CN102993024B - Method for producing N,N'-dimethyl cyclohexanediamine - Google Patents
Method for producing N,N'-dimethyl cyclohexanediamine Download PDFInfo
- Publication number
- CN102993024B CN102993024B CN201210383740.9A CN201210383740A CN102993024B CN 102993024 B CN102993024 B CN 102993024B CN 201210383740 A CN201210383740 A CN 201210383740A CN 102993024 B CN102993024 B CN 102993024B
- Authority
- CN
- China
- Prior art keywords
- cyclohexanediamine
- dimethyl
- reaction
- add
- production method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- ROHGINRQAFHUPY-UHFFFAOYSA-N 1-n,1-n'-dimethylcyclohexane-1,1-diamine Chemical compound CNC1(NC)CCCCC1 ROHGINRQAFHUPY-UHFFFAOYSA-N 0.000 title claims abstract description 7
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 230000001035 methylating effect Effects 0.000 claims abstract description 6
- 238000007069 methylation reaction Methods 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- YGBFHAIFQIZTSB-UHFFFAOYSA-N 4,4-dimethylcyclohexane-1,1-diamine Chemical compound CC1(C)CCC(N)(N)CC1 YGBFHAIFQIZTSB-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006277 sulfonation reaction Methods 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SSJXIUAHEKJCMH-OLQVQODUSA-N (1s,2r)-cyclohexane-1,2-diamine Chemical compound N[C@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-OLQVQODUSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- -1 aryl benzene sulfonyl chloride Chemical compound 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 2
- 230000011987 methylation Effects 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Abstract
The invention discloses a method for producing N,N'-dimethyl cyclohexanediamine, which comprises the following steps of: reacting cyclohexanediamine with aryl benzene sulfonyl chloride to protect the nitrogenous base; implementing a methylation by a methylating reagent; and removing aryl benzenesulfonyl by hydrolysis of sulfuric acid, to obtain the target product N,N'-dimethyl cyclohexanediamine. The method for producing N,N'-dimethyl cyclohexanediamine disclosed by the invention is simple in process, low in raw material cost, toxic-free in production process and high in product purity to be greater than 98%.
Description
technical field
The present invention relates to a kind of N, the production method of N ' dimethyl cyclohexanediamine.
background technology
N, N ' dimethyl cyclohexanediamine, molecular formula is C
8h
17n, has another name called dimethylcyclohexylamine, and main application is the catalyzer as rigid urethane foam, is used in that refrigerator hard bubbles, sheet material, spraying, in-site pouring hard polyurethane foam.Document (Journal of the American Chemical Society, 2002,124 (39): 11684-11688) reported a kind of N, the production method of N ' dimethyl cyclohexanediamine, first cyclohexanediamine is reacted with chloro-formic ester or manthanoate, then adopt lithium aluminium hydride reduction above-mentioned for hazardous substance reactant obtains target product, the shortcoming of the method is: reaction raw materials price, strong reductant lithium aluminum hydride has severe toxicity.Therefore, finding a safer operational path reliable, that be easy to industrialization production replaces the technique of above-mentioned danger to become very meaningful.
summary of the invention
The object of this invention is to provide a kind of low cost, the N that easy to operate, technique is simple, safe and reliable, the production method of N ' dimethyl cyclohexanediamine.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of N, the production method of N ' dimethyl cyclohexanediamine, is characterized in that: comprise the following steps: successively
1) sulfonation reaction: cyclohexanediamine is added in solvent, be uniformly mixed liquid, above-mentioned mixed solution is dropwise joined in the mixing solutions of fragrant benzene sulfonyl chloride and pyridine, drip process control temp below 60 ℃, drip and finish, be placed at the temperature of 10-100 ℃ and react 7h, after end, add hydrochloric acid to adjust pH to 6-7, leave standstill 24h, processing obtains intermediate N, N '-dialkyl benzene alkylsulfonyl cyclohexanediamine;
2) methylate: by step 1) N, N '-dialkyl benzene alkylsulfonyl cyclohexanediamine is dissolved in acetonitrile, add potassium carbonate powder, under normal temperature, stir 1h, be placed in ice bath and carry out methylation reaction with methylating reagent, aftertreatment obtains intermediate N, N '-dimethyl-N, N '-dialkyl benzene alkylsulfonyl cyclohexanediamine;
3) hydrolysis: in step 2) add the vitriol oil to be heated to 60-150 ℃ of hydrolysis reaction 4 hours in intermediate, then add frozen water, slowly add in sodium hydroxide and after, by extracted with diethyl ether, aftertreatment obtains target product N, N ' dimethyl cyclohexanediamine, and reaction process is as follows:
Wherein, R is C
0-C
15benzene sulfonamide acyl group.
