CN103483581A - Transparent polyamide and synthetic method thereof - Google Patents

Transparent polyamide and synthetic method thereof Download PDF

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CN103483581A
CN103483581A CN201310430548.5A CN201310430548A CN103483581A CN 103483581 A CN103483581 A CN 103483581A CN 201310430548 A CN201310430548 A CN 201310430548A CN 103483581 A CN103483581 A CN 103483581A
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salt
polyamide
transparent
diamine
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CN103483581B (en
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王庭慰
邹盛之
韩硕
王莉莉
项尚林
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Nanjing Tech University
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Abstract

The invention discloses a transparent polyamide and a synthesis method thereof, wherein the polyamide has good transparency and wear resistance. The transparent polyamide of the invention has the following structural formula I:
Figure DDA0000384822390000011
wherein: r1Represented by polymethylene- (CH)2)aA is an integer between 6 and 10; r2Represented by polymethylene- (CH)2)bB is an integer of 4-10; r3The compound is a molecular group which is composed of carbon and hydrogen elements and contains a side group or a ring structure; r4Represented by a molecular group containing a pendant group or a cyclic structure, which may be bonded to R, formed by carbon or hydrogen3The same or different; x and y are integers, and the sum of x and y is between 150 and 250.

Description

A kind of transparent polyamide and synthetic method thereof
Technical field
The present invention relates to its synthetic method of a kind of polymeric amide, more specifically to a kind of transparent polyamide and synthetic method thereof.
Background technology
Nylon (polymeric amide) is that to be applied to the earliest be also a kind of thermoplastic engineering plastic that Present Domestic is most widely used outward.It has good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, certain flame retardant resistance is arranged, be easy to processing, be suitable for by glass fibre and other filler filling enhancing modified, steady-state growth in the cut-throat competition with other engineering plastics for many years, its demand still occupy the first place of five large-engineering plastics so far always.In many application, special at some to the exigent occasion of the physical and mechanical properties of transparent material, general transparent material oneself through not meeting people's requirement, so be the research to transparent polyamide, especially more noticeable.
Transparent nylon belongs to special nylon, some external companies have launched research to this, and realized suitability for industrialized production, " Trogamid " T developed as Dynamid Nobel company, the PACP9/6 that Phillips petrodeum company develops, " Isonamid " PA-7030 that " Grilamid " TR-55 that EMS company develops and Dow Chemical company develop.And at home, less about the research of transparent nylon, start late, and suitability for industrialized production is blank especially, complete dependence on import, and the domestic market demand amount is large, and every annual requirement is more than 10000 tons, and mainly from external import, price is up to ten thousand yuan of 15-20.Therefore the transparent polyamide material that exploitation has independent intellectual property right, fill the domestic gaps, significant to the fast development of domestic relevant industries.
Tradition fatty polyamide (PA-46, PA-66, PA-610 etc.) occupies very important status in polyamide resin, and its output accounts for more than 90%, therefore no matter in output, range of application, or over-all properties and price equilibrium ratio, absolute predominance is arranged.In addition, from raw material, abundanter, industrial scale is large, technology maturation.If therefore in amorphous polyamide salt, mix fatty polyamide salt, can under the prerequisite that keeps its transparency, reduce costs, improve over-all properties.
The cyclic aliphatic diprotic acid can hinder the polyamide segment of synthesized and the motion of macromolecular chain, hinders its macromolecule crystallization, also can make its macromole keep certain snappiness.At present, considerably less with the bibliographical information of the synthetic transparent polyamide of cyclic aliphatic diprotic acid, almost do not have.The bibliographical information of amorphous polyamide salt and the copolymerization of traditional fatty polyamide salt is also considerably less, almost do not have.
About disclosed similar techniques has: the mixture that for patent US3847977, hexanolactam, two (4-aminocyclohexyl) methane and molar fraction are 50% above terephthalic acid and m-phthalic acid is raw material, through polycondensation, prepares transparence polymeric amide preferably.The shortcoming of this product is that water-intake rate is high, and with easily becoming blushing after boiling water treating.Take trimethylammonium hexanediamine (TMD) and terephthalic acid in patent US3962400 is raw material, and by batchwise polymerization method method technique, melt phase polycondensation makes the transparent polyamide of high molecular.Adopt laurolactam, 4 in patent EP2324672,4 '-diamino-3,3 '-dimethyl-dicyclohexyl methyl hydride, the m-phthalic acid that mol ratio is 95:5 and terephthaldehyde's acid mixture have synthesized the transparent polyamide with excellent optical property, thermomechanical property, dimensional stability.The aliphatics lactan that patent CN1092087 be take ring grease diamines, m-phthalic acid, terephthalic acid and contained at least 7 carbon atoms and be raw material, melt phase polycondensation obtains a kind of transparent polyamide of height chemical-resistant reagent.
