CN104558582B - Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst - Google Patents
Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst Download PDFInfo
- Publication number
- CN104558582B CN104558582B CN201410795131.3A CN201410795131A CN104558582B CN 104558582 B CN104558582 B CN 104558582B CN 201410795131 A CN201410795131 A CN 201410795131A CN 104558582 B CN104558582 B CN 104558582B
- Authority
- CN
- China
- Prior art keywords
- ternary
- polymerization
- iron
- catalyst
- hydrin
- 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
Abstract
The invention discloses a method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using a three-element iron catalyst, belonging to the field of polymer preparation and solving the problem of low activity of the catalyst for synthesizing polyepichlorohydrin from polymerization, and small molecular weight and wide PDI distribution of the obtained product in the prior art. The three-element iron catalyst (iron compound, alkyl aluminum compound or electron donor) is adopted to catalyze epichlorohydrin homopolymerization to obtain the polyepichlorohydrin, of which the molecular weight is 10000 above, the polymer color is light and the PDI distribution is 1.2 or so; and the reaction is easy to control. The catalyst is easy to prepare and has the advantage of high polymer yield. The iron compound is iron naphthenate, iron neodecanoate, iron isooctoate or the like; the organic aluminum compound is triisobutylaluminum, triethyl aluminum, sesquialuminum or the like; and the electron donor is tri-ortho-methylphenyl phosphite, diethyl phosphite, tributyl phosphate or the like.
Description
Technical field
The present invention relates to Polymer Synthesizing field, particularly to a kind of polymerization of ternary Fe-series catalyst Epichlorohydrin
The method preparing Hydrin.
Background technology
Hydrin is to be prepared through epoxychloropropane ring-opening polymerisation, contains-c-o-c- ehter bond, side in its main chain
There is chloromethyl on chain, there is good oil resistant, solvent resistant, acidproof, resistance to weather, resistance to gas infiltration.
The method of the disclosed multiple catalytic polymerization epoxychloropropane of prior art, such as jp04198319 propose with sbcl5For
Catalyst, ethylene glycol is initiator, prepares Based On Hydroxy-terminated Polyepichlorohydrin；The Chinese invention of Application No. 200810187705.3
Patent proposes with bimetallic cyanide complex as catalyst, the terminal hydroxy group epoxychloropropane polyhydric alcohol of preparation low-molecular-weight.But
It is that catalyst that in prior art, catalytic polymerization epoxychloropropane is used mostly is lewis acid catalyst series, Protic Acid Catalyzed
Agent, trialkyloxonium salt catalyst, the activity of above-mentioned catalyst is relatively low, and the polymer obtaining mostly is oligomer, high molecular poly-
Compound yield is relatively low；In addition, the Hydrin molecular weight that in prior art, Epichlorohydrin ring-opening polymerisation obtains is little,
Pdi wider distribution, more than 3.0.
Content of the invention
In order to solve in prior art, Epichlorohydrin synthesis Hydrin catalyst activity is low, products therefrom
The problem that molecular weight is little, pdi distribution is wide, the invention provides a kind of polymerization preparation of ternary Fe-series catalyst Epichlorohydrin
The method of Hydrin.
The technical scheme is that
A kind of ternary Fe-series catalyst, including iron series compound, alkyl aluminum compound and three kinds of components of electron donor, described
Iron series compound is iron naphthenate, ferric carboxylate, ferric acetyl acetonade, isooctyl acid ferrum, the different pungent ferrum of phosphorous acid two, 2,6- bis-imine pyridine
Any one or a few in ferrum, neodecanoic acid ferrum；Described alkyl aluminum compound be triisobutyl aluminium, triethyl aluminum, sesquialter aluminum, one
Any one or a few in chlorodiethyl aluminium, alkyl-al hydride；Described electron donor is three o-methyl-phenyl-phosphite esters, Asia
In diethyl phosphate, 1,10- o-phenanthroline, bipyridyl, ethylenediamine, tetramethylethylenediamine, tributyl phosphate any one or
Several.
Preferably, described iron series compound be iron naphthenate, neodecanoic acid ferrum, any one or a few in isooctyl acid ferrum；
Described alkyl aluminum compound is triisobutyl aluminium or triethyl aluminum；Described electron donor is diethyl phosphite or tricresyl phosphate fourth
Ester.
Further, the amount ratio of each component meets [al]: [fe]=3:1-30:1, [p]: [fe]=1:1-10:1.
