CN1850871A - 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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- CN1850871A CN1850871A CN 200510066036 CN200510066036A CN1850871A CN 1850871 A CN1850871 A CN 1850871A CN 200510066036 CN200510066036 CN 200510066036 CN 200510066036 A CN200510066036 A CN 200510066036A CN 1850871 A CN1850871 A CN 1850871A
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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 and preparation method and application for preparing wide/dual-peak distributed high density polyethylene.
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 reactors in series 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, but because molecular weight distribution is narrow, thereby make its processing characteristics relatively poor relatively, 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, the high molecular part degree of branching is lower in the resin of gained, even there is not branching, and the low molecular weight part degree of branching is higher, and this material can not reach the balanced compatibility of processing characteristics and intensity.
Composite between the 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, specifically, be to adopt the compound and composite catalyst system of the suitable preparation wide/dual-peak distributed high density polyethylene that obtains of a kind of half cyclopentadienyl catalyst and metallocene catalyst; 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 half cyclopentadinyl compound that is used for vinyl polymerization has following general formula [1]: be disclosed among the CN01141472.3:
R in the formula [1]
1Be that substituting group on the salicylidene phenyl ring is selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, preferred hydrogen or C
1～C
4Alkyl, concrete as methyl, ethyl, propyl group or the tertiary butyl, replace and can be 3～6, preferred 3 or 6 replacements, substituting groups are positioned at the ortho position or the contraposition of hydroxyl.
R in the formula [1]
2Substituting group on the N is selected from C
1～C
8Alkyl, cycloalkyl or C
6～C
12Aryl, preferred C
1～C
8Cycloalkyl, more preferably cyclohexyl.
R
3Be the substituting group on the cyclopentadienyl skeleton, be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, preferred hydrogen or C
1～C
4Alkyl, concrete as hydrogen, methyl, ethyl, more preferably hydrogen; M is selected from Ti, Zr or Hf, preferred Zr.
A kind of metallocene-ether-inorganic salt three component the adductss that are used for preparing the composite catalyst system of wide/dual-peak distributed high density polyethylene of the present invention are disclosed among the CN98103034.3, and it consists of 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; The cyclopentadienyl of preferred cyclopentadienyl or replacement, Cp ＇, Cp " can be identical or different, and can contain one or more substituting groups, substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl or aralkoxy, preferred C
1～C
12Alkyl, 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; Preferred ether is ether or tetrahydrofuran (THF), more preferably tetrahydrofuran (THF).
M ＇ Q
2/nBe inorganic salt, M ＇ is selected from basic metal or alkaline-earth metal; Preferred lithium or magnesium, preferably lithium; N=1 or 2, when M ＇ is basic metal, n=2; When M ＇ is alkaline-earth metal, n=1; Preferred n=2.
The mol ratio of above-mentioned half cyclopentadinyl compound and metallocene adduct is 0.01～300: 1, 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 kind of material combines with Intermolecular Forces with another kind of 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, and as fluorenes or indenes, described cyclopentadiene and derivative thereof also can contain one or more substituting groups, and substituting group is selected from C
1～C
12Alkyl, alkoxyl group, silylation, aryl or aralkoxy, preferred C
1～C
12Alkyl; More preferred Cyclopeutadiene type metallocene ligand compound 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), more preferably tetrahydrofuran (THF).
Described alkaline reagents is the organic compound of basic metal or alkaline-earth metal, and preferred alkyl lithium, lithium aryl are best with the 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 half cyclopentadinyl 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 Organoaluminoxy alkane preferable methyl aikyiaiurnirsoxan beta MAO, modification.
Carrying method of the present invention is that promotor is at first loaded on the carrier, obtains carrier loaded cocatalyst B component, then two kinds of above-mentioned half cyclopentadinyl compound and metallocene adducts of catalyst activity component is loaded on the B component by a certain percentage.The aluminium on the B component and the mol ratio in active centre are 10～2000, preferred 20～500.
Carrying method of the present invention is as follows:
Processing with (1) 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., and with toluene, 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 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 collocation is very unreasonable, all can not reach ideal effect.The composite catalyst system of forming by half cyclopentadinyl 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.
Description of drawings:
Concrete 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.
Synthesizing of compound (A):
Two (3-tertiary butyl salicylidene cyclohexyl)-(cyclopentadienyl) zirconium chlorides.
(1) preparation ligand compound 3-tertiary butyl salicylidene hexahydroaniline:
Get 17.8g (0.1mol) 3-tertiary butyl salicylic aldehyde and 0.2mol hexahydroaniline and join in the 100ml ethanol medium, be heated to backflow under stirring, reacted 2 hours, be cooled to room temperature, promptly have a large amount of crystal to produce.Filtration, solid finally obtain part 3-tertiary butyl salicylidene aniline, productive rate 92% with 30ml alcohol solvent recrystallization.
