技术领域technical field
本发明涉及一种对聚丙烯酸膜耐水性及柔顺性进行改进的方法，属于聚合物薄膜制备技术领域。The invention relates to a method for improving the water resistance and flexibility of polyacrylic acid films, and belongs to the technical field of polymer film preparation.
背景技术Background technique
聚丙烯酸是一种具有良好的生物相容性和生物可降解性的生物材料，聚丙烯酸膜可用作人造皮肤等，但聚丙烯酸膜亲水性太强且较僵硬，缺乏较好的耐水性及柔顺性，从而一定程度上限制了其应用。聚己内酯和聚丙二醇（分子量2000以上）是具有优良的生物相容性和生物可降解性的生物材料，具有疏水性和柔顺性。先将聚己内酯链段和聚丙二醇链段同时引入聚丙烯酸链段形成聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物，然后再将聚丙二醇链段加入聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物形成共混物，制得改性聚丙烯酸膜，从而极大地提高了聚丙烯酸膜的耐水性及柔顺性。Polyacrylic acid is a biomaterial with good biocompatibility and biodegradability. Polyacrylic acid film can be used as artificial skin, etc., but polyacrylic acid film is too hydrophilic and stiff, and lacks good water resistance. and flexibility, which limits its application to a certain extent. Polycaprolactone and polypropylene glycol (more than 2000 molecular weight) are biomaterials with excellent biocompatibility and biodegradability, and are hydrophobic and flexible. First, the polycaprolactone segment and the polypropylene glycol segment are simultaneously introduced into the polyacrylic acid segment to form a polyacrylic acid-polycaprolactone-polypropylene glycol double graft copolymer, and then the polypropylene glycol segment is added to the polyacrylic acid-polycaprolactone The ester-polypropylene glycol double-graft copolymer forms a blend to prepare a modified polyacrylic acid film, thereby greatly improving the water resistance and flexibility of the polyacrylic acid film.
发明内容Contents of the invention
本发明的目的在于提供一种操作简单及效果较好的对聚丙烯酸膜耐水性及柔顺性进行改进的方法。其技术方案为：The purpose of the present invention is to provide a method for improving the water resistance and flexibility of polyacrylic acid film with simple operation and good effect. Its technical solution is:
一种聚己内酯与聚丙二醇改善聚丙烯酸膜耐水性及柔顺性的方法，其特征在于：改性膜中聚丙烯酸链段的分子量为85000～92000，聚己内酯链段的分子量为2700～2800，聚丙二醇链段的分子量为2700～2800；其改性方法采用以下步骤：A method for improving the water resistance and flexibility of polyacrylic acid film with polycaprolactone and polypropylene glycol, characterized in that: the molecular weight of the polyacrylic acid segment in the modified film is 85000-92000, and the molecular weight of the polycaprolactone segment is 2700 ~2800, the molecular weight of the polypropylene glycol segment is 2700~2800; the modification method adopts the following steps:
1）聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物的合成：在干燥反应器内加入羟基封端的聚己内酯单十二烷基醚、羟基封端的聚丙二醇单丁醚、溶剂、缩合剂和聚丙烯酸，惰性气氛下，于29～33℃搅拌反应2～3天，终止反应，通过过滤、透析、干燥，得到目标物；1) Synthesis of polyacrylic acid-polycaprolactone-polypropylene glycol double-graft copolymer: add hydroxyl-terminated polycaprolactone monolauryl ether, hydroxyl-terminated polypropylene glycol monobutyl ether, and solvent in a drying reactor , condensing agent and polyacrylic acid, under an inert atmosphere, stirred and reacted at 29-33°C for 2-3 days, terminated the reaction, and obtained the target product by filtration, dialysis and drying;
2）聚己内酯与聚丙二醇改性的聚丙烯酸膜的制备：在干燥反应器内加入聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物、聚丙二醇单丁醚和溶剂，惰性气氛下，于49～52℃搅拌混合50～60分钟后，用流延法成膜并干燥，得到目标物。2) Preparation of polyacrylic acid film modified by polycaprolactone and polypropylene glycol: add polyacrylic acid-polycaprolactone-polypropylene glycol double graft copolymer, polypropylene glycol monobutyl ether and solvent in a dry reactor, inert atmosphere After stirring and mixing at 49-52°C for 50-60 minutes, the film was formed by casting method and dried to obtain the target product.
所述的一种聚己内酯与聚丙二醇改善聚丙烯酸膜耐水性及柔顺性的方法，步骤1）中，聚己内酯单十二烷基醚与聚丙烯酸的摩尔比为15～25:1，聚丙二醇单丁醚与聚丙烯酸的摩尔比为15～25:1。In the method for improving the water resistance and flexibility of polyacrylic acid film with polycaprolactone and polypropylene glycol, in step 1), the molar ratio of polycaprolactone monolauryl ether to polyacrylic acid is 15-25: 1. The molar ratio of polypropylene glycol monobutyl ether to polyacrylic acid is 15-25:1.
