CN104448841B - A kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid - Google Patents
A kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid Download PDFInfo
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- CN104448841B CN104448841B CN201510004506.4A CN201510004506A CN104448841B CN 104448841 B CN104448841 B CN 104448841B CN 201510004506 A CN201510004506 A CN 201510004506A CN 104448841 B CN104448841 B CN 104448841B
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Abstract
The present invention discloses a kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, use following steps: 1) add the poly (lactic acid-glycolic acid) monododecyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, stirring reaction 2～4 days, obtains poly-peptide poly (lactic acid-glycolic acid) block copolymer；2) amino-terminated poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and polyacrylic acid is added in dry reactor, stirring reaction 2～3 days, obtain polyacrylic acid poly (lactic acid-glycolic acid) graft copolymer；3) add poly-peptide poly (lactic acid-glycolic acid) block copolymer, polyacrylic acid poly (lactic acid-glycolic acid) graft copolymer and solvent in dry reactor, after stirring mixing 40～50 minutes, by the tape casting film forming and be dried, obtain object of the present invention.Preparation technology of the present invention is simple, and the hydrophilic of gained Modified Membrane and compliance have had large increase.
Description
Technical field
The present invention relates to a kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, belong to 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 artificial skin etc., but poly-peptide film is more stiff, lack hydrophilic, thus limits its application to a certain extent.Poly-(D, L) y has preferable biocompatibility and biodegradability, softer.Polyacrylic acid has preferable biocompatibility and biodegradability, and has excellent hydrophilic.First poly (lactic acid-glycolic acid) segment is introduced respectively poly-peptide segment and polyacrylic acid segment forms poly-peptide-poly (lactic acid-glycolic acid) block copolymer and poly acrylic acid-poly y graft copolymer, two kinds of copolymers are mixed to form the blend with the preferable compatibility the most again, prepare modified poly-peptide film, thus drastically increase hydrophilic and the compliance of poly-peptide film.There is not been reported to the research that poly-peptide film hydrophilic and compliance improve for current poly (lactic acid-glycolic acid) and polyacrylic acid.
Summary of the invention
It is an object of the invention to provide the method that poly-peptide film hydrophilic and compliance are preferably improved by a kind of simple to operate and effect.Its technical scheme is:
A kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, 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 polyacrylic acid segment is 5000～6000；Its method of modifying employing following steps:
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) block 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 25～30 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtaining object, wherein, poly-peptide homopolymer uses poly-(r-benzyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester)；
2) synthesis of poly acrylic acid-poly y graft copolymer: add amino-terminated poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, under inert atmosphere, in 25～35 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) poly (lactic acid-glycolic acid) and the preparation of polyacrylic acid modified poly-peptide film: add poly-peptide-poly (lactic acid-glycolic acid) block copolymer, poly acrylic acid-poly y graft copolymer and solvent in dry reactor, under inert atmosphere, after 40～50 DEG C of stirring mixing 40～50 minutes, by the tape casting film forming and be dried, obtain object.
The method that described a kind of poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, in step 1), condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent uses dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that described a kind of poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, in step 1), poly (lactic acid-glycolic acid) monododecyl ether uses poly-(D, L) y monododecyl ether (lactic acid and glycolic mol ratio: 50/50), poly (lactic acid-glycolic acid) monododecyl ether is 7～15:1 with the mol ratio of poly-peptide homopolymer；Condensing agent is 1.08～1.8:1 with the mol ratio of poly-peptide homopolymer.
The method that described a kind of poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, step 2) in, condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent uses dimethyl sulfoxide, and reactant solution concentration is 5～15 g:100 ml.
The method that described a kind of poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, step 2) in, poly (lactic acid-glycolic acid) monododecyl ether uses poly-(D, L) y monododecyl ether (lactic acid and glycolic mol ratio: 50/50), poly (lactic acid-glycolic acid) monododecyl ether and polyacrylic mol ratio are 3～6:1；Condensing agent and polyacrylic mol ratio are 1.08～1.8:1.
