CN104558582A - 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
- CN104558582A CN104558582A CN201410795131.3A CN201410795131A CN104558582A CN 104558582 A CN104558582 A CN 104558582A CN 201410795131 A CN201410795131 A CN 201410795131A CN 104558582 A CN104558582 A CN 104558582A
- Authority
- CN
- China
- Prior art keywords
- iron
- ternary
- polymerization
- hydrin
- epichlorohydrin
- 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.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 the method for Hydrin is prepared in a kind of ternary Fe-series catalyst Epichlorohydrin polymerization.
Background technology
Hydrin is through epoxy chloropropane ring-opening polymerization preparation, and containing-C-O-C-ehter bond in its main chain, side chain exists chloromethyl, has good oil resistant, solvent resistant, acidproof, resistance to weather, against gas transmission is permeated.
Prior art discloses the method for multiple catalyzed polymerization epoxy chloropropane, as JP04198319 proposes with SbCl
5for catalyzer, ethylene glycol is initiator, prepares Based On Hydroxy-terminated Polyepichlorohydrin; Application number be 200810187705.3 Chinese invention patent propose to be catalyzer with bimetallic cyanide complex, prepare low-molecular-weight terminal hydroxy group epoxy chloropropane polyvalent alcohol.But the catalyzer that in prior art, catalyzed polymerization epoxy chloropropane uses mostly is Lewis acid catalyst series, bronsted acid catalyst, trialkyloxonium salt catalyzer, the activity of above-mentioned catalyzer is lower, the polymkeric substance obtained mostly is oligomer, and the polymer yield of high molecular is lower; In addition, the Hydrin molecular weight that in prior art, Epichlorohydrin ring-opening polymerization obtains is little, and PDI wider distribution, more than 3.0.
Summary of the invention
In order to solve in prior art, Epichlorohydrin synthesis Hydrin catalyst activity is low, products therefrom molecular weight is little, PDI distributes wide problem, the invention provides the method that Hydrin is prepared in the polymerization of a kind of ternary Fe-series catalyst Epichlorohydrin.
Technical scheme of the present invention is:
A kind of ternary Fe-series catalyst, comprise iron series compound, alkylaluminium cpd and electron donor three kinds of components, described iron series compound is any one or a few in iron naphthenate, ferric carboxylate, ferric acetyl acetonade, isocaprylic acid iron, the different pungent iron of phosphorous acid two, 2,6-bis-imine pyridine iron, neodecanoic acid iron; Described alkylaluminium cpd is any one or a few in triisobutyl aluminium, triethyl aluminum, sesquialter aluminium, aluminium diethyl monochloride, alkyl-al hydride; Described electron donor is any one or a few in three o-methyl-phenyl-phosphorous acid esters, diethyl phosphite, 1,10-o-phenanthroline, dipyridyl, quadrol, Tetramethyl Ethylene Diamine, tributyl phosphate.
Preferably, described iron series compound is any one or a few in iron naphthenate, neodecanoic acid iron, isocaprylic acid iron; Described alkylaluminium cpd is triisobutyl aluminium or triethyl aluminum; Described electron donor is diethyl phosphite or tributyl phosphate.
Further, the amount ratio of each component meets [Al]: [Fe]=3:1-30:1, [P]: [Fe]=1:1-10:1.
The method of Hydrin is prepared in ternary Fe-series catalyst Epichlorohydrin polymerization described in employing, take epoxy chloropropane as reaction substrate, with described ternary Fe-series catalyst for catalyzer, in varsol, temperature controls between 40-80 DEG C, and reaction 1-140h, after polymerization terminates, using 5% ethanol solution hydrochloride as terminator termination reaction, repeatedly rinse also drying treatment through ethanol and obtain Hydrin.
Preferably, described varsol is through anhydrous and oxygen-free process.With removing micro-moisture wherein and oxygen
Preferably, the one in described varsol hexanaphthene, normal hexane, solvent oil, benzene, toluene or its composition.
