CN1353118A - Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application - Google Patents
Catalyst for polymerizing semi-metallocene with olefin and its preparing process and application Download PDFInfo
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Abstract
A semi-metallocene catalyst for homopolymerizing or copolymerizing alpha-olefin has a formula: [O,N]CpMX2, where [O,N] is the group formed by 8-hydroxyquinoline derivative, Cp is the group containing cyclopentadiene skeleton, M is chosen from metals in IVB family (Zr or Ti), and X is chosen from halogen, C1-C18 alkyl, C1-C18 alkoxy or alkaryl. It has high catalytic activity, and the produced olefin polymer has moderate molecular wt. and narrow molecular wt. distribution.
Description
The present invention relates to a kind of olefin polymerization catalysis and preparation method thereof and application, specifically, is a kind of catalyst for polymerizing semi-metallocene with olefin and preparation method thereof and application.
In recent years, polyolefin catalyst with big π key part is developed rapidly, continue typical be the transistion metal compound of part with cyclopentadiene and derivative thereof after, the another kind of application of transition metal complex aspect polyolefin catalyst that contains coordination heteroatom ligands such as aerobic, nitrogen causes that more and more people pay attention to and pay close attention to.
USP5,539,124 disclose a kind of transition metal compound catalizer that contains pyrrole ring.The general expression of this catalyzer is: (L) m (Cp) qM (Y) n (B) p, L in the formula is part or ligand mixture, this part contains at least two condensed ring, one of them condensed ring is a pyrrole ring, Cp is the group that contains cyclopentadiene, can be bonded to bridge each other between two L parts or L and the Cp, B is a Lewis alkali, and Y is selected from halogen, C
1～C
20Alkoxyl group, C
1～C
20Siloxy, N (R
1)
2Or their mixture, M is Ti or Zr, and m is 1～4, and n is 0～2, and p is 0～2, q is 0～1, and m+n+q=4.This catalyzer can be used for catalysis in olefine polymerization, polymerization as ethene, but catalytic activity is lower, be catalyzer for example with two pyrroles's zirconium dichlorides, with MAO is promotor, at 110 ℃, when carrying out ethylene polymerization under the 1.0MPa pressure, catalyst activity only is equivalent to every gram catalyzer and per hour produces 1.5 kilograms of polyethylene.
It is CpML that CN1169736A discloses general formula
m 1Y
3-mOlefin polymerization catalysis, wherein Cp is the group with cyclopentadienyi skeleton, M is Ti, Zr or Hf, L
1The negative monovalence bidentate anion ligand of representative, the X of bonding on the C atom in this part
1, X
2With N be respectively ligating atom, and X
1Be O, S, Se or Te, X
2Be S, Se or Te, Y represents halogen atom, C
1～C
20Alkoxyl group or by C
1～C
20The amino that alkyl replaces etc., m is 1,2 or 3.The characteristics of this catalyst system are to have selected a series of negative monovalence bidentate anion ligands for use, and have shown higher activity.
People such as Xiaohong Bei are at Organometallics 1997,16, and 3282-3302 publishes an article and discussed synthetic, the structure and the ethylene polymerization activity of the complex compound that with the oxine is part.Its synthetic is the zirconium with two oxine parts or the title complex of hafnium, and activity was lower when this material was used for vinyl polymerization.
The purpose of this invention is to provide a kind of catalyst for polymerizing semi-metallocene with olefin than high polymerization activity and preparation method thereof that has.
Another object of the present invention provides the application of above-mentioned catalyzer aspect synthesis of polyolefins.
Catalyzer provided by the invention is a kind of transition metal complex, and one of two part wherein are luxuriant and derivative, and another is the monovalence bidentate ligand, and specifically, the general expression that described catalyzer has is: [O, N] CpMX
2, wherein [O, N] is the group of oxine derivative formation, and Cp is the group that contains cyclopentadienyl skeleton, and M is selected from IVB family metal, and as titanium, zirconium or hafnium, X is identical or different group, is selected from halogen, C
1～C
18Alkyl, C
1～C
18Alkoxyl group or alkaryl.
