CN111269558A - 一种置留针固定敷料面层聚氨酯半透膜的制备方法 - Google Patents

一种置留针固定敷料面层聚氨酯半透膜的制备方法 Download PDF

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CN111269558A
CN111269558A CN202010218009.5A CN202010218009A CN111269558A CN 111269558 A CN111269558 A CN 111269558A CN 202010218009 A CN202010218009 A CN 202010218009A CN 111269558 A CN111269558 A CN 111269558A
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孙凯
徐红纳
闫磊
王妍
桂金秋
蔡克瑞
刘春玲
崔荣军
韩彦龙
晁岳刚
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Mudanjiang Medical University
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Abstract

本发明公开了一种置留针固定敷料面层聚氨酯半透膜的制备方法，涉及聚氨酯材料技术领域，先利用聚醚二元醇和甲苯二异氰酸酯合成‑NCO封端的聚氨酯预聚体，再以N‑羟乙基丙烯酰胺作为改性剂，聚氨酯预聚体结构上的‑NCO与N‑羟乙基丙烯酰胺结构上的‑OH反应生成酰胺改性聚氨酯预聚体，并通过辅料的配合添加制得聚氨酯半透膜；所制聚氨酯半透膜的防水透气性能好，远优于本领域的常规聚氨酯薄膜，从而很好地满足置留针固定敷料的使用要求。