There is following shortcoming in above prior art: only use in building-up process ring grease diamines and the branched aliphatic diamine that price is higher, thereby cost is higher.Simultaneously at present the high-performance transparent nylon is produced only for abroad, so exploitation has independent intellectual property right, transparent nylon that production cost is lower has important research and application value.
Summary of the invention:
The objective of the invention is to solve above-mentioned problems of the prior art with not enough, a kind of transparent polyamide is provided, this polymeric amide has the good transparency and wear resistance.
The present invention also provides the preparation method with this transparent polyamide, and the method is simple and convenient, and cost is lower.
The present invention is achieved by the following technical solutions:
Transparent polyamide of the present invention, it has the structural formula of following I:
Figure BDA0000384822380000021
Wherein:
R 1that represent is polymethylene-(CH 2) a-, a is the integer between 6~10;
R 2that represent is polymethylene-(CH 2) b-, b is the integer between 4~10;
R 3what represent is the molecular radical that contains side group or ring texture formed with carbon, protium;
R 4representative be the molecular radical that contains side group or ring texture formed with carbon, protium, can with R 3identical or different;
X and y are integer, and itself and x+y are between 150~250.
The preparation method of the transparent polyamide that the present invention is above-mentioned, it comprises the following steps:
(1) polyamide salt is synthetic:
1. amorphous polyamide salt is synthetic: by the diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make amorphous polyamide salt; If not the crystalline state polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out amorphous polyamide dry;
2. fatty polyamide salt is synthetic: by the aliphatic diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make fatty polyamide salt; If fatty polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out fatty polyamide dry;
(2) polymeric amide is synthetic: by 50~100 weight part amorphous polyamide salt, and 0~50 weight part fatty polyamide salt, 0.1~2 weight part catalyzer, 0.1~1 weight part oxidation inhibitor adds in reactor successively; The hybrid reaction system is warming up to 190~240 ℃ under the condition vacuumized, and is incubated 4~6h; Continue to keep subsequently its vacuum state, be warming up to 260 ℃~310 ℃, then be incubated discharging after 4~6h, make transparent polyamide.
The preparation method of transparent polyamide of the present invention, in the synthesis step that its further technical scheme is described amorphous polyamide salt, diamine is the diamine that contains unsymmetrical structure or the diamine that contains benzene ring structure, and described diprotic acid is the diprotic acid that contains ring texture; Further technical scheme is that the described diamine that contains unsymmetrical structure is the trimethylammonium hexanediamine; The described diamine that contains benzene ring structure is Ursol D, mphenylenediamine, p dimethylamine or m-xylene diamine; The described diprotic acid that contains ring texture is to cyclohexyl dioctyl phthalate, terephthalic acid or m-phthalic acid.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that described fatty polyamide salt is one or more in polymeric amide-46 salt, polymeric amide-66 salt, polymeric amide-610 salt, polymeric amide-1010 salt.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that described organic solvent is ethanol.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that the catalyzer described in step (2) is one or more in sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that the oxidation inhibitor described in step (2) is tin protochloride.
The reaction equation of this reaction is:
Figure BDA0000384822380000031
Compared with prior art the present invention has following beneficial effect:
1) aliphatic diamine used in the present invention and aliphatic dibasic acid all can be from oil or Viscotrol C, and cost is lower; 2) polymeric amide that the present invention makes has the good transparency, plants thus the film transmittance that polymeric amide prepares and can reach more than 80%, and mist degree can reach below 40%; 3) the polymeric amide hardness that the present invention makes except the good transparency also is better than traditional polythene PE for the preparation of the transparent plastics product, polypropylene PP, polyester PET etc., has improved the wear resistance of transparent plastics product; 4) in the present invention, the equipment for the preparation of transparent polyamide is simple, effectively reduces cost; 5) the preparation process continuous and compact of transparent polyamide in the present invention, effectively shortened polymerization cycle, improved working efficiency.