The method preparing Hydrin using described ternary Fe-series catalyst Epichlorohydrin polymerization, with ring
Oxygen chloropropane is reaction substrate, and with described ternary Fe-series catalyst as catalyst, in varsol, temperature control is in 40-80
Between DEG C, react 1-140h, after polymerization terminates, using 5% ethanol solution hydrochloride as terminator terminating reaction, repeatedly rush through ethanol
Wash and dried obtains Hydrin.
Preferably, described varsol is processed through anhydrous and oxygen-free.To remove micro-moisture therein and oxygen
Preferably, one of described varsol hexamethylene, normal hexane, solvent naphtha, benzene, toluene or combinations thereof.
Preferably, the sequencing that described ternary Fe-series catalyst adds is iron series compound, alkyl aluminum compound, to electricity
Daughter.Empirical tests, add compared with other addition sequences according to this order, obtained catalyst system and catalyzing activity is higher.
Preferably, reaction temperature is 50-70 DEG C, and the response time is 3-12h.
Preferably, using 5% ethanol solution hydrochloride as terminator terminating reaction.
The invention has the benefit that
The present invention adopts ternary Fe-series catalyst (iron compound, organo-aluminum compound, electron donor) to be catalyzed epoxy chloropropionate
Alkane is all polymerized, and, more than 10000, polymer color is shallow for the Hydrin molecular weight obtaining, and pdi is distributed in 1.2 about, and
Reaction is easily controllable.Used catalyst easily preparation and low cost, polymer yield is high.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Have technology description in required use accompanying drawing be briefly described it should be apparent that, drawings in the following description be only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, also may be used
So that other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the infrared spectrum of gained Hydrin of the present invention.
Specific embodiment
Embodiment 1
The 20ml hexane processing through anhydrous and oxygen-free and 7.8ml epoxy is sequentially added in the schlenk polymerization bottle of 100 ml
Chloropropane, after heating 15 min in 70 DEG C of water-bath, sequentially add 0.5 ml isooctyl acid ferrous solution (0.1 mol/l's
Hexane solution), 0.25 ml triethyl aluminium solution (hexane solution of 1 mol/l), 0.5 ml diethyl phosphite solution (0.2
The hexane solution of mol/l).Polymerization bottle is put into 70 DEG C of water-bath, react 2 hours.After reaction terminates, add 5% hydrochloric acid second
Alcoholic solution terminates polymerization, pours out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, and drying is weighed after processing, polymerization
Thing yield is 41.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 12000, molecular weight distribution
For 1.15.
Embodiment 2
The 20ml hexane processing through anhydrous and oxygen-free and 7.8ml epoxy is sequentially added in the schlenk polymerization bottle of 100 ml
Chloropropane, after heating 15 min in 70 DEG C of water-bath, sequentially add 0.5 ml isooctyl acid ferrous solution (0.1 mol/l's
Hexane solution), 1.0ml triisobutyl aluminum solutions (hexane solution of 1mol/l), 0.5ml diethyl phosphite solution (0.2
The hexane solution of mol/l), polymerization bottle is put into 70 DEG C of water-bath, react 2 hours.After reaction terminates, add 5% hydrochloric acid second
Alcoholic solution carries out terminating polymerization, pours out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, and drying is weighed after processing,
Polymer yield is 68.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 15200, molecular weight
It is distributed as 1.31.
Embodiment 3
The 20ml hexane processing through anhydrous and oxygen-free and 7.8ml epoxy is sequentially added in the schlenk polymerization bottle of 100 ml
Chloropropane, after heating 15min in 50 DEG C of water-bath, (0.1 mol/l's is own to sequentially add 0.5ml neodecanoic acid ferrous solution
Alkane solution), 1.2 ml triisobutyl aluminum solutions (hexane solution of 1 mol/l), 0.6 ml tributyl phosphate solution (0.2 mol/
The hexane solution of l), polymerization bottle is put into 50 DEG C of water-bath, react 6 hours.After reaction terminates, the acidic alcohol of addition 5% is molten
Liquid carries out terminating polymerization, pours out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, and drying is weighed after processing, polymerization
Thing yield is 56.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 13600, molecular weight distribution
For 1.21.
Embodiment 4
The 40ml hexane processing through anhydrous and oxygen-free and 16ml epoxy chlorine is sequentially added in the schlenk polymerization bottle of 100 ml
Propane, after heating 25 min, sequentially adds the 1.0ml iron naphthenate solution (hexane of 0.1 mol/l in 60 DEG C of water-bath
Solution), 2.4 ml triisobutyl aluminum solutions (hexane solution of 1 mol/l), 1.2ml diethyl phosphite solution (0.2 mol/l
Hexane solution), polymerization bottle is put into 60 DEG C of water-bath, reacts 4 hours.After reaction terminates, the acidic alcohol of addition 5% is molten
Liquid carries out terminating polymerization, pours out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, and drying is weighed after processing, polymerization
Thing yield is 49.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 14500, molecular weight distribution
For 1.25.