Particularly, the structure expression that has of catalyzer of the present invention is as follows:
In the formula, Cp is single the replacement or polysubstituted cyclopentadienyl group, and substituting group is selected from hydrogen, C respectively
1～C
18Alkyl, C
1～C
18Perfluoroalkyl, C
6～C
18Alkaryl or aralkyl, wherein two of the polysubstituted cyclopentadiene group adjacent substituting groups can be interconnected to condensed ring;
R is selected from hydrogen, C
1～C
6Alkyl, C
1～C
6Perfluoroalkyl, nitro, C
6～C
14Alkaryl or aralkyl;
M is selected from titanium or zirconium;
X is selected from chlorine, benzyl, C
1～C
12Alkyl or alkoxyl group.
The preferred hydrogen of R, C in the described catalyst structure formula
1～C
3Alkyl, C
1～C
3Alkoxyl group or nitro, more preferably hydrogen, methyl or nitro, it replaces the position can be on a position in 2～7 in the quinoline; The preferred cyclopentadienyl of Cp, indenyl, fluorenyl, or C
1～C
6The alkyl list replaces or polysubstituted above-mentioned group, as methyl cyclopentadiene, ethyl cyclopentadiene, propyl group cyclopentadiene, sec.-propyl cyclopentadiene, butyl cyclopentadiene, isobutyl-cyclopentadiene, pentamethyl-cyclopentadiene, more preferably cyclopentadienyl, C
1～C
4The mono-substituted cyclopentadienyl of alkyl, or indenyl; Preferred chlorine of X or benzyl.
The comparatively preferred catalyzer of the present invention comprises: (oxine base) (cyclopentadienyl) titanium dichloride, (2-methyl-oxine base) (cyclopentadienyl) titanium dichloride; (oxine base) (tertiary butyl-cyclopentadienyl) titanium dichloride, (2-methyl-oxine base) (tertiary butyl-cyclopentadienyl) titanium dichloride; (oxine base) (pentamethyl--cyclopentadienyl) titanium dichloride, (2-methyl-oxine base) (pentamethyl--cyclopentadienyl) titanium dichloride; (oxine base) (indenyl) titanium dichloride, (2-methyl-oxine base) (indenyl) titanium dichloride; (oxine base) (fluorenyl) titanium dichloride, (2-methyl-oxine base) (fluorenyl) titanium dichloride; (oxine base) (cyclopentadienyl) zirconium dichloride, (2-methyl-oxine base) (cyclopentadienyl) zirconium dichloride; (oxine base) (tertiary butyl-cyclopentadienyl) zirconium dichloride, (2-methyl-oxine base) (tertiary butyl-cyclopentadienyl) zirconium dichloride; (oxine base) (pentamethyl--cyclopentadienyl) zirconium dichloride, (2-methyl-oxine base) (pentamethyl--cyclopentadienyl) zirconium dichloride; (oxine base) (indenyl) zirconium dichloride, (2-methyl-oxine base) (indenyl) zirconium dichloride; (oxine base) (fluorenyl) zirconium dichloride, (2-methyl-oxine base) (fluorenyl) zirconium dichloride.
Catalyzer of the present invention can prepare with following three kinds of methods, and first method comprises the steps:
(1) in ether solvent, making strongly alkaline compound and general formula is H[O, N] the oxine analog derivative be 1: 1 ratio stirring reaction in molar ratio, remove and desolvate, obtain oxine base salt,
(2) in organic solvent, make oxine base salt and semi-metallocene Compound C pMX
3Mol ratio such as press and under reflux temperature, react, filter, gained filtrate is concentrated into solid separate out, collect solid and obtain catalyzer [O, N] CpMX
2
(1) step of aforesaid method, described strongly alkaline compound was selected from basic metal, alkalimetal hydride, alkali metal alkyl compound, alkali metal amino compound or alkyl halide magnesium, preferred lithium, sodium, potassium, sodium hydride, potassium hydride KH, butyllithium, sodium amide (NaNH
2), methylmagnesium-chloride or benzyl magnesium bromide, described ether solvent is selected from ether or tetrahydrofuran (THF).(1) going on foot suitable temperature of reaction is-80～100 ℃, preferably-20～80 ℃, reaction times is 0.5～48 hour, can earlier strongly alkaline compound be dissolved in the ether during operation, the ethereal solution that adds the oxine analog derivative again, also can be opposite, the add-on of ether solvent should be controlled at 10～20 times of reactant gross weight.
