CN103937269A - Method for modifying water proofness of polyvinyl alcohol membrane by polypeptide and polycaprolactone - Google Patents
Method for modifying water proofness of polyvinyl alcohol membrane by polypeptide and polycaprolactone Download PDFInfo
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- CN103937269A CN103937269A CN201410108952.5A CN201410108952A CN103937269A CN 103937269 A CN103937269 A CN 103937269A CN 201410108952 A CN201410108952 A CN 201410108952A CN 103937269 A CN103937269 A CN 103937269A
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Abstract
The invention discloses a method for modifying water proofness of a polyvinyl alcohol membrane by polypeptide and polycaprolactone, which comprises the following steps: 1)synthesis of a terminal-NCO group-containing polypeptide homopolymer: adding the polypeptide homopolymer, diisocyanate, a catalyst and a solvent in a drying reactor, stirring for reaction at the temperature of 50-55 DEG C to obtain a target object; 2)synthesis of a polyvinyl alcohol-polypeptide graft copolymer: adding the terminal-NCO group-containing polypeptide homopolymer, polyvinyl alcohol, the solvent and the catalyst in the drying reactor, stirring for reaction at the temperature of 50-55 DEG C to obtain a target object; and 3)preparation of the polyvinyl alcohol membrane modified by polypeptide and polycaprolactone: adding the polyvinyl alcohol-polypeptide graft copolymer, polycaprolactone and the solvent in the drying reactor, stirring and mixing at the temperature of 40-50 DEG C, forming the membrane by a tape casting method, and drying to obtain the target object. The method has the advantages of simple technology and easy grasping, and the water proofness of the modified membrane is greatly increased.
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.Poly-peptide and polycaprolactone are the biomaterials with biocompatibility and biodegradability, have good hydrophobicity and have each other good blend.First poly-peptide segment is introduced to polyvinyl alcohol segments and formed polyvinyl alcohol-poly-polypeptide grafted copolymer to improve the blend of polyvinyl alcohol, and then add polyvinyl alcohol-poly-polypeptide grafted copolymer to form blend polycaprolactone segment, make modified PVA membrane, thereby greatly improved the water tolerance of polyvinyl alcohol film.At present with poly-peptide and polycaprolactone, 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 poly-peptide and polycaprolactone 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 poly-peptide segment is 2000～3000, and the molecular weight of polycaprolactone segment is 4000～6000; Its method of modifying adopts following steps:
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group: add poly-peptide homopolymer, 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) synthesizing of polyvinyl alcohol-poly-polypeptide grafted copolymer: add the poly-peptide homopolymer, 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, makes target compound by filtering, dialyse, being dried;
3) preparation of the polyvinyl alcohol film of poly-peptide and polycaprolactone modification: add polyvinyl alcohol-poly-polypeptide grafted copolymer, polycaprolactone and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50～70 minutes in 40～50 DEG C, by casting method film forming dry, obtain target compound.
Described a kind of poly-peptide and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-Pidolidone ester) or poly-(r-methyl-Pidolidone ester), vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and poly-peptide homopolymer is 15～25:1.
Described a kind of poly-peptide and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, in step 1), catalyzer adopts dibutyl tin laurate, add-on is 3～5 ‰ of poly-peptide homopolymer and vulcabond gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
Described a kind of poly-peptide and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, step 2) in, the poly-peptide homopolymer 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 poly-peptide homopolymer gross weight that contains end-NCO group, and solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
Described a kind of poly-peptide and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, and in step 3), the mass percent of polycaprolactone 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, described poly-peptide and polycaprolactone improve 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, described polyvinyl alcohol modification film water tolerance is greatly improved.
