CN104559211B - A kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid - Google Patents
A kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid Download PDFInfo
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- CN104559211B CN104559211B CN201510004833.XA CN201510004833A CN104559211B CN 104559211 B CN104559211 B CN 104559211B CN 201510004833 A CN201510004833 A CN 201510004833A CN 104559211 B CN104559211 B CN 104559211B
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Abstract
The present invention discloses a kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, using following steps：1）Add PPDO monododecyl ether, solvent, condensing agent and poly- peptide homopolymer, the stirring reaction 3～4 days of carboxy blocking in dry reactor, obtain poly- peptide PPDO block copolymer；2）Add amino-terminated PPDO monododecyl ether, solvent, condensing agent and polyacrylic acid, stirring reaction 2～3 days in dry reactor, obtain polyacrylic acid PPDO graft copolymer；3）Poly- peptide PPDO block copolymer, polyacrylic acid PPDO graft copolymer and solvent is added in dry reactor, after stirring mixing 40～50 minutes, with the tape casting film forming and dry, obtain object of the present invention.Preparation process is simple of the present invention, the hydrophilic of gained Modified Membrane and compliance have large increase.
Description
Technical field
The present invention relates to a kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid,
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.Gather to dioxocyclohex
Ketone has preferable biocompatibility and biodegradability, soft.Polyacrylic acid have preferable biocompatibility and
Biodegradability, and there is preferable hydrophilic.First PPDO segment is introduced poly- peptide segment respectively and gather
Acrylate forms poly- peptide-PPDO block copolymer and poly acrylic acid-poly Lanthanum Isopropoxide graft copolymerization
Then two kinds of copolymers are mixed to form the blend with the preferable compatibility by thing again, and modified poly- peptide film is obtained, thus greatly
Improve hydrophilic and the compliance of poly- peptide film.Use at present PPDO and polyacrylic acid to poly- peptide film hydrophilic and soft
There is not been reported for the pliable research improving.
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 method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, its feature exists
In：In Modified Membrane, the molecular weight of poly- peptide segment is 80000～90000, the molecular weight of PPDO segment is 3000～
4000, the molecular weight of polyacrylic acid segment is 5000～6000；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-PPDO block copolymer：The poly- of carboxy blocking is added in dry reactor
Lanthanum Isopropoxide monododecyl ether, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, anti-in 20～30 DEG C of stirrings
Answer 3～4 days, terminating reaction, by filtering, dialysing, be dried, obtain object, wherein, poly- peptide homopolymer is using poly-（R- benzene first
Base-L-Glutamic Acid ester）, poly-（R- ethyl-L-glutamate ester）Or it is poly-（R- methyl-L-Glutamic Acid ester）；
2）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer：Add amino-terminated in dry reactor
PPDO monododecyl ether, solvent, condensing agent and polyacrylic acid, under inert atmosphere, stir in 25～35 DEG C
Reaction 2～3 days, terminating reaction, by filtering, dialysing, be dried, obtain object；
3）PPDO and the preparation of polyacrylic acid modified poly- peptide film：Add in dry reactor poly- peptide-
PPDO block copolymer, poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer and solvent, under inert atmosphere,
After 40～50 DEG C of stirring mixing 40～50 minutes, with the tape casting film forming and dry, obtain object.
The method that a kind of described PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step
1）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- diformazan
Aminopropyl）Carbodiimide, solvent adopts dimethylformamide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step
1）In, PPDO monododecyl ether is 7～15 with the mol ratio of poly- peptide homopolymer:1；Condensing agent and poly- peptide homopolymerization
The mol ratio of thing is 1.08～1.8:1.
The method that a kind of described PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step
2）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- diformazan
Aminopropyl）Carbodiimide, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step
2）In, PPDO monododecyl ether and polyacrylic mol ratio are 3～6:1；Condensing agent with polyacrylic
Mol ratio is 1.08～1.8:1.
