CN104530721B - A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol - Google Patents
A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol Download PDFInfo
- Publication number
- CN104530721B CN104530721B CN201510002740.3A CN201510002740A CN104530721B CN 104530721 B CN104530721 B CN 104530721B CN 201510002740 A CN201510002740 A CN 201510002740A CN 104530721 B CN104530721 B CN 104530721B
- Authority
- CN
- China
- Prior art keywords
- poly
- peptide
- polyurethanes
- polyvinyl alcohol
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, employing following steps: 1) in dry reactor, add diisocyanate, PTMG, catalysts and solvents, under inert atmosphere, reaction a period of time, add butanediol and react a period of time, add 3 hydracrylic acid reactions, the polyurethanes of end carboxyl must be contained；2) add containing the polyurethanes of end carboxyl, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, react 2～3 days, obtain poly-peptide polyurethane block copolymers；3) in dry reactor, add poly-peptide polyurethane block copolymers, polyethylene alcohol and solvent, under inert atmosphere, mix a period of time, 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 polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, 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.Polyurethanes has preferable biocompatibility and a biodegradability, softer and have the preferable compatibility with polyvinyl alcohol.Polyvinyl alcohol has preferable biocompatibility and biodegradability, and has preferable hydrophilic.First polyurethanes segment is introduced poly-peptide segment by amidation process and form poly-peptide-polyurethane block copolymers to improve the blended property of poly-peptide, polyvinyl alcohol segments is added poly-peptide-polyurethane block copolymers the most again and forms blend, prepare modified poly-peptide film, thus drastically increase hydrophilic and the compliance of poly-peptide film.There is not been reported with the research that compliance improves to poly-peptide film hydrophilic for current polyurethanes and polyvinyl alcohol.
Summary of the invention
It is an object of the invention to provide the method that poly-peptide film hydrophilic is preferably improved by a kind of simple to operate and effect with compliance.Its technical scheme is:
A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, it is characterized in that: in Modified Membrane, the molecular weight of poly-peptide segment is 80000～90000, the molecular weight of polyurethanes segment is 4000～5000, and the molecular weight of polyvinyl alcohol segments is 6000～7000；Its method of modifying employing following steps:
1) synthesis of the polyurethanes containing end-COOH group: add diisocyanate, PTMG, catalysts and solvents in dry reactor, under inert atmosphere, after 45～50 DEG C of stirring reactions 45～50 minutes, add 1,4-butanediol reacts 10～15 minutes, add 3-hydracrylic acid to react 5～10 minutes, terminate reaction, obtain object；
2) synthesis of poly-peptide-polyurethane block copolymers: add in dry reactor containing the polyurethanes of end-COOH group, solvent, condensing agent and poly-peptide homopolymer, under inert atmosphere, reaction is terminated after 25～35 DEG C of stirrings are reacted 2～3 days, by filtering, dialysing, it is dried, obtain object, wherein, poly-peptide homopolymer uses poly-(r-benzyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester)；
3) preparation of the poly-peptide film of polyurethanes and polyvinyl alcohol modification: add poly-peptide-polyurethane block copolymers, polyethylene alcohol 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 polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, in step 1), diisocyanate uses 2,4 toluene diisocyanate, diisocyanate to be 0.001～0.08 with the difference of the molal quantity of glycol；Catalyst uses dibutyl tin laurate, and addition is the 3～5 ‰ of diisocyanate and PTMG gross weight；Solvent uses dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that described a kind of polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, step 2) in, 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 polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, step 2) in, polyurethanes is 6～18:1 with the mol ratio of poly-peptide homopolymer；Condensing agent is 1.07～1.8:1 with the mol ratio of poly-peptide homopolymer.
The method that described a kind of polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, in step 3), polyvinyl alcohol segments mass percent in Modified Membrane is 2～4%, and 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 polyurethanes described in and polyvinyl alcohol improve the method for poly-peptide film hydrophilic and compliance, use progressively addition polymerization, amidation process 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 the polyurethanes containing end-COOH group
5.5 gram 2 is added in dry reactor, 4-toluene di-isocyanate(TDI), 17.2 grams of PTMG (molecular weight is 1000), adding 350 ml solvent dimethylformamides, the another dibutyl tin laurate adding above-mentioned reactant gross weight 3 ‰, under inert atmosphere, after 45 DEG C of stirring reactions 45 minutes, add 0.81 gram of BDO to react 10 minutes, add 1.22 grams of 3-hydracrylic acids and react 5 minutes, terminate reaction, obtain object；
2) synthesis of poly-peptide-polyurethane block copolymers
In dry reactor, add 16.1 grams poly-(r-benzyl-Pidolidone ester) (molecular weight is 80000) and 9 grams of polyurethanes containing end-COOH group, add 305 ml dimethylformamides, add 0.046 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) preparation of the poly-peptide film of polyurethanes and polyvinyl alcohol modification
12 grams of poly-peptide-polyurethane block copolymers and 46 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the polyvinyl alcohol (molecular weight is 6000) 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 13.4% and 7.8% before modified.
