CN106674426A - Thermo-sensitive hydrogel based on ATRP - Google Patents
Thermo-sensitive hydrogel based on ATRP Download PDFInfo
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- CN106674426A CN106674426A CN201611254062.0A CN201611254062A CN106674426A CN 106674426 A CN106674426 A CN 106674426A CN 201611254062 A CN201611254062 A CN 201611254062A CN 106674426 A CN106674426 A CN 106674426A
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- temperature
- sensitive hydrogel
- hydrogel
- atrp
- polymerization
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
- C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to thermo-sensitive hydrogel based on atom transfer radical polymerization (ATRP). An active ATRP method is adopted to initiate monomers into polymerization and crosslinking. Polymer chains are in a relaxed state in the polymerization reaction, macromolecule hydrogel which is narrow in molecular weight distribution and controllable in molecular weight and crosslinking density is generated in the polymerization reaction, and the obtained hydrogel is consistent and uniform in composition. When small change takes place at a temperature adjacent to the low critical solution temperature (LCST), the thermo-sensitive hydrogel shows an obvious phase transformation effect. The invention further provides a preparation method of the thermo-sensitive hydrogel based on ATRP. The method is simple in process and mild in reaction condition. The polymer hydrogel is made through a one-step organic synthetic method, is aqueous and eco-friendly, and has LCST in a range of 30-40 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogel, more particularly to a kind of temperature sensitive type water-setting based on ATRP polymerization
Glue, belongs to hydrogel environmental technology field.
Technical background
Hydrogel is hydrated cross-linked polymerization system aqueous under poised state, and hydrogel is the water with cross-linked network
A part of hydrophobic group and hydrophilic residue, hydrophilic residue and water molecules are introduced in soluble macromolecular, hydrone is connected to
Netted inside, and the cross linked polymer of hydrophobic residue water-swellable.Hydrogel has good hydrophilic, there is very strong molten in water
Swollen ability, but it is water insoluble.Hydrogel locates in use solvent swelling state, quite soft, and with caoutchouc elasticity, can be with
Reduce mechanical impacts and stimulation to peripheral cell and tissue.
Temperature-sensitive hydrogel is a kind of stimulating responsive hydrogel studied and be most widely used, when ambient temperature is at it
When lower critical solution temperature (LCST) nearby occurs minor variations, temperature-sensitive hydrogel can show obvious phase in version
Energy.In experimental implementation, this phase in version performance is particularly conducive to carry out cell manipulation, such as can easily to cold true Thermo-sensitive
Culture medium is added in hydrogel, cell centrifugation collection can be carried out by way of lowering the temperature to culture bottle.In gel state, it
Highly lipophilic is that cell propagation, cell signalling, gaseous mass exchange and cell and tissue are carried to defence of shearing force etc.
Very effective growing environment is supplied.In recent years Many researchers have reported its potential application in biomedical aspect, such as medicine
Thing controlled release, bio-separation etc..
Chinese patent CN201210571657.4 is related to a kind of porous temperature-sensitive hydrogel slow release formulation and preparation method thereof.With poly-
NIPA porous temperature-sensitive hydrogel is carrier, the medicine in load in gel, using poly-N-isopropyl acryloyl
The temperature sensitive properties of amine are realizing the control release to medicine.As LCST of the temperature less than hydrogel, drug release is very
Slowly, and when temperature is higher than its LCST, rate of release is accelerated.
Chinese patent CN201110386870.3 disclose it is a kind of can In-sltu reinforcement temperature sensitive polymer synthetic method, by double
Key function monomer homopolymerization is obtained, or is obtained with a kind of copolymerization in carbonic ester, lactone, lactide by double bond function monomer.Water-setting
Glue is liquid form when compared with low temperature, and under physiological temp is gel form, can easily introduce bioactive molecule and life
Thing signal, gives material special biological activity, and hydrogel is under physiological environment, can gradually degrade.