Embodiment
Transparency, be the WGW photoelectricity mist degree instrument that adopts Physical Optics Instrument FActory, Shanghai Precision Science Instrument Co., L to produce in an embodiment, by standard method of test GR/T2410-2008, undertaken.
Embodiment 1
The preparation method of transparent polyamide salt-polyamide 66 salt copolymer, its preparation process is:
(1) polyamide salt is synthetic:
1. amorphous polyamide salt is synthetic: take 8.609g(0.05mol) to the cyclohexyl dioctyl phthalate, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ makes the cyclohexyl dioctyl phthalate is dissolved.Take in addition 7.915g(0.05mol) the trimethylammonium hexanediamine, be placed in the 250mL Erlenmeyer flask that 60ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved the trimethylammonium hexanediamine.Subsequently the spirituous solution of trimethylammonium hexanediamine is poured in the spirituous solution to the cyclohexyl dioctyl phthalate, the vibration Erlenmeyer flask, salt out amorphous polyamide.During not heat release of reaction system, amorphous polyamide salt is filtered in bottle, be placed in the vacuum drying oven of 40 ℃ and dry.
2. polymeric amide-66 salt is synthetic: take 7.307g(0.05mol) hexanodioic acid, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved hexanodioic acid.Take in addition 5.815g(0.05mol) hexanediamine, be placed in the 250mL Erlenmeyer flask that 60ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved hexanediamine.Subsequently the spirituous solution of hexanediamine is poured in the spirituous solution of own dioctyl phthalate, the vibration Erlenmeyer flask, salt out polymeric amide-66.During not heat release of reaction system, polymeric amide-66 salt is filtered in bottle, be placed in the vacuum drying oven of 40 ℃ and dry.
(2) polymeric amide is synthetic: by 2.7 gram amorphous polyamide salt, 0.3 gram polymeric amide-66 salt adds in test tube successively, adds subsequently 2 of the SODIUM PHOSPHATE, MONOBASIC of concentration 0.075g/mL, 1 of the stannous chloride solution of concentration 0.075g/mL.Test tube is evacuated to vacuum tightness is-0.095~-0.10MPa between, with post-heating test tube to 180 ℃, now, invisible spectro polyamide 66 salt starts melting reaction, emits a large amount of water vapour.The reaction liberated heat makes temperature of reaction system continue to rise, and reaches the fusing point (210 ℃) of transparent polyamide salt, the melting of transparent polyamide salt reaction.After the test tube inner salt all melts, regulate design temperature, make 230 ℃ of its insulations, pressurize-0.10MPa, 5h, generate the prepolymer of wax-like transparent polyamide salt-polyamide 66 salt copolymer in vitro.Afterwards, keep in vitro original vacuum tightness, and progressively heat up.When temperature rises to 270 ℃ of left and right, prepolymer starts to melt and reacts and emit a large amount of water vapour.Continue to be warming up to 300 ℃, be incubated 300 ℃, after pressurize-0.1MPa, 4h, still keep in vitro original vacuum tightness, reaction system is slowly cooled to room temperature, take out product.Its structure through result after phenetic analysis as scheme lower as shown in.The film transmittance of making through this polymeric amide can reach 88.0%, and mist degree can reach 39.0%.
Figure BDA0000384822380000041
Embodiment 2
The preparation method of transparent polyamide, its preparation process is:
(1) polyamide salt is synthetic:
Synthesizing of amorphous polyamide salt: take 8.609g(0.05mol) to the cyclohexyl dioctyl phthalate, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ makes the cyclohexyl dioctyl phthalate is dissolved.Take in addition 7.915g(0.05mol) the trimethylammonium hexanediamine, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved the trimethylammonium hexanediamine.Subsequently the spirituous solution of trimethylammonium hexanediamine is poured in the spirituous solution to the cyclohexyl dioctyl phthalate, the vibration Erlenmeyer flask, salt out amorphous polyamide.During not heat release of reaction system, amorphous polyamide salt is filtered in bottle, be placed in the vacuum drying oven of 40 ℃ and dry.
(2) polymeric amide is synthetic: 3 gram transparent polyamide salt are added in test tube, add subsequently 2 of the SODIUM PHOSPHATE, MONOBASIC of concentration 0.075g/mL, 1 of the stannous chloride solution of concentration 0.075g/mL.Test tube is evacuated to vacuum tightness is-0.095~-0.10MPa between, with post-heating test tube to 210 ℃, the melting of transparent polyamide salt reaction in reactor, emit a large amount of water vapour, after the whole meltings of test tube inner salt, regulate design temperature, make 230 ℃ of its insulations, pressurize-0.10MPa, 5h, generate wax-like polyamide prepolymer polymers in vitro.Afterwards, keep in vitro original vacuum tightness, continue to heat up.When temperature rises to 270 ℃, prepolymer starts to melt and reacts and emit a large amount of water vapour.Continue to be warming up to 300 ℃, be incubated 300 ℃, after pressurize-0.1MPa, 4h, still keep in vitro original vacuum tightness, reaction system is slowly cooled to room temperature, break test tube into pieces, take out product.Its structure result after phenetic analysis is as follows.The film transmittance of making through this polymeric amide can reach 85.8%.Mist degree can reach 37.4%.
Figure BDA0000384822380000051

