CN104559221A - Method for improving hydrophilicity and flexibility of polypeptide film by poly lactic acid-glycolic acid and waterborne polyurethane - Google Patents
Method for improving hydrophilicity and flexibility of polypeptide film by poly lactic acid-glycolic acid and waterborne polyurethane Download PDFInfo
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- CN104559221A CN104559221A CN201510014849.9A CN201510014849A CN104559221A CN 104559221 A CN104559221 A CN 104559221A CN 201510014849 A CN201510014849 A CN 201510014849A CN 104559221 A CN104559221 A CN 104559221A
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Abstract
The invention discloses a method for improving hydrophilicity and flexibility of a polypeptide film by poly lactic acid-glycolic acid and waterborne polyurethane. The method comprises the following steps: 1) adding carboxyl-terminated poly lactic acid-glycolic acid, a solvent, a condensation agent and a polypeptide homopolymer into a reactor to obtain polypeptide-poly lactic acid-glycolic acid; 2) adding diisocyanate, polytetrahydrofuran, a catalyst and the solvent into the reactor for reacting for a period of time, adding dimethylolpropionic acid for reacting for a period of time, adding butanediol for reacting for a period of time, and adding butanol for reacting to obtain waterborne polyurethane; 3) adding amino-terminated poly lactic acid-glycolic acid, the solvent, the condensation agent and waterborne polyurethane into the reactor for reacting to obtain waterborne polyurethane-poly lactic acid-glycolic acid; and 4) adding polypeptide-poly lactic acid-glycolic acid, waterborne polyurethane-poly lactic acid-glycolic acid and the solvent into the reactor, mixing for a period of time, forming a film by a tape casting method, and drying to obtain a target object. The method disclosed by the invention is simple in preparation process, and the hydrophilicity and flexibility of the obtained modified film are greatly improved.
Description
Technical field
The present invention relates to a kind of method that poly (lactic acid-glycolic acid) and aqueous polyurethane improve poly-peptide film wetting ability and kindliness, belong to field of polymer film preparing technology.
Background technology
Poly-peptide a kind ofly has good biocompatibility and the biomaterial of biodegradability, and poly-peptide film can be used as artificial skin etc., but poly-peptide film more stiff, lack wetting ability, thus limit its application to a certain extent.Poly-(D, L) y has good biocompatibility and biodegradability, softer.Aqueous polyurethane has good biocompatibility and biodegradability, and has good wetting ability.First poly (lactic acid-glycolic acid) segment is introduced respectively poly-peptide segment and aqueous polyurethane segment forms poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer and aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer, and then two kinds of multipolymers are mixed to form the blend with better consistency, obtained modification gathers peptide film, thus drastically increases wetting ability and the kindliness of poly-peptide film.There is not been reported to the research that poly-peptide film wetting ability and kindliness are improved for current poly (lactic acid-glycolic acid) and aqueous polyurethane.
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 poly-peptide film wetting ability and kindliness are improved.Its technical scheme is:
A kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 80000 ~ 90000, the molecular weight of poly (lactic acid-glycolic acid) segment is 3000 ~ 4000, and the molecular weight of aqueous polyurethane segment is 5000 ~ 7000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer: add the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 25 ~ 30 DEG C of stirring reactions 3 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound, wherein, poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester);
2) synthesis of aqueous polyurethane: add vulcabond, PTMG, catalysts and solvents in dry reactor, under inert atmosphere, in 40 ~ 50 DEG C of stirring reactions after 40 ~ 60 minutes, add dimethylol propionic acid reaction 15 ~ 20 minutes, add BDO reaction 10 ~ 15 minutes, then add butanols reaction 5 ~ 10 minutes, termination reaction, obtains target compound;
3) synthesis of aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer: add amino-terminated poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and aqueous polyurethane in dry reactor, under inert atmosphere, in 20 ~ 35 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
4) preparation of poly (lactic acid-glycolic acid) and waterborne polyurethane modified poly-peptide film: add poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer, aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 40 ~ 50 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, in step 1), condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, in step 1), poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, L) y monododecyl ether (lactic acid and oxyacetic acid mol ratio: 50/50), the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and poly-peptide homopolymer is 7 ~ 16:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.08 ~ 1.8:1.