所述的一种聚己内酯与聚丙二醇改善聚丙烯酸膜耐水性及柔顺性的方法，步骤1）中，缩合剂采用N,N’-二环己基碳二亚胺、N,N’-二异丙基碳二亚胺或3-乙基-1-（3-二甲氨丙基）碳二亚胺，缩合剂与聚丙烯酸的摩尔比为1.06～1.8:1，溶剂采用二甲基亚砜，反应物溶液浓度为5～15 g:100 ml。In the method for improving the water resistance and flexibility of polyacrylic acid film with polycaprolactone and polypropylene glycol, in step 1), the condensing agent isN,N' -dicyclohexylcarbodiimide,N,N'- Diisopropyl carbodiimide or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the molar ratio of condensing agent to polyacrylic acid is 1.06～1.8:1, and the solvent is dimethyl Sulfoxide, the concentration of the reactant solution is 5-15 g:100 ml.
所述的一种聚己内酯与聚丙二醇改善聚丙烯酸膜耐水性及柔顺性的方法，步骤2）中，聚丙二醇单丁醚在改性膜中的质量百分比为2～3%，溶剂采用二甲基亚砜，混合物溶液浓度为25～30 g:100 ml。In the method for improving the water resistance and flexibility of polyacrylic acid film with polycaprolactone and polypropylene glycol, in step 2), the mass percentage of polypropylene glycol monobutyl ether in the modified film is 2-3%, and the solvent adopts Dimethyl sulfoxide, the concentration of the mixture solution is 25-30 g:100 ml.
本发明与现有技术相比，其优点为：Compared with the prior art, the present invention has the advantages of:
1、所述的一种聚己内酯与聚丙二醇改善聚丙烯酸膜耐水性及柔顺性的方法，采用一种聚合物与两种不同大单体同时进行酯化的反应以及共混两种手段，操作简单、易于掌握；1. The method for improving the water resistance and flexibility of polyacrylic acid film with polycaprolactone and polypropylene glycol, adopts two methods of simultaneously esterifying a polymer and two different macromonomers and blending , simple operation, easy to master;
2、所述的聚丙烯酸改性膜耐水性及柔顺性有了较大的提高。2. The water resistance and flexibility of the polyacrylic acid modified film have been greatly improved.
具体实施方式detailed description
实施例1Example 1
1）聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物的制备1) Preparation of polyacrylic acid-polycaprolactone-polypropylene glycol double graft copolymer
在干燥反应器内加入17.1克聚丙烯酸（分子量为85000）、10.5克羟基封端的聚己内酯单十二烷基醚（分子量为2700）和10.5克羟基封端的聚丙二醇单丁醚（分子量为2700），加入381 ml二甲基亚砜，再加入0.052克N,N’-二环己基碳二亚胺，惰性气氛下，于29℃搅拌反应2天，终止反应，通过过滤、透析、干燥，得到目标物；Add 17.1 grams of polyacrylic acid (molecular weight: 85000), 10.5 grams of hydroxyl-terminated polycaprolactone monolauryl ether (molecular weight: 2700) and 10.5 grams of hydroxyl-terminated polypropylene glycol monobutyl ether (molecular weight: 2700), add 381 ml of dimethyl sulfoxide, and then add 0.052 g ofN,N' -dicyclohexylcarbodiimide, under an inert atmosphere, stir and react at 29°C for 2 days, terminate the reaction, filter, dialyze, and dry , get the target object;
2）聚己内酯与聚丙二醇改性的聚丙烯酸膜的制备2) Preparation of polyacrylic acid film modified by polycaprolactone and polypropylene glycol
在干燥反应器内加入10克聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物和37 ml二甲基亚砜溶剂，另加入占改性膜总重量2%的聚丙二醇单丁醚（分子量为2700），惰性气氛下，于49℃搅拌混合50分钟，用流延法成膜，在50℃真空干燥箱中干燥得到目标物。Add 10 grams of polyacrylic acid-polycaprolactone-polypropylene glycol double-graft copolymer and 37 ml of dimethyl sulfoxide solvent in the dry reactor, and add polypropylene glycol monobutyl ether (PPG) that accounts for 2% of the total weight of the modified membrane ( The molecular weight is 2700), under an inert atmosphere, stirred and mixed at 49°C for 50 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.
经测试：本发明目标物与水的表面接触角及其断裂伸长率分别比改性前提高了11.9°和10.2%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 11.9° and 10.2% compared with those before modification.
