CN1966536A - Spherical carrier loaded late transition metal catalyst and its preparing process - Google Patents
Spherical carrier loaded late transition metal catalyst and its preparing process Download PDFInfo
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Abstract
This invention relates to carried spherical transition metal catalysts and their production method, involving carried post-transition metal catalysts, which includes montmorillonite, magnesium chloride alcohol complex and post-transition metal compound catalyst, wherein the late transition metal compound catalyst loads montmorillonite and magnesium chloride alcohol complexes. The catalysts are used for the ethylene polymerization or copolymerization catalyst composition. The said method includes mixing spherical carrier with a diluent, adding hexane solution of alkyl aluminum, filtering the liquid, washing with hexane to obtain the solid, preparing toluene solution of the solid, adding toluene solution of post-transition metal complexes, filtering liquid, and washing the solid with toluene and hexane. The invention avoids the expensive prices of methylaluminoxane, and has high catalytic activity for ethylene polymerization or copolymerization. The polymers prepared have good particle morphology, and spherical polymer can be obtained with high packing density.
Description
Technical field
The present invention relates to a kind of carried post-transition metal series catalysts, particularly relate to the high-efficiency polyethylene post-transition metal catalyst of the spherical mixed carrier of a kind of polynite/magnesium dichloride alcohol adduct, and preparation method thereof.
Background technology
In the evolution of olefin polymerization catalysis, after metallocene catalyst, the late transition metal catalyst that middle nineteen nineties is found has obtained great development and concern.1998, Englishize scholar Gibson under Americanized scholar Brookhart under E.I.Du Pont Company supports and BP company support has independently found the novel N of a class separately, N, N-tridentate ligand iron, cobalt complex, this class complex compound combines with methylaluminoxane (MAO) has very high catalytic activity to the ethene polymerization in homogeneous phase, quite active with the most active Ziegler-Natta catalyst or metallocene catalyst, in addition higher, and this is first iron complex to be used for catalysis in olefine polymerization.Late transition metal catalyst belongs to the catalyst system at single-activity center, and its performance can compare favourably with metallocene catalyst in all many-sides, has that polymer architecture is controlled, polymericular weight and an adjustable advantage of the degree of branching.Particularly Fe diimine pyridine catalyst system (WO9827124, WO9830612) vinyl polymerization is active high, has a good application prospect.
At present, the characteristics of Fe-series catalyst are affirmed by many achievements in research, but also there are some significant disadvantages in they, as: bimolecular easily takes place and associates and inactivation in the activity of such catalysts center, in polymerization process, need a large amount of methylaluminoxane (MAO) or polyfluoro boron compound as promotor, and the two synthetic cost makes Application of Catalyst be subjected to certain restriction all than higher; In addition, olefinic polymerization is to carry out in homogeneous phase, and the polymer beads form that obtains is bad, can't use on widely used slurry process or gas phase polymerization technology.
The main path that addresses these problems is exactly the loadization of catalyzer, can improve the form of polymkeric substance after the load, improves the bulk density of polymkeric substance; Reduce the consumption of promotor significantly, reduce the production cost of polyolefin products, improve the added value of polyolefin products.
At present, in the load research of late transition metal catalyst, SiO2, MgCl2, Al2O3 are that the report of carrier is more, the silica gel that main employing has good particle form is carrier, as the silica gel activating Fe series catalysts of aluminum alkyls that used a kind of load among the WO01/32723, can use aluminum alkyls to be promotor, its catalytic activity is higher; On magnesium chloride support, aspect the loaded late transition metal catalyst, study fewerly.CN1091748 discloses the late transition metal catalyst and the method for making thereof of a kind of spherical magnesium dichloride alcohol adduct load, and promotor mainly adopts aluminum alkyls, and catalytic activity is higher during catalyzed ethylene polymerization.But this patent does not relate to the Preparation of catalysts and the application of the ball type carrier that contains polynite.
Summary of the invention
The object of the invention is to provide a kind of catalyst component that is used for vinyl polymerization or copolymerization, this catalyst activity component is a loaded late transition metal title complex on magnesium chloride alcohol adduct and polynite mixing ball type carrier, need only use aluminum alkyls as promotor, saved expensive methylaluminoxane (MAO), after it is used for vinyl polymerization or copolymerization, the catalytic activity height, the resulting polymers particle form is good, can obtain the spherical polymer resin, have higher tap density.The present invention also provides above-mentioned Preparation of catalysts method.
