CN103834180A - Method for improving flexibility of polypeptide membrane by using polycaprolactone and polypropylene glycol - Google Patents
Method for improving flexibility of polypeptide membrane by using polycaprolactone and polypropylene glycol Download PDFInfo
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- CN103834180A CN103834180A CN201410075488.4A CN201410075488A CN103834180A CN 103834180 A CN103834180 A CN 103834180A CN 201410075488 A CN201410075488 A CN 201410075488A CN 103834180 A CN103834180 A CN 103834180A
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Abstract
The invention discloses a method for improving flexibility of a polypeptide membrane by using polycaprolactone and polypropylene glycol. The method comprises the following steps: 1) synthesizing a polypeptide-polycaprolactone grafted copolymer, adding a polypeptide homopolymer, polycaprolactone mono dodecyl ether, a solvent and a catalyst into a dry reactor, stirring for reaction for 3-4 days at 55-58 DEG C in the presence of inert atmosphere, subsequently filtering, dialyzing and drying to obtain a target object; 2) preparing the polycaprolactone and polypropylene glycol modified polypeptide membrane, namely, adding the polypeptide-polycaprolactone grafted copolymer, polypropylene glycol and a solvent into the dry reactor, stirring and mixing for 50-70 minutes at 40-50 DEG C, filming by using a tape casting method, and drying so as to obtain the target object. The method is simple in preparation process and easy to master, and the flexibility of the obtained modified membrane is greatly improved.
Description
Technical field
The present invention relates to one poly-peptide film kindliness is carried out to improved method, belong to field of polymer film preparing technology.
Background technology
Poly-peptide is a kind of have good biocompatibility and biomaterial of biodegradability, and poly-peptide film can be used as artificial skin etc., but poly-peptide is more stiff, and poly-peptide film lacks good kindliness, thereby has limited to a certain extent its application.Polycaprolactone and polypropylene glycol have good biocompatibility and biodegradability, soft and have each other a good blend.First polycaprolactone segment is introduced to poly-peptide segment and formed poly-peptide-polycaprolactone graft copolymer to improve the blend of poly-peptide, and then add poly-peptide-polycaprolactone graft copolymer to form blend polypropylene glycol segment, make the poly-peptide film of modification, thereby greatly improved the kindliness of poly-peptide film.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate and effect preferably poly-peptide film kindliness to be carried out to improved method.Its technical scheme is:
One is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 60000~80000, the molecular weight of polycaprolactone segment is 1000~2000, and the molecular weight of polypropylene glycol segment is 4000~5000; Its method of modifying adopts following steps:
1) poly-peptide-polycaprolactone graft copolymer is synthetic: in dry reactor, add poly-peptide homopolymer, polycaprolactone monododecyl ether, solvent and catalyzer, under inert atmosphere, after 3~4 days, make target compound by filtering, dialyse, being dried in 55~58 ℃ of stirring reactions;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified: add poly-peptide-polycaprolactone graft copolymer, polypropylene glycol and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50~70 minutes in 40~50 ℃, by casting method film forming dry, obtain target compound.
Described one is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-Pidolidone ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of polycaprolactone monododecyl ether and poly-peptide homopolymer is 15~25:1.
Described one is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, in step 1), catalyzer adopts tosic acid, the mol ratio of catalyzer and poly-peptide homopolymer is 25~45:1, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
Described one is carried out improved method, step 2 with polycaprolactone and polypropylene glycol to poly-peptide film kindliness) in, the mass percent of polypropylene glycol in modified membrane is 1~3%, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1, described polycaprolactone and polypropylene glycol improve the method for poly-peptide film kindliness, adopt graft copolymerization and two kinds of means of blend, simple to operate, be easy to grasp;
2, described poly-peptide modified membrane kindliness is greatly improved.
Embodiment
embodiment 1
1) poly-peptide-polycaprolactone graft copolymer is synthetic:
In dry reactor, adding 12 gram molecular weights is polycaprolactone monododecyl ether, the 0.9 gram of tosic acid that 60000 poly-(r-phenmethyl-Pidolidone esters), 3.1 gram molecular weights are 1000, add again 260 milliliter 1,1,2-trichloroethane solvent, under inert atmosphere, in 55 ℃ of stirring reactions after 3 days, termination reaction, then by filtering, dialysis, the dry target compound that makes;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified:
In dry reactor, add 10 grams of poly-peptide-polycaprolactone graft copolymers and 38 milliliter 1,1,2-trichloroethane solvent, separately add the polypropylene glycol (molecular weight is 4000) that accounts for modified membrane gross weight 1%, under inert atmosphere, be uniformly mixed after 50 minutes in 40 ℃, use casting method film forming, the dry target compound that obtains in 50 ℃ of vacuum drying ovens.
After tested: the elongation at break of target compound of the present invention has improved 13.2% before than modification.
embodiment 2
1) poly-peptide-polycaprolactone graft copolymer is synthetic:
In dry reactor, adding 12 gram molecular weights is polycaprolactone monododecyl ether, the 0.91 gram of tosic acid that 70000 poly-(r-ethyl-Pidolidone esters), 5.3 gram molecular weights are 1500, add again 225 milliliter 1,1,2-trichloroethane solvent, under inert atmosphere, in 56 ℃ of stirring reactions after 4 days, termination reaction, then by filtering, dialysis, the dry target compound that makes;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified:
In dry reactor, add 10 grams of poly-peptide-polycaprolactone graft copolymers and 36 milliliter 1,1,2-trichloroethane solvent, separately add the polypropylene glycol (molecular weight is 4500) that accounts for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed after 60 minutes in 45 ℃, use casting method film forming, the dry target compound that obtains in 50 ℃ of vacuum drying ovens.
