[go: up one dir, main page]

CN105694475B - A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate - Google Patents

A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate Download PDF

Info

Publication number
CN105694475B
CN105694475B CN201610148957.XA CN201610148957A CN105694475B CN 105694475 B CN105694475 B CN 105694475B CN 201610148957 A CN201610148957 A CN 201610148957A CN 105694475 B CN105694475 B CN 105694475B
Authority
CN
China
Prior art keywords
polyvinyl alcohol
poly
polytrimethylene carbonate
peptide
water resistance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610148957.XA
Other languages
Chinese (zh)
Other versions
CN105694475A (en
Inventor
朱国全
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University of Technology
Original Assignee
Shandong University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University of Technology filed Critical Shandong University of Technology
Priority to CN201610148957.XA priority Critical patent/CN105694475B/en
Publication of CN105694475A publication Critical patent/CN105694475A/en
Application granted granted Critical
Publication of CN105694475B publication Critical patent/CN105694475B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/027—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyester or polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

本发明公开一种聚肽与聚三亚甲基碳酸酯改进聚乙烯醇膜耐水性及柔顺性的方法，采用以下步骤：1）聚乙烯醇‑聚肽‑聚三亚甲基碳酸酯双接枝共聚物的合成：在干燥反应器内加入羧基封端的聚肽均聚物、羧基封端的聚三亚甲基碳酸酯单十二烷基醚、溶剂、缩合剂和聚乙烯醇，于25～35℃反应2～3天，通过过滤、透析、干燥，得到目标物；2）聚肽与聚三亚甲基碳酸酯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‑聚三亚甲基碳酸酯双接枝共聚物、聚三亚甲基碳酸酯单十二烷基醚和溶剂，于47～50℃混合50～60分钟后，用流延法成膜并干燥，得到本发明目标物。本发明制备工艺简单、易于掌握，所得改性膜耐水性及柔顺性有了很大的提高。The invention discloses a method for improving the water resistance and flexibility of polyvinyl alcohol film with polypeptide and polytrimethylene carbonate. The following steps are adopted: 1) double graft copolymerization of polyvinyl alcohol-polypeptide-polytrimethylene carbonate Synthesis of the product: add carboxyl-terminated polypeptide homopolymer, carboxyl-terminated polytrimethylene carbonate monododecyl ether, solvent, condensing agent and polyvinyl alcohol into a dry reactor, and react at 25-35 °C After 2 to 3 days, the target substance is obtained by filtration, dialysis, and drying; 2) Preparation of polyvinyl alcohol film modified by polypeptide and polytrimethylene carbonate: add polyvinyl alcohol-polypeptide-into the drying reactor Polytrimethylene carbonate double-graft copolymer, polytrimethylene carbonate monododecyl ether and solvent are mixed at 47-50°C for 50-60 minutes, then cast into a film and dried to obtain this product object of invention. The preparation process of the invention is simple and easy to master, and the water resistance and flexibility of the obtained modified membrane are greatly improved.

Description

一种聚肽与聚三亚甲基碳酸酯改进聚乙烯醇膜耐水性及柔顺 性的方法A Polypeptide and Polytrimethylene Carbonate Improve the Water Resistance and Softness of Polyvinyl Alcohol Film sexual method

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，具有优良的疏水性。聚三亚甲基碳酸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。先将聚肽链段和聚三亚甲基碳酸酯链段同时引入聚乙烯醇链段形成聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物，然后再将聚三亚甲基碳酸酯链段加入聚乙烯醇-聚肽-聚三亚甲基碳酸酯双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 excellent hydrophobicity. Polytrimethylene carbonate is a biomaterial with excellent biocompatibility and biodegradability, and has good hydrophobicity and flexibility. First, the polypeptide segment and the polytrimethylene carbonate segment are simultaneously introduced into the polyvinyl alcohol segment to form a polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer, and then the polytrimethylene carbonate The polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer is added to the ester segment to form a blend to prepare a modified polyvinyl alcohol film, which greatly improves the water resistance and flexibility of the polyvinyl alcohol film sex.

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:

一种聚肽与聚三亚甲基碳酸酯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85000～90000，聚肽链段的分子量为2500～2700，聚三亚甲基碳酸酯链段的分子量为2500～2700；其改性方法采用以下步骤：A method for improving the water resistance and flexibility of polyvinyl alcohol film with polypeptide and polytrimethylene carbonate, characterized in that: the molecular weight of the polyvinyl alcohol segment in the modified film is 85000-90000, and the molecular weight of the polypeptide segment 2500-2700, the molecular weight of the polytrimethylene carbonate segment is 2500-2700; the modification method adopts the following steps:

