CN103819908B - A kind of method that PPDO and urethane improve poly-peptide film kindliness - Google Patents
A kind of method that PPDO and urethane improve poly-peptide film kindliness Download PDFInfo
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- CN103819908B CN103819908B CN201410092889.0A CN201410092889A CN103819908B CN 103819908 B CN103819908 B CN 103819908B CN 201410092889 A CN201410092889 A CN 201410092889A CN 103819908 B CN103819908 B CN 103819908B
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Abstract
The present invention discloses a kind of method that PPDO and urethane improve poly-peptide film kindliness, adopt following steps: 1) add poly-peptide homopolymer, PPDO monododecyl ether, solvent and catalyzer in dry reactor, in 55 ~ 58 DEG C of stirring reactions after 3 ~ 4 days, obtain poly-peptide-PPDO graft copolymer; 2) add vulcabond, polypropylene glycol, polyoxyethylene glycol, catalysts and solvents in dry reactor, in 40 ~ 50 DEG C of stirring reactions 40 ~ 60 minutes, add BDO reaction 10 ~ 15 minutes, then add butanols reaction 5 ~ 10 minutes, obtain urethane; 3) poly-peptide-PPDO graft copolymer, urethane and solvent is added in dry reactor, after being uniformly mixed 40 ~ 60 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound of the present invention.Preparation technology of the present invention is simple, be easy to grasp, and gained modified membrane kindliness is greatly improved.
Description
Technical field
The present invention relates to a kind of method that poly-peptide film kindliness is improved, 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 is more stiff, and poly-peptide film lacks good kindliness, thus limit its application to a certain extent.PPDO and urethane have good biocompatibility and biodegradability, soft and have good blended property each other.First PPDO segment is introduced poly-peptide segment and form poly-peptide-PPDO graft copolymer to improve the blended property of poly-peptide, and then urethane segment is added poly-peptide-PPDO graft copolymer formation blend, obtained modification gathers peptide film, thus drastically increases the kindliness of poly-peptide film.
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 kindliness is improved.Its technical scheme is:
A kind of method that PPDO and urethane improve poly-peptide film kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 60000 ~ 80000, the molecular weight of PPDO segment is 1000 ~ 2000, and the molecular weight of urethane segment is 4000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-PPDO graft copolymer: add poly-peptide homopolymer, PPDO monododecyl ether, solvent and catalyzer in dry reactor, under inert atmosphere, in 55 ~ 58 DEG C of stirring reactions after 3 ~ 4 days, by filtration, dialysis, drying, obtain target compound;
2) synthesis of urethane: add vulcabond, polypropylene glycol, polyoxyethylene glycol, catalysts and solvents in dry reactor, under inert atmosphere, in 40 ~ 50 DEG C of stirring reactions after 40 ~ 60 minutes, add 1,4-butyleneglycol reaction 10 ~ 15 minutes, add butanols reaction 5 ~ 10 minutes again, termination reaction, obtains target compound;
3) preparation of PPDO and polyurethane-modified poly-peptide film: add poly-peptide-PPDO graft copolymer, urethane and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 40 ~ 60 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
The method that described a kind of PPDO and urethane improve poly-peptide film kindliness, in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of PPDO monododecyl ether and poly-peptide homopolymer is 15 ~ 25:1.
The method that described a kind of PPDO and urethane improve poly-peptide film kindliness, in step 1), catalyzer adopts tosic acid, the mol ratio of catalyzer and poly-peptide homopolymer is 25 ~ 45:1, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5 ~ 15g:100ml.
The method that described a kind of PPDO and urethane improve poly-peptide film kindliness, step 2) in, vulcabond adopts 2,4 toluene diisocyanate, and the difference of the mole number of vulcabond and glycol is 0.001 ~ 0.08.
The method that described a kind of PPDO and urethane improve poly-peptide film kindliness, step 2) in, catalyzer adopts dibutyl tin laurate, add-on is 3 ~ 5 ‰ of vulcabond and polypropylene glycol and polyoxyethylene glycol gross weight, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5 ~ 15g:100ml.
