CN104559210A - Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol - Google Patents
Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol Download PDFInfo
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- CN104559210A CN104559210A CN201510004459.3A CN201510004459A CN104559210A CN 104559210 A CN104559210 A CN 104559210A CN 201510004459 A CN201510004459 A CN 201510004459A CN 104559210 A CN104559210 A CN 104559210A
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Abstract
The invention discloses a method for improving the hydrophily and flexibility of a polypeptide film by polypropylene glycol and polyethylene glycol. The method comprises the following steps: (1) adding carboxy terminated poly(propylene glycol) monobutyl ether, a solvent, a condensing agent and a polypeptide homopolymer into a dried reactor, and stirring to react at 20-30 DEG C for 3-4 days to obtain a polypeptide-polypropylene glycol segmented copolymer; (2) adding carboxy terminated poly(propylene glycol) monobutyl ether, a solvent, a condensing agent and amino-terminated methoxy polyethylene glycol into a dried reactor, and stirring to react at 25-35 DEG C for 2-3 days to obtain a polyethylene glycol-polypropylene glycol segmented copolymer; (3) adding the polypeptide-polypropylene glycol segmented copolymer, the polyethylene glycol-polypropylene glycol segmented copolymer and a solvent into a dried reactor, stirring and mixing at 40-50 DEG C for 30-40 minutes, forming a film by a tape casting method, and drying to obtain the target object. The preparation process is simple, and the hydrophily and flexibility of the modified film can be greatly improved.
Description
Technical field
The present invention relates to a kind of method that polypropylene glycol and polyoxyethylene glycol 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.Polypropylene glycol has good biocompatibility and biodegradability, softer and have good consistency with polyoxyethylene glycol.Polyoxyethylene glycol has good biocompatibility and biodegradability, softer and have good wetting ability.First polypropylene glycol segment is introduced poly-peptide segment respectively and polyoxyethylene glycol segment forms poly-peptide-polyethylene glycol block multipolymer and PLURONIC F-127, 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 polypropylene glycol and polyoxyethylene 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 poly-peptide film wetting ability and kindliness are improved.Its technical scheme is:
A kind of polypropylene glycol and polyoxyethylene glycol 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 polypropylene glycol segment is 3000 ~ 4000, and the molecular weight of polyoxyethylene glycol segment is 5000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polyethylene glycol block multipolymer: add the polypropylene glycol monobutyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 20 ~ 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 PLURONIC F-127: add the polypropylene glycol monobutyl ether of carboxy blocking, solvent, condensing agent and amino-terminated poly glycol monomethyl ether in dry reactor, under inert atmosphere, in 25 ~ 35 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of polypropylene glycol and poly ethyldiol modified poly-peptide film: add poly-peptide-polyethylene glycol block multipolymer, PLURONIC F-127 and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 30 ~ 40 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of polypropylene glycol and polyoxyethylene glycol 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 formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of polypropylene glycol and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, and in step 1), the mol ratio of polypropylene glycol monobutyl ether and poly-peptide homopolymer is 7 ~ 15:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.08 ~ 1.8:1.
Described a kind of polypropylene glycol and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, step 2) in, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent adopts dimethyl formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of polypropylene glycol and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, step 2) in, the mol ratio of polypropylene glycol monobutyl ether and poly glycol monomethyl ether is 3 ~ 9:1; The mol ratio of condensing agent and poly glycol monomethyl ether is 1.09 ~ 1.8:1.
Described a kind of polypropylene glycol and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, in step 3), the mass percent of PLURONIC F-127 in modified membrane is 1 ~ 4%, solvent adopts 1,2-ethylene dichloride or 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 polypropylene glycol described in and polyoxyethylene glycol improve poly-peptide film wetting ability and the method for kindliness, adopt amidate action and blended two 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-polyethylene glycol block multipolymer
In dry reactor, add the polypropylene glycol monobutyl 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 300 ml dimethyl formamides, then add 0.048 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of PLURONIC F-127
In dry reactor, add the polypropylene glycol monobutyl ether (molecular weight is 3000) of 3 grams of amino-terminated poly glycol monomethyl ethers (molecular weight is 5000) and 9 grams of carboxy blockings, add 160 ml dimethyl formamides, then add 0.145 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions termination reaction after 2 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of polypropylene glycol and poly ethyldiol modified poly-peptide film
12.5 grams of poly-peptide-polyethylene glycol block multipolymers and 45.8 ml 1 are added in dry reactor, 2-dichloroethane solvent, separately add the PLURONIC F-127 accounting for modified membrane gross weight 1%, under inert atmosphere, 30 minutes are uniformly mixed 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 11.5% and 13.2% before modified.
embodiment 2
1) synthesis of poly-peptide-polyethylene glycol block multipolymer
The polypropylene glycol monobutyl 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 formamides, add 0.031 gram of N again, N '-DIC, under inert atmosphere, in 25 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of PLURONIC F-127
In dry reactor, add the polypropylene glycol monobutyl ether (molecular weight is 3500) of 3 grams of amino-terminated poly glycol monomethyl ethers (molecular weight is 5500) and 9 grams of carboxy blockings, add 155 ml dimethyl formamides, 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;
3) preparation of polypropylene glycol and poly ethyldiol modified poly-peptide film
12.6 grams of poly-peptide-polyethylene glycol block multipolymers and 45.5 ml 1 are added in dry reactor, 1,2-Separator, separately add the PLURONIC F-127 accounting for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed 35 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 12.6% and 14.3% before modified.
