CN1850872A - Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene - Google Patents
Composite catalytic system for preparing wide/dual-peak distributed high density polyethylene Download PDFInfo
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- CN1850872A CN1850872A CN 200510066037 CN200510066037A CN1850872A CN 1850872 A CN1850872 A CN 1850872A CN 200510066037 CN200510066037 CN 200510066037 CN 200510066037 A CN200510066037 A CN 200510066037A CN 1850872 A CN1850872 A CN 1850872A
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Abstract
The invention supplies a compounding catalyst system used to make wide/bimodal distribution high density polyethylene. It could take catalysis olefinic polymerization or copolymerizing to make bimodal distribution high density polyethylene.
Description
Technical field:
The present invention relates to a kind of composite catalyst system for preparing wide/dual-peak distributed high density polyethylene and preparation method thereof and its application in olefinic polymerization.
Background technology:
Prepare the method that molecular weight is bimodal/wide distribution polymer melt blending method, step reaction method and single reactor method are arranged.Melt blending method be with the resin of two kinds of different molecular weights by the blending of fused method, this method exists homogeneity difference and the high problem of running cost.Step reaction method adopts the polymerization reactor series connection more, adopts different technology in the differential responses stage, and there is the high problem of running cost equally in it, and complicated operation.Single reactor mixed catalyst method is to utilize the performance difference at two kinds of catalyzer different activities centers, and different chain termination speeds are widened the molecular weight distribution of resin.
The method of producing wide/dual-peak distributed high density polyethylene at present mainly is to adopt two or more polymerization reactor series connection with chain-transfer agent of different concns, in this polymerization technique, the reactor that the hydrogen add-on is few is produced high-molecular weight polymer, the reactor that the hydrogen add-on is many is produced low-molecular weight polymer, finally obtains the polymkeric substance that wide/double peak distributes.
Single site catalysts (SSC) resulting polymers narrow molecular weight distribution, side chain is evenly distributed, good mechanical property, thereby but because narrow molecular weight distribution makes its processing characteristics relatively poor, by with the composite use of other catalyzer, can improve the processing characteristics of single site catalysts resin.
About report composite early of traditional Ziegler/Natta catalyzer and single site catalysts is arranged, WO 99/03899 as Mobil, this type catalyst since the metallocene catalyst copolymerization performance than Ziegler/Natta catalyzer copolymerization performance excellence many, and the molecular weight of Ziegler/Natta catalyzer resulting polymers is relatively large, thereby cause in the resin of gained high molecular part branching very low, even there is not branching, and low molecular weight part branching is higher, this material can not reach the equilibrium of processing characteristics and intensity, does not reach the composite effect of ideal.
Composite between different types of single site catalysts also has report, US6340730B1 adopts a kind of non cyclopentadienyl catalyst and a kind of half cyclopentadienyl catalyst to carry out composite, non cyclopentadienyl catalyst synthetic macromolecule amount low density part wherein, half cyclopentadienyl catalyst synthesizes the lower molecular weight high density product, and the mean density of polymkeric substance is 0.950g/cm
3About.Hexene/ethene is about 0.011 (mol ratio).The molecular weight distribution broad of same non cyclopentadienyl catalyst its resulting polymers in another piece patent US6265513B1, Mw/Mn＞10 are not a kind of single-site catalysts.
Therefore how to utilize the advantage of single site catalysts resulting polymers narrow molecular weight distribution, choose suitable single site catalysts carry out composite, thereby the processing characteristics of improving polymkeric substance is very important.
Summary of the invention:
One of purpose of the present invention provides and is adapted at preparation wide/dual-peak distributed high density polyethylene composite catalyst system in the single reactor, and two of purpose of the present invention provides the preparation method of the composite catalyst system that is suitable for slurry or gas-phase polymerization process; Three of purpose of the present invention provides and adopts above-mentioned composite catalyst system to prepare the polymerization process that molecular weight is the high-density polyethylene resin of wide/double peak distribution.