The objective of the invention is to be achieved through the following technical solutions:
Spherical carrier loaded late transition metal catalyst, comprise polynite, magnesium chloride alcohol adduct and rear transition metal compound catalyst, it is by forming on load polynite of rear transition metal compound catalyst and the magnesium chloride alcohol adduct mixing ball type carrier, wherein the content of magnesium dichloride is 50～100 heavy %, and the content of transition metal is 0.1～10 heavy %.
Polynite in the catalyst component of the present invention is for being sodium-based montmorillonite, K-polynite, Ca-polynite, Li-polynite, organo montmorillonite, hcl acidifying organo montmorillonite, sulfuric acid acidation organo montmorillonite, hcl acidifying sodium-based montmorillonite, sulfuric acid acidation sodium-based montmorillonite.
Rear transition metal compound catalyst component in the catalyst component of the present invention be by:
A kind of late transition metal complex by polynite and the load of magnesium chloride alcohol adduct mixed carrier, its structure is shown in general formula 1 formula:
Wherein, R1-R6 respectively is identical alkyl or different alkyl and hydrogen atoms; M is transition-metal Fe or Co; X is a halogen; Synthetic method is: under the condition of standard anhydrous and oxygen-free, with 2, the 6-diacetyl pyridine joins in the anhydrous methanol with the aniline that has different substituents, drip a spot of Glacial acetic acid as catalyzer, 0～80 ℃ of reaction 1～72 hour, left standstill 1～48 hour at subzero 40 ℃～0 ℃, part is separated out, with anhydrous methanol washing, drying; 2, the mol ratio of 6-diacetyl pyridine and substituted aniline is: 1/1.0～1/10; Under the condition of standard anhydrous and oxygen-free, with organic solvents such as tetrahydrofuran (THF) or methyl alcohol is solvent, the part that makes and the moisture or anhydrous halide of FeCl24H2O or other Fe or Co were at room temperature reacted 1～72 hour, with anhydrous diethyl ether or heptane wash, filtration, the dry a component that gets, wherein part and halogenide mol ratio are: 0.5/1～5/1;
Alkylaluminium cpd; Be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, be preferably triethyl aluminum, three hexyl aluminium; Amount ratio is 100～5000 with the Al/M molar ratio computing between B component and the component A, is preferably 150～2000.
Among the catalyst component A of the present invention, the content of described M in catalyzer is preferably 0.1～5% (weight).
Catalyst component sodium-based montmorillonite of the present invention, its preparation method is: calcium-base montmorillonite is mixed being made into water slurry with distilled water, through 3～4 stirrings, sedimentation, the each stirring 10～20 minutes, sedimentation 0.5～10 hour is extracted upper strata suspension and is added the trisodium phosphate that is equivalent to 0.1～1 times of calcium-base montmorillonite weight, stirring, sedimentation, the Sodium Fluoride that adds 0.1～1 times of calcium-base montmorillonite weight again, stirring, sedimentation both get.The preparation method of described organo montmorillonite is: sodium-based montmorillonite is added form suspension in the distilled water, add the intercalator that is dissolved in the dehydrated alcohol, intercalator and sodium-based montmorillonite mass ratio are 0.05/1～1/1,25～80 ℃ of isothermal reactions 0.5～48 hour, product is washed till neutrality with distilled water, suction filtration, product is 40～120 ℃ of oven dry down.
The complex compound of the magnesium dichloride alcohol in the catalyst component of the present invention, wherein alcohol is the low-carbon alcohol of C1-C4, preferred alcohol.
The spherical carrier loaded late transition metal catalyst making method, the catalyst spherical carrier of catalyst component of the present invention, the alcohol adduct of magnesium chloride is the low-carbon alcohol of C1-C4 and anhydrous magnesium dichloride to be mixed under the low temperature react in dispersion agent, magnesium dichloride is 1: 2.0～4.5 with the mol ratio of alcohol, after adding different polynites, at 100～140 ℃ behind heating and melting, under high-speed stirring through inert solvent in-60～0 ℃ of following quick cooling, obtain containing the spheroidal particle carrier of polynite/magnesium dichloride alcohol adduct.After washing, drying, promptly obtain magnesium chloride alcohol adduct spheroidal particle.Dispersion agent employing varsol such as kerosene, paraffin oil, vaseline oil, white oil etc. also add some tensio-active agents or silicoorganic compound.Inert solvent adopts varsol kerosene, hexane, pentane, heptane, benzene etc.
