CN103834180B - A kind of method that polycaprolactone and polypropylene glycol improve poly-peptide film kindliness - Google Patents

A kind of method that polycaprolactone and polypropylene glycol improve poly-peptide film kindliness Download PDF

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CN103834180B
CN103834180B CN201410075488.4A CN201410075488A CN103834180B CN 103834180 B CN103834180 B CN 103834180B CN 201410075488 A CN201410075488 A CN 201410075488A CN 103834180 B CN103834180 B CN 103834180B
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poly
peptide
polycaprolactone
polypropylene glycol
kindliness
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CN103834180A (en
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朱国全
王发刚
柳玉英
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Shandong University of Technology
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Shandong University of Technology
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Abstract

The present invention discloses a kind of method that polycaprolactone and polypropylene glycol improve poly-peptide film kindliness, adopt following steps: the 1) synthesis of poly-peptide-polycaprolactone graft copolymer: add poly-peptide homopolymer, polycaprolactone monododecyl ether, solvent and catalyzer in dry reactor, under inert atmosphere, in 55 ~ 58 DEG C of stirring reactions after 3 ~ 4 days, by filtration, dialysis, dry obtained target compound; 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, after being uniformly mixed 50 ~ 70 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound of the present invention.Preparation technology of the present invention is simple, be easy to grasp, and gained modified membrane kindliness is greatly improved.

Description

A kind of method that polycaprolactone and polypropylene glycol improve poly-peptide film kindliness
Technical field
The present invention relates to a kind of method that poly-peptide film kindliness is improved, 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 is more stiff, and poly-peptide film lacks good kindliness, thus limit its application to a certain extent.Polycaprolactone and polypropylene glycol have good biocompatibility and biodegradability, soft and have good blended property each other.First polycaprolactone segment is introduced poly-peptide segment and form poly-peptide-polycaprolactone graft copolymer to improve the blended property of poly-peptide, and then polypropylene glycol segment is added poly-peptide-polycaprolactone graft copolymer formation blend, obtained modification gathers peptide film, thus drastically increases 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 to the method that poly-peptide film kindliness is improved.Its technical scheme is:
A kind of method that polycaprolactone and polypropylene glycol improve 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) synthesis of poly-peptide-polycaprolactone graft copolymer: add poly-peptide homopolymer, polycaprolactone monododecyl ether, solvent and catalyzer in dry reactor, under inert atmosphere, in 55 ~ 58 DEG C of stirring reactions after 3 ~ 4 days, by filtration, dialysis, dry obtained target compound;
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, after being uniformly mixed 50 ~ 70 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
The method that described a kind of polycaprolactone and polypropylene glycol improve poly-peptide film kindliness, in step 1), poly-peptide homopolymer adopts poly-(r-phenmethyl-Pidolidone ester), poly-(r-ethyl-L-glutamate ester) or poly-(r-methyl-Pidolidone ester), and the mol ratio of polycaprolactone monododecyl ether and poly-peptide homopolymer is 15 ~ 25:1.
The method that described a kind of polycaprolactone and polypropylene glycol improve 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 ~ 15g:100ml.
The method that described a kind of polycaprolactone and polypropylene glycol improve poly-peptide film kindliness, 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 ~ 30g:100ml.
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 blended two kinds of means, simple to operate, be easy to grasp;
2, described poly-peptide modified membrane kindliness is greatly improved.
Embodiment
embodiment 1
1) synthesis of poly-peptide-polycaprolactone graft copolymer:
12 gram molecular weights are 60000 poly-(r-phenmethyl-Pidolidone esters), 3.1 gram molecular weights are 1000 polycaprolactone monododecyl ether, 0.9 gram of tosic acid is added in dry reactor, add 260 milliliter 1 again, 1,2-Separator, under inert atmosphere, in 55 DEG C of stirring reactions after 3 days, termination reaction, then by filtration, dialysis, dry obtained target compound;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified:
10 grams of poly-peptide-polycaprolactone graft copolymers and 38 milliliter 1 is added in dry reactor, 1,2-Separator, separately add the polypropylene glycol (molecular weight is 4000) accounting for modified membrane gross weight 1%, under inert atmosphere, after being uniformly mixed 50 minutes in 40 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the elongation at break of target compound of the present invention is than improve 13.2% before modified.
embodiment 2
1) synthesis of poly-peptide-polycaprolactone graft copolymer:
12 gram molecular weights are 70000 poly-(r-ethyl-L-glutamate esters), 5.3 gram molecular weights are 1500 polycaprolactone monododecyl ether, 0.91 gram of tosic acid is added in dry reactor, add 225 milliliter 1 again, 1,2-Separator, under inert atmosphere, in 56 DEG C of stirring reactions after 4 days, termination reaction, then by filtration, dialysis, dry obtained target compound;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified:
10 grams of poly-peptide-polycaprolactone graft copolymers and 36 milliliter 1 is added in dry reactor, 1,2-Separator, separately add the polypropylene glycol (molecular weight is 4500) accounting for modified membrane gross weight 2%, under inert atmosphere, after being uniformly mixed 60 minutes in 45 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the elongation at break of target compound of the present invention is than improve 16.4% before modified.
embodiment 3
1) synthesis of poly-peptide-polycaprolactone graft copolymer:
12 gram molecular weights are 80000 poly-(r-methyl-Pidolidone esters), 7.2 gram molecular weights are 2000 polycaprolactone monododecyl ether, 1.03 grams of tosic acid are added in dry reactor, add 180 milliliters of dimethyl sulfoxide (DMSO) again, under inert atmosphere, in 58 DEG C of stirring reactions after 3 days, termination reaction, then by filtration, dialysis, dry obtained target compound;
2) preparation of the poly-peptide film of polycaprolactone and polypropylene glycol modified:
10 grams of poly-peptide-polycaprolactone graft copolymers and 35.5 milliliters of dimethyl sulfoxide (DMSO) are added in dry reactor, separately add the polypropylene glycol (molecular weight is 5000) accounting for modified membrane gross weight 3%, under inert atmosphere, after being uniformly mixed 70 minutes in 50 DEG C, use casting method film forming, in 50 DEG C of vacuum drying ovens, drying obtains target compound.
After tested: the elongation at break of target compound of the present invention is than improve 18.6% before modified.

