CN104559207B - Method for improving hydrophilic property and flexibility of polypeptide film by adopting polyurethane and polyacrylic acid - Google Patents
Method for improving hydrophilic property and flexibility of polypeptide film by adopting polyurethane and polyacrylic acid Download PDFInfo
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- CN104559207B CN104559207B CN201510001190.3A CN201510001190A CN104559207B CN 104559207 B CN104559207 B CN 104559207B CN 201510001190 A CN201510001190 A CN 201510001190A CN 104559207 B CN104559207 B CN 104559207B
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- peptide
- polyacrylic acid
- polyurethanes
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Abstract
The invention discloses a method for improving the hydrophilic property and flexibility of a polypeptide film by adopting polyurethane and polyacrylic acid. The method comprises the following steps: 1) adding diisocyanate, polytetramethylene ether glycol, a catalyst and a solvent into a drying reactor, reacting for a period of time under an inert atmosphere, adding butanediol for reaction for a period of time, and then adding 3-hydroxypropionic acid for reaction, so as to obtain the polyurethane containing end carboxyl groups; 2) adding the polyurethane containing end carboxyl groups, a solvent, a condensing agent and a polypeptide homopolymer into the drying reactor, and reacting for 3-4 days under the inert atmosphere, so as to obtain a polypeptide-polyurethane segmented copolymer; 3) adding the polypeptide-polyurethane segmented copolymer, the polyacrylic acid and a solvent into the drying reactor, mixing for a period of time under the inert atmosphere, and performing film formation by adopting a tape-casting method, so as to obtain the target object. According to the invention, the preparation technology is simple, and the hydrophilic property and flexibility of the obtained modified film are greatly improved.
Description
Technical field
The present invention relates to a kind of method that polyurethanes improves poly- peptide film hydrophilic and compliance with polyacrylic acid, 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 hydrophilic, thus limiting its application to a certain extent.Polyurethanes
There is preferable biocompatibility and biodegradability, softer and have the preferable compatibility with polyacrylic acid.Polyacrylic acid
There is preferable biocompatibility and biodegradability, and there is preferable hydrophilic.First by polyurethanes segment
Poly- peptide segment is introduced by amidation process and forms the blending that poly- peptide-polyurethane block copolymers improve poly- peptide,
Then again polyacrylic acid segment is added poly- peptide-polyurethane block copolymers to form blend, modified poly- peptide film is obtained,
Thus drastically increasing hydrophilic and the compliance of poly- peptide film.Use polyurethanes and polyacrylic acid at present to poly- peptide film parent
There is not been reported for the research that aqueouss and compliance improve.
Content of the invention
It is an object of the invention to provide one kind is simple to operate and effect is preferably entered with compliance to poly- peptide film hydrophilic
The improved method of row.Its technical scheme is：
A kind of polyurethanes and polyacrylic acid improve poly- peptide film hydrophilic 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 polyurethanes segment is 4000～6000,
The molecular weight of polyacrylic acid segment is 6000～7000；Its method of modifying adopts following steps：
1）The synthesis of the polyurethanes containing end-COOH group：Add diisocyanate in dry reactor, gather
Oxolane ether glycol, catalysts and solvents, under inert atmosphere, after 45～50 DEG C of stirring reactions 45～50 minutes, add 1,
4- butanediol reacts 10～15 minutes, adds 3- hydracrylic acid and reacts 5～10 minutes, and terminating reaction obtains object；
2）The synthesis of poly- peptide-polyurethane block copolymers：Add in dry reactor and contain end-COOH group
Polyurethanes, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, after 20～35 DEG C of stirring reactions 3～4 days
Terminating reaction, by filtering, dialysing, be dried, obtains object, and wherein, poly- peptide homopolymer is using poly-（R- benzyl-L- paddy ammonia
Acid esters）, poly-（R- ethyl-L-glutamate ester）Or it is poly-（R- methyl-L-Glutamic Acid ester）；
3）Polyurethanes and the preparation of polyacrylic acid modified poly- peptide film：Poly- peptide-poly- is added in dry reactor
Urethane block copolymers, polyacrylic acid and solvent, under inert atmosphere, in 40～50 DEG C of stirring mixing 40～50 minutes
Afterwards, with the tape casting film forming and dry, obtain object.
