CN1255376C - Preparation method of tetraacetylethylenediamine - Google Patents
Preparation method of tetraacetylethylenediamine Download PDFInfo
- Publication number
- CN1255376C CN1255376C CNB021122431A CN02112243A CN1255376C CN 1255376 C CN1255376 C CN 1255376C CN B021122431 A CNB021122431 A CN B021122431A CN 02112243 A CN02112243 A CN 02112243A CN 1255376 C CN1255376 C CN 1255376C
- Authority
- CN
- China
- Prior art keywords
- reaction
- preparation
- ethylenediamine
- quadrol
- ethylene diamine
- 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 - Lifetime
Links
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 26
- WNYIBZHOMJZDKN-UHFFFAOYSA-N n-(2-acetamidoethyl)acetamide Chemical compound CC(=O)NCCNC(C)=O WNYIBZHOMJZDKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical group CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 13
- 239000000047 product Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004061 bleaching Methods 0.000 abstract description 3
- 238000007039 two-step reaction Methods 0.000 abstract description 3
- 239000012190 activator Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010792 warming Methods 0.000 description 6
- SGVUHPSBDNVHKL-UHFFFAOYSA-N 1,3-dimethylcyclohexane Chemical compound CC1CCCC(C)C1 SGVUHPSBDNVHKL-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- -1 it can make SPC-D Chemical compound 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-O triethanolammonium Chemical compound OCC[NH+](CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-O 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of tetraacetylethylenediamine belongs to the technical field of preparation of bleaching activators in detergents. It is prepared through synthesizing diacetyl ethylenediamine from ethylenediamine and acetic acid, and synthesizing tetraacetyl ethylenediamine from resultant and acetic anhydride. The present invention features that solvent capable of azeotroping with acetic acid and producing no side reaction with acetic acid and acetic anhydride is added during the synthesis reaction, and catalyst is added during both synthesis reactions. In the first step, ethylenediamine is dripped into acetic acid solution at the temperature of less than 80 ℃, and the temperature is raised, the reflux is carried out and the dehydration is carried out; the second reaction step is carried out at a temperature not exceeding 132 ℃. The filtrate of the two-step reaction can be recycled, which is favorable for improving the purity of the product and reducing the consumption of raw materials and energy. The tetraacetylethylenediamine prepared by the method has white appearance and purity of more than 99 percent, and has obvious benefit.
Description
Technical field
The present invention relates to tetraacetyl ethylene diamine preparation technology, belong to the preparing technical field of bleach-activating agent in the washing composition.
Background technology
Tetraacetyl ethylene diamine (TAED), it can make SPC-D, Sodium peroxoborate that bleaching action takes place at normal temperatures under content 0.5～5% situation, is a kind of activator that can adapt to cold bleaching therefore.At present, the synthetic preparation of TAED is many to be raw material with quadrol, acetate and diacetyl oxide, adopts for two steps with still preparation technology.English Patent GB1335204 is open, and the first step is synthesized oxalyl quadrol (DAED) with quadrol and acetate earlier, and then carries out the second step acetylize with diacetyl oxide.Europe patent EP8369 is open, adopts operate continuously, and is directly synthetic on distillation column by quadrol and diacetyl oxide, but it need use all acetylize raw materials of expensive diacetyl oxide conduct, and cost is high.English Patent GB20-96133A, GB2106903A openly adopts the reactor of twin columns, and first post is finished acetate and reacting ethylenediamine, and second post carries out the diacetyl oxide acetylization reaction, and by product returns the first post reuse and substitutes acetate.
In the two step method building-up reactions, for improving reaction efficiency, adopt usually to add dewatering agent, form and the water azeotropic.In the reaction of second step, add as catalyzer such as phosphoric acid, sulfuric acid, boric acid, zinc acetates.But the dewatering agent that adds can produce side reaction with acetate, diacetyl oxide usually.Simultaneously, because the speed of response of diacetyl oxide and diacetyl ethylenediamine is slower, need come fast reaction speed by improving temperature of reaction, therefore general temperature of reaction is more than 135 ℃, to obtain higher yield.But the raising of temperature of reaction can make side reaction increase, and the product color of acquisition is deepened and influenced the product appearance quality of TAED.