Embodiment
2
1) synthesis of the polyurethanes containing end-COOH group
6.05 gram 2 is added in dry reactor, 4-toluene di-isocyanate(TDI), 19 grams of PTMG (molecular weight is 1000), adding 353 ml solvent dimethylformamides, the another dibutyl tin laurate adding above-mentioned reactant gross weight 4 ‰, under inert atmosphere, after 47 DEG C of stirring reactions 47 minutes, add 0.88 gram of BDO to react 12 minutes, add 1.32 grams of 3-hydracrylic acids and react 7 minutes, terminate reaction, obtain object；
2) synthesis of poly-peptide-polyurethane block copolymers
In dry reactor, add 16.5 grams poly-(r-ethyl-L-glutamate ester) (molecular weight is 85000) and 9 grams of polyurethanes containing end-COOH group, add 312 ml dimethylformamides, add 0.028 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) preparation of the poly-peptide film of polyurethanes and polyvinyl alcohol modification
12.3 grams of poly-peptide-polyurethane block copolymers and 45 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the polyvinyl alcohol (molecular weight is 6500) 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 14.6% and 8.6% before modified.
Embodiment
3
1) synthesis of the polyurethanes containing end-COOH group
6.6 gram 2 is added in dry reactor, 4-toluene di-isocyanate(TDI), 21 grams of PTMG (molecular weight is 1000), adding 360 ml solvent dimethylformamides, the another dibutyl tin laurate adding above-mentioned reactant gross weight 5 ‰, under inert atmosphere, after 50 DEG C of stirring reactions 50 minutes, add 0.92 gram of BDO to react 15 minutes, add 1.84 grams of 3-hydracrylic acids and react 10 minutes, terminate reaction, obtain object；
2) synthesis of poly-peptide-polyurethane block copolymers
16.8 grams poly-(r-methyl-Pidolidone ester) (molecular weight is 90000) and 9.9 grams of polyurethanes containing end-COOH group are added in dry reactor, add 315 ml dimethylformamides, add 0.046 gram of 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, under inert atmosphere, reaction is terminated after 35 DEG C of stirrings are reacted 3 days, by filtering, dialysing, it is dried, obtains object；
3) preparation of the poly-peptide film of polyurethanes and polyvinyl alcohol modification
13 grams of poly-peptide-polyurethane block copolymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, another addition accounts for the polyvinyl alcohol (molecular weight is 7000) 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 15.5% and 9.3% before modified.
Claims (4)
1. the method that a polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, it is characterized in that: in Modified Membrane, the molecular weight of poly-peptide segment is 80000～90000, the molecular weight of polyurethanes segment is 4000～5000, and the molecular weight of polyvinyl alcohol segments is 6000～7000；Its method of modifying employing following steps:
1) synthesis of the polyurethanes containing end-COOH group: add diisocyanate, PTMG, catalysts and solvents in dry reactor, under inert atmosphere, after 45～50 DEG C of stirring reactions 45～50 minutes, add 1,4-butanediol reacts 10～15 minutes, add 3-hydracrylic acid to react 5～10 minutes, terminate reaction, obtain object；
2) synthesis of poly-peptide-polyurethane block copolymers: add the polyurethanes containing end-COOH group in dry reactor, solvent, condensing agent and poly-peptide homopolymer, under inert atmosphere, reaction is terminated after 25～35 DEG C of stirrings are reacted 2～3 days, by filtering, dialysis, it is dried, obtain object, wherein, poly-peptide homopolymer uses poly-(γ-benzyl-Pidolidone ester), poly-(γ-ethyl-L-glutamate ester) or poly-(γ-methyl-Pidolidone ester), condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3-ethyl-1-(3-dimethylaminopropyl) carbodiimide, solvent uses dimethylformamide, reactant solution concentration is 5～15 g:100 ml；
3) preparation of the poly-peptide film of polyurethanes and polyvinyl alcohol modification: add poly-peptide-polyurethane block copolymers, polyethylene alcohol 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 polyurethanes the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, it is characterized in that: in step 1), diisocyanate uses 2,4 toluene diisocyanate, diisocyanate to be 0.001～0.08 with the difference of the molal quantity of glycol；Catalyst uses dibutyl tin laurate, and addition is the 3～5 ‰ of diisocyanate and PTMG gross weight；Solvent uses dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of polyurethanes the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, it is characterised in that: step 2) in, polyurethanes is 6～18:1 with the mol ratio of poly-peptide homopolymer；Condensing agent is 1.07～1.8:1 with the mol ratio of poly-peptide homopolymer.
