CN103819700A - Method for improving flexibility of polypeptide film with poly trimethylene carbonate and polytetrahydrofuran ether glycol - Google Patents
Method for improving flexibility of polypeptide film with poly trimethylene carbonate and polytetrahydrofuran ether glycol Download PDFInfo
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- CN103819700A CN103819700A CN201410080561.7A CN201410080561A CN103819700A CN 103819700 A CN103819700 A CN 103819700A CN 201410080561 A CN201410080561 A CN 201410080561A CN 103819700 A CN103819700 A CN 103819700A
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Abstract
The invention discloses a method for improving the flexibility of a polypeptide film with poly trimethylene carbonate and polytetrahydrofuran ether glycol. The method comprises the following steps: (1) adding polypeptide homopolymers, diisocyanate, catalysts and solvents into a drying reactor and reacting under the temperature of 50-55 DEG for 40-60 minutes to obtain a polypeptide homopolymer that contains end-NCO groups; (2) adding the polypeptide homopolymer that contains end-NCO groups, catalysts and solvents into the drying reactor, further adding poly trimethylene carbonate monododecyl ether, and reacting under the temperature of 40-50 DEG for 50-60 minutes to obtain a polypeptide-poly trimethylene carbonate diblock copolymer; (3) adding the polypeptide-poly trimethylene carbonate diblock copolymer, polytetrahydrofuran ether glycol and solvents into the drying reactor, reacting under the temperature of 40-50 DEG for 60-70 minutes, and film forming and drying by a tape casting to obtain the target object provided by the invention. According to the invention, the preparation technology is simple, and the flexibility of the obtained modified film 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.PTMC and PTMG have good biocompatibility and biodegradability, soft and have each other a good blend.First PTMC segment is introduced to poly-peptide segment and formed poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock to improve the blend of poly-peptide, and then add poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock to form blend PTMG segment, make the poly-peptide film of modification, thereby greatly improved the kindliness of poly-peptide film.By PTMC and PTMG, poly-peptide film kindliness is carried out to improved research at present and there is not yet report.
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:
A kind of PTMC and PTMG are improved the method for 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 PTMC segment is 3000～5000, and the molecular weight of PTMG segment is 4000～5000; Its method of modifying adopts following steps:
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group: add poly-peptide homopolymer, vulcabond, catalysts and solvents in dry reactor, under inert atmosphere, in 50～55 ℃ of stirring reactions 40～60 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is synthetic: in dry reactor, add the poly-peptide homopolymer, the catalysts and solvents that contain end-NCO group, add again PTMC monododecyl ether, under inert atmosphere, in 40～50 ℃ of stirring reactions 50～60 minutes, termination reaction, obtains target compound by filtering, dialyse, being dried;
3) preparation of the poly-peptide film of PTMC and PTMG modification: add poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, PTMG and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 60～70 minutes in 40～50 ℃, by casting method film forming dry, obtain target compound.
Described a kind of PTMC and PTMG are improved the method for 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), vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and poly-peptide homopolymer is 15～25:1.
Described a kind of PTMC and PTMG are improved the method for poly-peptide film kindliness, in step 1), catalyzer adopts dibutyl tin laurate, add-on is 3～5 ‰ of poly-peptide homopolymer and vulcabond gross weight, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5～15 g:100 ml.
Described a kind of PTMC and PTMG are improved the method for poly-peptide film kindliness, step 2) in, PTMC monododecyl ether is 15～25:1 with the mol ratio of the poly-peptide homopolymer that contains end-NCO group.
Described a kind of PTMC and PTMG are improved the method for poly-peptide film kindliness, step 2) in, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), catalyzer adopts dibutyl tin laurate, and catalyzer add-on is PTMC monododecyl ether and 3～5 ‰ of the poly-peptide homopolymer gross weight that contains end-NCO group, and reactant solution concentration is 5～15 g:100 ml.
Described a kind of PTMC and PTMG are improved the method for poly-peptide film kindliness, in step 3), the mass percent of PTMG in modified membrane is 1～4%, 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 PTMC and PTMG are improved the method for poly-peptide film kindliness, adopt block 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) synthesizing of the poly-peptide homopolymer that contains end-NCO group:
In dry reactor, add 20 gram molecular weights be 60000 poly-(r-phenmethyl-Pidolidone ester), 0.9 gram 2,4-tolylene diisocyanate and 280 ml dimethyl sulfoxide solvents, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 50 ℃ of stirring reactions 40 minutes, termination reaction, removes excessive vulcabond by dialysis method and obtains target compound;
2) poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is synthetic:
In dry reactor, add 15 grams containing poly-(r-phenmethyl-Pidolidone ester) of end-NCO group, PTMC monododecyl ether and the 420 ml dimethyl sulfoxide solvents that 11.8 gram molecular weights are 3000, add again the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 40 ℃ of stirring reactions 50 minutes, termination reaction, obtains target compound by filtering, dialyse, being dried;
3) preparation of the poly-peptide film of PTMC and PTMG modification:
In dry reactor, add 12 grams of poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks and 47 ml dimethyl sulfoxide solvents, separately add the PTMG (molecular weight is 4000) that accounts for modified membrane gross weight 1%, under inert atmosphere, be uniformly mixed 60 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 12.4% before than modification.
