CN104530721A - Method for improving hydrophilia and flexibility of polypeptide film through polyurethane and polyvinyl alcohol - Google Patents
Method for improving hydrophilia and flexibility of polypeptide film through polyurethane and polyvinyl alcohol Download PDFInfo
- Publication number
- CN104530721A CN104530721A CN201510002740.3A CN201510002740A CN104530721A CN 104530721 A CN104530721 A CN 104530721A CN 201510002740 A CN201510002740 A CN 201510002740A CN 104530721 A CN104530721 A CN 104530721A
- Authority
- CN
- China
- Prior art keywords
- polyurethane
- poly
- polyvinyl alcohol
- peptide
- 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.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a method for improving hydrophilia and flexibility of polypeptide film through polyurethane and polyvinyl alcohol. The method comprises the first step of adding diisocyanate, polytetramethylene ether glycol, a catalyst and a solvent into a dry reactor to conduct reaction for a time under the inert atmosphere, adding butanediol to react for a time, adding 3-hydroxypropionic acid to react, and obtaining polyurethane containing terminal carboxyl group; the second step of adding the polyurethane containing terminal carboxyl group, the solvent, a condensating agent, and polypeptide copolymer into another dry reactor to react for two to three days under the inert atmosphere, and obtaining polypeptide-polyurethane block copolymer; the third step of adding the polypeptide-polyurethane block copolymer, the polyvinyl alcohol, and the solvent into a third dry reactor to mix for a time under the inert atmosphere, forming film through tape casting and drying the film, and obtaining the target object of the method for improving the hydrophilia and the flexibility of the polypeptide film through the polyurethane and the polyvinyl alcohol. The method for improving the hydrophilia and the flexibility of the polypeptide film through the polyurethane and the polyvinyl alcohol has the advantages that the preparation technology is simple, and the hydrophilia and the flexibility of the modified film are greatly improved.
Description
Technical field
The present invention relates to a kind of method that polyurethane(s) and polyvinyl alcohol 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.Polyurethane(s) has good biocompatibility and biodegradability, softer and have good consistency with polyvinyl alcohol.Polyvinyl alcohol has good biocompatibility and biodegradability, and has good wetting ability.First polyurethane(s) segment is introduced poly-peptide segment by amidate action and form poly-peptide-polyurethane block copolymers to improve the blended property of poly-peptide, and then polyvinyl alcohol segments is added poly-peptide-polyurethane block copolymers formation blend, 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 polyurethane(s) and polyvinyl alcohol.
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 polyurethane(s) and polyvinyl alcohol 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 polyurethane(s) segment is 4000 ~ 5000, and the molecular weight of polyvinyl alcohol segments is 6000 ~ 7000; Its method of modifying adopts following steps:
1) synthesis of the polyurethane(s) containing end-COOH group: add vulcabond, PTMG, catalysts and solvents in dry reactor, under inert atmosphere, in 45 ~ 50 DEG C of stirring reactions after 45 ~ 50 minutes, add 1,4-butyleneglycol reaction 10 ~ 15 minutes, add 3-hydroxy-propionic acid reaction 5 ~ 10 minutes again, termination reaction, obtains target compound;
2) synthesis of poly-peptide-polyurethane block copolymers: add the polyurethane(s) containing end-COOH group, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 25 ~ 35 DEG C of stirring reactions termination reaction after 2 ~ 3 days, 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);
3) preparation of the poly-peptide film of polyurethane(s) and polyvinyl alcohol modification: add poly-peptide-polyurethane block copolymers, polyethylene alcohol 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 polyurethane(s) and polyvinyl alcohol improve the method for poly-peptide film wetting ability and kindliness, and in step 1), vulcabond adopts 2,4 toluene diisocyanate, and the difference of the mole number of vulcabond and glycol is 0.001 ~ 0.08; Catalyzer adopts dibutyl tin laurate, and add-on is 3 ~ 5 ‰ of vulcabond and PTMG gross weight; Solvent adopts dimethyl formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of polyurethane(s) and polyvinyl alcohol 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 polyurethane(s) and polyvinyl alcohol improve the method for poly-peptide film wetting ability and kindliness, step 2) in, the mol ratio of polyurethane(s) and poly-peptide homopolymer is 6 ~ 18:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.07 ~ 1.8:1.