1）聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物的合成：在干燥反应器内加入羧基封端的聚肽均聚物、羧基封端的聚三亚甲基碳酸酯单十二烷基醚、溶剂、缩合剂和聚乙烯醇，惰性气氛下，于25～35℃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 polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer: add carboxy-terminated polypeptide homopolymer, carboxyl-terminated polytrimethylene carbonate Alkyl ether, solvent, condensing agent and polyvinyl alcohol, under an inert atmosphere, stirred and reacted at 25-35°C for 2-3 days, terminated the reaction, obtained the target product by filtration, dialysis and drying;

2）聚肽与聚三亚甲基碳酸酯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-聚三亚甲基碳酸酯双接枝共聚物、聚三亚甲基碳酸酯单十二烷基醚和溶剂，惰性气氛下，于47～50℃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 polytrimethylene carbonate: add polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer, polytrimethylene Carbonate monododecyl ether and a solvent are stirred and mixed at 47-50° 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三亚甲基碳酸酯改进聚乙烯醇膜耐水性及柔顺性的方法，步骤1）中，聚三亚甲基碳酸酯单十二烷基醚与聚乙烯醇的摩尔比为15～25:1，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 polytrimethylene carbonate, in step 1), the moles of polytrimethylene carbonate monolauryl ether and polyvinyl alcohol The ratio is 15 to 25:1, and the homopolymer of peptide is poly(r-benzyl-L-glutamate), poly(r-ethyl-L-glutamate) or poly(r-formyl base-L-glutamate), the molar ratio of peptide homopolymer to polyvinyl alcohol is 15-25:1.

所述的一种聚肽与聚三亚甲基碳酸酯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 polytrimethylene carbonate, in step 1), the condensing agent is N,N' -dicyclohexylcarbodiimide, 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, solvent Dimethyl sulfoxide is used, and the concentration of the reactant solution is 5-15 g:100 ml.

所述的一种聚肽与聚三亚甲基碳酸酯改进聚乙烯醇膜耐水性及柔顺性的方法，步骤2）中，聚三亚甲基碳酸酯单十二烷基醚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 with polypeptide and polytrimethylene carbonate, in step 2), the polytrimethylene carbonate monolauryl ether in the modified film The mass percentage 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、所述的一种聚肽与聚三亚甲基碳酸酯改进聚乙烯醇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 polyvinyl alcohol film by using a kind of polypeptide and polytrimethylene carbonate, adopts a kind of polymer and two kinds of different macromonomers to carry out esterification reaction and blending at the same time Two means, simple to operate and easy to grasp;

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-聚三亚甲基碳酸酯双接枝共聚物的制备1) Preparation of polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer

在干燥反应器加入18克聚乙烯醇（分子量为85000）、9.3克羧基封端的聚（r-苯甲基-L-谷氨酸酯）（分子量为2500）和9.2克羧基封端的聚三亚甲基碳酸酯单十二烷基醚（分子量为2500），加入340 ml二甲基亚砜，再加入0.056克N,N’-二环己基碳二亚胺，惰性气氛下，于25℃搅拌反应2天，终止反应，通过过滤、透析、干燥，得到目标物；Add 18 g of polyvinyl alcohol (molecular weight 85,000), 9.3 g of carboxy-terminated poly(r-benzyl-L-glutamate) (molecular weight of 2,500) and 9.2 g of carboxy-terminated polytrimethylene to a dry reactor Carbonate monododecyl ether (molecular weight: 2500), add 340 ml dimethyl sulfoxide, then add 0.056 g N,N' -dicyclohexylcarbodiimide, and stir the reaction at 25°C under an inert atmosphere After 2 days, the reaction was terminated, and the target object was obtained by filtration, dialysis, and drying;

2）聚肽与聚三亚甲基碳酸酯改性的聚乙烯醇膜的制备2) Preparation of Polyvinyl Alcohol Membrane Modified by Polypeptide and Polytrimethylene Carbonate

在干燥反应器内加入10克聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物和37ml二甲基亚砜溶剂，另加入占改性膜总重量2%的聚三亚甲基碳酸酯单十二烷基醚（分子量为2500），惰性气氛下，于47℃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-polytrimethylene carbonate double graft copolymer and 37ml dimethyl sulfoxide solvent in the dry reactor, and add polytrimethylene which accounts for 2% of the total weight of the modified membrane Carbonate monododecyl ether (molecular weight: 2500), stirred and mixed at 47°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12.2°和12.8%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 12.2° and 12.8% compared with those before modification.