Embodiment 5
The 20ml hexane processing through anhydrous and oxygen-free and 7.8ml epoxy is sequentially added in the schlenk polymerization bottle of 100 ml
Chloropropane, after heating 15 min in 60 DEG C of water-bath, sequentially add 0.6ml acetylacetone,2,4-pentanedione ferrous solution (0.1 mol/l's
Hexane solution), 1.2 ml times with aluminum solutions (hexane solution of 1 mol/l), 0.0.6ml tri- o-methyl-phenyl-phosphite ester solution
(hexane solution of 0.2 mol/l), puts into polymerization bottle 60 DEG C of water-bath, reacts 4 hours.After reaction terminates, add 5%
Ethanol solution hydrochloride carries out terminating polymerization, pours out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, after drying is processed
Weigh, polymer yield is 62.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 11300, point
Son amount is distributed as 1.37.
Embodiment 6
The 20ml hexane processing through anhydrous and oxygen-free and 7.8ml epoxy is sequentially added in the schlenk polymerization bottle of 100 ml
Chloropropane, after heating 25 min in 50 DEG C of water-bath, sequentially add 0. 5ml iron naphthenate solution (0.1 mol/l's
Hexane solution), 1.0 ml triethyl aluminium solution (hexane solution of 1 mol/l), 0.5ml diethyl phosphite solution (0.2
The hexane solution of mol/l), polymerization bottle is put into 50 DEG C of water-bath, react 6 hours.After reaction terminates, add 5% hydrochloric acid second
Alcoholic solution carries out terminating polymerization, pours out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, and drying is weighed after processing,
Polymer yield is 45.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 14800, molecular weight
It is distributed as 1.32.
Embodiment 7
The 20ml hexane processing through anhydrous and oxygen-free and 7.8ml epoxy is sequentially added in the schlenk polymerization bottle of 100 ml
Chloropropane, after heating 10 min, sequentially adds the 0.5ml carboxylic acid ferrous solution (hexane of 0.1 mol/l in 70 DEG C of water-bath
Solution), 1.2 ml triisobutyl aluminum solutions (hexane solution of 1 mol/l) 0.6ml tributyl phosphate solution (0.2 mol/l's
Hexane solution), polymerization bottle is put into 70 DEG C of water-bath, react 5 hours.After reaction terminates, add 5% ethanol solution hydrochloride
Carry out terminating polymerization, pour out supernatant, the substantial amounts of ethanol purge of the polymer obtaining, drying is weighed after processing, polymer
Yield is 39.0%.Gpc test is carried out to polymer samples, obtaining polymer number-average molecular weight is 15700, and molecular weight distribution is
1.44.
Embodiment 2 gained homopolymer is carried out ft-ir(nicelet ffir 10dx infrared spectrometer) to test, spectrogram is shown in
Accompanying drawing 1.As shown in figure 1,1114 cm-1For c-o-c vibration absorption peak, 704 and 746 cm-1For c-cl vibration absorption peak, 3480
cm-1Left and right is hydroxyl absorption peak, and the structural formula of gained homopolymer is as follows.
Claims (6)
1. the polymerization of ternary Fe-series catalyst Epichlorohydrin prepare Hydrin method it is characterised in that: with ring
Oxygen chloropropane be reaction substrate, with ternary Fe-series catalyst as catalyst, in varsol, temperature control 40-80 DEG C it
Between, react 1-140h, terminating reaction, process and obtain Hydrin；Described ternary Fe-series catalyst, including ferrum system chemical combination
Thing, alkyl aluminum compound and three kinds of components of electron donor, described iron series compound is ferric carboxylate, ferric acetyl acetonade, 2,6- bis- are sub-
Any one or a few in amine pyridine iron；Described alkyl aluminum compound is triisobutyl aluminium, triethyl aluminum, sesquialter aluminum, a chlorine
Any one or a few in diethyl aluminum, alkyl-al hydride；Described electron donor is three o-methyl-phenyl-phosphite esters, phosphorous
In diethyl phthalate, 1,10- o-phenanthroline, bipyridyl, ethylenediamine, tetramethylethylenediamine, tributyl phosphate any one or several
Kind；The amount ratio of each component meets [al]: [fe]=3:1-30:1, [p]: [fe]=1:1-10:1.
2. the method that Hydrin is prepared in ternary Fe-series catalyst Epichlorohydrin polymerization as claimed in claim 1,
It is characterized in that: described varsol is processed through anhydrous and oxygen-free.