embodiment 2
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group:
In dry reactor, add 20 gram molecular weights be 70000 poly-(r-ethyl-Pidolidone ester), 1.02 gram 2,4-tolylene diisocyanate and 217 ml 1,1,2-trichloroethane solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 52 ℃ of stirring reactions 50 minutes, termination reaction, removes excessive vulcabond by dialysis method and obtains target compound;
2) poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is synthetic:
In dry reactor, add 15 grams containing poly-(r-ethyl-Pidolidone ester) of end-NCO group, PTMC monododecyl ether and 430 ml 1 that 17.1 gram molecular weights are 4000,1,2-trichloroethane solvent, add again the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 45 ℃ of stirring reactions 55 minutes, termination reaction, by filtering, dialysis, the dry target compound that obtains;
3) preparation of the poly-peptide film of PTMC and PTMG modification:
In dry reactor, add 12 grams of poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks and 45 ml 1,1,2-trichloroethane solvent, separately add the PTMG (molecular weight is 4500) that accounts for modified membrane gross weight 2%, under inert atmosphere, be uniformly mixed 65 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 14.6% before than modification.
embodiment 3
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group:
In dry reactor, add 20 gram molecular weights be 80000 poly-(r-methyl-Pidolidone ester), 0.96 gram 2,4-tolylene diisocyanate and 150 ml dimethyl sulfoxide solvents, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 55 ℃ of stirring reactions 60 minutes, termination reaction, removes excessive vulcabond by dialysis method and obtains target compound;
2) poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is synthetic:
In dry reactor, add 15 grams containing poly-(r-methyl-Pidolidone ester) of end-NCO group, PTMC monododecyl ether and the 355 ml dimethyl sulfoxide solvents that 20.1 gram molecular weights are 5000, add again the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 50 ℃ of stirring reactions 60 minutes, termination reaction, obtains target compound by filtering, dialyse, being dried;
3) preparation of the poly-peptide film of PTMC and PTMG modification:
In dry reactor, add 12 grams of poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks and 43 ml dimethyl sulfoxide solvents, separately add the PTMG (molecular weight is 5000) that accounts for modified membrane gross weight 4%, under inert atmosphere, be uniformly mixed 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 16.5% before than modification.
Claims (6)
1. a PTMC and PTMG are improved the method for 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 PTMC segment is 3000～5000, and the molecular weight of PTMG segment is 4000～5000; Its method of modifying adopts following steps:
1) synthesizing of the poly-peptide homopolymer that contains end-NCO group: add poly-peptide homopolymer, vulcabond, catalysts and solvents in dry reactor, under inert atmosphere, in 50～55 ℃ of stirring reactions 40～60 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock is synthetic: in dry reactor, add the poly-peptide homopolymer, the catalysts and solvents that contain end-NCO group, add again PTMC monododecyl ether, under inert atmosphere, in 40～50 ℃ of stirring reactions 50～60 minutes, termination reaction, obtains target compound by filtering, dialyse, being dried;
3) preparation of the poly-peptide film of PTMC and PTMG modification: add poly-peptide-PTMC Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, PTMG and solvent in dry reactor, under inert atmosphere, be uniformly mixed after 60～70 minutes in 40～50 ℃, by casting method film forming dry, obtain target compound.
2. a kind of PTMC according to claim 1 and PTMG are improved the method for 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), vulcabond adopts 2,4-tolylene diisocyanate, the mol ratio of vulcabond and poly-peptide homopolymer is 15～25:1.
3. a kind of PTMC according to claim 1 and PTMG are improved the method for poly-peptide film kindliness, it is characterized in that: in step 1), catalyzer adopts dibutyl tin laurate, add-on is 3～5 ‰ of poly-peptide homopolymer and vulcabond gross weight, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), reactant solution concentration is 5～15 g:100 ml.
4. a kind of PTMC according to claim 1 and PTMG are improved the method for poly-peptide film kindliness, it is characterized in that: step 2) in, PTMC monododecyl ether is 15～25:1 with the mol ratio of the poly-peptide homopolymer that contains end-NCO group.
5. a kind of PTMC according to claim 1 and PTMG are improved the method for poly-peptide film kindliness, it is characterized in that: step 2) in, solvent adopts 1,1,2-trichloroethane or dimethyl sulfoxide (DMSO), catalyzer adopts dibutyl tin laurate, and catalyzer add-on is PTMC monododecyl ether and 3～5 ‰ of the poly-peptide homopolymer gross weight that contains end-NCO group, and reactant solution concentration is 5～15 g:100 ml.
6. a kind of PTMC according to claim 1 and PTMG are improved the method for poly-peptide film kindliness, it is characterized in that: in step 3), the mass percent of PTMG in modified membrane is 1～4%, 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497593A (en) * | 2015-01-05 | 2015-04-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polyurethane and polyvinylpyrrolidone improved polypeptide film |
| CN104559225A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polytrimethylene carbonate and waterborne polyurethane |
| CN104559216A (en) * | 2015-01-06 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid |
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| CN102181061A (en) * | 2011-03-20 | 2011-09-14 | 山东理工大学 | Polyurethane-polypeptide graft copolymer and preparation method thereof |
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181061A (en) * | 2011-03-20 | 2011-09-14 | 山东理工大学 | Polyurethane-polypeptide graft copolymer and preparation method thereof |
| 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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497593A (en) * | 2015-01-05 | 2015-04-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polyurethane and polyvinylpyrrolidone improved polypeptide film |
| CN104497593B (en) * | 2015-01-05 | 2017-02-08 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polyurethane and polyvinylpyrrolidone improved polypeptide film |
| CN104559216A (en) * | 2015-01-06 | 2015-04-29 | 山东理工大学 | Method for improving hydrophily and flexibility of polypeptide membrane by poly(trimethylene carbonate) and polyacrylic acid |
| CN104559225A (en) * | 2015-01-12 | 2015-04-29 | 山东理工大学 | Method for improving hydrophilicity and flexibility of polypeptide film by polytrimethylene carbonate and waterborne polyurethane |
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