Summary of the invention
The objective of the invention is to design and a kind ofly can suppress side reaction, reduce raw material and energy consumption, the preparation method of two step synthesis of acetyl quadrols of good product quality.
Purpose of the present invention is achieved through the following technical solutions:
By quadrol and acetate synthesis of diacetyl ethylenediamine, by diacetyl ethylenediamine and the synthetic tetraacetyl ethylene diamine of diacetyl oxide, it is characterized in that in building-up reactions, adding and acetate azeotropic solvent again; Add the tungstosilicic acid triethanolamine salt in the building-up reactions, chlorination four tertiary butyl ammoniums, a kind of mixture with several of atlapulgite and tosic acid is a catalyzer; The mol ratio of quadrol and acetic acidreaction 1: 2.3～3.0,90～120 ℃ of reaction dehydration temperaturres; Diacetyl ethylenediamine and acetic anhydride mol ratio are 1: 4～9,110～132 ℃ of synthesis reaction temperatures.
Described azeotropic solvent is diisobutyl ether, toluene, ethylbenzene, dimethylbenzene, chlorobenzene, 1,3-dimethyl cyclohexane, octane a kind of or several mixing solutions, add-on is that 80～800%, second when reaction step of quadrol is 30～400% of diacetyl ethylenediamine.
Described catalyzer add-on the first step reaction is 1～3% of quadrol; The reaction of second step is 1～10% of diacetyl ethylenediamine.
The described the first step is reflected at and is lower than in the mixed solution that quadrol under 80 ℃ of temperature adds acetate and azeotropic solvent, drips the back temperature rising reflux and dewaters.
After adding reactant, described building-up reactions filtrate can be recycled.
The present invention building-up reactions need add can with acetate azeotropic solvent, these solvents comprise diisobutyl ether, 1,3-dimethyl cyclohexane, toluene, ethylbenzene, dimethylbenzene, o-Xylol, octane, chlorobenzene, benzene.These solvents can not produce side reaction with acetate and diacetyl oxide usually.
Another technique effect of the present invention is to add catalyzer in the first step reaction, and the used catalyzer of two-step reaction has and the better activation of reactant, thereby synthesis reaction temperature is reduced, and helps improving the color and luster of reaction product.
The filtrate that the 3rd technique effect of the present invention is two-step reaction can reuse, and perhaps the first step reaction solution can be used for the reaction of second step, so not only can cut down the consumption of raw materials, and the recycled of mother liquor, can improve the purity of crystallized product.
Measure through simultaneous test, the performance comparison of the tetraacetyl ethylene diamine of the TAED of the present invention's preparation and the preparation of common two-step approach is as follows:
| Title | Product appearance | Purity | Remarks |
| Usual way | Yellow | 98.7％ | |
| The present invention | White | 99.4％ |
Embodiment
Embodiment one
At 1000ML thermometer, tower separator column are housed, in the four-hole reaction flask of dropping funnel, agitator, add chlorobenzene 400 grams, glacial acetic acid 288 grams, tosic acid 1.2 grams, agitation and dropping 120 gram quadrols dropwised through 40 minutes under＜80 ℃ of temperature, be warming up to 100 ℃ then, refluxed 1 hour, dewatered 1 hour, be cooled to 20 ℃, washing, oven dry get diacetyl ethylenediamine 270 grams.
Get diacetyl ethylenediamine 86.4 grams, add tungstosilicic acid trolamine 1.3 grams, chlorobenzene 100 restrains, and diacetyl oxide 550 grams stir and are warming up to 125 ℃, are incubated 3 hours, react after 6 hours, are warming up to 132 ℃, and cooling is then filtered, and gets content 99.4%TAED65.66 gram.
Embodiment two
The first step reaction solution reuse in the example one adds acetate 288 and restrains, and tosic acid 1.2 grams drip quadrol 120 grams, and operation gets diacetyl ethylenediamine 285.3 grams with embodiment one.
Filtrate adding diacetyl ethylenediamine 86.4 grams of second step reaction in the example one, atlapulgite 1.3 grams, chlorobenzene 100 grams, diacetyl oxide 150 grams are warming up to 125 ℃, react 8 hours, and cold filtration gets the TAED102.6 gram.
