CN103881398A - Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone) - Google Patents
Method for improving water resistance of polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone) Download PDFInfo
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- CN103881398A CN103881398A CN201410109040.XA CN201410109040A CN103881398A CN 103881398 A CN103881398 A CN 103881398A CN 201410109040 A CN201410109040 A CN 201410109040A CN 103881398 A CN103881398 A CN 103881398A
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Abstract
The invention discloses a method for improving water resistance of a polyvinyl alcohol film by using poly(trimethylene carbonate) and poly(p-dioxanone). The method comprises the following steps of (1) adding poly(trimethylene carbonate), diisocyanate, a catalyst and a solvent into a drying reactor, and reacting while stirring at the temperature of 50-55 DEG C to obtain end-NCO group contained poly(trimethylene carbonate); (2) adding end-NCO group contained poly(trimethylene carbonate), polyvinyl alcohol, a solvent and a catalyst into the drying reactor, and reacting while stirring at the temperature of 50-55 DEG C to obtain a polyvinyl alcohol and poly(trimethylene carbonate) grafted copolymer; (3) adding the polyvinyl alcohol and poly(trimethylene carbonate) grafted copolymer, poly(p-dioxanone) and a solvent into the drying reactor, stirring and mixing at the temperature of 40-50 DEG C, filming by using a tape casting method and drying to obtain a target product required by the invention. The method is simple in preparation process and easy to master, and the water resistance of the obtained modified film is greatly improved.
Description
Technical field
The present invention relates to one polyvinyl alcohol film water tolerance is 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 wetting ability is too strong, polyvinyl alcohol film lacks good water tolerance, thereby has limited to a certain extent its application.PTMC and PPDO are the biomaterials with biocompatibility and biodegradability, have good water tolerance and have each other good blend.First PTMC segment is introduced to polyvinyl alcohol segments and formed polyvinyl alcohol-PTMC graft copolymer to improve the blend of polyvinyl alcohol, and then add polyvinyl alcohol-PTMC graft copolymer to form blend PPDO segment, make modified PVA membrane, thereby greatly improved the water tolerance of polyvinyl alcohol film.At present by PTMC and PPDO, polyvinyl alcohol film water tolerance is carried out to improved research and there is not yet report.
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 water tolerance to be carried out to improved method.Its technical scheme is:
A kind of PTMC and PPDO are improved 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 PTMC segment is 2000～3000, and the molecular weight of PPDO segment is 4000～5000; Its method of modifying adopts following steps:
1) synthesizing of the PTMC that contains end-NCO group: add PTMC, vulcabond, catalysts and solvents in dry reactor, under inert atmosphere, in 50～55 DEG C of stirring reactions 40～60 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) polyvinyl alcohol-PTMC graft copolymer is synthetic: add the PTMC, polyvinyl alcohol, solvent and the catalyzer that contain end-NCO group at dry reactor, under inert atmosphere, in 50～55 DEG C of stirring reactions 40～60 minutes, termination reaction, by filtering, dialyse, being dried, make target compound;
3) preparation of the polyvinyl alcohol film of PTMC and PPDO modification: add polyvinyl alcohol-PTMC graft copolymer, PPDO and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 60～70 minutes in 40～50 DEG C, by casting method film forming dry, obtain target compound.
Described a kind of PTMC and PPDO are improved the method for polyvinyl alcohol film water tolerance, in step 1), PTMC adopts PTMC monododecyl ether, vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and PTMC is 15～25:1.
Described a kind of PTMC and PPDO are improved the method for polyvinyl alcohol film water tolerance, in step 1), catalyzer adopts dibutyl tin laurate, add-on is 3～5 ‰ of PTMC and vulcabond gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
Described a kind of PTMC and PPDO are improved the method for polyvinyl alcohol film water tolerance, step 2) in, the PTMC that contains end-NCO group and the mol ratio of polyvinyl alcohol are 15～25:1; Catalyzer adopts dibutyl tin laurate, and add-on is polyvinyl alcohol and 3～5 ‰ of the PTMC gross weight that contains end-NCO group; Solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
Described a kind of PTMC and PPDO are improved the method for polyvinyl alcohol film water tolerance, in step 3), the mass percent of PPDO in modified membrane is 1～3%, and solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1. the PTMC described in and PPDO are improved the method for polyvinyl alcohol film water tolerance, adopt graft copolymerization and two kinds of means of blend, simple to operate, be easy to grasp;
2. the polyvinyl alcohol modification film water tolerance described in is greatly improved.
Embodiment
embodiment 1
1) synthesizing of the PTMC that contains end-NCO group:
In dry reactor, adding 12 gram molecular weights is 2000 PTMC monododecyl ether, 16.8 gram 2,4-tolylene diisocyanate and 280 ml dimethyl sulfoxide solvents, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 50 DEG C of stirring reactions 40 minutes, termination reaction, removes excessive vulcabond by dialysis method, obtains target compound;
2) polyvinyl alcohol-PTMC graft copolymer is synthetic:
In dry reactor, add 10 grams of PTMC that contain end-NCO group, 8.5 grams of polyvinyl alcohol (molecular weight is 30000) and 200 ml dimethyl sulfoxide solvents, add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 50 DEG C of stirring reactions after 40 minutes, termination reaction, by filtering, dialyse, being dried, make target compound again;
3) preparation of the polyvinyl alcohol film of PTMC and PPDO modification:
In dry reactor, add 9 grams of polyvinyl alcohol-PTMC graft copolymers and 34 ml dimethyl sulfoxide solvents, separately add the PPDO (molecular weight is 4000) that accounts for modified membrane gross weight 1%, under inert atmosphere, be uniformly mixed 60 minutes in 40 DEG C, use casting method film forming, the dry target compound that obtains in 50 DEG C of vacuum drying ovens.