Described a kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, step 2) in, vulcabond adopts 2,4-tolylene diisocyanate, the difference of the mole number of vulcabond and glycol is 0.001 ~ 0.08, and catalyzer adopts dibutyl tin laurate, and add-on is 3 ~ 5 ‰ of vulcabond and PTMG gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, in step 3), condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, in step 3), poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, L) y monododecyl ether (lactic acid and oxyacetic acid mol ratio: 50/50), the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and aqueous polyurethane is 3 ~ 7:1; The mol ratio of condensing agent and aqueous polyurethane is 1.07 ~ 1.8:1.
Described a kind of poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, in step 4), aqueous polyurethane-the mass percent of poly (lactic acid-glycolic acid) graft copolymer in modified membrane is 2 ~ 4%, solvent adopts 1,1,2-trichloroethane, mixture solution concentration is 25 ~ 35 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1. the poly (lactic acid-glycolic acid) described in and aqueous polyurethane improve poly-peptide film wetting ability and the method for kindliness, adopt amidate action, progressively addition polymerization and blended three kinds of means, simple to operate, be easy to grasp;
2. the poly-peptide modified membrane wetting ability described in and kindliness are greatly improved.
Embodiment
embodiment 1
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer
In dry reactor, add the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 3000) of 16.1 grams of poly-(r-phenmethyl-Pidolidone ester) (molecular weight are 80000) and 7 grams of carboxy blockings, add 302 ml dimethyl sulfoxide (DMSO), then add 0.048 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of aqueous polyurethane
5.71 gram 2 is added in dry reactor, 4-tolylene diisocyanate, 15 grams of PTMG (molecular weight is 1000), add 310 ml dmso solutions, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 40 DEG C of stirring reactions after 40 minutes, add 0.4 gram of dimethylol propionic acid and react 15 minutes, add 0.97 gram 1,4-butyleneglycol reacts 10 minutes, add 1.22 grams of butanols again and react 5 minutes, termination reaction, obtain target compound;
3) synthesis of aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer
In dry reactor, add 3 grams of aqueous polyurethanes and 9 grams of amino-terminated poly (lactic acid-glycolic acid) monododecyl ethers (molecular weight is 3000), add 163 ml dimethyl sulfoxide (DMSO), then add 0.145 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions termination reaction after 2 days, by filtering, dialysis, dry, obtains target compound;
4) preparation of poly (lactic acid-glycolic acid) and waterborne polyurethane modified poly-peptide film
12.5 grams of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymers and 45.8 ml 1 are added in dry reactor, 1,2-Separator, separately add the aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer accounting for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed 40 minutes in 40 DEG C, use casting method film forming, dry in 50 DEG C of vacuum drying ovens, obtain target compound.
After tested: the hydrophilic rate of target compound of the present invention and elongation at break are respectively than improve 12.3% and 12.9% before modified.
embodiment 2
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 3500) of 16.3 grams of poly-(r-ethyl-L-glutamate ester) (molecular weight are 85000) and 7 grams of carboxy blockings is added in dry reactor, add 305 ml dimethyl sulfoxide (DMSO), add 0.031 gram of N again, N '-DIC, under inert atmosphere, in 27 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of aqueous polyurethane
5.71 gram 2 is added in dry reactor, 4-tolylene diisocyanate, 15.1 grams of PTMG (molecular weight is 1000), add 312 ml dmso solutions, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 45 DEG C of stirring reactions after 50 minutes, add 0.4 gram of dimethylol propionic acid and react 17 minutes, add 0.97 gram 1,4-butyleneglycol reacts 12 minutes, add 1.21 grams of butanols again and react 7 minutes, termination reaction, obtain target compound;
3) synthesis of aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer
In dry reactor, add 3 grams of aqueous polyurethanes and 9 grams of amino-terminated poly (lactic acid-glycolic acid) monododecyl ethers (molecular weight is 3500), add 155 ml dimethyl sulfoxide (DMSO), then add 0.08 gram
n, N '-DIC, under inert atmosphere, in 28 DEG C of stirring reactions termination reaction after 3 days, by filtering, dialysis, dry, obtains target compound;
4) preparation of poly (lactic acid-glycolic acid) and waterborne polyurethane modified poly-peptide film
12.6 grams of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymers and 45.5 ml 1 are added in dry reactor, 1,2-Separator, separately add the aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer accounting for modified membrane gross weight 3%, under inert atmosphere, be uniformly mixed 45 minutes in 45 DEG C, use casting method film forming, dry in 50 DEG C of vacuum drying ovens, obtain target compound.