1H NMR(CDCl
3，500MHz)δ：13.93(br，1H，D
2O，OH)，8.64(s，1H，CH＝N)，7.46～6.96(m，8H，arom)，1.47(s，9H，C(CH
3)
3)
(2) lithium salts of preparation 3-tertiary butyl salicylidene hexahydroaniline:
In 100ml Schlenk bottle, add 2.910g (11.5mmol) 3-tertiary butyl salicylidene hexahydroaniline and 30ml tetrahydrofuran (THF), solution is cooled to-70 ℃, under agitation Dropwise 5 .72ml (2.0113molL
-1, 11.5mmol) butyllithium dropwises, and rises to room temperature naturally, stirs 3 hours, gets the tetrahydrofuran solution of 3-tertiary butyl salicylidene hexahydroaniline lithium salts.
(3) preparation catalyzer:
Tetrahydrofuran solution with above-mentioned 3-tertiary butyl salicylidene hexahydroaniline lithium salts is cooled to-70 ℃, and slowly is added drop-wise to 1.213g (3.4mmol) CpZrCl under this temperature
3In the 30ml tetrahydrofuran solution of DME, rise to room temperature then naturally, stirring is spent the night.Decompression is drained reaction solution down, adds 30ml toluene, filters, and filtrate was placed 18 hours at-20 ℃, separates out 0.62g white crystal catalyzer F: two (3-tertiary butyl salicylidene cyclohexyl)-(cyclopentadienyl) zirconium chlorides, productive rate 62%.Its structure is as shown below:
1H NMR:(CDCl
3, δ, ppm) analytical value: 8.22 (s, 2H, CH=N), 7.58～7.12 (m, 6H, Ar-H), 6.73 (s, 5H, C
5H
5), 1.38 (s, 18H,
tBu-H), 2.25～1.12 (m, 22H, cyclo-C
6H
11).Anal.Calcd：C，66.11；H，7.54；N，3.95。Found：C，66.37；H，7.69；N，4.03。MS(70eV)m/z(％)：706.3(46，[M]
+)，671.3(9，[M-Cl]
+)，655.3(100，[M-Cp]
+)，448.1(50，[M-
tBuOC
6H
4CH＝NC
6H
11]
+)；
IR(KBr)v：3087m，3020m，2965w，2923w，1609vs，1585s，1551s，1496s，1474vs，1442s，1396s，1395s，1231m，1303vs，1283vs，1264s，1222s，1187m，1174w，1150s，1122s，1110m，1053w，1022s，976s，925m，862m，847s，820vs，808s，791m，778m，762s，749s，732s cm
-1。
Embodiment 2
Metallocene compound B's is synthetic: (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's is synthetic: (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%=17.5 (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 the activation conditions of 20 gram activation with nitrogen replacement, 4 hours), add 30ml toluene, system is warming up to 50 ℃, drip the toluene solution (contain 11gMAO wherein a value be 20) of MAO, reacted 4 hours, and filtered, use 30ml toluene wash 3 times, use hexane wash then 2 times, drain, obtain mobile well white support, Al% :～14 (ICP).
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 63mg compd A, Al/Zr=100), stir reaction 30min down, filter, use the 30ml hexane wash, filter, drying obtains mobile well pale yellow powder, i.e. 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, i.e. 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, i.e. catalyzer F.
Embodiment 8
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=3 (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 9
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=50) of C, C/A=1 (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 10～18
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 5～9 obtains, feed ethene, and at 1.0Mpa, 80 ℃ are reacted certain hour down.The cooling after-filtration, drying obtains polymer powders.The polymerization result data see Table 1.
The catalyzer that embodiment 11, embodiment 13 and embodiment 17 are obtained is used for vinyl polymerization, and the GPC curve of gained PE is seen Fig. 1.Adopt 135 ℃ of high temperature GPC, orthodichlorobenzene is a solvent.
The GPC graphic representation of the PE that curve 1 obtains for the half cyclopentadienyl catalyst D polymerization of embodiment 11 usefulness among the figure; The GPC graphic representation of the PE that curve 2 obtains for embodiment 13 usefulness metallocene catalyst E polymerizations; The GPC graphic representation of the PE that curve 3 obtains for embodiment 17 usefulness composite catalyst B/A polymerizations.The peak of curve 3 is obviously milder than the peak of curve 2 and curve 1 as can be seen from Fig. 1, illustrates composite catalyst with curve 3 representatives to carry out molecular weight distribution that polymerization obtains to carry out the molecular weight distribution that polymerization obtains than the catalyzer with curve 1 or curve 2 representatives wide.