The above-mentioned mat woven of fine bamboo strips (2) step, described organic solvent was selected from ether, tetrahydrofuran (THF), methylene dichloride or toluene.Its suitable temperature is-20～150 ℃, and preferred 0～80 ℃, the reaction times is 0.5～48 hour, is preferably 2～24 hours.The organic solvent usage quantity should be 10～20 times of reactant.
Second kind of preparation method of described catalyzer is combined into a step with first kind of preparation method, specifically comprise with etc. the general formula of mol ratio be H[O, N] oxine analog derivative and semi-metallocene Compound C pMX
3Be dissolved in the organic solvent, add excessive strongly alkaline compound reaction again, filter, gained filtrate is concentrated into solid separates out, collect solid and promptly get catalyzer [O, N] CpMX
2
Described organic solvent of this method and strongly alkaline compound are identical with first kind of preparation method.Its suitable temperature of reaction be-80～100 ℃, and preferably-20～50 ℃, the reaction times is 0.5～72 hour, and preferred 2～24 hours, the organic solvent usage quantity should be oxine analog derivative and semi-metallocene compound summation 10～30 times during reaction.The mol ratio of strongly alkaline compound and oxine analog derivative is 1.1～100: 1, preferred 1.5～50: 1.
Catalyzer of the present invention also can adopt the preparation of the third method, and concrete steps are included in the organic solvent, and the general formula of mol ratios such as adding is H[O, N] oxine analog derivative and semi-metallocene Compound C pMX
3Stir, add and H[O N again] tertiary amine of equimolar amount, fully stir, solids removed by filtration is concentrated into solid with gained filtrate and separates out, and collects solid and promptly gets catalyzer [O, N] CpMX
2
The described tertiary amine of the third method is selected from triethylamine, and organic solvent is selected from ether, tetrahydrofuran (THF), methylene dichloride or toluene.Suitable temperature of reaction is-50～150 ℃, preferably-10～100 ℃, the reaction times that adds behind the tertiary amine is 0.5～72 hour hour, and preferred 1～36 hour, the organic solvent usage quantity should be oxine analog derivative and semi-metallocene compound summation 10～30 times during reaction.
The catalyzer that described three kinds of methods obtain at last all need wash, or recrystallization.Be used to wash or the solvent of recrystallization is selected from alkane preferred C
5～C
10Alkane or their mixture, suitable alkane is normal hexane, hexanaphthene, Skellysolve A or normal heptane.
Used oxine analog derivative H[O in the described method, N] preferred oxine, or single substituent oxine derivative is arranged.Substituent R is C herein
1～C
6Alkyl, C
1～C
6Perfluoroalkyl, nitro, C
6～C
14Alkaryl or aralkyl; Substituent position can be in the optional position among 2～7 of quinolyl, preferred 2 or 7.
Described semi-metallocene Compound C pMX
3In each symbol definition identical with catalyzer, can adopt the commercial goods or prepare with ordinary method.Its preparation method is: will have the compound of cyclopentadienyl skeleton and the salt that this compound is made in the strongly alkaline compound reaction earlier, again with this salt and transistion metal compound MX
4Reaction gets final product.
Olefine polymerizing process provided by the invention comprises that with catalyzer of the present invention be Primary Catalysts, is promotor with aikyiaiurnirsoxan beta, aluminum alkyls, alkyl aluminum halide or their mixture, makes C
2～C
14'alpha '-olefin monomers polymerization under polymerizing condition, during polymerization in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 10～5000: 1, preferred 50～2000: 1, more preferably 100～1000: 1.
