CN111100318A - 一种热塑性聚氨酯多孔膜的制备方法 - Google Patents
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Abstract
本发明公开了一种热塑性聚氨酯多孔膜的制备方法,该法可制备出不同孔结构的热塑性聚氨酯多孔膜,该法通过控制致孔剂含量与凝固浴来控制热塑性聚氨酯多孔薄膜的孔隙率与水蒸气透过率;该方法首先将热塑性聚氨酯或者热塑性聚氨酯及致孔剂溶解于溶剂之中,之后利用刮刀在平板上进行刮膜,在不同温度下浸泡在凝固浴中使其发生相分离,之后将膜在流水中浸泡洗出残余的溶剂及致孔剂,得到热塑性聚氨酯多孔薄膜。该制备方法简单、操作方便,可根据需要制备出不同水蒸气透过率与孔隙率的热塑性聚氨酯多孔薄膜,并且拥有良好的力学性能、生物相容性及化学稳定性,可应用于医用敷料、面料、皮革等领域,具有良好的应用前景。
Description
技术领域
本发明属于膜工程与科学技术领域,具体地说,涉及一种热塑性聚氨酯多孔膜的制备方法。
背景技术
生物基可降解热塑性聚氨酯(TPU)具有优异的力学性能、化学稳定性和良好的生物相容性及可降解性。在生物医学有着广泛应用,如医用敷料、导管、人造血管和心脏瓣膜。通过相分离、静电纺丝工艺、发泡或3D凝胶打印等方法,可将TPU制备成为多孔的膜结构。多孔TPU薄膜由于其具有良好的力学性能和可调节的多孔结构,被广泛应用于的伤口敷料、组织工程支架和分离膜等。生物基热塑性聚氨酯材料由于其可降解性及传统TPU的优异性能,可广泛用于医疗领域,如人工心脏、人工血管、组织工程支架、药物缓释及医用敷料领域有广泛应用。目前生物基热塑性聚氨酯材料属于较新型的材料,利用相分离法成膜并进行孔结构调节及性能调节的研究较少。
相分离法一般包括热致相分离、非溶剂致相分离及复合热致相分离法。其中非溶剂致相分离法是制备热塑性聚氨酯多孔薄膜常用的方法,非溶剂致相分离法又分为溶剂蒸发法、蒸气沉淀法和浸入沉淀法。浸入沉淀是应用最广泛的非溶剂致相分离,该方法是将高聚物溶液在支撑体上刮成一定厚度的薄层,然后浸入到非溶剂中,非溶剂和溶剂的交换使体系发生相分离。非溶剂致相分离方法制得的薄膜内部孔结构不均匀,表面具有皮层。
综上所述,通过非溶剂致相分离法得到的热塑性聚氨酯多孔薄膜具有致密的皮层,内部孔结构不均匀,对于薄膜透湿性能、透气性能及吸水性能具有影响,限制了其应用范围。
发明内容
本发明的技术目的是克服现有技术的不足,提供一种条件简单易于控制的热塑性聚氨酯多孔薄膜的制备方法,该制备方法可制备出不同孔结构和通透性的生物基热塑性聚氨酯多孔薄膜,同时保持生物基热塑性聚氨酯薄膜优异的力学性能、生物相容性、化学稳定性及可降解性。
为了实现上述目的,本发明采用如下技术方案:
一种热塑性聚氨酯多孔膜的制备方法,包括以下步骤:
(1)在45~85℃搅拌条件下,将生物基热塑性聚氨酯与有机溶剂均匀混合、溶解、过滤、脱泡后,得到质量浓度为15-40wt.%的聚合物铸膜液;
(2)将步骤(1)得到的聚合物铸膜液倾倒于聚四氟乙烯平板上,并用刮刀刮膜;
(3)将步骤(2)制得的薄膜放入不同温度的凝固浴中,通过相分离法成膜;相分离是利用水或非溶剂置换聚合物溶液中的溶剂,以得到具有三维网络结构的聚合物微孔薄膜;
(4)将步骤(3)制得的薄膜取出,置于去离子水中浸泡1-12h,拿出在30-50℃下烘3-12h即得到所述生物基热塑性聚氨酯多孔膜。
作为优选的,在上述的制备方法中,所述生物基热塑性聚氨酯材料硬度为85A~90A。
作为优选的,在上述的制备方法中,所述有机溶剂为N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种。
作为优选的,在上述的制备方法中,步骤(2)所述生物基热塑性聚氨酯与有机溶剂的混合中还添加致孔剂。
