CN104559212B - 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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- CN104559212B CN104559212B CN201510004834.4A CN201510004834A CN104559212B CN 104559212 B CN104559212 B CN 104559212B CN 201510004834 A CN201510004834 A CN 201510004834A CN 104559212 B CN104559212 B CN 104559212B
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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) improves poly- peptide film hydrophily and compliance with polyethylene glycol, belong to
In field of polymer film preparing technology.
Background technology
Poly- peptide is a kind of biomaterial with good biocompatibility and biodegradability, and poly- peptide film can be used as people
Make skin etc., but poly- peptide film is more stiff, lack hydrophily, thus limiting its application to a certain extent.Poly-（D,L）Lactic acid second
Alkyd has preferable biocompatibility and a biodegradability, softer and have preferable compatibility with polyethylene glycol.Poly- second
Glycol has preferable biocompatibility and a biodegradability, softer and have good hydrophily.First by PLA second
Alkyd segment introduces poly- peptide segment respectively and polyethylene glycol segment forms poly- peptide-poly (lactic acid-glycolic acid) block copolymer and poly- second two
Then two kinds of copolymers are mixed to form the blend with preferable compatibility by alcohol-poly (lactic acid-glycolic acid) block copolymer again, system
Obtain modified poly- peptide film, thus drastically increasing hydrophily and the compliance of poly- peptide film.Use poly (lactic acid-glycolic acid) and poly- second at present
There is not been reported to the research that poly- peptide film hydrophily and compliance improve for glycol.
Content of the invention
It is an object of the invention to provide one kind is simple to operate and effect is preferably entered to poly- peptide film hydrophily and compliance
The improved method of row.Its technical scheme is：
A kind of poly (lactic acid-glycolic acid) and polyethylene glycol improve poly- peptide film hydrophily and compliance method it is characterised in that：
In Modified Membrane, the molecular weight of poly- peptide segment is 80000～90000, and the molecular weight of poly (lactic acid-glycolic acid) segment is 3000～4000,
The molecular weight of polyethylene glycol segment is 5000～7000；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-poly (lactic acid-glycolic acid) block copolymer：The poly- breast of carboxy blocking is added in dry reactor
Sour glycolic monododecyl ether, solvent, condensing agent and poly- peptide homopolymers, under inert atmosphere, in 20～30 DEG C of stirring reactions 2～
3 days, terminating reaction, by filtering, dialysing, be dried, obtain object, wherein, poly- peptide homopolymers is using poly-（R- benzyl-L-
Glutamate）, poly-（R- ethyl-L-glutamate ester）Or it is poly-（R- methyl-Pidolidone ester）；
2）The synthesis of polyethylene glycol-polylactic acid glycolic block copolymer：Carboxy blocking is added in dry reactor
Poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and amino-terminated poly glycol monomethyl ether, under inert atmosphere, in
25～35 DEG C of stirring reactions 3～4 days, terminating reaction, by filtering, dialysis, it is dried, obtain object；
3）Poly (lactic acid-glycolic acid) and the preparation of poly ethyldiol modified poly- peptide film：Poly- peptide-poly- is added in dry reactor
Y block copolymer, polyethylene glycol-polylactic acid glycolic block copolymer and solvent, under inert atmosphere, in 40～
After 50 DEG C are stirred mixing 40～50 minutes, with the tape casting film forming and dry, obtain object.
The method that a kind of described poly (lactic acid-glycolic acid) improves poly- peptide film hydrophily and compliance with polyethylene glycol, step 1）
In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- diformazan ammonia
Propyl group）Carbodiimide, solvent adopts dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described poly (lactic acid-glycolic acid) improves poly- peptide film hydrophily and compliance with polyethylene glycol, step 1）
In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y monododecyl ether（Lactic acid and glycolic mole
Than：50/50）, poly (lactic acid-glycolic acid) monododecyl ether is 7～15 with the mol ratio of poly- peptide homopolymers:1；Condensing agent and poly- peptide
The mol ratio of homopolymers is 1.08～1.8:1.
The method that a kind of described poly (lactic acid-glycolic acid) improves poly- peptide film hydrophily and compliance with polyethylene glycol, step 2）
In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- diformazan ammonia
Propyl group）Carbodiimide, solvent adopts dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described poly (lactic acid-glycolic acid) improves poly- peptide film hydrophily and compliance with polyethylene glycol, step 2）
In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y monododecyl ether（Lactic acid and glycolic mole
Than：50/50）, poly (lactic acid-glycolic acid) monododecyl ether is 3～10 with the mol ratio of poly glycol monomethyl ether:1；Condensing agent with
The mol ratio of poly glycol monomethyl ether is 1.07～1.8:1.