As the aikyiaiurnirsoxan beta of promotor can be linear or the cyclic polymkeric substance, and preferred aikyiaiurnirsoxan beta is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide; The preferred trimethyl aluminium of aluminum alkyls, triethyl aluminum or triisobutyl aluminium, the preferred aluminium diethyl monochloride of alkyl aluminum halide.Highly preferred promotor is a methylaluminoxane.
Be used for polymeric 'alpha '-olefin monomers optimal ethylene, propylene, butylene, hexene, vinylbenzene or the mixture of the two arbitrarily between them.Polyolefin products such as polyethylene or polystyrene be can produce with catalyzer of the present invention, ethene and other alpha-olefin also can be produced, as the copolymerized product of propylene, butylene, hexene.Polymerizing condition is 0～150 ℃, 0.01～10MPa, and comparatively preferred condition is 20～100 ℃, 0.1～5.0MPa.
Polymerization technique can adopt solution polymerization, and as slurry polymerization, the solvent during polymerization can be selected organic solvents such as alkane, aromatic hydrocarbons or halogenated alkane for use.Also can adopt the gas phase bulk technique to produce olefin polymer.
Catalyzer of the present invention is a title complex of introducing monovalence bidentate oxine base and derivative ligand formation in transition metal half cyclopentadinyl compound, and this catalyzer is compared with the non-half metallocene with two oxine bases and derivative ligand has higher olefinic polyreaction activity.Compare with metallocene catalyst and can save the consumption of promotor methylaluminoxane greatly.The polymkeric substance that makes with catalyzer of the present invention has moderate molecular weight and narrow molecular weight distribution.
Further specify the present invention below by example, but the present invention is not limited to this.
Cp represents cyclopentadienyl in the example, and Ind represents indenyl.Preparation of catalysts all uses the Schlenk instrument to carry out under high pure nitrogen protection, and used organic solvent is new dry the mistake.
Example 1
Preparation (oxine base) (cyclopentadienyl) titanium dichloride [(C
9H
6NO) CpTiCl
2].
In 30 milliliters of toluene, add oxine (C
9H
7NO) (connection chemical reagent factory produces in Beijing) 2 mmoles and CpTiCl
3(Sweden, ACR S company produce) 2 mmoles stir, and add sodium amide (the sharp fine chemicals of Peking blue company limited produces) 1.2 grams (30 mmole), and 80 ℃ of back flow reaction 4 hours are cooled to room temperature.Filter, decompression concentrated filtrate down adds 5 milliliters of the new normal hexanes that steams to about 5 milliliters, filters, and the gained solid is washed twice, 30 ℃ of vacuum-drying with 10 ml n-hexanes and got 0.53 gram xanchromatic solid catalyst A:(C
9H
6NO) CpTiCl
2, productive rate is 81.0 heavy %.
The ultimate analysis value of catalyst A is (heavy %),
C：51.54??H：3.62??N：4.65??Ti：14.19
Example 2
Preparation (2-methyl-oxine base) (cyclopentadienyl) titanium dichloride [(C
10H
8NO) CpTiCl
2].
(1) preparation 2-methyl-oxine lithium salts (C
10H
9NO) Li
Get 3 mmole 2-methyl-oxine (Sweden, ACR S company produces), with 10 milliliters of exsiccant ether stirring and dissolving, splashing into concentration under 0 ℃ is 1.2 milliliters of (Sweden of hexane solution of 2.5M n-Butyl Lithium, ACR S company produces), generate white precipitate immediately, room temperature reaction 2 hours, milk sap is white in color.
