CN104559213B - A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol - Google Patents
A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol Download PDFInfo
- Publication number
- CN104559213B CN104559213B CN201510004846.7A CN201510004846A CN104559213B CN 104559213 B CN104559213 B CN 104559213B CN 201510004846 A CN201510004846 A CN 201510004846A CN 104559213 B CN104559213 B CN 104559213B
- Authority
- CN
- China
- Prior art keywords
- poly
- ptmc
- peptide
- polyethylene glycol
- block copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention discloses a kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, using following steps：1）Add PTMC monododecyl ether, solvent, condensing agent and the poly- peptide homopolymer of carboxy blocking in dry reactor, react 3～4 days, obtain poly- peptide PTMC block copolymer；2）Add PTMC monododecyl ether, solvent, condensing agent and the amino-terminated poly glycol monomethyl ether of carboxy blocking in dry reactor, react 2～3 days, obtain Polyethylene Glycol PTMC block copolymer；3）Poly- peptide PTMC block copolymer, Polyethylene Glycol PTMC block copolymer and solvent is added in dry reactor, after 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 PTMC improves the side of poly- peptide film hydrophilic and compliance with Polyethylene Glycol
Method, belongs 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.Polytrimethylene carbon
Acid esters has preferable biocompatibility and biodegradability, softer.Polyethylene Glycol have preferable biocompatibility and
Biodegradability, softer and there is good hydrophilic.First PTMC segment is introduced poly- peptide chain respectively
Section and Polyethylene Glycol segment form poly- peptide-PTMC block copolymer and polyethylene glycol trimethylene carbonic acid
Then two kinds of copolymers are mixed to form the blend with the preferable compatibility by ester block copolymer again, and modified poly- peptide film is obtained,
Thus drastically increasing hydrophilic and the compliance of poly- peptide film.Use PTMC and Polyethylene Glycol at present to poly- peptide
There is not been reported for the research that film hydrophilic and compliance improve.
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 PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, its feature exists
In：In Modified Membrane, the molecular weight of poly- peptide segment is 80000～92000, and the molecular weight of PTMC segment is 3000
～4000, the molecular weight of Polyethylene Glycol segment is 5000～7100；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-PTMC block copolymer：Carboxy blocking is added in dry reactor
PTMC monododecyl ether, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, stir in 25～30 DEG C
Mix reaction 3～4 days, terminating reaction, by filtering, dialysing, be dried, obtain object, 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 polyethylene glycol trimethylene carbonate block copolymer：Carboxyl envelope is added in dry reactor
The PTMC monododecyl ether at end, solvent, condensing agent and amino-terminated poly glycol monomethyl ether, indifferent gas
Under atmosphere, in 25～35 DEG C of stirring reactions 2～3 days, terminating reaction, by filtering, dialysis, it is dried, obtain object；
3）PTMC and the preparation of poly ethyldiol modified poly- peptide film：Add poly- in dry reactor
Peptide-PTMC block copolymer, polyethylene glycol trimethylene carbonate block copolymer and solvent, inertia
Under 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 PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, step
Rapid 1）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- bis-
First aminopropyl）Carbodiimide, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, step
Rapid 1）In, PTMC monododecyl ether is 8～16 with the mol ratio of poly- peptide homopolymer:1；Condensing agent and poly- peptide
The mol ratio of homopolymer is 1.08～1.8:1.
The method that a kind of described PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, step
Rapid 2）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 3- ethyl -1-（3- bis-
First aminopropyl）Carbodiimide, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5～15 g:100 ml.
The method that a kind of described PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, step
Rapid 2）In, PTMC monododecyl ether is 3～9 with the mol ratio of poly glycol monomethyl ether:1；Condensing agent with
The mol ratio of poly glycol monomethyl ether is 1.07～1.8:1.
The method that a kind of described PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, step
Rapid 3）In, mass percent in Modified Membrane for the polyethylene glycol trimethylene carbonate block copolymer is 1～4%, solvent
Using vinyl trichloride, mixture solution concentration is 25～35 g:100 ml.
