CN105754354A - Method for improving water resistance and compliance of polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol - Google Patents
Method for improving water resistance and compliance of polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol Download PDFInfo
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- CN105754354A CN105754354A CN201610123803.5A CN201610123803A CN105754354A CN 105754354 A CN105754354 A CN 105754354A CN 201610123803 A CN201610123803 A CN 201610123803A CN 105754354 A CN105754354 A CN 105754354A
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- Prior art keywords
- polyvinyl alcohol
- polycaprolactone
- polyethylene glycol
- ppdo
- compliance
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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
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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
- C08J2487/00—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
- 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 compliance of a polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol. The method adopts the steps of: 1) synthesis of polyvinyl alcohol-poly(p-dioxanone) graft copolymer: adding carboxyl terminated poly(p-dioxanone) monoundecyl ether, a solvent, a condensing agent and polyvinyl alcohol into a drying reactor, carrying out stirring reaction at 27-33DEG C for 2-4d, then terminating the reaction, and performing filtering, dialyzing and drying to obtain a target object; and 2) preparation of the polyvinyl alcohol film modified with poly(p-dioxanone) and polycaprolactone-polyethylene glycol: adding the polyvinyl alcohol-poly(p-dioxanone) graft copolymer, polycaprolactone-polyethylene glycol and a solvent into a drying reactor, conducting mixing at 45-51DEG C for 55-60min, then performing film formation by tape casting, and carrying out drying, thus obtaining the target object of the invention. The preparation process involved in the invention is simple and is easy to master, and the obtained modified film has substantially improved water resistance and compliance.
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 hydrophily is the strongest and more stiff, lacks preferable resistance to water and compliance, thus limit its application to a certain extent.PPDO is the biomaterial with excellent biocompatibility and biodegradability, has good hydrophobicity and preferable compliance.Polycaprolactone-polyethylene glycol is the biomaterial with excellent biocompatibility and biodegradability, and polycaprolactone has good hydrophobicity and compliance, and polyethylene glycol has compliance and has the most blended property with polyvinyl alcohol.First PPDO segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-PPDO graft copolymer, polycaprolactone-polyethylene glycol is added polyvinyl alcohol-PPDO graft copolymer the most again and forms blend, prepare modified PVA membrane, thus drastically increase 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 preferably improved by a kind of simple to operate and effect.Its technical scheme is:
A kind of PPDO improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 82000～93000, the molecular weight of PPDO segment is 2400～2600, and the molecular weight of polycaprolactone-polyethylene glycol is 5100～5500；Its method of modifying employing following steps:
1) synthesis of polyvinyl alcohol-PPDO graft copolymer: add PPDO list undecyl ether, solvent, condensing agent and the polyvinyl alcohol of carboxy blocking in dry reactor, under inert atmosphere, in 27～33 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
2) preparation of the polyvinyl alcohol film that PPDO is modified with polycaprolactone-polyethylene glycol: add polyvinyl alcohol-PPDO graft copolymer, polycaprolactone-polyethylene glycol and solvent in dry reactor, under inert atmosphere, after 45～51 DEG C of stirring mixing 55～60 minutes, by the tape casting film forming and be dried, obtain object.
Described a kind of PPDO improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, and in step 1), PPDO list undecyl ether is 15～25:1 with the mol ratio of polyvinyl alcohol.
Described a kind of PPDO improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, and in step 1), condensing agent usesN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, condensing agent is 1.08～1.8:1 with the mol ratio of polyvinyl alcohol, and solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
Described a kind of PPDO improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, step 2) in, polycaprolactone-polyethylene glycol uses polycaprolactone-polyethylene glycol diblock copolymer, and the weight ratio of polycaprolactone and polyethylene glycol is 90/10, polycaprolactone-polyethylene glycol mass percent in Modified Membrane is 2～3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30 g:100 ml.
Compared with prior art, its advantage is the present invention:
1, described PPDO and polycaprolactone-polyethylene glycol improve polyvinyl alcohol film resistance to water and the method for compliance, use esterification and two kind means are blended, 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 19 grams of polyvinyl alcohol (molecular weight is 82000) and the PPDO list undecyl ether (molecular weight is 2400) of 10.5 grams of carboxy blockings at dry reactor, add 285 ml dimethyl sulfoxide (DMSO)s, add 0.058 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 27 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
2) preparation of the polyvinyl alcohol film that PPDO is modified with polycaprolactone-polyethylene glycol
10 grams of polyvinyl alcohol-PPDO graft copolymers and 37 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the polycaprolactone-polyethylene glycol (molecular weight is 5100) of Modified Membrane gross weight 2%, under inert atmosphere, in 45 DEG C of stirring mixing 55 minutes, use the tape casting film forming, in 50 DEG C of vacuum drying chambers, be dried to obtain object.
