CN107964085A - 一种多嵌段聚氨酯形状记忆高分子材料及其制备方法 - Google Patents
一种多嵌段聚氨酯形状记忆高分子材料及其制备方法 Download PDFInfo
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Abstract
本发明提出一种基于丙交酯和1,4‑对二氧环己酮的多嵌段聚氨酯形状记忆高分子材料,它是以端羟基聚(丙交酯‑co‑1,4‑对二氧环己酮)为软段,以二异氰酸酯与含活泼氢的双官能团小分子形成的氨酯链段或脲基链段产物为硬段,形状记忆温度为20‑55℃。本发明进一步还提出该材料的制备方法。本发明提供的基于丙交酯和1,4‑对二氧环己酮的形状记忆高分子材料是一种集良好生物可降解性、生物相容性、高力学强度与柔韧性,以及形状记忆性能于一身的高分子材料,其形变温度可调节在人体温度附近,因此适用于外科手术或医疗器械植入体。
Description
技术领域
本发明涉及一种多嵌段聚氨酯形状记忆高分子材料及其制备方法,属于生物医用高分子材料领域。
背景技术
形状记忆是指具有某一种初始状态的制品,经过形变并定型后,在特定的外界刺激下自动恢复原始形态的现象。目前研究的形状记忆材料主要有形状记忆合金、陶瓷和高分子材料。其中,形状记忆高分子材料可分为三大类:温度敏感型、光敏感型和离子敏感型。对于温度敏感型形状记忆高分子材料,其形状记忆性能常常由材料的组成、结构和加工工艺决定。形状记忆高分子材料通常含有软段和硬段并具有软段硬段两相分离结构,硬段的功能是保持原始形态,而软段的功能是提供形变并保持形变。
形状记忆材料被广泛应用于工业和医疗器械领域。其中,Ni-Ti合金形状记忆材料,由于具有体积小、重量轻、形变大和支撑力强等优点已被应用于临床。但是,Ni-Ti合金在长期植入体内后,镍离子的渗出有损健康;此外,Ni-Ti合金中Ni含量的微小变化会影响材料的性能,而且这种影响很难人为控制。形状记忆高分子材料由于其设计灵活、加工方便,且通过选择合适的单体实现良好的生物相容性和生物可降解性,因而成为了取代形状记忆合金的理想选择。
发明内容
本发明的目的在于提供一种基于丙交酯和1,4-对二氧环己酮的多嵌段聚氨酯形状记忆高分子材料。
本发明提供的基于LA和PDO的多嵌段聚氨酯形状记忆高分子材料,它是由LA与PDO形成的两端带羟基的聚(丙交酯-co-1,4-对二氧环己酮)(HO-P(LA-co-PDO)-OH),与二异氰酸酯和小分子二醇或小分子二胺反应而成。HO-P(LA-co-PDO)-OH是软段,二异氰酸酯与小分子二醇或小分子二胺形成的氨酯链段或脲基链段是硬段,二者共同组成了基于LA和PDO的多嵌段聚氨酯形状记忆聚合物。
本发明中,基于LA和PDO的多嵌段聚氨酯形状记忆聚合物的硬段中,二异氰酸酯与小分子二醇火小分子二胺形成的氨酯键或脲键是刚性基团,不易发生变形,并且氨酯键或脲键间可形成大量的N-H和O-H氢键,因此,在整个体系中充当了物理交联点,形成了硬段相区。而两端带羟基的聚(丙交酯-co-1,4-对二氧环己酮)软段(HO-P(LA-co-PDO)-OH)是由LA、PDO与小分子二醇反应而成,主要是由酯键和醚键组成,调节DL-LA与PDO的摩尔比以及小分子二醇的用量可调节HO-P(LA-co-PDO)-OH的分子量和共聚物的单体组成,从而进一步调节HO-P(LA-co-PDO)-OH的玻璃化转变温度Tg,将Tg控制在20-55℃。在本发明中,Tg即为变形温度。将该聚氨酯在高于变形温度时加工成一定形状(永久形状),然后改变形状并在冷却至低于该温度时定型(临时形状);当再次受热,温度高于变形温度时,该聚氨酯的临时形状能迅速恢复到永久形状,表现出形状记忆的性能。
本发明提供的基于LA和PDO的多嵌段聚氨酯形状记忆聚合物,其分子链的基本组成是LA、PDO、小分子二醇或小分子二胺,基本连接时酯键、醚键、氨酯键或脲键,都可以通过水解或酶解的方式断裂成小分子化合物,因此,具有可降解性。
本发明的另一目的在于提供一种基于LA和PDO的多嵌段聚氨酯形状记忆聚合物的合成方法,其制备过程包括两个部分:
(1)端羟基聚(丙交酯-co-1,4-对二氧环己酮)的制备,即软段HO-P(LA-co-PDO)-OH的制备:以小分子二元醇为助引发剂,辛酸亚锡为引发剂,丙交酯和1,4-对二氧环己酮在130-150℃下真空熔融开环聚合而成,反应时间8-36小时;其中,小分子二醇选自乙二醇、丁二醇、二乙醇胺或其他含两个羟基的小分子物质;调节小分子二醇的用量,以及丙交酯和1,4-对二氧环己酮的摩尔比,将端羟基聚(丙交酯-co-1,4-对二氧环己酮)软段的分子量调节在2000-20000之间;