The method that described a kind of poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, in step 3), poly acrylic acid-poly y graft copolymer mass percent in Modified Membrane is 2～4%, solvent uses dimethyl sulfoxide, and mixture solution concentration is 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention:
1. the poly (lactic acid-glycolic acid) described in and polyacrylic acid improve the method for poly-peptide film hydrophilic and compliance, use amidation process and two kind means are blended, simple to operate, be prone to grasp；
2. the poly-peptide Modified Membrane hydrophilic described in is greatly improved with compliance.
Detailed description of the invention
Embodiment
1
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) block copolymer
In dry reactor, add 16.1 grams poly-(r-benzyl-Pidolidone ester) (molecular weight is 80000) and the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 3000) of 7 grams of carboxy blockings, add 300 ml dimethylformamides, add 0.048 gramN,N ’-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 2 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
2) synthesis of poly acrylic acid-poly y graft copolymer
In dry reactor, add 3.5 grams of polyacrylic acid (molecular weight is 5000) and 9 grams of amino-terminated poly (lactic acid-glycolic acid) monododecyl ethers (molecular weight is 3000), add 160 ml dimethyl sulfoxide, add 0.165 gramN,N ’-dicyclohexylcarbodiimide, under inert atmosphere, terminates reaction after 25 DEG C of stirrings are reacted 2 days, by filtering, dialysing, is dried, obtains object；
3) poly (lactic acid-glycolic acid) and the preparation of polyacrylic acid modified poly-peptide film
12.5 grams of poly-peptide-poly (lactic acid-glycolic acid) block copolymers and 45.8 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the poly acrylic acid-poly y graft copolymer of Modified Membrane gross weight 2%, under inert atmosphere, in 40 DEG C of stirring mixing 40 minutes, use the tape casting film forming, 50 DEG C of vacuum drying ovens are dried, obtain object.
After tested: the hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.9% and 13.8% before modified.
Embodiment
2
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) block copolymer
16.3 grams poly-(r-ethyl-L-glutamate ester) (molecular weight is 85000) and the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 3500) of 7 grams of carboxy blockings is added in dry reactor, add 305 ml dimethylformamides, add 0.031 gram of N, N '-DIC, under inert atmosphere, in 27 DEG C of stirring reactions 3 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
2) synthesis of poly acrylic acid-poly y graft copolymer
In dry reactor, add 3 grams of polyacrylic acid (molecular weight is 5500) and 9 grams of amino-terminated poly (lactic acid-glycolic acid) monododecyl ethers (molecular weight is 3500), add 155 ml dimethyl sulfoxide, add 0.08 gramN,N ’-DIC, under inert atmosphere, terminates reaction after 28 DEG C of stirrings are reacted 3 days, by filtering, dialysing, is dried, obtains object；
3) poly (lactic acid-glycolic acid) and the preparation of polyacrylic acid modified poly-peptide film
12.6 grams of poly-peptide-poly (lactic acid-glycolic acid) block copolymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the poly acrylic acid-poly y graft copolymer of Modified Membrane gross weight 3%, under inert atmosphere, in 45 DEG C of stirring mixing 45 minutes, use the tape casting film forming, 50 DEG C of vacuum drying ovens are dried, obtain object.
After tested: the hydrophilic rate of object of the present invention and elongation at break are respectively than improve 13.4% and 14.6% before modified.
Embodiment
3
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) block copolymer
16.5 grams poly-(r-methyl-Pidolidone ester) (molecular weight is 90000) and the poly (lactic acid-glycolic acid) monododecyl ether (molecular weight is 4000) of 7 grams of carboxy blockings is added in dry reactor, 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 4 days, terminate reaction, by filtering, dialysing, be dried, obtain object；
2) synthesis of poly acrylic acid-poly y graft copolymer
3.1 grams of polyacrylic acid (molecular weight is 6000) and 9.2 grams of amino-terminated poly (lactic acid-glycolic acid) monododecyl ethers (molecular weight is 4000) are added in dry reactor, add 158 ml dimethyl sulfoxide, add 0.141 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, reaction is terminated after 35 DEG C of stirrings are reacted 2 days, by filtering, dialysing, it is dried, obtains object；
3) poly (lactic acid-glycolic acid) and the preparation of polyacrylic acid modified poly-peptide film
12.8 grams of poly-peptide-poly (lactic acid-glycolic acid) block copolymers and 45.4 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the poly acrylic acid-poly y graft copolymer of Modified Membrane gross weight 4%, under inert atmosphere, in 50 DEG C of stirring mixing 50 minutes, use the tape casting film forming, 50 DEG C of vacuum drying ovens are dried, obtain object.
