CN105585852A - Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) - Google Patents
Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) Download PDFInfo
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- CN105585852A CN105585852A CN201610149295.8A CN201610149295A CN105585852A CN 105585852 A CN105585852 A CN 105585852A CN 201610149295 A CN201610149295 A CN 201610149295A CN 105585852 A CN105585852 A CN 105585852A
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- polyvinyl alcohol
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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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- 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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Abstract
The invention discloses a method for improving water resistance and flexibility of a polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone). The method includes the following steps that firstly, polyvinyl alcohol-polycaprolactone-poly(p-dioxanone) dual-grated copolymer is synthesized; in a dry reactor, carboxyl-terminated polycaprolactone mono-laurylether, carboxyl-terminated poly(p-dioxanone) mono-tridecyl ether, a solvent, a condensing agent and polyvinyl alcohol are added, a stirring reaction is performed for 2-4 days at 28-34 DEG C, and the target object is obtained; secondly, the polyvinyl alcohol film modified through polycaprolactone and poly(p-dioxanone) is prepared, wherein the polyvinyl alcohol-polycaprolactone-poly(p-dioxanone) dual-grated copolymer, poly(p-dioxanone) mono-tridecyl ether and a solvent are added in a dry reactor, a stirring reaction is performed for 50-60 min at 50-53 DEG C, film forming and drying are performed, and the target object is obtained. The preparation technology is simple and can be easily mastered, and the water resistance and flexibility of the obtained modified film are greatly improved.
Description
Technical field
The present invention relates to one polyvinyl alcohol film resistance to water and compliance are carried out to improved method, belong to field of polymer film preparing technology.
Background technology
Polyvinyl alcohol is a kind of have good biocompatibility and biomaterial of biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol film hydrophily is too strong and more stiff, lacks good resistance to water and compliance, thereby limited to a certain extent its application. Polycaprolactone and PPDO are to have good biocompatibility and the biomaterial of biodegradability, have good hydrophobicity and compliance. First polycaprolactone segment and PPDO segment are introduced to polyvinyl alcohol segments formation polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer simultaneously, and then add polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer to form blend PPDO segment, make modified PVA membrane, thereby greatly improved resistance to water and the compliance of polyvinyl alcohol film.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate and effect preferably polyvinyl alcohol film resistance to water and compliance to be carried out to improved method. Its technical scheme is:
A kind of polycaprolactone and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 88000～93000, the molecular weight of polycaprolactone segment is 2700～2800, and the molecular weight of PPDO segment is 2700～2800; Its method of modifying adopts following steps:
1) synthesizing of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer: add the polycaprolactone monododecyl ether of carboxy blocking, PPDO list tridecyl ether, solvent, condensing agent and the polyvinyl alcohol of carboxy blocking in dry reactor, under inert atmosphere, in 28～34 DEG C of stirring reactions 2～4 days, cessation reaction, by filtering, dialyse, being dried, obtain object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PPDO modification: add polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer, PPDO list tridecyl ether and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50～60 minutes in 50～53 DEG C, by the tape casting film forming dry, obtain object.
Described a kind of polycaprolactone and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15～25:1, and the mol ratio of PPDO list tridecyl ether and polyvinyl alcohol is 15～25:1.
Described a kind of polycaprolactone and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, and 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 (DMSO), and reactant solution concentration is 5～15g:100ml.
Described a kind of polycaprolactone and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, step 2) in, the mass percent of PPDO list tridecyl ether in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30g:100ml.
Compared with prior art, its advantage is in the present invention:
1, described a kind of polycaprolactone and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, and reaction and two kinds of means of blend of adopting a kind of polymer large monomers different from two kinds to carry out esterification simple to operate, be easy to grasp simultaneously;
2, described polyvinyl alcohol modification film resistance to water and compliance is enhanced.
Detailed description of the invention
Embodiment 1
1) preparation of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2700) of 18.2 grams of polyvinyl alcohol (molecular weight is 88000), 10.3 grams of carboxy blockings and the PPDO list tridecyl ether (molecular weight is 2700) of 10.2 grams of carboxy blockings at dry reactor, add 355ml dimethyl sulfoxide (DMSO), then add 0.056 gramN,N’-dicyclohexylcarbodiimide, under inert atmosphere, in 28 DEG C of stirring reactions 2 days, cessation reaction, by filtering, dialysis, dry, obtains object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PPDO modification
In dry reactor, add 10 grams of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymers and 37ml dimethyl sulfoxide solvent, separately add the PPDO list tridecyl ether (molecular weight is 2700) that accounts for Modified Membrane gross weight 2%, under inert atmosphere, be uniformly mixed 50 minutes in 50 DEG C, use the tape casting film forming, the dry object that obtains in 50 DEG C of vacuum drying chambers.
