CN106674918A - Polyhydroxybutyrate-containing nano-tube composite wire preparation method - Google Patents
Polyhydroxybutyrate-containing nano-tube composite wire preparation method Download PDFInfo
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- CN106674918A CN106674918A CN201510746315.5A CN201510746315A CN106674918A CN 106674918 A CN106674918 A CN 106674918A CN 201510746315 A CN201510746315 A CN 201510746315A CN 106674918 A CN106674918 A CN 106674918A
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Abstract
The invention discloses a polyhydroxybutyrate-containing nano-tube composite wire preparation method. The technical scheme of the present invention comprises that 1, the components of the formula comprise PBS, polyhydroxybutyrate, a polyolefin ionomer, halloysite nano-tubes, a coupling agent, a nucleating agent, a chain extender, and the like according to a weight ratio; and 2, the preparation method comprises: (1) drying, (2) material weighing, (3) high speed kneading, (4) melting extrusion, (5) cooling traction, and (6) coiling bundling. According to the present invention, the fully degradable biological materials such as the PBS and the halloysite nano-tubes are used to prepare the polymer material suitable for 3D printing, such that the printing temperature is low, and the tensile strength and the flexibility are good.
Description
Technical field
The invention belongs to a kind of preparation method of nanotube composite wire.
Background technology
3D printing technique can be divided into laser fusing-covering forming technique (LCF), thaw collapse product rapid shaping technique (FDM), Selective Laser Sintering (SLS), Stereo Lithography technology (SLA), molded through three-dimensional printing (3DP) etc..FDM is a kind of quick, safe, cheap quick shaping process, its easy operation, device therefor low cost, and concise in technology can be more with material category, relatively inexpensive and utilization rate is high, and suitable office environment is used.At present FDM systems account for 30% in global mounted rapid prototyping system, are the mainstream technologys that currently a popular desktop 3D printer is adopted.
In building-up process, due to higher to pressure and vacuum level requirements, it is difficult to prepare the PBS of HMW by being directly synthesized, its mechanical property is poor for poly butylene succinate (PBS), causes its application to be subject to certain restrictions.Poly butyric ester (PHB) performance is that a kind of forming is easy with PP almost, the thermoplastic resin of fully biodegradable, and its intensity and hardness are all higher.Therefore the toughness and tensile strength of PBS can further be improved by both blending and modifyings, increases its modulus, widen its range of application so as to which performance better adapts to the requirement of 3D printing moulding material.
Pure PBS directly applies to 3D printing and there is a problem of thermal contraction, and along with PBS main chains are aliphatic carbon oxygen chain composition, toughness and tensile strength need further raising.Galapectite is a kind of natural aluminosilicate clays, is crimped under natural endowment by kaolinic lamella and is formed, and is mainly existed in nature with the form of many walls nanotube shape, and pipe range is 500-1000nm, and internal diameter is 10-20nm, and external diameter is 20-40nm.The lamella of halloysite nanotubes is formed by the silicon-oxy tetrahedron of outer layer and the alumina octahedral regular array of internal layer, and outer surface is mainly Si-O-Si keys and a small amount of silicone hydroxyl composition, and inwall is mainly aluminium hydroxyl.Special surface charge distribution, larger draw ratio, makes halloysite nanotubes more readily dispersible, it is not easy to reunite.Additionally, halloysite nanotubes are cheap, wide advantage of originating so as to be increasingly subject to the attention of researcher as filling or the material modified application in polymer composite.
The content of the invention
Based on above-mentioned background and problem, it is an object of the invention to provide a kind ofContaining polyolefin ionomersThe preparation method of nanotube composite wire.The present invention is using the degradable biomaterial poly butylene succinate (PBS) of energy、Poly butyric ester,Polyolefin ionomersThe macromolecular material suitable for 3D printing is prepared with halloysite nanotubes, compared with traditional PLA (PLA) wire rod, with relatively low print temperature, preferable tensile strength and pliability, it is adaptable to various 3D shapings.