A kind of composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene of the present invention comprises following component;
A. (1) a kind of early transition metal title complex that is used for vinyl polymerization has following general formula [1]:
Wherein: M is the 4th family's early transition metal, preferred zirconium and titanium;
N is more than or equal to 2;
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, 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, substituted-phenyl.
(2) a kind of metallocene-ether-inorganic salt three component adductss are disclosed among the CN98103034.3, have following general formula: Cp ＇ Cp " MQ
2RXR ＇ nM ＇ Q
2/n
In the formula, Cp ＇ Cp " MQ
2Be metallocene compound, Cp ＇, Cp and " be the metallocene part, be selected from the cyclopentadiene derivant base, described cyclopentadiene derivant base comprises cyclopentadienyl, indenyl, fluorenyl; Be preferably the cyclopentadienyl of cyclopentadienyl or replacement, part can be identical or different, and the hydrogen atom in the part can be replaced by one or more substituting groups, and substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl or aralkoxy; Be preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-.
Described metallocene part Cp ＇, Cp " between, also can be connected by a bridge linkage group, bridge linkage group can be C
1～C
4Carbon bridge, silicon bridge or germanium bridge; Can there be bridging, i.e. non-bridged combined metal compound, preferably non-bridged combined metal compound yet.
M is selected from any one in the IVB family element in the periodic table of elements, and preferred Zr or Ti are preferably Zr; Q is selected from halogen, is preferably chlorine.
RXR is ether or cyclic ethers, and R and R ＇ can be identical or different, are selected from C
1～C
6Alkyl, X is an oxygen; RXR ＇ is preferably ether, and tetrahydrofuran (THF) is with tetrahydrofuran (THF) the best; Inorganic salt M ＇ Q
2/nIn, M ＇ is selected from basic metal or alkaline-earth metal; N=1 or 2, when M ＇ is basic metal, n=2; When M ＇ is alkaline-earth metal, n=1; M ＇ is preferably lithium or magnesium, is preferably lithium.
Mol ratio is 0.01～300: 1 between transition metal complex (1) and the metallocene adduct (2), preferred 0.1～100: 1, more preferably 0.1～50: 1, most preferably 0.1～30: 1.
B. the aikyiaiurnirsoxan beta of loading with through carrier; In the B component among aluminium and the component A mol ratio in the included active centre in (1) and (2) be 10～2000; Be preferably 20-500;
Adducts of the present invention is a certain material when forming crystal, and another kind of material joins in an orderly manner in the crystal defect of this material and forms, and a material combines with Intermolecular Forces with another material.
Metallocene adduct preparation method provided by the invention is: be solvent with the ethers,-10～30 ℃, preferably-5～10 ℃, making the reaction of Cyclopeutadiene type metallocene ligand compound and alkaline reagents generate the part negative ion, then at-78～30 ℃, is MQ with part negative ion and the general formula that generates
4Metal halide reaction, when metallocene compound forms, metallocene compound forms metallocene adduct with inorganic salt and ether solvent that reaction discharges, preferably remove 50～98% solvent, add alkane resistates is disperseed, filters, is drying to obtain the metallocene adduct solid phase prod.
Cyclopeutadiene type metallocene ligand compound comprises cyclopentadiene and derivative thereof among the above-mentioned preparation method, as fluorenes or indenes, described cyclopentadiene and derivative thereof also can contain one or more substituting groups, preferred mono-substituted cyclopentadiene, polysubstituted cyclopentadiene, indenes, fluorenes; Substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl or aralkoxy, preferred C
1～C
12Alkyl; More preferred Cyclopeutadiene type compounds is cyclopentadiene, n-propyl cyclopentadiene, methyl butyl cyclopentadiene, tetramethyl-ring pentadiene, pentamethyl-cyclopentadiene, indenes.