Spherical carrier loaded late transition metal catalyst making method of the present invention, be used for vinyl polymerization or copolymerization catalyst component, wherein the preparation method is as follows: with ball type carrier and mixing diluents, slurries are made in stirring, the hexane solution that slowly adds aluminum alkyls under-60 ℃～room temperature, and under this temperature, reacted 1～48 hour, filter out liquid, the solids that obtains with hexane wash.Again this solids is made the solid slurry of toluene, at 20～100 ℃ of toluene solutions that add late transition metal complex down, reacted 0.5～6 hour, after stopping to stir liquid is leached, with toluene, hexane wash solids, obtain containing the catalyst component of late transition metal complex.
Spherical carrier loaded late transition metal catalyst making method of the present invention, be used for vinyl polymerization or the copolymerization catalyst method for preparing ingredients thereof is: after ball type carrier and mixing diluents cooling, the hexane solution that adds aluminum alkyls, wherein said aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, be preferably triethyl aluminum, the weight content of aluminium in catalyzer is 0.1～15%.
Spherical carrier loaded late transition metal catalyst making method of the present invention in the catalyst component, is used for the preparation method of vinyl polymerization or copolymerization catalyst component, and used thinner is hexane, pentane, heptane, benzene, toluene.
The catalyzer that the present invention is used for vinyl polymerization or copolymerization is applicable to slurry polymerization and vapour phase polymerization mode, can be used for the equal polymerization of ethene, also can be used for the copolymerization of ethene and other alpha-olefin, comonomer can be propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene etc.
Advantage of the present invention and effect are:
Polymerization or copolymerization that catalyzer of the present invention is used for ethene compared with prior art have following tangible advantage: the late transition metal complex catalyst that the present invention adopts simple chemical process modified montmorillonoid and magnesium compound to prepare the ball type carrier back loading is used for vinyl polymerization or copolymerization has the catalytic activity height, the polymer beads form is good, is spheroidal particle; Go for vapour phase polymerization and slurry polymerization processes; Use aluminum alkyls to replace expensive MAO as promotor in polymerization process, catalyzer has very high activity, greatly reduces the cost of the synthetic and polyreaction of catalyzer.Synthetic and polymerization technique approaches to be used at present the commercial catalysts of manufacture of polyolefins, easier realization industrial production.
Description of drawings
Fig. 1 is one of spherical polyethylene polarisation photo figure of the present invention;
Fig. 2 is two of spherical polyethylene polarisation photo figure of the present invention.
Embodiment
Further specify the present invention with reference to the accompanying drawings in conjunction with the embodiments.
Accompanying drawing 1,2 is spherical polyethylene polarisation photo (possibility is unintelligible behind the photo prints, but does not influence the understanding to the present techniques scheme).
Scope of the present invention is not limited to following these embodiment.
The all synthetic and polyreactions of the present invention all are to carry out under the reaction conditions of anhydrous and oxygen-free.
Wherein the slurry polymerization of typical ethene carries out according to method described below:
The ball type carrier catalyst levels is 1～1000 milligram, and the Al/Fe mol ratio is 10～2000; Can carry out the slurry polymerization of ethene in organic solvents such as hexane, heptane, octane, decane, benzene, toluene, polymeric reaction temperature is subzero 20～100 ℃, and ethylene pressure is 0.1～20Mpa.Described promotor triethyl aluminum also can be trimethyl aluminium, triisobutyl aluminium, aluminium diethyl monochloride.
For example typical polymerization is: in 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 500 milliliters of hexane solvents then, with still temperature rise to 30 ℃, under stirring fast, flow down at hexane and to add promotor triethyl aluminum and supported catalysts successively, add when hexane is 1000 milliliters and stop to feed in raw material.Feed ethene, pressure is risen to and keeps 1.0MPa, after polyreaction is carried out 20 minutes～1 hour, stop to feed ethylene gas and end polyreaction, open blow-off valve, cooling, discharging.With polymer filtration, with after 95% washing with alcohol in 60 ℃ of following vacuum-dryings.
