CN104559212A - Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol - Google Patents
Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol Download PDFInfo
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Abstract
The invention discloses a method for improving the hydrophily and flexibility of a polypeptide film by poly(lactic acid-glycolic acid) and polyethylene glycol. The method comprises the following steps: (1) adding carboxy terminated poly(lactic acid-glycolic acid) monododecyl ether, a solvent, a condensing agent and a polypeptide homopolymer into a dried reactor, and reacting for 2-3 days to obtain a polypeptide-poly(lactic acid-glycolic acid) segmented copolymer; (2) adding carboxy terminated poly(lactic acid-glycolic acid) monododecyl 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-poly(lactic acid-glycolic acid) segmented copolymer; (3) adding the polypeptide-poly(lactic acid-glycolic acid) segmented copolymer, the polyethylene glycol-poly(lactic acid-glycolic acid) segmented copolymer and a solvent into the dried reactor, stirring and 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-glycolic 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) y 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 poly (lactic acid-glycolic acid) segment is introduced respectively poly-peptide segment and polyoxyethylene glycol segment forms poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer and polyethylene glycol-polylactic acid oxyacetic 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-glycolic 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-glycolic 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 poly (lactic acid-glycolic acid) 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-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 20 ~ 30 DEG C of stirring reactions 2 ~ 3 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 oxyacetic acid segmented copolymer: add the poly (lactic acid-glycolic acid) monododecyl 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-glycolic acid) and poly ethyldiol modified poly-peptide film: add poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer, polyethylene glycol-polylactic acid oxyacetic 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-glycolic 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 formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly (lactic acid-glycolic acid) and polyoxyethylene glycol 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 ~ 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-glycolic 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 formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of poly (lactic acid-glycolic acid) and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, step 2) in, 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 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-glycolic acid) and polyoxyethylene glycol improve the method for poly-peptide film wetting ability and kindliness, in step 3), the mass percent of polyethylene glycol-polylactic acid oxyacetic acid segmented copolymer in modified membrane is 1 ~ 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 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-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 formamides, then add 0.048 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 2 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of polyethylene glycol-polylactic acid oxyacetic acid segmented copolymer
In dry reactor, add the poly (lactic acid-glycolic acid) monododecyl 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 formamides, 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-glycolic acid) and poly ethyldiol 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 polyethylene glycol-polylactic acid oxyacetic acid segmented copolymer accounting for modified membrane gross weight 1%, 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 12.1% 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 formamides, add 0.031 gram of N again, N '-DIC, under inert atmosphere, in 25 DEG C of stirring reactions 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of polyethylene glycol-polylactic acid oxyacetic acid segmented copolymer
In dry reactor, add the poly (lactic acid-glycolic acid) monododecyl 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 formamides, 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-glycolic acid) and poly ethyldiol 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 polyethylene glycol-polylactic acid oxyacetic acid segmented copolymer accounting for modified membrane gross weight 2%, 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 13.5% 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 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 polyethylene glycol-polylactic acid oxyacetic acid segmented copolymer
The poly (lactic acid-glycolic acid) monododecyl 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 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 3 days, by filtration, dialysis, drying, obtain target compound;
3) preparation of poly (lactic acid-glycolic acid) and poly ethyldiol modified poly-peptide film
12.8 grams of poly-peptide-poly (lactic acid-glycolic acid) segmented copolymers and 45.3 ml 1 are added in dry reactor, 1,2-Separator, separately add the polyethylene glycol-polylactic acid oxyacetic 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 13.4% and 14.2% before modified.
Claims (6)
1. a poly (lactic acid-glycolic 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 poly (lactic acid-glycolic acid) 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-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 20 ~ 30 DEG C of stirring reactions 2 ~ 3 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 oxyacetic acid segmented copolymer: add the poly (lactic acid-glycolic acid) monododecyl 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-glycolic acid) and poly ethyldiol modified poly-peptide film: add poly-peptide-poly (lactic acid-glycolic acid) segmented copolymer, polyethylene glycol-polylactic acid oxyacetic 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-glycolic 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 formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
3. a kind of poly (lactic acid-glycolic 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-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 ~ 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-glycolic 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 formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
5. a kind of poly (lactic acid-glycolic 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-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 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-glycolic 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 oxyacetic acid segmented copolymer in modified membrane is 1 ~ 4%, solvent adopts 1,1,2-trichloroethane, mixture solution concentration is 25 ~ 35 g:100 ml.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504303A (en) * | 2016-03-03 | 2016-04-20 | 山东理工大学 | Polyvinyl alcohol-polypeptide-polycaprolactone-poly lactic acid-glycolic acid triple-graft copolymer preparation method |
| CN105542479A (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 poly(p-dioxanone) and poly lactic acid-glycolic acid |
| CN105542482A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(p-dioxanone) and poly(lactic acid-glycolic acid) |
| CN105622950A (en) * | 2016-02-29 | 2016-06-01 | 山东理工大学 | Preparation method of polyvinyl alcohol-poly(trimethylene carbonate)-poly(lactic acid-glycolic acid) dual-grafted copolymer |
| CN105732994A (en) * | 2016-03-03 | 2016-07-06 | 山东理工大学 | Method for preparing polyvinyl alcohol-polytrimethylene carbonate-poly lactic acid-glycolic acid double-grafted copolymer |
| CN111888523A (en) * | 2020-09-08 | 2020-11-06 | 尹振宇 | Preparation method of polylactic acid gel for improving skin |
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| 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 |
| CN103865274A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide film by poly(lactic acid-glycolic acid) and poly(caprolactone-lactide) |
| CN103937002A (en) * | 2014-04-11 | 2014-07-23 | 山东理工大学 | Preparation method of polypeptide-polylactic-co-glycolic acid-polyvinylpyrrolidone double-grafted copolymer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622950A (en) * | 2016-02-29 | 2016-06-01 | 山东理工大学 | Preparation method of polyvinyl alcohol-poly(trimethylene carbonate)-poly(lactic acid-glycolic acid) dual-grafted copolymer |
| CN105504303A (en) * | 2016-03-03 | 2016-04-20 | 山东理工大学 | Polyvinyl alcohol-polypeptide-polycaprolactone-poly lactic acid-glycolic acid triple-graft copolymer preparation method |
| CN105732994A (en) * | 2016-03-03 | 2016-07-06 | 山东理工大学 | Method for preparing polyvinyl alcohol-polytrimethylene carbonate-poly lactic acid-glycolic acid double-grafted copolymer |
| CN105542479A (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 poly(p-dioxanone) and poly lactic acid-glycolic acid |
| CN105542482A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(p-dioxanone) and poly(lactic acid-glycolic acid) |
| CN111888523A (en) * | 2020-09-08 | 2020-11-06 | 尹振宇 | Preparation method of polylactic acid gel for improving skin |
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