The purpose of the present invention is achieved by the following technical solution：
One kind of the present inventionContaining polyolefin ionomersThe preparation method of nanotube composite wire,
1）Percentage of weight formula is as follows：
PBS
50-62
Poly butyric ester
15-17
Polyolefin ionomers5-7
Halloysite nanotubes
9-20
Coupling agent
5-10
Nucleator
0.1-2
Chain extender
0.1-1
Crosslinking agent
0.1-1
Antioxidant
0.2-1
Lubricant
0.2-2；
InstituteStatePolyolefin ionomers prepared by following methods： 1 ）Maleic acid lanthanum, glycolic and water are first put into toward banbury, is well mixed at 40 DEG C, obtain paste；It is 1 to put into again by weight ratio:The mixing polyolefin that 1 polypropylene is mixed with polyethylene, and cumyl peroxide, secondary to be well mixed, melting graft reaction 7 minutes at being warming up to 190 DEG C, discharging, cooling obtain polyolefin ionomers；
Described coupling agent adopts 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea；
Described nucleator is using silica or titanium dioxide；
Described chain extender adopts phthalic anhydride；
Described antioxidant adopts Tea Polyphenols；
Described lubricant is using magnesium stearate or white oil；
Described 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea is prepared by following methods：1）In electromagnetic agitation, the there-necked flask of attemperating unit is equipped with, by 4,4,- dibromo diphenylamines is dissolved in dichloromethane, continuously adds triethylamine, adds Solid triphosgene, backflow, stirring under room temperature, thin layer tracing detection reacts, and reaction is stopped after 24h, after reaction terminates, vacuum distillation removes dichloromethane, and crude product is purified with pillar layer separation, and eluent is petroleum ether：Dichloromethane=2：1, obtain intermediate N, N- bis- (4- bromophenyls) carbamyl chloride；2）Above-mentioned intermediate N is sequentially added in the there-necked flask of electromagnetic agitation is equipped with, N- bis- (4- bromophenyls) carbamyl chloride, ether, triethylamine, 3- aminopropyl triethoxysilanes are passed through N2Protection, thin layer tracing detection reaction is reacted after 12h under room temperature and is stopped, and reaction filters white precipitate after terminating, and filtrate decompression is distilled off ether, and crude product is purified with pillar layer separation, and eluent is petroleum ether：Ethyl acetate=3：1, obtain 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea；
2）Preparation method, comprises the steps：
A. PBS is vacuum dried；
B. according to formula, weigh dried PBS, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, coupling agent, nucleator, chain extender, crosslinking agent, antioxidant, lubricant；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 1000-4000
Rpm/min, high-speed stirred 5-30min；
D. by the PBS being well mixed, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, coupling agent, nucleator, chain extender, crosslinking agent, antioxidant, lubricant are added to screw extruder charge door, and screw extruder parameter is：One 85-130 DEG C of area, two 100-150 DEG C of areas, three 120-160 DEG C of areas, four 120-150 DEG C of areas, five 120-160 DEG C of areas, rotating speed is 10-150rpm/min, extruding pelletization；
E. will granulate in step D after son is dried and be extruded and processed into filament with screw extruder, obtain the extrusion of wire of 1.75 ± 0.05mm or 3 ± 0.05mm.
