CN104559222A - Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and carboxymethyl chitosan - Google Patents
Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and carboxymethyl chitosan Download PDFInfo
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- CN104559222A CN104559222A CN201510014850.1A CN201510014850A CN104559222A CN 104559222 A CN104559222 A CN 104559222A CN 201510014850 A CN201510014850 A CN 201510014850A CN 104559222 A CN104559222 A CN 104559222A
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Abstract
The invention discloses a method for improving hydrophilicity and flexibility of a polypeptide film by polycaprolactone and carboxymethyl chitosan. The method comprises the following steps: 1) adding carboxyl-terminated polycaprolactone monotridecyl ether, a solvent, a condensation agent and a polypeptide homopolymer into a drying reactor and reacting for 2-4 days to obtain a polypeptide-polycaprolactone block copolymer; 2) adding amino-terminated polycaprolactone monotridecyl ether, the solvent, the condensation agent and carboxymethyl chitosan into the drying reactor and reacting for 2-3 days to obtain a carboxymethyl chitosan-polycaprolactone graft copolymer; and 3) adding the polypeptide-polycaprolactone block copolymer, the carboxymethyl chitosan-polycaprolactone graft copolymer and the solvent into the drying reactor, mixing for 40-50min, then 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 polycaprolactone and cm-chitosan 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.Polycaprolactone has good biocompatibility and biodegradability, softer.Cm-chitosan has good biocompatibility and biodegradability, and has good wetting ability.First polycaprolactone segment is introduced respectively poly-peptide segment and cm-chitosan segment forms poly-peptide-polycaprolactone block polymer and cm-chitosan-polycaprolactone 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 polycaprolactone and cm-chitosan.
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 polycaprolactone and cm-chitosan 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 ~ 92000, the molecular weight of polycaprolactone segment is 3000 ~ 4000, and the molecular weight of cm-chitosan segment is 5000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polycaprolactone block polymer: add the polycaprolactone list tridecyl 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 2 ~ 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 cm-chitosan-polycaprolactone graft copolymer: add amino-terminated polycaprolactone list tridecyl ether, solvent, condensing agent and cm-chitosan 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 the poly-peptide film of polycaprolactone and cm-chitosan modification: add poly-peptide-polycaprolactone block polymer, cm-chitosan-polycaprolactone 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 polycaprolactone and cm-chitosan 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 polycaprolactone and cm-chitosan improve the method for poly-peptide film wetting ability and kindliness, and in step 1), the mol ratio of polycaprolactone list tridecyl 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 polycaprolactone and cm-chitosan 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of polycaprolactone and cm-chitosan improve the method for poly-peptide film wetting ability and kindliness, step 2) in, cm-chitosan adopts cm-chitosan (carboxylated degree is 70%), and the mol ratio of polycaprolactone list tridecyl ether and cm-chitosan is 3 ~ 6:1; The mol ratio of condensing agent and cm-chitosan is 1.08 ~ 1.8:1.
Described a kind of polycaprolactone and cm-chitosan improve the method for poly-peptide film wetting ability and kindliness, in step 3), cm-chitosan-the mass percent of polycaprolactone graft copolymer in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 35 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1. the polycaprolactone described in and cm-chitosan 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-polycaprolactone block polymer
In dry reactor, add the polycaprolactone list tridecyl ether (molecular weight is 3000) of 16.2 grams of poly-(r-phenmethyl-Pidolidone ester) (molecular weight are 80000) and 7 grams of carboxy blockings, add 308 ml dimethyl sulfoxide (DMSO), then add 0.048 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of cm-chitosan-polycaprolactone graft copolymer
In dry reactor, add 3.5 grams of cm-chitosan (molecular weight is 5000) and 9 grams of amino-terminated polycaprolactone list tridecyl ethers (molecular weight is 3000), add 163 ml dimethyl sulfoxide (DMSO), then add 0.165 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 the poly-peptide film of polycaprolactone and cm-chitosan modification
12.4 grams of poly-peptide-polycaprolactone block polymers and 45.7 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the cm-chitosan-polycaprolactone graft copolymer accounting for modified membrane gross weight 2%, under inert atmosphere, 40 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 13.1% and 12.5% before modified.
