CN103664469B - Cyclopentadiene-containing star compounds and preparation method thereof - Google Patents
Cyclopentadiene-containing star compounds and preparation method thereof Download PDFInfo
- Publication number
- CN103664469B CN103664469B CN201210347874.5A CN201210347874A CN103664469B CN 103664469 B CN103664469 B CN 103664469B CN 201210347874 A CN201210347874 A CN 201210347874A CN 103664469 B CN103664469 B CN 103664469B
- Authority
- CN
- China
- Prior art keywords
- cyclopentadiene
- preparation
- star
- catalyst
- molecular weight
- 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
- 0 *C1C=CC=C1 Chemical compound *C1C=CC=C1 0.000 description 3
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to cyclopentadiene-containing star compounds and a preparation method thereof. The preparation method comprises the following step: in the presence of inorganic alkali, reacting cyclopentadiene and derivatives thereof and star halide, thus preparing the cyclopentadiene-containing star compounds. The preparation method of the cyclopentadiene-containing star compounds is simple in synthesis process, high in yield, accessible in raw materials and mild in reaction conditions. The cyclopentadiene-containing star compounds can be used as a branching agent for preparing a star rare earth catalyst through preparation reaction of the rare earth catalyst for conjugated diene polymerization, thereby preparing a star branched polymer and lowering the viscosity of a polymer solution.
Description
Technical field
The present invention relates to class star compound and preparation method thereof, relate in particular to a class and contain star compound of cyclopentadiene and preparation method thereof.
Background technology
Cyclopentadiene contains unsaturated conjugated double bond, chemical property is very active, can carry out being polymerized, hydrogenation, halogenation, addition, the reaction such as condensation and reduction, be mainly used in synthetic rubber and petroleum resin, purposes is as follows: with cyclopentadiene and dicyclopentadiene for Third monomer synthesizes ethylene-propylene rubber(EPR); Cyclopentadiene and dicyclopentadiene thermopolymerization, can obtain petroleum resin, for tackifier, softening agent, coating, sanitas and ink etc.; The synthesis etc. of metallocene catalyst for olefine polymerization is used for as part.
When cyclopentadiene is used for olefinic polymerization metallocene catalyst synthetic ligands, according to the difference of catalyst structure, be divided into monocyclopentadienyl coordination system and bridge-type many cyclopentadienyl ligand system.As CN1461757 discloses a kind of monocyclopentadienyl polyolefin catalyst and preparation method thereof.This catalyzer coordinates with aluminum alkyls or aluminum alkoxide and is used for olefinic polymerization, can obtain the polymkeric substance of high molecular and wide molecular weight distribution.
CN101935366A discloses a kind of for reducing melt index and the biscyclopentadienyl catalyst system increasing polymer-through-out rate, the invention provides the polymerization process of bifunctional catalyst system and these bifunctional catalyst systems of employing.Disclosed polymerization process can be higher productivity produce olefin polymer, and these olefin polymers can have higher molecular weight and/or lower melt index.
CN96101442.3 discloses the preparation method by the Dicyclopentadiene (DCPD) based compound of single carbon atom bridge joint, and it comprises makes carbonyl compound and cyclopentadienyl compounds react under a kind of alkali exists.Can be used for preparing ansa-metallocene with the compound that high yield obtains by the simple single stage method of this invention, it is the active catalyst component in olefin polymerization process.
CN96110141.5 discloses a kind of preparation technology of carbon-bridged dicyclic pentylene compound, this technique uses at least one alkali and a kind of phase-transfer catalyst, one or both cyclopentadiene compounds and a kind of carbonyl compound are reacted, the bridge dicyclopentadiene part that final synthesis obtains, will be used for the preparation of the olefin copolymer with elastic performance.
And bridge-type three cyclopentadienyl compounds seldom adopts in the preparation process of alkene catalyst.Consider the chemically reactive of cyclopentadiene and the star structure of bridge-type three cyclopentadienyl compounds, can predict that this compounds will have good application prospect at non-linear synthetic rubber and petroleum resin field.
Summary of the invention
The object of the invention is proposition one class and contain star compound of cyclopentadiene and preparation method thereof.Such compound synthesis technology is simple, and productive rate is higher, and raw material is easy to get, and reaction conditions is gentle.