作为优选的,在上述的制备方法中,所述致孔剂为聚乙二醇,重均分子量在1000~4000;致孔剂在铸膜液中浓度用质量百分数表示为0~15%。
作为优选的,在上述的制备方法中,所述非溶剂为甲醇、乙醇的一种。
作为优选的,在上述的制备方法中,可通过调节凝固浴温度来得到不同孔结构生物基热塑性聚氨酯微孔膜,凝固浴温度在25-55℃。
本发明与现有技术相比,具有以下有益效果:
(1)本发明可根据需要制备出不同水蒸气透过率与孔隙率的热塑性聚氨酯多孔薄膜,本发明通过控制致孔剂含量与凝固浴来控制热塑性聚氨酯多孔薄膜的孔隙率与水蒸气透过率;制备方法可在相同组分下,调节薄膜表面孔密度,以控制通透性,且上表面孔径均在5μm以下,可有效阻隔细菌的入侵。
(2)具有优异的力学性能,拉伸断裂强度可达以上4Mpa,同时断裂伸长率达600%以上。
(3)具有外形美观,手感舒适的特点,下表面由于表面孔密度更大,手感更加柔软。
(4)具有海绵状结构,具备良好的吸湿性能,吸湿率达100%以上,且表面孔径小于10μm,如用于医用敷料,具备抵御外界细菌及吸收渗出液的双重功能。
(5)具有工艺简单,对设备要求低,能耗低,性能易于控制的特点。
(6)本发明制备过程的溶剂、凝固浴均可回收利用,绿色环保。
(7)本发明使用的生物基可降解热塑性聚氨酯可自然降解,环境友好,成品具有良好的生物相容性,安全性能优异。可应用于医用敷料、面料、皮革等领域,具有良好的应用前景。
附图说明
图1为实施例1热塑性聚氨酯多孔薄膜在500倍下的扫描电镜图像,a,b,c,d分别代表25℃、35℃、45℃、55℃凝固浴温度制备的薄膜;
图2为实施例1热塑性聚氨酯多孔薄膜断面在1000倍下的扫描电镜图像,a,b,c,d分别代表25℃、35℃、45℃、55℃凝固浴温度制备的薄膜;
图3为实施例2热塑性聚氨酯多孔薄膜在500倍下的扫描电镜图像,a,b,c,d分别代表25℃、35℃、45℃、55℃凝固浴温度制备的薄膜;
图4为实施例2热塑性聚氨酯多孔薄膜断面在1000倍下的扫描电镜图像,a,b,c,d分别代表25℃、35℃、45℃、55℃凝固浴温度制备的薄膜;
图5为实施例1热塑性聚氨酯多孔薄膜的水蒸气透过率;
图6为实施例2热塑性聚氨酯多孔薄膜的水蒸气透过率。
具体实施方式
实施例1:
将5g硬度为85A的生物基热塑性聚氨酯,20g N,N-二甲基甲酰胺,在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃、35℃、45℃、55℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜。所得薄膜孔隙率为56.4%随凝固浴温度提升,该膜的内部孔结构均匀性提升,透湿性能及力学性能均有所提升。所得薄膜孔隙率变化不大,平均孔隙率为56.3%。
实施例2:
将5g硬度为85A的生物基热塑性聚氨酯,20g N,N-二甲基甲酰胺,1.25g聚乙二醇(Mn2000)在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃、35℃、45℃、55℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜,随凝固浴温度提升,该膜的表面孔密度、内部孔结构均匀性提升,透湿性能及力学性能均有所提升。所得薄膜孔隙率随温度变化不大,平均孔隙率为66.2%,凝固浴温度为55℃时,表面孔密度远大于实施例1中制得薄膜。
实施例3:
将5g硬度为85A的生物基热塑性聚氨酯,20g N,N-二甲基甲酰胺,3.125g聚乙二醇(Mn2000)在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃、35℃、45℃、55℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜,随凝固浴温度提升,该膜的表面孔密度、内部孔结构均匀性提升,透湿性能及力学性能均有所提升。随凝固浴温度变化所得薄膜孔隙率变化不大,平均孔隙率为78.1%,凝固浴温度为35℃、45℃、55℃时,表面孔密度远大于实施例1中制得薄膜。
