技术领域technical field
本发明涉及一种对聚乙烯醇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 a polyvinyl alcohol film, belonging to the technical field of polymer film preparation.
背景技术Background technique
聚乙烯醇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，聚乙烯醇膜可用作人造皮肤等，但聚乙烯醇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。聚肽是具有优良的生物相容性和生物可降解性的生物材料，具有良好的疏水性。聚对二氧环己酮-聚乙烯吡咯烷酮是具有优良的生物相容性和生物可降解性的生物材料，聚对二氧环己酮链段具有良好的疏水性和柔顺性，聚乙烯吡咯烷酮链段与聚乙烯醇链段有较好的共混性。先将聚肽链段引入聚乙烯醇链段形成聚乙烯醇-聚肽接枝共聚物，然后再将聚对二氧环己酮-聚乙烯吡咯烷酮加入聚乙烯醇-聚肽接枝共聚物形成共混物，制得改性聚乙烯醇膜，从而极大地提高了聚乙烯醇膜的耐水性及柔顺性。Polyvinyl alcohol is a biomaterial with good biocompatibility and biodegradability. Polyvinyl alcohol film can be used as artificial skin, etc., but the hydrophilicity of polyvinyl alcohol film is too strong and stiff, and lacks good Water resistance and flexibility, which limits its application to some extent. Polypeptide is a biomaterial with excellent biocompatibility and biodegradability, and has good hydrophobicity. Polydioxanone-polyvinylpyrrolidone is a biological material with excellent biocompatibility and biodegradability. The polydioxanone segment has good hydrophobicity and flexibility, and the polyvinylpyrrolidone chain Segment and polyvinyl alcohol segment have better blendability. First, the polypeptide segment is introduced into the polyvinyl alcohol segment to form a polyvinyl alcohol-polypeptide graft copolymer, and then polydioxanone-polyvinylpyrrolidone is added to the polyvinyl alcohol-polypeptide graft copolymer to form The blend is used to prepare a modified polyvinyl alcohol film, thereby greatly improving the water resistance and flexibility of the polyvinyl alcohol 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乙烯醇膜耐水性及柔顺性进行改进的方法。其技术方案为：The object of the present invention is to provide a method for improving the water resistance and flexibility of polyvinyl alcohol film with simple operation and good effect. Its technical solution is:
一种聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改进聚乙烯醇膜耐水性及柔顺性的方法，其特征在于：改性膜中聚乙烯醇链段的分子量为85000～95000，聚肽链段的分子量为2400～2500，聚对二氧环己酮-聚乙烯吡咯烷酮的分子量为4900～5500；其改性方法采用以下步骤：A method for improving the water resistance and flexibility of a polyvinyl alcohol film with a polypeptide and polydioxanone-polyvinylpyrrolidone, characterized in that: the molecular weight of the polyvinyl alcohol segment in the modified film is 85,000 to 95,000, and the polyvinyl alcohol The molecular weight of the peptide segment is 2400-2500, and the molecular weight of polydioxanone-polyvinylpyrrolidone is 4900-5500; the modification method adopts the following steps:
1）聚乙烯醇-聚肽接枝共聚物的合成：在干燥反应器内加入羧基封端的聚肽均聚物、溶剂、缩合剂和聚乙烯醇，惰性气氛下，于28～31℃搅拌反应2～4天，终止反应，通过过滤、透析、干燥，得到目标物；1) Synthesis of polyvinyl alcohol-polypeptide graft copolymer: Add carboxy-terminated homopolymer of polypeptide, solvent, condensation agent and polyvinyl alcohol into a dry reactor, and stir and react at 28-31°C under an inert atmosphere After 2 to 4 days, the reaction is terminated, and the target product is obtained by filtration, dialysis, and drying;
2）聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改性的聚乙烯醇膜的制备：在干燥反应器内加入聚乙烯醇-聚肽接枝共聚物、聚对二氧环己酮-聚乙烯吡咯烷酮和溶剂，惰性气氛下，于49～55℃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 polyvinyl alcohol film modified by polypeptide and polydioxanone-polyvinylpyrrolidone: add polyvinyl alcohol-polypeptide graft copolymer, polydioxanone - Polyvinylpyrrolidone and a solvent are stirred and mixed at 49-55° C. for 50-60 minutes under an inert atmosphere, and then formed into a film by casting method and dried to obtain the target product.