(2) preparation catalyzer
CpTiCl with 3 mmoles
3The solution that forms with 10 milliliters of toluene is cooled to 0 ℃, splashes into the above-mentioned (C that makes
10H
9NO) Li white milk sap, solution becomes orange, stirring at room 4 hours.Filter, wash twice with 10 milliliters of toluene, refilter after gained filtrate is concentrated into about 5 milliliters, solid is 30 ℃ of vacuum-dryings, 0.77 restrain the yellow solid catalyst B: (C
10H
8NO) CpTiCl
2, productive rate is 72.0 heavy %.
The ultimate analysis value of catalyst B is (heavy %),
C：51.28??H：4.19??N：4.62??Ti：13.14
Example 3
Preparation (5-nitro-oxine base) (cyclopentadienyl) titanium dichloride [(C
9H
5N
2O
3) CpTiCl
2].
In 20 milliliters of methylene dichloride, add 5-nitro-oxine (C
9H
6N
2O
3) (Sweden, ACR S company produce) 5 mmoles and 5 mmole triethylamines (the sharp fine chemicals of Peking blue company limited), stir, splash into 5 mmole CpTiCl under 0 ℃
3With the solution that 20 milliliters of methylene dichloride form, solution becomes red-brown, and 25 ℃ were reacted 12 hours.Filter, the solvent in the filtrate is removed in decompression down, washes twice, 30 ℃ of vacuum-drying with 10 milliliters of ether again, gets the red solid catalyst C:(C of 1.80 grams
9H
5N
2O
3) CpTiCl
2, productive rate is 96.0 heavy %.
The ultimate analysis value of catalyzer C is (heavy %),
C：44.30??H：3.35??N：7.80??Ti：11.92
Example 4
Preparation (oxine base) (indenyl) titanium dichloride [(C
9H
6NO) (Ind) TiCl
2].
Prepare catalyzer D by example 1 method, different is with (Ind) TiCl
3(Sweden, ACR S company produces) replaced C pTiCl
3React, catalyst production is 78.3 heavy %.
The ultimate analysis value of catalyzer D is (heavy %),
C：57.69??H:4.12??N：4.18??Ti：11.89
Example 5
This examples preparation (2-methyl-oxine base) (cyclopentadienyl) zirconium dichloride [(C
10H
8NO) CpZrCl
2].
Method preparation by example 1 is tapered agent E, and different is to use CpZrCl
3(Sweden, ACR S company produces) replaced C pTiCl
3, 80 ℃ of back flow reaction 6 hours, ultimate yield are 64 heavy %.
The ultimate analysis value of catalyzer E is (heavy %),
C：47.14??H：3.94??N：4.11??Zr：22.84
Example 6
Preparation (oxine base) (tertiary butyl-cyclopentadienyl) titanium dichloride [(C
9H
6NO) (tBuCp) TiCl
2].
Method by example 1 prepares catalyzer F, and different is with (tertiary butyl-cyclopentadiene) titanous chloride (Sweden, ACR S company produces) replaced C pTiCl
3React, the productive rate of catalyzer F is 85.6 heavy %.
The ultimate analysis value of catalyzer F is (heavy %),
C：55.86??H：4.97??N：3.24??Ti：11.93
Example 7
Preparation (2-methyl-oxine base) (cyclopentadienyl) zirconium dichloride [(C
10H
8NO) CpZrCl
2].
Method by example 2 prepares catalyzer G, and different is (1) step to replace butyllithium with sodium hydride, and (2) use CpZrCl in the step
3Replaced C pTiCl
3, the productive rate of catalyzer G is 76.5 heavy %.
The ultimate analysis value of catalyzer G is (heavy %),
C：46.22??H：3.12???N：3.34??Zr：22.78
Comparative Examples 1
Preparation two (2-methyl-oxine base) zirconium dichloride [(C
10H
8NO)
2ZrC]
2] catalyzer.
Under the room temperature, in 50 milliliters of ether, add 2.5 gram ZrCl
4(10.7 mmole) and 3.6 gram 2-methyl-oxine base lithiums (20.2 mmole), stirring reaction 2 days makes yellow solid catalyzer H except that desolvating under the vacuum, and productive rate is 83.6 heavy %.