Described ether solvent is ether or the cyclic ethers with general formula R XR ＇, and wherein R and R ＇ can be identical or different, are selected from C
1～C
6Alkyl, X is an oxygen; Preferred ether is ether or tetrahydrofuran (THF), and more preferred ether is tetrahydrofuran (THF).
Described alkaline reagents is the organic compound of basic metal or alkaline-earth metal, preferred alkyl lithium, lithium aryl, most preferably butyllithium.
Described MQ
4M in the metallic compound is selected from any element of IVB family in the periodic table of elements, preferred zirconium or titanium, most preferably zirconium; Q is a halogen, preferred chlorine.
Described alkane is selected from C
5～C
12Alkane, preferred boiling range is 60～90 ℃ of sherwood oils.The add-on of alkane is preferably 1～10 times of adducts slurry volume.
The composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene of the present invention is to load on inorganic or organic carrier with metallocene adduct by certain mol proportion and promotor above-mentioned early transition metal compound.Described carrier is an inorganic oxide, butter, and polymkeric substance or their mixture, best with silicon-dioxide (silica gel).
Described promotor is meant aikyiaiurnirsoxan beta, and its structural formula is:
Or
Wherein R represents C
1～C
12Alkyl is preferably methyl, a represents 4～30 integer, is preferably 10～30 integer, the methylaluminoxane MMAO of aikyiaiurnirsoxan beta preferable methyl aikyiaiurnirsoxan beta MAO, modification.
Carrying method of the present invention is at first to load on promotor on the carrier, obtain carrier loaded cocatalyst B component, then two kinds of above-mentioned early transition metal compound and metallocene adducts of catalyst activity component are loaded on the B component by a certain percentage.The mol ratio in the included active centre in (1) and (2) is 10～2000 among aluminium on the B component and the component A, preferred 20～500.
Carrying method of the present invention is as follows;
(1) processing of carrier: with carrier roasting under condition of nitrogen gas, temperature is 200～800 ℃, and the time is 1～24 hour.Carrier after the roasting can directly use.
(2) loading with of aikyiaiurnirsoxan beta: under condition of nitrogen gas, add carrier, aikyiaiurnirsoxan beta and solvent through above-mentioned processing, be warming up to 30～80 ℃, be preferably 40～60 ℃, stirring reaction 3～6 hours, then with solvent wash for several times, vacuum-drying obtains mobile pressed powder.Wherein solvent can adopt aromatic hydrocarbons or aliphatic hydrocarbon, as toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene etc., and preferred toluene.
(3) loadization of catalyst activity component: the carrier that contains aikyiaiurnirsoxan beta that will obtain through above-mentioned (2) and the mixture of early transition metal compound and metallocene adduct react in solvent, under 0～40 ℃, 1～120 minute time, slurries can be directly used in polyreaction; Or remove to desolvate and obtain mobile solid catalyst, be used for polyreaction.Solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexanaphthene etc., selects toluene, and hexane or both mixtures are best.
Polymerization process of the present invention has basic aluminum compound as clear assorted agent for adding in reaction medium, add slurries or the solid catalyst that obtains in (3) then, heats up, adds vinyl polymerization.
Described organo-aluminium compound is trimethyl aluminium, triethyl aluminum, three n-butylaluminum, triisobutyl aluminium, and a kind of in three hexyl aluminium, aluminium diethyl monochloride, the ethyl aluminum dichloride or their mixture, the best is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium.In the above-mentioned organo-aluminium compound among Al and the component A mol ratio in the included active centre in (1) and (2) be 10～2000, be preferably 30～200.
Polymerization temperature is 0 ℃～150 ℃, is preferably 0 ℃～90 ℃.
Polymerization pressure is 0.1～10.0MPa, preferred 0.1～2.0MPa.
Described reaction medium is a nonpolar medium, as: C
3～10Saturated alkane, comprise paraffinic hydrocarbons and naphthenic hydrocarbon, preferred normal hexane.