The method that a kind of described PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid, step
3）In, mass percent in Modified Membrane for the poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer is 1～4%, and solvent adopts
Dimethyl sulfoxide, mixture solution concentration is 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention：
1. the method that the PPDO described in improves poly- peptide film hydrophilic and compliance with polyacrylic acid, using acyl
Aminating reaction and blending two 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-PPDO block copolymer
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 PPDO monododecyl ether of base end-blocking（Molecular weight is 3000）, add 300 ml dimethylformamides, then plus
Enter 0.048 gramN,N’- dicyclohexylcarbodiimide, under inert atmosphere, in 20 DEG C of stirring reactions 3 days, terminating reaction, by mistake
Filter, dialyse, be dried, obtain object；
2）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
3.5 grams of polyacrylic acid are added in dry reactor（Molecular weight is 5000）Amino-terminated with 9 grams gathers to dioxy
Ketohexamethylene monododecyl ether（Molecular weight is 3000）, add 160 ml dimethyl sulfoxide, add 0.165 gramN,N’- bicyclo-
Hexyl carbodiimide, under inert atmosphere, terminating reaction after 25 DEG C of stirring reactions 2 days, by filtering, dialysis, it is dried, obtain mesh
Mark thing；
3）PPDO and the preparation of polyacrylic acid modified poly- peptide film
12.5 grams of poly- peptide-PPDO block copolymers and 45.8 ml dimethyl are added in dry reactor
Sulfoxide solvent, another addition accounts for the poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer of Modified Membrane gross weight 1%, inert atmosphere
Under, in 40 DEG C of stirring mixing 40 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying ovens, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.7% He before modified
13.1%.
Embodiment 2
1）The synthesis of poly- peptide-PPDO block copolymer
Add 16.3 grams to gather in dry reactor（R- ethyl-L-glutamate ester）（Molecular weight is 85000）With 7 grams of carboxyls
The PPDO monododecyl ether of end-blocking（Molecular weight is 3500）, add 305 ml dimethylformamides, add
0.031 gram of N, N '-DIC, under inert atmosphere, in 25 DEG C of stirring reactions 4 days, terminating reaction, by filtering,
Dialyse, be dried, obtain object；
2）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
3 grams of polyacrylic acid are added in dry reactor（Molecular weight is 5500）Amino-terminated with 9 grams gathers to dioxy ring
Hexanone monododecyl ether（Molecular weight is 3500）, add 155 ml dimethyl sulfoxide, add 0.08 gramN,N’- diisopropyl
Base carbodiimide, under inert atmosphere, terminating reaction after 28 DEG C of stirring reactions 3 days, by filtering, dialysis, it is dried, obtain target
Thing；
3）PPDO and the preparation of polyacrylic acid modified poly- peptide film
12.6 grams of poly- peptide-PPDO block copolymers and 45.5 ml dimethyl are added in dry reactor
Sulfoxide solvent, another addition accounts for the poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer of Modified Membrane gross weight 2%, inert atmosphere
Under, in 45 DEG C of stirring mixing 45 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying ovens, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 13.2% He before modified
13.9%.
Embodiment 3
1）The synthesis of poly- peptide-PPDO block copolymer
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 PPDO monododecyl ether of end-blocking（Molecular weight is 4000）, add 310 ml dimethylformamides, add
0.046 gram of 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, under inert atmosphere, in 30 DEG C of stirring reactions 3 days, terminating reaction,
By filtering, dialysing, be dried, obtain object；
2）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer
3.1 grams of polyacrylic acid are added in dry reactor（Molecular weight is 6000）Amino-terminated with 9.2 grams gathers to two
Oxygen Ketohexamethylene monododecyl ether（Molecular weight is 4000）, add 158 ml dimethyl sulfoxide, add 0.141 gram of 3- ethyl-
1-（3- dimethylaminopropyl）Carbodiimide, under inert atmosphere, terminating reaction after 35 DEG C of stirring reactions 2 days, by filtering, thoroughly
Analyse, be dried, obtain object；
3）PPDO and the preparation of polyacrylic acid modified poly- peptide film
12.8 grams of poly- peptide-PPDO block copolymers and 45.4 ml dimethyl are added in dry reactor
Sulfoxide solvent, another addition accounts for the poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer of Modified Membrane gross weight 4%, inert atmosphere
Under, in 50 DEG C of stirring mixing 50 minutes, use the tape casting film forming, be dried in 50 DEG C of vacuum drying ovens, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 14.3% He before modified
14.8%.
