CN103865275B - A kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance - Google Patents
A kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance Download PDFInfo
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- CN103865275B CN103865275B CN201410145063.6A CN201410145063A CN103865275B CN 103865275 B CN103865275 B CN 103865275B CN 201410145063 A CN201410145063 A CN 201410145063A CN 103865275 B CN103865275 B CN 103865275B
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Abstract
The present invention discloses a kind of method that poly(lactic acid) and polypropylene glycol improve polyvinyl alcohol film water tolerance, adopt following steps: the synthesis of the poly(lactic acid) 1) containing end-NCO group: add poly(lactic acid), vulcabond, catalysts and solvents in dry reactor, in 50 ~ 55 DEG C of stirring reactions, obtain target compound; 2) synthesis of polyvinyl alcohol-polylactic acid graft copolymer: add poly(lactic acid), polyvinyl alcohol, solvent and the catalyzer containing end-NCO group at dry reactor, in 50 ~ 55 DEG C of stirring reactions, obtain target compound; 3) preparation of the polyvinyl alcohol film of poly(lactic acid) and polypropylene glycol modified: add polyvinyl alcohol-polylactic acid graft copolymer, polypropylene glycol and solvent in dry reactor, is uniformly mixed in 40 ~ 50 DEG C, also dry by casting method film forming, obtains target compound of the present invention.Preparation technology of the present invention is simple, be easy to grasp, and gained modified membrane water tolerance is greatly improved.
Description
Technical field
The present invention relates to a kind of method that polyvinyl alcohol film water tolerance is improved, belong to field of polymer film preparing technology.
Background technology
Polyvinyl alcohol a kind ofly has good biocompatibility and the biomaterial of biodegradability, polyvinyl alcohol film can be used as artificial skin etc., but polyvinyl alcohol wetting ability is too strong, and polyvinyl alcohol film lacks good water tolerance, thus limit its application to a certain extent.Poly(lactic acid) and polypropylene glycol are the biomaterials with biocompatibility and biodegradability, have hydrophobicity and have good blended property each other.First polylactic acid chain segment is introduced polyvinyl alcohol segments and form polyvinyl alcohol-polylactic acid graft copolymer to improve the blended property of polyvinyl alcohol, and then polypropylene glycol segment is added polyvinyl alcohol-polylactic acid graft copolymer formation blend, obtained modified PVA membrane, thus drastically increase the water tolerance of polyvinyl alcohol film.There is not been reported to the research that polyvinyl alcohol film water tolerance is improved for current poly(lactic acid) and polypropylene glycol.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate and effect preferably to the method that polyvinyl alcohol film water tolerance is improved.Its technical scheme is:
A kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 30000 ~ 50000, the molecular weight of polylactic acid chain segment is 2000 ~ 3000, and the molecular weight of polypropylene glycol segment is 4000 ~ 5000; Its method of modifying adopts following steps:
1) synthesis of the poly(lactic acid) containing end-NCO group: add poly(lactic acid), vulcabond, catalysts and solvents in dry reactor, under inert atmosphere, in 50 ~ 55 DEG C of stirring reactions 50 ~ 70 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) synthesis of polyvinyl alcohol-polylactic acid graft copolymer: add poly(lactic acid), polyvinyl alcohol, solvent and the catalyzer containing end-NCO group at dry reactor, under inert atmosphere, in 50 ~ 55 DEG C of stirring reactions 50 ~ 70 minutes, termination reaction, by filtration, dialysis, dry obtained target compound;
3) preparation of the polyvinyl alcohol film of poly(lactic acid) and polypropylene glycol modified: add polyvinyl alcohol-polylactic acid graft copolymer, polypropylene glycol and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 70 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, in step 1), poly(lactic acid) adopts poly(lactic acid) monododecyl ether, and vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and poly(lactic acid) is 15 ~ 25:1.
Described a kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, in step 1), catalyzer adopts dibutyl tin laurate, add-on is 3 ~ 5 ‰ of poly(lactic acid) and vulcabond gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
Described a kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, step 2) in, be 15 ~ 25:1 containing the poly(lactic acid) of end-NCO group and the mol ratio of polyvinyl alcohol; Catalyzer adopts dibutyl tin laurate, and add-on is 3 ~ 5 ‰ of polyvinyl alcohol and the poly(lactic acid) gross weight containing end-NCO group; Solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100ml.
