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。聚己内酯是具有优良的生物相容性和生物可降解性的生物材料，具有良好的疏水性和柔顺性。聚肽-聚乙烯吡咯烷酮是具有良好的生物相容性和生物可降解性的生物材料，聚肽链段具有很好的疏水性，聚乙烯吡咯烷酮链段与聚乙烯醇链段有较好的共混性。先将聚己内酯链段引入聚乙烯醇链段形成聚乙烯醇-聚己内酯接枝共聚物，然后再将聚肽-聚乙烯吡咯烷酮加入聚乙烯醇-聚己内酯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. Polycaprolactone is a biomaterial with excellent biocompatibility and biodegradability, good hydrophobicity and flexibility. Polypeptide-polyvinylpyrrolidone is a biological material with good biocompatibility and biodegradability. Polypeptide segments have good hydrophobicity, and polyvinylpyrrolidone segments and polyvinyl alcohol segments have good co- Mixed. Firstly, the polycaprolactone segment is introduced into the polyvinyl alcohol segment to form a polyvinyl alcohol-polycaprolactone graft copolymer, and then the polypeptide-polyvinylpyrrolidone is added to the polyvinyl alcohol-polycaprolactone graft copolymer A blend is formed 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:
一种用聚己内酯与聚肽-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81000～90000，聚己内酯链段的分子量为2100～3000，聚肽-聚乙烯吡咯烷酮的分子量为4000～5000；其改性方法采用以下步骤：A method for improving the water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polypeptide-polyvinylpyrrolidone, characterized in that: the molecular weight of the polyvinyl alcohol segment in the modified film is 81000-90000, polycaprolactone The molecular weight of the ester segment is 2100-3000, and the molecular weight of the polypeptide-polyvinylpyrrolidone is 4000-5000; the modification method adopts the following steps:
1）聚乙烯醇-聚己内酯接枝共聚物的合成：在干燥反应器内加入羧基封端的聚己内酯单十二烷基醚、溶剂、缩合剂和聚乙烯醇，惰性气氛下，于28～35℃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-polycaprolactone graft copolymer: add carboxy-terminated polycaprolactone monododecyl ether, solvent, condensing agent and polyvinyl alcohol in a dry reactor, under an inert atmosphere, Stir the reaction at 28-35°C for 2-4 days, terminate the reaction, and obtain the target product through filtration, dialysis and drying;
2）聚己内酯与聚肽-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-聚己内酯接枝共聚物、聚肽-聚乙烯吡咯烷酮和溶剂，惰性气氛下，于45～52℃搅拌混合50～65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 polycaprolactone and polypeptide-polyvinylpyrrolidone: add polyvinyl alcohol-polycaprolactone graft copolymer, polypeptide-polyvinylpyrrolidone and solvent into the drying reactor , under an inert atmosphere, stir and mix at 45-52°C for 50-65 minutes, then form a film by casting method and dry to obtain the target product.
所述的一种用聚己内酯与聚肽-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，聚己内酯单十二烷基醚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 by using polycaprolactone and polypeptide-polyvinylpyrrolidone, in step 1), the polycaprolactone monolauryl ether and polyvinyl alcohol The molar ratio is 15-25:1.
所述的一种用聚己内酯与聚肽-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1.08～1.8:1，溶剂采用二甲基亚砜，反应物溶液浓度为5～15g:100ml。In the method for improving the water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polypeptide-polyvinylpyrrolidone, in step 1), the condensing agent isN,N' -dicyclohexylcarbodiimide ,N,N' -diisopropylcarbodiimide or 3-ethyl-1-(3-dimethylaminopropyl)carbodiimide, the molar ratio of condensing agent to polyvinyl alcohol is 1.08～1.8: 1. The solvent is dimethyl sulfoxide, and the concentration of the reactant solution is 5-15g:100ml.
所述的一种用聚己内酯与聚肽-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，聚肽-聚乙烯吡咯烷酮采用聚肽-聚乙烯吡咯烷酮二嵌段共聚物，聚肽采用聚（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），聚肽与聚乙烯吡咯烷酮的重量比为90/10，聚肽-聚乙烯吡咯烷酮在改性膜中的质量百分比为1～3%，溶剂采用二甲基亚砜，混合物溶液浓度为25～30g:100ml。The method for improving the water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polypeptide-polyvinylpyrrolidone, in step 2), the polypeptide-polyvinylpyrrolidone is embedded with polypeptide-polyvinylpyrrolidone Segment copolymers, polypeptides are poly(r-benzyl-L-glutamate), poly(r-ethyl-L-glutamate) or poly(r-methyl-L-glutamate) ester), the weight ratio of polypeptide to polyvinylpyrrolidone is 90/10, the mass percentage of polypeptide-polyvinylpyrrolidone in the modified membrane is 1-3%, the solvent is dimethyl sulfoxide, and the concentration of the mixture solution is 25% ~30g: 100ml.
