CN101280031B - Catalyst system for preparing dual-peak or widely distributed polyethylene and its application - Google Patents
Catalyst system for preparing dual-peak or widely distributed polyethylene and its application Download PDFInfo
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- CN101280031B CN101280031B CN200710065207A CN200710065207A CN101280031B CN 101280031 B CN101280031 B CN 101280031B CN 200710065207 A CN200710065207 A CN 200710065207A CN 200710065207 A CN200710065207 A CN 200710065207A CN 101280031 B CN101280031 B CN 101280031B
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Abstract
The invention adopts a Schiff base single-site catalyst which can produce low-molecular-weight polyethylene and has poor copolymerization performance. After being compounded with the existing Ziegler-Natta catalyst, the Schiff base single-site catalyst can be used for the preparation of broad bimodal distribution polyethylene and is able to realize the typical bimodal polyethylene production with low branching degree of low molecular weight and high branching degree of high molecular weight in a single reactor.
Description
Technical field:
The catalyzer that the present invention relates to use in the olefinic polymerization, catalyst system with and preparation method thereof, relate to the preparation method of the polyvinyl resin of bimodal or wide distribution.
Prior art
The bimodal polyethylene product has characteristics such as good mechanical property, good toughness and easy processing, so attention of production of resins manufacturer extremely both at home and abroad and user's favor, the consumption of global high-performance bimodal polyethylene rises year by year.The method of existing preparation Bi-modal polyethylene resin has following three classes:
(1) two kind of polymer blending, this method not only cost improve, and are difficult to reach fully evenly fusion and influence performance of resin;
(2) by the grading reactor stage feeding polymerization, can implement all to mix in the reactor, it is big that handiness is adjusted in operation, but the high problem of influential efficient and cost;
(3) in single reaction vessel, adopt bimetal or many metal active constituents catalyzer, utilize the polymerization behavior that they have nothing in common with each other, the bimodal molded breadth distribution polyethylene of direct production in single reaction vessel, theoretically, this method is the most worth expectation, but in fact wanting the comprehensive poly behavior of closing is one, and difficulty is big.
In the US Patent PublicationNumber 20050003950 and 20040186251 of CN1413222A, the EXXONMOBIL of the US of Univation Technologies Patent Publication Number 20050054519 and CN1678640A, UCC, all adopt Ziegler-Natta catalyst and metallocene compound mode in single reaction vessel, to produce bimodal wide distribution polyethylene resin.
From above prior art as can be seen, use the compound system of Ziegler-Natta catalyst and metallocene can in single reaction vessel, produce bimodal wide distribution polyethylene resin, will find that there is more serious problem in this catalyst system but anatomize.The basic characteristics of typical bimodal wide distribution polyethylene resin are that the low molecular weight part reduced branching degree is to improve Drawing abillity, the high degree of branching of high molecular part to improve the mechanical property of material.But the polymkeric substance that the compound system of Ziegler-Natta catalyst and metallocene catalyst obtains is on the contrary, show as the high degree of branching of polymer low-molecular amount part, high molecular part reduced branching degree, this is that can to make that metallocene catalyst synthetic molecular weight of polyethylene becomes very low because add hydrogen when polymerization, and metallocene catalyst is better than the copolymerization performance of Ziegler-Natta catalyst, causes comonomer to be copolymerized to one section of lower molecular weight thus.
The present invention chooses the western Buddhist alkali single site catalysts that can produce low molecular weight polyethylene and copolymerization performance difference, with the compound preparation that is used for bimodal wide distribution polyethylene of existing Ziegler-Natta catalyst, solve the problem that a large amount of side chains appear in low molecular weight part, can in single reactor, realize the poly production of typical double-peak of lower molecular weight reduced branching degree, the high degree of branching of high molecular.
The content of invention
One of purpose of the present invention is to set up the complex catalyst system of a Ziegler-natta catalyst/western Buddhist alkali single-site catalysts, and this system is used for vinyl polymerization can prepare bimodal wide distribution polyethylene resin.
Another object of the present invention is to use the method for complex catalyst system wide distribution polyethylene resin of production typical double-peak in single reactor of Ziegler-natta catalyst/western Buddhist alkali single-site catalysts.
