎后,即可模塑、注射或挤出成型。
上述实施例所制目标产品经成膜后,膜的机械性能及抗菌性能见下表
样品 拉伸强度 MPa 断裂伸长率 金黄色葡萄球菌杀菌率 大肠杆菌杀菌率
实施例1 23.5 750% >99% >99%
实施例2 20.5 740% >99% >99%
实施例3 28.9 800% >99% >99%
实施例4 29.8 650% >99% >99%
实施例5 37.5 620% >99% >99%
实施例6 27.8 890% >99% >99%
实施例7 30.9 770% >99% >99%

Claims (5)

1.一种低成本高抗菌性能聚氨酯弹性体的制备方法,其特征在于制备步骤为:于反应釜中加入聚醚二元醇和高分子双羟基季铵盐抗菌剂的混合多元醇,经脱水后加入异氰酸酯和小分子二元醇扩链剂,50-80℃反应,降至室温,即制得抗菌聚氨酯;
其中,所用聚醚二元醇为聚乙二醇、聚丙二醇或聚四氢呋喃二醇,高分子双羟基季铵盐为双羟基聚环氧氯丙烷季铵盐,小分子二元醇扩链剂为乙二醇、丁二醇、1,4-环己烷二甲醇,1,4-双(2-羟乙氧基)苯,优选异氰酸酯基团与羟基的摩尔比为1:1。
2.根据权利要求1所述的一种低成本高抗菌性能聚氨酯弹性体的制备方法,其特征在于所述聚乙二醇分子量为1000-10000,聚丙二醇的分子量为1000-10000,聚四氢呋喃二醇的分子量为1000-3000。
3.根据权利要求1所述的一种低成本高抗菌性能聚氨酯弹性体的制备方法,其特征在于所述双羟基聚环氧氯丙烷季铵盐的分子量为500-3000,季铵化百分数为10%-70%,结构如下所示:
4.根据权利要求1所述的一种低成本高抗菌性能聚氨酯弹性体的制备方法,其特征在于所述异氰酸酯为甲苯二异氰酸酯、二苯甲烷二异氰酸酯、多亚甲基多苯基多异氰酸酯、奈二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种混合物。
5.根据权利要求1所述的一种低成本高抗菌性能聚氨酯弹性体的制备方法,其特征在于所述扩链剂为乙二醇,1,4-丁二醇,1,6-己二醇中的一种或几种混合物。
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