Described a kind of polyurethane(s) and polyvinyl alcohol improve the method for poly-peptide film wetting ability and kindliness, in step 3), the mass percent of polyvinyl alcohol segments in modified membrane is 2 ~ 4%, and solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 35 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1. the polyurethane(s) described in and polyvinyl alcohol improve poly-peptide film wetting ability and the method for kindliness, adopt progressively addition polymerization, amidate action and blended three 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 the polyurethane(s) containing end-COOH group
5.5 gram 2 is added in dry reactor, 4-tolylene diisocyanate, 17.2 grams of PTMG (molecular weight is 1000), add 350 ml solvent dimethylformamides, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 45 DEG C of stirring reactions after 45 minutes, add 0.81 gram of BDO and react 10 minutes, then add 1.22 grams of 3-hydroxy-propionic acids and react 5 minutes, termination reaction, obtains target compound;
2) synthesis of poly-peptide-polyurethane block copolymers
In dry reactor, add 16.1 grams of poly-(r-phenmethyl-Pidolidone ester) (molecular weight are 80000) and 9 grams of polyurethane(s) containing end-COOH group, add 305 ml dimethyl formamides, then add 0.046 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions termination reaction after 2 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of the poly-peptide film of polyurethane(s) and polyvinyl alcohol modification
12 grams of poly-peptide-polyurethane block copolymers and 46 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the polyvinyl alcohol (molecular weight is 6000) accounting for modified membrane gross weight 2%, under inert atmosphere, 40 minutes are uniformly mixed 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 13.4% and 7.8% before modified.
embodiment 2
1) synthesis of the polyurethane(s) containing end-COOH group
6.05 gram 2 is added in dry reactor, 4-tolylene diisocyanate, 19 grams of PTMG (molecular weight is 1000), add 353 ml solvent dimethylformamides, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 47 DEG C of stirring reactions after 47 minutes, add 0.88 gram of BDO and react 12 minutes, then add 1.32 grams of 3-hydroxy-propionic acids and react 7 minutes, termination reaction, obtains target compound;
2) synthesis of poly-peptide-polyurethane block copolymers
In dry reactor, add 16.5 grams of poly-(r-ethyl-L-glutamate ester) (molecular weight are 85000) and 9 grams of polyurethane(s) containing end-COOH group, add 312 ml dimethyl formamides, then add 0.028 gram
n, N '-DIC, under inert atmosphere, in 28 DEG C of stirring reactions termination reaction after 3 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of the poly-peptide film of polyurethane(s) and polyvinyl alcohol modification
12.3 grams of poly-peptide-polyurethane block copolymers and 45 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the polyvinyl alcohol (molecular weight is 6500) accounting for modified membrane gross weight 3%, under inert atmosphere, 45 minutes are uniformly mixed 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 14.6% and 8.6% before modified.
embodiment 3
1) synthesis of the polyurethane(s) containing end-COOH group
6.6 gram 2 is added in dry reactor, 4-tolylene diisocyanate, 21 grams of PTMG (molecular weight is 1000), add 360 ml solvent dimethylformamides, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 50 DEG C of stirring reactions after 50 minutes, add 0.92 gram of BDO and react 15 minutes, then add 1.84 grams of 3-hydroxy-propionic acids and react 10 minutes, termination reaction, obtains target compound;
2) synthesis of poly-peptide-polyurethane block copolymers
16.8 grams of poly-(r-methyl-Pidolidone ester) (molecular weight are 90000) and 9.9 grams of polyurethane(s) containing end-COOH group are added in dry reactor, add 315 ml dimethyl formamides, add 0.046 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 the poly-peptide film of polyurethane(s) and polyvinyl alcohol modification
13 grams of poly-peptide-polyurethane block copolymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the polyvinyl alcohol (molecular weight is 7000) accounting for modified membrane gross weight 4%, under inert atmosphere, 50 minutes are uniformly mixed 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 15.5% and 9.3% before modified.
Claims (5)
1. a polyurethane(s) and polyvinyl alcohol 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 polyurethane(s) segment is 4000 ~ 5000, and the molecular weight of polyvinyl alcohol segments is 6000 ~ 7000; Its method of modifying adopts following steps:
1) synthesis of the polyurethane(s) containing end-COOH group: add vulcabond, PTMG, catalysts and solvents in dry reactor, under inert atmosphere, in 45 ~ 50 DEG C of stirring reactions after 45 ~ 50 minutes, add 1,4-butyleneglycol reaction 10 ~ 15 minutes, add 3-hydroxy-propionic acid reaction 5 ~ 10 minutes again, termination reaction, obtains target compound;
2) synthesis of poly-peptide-polyurethane block copolymers: add the polyurethane(s) containing end-COOH group, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 25 ~ 35 DEG C of stirring reactions termination reaction after 2 ~ 3 days, 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);
3) preparation of the poly-peptide film of polyurethane(s) and polyvinyl alcohol modification: add poly-peptide-polyurethane block copolymers, polyethylene alcohol 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 polyurethane(s) according to claim 1 and polyvinyl alcohol improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 1), vulcabond adopts 2,4 toluene diisocyanate, and the difference of the mole number of vulcabond and glycol is 0.001 ~ 0.08; Catalyzer adopts dibutyl tin laurate, and add-on is 3 ~ 5 ‰ of vulcabond and PTMG gross weight; Solvent adopts dimethyl formamide, and reactant solution concentration is 5 ~ 15 g:100 ml.