Compared with prior art, its advantage is the present invention：
1. the method that the PTMC described in improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, adopts
Amidation process 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-PTMC block copolymer
Add 16.2 grams to gather in dry reactor（R- benzyl-L-Glutamic Acid ester）（Molecular weight is 80000）With 7 grams of carboxylics
The PTMC monododecyl ether of base end-blocking（Molecular weight is 3000）, add 300 ml dimethyl sulfoxide, then plus
Enter 0.048 gramN,N’- dicyclohexylcarbodiimide, under inert atmosphere, in 25 DEG C of stirring reactions 3 days, terminating reaction, by mistake
Filter, dialyse, be dried, obtain object；
2）The synthesis of polyethylene glycol trimethylene carbonate block copolymer
3 grams of amino-terminated poly glycol monomethyl ethers are added in dry reactor（Molecular weight is 5000）With 9 grams of carboxyls
The PTMC monododecyl ether of end-blocking（Molecular weight is 3000）, add 160 ml dimethyl sulfoxide, add
0.145 gramN,N’- dicyclohexylcarbodiimide, under inert atmosphere, terminating reaction after 25 DEG C of stirring reactions 2 days, by filtering,
Dialyse, be dried, obtain object；
3）PTMC and the preparation of poly ethyldiol modified poly- peptide film
Add 12.5 grams of poly- peptide-PTMC block copolymers and 45.8 ml 1,1 in dry reactor,
2- Separator, another addition accounts for the polyethylene glycol trimethylene carbonate block copolymer of Modified Membrane gross weight 1%, lazy
Property atmosphere under, in 40 DEG C stirring mixing 40 minutes, use the tape casting film forming, in 50 DEG C of vacuum drying ovens be dried, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 11.6% He before modified
13.3%.
Embodiment 2
1）The synthesis of poly- peptide-PTMC 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 PTMC monododecyl ether of end-blocking（Molecular weight is 3500）, add 305 ml dimethyl sulfoxide, add
0.031 gram of N, N '-DIC, under inert atmosphere, in 27 DEG C of stirring reactions 4 days, terminating reaction, by filtering,
Dialyse, be dried, obtain object；
2）The synthesis of polyethylene glycol trimethylene carbonate block copolymer
3 grams of amino-terminated poly glycol monomethyl ethers are added in dry reactor（Molecular weight is 6000）With 9 grams of carboxyls
The PTMC monododecyl ether of end-blocking（Molecular weight is 3500）, add 155 ml dimethyl sulfoxide, add
0.08 gramN,N’- DIC, under inert atmosphere, terminating reaction after 28 DEG C of stirring reactions 3 days, by filtering,
Dialyse, be dried, obtain object；
3）PTMC and the preparation of poly ethyldiol modified poly- peptide film
Add 12.6 grams of poly- peptide-PTMC block copolymers and 45.5 ml 1,1 in dry reactor,
2- Separator, another addition accounts for the polyethylene glycol trimethylene carbonate block copolymer of Modified Membrane gross weight 2%, lazy
Property atmosphere under, in 45 DEG C stirring mixing 45 minutes, use the tape casting film forming, in 50 DEG C of vacuum drying ovens be dried, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.1% He before modified
14.1%.
Embodiment 3
1）The synthesis of poly- peptide-PTMC block copolymer
Add 16.5 grams to gather in dry reactor（R- methyl-L-Glutamic Acid ester）（Molecular weight is 92000）With 7 grams of carboxyls
The PTMC monododecyl ether of end-blocking（Molecular weight is 4000）, add 310 ml dimethyl sulfoxide, 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 polyethylene glycol trimethylene carbonate block copolymer
3.1 grams of amino-terminated poly glycol monomethyl ethers are added in dry reactor（Molecular weight is 7100）With 9.2 grams
The PTMC monododecyl ether of carboxy blocking（Molecular weight is 4000）, add 158 ml dimethyl sulfoxide, then
Add 0.141 gram of 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, under inert atmosphere, terminates after 35 DEG C of stirring reactions 2 days
Reaction, by filtering, dialysing, be dried, obtains object；
3）PTMC and the preparation of poly ethyldiol modified poly- peptide film
Add 12.8 grams of poly- peptide-PTMC block copolymers and 45.4 ml 1,1 in dry reactor,
2- Separator, another addition accounts for the polyethylene glycol trimethylene carbonate block copolymer of Modified Membrane gross weight 4%, lazy
Property atmosphere under, in 50 DEG C stirring mixing 50 minutes, use the tape casting film forming, in 50 DEG C of vacuum drying ovens be dried, obtain object.
After tested：The hydrophilic rate of object of the present invention and elongation at break are respectively than improve 12.9% He before modified
14.6%.
Claims (6)
1. a kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol, its feature exists
In：In Modified Membrane, the molecular weight of poly- peptide segment is 80000～92000, and the molecular weight of PTMC segment is 3000
～4000, the molecular weight of Polyethylene Glycol segment is 5000～7100；Its method of modifying adopts following steps：
1）The synthesis of poly- peptide-PTMC block copolymer：Poly- the three of carboxy blocking is added in dry reactor
Carbonate monododecyl ether, solvent, condensing agent and poly- peptide homopolymer, under inert atmosphere, anti-in 25～30 DEG C of stirrings
Answer 3～4 days, terminating reaction, by filtering, dialysing, be dried, obtain object, wherein, poly- peptide homopolymer is using poly-（γ-benzene first
Base-L-Glutamic Acid ester）, poly-（γ-ethyl-L-glutamate ester）Or it is poly-（γ-methyl-L-Glutamic Acid ester）；
2）The synthesis of polyethylene glycol trimethylene carbonate block copolymer：Carboxy blocking is added in dry reactor
PTMC monododecyl ether, solvent, condensing agent and amino-terminated poly glycol monomethyl ether, inert atmosphere
Under, in 25～35 DEG C of stirring reactions 2～3 days, terminating reaction, by filtering, dialysis, it is dried, obtain object；
3）PTMC and the preparation of poly ethyldiol modified poly- peptide film：Poly- peptide-poly- is added in dry reactor
Trimethylene carbonate block copolymer, polyethylene glycol trimethylene carbonate block copolymer and solvent, inert atmosphere
Under, after 40～50 DEG C of stirring mixing 40～50 minutes, with the tape casting film forming and dry, obtain object, wherein, poly- second two
Alcohol-mass percent in Modified Membrane for the PTMC block copolymer is 1～4%.