After tested: the hydrophilic rate of target compound of the present invention and elongation at break are respectively than improve 12.8% and 13.6% before modified.
embodiment 3
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer
The poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 4000) of 16.5 grams of poly-(r-methyl-Pidolidone ester) (molecular weight are 90000) and 7 grams of carboxy blockings is added in dry reactor, add 310 ml dimethyl sulfoxide (DMSO), add 0.046 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) synthesis of aqueous polyurethane
5.71 gram 2 is added in dry reactor, 4-tolylene diisocyanate, 15.1 grams of PTMG (molecular weight is 1000), add 314 ml dmso solutions, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 50 DEG C of stirring reactions after 60 minutes, add 0.4 gram of dimethylol propionic acid and react 20 minutes, add 0.96 gram 1,4-butyleneglycol reacts 15 minutes, add 1.23 grams of butanols again and react 10 minutes, termination reaction, obtain target compound;
3) synthesis of aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer
3.1 grams of aqueous polyurethanes and 9.2 grams of amino-terminated poly (lactic acid-glycolic acid) monododecyl ethers (molecular weight is 4000) are added in dry reactor, add 160 ml dimethyl sulfoxide (DMSO), add 0.141 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions termination reaction after 2 days, by filtration, dialysis, drying, obtain target compound;
4) preparation of poly (lactic acid-glycolic acid) and waterborne polyurethane modified poly-peptide film
12.8 grams of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymers and 45.4 ml 1 are added in dry reactor, 1,2-Separator, separately add the aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer accounting for modified membrane gross weight 4%, under inert atmosphere, be uniformly mixed 50 minutes in 50 DEG C, use casting method film forming, dry in 50 DEG C of vacuum drying ovens, obtain target compound.
After tested: the hydrophilic rate of target compound of the present invention and elongation at break are respectively than improve 14.3% and 15.5% before modified.
Claims (7)
1. a poly (lactic acid-glycolic acid) and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 80000 ~ 90000, the molecular weight of poly (lactic acid-glycolic acid) segment is 3000 ~ 4000, and the molecular weight of aqueous polyurethane segment is 5000 ~ 7000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer: add the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 25 ~ 30 DEG C of stirring reactions 3 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound, wherein, poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester);
2) synthesis of aqueous polyurethane: add vulcabond, PTMG, catalysts and solvents in dry reactor, under inert atmosphere, in 40 ~ 50 DEG C of stirring reactions after 40 ~ 60 minutes, add dimethylol propionic acid reaction 15 ~ 20 minutes, add BDO reaction 10 ~ 15 minutes, then add butanols reaction 5 ~ 10 minutes, termination reaction, obtains target compound;
3) synthesis of aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer: add amino-terminated poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and aqueous polyurethane in dry reactor, under inert atmosphere, in 20 ~ 35 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
4) preparation of poly (lactic acid-glycolic acid) and waterborne polyurethane modified poly-peptide film: add poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer, aqueous polyurethane-poly (lactic acid-glycolic acid) graft copolymer and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 40 ~ 50 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of poly (lactic acid-glycolic acid) according to claim 1 and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 1), condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
3. a kind of poly (lactic acid-glycolic acid) according to claim 1 and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 1), poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, L) y monododecyl ether (lactic acid and oxyacetic acid mol ratio: 50/50), the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and poly-peptide homopolymer is 7 ~ 16:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.08 ~ 1.8:1.
4. a kind of poly (lactic acid-glycolic acid) according to claim 1 and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: step 2) in, vulcabond adopts 2,4-tolylene diisocyanate, the difference of the mole number of vulcabond and glycol is 0.001 ~ 0.08, catalyzer adopts dibutyl tin laurate, add-on is 3 ~ 5 ‰ of vulcabond and PTMG gross weight, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
5. a kind of poly (lactic acid-glycolic acid) according to claim 1 and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 3), condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent adopts dimethyl sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
6. a kind of poly (lactic acid-glycolic acid) according to claim 1 and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 3), poly (lactic acid-glycolic acid) monododecyl ether adopts poly-(D, L) y monododecyl ether (lactic acid and oxyacetic acid mol ratio: 50/50), the mol ratio of poly (lactic acid-glycolic acid) monododecyl ether and aqueous polyurethane is 3 ~ 7:1; The mol ratio of condensing agent and aqueous polyurethane is 1.07 ~ 1.8:1.
7. a kind of poly (lactic acid-glycolic acid) according to claim 1 and aqueous polyurethane improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 4), aqueous polyurethane-the mass percent of poly (lactic acid-glycolic acid) graft copolymer in modified membrane is 2 ~ 4%, solvent adopts 1,1,2-trichloroethane, mixture solution concentration is 25 ~ 35 g:100 ml.
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