Effectively, cyclohexanediamine described in step 1) is 1,2 cyclohexanediamine or 1,3 cyclohexanediamine or Isosorbide-5-Nitrae cyclohexanediamine, described fragrant benzene sulfonyl chloride be adjacent, or contraposition C
0-C
15alkylbenzene sulfonyl chloride, described solvent is pyridine or triethylamine.
Effectively, temperature of reaction described in step 1) is 10-35 ℃.
Effectively, step 2) described in methylating reagent be methyl iodide, monobromethane or methyl-sulfate.
The invention has the advantages that: the present invention piles nitrogen base in cyclohexanediamine by sulfonation reaction and protects; carrying out methylation reaction with methylating reagent; finally hydrolysis is removed fragrant benzene sulfonyl chloride and is made N; N ' dimethyl cyclohexanediamine; technique of the present invention is simple, raw materials cost is low, production process is nontoxic, and product purity is greater than 98%.
Embodiment
In order to make the public can fully understand technical spirit of the present invention and beneficial effect; applicant will describe in detail the specific embodiment of the present invention below; but applicant is not the restriction to technical scheme to the description of embodiment, anyly changes in the form rather than substance and all should be considered as protection scope of the present invention according to the present invention design.
Embodiment 1
Step 1: the sulfonation of cyclohexanediamine
By 1 of 20mmol, 2-cyclohexanediamine is dissolved in 10ml pyridine, above-mentioned solution is dropwise joined in the 10ml pyridine solution that is mixed with 40mmol Tosyl chloride, when dropping, control temperature below 60 ℃, when solution colour, is dripped and finishes while becoming garnet from colourless, be placed under normal temperature and react 7h, stopped reaction, add 15% hydrochloric acid to adjust pH to 6-7, leave standstill 24h, filter, and use respectively 10ml water washing solid 3 times, obtain 6.5g white powder solid.
Step 2: methylate
Step 1 product 7.18mmol is dissolved in 60ml acetonitrile, adds 28.7mmol potassium carbonate powder, under normal temperature, stir 1h, be placed under ice bath and add 28.7mmol methyl iodide, under ice bath, react 30min, under room temperature, react 12h again after removing ice bath, stopped reaction, revolves to steam and removes acetonitrile, adds 20ml water, methylene dichloride (30ml × 3) extraction, merge organic layer, washing (90ml × 2), anhydrous sodium sulfate drying 2h, revolve and steam except desolventizing, separate and obtain product 2.89g.
Step 3: hydrolysis
In step 2 product 4.48mmol, add the 35.84mmol vitriol oil, be heated to 80 ℃ of reaction 4h.Stopped reaction adds 60ml frozen water in reaction solution, slowly adds 71.68mmol sodium hydroxide, stirs 1h, with ether (60ml × 3) extraction, merges organic layer, and washing, revolves and steam except desolventizing, and rectifying obtains product 0.35g, and product purity is 98.3%.
Embodiment 2
Step 1: the sulfonation of cyclohexanediamine
Isosorbide-5-Nitrae-cyclohexanediamine of 20mmol is dissolved in 10ml pyridine, above-mentioned solution is dropwise joined in the 10ml pyridine solution that is mixed with 40mmol Tosyl chloride, when dropping, control temperature below 60 ℃, when solution colour, is dripped and finishes while becoming garnet from colourless, be placed under normal temperature and react 7h, stopped reaction, add 15% hydrochloric acid to adjust pH to 6-7, leave standstill 24h, filter, and use respectively 10ml water washing solid 3 times, obtain 7.3g white powder solid.
Step 2: methylate
Step 1 product 7.18mmol is dissolved in 60ml acetonitrile, adds 28.7mmol potassium carbonate powder, under normal temperature, stir 1h, be placed under ice bath and add 28.7mmol methyl iodide, under ice bath, react 30min, under room temperature, react 12h again after removing ice bath, stopped reaction, revolves to steam and removes acetonitrile, adds 20ml water, methylene dichloride (30ml × 3) extraction, merge organic layer, washing (90ml × 2), anhydrous sodium sulfate drying 2h, revolve and steam except desolventizing, separate and obtain product 3.12g.