3. the side of Hydrin is prepared in ternary Fe-series catalyst Epichlorohydrin polymerization as claimed in claim 1 or 2
Method it is characterised in that: described varsol be one of hexamethylene, normal hexane, solvent naphtha, benzene, toluene or combinations thereof.
4. the method that Hydrin is prepared in ternary Fe-series catalyst Epichlorohydrin polymerization as claimed in claim 1,
It is characterized in that: the sequencing that described ternary Fe-series catalyst adds is iron series compound, alkyl aluminum compound, electron
Body.
5. the method that Hydrin is prepared in ternary Fe-series catalyst Epichlorohydrin polymerization as claimed in claim 1,
It is characterized in that: reaction temperature is 50-70 DEG C, and the response time is 3-12h.
6. the method that Hydrin is prepared in ternary Fe-series catalyst Epichlorohydrin polymerization as claimed in claim 1,
It is characterized in that: the ethanol solution hydrochloride using 5% is as terminator terminating reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410795131.3A CN104558582B (en) | 2014-12-19 | 2014-12-19 | Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410795131.3A CN104558582B (en) | 2014-12-19 | 2014-12-19 | Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104558582A CN104558582A (en) | 2015-04-29 |
| CN104558582B true CN104558582B (en) | 2017-01-18 |
Family
ID=53075717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410795131.3A Active CN104558582B (en) | 2014-12-19 | 2014-12-19 | Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104558582B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279662B (en) * | 2016-08-30 | 2018-05-11 | 山东玉皇化工有限公司 | A kind of ternary Fe-series catalyst and its Epichlorohydrin and butadiene copolymer prepare the application of polymer |
| CN106632764B (en) * | 2016-10-17 | 2018-10-26 | 曲阜师范大学 | A kind of Fe-series catalyst and preparation method thereof and the application in isoprene polymerization |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457186A (en) * | 1964-09-30 | 1969-07-22 | Columbian Carbon | Homogeneous iron coordination catalysts |
| US4168244A (en) * | 1974-11-22 | 1979-09-18 | The Goodyear Tire & Rubber Company | Catalyst composition consisting essentially of iron compounds, organometallic compounds and nitrogen compounds |
| CN1343730A (en) * | 2001-10-26 | 2002-04-10 | 中国科学院长春应用化学研究所 | Process for preparing meta-copolymerized 1,2-butadiene catalyst |
| CN1557847A (en) * | 2002-12-27 | 2004-12-29 | 中国科学院长春应用化学研究所 | Process for preparing high vinyl polybutadiene rubber |
| CN102190745A (en) * | 2011-03-15 | 2011-09-21 | 中国科学院长春应用化学研究所 | Iron-based catalyst for pentadiene polymerization and method for preparing polypentadiene |
| CN102731767A (en) * | 2012-08-07 | 2012-10-17 | 江汉大学 | Method for preparing copolymer chlorohydrin rubber by precipitation polymerization |
-
2014
- 2014-12-19 CN CN201410795131.3A patent/CN104558582B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3457186A (en) * | 1964-09-30 | 1969-07-22 | Columbian Carbon | Homogeneous iron coordination catalysts |
| US4168244A (en) * | 1974-11-22 | 1979-09-18 | The Goodyear Tire & Rubber Company | Catalyst composition consisting essentially of iron compounds, organometallic compounds and nitrogen compounds |
| CN1343730A (en) * | 2001-10-26 | 2002-04-10 | 中国科学院长春应用化学研究所 | Process for preparing meta-copolymerized 1,2-butadiene catalyst |
| CN1557847A (en) * | 2002-12-27 | 2004-12-29 | 中国科学院长春应用化学研究所 | Process for preparing high vinyl polybutadiene rubber |
| CN102190745A (en) * | 2011-03-15 | 2011-09-21 | 中国科学院长春应用化学研究所 | Iron-based catalyst for pentadiene polymerization and method for preparing polypentadiene |
| CN102731767A (en) * | 2012-08-07 | 2012-10-17 | 江汉大学 | Method for preparing copolymer chlorohydrin rubber by precipitation polymerization |
Non-Patent Citations (2)
| Title |
|---|
| "Cp2Fe-Al(i-Bu)3催化环氧氯丙烷聚合";毛利民等;《第二届全国橡胶制品技术研讨会》;20040810;第219-222页 * |
| "Study of the catalytic polymerization of epichlorohydrin";T.E. Lipatova et al.;《Polymer Science U.S.S.R》;20030425;第9卷(第6期);第1378-1383页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558582A (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Valente et al. | Borohydrido rare earth based coordinative chain transfer copolymerization: A convenient tool for tuning the microstructure of isoprene/styrene copolymers | |
