CN116355338B - 一种自黏附柔性复合膜及其制备方法和应用 - Google Patents
一种自黏附柔性复合膜及其制备方法和应用 Download PDFInfo
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 25
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 14
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
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- LPBCKGCDISBXBI-UHFFFAOYSA-N (2-borono-3-phenylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=CC=CC=2)=C1B(O)O LPBCKGCDISBXBI-UHFFFAOYSA-N 0.000 claims description 4
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- PGHSKTKIQIBATG-ZAAWVBGYSA-N 2-(3,4-dihydroxyphenyl)-5,7-dihydroxy-3-[(2s,3r,4s,5s,6r)-3,4,5-trihydroxy-6-[[(2r,3r,4r,5r,6s)-3,4,5-trihydroxy-6-methyloxan-2-yl]oxymethyl]oxan-2-yl]oxychromen-4-one;hydrate Chemical compound O.O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 PGHSKTKIQIBATG-ZAAWVBGYSA-N 0.000 claims description 2
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- 125000005619 boric acid group Chemical group 0.000 claims description 2
- CWVRJTMFETXNAD-JUHZACGLSA-N chlorogenic acid Chemical compound O[C@@H]1[C@H](O)C[C@@](O)(C(O)=O)C[C@H]1OC(=O)\C=C\C1=CC=C(O)C(O)=C1 CWVRJTMFETXNAD-JUHZACGLSA-N 0.000 claims description 2
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- FAARLWTXUUQFSN-UHFFFAOYSA-N methylellagic acid Natural products O1C(=O)C2=CC(O)=C(O)C3=C2C2=C1C(OC)=C(O)C=C2C(=O)O3 FAARLWTXUUQFSN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
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Abstract
本发明涉及一种自黏附柔性复合膜及其制备方法和应用,由交联剂溶液、聚乙烯醇、多元醇和去离子水反应制成,该交联剂溶剂由含邻苯二酚单体、能形成交联结构的多臂硼酸单体、碱和去离子水混合反应制成,该多元醇为一缩二乙二醇或三缩乙二醇。本发明将黏性因子邻苯二酚引入了硼酸酯聚合物体系中,同时借助了多元醇的增韧作用,使制备的薄膜具有优异的柔韧性、自黏附能力、良好的生物相容性以及出色的机械强度和化学稳定性。
Description
技术领域
本发明属于功能性复合膜材料技术领域,具体涉及了一种自黏附柔性复合膜及其制备方法和应用。
背景技术
皮肤贴片是一种新型的医疗材料,它可以贴附在皮肤表面,通过渗透、吸收、反应等方式将药物、生物传感器等物质传递到人体内部,具有精准治疗、快速吸收、方便携带、无创伤等优点。随着人们对健康的需求和对生活质量的要求不断提高,皮肤贴片在医疗、美容、保健等领域中得到了越来越广泛的应用和发展。
高分子材料具有生物相容性好、柔韧性高、透气性好、吸附性强、耐水性好和可降解性等优点,是皮肤贴片的主要材料之一。通过调节高分子材料的物理、化学、生物学性质,可以满足不同的应用需求。
聚乙烯醇(PVA)是一种生物相容性良好的高分子材料,对机体和组织细胞无毒、无刺激,具有较好的降解性能,因此,被广泛应用于医疗领域中的皮肤贴片制备。但是PVA制备的薄膜具有较高的拉伸模量,弹性较低,遇水溶解,与皮肤的贴合性较差,需要采用粘合剂进行加固。因此,为了提高PVA薄膜的弹性和机械性能,现有技术中,本领域普通技术人员会将PVA与其他聚合物交联或共混以改善机械性能,常用的交联方式包括物理交联和化学交联。
