CN104045651B - Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene - Google Patents

Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene Download PDF

Info

Publication number
CN104045651B
CN104045651B CN201410184616.9A CN201410184616A CN104045651B CN 104045651 B CN104045651 B CN 104045651B CN 201410184616 A CN201410184616 A CN 201410184616A CN 104045651 B CN104045651 B CN 104045651B
Authority
CN
China
Prior art keywords
dithiophene
cyclopentano
reaction
preparation
cyclopentyldithiophene
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
Application number
CN201410184616.9A
Other languages
Chinese (zh)
Other versions
CN104045651A (en
Inventor
郭文娟
朱祥伟
裴梅山
丁峰
刘俊芝
王小超
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201410184616.9A priority Critical patent/CN104045651B/en
Publication of CN104045651A publication Critical patent/CN104045651A/en
Application granted granted Critical
Publication of CN104045651B publication Critical patent/CN104045651B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The present invention relates a preparation method of cyclopentyldithiophene with a side chain comprising a biquaternary ammonium salt group and a conjugated polyelectrolyte of the cyclopentyldithiophene. The preparation method is as follows: using 4H-cyclopentyl [2,1-B: 3,4-B'] dithiophene as a starting material for bromination reaction with dibromopropane, then amino reaction with dimethylamine and then quaternary ammonium salinization reaction with methyl bromide to prepare a water soluble cyclopentyldithiophene derivative, then using ferric chloride to cause the occurrence of polymerization reaction. Product purity is over 96%. The preparation method has the advantages of simple reaction process, easy operation, easily obtained raw materials, low production cost, high product yield, high product purity and the like.