Described a kind of poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, and in step 3), the mass percent of polypropylene glycol in modified membrane is 2 ~ 4%, and 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. the poly(lactic acid) described in and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, adopt graft copolymerization and blended two kinds of means, simple to operate, be easy to grasp;
2. the polyvinyl alcohol modification film water tolerance described in is greatly improved.
Embodiment
embodiment 1
1) synthesis of the poly(lactic acid) containing end-NCO group:
Add in dry reactor 12 gram molecular weights be 2000 poly(lactic acid) monododecyl ether, 16.8 gram 2,4-tolylene diisocyanate and 280ml dimethyl sulfoxide solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 50 DEG C of stirring reactions 50 minutes, termination reaction, removes excessive vulcabond by dialysis method, obtains target compound;
2) synthesis of polyvinyl alcohol-polylactic acid graft copolymer:
In dry reactor, add 10 grams contain the poly(lactic acid) monododecyl ether of end-NCO group, 8.5 grams of polyvinyl alcohol (molecular weight is 30000) and 200ml dimethyl sulfoxide solvent, add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 50 DEG C of stirring reactions after 50 minutes, termination reaction, again by filtration, dialysis, drying, obtained target compound;
3) preparation of the polyvinyl alcohol film of poly(lactic acid) and polypropylene glycol modified:
9 grams of polyvinyl alcohol-polylactic acid graft copolymers and 34ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polypropylene glycol (molecular weight is 4000) accounting for modified membrane gross weight 2%, under inert atmosphere, 50 minutes are uniformly mixed in 40 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the surface contact angle of target compound of the present invention and water is than improve 12.1 ° before modified.
embodiment 2
1) synthesis of the poly(lactic acid) containing end-NCO group:
Add in dry reactor 12 gram molecular weights be 2500 poly(lactic acid) monododecyl ether, 16.7 gram 2,4-tolylene diisocyanate and 290ml dimethyl sulfoxide solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 52 DEG C of stirring reactions 60 minutes, termination reaction, removes excessive vulcabond by dialysis method, obtains target compound;
2) synthesis of polyvinyl alcohol-polylactic acid graft copolymer:
Poly(lactic acid) monododecyl ether, 7.9 grams of polyvinyl alcohol (molecular weight is 40000) that 10 grams contain end-NCO group are added in dry reaction bottle, add 210ml dmso solution, add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 52 DEG C of stirring reactions after 60 minutes, termination reaction, then by filtration, dialysis, drying, obtained target compound;
3) preparation of the polyvinyl alcohol film of poly(lactic acid) and polypropylene glycol modified:
9 grams of polyvinyl alcohol-polylactic acid graft copolymers and 33ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polypropylene glycol (molecular weight is 4500) accounting for modified membrane gross weight 3%, under inert atmosphere, 60 minutes are uniformly mixed in 45 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the surface contact angle of target compound of the present invention and water is than improve 13.4 ° before modified.
embodiment 3
1) synthesis of the poly(lactic acid) containing end-NCO group:
Add in dry reactor 12 gram molecular weights be 3000 poly(lactic acid) monododecyl ether, 15.1 gram 2,4-tolylene diisocyanate and 270ml dimethyl sulfoxide solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 55 DEG C of stirring reactions 70 minutes, termination reaction, removes excessive vulcabond by dialysis method, obtains target compound;
2) synthesis of polyvinyl alcohol-polylactic acid graft copolymer:
Poly(lactic acid) monododecyl ether, 7.16 grams of polyvinyl alcohol (molecular weight is 50000) that 10 grams contain end-NCO group are added in the reaction flask of drying, add 205ml dmso solution, add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 55 DEG C of stirring reactions after 70 minutes, termination reaction, then by filtration, dialysis, drying, obtained target compound;
3) preparation of the polyvinyl alcohol film of poly(lactic acid) and polypropylene glycol modified:
9 grams of polyvinyl alcohol-polylactic acid graft copolymers and 32ml dimethyl sulfoxide solvent is added in dry reactor, separately add the polypropylene glycol (molecular weight is 5000) accounting for modified membrane gross weight 4%, under inert atmosphere, 70 minutes are uniformly mixed in 50 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the surface contact angle of target compound of the present invention and water is than improve 14.4 ° before modified.
