CN104497590B - Method for improving hydrophilicity and flexibility of polycaprolactone and polyacrylamide improved polypeptide film - Google Patents
Method for improving hydrophilicity and flexibility of polycaprolactone and polyacrylamide improved polypeptide film Download PDFInfo
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- CN104497590B CN104497590B CN201510001225.3A CN201510001225A CN104497590B CN 104497590 B CN104497590 B CN 104497590B CN 201510001225 A CN201510001225 A CN 201510001225A CN 104497590 B CN104497590 B CN 104497590B
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- polycaprolactone
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Abstract
The invention discloses a method for improving the hydrophilicity and flexibility of a polycaprolactone and polyacrylamide improved polypeptide film. The method comprises the following steps of (1) adding carboxyl-terminated polycaprolactone monotridecyl ether, a solvent, a condensing agent and a polypeptide homopolymer into a drying reactor, and reacting for 3-4 days while stirring to obtain a polypeptide-polycaprolactone block copolymer; (2) adding isocyanato-terminated polycaprolactone monotridecyl ether, a solvent, a catalyst and polyacrylamide into the drying reactor, and reacting for 50-60 minutes while stirring to obtain a polyacrylamide-polycaprolactone grafted copolymer; and (3) adding the polypeptide-polycaprolactone block copolymer, the polyacrylamide-polycaprolactone grafted copolymer and a solvent into the drying reactor, stirring and mixing for 40-50 minutes, then, forming a film by using a tape casting method, and drying to obtain a target product, namely the polycaprolactone and polyacrylamide improved polypeptide film. The preparation process is simple; and the hydrophilicity and flexibility of the obtained improved film are greatly improved.
Description
Technical field
The present invention relates to a kind of method that polycaprolactone improves poly- peptide film hydrophilic and compliance with polyacrylamide, belong to
Field of polymer film preparing technology.
Background technology
Poly- peptide is a kind of biomaterial with good biocompatibility and biodegradability, and poly- peptide film can be used as people
Make skin etc., but poly- peptide film is more stiff, lack hydrophilic, thus limiting its application to a certain extent.Polycaprolactone has
Preferably biocompatibility and biodegradability, soft.Polyacrylamide has preferable biocompatibility and biology
Degradability, and there is preferable hydrophilic.First polycaprolactone segment is introduced poly- peptide segment and polyacrylamide chain respectively
Section forms poly- peptide-polycaprolactone block polymer and polyacrylamide-polycaprolactone graft copolymer, then again by two kinds of copolymerization
Thing is mixed to form the blend with the preferable compatibility, modified poly- peptide film is obtained, thus drastically increasing the hydrophilic of poly- peptide film
Property and compliance.The research with polycaprolactone and polyacrylamide, poly- peptide film hydrophilic and compliance being improved at present is not yet
Appear in the newspapers.
Content of the invention
It is an object of the invention to provide one kind is simple to operate and effect is preferably entered to poly- peptide film hydrophilic and compliance
The improved method of row.Its technical scheme is：
A kind of polycaprolactone and polyacrylamide improve poly- peptide film hydrophilic and compliance method it is characterised in that：Change
Property film in the molecular weight of poly- peptide segment be 80000～90000, the molecular weight of polycaprolactone segment is 3000～4000, polypropylene
The molecular weight of amide segment is 5000～6000；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-polycaprolactone block polymer：The polycaprolactone of carboxy blocking is added in dry reactor
Single tridecyl ether, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, in 20～30 DEG C of stirring reactions 3～4 days, terminate
Reaction, by filtering, dialysing, be dried, obtains object, and wherein, poly- peptide homopolymer is using poly-（R- benzyl-L-Glutamic Acid
Ester）, poly-（R- ethyl-L-glutamate ester）Or it is poly-（R- methyl-L-Glutamic Acid ester）；
2）The synthesis of polyacrylamide-polycaprolactone graft copolymer：Isocyano end-blocking is added in dry reactor
Polycaprolactone list tridecyl ether, solvent, catalyst and polyacrylamide, under inert atmosphere, in 60～65 DEG C of stirring reactions
50～60 minutes, terminating reaction, by filtering, dialysing, be dried, obtain object；
3）The preparation of the polycaprolactone poly- peptide film modified with polyacrylamide：Add in dry reactor poly- peptide-poly- oneself
Lactone block copolymer, polyacrylamide-polycaprolactone graft copolymer and solvent, under inert atmosphere, stir in 40～50 DEG C
After mixing 40～50 minutes, with the tape casting film forming and dry, obtain object.