Above-mentioned 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea is prepared by following method for optimizing：1）In electromagnetic agitation, the 100ml there-necked flasks of attemperating unit is equipped with, by 4,4,- dibromo diphenylamines (0.8175g, in 2.5mmol) being dissolved in 50ml dichloromethane, continuously add triethylamine (1.515g, 15mmol), Solid triphosgene (2.673g, 9mmol) is added, backflow, stirring under room temperature, thin layer tracing detection reacts, and reaction is stopped after 24h.After reaction terminates, vacuum distillation removes dichloromethane, crude product column chromatography (petroleum ether：Dichloromethane=2：1) separating-purifying, obtains intermediate N, N- bis- (4- bromophenyls) carbamyl chloride；2）Above-mentioned intermediate N is sequentially added in the 100ml there-necked flasks of electromagnetic agitation are equipped with, N- bis- (4- bromophenyls) carbamyl chloride (0.934g, 2.4mmol), ether 50ml, triethylamine (0.606g, 6mmol), 3- aminopropyl triethoxysilanes (0.884g, 4mmol), it is passed through N2Protection, thin layer tracing detection reaction is reacted after 12h under room temperature and is stopped.Reaction filters white precipitate after terminating, and filtrate decompression is distilled off ether, crude product column chromatography (petroleum ether：Ethyl acetate=3：1) separating-purifying, obtains 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea.
Advantages of the present invention and feature are：The present invention is using the degradable biomaterial poly butylene succinate (PBS) of energy、Poly butyric ester,Polyolefin ionomersThe macromolecular material suitable for 3D printing is prepared with halloysite nanotubes.Poly butyric ester is that a kind of forming is easy, the thermoplastic resin of fully biodegradable, its intensity and hardness it is all higher, halloysite nanotubes have higher draw ratio and uniqueness surface chemical property, it can be linked into inorganic network by hydrogen bond action or electric charge transferPolyolefin ionomers have improves polybutadieneSour butanediol ester (PBS)WithPoly butyric esterDispersiveness and compatibilization feature,1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea action of coupling agents, reduce can silica or titanium dioxide average grain diameter, uniformity is significantly improved so that having stronger interface cohesion to act between halloysite nanotubes and PBS, poly butyric ester matrix, load is set smoothly to be delivered to halloysite nanotubes by matrix, so as to play enhanced effect.The wire rod of preparation, with relatively low print temperature, preferable tensile strength and pliability, it is adaptable to various 3D forming techniques, has broad application prospects compared with traditional PLA (PLA) wire rod in 3D printing field.
The extrusion of wire of 1.75 ± 0.05mm that the present invention is obtained carries out 3D printing test, and 140 DEG C of print temperature, print procedure is smooth, and printing product surface is smooth well-balanced, appearance looks elegant, dimensionally stable.
Specific embodiment
The present invention is described in further details with reference to specific embodiment, but this should not be interpreted as the scope of the present invention and be only limitted to following instance.
Following embodiments 1 With 2 Polyolefin ionomers used adopt what is prepared with the following method,300g kilogram of maleic acid lanthanum, 75g glycolics and 500g water are first put into toward banbury, is well mixed at 40 DEG C, obtain paste；10 kilograms are put into again（10000g）It is 1 by weight ratio:The mixing polyolefin that 1 polypropylene is mixed with polyethylene, and 100g cumyl peroxide DCP, secondary to be well mixed, melting graft reaction 7 minutes at being warming up to 190 DEG C, discharging, cooling obtain polyolefin ionomers.Jing measures maleic acid lanthanum with polyolefinic percent grafting average out to 3.92%.