2. a kind of PTMC according to claim 1 and Polyethylene Glycol improve poly- peptide film hydrophilic with submissive
The method of property it is characterised in that：Step 1）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-diisopropyl carbon
Diimine or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5
～15 g:100 ml.
3. a kind of PTMC according to claim 1 and Polyethylene Glycol improve poly- peptide film hydrophilic with submissive
The method of property it is characterised in that：Step 1）In, the mol ratio of PTMC monododecyl ether and poly- peptide homopolymer
For 8～16:1；Condensing agent is 1.08～1.8 with the mol ratio of poly- peptide homopolymer:1.
4. a kind of PTMC according to claim 1 and Polyethylene Glycol improve poly- peptide film hydrophilic with submissive
The method of property it is characterised in that：Step 2）In, condensing agent adopts N, N '-dicyclohexylcarbodiimide, N, N '-diisopropyl carbon
Diimine or 3- ethyl -1-（3- dimethylaminopropyl）Carbodiimide, solvent adopts dimethyl sulfoxide, and reactant solution concentration is 5
～15 g:100 ml.
5. a kind of PTMC according to claim 1 and Polyethylene Glycol improve poly- peptide film hydrophilic with submissive
The method of property it is characterised in that：Step 2）In, PTMC monododecyl ether is rubbed with poly glycol monomethyl ether
That ratio is 3～9:1；Condensing agent is 1.07～1.8 with the mol ratio of poly glycol monomethyl ether:1.
6. a kind of PTMC according to claim 1 and Polyethylene Glycol improve poly- peptide film hydrophilic with submissive
The method of property it is characterised in that：Step 3）In, solvent adopts vinyl trichloride, and mixture solution concentration is 25～35 g:
100 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510004846.7A CN104559213B (en) | 2015-01-06 | 2015-01-06 | A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510004846.7A CN104559213B (en) | 2015-01-06 | 2015-01-06 | A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104559213A CN104559213A (en) | 2015-04-29 |
| CN104559213B true CN104559213B (en) | 2017-03-08 |
Family
ID=53076324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510004846.7A Expired - Fee Related CN104559213B (en) | 2015-01-06 | 2015-01-06 | A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104559213B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105560179B (en) * | 2016-01-06 | 2019-02-05 | 四川大学 | MPEG-PTMC di-block copolymer carrier micelle and its preparation method and application |
| CN105732992B (en) * | 2016-02-29 | 2019-02-19 | 山东理工大学 | A kind of preparation method of polyvinyl alcohol-polytrimethylene carbonate-polydioxanone dual graft copolymer |
| CN105647194A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polycaprolactone and polypeptide |
| CN105694474B (en) * | 2016-03-07 | 2018-07-10 | 山东理工大学 | A kind of method being improved with polytrimethylene carbonate and poly (lactic acid-glycolic acid) to polyvinyl alcohol film water resistance and compliance |
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
| CN105647195A (en) * | 2016-03-07 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol film by polytrimethylene carbonate and polycaprolactone |
| CN105504322B (en) * | 2016-03-07 | 2018-02-02 | 山东理工大学 | A kind of method being improved with PTMC and PPDO to polyvinyl alcohol film water resistance and compliance |
| CN105542485A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone-polyvinylpyrrolidone |
| CN105670309A (en) * | 2016-03-16 | 2016-06-15 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane through polypeptide and polycaprolactone |
| CN105694476B (en) * | 2016-03-16 | 2018-07-13 | 山东理工大学 | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with poly (lactic acid-glycolic acid) |
| CN105542483B (en) * | 2016-03-16 | 2018-07-13 | 山东理工大学 | A kind of method that polytrimethylene carbonate improves polyvinyl alcohol film water resistance and compliance with polydioxanone |
| CN105542481A (en) * | 2016-03-16 | 2016-05-04 | 山东理工大学 | Method for modifying water resistance and flexibility of polyvinyl alcohol membrane through poly(trimethylene carbonate) and polycaprolactone |
| CN110690485A (en) * | 2019-09-20 | 2020-01-14 | 长春工业大学 | Composite high-temperature proton exchange membrane for fuel cell and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819701A (en) * | 2014-03-10 | 2014-05-28 | 山东理工大学 | Method for improving polypeptide membrane flexibility by adopting poly trimethylene carbonate and PTMG |
| CN103819906A (en) * | 2014-03-10 | 2014-05-28 | 山东理工大学 | Method for improving polypeptide membrane flexibility by adopting polypropylene glycol and poly trimethylene carbonate |