After tested: the elongation at break of target compound of the present invention has improved 16.4% before than modification.
embodiment 3
1) poly-peptide-polycaprolactone graft copolymer is synthetic:
In dry reactor, adding 12 gram molecular weights is polycaprolactone monododecyl ether, the 1.03 grams of tosic acid that 80000 poly-(r-methyl-Pidolidone esters), 7.2 gram molecular weights are 2000, add again 180 milliliters of dimethyl sulfoxide (DMSO), under inert atmosphere, in 58 ℃ of stirring reactions after 3 days, termination reaction, then make target compound by filtering, dialyse, being dried;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified:
In dry reactor, add 10 grams of poly-peptide-polycaprolactone graft copolymers and 35.5 milliliters of dimethyl sulfoxide (DMSO), separately add the polypropylene glycol (molecular weight is 5000) that accounts for modified membrane gross weight 3%, under inert atmosphere, be uniformly mixed after 70 minutes in 50 ℃, use casting method film forming, the dry target compound that obtains in 50 ℃ of vacuum drying ovens.
After tested: the elongation at break of target compound of the present invention has improved 18.6% before than modification.
Claims (4)
1. one kind is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, it is characterized in that: in modified membrane, the molecular weight of poly-peptide segment is 60000~80000, the molecular weight of polycaprolactone segment is 1000~2000, and the molecular weight of polypropylene glycol segment is 4000~5000; Its method of modifying adopts following steps:
1) poly-peptide-polycaprolactone graft copolymer is synthetic: in dry reactor, add poly-peptide homopolymer, polycaprolactone monododecyl ether, solvent and catalyzer, under inert atmosphere, after 3~4 days, make target compound by filtering, dialyse, being dried in 55~58 ℃ of stirring reactions;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified: add poly-peptide-polycaprolactone graft copolymer, polypropylene glycol and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 50~70 minutes in 40~50 ℃, by casting method film forming dry, obtain target compound.
2. one according to claim 1 is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, it is characterized in that: in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-Pidolidone ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of polycaprolactone monododecyl ether and poly-peptide homopolymer is 15~25:1.
3. one according to claim 1 is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, it is characterized in that: in step 1), catalyzer adopts tosic acid, the mol ratio of catalyzer and poly-peptide homopolymer is 25~45:1, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5~15 g:100 ml.
4. one according to claim 1 is carried out improved method with polycaprolactone and polypropylene glycol to poly-peptide film kindliness, it is characterized in that: step 2) in, the mass percent of polypropylene glycol in modified membrane is 1~3%, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), mixture solution concentration is 25~30 g:100 ml.
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104479157A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol |
CN104497589A (en) * | 2015-01-05 | 2015-04-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypropylene glycol and polyacrylamide improved polypeptide film |
CN104497590A (en) * | 2015-01-05 | 2015-04-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polycaprolactone and polyacrylamide improved polypeptide film |
CN104559222A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and carboxymethyl chitosan |
CN104559209A (en) * | 2015-01-05 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by polycarbamate and polyethylene glycol |
CN104559219A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and waterborne polyurethane |
CN106977933A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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 |
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CN102181060A (en) * | 2011-03-20 | 2011-09-14 | 山东理工大学 | Polyvinyl alcohol-polypeptide-polyethylene glycol graft copolymer and preparation method thereof |
CN102336913A (en) * | 2011-07-01 | 2012-02-01 | 山东理工大学 | Poly(N-isopropyl acrylamide)-polyurethane-polypeptide block-graft copolymer and preparation method thereof |
CN103224627A (en) * | 2013-05-09 | 2013-07-31 | 山东理工大学 | Preparation method of polylactic acid glycollic acid-polypeptide-polyethylene glycol diblock-grafted copolymer |
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Patent Citations (3)
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CN102181060A (en) * | 2011-03-20 | 2011-09-14 | 山东理工大学 | Polyvinyl alcohol-polypeptide-polyethylene glycol graft copolymer and preparation method thereof |
CN102336913A (en) * | 2011-07-01 | 2012-02-01 | 山东理工大学 | Poly(N-isopropyl acrylamide)-polyurethane-polypeptide block-graft copolymer and preparation method thereof |
CN103224627A (en) * | 2013-05-09 | 2013-07-31 | 山东理工大学 | Preparation method of polylactic acid glycollic acid-polypeptide-polyethylene glycol diblock-grafted copolymer |
Cited By (12)
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CN104497589A (en) * | 2015-01-05 | 2015-04-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypropylene glycol and polyacrylamide improved polypeptide film |
CN104497590A (en) * | 2015-01-05 | 2015-04-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polycaprolactone and polyacrylamide improved polypeptide film |
CN104559209A (en) * | 2015-01-05 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by polycarbamate and polyethylene glycol |
CN104479157A (en) * | 2015-01-06 | 2015-04-01 | 山东理工大学 | Method for improving hydrophilia and flexibility of polypeptide membrane through polycaprolactone and polyethylene glycol |
CN104479157B (en) * | 2015-01-06 | 2017-07-11 | 山东理工大学 | A kind of method that polycaprolactone improves poly- peptide film hydrophily and compliance with polyethylene glycol |
CN104559222A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and carboxymethyl chitosan |
CN104559219A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and waterborne polyurethane |
CN104559222B (en) * | 2015-01-12 | 2017-02-22 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and carboxymethyl chitosan |
CN104559219B (en) * | 2015-01-12 | 2017-06-16 | 山东理工大学 | A kind of method that polycaprolactone improves poly- peptide film hydrophily and compliance with aqueous polyurethane |
CN106977933A (en) * | 2017-05-22 | 2017-07-25 | 山东理工大学 | A kind of method that MPEGPLA improves polypropylene sorrel water resistance and compliance with polypropylene glycol |
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 |
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