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than having improved 12.7 ° and 12.3% before modification.
Embodiment 2
1) preparation of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2700) of 21.6 grams of polyvinyl alcohol (molecular weight is 90000), 11.8 grams of carboxy blockings and the PPDO list tridecyl ether (molecular weight is 2700) of 11.8 grams of carboxy blockings at dry reactor, add 441ml dimethyl sulfoxide (DMSO), then add 0.038 gramN,N’-DIC, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, cessation reaction, by filtering, dialysis, dry, obtains object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PPDO modification
In dry reactor, add 10 grams of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymers and 36.5ml dimethyl sulfoxide solvent, separately add the PPDO list tridecyl ether (molecular weight is 2700) that accounts for Modified Membrane gross weight 3%, under inert atmosphere, be uniformly mixed 55 minutes in 51 DEG C, use the tape casting film forming, the dry object that obtains in 50 DEG C of vacuum drying chambers.
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than having improved 13.4 ° and 13.1% before modification.
Embodiment 3
1) preparation of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer
Add the polycaprolactone monododecyl ether (molecular weight is 2800) of 22 grams of polyvinyl alcohol (molecular weight is 93000), 12.1 grams of carboxy blockings and the PPDO list tridecyl ether (molecular weight is 2800) of 12.2 grams of carboxy blockings at dry reactor, add 455ml dimethyl sulfoxide (DMSO), add again 0.057 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, in 34 DEG C of stirring reactions 4 days, cessation reaction, by filtering, dialyse, being dried, obtains object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PPDO modification
In dry reactor, add 9.6 grams of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymers and 35ml dimethyl sulfoxide solvent, separately add the PPDO list tridecyl ether (molecular weight is 2800) that accounts for Modified Membrane gross weight 4%, under inert atmosphere, be uniformly mixed 60 minutes in 53 DEG C, use the tape casting film forming, the dry object that obtains in 50 DEG C of vacuum drying chambers.
After tested: the surface contact angle of object of the present invention and water and elongation at break thereof are respectively than having improved 13.6 ° and 13.8% before modification.
Claims (4)
1. a polycaprolactone and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, it is characterized in that: in Modified Membrane, the molecular weight of polyvinyl alcohol segments is 88000～93000, the molecular weight of polycaprolactone segment is 2700～2800, and the molecular weight of PPDO segment is 2700～2800; Its method of modifying adopts following steps:
1) synthesizing of polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer: add the polycaprolactone monododecyl ether of carboxy blocking, PPDO list tridecyl ether, solvent, condensing agent and the polyvinyl alcohol of carboxy blocking in dry reactor, under inert atmosphere, in 28～34 DEG C of stirring reactions 2～4 days, cessation reaction, by filtering, dialyse, being dried, obtain object;
2) preparation of the polyvinyl alcohol film of polycaprolactone and PPDO modification: add polyvinyl alcohol-polycaprolactone-PPDO dual graft copolymer, PPDO list tridecyl ether and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50～60 minutes in 50～53 DEG C, by the tape casting film forming dry, obtain object.
2. a kind of polycaprolactone according to claim 1 and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, it is characterized in that: in step 1), the mol ratio of polycaprolactone monododecyl ether and polyvinyl alcohol is 15～25:1, and the mol ratio of PPDO list tridecyl ether and polyvinyl alcohol is 15～25:1.
3. a kind of polycaprolactone according to claim 1 and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, it is characterized 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 (DMSO), and reactant solution concentration is 5～15g:100ml.
4. a kind of polycaprolactone according to claim 1 and PPDO improve the method for polyvinyl alcohol film resistance to water and compliance, it is characterized in that: step 2) in, the mass percent of PPDO list tridecyl ether in Modified Membrane is 2～4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30g:100ml.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610149295.8A CN105585852A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
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| CN201610149295.8A CN105585852A (en) | 2016-03-16 | 2016-03-16 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
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Cited By (7)
| 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 |
| CN106977930A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106977949A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polycaprolactone is improved with PPDO to polypropylene sorrel water resistance and compliance |
| CN106987127A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO |
| 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 |
| CN107011666A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance |
| CN107057376A (en) * | 2017-05-25 | 2017-08-18 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO |
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| 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 |
| 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 |
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2016
- 2016-03-16 CN CN201610149295.8A patent/CN105585852A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
Cited By (7)
| 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 |
| CN106977930A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106987127A (en) * | 2017-05-22 | 2017-07-28 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO |
| 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 |
| CN107011666A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method being improved with polycaprolactone and PPDO to polypropylene sorrel water resistance and compliance |
| CN106977949A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polycaprolactone is improved with PPDO to polypropylene sorrel water resistance and compliance |
| CN107057376A (en) * | 2017-05-25 | 2017-08-18 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with PPDO |
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Application publication date: 20160518 |