Claims (6)
1. a kind of PPDO and polyacrylic acid improve poly- peptide film hydrophilic and compliance method it is characterised in that：
In Modified Membrane, the molecular weight of poly- peptide segment is 80000～90000, the molecular weight of PPDO segment is 3000～
4000, the molecular weight of polyacrylic acid segment is 5000～6000；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-PPDO block copolymer：Gathering to two of carboxy blocking is added in dry reactor
Oxygen Ketohexamethylene monododecyl ether, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, in 20～30 DEG C of stirring reactions 3～
4 days, terminating reaction, by filtering, dialysing, be dried, obtain object, wherein, poly- peptide homopolymer is using poly-（γ-benzyl-L-
Glutamate）, poly-（γ-ethyl-L-glutamate ester）Or it is poly-（γ-methyl-L-Glutamic Acid ester）；
2）The synthesis of poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer：Amino-terminated gathering is added in dry reactor
Lanthanum Isopropoxide monododecyl ether, solvent, condensing agent and polyacrylic acid, under inert atmosphere, in 25～35 DEG C of stirring reactions 2
～3 days, terminating reaction, by filtering, dialysing, be dried, obtain object；
3）PPDO and the preparation of polyacrylic acid modified poly- peptide film：Poly- peptide-poly- right is added in dry reactor
Dioxanone block copolymer, poly acrylic acid-poly Lanthanum Isopropoxide graft copolymer and solvent, under inert atmosphere, in 40
After～50 DEG C of stirring mixing 40～50 minutes, with the tape casting film forming and drying, obtain object, wherein, poly acrylic acid-poly is to two
Mass percent in Modified Membrane for the oxygen Ketohexamethylene graft copolymer is 1～4%.
2. a kind of PPDO according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 1）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-diisopropyl carbon two
Imines or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethylformamide, and reactant solution concentration is 5
～15 g:100 ml.
3. a kind of PPDO according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 1）In, PPDO monododecyl ether is 7 with the mol ratio of poly- peptide homopolymer
～15:1；Condensing agent is 1.08～1.8 with the mol ratio of poly- peptide homopolymer:1.
4. a kind of PPDO according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 2）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-diisopropyl carbon two
Imines or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethyl sulfoxide, reactant solution concentration be 5～
15 g:100 ml.
5. a kind of PPDO according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 2）In, PPDO monododecyl ether and polyacrylic mol ratio be 3～
6:1；Condensing agent and polyacrylic mol ratio are 1.08～1.8:1.
6. a kind of PPDO according to claim 1 and polyacrylic acid improve poly- peptide film hydrophilic and compliance
Method it is characterised in that：Step 3）In, solvent adopts dimethyl sulfoxide, and mixture solution concentration is 25～35 g:100
ml.
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| CN105732993A (en) * | 2016-02-29 | 2016-07-06 | 山东理工大学 | Preparation method of polyvinyl alcohol-polydioxanone-polypeptide double graft copolymer |
| CN105694060A (en) * | 2016-03-03 | 2016-06-22 | 山东理工大学 | Method for preparing polyvinyl alcohol-poly (p-dioxanone)-polypeptide dual-grafted copolymer |
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| CN103804916A (en) * | 2014-03-14 | 2014-05-21 | 山东理工大学 | Method for improving hydrophilicity of polypeptide membrane by using polylactic acid and polyacrylic acid |
| CN103865087A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| CN103865089A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
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| CN103865087A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| CN103865089A (en) * | 2014-03-10 | 2014-06-18 | 山东理工大学 | Method for improving flexibility of polypeptide membrane by polylactic acid and polydioxanone |
| CN103804916A (en) * | 2014-03-14 | 2014-05-21 | 山东理工大学 | Method for improving hydrophilicity of polypeptide membrane by using polylactic acid and polyacrylic acid |
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