所述的一种聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改进聚乙烯醇膜耐水性及柔顺性的方法，步骤1）中，聚肽均聚物采用聚（r-苯甲基-L-谷氨酸酯）、聚（r-乙基-L-谷氨酸酯）或聚（r-甲基-L-谷氨酸酯），聚肽均聚物与聚乙烯醇的摩尔比为15～25:1。In the method for improving the water resistance and flexibility of polyvinyl alcohol film with polypeptide and polydioxanone-polyvinylpyrrolidone, in step 1), the polypeptide homopolymer is made of poly(r-benzyl -L-glutamate), poly(r-ethyl-L-glutamate) or poly(r-methyl-L-glutamate), moles of peptide homopolymer to polyvinyl alcohol The ratio is 15-25:1.
所述的一种聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改进聚乙烯醇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，缩合剂与聚乙烯醇的摩尔比为1.07～1.8:1，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 polyvinyl alcohol film with polypeptide and polydioxanone-polyvinylpyrrolidone, in step 1), the condensing agent isN,N' -dicyclohexylcarbodi imine,N,N' -diisopropylcarbodiimide or 3-ethyl-1-(3-dimethylaminopropyl)carbodiimide, the molar ratio of condensing agent to polyvinyl alcohol is 1.07～ 1.8:1, the solvent is dimethyl sulfoxide, and the concentration of the reactant solution is 5-15 g:100 ml.
所述的一种聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改进聚乙烯醇膜耐水性及柔顺性的方法，步骤2）中，聚对二氧环己酮-聚乙烯吡咯烷酮采用聚对二氧环己酮-聚乙烯吡咯烷酮二嵌段共聚物，聚对二氧环己酮与聚乙烯吡咯烷酮的重量比为90/10，聚对二氧环己酮-聚乙烯吡咯烷酮在改性膜中的质量百分比为2～4%，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 a polyvinyl alcohol film by using a polypeptide and polydioxanone-polyvinylpyrrolidone, in step 2), the polydioxanone-polyvinylpyrrolidone is polyvinylpyrrolidone Dioxanone-polyvinylpyrrolidone diblock copolymer, the weight ratio of polydioxanone and polyvinylpyrrolidone is 90/10, polydioxanone-polyvinylpyrrolidone in the modified film The mass percentage in the mixture is 2-4%, the solvent is dimethyl sulfoxide, and 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、所述的聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改进聚乙烯醇膜耐水性及柔顺性的方法，采用酯化反应和共混两种手段，操作简单、易于掌握；1. The method for improving the water resistance and flexibility of the polyvinyl alcohol film by the polypeptide and polydioxanone-polyvinylpyrrolidone adopts two methods of esterification reaction and blending, which are simple to operate and easy to master;
2、所述的聚乙烯醇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 polyvinyl alcohol modified film have been greatly improved.
具体实施方式Detailed ways
实施例1Example 1
1）聚乙烯醇-聚肽接枝共聚物的制备1) Preparation of polyvinyl alcohol-polypeptide graft copolymer
在干燥反应器加入20克聚乙烯醇（分子量为85000）和9.8克羧基封端的聚（r-苯甲基-L-谷氨酸酯）（分子量为2400），加入295 ml二甲基亚砜，再加入0.062克N,N’-二环己基碳二亚胺，惰性气氛下，于28℃搅拌反应2天，终止反应，通过过滤、透析、干燥，得到目标物；Add 20 g of polyvinyl alcohol (molecular weight: 85,000) and 9.8 g of carboxy-terminated poly(r-benzyl-L-glutamate) (molecular weight: 2,400) to the dry reactor, add 295 ml of dimethyl sulfoxide , then add 0.062 g ofN,N' -dicyclohexylcarbodiimide, under an inert atmosphere, stir and react at 28°C for 2 days, terminate the reaction, and obtain the target product by filtration, dialysis, and drying;
2）聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改性的聚乙烯醇膜的制备2) Preparation of polyvinyl alcohol film modified by polypeptide and polydioxanone-polyvinylpyrrolidone
在干燥反应器内加入10克聚乙烯醇-聚肽接枝共聚物和37 ml二甲基亚砜溶剂，另加入占改性膜总重量2%的聚对二氧环己酮-聚乙烯吡咯烷酮（分子量为4900），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 polyvinyl alcohol-polypeptide graft copolymer and 37 ml of dimethyl sulfoxide solvent into the dry reactor, and add polydioxanone-polyvinylpyrrolidone accounting for 2% of the total weight of the modified membrane (molecular weight is 4900), stirred and mixed at 49°C for 50 minutes under an inert atmosphere, formed into 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12.3%。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 12.3% compared with those before modification.
