CN104497591B - A kind of method that polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide - Google Patents
A kind of method that polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide Download PDFInfo
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- CN104497591B CN104497591B CN201510001624.XA CN201510001624A CN104497591B CN 104497591 B CN104497591 B CN 104497591B CN 201510001624 A CN201510001624 A CN 201510001624A CN 104497591 B CN104497591 B CN 104497591B
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Abstract
The present invention discloses a kind of method that polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, use following steps: 1) add the polylactic acid list myristyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, stirring reaction 3～4 days, obtains poly-peptide polylactic-acid block copolymer；2) add polylactic acid list myristyl ether, solvent, catalyst and the polyacrylamide of isocyano end-blocking, stirring reaction 50～60 minutes in dry reactor, obtain polyacrylamide polylactic acid graft copolymer；3) add poly-peptide polylactic-acid block copolymer, polyacrylamide polylactic 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 polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, 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) lactic acid has preferable biocompatibility and biodegradability, soft.Polyacrylamide has preferable biocompatibility and biodegradability, and has preferable hydrophilic.First polylactic acid chain segment is introduced respectively poly-peptide segment and polyacrylamide segment forms poly-peptide-polylactic-acid block copolymer and polyacrylamide-polylactic acid 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 polylactic acid and polyacrylamide.
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 polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, 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 polyacrylamide segment is 5000～6000；Its method of modifying employing following steps:
1) synthesis of poly-peptide-polylactic-acid block copolymer: add the polylactic acid list myristyl 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 3～4 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 polyacrylamide-polylactic acid graft copolymer: add polylactic acid list myristyl ether, solvent, catalyst and the polyacrylamide of isocyano end-blocking in dry reactor, under inert atmosphere, in 60～65 DEG C of stirring reactions 50～60 minutes, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of the poly-peptide film that polylactic acid is modified with polyacrylamide: add poly-peptide-polylactic-acid block copolymer, polyacrylamide-polylactic acid 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 polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, 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 polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, in step 1), polylactic acid list myristyl ether uses poly-(D, L) lactic acid list myristyl ether, polylactic acid list myristyl ether to be 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 polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, step 2) in, solvent uses dimethylformamide, catalyst uses dibutyl tin laurate, catalyst charge is the 3～5 ‰ of polylactic acid list myristyl ether and polyacrylamide gross weight, and reactant solution concentration is 5～15 g:100 ml.
The method that described a kind of polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, step 2) in, polylactic acid list myristyl ether uses poly-(D, L) lactic acid list myristyl ether, polylactic acid list myristyl ether to be 3～7:1 with the mol ratio of polyacrylamide.
The method that described a kind of polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, in step 3), polyacrylamide-polylactic acid graft copolymer mass percent in Modified Membrane is 2～4%, and solvent uses dimethylformamide, and mixture solution concentration is 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention:
1. the polylactic acid described in and polyacrylamide improve the method for poly-peptide film hydrophilic and compliance, use amidation process, additive reaction and three 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-polylactic-acid block copolymer
In dry reactor, add 16.1 grams poly-(r-benzyl-Pidolidone ester) (molecular weight is 80000) and the polylactic acid list myristyl 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 20 DEG C of stirring reactions 3 days, terminates reaction, by filtering, dialysing, is dried, obtains object；
2) synthesis of polyacrylamide-polylactic acid graft copolymer
3.5 grams of polyacrylamides (molecular weight is 5000) and the polylactic acid list myristyl ether (molecular weight is 3000) of 9 grams of isocyano end-blockings and 160 ml dimethylformamides are added in dry reactor, add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 60 DEG C of stirring reactions 50 minutes, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of the poly-peptide film that polylactic acid is modified with polyacrylamide
12.5 grams of poly-peptide-polylactic-acid block copolymers and 45.8 ml solvent dimethylformamides are added in dry reactor, another addition accounts for the polyacrylamide-polylactic acid 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 12.6% and 13.1% before modified.