硼酸酯键是一类生物相容性良好的动态共价键,可以与具有二醇结构的功能性嵌段共聚物形成交联网络,因此,将硼酸基团作为交联剂,与PVA中的邻羟基反应,可制备具有更高强度、更好稳定性和生物相容性的薄膜材料,并且通过调节体系的pH值、pKa(酸度系数)或外部环境,硼酸酯键能够可逆地生成和断裂。但是使用硼酸交联PVA制备皮肤贴片仍然存在一些问题:由于硼酸酯是一种刚性分子,所以制备的硼酸酯/PVA薄膜贴片的模量高且弹性较差。举例来说,Chen等人(Chen M,Wu Y,Chen B,Tucker AM,Jagota A,YangS.Fast,strong,and reversible adhesives with dynamic covalent bonds forpotential use in wound dressing.Proc Natl Acad Sci U S A.2022Jul 19;119(29):e2203074119.)通过硼酸酯键交联PVA制备了一种可逆的粘合剂作为伤口敷料,虽然该薄膜可以在不需要额外助剂的情况下实现自我修复和再生,但是其杨氏模量高达1160MPa,几乎没有弹性。
综上所述,虽然皮肤贴片在药物传递和医疗美容等方面已经取得了显著的进展,但仍然存在一些缺点需要克服:
(1)与皮肤粘合困难:现有技术中的皮肤贴片与皮肤之间的粘合较困难,需要另外使用粘合剂来固定;此外,目前的皮肤贴片的粘着力不足导致其较容易脱落,使用效果较差。
(2)弹性或强度较差:现有技术中的皮肤贴片的弹性不足,导致在人体运动时,皮肤贴片无法适应皮肤或关节的运动,从而导致皮肤贴片的撕裂或变形,影响皮肤贴片的使用效果和稳定性。
(3)不能重复使用:现有技术中的皮肤贴片多为一次性产品,通常以胶水或粘合剂为主要成分,这些成分在使用一次后大多失去粘性或导致皮肤过敏,甚至增加交叉感染的风险,因此无法重复使用。
发明内容
本发明目的在于克服现有技术缺陷,提供一种自黏附柔性复合膜。
本发明目的在于克服现有技术缺陷,提供上述自黏附柔性复合膜的制备方法。
本发明的另一目的在于提供上述自黏附柔性复合膜的应用。
本发明的技术方案如下:
一种自黏附柔性复合膜,由交联剂溶液、聚乙烯醇、多元醇和去离子水反应制成,该交联剂溶剂由含邻苯二酚单体、能形成交联结构的多臂硼酸单体、碱和去离子水混合反应制成,该多元醇为一缩二乙二醇或三缩乙二醇。
在本发明的一个优选实施方案中,所述含邻苯二酚单体为5,5′,6,6′-四羟基-3,3,3′,3′-四甲基-1,1′-螺双茚满、绿原酸、单宁酸、芸香苷水合物、鞣花酸和联苯二硼酸中的至少一种。
在本发明的一个优选实施方案中,所述多臂硼酸单体为硼酸、对苯二硼酸和联苯二硼酸中的至少一种。
进一步优选的,所述多臂硼酸单体为硼酸。
在本发明的一个优选实施方案中,所述碱为氢氧化钾、氢氧化钠和柠檬酸钠中的至少一种。
在本发明的一个优选实施方案中,所述含邻苯二酚单体和多臂硼酸单体的摩尔比为1-2∶1-2。
进一步优选的,所述聚乙烯醇与多元醇的质量比为0.8-1.2:0.8-1.2。
上述自黏附柔性复合膜的制备方法,包括如下步骤:
(1)将含邻苯二酚单体、能形成交联结构的多臂硼酸单体、碱和去离子水混合均匀,于85-95℃反应0.8-1.2h,接着加碱调节pH至9,获得交联剂溶液;
(2)将聚乙烯醇、多元醇和去离子水混合,于85-95℃搅拌至完全溶解;
(3)在步骤(2)所得的物料中滴加入步骤(1)所得的交联剂溶液,搅拌成均匀状态,然后倒入模具中,自然流平,再烘干,即得所述自黏附柔性复合膜。
上述自黏附柔性复合膜在制备皮肤贴片中的应用。
一种皮肤贴片,其原料包括上述自黏附柔性复合膜。本发明的有益效果是:
1、如图1所示,本发明将黏性因子邻苯二酚引入了硼酸酯聚合物体系中,同时借助了多元醇的增韧作用,使制备的薄膜具有优异的柔韧性、自黏附能力、自愈合能力、良好的生物相容性以及出色的机械强度和化学稳定性,且可回收利用;因此,可以大大提高皮肤贴片的舒适性和可靠性,并且可以广泛应用于医疗、美容、健身等领域;
对于优异的柔韧性:由于体系中引入了多元醇,多元醇可以与硼酸酯分子中的羟基发生反应,并与PVA分子中的羟基形成氢键。因此在硼酸酯分子链中引入多元醇交联结构,增强了硬质相的连通性,同时PVA与硼酸酯之间形成了更好的相容性,使制备的硼酸酯/PVA薄膜保留了其高强度的同时也获得了良好的柔性,能够拉伸至10倍以上而不发生断裂。
对于自黏附能力:邻苯二酚是一种黏附剂,具有良好的亲水性,能够吸附周围环境中的水分子,形成水合层,在潮湿环境中,邻苯二酚的水合层会与周围水分子相互作用,增加了与其他物质的接触面积和黏附力。此外,邻苯二酚还具有分子间氢键和范德华力等相互作用力,能够与其他分子相互吸引。这些作用力使其在潮湿环境中具有良好的黏附性能。因此,将邻苯二酚基团嵌入到动态硼酸酯聚合物中制备皮肤贴片,能够实现在潮湿环境下与皮肤良好的贴合。
