CN104559214A - Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid - Google Patents
Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid Download PDFInfo
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- CN104559214A CN104559214A CN201510004852.2A CN201510004852A CN104559214A CN 104559214 A CN104559214 A CN 104559214A CN 201510004852 A CN201510004852 A CN 201510004852A CN 104559214 A CN104559214 A CN 104559214A
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Abstract
The invention discloses a method for improving the hydrophily and flexibility of a polypeptide film by polypropylene glycol and polyacrylic acid. The method comprises the following steps: (1) adding carboxy terminated butoxypolypropylene glycol, a solvent, a condensing agent and a polypeptide homopolymer into a dried reactor, and stirring to react at 20-30 DEG C for 3-4 days to obtain a polypeptide-polypropylene glycol segmented copolymer; (2) adding amino terminated butoxypolypropylene glycol, a solvent, a condensing agent and polyacrylic acid into the dried reactor, and stirring to react at 25-35 DEG C for 2-3 days to obtain a polyacrylic acid-polypropylene glycol grafted copolymer; (3) adding the polypeptide-polypropylene glycol segmented copolymer, the polyacrylic acid-polypropylene glycol grafted copolymer and a solvent into a dried reactor, stirring and mixing at 40-50 DEG C for 40-50 minutes, forming a film by a tape casting method, and drying to obtain the target object. The preparation process is simple, and the hydrophily and flexibility of the modified film can be greatly improved.
Description
Technical field
The present invention relates to a kind of method that polypropylene glycol 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.Polypropylene glycol has good biocompatibility and biodegradability, soft.Polyacrylic acid has good biocompatibility and biodegradability, and has good wetting ability.First polypropylene glycol segment is introduced respectively poly-peptide segment and polyacrylic acid segment forms poly-peptide-polyethylene glycol block multipolymer and poly acrylic acid-poly propylene glycol graft copolymer, and then two kinds of multipolymers are mixed to form the blend with better consistency, 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 polypropylene glycol 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 polypropylene glycol 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 polypropylene glycol segment is 3000 ~ 4000, and the molecular weight of polyacrylic acid segment is 5000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polyethylene glycol block multipolymer: add the polypropylene glycol monobutyl 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, termination reaction, 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);
2) synthesis of poly acrylic acid-poly propylene glycol graft copolymer: add amino-terminated polypropylene glycol monobutyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, under inert atmosphere, in 25 ~ 35 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of polypropylene glycol and polyacrylic acid modified poly-peptide film: add poly-peptide-polyethylene glycol block multipolymer, poly acrylic acid-poly propylene glycol graft copolymer and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 30 ~ 40 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
Described a kind of polypropylene glycol and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, in step 1), 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 polypropylene glycol and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, and in step 1), the mol ratio of polypropylene glycol monobutyl ether and poly-peptide homopolymer is 7 ~ 15:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.08 ~ 1.8:1.
Described a kind of polypropylene glycol 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
Described a kind of polypropylene glycol and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, step 2) in, polypropylene glycol monobutyl ether and polyacrylic mol ratio are 3 ~ 6:1; Condensing agent and polyacrylic mol ratio are 1.08 ~ 1.8:1.
Described a kind of polypropylene glycol and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, in step 3), the mass percent of poly acrylic acid-poly propylene glycol graft copolymer in modified membrane is 1 ~ 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 polypropylene glycol described in and polyacrylic acid improve poly-peptide film wetting ability and the method for kindliness, adopt amidate action and blended two 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 poly-peptide-polyethylene glycol block multipolymer
In dry reactor, add the polypropylene glycol monobutyl ether (molecular weight is 3000) of 16.1 grams of poly-(r-phenmethyl-Pidolidone ester) (molecular weight are 80000) and 7 grams of carboxy blockings, add 300 ml dimethyl formamides, then add 0.048 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of poly acrylic acid-poly propylene glycol graft copolymer
In dry reactor, add 3.5 grams of polyacrylic acid (molecular weight is 5000) and 9 grams of amino-terminated polypropylene glycol monobutyl ether (molecular weight is 3000), add 160 ml dimethyl sulfoxide (DMSO), then add 0.165 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 polypropylene glycol and polyacrylic acid modified poly-peptide film
12.5 grams of poly-peptide-polyethylene glycol block multipolymers and 45.8 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the poly acrylic acid-poly propylene glycol graft copolymer accounting for modified membrane gross weight 1%, under inert atmosphere, 30 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 12.5% and 12.8% before modified.
embodiment 2
1) synthesis of poly-peptide-polyethylene glycol block multipolymer
The polypropylene glycol monobutyl ether (molecular weight is 3500) of 16.3 grams of poly-(r-ethyl-L-glutamate ester) (molecular weight are 85000) and 7 grams of carboxy blockings is added in dry reactor, add 305 ml dimethyl formamides, add 0.031 gram of N again, N '-DIC, under inert atmosphere, in 25 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of poly acrylic acid-poly propylene glycol graft copolymer
In dry reactor, add 3 grams of polyacrylic acid (molecular weight is 5500) and 9 grams of amino-terminated polypropylene glycol monobutyl ether (molecular weight is 3500), add 155 ml dimethyl sulfoxide (DMSO), then add 0.08 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 polypropylene glycol and polyacrylic acid modified poly-peptide film
12.6 grams of poly-peptide-polyethylene glycol block multipolymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the poly acrylic acid-poly propylene glycol graft copolymer accounting for modified membrane gross weight 2%, under inert atmosphere, 35 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 13.5% and 13.3% before modified.