(2)多嵌段聚氨酯的制备:将HO-P(LA-co-PDO)-OH与二异氰酸酯、辛酸亚锡按一定比例混合均匀后,先反应形成两端含异氰酸酯的预聚体,然后再加入小分子二醇或小分子二胺,制得基于LA和PDO的多嵌段聚氨酯形状记忆聚合物。
在软段HO-P(LA-co-PDO)-OH的制备中,所用的助引发剂小分子二醇可以是乙二醇,丙二醇,丁二醇,或其他的含两个羟基的小分子化合物。调节助引发剂小分子二醇的用量,可调节HO-P(LA-co-PDO)-OH的分子量。通常,随助引发剂小分子二醇用量的增加,HO-P(LA-co-PDO)-OH的分子量逐渐减小。同事,由于DL-LA的开环聚合活性高于PDO的开环聚合活性,因此,随DL-LA与PDO摩尔比的减小,HO-P(LA-co-PDO)-OH的分子量也逐渐减小。总体而言,调节助引发剂小分子二醇的用量以及DL-LA与PDO的摩尔比,可将HO-P(LA-co-PDO)-OH的分子量控制在2000-20000之间,并进一步将HO-P(LA-co-PDO)-OH的Tg控制在20-55℃。当将Tg调节在体温附近时,则可适用于外科手术或医疗植入体。
在本发明多嵌段聚氨酯的制备中,所使用的二异氰酸酯选自脂肪族二异氰酸酯、芳香族二异氰酸酯、脂环族二异氰酸酯及其混合物。所述脂肪族二异氰酸酯是1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或4,4’-二环己基甲烷二异氰酸酯;所述芳香族二异氰酸酯是4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或苯二亚甲基二异氰酸酯。作为扩链剂的小分子二元醇可以是乙二醇、丙二醇、丁二醇和其他的含两个羟基的小分子化合物,小分子二胺可以是乙二胺、丙二胺、丁二胺、己二胺和其他含两个氨基的小分子化螯合物。
在本发明多嵌段聚氨酯的制备中,二异氰酸酯与端羟基聚(丙交酯-co-1,4-对二氧环己酮)的摩尔用量之比控制在3:1-1.1:1,辛酸亚锡与端羟基聚(丙交酯-co-1,4-对二氧环己酮)的摩尔用量之比控制在0.001~0.01,与而作为扩链剂的小分子二醇或小分子二胺的摩尔用量为二异氰酸酯摩尔用量的0.4~1.0。为了得到高分子量的多嵌段聚氨酯,二异氰酸酯的摩尔用量最好等于端羟基聚(丙交酯-co-1,4-对二氧环己酮)与小分子二醇或小分子二胺的摩尔用量之和。更好地,为了获得软硬段分布均匀的高分子量的多嵌段聚氨酯,二异氰酸酯的摩尔用量等于端羟基聚(丙交酯-co-1,4-对二氧环己酮)与小分子二醇或小分子二胺的摩尔用量之和,且二异氰酸酯的摩尔用量与端羟基聚的摩尔用量之比为2:1,二异氰酸酯的摩尔用量与小分子二醇或小分子二胺的摩尔用量之比为2:1。
由于聚乳酸(PLA)和聚对二氧环己酮(PPDO)都是FDA批准使用的具有良好生物相容性和生物可降解性的生物高分子材料。PLA力学强度高,但脆性较大,而PPDO柔韧性好,二者结合可实现材料的高强度高韧性。因此,本发明提供的基于LA和PDO的形状记忆高分子材料是一种集良好生物可降解性、生物相容性、高力学强度与柔韧性,以及形状记忆性能于一身的高分子材料。其变形温度可调节在人体温度附近,因此适用于外科手术或医疗器械植入体。
具体实施方式
实施例分为两部分:第一部分,软段HO-P(LA-co-PDO)-OH的制备;第二部分,形状记忆性聚氨酯的合成。
第一部分,软段HO-P(LA-co-PDO)-OH的制备
实施例1
称取经过蒸馏、重结晶的D,L-丙交酯(LA)5.000g(0.03472mol),经过四次重结晶的1,4-对二氧环己酮(PDO)1.25mL(密度:1.266g/mL,0.01551mol),辛酸亚锡(T-9)的氯仿溶液16.1uL(3.4×10-6mol),乙二醇32uL,充分混合均匀,抽真空10~20min。密封后,置入130℃恒温油浴中,持续16hr。反应产物经丙酮溶解后,用正己烷提纯,常温真空干燥,得3.8g端羟基聚合物HO-P(LA-co-PDO)-OH。端羟基分析法测得其数均分子量为2100,Tg=20.54℃。
实施例2