Step 3: hydrolysis
In step 2 product 4.48mmol, add the 35.84mmol vitriol oil, be heated to 80 ℃ of reaction 4h.Stopped reaction adds 60ml frozen water in reaction solution, slowly adds 71.68mmol sodium hydroxide, stirs 1h, with ether (60ml × 3) extraction, merges organic layer, and washing, revolves and steam except desolventizing, and rectifying obtains product 0.45g, and product purity is 98.8%.
Claims (4)
1. a N, the production method of N ' dimethyl cyclohexanediamine, is characterized in that: comprise the following steps: successively
1) sulfonation reaction: cyclohexanediamine is added in solvent, be uniformly mixed liquid, above-mentioned mixed solution is dropwise joined in the mixing solutions of fragrant benzene sulfonyl chloride and pyridine, drip process control temp below 60 ℃, drip and finish, be placed at the temperature of 10-100 ℃ and react 7h, after end, add hydrochloric acid to adjust pH to 6-7, leave standstill 24h, processing obtains intermediate N, N '-dialkyl benzene alkylsulfonyl cyclohexanediamine;
2) methylate: by step 1) N, N '-dialkyl benzene alkylsulfonyl cyclohexanediamine is dissolved in acetonitrile, add potassium carbonate powder, under normal temperature, stir 1h, be placed in ice bath and carry out methylation reaction with methylating reagent, aftertreatment obtains intermediate N, N '-dimethyl-N, N '-dialkyl benzene alkylsulfonyl cyclohexanediamine;
3) hydrolysis: in step 2) add the vitriol oil to be heated to 60-150 ℃ of hydrolysis reaction 4 hours in intermediate, then add frozen water, slowly add in sodium hydroxide and after, by extracted with diethyl ether, aftertreatment obtains target product N, N ' dimethyl cyclohexanediamine, and reaction process is as follows:
Wherein, R is C
0-C
15benzene sulfonamide acyl group.
2. a kind of N according to claim 1, the production method of N ' dimethyl cyclohexanediamine, is characterized in that: cyclohexanediamine described in step 1) is 1,2 cyclohexanediamine or 1,3 cyclohexanediamine or Isosorbide-5-Nitrae cyclohexanediamine, described fragrant benzene sulfonyl chloride be adjacent, or contraposition C
0-C
15alkylbenzene sulfonyl chloride, described solvent is pyridine or triethylamine.
3. a kind of N according to claim 1, the production method of N ' dimethyl cyclohexanediamine, is characterized in that: temperature of reaction described in step 1) is 10-35 ℃.
4. a kind of N according to claim 1, the production method of N ' dimethyl cyclohexanediamine, is characterized in that: step 2) described in methylating reagent be methyl iodide, monobromethane or methyl-sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210383740.9A CN102993024B (en) | 2012-10-11 | 2012-10-11 | Method for producing N,N'-dimethyl cyclohexanediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210383740.9A CN102993024B (en) | 2012-10-11 | 2012-10-11 | Method for producing N,N'-dimethyl cyclohexanediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102993024A CN102993024A (en) | 2013-03-27 |
| CN102993024B true CN102993024B (en) | 2014-06-18 |
Family
ID=47922208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210383740.9A Expired - Fee Related CN102993024B (en) | 2012-10-11 | 2012-10-11 | Method for producing N,N'-dimethyl cyclohexanediamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102993024B (en) |
-
2012
- 2012-10-11 CN CN201210383740.9A patent/CN102993024B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| An efficient synthesis of tetrasubstituted cyclohexyl-1,2-diamines;Hitesh Arjan等;《Tetrahedron Letters》;20051231;第46卷(第11期);1921-1925 * |
| Contrasitive Photoreduction Pathways of Benzophenones Governed by Regiospecific Deprotonation of Imidazoline Radical Cations and Additive Effects;Eietsu Hasegawa等;《J. Org. Chem》;20051018;第70卷(第23期);附加信息 * |
| Eietsu Hasegawa等.Contrasitive Photoreduction Pathways of Benzophenones Governed by Regiospecific Deprotonation of Imidazoline Radical Cations and Additive Effects.《J. Org. Chem》.2005,第70卷(第23期),附加信息. |