Specifically, a class disclosed in this invention is containing the star compound of cyclopentadiene, and its general structure is such as formula shown in I:
(formula I)
Wherein R
1for H, the one in methyl or ethyl;
A class disclosed in this invention is containing the preparation method of the star compound of cyclopentadiene, and its step is as follows:
Under argon shield, cyclopentadiene or derivatives thereof is dissolved in tetrahydrofuran (THF), then adds mineral alkali, heated and stirred backflow 0.5 ~ 2h, then adds trihalogenated benzene, continues backflow 0.5 ~ 3h in reaction system.After cooling, reaction solution is transferred in separating funnel, adds ethyl acetate, organic layer washed with water three times.By organic layer under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal.The mol ratio of mineral alkali and cyclopentadiene and derivative thereof is (0.3 ~ 1.3): 1, and the mol ratio of trihalogenated benzene and cyclopentadiene and derivative thereof is (0.1 ~ 0.6): 1.
In above-mentioned preparation method, described cyclopentadiene derivant is 5-methyl isophthalic acid, the one in 3-cyclopentadiene or 5-ethyl-1，3-cyclopentadiene.
In above-mentioned preparation method, described mineral alkali is NaH or CaH
2in one.
In above-mentioned preparation method, described trihalogenated benzene is the one in 1,3,5-trichlorobenzene or 1,3,5-tribromo-benzene.
Beneficial effect of the present invention is:
A class disclosed in this invention is containing the preparation method of the star compound of cyclopentadiene, and its synthesis technique is simple, and productive rate is higher, and raw material is easy to get, and reaction conditions is gentle.
A class disclosed in this invention, containing the star compound of cyclopentadiene, at conjugate diene polymerization with in rare earth catalyst preparation feedback, can be used as branching agent and prepares star-like rare earth catalyst (shown in II), wherein
for polyisoprene segments, Nd is catalyst activity point, and in the course of the polymerization process, conjugated diene carries out chainpropagation along this star-like catalyst activity point, finally obtains the polymerisate in star-branched structure; Do not reduce in maintenance rare earth catalyst activity, under the narrow and suitable Isosorbide-5-Nitrae-structural content of molecular weight distribution is greater than the prerequisite of 98%, significantly can reduces the soltion viscosity of polymkeric substance, bring convenience to processes such as the heat transfer in industrial production, conveying, glue spraying and cohesions.
(formula II)
Embodiment
Following examples are further described feature of the present invention, but protection scope of the present invention is not by the restriction of these embodiments.
1, Main Analysis characterizing method
The limiting viscosity of polymkeric substance utilizes dark type viscometer to test at 30 DEG C, and using toluene as solvent, calculation formula is [η]=[2 (η
sp-ln η
r)]
1/2/ c, wherein η
r=t/t
0, η
spη
r-1, t is concentration is the flowing time of the polymkeric substance toluene solution of c, t
0for the flowing time of toluene; Middle average molecular weight (the M of multipolymer
w) and molecular weight distribution (M
w/ M
n) utilize gel permeation chromatography (GPC) to characterize, take polystyrene standards as calibration curve; Suitable Isosorbide-5-Nitrae-the structural content of multipolymer utilizes fourier infrared (FTIR) to characterize.Nucleus magnetic resonance
1h NMR data come from BrukerAC-300 nuclear magnetic resonance analyser, and chemical shift δ unit is ppm, is inside designated as tetramethylsilane.
2, raw material specification and source
Divinyl, isoprene Petrochina Lanzhou Petrochemical Company, polymerization-grade;
High and new technology industrial development zone, carboxylic acid neodymium Ningbo Yu Ling Chemical Industry Science Co., Ltd, 0.5M hexane solution;
Aluminum alkyls and alkyl-al hydride Nanjing communications and liaison Chemical Co., Ltd., purity > 97%;
Alkyl aluminum halide lark prestige Science and Technology Ltd., 0.8M hexane solution;
Other reagent AlfaAesar (Tianjin) Chemical Co., Ltd., SILVER REAGENT.
Embodiment 1
Formula I syntheti c route is as follows:
Its step is as follows:
Work as R
1for methyl: under argon shield; tetrahydrofuran (THF) (150mL) is added successively, 5-methyl isophthalic acid, 3-cyclopentadiene (24g in 250mL round-bottomed bottle; 300mmol); NaH(7.92g, 330mmol) after induction stirring reflux 1h, then add 1; 3; 5-tribromo-benzene (28.3g, 90mmol), continues backflow 2h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (200mL), organic layer washed with water three times (each 50mL).By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal (26.7g, yield 95%).Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 1.56(s, 9H, CH
3), 6.25(d, 6H, CH), 6.35(t, 6H, CH), 6.90(s, 3H, PhH).