Following embodiments
1
With
2
Used
1,1-
Two
(4
- bromophenyl
)-3-(3-
Triethoxy silicon substrate
)
Propyl group urea preparation method：
1
）It is being equipped with electromagnetic agitation, attemperating unit
100ml
In there-necked flask, will
4,4
,
-
Dibromo diphenylamines
(0.8175g
,
2.5mmol)
It is dissolved in
50ml
In dichloromethane, triethylamine is continuously added
(1.515g
,
15mmol)
, add Solid triphosgene
(2.673g
,
9mmol)
, backflow, stirring under room temperature, the reaction of thin layer tracing detection,
24h
Stop reaction afterwards.After reaction terminates, vacuum distillation removes dichloromethane, crude product column chromatography
(
Petroleum ether：Dichloromethane
=2
：
1)
Separating-purifying, obtains slightly yellow solid intermediate
0.84g
, Jing
1
H-NMR
Test as intermediate
N,N-
Two
(4-
Bromophenyl
)
Carbamyl chloride, yield
86.3%
；
2
）It is being equipped with electromagnetic agitation
100ml
The intermediate of above-mentioned embodiment synthesis is sequentially added in there-necked flask
N,N-
Two
(4-
Bromophenyl
)
Carbamyl chloride
(0.934g
,
2.4mmol)
, ether
50ml
, triethylamine
(0.606g
,
6mmol)
、
3-
Aminopropyl
Triethoxysilane
(0.884g
,
4mmol)
, it is passed through
N
2
Protection, thin layer tracing detection reaction, reacts under room temperature
12h
After stop.Reaction filters white precipitate after terminating, and filtrate decompression is distilled off ether, the conventional column chromatography of crude product
(
Petroleum ether：Ethyl acetate
=3
：
1)
Separating-purifying, obtains faint yellow solid
1.14g
, Jing
1
H-NMR
Test as target product i.e.
1,1-
Two
(4
- bromophenyl
)-3-(3-
Triethoxy silicon substrate
)
Propyl group urea, yield
82.7%
。
Embodiment
1
It is of the present invention a kind of for 3D printingContainPoly butyric ester'sNanotube composite wire, it is characterised in that：According to percentage of weight formula：
PBS
54
Poly butyric ester
16
Polyolefin ionomers
6
Halloysite nanotubes
14
1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea
7
Silica
1
Phthalic anhydride 0.4
Trihydroxy methyl propane trimethyl acrylic ester
0.6
Tea Polyphenols
0.5
White oil
0.5。
Preparation method, comprises the steps：
A. PBS is dried into 12h in 80 DEG C of vacuum drying chambers；
B. according to the formula of step 1, weigh dried PBS, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea, silica, phthalic anhydride, trihydroxy methyl propane trimethyl acrylic ester, Tea Polyphenols, white oil；
C. each group after weighing is placed in high-speed kneading machine, keeps the rpm/min of rotating speed 3000, high-speed stirred 25min；
D. by the PBS being well mixed, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea, silica, phthalic anhydride, trihydroxy methyl propane trimethyl acrylic ester, Tea Polyphenols, white oil are added to double screw extruder charge door, and double screw extruder parameter is：One 100 DEG C of area, two 125 DEG C of areas, three 135 DEG C of areas, four 135 DEG C of areas, five 133 DEG C of areas, rotating speed is 100rpm/min, extruding pelletization；
E. will granulate in step D after son is dried and be extruded and processed into filament with single screw extrusion machine, extruder temperature is set as 90 DEG C of an area, two 110 DEG C of areas, three 130 DEG C of areas, and four 120 DEG C of areas obtain the extrusion of wire of 1.75 ± 0.05mm or 3 ± 0.05mm.
F. the extrusion of wire of the 1.75 ± 0.05mm obtained in E steps is carried out into 3D printing test, 145 DEG C of print temperature, print procedure is smooth, and printing product surface is smooth well-balanced, appearance looks elegant, dimensionally stable.
G. by injection mo(u)lding after the particle obtained in D steps drying, injection batten carries out respectively tensile property test (GB/T1040.2-2006), bending strength (GB/T1446-2006) and impact property test (GB/T1943-2008), and test result is shown in Table 1.
