CN105670306A - Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(p-dioxanone) and polypeptide - Google Patents
Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(p-dioxanone) and polypeptide Download PDFInfo
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- CN105670306A CN105670306A CN201610125953.XA CN201610125953A CN105670306A CN 105670306 A CN105670306 A CN 105670306A CN 201610125953 A CN201610125953 A CN 201610125953A CN 105670306 A CN105670306 A CN 105670306A
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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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- 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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- 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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- 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The invention discloses a method for improving the water resistance and flexibility of a polyvinyl alcohol film by using poly(p-dioxanone) and polypeptide. The method comprises the following steps: 1) adding carboxyl-capped poly(p-dioxanone) monododecyl ether, a solvent, a condensing agent and polyvinyl alcohol into a drying reactor for reacting to obtain a polyvinyl alcohol-poly(p-dioxanone) graft copolymer; 2) adding the polyvinyl alcohol-poly(p-dioxanone) graft copolymer, carboxyl-capped polypeptide homopolymer, a solvent and a condensing agent into the drying reactor for reacting to obtain a polyvinyl alcohol-poly(p-dioxanone)-polypeptide binary graft copolymer; and 3) adding the polyvinyl alcohol-poly(p-dioxanone)-polypeptide binary graft copolymer, poly(p-dioxanone) monododecyl ether and a solvent into the drying reactor, and mixing to obtain a film which is the target object. The method disclosed by the invention is simple in preparation technology and easy to master; and the water resistance and flexibility of the obtained modified film are greatly improved.
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. PPDO is to have the biomaterial of excellent biocompatibility and biodegradability, has good hydrophobicity and compliance. First PPDO segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-PPDO graft copolymer, again poly-peptide segment is introduced and the polyvinyl alcohol segments in polyvinyl alcohol-PPDO graft copolymer obtains polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer, then PPDO segment is added polyvinyl alcohol-PPDO-poly-peptide 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 polyvinyl alcohol film resistance to water and compliance are improved by PPDO and poly-peptide, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 83000～92000, the molecular weight of PPDO segment is 2700～2900, and the molecular weight of poly-peptide segment is 2200～2400; Its method of modifying adopts following steps:
1) preparation of polyvinyl alcohol-PPDO graft copolymer: add the PPDO monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 27～34 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer: add polyvinyl alcohol-PPDO graft copolymer, the poly-peptide homopolymer of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 27～35 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
3) preparation of the polyvinyl alcohol film that PPDO is modified with poly-peptide: add polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer, PPDO monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 48～52 DEG C, by the tape casting film forming and dry, obtain object.
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PPDO and poly-peptide, in step 1), the mol ratio of PPDO monododecyl ether and polyvinyl alcohol is 15～25:1.
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PPDO and poly-peptide, 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 1.07～1.9:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml.
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PPDO and poly-peptide, step 2) in, 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 the polyvinyl alcohol segments in poly-peptide homopolymer and polyvinyl alcohol-PPDO graft copolymer is 15～25:1.
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PPDO and poly-peptide, step 2) in, condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of the polyvinyl alcohol segments in condensing agent and polyvinyl alcohol-PPDO graft copolymer is 1.07～1.9:1, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml.
The method that polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PPDO and poly-peptide, in step 3), PPDO 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 polyvinyl alcohol film resistance to water and compliance are improved by described a kind of PPDO and poly-peptide, adopts two step esterifications and blended three kinds of means, 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-PPDO graft copolymer
Add the PPDO monododecyl ether (molecular weight is 2700) of 18 grams of polyvinyl alcohol (molecular weight is 83000) and 10.5 grams of carboxy blockings at dry reactor, add 262ml dimethyl sulfoxide, add 0.056 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object;
2) preparation of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer
Add poly-(r-benzyl-Pidolidone ester) (molecular weight is 2200) of 10 grams of polyvinyl alcohol-PPDO graft copolymers and 4.7 grams of carboxy blockings at dry reactor, add 146ml dimethyl sulfoxide, add 0.031 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysis, dry, obtains object;
3) preparation of the polyvinyl alcohol film that PPDO is modified with poly-peptide
10 grams of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer and 37ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PPDO monododecyl ether (molecular weight is 2700) of Modified Membrane gross weight 2%, under inert atmosphere, in 48 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 12.3 ° and 12.6% before modified.