实施例2Example 2

1）聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物的制备1) Preparation of polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer

在干燥反应器加入21.5克聚乙烯醇（分子量为87000）、11.3克羧基封端的聚（r-乙基-L-谷氨酸酯）（分子量为2600）和11.4克羧基封端的聚三亚甲基碳酸酯单十二烷基醚（分子量为2600），加入410 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 21.5 g of polyvinyl alcohol (molecular weight: 87,000), 11.3 g of carboxy-terminated poly(r-ethyl-L-glutamate) (molecular weight: 2,600) and 11.4 g of carboxy-terminated polytrimethylene to a dry reactor Carbonate monododecyl ether (molecular weight: 2600), add 410 ml dimethyl sulfoxide, then add 0.039 g N,N' -diisopropylcarbodiimide, stir and react at 30°C under an inert atmosphere After 3 days, the reaction was terminated, and the target object was obtained by filtration, dialysis, and drying;

2）聚肽与聚三亚甲基碳酸酯改性的聚乙烯醇膜的制备2) Preparation of Polyvinyl Alcohol Membrane Modified by Polypeptide and Polytrimethylene Carbonate

在干燥反应器内加入10克聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物和36ml二甲基亚砜溶剂，另加入占改性膜总重量3%的聚三亚甲基碳酸酯单十二烷基醚（分子量为2600），惰性气氛下，于48℃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-polytrimethylene carbonate double graft copolymer and 36ml dimethyl sulfoxide solvent in the drying reactor, and add polytrimethylene which accounts for 3% of the total weight of the modified membrane Carbonate monododecyl ether (molecular weight: 2600), stirred and mixed at 48°C for 55 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12.9°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 12.9° and 13.6% compared with those before modification.

实施例3Example 3

1）聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物的制备1) Preparation of polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer

在干燥反应器加入22克聚乙烯醇（分子量为90000）、12克羧基封端的聚（r-甲基-L-谷氨酸酯）（分子量为2700）和12.1克羧基封端的聚三亚甲基碳酸酯单十二烷基醚（分子量为2700），加入430 ml二甲基亚砜，再加入0.061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2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: 90,000), 12 g of carboxy-terminated poly(r-methyl-L-glutamate) (molecular weight: 2,700) and 12.1 g of carboxy-terminated polytrimethylene to a dry reactor Carbonate monolauryl ether (molecular weight 2700), add 430 ml dimethyl sulfoxide, then add 0.061 g 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, inert atmosphere , stirred and reacted at 35°C for 2 days, terminated the reaction, and obtained the target product by filtration, dialysis, and drying;

2）聚肽与聚三亚甲基碳酸酯改性的聚乙烯醇膜的制备2) Preparation of Polyvinyl Alcohol Membrane Modified by Polypeptide and Polytrimethylene Carbonate

在干燥反应器内加入9.5克聚乙烯醇-聚肽-聚三亚甲基碳酸酯双接枝共聚物和35ml二甲基亚砜溶剂，另加入占改性膜总重量4%的聚三亚甲基碳酸酯单十二烷基醚（分子量为2700），惰性气氛下，于50℃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 polyvinyl alcohol-polypeptide-polytrimethylene carbonate double graft copolymer and 35ml of dimethyl sulfoxide solvent in the dry reactor, and add polytrimethylene which accounts for 4% of the total weight of the modified membrane Carbonate monododecyl ether (molecular weight: 2700), stirred and mixed at 50°C for 60 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13.4°和14.5%。After testing: the surface contact angle of the object of the present invention and water and its elongation at break are respectively increased by 13.4° and 14.5% compared with those before modification.

Claims (4)

1. a kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate, feature exist In：The molecular weight of polyvinyl alcohol segments is 85000~90000 in Modified Membrane, and the molecular weight of poly- peptide segment is 2500~2700, is gathered The molecular weight of trimethylene carbonate segment is 2500~2700；Its method of modifying uses following steps：
1）The synthesis of the poly- peptide of polyvinyl alcohol-- polytrimethylene carbonate dual graft copolymer：Carboxyl is added in dry reactor The poly- peptide homopolymer of sealing end, polytrimethylene carbonate monododecyl ether, solvent, condensing agent and the polyethylene of carboxy blocking Alcohol under inert atmosphere, is stirred to react 2~3 days in 25~35 DEG C, is terminated reaction, by filtering, dialysis, drying, is obtained target Object, wherein poly- peptide homopolymer is using poly-（γ-benzyl-Pidolidone ester）, it is poly-（γ-ethyl-L-glutamate ester）Or it is poly-（γ- Methyl-Pidolidone ester）, the molar ratio of poly- peptide homopolymer and polyvinyl alcohol is 15~25:1；
2）The preparation for the polyvinyl alcohol film that poly- peptide is modified with polytrimethylene carbonate：Polyethylene is added in dry reactor The poly- peptide of alcohol-- polytrimethylene carbonate dual graft copolymer, polytrimethylene carbonate monododecyl ether and solvent, inertia Under atmosphere, it is stirred 50 in 47~50 DEG C~after sixty minutes, it is formed a film and is dried with the tape casting, obtain object.
2. a kind of poly- peptide according to claim 1 and polytrimethylene carbonate improve polyvinyl alcohol film water resistance and submissive The method of property, it is characterised in that：Step 1）In, the molar ratio of polytrimethylene carbonate monododecyl ether and polyvinyl alcohol is 15~25:1.
3. a kind of poly- peptide according to claim 1 and polytrimethylene carbonate improve polyvinyl alcohol film water resistance and submissive The method of property, it is characterised in that：Step 1）In, condensing agent usesN,N’Dicyclohexylcarbodiimide,N,N’Diisopropyl carbon Diimine or 3- ethyls -1-（3- dimethylaminopropyls）The molar ratio of carbodiimide, condensing agent and polyvinyl alcohol is 1.07~1.8: 1, solvent uses dimethyl sulfoxide (DMSO), a concentration of 5~15 g of reactant solution:100 ml.
4. a kind of poly- peptide according to claim 1 and polytrimethylene carbonate improve polyvinyl alcohol film water resistance and submissive The method of property, it is characterised in that：Step 2）In, quality percentage of the polytrimethylene carbonate monododecyl ether in Modified Membrane Than being 2~4%, solvent uses dimethyl sulfoxide (DMSO), a concentration of 25~30 g of mixture solution:100 ml.
CN201610148957.XA 2016-03-16 2016-03-16 A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate Expired - Fee Related CN105694475B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610148957.XA CN105694475B (en) 2016-03-16 2016-03-16 A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610148957.XA CN105694475B (en) 2016-03-16 2016-03-16 A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate

Publications (2)

Publication Number Publication Date
CN105694475A CN105694475A (en) 2016-06-22
CN105694475B true CN105694475B (en) 2018-07-13

Family

ID=56221811

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610148957.XA Expired - Fee Related CN105694475B (en) 2016-03-16 2016-03-16 A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate

Country Status (1)

Country Link
CN (1) CN105694475B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761711A2 (en) * 1995-08-31 1997-03-12 Dainichiseika Color & Chemicals Mfg. Co. Ltd. PVA-base thermoplastic copolymer, and its production process and use
CN103881398A (en) * 2014-03-24 2014-06-25 山东理工大学 Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone)
CN103937269A (en) * 2014-03-24 2014-07-23 山东理工大学 Method for modifying water proofness of polyvinyl alcohol membrane by polypeptide and polycaprolactone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761711A2 (en) * 1995-08-31 1997-03-12 Dainichiseika Color & Chemicals Mfg. Co. Ltd. PVA-base thermoplastic copolymer, and its production process and use
CN103881398A (en) * 2014-03-24 2014-06-25 山东理工大学 Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone)
CN103937269A (en) * 2014-03-24 2014-07-23 山东理工大学 Method for modifying water proofness of polyvinyl alcohol membrane by polypeptide and polycaprolactone

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Polyelectrolyte complex/PVA membranes for diffusion dialysis;Cong Wang，等;《Journal of Hazardous Materials》;20130719;第261卷;第114-122页 *
聚乙烯醇／聚氨酯共混薄膜制备及性能研究;朱国全，等;《山东理工大学学报（自然科学版）》;20120930;第26卷(第5期);第21-25页 *

Also Published As

Publication number Publication date
CN105694475A (en) 2016-06-22

Similar Documents

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
CN104479158B (en) A kind of method that PPDO 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
CN105542207A (en) Method for improving water resistance and flexibility of polyvinyl alcohol film through polypropylene glycol and polypeptide-polyvinylpyrrolidone
CN105566663B (en) A method of improving polyvinyl alcohol film water resistance and compliance with polydioxanone and P (CPP-SA)-polyethylene glycol
CN104559212B (en) Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol
CN105647196A (en) Method using polypeptide and polypropylene glycol-polyvinyl pyrrolidone to improve water resistance and flexibility of polyvinyl alcohol membrane
CN105542480B (en) The method that one kind polycaprolactone improves polyvinyl alcohol film water resistance and compliance with P (CPP SA) polyethylene glycol
CN105542178A (en) Method for improving water resistance and flexibility of polyvinyl alcohol film through poly(trimethylene carbonate) and polypeptide
CN104559216A (en) Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid
CN105694475B (en) A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate
CN104559211B (en) A kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid
CN105670306A (en) Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(p-dioxanone) and polypeptide
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
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
CN107118566A (en) A kind of method being improved with PPDO and polypropylene glycol to polypropylene sorrel water resistance and compliance
CN105778521A (en) Method for improving water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polypeptide-polyethylene glycol
CN106977930A (en) A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with polypropylene glycol
CN107011681A (en) A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PPDO
CN105542209A (en) Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone)
CN107011670A (en) A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA
CN106977952A (en) A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO

Legal Events

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: 20180713

Termination date: 20190316