Description

一种置留针固定敷料面层聚氨酯半透膜的制备方法
技术领域：
本发明涉及聚氨酯材料技术领域，具体涉及一种置留针固定敷料面层聚氨酯半透膜的制备方法。
背景技术：
置留针适用于需要长期输液的人群，免去了每天扎针的苦恼。为了固定置留针以及防止针头被污染，通常利用敷料来覆盖以固定置留针。
目前，敷料面层通常为塑料薄膜，利用其透明性以便于观察置留针的情况。而敷料所用塑料薄膜不仅要求其具有透明性，还需具备透气和防水性能，其目的是为了避免因敷料内部水汽难以扩散蒸发或者留针处沾水后水分进入敷料内部而使敷料在皮肤上的服帖性下降甚至因污染针头而造成感染。尤其在高温季节，如果敷料所用塑料薄膜的透气性不好，将会造成敷料与留针处皮肤的严重粘连，进而可能会引发皮肤炎症。
发明内容：
本发明所要解决的技术问题在于提供一种置留针固定敷料面层聚氨酯半透膜的制备方法，通过改变聚氨酯预聚体的化学结构和功能助剂的配合添加来优化所制聚氨酯半透膜的透气性和防水性，以满足置留针固定敷料对聚氨酯半透膜的使用要求。
本发明所要解决的技术问题采用以下的技术方案来实现：
一种置留针固定敷料面层聚氨酯半透膜的制备方法，包括以下制备步骤：
(1)聚氨酯预聚体的合成：将聚醚二元醇经真空脱水后加热至80-90℃，再加入甲苯二异氰酸酯，并于80-90℃下反应，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入N-羟乙基丙烯酰胺和浓硫酸，加热至70-80℃反应，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括硅酸镁铝、氧化聚乙烯、氢化蓖麻油；
(4)聚氨酯半透膜的成型：向上述所制酰胺改性聚氨酯预聚体中加入乙醇配成溶液，再加入辅料和水，加热至回流状态搅拌，流延成膜，加热除去乙醇，经室温固化得到聚氨酯半透膜。
所述聚醚二元醇选自聚醚二元醇N-210、N-220、N-240中的一种。
所述聚醚二元醇、甲苯二异氰酸酯、N-羟乙基丙烯酰胺的摩尔比为1:2-4:1。
所述浓硫酸的用量为聚醚二元醇、甲苯二异氰酸酯与N-羟乙基丙烯酰胺总质量的0.1-0.5％。
所述硅酸镁铝、氧化聚乙烯、氢化蓖麻油的质量比为5-10:1-5:1-5。
所述酰胺改性聚氨酯预聚体、乙醇、辅料、水的质量比为50:30-80:5-15:1-10。
硅酸镁铝作为无机填料，利用其胶体性质和吸附性能以起到增稠和填充的作用。
氧化聚乙烯作为增塑剂和分散剂，作用是优化聚氨酯的成膜性。
氢化蓖麻油作为润滑剂，作用是改善聚氨酯的流动性。
基于从辅料角度来优化聚氨酯半透膜的水透气性能的目的，本发明还对上述辅料组分进行了添加，所述辅料还包括二氢茉莉酮酸甲酯。
所述二氢茉莉酮酸甲酯与硅酸镁铝的质量比为1-5:5-10。
二氢茉莉酮酸甲酯的化学名称是2-戊基环戊酮-3-乙酸甲酯，通常在香水和化妆品配方中作为香精使用，而在本发明中通过二氢茉莉酮酸甲酯作为辅料组分的添加能够明显改善聚氨酯半透膜的防水透气性能。
二氢茉莉酮酸甲酯虽然能够优化聚氨酯半透膜的防水透气性能，但由于其香味明显，部分人群不接受这种味道，因此本发明还尝试采用脯氨酸双(叔丁基氨基)丙酯替代二氢茉莉酮酸甲酯，并发现脯氨酸双(叔丁基氨基)丙酯能够更加优化聚氨酯半透膜的防水透气性能。
所述辅料还包括脯氨酸双(叔丁基氨基)丙酯，由脯氨酸与1,3-双(叔丁基氨基)-2-丙醇制成。
反应方程式如下：
Figure BDA0002425091180000031
本发明的有益效果是：本发明先利用聚醚二元醇和甲苯二异氰酸酯合成-NCO封端的聚氨酯预聚体，再以N-羟乙基丙烯酰胺作为改性剂，聚氨酯预聚体结构上的-NCO与N-羟乙基丙烯酰胺结构上的-OH反应生成酰胺改性聚氨酯预聚体，并通过辅料的配合添加制得聚氨酯半透膜；所制聚氨酯半透膜的防水透气性能好，远优于本领域的常规聚氨酯薄膜，从而很好地满足置留针固定敷料的使用要求。
具体实施方式：
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施例，进一步阐述本发明。
以下原料的来源：
聚醚二元醇N-210购自上海金锦乐实业有限公司；甲苯二异氰酸酯购自济南莱恩化工有限责任公司；N-羟乙基丙烯酰胺和二氢茉莉酮酸甲酯购自上海源叶生物科技有限公司；98％浓硫酸购自扬州市华富化工有限公司；硅酸镁铝购自广州亿峰化工科技有限公司；氧化聚乙烯购自南京扬子精细化工有限责任公司；氢化蓖麻油购自上海众燊新材料科技有限公司；脯氨酸购自无锡久信生物科技有限公司；1,3-双(叔丁基氨基)-2-丙醇购自上海平果医药科技有限公司。
实施例1
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入5.75g N-羟乙基丙烯酰胺和0.4g 98％浓硫酸，加热至80℃反应5h，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括8g硅酸镁铝、3g氧化聚乙烯、2g氢化蓖麻油；
(4)聚氨酯半透膜的成型：向上述所制50g酰胺改性聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
实施例2
将实施例1中的辅料用量修改为5g，其余同实施例1。
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入5.75g N-羟乙基丙烯酰胺和0.4g 98％浓硫酸，加热至80℃反应5h，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括5g硅酸镁铝、3g氧化聚乙烯、2g氢化蓖麻油；
(4)聚氨酯半透膜的成型：向上述所制50g酰胺改性聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
对照例1
将实施例1中的氢化蓖麻油去除，其余同实施例1。
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入5.75g N-羟乙基丙烯酰胺和0.4g 98％浓硫酸，加热至80℃反应5h，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括8g硅酸镁铝、3g氧化聚乙烯；
(4)聚氨酯半透膜的成型：向上述所制50g酰胺改性聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
对照例2
将实施例1中的氧化聚乙烯去除，其余同实施例1。
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入5.75g N-羟乙基丙烯酰胺和0.4g 98％浓硫酸，加热至80℃反应5h，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括8g硅酸镁铝、2g氢化蓖麻油；
(4)聚氨酯半透膜的成型：向上述所制50g酰胺改性聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
对照例3
将实施例1中的聚氨酯预聚体的接枝改性去除，其余同实施例1。
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)辅料的准备：辅料包括8g硅酸镁铝、3g氧化聚乙烯、2g氢化蓖麻油；
(3)聚氨酯半透膜的成型：向上述所制50g聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
实施例3
在实施例1的辅料中增加3g二氢茉莉酮酸甲酯，其余同实施例1。
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入5.75g N-羟乙基丙烯酰胺和0.4g 98％浓硫酸，加热至80℃反应5h，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括8g硅酸镁铝、3g氧化聚乙烯、3g二氢茉莉酮酸甲酯、2g氢化蓖麻油；
(4)聚氨酯半透膜的成型：向上述所制50g酰胺改性聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
实施例4
将实施例3中的二氢茉莉酮酸甲酯替换为等量的脯氨酸双(叔丁基氨基)丙酯，其余同实施例1。
(1)聚氨酯预聚体的合成：将50g聚醚二元醇N-210经真空脱水后加热至85℃，再加入25g甲苯二异氰酸酯，并于85℃下反应5h，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入5.75g N-羟乙基丙烯酰胺和0.4g 98％浓硫酸，加热至80℃反应5h，得到酰胺改性聚氨酯预聚体；
(3)脯氨酸双(叔丁基氨基)丙酯的制备：向水中加入2.3g脯氨酸与4g 1,3-双(叔丁基氨基)-2-丙醇，并滴加0.06g 98％浓硫酸作为催化剂，加热至80℃反应2h，减压浓缩除去水分，浓缩剩余物即为脯氨酸双(叔丁基氨基)丙酯；1H NMR(CDCl3,400MHz),δ:5.51(s,2H),4.56(m,1H),3.57(m,1H),2.80(m,2H),2.76(d,4H),2.01(m,1H),1.98-1.66(m,4H),1.23(s,18H)；ESI-MS:m/z＝301.26[M+2]+.
(4)辅料的准备：辅料包括8g硅酸镁铝、3g氧化聚乙烯、3g脯氨酸双(叔丁基氨基)丙酯、2g氢化蓖麻油；
(5)聚氨酯半透膜的成型：向上述所制50g酰胺改性聚氨酯预聚体中加入45g乙醇配成溶液，再加入8g辅料和4g水，加热至回流状态搅拌15min，流延成膜，加热除去乙醇，经室温固化12h得到厚度0.5mm的聚氨酯半透膜。
对照例4
专利CN 103910969A实施例4所制聚氨酯薄膜。
对上述所制酰胺改性聚氨酯预聚体经水洗除去未反应的N-羟乙基丙烯酰胺，再进行红外光谱检测。结果显示红外光谱中在1680cm-1处出现酰胺的收缩振动峰，说明N-羟乙基丙烯酰胺确实被接枝到聚氨酯预聚体上。
防水透气性能测试试验：
对上述所制聚氨酯半透膜进行防水透气性能测试，测试结果如表1所示。
透气性测试方法按照标准ASTM D737-2018，以透湿量为指标。
防水性测试方法按照标准JIS L1099-2006 B法，以耐静水压为指标。
Figure BDA0002425091180000061
Figure BDA0002425091180000071
由表1可知，实施例1-4相对于对照例1-3来说，通过所述辅料的添加和对聚氨酯预聚体的所述接枝改性明显改善了最终所制聚氨酯半透膜的防水透气性能，并且所述辅料中氢化蓖麻油、氧化聚乙烯、二氢茉莉酮酸甲酯、脯氨酸双(叔丁基氨基)丙酯的添加有效提高了所制聚氨酯半透膜的防水透气性能。
皮肤刺激性测试试验：
取20只重量在2-2.5kg的白兔，试验前背部剃毛，皮肤无受损，背部皮肤划分为4个区域；将实施例1、实施例3、实施例4所制聚氨酯半透膜(由于其他实施例和对照例并未添加新的制备原料，因此不对其进行皮肤刺激性试验)分别贴敷于其中3个区域，剩余1个区域作为空白对照；分别于24h、48h、72h后观察皮肤状态，并记录皮肤情况。
结果显示，实施例1、实施例3、实施例4所制聚氨酯半透膜使用安全，无过敏及皮肤刺激性问题发生。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (8)