Existing more using traditional radical polymerization with regard to temperature-sensitive hydrogel, radical polymerization is in a short period of time
There is thousands of monomer just plus reaction forms polymer chain.Simultaneously because the monomer reaction time is very fast, cause polymer chain
Form lax without the time, microgel is formed in the polymer, cause that hydrogel structure is uneven, many performances are impacted.It is living
Property controllable free-radical reaction system in, polymer have the sufficient time relax, but with regard to active controllable free-radical reaction prepare temperature
The report of quick hydrogel is less.
The content of the invention
The primary and foremost purpose of the present invention aims to provide a kind of temperature-sensitive hydrogel based on ATRP polymerization.
Another object of the present invention provides a kind of preparation method of the temperature sensitive type based on ATRP polymerization.
To overcome the shortcoming of prior art presence with a kind of not enough, temperature sensitive type water based on ATRP polymerization of the present invention
Gel, it is characterised in that due to using the polymerization of active atomic transferring free-radical polymerization method (ATRP method) trigger monomer, crosslinking, gathering
Compound chain can in the polymerization be in relaxed state, and polyreaction generates narrow molecular weight distribution and molecular weight, crosslink density can
The macromolecule hydrogel of control, and hydrogel composition consistent and uniform, when there are minor variations near lower critical solution temperature, temperature
Quick property hydrogel can show obvious phase in version performance.
A kind of temperature-sensitive hydrogel based on ATRP polymerization of the present invention, its preparation method comprises the steps：
A) preparation of hydrogel：Under the conditions of inert atmosphere protection, at room temperature by 200~400 parts of deionized waters, 50~
100 parts of intensive polar solvents, 10~20 parts of polymerized monomers, 15~30 parts of cross-linking monomers, 0.05~0.1 part of surfactant are added to
In reaction unit, stirring starts condensing units work, then sequentially adds 0.2~1 part of catalyst, 0.5~3 part of part；Wait to mix
After closing uniformly, continue 0.5~1h of logical nitrogen, 0.2~1 part of initiator of Deca after completion of dropping, seals reaction into reaction unit
Device, at 40~60 DEG C 2~48h is reacted, and obtains transparent resilient jelly；
B) hydrogel is purified：The jelly in a) step is taken out, first copper ion, Ran Hou is displaced with immersion in dilute hydrochloric acid
24h is soaked in deionized water, every 2h a water is changed, to remove impurity, be put in vacuum drying oven 40 DEG C and dry to constant weight, obtained
A kind of temperature-sensitive hydrogel.
Hydrogel Thermo-sensitive is determined：In the deionized water that dried hydrogel sample is placed under different temperatures, swelling equilibrium
Afterwards, hydrogel is taken out, dries the moisture on its surface, weighed, calculate the equilibrium swelling ratio at a temperature of each, determined minimum critical molten
Solution temperature (LCST).
Described intensive polar solvent is in methanol, DMF, tetrahydrofuran, dimethyl sulfoxide, dioxane
The combination of one or more.
Described polymerized monomer is to NIPA, both N hydroxymethyl acrylamides mixture, mass ratio
For 1:2~1:6.
Described cross-linking monomer be N, N ' methylene-bisacrylamides.
Described surfactant is dodecylbenzene sodium sulfonate, cetyl trimethylammonium bromide, polyoxyethylene nonyl phenyl second
One or more in alkene ether, high-carbon fatty alcohol polyoxyethylene ether, fatty glyceride, fatty acid sorbitan, polyvinyl alcohol
Combination.
Described catalyst is one or more in cuprous bromide, Cu-lyt., cuprous bromide, copper bromide；Enter
One step ground, preferably Cu-lyt..
Described part be PMDETA, three (2- dimethyl aminoethyls) amine, 2,2 '-bipyridyl, N,
N, N ', N ', N "-PMDETA, N, N, N ', N ', N "-pentamethyl acrylic acid methyl ester. base diethylene triamine, N,
N, N ', N ', N ", N "-hexamethyl n-butyl acrylate base triethylene tetraamine, N, N, N ', N ', N ", N "-hexamethyl acrylic acid first
One or more in ester group triethylene tetraamine；Further, it is preferable to be PMDETA.
