CN104559217B - A kind of method that PLA improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan - Google Patents
A kind of method that PLA improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan Download PDFInfo
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- CN104559217B CN104559217B CN201510014807.5A CN201510014807A CN104559217B CN 104559217 B CN104559217 B CN 104559217B CN 201510014807 A CN201510014807 A CN 201510014807A CN 104559217 B CN104559217 B CN 104559217B
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Abstract
The present invention discloses a kind of method that PLA improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan, using following steps：1）PLA list myristyl ether, solvent, condensing agent and the poly- peptide homopolymers of carboxy blocking are added in dry reactor, is reacted 3~4 days, obtain poly- peptide polylactic-acid block copolymer；2）Amino-terminated PLA list myristyl ether, solvent, condensing agent and carboxymethyl chitosan are added in dry reactor, is reacted 2~3 days, obtain carboxymethyl chitosan polylactic acid graft copolymer；3）Poly- peptide polylactic-acid block copolymer, carboxymethyl chitosan polylactic acid graft copolymer and solvent are added in dry reactor, after mixing 40~50 minutes, with the tape casting film forming and drying, object of the present invention is obtained.Preparation process is simple of the present invention, hydrophily and the compliance of gained Modified Membrane have large increase.
Description
Technical field
The present invention relates to a kind of method that PLA and carboxymethyl chitosan improve poly- peptide film hydrophily and compliance, 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
Skin etc. is made, but poly- peptide film is more stiff, lack hydrophily, so as to limit its application to a certain extent.It is poly-（D,L）Lactic acid has
There are preferable biocompatibility and biodegradability, it is softer.Carboxymethyl chitosan has preferable biocompatibility and life
Biodegradable, and with preferable hydrophily.Polylactic acid chain segment is first introduced poly- peptide segment and carboxymethyl chitosan respectively
Segment forms poly- peptide-polylactic-acid block copolymer and carboxymethyl chitosan-polylactic acid graft copolymer, then again by two kinds of copolymerization
Thing is mixed to form the blend with preferable compatibility, the poly- peptide film that is modified is obtained, so as to drastically increase the hydrophilic of poly- peptide film
Property and compliance.The research that current PLA and carboxymethyl chitosan are improved to poly- peptide film hydrophily and compliance is not yet
Appear in the newspapers.
The content of the invention
Preferably poly- peptide film hydrophily and compliance are entered it is an object of the invention to provide a kind of simple to operate and effect
The improved method of row.Its technical scheme is：
A kind of method that PLA improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan, it is characterised in that：Change
Property film in the molecular weight of poly- peptide segment be 80000~90000, the molecular weight of polylactic acid chain segment is 3000~4000, carboxymethyl shell
The molecular weight of glycan segment is 5000~6000；Its method of modifying uses following steps：
1）The synthesis of poly- peptide-polylactic-acid block copolymer：The PLA list ten of carboxy blocking is added in dry reactor
Tetraalkyl ether, solvent, condensing agent and poly- peptide homopolymers, under inert atmosphere, in 25~35 DEG C of stirring reactions 3~4 days, terminate anti-
Should, by filtering, dialysis, dry, object is obtained, wherein, poly- peptide homopolymers is using poly-（R- benzyls-Pidolidone ester）、
It is poly-（R- ethyl-L-glutamate esters）Or it is poly-（R- methyl-Pidolidone ester）；
2）The synthesis of carboxymethyl chitosan-polylactic acid graft copolymer：Amino-terminated gathering is added in dry reactor
Lactic acid list myristyl ether, solvent, condensing agent and carboxymethyl chitosan, under inert atmosphere, in 25~30 DEG C of stirring reactions 2~3
My god, terminating reaction by filtering, dialysis, is dried, and obtains object；
3）The preparation of the poly- peptide film that PLA is modified with carboxymethyl chitosan：Poly- peptide-poly- breast is added in dry reactor
Sour block copolymer, carboxymethyl chitosan-polylactic acid graft copolymer and solvent, it is mixed in 40~50 DEG C of stirrings under inert atmosphere
After closing 40~50 minutes, with the tape casting film forming and drying, object is obtained.