Embodiment three
In 1000ML four-hole reaction flask, add acetate 100.8 grams, chlorobenzene 300 grams, tosic acid 0.36 gram under＜80 ℃ of temperature, drips quadrol 36 grams, temperature rising reflux 1 hour, add diacetyl oxide 559 grams then, chlorination four tertiary butyl ammoniums 1.3 grams are warming up to 125 ℃, insulation reaction 3 hours, distilled 8 hours, cold filtration obtains the TAED70.3 gram.
Embodiment four
In 1000ML four-hole reaction flask, add acetate 100.8 grams, chlorobenzene 300 grams, atlapulgite 0.36 gram, temperature is controlled at below 80 ℃, drips 36 gram quadrols, finish intensification, refluxed 1 hour, add the filtrate of example three, add tungstosilicic acid triethanol ammonium 1.3 grams, be warming up to 125 ℃, insulation refluxed 3 hours, distilled 8 hours, cold filtration obtains the TAED103.4 gram.
Claims (5)
1. the preparation method of a tetraacetyl ethylene diamine by quadrol and acetate synthesis of diacetyl ethylenediamine, by diacetyl ethylenediamine and the synthetic tetraacetyl ethylene diamine of diacetyl oxide, is characterized in that adding and acetate azeotropic solvent in building-up reactions again; Add the tungstosilicic acid triethanolamine salt in the building-up reactions, chlorination four tertiary butyl ammoniums, the mixture of any one or more of atlapulgite and tosic acid is a catalyzer; Quadrol and acetic acidreaction mol ratio 1: 2.3～3.0,90～120 ℃ of temperature of reaction; Diacetyl ethylenediamine and acetic anhydride mol ratio 1: 4～9,110～132 ℃ of synthesis reaction temperatures.
2. the preparation method of tetraacetyl ethylene diamine according to claim 1, it is characterized in that described azeotropic solvent is diisobutyl ether, toluene, ethylbenzene, dimethylbenzene, chlorobenzene, 1, the mixing solutions of any one or more of 3-dimethyl cyclohexane, octane, the first step reaction add-on is that add-on is 30～400% of a diacetyl ethylenediamine weight when reacting in 80～800%, second step of quadrol weight.
3. the preparation method of tetraacetyl ethylene diamine according to claim 1 is characterized in that described catalyzer add-on the first step reaction is 1～3% of quadrol weight; The reaction of second step is 1～10% of diacetyl ethylenediamine weight.
4. the preparation method of tetraacetyl ethylene diamine according to claim 1 is characterized in that the described the first step is reflected to be lower than in the mixed solution that quadrol under 80 ℃ of temperature adds acetate and azeotropic solvent, drips the back temperature rising reflux and dewaters.
5. the preparation method of tetraacetyl ethylene diamine according to claim 1 is characterized in that recycling after building-up reactions filtrate is added reactant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021122431A CN1255376C (en) | 2002-06-27 | 2002-06-27 | Preparation method of tetraacetylethylenediamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021122431A CN1255376C (en) | 2002-06-27 | 2002-06-27 | Preparation method of tetraacetylethylenediamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1463963A CN1463963A (en) | 2003-12-31 |
| CN1255376C true CN1255376C (en) | 2006-05-10 |
Family
ID=29742104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021122431A Expired - Lifetime CN1255376C (en) | 2002-06-27 | 2002-06-27 | Preparation method of tetraacetylethylenediamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1255376C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101397263B (en) * | 2008-11-06 | 2013-03-13 | 浙江金科日化原料有限公司 | Method for preparing diacetyl ethylenediamine |
| CN101891644A (en) * | 2009-11-19 | 2010-11-24 | 华东理工大学 | Method for synthesizing tetraacetyl ethylene diamine |