The ultimate analysis value of catalyzer H is (heavy %),
C：49.88??H：4.11???N：5.31??Zr：18.56
Example 8～15
Following example carries out the normal pressure ethylene polymerization, the preparation polyethylene.
The toluene solution of used methylaluminoxane (MAO) is produced by U.S. Albemarle company in the example, and concentration is 10 heavy %.
With 250 milliliters of reactors that have a stirring with nitrogen replacement three times, again with twice of ethene displacement, feed ethylene gas, add 50 milliliters of exsiccant toluene, the toluene solution that adds 2 milliliters of MAO, stir, catalyzer is mixed the back add reactor with the toluene solution of 1.5 milliliters of MAO, catalyst levels is 1.0 * 10
-5Mole, the Al/M ratio is about 500: 1,30 ℃ of isothermal reactions 0.5 hour.After stopping to stir,, use the small amount of hydrochloric acid termination reaction more earlier with 20 milliliters of ethanol.Reactant continue was stirred 1 hour, filters, and use ethanol, water, washing with alcohol successively, 60 ℃ of vacuum-drying 4 hours, polyethylene.Each example is used for the catalyzer and the activity of polyreaction, and the molecular weight Mw and the molecular weight distribution of resulting polymers see Table 1.Polymkeric substance weight-average molecular weight and molecular weight distribution are measured with gel permeation chromatography (GPC), and used instrument is PL-GPC200 (production of Britain Polymer Laboratories company).
Example 16
This example carries out the reaction of normal pressure styrene polymerization with catalyzer of the present invention, the preparation syndiotactic polystyrene.
With SILVER REAGENT vinylbenzene, underpressure distillation again after dewatering with hydrolith, the lucifuge cryopreservation is stand-by.Under nitrogen protection, 50 milliliters of reaction flasks are placed oil bath, use magnetic stirrer.In reaction flask, add the toluene solution of 20 milliliters of toluene, 7 milliliters of MAO, the catalyst A of 0.01 gram, 10 milliliters of vinylbenzene, the Al/Ti mol ratio is 500: 1 in the reaction system, react after 1 hour, stop with acidifying ethanol, polymkeric substance water and ethanol wash respectively three times, 70 ℃ of vacuum-dryings, obtain polystyrene, activity of such catalysts is 7.4 * 10
5Gram PS/ mole Ti hour.Polystyrene molecular weight M
wBe 8.80 * 10
4, molecular weight distribution M
w/ M
nBe 5.32, a normality is 98.7%, fusing point T
mIt is 270.6 ℃.
The M of polystyrene
wAnd M
w/ M
nIs that solvent is measured (waters150C chromatographic instrument) with GPC at 135 ℃ with the orthodichlorobenzene.Normality is by continuous extraction after three hours in ebullient acetone between polystyrene, decided by the amount of insolubles.Table 1
| Instance number | The catalyzer numbering | The catalyst molecule formula | Active (during gram PE/ mole M) | ??????Mw ????(×10 4) | ??Mw/Mn |
| ???8 | ???A | ????(C 9H 6NO)CpTiCl 2 | ????1.3×10 5 | ?????25.6 | ???2.4 |
| ???9 | ???B | ????(C 10H 8NO)CpTiCl 2 | ????2.2×10 5 | ?????21.4 | ???2.4 |
| ???10 | ???C | ????(C 9H 5N 2O 3)CpTiCl 2 | ????0.4×10 5 | ??????- | ????- |
| ???11 | ???D | ???(C 9H 6NO)(Ind)TiCl 2 | ????2.6×10 5 | ?????32.5 | ???2.1 |
| ???12 | ???E | ????(C 10H 8NO)CpZrCl 2 | ????1.6×10 5 | ?????21.4 | ???2.5 |
| ???13 | ???F | ??(C 9H 6NO)(tBuCp)TiCl 2 | ????1.5×10 5 | ??????- | ????- |
| ???14 | ???G | ????(C 10H 8NO)CpZrCl 2 | ????1.8×10 5 | ??????- | ????- |
| ???15 | ???H | ????(C 10H 8NO) 2ZrCl 2 | ????3.9×10 3 | ??????- | ????- |
*M represents Ti or Zr in table 1 and the example 8～15.