The composite catalyst of Ziegler-natta catalyst of the present invention/western Buddhist alkali single-site catalysts is meant that the contract early transition metal composition catalyst of imines of the bridging double salicylaldehyde with a Ziegler-Natta catalyst and a loadization is mixed in proportion back gained catalyzer and is called composite catalyst.Above-mentioned composite catalyst is formed complex catalyst system with promotor.
The present invention is used to prepare the catalyst system of bimodal or wide distribution polyethylene, comprises following component:
(1) a kind of Ziegler-natta catalyst:
Comprise the complex compound that a carrier, titanium active ingredient or titanium and other component form.Carrier is generally the complex carrier of silicon-dioxide, magnesium chloride, aluminium dioxide or their compositions, as SiO
2/ MgCl
2Complex carrier.The complex compound that titanium active ingredient or titanium and other component form loads on the above-mentioned carrier.The valence state of titanium is generally 3+, 4+;
(2) the bridging double salicylaldehyde of the loadization early transition metal composition catalyst of imines that contracts:
Be that the contract early transition metal title complex of imines of bridging double salicylaldehyde is carried on the complex carrier silicon-dioxide, magnesium chloride, aluminium dioxide or their formed (as SiO
2/ MgCl
2Complex carrier) goes up and the contract early transition metal composition catalyst of imines of the bridging double salicylaldehyde of the loadization that forms;
The bridging double salicylaldehyde contracts the structure of early transition metal title complex of imines shown in general formula 1,
General formula 1
Wherein: M is the 4th family's early transition metal;
N is the integer more than or equal to 2, and m is the integer that satisfies the M valence state,
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, is preferably a kind of in hydrogen, halogen, alkyl, allyl group, cyclopentadienyl, alkoxyl group, the fragrant-oxyl; Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, m-phenoxy, to phenoxy group or naphthyloxy.When m is 2 or when bigger, a plurality of X groups can be identical or different.
R
1-R
8Identical or different, be hydrogen atom, halogen atom, C
1-C
20Aliphatic group, C
3-C
20Cyclic hydrocarbon radical or C
6-C
20Aryl radical, arbitrary hydrogen on its described alkyl or carbon atom can randomly be replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atoms; Be specially hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, tristane base, 2-phenyl-sec.-propyl, methoxyl group, oxyethyl group or uncle's propoxy-;
R
9-R
10Identical or different, be selected from replacement or unsubstituted C
1-C
20Aliphatic group or C
6-C
30Aryl radical; Be specially phenyl, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl or the trityl of n-hexyl, phenyl, nitro replacement; R
1-R
10In two or more groups can be incorporated into ring;
Y is a bridge joint group, is C
1-C
20Aliphatic group or C
6-C
20Aryl radical, the arbitrary hydrogen on its described alkyl or carbon atom can randomly be replaced by heteroatomss such as halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, Siliciumatoms.Be specially methylene radical, ethylidene, propylidene, butylidene, ethylene group, isopropylidene, isobutylidene, phenyl or substituted-phenyl.
(3) promotor of the present invention is an organo-aluminium compound, as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-butyl aluminum, three hexyl aluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, the best are trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, three hexyl aluminium.In the above-mentioned organo-aluminium compound in Al and the Ziegler-Natta catalyst mol ratio of Ti be 1～2000, be preferably 10～500.
(4) the contract weight ratio of imines Zr catalyst of the bridging double salicylaldehyde of Ziegler-natta catalyst and loadization is 0.1: 1～10: 1 in the composite catalyst of the present invention, preferred 0.2: 1～2: 1.The contract preparation of imines Zr catalyst of the bridging double salicylaldehyde of loadization
The bridging double salicylaldehyde of the loadization of the present invention imines Zr catalyst that contracts is meant the above-mentioned bridging double salicylaldehyde imines zirconium complex that contracts is loaded on the complex carrier silicon-dioxide, magnesium chloride, aluminium dioxide or their formed (as SiO
2/ MgCl
2Complex carrier) on.Preferred negative is downloaded on silicon-dioxide, the magnesium chloride support.
Its carrying method is as follows usually; in the reaction flask that silicon-dioxide after a certain amount of activation dehydration or magnesium chloride are joined nitrogen protection; after adding certain solvent dispersion; add MAO solution,, add an amount of selected bridging double salicylaldehyde imines early transition metal title complex that contracts then 0-80 ℃ of reaction 4 hours down; reacted 0.5-2 hour down at 0-80 ℃; filter drying, the bridging double salicylaldehyde that obtains the loadization of the good fluidity imines early transition metal catalyzer that contracts.