A kind of described PLA improves the method for poly- peptide film hydrophily and compliance, step 1 with carboxymethyl chitosan）
In, condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyls -1-（3- diformazan ammonia
Propyl group）Carbodiimide, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
A kind of described PLA improves the method for poly- peptide film hydrophily and compliance, step 1 with carboxymethyl chitosan）
In, PLA list myristyl ether is using poly-（D,L）Lactic acid list myristyl ether, PLA list myristyl ether and poly- peptide homopolymerization
The mol ratio of thing is 7~15:1；Condensing agent is 1.08~1.8 with the mol ratio of poly- peptide homopolymers:1.
A kind of described PLA improves the method for poly- peptide film hydrophily and compliance, step 2 with carboxymethyl chitosan）
In, condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyls -1-（3- diformazan ammonia
Propyl group）Carbodiimide, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:100 ml.
A kind of described PLA improves the method for poly- peptide film hydrophily and compliance, step 2 with carboxymethyl chitosan）
In, PLA list myristyl ether is using poly-（D,L）Lactic acid list myristyl ether, carboxymethyl chitosan uses carboxymethyl chitosan
（Carboxylated degree is 70%）, PLA list myristyl ether is 3~6 with the mol ratio of carboxymethyl chitosan:1；Condensing agent and carboxylic
The mol ratio of methyl chitosan is 1.08~1.8:1.
A kind of described PLA improves the method for poly- peptide film hydrophily and compliance, step 3 with carboxymethyl chitosan）
In, mass percent of the carboxymethyl chitosan-polylactic acid graft copolymer in Modified Membrane is 1~4%, and solvent uses 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 PLA described in improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan, using amidatioon
Reaction and blending two kinds of means, it is simple to operate, be easy to grasp；
2. the poly- peptide Modified Membrane hydrophily described in is greatly improved with compliance.
Specific embodiment
Embodiment 1
1）The synthesis of poly- peptide-polylactic-acid block copolymer
16.1 grams are added in dry reactor to gather（R- benzyls-Pidolidone ester）（Molecular weight is 80000）With 7 grams of carboxylics
The PLA list myristyl ether of base end-blocking（Molecular weight is 3000）, 300 ml dimethyl sulfoxide (DMSO)s are added, add 0.048 gramN,N’- dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 3 days, terminating reaction, by filtering, dialysis, dry
It is dry, obtain object；
2）The synthesis of carboxymethyl chitosan-polylactic acid graft copolymer
3.5 grams of carboxymethyl chitosans are added in dry reactor（Molecular weight is 5000）The poly- breast amino-terminated with 9 grams
Sour list myristyl ether（Molecular weight is 3000）, 160 ml dimethyl sulfoxide (DMSO)s are added, add 0.165 gramN,N’- dicyclohexyl
Carbodiimide, under inert atmosphere, in terminating reaction after 25 DEG C of stirring reactions 2 days, by filtering, dialysis, dries, and obtains target
Thing；
3）The preparation of the poly- peptide film that PLA is modified with carboxymethyl chitosan
Add 12.5 grams of poly- peptide-polylactic-acid block copolymers and 45.8 ml dimethyl sulfoxide (DMSO)s molten in dry reactor
Agent, it is another to add the carboxymethyl chitosan-polylactic acid graft copolymer for accounting for Modified Membrane gross weight 1%, under inert atmosphere, stirred in 40 DEG C
Mixing 40 minutes is mixed, the tape casting film forming is used, dried in 50 DEG C of vacuum drying chambers, obtain object.