The method that a kind of described poly (lactic acid-glycolic acid) improves poly- peptide film hydrophily and compliance with polyethylene glycol, step 3）
In, mass percent in Modified Membrane for the polyethylene glycol-polylactic acid glycolic block copolymer is 1～4%, and solvent adopts 1,1,
2- trichloroethanes, mixture solution concentration is 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention：
1. the method that the poly (lactic acid-glycolic acid) described in improves poly- peptide film hydrophily and compliance with polyethylene glycol, using acid amides
Change reaction and blending two kinds of means, simple to operate, be easy to grasp；
2. the poly- peptide Modified Membrane hydrophily described in is greatly improved with compliance.
Specific embodiment
Embodiment 1
1）The synthesis of poly- peptide-poly (lactic acid-glycolic acid) block copolymer
Add 16.1 grams to gather in dry reactor（R- benzyl-Pidolidone ester）（Molecular weight is 80000）With 7 grams of carboxylics
The poly (lactic acid-glycolic acid) monododecyl ether of base end-blocking（Molecular weight is 3000）, add 302 ml dimethylformamides, add
0.048 gramN ,N ’- dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 2 days, terminating reaction, by mistake
Filter, dialyse, be dried, obtain object；
2）The synthesis of polyethylene glycol-polylactic acid glycolic block copolymer
3 grams of amino-terminated poly glycol monomethyl ethers are added in dry reactor（Molecular weight is 5000）With 9 grams of carboxyls
The poly (lactic acid-glycolic acid) monododecyl ether of end-blocking（Molecular weight is 3000）, add 162 ml dimethylformamides, add
0.145 gramN ,N ’- dicyclohexylcarbodiimide, under inert atmosphere, terminating reaction after 25 DEG C of stirring reactions 3 days, by mistake
Filter, dialyse, be dried, obtain object；
3）Poly (lactic acid-glycolic acid) and the preparation of poly ethyldiol modified poly- peptide film
12.5 grams of poly- peptide-poly (lactic acid-glycolic acid) block copolymers and 45.8 ml 1,1,2- tri- are added in dry reactor
Chloroethene alkane solvents, another addition accounts for the polyethylene glycol-polylactic acid glycolic block copolymer of Modified Membrane gross weight 1%, inert atmosphere
Under, in 40 DEG C of stirring mixing 40 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying chambers, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.1% He before modified
12.9%.
Embodiment 2
1）The synthesis of poly- peptide-poly (lactic acid-glycolic acid) block copolymer
Add 16.3 grams to gather in dry reactor（R- ethyl-L-glutamate ester）（Molecular weight is 85000）With 7 grams of carboxyls
The poly (lactic acid-glycolic acid) monododecyl ether of end-blocking（Molecular weight is 3500）, add 305 ml dimethylformamides, add
0.031 gram of N, N '-DIC, under inert atmosphere, in 25 DEG C of stirring reactions 3 days, terminating reaction, by filtering,
Dialyse, be dried, obtain object；
2）The synthesis of polyethylene glycol-polylactic acid glycolic block copolymer
3 grams of amino-terminated poly glycol monomethyl ethers are added in dry reactor（Molecular weight is 6000）With 9 grams of carboxyls
The poly (lactic acid-glycolic acid) monododecyl ether of end-blocking（Molecular weight is 3500）, add 155 ml dimethylformamides, add
0.08 gramN ,N ’- DIC, under inert atmosphere, terminating reaction after 28 DEG C of stirring reactions 4 days, by mistake
Filter, dialyse, be dried, obtain object；
3）Poly (lactic acid-glycolic acid) and the preparation of poly ethyldiol modified poly- peptide film
12.6 grams of poly- peptide-poly (lactic acid-glycolic acid) block copolymers and 45.5 ml 1,1,2- tri- are added in dry reactor
Chloroethene alkane solvents, another addition accounts for the polyethylene glycol-polylactic acid glycolic block copolymer of Modified Membrane gross weight 2%, inert atmosphere
Under, in 45 DEG C of stirring mixing 45 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying chambers, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.8% He before modified
13.5%.
Embodiment 3
1）The synthesis of poly- peptide-poly (lactic acid-glycolic acid) block copolymer
Add 16.5 grams to gather in dry reactor（R- methyl-Pidolidone ester）（Molecular weight is 90000）With 7 grams of carboxyls
The poly (lactic acid-glycolic acid) monododecyl ether of end-blocking（Molecular weight is 4000）, add 310 ml dimethylformamides, add
0.046 gram of 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction,
By filtering, dialysing, be dried, obtain object；
2）The synthesis of polyethylene glycol-polylactic acid glycolic block copolymer
3.1 grams of amino-terminated poly glycol monomethyl ethers are added in dry reactor（Molecular weight is 7000）With 9.2 grams
The poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking（Molecular weight is 4000）, add 158 ml dimethylformamides, then plus
Enter 0.141 gram of 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, under inert atmosphere, terminates anti-after 35 DEG C of stirring reactions 3 days
Should, by filtering, dialysing, be dried, obtain object；
3）Poly (lactic acid-glycolic acid) and the preparation of poly ethyldiol modified poly- peptide film
12.8 grams of poly- peptide-poly (lactic acid-glycolic acid) block copolymers and 45.3 ml 1,1,2- tri- are added in dry reactor
Chloroethene alkane solvents, another addition accounts for the polyethylene glycol-polylactic acid glycolic block copolymer of Modified Membrane gross weight 4%, inert atmosphere
Under, in 50 DEG C of stirring mixing 50 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying chambers, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 13.4% He before modified
14.2%.
