CN1453070A - SiO2 loaded double-metal catalyst and its prepn and use - Google Patents
SiO2 loaded double-metal catalyst and its prepn and use Download PDFInfo
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- CN1453070A CN1453070A CN 02118643 CN02118643A CN1453070A CN 1453070 A CN1453070 A CN 1453070A CN 02118643 CN02118643 CN 02118643 CN 02118643 A CN02118643 A CN 02118643A CN 1453070 A CN1453070 A CN 1453070A
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Abstract
The catalyst consists of SiO2 as carrier 100 weight portions, MAO 0-1600 weight portions, co-catalyst Cp2ZrCl2 0-80 weight portions and halide of bidentate nitrogen ligand N^N NiX2 as oligomerization catalyst 0-80 weight portions. The present invention also discloses the preparation process and the application in olefin polymerization of the catalyst. The catalyst has simple preparation process, easy-to-obtain material, low cost, high catalytic activity and capacity of producing polyethylene with different branching degree.
Description
Technical field
The present invention relates to a kind of SiO
2Bimetallic catalyst catalyst of polyethylene system of load and its production and use.
Background technology
People contain the polyethylene product of side chain usually by following several method preparation:
The one, utilize traditional Ziegler-Natta catalyst or metallocene catalyst copolymerization of ethylene and 'alpha '-olefin monomers, but the conversion ratio of 'alpha '-olefin monomers is not high usually;
The 2nd, by the special construction catalyst under certain conditions directly polymerizing ethylene monomer obtain polyethylene (J.Polym.Sci., Polym.Chem.1984,22,3027 of side chain.J.Am.Chem.Soc., 1995,117,6414), but catalyst activity is not high and preparation cost is higher;
The 3rd, utilize homogeneous phase catalyst for copolymerization metallocene or and the unique vinyl monomer of catalyst for oligomerization in-situ copolymerization (Macromol.Rapid Commun., 1999,20,139), but can't directly apply on the existing industrial polyplant, industrialization still needs loadization, and this is because homogeneous catalyst can't be controlled and sticking easily still the form of polymerizate.
Summary of the invention
The object of the invention is to provide a kind of industrialized SiO that is easy to
2The load bimetallic catalyst prepares branched polyethylene, and wherein carrier is SiO
2, catalyst for copolymerization is a metallocene catalyst, catalyst for oligomerization is that cost is lower, the halide (N of the simple bidentate nitrogen of synthetic route coordination nickel
⌒N NiX
2).
Catalyst system and catalyzing of the present invention comprises SiO
2Carrier, catalyst for oligomerization, catalyst for copolymerization and co-catalyst.
SiO of the present invention
2The carrier bimetallic catalyst, in weight portion, form by following component and content:
SiO
2 100
0-1600 is preferred for MAO (MAO): 600-1000
Cp
2ZrCl
20-80 is preferred: 5-60
N
⌒N NiX
20-80 is preferred: 5-60
Use unique carrier S iO
2Load metallocene catalyst and back transition N
⌒N NiX
2The Preparation of Catalyst branched polyethylene, wherein the effect of catalyst for oligomerization is to be alpha-olefin and internal olefin with ethylene oligomerization, utilizes the copolymerization metallocene catalyst that alkene and ethene are produced copolymerization then, has realized the combined polymerization of ethene and alpha-olefin and internal olefin.Wherein said SiO
2Be Daqing Petrochemical Complex 955# silica gel, catalyst for copolymerization adopts metallocene catalyst Cp
2ZrCl
2, described catalyst for oligomerization is the halide (N of bidentate nitrogen coordination nickel
⌒N NiX
2) catalyst, general formula is:
SiO of the present invention
2The preparation method of the bimetallic catalyst of load follows these steps to carry out: 1. the halid preparation of catalyst for oligomerization bidentate nitrogen coordination nickel
X＝Cl，Br，F
R＝Me，Ethyl，H，C
6H
5，iPr，X，C
10H
7-，NO
2
R
4＝R
5＝R
6＝R
7＝R
8＝H
R
4＝R
5＝R
6＝R
8＝H，R
7＝Me
R
4＝R
7＝R
8＝H，R
5＝R
6＝Me
R
5＝R
6＝R
7＝R
8＝H，R
4＝Me
The bidentate nitrogen ligands of purifying and nickel halogenide be blended in to be dissolved in the appropriate solvent that is equivalent to nickel halogenide 15-20 times weight in 1: 1 in molar ratio make according to document (Chin.Chem.Let., 12,691-692,2001) reaction.Wherein in the general structure (1), R ' and R " can be hydrogen atom and phenyl, methyl and phenyl, methyl and 2-pyridine radicals and 8-aminoquinoline and camphor reaction gained part.R in the general formula (3)
4, R
5, R
6, R
7, R
8Can be respectively hydrogen atom, methyl, ethyl, phenyl, 2-pyridine radicals, isopropyl etc.2.SiO
2The preparation of carrier bimetallic catalyst
With described SiO
2100 parts in carrier is packed into dry, N
2In the reaction bulb of protection, add 1700-6000 part then, the solvent toluene of preferred 2500-4800 part drying stirs 30～150min.Add 0～1200 part of MAO preliminary treatment SiO
2Carrier, best 200～600 parts, after 2～6h is stirred in 60 ℃ of reactions, for several times with the hot toluene filter wash; Add 1700-6000 part dry toluene again, slowly add 0～80 part Cp after stirring
2ZrCl
2And N
⌒N NiX
2, 5～60 parts of the bests, wherein N
⌒N NiX
2And Cp
2ZrCl
2Mol ratio be 0～40, best 1～20, behind reaction 8～24h, the gained slurry filters, and with the hot toluene washing for several times, does not have polymerization activity until leaching clear liquid, the suction filtration drying obtains faint yellow catalyst.Carry out the content of contained Zr of elementary analysis and Ni.SiO of the present invention
2The purposes of the bimetallic catalyst of load is with the MAO to be that co-catalyst carries out vinyl polymerization:
Described SiO
2The Cp of load
2ZrCl
2And N
⌒N NiX
2Carry out vinyl polymerization: will have 250 milliliters of there-necked flasks of the drying that stirs magneton, carry out nitrogen, ethene displacement three times successively, and make reaction system in the ethylene gas environment, add 50 milliliters of toluene, reaction temperature is-30-80 ℃.By the MAO/ catalyst molar ratio is 50～5000, and optimal proportion is 500～2000, adds co-catalyst MAO, reacts the acidic alcohol cessation reaction of adding 5% after 15-60 minute.
Advantage of the present invention is as follows: 1. the catalyst system therefor preparation is simple, and raw material is easy to get.2.SiO
2The carrier bimetallic catalyst has been realized in-situ modified to vinyl polymerization, can obtain different melting points according to the different proportion of two kinds of catalyst of load, and the polyethylene of the different degrees of branching is to satisfy different needs.3.SiO
2In the carrier bimetallic catalyst, two kinds of metal active centers do not have mutual interference effect, and no ligand exchange or reaction take place between two kinds of catalyst.4. the catalyst system and catalyzing catalytic activity is higher, and is active in 10
5The per hour every atmospheric pressure of the gram every mol catalyst of ethene.
The specific embodiment
The following examples can make this professional skill state personnel more fully to understand the present invention, be not described in detail it but limit the present invention in any way.
Embodiment 1
1). Preparation of catalysts: with the 8-aminoquinoline is that part and nickel chloride were blended in to react in acetone-alcohol mixed solvent of 1: 1 and make in 1: 1 in molar ratio.
2). catalyst Cp
2ZrCl
2Load with 8-aminoquinoline nickel chloride
With SiO
23.0g and electromagnetic agitation dry, the N that packs into
2In the special reaction bulb of 1000mL gas shiled, that have filter, add the toluene of 60mL drying under 60 ℃ of temperature, behind the stirring 30min, add 20mLMAO, reaction 4h behind the dry abundant filter wash of toluene 50mL, adds catalyst Cp again
2ZrCl
22 μ mol, 10 μ mol 8-aminoquinoline nickel chloride catalyst agent.Reaction 12h, color is by the colourless rufous that becomes, and the gained slurry filters, with hot toluene 50mL washing for several times, there is not polymerization activity until leaching clear liquid, the suction filtration drying, obtaining faint yellow supported catalyst, is 0.473% through ICP-AES test Zr content, and Ni content is 0.437%.
3). vinyl polymerization
Will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement twice, the maintenance pressure of the inside of a bottle is 770mmHg, adds 50mL toluene, stir and add 6.5mLMAO and load weighted example carried catalyst 0.0726g down at first successively, Al/Zr is 1000, and reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 1.546g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 4.10 * 10
5GPE/molZr.hr, GPC tests Mw=1221706, Mw/Mn=3.65, Tm=127.8, degree of crystallinity is 23.2%, the degree of branching is 2.1CH
3/ 1000CH
2
Embodiment 21). Preparation of catalysts: with embodiment 12). the load of catalyst: with embodiment 13). vinyl polymerization
Will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement twice, the maintenance pressure of the inside of a bottle is 770mmHg, adds 50mL toluene, stir and add 4.0mLMAO and load weighted example carried catalyst 0.0896g down at first successively, Al/Zr is 500, and reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 1.257g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 2.72 * 10
5GPE/molZr.hr, GPC tests Mw=673982, Mw/Mn=3.09, Tm=126.1, degree of crystallinity is 21.1%, the degree of branching is 6.2CH
3/ 1000CH
2
Embodiment 31). Preparation of catalysts: with embodiment 12). the load of catalyst: with embodiment 13). vinyl polymerization: will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, twice of ethene displacement, the maintenance pressure of the inside of a bottle is 770mmHg, add 50mL toluene, stir and add 11.86mLMAO and load weighted example carried catalyst 0.0673g down at first successively, Al/Zr is 2000, reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 1.264g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 3.60 * 10
5GPE/molZr.hr, GPC tests Mw=1073189, Mw/Mn=3.47, Tm=127.8 ℃, degree of crystallinity is 32.3%, the degree of branching is 1.9CH
3/ 1000CH
2
Embodiment 41). Preparation of catalysts: with embodiment 12). the load of catalyst: with embodiment 13). vinyl polymerization: will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, twice of ethene displacement, the maintenance pressure of the inside of a bottle is 770mmHg, add 50mL toluene, stir and add 6.4mLMAO and load weighted example carried catalyst 0.0717g down at first successively, Al/Zr is 300, reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 1.36g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 1.13 * 10
5GPE/molZr.hr, GPC tests Mw=259591, Mw/Mn=2.98, Tm=122.9 ℃, degree of crystallinity is 20.6%, the degree of branching is 9.8CH
3/ 1000CH
2
Embodiment 51). Preparation of catalysts: with embodiment 12). the load of catalyst: with embodiment 13). vinyl polymerization: will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, twice of ethene displacement, the maintenance pressure of the inside of a bottle is 770mmHg, add 50mL toluene, stir and add 5.8mLMAO and load weighted example carried catalyst 0.0412g down at first successively, Al/Zr is 1500, reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 1.36g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 11.78 * 10
5GPE/molZr.hr, GPC tests Mw=352320, Mw/Mn=3.81, Tm=127.8 ℃, degree of crystallinity is 34.6%, the degree of branching is 1.6CH
3/ 1000CH
2Embodiment 61). Preparation of catalysts: with embodiment 12). catalyst Cp
2ZrCl
2Load with 8-aminoquinoline nickel chloride
With SiO
23.0g and electromagnetic agitation dry, the N that packs into
2In the special reaction bulb of 1000mL gas shiled, that have filter, add the toluene of 60mL drying under 60 ℃ of temperature, behind the stirring 30min, add 20mLMAO, reaction 4h behind the dry abundant filter wash of toluene 50mL, adds catalyst Cp again
2ZrCl
22 μ mol, 20 μ mol 8-aminoquinoline nickel chloride catalyst agent.Reaction 12h, color is by the colourless rufous that becomes, and the gained slurry filters, with hot toluene 50mL washing for several times, there is not polymerization activity until leaching clear liquid, the suction filtration drying, obtaining faint yellow supported catalyst, is 0.84% through ICP-AES test Zr content, and Ni content is 0.19%.3). vinyl polymerization
Will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement twice, the maintenance pressure of the inside of a bottle is 770mmHg, adds 50mL toluene, stir and add 2.9mLMAO and load weighted example carried catalyst 0.0422g down at first successively, Al/Zr is 1000, and reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 0.38g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 0.55 * 10
5GPE/molZr.hr, GPC tests Mw=3130685, Mw/Mn=6.75, Tm=125.5, degree of crystallinity is 11.1%, the degree of branching is 7.2CH
3/ 1000CH
2
Embodiment 71). Preparation of catalysts: with embodiment 12). catalyst Cp
2ZrCl
2Load with 8-aminoquinoline nickel chloride
With SiO
23.0g and electromagnetic agitation dry, the N that packs into
2In the special reaction bulb of 1000mL gas shiled, that have filter, add the toluene of 60mL drying under 60 ℃ of temperature, behind the stirring 30min, add 20mLMAO, reaction 4h behind the dry abundant filter wash of toluene 50mL, adds catalyst Cp again
2ZrCl
25 μ mol, 5 μ mol 8-aminoquinoline nickel chloride catalyst agent.Reaction 12h, color is by the colourless rufous that becomes, and the gained slurry filters, with hot toluene 50mL washing for several times, there is not polymerization activity until leaching clear liquid, the suction filtration drying, obtaining faint yellow supported catalyst, is 0.46% through ICP-AES test Zr content, and Ni content is 0.19%.3). vinyl polymerization
Will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement twice, the maintenance pressure of the inside of a bottle is 770mmHg, adds 50mL toluene, stir and add 2.7mLMAO and load weighted example carried catalyst 0.0627g down at first successively, Al/Zr is 1000, and reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 0.810g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 2.56 * 10
5GPE/molZr.hr, GPC tests Mw=84795, Mw/Mn=3.19, Tm=126.3, degree of crystallinity is 36.2%, the degree of branching is 3.4CH
3/ 1000CH
2
Embodiment 81). Preparation of catalysts: with embodiment 12). catalyst Cp
2ZrCl
2Load with 8-aminoquinoline nickel chloride
With SiO
23.0g and electromagnetic agitation dry, the N that packs into
2In the special reaction bulb of 1000mL gas shiled, that have filter, under 60 ℃ of temperature, add the toluene of 60mL drying, behind the stirring 30min; add 20mLMAO; reaction 4h behind the dry abundant filter wash of toluene 50mL, adds 5 μ mol 8-aminoquinoline nickel chloride catalyst agent again.Reaction 12h, color is by the colourless rufous that becomes, and the gained slurry filters, and with hot toluene 50mL washing for several times, does not have polymerization activity until leaching clear liquid, and the suction filtration drying obtains faint yellow supported catalyst, is 0.526% through ICP-AES test Ni content.3). vinyl polymerization
Will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement twice, the maintenance pressure of the inside of a bottle is 770mmHg, adds 50mL toluene, stir and add 6.4mLMAO and load weighted example carried catalyst 0.0717g down at first successively, Al/Zr is 1000, and reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, product is analyzed through GC-MS and is 0.66g, and it is distributed as C4:40%, C6:60%.
Embodiment 91). Preparation of catalysts: work as R
4=R
5=R
6=R
7=R
8During=H, part is a quinoxaline, is blended in the carrene reaction in 1: 1 in molar ratio with nickelous bromide and makes.2). catalyst Cp
2ZrCl
2Load with the quinoxaline nickel chloride
With SiO
23.0g and electromagnetic agitation dry, the N that packs into
2In the special reaction bulb of 1000mL gas shiled, that have filter, under 60 ℃ of temperature, add the toluene of 60mL drying, behind the stirring 30min; add 20mLMAO; reaction 4h behind the dry abundant filter wash of toluene 50mL, adds 5 μ mol 8-aminoquinoline nickel chloride catalyst agent again.Reaction 12h, color is by the colourless rufous that becomes, and the gained slurry filters, with hot toluene 50mL washing for several times, there is not polymerization activity until leaching clear liquid, the suction filtration drying, obtaining faint yellow supported catalyst, is 0.63% through ICP-AES test Zr content, and Ni content is 0.245%.。3). vinyl polymerization
Will be through abundant dry 250mL there-necked flask vacuum nitrogen filling gas displacement three times, ethene displacement twice, the maintenance pressure of the inside of a bottle is 770mmHg, adds 50mL toluene, stir and add 3.3mLMAO and load weighted example carried catalyst 0.0652g down at first successively, Al/Zr is 1000, and reaction temperature is a normal temperature, reaction time 60min, reactant liquor is poured in the acidifying ethanol and is stopped, filtration obtains polymer, obtains polyethylene 0.44g through 50 ℃ of following vacuum drying 24h oven dry, and activity is 0.97 * 10
5GPE/molZr.hr, GPC tests Mw=802375, Mw/Mn=6.10, Tm=123.8, degree of crystallinity is 19.8%, the degree of branching is 7.6CH
3/ 1000CH
2
Claims (7)
1. SiO
2The bimetallic catalyst of load is characterized in that, described catalyst system and catalyzing comprises SiO
2Carrier, catalyst for oligomerization, catalyst for copolymerization and co-catalyst; SiO
2Carried catalyst is made up of following component and content in weight portion:
SiO
2 100
MAO (MAO) 0-1600
Cp
2ZrCl
2Halide (the N of 0-80 bidentate nitrogen coordination nickel
⌒N NiX
2) 0-80
Described SiO
2, be grand celebration chemical general factory 955# silica gel.
2. SiO according to claim 1
2The bimetallic catalyst of load is characterized in that SiO
2Carrier catalysis, in weight portion, its optimum ratio is:
SiO
2 100
MAO (MAO) is preferred: 600-1000
Cp
2ZrCl
2Preferably: 5-60
Halide (the N of bidentate nitrogen coordination nickel
⌒N NiX
2) preferred: 5-60
Described SiO
2, be grand celebration chemical general factory 955# silica gel.
3. SiO according to claim 1
2The bimetallic catalyst of load is characterized in that, the halide (N of described catalyst for oligomerization bidentate nitrogen coordination nickel
⌒N NiX
2) as figure below:
X＝Cl，Br，F
R＝Me，Ethyl，H，C
6H
5，iPr，X，C
10H
7-，NO
2
R
4＝R
5＝R
6＝R
7＝R
8＝H
R
4＝R
5＝R
6＝R
8＝H，R
7＝Me
R
4＝R
7＝R
8＝H，R
5＝R
6＝Me
R
5＝R
6＝R
7＝R
8＝H，R
4＝Me
4. SiO
2The preparation method of the bimetallic catalyst of load is characterized in that, in weight portion, carries out according to the following steps:
1) the halid preparation of catalyst for oligomerization bidentate nitrogen coordination nickel
The bidentate nitrogen ligands of purifying and 1: 1 in molar ratio mixed dissolution of nickel halogenide reacted in the appropriate solvent that is equivalent to nickel halogenide 15-20 times weight make; Wherein in the general structure (1), R ' and R " can be hydrogen atom and phenyl, methyl and phenyl, methyl and 2-pyridine radicals and 8-aminoquinoline and camphor reaction gained part; R in the general formula (3)
4, R
5, R
6, R
7, R
8Can be respectively hydrogen atom, methyl, ethyl, phenyl, 2-pyridine radicals, isopropyl etc.;
2) with described SiO
2100 parts in carrier is packed into dry, N
2In the reaction bulb of protection, add the solvent toluene of 1700-6000 part drying then, stir 30～150min, add 0～1200 part of MAO preliminary treatment SiO
2, after 2～6h is stirred in 60 ℃ of reactions, use the hot toluene filter wash; Add 1700-6000 part dry toluene again, slowly add 0～80 part Cp after slow the stirring
2ZrCl
2And N
⌒N NiX
2, Cp wherein
2ZrCl
2And N
⌒N NiX
2Mol ratio be 0～16, behind reaction 8～24h, the gained slurry filters, with the hot toluene washing, the suction filtration drying obtains faint yellow SiO
2Carried catalyst.
5. SiO according to claim 4
2The preparation method of the bimetallic catalyst of load is characterized in that, the solvent toluene of the solvent toluene drying of described drying is preferably 2500-4800; MAO preliminary treatment SiO
2Best 200-600; The slow Cp that adds
2ZrCl
2And N
⌒N NiX
2, best 5～60 parts; Cp wherein
2ZrCl
2And N
⌒N NiX
2Mol ratio, the best is 1～10.
6. SiO
2The purposes of the bimetallic catalyst of load is characterized in that, is co-catalyst with the MAO, and the Al/Zr mol ratio is 50～3000 to carry out vinyl polymerization: described SiO
2The Cp of load
2ZrCl
2And N
⌒N NiX
2To carry out vinyl polymerization, will have 250 milliliters of there-necked flasks of the drying that stirs magneton, carry out nitrogen, ethene displacement three times successively, make reaction system in the ethylene gas environment, add 50 milliliters of toluene, reaction temperature is-30-80 ℃; By the MAO/ catalyst molar ratio is 50～5000, adds co-catalyst MAO, reacts the acidic alcohol cessation reaction of adding 5% after 15-60 minute.
7. SiO according to claim 6
2The purposes of the bimetallic catalyst of load is characterized in that, presses the MAO/ catalyst molar ratio, and optimal proportion is 500～2000.
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|---|---|---|---|
| CN 02118643 CN1453070A (en) | 2002-04-27 | 2002-04-27 | SiO2 loaded double-metal catalyst and its prepn and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02118643 CN1453070A (en) | 2002-04-27 | 2002-04-27 | SiO2 loaded double-metal catalyst and its prepn and use |
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Family
ID=29257407
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722821B1 (en) | 2013-03-18 | 2014-05-13 | King Fahd University Of Petroleum And Minerals | Method of making polyolefin with a silicon nitride nano-filler |
| CN103894230A (en) * | 2012-12-28 | 2014-07-02 | 中国石油天然气股份有限公司 | Preparation and application of supported iron catalyst |
| CN108786918A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate |
| CN108786919A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate |
-
2002
- 2002-04-27 CN CN 02118643 patent/CN1453070A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103894230A (en) * | 2012-12-28 | 2014-07-02 | 中国石油天然气股份有限公司 | Preparation and application of supported iron catalyst |
| CN103894230B (en) * | 2012-12-28 | 2016-04-06 | 中国石油天然气股份有限公司 | Preparation and application of supported iron catalyst |
| US8722821B1 (en) | 2013-03-18 | 2014-05-13 | King Fahd University Of Petroleum And Minerals | Method of making polyolefin with a silicon nitride nano-filler |
| CN108786918A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate |
| CN108786919A (en) * | 2017-05-05 | 2018-11-13 | 中国石油化工股份有限公司 | The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate |
| CN108786919B (en) * | 2017-05-05 | 2020-07-21 | 中国石油化工股份有限公司 | Supported metallocene catalyst, preparation method and application thereof, and preparation method of methyl acrylate |
| CN108786918B (en) * | 2017-05-05 | 2020-07-24 | 中国石油化工股份有限公司 | Supported metallocene catalyst, preparation method and application thereof, and preparation method of methyl acrylate |
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