embodiment 3
1) synthesis of poly-peptide-polyethylene glycol block multipolymer
The polypropylene glycol monobutyl 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 formamides, 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 PLURONIC F-127
The polypropylene glycol monobutyl ether (molecular weight is 4000) of 3.1 grams of amino-terminated poly glycol monomethyl ethers (molecular weight is 6000) and 9.2 grams of carboxy blockings is added in dry reactor, add 158 ml dimethyl formamides, 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;
3) preparation of polypropylene glycol and poly ethyldiol modified poly-peptide film
12.8 grams of poly-peptide-polyethylene glycol block multipolymers and 45.4 ml 1 are added in dry reactor, 2-dichloroethane solvent, separately add the PLURONIC F-127 accounting for modified membrane gross weight 4%, under inert atmosphere, 40 minutes are uniformly mixed 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 13.1% and 15.2% before modified.
Claims (6)
1. a polypropylene glycol and polyoxyethylene glycol 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 polypropylene glycol segment is 3000 ~ 4000, and the molecular weight of polyoxyethylene glycol segment is 5000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polyethylene glycol block multipolymer: add the polypropylene glycol monobutyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 20 ~ 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 PLURONIC F-127: add the polypropylene glycol monobutyl ether of carboxy blocking, solvent, condensing agent and amino-terminated poly glycol monomethyl ether in dry reactor, under inert atmosphere, in 25 ~ 35 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of polypropylene glycol and poly ethyldiol modified poly-peptide film: add poly-peptide-polyethylene glycol block multipolymer, PLURONIC F-127 and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 30 ~ 40 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of polypropylene glycol according to claim 1 and polyoxyethylene glycol 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 formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
3. a kind of polypropylene glycol according to claim 1 and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, and it is characterized in that: in step 1), the mol ratio of polypropylene glycol monobutyl ether and poly-peptide homopolymer is 7 ~ 15:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.08 ~ 1.8:1.
4. a kind of polypropylene glycol according to claim 1 and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: step 2) in, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent adopts dimethyl formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
5. a kind of polypropylene glycol according to claim 1 and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: step 2) in, the mol ratio of polypropylene glycol monobutyl ether and poly glycol monomethyl ether is 3 ~ 9:1; The mol ratio of condensing agent and poly glycol monomethyl ether is 1.09 ~ 1.8:1.
6. a kind of polypropylene glycol according to claim 1 and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 3), the mass percent of PLURONIC F-127 in modified membrane is 1 ~ 4%, solvent adopts 1,2-ethylene dichloride or 1,1,2-trichloroethane, mixture solution concentration is 25 ~ 35 g:100 ml.
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| CN201510004459.3A CN104559210B (en) | 2015-01-06 | 2015-01-06 | Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol |
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| CN201510004459.3A CN104559210B (en) | 2015-01-06 | 2015-01-06 | Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542207A (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 polypropylene glycol and polypeptide-polyvinylpyrrolidone |
| CN105669987A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-poly(lactide-glycolide) graft copolymer |
| CN107118566A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of method being improved with PPDO and polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN110551303A (en) * | 2019-09-17 | 2019-12-10 | 江南大学 | Method for preparing flexible conductive silk fibroin membrane by enzyme method |
Citations (4)
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| EP1482997A1 (en) * | 2002-02-27 | 2004-12-08 | Medtronic, Inc. | AnB BLOCK COPOLYMERS CONTAINING POLY(VINYL PYRROLIDONE) UNITS, MEDICAL DEVICES, AND METHODS |
| CN103804914A (en) * | 2014-03-10 | 2014-05-21 | 山东理工大学 | Method for improving hydrophilicity of polypeptide membrane by using polypropylene glycol and polyvinyl alcohol |
| CN103865088A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide membrane by polycaprolactone and polyethylene glycol |
| CN103865086A (en) * | 2014-03-04 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polycaprolactone and polypropylene glycol |
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2015
- 2015-01-06 CN CN201510004459.3A patent/CN104559210B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1482997A1 (en) * | 2002-02-27 | 2004-12-08 | Medtronic, Inc. | AnB BLOCK COPOLYMERS CONTAINING POLY(VINYL PYRROLIDONE) UNITS, MEDICAL DEVICES, AND METHODS |
| CN103865086A (en) * | 2014-03-04 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polycaprolactone and polypropylene glycol |
| CN103804914A (en) * | 2014-03-10 | 2014-05-21 | 山东理工大学 | Method for improving hydrophilicity of polypeptide membrane by using polypropylene glycol and polyvinyl alcohol |
| CN103865088A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide membrane by polycaprolactone and polyethylene glycol |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669987A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-poly(lactide-glycolide) graft copolymer |
| CN105542207A (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 polypropylene glycol and polypeptide-polyvinylpyrrolidone |
| CN107118566A (en) * | 2017-05-22 | 2017-09-01 | 山东理工大学 | A kind of method being improved with PPDO and polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN110551303A (en) * | 2019-09-17 | 2019-12-10 | 江南大学 | Method for preparing flexible conductive silk fibroin membrane by enzyme method |
| CN110551303B (en) * | 2019-09-17 | 2021-08-17 | 江南大学 | Method for preparing flexible conductive silk fibroin membrane by enzyme method |
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