After tested: object of the present invention improves 12.4 ° and 12.8% before modified with surface contact angle and the elongation at break ratio respectively thereof of water.
Embodiment
2
1) preparation of polyvinyl alcohol-PPDO graft copolymer
Add 22 grams of polyvinyl alcohol (molecular weight is 88000) and the PPDO list undecyl ether (molecular weight is 2500) of 11.6 grams of carboxy blockings at dry reactor, add 312 ml dimethyl sulfoxide (DMSO)s, add 0.039 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
2) preparation of the polyvinyl alcohol film that PPDO is modified with polycaprolactone-polyethylene glycol
9.9 grams of polyvinyl alcohol-PPDO graft copolymers and 36 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the polycaprolactone-polyethylene glycol (molecular weight is 5300) of Modified Membrane gross weight 3%, under inert atmosphere, in 48 DEG C of stirring mixing 58 minutes, use the tape casting film forming, in 50 DEG C of vacuum drying chambers, be dried to obtain object.
After tested: object of the present invention improves 13.1 ° and 13.4% before modified with surface contact angle and the elongation at break ratio respectively thereof of water.
Embodiment
3
1) preparation of polyvinyl alcohol-PPDO graft copolymer
22.6 grams of polyvinyl alcohol (molecular weight is 93000) and the PPDO list undecyl ether (molecular weight is 2600) of 12 grams of carboxy blockings are added at dry reactor, add 333 ml dimethyl sulfoxide (DMSO)s, add 0.061 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 33 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialysing, be dried, obtain object；
2) preparation of the polyvinyl alcohol film that PPDO is modified with polycaprolactone-polyethylene glycol
9.5 grams of polyvinyl alcohol-PPDO graft copolymers and 34 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the polycaprolactone-polyethylene glycol (molecular weight is 5500) of Modified Membrane gross weight 2%, under inert atmosphere, in 51 DEG C of stirring mixing 60 minutes, use the tape casting film forming, in 50 DEG C of vacuum drying chambers, be dried to obtain object.
After tested: object of the present invention improves 13.7 ° and 14.5% before modified with surface contact angle and the elongation at break ratio respectively thereof of water.
Claims (4)
1. one kind is improved polyvinyl alcohol film resistance to water and the method for compliance with PPDO with polycaprolactone-polyethylene glycol, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 82000～93000, the molecular weight of PPDO segment is 2400～2600, and the molecular weight of polycaprolactone-polyethylene glycol is 5100～5500；Its method of modifying employing following steps:
1) synthesis of polyvinyl alcohol-PPDO graft copolymer: add PPDO list undecyl ether, solvent, condensing agent and the polyvinyl alcohol of carboxy blocking in dry reactor, under inert atmosphere, in 27～33 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
2) preparation of the polyvinyl alcohol film that PPDO is modified with polycaprolactone-polyethylene glycol: add polyvinyl alcohol-PPDO graft copolymer, polycaprolactone-polyethylene glycol and solvent in dry reactor, under inert atmosphere, after 45～51 DEG C of stirring mixing 55～60 minutes, by the tape casting film forming and be dried, obtain object.
A kind of PPDO the most according to claim 1 improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, it is characterized in that: in step 1), PPDO list undecyl ether is 15～25:1 with the mol ratio of polyvinyl alcohol.
A kind of PPDO the most according to claim 1 improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, it is characterised in that: in step 1), condensing agent usesN,N’-dicyclohexylcarbodiimide,N,N’-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, condensing agent is 1.08～1.8:1 with the mol ratio of polyvinyl alcohol, and solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
A kind of PPDO the most according to claim 1 improves polyvinyl alcohol film resistance to water and the method for compliance with polycaprolactone-polyethylene glycol, it is characterized in that: step 2) in, polycaprolactone-polyethylene glycol uses polycaprolactone-polyethylene glycol diblock copolymer, and the weight ratio of polycaprolactone and polyethylene glycol is 90/10, polycaprolactone-polyethylene glycol mass percent in Modified Membrane is 2～3%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30 g:100 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123803.5A CN105754354A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610123803.5A CN105754354A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol |
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| CN105754354A true CN105754354A (en) | 2016-07-13 |
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| CN201610123803.5A Pending CN105754354A (en) | 2016-03-07 | 2016-03-07 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947262A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106977928A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with MPEGPLA and PPDO to polypropylene sorrel water resistance and compliance |
| CN107011674A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| 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) |
| 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 CN201610123803.5A patent/CN105754354A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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) |
| CN103865275A (en) * | 2014-04-11 | 2014-06-18 | 山东理工大学 | Method for improving the water resistance of polyethylene glycol film modified by polylactic acid and polyvinyl alcohol |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106947262A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO |
| CN106977928A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with MPEGPLA and PPDO to polypropylene sorrel water resistance and compliance |
| CN107011674A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO |
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Application publication date: 20160713 |