Preferably, the sequencing that described ternary Fe-series catalyst adds is iron series compound, alkylaluminium cpd, electron donor.Empirical tests, adds compared with other addition sequences according to this order, and obtained catalyst system activity is higher.
Preferably, temperature of reaction is 50-70 DEG C, and the reaction times is 3-12h.
Preferably, adopt the ethanol solution hydrochloride of 5% as terminator termination reaction.
Beneficial effect of the present invention is:
The present invention adopts ternary Fe-series catalyst (iron cpd, organo-aluminium compound, electron donor) Epichlorohydrin to be all polymerized, the Hydrin molecular weight obtained is more than 10000, polymer color is shallow, and PDI is distributed in about 1.2, and reaction is easy to control.Used catalyst easily prepares and cost is low, and polymer yield is high.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the infrared spectrum of gained Hydrin of the present invention.
Embodiment
Embodiment 1
The 20mL hexane through anhydrous and oxygen-free process and 7.8mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 15 min in the water-bath of 70 DEG C after, then add 0.5 mL isocaprylic acid ferrous solution (hexane solution of 0.1 mol/L), 0.25 mL triethyl aluminium solution (hexane solution of 1 mol/L), 0.5 mL diethyl phosphite solution (hexane solution of 0.2 mol/L) successively.Polymerization bottle is put into the water-bath of 70 DEG C, react 2 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% stops polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 41.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance number-average molecular weight is 12000, and molecular weight distribution is 1.15.
Embodiment 2
The 20mL hexane through anhydrous and oxygen-free process and 7.8mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 15 min in the water-bath of 70 DEG C after, add 0.5 ml isocaprylic acid ferrous solution (hexane solution of 0.1 mol/L), 1.0mL triisobutyl aluminum solutions (hexane solution of 1mol/L), 0.5mL diethyl phosphite solution (hexane solution of 0.2 mol/L) more successively, polymerization bottle is put into the water-bath of 70 DEG C, react 2 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% carries out termination polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 68.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance number-average molecular weight is 15200, and molecular weight distribution is 1.31.
Embodiment 3
The 20mL hexane through anhydrous and oxygen-free process and 7.8mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 15min in the water-bath of 50 DEG C after, add 0.5mL neodecanoic acid ferrous solution (hexane solution of 0.1 mol/L), 1.2 mL triisobutyl aluminum solutions (hexane solution of 1 mol/L), 0.6 mL tributyl phosphate solution (hexane solution of 0.2 mol/L) more successively, polymerization bottle is put into the water-bath of 50 DEG C, react 6 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% carries out termination polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 56.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance number-average molecular weight is 13600, and molecular weight distribution is 1.21.
Embodiment 4
The 40mL hexane through anhydrous and oxygen-free process and 16mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 25 min in the water-bath of 60 DEG C after, add 1.0mL iron naphthenate solution (hexane solution of 0.1 mol/L), 2.4 mL triisobutyl aluminum solutions (hexane solution of 1 mol/L), 1.2ml diethyl phosphite solution (hexane solution of 0.2 mol/L) more successively, polymerization bottle is put into the water-bath of 60 DEG C, react 4 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% carries out termination polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 49.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance number-average molecular weight is 14500, and molecular weight distribution is 1.25.
Embodiment 5
The 20mL hexane through anhydrous and oxygen-free process and 7.8mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 15 min in the water-bath of 60 DEG C after, add 0.6mL methyl ethyl diketone ferrous solution (hexane solution of 0.1 mol/L) more successively, 1.2 mL doubly accompany aluminum solutions (hexane solution of 1 mol/L), 0.0.6mL tri-o-methyl-phenyl-phosphorous acid ester solution (hexane solution of 0.2 mol/L), polymerization bottle is put into the water-bath of 60 DEG C, react 4 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% carries out termination polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 62.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance number-average molecular weight is 11300, and molecular weight distribution is 1.37.