The method that a kind of described polycaprolactone improves poly- peptide film hydrophilic and compliance with polyacrylamide, step 1）
In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- diformazan ammonia
Propyl group）Carbodiimide, solvent adopts dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described polycaprolactone improves poly- peptide film hydrophilic and compliance with polyacrylamide, step 1）
In, polycaprolactone list tridecyl ether is 7～15 with the mol ratio of poly- peptide homopolymer:1；Condensing agent and poly- peptide homopolymer mole
Than for 1.08～1.8:1.
The method that a kind of described polycaprolactone improves poly- peptide film hydrophilic and compliance with polyacrylamide, step 2）
In, solvent adopts dimethylformamide, and catalyst adopts dibutyl tin laurate, and catalyst charge is polycaprolactone list ten
Trialkyl ether and 3～the 5 ‰ of polyacrylamide gross weight.
The method that a kind of described polycaprolactone improves poly- peptide film hydrophilic and compliance with polyacrylamide, step 2）
In, polycaprolactone list tridecyl ether is 3～7 with the mol ratio of polyacrylamide:1, reactant solution concentration is 5～15 g:
100 ml.
The method that a kind of described polycaprolactone improves poly- peptide film hydrophilic and compliance with polyacrylamide, step 3）
In, polyacrylamide-mass percent in Modified Membrane for the polycaprolactone graft copolymer is 1～4%, and solvent adopts dimethyl
Methanamide, mixture solution concentration is 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention：
1. the method that the polycaprolactone described in improves poly- peptide film hydrophilic and compliance with polyacrylamide, using amidatioon
Reaction, additive reaction and blending three kinds of means, simple to operate, be easy to grasp；
2. the poly- peptide Modified Membrane hydrophilic described in is greatly improved with compliance.
Specific embodiment
Embodiment 1
1）The synthesis of poly- peptide-polycaprolactone block polymer
Add 16.1 grams to gather in dry reactor（R- benzyl-L-Glutamic Acid ester）（Molecular weight is 80000）With 7 grams of carboxylics
The polycaprolactone list tridecyl ether of base end-blocking（Molecular weight is 3000）, add 300 ml dimethylformamides, add
0.048 gramN,N’- dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 3 days, terminating reaction, by filtering,
Dialyse, be dried, obtain object；
2）The synthesis of polyacrylamide-polycaprolactone graft copolymer
3.5 grams of polyacrylamides are added in dry reactor（Molecular weight is 5000）With gathering of 9 grams of isocyano end-blockings
Caprolactone list tridecyl ether（Molecular weight is 3000）With 160 ml dimethylformamides, add above-mentioned reactant gross weight
3 ‰ dibutyl tin laurate, under inert atmosphere, in 60 DEG C of stirring reactions 50 minutes, terminating reaction, by filtering, dialysis,
It is dried, obtain object；
3）The preparation of the polycaprolactone poly- peptide film modified with polyacrylamide
12.5 grams of poly- peptide-polycaprolactone block polymers and 45.8 ml dimethylformamides are added in dry reactor
Solvent, another addition accounts for the polyacrylamide-polycaprolactone graft copolymer of Modified Membrane gross weight 1%, under inert atmosphere, in 40 DEG C
Stirring mixing 40 minutes, uses the tape casting film forming, is dried, obtains object in 50 DEG C of vacuum drying ovens.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 11.8% He before modified
12.2%.
Embodiment 2
1）The synthesis of poly- peptide-polycaprolactone block polymer
Add 16.3 grams to gather in dry reactor（R- ethyl-L-glutamate ester）（Molecular weight is 85000）With 7 grams of carboxyls
The polycaprolactone list tridecyl ether of end-blocking（Molecular weight is 3500）, add 305 ml dimethylformamides, add 0.031
Gram N, N '-DIC, under inert atmosphere, in 25 DEG C of stirring reactions 4 days, terminating reaction, by filtering, dialysis,
It is dried, obtain object；
2）The synthesis of polyacrylamide-polycaprolactone graft copolymer
3.5 grams of polyacrylamides are added in dry reactor（Molecular weight is 5500）With gathering of 9 grams of isocyano end-blockings
Caprolactone list tridecyl ether（Molecular weight is 3500）With 160 ml dimethylformamides, add above-mentioned reactant gross weight
4 ‰ dibutyl tin laurate, under inert atmosphere, in 62 DEG C of stirring reactions 55 minutes, terminating reaction, by filtering, dialysis,
It is dried, obtain object；
3）The preparation of the polycaprolactone poly- peptide film modified with polyacrylamide
12.6 grams of poly- peptide-polycaprolactone block polymers and 45.5 ml dimethylformamides are added in dry reactor
Solvent, another addition accounts for the polyacrylamide-polycaprolactone graft copolymer of Modified Membrane gross weight 2%, under inert atmosphere, in 45 DEG C
Stirring mixing 45 minutes, uses the tape casting film forming, is dried, obtains object in 50 DEG C of vacuum drying ovens.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.6% He before modified
13.3%.