Claims (8)

1. a transparent polyamide is characterized in that having the structural formula of following I:
Figure FDA0000384822370000011
Wherein:
R 1that represent is polymethylene-(CH 2) a-, a is the integer between 6~10;
R 2that represent is polymethylene-(CH 2) b-, b is the integer between 4~10;
R 3what represent is the molecular radical that contains side group or ring texture formed with carbon, protium;
R 4representative be the molecular radical that contains side group or ring texture formed with carbon, protium, can with R 3identical or different;
X and y are integer, and itself and x+y are between 150~250.
2. the preparation method of transparent polyamide as claimed in claim 1 is characterized in that comprising the following steps:
(1) polyamide salt is synthetic:
1. amorphous polyamide salt is synthetic: by the diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make amorphous polyamide salt; If not the crystalline state polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out amorphous polyamide dry;
2. fatty polyamide salt is synthetic: by the aliphatic diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make fatty polyamide salt; If fatty polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out fatty polyamide dry;
(2) polymeric amide is synthetic: by 50~100 weight part amorphous polyamide salt, and 0~50 weight part fatty polyamide salt, 0.1~2 weight part catalyzer, 0.1~1 weight part oxidation inhibitor adds in reactor successively; The hybrid reaction system is warming up to 190~240 ℃ under the condition vacuumized, and is incubated 4~6h; Continue to keep subsequently its vacuum state, be warming up to 260 ℃~310 ℃, then be incubated discharging after 4~6h, make transparent polyamide.
3. the preparation method of transparent polyamide according to claim 2, it is characterized in that diamine in the synthesis step of described amorphous polyamide salt is the diamine that contains unsymmetrical structure or the diamine that contains benzene ring structure, described diprotic acid is the diprotic acid that contains ring texture.
4. the preparation method of transparent polyamide according to claim 3, is characterized in that the described diamine that contains unsymmetrical structure is the trimethylammonium hexanediamine; The described diamine that contains benzene ring structure is Ursol D, mphenylenediamine, p dimethylamine or m-xylene diamine; The described diprotic acid that contains ring texture is to cyclohexyl dioctyl phthalate, terephthalic acid or m-phthalic acid.
5. the preparation method of transparent polyamide according to claim 2, is characterized in that described fatty polyamide salt is one or more in polymeric amide-46 salt, polymeric amide-66 salt, polymeric amide-610 salt, polymeric amide-1010 salt.
6. the preparation method of transparent polyamide according to claim 2, is characterized in that described organic solvent is ethanol.
7. the preparation method of transparent polyamide according to claim 2, is characterized in that the catalyzer described in step (2) is one or more in sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC.
8. the preparation method of transparent polyamide according to claim 2, is characterized in that the oxidation inhibitor described in step (2) is tin protochloride.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111454448A (en) * 2019-05-14 2020-07-28 住华科技股份有限公司 Polyamide and method for producing same
CN118580488A (en) * 2024-08-07 2024-09-03 山东广垠新材料有限公司 High-toughness copolymerized transparent polyamide and preparation method thereof

Citations (2)

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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3646156A (en) * 1968-10-30 1972-02-29 Dynamit Nobel Ag Polyamide containers of 2 2 4 and/or 2 4 4 tri-methyl hexamethylene diamine
CN103122065A (en) * 2013-02-05 2013-05-29 中北大学 Preparation method of transparent polyamide-polyamide 11 copolymer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李巍: "多元共缩聚透明聚酰胺的制备、结构与性能", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 4, 15 April 2013 (2013-04-15) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111454448A (en) * 2019-05-14 2020-07-28 住华科技股份有限公司 Polyamide and method for producing same
CN111454448B (en) * 2019-05-14 2023-03-28 住华科技股份有限公司 Polyamide and method for producing same
CN118580488A (en) * 2024-08-07 2024-09-03 山东广垠新材料有限公司 High-toughness copolymerized transparent polyamide and preparation method thereof

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