Claims (4)

1. the method poly-peptide film kindliness improved with polycaprolactone and polypropylene glycol, 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) synthesis of poly-peptide-polycaprolactone graft copolymer: add poly-peptide homopolymer, polycaprolactone monododecyl ether, solvent and catalyzer in dry reactor, under inert atmosphere, in 55 ~ 58 DEG C of stirring reactions after 3 ~ 4 days, by filtration, dialysis, dry obtained 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) 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, after being uniformly mixed 50 ~ 70 minutes in 40 ~ 50 DEG C, also dry by casting method film forming, obtain target compound.
2. the method improved poly-peptide film kindliness of a kind of polycaprolactone according to claim 1 and polypropylene glycol, it is characterized in that: in step 1), the mol ratio of polycaprolactone monododecyl ether and poly-peptide homopolymer is 15 ~ 25:1.
3. a kind of polycaprolactone according to claim 1 and polypropylene glycol method that poly-peptide film kindliness is improved, 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 ~ 15g:100ml.
4. a kind of polycaprolactone according to claim 1 and polypropylene glycol method that poly-peptide film kindliness is improved, 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 ~ 30g:100ml.
CN201410075488.4A 2014-03-04 2014-03-04 A kind of method that polycaprolactone and polypropylene glycol improve poly-peptide film kindliness Expired - Fee Related CN103834180B (en)

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CN104497589B (en) * 2015-01-05 2017-02-08 山东理工大学 Method for improving hydrophilicity and flexibility of polypropylene glycol and polyacrylamide improved polypeptide film
CN104559209B (en) * 2015-01-05 2017-01-18 山东理工大学 Method for improving hydrophily and flexibility of polypeptide membrane by polycarbamate and polyethylene glycol
CN104497590B (en) * 2015-01-05 2017-02-08 山东理工大学 Method for improving hydrophilicity and flexibility of polycaprolactone and polyacrylamide improved polypeptide film
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
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
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
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
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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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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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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