Work as R
1for H: step is the same, and now raw material is 1，3-cyclopentadiene, yield 90%.Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 4.02(d, 3H, CH), 6.21(t, 6H, CH) and, 6.32(t, 6H, CH), 6.82(s, 3H, PhH).
Work as R
1for ethyl: step is the same, and now raw material is 5-ethyl-1，3-cyclopentadiene, yield 93%.Nucleus magnetic resonance:
1h-NMR(300MHz, CDCl
3, ppm): δ 0.82(t, 9H, CH
3), 1.53(q, 6H, CH
2), 6.33(d, 6H, CH), 6.43(t, 6H, CH), 6.96(s, 3H, PhH).
Embodiment 2
Formula I syntheti c route is as follows:
Work as R
1for methyl: under argon shield, add tetrahydrofuran (THF) (20mL) successively in 50mL round-bottomed bottle, 5-methyl isophthalic acid, 3-cyclopentadiene (4g, 50mmol), CaH
2after (1.3g, 30mmol) induction stirring reflux 0.8h, then add 1,3,5-trichlorobenzene (2.7g, 15mmol), continue backflow 1.5h.After cooling, reaction solution is transferred in separating funnel, and adds ethyl acetate (70mL), organic layer washed with water three times (each 50mL).By organic solvent under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtains clear crystal, obtains clear crystal (4.3g, yield 92%).
Work as R
1for H: step is the same, and now raw material is 1，3-cyclopentadiene, yield 90%.
Work as R
1for ethyl: step is the same, and now raw material is 5-ethyl-1，3-cyclopentadiene, yield 96%.
Embodiment 3
Under argon shield, in the catalyzer configuration bottle of drying, add 0.03mmol neodymium iso-octanate, 0.75mmol triisobutyl aluminium, 0.15mmol diethyl aluminium hydride, 0.09mmol diethylaluminum chloride, 0.3mmol isoprene, 0.02mmol formula I (R
1for methyl) mix after in 25 DEG C of ageing 60min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.3mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 1 × 10 with the mol ratio of monomer
-4.Be polymerized after 5 hours at 50 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 89.0%, weight-average molecular weight (M
w) be 6 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.9, polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.4dL/g.
Comparative example 3
In catalyst preparation process, replace formula I with toluene, other condition is with embodiment 3.Polymer yield is 89.7%, weight-average molecular weight (M
w) be 5.7 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.4, polymkeric substance is 98.3% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.2dL/g.
Embodiment 4
Under argon shield, in the catalyzer configuration bottle of drying, add 0.036mmol n-nonanoic acid neodymium, 0.6mmol triisobutyl aluminium, 0.4mmol hydrogenation dibutyl aluminium, 0.08mmol di-isobutyl aluminum chloride, 0.8mmol isoprene, 0.06mmol formula I (R
1for ethyl) mix after in 27 DEG C of ageing 50min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.6mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 6 × 10 with the mol ratio of monomer
-5.Be polymerized after 4 hours at 55 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 85.0%, weight-average molecular weight (M
w) be 8.3 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.6, polymkeric substance is 98.7% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.3dL/g.
Comparative example 4
In catalyst preparation process, replace formula I with vinyl benzene, other condition is with embodiment 4.Polymer yield is 84.5%, weight-average molecular weight (M
w) be 8.0 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.7, polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.7dL/g.
Embodiment 5
Under argon shield, in the catalyzer configuration bottle of drying, add 0.02mmol neodymium caprate, 0.8mmol diisobutylaluminium hydride, 0.03mmol sesquialter ethylmercury chloride aluminium, 0.1mmol isoprene, 0.1mmol formula I (R
1for H) mix after in 35 DEG C of ageing 60min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 1mol isoprene in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 2 × 10 with the mol ratio of monomer
-5.Be polymerized after 5 hours at 70 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 92.0%, weight-average molecular weight (M
w) be 7.3 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.7, polymkeric substance is 98.9% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.2dL/g.
Comparative example 5
In catalyst preparation process, replace formula I with dimethylbenzene, other condition is with embodiment 5.Polymer yield is 91.5%, weight-average molecular weight (M
w) be 9.0 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.8, polymkeric substance is 98.8% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.0dL/g.