Claims (16)
1, a kind of catalyst for polymerizing semi-metallocene with olefin, the general expression that has is: [O, N] CpMX
2, wherein [O, N] is the group of oxine derivative formation, and Cp is the group that contains cyclopentadienyl skeleton, and M is selected from IVB family metal, and X is identical or different group, is selected from halogen, C
1～C
18Alkyl, C
1～C
18Alkoxyl group or alkaryl.
2,, it is characterized in that catalyzer has following structure expression according to the described catalyzer of claim 1:
In the formula, Cp is single the replacement or polysubstituted cyclopentadienyl group, and substituting group is selected from hydrogen, C respectively
1～C
18Alkyl, C
1～C
18Perfluoroalkyl, C
6～C
18Alkaryl or aralkyl, wherein two of the polysubstituted cyclopentadiene group adjacent substituting groups can be interconnected to condensed ring;
R is selected from hydrogen, C
1～C
6Alkyl, C
1～C
6Perfluoroalkyl, nitro, C
6～C
14Alkaryl or aralkyl;
M is selected from titanium or zirconium;
X is selected from chlorine, benzyl, C
1～C
12Alkyl or alkoxyl group.
3,, it is characterized in that R is selected from hydrogen, C according to the described catalyzer of claim 2
1～C
3Alkyl, C
1～C
3Alkoxyl group or nitro; Cp is selected from cyclopentadienyl, indenyl, fluorenyl, or C
1～C
6The alkyl list replaces or polysubstituted above-mentioned group, and X is a chlorine.
4, according to the described catalyzer of claim 3, it is characterized in that R is hydrogen, methyl or nitro, Cp is cyclopentadienyl, C
1～C
4The mono-substituted cyclopentadienyl of alkyl, or indenyl.
5, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) in ether solvent, making strongly alkaline compound and general formula is H[O, N] the oxine analog derivative be 1: 1 ratio stirring reaction in molar ratio, remove and desolvate, obtain oxine base salt,
(2) in organic solvent, make oxine base salt and semi-metallocene Compound C pMX
3Mol ratio such as press and under reflux temperature, react, filter, gained filtrate is concentrated into solid separate out, collect solid and obtain catalyzer [O, N] CpMX
2
6, in accordance with the method for claim 5, it is characterized in that the strongly alkaline compound described in (1) is selected from basic metal, alkalimetal hydride, alkali metal alkyl compound, alkali metal amino compound or alkyl halide magnesium.
7, in accordance with the method for claim 6, it is characterized in that described strongly alkaline compound is selected from lithium, sodium, potassium, sodium hydride, potassium hydride KH, butyllithium, sodium amide, methylmagnesium-chloride or benzyl magnesium bromide.
8, in accordance with the method for claim 5, it is characterized in that the ether solvent described in (1) is selected from ether or tetrahydrofuran (THF), (2) step, described organic solvent was selected from ether, tetrahydrofuran (THF), methylene dichloride or toluene.
9, the described Preparation of catalysts method of a kind of claim 1, comprise with etc. the general formula of mol ratio be H[O, N] oxine analog derivative and semi-metallocene Compound C pMX
3Be dissolved in the organic solvent, add excessive strongly alkaline compound reaction again, filter, gained filtrate is concentrated into solid separates out, collect solid and promptly get catalyzer [O, N] CpMX
2
10, in accordance with the method for claim 9, it is characterized in that organic solvent is selected from ether, tetrahydrofuran (THF), methylene dichloride or toluene.
11, in accordance with the method for claim 9, it is characterized in that described strongly alkaline compound is selected from lithium, sodium, potassium, sodium hydride, potassium hydride KH, butyllithium, sodium amide, methylmagnesium-chloride or benzyl magnesium bromide.