对于自愈合能力:硼酸酯键是一种动态化学键,当皮肤贴片遭受损伤时,其中的硼酸酯键会断裂,从而形成自由基,自由基会与周围的水分子反应形成羟基,并与周围的硼酸酯键重组,从而实现自愈合。
对于可回收利用:传统的共价交联通常会导致永久键合,从而使得材料难以被回收或再加工。在硼酸酯聚合物材料中,硼酸酯键的动态可逆特性极大促进了材料的可回收性:通过对环境刺激的改变(如pH、糖类分子等),硼酸酯键可以反复形成和断开。
2、制备工艺简单、成本低廉,同时材料无毒、环保。
附图说明
图1为本发明制备的自黏附柔性复合膜的机理示意图。
图2为实施例1中未添加多元醇和添加多元醇改性后的硼酸酯/PVA聚合物柔性复合膜的拉伸应力-应变曲线。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)将0.17g TTS(0.5mmol)、0.0325g H3BO3(0.525mmol)、0.03g KOH(0.525mmol)溶于4mL去离子水中,90℃下反应1h,得到橙色溶液,加入少量KOH后将溶液的pH调节至9,即交联剂溶液。
(2)将1g PVA溶解在18g去离子水中,然后加入1g一缩二乙二醇,在90℃下机械搅拌1h直至PVA完全溶解。
(3)将步骤(1)制得的交联剂溶液滴加到步骤(2)所得的物料中,搅拌30min,形成均匀的、具有一定黏度的液体。
(4)将步骤(3)所得的物料倒入聚四氟乙烯模具,流平后,50℃烘干20h,即得所述自黏附柔性复合膜;
作为对比,将改变步骤(2),不添加上述1g一缩二乙二醇,其余步骤相同,制得未添加多元醇的复合膜,与本实施例制得的自黏附柔性复合膜进行性能对比,结果如图2和表1所示。
表1
实施例2
(1)将0.18g CA(0.5mmol)、0.087g对苯二硼酸(0.525mmol)、0.021g NaOH(0.525mmol)溶于4mL去离子水中,90℃反应1h,得到无色透明溶液,加入NaOH将溶液pH调节到9,即交联剂溶液。
(2)将1g PVA溶解在18g去离子水中,再加入1g三缩乙二醇,在90℃下机械搅拌1h直至PVA完全溶解。
(3)将步骤(1)制得的交联剂溶液滴加到步骤(1)所得的物料中,搅拌30min,形成均匀的、具有一定黏度的液体。
(4)将步骤(3)所得的物料倒入聚四氟乙烯模具,过夜流平后,50℃烘干20h,即得所述自黏附柔性复合膜。
实施例3至5
同实施例1的工艺条件,在步骤(1)中改变含邻苯二酚单体的种类,合成出不同的交联剂,结果见表2。
表2
实施例6至8
同实施例1的工艺条件,在步骤(1)中改变含邻苯二酚单体和多臂硼酸单体的添加量,以制备不同配方组分的交联剂,结果见表3。
表3
下表4为实施例1至8中制得自黏附柔性复合膜对应的机械性能数据。
表4
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (9)
1.一种自黏附柔性复合膜,其特征在于:由交联剂溶液、聚乙烯醇、多元醇和去离子水反应制成,该交联剂溶液由含邻苯二酚单体、能形成交联结构的多臂硼酸单体、碱和去离子水混合反应制成,该多元醇为一缩二乙二醇或三缩乙二醇,
其制备方法包括如下步骤:
(1)将含邻苯二酚单体、能形成交联结构的多臂硼酸单体、碱和去离子水混合均匀,于85-95℃反应0.8-1.2h,接着加碱调节pH至9,获得交联剂溶液;
(2)将聚乙烯醇、多元醇和去离子水混合,于85-95℃搅拌至完全溶解;
(3)在步骤(2)所得的物料中滴加入步骤(1)所得的交联剂溶液,搅拌成均匀状态,然后倒入模具中,自然流平,再烘干,即得所述自黏附柔性复合膜。
2.如权利要求1所述的一种自黏附柔性复合膜,其特征在于:所述含邻苯二酚单体为5,5',6,6'-四羟基-3,3,3',3'-四甲基-1,1'-螺双茚满、绿原酸、单宁酸、芸香苷水合物、鞣花酸和联苯二硼酸中的至少一种。
3.如权利要求1所述的一种自黏附柔性复合膜,其特征在于:所述多臂硼酸单体为硼酸、对苯二硼酸和联苯二硼酸中的至少一种。
4.如权利要求3所述的一种自黏附柔性复合膜,其特征在于:所述多臂硼酸单体为硼酸。
5.如权利要求1所述的一种自黏附柔性复合膜,其特征在于:所述碱为氢氧化钾、氢氧化钠和柠檬酸钠中的至少一种。
6. 如权利要求1所述的一种自黏附柔性复合膜,其特征在于:所述含邻苯二酚单体和多臂硼酸单体的摩尔比为1-2: 1-2。
7.如权利要求6所述的一种自黏附柔性复合膜,其特征在于:所述聚乙烯醇与多元醇的质量比为0.8-1.2:0.8-1.2。
8.权利要求1至7中任一权利要求所述的自黏附柔性复合膜在制备皮肤贴片中的应用。
9.一种皮肤贴片,其特征在于:其原料包括权利要求1至7中任一权利要求所述的自黏附柔性复合膜。
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