Catalyst system of the present invention can be used for the polymerization or the copolymerization of alkene, be specially adapted to that ethylene homo closes or the copolymerization of ethene and other alpha-olefin, wherein alpha-olefin adopts a kind of in propylene, butylene, amylene, hexene, octene, the 4-methylpentene-1; Polymerization technique can adopt slurry process, vapor phase process.The density of gained polyvinyl resin is at 0.967～0.948g/cm
3, melting index (MI
2.16kg): 0.01～10g/10min, MI
21.6kg/ MI
2.16kg=100～200, Mw/Mn=5～20, this resin can be used for preparing high-density film or tubing.
Provided by the invention have double activity center's composite catalyst system and compared with the prior art have the following advantages: though adopt the prior art of composite catalyst system a lot, because mismatch all can not reach ideal effect.The composite catalyst system of forming by early transition metal compound and metallocene adduct that is used to prepare wide/dual-peak distributed high density polyethylene provided by the invention, two kinds of active centre performance collocation rationally, reached preparation wide/dual-peak distributed high density polyethylene desired result, not only make resin obtain the ideal mechanical property, and improved the processing characteristics of resin.
Embodiment:
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.
Embodiment 1
Compd A: (L2)
3Zr
2Cl
4Synthetic
1, synthetic ligands L2
Under the nitrogen atmosphere, add 5 of 2.0g (5.05mmol) in the 250ml there-necked flask, 5 '-isopropylidene-two (the 3-tertiary butyl-2-hydroxy benzaldehyde) is used the 60ml dissolve with methanol, add the hexahydroaniline of 1.39ml (12.12mmol) and the formic acid of 0.6ml then, stirring at room reaction 24 hours.Filter out precipitation, and vacuum-drying, obtain ligand L 2 yellow powders of 0.7g (1.25mmol, yield are 24.8%).
Its structural formula is as follows:
Ligand L 2
CI-mass spectrum: 558M
+
2, synthetic metal complexes (L2)
3Zr
2Cl
4
Under the nitrogen atmosphere, in there-necked flask, add above-mentioned synthetic 1.07g (1.92mmol) ligand L 2, add the dissolving of 50ml tetrahydrofuran (THF), be cooled to then below-70 ℃, slowly drip 1.60ml (2.56mmol) n-butyllithium solution, reaction is 1 hour under this temperature, slowly is warming up to room temperature, reacts 4 hours; This liquid is transferred in the constant voltage minim pipette,, slowly be added drop-wise to and be dissolved with 0.48g (1.28mmol) ZrCl below-70 ℃
4The tetrahydrofuran solution of 50ml 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, with the methylene dichloride dissolving, filters out insolubles, adds anhydrous diethyl ether in the filtrate, obtains 0.60g metal complexes (L2)
3Zr
2Cl
4Yellow powder.
Its structural formula is as follows:
Embodiment 2
Metallocene compound B:(Me
4Cp)
2ZrCl
2The preparation of adducts:
Under the nitrogen atmosphere, in there-necked flask, add 20g (0.164mol) the tetramethyl-ring pentadiene that newly steams, add the dissolving of 200ml tetrahydrofuran (THF), be cooled to then below-70 ℃, slowly drip 65.6ml (0.164mol) n-butyllithium solution (2.5M), reaction is 1 hour under this temperature, slowly is warming up to room temperature, reacts 4 hours; This liquid is transferred in the constant voltage minim pipette,, slowly be added drop-wise to and be dissolved with 19.1g (0.082mol) ZrCl below-70 ℃
4The tetrahydrofuran solution of 100ml in, after dripping off, rise to room temperature gradually, then reacted about 18 hours; Underpressure distillation behind the evaporate to dryness, disperses with hexane, filters, and uses hexane wash 2 times, obtains 39g purple metallocene adduct B powder, Zr%=18 (ICP), and in Zr, yield is 94.1%.