After tested：The hydrophilic rate and elongation at break of object of the present invention respectively than improve 13.3% He before modified
12.2%。
Embodiment 2
1）The synthesis of poly- peptide-polylactic-acid block copolymer
16.3 grams are added in dry reactor to gather（R- ethyl-L-glutamate esters）（Molecular weight is 85000）With 7 grams of carboxyls
The PLA list myristyl ether of end-blocking（Molecular weight is 3500）, 305 ml dimethyl sulfoxide (DMSO)s are added, 0.031 gram of N is added,
N '-DIC, under inert atmosphere, in 29 DEG C of stirring reactions 4 days, terminating reaction by filtering, dialysis, was dried,
Obtain object；
2）The synthesis of carboxymethyl chitosan-polylactic acid graft copolymer
3 grams of carboxymethyl chitosans are added in dry reactor（Molecular weight is 5500）The PLA amino-terminated with 9 grams
Single myristyl ether（Molecular weight is 3500）, 155 ml dimethyl sulfoxide (DMSO)s are added, add 0.08 gramN,N’- diisopropyl carbon
Diimine, under inert atmosphere, in terminating reaction after 27 DEG C of stirring reactions 3 days, by filtering, dialysis, dries, and obtains object；
3）The preparation of the poly- peptide film that PLA is modified with carboxymethyl chitosan
Add 12.6 grams of poly- peptide-polylactic-acid block copolymers and 45.5 ml dimethyl sulfoxide (DMSO)s molten in dry reactor
Agent, it is another to add the carboxymethyl chitosan-polylactic acid graft copolymer for accounting for Modified Membrane gross weight 2%, under inert atmosphere, stirred in 45 DEG C
Mixing 45 minutes is mixed, the tape casting film forming is used, dried in 50 DEG C of vacuum drying chambers, obtain object.
After tested：The hydrophilic rate and elongation at break of object of the present invention respectively than improve 13.8% He before modified
13.3%。
Embodiment 3
1）The synthesis of poly- peptide-polylactic-acid block copolymer
16.5 grams are added in dry reactor to gather（R- methyl-Pidolidone ester）（Molecular weight is 90000）With 7 grams of carboxyls
The PLA list myristyl ether of end-blocking（Molecular weight is 4000）, 310 ml dimethyl sulfoxide (DMSO)s are added, add 0.046 gram of 3-
Ethyl -1-（3- dimethylaminopropyls）Carbodiimide, under inert atmosphere, in 35 DEG C of stirring reactions 3 days, terminating reaction, by filtering,
Dialyse, dry, obtain object；
2）The synthesis of carboxymethyl chitosan-polylactic acid graft copolymer
3.1 grams of carboxymethyl chitosans are added in dry reactor（Molecular weight is 6000）Amino-terminated with 9.2 grams is poly-
Lactic acid list myristyl ether（Molecular weight is 4000）, 158 ml dimethyl sulfoxide (DMSO)s are added, add 0.141 gram of 3- ethyls -1-
（3- dimethylaminopropyls）Carbodiimide, under inert atmosphere, in terminating reaction after 30 DEG C of stirring reactions 2 days, by filtering, dialysis,
Dry, obtain object；
3）The preparation of the poly- peptide film that PLA is modified with carboxymethyl chitosan
Add 12.8 grams of poly- peptide-polylactic-acid block copolymers and 45.4 ml dimethyl sulfoxide (DMSO)s molten in dry reactor
Agent, it is another to add the carboxymethyl chitosan-polylactic acid graft copolymer for accounting for Modified Membrane gross weight 4%, under inert atmosphere, stirred in 50 DEG C
Mixing 50 minutes is mixed, the tape casting film forming is used, dried in 50 DEG C of vacuum drying chambers, obtain object.
