CN103509055B - A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester - Google Patents
A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester Download PDFInfo
- Publication number
- CN103509055B CN103509055B CN201310470321.3A CN201310470321A CN103509055B CN 103509055 B CN103509055 B CN 103509055B CN 201310470321 A CN201310470321 A CN 201310470321A CN 103509055 B CN103509055 B CN 103509055B
- Authority
- CN
- China
- Prior art keywords
- butyl
- dimethoxy
- xenol
- microwave
- chloride
- 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.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of diphosphite three (3,3' di-t-butyl 5,5' dimethoxy 2,2' xenol) microwave synthesis method of ester, the trialkyl phosphite and 3 that the method is 1:1 10:1 with mol ratio, 3' di-t-butyl 5,5' dimethoxy 2,2' xenol is raw material, and aryl replaces phosphorus chloride or alkyl replacement phosphorus chloride is catalyst, diphosphite three (3 is synthesized under solvent-free microwave radiation condition, 3' di-t-butyl 5,5' dimethoxy 2,2' xenol) ester, microwave irradiation power is 100 1000w, and the microwave reaction time is 5 30 minutes.Present invention process has the features such as bis-phosphite productivity is high, by-product is few, the response time is short, solvent-free process, environmental friendliness are pollution-free, post processing is simple.
Description
Technical field
What the present invention related to is a kind of diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol) ester
Microwave synthesis method.
Background technology
Containing two in diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol) ester ligand molecular structure
Individual coordinating phosphorus atoms, can be with the metal complex of the transition-metal catalyst double chelating ligands of coordination formation, and this part is at transition gold
Belong in catalytic reaction and have important effect.
Synthetic method disclosed in prior art is broadly divided into two steps: (1) Phosphorous chloride. and 3,3'-di-t-butyl-5,5'-diformazan
The reaction of epoxide-2,2'-xenol generates the double phenoxy group phosphine chloromethylated intermediate of 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-；
(2) this intermediate reacts raw again under the effect of acid binding agent with 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol
Become diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol) ester.
Existing public technology all use Phosphorous chloride. as phosphorization reagent 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-
Xenol reacts.But, Phosphorous chloride. gas is poisonous, has strong impulse and severe corrosive, sucks Phosphorous chloride. gas
Conjunctiva inflammation, laryngalgia and eye tissue can be made after body to destroy, lung and mucosa are had stimulation.Above characteristic makes to use
When Phosphorous chloride. operates the most difficult, operator and environment can be caused huge harm.And owing to technique using
The chloride ion that the acid binding agent of organic base etc (such as triethylamine, pyridine etc.) produces during carrying out adsorption reaction, can be formed big
The organic basis of hydrochloride side-product of amount.And use the diphosphite three (3,3'-di-t-butyl-5,5'-diformazan that this technique obtains
Epoxide-2,2'-xenol) in the thick product of ester containing substantial amounts of chloride ion impurities, need to use complex method to remove
Go guarantee chloride ion impurities will not make catalyst poisoning.
Summary of the invention
It is an object of the invention to provide a kind of diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol)
The microwave synthesis method of ester, is the series of problems that raw material brings in order to solve employing Phosphorous chloride. in prior art.