embodiment 2
1) synthesis of poly-peptide-polycaprolactone block polymer
The polycaprolactone list tridecyl 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 310 ml dimethyl sulfoxide (DMSO), add 0.031 gram of N again, N '-DIC, under inert atmosphere, in 27 DEG C of stirring reactions 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of cm-chitosan-polycaprolactone graft copolymer
In dry reactor, add 3 grams of cm-chitosan (molecular weight is 5500) and 9 grams of amino-terminated polycaprolactone list tridecyl ethers (molecular weight is 3500), add 158 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;
3) preparation of the poly-peptide film of polycaprolactone and cm-chitosan modification
12.6 grams of poly-peptide-polycaprolactone block polymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the cm-chitosan-polycaprolactone graft copolymer accounting for modified membrane gross weight 3%, under inert atmosphere, 45 minutes are uniformly mixed 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 13.8% and 13.2% before modified.
embodiment 3
1) synthesis of poly-peptide-polycaprolactone block polymer
The polycaprolactone list tridecyl ether (molecular weight is 4000) of 16.5 grams of poly-(r-methyl-Pidolidone ester) (molecular weight are 92000) 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 4 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) synthesis of cm-chitosan-polycaprolactone graft copolymer
3.1 grams of cm-chitosan (molecular weight is 6000) and 9.2 grams of amino-terminated polycaprolactone list tridecyl ethers (molecular weight is 4000) are added in dry reactor, add 158 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;
3) preparation of the poly-peptide film of polycaprolactone and cm-chitosan modification
12.8 grams of poly-peptide-polycaprolactone block polymers and 45.4 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the cm-chitosan-polycaprolactone graft copolymer accounting for modified membrane gross weight 4%, under inert atmosphere, 50 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 15.3% and 16.2% before modified.
Claims (6)
1. a polycaprolactone and cm-chitosan 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 ~ 92000, the molecular weight of polycaprolactone segment is 3000 ~ 4000, and the molecular weight of cm-chitosan segment is 5000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polycaprolactone block polymer: add the polycaprolactone list tridecyl 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 2 ~ 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 cm-chitosan-polycaprolactone graft copolymer: add amino-terminated polycaprolactone list tridecyl ether, solvent, condensing agent and cm-chitosan 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 the poly-peptide film of polycaprolactone and cm-chitosan modification: add poly-peptide-polycaprolactone block polymer, cm-chitosan-polycaprolactone 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 polycaprolactone according to claim 1 and cm-chitosan 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 polycaprolactone according to claim 1 and cm-chitosan improve the method for poly-peptide film wetting ability and kindliness, and it is characterized in that: in step 1), the mol ratio of polycaprolactone list tridecyl 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 polycaprolactone according to claim 1 and cm-chitosan 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
5. a kind of polycaprolactone according to claim 1 and cm-chitosan improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: step 2) in, cm-chitosan adopts cm-chitosan (carboxylated degree is 70%), and the mol ratio of polycaprolactone list tridecyl ether and cm-chitosan is 3 ~ 6:1; The mol ratio of condensing agent and cm-chitosan is 1.08 ~ 1.8:1.
6. a kind of polycaprolactone according to claim 1 and cm-chitosan improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 3), cm-chitosan-the mass percent of polycaprolactone graft copolymer in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 35 g:100 ml.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669989A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-polycaprolactone-polypeptide double-graft copolymer |
| CN106757496A (en) * | 2016-12-05 | 2017-05-31 | 华东理工大学 | Containing the two-component polymer superfine fibre and its preparation that synthesize poly- peptide and shitosan |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834180A (en) * | 2014-03-04 | 2014-06-04 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by using polycaprolactone and polypropylene glycol |
| CN103865090A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide film by using polycaprolactone and polyethylene glycol |
| 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 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834180A (en) * | 2014-03-04 | 2014-06-04 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by using polycaprolactone and polypropylene glycol |
| 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 |
| CN103865090A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide film by using polycaprolactone and polyethylene glycol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669989A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-polycaprolactone-polypeptide double-graft copolymer |
| CN106757496A (en) * | 2016-12-05 | 2017-05-31 | 华东理工大学 | Containing the two-component polymer superfine fibre and its preparation that synthesize poly- peptide and shitosan |
| CN106757496B (en) * | 2016-12-05 | 2020-09-22 | 华东理工大学 | Double-component polymer superfine fiber containing synthetic polypeptide and chitosan and preparation thereof |
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