Embodiment
2
1) synthesis of poly-peptide-polylactic-acid block copolymer
16.3 grams poly-(r-ethyl-L-glutamate ester) (molecular weight is 85000) and the polylactic acid list myristyl 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 25 DEG C of stirring reactions 4 days, terminate reaction, by filtering, dialysing, it is dried, obtains object；
2) synthesis of polyacrylamide-polylactic acid graft copolymer
3.5 grams of polyacrylamides (molecular weight is 5500) and the polylactic acid list myristyl ether (molecular weight is 3500) of 9 grams of isocyano end-blockings and 160 ml dimethylformamides are added in dry reactor, add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 62 DEG C of stirring reactions 55 minutes, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of the poly-peptide film that polylactic acid is modified with polyacrylamide
12.6 grams of poly-peptide-polylactic-acid block copolymers and 45.5 ml solvent dimethylformamides are added in dry reactor, another addition accounts for the polyacrylamide-polylactic acid 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 13.2% and 13.8% before modified.
Embodiment
3
1) synthesis of poly-peptide-polylactic-acid block copolymer
16.5 grams poly-(r-methyl-Pidolidone ester) (molecular weight is 90000) and the polylactic acid list myristyl 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 3 days, terminate reaction, by filtering, dialysing, be dried, obtain object；
2) synthesis of polyacrylamide-polylactic acid graft copolymer
3.5 grams of polyacrylamides (molecular weight is 6000) and the polylactic acid list myristyl ether (molecular weight is 4000) of 9 grams of isocyano end-blockings and 160 ml dimethylformamides are added in dry reactor, add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 65 DEG C of stirring reactions 60 minutes, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of the poly-peptide film that polylactic acid is modified with polyacrylamide
12.8 grams of poly-peptide-polylactic-acid block copolymers and 45.4 ml solvent dimethylformamides are added in dry reactor, another addition accounts for the polyacrylamide-polylactic acid 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 15.2% before modified.
Claims (6)
1. the method that a polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide, 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 polyacrylamide segment is 5000～6000；Its method of modifying employing following steps:
1) synthesis of poly-peptide-polylactic-acid block copolymer: add the polylactic acid list myristyl 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 3～4 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 polyacrylamide-polylactic acid graft copolymer: add polylactic acid list myristyl ether, solvent, catalyst and the polyacrylamide of isocyano end-blocking in dry reactor, under inert atmosphere, in 60～65 DEG C of stirring reactions 50～60 minutes, terminate reaction, by filtering, dialysing, it is dried, obtains object；
3) preparation of the poly-peptide film that polylactic acid is modified with polyacrylamide: add poly-peptide-polylactic-acid block copolymer, polyacrylamide-polylactic acid 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 polylactic acid the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylamide, 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 polylactic acid the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylamide, it is characterized in that: in step 1), polylactic acid list myristyl ether uses poly-(D, L) lactic acid list myristyl ether, polylactic acid list myristyl 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 polylactic acid the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylamide, it is characterized in that: step 2) in, solvent uses dimethylformamide, catalyst uses dibutyl tin laurate, catalyst charge is the 3～5 ‰ of polylactic acid list myristyl ether and polyacrylamide gross weight, and reactant solution concentration is 5～15 g:100 mL.
The method that a kind of polylactic acid the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylamide, it is characterized in that: step 2) in, polylactic acid list myristyl ether uses poly-(D, L) lactic acid list myristyl ether, polylactic acid list myristyl ether is 3～7:1 with the mol ratio of polyacrylamide.
The method that a kind of polylactic acid the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyacrylamide, it is characterized in that: in step 3), polyacrylamide-polylactic acid graft copolymer mass percent in Modified Membrane is 2～4%, solvent uses dimethylformamide, and mixture solution concentration is 25～35 g:100 mL.
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| KR101249389B1 (en) * | 2010-10-28 | 2013-04-03 | 재단법인대구경북과학기술원 | Stimulus-responsive hydrogel |
| CN102336913A (en) * | 2011-07-01 | 2012-02-01 | 山东理工大学 | Poly(N-isopropyl acrylamide)-polyurethane-polypeptide block-graft copolymer and preparation method thereof |
| CN103865087B (en) * | 2014-03-10 | 2016-06-08 | 山东理工大学 | A kind of method that poly-peptide film kindliness is improved by poly(lactic acid) and PPDO |
| CN103804915A (en) * | 2014-03-14 | 2014-05-21 | 山东理工大学 | Method for improving hydrophilicity of polypeptide membrane by using polylactic acid and polyacrylic acid |
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