CN104559216A - Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid - Google Patents
Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid Download PDFInfo
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- CN104559216A CN104559216A CN201510004854.1A CN201510004854A CN104559216A CN 104559216 A CN104559216 A CN 104559216A CN 201510004854 A CN201510004854 A CN 201510004854A CN 104559216 A CN104559216 A CN 104559216A
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Abstract
The invention discloses a method for improving the hydrophily and flexibility of a polypeptide film by poly(trimethylene carbonate) and polyacrylic acid. The method comprises the following steps: (1) adding carboxy terminated poly(trimethylene carbonate) monotridecyl ether, a solvent, a condensing agent and a polypeptide homopolymer into a dried reactor, and reacting for 3-4 days to obtain a polypeptide-poly(trimethylene carbonate) segmented copolymer; (2) adding amino terminated poly(trimethylene carbonate) monotridecyl ether, a solvent, a condensing agent and polyacrylic acid into a dried reactor, and reacting for 2-3 days to obtain a polyacrylic acid-poly(trimethylene carbonate) grafted copolymer; (3) adding the polypeptide-poly(trimethylene carbonate) segmented copolymer, the polyacrylic acid-poly(trimethylene carbonate) grafted copolymer and a solvent into a dried reactor, mixing 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 PTMC 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.PTMC has good biocompatibility and biodegradability, softer.Polyacrylic acid has good biocompatibility and biodegradability, and has good wetting ability.First PTMC segment is introduced respectively poly-peptide segment and polyacrylic acid segment forms poly-peptide-PTMC segmented copolymer and poly acrylic acid-poly trimethylene carbonate 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 PTMC 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 PTMC 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 PTMC 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-PTMC segmented copolymer: add the PTMC list tridecyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 25 ~ 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 trimethylene carbonate graft copolymer: add amino-terminated PTMC list tridecyl 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 PTMC and polyacrylic acid modified poly-peptide film: add poly-peptide-PTMC segmented copolymer, poly acrylic acid-poly trimethylene carbonate graft copolymer 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 PTMC 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 PTMC and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, and in step 1), the mol ratio of PTMC list tridecyl 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 PTMC 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 PTMC and polyacrylic acid improve the method for poly-peptide film wetting ability and kindliness, step 2) in, PTMC list tridecyl 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 PTMC 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 trimethylene carbonate graft copolymer in modified membrane is 2 ~ 4%, 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 PTMC 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-PTMC segmented copolymer
The PTMC list tridecyl 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 is added in dry reactor, add 300 ml dimethyl formamides, then add 0.048 gram
n, N '-dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 3 days, termination reaction, by filtering, dialysis, dry, obtains target compound;
2) synthesis of poly acrylic acid-poly trimethylene carbonate graft copolymer
In dry reactor, add 3.5 grams of polyacrylic acid (molecular weight is 5000) and 9 grams of amino-terminated PTMC list tridecyl ethers (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 PTMC and polyacrylic acid modified poly-peptide film
12.5 grams of poly-peptide-PTMC segmented copolymers and 45.8 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the poly acrylic acid-poly trimethylene carbonate graft copolymer 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 13.1% and 12.8% before modified.
embodiment 2
1) synthesis of poly-peptide-PTMC segmented copolymer
The PTMC list tridecyl 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 27 DEG C of stirring reactions 4 days, termination reaction, by filtration, dialysis, drying, obtain target compound;
2) synthesis of poly acrylic acid-poly trimethylene carbonate graft copolymer
In dry reactor, add 3 grams of polyacrylic acid (molecular weight is 5500) and 9 grams of amino-terminated PTMC list tridecyl ethers (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 PTMC and polyacrylic acid modified poly-peptide film
12.6 grams of poly-peptide-PTMC segmented copolymers and 45.5 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the poly acrylic acid-poly trimethylene carbonate graft copolymer 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 13.7% and 13.6% before modified.
embodiment 3
1) synthesis of poly-peptide-PTMC segmented copolymer
The PTMC list tridecyl 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 trimethylene carbonate graft copolymer
3.1 grams of polyacrylic acid (molecular weight is 6000) and 9.2 grams of amino-terminated PTMC list tridecyl ethers (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 PTMC and polyacrylic acid modified poly-peptide film
12.8 grams of poly-peptide-PTMC segmented copolymers and 45.4 ml dimethyl sulfoxide solvents are added in dry reactor, separately add the poly acrylic acid-poly trimethylene carbonate graft copolymer 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 14.8% and 14.2% before modified.
Claims (6)
1. a PTMC 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 PTMC 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-PTMC segmented copolymer: add the PTMC list tridecyl ether of carboxy blocking, solvent, condensing agent and poly-peptide homopolymer in dry reactor, under inert atmosphere, in 25 ~ 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 trimethylene carbonate graft copolymer: add amino-terminated PTMC list tridecyl 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 PTMC and polyacrylic acid modified poly-peptide film: add poly-peptide-PTMC segmented copolymer, poly acrylic acid-poly trimethylene carbonate graft copolymer 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 PTMC 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 PTMC 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), the mol ratio of PTMC list tridecyl 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 PTMC 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 PTMC 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, PTMC list tridecyl 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 PTMC 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 trimethylene carbonate graft copolymer 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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Cited By (3)
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CN106977939A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with PTMC and PPDO to polypropylene sorrel water resistance and compliance |
CN106987138A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
CN107011680A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone is improved with PTMC to polypropylene sorrel water resistance and compliance |
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CN103804915A (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 |
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 |
CN103819700A (en) * | 2014-03-07 | 2014-05-28 | 山东理工大学 | Method for improving flexibility of polypeptide film with poly trimethylene carbonate and polytetrahydrofuran ether glycol |
CN103865071A (en) * | 2014-03-24 | 2014-06-18 | 山东理工大学 | Preparation method of polypeptide-poly trimethylene carbonate-MPEGPLA (mono-methoxyl poly(ethylene glycol)-poly(lactic acid) dual-graft copolymer |
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2015
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CN1900144A (en) * | 2006-07-14 | 2007-01-24 | 华东理工大学 | Poly propenoic acid/polypeptide grafted copolymer and its preparing method and use |
CN103819700A (en) * | 2014-03-07 | 2014-05-28 | 山东理工大学 | Method for improving flexibility of polypeptide film with poly trimethylene carbonate and polytetrahydrofuran ether glycol |
CN103804915A (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 |
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 |
CN103865071A (en) * | 2014-03-24 | 2014-06-18 | 山东理工大学 | Preparation method of polypeptide-poly trimethylene carbonate-MPEGPLA (mono-methoxyl poly(ethylene glycol)-poly(lactic acid) dual-graft copolymer |
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CN106977939A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method being improved with PTMC and PPDO to polypropylene sorrel water resistance and compliance |
CN106987138A (en) * | 2017-05-25 | 2017-07-28 | 山东理工大学 | A kind of method that MPEGPLA is improved with PTMC to polypropylene sorrel water resistance and compliance |
CN107011680A (en) * | 2017-05-25 | 2017-08-04 | 山东理工大学 | A kind of method that polycaprolactone is improved with PTMC to polypropylene sorrel water resistance and compliance |
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