实施例2Example 2
1）聚乙烯醇-聚肽接枝共聚物的制备1) Preparation of polyvinyl alcohol-polypeptide graft copolymer
在干燥反应器加入21克聚乙烯醇（分子量为90000）和10.6克羧基封端的聚（r-乙基-L-谷氨酸酯）（分子量为2500），加入300 ml二甲基亚砜，再加入0.039克N,N’-二异丙基碳二亚胺，惰性气氛下，于30℃搅拌反应3天，终止反应，通过过滤、透析、干燥，得到目标物；Add 21 g of polyvinyl alcohol (molecular weight: 90,000) and 10.6 g of carboxy-terminated poly(r-ethyl-L-glutamate) (molecular weight: 2,500) into the dry reactor, add 300 ml of dimethyl sulfoxide, Then add 0.039 g ofN,N' -diisopropylcarbodiimide, stir and react at 30° C. for 3 days under an inert atmosphere, terminate the reaction, and obtain the target product by filtration, dialysis, and drying;
2）聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改性的聚乙烯醇膜的制备2) Preparation of polyvinyl alcohol film modified by polypeptide and polydioxanone-polyvinylpyrrolidone
在干燥反应器内加入10克聚乙烯醇-聚肽接枝共聚物和36 ml二甲基亚砜溶剂，另加入占改性膜总重量3%的聚对二氧环己酮-聚乙烯吡咯烷酮（分子量为5200），惰性气氛下，于52℃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 10 grams of polyvinyl alcohol-polypeptide graft copolymer and 36 ml of dimethyl sulfoxide solvent into the drying reactor, and add polydioxanone-polyvinylpyrrolidone accounting for 3% of the total weight of the modified membrane (molecular weight is 5200), stirred and mixed at 52°C for 55 minutes under an inert atmosphere, 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12.4°和13.5%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 12.4° and 13.5% compared with those before modification.
实施例3Example 3
1）聚乙烯醇-聚肽接枝共聚物的制备1) Preparation of polyvinyl alcohol-polypeptide graft copolymer
在干燥反应器加入22克聚乙烯醇（分子量为95000）和10.5克羧基封端的聚（r-甲基-L-谷氨酸酯）（分子量为2500），加入315 ml二甲基亚砜，再加入0.058克3-乙基-1-（3-二甲氨丙基）碳二亚胺，惰性气氛下，于31℃搅拌反应4天，终止反应，通过过滤、透析、干燥，得到目标物；Add 22 g of polyvinyl alcohol (molecular weight: 95,000) and 10.5 g of carboxy-terminated poly(r-methyl-L-glutamate) (molecular weight: 2,500) into the dry reactor, add 315 ml of dimethyl sulfoxide, Then add 0.058 g of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under an inert atmosphere, stir and react at 31°C for 4 days, terminate the reaction, and obtain the target product by filtration, dialysis and drying ;
2）聚肽与聚对二氧环己酮-聚乙烯吡咯烷酮改性的聚乙烯醇膜的制备2) Preparation of polyvinyl alcohol film modified by polypeptide and polydioxanone-polyvinylpyrrolidone
在干燥反应器内加入9.6克聚乙烯醇-聚肽接枝共聚物和35 ml二甲基亚砜溶剂，另加入占改性膜总重量4%的聚对二氧环己酮-聚乙烯吡咯烷酮（分子量为5500），惰性气氛下，于55℃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 9.6 grams of polyvinyl alcohol-polypeptide graft copolymer and 35 ml of dimethyl sulfoxide solvent into the dry reactor, and add polydioxanone-polyvinylpyrrolidone accounting for 4% of the total weight of the modified membrane (molecular weight is 5500), stirred and mixed at 55°C for 60 minutes under an inert atmosphere, 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13.3°和14.9%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 13.3° and 14.9% compared with those before modification.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148962.0ACN105601967B (en) | 2016-03-16 | 2016-03-16 | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polydioxanone-polyvinylpyrrolidone |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148962.0ACN105601967B (en) | 2016-03-16 | 2016-03-16 | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polydioxanone-polyvinylpyrrolidone |
| Publication Number | Publication Date |
|---|---|
| CN105601967A CN105601967A (en) | 2016-05-25 |
| CN105601967Btrue CN105601967B (en) | 2018-07-27 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610148962.0AExpired - Fee RelatedCN105601967B (en) | 2016-03-16 | 2016-03-16 | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polydioxanone-polyvinylpyrrolidone |
| Country | Link |
|---|---|
| CN (1) | CN105601967B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911380A (en)* | 2012-10-29 | 2013-02-06 | 北京爱美客生物科技有限公司 | Hyaluronan and biodegradable high polymer modified material and preparation method |