The present invention provides the microwave of a kind of diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol) ester
Synthetic method, it is characterised in that it comprises the following steps:
A) it is the trialkyl phosphite of 1:1-10:1,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-by mol ratio
Xenol and account for the organic chloride phosphine catalyst of raw material gross weight 0.5-10.0% and be placed in microwave reaction device, at power be
Under the microwave radiation of 100-1000w, react 5-30 minute, described organic chloride phosphine catalyst selected from phenyl replace phosphonium chloride and
Alkyl replaces the one in phosphonium chloride, and it is di-t-butylchlorophosphine that alkyl replaces phosphonium chloride；
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3'-di-t-butyls
-5,5'-dimethoxy-2,2'-xenol) ester product A；
Wherein, chemical equation is as follows:
According to preparation method of the present invention, it is characterised in that it comprises the following steps:
A) by mol ratio be the trialkyl phosphite of 1:1-3:1,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-connection
Phenol and account for the phenyl of raw material gross weight 2.0-5.0% and replace phosphonium chloride or alkyl and replace phosphonium chloride catalyst to be placed in microwave anti-
Answering in device, arranging microwave irradiation power is 200-500w, and the response time is 10-20 minute, wherein said tricresyl phosphite alkane
Base ester one in NSC 6513, NSC 5284, tripropyl phosphite and tributyl phosphite, phenyl takes
For phosphonium chloride one in phenylphosphonic dichloride, diphenyl phosphine chloride, it is di-t-butyl phosphorus chloride that alkyl replaces phosphorus chloride；
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3'-di-t-butyls
-5,5'-dimethoxy-2,2'-xenol) ester product, the organic solvent used by recrystallization selected from benzene, toluene, ethyl acetate,
One or more in acetonitrile, normal hexane, petroleum ether, ethanol and ether.
According to preparation method of the present invention, it is characterised in that it comprises the following steps:
A) by mol ratio be the trialkyl phosphite of 1:1-3:1,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-connection
Phenol and account for raw material gross weight 2.0-5.0% phenyl replace phosphonium chloride catalyst be placed in microwave reaction device, microwave is set
Radiant power is 200-500w, and the response time is 10-20 minute, and wherein said trialkyl phosphite is selected from phosphorous acid front three
One in ester, NSC 5284, phenyl replaces phosphonium chloride one in phenylphosphonic dichloride, diphenyl phosphine chloride；
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3'-di-t-butyls
-5,5'-dimethoxy-2,2'-xenol) ester product, the organic solvent used by recrystallization is selected from toluene, normal hexane, oil
One or more in ether and ethyl acetate.
The inventive method replaces Phosphorous chloride. as raw material and 3,3'-di-t-butyl-5,5'-dimethoxy using trialkyl phosphite
Base-2,2'-xenol synthesizes diphosphite three under microwave action, and (3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-joins
Phenol) ester, have that bis-phosphite product yield is high, by-product is few, the response time is short, solvent-free process, environmental friendliness
The advantages such as pollution-free, post processing is simple.
Detailed description of the invention
The present invention will be further described for the following examples, but not thereby limiting the invention.
Embodiment 1
By the NSC 5284 of 14.5 grams, 37.4 grams of 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenols and
2.7 grams of diphenyl phosphine chloride catalyst are placed in microwave reaction device, at the microwave spoke that power is 200w after mixing and stirring
Penetrate lower reaction 25 minutes, thick product toluene and normal hexane mixed solvent recrystallization will be reacted after having reacted, obtain product,
Through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, for diphosphite three (3,3'-di-t-butyl-5,5'-
Dimethoxy-2,2'-xenol) ester, yield 90% (yield with 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-biphenyl
Calculate on the basis of phenol).
Embodiment 2
By the NSC 5284 of 46.7 grams, 37.4 grams of 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenols and
1.0 grams of phenylphosphonic dichloride catalyst are placed in microwave reaction device, at the microwave spoke that power is 300w after mixing and stirring
Penetrate lower reaction 20 minutes, thick product toluene and normal hexane recrystallization will be reacted after having reacted, obtain product, through nuclear-magnetism
Resonance hydrogen spectrum, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, for diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy
Base-2,2'-xenol) ester, (with 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol is base to yield to yield 89%
Quasi-calculating).
Embodiment 3
By the NSC 6513 of 25.4 grams, 37.4 grams of 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenols and
6.2 grams of diphenyl phosphine chloride catalyst are placed in microwave reaction device, at the microwave spoke that power is 500w after mixing and stirring
Penetrate lower reaction 15 minutes, thick product ethyl acetate and petroleum ether mixed solvent recrystallization will be reacted after having reacted, obtain
Product, through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, for diphosphite three (3,3'-di-t-butyls
-5,5'-dimethoxy-2,2'-xenol) ester, yield 91% (yield with 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-
Calculate on the basis of xenol).