Embodiment 6
Under argon shield, in the catalyzer configuration bottle of drying, add 0.05mmol capric acid neodymium, 0.25mmol tri-butyl aluminum, 1.5mmol diethyl aluminium hydride, 0.15mmol chlorination dibutyl aluminium, 1.25mmol isoprene, 0.1mmol formula I (R
1for methyl) mix after in 20 DEG C of ageing 30min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.25mol divinyl in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 2 × 10 with the mol ratio of monomer
-4.Be polymerized after 4.5 hours at 40 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 80.0%, weight-average molecular weight (M
w) be 4.5 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, polymkeric substance is 99.0% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 2.6dL/g.
Comparative example 6
In catalyst preparation process, replace formula I with Vinylstyrene, other condition is with embodiment 6.Polymer yield is 79.5%, weight-average molecular weight (M
w) be 4.2 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.1, polymkeric substance is 98.9% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.3dL/g.
Embodiment 7
Under argon shield, in the catalyzer configuration bottle of drying, add 0.01mmol neodymium iso-octanate, 0.05mmol triethyl aluminum, 0.30mmol hydrogenation dibutyl aluminium, 0.04mmol di-isobutyl aluminum chloride, 0.05mmol isoprene, 0.15mmol formula I (R
1for methyl) mix after in 25 DEG C of ageing 45min, prepare homogeneous catalyst, for subsequent use.
Under argon shield, add the cyclohexane solution of 0.05mol divinyl and 0.05mol isoprene in the polymerization reactor of drying, then add the above catalyst solution prepared, catalyst component is a) 1 × 10 with the mol ratio of monomer
-4.Be polymerized after 5.5 hours at 80 DEG C, add the ethanolic soln termination reaction of the BHT of 1wt%, washing is placed in 45 DEG C of vacuum drying ovens and is dried to constant weight, and polymer yield is 78.0%, weight-average molecular weight (M
w) be 6.5 × 10
5, molecular weight distributing index (M
w/ M
n) be 1.6, polymkeric substance is 98.2% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 3.0dL/g.
Comparative example 7
In catalyst preparation process, replace formula I with naphthalene, other condition is with embodiment 7.Polymer yield is 79.0%, weight-average molecular weight (M
w) be 6.2 × 10
5, molecular weight distributing index (M
w/ M
n) be 2.6, polymkeric substance is 98.1% along Isosorbide-5-Nitrae-structural content, and soltion viscosity (η) is 4.0dL/g.
As can be seen from above embodiment and comparative example result, such is containing the preparation method of the star compound of cyclopentadiene, and its synthesis technique is simple, and productive rate is higher, and raw material is easy to get, and reaction conditions is gentle.Relative to prior art, the star-like rare earth catalyst prepared by star compound of the present invention is used in conjugate diene polymerization process, do not reduce at maintenance catalyst activity, molecular weight distribution is narrow and along 1, under 4-structural content is greater than the prerequisite of 98%, significantly can reduce the soltion viscosity of polymkeric substance.
Claims (5)
1. a class is containing the star-like compound of cyclopentadiene, and its general structure is such as formula shown in I:
Wherein R
1for H, the one in methyl or ethyl.
2. the preparation method of a star-like compound according to claim 1, it is characterized in that comprising the following steps: under argon shield, cyclopentadiene or derivatives thereof is dissolved in tetrahydrofuran (THF), then mineral alkali is added, heated and stirred backflow 0.5 ~ 2h, then in reaction system, trihalogenated benzene is added, continue backflow 0.5 ~ 3h, after cooling, reaction solution is transferred in separating funnel, add ethyl acetate, organic layer washed with water three times, by organic layer under reduced pressure evaporate to dryness, solid with ethyl acetate recrystallization, obtain clear crystal, the mol ratio of mineral alkali and cyclopentadiene or derivatives thereof is (0.3 ~ 1.3) ︰ 1, the mol ratio of trihalogenated benzene and cyclopentadiene or derivatives thereof is (0.1 ~ 0.6) ︰ 1.
3. preparation method according to claim 2, is characterized in that described cyclopentadiene derivant is 5-methyl isophthalic acid, the one in 3-cyclopentadiene or 5-ethyl-1，3-cyclopentadiene.
4. preparation method according to claim 2, is characterized in that described mineral alkali is NaH or CaH
2in one.