The method that a kind of described polyurethanes improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step 1）
In, diisocyanate adopts 2,4 toluene diisocyanate, and the difference of diisocyanate and the molal quantity of glycol is 0.001～
0.08；Catalyst adopts dibutyl tin laurate, and addition is the 3 of diisocyanate and PTMG gross weight
～5 ‰；Solvent adopts dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described polyurethanes improves poly- peptide film hydrophilic and compliance with polyacrylic acid, 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 polyurethanes improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step 2）
In, polyurethanes is 6～16 with the mol ratio of poly- peptide homopolymer:1；Condensing agent is 1.07 with the mol ratio of poly- peptide homopolymer
～1.8:1.
The method that a kind of described polyurethanes improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step 3）
In, mass percent in Modified Membrane for the polyacrylic acid segment is 2～4%, and solvent adopts dimethyl sulfoxide, and mixture solution is dense
Spend for 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention：
1. the method that the polyurethanes described in improves poly- peptide film hydrophilic and compliance with polyacrylic acid, using progressively
Addition polymerization, amidation process and blending three kinds of means, simple to operate, be easy to grasp；
2. the poly- peptide Modified Membrane hydrophilic described in is greatly improved with compliance.
Specific embodiment
Embodiment 1
1）The synthesis of the polyurethanes containing end-COOH group
5.5 grams of 2,4 toluene diisocyanates, 17.2 grams of PTMG are added in dry reactor（Molecule
Measure as 1000）, add 350 ml solvent dimethylformamides, separately add tin dilaurate two fourth of above-mentioned reactant gross weight 3 ‰
Ji Xi, under inert atmosphere, after 45 DEG C of stirring reactions 45 minutes, adds 0.81 gram of BDO to react 10 minutes, adds
1.22 grams of 3- hydracrylic acids react 5 minutes, and terminating reaction obtains object；
2）The synthesis of poly- peptide-polyurethane block copolymers
Add 16.1 grams to gather in dry reactor（R- benzyl-L-Glutamic Acid ester）（Molecular weight is 80000）Contain with 9 grams
There is the polyurethanes of end-COOH group, add 305 ml dimethylformamides, add 0.046 gramN,N’- two hexamethylenes
Base carbodiimide, under inert atmosphere, terminating reaction after 20 DEG C of stirring reactions 3 days, by filtering, dialysis, it is dried, obtain target
Thing；
3）Polyurethanes and the preparation of polyacrylic acid modified poly- peptide film
Add 12 grams of poly- peptide-polyurethane block copolymers and 46 ml dimethyl sulfoxide molten in dry reactor
Agent, another addition accounts for the polyacrylic acid of Modified Membrane gross weight 2%（Molecular weight is 6000）, under inert atmosphere, stir mixing 40 in 40 DEG C
Minute, use the tape casting film forming, be dried in 50 DEG C of vacuum drying ovens, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.6% and 7.6% before modified.
Embodiment 2
1）The synthesis of the polyurethanes containing end-COOH group
6.05 grams of 2,4 toluene diisocyanates, 19 grams of PTMG are added in dry reactor（Molecule
Measure as 1000）, add 353 ml solvent dimethylformamides, separately add tin dilaurate two fourth of above-mentioned reactant gross weight 4 ‰
Ji Xi, under inert atmosphere, after 47 DEG C of stirring reactions 47 minutes, adds 0.88 gram of BDO to react 12 minutes, adds
1.32 grams of 3- hydracrylic acids react 7 minutes, and terminating reaction obtains object；
2）The synthesis of poly- peptide-polyurethane block copolymers
Add 16.5 grams to gather in dry reactor（R- ethyl-L-glutamate ester）（Molecular weight is 85000）Contain with 9 grams
The polyurethanes of end-COOH group, adds 312 ml dimethylformamides, adds 0.028 gramN,N’- diisopropyl
Carbodiimide, under inert atmosphere, terminating reaction after 28 DEG C of stirring reactions 4 days, by filtering, dialysis, it is dried, obtain target
Thing；
3）Polyurethanes and the preparation of polyacrylic acid modified poly- peptide film
12.3 grams of poly- peptide-polyurethane block copolymers and 45 ml dimethyl sulfoxide are added in dry reactor
Solvent, another addition accounts for the polyacrylic acid of Modified Membrane gross weight 3%（Molecular weight is 6500）, under inert atmosphere, in 45 DEG C of stirring mixing
45 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying ovens, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 13.8% and 8.4% before modified.