Description

A kind of side chain group containing bi-quaternary ammonium salt cyclopentano Dithiophene and its conjugated polyelectrolytes Preparation method
Technical field
A kind of side chain group containing bi-quaternary ammonium salt cyclopentano Dithiophene and its preparation method of conjugated polyelectrolytes.This synthesis side Method, is sequentially passed through and dibromopropane bromination reaction, with diformazan for initiation material with 4h- cyclopentano [2,1-b:3,4-b] Dithiophene The aminated reaction of amine, and react preparation with bromomethane quaternization there is excellent water miscible cyclopentano Dithiophene derivative list Body, and cause the polymerisation of this monomer with ferric trichloride.
Background technology
Water-Soluble Conjugated Polyelectrolytes by the excellent photoelectric property of traditional conjugated polymer and gather electrolysis due to it at present The excellent water solubility of matter is combined as a whole, in the preparation of material for optoelectronic devices of new generation and chemical-biological fluorescent optical sensor Obtain substantial amounts of application.Such compound low toxic and environment-friendly, and because side chain carries hydrophilic and ionic groups, there is good water Dissolubility, workable in applications such as photoelectric material processing, biological detection, present more preferable than traditional conducting polymer Practical value.At present widely used Water-Soluble Conjugated Polyelectrolytes by its polymer conjugated backbone classification mainly have poly- Fluorenes class, polythiophene class, polyaniline compound etc., and the synthesis of cyclopentano Dithiophene class conjugated polyelectrolytes and application are still in blank Phase.
Cyclopentano Dithiophene and its derivative are a kind of emerging organic photoelectrical materials.Due to dividing of such organic compound Sub- condensed cyclic structure is symmetrical, and flatness is good, has relatively low energy gap, such compound, as an analog derivative of thiophene, is having The aspects such as machine solar cell, OTFT, Organic Light Emitting Diode and conducting polymer present important application It is worth.
The cyclopentano Dithiophene being widely used at present and its modified derivative are mainly non-water-soluble, including ring penta [2,1-b:3,4-b'] 1,4-Dithiapentalene -4- ketone and analogue, 4 upper rings penta [2,1-b:3,4-b'] being grafted alkyl side chain 1,4-Dithiapentalene and its analogue, above a few class compounds are poor due to its water solubility, limit such photoelectricity compound and exist The application of biological detection aspect.Water-soluble cyclopentano Dithiophene class conjugated polyelectrolytes are due to the plane symmetry of its condensed ring skeleton Good, conjugated degree is high, can eliminate the adverse effect brought due to main chain rotation in the solution, thus show and preferably should With being worth.
Content of the invention
The purpose of the present invention is synthesizing water-solubility cyclopentano Dithiophene monomer 4,4 '-two (3-n,n,n-Front three ammonium propyl group) Cyclopentano Dithiophene bromide simultaneously causes its polymerization, realizes the preparation of water-soluble cyclopentano Dithiophene conjugated polyelectrolytes and answers With.
The invention is characterized in that with 4h- cyclopentano [2,1-b:3,4-b] Dithiophene for initiation material, passing through and dibromo third Alkane reacts bromination, aminated after react with dimethylamine, and prepared 4,4 '-two (3- of quaternization after reacting with bromomethanen,n, n-Front three ammonium propyl group) cyclopentano Dithiophene bromide, and by chemical oxidization method with ferric trichloride for initiator polymerized monomer Synthesis poly- 4,4 '-two (3- of subject polymern,n,n-Front three ammonium propyl group) cyclopentano Dithiophene.
The main contents of this synthetic method are described below: the synthesis of 4,4 '-two (3- bromopropyl) cyclopentano Dithiophene (1): Using KI as catalyst, under nitrogen atmosphere, 4h- cyclopentano [2,1-b:3,4-b] Dithiophene, dibromopropane are containing hydrogen-oxygen Change stirring generation substitution reaction under darkroom in the dimethyl sulphoxide solution of potassium.Molar ratio is: 4h- cyclopentano [2,1-b: 3,4-b] Dithiophene: dibromopropane: potassium hydroxide: KI=1:2.5:5:0.06, reaction temperature is 25 DEG C, and the reaction time is 12 ~ 14 h, are that solvent column chromatography obtains faint yellow oil product with n-hexane.
The synthesis of 4,4 '-two (3- dimethylamino-propyl) cyclopentano Dithiophene (2): (3- bromine third 4,4 '-two under nitrogen atmosphere Base) cyclopentano Dithiophene, dimethylamine carry out aminated reaction in methanol solution.Molar ratio is: 4,4 '-two (3- diformazans Aminocarbonyl propyl) cyclopentano two thiophene: dimethylamine=1:2.3, reaction temperature is 25 DEG C, and the reaction time is 48 ~ 72 h, with n-hexane: second Acetoacetic ester: methyl alcohol: the solution of triethylamine=30:6:5:1 obtains faint yellow oil product for solvent column chromatography.
4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano Dithiophene bromide (3) synthesis: 4 under nitrogen atmosphere, 4 '-two (3- dimethylamino-propyl) cyclopentano Dithiophene, bromomethane carry out quaterisation in acetonitrile solution.Molar ratio For: 4,4 '-two (3- dimethylamino-propyl) cyclopentano Dithiophene: bromomethane=1:8.Reaction temperature is 25 DEG C, and the reaction time is 48 ~ 72 h, separate out product as white needles from acetonitrile solution.
Poly- 4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano Dithiophene (4) synthesis: nitrogen protection under with trichlorine Change iron trigger monomer 4,4 '-two (3- in anhydrous chloroform as initiatorn,n,n-Front three ammonium propyl group) cyclopentano Dithiophene gather Close.Molar ratio is: 4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano two thiophene bromide: ferric trichloride=1:5, instead Temperature is answered to be 5 DEG C, the reaction time is 12 ~ 24 h.Reaction terminates rear product and goes to adulterate, and carries out ion friendship with tetrabutylammonium chloride Change, Soxhlet extraction obtains atropurpureus powder after removing small molecule.
The present invention compared with prior art, has the advantage that
(1) synthetic route of the present invention is carried out at normal temperatures, need not heat etc. and to process, reduce the difficulty of reaction, thus The yield of target compound can be improved to a certain extent, reduce reaction cost.
(2) each step reaction in synthetic route is easy to operate, and each step reactor product is easily separated to be purified and high income.
(3) in the synthetic route of the present invention, used raw material is easy to get, low production cost.
Fig. 1 is poly- 4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano Dithiophene synthetic route chart.
Embodiment:
For ease of further understanding the present invention, the following example elaborates details particularly.
Embodiment 1
The synthesis of 4,4 '-two (3- bromopropyl) cyclopentano Dithiophene (1)
The KI of 0.2g 4h- cyclopentano [2,1-b:3,4-b] Dithiophene, 0.68g dibromopropane and 6mg is dissolved in The dimethyl sulphoxide solution of 3ml, under nitrogen protection, liquid mixed above is slowly added dropwise to 3ml and contains the two of 0.25g potassium hydroxide In methyl sulfoxide solution, by reaction unit under darkroom stirring reaction 14 hours.Add 30ml distilled water that reaction is quenched, use dichloro Dichloromethane extraction product, and with saturated nacl aqueous solution cleaning product 2 to 3 times, divide liquid with separatory funnel, take upper strata aubergine Solution anhydrous magnesium sulfate is dried, filters, and is that solvent column chromatography obtains faint yellow oily and produces with n-hexane after concentrated by rotary evaporation solution Thing 4,4 '-two (3- bromopropyl) cyclopentano Dithiophene (534mg, yield: 53%).
The synthesis of 4,4 '-two (3- dimethylamino-propyl) cyclopentano Dithiophene (2)
Compound concentration is the dimethylamine methanol solution of 12mol/l, by 4,4 '-two (3- bromopropyl) cyclopentano Dithiophene (534mg) after revolving removes solvent and be vacuum dried, add 5ml dimethylamine methanol solution, ultrasonic 30 minutes anti-under normal temperature Answer 24h.Reaction terminates rear revolving and removes solvent, adds chloroform extraction product, and the sodium bicarbonate solution being 5% with mass fraction Cleaning product 2 to 3 times, divides liquid with separatory funnel, takes upper strata yellow solution anhydrous magnesium sulfate to be dried, filters, concentrated by rotary evaporation is molten N-hexane: ethyl acetate: methyl alcohol is used: the solution of triethylamine=30:6:5:1 obtains faint yellow oil for solvent column chromatography after liquid Shape produces.With isopyknic n-hexane and ethyl acetate solution washed product, revolving is dried and obtains light yellow product 4,4 '-two (3- Dimethylamino-propyl) cyclopentano Dithiophene (338mg, 76%).
4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano Dithiophene bromide (3) synthesis
Compound concentration is the bromomethane acetonitrile solution of 4mol/l, by 4,4 '-two (3- dimethylamino-propyl) cyclopentano two thiophene Fen (338 mg) revolving remove solvent after and be vacuum dried, add 4ml prepare bromomethane acetonitrile solution, stirring reaction under normal temperature After 24h, in solution, separate out white, needle-shaped crystals, after revolving removes solvent, with n-hexane cleaning product 3 times, dry filter obtains White solid product (443 mg, 85%).
Poly- 4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano Dithiophene (4) synthesis
Monomer 4,4 '-two (3-n,n,n-Front three ammonium propyl group) cyclopentano Dithiophene (400 mg) ultrasonic disperse is in anhydrous chlorine In imitative, be rapidly added 660mg anhydrous ferric trichloride, under nitrogen atmosphere, at 5 DEG C of temperature, cause polymerization 24h, after reaction terminates plus A small amount of methyl alcohol is quenched reaction, and reactant is leached, and takes filter residue to add hydrazine hydrate/methanol solution dissolving, adds tetrabutylammonium chloride to enter Row ion exchange four times, to remove deionization, removes low polymer with acetone/methanol solution soxhlet extraction, finally gives purple black Color powder polymer (169mg, 42%).