Embodiment
embodiment 1
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group:
In dry reactor, add 12 gram molecular weights be 2000 poly-(r-phenmethyl-Pidolidone ester), 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) synthesizing of polyvinyl alcohol-poly-polypeptide grafted copolymer:
In dry reactor, add 10 grams of poly-peptide homopolymer 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 poly-peptide and polycaprolactone modification:
In dry reactor, add 9 grams of polyvinyl alcohol-poly-polypeptide grafted copolymer and 34 ml dimethyl sulfoxide solvents, separately add the polycaprolactone (molecular weight is 4000) that accounts for modified membrane gross weight 1%, under inert atmosphere, be uniformly mixed 50 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 11.2 ° before than modification.
embodiment 2
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group:
In dry reactor, add 12 gram molecular weights be 2500 poly-(r-ethyl-Pidolidone ester), 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) synthesizing of polyvinyl alcohol-poly-polypeptide grafted copolymer:
In dry reaction flask, add 10 grams of poly-peptide homopolymer 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 by filtering, dialyse, being dried, make target compound;
3) preparation of the polyvinyl alcohol film of poly-peptide and polycaprolactone modification:
In dry reactor, add 9 grams of polyvinyl alcohol-poly-polypeptide grafted copolymer and 33 ml dimethyl sulfoxide solvents, separately add the polycaprolactone (molecular weight is 5000) that accounts for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed 60 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 12.8 ° before than modification.
embodiment 3
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group:
In dry reactor, add 12 gram molecular weights be 3000 poly-(r-methyl-Pidolidone ester), 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) synthesizing of polyvinyl alcohol-poly-polypeptide grafted copolymer:
In dry reaction flask, add 10 grams of poly-peptide homopolymer 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 poly-peptide and polycaprolactone modification:
In dry reactor, add 9 grams of polyvinyl alcohol-poly-polypeptide grafted copolymer and 32 ml dimethyl sulfoxide solvents, separately add the polycaprolactone (molecular weight is 6000) 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 13.6 ° before than modification.
Claims (6)
1. a poly-peptide and polycaprolactone 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 poly-peptide segment is 2000～3000, and the molecular weight of polycaprolactone segment is 4000～6000; Its method of modifying adopts following steps:
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group: add poly-peptide homopolymer, 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) synthesizing of polyvinyl alcohol-poly-polypeptide grafted copolymer: add the poly-peptide homopolymer, 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, makes target compound by filtering, dialyse, being dried;
3) preparation of the polyvinyl alcohol film of poly-peptide and polycaprolactone modification: add polyvinyl alcohol-poly-polypeptide grafted copolymer, polycaprolactone and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50～70 minutes in 40～50 DEG C, by casting method film forming dry, obtain target compound.
2. a kind of poly-peptide according to claim 1 and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-Pidolidone ester) or poly-(r-methyl-Pidolidone ester), vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and poly-peptide homopolymer is 15～25:1.
3. a kind of poly-peptide according to claim 1 and polycaprolactone 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-peptide homopolymer and vulcabond gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5～15 g:100 ml.
4. a kind of poly-peptide according to claim 1 and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: step 2) in, the poly-peptide homopolymer that contains end-NCO group and the mol ratio of polyvinyl alcohol are 15～25:1.
5. a kind of poly-peptide according to claim 1 and polycaprolactone 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 polyvinyl alcohol and 3～5 ‰ of the poly-peptide homopolymer 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 poly-peptide according to claim 1 and polycaprolactone improve the method for polyvinyl alcohol film water tolerance, it is characterized in that: in step 3), the mass percent of polycaprolactone in modified membrane is 1～3%, and solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25～30 g:100 ml.
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| CN105542178A (en) * | 2016-03-07 | 2016-05-04 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through poly(trimethylene carbonate) and polypeptide |
| CN105542209A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) |
| CN105542485A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone |
| CN105566648A (en) * | 2016-03-03 | 2016-05-11 | 山东理工大学 | Method for preparing polyving akohol-polycaprolactone-polypeptide double graft copolymer |
| CN105566641A (en) * | 2016-02-29 | 2016-05-11 | 山东理工大学 | Preparation method of PVA (Polyvinyl Alcohol)-polypeptide grafting copolymer |
| CN105585852A (en) * | 2016-03-16 | 2016-05-18 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
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| CN105585852A (en) * | 2016-03-16 | 2016-05-18 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film through polycaprolactone and poly(p-dioxanone) |
| CN105542209A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and poly(p-dioxanone) |
| CN105694475B (en) * | 2016-03-16 | 2018-07-13 | 山东理工大学 | A kind of method that poly- peptide improves polyvinyl alcohol film water resistance and compliance with polytrimethylene carbonate |
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