CN105694475A - Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly trimethylene carbonate - Google Patents

Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly trimethylene carbonate Download PDF

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Publication number
CN105694475A
CN105694475A CN201610148957.XA CN201610148957A CN105694475A CN 105694475 A CN105694475 A CN 105694475A CN 201610148957 A CN201610148957 A CN 201610148957A CN 105694475 A CN105694475 A CN 105694475A
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polyvinyl alcohol
poly
ptmc
peptide
trimethylene carbonate
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CN105694475B (en
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朱国全
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Shandong University of Technology
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Shandong University of Technology
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    • 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

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  • 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

The invention discloses a method for improving the water resistance and flexibility of a polyvinyl alcohol membrane through polypeptide and poly trimethylene carbonate. The method includes the following steps of 1, synthesis of a polyvinyl alcohol-polypeptide-poly trimethylene carbonate double-grafted copolymer, wherein a carboxyl-terminated polypeptide homopolymer, carboxyl-terminated poly trimethylene carbonate monododecyl ether, a solvent, a condensing agent and polyvinyl alcohol are added to a drying reactor, a reaction is conducted for 2-3 days at the temperature of 25-35 DEG C, and the target object is obtained after filtering, dialysis and drying; 2, preparation of the polypeptide and poly trimethylene carbonate modified polyvinyl alcohol membrane, wherein the polyvinyl alcohol-polypeptide-poly trimethylene carbonate double-grafted copolymer, poly trimethylene carbonate monododecyl ether and the solvent are added to the drying reactor, after mixing is conducted for 50-60 min at the temperature of 47-50 DEG C, film forming is conducted through tape casting, drying is conducted, and the target object is obtained. The preparation process is simple, grasping is easy, and the water resistance and flexibility of the obtained modified membrane are greatly improved.

Description

A kind of method that poly-peptide improves polyvinyl alcohol film resistance to water and compliance with PTMC
Technical field
The present invention relates to a kind of method that polyvinyl alcohol film resistance to water and compliance are improved, belong to field of polymer film preparing technology。
Background technology
Polyvinyl alcohol is a kind of biomaterial with good biocompatibility and biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol film hydrophilic is too strong and more stiff, lack good resistance to water and compliance, thus limiting its application to a certain extent。Poly-peptide is the biomaterial with excellent biocompatibility and biodegradability, has excellent hydrophobicity。PTMC is to have the biomaterial of excellent biocompatibility and biodegradability, has good hydrophobicity and compliance。First poly-peptide segment and PTMC segment are simultaneously introduced polyvinyl alcohol segments and form polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer, then PTMC segment is added polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer again and forms blend, prepare modified PVA membrane, thus drastically increasing resistance to water and the compliance of polyvinyl alcohol film。
Summary of the invention
It is an object of the invention to provide the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of simple to operate and effect preferably。Its technical scheme is:
A kind of method that poly-peptide improves polyvinyl alcohol film resistance to water and compliance with PTMC, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 85000～90000, the molecular weight of poly-peptide segment is 2500～2700, and the molecular weight of PTMC segment is 2500～2700；Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer: add the poly-peptide homopolymer of carboxy blocking, the PTMC monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 25～35 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object；
2) preparation of the polyvinyl alcohol film that poly-peptide is modified with PTMC: add polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer, PTMC monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 47～50 DEG C, by the tape casting film forming and dry, obtain object。
The method that described a kind of poly-peptide improves polyvinyl alcohol film resistance to water and compliance with PTMC, in step 1), the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15～25:1, poly-peptide homopolymer employing poly-(r-benzyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), the mol ratio of poly-peptide homopolymer and polyvinyl alcohol is 15～25:1。
The method that described a kind of poly-peptide improves polyvinyl alcohol film resistance to water and compliance with PTMC, in step 1), condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.07～1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
The method that described a kind of poly-peptide improves polyvinyl alcohol film resistance to water and compliance with PTMC, step 2) in, PTMC monododecyl ether mass percent in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25～30g:100ml。
Compared with prior art, its advantage is the present invention:
1, the method that described a kind of poly-peptide and PTMC improve polyvinyl alcohol film resistance to water and compliance, adopts reaction and blended two kinds of means that a kind of polymer and two kinds of different polymeric monomer carry out being esterified simultaneously, simple to operate, be prone to grasp；
2, described polyvinyl alcohol modification film resistance to water and compliance are enhanced。
Detailed description of the invention
Embodiment 1
1) preparation of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer
The PTMC monododecyl ether (molecular weight is 2500) gathering (r-benzyl-Pidolidone ester) (molecular weight is 2500) and 9.2 grams of carboxy blockings of 18 grams of polyvinyl alcohol (molecular weight is 85000), 9.3 grams of carboxy blockings is added at dry reactor, add 340ml dimethyl sulfoxide, add 0.056 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object；
2) preparation of the polyvinyl alcohol film that poly-peptide is modified with PTMC
10 grams of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC monododecyl ether (molecular weight is 2500) of Modified Membrane gross weight 2%, under inert atmosphere, in 47 DEG C of stirring mixing 50 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object。
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 12.2 ° and 12.8% before modified。
Embodiment 2
1) preparation of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer
The PTMC monododecyl ether (molecular weight is 2600) gathering (r-ethyl-L-glutamate ester) (molecular weight is 2600) and 11.4 grams of carboxy blockings of 21.5 grams of polyvinyl alcohol (molecular weight is 87000), 11.3 grams of carboxy blockings is added at dry reactor, add 410ml dimethyl sulfoxide, add 0.039 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysis, dry, obtains object；
2) preparation of the polyvinyl alcohol film that poly-peptide is modified with PTMC
10 grams of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer and 36ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC monododecyl ether (molecular weight is 2600) of Modified Membrane gross weight 3%, under inert atmosphere, in 48 DEG C of stirring mixing 55 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object。
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 12.9 ° and 13.6% before modified。
Embodiment 3
1) preparation of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer
The PTMC monododecyl ether (molecular weight is 2700) gathering (r-methyl-Pidolidone ester) (molecular weight is 2700) and 12.1 grams of carboxy blockings of 22 grams of polyvinyl alcohol (molecular weight is 90000), 12 grams of carboxy blockings is added at dry reactor, add 430ml dimethyl sulfoxide, add 0.061 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions 2 days, terminate reaction, by filtering, dialyse, drying, obtain object；
2) preparation of the polyvinyl alcohol film that poly-peptide is modified with PTMC
9.5 grams of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer and 35ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PTMC monododecyl ether (molecular weight is 2700) of Modified Membrane gross weight 4%, under inert atmosphere, in 50 DEG C of stirring mixing 60 minutes, use the tape casting film forming, dry in 50 DEG C of vacuum drying ovens and obtain object。
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than improve 13.4 ° and 14.5% before modified。