实施例4:
将5g硬度为85A的生物基热塑性聚氨酯,20g N,N-二甲基甲酰胺,1.25g聚乙二醇(Mn1000)在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜,该膜孔隙率为62.6%,表面孔密度与尺寸与实施例1中相差不大,水蒸气透过率为2226.85g/m2.d。
实施例5:
将5g硬度为85A的生物基热塑性聚氨酯,20g N,N-二甲基甲酰胺,1.25g聚乙二醇(Mn4000)在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜,该膜孔隙率为63.1%,表面孔密度及尺寸略大于实施例1中薄膜,水蒸气透过率为2445.62g/m2.d。
实施例6:
将5g硬度为90A的生物基热塑性聚氨酯,20g N,N-二甲基甲酰胺,1.25g聚乙二醇(Mn2000)在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜,该膜孔隙率为60.7%,表面孔密度及尺寸略大于实施例1中薄膜,水蒸气透过率为2352.52g/m2.d。
实施例7:
将5g硬度为90A的生物基热塑性聚氨酯,20g N,N-二甲基乙酰胺,1.25g聚乙二醇(Mn2000)在65℃加热、搅拌下均匀混合、溶解、过滤、脱泡后得到生物基热塑性聚氨酯铸膜液;将其浇铸在玻璃平板上,用刮刀刮制成350μm厚的薄膜,并将其置于70%的空气湿度环境下20s,放入温度为25℃的乙醇凝固浴中浸泡20min,取出该膜,在去离子水中浸泡1h,拿出在40℃下烘3h即得热塑性聚氨酯多孔薄膜,该膜孔隙率为60.7%,表面孔密度及尺寸略大于实施例1中薄膜,水蒸气透过率为2429.21g/m2.d。
注:以上实施例中使用的生物基热塑性聚氨酯弹性体可从市场上购得,本发明所使用生物基热塑性聚氨酯弹性体为美国 Estane公司的54321 TPU以及54353 TPU。
Claims (7)
1.一种热塑性聚氨酯多孔膜的制备方法,其特征在于包括以下步骤:
(1)在45~85℃搅拌条件下,将生物基热塑性聚氨酯与有机溶剂均匀混合、溶解、过滤、脱泡后,得到质量浓度为15-40wt.%的聚合物铸膜液;
(2)将步骤(1)得到的聚合物铸膜液倾倒于聚四氟乙烯平板上,并用刮刀刮膜;
(3)将步骤(2)制得的薄膜放入不同温度的凝固浴中,通过相分离法成膜;相分离是利用水或非溶剂置换聚合物溶液中的溶剂,以得到具有三维网络结构的聚合物微孔薄膜;
(4)将步骤(3)制得的薄膜取出,置于去离子水中浸泡1-12h,拿出在30-50℃下烘3-12h即得到所述生物基热塑性聚氨酯多孔膜。
2.如权利要求1所述的制备方法,其特征在于,所述生物基热塑性聚氨酯材料硬度为85A~90A。
3.如权利要求1所述的制备方法,其特征在于,所述有机溶剂为N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种。
4.如权利要求1所述的制备方法,其特征在于,步骤(2)所述生物基热塑性聚氨酯与有机溶剂的混合中还添加致孔剂。
5.如权利要求4所述的制备方法,其特征在于,所述致孔剂为聚乙二醇,重均分子量在1000~4000;致孔剂在铸膜液中浓度用质量百分数表示为0~15%。
6.如权利要求1所述的制备方法,其特征在于,所述非溶剂为甲醇、乙醇的一种。
7.如权利要求1所述的制备方法,其特征在于,可通过调节凝固浴温度来得到不同孔结构生物基热塑性聚氨酯微孔膜,凝固浴温度在25-55℃。
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