embodiment 3
1) synthesis of poly-peptide-polyethylene glycol block multipolymer
The polypropylene glycol monobutyl ether (molecular weight is 4000) of 16.5 grams of poly-(r-methyl-Pidolidone ester) (molecular weight are 90000) and 7 grams of carboxy blockings is added in dry reactor, add 310 ml dimethyl formamides, add 0.046 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, termination reaction, by filtration, dialysis, drying, obtains target compound;
2) synthesis of poly acrylic acid-poly propylene glycol graft copolymer
3.1 grams of polyacrylic acid (molecular weight is 6000) and 9.2 grams of amino-terminated polypropylene glycol monobutyl ether (molecular weight is 4000) are added in dry reactor, add 158 ml dimethyl sulfoxide (DMSO), add 0.141 gram of 3-ethyl-1-(3-dimethylaminopropyl again) carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions termination reaction after 2 days, by filtration, dialysis, drying, obtain target compound;
3) preparation of polypropylene glycol and polyacrylic acid modified poly-peptide film
12.8 grams of poly-peptide-polyethylene glycol block multipolymers and 45.4 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the poly acrylic acid-poly propylene glycol graft copolymer accounting for modified membrane gross weight 4%, under inert atmosphere, 40 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 14.6% and 13.8% before modified.
Claims (6)
1. a polypropylene glycol 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 polypropylene glycol segment is 3000 ~ 4000, and the molecular weight of polyacrylic acid segment is 5000 ~ 6000; Its method of modifying adopts following steps:
1) synthesis of poly-peptide-polyethylene glycol block multipolymer: add the polypropylene glycol monobutyl 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, termination reaction, 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);
2) synthesis of poly acrylic acid-poly propylene glycol graft copolymer: add amino-terminated polypropylene glycol monobutyl ether, solvent, condensing agent and polyacrylic acid in dry reactor, under inert atmosphere, in 25 ~ 35 DEG C of stirring reactions 2 ~ 3 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
3) preparation of polypropylene glycol and polyacrylic acid modified poly-peptide film: add poly-peptide-polyethylene glycol block multipolymer, poly acrylic acid-poly propylene glycol graft copolymer and solvent in dry reactor, under inert atmosphere, after being uniformly mixed 30 ~ 40 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. a kind of polypropylene glycol 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), 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.
3. a kind of polypropylene glycol according to claim 1 and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, and it is characterized in that: in step 1), the mol ratio of polypropylene glycol monobutyl ether and poly-peptide homopolymer is 7 ~ 15:1; The mol ratio of condensing agent and poly-peptide homopolymer is 1.08 ~ 1.8:1.
4. a kind of polypropylene glycol 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 sulfoxide (DMSO), and reactant solution concentration is 5 ~ 15 g:100 ml.
5. a kind of polypropylene glycol 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, polypropylene glycol monobutyl ether and polyacrylic mol ratio are 3 ~ 6:1; Condensing agent and polyacrylic mol ratio are 1.08 ~ 1.8:1.
6. a kind of polypropylene glycol 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 poly acrylic acid-poly propylene glycol graft copolymer in modified membrane is 1 ~ 4%, solvent adopts dimethyl sulfoxide (DMSO), and mixture solution concentration is 25 ~ 35 g:100 ml.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647196A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method using polypeptide and polypropylene glycol-polyvinyl pyrrolidone to improve water resistance and flexibility of polyvinyl alcohol membrane |
| CN106977929A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with PTMC and polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN106977935A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106987137A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that polypropylene glycol is improved with PTMC to polypropylene sorrel water resistance and compliance |
| CN107011676A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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| US6861503B2 (en) * | 2002-02-27 | 2005-03-01 | Poly-Med, Inc. | Interlinked solid polyethylene glycols and copolymers thereof |
| CN103804916A (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 |
| CN103819907A (en) * | 2014-03-10 | 2014-05-28 | 山东理工大学 | Method for improving polypeptide membrane hydrophilicity by adopting polypropylene glycol and polyvinyl alcohol |
| CN103865088A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide membrane by polycaprolactone and polyethylene glycol |
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2015
- 2015-01-06 CN CN201510004852.2A patent/CN104559214B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6861503B2 (en) * | 2002-02-27 | 2005-03-01 | Poly-Med, Inc. | Interlinked solid polyethylene glycols and copolymers thereof |
| CN103819907A (en) * | 2014-03-10 | 2014-05-28 | 山东理工大学 | Method for improving polypeptide membrane hydrophilicity by adopting polypropylene glycol and polyvinyl alcohol |
| CN103865088A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide membrane by polycaprolactone and polyethylene glycol |
| CN103804916A (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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647196A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method using polypeptide and polypropylene glycol-polyvinyl pyrrolidone to improve water resistance and flexibility of polyvinyl alcohol membrane |
| CN106977929A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with PTMC and polypropylene glycol to polypropylene sorrel water resistance and compliance |
| CN106977935A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN107011676A (en) * | 2017-05-22 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
| CN106987137A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that polypropylene glycol is improved with PTMC to polypropylene sorrel water resistance and compliance |
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