Table 1
| 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) |
| 10 11 12 13 14 15 16 17 18 | D D E E F F B/A B/A C/A | - - - - - - 3 3 1 | 0 10 0 10 0 10 0 10 10 | 60 60 60 60 60 60 60 60 60 | 4200 5970 1256 1400 2566 2735 2131 2300 2817 | 23.15 28.03 0.14 0.046 0.136 0.312 0.066 0.047 1.95 | - - 4.19 1.91 2.86 - 5.84 7.09 102.21 | - - 30 41.5 21 - 88.4 150.8 52.41 | 4.02 4.07 - 24 - - - 17.1 15.5 | 3.9 4.43 - 3.35 - - - 17.94 11.29 | 0.9669 0.9650 0.9531 0.9367 - - 0.9578 0.9528 0.9527 |
Claims (9)
1. composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene is characterized in that comprising following component:
A. (1) a kind of half cyclopentadinyl compound that is used for vinyl polymerization has following general formula [1]:
R in the formula [1]
1Be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, R
2Be selected from C
1～C
8Alkyl, cycloalkyl or C
6～C
12Aryl, R
3Be selected from hydrogen, C
1～C
12Alkyl, C
1～C
12Alkoxyl group or C
6～C
12Aryl, M is selected from Ti, Zr or Hf;
(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, wherein 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 half cyclopentadinyl compound (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, is used for half cyclopentadinyl compound of vinyl polymerization among the component A (1), R in the formula [1]
1Be selected from hydrogen or C
1～C
4Alkyl, replace the position and can be 3～6; R
2Be the substituting group on the N, preferred C
1～C
8Alkyl, cycloalkyl or C
6～C
12Aryl, R
3Preferred hydrogen or C
1～C
4Alkyl; The preferred Zr of M;
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/nIn, M ' is preferably lithium;
Mol ratio is preferably 0.1～50 between half cyclopentadinyl compound (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. according to claim 2ly be used to prepare the wide/dual-peak distributed high density polyethylene composite catalyst system, it is characterized in that, be used for half cyclopentadinyl compound of vinyl polymerization among the component A (1), R in the formula [1]
1Be selected from methyl, ethyl, propyl group, the tertiary butyl replaces position preferred 3 or 6, R
2Preferred cyclohexyl; R
3Preferred hydrogen; Mol ratio the best is 0.1～30: 1 between half cyclopentadinyl compound (1) and the metallocene adduct (2).
4. 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.
5. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 4,, it is characterized in that the described carrier of B component is silicon-dioxide (silica gel).
6. 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.
7. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 6 is characterized in that R is preferably methyl in the aikyiaiurnirsoxan beta, and a is preferably 10～30 integer.
8. 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.
9. the composite catalyst system that is used to prepare wide/dual-peak distributed high density polyethylene according to claim 8, 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161536A (en) * | 2008-01-07 | 2009-07-23 | Sk Energy Co Ltd | Transition metal compound and transition metal catalyst composition containing the same and used for producing ethylene homopolymer or copolymer |
| CN102453119A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method thereof |
| CN105566519A (en) * | 2014-10-17 | 2016-05-11 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
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| US5525678A (en) * | 1994-09-22 | 1996-06-11 | Mobil Oil Corporation | Process for controlling the MWD of a broad/bimodal resin produced in a single reactor |
| US6103657A (en) * | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
| CN1060780C (en) * | 1998-05-08 | 2001-01-17 | 中国石油化工集团公司 | Metallocene adduct, its preparation and use in olefin synthesis |
| CN1160381C (en) * | 2001-09-27 | 2004-08-04 | 中国石油化工股份有限公司 | Olefine polymerization catalyst containing double schiff base ligand and preparing method and use |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009161536A (en) * | 2008-01-07 | 2009-07-23 | Sk Energy Co Ltd | Transition metal compound and transition metal catalyst composition containing the same and used for producing ethylene homopolymer or copolymer |
| CN102453119A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method thereof |
| CN102453119B (en) * | 2010-10-19 | 2013-09-25 | 中国石油化工股份有限公司 | Loaded non-metallocene catalyst and preparation method thereof |
| CN105566519A (en) * | 2014-10-17 | 2016-05-11 | 中国石油化工股份有限公司 | Supported metallocene catalyst and preparation method and application thereof |
| CN105566519B (en) * | 2014-10-17 | 2018-10-16 | 中国石油化工股份有限公司 | Carried metallocene catalyst and its preparation method and application |
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