CN104559215A - Method for improving hydrophily and flexibility of polypeptide membrane by polylactic acid and polyethylene glycol - Google Patents
Method for improving hydrophily and flexibility of polypeptide membrane by polylactic acid and polyethylene glycol Download PDFInfo
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- CN104559215A CN104559215A CN201510004853.7A CN201510004853A CN104559215A CN 104559215 A CN104559215 A CN 104559215A CN 201510004853 A CN201510004853 A CN 201510004853A CN 104559215 A CN104559215 A CN 104559215A
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Abstract
The invention discloses a method for improving the hydrophily and flexibility of a polypeptide film by polylactic acid and polyethylene glycol. The method comprises the following steps: (1) adding carboxy terminated polylactic monotetradecyl ether, a solvent, a condensing agent and a polypeptide homopolymer into a dried reactor, and reacting for 2-4 days to obtain a polypeptide-polylactic acid segmented copolymer; (2) adding carboxy terminated polylactic monotetradecyl ether, a solvent, a condensing agent and amino-terminated methoxy polyethylene glycol into a dried reactor, and reacting for 3-4 days to obtain a polyethylene glycol-polylactic acid segmented copolymer; (3) adding the polypeptide-polylactic acid segmented copolymer, the polyethylene glycol-polylactic acid segmented copolymer and a solvent into a dried reactor, mixing for 40-50 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 poly(lactic acid) 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.Poly-(D, L) lactic acid has good biocompatibility and biodegradability, softer.Polyoxyethylene glycol has good biocompatibility and biodegradability, softer and have good wetting ability.First polylactic acid chain segment is introduced respectively poly-peptide segment and polyoxyethylene glycol segment forms poly-peptide-polylactic-acid block copolymer and polyethylene glycol-polylactic acid segmented 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) 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 poly(lactic acid) 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 polylactic acid chain segment is 3000 ~ 4000, and the molecular weight of polyoxyethylene glycol segment is 5000 ~ 7000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polylactic-acid block copolymer: add the poly(lactic acid) list myristyl 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 polyethylene glycol-polylactic acid segmented copolymer: add the poly(lactic acid) list myristyl 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 3 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of poly(lactic acid) and poly ethyldiol modified poly-peptide film: add poly-peptide-polylactic-acid block copolymer, polyethylene glycol-polylactic acid segmented 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) 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly(lactic acid) and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, in step 1), poly(lactic acid) list myristyl ether adopts poly-(D, L) lactic acid list myristyl ether, and the mol ratio of poly(lactic acid) list myristyl 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 poly(lactic acid) 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly(lactic acid) and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, step 2) in, poly(lactic acid) list myristyl ether adopts poly-(D, L) lactic acid list myristyl ether, and the mol ratio of poly(lactic acid) list myristyl ether and poly glycol monomethyl ether is 3 ~ 10:1; The mol ratio of condensing agent and poly glycol monomethyl ether is 1.07 ~ 1.8:1.
Described a kind of poly(lactic acid) and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, and in step 3), the mass percent of polyethylene glycol-polylactic acid segmented 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) 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-polylactic-acid block copolymer
In dry reactor, add the poly(lactic acid) list myristyl 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 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of polyethylene glycol-polylactic acid segmented copolymer
In dry reactor, add the poly(lactic acid) list myristyl 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 162 ml dimethyl sulfoxide (DMSO), then add 0.145 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions termination reaction after 3 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of poly(lactic acid) and poly ethyldiol modified poly-peptide film
12.5 grams of poly-peptide-polylactic-acid block copolymers and 45.8 ml 1 are added in dry reactor, 1,2-Separator, separately add the polyethylene glycol-polylactic acid segmented 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 11.7% and 12.8% before modified.
embodiment 2
1) synthesis of poly-peptide-polylactic-acid block copolymer
The poly(lactic acid) list myristyl 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 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of polyethylene glycol-polylactic acid segmented copolymer
In dry reactor, add the poly(lactic acid) list myristyl ether (molecular weight is 3500) of 3 grams of amino-terminated poly glycol monomethyl ethers (molecular weight is 6000) and 9 grams of carboxy blockings, 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 4 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of poly(lactic acid) and poly ethyldiol modified poly-peptide film
12.6 grams of poly-peptide-polylactic-acid block copolymers and 45.5 ml 1 are added in dry reactor, 1,2-Separator, separately add the polyethylene glycol-polylactic acid segmented 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 12.4% and 13.7% before modified.