Claims (4)

1. a kind of preparation method of side chain group containing bi-quaternary ammonium salt cyclopentano Dithiophene conjugated polyelectrolytes it is characterised in that with 4h- cyclopentano [2,1-b:3,4-b'] Dithiophene is initiation material, through reacting bromination with dibromopropane, after reacting with dimethylamine Aminated, and quaternization preparation has the cyclopentano Dithiophene derivative of good aqueous solubility after reacting with bromomethane, is used in combination Ferric trichloride causes its polymerization；Wherein bromination is using KI as catalyst, 4h- cyclopentano under nitrogen atmosphere [2,1-b:3, 4-b'] Dithiophene, dibromopropane carry out reaction in the dimethyl sulphoxide solution containing potassium hydroxide under darkroom and generate 4,4'- Double (3- bromopropyl) -4h- cyclopentano [2,1-b:3,4-b'] Dithiophene；Molar ratio 4h- cyclopentano [2,1-b:3,4-b'] Dithiophene: dibromopropane: potassium hydroxide: KI is 1:2.5:5:0.06, reaction temperature is 25 DEG C, and the reaction time is 12- 14h.
2. preparation method as claimed in claim 1 is it is characterised in that described aminated reaction is that 4,4'- is double under nitrogen atmosphere (3- bromopropyl) -4h- cyclopentano [2,1-b:3,4-b'] Dithiophene, dimethylamine carry out reaction in methanol solution and generate 4,4'- Double (3- dimethylamino-propyl) -4h- cyclopentano [2,1-b:3,4-b'] Dithiophene.
3. preparation method as claimed in claim 1 is it is characterised in that the reaction of described quaternization is under nitrogen atmosphere 4,4'- Double (3- dimethylamino-propyl) -4h- cyclopentano [2,1-b:3,4-b'] Dithiophene, bromomethane carry out quaternized in acetonitrile solution Reaction generates double (3- trimethylammonium bromide base propyl group) -4h- cyclopentano [2,1-b:3,4-b'] Dithiophene of 4,4'-.
4. preparation method as claimed in claim 1 is it is characterised in that described polymerisation is the list that will be prepared using ferric trichloride Double (3- trimethylammonium bromide base propyl group) -4h- cyclopentano [2,1-b:3,4-b'] Dithiophene of body 4,4'- causes in anhydrous chloroform Polymerisation, goes to adulterate by product, carries out ion exchange using tetrabutylammonium chloride, and Soxhlet extraction post processing is obtained.
CN201410184616.9A 2014-05-05 2014-05-05 Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene Expired - Fee Related CN104045651B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410184616.9A CN104045651B (en) 2014-05-05 2014-05-05 Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410184616.9A CN104045651B (en) 2014-05-05 2014-05-05 Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene

Publications (2)

Publication Number Publication Date
CN104045651A CN104045651A (en) 2014-09-17
CN104045651B true CN104045651B (en) 2017-01-25

Family

ID=51499093

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410184616.9A Expired - Fee Related CN104045651B (en) 2014-05-05 2014-05-05 Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene

Country Status (1)

Country Link
CN (1) CN104045651B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104892626B (en) * 2015-05-29 2017-03-22 石家庄学院 Semicarbazide dihydroartemisinin derivative as well as preparation method and application of semicarbazide dihydroartemisinin derivative

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8158275B2 (en) * 2006-02-22 2012-04-17 Osaka University Fluorine-containing compound and method for producing same, fluorine-containing polymer, organic thin film, and organic thin film device
CN101921224B (en) * 2010-05-21 2012-01-18 中国人民解放军军事医学科学院生物工程研究所 1-(3-aminopropyl) piperazine-4-aminoamide compound as well as preparation method and application thereof

Also Published As

Publication number Publication date
CN104045651A (en) 2014-09-17

Similar Documents

Publication Publication Date Title
CN106243352B (en) A kind of polyphenylene triazole formic acid esters and preparation method and application
CN106967217A (en) Polyimidazole class compound and its in-situ preparation method and application
CN110229315A (en) A kind of broad-band gap copolymer acceptor material and preparation method thereof based on imidodicarbonic diamide
CN101037446A (en) Synthesizing method of vinorelbine tartrate
CN104045651B (en) Preparation method of cyclopentyldithiophene with side chain comprising biquaternary ammonium salt group and conjugated polyelectrolyte of cyclopentyldithiophene
CN107325284A (en) A kind of hyperbranched poly phenyl triazole formic acid esters and preparation method and application
CN114315701B (en) Bipyridine ligand containing AIE and ACQ groups, amphiphilic diamond-shaped supramolecular metal ring and application
CN109880088B (en) Poly (trimethylsilyl) triazole and preparation method and application thereof
Debela et al. Postfunctionalization of Keggin silicotungstates by general coupling procedures
CN101440158A (en) Furan glycidyl ether or ester-epoxypropane-CO2 copolymer and preparation thereof
CN102391139B (en) Energy-saving and environmentally-friendly process for synthesizing alkyl betaine
CN107311960A (en) The synthetic method of 1,2,3 diazosulfide class compound
Guo et al. Synthesis and characterization of S, N-heteroacenes by Bischler-Napieralski reaction
CN103275153B (en) A kind of preparation method of fidaxomicin crystal
EP2882794A1 (en) Glycidyl 4-functionalized-1,2,3-triazole polymer derivatives and method for synthesis of the same
CN102911054A (en) Preparation method of 4,4,4-trifluoro-2-butenoate
CN101899673A (en) Synthesis method of 3-oxo cyclohexane-1-caboxylate
CN108690192B (en) Xanthene structure-containing polypyrazole and preparation method thereof
CN110669229B (en) Dynamic imine macrocycle-based supramolecular polymer and preparation method thereof
CN103626984A (en) Poly (carbonate-ether) dithiol oligomer and preparation method thereof
CN108083963B (en) Synthetic method of diarylethene
Xue et al. Synthesis and characterization of the first soluble nonracemic chiral main-chain perylene tetracarboxylic diimide polymers
CN101293959B (en) Hyperbranched conjugated polymer sensing material, preparation method and application thereof
CN109456301B (en) Crown ether-containing HBC compound and preparation and application thereof
CN108675971B (en) Method for preparing 2, 5-furan dicarbaldehyde

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: 20170125

Termination date: 20210505