The preparation method of polynite among the embodiment:
Be used for that the sodium polynite prepares according to the methods below in the component of catalyzer of embodiment: the calcium-base montmorillonite that takes by weighing 400g, adding 1600ml distilled water is modulated into 20% water slurry, carry out stirring the first time (about 20 minutes), leave standstill and carry out the stirring second time (about 10 minutes) after 8～10 hours, stop to stir, after sedimentation is left standstill 10 hours, stir (about 10 minutes) for the third time, after leaving standstill 2 hours, extract the top aaerosol solution, add the water dilution of 1 times of amount.Fully stir about is 20 minutes, leaves standstill about 4 hours.Extract top suspension, add the 20g sodium pyrosulfate, stir about 20 minutes, standing sedimentation is 12 hours again, extracts top suspension, is the calcium-base montmorillonite suspension of purification.Add the water dilution of 2 times of amounts in the calcium-base montmorillonite suspension of above-mentioned purification, add the 16g Sodium Fluoride again, stir about 20 minutes left standstill 24 hours, extracted top suspension and was sodium-based montmorillonite 80 ℃ of following dryings.The component organo montmorillonite that is used for the catalyzer of embodiment prepares according to the methods below: in the 1000ml there-necked flask, add 600ml distilled water, take by weighing the 30g sodium-based montmorillonite and slowly add while stirring in the there-necked flask, heating.Take by weighing the 10g hexadecyl trimethyl ammonium bromide, add the 0.2g dehydrated alcohol, heating for dissolving.When being warmed up to 70 ℃ of left and right sides, polynite distilled water suspension adds 3g intercalator solution.Stir about is 2 minutes fast, recovers original stirring velocity.Simultaneously temperature was risen to 80 ℃ and isothermal reaction about two hours.Product is washed with distilled water to neutrality, and suction filtration 80 ℃ of oven dry down, is pulverized, and sieves, i.e. organo montmorillonite.
The Fe catalyzer is synthetic among the embodiment: in the 100ml there-necked flask, add 0.506 gram 2 successively, and the 6-diacetyl pyridine, the 50ml anhydrous methanol, 2.5ml2,6-diisopropyl aniline and 9ml Glacial acetic acid are heated to 70 ℃ of constant temperature, react 8 hours.Brown-red solution is left standstill, and cool to room temperature is put into low temperature thermostat bath then, subzero 30 ℃ of coolings 10 hours, the faint yellow solid powder of separating out is washed to methyl alcohol repeatedly colourless with anhydrous methanol, with nitrogen resulting product is dried up.(for ligand 1) adds 0.25 gram ligand 1,95mgFeCl24H2O and 10ml tetrahydrofuran (THF) successively in the 100ml there-necked flask.At room temperature reacted 12 hours.Reaction after finishing is left standstill product, adds the 30ml anhydrous diethyl ether product is separated out, and with ether the product that obtains is washed repeatedly, dry up with nitrogen, obtain the blue solid powder, be 2, two [1-(2, the 6-diisopropyl aniline)] the ethylpyridine ferrous chloride of 6-abbreviate the Fe catalyzer as.
Embodiment 1
(1) ball type carrier is synthetic:
Reflux exchanger, mechanical stirrer and thermometer are being housed, in 500 milliliters of glass reactors after nitrogen is fully replaced, add 26.2 milliliters of dehydrated alcohols, Magnesium Chloride Anhydrous 14.25 grams, add under 40 milliliters of liquid paraffin, 40 milliliters of stirrings of silicone oil low-temp reaction after 0.5～3 hour, add organo montmorillonite 0.75 gram, keep 120 ℃ of temperature certain hours.In another volume is 250 milliliters the reaction flask that has agitator, the silicone oil that adds 80 milliliters of liquid paraffin and equal volume in advance, be preheating to 120 ℃, the mixture of aforementioned preparation is pressed into rapidly in first reactor, keep under 120 ℃ of temperature, with 1500 rev/mins of high-speed stirring of rotating speed, stir down material to be transferred to and add 600 milliliters of hexanes in advance and be cooled in-40 ℃ the 3rd reactor, finish until the material transfer, outlet temperature is no more than 0 ℃, suction filtration, use hexane wash, flush away whiteruss and white oil are after vacuum-drying obtains spherical mixed carrier particulate.