实施例2Example 2
1）聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物的制备1) Preparation of polyacrylic acid-polycaprolactone-polypropylene glycol double graft copolymer
在干燥反应器内加入20.3克聚丙烯酸（分子量为87000）、11.8克羟基封端的聚己内酯单十二烷基醚（分子量为2800）和11.8克羟基封端的聚丙二醇单丁醚（分子量为2800），加入441 ml二甲基亚砜，再加入0.036克N,N’-二异丙基碳二亚胺，惰性气氛下，于31℃搅拌反应3天，终止反应，通过过滤、透析、干燥，得到目标物；Add 20.3 grams of polyacrylic acid (molecular weight: 87000), 11.8 grams of hydroxyl-terminated polycaprolactone monolauryl ether (molecular weight: 2800) and 11.8 grams of hydroxyl-terminated polypropylene glycol monobutyl ether (molecular weight: 2800), add 441 ml of dimethyl sulfoxide, and then add 0.036 g ofN,N' -diisopropylcarbodiimide, under an inert atmosphere, stir the reaction at 31°C for 3 days, terminate the reaction, and filter, dialyze, Dry to obtain the target object;
2）聚己内酯与聚丙二醇改性的聚丙烯酸膜的制备2) Preparation of polyacrylic acid film modified by polycaprolactone and polypropylene glycol
在干燥反应器内加入9.9克聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物和36 ml二甲基亚砜溶剂，另加入占改性膜总重量2%的聚丙二醇单丁醚（分子量为2800），惰性气氛下，于50℃搅拌混合55分钟，用流延法成膜，在50℃真空干燥箱中干燥得到目标物。Add 9.9 grams of polyacrylic acid-polycaprolactone-polypropylene glycol double-graft copolymer and 36 ml of dimethyl sulfoxide solvent in the drying reactor, and add polypropylene glycol monobutyl ether (PPG) accounting for 2% of the total weight of the modified membrane in addition. The molecular weight is 2800), under an inert atmosphere, stirred and mixed at 50°C for 55 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.
经测试：本发明目标物与水的表面接触角及其断裂伸长率分别比改性前提高了12.5°和10.8%。After testing: the surface contact angle of the object of the present invention with water and the elongation at break are respectively increased by 12.5° and 10.8% compared with those before modification.
实施例3Example 3
1）聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物的制备1) Preparation of polyacrylic acid-polycaprolactone-polypropylene glycol double graft copolymer
在干燥反应器内加入21.5克聚丙烯酸（分子量为92000）、12.4克羟基封端的聚己内酯单十二烷基醚（分子量为2800）和12.4克羟基封端的聚丙二醇单丁醚（分子量为2800），加入463ml二甲基亚砜，再加入0.056克3-乙基-1-（3-二甲氨丙基）碳二亚胺，惰性气氛下，于33℃搅拌反应2天，终止反应，通过过滤、透析、干燥，得到目标物；Add 21.5 grams of polyacrylic acid (molecular weight: 92000), 12.4 grams of hydroxyl-terminated polycaprolactone monolauryl ether (molecular weight: 2800) and 12.4 grams of hydroxyl-terminated polypropylene glycol monobutyl ether (molecular weight: 2800), add 463ml dimethyl sulfoxide, then add 0.056 g 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, stir and react at 33°C for 2 days to terminate the reaction , by filtering, dialysis and drying, the target object is obtained;
2）聚己内酯与聚丙二醇改性的聚丙烯酸膜的制备2) Preparation of polyacrylic acid film modified by polycaprolactone and polypropylene glycol
在干燥反应器内加入9.5克聚丙烯酸-聚己内酯-聚丙二醇双接枝共聚物和35 ml二甲基亚砜溶剂，另加入占改性膜总重量3%的聚丙二醇单丁醚（分子量为2800），惰性气氛下，于52℃搅拌混合60分钟，用流延法成膜，在50℃真空干燥箱中干燥得到目标物。Add 9.5 grams of polyacrylic acid-polycaprolactone-polypropylene glycol double-graft copolymer and 35 ml of dimethyl sulfoxide solvent in the dry reactor, and add polypropylene glycol monobutyl ether (PPG) that accounts for 3% of the total weight of the modified membrane in addition. The molecular weight is 2800), under an inert atmosphere, stirred and mixed at 52°C for 60 minutes, formed a film by casting method, and dried in a vacuum oven at 50°C to obtain the target product.
经测试：本发明目标物与水的表面接触角及其断裂伸长率分别比改性前提高了13.4°和11.7%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 13.4° and 11.7% compared with those before modification.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710362969.7ACN107011676A (en) | 2017-05-22 | 2017-05-22 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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| CN201710362969.7ACN107011676A (en) | 2017-05-22 | 2017-05-22 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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| CN107011676Atrue CN107011676A (en) | 2017-08-04 |
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| CN201710362969.7AWithdrawnCN107011676A (en) | 2017-05-22 | 2017-05-22 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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