Embodiment 4
By the NSC 6513 of 14.3 grams, 37.4 grams of 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenols and
2.0 grams of diphenyl phosphine chloride catalyst are placed in microwave reaction device, at the microwave spoke that power is 300w after mixing and stirring
Penetrate lower reaction 20 minutes, thick product toluene and alcohol mixed solvent recrystallization will be reacted after having reacted, obtain product,
Through proton nmr spectra, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, for diphosphite three (3,3'-di-t-butyl-5,5'-
Dimethoxy-2,2'-xenol) ester, yield 88% (yield with 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-biphenyl
Calculate on the basis of phenol).
Embodiment 5
By the NSC 6513 of 100.9 grams, 37.4 grams of 3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenols with
And 0.7 gram of di-t-butylchlorophosphine catalyst is placed in microwave reaction device, it is 100w's at power after mixing and stirring
React 15 minutes under microwave radiation, thick product Diethyl ether recrystallization will be reacted after having reacted, obtain product, through nuclear-magnetism altogether
The hydrogen that shakes spectrum, phosphorus spectrum and efficient liquid phase chromatographic analysis checking, for diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy
-2,2'-xenol) ester, (, with 3,3'-di-t-butyl-5,5'-dimethoxy-2, on the basis of 2'-xenol for yield for yield 79%
Calculate).
Claims (3)
1. the microwave synthesis method of diphosphite three (3,3'-di-t-butyl-5,5'-dimethoxy-2, a 2'-xenol) ester, its
It is characterised by, comprises the following steps:
A) it is the trialkyl phosphite of 1:1-10:1,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-biphenyl by mol ratio
Phenol and account for the organic chloride phosphine catalyst of raw material gross weight 0.5-10.0% and be placed in microwave reaction device, at power
For under the microwave radiation of 100-1000w, reacting 5-30 minute, described organic chloride phosphine catalyst takes selected from phenyl
Replacing the one in phosphonium chloride for phosphonium chloride and alkyl, it is di-t-butylchlorophosphine that alkyl replaces phosphonium chloride；
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3'-di-t-butyl-5,5'-
Dimethoxy-2,2'-xenol) ester product A；
Wherein, chemical equation is as follows:
Method the most according to claim 1, it is characterised in that comprise the following steps:
A) it is the trialkyl phosphite of 1:1-3:1,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol by mol ratio
And the phenyl accounting for raw material gross weight 2.0-5.0% replaces phosphonium chloride or alkyl replaces phosphonium chloride catalyst and is placed in microwave
In reaction unit, arranging microwave irradiation power is 200-500w, and the response time is 10-20 minute, wherein said Asia
Trialkylphosphate is in NSC 6513, NSC 5284, tripropyl phosphite and tributyl phosphite
One, phenyl replaces phosphonium chloride one in phenylphosphonic dichloride, the diphenyl phosphine chloride, and alkyl replaces chlorine
Changing phosphorus is di-t-butyl phosphorus chloride；
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3'-di-t-butyl-5,5'-
Dimethoxy-2,2'-xenol) ester product, the organic solvent used by recrystallization selected from benzene, toluene, ethyl acetate,
One or more in acetonitrile, normal hexane, petroleum ether, ethanol and ether.