3. a kind of polyurethane(s) according to claim 1 and polyvinyl alcohol 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.
4. a kind of polyurethane(s) according to claim 1 and polyvinyl alcohol improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: step 2) in, the mol ratio of polyurethane(s) and poly-peptide homopolymer is 6 ~ 18:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.07 ~ 1.8:1.
5. a kind of polyurethane(s) according to claim 1 and polyvinyl alcohol improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 3), the mass percent of polyvinyl alcohol segments in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), 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 true CN104530721A (en) | 2015-04-22 |
| CN104530721B 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) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105566641A (en) * | 2016-02-29 | 2016-05-11 | 山东理工大学 | Preparation method of PVA (Polyvinyl Alcohol)-polypeptide grafting copolymer |
| CN105669989A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-polycaprolactone-polypeptide double-graft copolymer |
-
2015
- 2015-01-05 CN CN201510002740.3A patent/CN104530721B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 朱国全等: ""聚乙烯醇／聚氨酯共混薄膜制备及性能研究"", 《山东理工大学学报（自然科学版）》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566641A (en) * | 2016-02-29 | 2016-05-11 | 山东理工大学 | Preparation method of PVA (Polyvinyl Alcohol)-polypeptide grafting copolymer |
| CN105669989A (en) * | 2016-02-29 | 2016-06-15 | 山东理工大学 | Preparation method for polyvinyl alcohol-polycaprolactone-polypeptide double-graft 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104530721B (en) | 2016-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788607A (en) | Method for improving hydrophilicity of polypeptide film through p-dioxanone and waterborne polyurethane | |
| CN104479158A (en) | Method for improving hydrophilia and flexibility of polypeptide membrane through polydioxanone and polyethylene glycol | |
| 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 | |
| CN104479157A (en) | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol | |
| CN104448841A (en) | Method for improving hydrophilia and flexibility of poly peptide film through poly (lactic acid-glycolic acid) (PLGA) and polyacrylic acid | |
| CN103865088A (en) | Method for improving hydrophilia of polypeptide membrane by polycaprolactone and polyethylene glycol | |
| CN104530721A (en) | Method for improving hydrophilia and flexibility of polypeptide film through polyurethane and polyvinyl alcohol | |
| CN104559212A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol | |
| CN103819908B (en) | A kind of method that PPDO and urethane improve poly-peptide film kindliness | |
| CN104559214A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid | |
| CN104559208A (en) | Method for improving hydrophilic property and flexibility of polypeptide film by adopting poly (lactic acid-glycolic acid) and polyacrylamide | |
| CN103804914A (en) | Method for improving hydrophilicity of polypeptide membrane by using polypropylene glycol and polyvinyl alcohol | |
| CN103819909A (en) | Method for improving flexibility of polypeptide film by poly (p-dioxanone) and polyurethane | |
| CN104559210A (en) | Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol | |
| CN104448843A (en) | Method for improving hydrophilia and flexibility of poly peptide film through polycaprolactone and polyacrylic acid | |
| CN104559218A (en) | Method for improving hydrophilicity and flexibility of polypeptide film by poly(p-dioxanone) and carboxymethyl chitosan | |
| CN104559206A (en) | Method for improving hydrophilic property and flexibility of polypeptide film by adopting poly trimethylene carbonate and polyacrylamide | |
| CN104559216A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid | |
| CN104559219A (en) | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and waterborne polyurethane | |
| CN104559221A (en) | Method for improving hydrophilicity and flexibility of polypeptide film by poly lactic acid-glycolic acid and waterborne polyurethane | |
| CN104530720A (en) | Method for improving hydrophilia and flexibility of polypeptide film through polyurethane and polyacrylamide | |
| CN104497592A (en) | Method for improving hydrophilicity and flexibility of polyurethane and carboxymethyl chitosan improved polypeptide film | |
| CN104497587A (en) | Method for improving hydrophilicity and flexibility of polyurethane and poly(hydroxyethyl methacrylate) improved polypeptide film | |
| CN104559211A (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(p-dioxanone) and polyacrylic acid |
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 |