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、所述的聚己内酯与聚肽-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 polyvinyl alcohol film by polycaprolactone and polypeptide-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 description
实施例1Example 1
1）聚乙烯醇-聚己内酯接枝共聚物的制备1) Preparation of polyvinyl alcohol-polycaprolactone graft copolymer
在干燥反应器加入20克聚乙烯醇（分子量为81000）和9.5克羧基封端的聚己内酯单十二烷基醚（分子量为2100），加入294ml二甲基亚砜，再加入0.063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 grams of polyvinyl alcohol (molecular weight: 81,000) and 9.5 grams of carboxy-terminated polycaprolactone monolauryl ether (molecular weight: 2,100) to the dry reactor, add 294 ml of dimethyl sulfoxide, and then add 0.063 grams ofN , N' -dicyclohexylcarbodiimide, under an inert atmosphere, stirred and reacted at 28°C for 2 days, terminated the reaction, and obtained the target product by filtration, dialysis, and drying;
2）聚己内酯与聚肽-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 polycaprolactone and polypeptide-polyvinylpyrrolidone
在干燥反应器内加入10克聚乙烯醇-聚己内酯接枝共聚物和37ml二甲基亚砜溶剂，另加入占改性膜总重量1%的聚（r-苯甲基-L-谷氨酸酯）-聚乙烯吡咯烷酮（分子量为4000），惰性气氛下，于45℃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-polycaprolactone graft copolymer and 37ml dimethyl sulfoxide solvent in dry reactor, add the poly(r-benzyl-L- glutamate)-polyvinylpyrrolidone (molecular weight: 4000), stirred and mixed at 45°C for 50 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12.1°和13.6%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 12.1° and 13.6% compared with those before modification.
实施例2Example 2
1）聚乙烯醇-聚己内酯接枝共聚物的制备1) Preparation of polyvinyl alcohol-polycaprolactone graft copolymer
在干燥反应器加入21克聚乙烯醇（分子量为85000）和11.5克羧基封端的聚己内酯单十二烷基醚（分子量为2500），加入305ml二甲基亚砜，再加入0.042克N,N’-二异丙基碳二亚胺，惰性气氛下，于32℃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 grams of polyvinyl alcohol (molecular weight: 85,000) and 11.5 grams of carboxy-terminated polycaprolactone monolauryl ether (molecular weight: 2,500) into the dry reactor, add 305 ml of dimethyl sulfoxide, and then add 0.042 grams ofN , N' -diisopropylcarbodiimide, under an inert atmosphere, stirred and reacted at 32°C for 3 days, terminated the reaction, and obtained the target product by filtration, dialysis, and drying;
2）聚己内酯与聚肽-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 polycaprolactone and polypeptide-polyvinylpyrrolidone
在干燥反应器内加入10克聚乙烯醇-聚己内酯接枝共聚物和36ml二甲基亚砜溶剂，另加入占改性膜总重量2%的聚（r-乙基-L-谷氨酸酯）-聚乙烯吡咯烷酮（分子量为4500），惰性气氛下，于48℃搅拌混合58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-polycaprolactone graft copolymer and 36 ml of dimethyl sulfoxide solvent in the drying reactor, and add poly(r-ethyl-L-glucose) accounting for 2% of the total weight of the modified membrane Amino acid ester)-polyvinylpyrrolidone (molecular weight: 4500), stirred and mixed at 48°C for 58 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12.8°和12.7%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 12.8° and 12.7% compared with those before modification.