Embodiment 3
1）The synthesis of the polyurethanes containing end-COOH group
6.6 grams of 2,4 toluene diisocyanates, 21 grams of PTMG are added in dry reactor（Molecular weight
For 1000）, add 360 ml solvent dimethylformamides, separately add the di lauric dibutyl of above-mentioned reactant gross weight 5 ‰
Stannum, under inert atmosphere, after 50 DEG C of stirring reactions 50 minutes, adds 0.92 gram of BDO to react 15 minutes, adds
1.84 grams of 3- hydracrylic acids react 10 minutes, and terminating reaction obtains object；
2）The synthesis of poly- peptide-polyurethane block copolymers
Add 16.8 grams to gather in dry reactor（R- methyl-L-Glutamic Acid ester）（Molecular weight is 90000）Contain with 9.9 grams
There is the polyurethanes of end-COOH group, add 315 ml dimethylformamides, add 0.046 gram of 3- ethyl -1-（3-
Dimethylaminopropyl）Carbodiimide, under inert atmosphere, terminating reaction after 35 DEG C of stirring reactions 3 days, by filtering, dialysis, dry
Dry, obtain object；
3）Polyurethanes and the preparation of polyacrylic acid modified poly- peptide film
13 grams of poly- peptide-polyurethane block copolymers and 45.5 ml dimethyl sulfoxide are added in dry reactor
Solvent, another addition accounts for the polyacrylic acid of Modified Membrane gross weight 4%（Molecular weight is 7000）, under inert atmosphere, in 50 DEG C of stirring mixing
50 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying ovens, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 14.7% and 9.1% before modified.
Claims (5)
1. a kind of polyurethanes and polyacrylic acid improve poly- peptide film hydrophilic 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 polyurethanes segment is 4000～6000, gathers
The molecular weight of acrylate is 6000～7000；Its method of modifying adopts following steps：
1）The synthesis of the polyurethanes containing end-COOH group：Diisocyanate, poly- tetrahydrochysene is added in dry reactor
Furan ether glycol, catalysts and solvents, under inert atmosphere, after 45～50 DEG C of stirring reactions 45～50 minutes, add Isosorbide-5-Nitrae-fourth
Glycol reacts 10～15 minutes, adds 3- hydracrylic acid and reacts 5～10 minutes, and terminating reaction obtains object；
2）The synthesis of poly- peptide-polyurethane block copolymers：Add poly- containing end-COOH group in dry reactor
Carbamate, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, terminate after 20～35 DEG C of stirring reactions 3～4 days
Reaction, by filtering, dialysing, be dried, obtains object, and wherein, poly- peptide homopolymer is using poly-（γ-benzyl-L-Glutamic Acid
Ester）, poly-（γ-ethyl-L-glutamate ester）Or it is poly-（γ-methyl-L-Glutamic Acid ester）；
3）Polyurethanes and the preparation of polyacrylic acid modified poly- peptide film：Poly- peptide-poly- amino is added in dry reactor
Formate-blocked copolymer, polyacrylic acid and solvent, under inert atmosphere, after 40～50 DEG C of stirring mixing 40～50 minutes, use
The tape casting film forming is simultaneously dried, and obtains object.
2. a kind of polyurethanes according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 1）In, diisocyanate adopts 2,4 toluene diisocyanate, diisocyanate and glycol
The difference of molal quantity is 0.001～0.08；Catalyst adopts dibutyl tin laurate, and addition is diisocyanate and poly- tetrahydrochysene
3～the 5 ‰ of furan ether glycol gross weight；Solvent adopts dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
3. a kind of polyurethanes according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic 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.
4. a kind of polyurethanes according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 2）In, polyurethanes is 6～16 with the mol ratio of poly- peptide homopolymer:1；Condensing agent with poly-
The mol ratio of peptide homopolymer is 1.07～1.8:1.
5. a kind of polyurethanes according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 3）In, mass percent in Modified Membrane for the polyacrylic acid segment is 2～4%, and solvent adopts two
Methyl sulfoxide, mixture solution concentration is 25～35 g:100 ml.
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| CN201510001190.3A CN104559207B (en) | 2015-01-05 | 2015-01-05 | Method for improving hydrophilic property and flexibility of polypeptide film by adopting polyurethane and polyacrylic acid |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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