Embodiment 3
Metallocene compound C:(n-BuMeCp)
2ZrCl
2The preparation of adducts:
Under the nitrogen atmosphere, in there-necked flask, add 20g (0.147mol) the methyl butyl cyclopentadiene that newly steams, add the dissolving of 200ml tetrahydrofuran (THF), be cooled to then below-70 ℃, slow Dropwise 5 8.9ml (0.147mol) n-butyllithium solution (2.5M), reaction is 1 hour under this temperature, slowly is warming up to room temperature, reacts 4 hours; This liquid is transferred in the constant voltage minim pipette,, slowly be added drop-wise to and be dissolved with 16.43g (0.074mol) ZrCl below-70 ℃
4The tetrahydrofuran solution of 100ml in, after dripping off, rise to room temperature gradually, then reacted about 18 hours; Underpressure distillation behind the evaporate to dryness, disperses with hexane, filters, and uses hexane wash 2 times, obtains the yellow metallocene adduct C of 35g powder, Zr%=175 (ICP), and in Zr, yield is 91%.
Embodiment 4
The preparation of loading type MAO (SMAO):
In the 250ml vial good, add good 955 silica gel (600 ℃ of activation conditions, 4 hours) of 20 gram activation, add 30ml toluene with nitrogen replacement, system is warming up to 50 ℃, drip the toluene solution (contain 11gMAO, wherein a value is 15) of MAO, reacted 4 hours, filter, with 30ml toluene wash 3 times, use hexane wash then 2 times, drain, obtain mobile well white support, Al% :～14 (ICP method mensuration).
Embodiment 5
The preparation of loaded catalyst D:
The SMAO that in the 250ml vial good, adds 2g embodiment 4 preparations with nitrogen replacement, add 20ml toluene, start stirring, the toluene solution that drips the 10ml compd A under the room temperature (contains the 70mg compd A, Al/Zr=100), stir reaction 30min down, filter, use the 30ml hexane wash, filter, drying obtains mobile well pale yellow powder catalyzer D.
Embodiment 6
The preparation of loaded catalyst E:
The SMAO that in the 250ml vial good, adds 2g embodiment 4 preparations with nitrogen replacement, add 20ml toluene, start stirring, the toluene solution that drips the 10ml compd B under the room temperature (contains the 105mg compd B, Al/Zr=50), stir reaction 30min down, filter, use the 30ml hexane wash, filter, drying obtains mobile well pale yellow powder catalyzer E.
Embodiment 7
The preparation of loaded catalyst F:
The SMAO that in the 250ml vial good, adds 2g embodiment 5 preparations with nitrogen replacement, add 20ml toluene, start stirring, the toluene solution that drips the 10ml Compound C under the room temperature (contains the 108mg Compound C, Al/Zr=50), stir reaction 30min down, filter, use the 30ml hexane wash, filter, drying obtains mobile well pale yellow powder catalyzer F.
Embodiment 8～10
Catalyst compounded preparation:
The SMAO that in the 250ml vial good, adds 2g embodiment 5 preparations with nitrogen replacement, add 20ml toluene, start stirring, drip the compd A of 10ml certain mol proportion and the toluene solution (Al/Zr=50) of B, B/A=0.7,1,2 (mol ratio) under the room temperature, stir reaction 30min down, filter, use the 30ml hexane wash, filter, drying obtains mobile well pale yellow powder.
Embodiment 11～13
Catalyst compounded preparation:
The SMAO that in the 250ml vial good, adds 2g embodiment 5 preparations with nitrogen replacement, add 20ml toluene, start stirring, drip the compd B of 10ml certain mol proportion and the toluene solution (Al/Zr=100) of C, C/A=0.3,0.7,1.7 (mol ratio) under the room temperature, stir reaction 30min down, filter, use the 30ml hexane wash, filter, drying obtains mobile well pale yellow powder.