Claims (6)
1. a poly(lactic acid) and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in modified membrane, the molecular weight of polyvinyl alcohol segments is 30000 ~ 50000, the molecular weight of polylactic acid chain segment is 2000 ~ 3000, and the molecular weight of polypropylene glycol segment is 4000 ~ 5000; Its method of modifying adopts following steps:
1) synthesis of the poly(lactic acid) containing end-NCO group: add poly(lactic acid), vulcabond, catalysts and solvents in dry reactor, under inert atmosphere, in 50 ~ 55 DEG C of stirring reactions 50 ~ 70 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound, wherein, vulcabond adopts 2,4 toluene diisocyanate;
2) synthesis of polyvinyl alcohol-polylactic acid graft copolymer: add poly(lactic acid), polyvinyl alcohol, solvent and the catalyzer containing end-NCO group at dry reactor, under inert atmosphere, in 50 ~ 55 DEG C of stirring reactions 50 ~ 70 minutes, termination reaction, by filtration, dialysis, dry obtained target compound;
3) preparation of the polyvinyl alcohol film of poly(lactic acid) and polypropylene glycol modified: add polyvinyl alcohol-polylactic acid graft copolymer, polypropylene glycol and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 50 ~ 70 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of poly(lactic acid) according to claim 1 and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 1), and poly(lactic acid) adopts poly(lactic acid) monododecyl ether, and the mol ratio of vulcabond and poly(lactic acid) is 15 ~ 25:1.
3. a kind of poly(lactic acid) according to claim 1 and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 1), catalyzer adopts dibutyl tin laurate, add-on is 3 ~ 5 ‰ of poly(lactic acid) and vulcabond gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100mL.
4. a kind of poly(lactic acid) according to claim 1 and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: step 2) in, be 15 ~ 25:1 containing the poly(lactic acid) of end-NCO group and the mol ratio of polyvinyl alcohol.
5. a kind of poly(lactic acid) according to claim 1 and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: step 2) in, catalyzer adopts dibutyl tin laurate, add-on is 3 ~ 5 ‰ of polyvinyl alcohol and the poly(lactic acid) gross weight containing end-NCO group, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15g:100mL.
6. a kind of poly(lactic acid) according to claim 1 and polypropylene glycol improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 3), the mass percent of polypropylene glycol in modified membrane is 2 ~ 4%, and solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 30g:100mL.
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| CN105694058A (en) * | 2016-02-29 | 2016-06-22 | 山东理工大学 | Method for preparing polyving akohol-poly(lactic acid-glycolic acid)-polypeptide double graft copolymer |
| CN105670304A (en) * | 2016-03-07 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by using polycaprolactone and polylactic acid-glycollic acid |
| CN105754354A (en) * | 2016-03-07 | 2016-07-13 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly(p-dioxanone) and polycaprolactone-polyethylene glycol |
| CN105647200A (en) * | 2016-03-16 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and poly(lactic acid-glycolic acid) |
| CN105670309A (en) * | 2016-03-16 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and polycaprolactone |
| CN106947260A (en) * | 2017-05-22 | 2017-07-14 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA |
| CN107011670A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that PPDO improves polypropylene sorrel water resistance and compliance with PLA |
| CN107011671A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that PTMC improves polypropylene sorrel water resistance and compliance with PLA |
| CN107011669A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method being improved with PPDO and PLA to polypropylene sorrel water resistance and compliance |
| CN107057377A (en) * | 2017-05-25 | 2017-08-18 | 山东理工大学 | A kind of method that MPEGPLA is improved with polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN112143079B (en) * | 2020-09-25 | 2023-07-11 | 福建琦峰科技有限公司 | Antibacterial breathable film and preparation method thereof |
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| CN103304851A (en) * | 2013-07-07 | 2013-09-18 | 华东理工大学 | High-starch-content waterproof totally-decomposed composite material and preparation method thereof |
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