After tested：The hydrophilic rate and elongation at break of object of the present invention respectively than improve 14.7% He before modified
15.4%。
Claims (6)
1. a kind of method that PLA improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan, it is characterised in that：It is modified
The molecular weight of poly- peptide segment is 80000~90000 in film, and the molecular weight of polylactic acid chain segment is 3000~4000, carboxymethyl chitosan
The molecular weight of sugar chain section is 5000~6000；Its method of modifying uses following steps：
1）The synthesis of poly- peptide-polylactic-acid block copolymer：The PLA list tetradecane of carboxy blocking is added in dry reactor
Base ether, solvent, condensing agent and poly- peptide homopolymers, under inert atmosphere, in 25~35 DEG C of stirring reactions 3~4 days, terminating reaction was led to
Filter, dialyse, dry, obtain object, wherein, poly- peptide homopolymers is using poly-（γ-benzyl-Pidolidone ester）, it is poly-
（γ-ethyl-L-glutamate ester）Or it is poly-（γ-methyl-Pidolidone ester）；
2）The synthesis of carboxymethyl chitosan-polylactic acid graft copolymer：Amino-terminated PLA is added in dry reactor
Single myristyl ether, solvent, condensing agent and carboxymethyl chitosan, under inert atmosphere, in 25~30 DEG C of stirring reactions 2~3 days, eventually
Only react, by filtering, dialysis, dry, obtain object；
3）The preparation of the poly- peptide film that PLA is modified with carboxymethyl chitosan：Add poly- peptide-PLA embedding in dry reactor
Section copolymer, carboxymethyl chitosan-polylactic acid graft copolymer and solvent, under inert atmosphere, in 40~50 DEG C of stirring mixing 40
After~50 minutes, with the tape casting film forming and drying, object is obtained.
2. a kind of PLA according to claim 1 improves the side of poly- peptide film hydrophily and compliance with carboxymethyl chitosan
Method, it is characterised in that：Step 1）In, condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC
Or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:
100 mL。
3. a kind of PLA according to claim 1 improves the side of poly- peptide film hydrophily and compliance with carboxymethyl chitosan
Method, it is characterised in that：Step 1）In, PLA list myristyl ether is using poly-（D,L）Lactic acid list myristyl ether, PLA list
Myristyl ether is 7~15 with the mol ratio of poly- peptide homopolymers:1；The mol ratio of condensing agent and poly- peptide homopolymers for 1.08~
1.8:1。
4. a kind of PLA according to claim 1 improves the side of poly- peptide film hydrophily and compliance with carboxymethyl chitosan
Method, it is characterised in that：Step 2）In, condensing agent uses N, N '-dicyclohexylcarbodiimide, N, N '-DIC
Or 3- ethyls -1-（3- dimethylaminopropyls）Carbodiimide, solvent uses dimethyl sulfoxide (DMSO), and reactant solution concentration is 5~15 g:
100 mL。
5. a kind of PLA according to claim 1 improves the side of poly- peptide film hydrophily and compliance with carboxymethyl chitosan
Method, it is characterised in that：Step 2）In, PLA list myristyl ether is using poly-（D,L）Lactic acid list myristyl ether, carboxymethyl shell
Glycan uses carboxymethyl chitosan（Carboxylated degree is 70%）, PLA list myristyl ether and carboxymethyl chitosan mole
Than being 3~6:1；Condensing agent is 1.08~1.8 with the mol ratio of carboxymethyl chitosan:1.
6. a kind of PLA according to claim 1 improves the side of poly- peptide film hydrophily and compliance with carboxymethyl chitosan
Method, it is characterised in that：Step 3）In, mass percent of the carboxymethyl chitosan-polylactic acid graft copolymer in Modified Membrane is 1
~4%, solvent uses dimethyl sulfoxide (DMSO), and mixture solution concentration is 25~35 g:100 mL.
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Citations (6)
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| CN103242536A (en) * | 2013-05-09 | 2013-08-14 | 山东理工大学 | Method for preparing polypeptide-polylactic acid-polyethyleneglycol dual-graft copolymer |
| 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 |
| CN103804915A (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 |
| 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 |
| 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 |
| CN103877584A (en) * | 2013-04-09 | 2014-06-25 | 青岛科技大学 | Preparation method for carboxymethyl chitosan polylactic acid chemical hydrogel drug carrier |
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2015
- 2015-01-12 CN CN201510014807.5A patent/CN104559217B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103877584A (en) * | 2013-04-09 | 2014-06-25 | 青岛科技大学 | Preparation method for carboxymethyl chitosan polylactic acid chemical hydrogel drug carrier |
| CN103242536A (en) * | 2013-05-09 | 2013-08-14 | 山东理工大学 | Method for preparing polypeptide-polylactic acid-polyethyleneglycol dual-graft copolymer |
| 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 |
| 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 |
| 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 |
| CN103804915A (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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