(2) preparation of supported catalysts:
Under nitrogen protection, join in 100 milliliters of there-necked flasks making ball type carrier in 2 grams (1), add 20 milliliters of hexanes, stir and make slurries, room temperature slowly added 10 milliliter of 1.33 mol in one hour triethyl aluminum hexane solution reacted 4 hours.Leach liquid then, solid is with twice of 20 milliliters of hexane wash.Again solid is stirred with 15 milliliters of toluene and make slurries, under 20 ℃, slowly drip 10 milliliters of Fe catalyzer toluene solutions that contain 20 milligrams, stirring reaction 4 hours by gained in (2).Reaction is left standstill after finishing, and leaches liquid, with 20 milliliters of toluene wash twice, then, with 20 milliliters of hexane wash twice, solid is dried up with nitrogen, obtains having the ball type carrier Fe series catalysts of good flowability.
(3) polymerization experiment: add the supported catalysts that contains 19.5 μ molFe, Al/Fe mol ratio 500, polymerization time 1 hour, catalytic activity is 6.1 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 2
With embodiment 1.Different is 24.8 milliliters of (1) middle dehydrated alcohols, and Magnesium Chloride Anhydrous 13.51 grams add the supported catalysts that contains 24.3 μ molFe, polymerization time 30 minutes in the 1.5 gram organo montmorillonites (3).
Catalytic activity is 3.3 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 3
With embodiment 1.Different is 23.5 milliliters of (1) middle dehydrated alcohols, and Magnesium Chloride Anhydrous 12.76 grams add the supported catalysts that contains 16.3 μ molFe, polymerization time 20 minutes, 30 ℃ of polymerization temperatures in the 2.25 gram organo montmorillonites (3).
Catalytic activity is 2.8 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 4
With embodiment 1.Different is 26.4 milliliters of (1) middle dehydrated alcohols, and Magnesium Chloride Anhydrous 14.3 grams add the supported catalysts that contains 15.34 μ molFe, polymerization time 10 minutes in the 0.753 gram sodium polynite (3).
Catalytic activity is 6.1 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 5
With embodiment 1.Different is 24.89 milliliters of (1) middle dehydrated alcohols, and Magnesium Chloride Anhydrous 13.52 grams add the supported catalysts that contains 15.87 μ molFe, polymerization time 20 minutes in the 1.54 gram sodium polynites (3).
Catalytic activity is 2.2 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 6
With embodiment 1.Different is 23.36 milliliters of (1) middle dehydrated alcohols, and Magnesium Chloride Anhydrous 12.68 grams add the supported catalysts that contains 15.87 μ molFe, polymerization time 20 minutes in the 2.246 gram sodium polynites (3).
Catalytic activity is 2.2 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 7
With embodiment 3.Different is to add the supported catalysts that contains 33.11 μ molFe, polymerization time 30 minutes in (3).And 40 ℃ of polymerization temperatures.
Catalytic activity is 7.1 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Embodiment 8
With embodiment 3.Different is to add the supported catalysts that contains 23.83 μ molFe, polymerization time 30 minutes in (3).And polymerization temperature is 21.5 ℃.
Catalytic activity is 2.21 * 106gPE/molFeh.It is spherical in shape by the electron microscopic observation resin particle that polymer morphology becomes.
Claims (9)
1. spherical carrier loaded late transition metal catalyst, it is characterized in that comprising polynite, magnesium chloride alcohol adduct and rear transition metal compound catalyst, it is by forming on load polynite of rear transition metal compound catalyst and the magnesium chloride alcohol adduct mixing ball type carrier, wherein the content of magnesium chloride alcohol adduct is 50～100 heavy %, and the content of transition metal is 0.1～10 heavy %.
2. spherical carrier loaded late transition metal catalyst according to claim 1 is characterized in that described polynite is sodium-based montmorillonite, K-polynite, Ca-polynite, Li-polynite, organo montmorillonite, hcl acidifying organo montmorillonite, sulfuric acid acidation organo montmorillonite, hcl acidifying sodium-based montmorillonite, sulfuric acid acidation sodium-based montmorillonite.
3. spherical carrier loaded late transition metal catalyst according to claim 1 is characterized in that described rear transition metal compound catalyst component is:
Mix spherical carrier loaded late transition metal complex by polynite and magnesium chloride alcohol adduct, its structure is shown in general formula 1 formula:
Wherein, R
1-R
6Respectively be identical alkyl or different alkyl and hydrogen atoms; M is transition-metal Fe or Co; X is a halogen;
Alkylaluminium cpd, be trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, be preferably triethyl aluminum, three hexyl aluminium; Amount ratio is 100～5000 with the Al/M molar ratio computing between B component and the component A, is preferably 150～2000.
4. spherical carrier loaded late transition metal catalyst according to claim 1 is characterized in that among the described component A, and the content of M in catalyzer is preferably 0.1～5 heavy %.
5. spherical carrier loaded late transition metal catalyst according to claim 1 is characterized in that described magnesium chloride alcohol adduct, and wherein alcohol is the low-carbon alcohol of C1-C4, preferred alcohol.
6. the spherical carrier loaded late transition metal catalyst making method is characterized in that its catalyst spherical carrier, and the preparation method comprises the steps: under the condition of standard anhydrous and oxygen-free, with C
1-C
4Low-carbon alcohol mix in dispersion agent with anhydrous magnesium dichloride, magnesium dichloride is 1: 2.0～4.5 with the mol ratio of alcohol, low temperature adds different polynites behind the reaction certain hour down, heat up after 100～140 ℃ of fusions, under high-speed stirring, use inert solvent in-60～0 ℃ of following quick cooling, after washing, drying, obtain containing the spheroidal particle carrier of polynite/magnesium dichloride alcohol adduct; Dispersion agent employing varsol such as kerosene, paraffin oil, vaseline oil, white oil etc. also add some tensio-active agents or silicoorganic compound; Inert solvent adopts varsol kerosene, hexane, pentane, heptane, benzene.
7. spherical carrier loaded late transition metal catalyst making method according to claim 6, it is characterized in that being used for vinyl polymerization or copolymerization catalyst component, its preparation method is as follows: with ball type carrier and mixing diluents, make slurries, the hexane solution that slowly adds aluminum alkyls under-60 ℃～room temperature, and under this temperature, reacted 2～6 hours, filter out liquid, the solid that obtains with hexane wash, again this solid is made toluene slurry, at 30～100 ℃ of toluene solutions that add late transition metal complex down, reacted 0.5～6 hour, after stopping to stir liquid is leached, use toluene, the hexane wash solid obtains containing the catalyst component of late transition metal complex.
8. spherical carrier loaded late transition metal catalyst making method according to claim 6, it is characterized in that, after ball type carrier and mixing diluents cooling, the hexane solution that adds aluminum alkyls, wherein said aluminum alkyls is trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, be preferably triethyl aluminum, the weight content of aluminium in catalyzer is 0.1～15%.
9. spherical carrier loaded late transition metal catalyst making method according to claim 6 is characterized in that, is used for the preparation method of vinyl polymerization or copolymerization catalyst component A, and used thinner is hexane, pentane, heptane, benzene, toluene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516424A (en) * | 2011-12-09 | 2012-06-27 | 沈阳工业大学 | Tetradentate titanium complex, composite carrier loaded tetradentate titanium catalyst, its preparation method and its application |
| CN108034014A (en) * | 2017-12-27 | 2018-05-15 | 安徽工业大学 | A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst |
| CN109535290A (en) * | 2018-11-26 | 2019-03-29 | 上海化工研究院有限公司 | It is suitble to the catalyst and its preparation method and application of production ultra-fine grain diameter polyolefin |
| CN112898459A (en) * | 2019-12-03 | 2021-06-04 | 中国石油天然气股份有限公司 | Preparation method of spherical modified montmorillonite and preparation method of spherical polyolefin catalyst |
-
2006
- 2006-11-10 CN CN 200610134241 patent/CN1966536A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516424A (en) * | 2011-12-09 | 2012-06-27 | 沈阳工业大学 | Tetradentate titanium complex, composite carrier loaded tetradentate titanium catalyst, its preparation method and its application |
| CN108034014A (en) * | 2017-12-27 | 2018-05-15 | 安徽工业大学 | A kind of preparation method of transition metal dichalcogenide/magnesium chloride load catalyst |
| CN109535290A (en) * | 2018-11-26 | 2019-03-29 | 上海化工研究院有限公司 | It is suitble to the catalyst and its preparation method and application of production ultra-fine grain diameter polyolefin |
| CN112898459A (en) * | 2019-12-03 | 2021-06-04 | 中国石油天然气股份有限公司 | Preparation method of spherical modified montmorillonite and preparation method of spherical polyolefin catalyst |
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