1.一种置留针固定敷料面层聚氨酯半透膜的制备方法，其特征在于，包括以下制备步骤：
(1)聚氨酯预聚体的合成：将聚醚二元醇经真空脱水后加热至80-90℃，再加入甲苯二异氰酸酯，并于80-90℃下反应，得到聚氨酯预聚体；
(2)聚氨酯预聚体的接枝改性：向上述所制聚氨酯预聚体中加入N-羟乙基丙烯酰胺和浓硫酸，加热至70-80℃反应，得到酰胺改性聚氨酯预聚体；
(3)辅料的准备：辅料包括硅酸镁铝、氧化聚乙烯、氢化蓖麻油；
(4)聚氨酯半透膜的成型：向上述所制酰胺改性聚氨酯预聚体中加入乙醇配成溶液，再加入辅料和水，加热至回流状态搅拌，流延成膜，加热除去乙醇，经室温固化得到聚氨酯半透膜。
2.根据权利要求1所述的制备方法，其特征在于：所述聚醚二元醇选自聚醚二元醇N-210、N-220、N-240中的一种。
3.根据权利要求1所述的制备方法，其特征在于：所述聚醚二元醇、甲苯二异氰酸酯、N-羟乙基丙烯酰胺的摩尔比为1:2-4:1。
4.根据权利要求1所述的制备方法，其特征在于：所述浓硫酸的用量为聚醚二元醇、甲苯二异氰酸酯与N-羟乙基丙烯酰胺总质量的0.1-0.5％。
5.根据权利要求1所述的制备方法，其特征在于：所述硅酸镁铝、氧化聚乙烯、氢化蓖麻油的质量比为5-10:1-5:1-5。
6.根据权利要求1所述的制备方法，其特征在于：所述酰胺改性聚氨酯预聚体、乙醇、辅料、水的质量比为50:30-80:5-15:1-10。
7.根据权利要求1所述的制备方法，其特征在于：所述辅料还包括二氢茉莉酮酸甲酯。
8.根据权利要求7所述的制备方法，其特征在于：所述二氢茉莉酮酸甲酯与硅酸镁铝的质量比为1-5:5-10。
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