The method that a kind of polyurethanes the most according to claim 1 improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol, it is characterized in that: in step 3), polyvinyl alcohol segments mass percent in Modified Membrane is 2～4%, solvent uses dimethyl sulfoxide, and mixture solution concentration is 25～35 g:100 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510002740.3A CN104530721B (en) | 2015-01-05 | 2015-01-05 | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510002740.3A CN104530721B (en) | 2015-01-05 | 2015-01-05 | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104530721A CN104530721A (en) | 2015-04-22 |
| CN104530721B true CN104530721B (en) | 2016-08-24 |
Family
ID=52846366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510002740.3A Expired - Fee Related CN104530721B (en) | 2015-01-05 | 2015-01-05 | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104530721B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669989A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-polycaprolactone-polypeptide double-graft copolymer |
| CN105566641A (en) * | 2016-02-29 | 2016-05-11 | 山东理工大学 | Preparation method of PVA (Polyvinyl Alcohol)-polypeptide grafting copolymer |
| CN105504300A (en) * | 2016-03-03 | 2016-04-20 | 山东理工大学 | Polyvinyl alcohol-polypeptide-poly(p-dioxanone)-poly lactic acid-glycolic acid triple-graft copolymer preparation method |
| CN105542178A (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(trimethylene carbonate) and polypeptide |
-
2015
- 2015-01-05 CN CN201510002740.3A patent/CN104530721B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104530721A (en) | 2015-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788607B (en) | A kind of PPDO and aqueous polyurethane improve the poly-hydrophilic method of peptide film | |
| CN104448841B (en) | A kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid | |
| CN104530721B (en) | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyvinyl alcohol | |
| CN103804865B (en) | A kind of method that PPDO and aqueous polyurethane improve poly-peptide film wetting ability | |
| CN104559213A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyethylene glycol | |
| CN104559212B (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol | |
| CN103865088A (en) | Method for improving hydrophilia of polypeptide membrane by polycaprolactone and polyethylene glycol | |
| CN103819908B (en) | A kind of method that PPDO and urethane improve poly-peptide film kindliness | |
| CN103819909A (en) | Method for improving flexibility of polypeptide film by poly (p-dioxanone) and polyurethane | |
| CN104559214A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid | |
| CN104530720B (en) | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with polyacrylamide | |
| CN104497587B (en) | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with poly hydroxy ethyl acrylate | |
| CN104497592B (en) | A kind of method that polyurethanes improves poly-peptide film hydrophilic and compliance with carboxymethyl chitosan | |
| CN104448843B (en) | A kind of method that polycaprolactone improves poly-peptide film hydrophily and compliance with polyacrylic acid | |
| CN104559221B (en) | A kind of method that poly (lactic acid-glycolic acid) improves poly- peptide film hydrophily and compliance with aqueous polyurethane | |
| CN104559219B (en) | A kind of method that polycaprolactone improves poly- peptide film hydrophily and compliance with aqueous polyurethane | |
| CN104479367B (en) | A kind of method that PLA improves poly-peptide film hydrophily and compliance with aqueous polyurethane | |
| CN104559216A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid | |
| CN104559209B (en) | Method for improving hydrophily and flexibility of polypeptide membrane by polycarbamate and polyethylene glycol | |
| CN104559224B (en) | Method for improving hydrophilicity and flexibility of polypeptide film by polypropylene glycol and waterborne polyurethane | |
| CN104559207B (en) | Method for improving hydrophilic property and flexibility of polypeptide film by adopting polyurethane and polyacrylic acid | |
| CN104497593B (en) | Method for improving hydrophilicity and flexibility of polyurethane and polyvinylpyrrolidone improved polypeptide film | |
| CN104559211A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(p-dioxanone) and polyacrylic acid | |
| CN104559215A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by polylactic acid and polyethylene glycol | |
| CN104559220B (en) | Method for improving hydrophilicity and flexibility of polypeptide film by poly(p-dioxanone) and waterborne polyurethane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160824 Termination date: 20180105 |