Embodiment
2
It is of the present invention a kind of for 3D printingContainPoly butyric ester'sNanotube composite wire, it is characterised in that：According to percentage of weight formula：
PBS
59.6
Poly butyric ester
16
Polyolefin ionomers
6
Halloysite nanotubes
10
1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea
5
Calcium carbonate
1
Toluene di-isocyanate(TDI)
0.5
Trihydroxy methyl propane triacrylate
0.4
1010
0.5
Stearic acid
1。
Preparation method, comprises the steps：
A. PBS is dried into 12h in 80 DEG C of vacuum drying chambers；
B. according to the formula of step 1, weigh dried PBS, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea, calcium carbonate, toluene di-isocyanate(TDI), trihydroxy methyl propane triacrylate, 1010, stearic acid；
C. each group after weighing is placed in high-speed kneading machine, keeps the rpm/min of rotating speed 3000, high-speed stirred 20min；
D. by the PBS being well mixed, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea, calcium carbonate, toluene di-isocyanate(TDI), trihydroxy methyl propane triacrylate, 1010, stearic acid are added to three-screw extruder charge door, and three-screw extruder parameter is：One 110 DEG C of area, two 123 DEG C of areas, three 131 DEG C of areas, four 132 DEG C of areas, five 127 DEG C of areas, rotating speed is 80rpm/min, extruding pelletization；
E. will granulate in step D after son is dried and be extruded and processed into filament with single screw extrusion machine, extruder temperature is set as 95 DEG C of an area, two 110 DEG C of areas, three 130 DEG C of areas, and four 125 DEG C of areas obtain the extrusion of wire of 1.75 ± 0.05mm or 3 ± 0.05mm.
F. the extrusion of wire of the 1.75 ± 0.05mm obtained in E steps is carried out into 3D printing test, 135 DEG C of print temperature, print procedure is smooth, and printing product surface is smooth well-balanced, appearance looks elegant, dimensionally stable.
G. by injection mo(u)lding after the particle obtained in D steps drying, injection batten carries out respectively tensile property test (GB/T1040.2-2006), bending strength (GB/T1446-2006) and impact property test (GB/T1943-2008), and test result is shown in Table 1.
The nanometer tube composite materials the performance test results of table 1.
| Sample | Tensile strength (MPa) | Bending strength (MPa) | Bending modulus (MPa) | Impact strength (kJ/m2) |
| Embodiment 1 | 37.7 | 34.6 | 800 | 17.6 |
| Embodiment 2 | 44.6 | 37.4 | 770 | 15.2 |
Claims (1)
1. a kind ofContainPoly butyric ester'sThe preparation method of nanotube composite wire, comprises the steps：
1）Percentage of weight formula is as follows：
PBS
50-62
Poly butyric ester 15-17
Polyolefin ionomers5-7
Halloysite nanotubes 9-20
Coupling agent 5-10
Nucleator 0.1-2
Chain extender 0.1-1
Crosslinking agent 0.1-1
Antioxidant 0.2-1
Lubricant 0.2-2；
Described coupling agent adopts 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea；
Described nucleator adopts calcium carbonate, silica or titanium dioxide；
Described chain extender is using trihydroxy methyl propane triacrylate or phthalic anhydride；
Described antioxidant is using 1010 or Tea Polyphenols；
Described lubricant is using stearic acid or white oil；
InstituteState's Polyolefin ionomers are prepared by following methods：1）Maleic acid lanthanum, glycolic and water are first put into toward banbury, is well mixed at 40 DEG C, obtain paste；It is 1 to put into again by weight ratio:The mixing polyolefin that 1 polypropylene is mixed with polyethylene, and cumyl peroxide, secondary to be well mixed, melting graft reaction 7 minutes at being warming up to 190 DEG C, discharging, cooling obtain polyolefin ionomers；