Polymerization methods
Catalyst system of the present invention is applicable to slurry polymerization processes, gas fluidized-bed process.The adding mode of catalyzer can be that the bridging double salicylaldehyde of Ziegler-Natta catalyst and loadization contracts the imines Zr catalyst respectively or mix the back and add, and also can be Z-N/bridging double salicylaldehyde of directly adding loadization imines early transition metal catalyzer that contracts.The adding of promotor can add before catalyzer in the reactor, also can add after catalyzer, can add continuously in the successive polymerization reaction process.
Catalyst system of the present invention has good ethylene homo and copolymerization polymerization activity, and the molecular weight of polyethylene that obtains distributes and is bimodal distribution.
The resulting bimodal polyethylene resins of the present invention has the characteristics of low molecular weight part reduced branching degree, the high degree of branching of high molecular part.
The complex catalyst system of Ziegler-natta catalyst of the present invention/western Buddhist alkali single-site catalysts is used for vinyl polymerization and obtains resin and have good particle form, goes for slurry process and vapor phase process polymerization technique.
Embodiment
Embodiment 1
(1) preparation of Ziegler-Natta catalyst
Under nitrogen protection, 955 silica gel of the Grace after 600 ℃ of activation, 10 grams are joined glass reactor, add 100 milliliters of hexanes and disperse silica gel; add 5.6 mmole triethyl aluminums then; 30 ℃ were reacted 0.5 hour down, dry up solvent with high pure nitrogen, the silica gel after obtaining handling.
Under nitrogen protection, 1.1 gram magnesium chlorides, 0.7 gram titanous chloride are joined in another glass reactor, add 70 ℃ of dissolvings of 100 milliliters of tetrahydrofuran (THF)s, contain above then solution being transferred in the reactor of handling back silica gel.Behind the stirring reaction 1 hour, dry up, obtain the pressed powder of good fluidity with high pure nitrogen.Add 100 milliliters of hexane dispersible solid powder then, add 10 mmole aluminium diethyl monochlorides and 4 mmole tri-n-hexyl aluminums, react after 0.5 hour, dry up hexane, obtain the Ziegler-natta catalyst A of good fluidity with high pure nitrogen.
(2) the load bridging double salicylaldehyde imines early transition metal Preparation of catalysts that contracts
(1) bridging double salicylaldehyde synthetic (the seeing Chinese patent ZL02129548.4) of imines zirconium complex that contract
Specific as follows:
A, synthetic ligands L2
Under the nitrogen atmosphere, in 500 milliliters of there-necked flasks, add and press 5 of Chinese patent ZL02129548.4 embodiment 1 method synthetic 4.0 grams, 5 '-isopropylidene-two (the 3-tertiary butyl-2-hydroxy benzaldehyde), dissolve with 120 ml methanol, add 2.78 milliliters hexahydroaniline and 1.2 milliliters formic acid then, stirring at room reaction 24 hours.Steam solvent, filter out precipitation, carry out pure crystallization with tetrahydrofuran (THF)/ether, drying obtains 4.2 ligand L 2 yellow powders that restrain.
Its structural formula is as follows:
Ligand L 2
CI-mass spectrum: 558M
+
B, synthetic metal complexes (L2)
3Zr
2Cl
4
Under the nitrogen atmosphere, in there-necked flask, add above-mentioned synthetic 2.14 gram ligand L 2, add 100 milliliters of tetrahydrofuran (THF) dissolvings, be cooled to then below-70 ℃, slowly drip 3.2 milliliters of n-butyllithium solutions, reaction is 1 hour under this temperature, slowly be warming up to room temperature, reacted 4 hours; This liquid is transferred in the constant voltage minim pipette,, slowly be added drop-wise to and be dissolved with 0.96 gram ZrCl below-70 ℃
450 milliliters tetrahydrofuran solution in, after dripping off, rise to room temperature gradually, then reacted about 18 hours, then, back flow reaction is 5 hours again; Underpressure distillation behind the evaporate to dryness, separates with the methylene dichloride apparatus,Soxhlet's, obtains 1.3 gram g metal complexess (L2)
3Zr
2Cl
4Yellow powder.
Its structural formula is as follows:
(2) the load bridging double salicylaldehyde preparation of imines Zr catalyst of contracting
Under the nitrogen protection; getting the silica gel (Grace 955) of 10 grams after the pyroprocessing joins in the reactor; MAO (methylaluminoxane) toluene solution that adds 70 milliliters of toluene and 65 milliliters of 10wt%; be warming up to 50 ℃; stirring reaction 4 hours; use 150 milliliters of toluene wash 3 times then, vacuum-drying obtains white solid powder (Al content is about 14.0wt%).In the reaction flask, add 100 milliliters of toluene and 0.78 gram above synthetic (L2) then
3Zr
2Cl
4Title complex, 25 ℃ of reactions 0.5 hour are filtered, and with hexane wash 3 times, drying obtains mobile yellow solid powder, is the load bridging double salicylaldehyde imines Zr catalyst B that contracts.
Embodiment 2
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively and make 29 milligrams of catalyst A, 60 milligrams of catalyst B among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 80 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 280 grams, the efficient of catalyzer is 3146 gram PE/ gram catalyzer hour, and polyethylene particle bulk density (BD) is 0.30g/ml, polyethylene weight-average molecular weight Mw 405000, Mw/Mn=26.5, polyvinyl resin density 0.9409 gram per centimeter
3
Embodiment 3
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively and make 34 milligrams of catalyst A, 78 milligrams of catalyst B among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1, charge into 0.01Mpa hydrogen, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 80 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 248 grams, the efficient of catalyzer is 2214 gram PE/ gram catalyzer hour, and polyethylene particle bulk density (BD) is 0.30g/ml, polyethylene weight-average molecular weight Mw288000, Mw/Mn=21.2, polyvinyl resin density 0.9456 gram per centimeter
3
Embodiment 4
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively and make 36 milligrams of catalyst A, 80 milligrams of catalyst B among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1, charge into 0.02Mpa hydrogen, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 80 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 258 grams, the efficient of catalyzer is 2224 gram PE/ gram catalyzer hour, and polyethylene particle bulk density (BD) is 0.29g/ml, polyethylene weight-average molecular weight Mw282000, Mw/Mn=18.4, polyvinyl resin density 0.9437 gram per centimeter
3
Embodiment 5
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively and make 30 milligrams of catalyst A, 67 milligrams of catalyst B among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1, charge into 0.03Mpa hydrogen, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 80 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 214 grams, the efficient of catalyzer is 2206 gram PE/ gram catalyzer hour, and polyethylene particle bulk density (BD) is 0.28g/ml, polyethylene weight-average molecular weight Mw255000, Mw/Mn=15.4, polyvinyl resin density 0.9427 gram per centimeter
3
Embodiment 6
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively and make 31 milligrams of catalyst A, 72 milligrams of catalyst B among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1, charge into 0.005Mpa hydrogen, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 85 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 293 grams, the efficient of catalyzer is 2844 gram PE/ gram catalyzer hour, polyethylene particle bulk density (BD) is 0.29g/ml, polyethylene weight-average molecular weight Mw422000, Mw/Mn=15.4.
Comparative example 1
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1 and make 47 milligrams of catalyst A, charge into 0.02Mpa hydrogen, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 80 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 220 grams, the efficient of catalyzer is 4680 gram PE/ gram catalyzer hour, and polyethylene particle bulk density (BD) is 0.27g/ml, polyethylene weight-average molecular weight Mw 603000, Mw/Mn=6.1, polyvinyl resin density 0.9335 gram per centimeter
3
Comparative example 2
In 2 liters stainless steel polymermaking autoclave, with nitrogen replacement three times, add 1000 milliliters of hexane solvents then, adding along with hexane, add successively among triethyl aluminum (TEA) 2 mmoles, 20 milliliters of hexenes, the embodiment 1 and make 135 milligrams of catalyst B, heat up then, charging into ethene in the time of 50 ℃ and keeping pressure is 1.0MPa, keeps 80 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 191 grams, the efficient of catalyzer is 1415 gram PE/ gram catalyzer hour, and polyethylene particle bulk density (BD) is 0.29g/ml, polyethylene weight-average molecular weight Mw 83600, Mw/Mn=7.95, polyvinyl resin density 0.9696 gram per centimeter
3
Claims (4)
1. catalyst system that is used to prepare bimodal or wide distribution polyethylene comprises following component:
(1) a kind of Ziegler-natta catalyst:
Comprise the complex compound that a carrier, titanium active ingredient or titanium and other component form, carrier is the complex carrier of silicon-dioxide, magnesium chloride, aluminium sesquioxide or their compositions, the complex compound that titanium active ingredient or titanium and other component form loads on the above-mentioned carrier, and the valence state of titanium is generally 3+, 4+;
(2) the bridging double salicylaldehyde of the loadization early transition metal composition catalyst of imines that contracts:
Be with bridging double salicylaldehyde the contract early transition metal composition catalyst of imines of bridging double salicylaldehyde that the early transition metal title complex of imines is carried on the loadization that the complex carrier silicon-dioxide, magnesium chloride, aluminium sesquioxide or their formed forms above that contracts;
The bridging double salicylaldehyde contracts the structure of early transition metal title complex of imines shown in general formula 1,
General formula 1
Wherein: M is the 4th family's early transition metal;
N is the integer more than or equal to 2, and m is the integer that satisfies the M valence state,
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido,
When m is 2 or when bigger, a plurality of X groups can be identical or different;
R
1-R
8Identical or different, be hydrogen atom, halogen atom, C
1-C
20Aliphatic group, C
3-C
20Cyclic hydrocarbon radical or C
6-C
20Aryl radical, arbitrary hydrogen on its described alkyl or carbon atom can be randomly replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom;
R
9-R
10Identical or different, be selected from replacement or unsubstituted C
1-C
20Aliphatic group or C
6-C
30Aryl radical; R
1-R
10In two or more groups can be incorporated into ring;
The bridging double salicylaldehyde of Ziegler-natta catalyst and the loadization ratio that the early transition metal composition catalyst of imines adds that contracts is: 0.1: 1～10: 1;
(3) promotor organo-aluminium compound; The mol ratio of Ti is 1～2000 in Al in the organo-aluminium compound and the Ziegler-Natta catalyst.
2. the catalyst system that is used to prepare bimodal or wide distribution polyethylene according to claim 1, the bridging double salicylaldehyde structure of early transition metal title complex of imines that contracts wherein, described M is the early transition metal zirconium, titanium; X is chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, butoxy, phenoxy group or naphthyloxy;
R
1-R
8Be selected from hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, tristane base, 2-phenyl-sec.-propyl, methoxyl group, oxyethyl group or uncle's propoxy-;
R
9-R
10Be selected from phenyl, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl or the trityl of n-hexyl, phenyl, nitro replacement;
Y is selected from methylene radical, ethylidene, propylidene, butylidene, ethylene group, phenyl or substituted-phenyl;
Described promotor is trimethyl aluminium, triethyl aluminum, tri-butyl aluminum, three hexyl aluminium;
The mol ratio of Ti is 10～500 in Al in the organo-aluminium compound and the Ziegler-Natta catalyst.
3. the catalyst system that is used to prepare bimodal or wide distribution polyethylene according to claim 1, wherein the contract weight ratio of early transition metal composition catalyst of imines of the bridging double salicylaldehyde of Ziegler-natta catalyst and loadization is 0.2: 1～2: 1.
4. the described catalyst system that is used to prepare bimodal or wide distribution polyethylene of one of claim 1～3, the application in vinyl polymerization or copolymerization.
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| CN101704910B (en) * | 2009-11-25 | 2011-08-03 | 中国石油天然气股份有限公司 | Transition metal olefin polymerization catalyst and preparation method thereof |
| WO2014170913A2 (en) | 2013-04-17 | 2014-10-23 | Reliance Industries Limited | A novel transition metal based pro-catalyst and a process for its preparation |
| CN105085749B (en) * | 2014-04-24 | 2017-12-19 | 中国石油化工股份有限公司 | Catalytic component and its catalyst for propylene polymerization |
| CN105085727B (en) * | 2014-04-24 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of catalytic component and its catalyst for olefinic polymerization |
| JP6804302B2 (en) | 2014-04-24 | 2020-12-23 | 中国石油化工股▲ふん▼有限公司 | Catalyst components for olefin polymerization and catalysts containing them |
| CN105482004B (en) * | 2015-12-04 | 2018-02-09 | 淄博新塑化工有限公司 | A kind of composite catalyst for being used to prepare wide/dual-peak distributed high density polyethylene |
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| CN1093093A (en) * | 1993-03-26 | 1994-10-05 | 化学工业部北京化工研究院 | vinyl polymerization or copolymerization catalyst |
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