| CN102030677B (en) * | 2010-11-19 | 2013-09-11 | 浙江大学 | Trigeminy decoloration method of TAED reacting liquid |
| CN109970589B (en) * | 2019-05-07 | 2022-04-08 | 山东泰和水处理科技股份有限公司 | Preparation method of tetraacetylethylenediamine |
| CN113788751B (en) * | 2021-08-12 | 2023-10-13 | 万华化学(四川)有限公司 | Purification method of byproduct acetic acid in linalyl acetate production |
-
2002
- 2002-06-27 CN CNB021122431A patent/CN1255376C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1463963A (en) | 2003-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2021102631A4 (en) | Method for preparing 2,4-dichloro-3,5-dinitrobenzotrifluoride | |
| CN1255376C (en) | Preparation method of tetraacetylethylenediamine | |
| CN102452934B (en) | Preparation method of sec-butyl acetate | |
| WO2004002942A1 (en) | Method of preparing tetraacetylethylenediamine | |
| CN102030669A (en) | Clean production method for glycine | |
| CN114230510B (en) | Collinear production process of hindered amine compound | |
| CN114797988A (en) | Synthesis of novel composite catalyst and method for preparing beta-isophorone | |
| CN112679342A (en) | Preparation method of trans, trans-4, 4' -dicyclohexyl dicarboxylic acid | |
| CN101397263B (en) | Method for preparing diacetyl ethylenediamine | |
| CN102503824B (en) | Process for synthesizing long-chain acylated citrate | |
| CN1332153A (en) | preparation method of tetraacetylethylenediamine | |
| CN114315577B (en) | A method for synthesizing ethyl 2-ethoxymethylene-4,4-difluoroacetoacetate | |
| CN111592451B (en) | Preparation method of 4- (4-phenylbutoxy) benzoic acid | |
| CN115433083B (en) | Production process of cetyl alcohol ester | |
| CN114437142B (en) | Preparation method of crotyl palladium chloride dimer | |
| CN109970589B (en) | Preparation method of tetraacetylethylenediamine | |
| CN112409227B (en) | Method for efficiently synthesizing 3-mercaptopropionic acid | |
| CN111302938B (en) | Synthesis method of trimethylolpropane triacrylate | |
| CN100595186C (en) | Method and catalyst for one-step synthesis of diaryl carbonate and dimethyl ether | |
| CN109400468B (en) | Preparation method of L-dibenzoyl dimethyl tartrate | |
| CN109438270B (en) | Preparation method of di (p-N, N-dialkyl aminobenzoic acid) -N-alkyl diethanol amine ester | |
| CN111777524B (en) | Post-treatment method for preparing naphthol AS-PH | |
| CN1911801A (en) | Technology for preparating boric acid, magnesium carbonate and sodium sulphate by combined method | |
| CN113717050A (en) | Synthesis process of succinic acid mono (allyloxy) ethyl ester | |
| CN117903218A (en) | Preparation method of neohesperidin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHEJIANG TIMES JINKE PEROXIDES CO., LTD. Free format text: FORMER OWNER: ZHEJIANG JINKE CHEMICAL ENGINEERING CO., LTD. Effective date: 20091204 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20091204 Address after: Shangyu Industrial Park, Hangzhou Bay, Zhejiang Patentee after: ZHEJIANG SHIDAI JINKE PEROXIDES Co.,Ltd. Address before: The old town of Zhejiang province Shangyu city Shangyu Fine Chemical Zone Patentee before: ZHEJIANG JINKE CHEMISTRY Co.,Ltd. |
|
| ASS | Succession or assignment of patent right |
Owner name: ZHEJIANG JINKE DAILY CHEMICAL MATERIALS CO., LTD. Free format text: FORMER OWNER: ZHEJIANG SHIDAI JINKE PEROXIDES CO., LTD. Effective date: 20110209 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20110209 Address after: 312369 Shangyu Industrial Park, Hangzhou Bay, Zhejiang Province Patentee after: ZHEJIANG JINKE HOUSEHOLD CHEMICAL MATERIALS Co.,Ltd. Address before: 312369 Shangyu Industrial Park, Hangzhou Bay, Zhejiang Province Patentee before: ZHEJIANG SHIDAI JINKE PEROXIDES Co.,Ltd. |
|
| CX01 | Expiry of patent term |
Granted publication date: 20060510 |
|
| CX01 | Expiry of patent term |