| CN105985472B (en) | A kind of preparation method of rare earth catalyst and preparation method thereof and polyisoprene | |
| CN104558582B (en) | Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst | |
| CN101812151A (en) | Method for preparing polybutadiene | |
| CN109053937A (en) | A kind of alkyl substituted pyridines amine Fe-series catalyst and the preparation method and application thereof | |
| CN103450373B (en) | Rare earth catalyst composition and rare earth catalyst and application thereof | |
| CN103030740B (en) | Poly-alpha-olefin drag reduction agent and preparation method thereof | |
| Boccia et al. | Novel stereoregular cis-1, 4 and trans-1, 2 poly (diene) s: Synthesis, characterization, and mechanistic considerations | |
| CN106279662B (en) | A kind of ternary Fe-series catalyst and its Epichlorohydrin and butadiene copolymer prepare the application of polymer | |
| CN104231133B (en) | A kind of rare earth catalyst and the method being used for preparing cis conjugated diene polymer thereof | |
| CN102532354B (en) | The homogeneous rare earth catalyst of neodymium series, its preparation method and application thereof | |
| CN102603940A (en) | Catalyst composition for preparing polyisoprene, preparation method of catalyst composition and preparation method of polyisoprene | |
| CN106256845A (en) | A kind of preparation method of high-molecular aliphatic polycarbonate | |
| CN103739833B (en) | A kind of method preparing polylactide | |
| CN101608003A (en) | The method of lower molecular weight liquid polyisoprene rubber in the mass polymerization preparation | |
| CN105777958A (en) | Long-chain branched polyolefin and preparation method thereof | |
| He et al. | Anionic polymerization of biomass‐derived furfuryl methacrylate: Controlling polymer tacticity and thermoreversibility | |
| CN105777963A (en) | Polymerization method of rare earth butadiene rubber with high Mooney viscosity | |
| CN114249849A (en) | High-branched-chain iron-based conjugated diene polymer and preparation method thereof | |
| CN114149571A (en) | Imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method | |
| CN103626890B (en) | The preparation method of a kind of rare-earth catalysis system and its preparation method and butadiene isoprene copolymer | |
| CN105085720B (en) | Rare earth catalyst composition and rare earth catalyst and its preparation method and application and a kind of method of isoprene polymerization | |
| CN113292707A (en) | Preparation method of terminal group functionalized hyperbranched polyolefin | |
| CN101845111A (en) | Method for preparing conjugated diene polymer | |
| CN102134293A (en) | Preparation method of 1,3-pentadiene polymer |
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: Jiao Junqing Inventor after: Wang Shengwei Inventor after: Zhu Luqun Inventor after: Hou Hongxia Inventor after: Su Zhongkui Inventor after: Chen Xiaoli Inventor after: Hu Zunyan Inventor after: Wang Yuqiang Inventor after: Chen Shuangxi Inventor after: Wang Ying Inventor before: Zhu Luqun Inventor before: Wang Shengwei Inventor before: Jiao Junqing Inventor before: Hou Hongxia Inventor before: Su Zhongkui Inventor before: Chen Xiaoli Inventor before: Hu Zunyan Inventor before: Wang Yuqiang Inventor before: Chen Shuangxi Inventor before: Wang Ying |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHU LUQUN JIAO JUNQING HOU HONGXIA SU ZHONGKUI CHEN XIAOLI HU ZUNYAN WANG YUQIANG CHEN SHUANGXI WANG YING WANG SHENGWEI TO: JIAO JUNQING ZHU LUQUN HOU HONGXIA SU ZHONGKUI CHEN XIAOLI HU ZUNYAN WANG YUQIANG CHEN SHUANGXI WANG YING WANG SHENGWEI |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20151211 Address after: 274500 Shandong city of Heze province Dongming County wusheng Qiao Xiang Yu Huang Miao Xing Zheng Cun Yu Huang Miao Village No. 92 Applicant after: Wang Jinshu Address before: 274512 Shandong city of Heze province Dongming County wusheng Industrial Development Zone Applicant before: Shandong Yuhuang Chemical Co., Ltd. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160920 Address after: 274000 No. 666, Huaihe Road, Heze, Shandong Applicant after: Heze Shandong jade jade Chemical Co., Ltd. Address before: 274500 Shandong city of Heze province Dongming County wusheng Qiao Xiang Yu Huang Miao Xing Zheng Cun Yu Huang Miao Village No. 92 Applicant before: Wang Jinshu |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |