CN101704910A - Transition metal olefin polymerization catalyst and preparation method thereof - Google Patents
Transition metal olefin polymerization catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of transition metal catalyst for olefin polymerization and preparation method thereof; Catalyst includes the transistion metal compound and (B) organoaluminoxane compound that (A) general formula is (I),M is the transition metal atoms of group ivb in the periodic table of elements in the transistion metal compound of logical formula (I),M is an integer between 1~6,R1~R6 be respectively H,Halogen,Alkyl etc.,N is a number for meeting M valence state,X be halogen,Alkyl etc.,This catalyst alkene (ethylene,Propylene) polymerization activity is higher,With excellent adjustability of structure,The activity of catalyst can be regulated and controled by adjusting ligand structure and kinds of transition metals.
Description
Technical field
The present invention relates to a kind of transition metal catalyst for olefin polymerization and preparation method thereof.
Background technology
The key of polyolefin industry development is polyolefin catalyst.The appearance of each class new catalyst all can bring the change of new polymerization technique and the development of polyolefine novel material.Early 1950s, Ziegler and Natta successively use TiCl
4-AlEt
3Synthetic high density polyethylene(HDPE) of catalyst system and TiCl
3-AlEt
2The Cl catalyst system synthesizes isotactic polyprophlene, has opened up new era of polyolefin industry.Early 1980s, Kaminsky and Sinn have found with the methylaluminoxane to be promotor, metallocene is the new type polyolefin catalyst system of Primary Catalysts, can not only prepare high density polyethylene(HDPE), LLDPE, isotactic polyprophlene, and can synthesize with products such as the very difficult synthetic syndiotactic polypropylene of traditional catalyst, syndiotactic polystyrenes.Nineteen ninety-five, people such as Brookhart have at first reported the late transition metal catalyst of diimide ligand, further promoted the development of olefin polymerization catalysis, a series of non-metallocene catalysts such as salicylic alidehyde imine type late transition metal catalyst, contain P, the SHOP type late transition metal catalyst of O part, benzene oxygen imines type early transition metal catalyzer is developed, the benzene oxygen imines type early transition metal catalyzer of particularly nearest Mitsui Chemicals company research, it is the FI catalyzer, shown very high olefinic polymerization catalysis activity, and can prepare the very big concern that some polyolefine materials with high added value are subjected to people by regulating ligand structure and kinds of transition metals.But the patent of FI catalyzer is almost covered by offshore company at present, so development of new high reactivity non-metallocene olefin polymerization catalyst has great importance.
Summary of the invention
The purpose of this invention is to provide a kind of is the early transition metal olefin polymerization catalysis and preparation method thereof of part with the phenol nitrone.
Olefin polymerization catalysis provided by the invention comprises that (A) general formula is the transistion metal compound of (I) and (B) organometallic compound, Organoaluminoxy hydride compounds or ionizable compound.
Wherein A is the transistion metal compound with general formula (I) expression,
In the formula: M is the transition metal atoms in the periodic table of elements IVB family; M is an integer of 1～6; R
1～R
6Can be identical or different; and be respectively hydrogen atom, halogen atom, alkyl, heterogeneous ring compound residue, contain oxygen base, nitrogenous base, contain boryl, contain sulfenyl, phosphorous-containigroups groups, contain silica-based, germanic base, contain tinbase, the silyl that hydrocarbon replaces, siloxy-, alkoxyl group, alkylthio, aryloxy, arylthio, acyl group, ester group, thioester substrate, amido, imide, amino, imido grpup, sulphur ester group, sulfonamido, cyano group or the nitro that hydrocarbon replaces; and two or more groups can be incorporated into ring in them; when m is 2 or when bigger, any two by R
1～R
6The expression group can in conjunction with.
N is a number that satisfies valence state;
X is hydrogen atom, halogen atom, alkyl, contain the oxygen base, contain sulfenyl, contain boryl, contain aluminium base, phosphorous-containigroups groups, contain halogen, heterogeneous ring compound residue, contain silica-based, germanic base or contain tinbase, when n is 2 or when bigger, a plurality of X bases can be identical or different, and can be incorporated into ring;
(B) be the Organoaluminoxy hydride compounds.
Transistion metal compound A of the present invention is 10～10000: 1 with Organoaluminoxy hydride compounds B Al/M ratio.
The catalytic systems for polymerization of olefins of being made up of transistion metal compound A and Organoaluminoxy hydride compounds B is used for the alkene solvent polymeric, and under 0～200 ℃, polymerization 5min makes the white polyolefin powder to 180min under 0.1～1MPa.
It is the transition-metal catalyst preparation method of part with the phenol nitrone that another object of the present invention provides a kind of.
The transistion metal compound A of olefin polymerization catalysis of the present invention prepares according to following steps: the phenol nitrone ligand that contains reactive hydrogen is under the effect of organic lithium salt (as n-Butyl Lithium) or sodium hydride, peel off reactive hydrogen atom, generate the sodium salt or the lithium salts of part.The precursor compound reaction of the lithium salts of this part or sodium salt and the 4th group 4 transition metal obtains organometallic compound.
Concrete reaction process is as follows: at N
2Under the protective condition, the tetrahydrofuran solution of phenol nitrone ligand slowly is added drop-wise in the tetrahydrofuran solution of NaH or n-Butyl Lithium, the mol ratio of phenol nitrone ligand and NaH or n-Butyl Lithium is 1: 1～10; Under 0 ℃～100 ℃ conditions, reacted 2～24 hours.Centrifugally remove unreacted raw material.Under-100 ℃ to 0 ℃ conditions, in the sodium salt of the phenol nitrone that obtains after proton peeled off or the tetrahydrofuran solution of the precursor compound that lithium salts slowly is added drop-wise to the 4th group 4 transition metal, reacted 2～24 hours.Solvent removed in vacuo, drip dichloromethane, the centrifugal NaCl of removing obtains the dichloromethane solution of clarifying transistion metal compound A, removes methylene dichloride with final vacuum, uses the hexane wash catalyzer.50 ℃ of following vacuum-dryings obtained transistion metal compound A powder in 1～10 hour.
All solvents that use in this method must carry out anhydrous and oxygen-free to be handled.
Precursor compound used in the present invention mainly is ZrCl
4, TiCl
4And HfCl
4
Transistion metal compound is 100～10000: 1 with the Al/Zr ratio of promotor in the described catalyzer.
Transistion metal compound is 10～10000: 1 with the Al/Ti ratio of promotor in the described catalyzer.
Described Organoaluminoxy hydride compounds is that triethyl aluminum, triisobutyl aluminium, methylaluminoxane, catalytic alkene mainly are ethene and propylene.
The olefin polymerization catalyst system that the present invention is designed, polymerization activity is higher, has excellent adjustability of structure, can regulate and control activity of such catalysts by regulating ligand structure and kinds of transition metals.
Description of drawings
The Primary Catalysts A's of Fig. 1 embodiment 1 preparation
1The H-NMR spectrogram;
Embodiment
Embodiment 1
The preparation of 1 Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of ligand 1 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.Under the cold condition, the upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2Tetrahydrofuran solution in.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add 10 milliliters of methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Concentrate as for, obtain yellow solid.Divide three each addings 4 milliliters of hexane wash.Solid is following dry 8 hours at 50 ℃.
The solvent polymeric of 2 alkene
Load onto magneton at 5 hours polymerization flask of 130 ℃ of dryings, vacuumized dry one hour.Add the 50ml dry toluene, a certain amount of MAO solution (Al/Zr=2000), under 30 ℃, stir treat that solution absorption ethene reaches capacity after, (2 μ/ml), polyreaction begins to add the toluene solution of 5ml catalyzer with syringe.Behind the reaction 30min, the acidifying ethanol with 10% stops polyreaction.Polymkeric substance is through water, and after the washing with alcohol, 60 ℃ are dried to constant weight.
Embodiment 2
The preparation of 1 Primary Catalysts A
The preparation of Primary Catalysts is same
2 solvent polymerics
The polymerizing condition operation is identical with 1, and Al/Zr changes 3000 into.
Embodiment 3
The preparation of 1 Primary Catalysts A
The preparation of Primary Catalysts is same
2 solvent polymerics
The polymerizing condition operation is identical with 1, and promotor changes TEA into.
Embodiment 4
The preparation of 1 Primary Catalysts A
The preparation of Primary Catalysts is same
2 solvent polymerics
The polymerizing condition operation is identical with 1, is changed to propylene gas by ethylene gas.
Embodiment 5
The preparation of 1 Primary Catalysts A
Preparation of Catalyst is same
2 solvent polymerics
Vacuumized under 70 ℃ of the 500ml polymermaking autoclaves dry two hours.Add the 100ml dry toluene, a certain amount of MAO solution (Al/Zr=2000), under 30 ℃, stir treat that solution absorption ethene reaches capacity after, (1 μ/ml), polyreaction begins to add the toluene solution of 2ml catalyzer with syringe.Behind the reaction 30min, the acidifying ethanol with 10% stops polyreaction.Polymkeric substance is through water, and after the washing with alcohol, 60 ℃ are dried to constant weight.
Embodiment 6
The preparation of 1 Primary Catalysts A
Preparation of Catalyst is same
2 solvent polymerics
Polymerizing condition is identical with five, and temperature of reaction is 60 ℃.
Embodiment 7
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of ligand 1 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to TiCl with conduit
4Hexane solution in.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain red solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 8
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of ligand 1 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of n-Butyl Lithium, stirred 5 hours in the ice-water bath.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to TiCl with conduit
4Hexane solution in.-68 ℃ were reacted 24 hours down.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain red solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 9
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of ligand 1 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of n-Butyl Lithium, stirred 5 hours in the ice-water bath.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to TiCl with conduit
4Hexane solution in.-68 ℃ were reacted 24 hours down.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain red solid.Recrystallization obtains red crystals in methylene dichloride and hexane mixing solutions.
Embodiment 10
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 2 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 11
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 3 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 12
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 4 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 13
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 5 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 14
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 6 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 15
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 7 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Embodiment 16
The preparation of Primary Catalysts A
The dry there-necked flask that dropping funnel and magneton are housed vacuumizes, and charges into nitrogen.The tetrahydrofuran solution of part 8 slowly is added drop-wise in the tetrahydrofuran (THF) suspension of excessive NaH.Stirring at room 5 hours.Reaction solution is transferred in the test tube of band arm.Centrifugal half hour.The upper strata stillness of night slowly is added drop-wise to ZrCl with conduit
4(THF)
2In.Room temperature reaction 24 hours.Solvent removed in vacuo obtains crude product.Add the 10ml methylene dichloride, stirring and dissolving.Centrifugal, supernatant liquid shifts.Be concentrated into driedly, obtain yellow solid.Divide the each 4ml of adding hexane wash three times.Solid is following dry 8 hours at 50 ℃.
Table 1.C
21H
26NO
2ZrCl
2/ MAO is the experimental result of catalyst system catalyzed polymerization
Table 2 ligand structure figure
Claims (9)
1. transition metal catalyst for olefin polymerization is characterized in that:
This catalyzer comprises that general formula is the transistion metal compound and the Organoaluminoxy hydride compounds of (I);
General formula (I):
In the formula: M is the transition metal atoms in the periodic table of elements IVB family;
M is the integer of 1-6;
R
1-R
6Can be identical or different; and be respectively hydrogen atom, halogen atom, alkyl, heterogeneous ring compound residue, contain oxygen base, nitrogenous base, contain boryl, contain sulfenyl, phosphorous-containigroups groups, contain silica-based, germanic base, contain tinbase, the silyl that hydrocarbon replaces, siloxy-, alkoxyl group, alkylthio, aryloxy, arylthio, acyl group, ester group, thioester substrate, amido, imide, amino, imido grpup, sulphur ester group, sulfonamido, cyano group or the nitro that hydrocarbon replaces; and two or more groups can be incorporated into ring in them; when m is 2 or when bigger, any two by R
1-R
6The expression group can in conjunction with;
N is a number that satisfies valence state;
X is hydrogen atom, halogen atom, alkyl, contain the oxygen base, contain sulfenyl, contain boryl, contain aluminium base, phosphorous-containigroups groups, contain halogen, heterogeneous ring compound residue, contain silica-based, germanic base or contain tinbase, when n is 2 or when bigger, a plurality of X bases can be identical or different, and can be incorporated into ring.
2. a kind of transition metal catalyst for olefin polymerization according to claim 1 is characterized in that: described transition metal atoms is Zr; Transistion metal compound is 100～10000: 1 with the Al/Zr ratio of Organoaluminoxy hydride compounds.
3. a kind of transition metal catalyst for olefin polymerization according to claim 1 is characterized in that: described transition metal atoms is Ti; Transistion metal compound is 10～10000: 1 with the Al/Ti ratio of Organoaluminoxy hydride compounds.
4. a kind of transition metal catalyst for olefin polymerization according to claim 1 is characterized in that: described Organoaluminoxy hydride compounds is triethyl aluminum, triisobutyl aluminium or methylaluminoxane.