| HiteshArjan等.Anefficientsynthesisoftetrasubstitutedcyclohexyl-1 2-diamines.《Tetrahedron Letters》.2005 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102993024A (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103304437B (en) | Method for synthesizing oseltamivir phosphate without using nitrine | |
| CN102675167B (en) | Preparation method of p-methylsulfonyl benzaldehyde | |
| CN102050788B (en) | Method for synthesizing halogen-free imidazole ionic liquid | |
| CN102993246A (en) | Method for synthesizing isopropyl-beta-D-thiogalactoside | |
| CN108707095A (en) | The continuous method for preparing sulfuric acid vinyl ester | |
| CN104910012A (en) | Method for preparing 1-ethylcyclohexyl acrylate | |
| CN103965125A (en) | Synthetic method of 3,3'-binitro-5,5'-di-1,2,4-triazole | |
| CN103232403B (en) | A kind of preparation method of nitrogen heterocyclic | |
| CN102993024B (en) | Method for producing N,N'-dimethyl cyclohexanediamine | |
| CN102584928B (en) | Preparation method for trans-glycyrrhizic acid | |
| CN104497088A (en) | Method for preparing 19- nor-4-androstene-3, 17-diketone | |
| CN104003934B (en) | The synthesis of the fluoro-2-pyridine carboxylic acid of the chloro-3-of 6- | |
| CN103709209A (en) | Isopropyl-beta-D-thiogalactoside preparation method | |
| CN102731315A (en) | Production method for N,N'dimethylcyclohexanediamine | |
| CN102731316B (en) | Production method for 1,2-N,N'dimethylcyclohexanediamine | |
| CN102531854A (en) | Synthesis method for 4-bromo-2, 6-difluoro-trifluoromethoxybenzene | |
| CN102153462A (en) | Method for synthesizing tanshinol | |
| CN102993025B (en) | Synthetic method of dimethyl cyclohexanediamine aromatic ring | |
| CN101781250A (en) | Method for synthesizing low bromine content iminazole ionic liquid | |
| CN103665063A (en) | Method for preparing isopropyl-beta-D-isopropylthiogalactoside | |
| CN102993165A (en) | Synthesis method of 5-chlorothiophene-2-formic acid | |
| CN105017232A (en) | Synthesis method of triazole bactericide | |
| CN103145626B (en) | Method for synthesizing 4-amino-2-(methylmercapto) pyrimidine-5-formaldehyde | |
| CN102617540A (en) | Method for preparing (S)-3,6-dioxo-5,6-isopropylidene-5,6-dyhydroxyl hexanoic acid tert-butyl ester | |
| CN103694285B (en) | A kind of preparation method of isopropyl-β-D-thiogalactoside(IPTG) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Yancheng Inventor before: Wang Defeng Inventor before: Shi Fei Inventor before: Wang Bingcai Inventor before: Zhang Yaobin Inventor before: Zhu Xiaofei Inventor before: Yu Jianjun |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: WANG DEFENG SHI FEI WANG BINGCAI ZHANG YAOBIN ZHU XIAOFEI YU JIANJUN TO: ZHANG YANCHENG |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161009 Address after: 226500 Zhang Yang village, Shi Zhuang Town, Jiangsu, Rugao Patentee after: Nantong Wanshun Chemical Technology Co., Ltd. Address before: 226500 Shi Zhuang Town, Nantong City, Jiangsu, Rugao Patentee before: Huafeng Chemical Co., Ltd., Nantong City |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161229 Address after: 226500 Zhang Yang village, Shi Zhuang Town, Jiangsu, Rugao Patentee after: Huafeng Chemical Co., Ltd., Nantong Address before: 226500 Zhang Yang village, Shi Zhuang Town, Jiangsu, Rugao Patentee before: Nantong Wanshun Chemical Technology Co., Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171214 Address after: 065402 Langfang city of Hebei province Xianghe County ZTE Backstreet No. 11 Tin Yuet District Building 3 room 2201 unit 2 Patentee after: Jiang Shulin Address before: 226500 Zhang Yang village, Shi Zhuang Town, Jiangsu, Rugao Patentee before: Huafeng Chemical Co., Ltd., Nantong City |
|
| 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: 20140618 Termination date: 20191011 |