Claims (4)

1. the method that a poly-peptide improves polyvinyl alcohol film resistance to water and compliance with PTMC, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 85000～90000, the molecular weight of poly-peptide segment is 2500～2700, and the molecular weight of PTMC segment is 2500～2700；Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer: add the poly-peptide homopolymer of carboxy blocking, the PTMC monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 25～35 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object；
2) preparation of the polyvinyl alcohol film that poly-peptide is modified with PTMC: add polyvinyl alcohol-poly-peptide-PTMC dual graft copolymer, PTMC monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 47～50 DEG C, by the tape casting film forming and dry, obtain object。
2. the method that a kind of poly-peptide according to claim 1 improves polyvinyl alcohol film resistance to water and compliance with PTMC, it is characterized in that: in step 1), the mol ratio of PTMC monododecyl ether and polyvinyl alcohol is 15～25:1, poly-peptide homopolymer employing poly-(r-benzyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), the mol ratio of poly-peptide homopolymer and polyvinyl alcohol is 15～25:1。
3. the method that a kind of poly-peptide according to claim 1 improves polyvinyl alcohol film resistance to water and compliance with PTMC, it is characterised in that: in step 1), condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of condensing agent and polyvinyl alcohol is 1.07～1.8:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml。
4. the method that a kind of poly-peptide according to claim 1 improves polyvinyl alcohol film resistance to water and compliance with PTMC, it is characterized in that: step 2) in, PTMC monododecyl ether mass percent in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25～30g:100ml。
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)

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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
CONG WANG，等: "Polyelectrolyte complex/PVA membranes for diffusion dialysis", 《JOURNAL OF HAZARDOUS MATERIALS》 *
朱国全，等: "聚乙烯醇／聚氨酯共混薄膜制备及性能研究", 《山东理工大学学报（自然科学版）》 *

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