5. preparation method according to claim 2, is characterized in that described trihalogenated benzene is the one in 1,3,5-trichlorobenzene or 1,3,5-tribromo-benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210347874.5A CN103664469B (en) | 2012-09-18 | 2012-09-18 | Cyclopentadiene-containing star compounds and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210347874.5A CN103664469B (en) | 2012-09-18 | 2012-09-18 | Cyclopentadiene-containing star compounds and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103664469A CN103664469A (en) | 2014-03-26 |
| CN103664469B true CN103664469B (en) | 2015-05-27 |
Family
ID=50303368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210347874.5A Active CN103664469B (en) | 2012-09-18 | 2012-09-18 | Cyclopentadiene-containing star compounds and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103664469B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1272924B (en) * | 1995-01-23 | 1997-07-01 | Spherilene Srl | PROCEDURE FOR THE PREPARATION OF CYCLOPENTADIENYL COMPOUNDS AND COMPOUNDS SO OBTAINABLE |
| DE19523595A1 (en) * | 1995-06-30 | 1997-01-02 | Hoechst Ag | Process for the preparation of a carbon-bridged biscyclopentadiene compound |
| US6177603B1 (en) * | 1998-06-12 | 2001-01-23 | Bridgestone Corporation | Organo zinc and rare earth catalyst system in the polymerization of conjugated dienes |
| DE19951841A1 (en) * | 1999-10-28 | 2001-05-03 | Bayer Ag | Catalyst based on rare earth compounds |
| CN1182158C (en) * | 2002-05-31 | 2004-12-29 | 中国石油化工股份有限公司 | Single metallocene polyolefine catalyst and its preparation method |
| ES2582396T3 (en) * | 2009-06-29 | 2016-09-12 | Chevron Phillips Chemical Company Lp | Dual metallocene catalyst systems to decrease the flow rate and increase the speed of polymer production |
| CN102115509B (en) * | 2010-12-31 | 2012-07-04 | 大连理工大学 | Starlike branched polybutadiene of rare earth catalyst system and preparation method thereof |
-
2012
- 2012-09-18 CN CN201210347874.5A patent/CN103664469B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103664469A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102585058B (en) | Polymerizing catalyst, preparation method, using method and polyolefin product prepared therefrom | |
| CN106397264A (en) | Diimine ligand compound, and complex and application thereof | |
| CN105289741B (en) | A kind of chrome catalysts of nitrogen phosphorus co-ordinating backbone and its application in catalysis ethylene oligomerization | |
| CN106397261A (en) | Diimine ligand compound, and complex and application thereof | |
| EP2810960B1 (en) | Polymerization-catalyst composition for conjugated-diene monomer | |
| CN102766087B (en) | Nickel composition containing benzhydryl-substituted imine pyridine, preparation method and application thereof | |
| CN105646598B (en) | Asymmetric Branched polyethylene containing naphthyl substituted and the preparation method and application thereof | |
| CN105037588B (en) | A kind of iso-indoles rare-earth metal catalyst, preparation method and application | |
| CN105693896B (en) | 1,2 asymmetric diimine nickel complex catalyst of acenaphthenequinone and preparation method and application | |
| CN102532379B (en) | Polymerization method for preparing rare earth isoprene rubber | |
| CN106397260A (en) | Diimine ligand compound, and nickel complex and application thereof | |
| CN103382238A (en) | Polymerization method for m-pentadiene petroleum resin | |
| CN107312115B (en) | Bis-indole rare earth metal catalyst, preparation method and application | |
| CN103664469B (en) | Cyclopentadiene-containing star compounds and preparation method thereof | |
| CN108658850A (en) | A kind of fluorine-containing pyridine imine class ligand, its transient metal complex and its application in polyisoprene synthesis | |
| CN106397263A (en) | Ligand compound and preparation thereof, and complex containing ligand compound | |
| CN102532354A (en) | Homogeneous neodymium rare earth catalyst, and preparation method and application thereof | |
| CN102050840A (en) | Naphthalene nucleus containing alpha-diketiminato nickel (II) composition as well as preparation method and application thereof | |
| CN103664468B (en) | 4-arm star compound containing cyclopentadiene, and preparation method and application of compound | |
| CN105126910B (en) | A kind of C2Symmetry imidazolylphenyl rare-earth metal catalyst, preparation method and application | |
| CN104151454B (en) | A kind of cobalt series catalyst and the application in 1,3-butadiene polymerization thereof | |
| CN100590135C (en) | Neutral non-bridged combined metal chromium catalyst and its use | |
| CN102802793A (en) | Catalyst for the hydrogenation of unsaturated compounds | |
| CN109467625A (en) | Aniline oximes catalyst and preparation method thereof | |
| CN106397262A (en) | Diimine ligand, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 |