Described 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea is prepared by following methods：1）In electromagnetic agitation, the there-necked flask of attemperating unit is equipped with, by 4,4,- dibromo diphenylamines is dissolved in dichloromethane, continuously adds triethylamine, adds Solid triphosgene, backflow, stirring under room temperature, thin layer tracing detection reacts, and reaction is stopped after 24h, after reaction terminates, vacuum distillation removes dichloromethane, and crude product is purified with pillar layer separation, and eluent is petroleum ether：Dichloromethane=2：1, obtain intermediate N, N- bis- (4- bromophenyls) carbamyl chloride；2）Above-mentioned intermediate N is sequentially added in the there-necked flask of electromagnetic agitation is equipped with, N- bis- (4- bromophenyls) carbamyl chloride, ether, triethylamine, 3- aminopropyl triethoxysilanes are passed through N2Protection, thin layer tracing detection reaction is reacted after 12h under room temperature and is stopped, and reaction filters white precipitate after terminating, and filtrate decompression is distilled off ether, and crude product is purified with pillar layer separation, and eluent is petroleum ether：Ethyl acetate=3：1, obtain 1,1- bis- (4-bromophenyl)-3- (3- triethoxy silicon substrates) propyl group urea；
2）Preparation method, comprises the steps：
A. PBS is vacuum dried；
B. according to formula, weigh dried PBS, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, coupling agent, nucleator, chain extender, crosslinking agent, antioxidant, lubricant；
C. each group after weighing is placed in high-speed kneading machine, keeps rotating speed 1000-4000 rpm/min, high-speed stirred 5-30min；
D. by the PBS being well mixed, poly butyric ester,Polyolefin ionomers,Halloysite nanotubes, coupling agent, nucleator, chain extender, crosslinking agent, antioxidant, lubricant are added to screw extruder charge door, and screw extruder parameter is：One 85-130 DEG C of area, two 100-150 DEG C of areas, three 120-160 DEG C of areas, four 120-150 DEG C of areas, five 120-160 DEG C of areas, rotating speed is 10-150rpm/min, extruding pelletization；
E. will granulate in step D after son is dried and be extruded and processed into filament with screw extruder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510746315.5A CN106674918A (en) | 2015-11-05 | 2015-11-05 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
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|---|---|---|---|
| CN201510746315.5A CN106674918A (en) | 2015-11-05 | 2015-11-05 | Polyhydroxybutyrate-containing nano-tube composite wire preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN106674918A true CN106674918A (en) | 2017-05-17 |
Family
ID=58857395
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403904A (en) * | 2022-10-12 | 2022-11-29 | 盐城瑞泽色母粒有限公司 | Biodegradable PBAT color master batch and fiber prepared from same |
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|---|---|---|---|---|
| CN102459462A (en) * | 2009-06-26 | 2012-05-16 | 梅塔玻利克斯公司 | Pha compositions comprising pbs and pbsa and methods for their production |
| CN103641955A (en) * | 2013-11-25 | 2014-03-19 | 福建师范大学 | Polyolefin ionomer and application thereof |
| CN103755733A (en) * | 2013-12-20 | 2014-04-30 | 福建师范大学 | Functional organosiloxane containing asymmetrical substituted urea and preparation method thereof |
| CN105017734A (en) * | 2015-07-10 | 2015-11-04 | 清华大学 | Polymeric material for 3D printing and preparation method of polymeric material |
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2015
- 2015-11-05 CN CN201510746315.5A patent/CN106674918A/en not_active Withdrawn
Patent Citations (4)
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| CN102459462A (en) * | 2009-06-26 | 2012-05-16 | 梅塔玻利克斯公司 | Pha compositions comprising pbs and pbsa and methods for their production |
| CN103641955A (en) * | 2013-11-25 | 2014-03-19 | 福建师范大学 | Polyolefin ionomer and application thereof |
| CN103755733A (en) * | 2013-12-20 | 2014-04-30 | 福建师范大学 | Functional organosiloxane containing asymmetrical substituted urea and preparation method thereof |
| CN105017734A (en) * | 2015-07-10 | 2015-11-04 | 清华大学 | Polymeric material for 3D printing and preparation method of polymeric material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115403904A (en) * | 2022-10-12 | 2022-11-29 | 盐城瑞泽色母粒有限公司 | Biodegradable PBAT color master batch and fiber prepared from same |
| CN115403904B (en) * | 2022-10-12 | 2024-01-30 | 盐城瑞泽色母粒有限公司 | Biodegradable PBAT color master batch and fiber prepared from same |
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Application publication date: 20170517 |