CN103865273A - Method for improving flexibility of polypeptide membrane by polypropylene glycol and poly-trimethylene carbonate - Google Patents
Method for improving flexibility of polypeptide membrane by polypropylene glycol and poly-trimethylene carbonate Download PDFInfo
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- CN103865273A CN103865273A CN201410084205.2A CN201410084205A CN103865273A CN 103865273 A CN103865273 A CN 103865273A CN 201410084205 A CN201410084205 A CN 201410084205A CN 103865273 A CN103865273 A CN 103865273A
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Abstract
The invention discloses a method for improving flexibility of a polypeptide membrane by polypropylene glycol and poly-trimethylene carbonate. The method comprises the following steps: (1) adding polypeptide homopolymer, diisocyanate, a catalyst and a solvent into a drying reactor, stirring to react for 40-50 minutes at 40-50 DEG C to obtain polypeptide homopolymer containing -NCO-terminated group; (2) adding the polypeptide homopolymer containing -NCO-terminated group, a catalyst and a solvent into the drying reactor, adding butoxypolypropylene glycol, and stirring to react for 50-60 minutes at 40-50 DEG C to obtain polypeptide-polypropylene glycol diblock copolymer; (3) adding the polypeptide-polypropylene glycol diblock copolymer, poly-trimethylene carbonate and a solvent into the drying reactor, stirring and mixing for 60-70 minutes at 40-50 DEG C, forming a membrane by using a tape casting method, and drying to obtain a target product. The preparation process is simple, and the flexibility of the 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.Polypropylene glycol and PTMC have good biocompatibility and biodegradability, soft and have each other a good blend.First polypropylene glycol segment is introduced to poly-peptide segment and formed poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock to improve the blend of poly-peptide, and then add poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock to form blend PTMC segment, make the poly-peptide film of modification, thereby greatly improved the kindliness of poly-peptide film.By polypropylene glycol and PTMC, 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 polypropylene glycol and PTMC 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 polypropylene glycol segment is 3000～5000, and the molecular weight of PTMC segment is 5000～6000; 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 40～50 ℃ of stirring reactions 40～50 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) poly-peptide-polypropylene glycol 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 polypropylene glycol monobutyl 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 polypropylene glycol and PTMC modification: add poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, PTMC 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 polypropylene glycol and PTMC 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 polypropylene glycol and PTMC 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 1,2-ethylene dichloride or 1,1,2-trichloroethane, reactant solution concentration is 5～15 g:100 ml.
Described a kind of polypropylene glycol and PTMC are improved the method for poly-peptide film kindliness, step 2) in, polypropylene glycol monobutyl ether is 15～25:1 with the mol ratio of the poly-peptide homopolymer that contains end-NCO group.
Described a kind of polypropylene glycol and PTMC are improved the method for poly-peptide film kindliness, step 2) in, solvent adopts 1,2-ethylene dichloride or 1,1,2-trichloroethane, catalyzer adopts dibutyl tin laurate, catalyzer add-on is polypropylene glycol monobutyl 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 polypropylene glycol and PTMC are improved the method for poly-peptide film kindliness, in step 3), the mass percent of PTMC in modified membrane is 2～4%, solvent adopts 1,2-ethylene dichloride or 1,1,2-trichloroethane, mixture solution concentration is 25～30 g:100 ml.
Compared with prior art, its advantage is in the present invention:
1, described polypropylene glycol and PTMC 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 286 ml 1,2-ethylene dichloride solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 3 ‰, under inert atmosphere, in 40 ℃ of stirring reactions 40 minutes, termination reaction, removed excessive vulcabond by dialysis method and obtains target compound;
2) poly-peptide-polypropylene glycol 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, polypropylene glycol monobutyl ether and 420 ml 1 that 11.8 gram molecular weights are 3000,2-ethylene dichloride solvent, 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 polypropylene glycol and PTMC modification:
In dry reactor, add 12 grams of poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks and 47 ml 1,2-ethylene dichloride solvent, separately add the PTMC (molecular weight is 5000) that accounts for modified membrane gross weight 2%, 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 12.6% 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 215 ml 1,1,2-trichloroethane solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 4 ‰, under inert atmosphere, in 45 ℃ of stirring reactions 45 minutes, termination reaction, removes excessive vulcabond by dialysis method and obtains target compound;
2) poly-peptide-polypropylene glycol 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, polypropylene glycol monobutyl ether and 410 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 polypropylene glycol and PTMC modification:
In dry reactor, add 12 grams of poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks and 45 ml 1,1,2-trichloroethane solvent, separately add the PTMC (molecular weight is 5500) that accounts for modified membrane gross weight 3%, 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 15.8% 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 155 ml 1,2-ethylene dichloride solvent, separately add the dibutyl tin laurate of above-mentioned reactant gross weight 5 ‰, under inert atmosphere, in 50 ℃ of stirring reactions 50 minutes, termination reaction, removed excessive vulcabond by dialysis method and obtains target compound;
2) poly-peptide-polypropylene glycol 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, polypropylene glycol monobutyl ether and 352 ml 1 that 20.1 gram molecular weights are 5000,2-ethylene dichloride solvent, 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 polypropylene glycol and PTMC modification:
In dry reactor, add 12 grams of poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblocks and 44 ml 1,2-ethylene dichloride solvent, separately add the PTMC (molecular weight is 6000) 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 16.8% before than modification.
Claims (6)
1. a polypropylene glycol and PTMC 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 polypropylene glycol segment is 3000～5000, and the molecular weight of PTMC segment is 5000～6000; 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 40～50 ℃ of stirring reactions 40～50 minutes, termination reaction, remove excessive vulcabond by dialysis method, obtain target compound;
2) poly-peptide-polypropylene glycol 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 polypropylene glycol monobutyl 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 polypropylene glycol and PTMC modification: add poly-peptide-polypropylene glycol Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock, PTMC 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 polypropylene glycol according to claim 1 and PTMC 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 polypropylene glycol according to claim 1 and PTMC 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 1,2-ethylene dichloride or 1,1,2-trichloroethane, reactant solution concentration is 5～15 g:100 ml.
4. a kind of polypropylene glycol according to claim 1 and PTMC are improved the method for poly-peptide film kindliness, it is characterized in that: step 2) in, polypropylene glycol monobutyl ether is 15～25:1 with the mol ratio of the poly-peptide homopolymer that contains end-NCO group.
5. a kind of polypropylene glycol according to claim 1 and PTMC are improved the method for poly-peptide film kindliness, it is characterized in that: step 2) in, solvent adopts 1,2-ethylene dichloride or 1,1,2-trichloroethane, catalyzer adopts dibutyl tin laurate, catalyzer add-on is polypropylene glycol monobutyl 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 polypropylene glycol according to claim 1 and PTMC are improved the method for poly-peptide film kindliness, it is characterized in that: in step 3), the mass percent of PTMC in modified membrane is 2～4%, solvent adopts 1,2-ethylene dichloride or 1,1,2-trichloroethane, mixture solution concentration is 25～30 g:100 ml.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977945A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PTMC |
| 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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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106977945A (en) * | 2017-05-25 | 2017-07-25 | 山东理工大学 | A kind of method that polypropylene glycol improves polypropylene sorrel water resistance and compliance with PTMC |
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