embodiment 3
1) synthesis of poly-peptide-polylactic-acid block copolymer
The poly(lactic acid) list myristyl 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 4 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) synthesis of polyethylene glycol-polylactic acid segmented copolymer
The poly(lactic acid) list myristyl ether (molecular weight is 4000) of 3.1 grams of amino-terminated poly glycol monomethyl ethers (molecular weight is 7000) and 9.2 grams of carboxy blockings is 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 3 days, by filtration, dialysis, drying, obtain target compound;
3) preparation of poly(lactic acid) and poly ethyldiol modified poly-peptide film
12.8 grams of poly-peptide-polylactic-acid block copolymers and 45.3 ml 1 are added in dry reactor, 1,2-Separator, separately add the polyethylene glycol-polylactic acid segmented 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 13.1% and 14.4% before modified.
Claims (6)
1. a poly(lactic acid) 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 polylactic acid chain segment is 3000 ~ 4000, and the molecular weight of polyoxyethylene glycol segment is 5000 ~ 7000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polylactic-acid block copolymer: add the poly(lactic acid) list myristyl 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 polyethylene glycol-polylactic acid segmented copolymer: add the poly(lactic acid) list myristyl 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 3 ~ 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of poly(lactic acid) and poly ethyldiol modified poly-peptide film: add poly-peptide-polylactic-acid block copolymer, polyethylene glycol-polylactic acid segmented 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) 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
3. a kind of poly(lactic acid) 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), poly(lactic acid) list myristyl ether adopts poly-(D, L) lactic acid list myristyl ether, the mol ratio of poly(lactic acid) list myristyl 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 poly(lactic acid) 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
5. a kind of poly(lactic acid) 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, poly(lactic acid) list myristyl ether adopts poly-(D, L) lactic acid list myristyl ether, the mol ratio of poly(lactic acid) list myristyl ether and poly glycol monomethyl ether is 3 ~ 10:1; The mol ratio of condensing agent and poly glycol monomethyl ether is 1.07 ~ 1.8:1.
6. a kind of poly(lactic acid) 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 polyethylene glycol-polylactic acid segmented 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977934A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance |
| CN107057375A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO |
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| CN101555316A (en) * | 2009-05-11 | 2009-10-14 | 山东大学 | Synthetic method of amino-terminated polyethylene glycol-polylactide block copolymer |
| CN101812227A (en) * | 2010-02-08 | 2010-08-25 | 中国科学院长春应用化学研究所 | Micelle based on non-linear polyethylene glycol-polylactic acid block copolymer and preparation method thereof |
| CN103224627A (en) * | 2013-05-09 | 2013-07-31 | 山东理工大学 | Preparation method of polylactic acid glycollic acid-polypeptide-polyethylene glycol diblock-grafted copolymer |
| CN103242536A (en) * | 2013-05-09 | 2013-08-14 | 山东理工大学 | Method for preparing polypeptide-polylactic acid-polyethyleneglycol dual-graft copolymer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555316A (en) * | 2009-05-11 | 2009-10-14 | 山东大学 | Synthetic method of amino-terminated polyethylene glycol-polylactide block copolymer |
| CN101812227A (en) * | 2010-02-08 | 2010-08-25 | 中国科学院长春应用化学研究所 | Micelle based on non-linear polyethylene glycol-polylactic acid block copolymer and preparation method thereof |
| CN103224627A (en) * | 2013-05-09 | 2013-07-31 | 山东理工大学 | Preparation method of polylactic acid glycollic acid-polypeptide-polyethylene glycol diblock-grafted copolymer |
| CN103242536A (en) * | 2013-05-09 | 2013-08-14 | 山东理工大学 | Method for preparing polypeptide-polylactic acid-polyethyleneglycol dual-graft copolymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977934A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with condensing model and PLA to polypropylene sorrel water resistance and compliance |
| CN107057375A (en) * | 2017-05-22 | 2017-08-18 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with PPDO |
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