Claims (6)
1. a kind of poly (lactic acid-glycolic acid) and polyethylene glycol improve poly- peptide film hydrophily and compliance method it is characterised in that：Change
Property film in the molecular weight of poly- peptide segment be 80000～90000, the molecular weight of poly (lactic acid-glycolic acid) segment is 3000～4000, gathers
The molecular weight of ethylene glycol segment is 5000～7000；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-poly (lactic acid-glycolic acid) block copolymer：The PLA second of carboxy blocking is added in dry reactor
Alkyd monododecyl ether, solvent, condensing agent and poly- peptide homopolymers, under inert atmosphere, in 20～30 DEG C of stirring reactions 2～3 days,
Terminating reaction, by filtering, dialysing, be dried, obtains object, and wherein, poly- peptide homopolymers is using poly-（R- benzyl-L- paddy ammonia
Acid esters）, poly-（R- ethyl-L-glutamate ester）Or it is poly-（R- methyl-Pidolidone ester）；
2）The synthesis of polyethylene glycol-polylactic acid glycolic block copolymer：The poly- breast of carboxy blocking is added in dry reactor
Sour glycolic monododecyl ether, solvent, condensing agent and amino-terminated poly glycol monomethyl ether, under inert atmosphere, in 25～
35 DEG C of stirring reactions 3～4 days, terminating reaction, by filtering, dialysis, it is dried, obtain object；
3）Poly (lactic acid-glycolic acid) and the preparation of poly ethyldiol modified poly- peptide film：Poly- peptide-PLA is added in dry reactor
Glycolic block copolymer, polyethylene glycol-polylactic acid glycolic block copolymer and solvent, under inert atmosphere, in 40～50 DEG C
After stirring mixing 40～50 minutes, with the tape casting film forming and dry, obtain object.
2. a kind of poly (lactic acid-glycolic acid) according to claim 1 and polyethylene glycol improve poly- peptide film hydrophily and compliance
Method it is characterised in that：Step 1）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, and N '-diisopropyl carbon two is sub-
Amine or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethylformamide, reactant solution concentration be 5～
15 g:100 ml.
3. a kind of poly (lactic acid-glycolic acid) according to claim 1 and polyethylene glycol improve poly- peptide film hydrophily and compliance
Method it is characterised in that：Step 1）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y list 12
Alkyl ether, wherein, lactic acid and glycolic mol ratio are 50/50, poly (lactic acid-glycolic acid) monododecyl ether and poly- peptide homopolymers
Mol ratio is 7～15:1；Condensing agent is 1.08～1.8 with the mol ratio of poly- peptide homopolymers:1.
4. a kind of poly (lactic acid-glycolic acid) according to claim 1 and polyethylene glycol improve poly- peptide film hydrophily and compliance
Method it is characterised in that：Step 2）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, and N '-diisopropyl carbon two is sub-
Amine or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethylformamide, reactant solution concentration be 5～
15 g:100 ml.
5. a kind of poly (lactic acid-glycolic acid) according to claim 1 and polyethylene glycol improve poly- peptide film hydrophily and compliance
Method it is characterised in that：Step 2）In, poly (lactic acid-glycolic acid) monododecyl ether is using poly-（D,L）Y list 12
Alkyl ether, wherein, lactic acid and glycolic mol ratio are 50/50, poly (lactic acid-glycolic acid) monododecyl ether and polyethyleneglycol first
The mol ratio of ether is 3～10:1；Condensing agent is 1.07～1.8 with the mol ratio of poly glycol monomethyl ether:1.
6. a kind of poly (lactic acid-glycolic acid) according to claim 1 and polyethylene glycol improve poly- peptide film hydrophily and compliance
Method it is characterised in that：Step 3）In, percent mass in Modified Membrane for the polyethylene glycol-polylactic acid glycolic block copolymer
For 1～4%, solvent adopts 1,1,2- trichloroethanes to ratio, and mixture solution concentration is 25～35 g:100 ml.
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| 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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| 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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|---|---|---|---|---|
| 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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