Method the most according to claim 1, it is characterised in that comprise the following steps:
A) it is the trialkyl phosphite of 1:1-3:1,3,3'-di-t-butyl-5,5'-dimethoxy-2,2'-xenol by mol ratio
And the phenyl accounting for raw material gross weight 2.0-5.0% replaces phosphonium chloride catalyst and is placed in microwave reaction device, arrange micro-
Wave radiation power is 200-500w, and the response time is 10-20 minute, and wherein said trialkyl phosphite is selected from Asia
One in trimethyl phosphate, NSC 5284, phenyl replaces phosphonium chloride selected from phenylphosphonic dichloride, diphenyl
One in phosphonium chloride；
B) thick product organic solvent recrystallization will be reacted after having reacted, obtain diphosphite three (3,3'-di-t-butyl-5,5'-
Dimethoxy-2,2'-xenol) ester product, the organic solvent used by recrystallization is selected from toluene, normal hexane, oil
One or more in ether and ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310470321.3A CN103509055B (en) | 2013-10-10 | 2013-10-10 | A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310470321.3A CN103509055B (en) | 2013-10-10 | 2013-10-10 | A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103509055A CN103509055A (en) | 2014-01-15 |
| CN103509055B true CN103509055B (en) | 2016-08-17 |
Family
ID=49892528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310470321.3A Active CN103509055B (en) | 2013-10-10 | 2013-10-10 | A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103509055B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041761A (en) * | 1985-09-05 | 1990-05-02 | 联合碳化公司 | The catalyged precursor composition of transition metal complex |
| US6172267B1 (en) * | 1997-10-28 | 2001-01-09 | Mitsubishi Chemical Corporation | Process for producing aldehydes and bisphosphite compound to be used for the process |
| CN1898253A (en) * | 2003-12-23 | 2007-01-17 | 奥克森诺奥勒芬化学股份有限公司 | Method for producing trivalent organophosphorus compounds |
| CN1986055A (en) * | 2006-12-22 | 2007-06-27 | 中国科学院上海有机化学研究所 | Catalyst system and catalyzing method of propylene hydrogenation and formylation |
| CN102177171A (en) * | 2008-10-08 | 2011-09-07 | 陶氏技术投资有限公司 | Slurry process for synthesis of bisphosphites |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesizing method for bis-phosphite ligand |
| KR20120060550A (en) * | 2010-12-02 | 2012-06-12 | 주식회사 엘지화학 | Hydroformylation Method Having Improved Catalyst Stability In Reaction |
| CN102702267A (en) * | 2012-06-16 | 2012-10-03 | 南雄志一精细化工有限公司 | Method for preparing novel high-efficiency phosphite antioxidant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8796481B2 (en) * | 2011-12-30 | 2014-08-05 | Basf Se | Crystalline solvate and non-solvated forms of 6,6′-[[3,3′,5,5′-tetrakis(1,1-dimethylethyl)-[1,1′biphenyl]-2,2′-diyl]bis(oxy)]bis-dibenzo [d,f] [1,3,2]-dioxaphosphepine |
-
2013
- 2013-10-10 CN CN201310470321.3A patent/CN103509055B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041761A (en) * | 1985-09-05 | 1990-05-02 | 联合碳化公司 | The catalyged precursor composition of transition metal complex |
| US6172267B1 (en) * | 1997-10-28 | 2001-01-09 | Mitsubishi Chemical Corporation | Process for producing aldehydes and bisphosphite compound to be used for the process |
| CN1898253A (en) * | 2003-12-23 | 2007-01-17 | 奥克森诺奥勒芬化学股份有限公司 | Method for producing trivalent organophosphorus compounds |
| CN1986055A (en) * | 2006-12-22 | 2007-06-27 | 中国科学院上海有机化学研究所 | Catalyst system and catalyzing method of propylene hydrogenation and formylation |
| CN102177171A (en) * | 2008-10-08 | 2011-09-07 | 陶氏技术投资有限公司 | Slurry process for synthesis of bisphosphites |
| CN102432638A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Synthesizing method for bis-phosphite ligand |
| KR20120060550A (en) * | 2010-12-02 | 2012-06-12 | 주식회사 엘지화학 | Hydroformylation Method Having Improved Catalyst Stability In Reaction |