5. the preparation method of a kind of transition metal catalyst for olefin polymerization according to claim 1 is characterized in that: general formula is as follows for the preparation method of the transistion metal compound of (I):
(1) at N
2Under the protective condition, the tetrahydrofuran solution of phenol nitrone ligand slowly is added drop-wise in the tetrahydrofuran solution of NaH or n-Butyl Lithium, under 0 ℃～100 ℃ conditions, reacted 2～24 hours, the mol ratio of phenol nitrone ligand and NaH or n-Butyl Lithium is 1: 1～10;
(2) centrifugally remove unreacted raw material, under-100 ℃ to 50 ℃ conditions, in the sodium salt of the phenol nitrone that obtains after proton peeled off or the tetrahydrofuran solution of the precursor compound that lithium salts slowly is added drop-wise to the 4th group 4 transition metal, the mol ratio of phenol nitrone ligand and transition metal is 0.1～10,0 ℃ to 100 ℃ reactions 2～24 hours;
(3) vacuum is removed tetrahydrofuran (THF) and is obtained crude product, drip dichloromethane, and the centrifugal NaCl of removing obtains the dichloromethane solution of clarifying transistion metal compound A, removes methylene dichloride with final vacuum;
(4) transistion metal compound for preparing is carried out purifying; Behind the purifying, 0 ℃～100 ℃ following vacuum-dryings obtained the transistion metal compound powder in 1～10 hour.
6. the preparation method of a kind of transition metal alkene catalyst according to claim 5 is characterized in that: the mol ratio of phenol nitrone ligand and transition metal is 0.5～6.
7. the preparation method of a kind of transition metal catalyst for olefin polymerization according to claim 5, it is characterized in that: sodium salt that the phenol nitrone ligand obtains or lithium salts must slowly be added drop-wise in the precursor compound of transistion metal compound, the dropping time was controlled at 5min to 5 hour, and dropping temperature is controlled at-100 ℃ to 50 ℃.
8. the preparation method of a kind of transition metal catalyst for olefin polymerization according to claim 5, it is characterized in that: it is 20 ℃ to 50 ℃ that the temperature of reaction of phenol nitrone ligand and NaH or n-Butyl Lithium is controlled at, 5～15 hours.
9. the preparation method of a kind of transition metal catalyst for olefin polymerization according to claim 5 is characterized in that: the purification process of transistion metal compound is for hexane wash three times or recrystallization; The used solvent of recrystallization is the mixed solvent of toluene, methylene dichloride, hexane, tetrahydrofuran (THF) or this kind solvent.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120217432A1 (en) * | 2009-11-19 | 2012-08-30 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Polymerizable coordination complexes and polymeric materials obtained from said monomers |
| CN104549510A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst and use method thereof |
| CN111943973A (en) * | 2020-08-25 | 2020-11-17 | 万华化学集团股份有限公司 | Bimetallic complex of phenoxy imine ligand skeleton, preparation method and application |
| CN112979590A (en) * | 2021-03-01 | 2021-06-18 | 安徽金轩科技有限公司 | Novel process for preparing 2-acetylfuran by using furan |
| US11814460B2 (en) | 2020-10-22 | 2023-11-14 | Exxonmobil Chemical Patents Inc. | Pyridyl hydroxyl amine catalyst compounds and systems for Olefin Polymerization |
| US11919981B2 (en) | 2020-10-22 | 2024-03-05 | Exxonmobil Chemical Patents Inc. | Monocyclopentadienyl pyridyl hydroxyl amine catalyst compounds and systems for olefin polymerization |
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| CN101280031B (en) * | 2007-04-06 | 2010-05-19 | 中国石油化工股份有限公司 | Catalyst system for preparing dual-peak or widely distributed polyethylene and its application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120217432A1 (en) * | 2009-11-19 | 2012-08-30 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Polymerizable coordination complexes and polymeric materials obtained from said monomers |
| CN104549510A (en) * | 2013-10-18 | 2015-04-29 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst and use method thereof |
| CN111943973A (en) * | 2020-08-25 | 2020-11-17 | 万华化学集团股份有限公司 | Bimetallic complex of phenoxy imine ligand skeleton, preparation method and application |
| CN111943973B (en) * | 2020-08-25 | 2023-06-09 | 万华化学集团股份有限公司 | Bimetallic complex of phenoxyimine ligand framework, preparation method and application |
| US11814460B2 (en) | 2020-10-22 | 2023-11-14 | Exxonmobil Chemical Patents Inc. | Pyridyl hydroxyl amine catalyst compounds and systems for Olefin Polymerization |
| US11919981B2 (en) | 2020-10-22 | 2024-03-05 | Exxonmobil Chemical Patents Inc. | Monocyclopentadienyl pyridyl hydroxyl amine catalyst compounds and systems for olefin polymerization |
| CN112979590A (en) * | 2021-03-01 | 2021-06-18 | 安徽金轩科技有限公司 | Novel process for preparing 2-acetylfuran by using furan |
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