实施例3Example 3
1）聚乙烯醇-聚己内酯接枝共聚物的制备1) Preparation of polyvinyl alcohol-polycaprolactone graft copolymer
在干燥反应器加入22克聚乙烯醇（分子量为90000）和13.5克羧基封端的聚己内酯单十二烷基醚（分子量为3000），加入300ml二甲基亚砜，再加入0.057克3-乙基-1-（3-二甲氨丙基）碳二亚胺，惰性气氛下，于35℃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 grams of polyvinyl alcohol (molecular weight: 90,000) and 13.5 grams of carboxy-terminated polycaprolactone monolauryl ether (molecular weight: 3,000) into the dry reactor, add 300 ml of dimethyl sulfoxide, and then add 0.057 grams of 3 -Ethyl-1-(3-dimethylaminopropyl)carbodiimide, stirred and reacted at 35°C for 4 days under an inert atmosphere, the reaction was terminated, and the target product was obtained by filtration, dialysis and drying;
2）聚己内酯与聚肽-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 polycaprolactone and polypeptide-polyvinylpyrrolidone
在干燥反应器内加入9.5克聚乙烯醇-聚己内酯接枝共聚物和34ml二甲基亚砜溶剂，另加入占改性膜总重量3%的聚（r-甲基-L-谷氨酸酯）-聚乙烯吡咯烷酮（分子量为5000），惰性气氛下，于52℃搅拌混合65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 polyvinyl alcohol-polycaprolactone graft copolymer and 34 ml of dimethyl sulfoxide solvent in the drying reactor, and add poly(r-methyl-L-glutane) accounting for 3% of the total weight of the modified membrane amino acid ester)-polyvinylpyrrolidone (molecular weight: 5000), stirred and mixed at 52°C for 65 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11.8%。After testing: the surface contact angle of the object of the present invention with water and the elongation at break are respectively increased by 13.3° and 11.8% compared with those before modification.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148963.5ACN105542486A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyving akohol membrane by polycaprolactone and polypeptide-polyvinylpyrrolidone |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610148963.5ACN105542486A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyving akohol membrane by polycaprolactone and polypeptide-polyvinylpyrrolidone |
| Publication Number | Publication Date |
|---|---|
| CN105542486Atrue CN105542486A (en) | 2016-05-04 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610148963.5APendingCN105542486A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyving akohol membrane by polycaprolactone and polypeptide-polyvinylpyrrolidone |
| Country | Link |
|---|---|
| CN (1) | CN105542486A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819905A (en)* | 2014-03-07 | 2014-05-28 | 山东理工大学 | Method for modifying hydrophilia of polypeptide membrane through adopting poly trimethylene carbonate and polyvinylpyrrolidone |
| CN103865091A (en)* | 2014-03-24 | 2014-06-18 | 山东理工大学 | Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid |
| CN103881110A (en)* | 2014-04-11 | 2014-06-25 | 山东理工大学 | Preparation method of polypeptide-poly(p-dioxanone)-polyvinylpyrrolidone dual-graft copolymer |
| CN104479157A (en)* | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819905A (en)* | 2014-03-07 | 2014-05-28 | 山东理工大学 | Method for modifying hydrophilia of polypeptide membrane through adopting poly trimethylene carbonate and polyvinylpyrrolidone |
| CN103865091A (en)* | 2014-03-24 | 2014-06-18 | 山东理工大学 | Method for improving water resisting performance of polyvinyl alcohol film from polycaprolactone and polylactic acid |
| CN103881110A (en)* | 2014-04-11 | 2014-06-25 | 山东理工大学 | Preparation method of polypeptide-poly(p-dioxanone)-polyvinylpyrrolidone dual-graft copolymer |
| CN104479157A (en)* | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol |
| Publication | Publication Date | Title |
|---|---|---|
| CN105542483B (en) | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with polydioxanone | |
| CN105542207A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone | |
| CN105542481A (en) | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone | |
| CN105670304A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid | |
| CN105566663B (en) | A method of improving polyvinyl alcohol film water resistance and compliance with polydioxanone and P (CPP-SA)-polyethylene glycol | |
| CN105647200A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) | |
| CN103865090A (en) | Method for improving hydrophilia of polypeptide film by using polycaprolactone and polyethylene glycol | |
| CN105647196A (en) | Method using polypeptide and polypropylene glycol-polyvinyl pyrrolidone to improve water resistance and flexibility of polyvinyl alcohol membrane | |
| CN105694477B (en) | A method of improving polyvinyl alcohol film water resistance and compliance with polydioxanone and P (CPP-SA)-polyvinylpyrrolidone | |
| CN105670307A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly(trimethylene carbonate)-polyvinylpyrrolidone | |
| CN105542486A (en) | Method for improving water resistance and flexibility of polyving akohol membrane by polycaprolactone and polypeptide-polyvinylpyrrolidone | |
| CN105670309A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and polycaprolactone | |
| CN105542209A (en) | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) | |
| CN105778523A (en) | Method for improving water tolerance and flexibility of polyvinyl alcohol membrane with poly (p-dioxanone) and polycaprolactone-polyvinyl pyrrolidone | |
| CN105670305A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polypeptide-polyethylene glycol | |
| CN105670308A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polycaprolactone and poly (p-dioxanone)-polyvinylpyrrolidone | |
| CN105542485A (en) | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone | |
| CN105542484A (en) | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(trimethylene carbonate)-polyvinylpyrrolidone | |
| CN105647194A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and polypeptide | |
| CN105601967B (en) | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polydioxanone-polyvinylpyrrolidone | |
| CN105647193A (en) | Method for improving water resistance and flexibility of polyvinyl alcohol film by polylactic acid-glycolic acid and polypeptide | |
| CN106977948A (en) | A method for improving the water resistance and flexibility of polyacrylic acid film by polylactic acid and polycaprolactone | |
| CN107011667A (en) | A kind of method being improved with PTMC and poly (lactic acid-glycolic acid) to polypropylene sorrel water resistance and compliance | |
| CN106977936A (en) | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance | |
| CN106977929A (en) | A kind of method being improved with PTMC and polypropylene glycol to polypropylene sorrel water resistance and compliance |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | Application publication date:20160504 | |
| RJ01 | Rejection of invention patent application after publication |