The method that described a kind of PPDO and urethane improve poly-peptide film kindliness, in step 3), the mass percent of urethane in modified membrane is 1 ~ 3%, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), mixture solution concentration is 25 ~ 30g:100ml.
Compared with prior art, its advantage is in the present invention:
1, described PPDO and urethane improve the method for poly-peptide film kindliness, adopt graft copolymerization and blended two kinds of means, simple to operate, be easy to grasp;
2, described poly-peptide modified membrane kindliness is greatly improved.
Embodiment
embodiment 1
1) synthesis of poly-peptide-PPDO graft copolymer:
12 gram molecular weights are 60000 poly-(r-phenmethyl-Pidolidone esters), 3.1 gram molecular weights are 1000 PPDO monododecyl ether, 0.9 gram of tosic acid is added in dry reactor, add 260 milliliter 1 again, 1,2-Separator, under inert atmosphere, in 55 DEG C of stirring reactions after 3 days, termination reaction, then by filtration, dialysis, dry obtained target compound;
2) synthesis of urethane:
In the reaction flask of drying, add 5.7 grams of 2,4 toluene diisocyanates, 12 grams of polypropylene glycols (molecular weight is 1000), 5 grams of polyoxyethylene glycol (molecular weight is 1000), add 350ml1,1,2-Separator, separately adds 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 0.7 gram of BDO and react 10 minutes, then add 1.2 grams of butanols and react 5 minutes, termination reaction, obtains target compound;
3) preparation of PPDO and polyurethane-modified poly-peptide film:
10 grams of poly-peptide-PPDO graft copolymers and 38 milliliter 1 is added in dry reactor, 1,2-Separator, separately add the urethane (molecular weight is 4000) accounting for modified membrane gross weight 1%, under inert atmosphere, after being uniformly mixed 40 minutes in 40 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the elongation at break of target compound of the present invention is than improve 12.8% before modified.
embodiment 2
1) synthesis of poly-peptide-PPDO graft copolymer:
12 gram molecular weights are 70000 poly-(r-ethyl-L-glutamate esters), 5.3 gram molecular weights are 1500 PPDO monododecyl ether, 0.91 gram of tosic acid is added in dry reactor, add 230 milliliter 1 again, 1,2-Separator, under inert atmosphere, in 56 DEG C of stirring reactions after 4 days, termination reaction, then by filtration, dialysis, dry obtained target compound;
2) synthesis of urethane:
In the reactor of drying, add 5.75 grams of 2,4 toluene diisocyanates, 14.6 grams of polypropylene glycols (molecular weight is 1000), 2.5 grams of polyoxyethylene glycol (molecular weight is 1000), add 355ml1,1,2-Separator, separately adds 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 0.8 gram of BDO and react 12 minutes, then add 1.3 grams of butanols and react 7 minutes, termination reaction, obtains target compound.
3) preparation of PPDO and polyurethane-modified poly-peptide film:
10 grams of poly-peptide-PPDO graft copolymers and 36 milliliter 1 is added in dry reactor, 1,2-Separator, separately add the urethane (molecular weight is 5000) accounting for modified membrane gross weight 2%, under inert atmosphere, after being uniformly mixed 50 minutes in 45 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the elongation at break of target compound of the present invention is than improve 13.8% before modified.
embodiment 3
1) synthesis of poly-peptide-PPDO graft copolymer:
12 gram molecular weights are 80000 poly-(r-methyl-Pidolidone esters), 7.2 gram molecular weights are 2000 PPDO monododecyl ether, 1.03 grams of tosic acid are added in dry reactor, add 177 milliliters of dimethyl sulfoxide (DMSO) again, under inert atmosphere, in 58 DEG C of stirring reactions after 3 days, termination reaction, then by filtration, dialysis, dry obtained target compound;
2) synthesis of urethane:
5.76 gram 2 is added in the reaction flask of drying, 4-tolylene diisocyanate, 14.05 grams of polypropylene glycols (molecular weight is 1000), 3 grams of polyoxyethylene glycol (molecular weight is 1000), add 358ml dimethyl sulfoxide solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 50 DEG C of stirring reactions after 60 minutes, add 0.8 gram of BDO and react 15 minutes, then add 1.21 grams of butanols and react 10 minutes, termination reaction, obtains target compound.