Described initiator is 2- chlorine propionic acid amide .s, 2- bromine propionic acid amide .s, 2- bromopropene acetoacetic esters, propylene bromide acetoacetic ester, 2-
One or more in isobutyl ethyl bromide, 2- bromopropene acetoacetic esters；Further, it is preferable to be 2- chlorine propionic acid amide. or 2-
Bromine propionic acid amide. or the two mixture.
A kind of advantage of the temperature-sensitive hydrogel preparation method based on ATRP polymerization of the present invention：Process is simple, reacts bar
Part is gentle, step methodology of organic synthesis synthesis, the polyalcohol hydrogel aqueous, environmental protective obtained by preparation, and LCST is at 30~40 DEG C.
Specific embodiment
A kind of temperature-sensitive hydrogel based on ATRP polymerization of the present invention is further described with reference to embodiment.
It is understood that specific embodiment described herein is used only for explaining related invention, rather than the restriction to the invention.
Embodiment 1
A kind of temperature-sensitive hydrogel based on ATRP polymerization, its preparation method is as follows：
A) preparation of hydrogel：Under the conditions of inert atmosphere protection, at room temperature by 250 parts of deionized waters, 50 parts of N, N-
Dimethylformamide, 2 parts of NIPAs, 8 parts of N hydroxymethyl acrylamides, 25 parts of N, N ' methylene bisacrylamide acyls
Amine, 0.05 part of dodecylbenzene sodium sulfonate are added in reaction unit, stirring, start condensing units work, are then sequentially added
0.1 part of cuprous bromide, 0.1 part of Cu-lyt., 0.8 part of PMDETA；It is to be mixed it is uniform after, continue logical nitrogen
0.5h, 0.2 part of chlorine propionic acid amide. of Deca after completion of dropping, seals reaction unit into reaction unit, and at 60 DEG C 48h is reacted, and obtains
Bright resilient jelly；
B) hydrogel is purified：The jelly in a) step is taken out, first copper ion, Ran Hou is displaced with immersion in dilute hydrochloric acid
24h is soaked in deionized water, every 2h a water is changed, to remove impurity, be put in vacuum drying oven 40 DEG C and dry to constant weight, obtained
A kind of temperature-sensitive hydrogel.
Thermo-sensitive is determined：In the deionized water that dried hydrogel sample is placed under different temperatures, after swelling equilibrium, remove
Hydrogel, dries the moisture on its surface, weighs, and calculates the equilibrium swelling ratio at a temperature of each, determines lowest critical solution temperature
(LCST), Jing determines the present embodiment LCST for 34.6 ± 1 DEG C.
Embodiment 2
A kind of temperature-sensitive hydrogel based on ATRP polymerization, its preparation method is as follows：
A) preparation of hydrogel：Under the conditions of inert atmosphere protection, at room temperature by 300 parts of deionized waters, 60 parts of methanol,
5 parts of NIPAs, 10 parts of N hydroxymethyl acrylamides, 30 parts of N, N ' methylene-bisacrylamides, 0.05 part 16
Alkyl trimethyl ammonium bromide is added in reaction unit, stirring, starts condensing units work, then sequentially adds 0.4 part of bromination
It is cuprous, 1 part 2,2 '-connection pyrrole；It is to be mixed it is uniform after, continue logical nitrogen 1h, 0.4 part of initiator 2- bromines propionic acid amide. of Deca is to reacting dress
In putting, after completion of dropping, reaction unit is sealed, at 40 DEG C 48h is reacted, obtain transparent resilient jelly；
B) hydrogel is purified：The jelly in a) step is taken out, first copper ion, Ran Hou is displaced with immersion in dilute hydrochloric acid
24h is soaked in deionized water, every 2h a water is changed, to remove impurity, be put in vacuum drying oven 40 DEG C and dry to constant weight, obtained
A kind of temperature-sensitive hydrogel.
Thermo-sensitive is determined：In the deionized water that dried hydrogel sample is placed under different temperatures, after swelling equilibrium, remove
Hydrogel, dries the moisture on its surface, weighs, and calculates the equilibrium swelling ratio at a temperature of each, determines lowest critical solution temperature
(LCST), Jing determines the present embodiment LCST for 34.0 ± 1 DEG C.
