CN104559207A - 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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- CN104559207A CN104559207A CN201510001190.3A CN201510001190A CN104559207A CN 104559207 A CN104559207 A CN 104559207A CN 201510001190 A CN201510001190 A CN 201510001190A CN 104559207 A CN104559207 A CN 104559207A
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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 polyurethane(s) and polyacrylic acid 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 polyacrylic acid.Polyacrylic acid 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 polyacrylic acid segment 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 polyacrylic acid.
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 polyacrylic acid 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 ~ 6000, and the molecular weight of polyacrylic acid segment 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 20 ~ 35 DEG C of stirring reactions termination reaction after 3 ~ 4 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 polyurethane(s) and polyacrylic acid modified poly-peptide film: add poly-peptide-polyurethane block copolymers, polyacrylic acid 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 polyacrylic acid 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 polyacrylic acid 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 polyacrylic acid 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 ~ 16:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.07 ~ 1.8:1.
Described a kind of polyurethane(s) and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, in step 3), the mass percent of polyacrylic acid segment 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 polyacrylic acid 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 20 DEG C of stirring reactions termination reaction after 3 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of polyurethane(s) and polyacrylic acid modified poly-peptide film
12 grams of poly-peptide-polyurethane block copolymers and 46 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the polyacrylic acid (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 12.6% and 7.6% 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 4 days, by filtering, dialysis, dry, obtains target compound;
3) preparation of polyurethane(s) and polyacrylic acid modified poly-peptide film
12.3 grams of poly-peptide-polyurethane block copolymers and 45 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the polyacrylic acid (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 13.8% and 8.4% 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 polyurethane(s) and polyacrylic acid modified poly-peptide film
13 grams of poly-peptide-polyurethane block copolymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the polyacrylic acid (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 14.7% and 9.1% before modified.
Claims (5)
1. a polyurethane(s) and polyacrylic acid 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 ~ 6000, and the molecular weight of polyacrylic acid segment 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 20 ~ 35 DEG C of stirring reactions termination reaction after 3 ~ 4 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 polyurethane(s) and polyacrylic acid modified poly-peptide film: add poly-peptide-polyurethane block copolymers, polyacrylic acid 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 polyacrylic acid 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 polyacrylic acid 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 polyacrylic acid 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 ~ 16:1; 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 polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, it is characterized in that: in step 3), the mass percent of polyacrylic acid segment in modified membrane is 2 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 35 g:100 ml.
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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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