Embodiment 2
1) preparation of polyvinyl alcohol-PPDO graft copolymer
Add the PPDO monododecyl ether (molecular weight is 2800) of 18.2 grams of polyvinyl alcohol (molecular weight is 88000) and 10.3 grams of carboxy blockings at dry reactor, add 263ml dimethyl sulfoxide, add 0.033 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 polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer
Add poly-(r-ethyl-L-glutamate ester) (molecular weight is 2300) of 10.3 grams of polyvinyl alcohol-PPDO graft copolymers and 4.8 grams of carboxy blockings at dry reactor, add 147ml dimethyl sulfoxide, add 0.019 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysis, dry, obtains object;
3) preparation of the polyvinyl alcohol film that PPDO is modified with poly-peptide
9.8 grams of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer and 36ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PPDO monododecyl ether (molecular weight is 2800) 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 12.7 ° and 13.5% before modified.
Embodiment 3
1) preparation of polyvinyl alcohol-PPDO graft copolymer
The PPDO monododecyl ether (molecular weight is 2900) of 18.3 grams of polyvinyl alcohol (molecular weight is 92000) and 10.4 grams of carboxy blockings is added at dry reactor, add 264ml dimethyl sulfoxide, add 0.049 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 2 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer
Poly-(r-methyl-Pidolidone ester) (molecular weight is 2400) of 10 grams of polyvinyl alcohol-PPDO graft copolymers and 4.7 grams of carboxy blockings is added at dry reactor, add 145ml dimethyl sulfoxide, add 0.026 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
3) preparation of the polyvinyl alcohol film that PPDO is modified with poly-peptide
9.5 grams of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer and 35ml dimethyl sulfoxide solvent is added in dry reactor, another addition accounts for the PPDO monododecyl ether (molecular weight is 2900) of Modified Membrane gross weight 4%, under inert atmosphere, in 52 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 13.5 ° and 13.9% before modified.
Claims (6)
1. method polyvinyl alcohol film resistance to water and compliance improved with PPDO and poly-peptide, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 83000～92000, the molecular weight of PPDO segment is 2700～2900, and the molecular weight of poly-peptide segment is 2200～2400; Its method of modifying adopts following steps:
1) preparation of polyvinyl alcohol-PPDO graft copolymer: add the PPDO monododecyl ether of carboxy blocking, solvent, condensing agent and polyvinyl alcohol in dry reactor, under inert atmosphere, in 27～34 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialyse, drying, obtain object;
2) preparation of polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer: add polyvinyl alcohol-PPDO graft copolymer, the poly-peptide homopolymer of carboxy blocking, solvent and condensing agent in dry reactor, under inert atmosphere, in 27～35 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialyse, drying, obtain object;
3) preparation of the polyvinyl alcohol film that PPDO is modified with poly-peptide: add polyvinyl alcohol-PPDO-poly-peptide dual graft copolymer, PPDO monododecyl ether and solvent in dry reactor, under inert atmosphere, after stirring mixing 50～60 minutes in 48～52 DEG C, by the tape casting film forming and dry, obtain object.
2. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PPDO according to claim 1 and poly-peptide, it is characterized in that: in step 1), the mol ratio of PPDO monododecyl ether and polyvinyl alcohol is 15～25:1.
3. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PPDO according to claim 1 and poly-peptide, 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 1.07～1.9:1, and solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml.
4. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PPDO according to claim 1 and poly-peptide, it is characterized in that: step 2) in, 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 the polyvinyl alcohol segments in poly-peptide homopolymer and polyvinyl alcohol-PPDO graft copolymer is 15～25:1.
5. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PPDO according to claim 1 and poly-peptide, it is characterised in that: step 2) in, condensing agent adoptsN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, the mol ratio of the polyvinyl alcohol segments in condensing agent and polyvinyl alcohol-PPDO graft copolymer is 1.07～1.9:1, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15g:100ml.
6. the method that polyvinyl alcohol film resistance to water and compliance are improved by a kind of PPDO according to claim 1 and poly-peptide, it is characterized in that: in step 3), PPDO monododecyl ether mass percent in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25～30g:100ml.
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| CN201610125953.XA CN105670306A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(p-dioxanone) and polypeptide |
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| CN201610125953.XA CN105670306A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using poly(p-dioxanone) and polypeptide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011681A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PPDO |
| CN107011679A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA is improved with PPDO to polypropylene sorrel water resistance and compliance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104479158A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polydioxanone and polyethylene glycol |
| 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 |
-
2016
- 2016-03-07 CN CN201610125953.XA patent/CN105670306A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104479158A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polydioxanone and polyethylene glycol |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 胡跃飞等: "《现代有机合成试剂 性质、制备和反应》", 31 July 2006 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011681A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PPDO |
| CN107011679A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA is improved with PPDO to polypropylene sorrel water resistance and compliance |
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Application publication date: 20160615 |