Embodiment 3
A kind of temperature-sensitive hydrogel based on ATRP polymerization, its preparation method is as follows：
A) preparation of hydrogel：Under the conditions of inert atmosphere protection, at room temperature by 400 parts of deionized waters, 50 parts of N, N-
Dimethylformamide, 3 parts of NIPAs, 7 parts of N hydroxymethyl acrylamides, 30 parts of N, N ' methylene bisacrylamide acyls
Amine, 0.1 part of polyvinyl alcohol are added in reaction unit, stirring, start condensing units work, then sequentially add 0.5 part of chlorination
Cuprous, 3 parts of PMDETAs；It is to be mixed it is uniform after, continue logical nitrogen 0.5h, 0.5 part of initiator 2- bromine third of Deca
Amide after completion of dropping, seals reaction unit into reaction unit, and at 50 DEG C 24h is reacted, and obtains transparent resilient jelly；
B) hydrogel is purified：The jelly in a) step is taken out, first copper ion, Ran Hou is displaced with immersion in dilute hydrochloric acid
24h is soaked in deionized water, every 2h a water is changed, to remove impurity, be put in vacuum drying oven 40 DEG C and dry to constant weight, obtained
A kind of temperature-sensitive hydrogel.
Thermo-sensitive is determined：In the deionized water that dried hydrogel sample is placed under different temperatures, after swelling equilibrium, remove
Hydrogel, dries the moisture on its surface, weighs, and calculates the equilibrium swelling ratio at a temperature of each, determines lowest critical solution temperature
(LCST), Jing determines the present embodiment LCST for 32.4 ± 1 DEG C.
Above description is only the preferred embodiment of the application and the explanation to institute's application technology principle.People in the art
Member should be appreciated that invention scope involved in the application, however it is not limited to the technology of the particular combination of above-mentioned technical characteristic
Scheme, while also should cover in the case of without departing from the inventive concept, is carried out by above-mentioned technical characteristic or its equivalent feature
Combination in any and other technical schemes for being formed.Such as features described above has similar work(with (but not limited to) disclosed herein
The technical scheme that the technical characteristic of energy is replaced mutually and formed.
Claims (8)
1. a kind of temperature-sensitive hydrogel based on ATRP polymerization, it is characterised in that：Described temperature-sensitive hydrogel, its preparation method
Comprise the steps：
A) preparation of hydrogel：Under the conditions of inert atmosphere protection, at a certain temperature by 200~400 parts of deionized waters, 50~
100 parts of intensive polar solvents, 10~20 parts of polymerized monomers, 15~30 parts of cross-linking monomers, 0.05~0.1 part of surfactant are added to
In reaction unit, stirring starts condensing units work, then sequentially adds 0.2~1 part of catalyst, 0.5~3 part of part；Wait to mix
After closing uniformly, continue 0.5~1h of logical nitrogen, 0.2~1 part of initiator of Deca after completion of dropping, seals reaction into reaction unit
Device, at 40~60 DEG C 2~48h is reacted, and obtains transparent resilient jelly；
B) hydrogel is purified：Take out jelly a) in step, first displace copper ion with immersion in dilute hydrochloric acid, then go from
24h is soaked in sub- water, every 2h a water is changed, to remove impurity, be put in vacuum drying oven 40 DEG C and dry to constant weight, obtain one kind
Temperature-sensitive hydrogel.
2. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Described is highly polar
Solvent is the combination of one or more in methanol, DMF, tetrahydrofuran, dimethyl sulfoxide, dioxane.
3. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Described polymerization list
Body is that, to NIPA, both N hydroxymethyl acrylamides mixture, mass ratio is 1:2~1:6.
4. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Described crosslinking list
Body is N, N ' methylene-bisacrylamides.
5. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Live on described surface
Property agent be dodecylbenzene sodium sulfonate, cetyl trimethylammonium bromide, NPE, high-carbon fatty alcohol polyoxy second
The combination of one or more in alkene ether, fatty glyceride, fatty acid sorbitan, polyvinyl alcohol.
6. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Described catalyst
For one or more in cuprous bromide, Cu-lyt., cuprous bromide, copper bromide；Further, it is preferable to be protochloride
Copper.
7. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Described part is
PMDETA, three (2- dimethyl aminoethyls) amine, 2,2 '-bipyridyl, N, N, N ', N ', N "-pentamethyl diethyl
Thiazolinyl triamine, N, N, N ', N ', N "-pentamethyl acrylic acid methyl ester. base diethylene triamine, N, N, N ', N ', N ", N "-hexamethyl third
Olefin(e) acid N-butyl base triethylene tetraamine, N, N, N ', N ', N ", N " in-hexamethyl acrylic acid methyl ester. base triethylene tetraamine one
Plant or several combinations；Further, it is preferable to be PMDETA.
8. a kind of temperature-sensitive hydrogel based on ATRP polymerization as claimed in claim 1, it is characterised in that：Described initiator
For 2- chlorine propionic acid amide .s, 2- bromine propionic acid amide .s, 2- bromopropene acetoacetic esters, propylene bromide acetoacetic ester, 2- isobutyl ethyl bromides, 2- bromines third
One or more in olefin(e) acid ethyl ester；Further, it is preferable to be 2- chlorine propionic acid amide. or 2- bromines propionic acid amide. or the two mixing
Thing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611254062.0A CN106674426A (en) | 2016-12-30 | 2016-12-30 | Thermo-sensitive hydrogel based on ATRP |
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| CN201611254062.0A CN106674426A (en) | 2016-12-30 | 2016-12-30 | Thermo-sensitive hydrogel based on ATRP |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109568648A (en) * | 2018-11-27 | 2019-04-05 | 合肥工业大学 | A kind of preparation method and applications with antibacterial and the irreversible composite hydrogel of thermal induction for promoting wound healing function |
| CN112251197A (en) * | 2020-10-23 | 2021-01-22 | 上海驰纺材料科技有限公司 | Phase-change microcapsule with full-band photo-thermal conversion function and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356197A (en) * | 2005-08-23 | 2009-01-28 | 卡内基梅隆大学 | Atom transfer radical polymerization in microemulsion and true emulsion polymerization |
| CN101481439A (en) * | 2009-01-15 | 2009-07-15 | 同济大学 | Preparation of thermosensitive degradable graft copolymer |
| CN103354815A (en) * | 2010-12-08 | 2013-10-16 | Atrp解决方案公司 | Improved control over controlled radical polymerization processes |
| CN104558350A (en) * | 2013-10-12 | 2015-04-29 | 中国石油大学(华东) | Hydrophilic super-macroporous polymer microsphere and preparation method thereof |
-
2016
- 2016-12-30 CN CN201611254062.0A patent/CN106674426A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101356197A (en) * | 2005-08-23 | 2009-01-28 | 卡内基梅隆大学 | Atom transfer radical polymerization in microemulsion and true emulsion polymerization |
| CN101481439A (en) * | 2009-01-15 | 2009-07-15 | 同济大学 | Preparation of thermosensitive degradable graft copolymer |
| CN103354815A (en) * | 2010-12-08 | 2013-10-16 | Atrp解决方案公司 | Improved control over controlled radical polymerization processes |
| CN104558350A (en) * | 2013-10-12 | 2015-04-29 | 中国石油大学(华东) | Hydrophilic super-macroporous polymer microsphere and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘虎等: ""乳液原子转移自由基聚合"", 《化学进展》 * |
| 蒋志飞: ""活性自由基聚合法制备聚丙烯酰胺及其水凝胶的研究"", 《中国优秀硕士学位论文全文数据库（工程科技Ⅰ辑）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109568648A (en) * | 2018-11-27 | 2019-04-05 | 合肥工业大学 | A kind of preparation method and applications with antibacterial and the irreversible composite hydrogel of thermal induction for promoting wound healing function |
| CN109568648B (en) * | 2018-11-27 | 2021-01-29 | 合肥工业大学 | Preparation method and application of heat-induced irreversible composite hydrogel with antibacterial and wound healing promoting functions |
| CN112251197A (en) * | 2020-10-23 | 2021-01-22 | 上海驰纺材料科技有限公司 | Phase-change microcapsule with full-band photo-thermal conversion function and preparation method thereof |
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Application publication date: 20170517 |