3) preparation of PPDO and polyurethane-modified poly-peptide film:
10 grams of poly-peptide-PPDO graft copolymers and 35.5 milliliters of dimethyl sulfoxide (DMSO) are added in dry reactor, separately add the urethane (molecular weight is 6000) accounting for modified membrane gross weight 3%, under inert atmosphere, after being uniformly mixed 60 minutes in 50 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the elongation at break of target compound of the present invention is than improve 14.9% before modified.
Claims (6)
1. the method poly-peptide film kindliness improved with PPDO and urethane, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 60000 ~ 80000, the molecular weight of PPDO segment is 1000 ~ 2000, and the molecular weight of urethane segment is 4000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-PPDO graft copolymer: add poly-peptide homopolymer, PPDO monododecyl ether, solvent and catalyzer in dry reactor, under inert atmosphere, in 55 ~ 58 DEG C of stirring reactions after 3 ~ 4 days, by filtration, dialysis, drying, obtain target compound;
2) synthesis of urethane: add vulcabond, polypropylene glycol, polyoxyethylene glycol, catalysts and solvents in dry reactor, under inert atmosphere, in 40 ~ 50 DEG C of stirring reactions after 40 ~ 60 minutes, add 1,4-butyleneglycol reaction 10 ~ 15 minutes, add butanols reaction 5 ~ 10 minutes again, termination reaction, obtains target compound;
3) preparation of PPDO and polyurethane-modified poly-peptide film: add poly-peptide-PPDO graft copolymer, urethane and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 40 ~ 60 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of PPDO according to claim 1 and urethane method that poly-peptide film kindliness is improved, it is characterized in that: in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of PPDO monododecyl ether and poly-peptide homopolymer is 15 ~ 25:1.
3. a kind of PPDO according to claim 1 and urethane method that poly-peptide film kindliness is improved, it is characterized in that: in step 1), catalyzer adopts tosic acid, the mol ratio of catalyzer and poly-peptide homopolymer is 25 ~ 45:1, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5 ~ 15g:100ml.
4. a kind of PPDO according to claim 1 and urethane method that poly-peptide film kindliness is improved, it is characterized in that: step 2) in, vulcabond adopts 2,4 toluene diisocyanate, and the difference of the mole number of vulcabond and glycol is 0.001 ~ 0.08.
5. a kind of PPDO according to claim 1 and urethane method that poly-peptide film kindliness is improved, it is characterized in that: step 2) in, catalyzer adopts dibutyl tin laurate, add-on is 3 ~ 5 ‰ of vulcabond and polypropylene glycol and polyoxyethylene glycol gross weight, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5 ~ 15g:100ml.
6. a kind of PPDO according to claim 1 and urethane method that poly-peptide film kindliness is improved, it is characterized in that: in step 3), the mass percent of urethane in modified membrane is 1 ~ 3%, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), mixture solution concentration is 25 ~ 30g:100ml.
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| CN104497588B (en) * | 2015-01-05 | 2017-02-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polydioxanone and polyacrylamide improved polypeptide film |
| CN104559209B (en) * | 2015-01-05 | 2017-01-18 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by polycarbamate and polyethylene glycol |
| CN104479158B (en) * | 2015-01-06 | 2017-09-08 | 山东理工大学 | A kind of method that PPDO improves poly- peptide film hydrophily and compliance with polyethylene glycol |
| CN104559218B (en) * | 2015-01-12 | 2017-06-16 | 山东理工大学 | A kind of method that PPDO improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan |
| CN104559220B (en) * | 2015-01-12 | 2017-02-22 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by poly(p-dioxanone) and waterborne polyurethane |
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