After tested: the surface contact angle of target compound of the present invention and water has improved 12.9 ° before than modification.
embodiment 2
1) synthesizing of the PTMC that contains end-NCO group:
In dry reactor, adding 12 gram molecular weights is 2500 PTMC monododecyl ether, 16.7 gram 2,4-tolylene diisocyanate and 290 ml dimethyl sulfoxide solvents, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 52 DEG C of stirring reactions 50 minutes, termination reaction, removes excessive vulcabond by dialysis method, obtains target compound;
2) polyvinyl alcohol-PTMC graft copolymer is synthetic:
In dry reactor, add 10 grams of PTMC monododecyl ethers that contain end-NCO group, 7.9 grams of polyvinyl alcohol (molecular weight is 40000), add 210 ml dmso solutions, add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 52 DEG C of stirring reactions after 50 minutes, termination reaction, then make target compound by filtering, dialyse, being dried;
3) preparation of the polyvinyl alcohol film of PTMC and PPDO modification:
In dry reactor, add 9 grams of polyvinyl alcohol-PTMC graft copolymers and 33 ml dimethyl sulfoxide solvents, separately add the PPDO (molecular weight is 4500) that accounts for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed 65 minutes in 45 DEG C, use casting method film forming, the dry target compound that obtains in 50 DEG C of vacuum drying ovens.
After tested: the surface contact angle of target compound of the present invention and water has improved 13.8 ° before than modification.
embodiment 3
1) synthesizing of the PTMC that contains end-NCO group:
In dry reactor, adding 12 gram molecular weights is 3000 PTMC monododecyl ether, 15.1 gram 2,4-tolylene diisocyanate and 270 ml dimethyl sulfoxide solvents, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 55 DEG C of stirring reactions 60 minutes, termination reaction, removes excessive vulcabond by dialysis method, obtains target compound;
2) polyvinyl alcohol-PTMC graft copolymer is synthetic:
In dry reaction flask, add 10 grams of PTMC that contain end-NCO group, 7.16 grams of polyvinyl alcohol (molecular weight is 50000), add 205 ml dmso solutions, add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 55 DEG C of stirring reactions after 60 minutes, termination reaction, then by filtering, dialyse, being dried, make target compound;
3) preparation of the polyvinyl alcohol film of PTMC and PPDO modification:
In dry reactor, add 9 grams of polyvinyl alcohol-PTMC graft copolymers and 32 ml dimethyl sulfoxide solvents, separately add the PPDO (molecular weight is 5000) that accounts for modified membrane gross weight 3%, under inert atmosphere, be uniformly mixed 70 minutes in 50 DEG C, use casting method film forming, the dry target compound that obtains in 50 DEG C of vacuum drying ovens.
After tested: the surface contact angle of target compound of the present invention and water has improved 14.9 ° before than modification.
Claims (6)
1. a PTMC and PPDO are improved 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 PTMC segment is 2000～3000, and the molecular weight of PPDO segment is 4000～5000; Its method of modifying adopts following steps:
1) synthesizing of the PTMC that contains end-NCO group: add PTMC, vulcabond, catalysts and solvents in dry reactor, under inert atmosphere, in 50～55 DEG C of stirring reactions 40～60 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) polyvinyl alcohol-PTMC graft copolymer is synthetic: add the PTMC, polyvinyl alcohol, solvent and the catalyzer that contain end-NCO group at dry reactor, under inert atmosphere, in 50～55 DEG C of stirring reactions 40～60 minutes, termination reaction, by filtering, dialyse, being dried, make target compound;
3) preparation of the polyvinyl alcohol film of PTMC and PPDO modification: add polyvinyl alcohol-PTMC graft copolymer, PPDO and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 60～70 minutes in 40～50 DEG C, by casting method film forming dry, obtain target compound.
2. a kind of PTMC according to claim 1 and PPDO are improved the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 1), PTMC adopts PTMC monododecyl ether, vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and PTMC is 15～25:1.
3. a kind of PTMC according to claim 1 and PPDO are improved 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 PTMC and vulcabond gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
4. a kind of PTMC according to claim 1 and PPDO are improved the method for polyvinyl alcohol film water tolerance, it is characterized in that: step 2) in, the PTMC that contains end-NCO group and the mol ratio of polyvinyl alcohol are 15～25:1.
5. a kind of PTMC according to claim 1 and PPDO are improved the method for polyvinyl alcohol film water tolerance, it is characterized in that: step 2) in, catalyzer adopts dibutyl tin laurate, add-on is polyvinyl alcohol and 3～5 ‰ of the PTMC gross weight that contains end-NCO group, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
6. a kind of PTMC according to claim 1 and PPDO are improved the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 3), the mass percent of PPDO in modified membrane is 1～3%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30 g:100 ml.
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