称取经过蒸馏、重结晶的D,L-丙交酯(LA)5.000g(0.03472mol),经过四次重结晶的1,4-对二氧环己酮(PDO)1.25mL(密度:1.266g/mL,0.01551mol),辛酸亚锡(T-9)的氯仿溶液16.1uL(3.4×10-6mol),乙二醇55uL,充分混合均匀,抽真空10~20min。密封后,置入130℃恒温油浴中,持续16hr。反应产物经丙酮溶解后,用正己烷提纯,常温真空干燥,得3.6g端羟基聚合物HO-P(LA-co-PDO)-OH。端羟基分析法测得其数均分子量为2400,Tg=21.98℃。
第二部分:形状记忆聚氨酯的合成
实施例3
将实施例1所得端羟基聚合物HO-P(LA-co-PDO)-OH、1,6-六亚甲基二异氰酸酯(HDI)和辛酸亚锡按摩尔比1.0:1.1:0.005混合后,加入15mL经严格除水的N,N二甲基甲酰胺,混合均匀。75℃下反应4hr后,冷却,将反应产物缓慢滴加到丁二醇的N,N二甲基甲酰胺溶液中(丁二醇与HO-P(LA-co-PDO)-OH的摩尔比为0.1:1)后,冰浴条件下持续反应2hr。产物经过N,N二甲基甲酰胺-水共沉淀提纯,无水乙醇浸泡后,常温下真空干燥,得多嵌段聚氨酯。玻璃化转变温度Tg=22.48℃(DSC测定)
实施例4
将实施例2所得端羟基聚合物HO-P(LA-co-PDO)-OH、4,4-二苯基甲烷二异氰酸酯(MDI)和辛酸亚锡按摩尔比1.0:1.1:0.005混合后,加入15mL经严格除水的N,N二甲基甲酰胺,混合均匀。75℃下反应4hr后,冷却,将反应产物缓慢滴加到己二胺的N,N二甲基甲酰胺溶液中(己二胺与HO-P(LA-co-PDO)-OH的摩尔比为0.1:1)后,冰浴条件下持续反应2hr。产物经过N,N二甲基甲酰胺-水共沉淀提纯,无水乙醇浸泡后,常温下真空干燥,得多嵌段聚氨酯。玻璃化转变温度Tg=25.02℃(DSC测定)。
Claims (6)
1.基于丙交酯和1,4-对二氧环己酮的多嵌段聚氨酯形状记忆高分子材料的合成方法,其合成包括以下两部分:
端羟基聚(丙交酯-co-1,4-对二氧环己酮)软段的制备:以辛酸亚锡为引发剂,小分子二醇为助引发剂,由丙交酯和1,4-对二氧环己酮在130-150℃下真空熔融开环聚合而成,反应时间8-36小时;其中,小分子二醇选自乙二醇、丁二醇、二乙醇胺或其他含两个羟基的小分子物质;调节小分子二醇的用量,以及丙交酯和1,4-对二氧环己酮的摩尔比,将端羟基聚(丙交酯-co-1,4-对二氧环己酮)软段的分子量调节在2000-20000之间;
多嵌段聚氨酯的制备:将端羟基聚(丙交酯-co-1,4-对二氧环己酮)与二异氰酸酯、辛酸亚锡按比例混合均匀后,先反应形成两端含异氰酸酯的预聚体,然后再加入小分子二醇或小分子二胺,制得基于丙交酯和1,4-对二氧环己酮的多嵌段聚氨酯形状记忆聚合物;二异氰酸酯与端羟基聚(丙交酯-co-1,4-对二氧环己酮)的摩尔用量之比控制在3:1-1.1:1,辛酸亚锡与端羟基聚(丙交酯-co-1,4-对二氧环己酮)的摩尔用量之比控制在0.001~0.01,而小分子二醇或小分子二胺的摩尔用量为二异氰酸酯摩尔用量的0.4~1.0。
2.如权利要求1所述的合成方法,其特征在于:所述二异氰酸酯的摩尔用量等于端羟基聚(丙交酯-co-1,4-对二氧环己酮)与小分子二醇或小分子二胺的摩尔用量之和。
3.如权利要求1所述的合成方法,其特征在于:所述二异氰酸酯的摩尔用量等于端羟基聚(丙交酯-co-1,4-对二氧环己酮)与小分子二醇或小分子二胺的摩尔用量之和,且二异氰酸酯的摩尔用量与端羟基聚的摩尔用量之比为2:1,二异氰酸酯的摩尔用量与小分子二醇或小分子二胺的摩尔用量之比为2:1。
4.如权利要求1、2或3所述的合成方法,其特征在于:所述二异氰酸酯选自脂肪族二异氰酸酯、芳香族二异氰酸酯、脂环族二异氰酸酯及其混合物。
5.如权利要求4所述的合成方法,其特征在于:所述脂肪族二异氰酸酯是1,6-六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或4,4’-二环己基甲烷二异氰酸酯;所述芳香族二异氰酸酯是4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯或苯二亚甲基二异氰酸酯。
6.如权利要求5所述的合成方法,其特征在于:所述小分子二元醇是乙二醇、丙二醇或丁二醇;所述小分子二胺是乙二胺、丙二胺、丁二胺或己二胺。
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