| CN102702267A (en) * | 2012-06-16 | 2012-10-03 | 南雄志一精细化工有限公司 | Method for preparing novel high-efficiency phosphite antioxidant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103509055A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Etkin et al. | The anionic zirconocene trihydride:[Cp* 2ZrH3]- | |
| Bange et al. | Light-Driven, Zirconium-Catalyzed Hydrophosphination with Primary Phosphines | |
| Ganushevich et al. | Nickel phosphanido hydride complex: an intermediate in the hydrophosphination of unactivated alkenes by primary phosphine | |
| Orain et al. | Investigation on the protonation of a trisubstituted [Fe2 (CO) 3 (PPh3)(κ2-phen)(μ-pdt)] complex: Rotated versus unrotated intermediate pathways | |
| Rad'kov et al. | Dialkyl rare earth complexes supported by potentially tridentate amidinate ligands: synthesis, structures, and catalytic activity in isoprene polymerization | |
| Rochat et al. | Organomagnesium‐Catalyzed Isomerization of Terminal Alkynes to Allenes and Internal Alkynes | |
| Baya et al. | Coordination and Rupture of Methyl C (sp3)− H Bonds in Osmium− Polyhydride Complexes with δ Agostic Interaction | |
| Roesky et al. | Yttrium and lanthanide diphosphanylamides: syntheses and structures of complexes with one {(Ph2P) 2N}− ligand in the coordination sphere | |
| Sangtrirutnugul et al. | Rhodium complexes containing a tridentate bis (8-quinolyl) methylsilyl ligand: Synthesis and reactivity | |
| Wallach et al. | Enhancing the Variability of [Ge9] Cluster Chemistry through Phosphine Functionalization | |
| Gunasekar et al. | Catalytic reactivity of an iridium complex with a proton responsive N-donor ligand in CO 2 hydrogenation to formate | |
| Furno et al. | 1, 2-bis (dimethylphosphino) ethanehydridomesitylidynetungsten (IV). Hydride activation via the trans influence | |
| Lee et al. | Synthesis, structure, and DFT calculation of (phosphino-o-carboranyl) silyl group 10 metal complexes: Formation of stable trans-Bis (P, Si-chelate) metal complexes | |
| Fecker et al. | Synthesis and coordination chemistry of an enantiomerically pure pentadienyl ligand | |
| CN103467524B (en) | A kind of microwave synthesis method of diphosphite three (3,3 ', 5,5 '-tetra-tert-2,2 '-xenol) ester | |
| CN103509055B (en) | A kind of microwave synthesis method of diphosphite three (3,3 '-di-t-butyl-5,5 '-dimethoxy-2,2 '-xenol) ester | |
| CN103509056B (en) | A kind of microwave synthesis method of diphosphite three (2,2 '-xenol) ester | |
| CN103467523B (en) | A kind of microwave synthesis method of diphosphite three (3,3 '-dimethyl-5,5 '-di-t-butyl-2,2 '-xenol) ester | |
| CN103467517B (en) | A kind of microwave synthesis method of diphosphite three (3,3 ', 5,5 '-tetramethyl--2,2 '-xenol) ester | |
| Ishiyama et al. | Synthesis and characterization of some zirconium and hafnium complexes with a phosphide-pendant cyclopentadienyl ligand | |
| Greño et al. | Group 4 Half-Sandwich Tris (trimethylsilylmethyl) Complexes: Thermal Decomposition and Reactivity with N, N-Dimethylamine–Borane | |
| Guo et al. | Reactivity of 1, 3-Disubstituted Indoles with Lithium Compounds: Substituents and Solvents Effects on Coordination and Reactivity of Resulting 1, 3-Disubstituted-2-Indolyl Lithium Complexes | |
| Chou et al. | Reactions of ruthenium acetylide and vinylidene complexes containing a 2-pyridyl group | |
| Jana et al. | Manganese and Rhenium Formyl Complexes of Diphosphanylborane Ligands: Stabilization of the Formyl Unit from Intramolecular B–O Bond Formation | |
| Yamamoto et al. | Synthesis and Reactions of Ditantalum Allyl Complexes Derived from Intramolecular C–H Bond Activation of the Methylene of the Ethyl Group Bound to Ditantallacyclopentadiene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| 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: 20161012 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee before: CNOOC Energy Development Co., Ltd. |