| CN103788607A (en)* | 2014-03-07 | 2014-05-14 | 山东理工大学 | Method for improving hydrophilicity of polypeptide film through p-dioxanone and waterborne polyurethane |
| CN103865089A (en)* | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911380A (en)* | 2012-10-29 | 2013-02-06 | 北京爱美客生物科技有限公司 | Hyaluronan and biodegradable high polymer modified material and preparation method |
| CN103788607A (en)* | 2014-03-07 | 2014-05-14 | 山东理工大学 | Method for improving hydrophilicity of polypeptide film through p-dioxanone and waterborne polyurethane |
| CN103865089A (en)* | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| Publication number | Publication date |
|---|---|
| CN105601967A (en) | 2016-05-25 |
| Publication | Publication Date | Title |
|---|---|---|
| CN104559213B (en) | A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol | |
| CN104479157B (en) | A kind of method that polycaprolactone improves poly- peptide film hydrophily and compliance with polyethylene glycol | |
| CN105542483B (en) | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with polydioxanone | |
| CN104479158A (en) | Method for improving hydrophilia and flexibility of polypeptide membrane through polydioxanone and polyethylene glycol | |
| CN103819905B (en) | A kind of method that PTMC and polyvinylpyrrolidone improve poly-peptide film wetting ability | |
| CN105542207A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone | |
| CN104559212B (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol | |
| CN104559214B (en) | Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid | |
| CN104559210B (en) | Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol | |
| CN105647196A (en) | Method using polypeptide and polypropylene glycol-polyvinyl pyrrolidone to improve water resistance and flexibility of polyvinyl alcohol membrane | |
| CN103865090A (en) | Method for improving hydrophilia of polypeptide film by using polycaprolactone and polyethylene glycol | |
| CN105542480B (en) | The method that one kind polycaprolactone improves polyvinyl alcohol film water resistance and compliance with P (CPP SA) polyethylene glycol | |
| CN104448843B (en) | A kind of method that polycaprolactone improves poly-peptide film hydrophily and compliance with polyacrylic acid | |
| CN104559206B (en) | Method for improving hydrophilic property and flexibility of polypeptide film by adopting poly trimethylene carbonate and polyacrylamide | |
| CN104559216A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid | |
| CN104559211B (en) | A kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid | |
| CN104559215B (en) | A kind of method that PLA improves poly- peptide film hydrophily and compliance with polyethylene glycol | |
| CN105601967B (en) | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polydioxanone-polyvinylpyrrolidone | |
| CN105694477B (en) | A method of improving polyvinyl alcohol film water resistance and compliance with polydioxanone and P (CPP-SA)-polyvinylpyrrolidone | |
| CN104559223B (en) | Method for improving hydrophilicity and flexibility of polypeptide film by polypropylene glycol and carboxymethyl chitosan | |
| CN105542484A (en) | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(trimethylene carbonate)-polyvinylpyrrolidone | |
| CN105778523A (en) | Method for improving water tolerance and flexibility of polyvinyl alcohol membrane with poly (p-dioxanone) and polycaprolactone-polyvinyl pyrrolidone | |
| CN104448842B (en) | A kind of method that polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylic acid | |
| CN105542485A (en) | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone | |
| CN105694475B (en) | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20180727 Termination date:20190316 |