Embodiment 6
The 20mL hexane through anhydrous and oxygen-free process and 7.8mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 25 min in the water-bath of 50 DEG C after, add 0. 5mL iron naphthenate solution (hexane solution of 0.1 mol/L), 1.0 mL triethyl aluminium solution (hexane solution of 1 mol/L), 0.5mL diethyl phosphite solution (hexane solution of 0.2 mol/L) more successively, polymerization bottle is put into the water-bath of 50 DEG C, react 6 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% carries out termination polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 45.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance number-average molecular weight is 14800, and molecular weight distribution is 1.32.
Embodiment 7
The 20mL hexane through anhydrous and oxygen-free process and 7.8mL epoxy chloropropane is added successively in the Schlenk polymerization bottle of 100 mL, heat 10 min in the water-bath of 70 DEG C after, add successively again 0.5mL ferric carboxylate solution (hexane solution of 0.1 mol/L), 1.2 mL triisobutyl aluminum solutions (hexane solution of 1 mol/L) 0.6mL tributyl phosphates solution (hexane solution of 0.2 mol/L), polymerization bottle is put into the water-bath of 70 DEG C, react 5 hours.After reaction terminates, the ethanol solution hydrochloride adding 5% carries out termination polymerization, and incline and supernatant liquor, a large amount of ethanol purge of the polymkeric substance obtained, weighs after drying process, and polymer yield is 39.0%.Carry out GPC test to polymer samples, obtaining polymkeric substance 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) 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 group absorption peak, and the structural formula of gained homopolymer is as follows.
Claims (9)
1. a ternary Fe-series catalyst, comprise iron series compound, alkylaluminium cpd and electron donor three kinds of components, it is characterized in that: described iron series compound is any one or a few in iron naphthenate, ferric carboxylate, ferric acetyl acetonade, isocaprylic acid iron, the different pungent iron of phosphorous acid two, 2,6-bis-imine pyridine iron, neodecanoic acid iron; Described alkylaluminium cpd is any one or a few in triisobutyl aluminium, triethyl aluminum, sesquialter aluminium, aluminium diethyl monochloride, alkyl-al hydride; Described electron donor is any one or a few in three o-methyl-phenyl-phosphorous acid esters, diethyl phosphite, 1,10-o-phenanthroline, dipyridyl, quadrol, Tetramethyl Ethylene Diamine, tributyl phosphate.
2. ternary Fe-series catalyst as claimed in claim 1, is characterized in that: described iron series compound is any one or a few in iron naphthenate, neodecanoic acid iron, isocaprylic acid iron; Described alkylaluminium cpd is triisobutyl aluminium or triethyl aluminum; Described electron donor is diethyl phosphite or tributyl phosphate.
3. ternary Fe-series catalyst as claimed in claim 2, is characterized in that: the amount ratio of each component meets [Al]: [Fe]=3:1-30:1, [P]: [Fe]=1:1-10:1.
4. adopt the polymerization of the ternary Fe-series catalyst Epichlorohydrin as described in any one of claim 1-3 to prepare the method for Hydrin, it is characterized in that: take epoxy chloropropane as reaction substrate, with described ternary Fe-series catalyst for catalyzer, in varsol, temperature controls between 40-80 DEG C, reaction 1-140h, termination reaction, process obtains Hydrin.
5. the method for Hydrin is prepared in the polymerization of ternary Fe-series catalyst Epichlorohydrin as claimed in claim 4, it is characterized in that: described varsol is through anhydrous and oxygen-free process.
6. as described in claim 4 or 5, the method for Hydrin is prepared in the polymerization of ternary Fe-series catalyst Epichlorohydrin, it is characterized in that: the one in described varsol hexanaphthene, normal hexane, solvent oil, benzene, toluene, tetrahydrofuran (THF) or its composition.
7. the method for Hydrin is prepared in the polymerization of ternary Fe-series catalyst Epichlorohydrin as claimed in claim 4, it is characterized in that: the sequencing that described ternary Fe-series catalyst adds is iron series compound, alkylaluminium cpd, electron donor.
8. the method for Hydrin is prepared in the polymerization of ternary Fe-series catalyst Epichlorohydrin as claimed in claim 4, and it is characterized in that: temperature of reaction is 50-70 DEG C, the reaction times is 3-12h.
