CN105647197A - Method for improving water resistance and flexibility of polyvinyl alcohol film by polypeptide and poly(lactic acid-glycolic acid) - Google Patents
Method for improving water resistance and flexibility of polyvinyl alcohol film by polypeptide and poly(lactic acid-glycolic acid) Download PDFInfo
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- CN105647197A CN105647197A CN201610148913.7A CN201610148913A CN105647197A CN 105647197 A CN105647197 A CN 105647197A CN 201610148913 A CN201610148913 A CN 201610148913A CN 105647197 A CN105647197 A CN 105647197A
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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
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- 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
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- 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
- C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences
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- 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
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- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
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- 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
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a method for improving the water resistance and the flexibility of a polyvinyl alcohol film by polypeptide and poly(lactic acid-glycolic acid). The method comprises the following steps of (1), the synthesis of a polyvinyl alcohol-polypeptide-poly(lactic acid-glycolic acid) double graft copolymer: adding a carboxyl-terminated polypeptide homopolymer, carboxyl-terminated poly(lactic acid-glycolic acid) monododecyl ether, a solvent, a condensating agent and polyvinyl alcohol into a dry reactor, stirring an obtained first mixture at 28 DEG C to 32 DEG C to carry out a reaction for 2 to 3 days, ending the reaction, and obtaining a target object through filtration, dialysis and drying; (2), the preparation of the polyvinyl alcohol film modified by the polypeptide and the poly(lactic acid-glycolic acid): adding the polyvinyl alcohol-polypeptide-poly(lactic acid-glycolic acid) double graft copolymer, the poly(lactic acid-glycolic acid) monododecyl ether and a solvent into a dry reactor, stirring and mixing an obtained second mixture for 50 to 60 minutes at a temperature of 49 DEG C to 51 DEG C, afterwards, forming the film by using a tape casting method and drying the film, so as to obtain a target object of the invention. The method is simple in preparation process and is easy to master; the water resistance and the flexibility of the obtained modified film are increased greatly.
Description
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. Poly-(D, Pfansteihl) glycolic (weight ratio of lactic acid and glycolic is 90/10) is the biomaterial with excellent biocompatibility and biodegradability, has good hydrophobicity and compliance. First poly-peptide segment and poly (lactic acid-glycolic acid) segment are simultaneously introduced polyvinyl alcohol segments and form polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer, then poly (lactic acid-glycolic acid) segment is added polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) 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 poly (lactic acid-glycolic acid), it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 83000��94000, the molecular weight of poly-peptide segment is 2500��2900, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2500��2900; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer: add the poly-peptide homopolymer of carboxy blocking, the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 28��32 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 poly (lactic acid-glycolic acid): add polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer, poly (lactic acid-glycolic acid) monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50��60 minutes in 49��51 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 poly (lactic acid-glycolic acid), in step 1), poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) glycolic monododecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol is 15��25:1, poly-peptide homopolymer adopts 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 poly (lactic acid-glycolic acid), 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 poly (lactic acid-glycolic acid), step 2) in, poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) glycolic monododecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, poly (lactic acid-glycolic acid) monododecyl ether mass percent in Modified Membrane is 2��4%, and 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 poly (lactic acid-glycolic acid) 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-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2500) gathering (r-benzyl-Pidolidone ester) (molecular weight is 2500) and 9.5 grams of carboxy blockings of 18 grams of polyvinyl alcohol (molecular weight is 83000), 9.5 grams of carboxy blockings is added at dry reactor, add 351ml dimethyl sulfoxide, add 0.056 gramN,N��-dicyclohexylcarbodiimide, under inert atmosphere, in 28 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 poly (lactic acid-glycolic acid)
10 grams of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2500) of Modified Membrane gross weight 2%, under inert atmosphere, in 49 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 12.4 �� and 12.6% before modified.
Embodiment 2
1) preparation of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2700) gathering (r-ethyl-L-glutamate ester) (molecular weight is 2700) and 11.7 grams of carboxy blockings of 21.5 grams of polyvinyl alcohol (molecular weight is 87000), 11.7 grams of carboxy blockings is added at dry reactor, add 433ml 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 poly (lactic acid-glycolic acid)
10 grams of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer and 36ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2700) of Modified Membrane gross weight 3%, under inert atmosphere, in 50 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 13.1 �� and 13.4% before modified.
Embodiment 3
1) preparation of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2900) gathering (r-methyl-Pidolidone ester) (molecular weight is 2900) and 12.3 grams of carboxy blockings of 22 grams of polyvinyl alcohol (molecular weight is 94000), 12.3 grams of carboxy blockings is added at dry reactor, add 448ml dimethyl sulfoxide, add 0.059 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 32 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 poly (lactic acid-glycolic acid)
9.5 grams of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer and 35ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 2900) of Modified Membrane gross weight 4%, under inert atmosphere, in 51 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 13.6 �� and 14.3% before modified.
Claims (4)
1. the method that a poly-peptide improves polyvinyl alcohol film resistance to water and compliance with poly (lactic acid-glycolic acid), it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 83000��94000, the molecular weight of poly-peptide segment is 2500��2900, and the molecular weight of poly (lactic acid-glycolic acid) segment is 2500��2900; Its method of modifying adopts following steps:
1) synthesis of polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer: add the poly-peptide homopolymer of carboxy blocking, the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 28��32 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 poly (lactic acid-glycolic acid): add polyvinyl alcohol-poly-peptide-poly (lactic acid-glycolic acid) dual graft copolymer, poly (lactic acid-glycolic acid) monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50��60 minutes in 49��51 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 poly (lactic acid-glycolic acid), it is characterized in that: in step 1), poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) glycolic monododecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and polyvinyl alcohol is 15��25:1, poly-peptide homopolymer adopts 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 poly (lactic acid-glycolic acid), 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 poly (lactic acid-glycolic acid), it is characterized in that: step 2) in, poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, Pfansteihl) glycolic monododecyl ether, and the weight ratio of lactic acid and glycolic is 90/10, poly (lactic acid-glycolic acid) monododecyl ether mass percent in Modified Membrane is 2��4%, and solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25��30g:100ml.
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| CN201610148913.7A CN105647197A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polypeptide and poly(lactic acid-glycolic acid) |
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| CN201610148913.7A CN105647197A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polypeptide and poly(lactic acid-glycolic acid) |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN104448841A (en) * | 2015-01-06 | 2015-03-25 | 山东理工大学 | Method for improving hydrophilia and flexibility of poly peptide film through poly (lactic acid-glycolic acid) (PLGA) and polyacrylic acid |
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2016
- 2016-03-16 CN CN201610148913.7A patent/CN105647197A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN104448841A (en) * | 2015-01-06 | 2015-03-25 | 山东理工大学 | Method for improving hydrophilia and flexibility of poly peptide film through poly (lactic acid-glycolic acid) (PLGA) and polyacrylic acid |
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