12, according to claim 9 or 11 described methods, the mol ratio that it is characterized in that described strongly alkaline compound and oxine analog derivative is 1.5～50: 1.
13, the described Preparation of catalysts method of a kind of claim 1 is included in the organic solvent, and the general formula of mol ratios such as adding is H[O, N] oxine analog derivative and semi-metallocene Compound C pMX
3Stir, add and H[O N again] tertiary amine of equimolar amount, fully stir, solids removed by filtration is concentrated into solid with gained filtrate and separates out, and collects solid and promptly gets catalyzer [O, N] CpMX
2
14, in accordance with the method for claim 13, it is characterized in that described tertiary amine is a triethylamine, organic solvent is ether, tetrahydrofuran (THF), methylene dichloride or toluene.
15, a kind of olefine polymerizing process comprises that with the described catalyzer of claim 1 be Primary Catalysts, is promotor with aikyiaiurnirsoxan beta, aluminum alkyls, alkyl aluminum halide or their mixture, makes C
2～C
14'alpha '-olefin monomers polymerization under polymerizing condition, during polymerization in the promotor in aluminium and the Primary Catalysts mol ratio of transition metal be 10～5000: 1.
16, in accordance with the method for claim 15, it is characterized in that described aikyiaiurnirsoxan beta is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide; Aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium or aluminium diethyl monochloride, and the mole of aluminium and transition metal is 50～2000: 1 during polymerization.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374204C (en) * | 2005-04-18 | 2008-03-12 | 中国科学院成都有机化学有限公司 | Catalyst system for synthesis of diphenyl carbonate by ester exchange reaction |
| CN111747995A (en) * | 2020-07-30 | 2020-10-09 | 上海化工研究院有限公司 | Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof |
| CN112646066A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Catalytic polymerization system and polymerization method for styrene polymerization and obtained polystyrene |
| CN112646065A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Novel single metallocene transition metal compound, catalyst composition containing same and application |
| CN112661880A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN114702531A (en) * | 2021-01-01 | 2022-07-05 | 中国石油化工股份有限公司 | Metallocene, catalyst containing same, synthesis and application thereof |
| WO2024078525A1 (en) * | 2022-10-11 | 2024-04-18 | 中国石油化工股份有限公司 | Phosphine-phenol half-metallocene complex, and preparation method therefor and use thereof |
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- 2000-11-02 CN CN 00130260 patent/CN1132856C/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374204C (en) * | 2005-04-18 | 2008-03-12 | 中国科学院成都有机化学有限公司 | Catalyst system for synthesis of diphenyl carbonate by ester exchange reaction |
| CN112646066A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Catalytic polymerization system and polymerization method for styrene polymerization and obtained polystyrene |
| CN112646065A (en) * | 2019-10-11 | 2021-04-13 | 中国石油化工股份有限公司 | Novel single metallocene transition metal compound, catalyst composition containing same and application |
| CN112646065B (en) * | 2019-10-11 | 2022-11-18 | 中国石油化工股份有限公司 | Novel single metallocene transition metal compound, catalyst composition containing same and application |
| CN112661880A (en) * | 2019-10-16 | 2021-04-16 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN112661880B (en) * | 2019-10-16 | 2023-12-08 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and preparation method and application thereof |
| CN111747995A (en) * | 2020-07-30 | 2020-10-09 | 上海化工研究院有限公司 | Nitrogen-containing aryloxy cyclopentadienyl titanium compound and preparation method and application thereof |
| CN114702531A (en) * | 2021-01-01 | 2022-07-05 | 中国石油化工股份有限公司 | Metallocene, catalyst containing same, synthesis and application thereof |
| WO2024078525A1 (en) * | 2022-10-11 | 2024-04-18 | 中国石油化工股份有限公司 | Phosphine-phenol half-metallocene complex, and preparation method therefor and use thereof |
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| CN1132856C (en) | 2003-12-31 |
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