Embodiment 14～37
The slurry polymerization test:
In 2 liters stainless steel autoclave, blow row through nitrogen, after ethene is repeatedly replaced, add the triethyl aluminum of 1 liter of hexane, comonomer hexene, 2 mmoles and the catalyzer that the foregoing description 5～13 obtains, feed ethene, and at 1.0Mpa, 80 ℃ are reacted certain hour down.The cooling after-filtration, drying obtains polymer powders.Data see Table 1.
Table 1 polymerization result
| Embodiment | Catalyzer | Ratio | 1-hexene (ml) | Time (min) | Active (gPE/gcat) | MI 2.16kg | MI 21.6kg | MI 21.6kg/ MI 2.16kg | Mw (×10 4) | Mw/Mn | Density (g/cm 3) |
| 14 15 16 17 18 19 20 21 22 23 24 25 26 | D D E E E F F F B/A B/A B/A B/A B/A | - - - - - - - - 0.7 0.7 1 1 1 | 0 10 0 10 20 0 10 20 0 10 0 5 10 | 60 60 60 60 60 60 60 60 60 60 60 60 60 | 1600 2100 1256 1400 1029 2566 2735 2044 1560 1850 1520 1720 1800 | 36.70 39.80 0.14 0.046 - 0.136 0.312 0.42 0.074 0.166 0.047 0.094 0.075 | - - 4.19 1.91 - 2.86 - - 7.95 12.46 5.31 9.49 5.98 | - - 30 41.5 - 21 - - 107 75 113 101 79.7 | 5.92 5.89 - 24 21 - - - 16.08 16.86 21.3 16.1 16.4 | 6.2 5.89 - 3.35 2.8 - - - - - 11.34 9.94 10.42 | 0.9669 0.9662 0.9531 0.9367 - - - - - - 0.9578 0.9571 0.9529 |
The continuous table of going up
| 27 28 29 30 31 32 33 34 35 36 37 | B/A B/A B/A B/A B/A C/A C/A C/A C/A C/A C/A | 1 1 1 2 2 0.3 0.3 0.7 0.7 1.7 1.7 | 10 10 10 0 10 10 20 5 10 10 20 | 120 180 240 60 60 60 60 60 60 60 60 | 2200 2650 2900 1560 1755 2250 2430 2250 2657 2343 2157 | 0.075 0.017 0.019 0.047 0.046 2.46 2.72 0.529 1.21 0.51 0.61 | 7.57 4.08 3.61 2.71 2.7 116.45 132.23 13.95 39.39 8.87 11.15 | 100.9 240 190 57.7 58.8 47.34 48.61 26.37 32.55 17.4 18.22 | - - - - - 11.6 - - 13.66 15.8 - | - - - - - 10.52 - - 11.45 7.44 - | - - - - - - - - - - - |
Claims (8)
1. a composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene is characterized in that, comprises following component;
A. (1) a kind of early transition metal title complex that is used for vinyl polymerization has following 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;
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 be randomly replaced by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, Siliciumatom;
(2) a kind of metallocene-ether-inorganic salt three component adductss have following general formula:
Cp′Cp″MQ
2·RXR′·nM′Q
2/n
In the formula, Cp ' Cp " MQ
2Be metallocene compound, wherein Cp ', Cp and " be the metallocene compound part, be selected from the cyclopentadiene derivant base, described cyclopentadiene derivant base comprises cyclopentadienyl, indenyl, fluorenyl; Part can be identical or different, and the hydrogen atom in the part can be replaced by one or more substituting groups, and substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl or aralkoxy; M is selected from any one in the IVB family element in the periodic table of elements; Q is selected from halogen;
RXR ' is ether or cyclic ethers, and R and R ' can be identical or different, are selected from C
1～C
6Alkyl, X is an oxygen;
M ' Q
2/nBe inorganic salt, M ' is selected from basic metal or alkaline-earth metal; N=1 or 2, when M ' is basic metal, n=2; When M ' is alkaline-earth metal, n=1;
Mol ratio is 0.01～300: 1 between transition metal complex (1) and the metallocene adduct (2);
B. the aikyiaiurnirsoxan beta of loading with through carrier; In the B component among aluminium and the component A mol ratio in the included active centre in (1) and (2) be 10～2000.
2. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 1 is characterized in that: transition metal complex among the component A (1), and described M is the early transition metal zirconium, titanium; X is chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy group, adjacent phenoxy group, m-phenoxy, to 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, isopropylidene, isobutylidene, phenyl, substituted-phenyl;
Metallocene-ether among the component A (2)-inorganic salt three component adductss, " be preferably the cyclopentadienyl of cyclopentadienyl or replacement, substituting group is preferably methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, and M is a zirconium for Cp ', Cp; Q is a chlorine, and RXR ' is preferably tetrahydrofuran (THF), M ' Q
2/nMiddle M ' is preferably lithium; Mol ratio is preferably 0.1～50 between transition metal complex (1) and the metallocene adduct (2): 1; In the B component among aluminium and the component A mol ratio in the included active centre in (1) and (2) be preferably 20-500.
3. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 1 is characterized in that, the described carrier of B component is an inorganic oxide, butter, polymkeric substance or their mixture.
4. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 3 is characterized in that, the described carrier of B component is a silica gel.
5. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 1 is characterized in that, wherein the aikyiaiurnirsoxan beta general structure is:
Or
Wherein R represents C
1-C
12Alkyl, a are represented 4～30 integer.
6. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 5 is characterized in that R is preferably methyl in the aikyiaiurnirsoxan beta, and a is preferably 10～30 integer.
7. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 1 is characterized in that, can be added with machine aluminium compound in olefin polymerization system.
8. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 7, it is characterized in that described organo-aluminium compound is selected from a kind of in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, aluminium diethyl monochloride, the ethyl aluminum dichloride or their mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101786019A (en) * | 2010-02-26 | 2010-07-28 | 中国石油天然气股份有限公司 | Transition metal catalyst containing cyclopentadienyl and preparation and application thereof |
| CN103421138A (en) * | 2013-07-21 | 2013-12-04 | 浙江大学 | Method for preparing wide/bimodal polyethylene with single reactor |
| CN110964143A (en) * | 2018-09-30 | 2020-04-07 | 中国石油天然气股份有限公司 | Polyethylene base resin for beverage bottle cap and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6103657A (en) * | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
| US6340730B1 (en) * | 1999-12-06 | 2002-01-22 | Univation Technologies, Llc | Multiple catalyst system |
| CN1177872C (en) * | 2000-09-13 | 2004-12-01 | 中国石油化工股份有限公司 | Catalyst system for prparing dual-peak or widely distributed polyethylene and its application |
| US6964937B2 (en) * | 2000-11-30 | 2005-11-15 | Univation Technologies, Llc | Bimetallic catalyst for producing polyethylene resins with bimodal molecular weight distribution, its preparation and use |
| CN1209387C (en) * | 2003-01-23 | 2005-07-06 | 浙江大学 | Catalyst for preparing polyethylene possessing distribution of molecular weight with doublet and/or broad peak |
| CN1247624C (en) * | 2003-02-17 | 2006-03-29 | 中国石油化工股份有限公司 | Catalyst component for polymerizing ethylene and catalyst thereof |
| CN1436798A (en) * | 2003-03-03 | 2003-08-20 | 中国科学院长春应用化学研究所 | Prepn of binuclear nickel-base olefine polymerizing quinone amine catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101786019A (en) * | 2010-02-26 | 2010-07-28 | 中国石油天然气股份有限公司 | Transition metal catalyst containing cyclopentadienyl and preparation and application thereof |
| CN103421138A (en) * | 2013-07-21 | 2013-12-04 | 浙江大学 | Method for preparing wide/bimodal polyethylene with single reactor |
| CN110964143A (en) * | 2018-09-30 | 2020-04-07 | 中国石油天然气股份有限公司 | Polyethylene base resin for beverage bottle cap and preparation method thereof |
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