After tested: the hydrophilic rate of object of the present invention and elongation at break are respectively than improve 14.3% and 15.1% before modified.
Claims (6)
1. the method that a poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid, 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 polyacrylic acid segment is 5000～6000；Its method of modifying employing following steps:
1) synthesis of poly-peptide-poly (lactic acid-glycolic acid) block 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 25～30 DEG C of stirring reactions 2～4 days, terminate reaction, by filtering, dialysing, it is dried, obtaining object, wherein, poly-peptide homopolymer uses poly-(γ-benzyl-Pidolidone ester), poly-(γ-ethyl-L-glutamate ester) or poly-(γ-methyl-Pidolidone ester)；
2) synthesis of poly acrylic acid-poly y graft copolymer: add amino-terminated poly (lactic acid-glycolic acid) monododecyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, under inert atmosphere, in 25～35 DEG C of stirring reactions 2～3 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) poly (lactic acid-glycolic acid) and the preparation of polyacrylic acid modified poly-peptide film: add poly-peptide-poly (lactic acid-glycolic acid) block copolymer, poly acrylic acid-poly y graft copolymer and solvent in dry reactor, under inert atmosphere, after 40～50 DEG C of stirring mixing 40～50 minutes, by the tape casting film forming and be dried, obtain object.
The method that a kind of poly (lactic acid-glycolic acid) the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylic acid, it is characterized in that: in step 1), condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent uses dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of poly (lactic acid-glycolic acid) the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylic acid, it is characterized in that: in step 1), poly (lactic acid-glycolic acid) monododecyl ether uses poly-(D, L) y monododecyl ether, and lactic acid is 50/50 with glycolic mol ratio, poly (lactic acid-glycolic acid) monododecyl ether is 7～15:1 with the mol ratio of poly-peptide homopolymer；Condensing agent is 1.08～1.8:1 with the mol ratio of poly-peptide homopolymer.
The method that a kind of poly (lactic acid-glycolic acid) the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylic acid, it is characterized in that: step 2) in, condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent uses dimethyl sulfoxide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of poly (lactic acid-glycolic acid) the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylic acid, it is characterized in that: step 2) in, poly (lactic acid-glycolic acid) monododecyl ether uses poly-(D, L) y monododecyl ether, and lactic acid is 50/50 with glycolic mol ratio, poly (lactic acid-glycolic acid) monododecyl ether and polyacrylic mol ratio are 3～6:1；Condensing agent and polyacrylic mol ratio are 1.08～1.8:1.
The method that a kind of poly (lactic acid-glycolic acid) the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylic acid, it is characterized in that: in step 3), poly acrylic acid-poly y graft copolymer mass percent in Modified Membrane is 2～4%, solvent uses dimethyl sulfoxide, 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 |
| CN105694059A (en) * | 2016-03-03 | 2016-06-22 | 山东理工大学 | Method for preparing polyvinyl alcohol-poly lactic acid-glycolic acid-polycaprolactone dual-grafted copolymer |
| CN105647193A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polylactic acid-glycolic acid and polypeptide |
| CN105694474B (en) * | 2016-03-07 | 2018-07-10 | 山东理工大学 | A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance |
| CN105647197A (en) * | 2016-03-16 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polypeptide and poly(lactic acid-glycolic acid) |
| CN105694476B (en) * | 2016-03-16 | 2018-07-13 | 山东理工大学 | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN106987139A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA lifts polypropylene sorrel water resistance and compliance with polylactide |
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| WO2012159084A1 (en) * | 2011-05-18 | 2012-11-22 | Baxter International, Inc. | Modification-dependent activity assays |
| 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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| WO2012159084A1 (en) * | 2011-05-18 | 2012-11-22 | Baxter International, Inc. | Modification-dependent activity assays |
| 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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