Embodiment 3
1）The synthesis of poly- peptide-polycaprolactone block polymer
Add 16.5 grams to gather in dry reactor（R- methyl-L-Glutamic Acid ester）（Molecular weight is 90000）With 7 grams of carboxyls
The polycaprolactone list tridecyl ether of end-blocking（Molecular weight is 4000）, add 310 ml dimethylformamides, add 0.046
Gram 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction, passes through
Filter, dialyse, be dried, obtain object；
2）The synthesis of polyacrylamide-polycaprolactone graft copolymer
3.5 grams of polyacrylamides are added in dry reactor（Molecular weight is 6000）With gathering of 9 grams of isocyano end-blockings
Caprolactone list tridecyl ether（Molecular weight is 4000）With 160 ml dimethylformamides, add above-mentioned reactant gross weight
5 ‰ dibutyl tin laurate, under inert atmosphere, in 65 DEG C of stirring reactions 60 minutes, terminating reaction, by filtering, dialysis,
It is dried, obtain object；
3）The preparation of the polycaprolactone poly- peptide film modified with polyacrylamide
12.8 grams of poly- peptide-polycaprolactone block polymers and 45.4 ml dimethylformamides are added in dry reactor
Solvent, another addition accounts for the polyacrylamide-polycaprolactone graft copolymer of Modified Membrane gross weight 4%, under inert atmosphere, in 50 DEG C
Stirring mixing 50 minutes, uses the tape casting film forming, is dried, obtains object in 50 DEG C of vacuum drying ovens.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 13.8% He before modified
14.9%.
Claims (6)
1. a kind of polycaprolactone and polyacrylamide improve poly- peptide film hydrophilic and compliance method it is characterised in that：Modified
In film, the molecular weight of poly- peptide segment is 80000～90000, and the molecular weight of polycaprolactone segment is 3000～4000, polyacrylamide
The molecular weight of amine segment is 5000～6000；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-polycaprolactone block polymer：The polycaprolactone list ten of carboxy blocking is added in dry reactor
Trialkyl ether, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, in 20～30 DEG C of stirring reactions 3～4 days, terminate anti-
Should, by filtering, dialysing, be dried, obtain object, wherein, poly- peptide homopolymer is using poly-（γ-benzyl-L-Glutamic Acid ester）、
Poly-（γ-ethyl-L-glutamate ester）Or it is poly-（γ-methyl-L-Glutamic Acid ester）；
2）The synthesis of polyacrylamide-polycaprolactone graft copolymer：The poly- of isocyano end-blocking is added in dry reactor
Caprolactone list tridecyl ether, solvent, catalyst and polyacrylamide, under inert atmosphere, in 60～65 DEG C of stirring reactions 50～
60 minutes, terminating reaction, by filtering, dialysing, be dried, obtain object；
3）The preparation of the polycaprolactone poly- peptide film modified with polyacrylamide：Poly- peptide-polycaprolactone is added in dry reactor
Block copolymer, polyacrylamide-polycaprolactone graft copolymer and solvent, under inert atmosphere, in 40～50 DEG C of stirring mixing
After 40～50 minutes, with the tape casting film forming and dry, obtain object, wherein, polyacrylamide-polycaprolactone graft copolymer
Mass percent in Modified Membrane is 1～4%.
2. a kind of polycaprolactone according to claim 1 and polyacrylamide improve the side of poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 1）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC
Or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethylformamide, and reactant solution concentration is 5～15
g:100 ml.
3. a kind of polycaprolactone according to claim 1 and polyacrylamide improve the side of poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 1）In, polycaprolactone list tridecyl ether is 7～15 with the mol ratio of poly- peptide homopolymer:1；Condensation
Agent is 1.08～1.8 with the mol ratio of poly- peptide homopolymer:1.
4. a kind of polycaprolactone according to claim 1 and polyacrylamide improve the side of poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 2）In, solvent adopts dimethylformamide, and catalyst adopts dibutyl tin laurate, catalyst
Addition is 3～the 5 ‰ of polycaprolactone list tridecyl ether and polyacrylamide gross weight.
5. a kind of polycaprolactone according to claim 1 and polyacrylamide improve the side of poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 2）In, polycaprolactone list tridecyl ether is 3～7 with the mol ratio of polyacrylamide:1, reaction
Thing solution concentration is 5～15 g:100 ml.
6. a kind of polycaprolactone according to claim 1 and polyacrylamide improve the side of poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 3）In, solvent adopts dimethylformamide, and mixture solution concentration is 25～35 g:100 ml.
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