| CN103865090A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide film by using polycaprolactone and polyethylene glycol |
-
2015
- 2015-01-06 CN CN201510004846.7A patent/CN104559213B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819701A (en) * | 2014-03-10 | 2014-05-28 | 山东理工大学 | Method for improving polypeptide membrane flexibility by adopting poly trimethylene carbonate and PTMG |
| CN103819906A (en) * | 2014-03-10 | 2014-05-28 | 山东理工大学 | Method for improving polypeptide membrane flexibility by adopting polypropylene glycol and poly trimethylene carbonate |
| CN103865090A (en) * | 2014-03-14 | 2014-06-18 | 山东理工大学 | Method for improving hydrophilia of polypeptide film by using polycaprolactone and polyethylene glycol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104559213A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104559213B (en) | A kind of method that PTMC improves poly- peptide film hydrophilic and compliance with Polyethylene Glycol | |
| CN104479158B (en) | A kind of method that PPDO improves poly- peptide film hydrophily and compliance with polyethylene glycol | |
| CN104479157B (en) | A kind of method that polycaprolactone improves poly- peptide film hydrophily and compliance with polyethylene glycol | |
| CN104448841B (en) | A kind of method that poly (lactic acid-glycolic acid) improves poly-peptide film hydrophilic and compliance with polyacrylic acid | |
| CN104559212B (en) | Method for improving hydrophily and flexibility of polypeptide membrane by poly(lactic acid-glycolic acid) and polyethylene glycol | |
| CN104559208B (en) | A kind of method that poly (lactic acid-glycolic acid) improves poly- peptide film hydrophilic and compliance with polyacrylamide | |
| CN104559214B (en) | Method for improving hydrophily and flexibility of polypeptide membrane by polypropylene glycol and polyacrylic acid | |
| CN104559210B (en) | Method for improving hydrophily and flexibility of polypeptide film by polypropylene glycol and polyethylene glycol | |
| CN104559218B (en) | A kind of method that PPDO improves poly- peptide film hydrophily and compliance with carboxymethyl chitosan | |
| CN104559206B (en) | Method for improving hydrophilic property and flexibility of polypeptide film by adopting poly trimethylene carbonate and polyacrylamide | |
| CN104448843B (en) | A kind of method that polycaprolactone improves poly-peptide film hydrophily and compliance with polyacrylic acid | |
| CN104559211B (en) | A kind of method that PPDO improves poly- peptide film hydrophilic and compliance with polyacrylic acid | |
| CN104497588B (en) | Method for improving hydrophilicity and flexibility of polydioxanone and polyacrylamide improved polypeptide film | |
| CN104559215B (en) | A kind of method that PLA improves poly- peptide film hydrophily and compliance with polyethylene glycol | |
| CN104559222B (en) | Method for improving hydrophilicity and flexibility of polypeptide film by polycaprolactone and carboxymethyl chitosan | |
| CN104559223B (en) | Method for improving hydrophilicity and flexibility of polypeptide film by polypropylene glycol and carboxymethyl chitosan | |
| CN104559226B (en) | Method for improving hydrophilicity and flexibility of polypeptide film by polytrimethylene carbonate and carboxymethyl chitosan | |
| CN104497590B (en) | Method for improving hydrophilicity and flexibility of polycaprolactone and polyacrylamide improved polypeptide film | |
| CN104530722B (en) | Method for improving hydrophilia and flexibility of polypeptide film through polylactic acid-glycolic acid and carboxymethyl chitosan | |
| CN104448842B (en) | A kind of method that polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylic acid | |
| CN104497591B (en) | A kind of method that polylactic acid improves poly-peptide film hydrophilic and compliance with polyacrylamide | |
| CN104497589B (en) | Method for improving hydrophilicity and flexibility of polypropylene glycol and polyacrylamide improved polypeptide film | |
| CN107057377A (en) | A kind of method that MPEGPLA is improved with polypropylene glycol to polypropylene sorrel water resistance and compliance | |
| CN106977936A (en) | A kind of polycaprolactone is with gathering（Lactide glycolide）The method for improving polypropylene sorrel water resistance and compliance | |
| CN106977954A (en) | A kind of method that MPEGPLA is improved with polycaprolactone to polypropylene sorrel water resistance and compliance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 Termination date: 20180106 |