9. the method for Hydrin is prepared in the polymerization of ternary Fe-series catalyst Epichlorohydrin as claimed in claim 4, it is characterized in that: adopt the ethanol solution hydrochloride of 5% as terminator termination 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 true CN104558582A (en) | 2015-04-29 |
| CN104558582B 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632764A (en) * | 2016-10-17 | 2017-05-10 | 曲阜师范大学 | Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization |
| 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 |
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 |
|---|
| T.E. LIPATOVA ET AL.: ""Study of the catalytic polymerization of epichlorohydrin"", 《POLYMER SCIENCE U.S.S.R》 * |
| 毛利民等: ""Cp2Fe-Al(i-Bu)3催化环氧氯丙烷聚合"", 《第二届全国橡胶制品技术研讨会》 * |
Cited By (3)
| 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 |
| CN106632764A (en) * | 2016-10-17 | 2017-05-10 | 曲阜师范大学 | Iron-based catalyst, preparation method of iron-based catalyst, and application of iron-based catalyst in isoprene polymerization |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104558582B (en) | 2017-01-18 |
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 | |
| CN102115509B (en) | Starlike branched polybutadiene of rare earth catalyst system and preparation method thereof | |
| CN106699967B (en) | Method for preparing high-vinyl butylbenzene copolymer by adopting molybdenum-based catalytic system | |
| CN104725564A (en) | Polymerization method of isoprene and butadiene | |
| CN103788273A (en) | Rare earth catalysis system star-branched polyisoprene and preparation method thereof | |
| CN105985472A (en) | Rare earth catalyst and preparation method thereof and polyisoprene preparation method | |
| Xu et al. | Silylium dual catalysis in living polymerization of methacrylates via In situ hydrosilylation of monomer | |
| CN104558582A (en) | Method for preparing polyepichlorohydrin by catalyzing epichlorohydrin polymerization by using three-element iron catalyst | |
| CN103450373B (en) | Rare earth catalyst composition and rare earth catalyst and application thereof | |
| CN102532354B (en) | The homogeneous rare earth catalyst of neodymium series, its preparation method and application thereof | |
| CN104231133B (en) | A kind of rare earth catalyst and the method being used for preparing cis conjugated diene polymer thereof | |
| CN102532378B (en) | Catalyst composition for preparing 1,2-polybutadiene, and preparation method for 1,2-polybutadiene | |
| CN102603940A (en) | Catalyst composition for preparing polyisoprene, preparation method of catalyst composition and preparation method of polyisoprene | |
| CN102585061A (en) | Catalyst for use in preparation of high cis-polyisoprene with narrow molecular weight distribution and preparation method and application thereof | |
| CN106279662B (en) | A kind of ternary Fe-series catalyst and its Epichlorohydrin and butadiene copolymer prepare the application of polymer | |
| CN101845111B (en) | Method for preparing conjugated diene polymer | |
| CN102190745A (en) | Iron-based catalyst for pentadiene polymerization and method for preparing polypentadiene | |
| CN101608003A (en) | The method of lower molecular weight liquid polyisoprene rubber in the mass polymerization preparation | |
| CN114149571A (en) | Imidazole ionic liquid catalyzed vinyl monomer and cyclic ester monomer hybrid polymerization method | |
| CN105330773A (en) | Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof | |
| CN104558451A (en) | High cis-butadiene-isoprene block copolymer and preparation method thereof | |
| CN114230696A (en) | Homogeneous rare earth catalyst and preparation method and application thereof | |
| CN105085720B (en) | Rare earth catalyst composition and rare earth catalyst and its preparation method and application and a kind of method of isoprene polymerization | |
| CN103626890B (en) | The preparation method of a kind of rare-earth catalysis system and its preparation method and butadiene isoprene copolymer | |
| CN103087112B (en) | The preparation method of Cobalt trifluoromethanesulfcomplex, complex, cobalt, sulfonic acid cobalt series catalyst and preparation method thereof and polyhutadiene |
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 of 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 |