CN1282671C - Magnesium compound loaded transition metal catalyst component, and its preparing method and use - Google Patents
Magnesium compound loaded transition metal catalyst component, and its preparing method and use Download PDFInfo
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- CN1282671C CN1282671C CN 03153153 CN03153153A CN1282671C CN 1282671 C CN1282671 C CN 1282671C CN 03153153 CN03153153 CN 03153153 CN 03153153 A CN03153153 A CN 03153153A CN 1282671 C CN1282671 C CN 1282671C
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Abstract
The present invention relates to a catalyst used for polymerization or copolymeration of ethylene, which comprises a late transitional metal catalyst carried on a magnesium compound and an alkyl aluminum compound. If used for polymerization or copolymeration of ethylene, the catalyst system has favorable catalytic activity which is generally 10<8>gPE/molFeh. Obtained resin has a favorable spherical particle shape and a favorable industrial application prospect.
Description
Technical field:
The present invention relates to a kind of late transition metal catalyst of load, and preparation method thereof and the application in olefinic polymerization
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.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.Fe diimine pyridine catalyst system (WO9827124, WO9830612) particularly, it is vinyl polymerization active high not only, and the polyvinyl resin molecular weight distribution that obtains is broad peak or bimodal shape, has a good application prospect.The problem that exists is to need a large amount of methylaluminoxane (MAO) or polyfluoro boron compound as promotor in polymerization process, 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.
At present, in the load research of late transition metal catalyst, the silica gel that main employing has good particle form is carrier, as the Keng-Yu Shih silica gel activating Fe series catalysts of aluminum alkyls that in WO 01/32723, used a kind of load, 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, CN1389479A discloses a kind of late transition metal catalyst and method for making thereof of carrierization, its carrier mainly adopts silica gel, promotor mainly adopts methylaluminoxane (MAO), though its shortcoming is that the application of magnesium dichloride as carrier also arranged, promotor adopts expensive methylaluminoxane (MAO), catalytic activity is lower during catalyzed ethylene polymerization, generally only is 10
5GPE/mol Fe h.
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 compound, 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, and narrow particle size distribution, higher tap density had.
The present invention also provides above-mentioned Preparation of catalysts method, and the application in vinyl polymerization or copolymerization.
To describe the present invention below.
A kind of vinyl polymerization or copolymerization catalyst of being used for comprises following component:
A) a kind of late transition metal complex by magnesium compound load, its structure is shown in general formula 1:
General formula 1
Wherein, R
1And R
7Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl, heterocyclic compound group; Wherein preferred C
6-C
30Aryl radical and substituted aroma alkyl, as, phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 6-xylyl, 2,4, the 6-trimethylphenyl, the 2-ethylphenyl, the 3-ethylphenyl, the 4-ethylphenyl, 2,6-diethyl phenyl, 2,4, the 6-trimethylphenyl, the 2-isopropyl phenyl, the 3-isopropyl phenyl, the 4-isopropyl phenyl, 2, the 6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, the 2-tert-butyl-phenyl, the 3-tert-butyl-phenyl, the 4-tert-butyl-phenyl, 2, the 6-di-tert-butyl-phenyl, 2,4,6-tri-tert phenyl, 2-phenmethyl phenyl, 3-phenmethyl phenyl, 4-phenmethyl phenyl, 2,4-diphenyl-methyl phenyl, 2,4,6-trityl phenyl, the 1-naphthyl, the 2-naphthyl, the 2-phenyl, the 3-phenyl, the 4-phenyl, 2,4-phenylbenzene phenyl, 2,4,6-triphenyl phenyl, 2-(diphenyl-methyl) phenyl, 3-(diphenyl-methyl) phenyl, 4-(diphenyl-methyl) phenyl, 2,4-two (diphenyl-methyl) phenyl, 2,4,6-three (diphenyl-methyl) phenyl, 2-(trityl) phenyl, 3-(trityl) phenyl, 4-(trityl) phenyl, 2,4-two (trityl) phenyl, 2,4,6-three (trityl) phenyl etc.
R
2-R
6Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl, heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2-R
6In two or more groups can be in ring.Preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the phenyl that nitro replaces, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, diphenyl-methyl, the tristane base, 2-phenyl-sec.-propyl, pyridyl, pyrryl, Azacyclyl, the oxa-cyclic group, the methyl-silicane base, dimetylsilyl, trimethyl silyl, the ethyl silicane base, the diethylsilane base, triethylsilyl, the diphenylmethylsilane base, the trityl group silyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, uncle's propoxy-, methylthio group, ethylmercapto group, phenoxy group, thiophenyl etc., wherein preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the tristane base, 2-phenyl-sec.-propyl, methoxyl group, oxyethyl group, uncle's propoxy-.
M is iron, the cobalt of the 8th family's metal, preferred iron;
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, is preferably a kind of in hydrogen atom, halogen, alkyl, allyl group, cyclopentadienyl, alkoxyl group, the fragrant-oxyl.Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, m-phenoxy, to phenoxy group, naphthyloxy.When n is 2 or when bigger, a plurality of X groups can be identical or different.
N is the integer that satisfies the M valence state; The content of M in catalyzer is 0.01-10% (weight), is preferably 0.1-5% (weight).
B) 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; Preferred triethyl aluminum, three hexyl aluminium.
Amount ratio is 100-5000 with the Al/M molar ratio computing between B component and the component A, preferred 150-2000.
Among the catalyst component A of the present invention, described magnesium compound is a magnesium dihalide, the complex compound of the water of magnesium dihalide or alcohol, a kind of by in the derivative that alkyl or-oxyl replaced of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.
Among the catalyst component A of the present invention, described magnesium compound is magnesium dichloride and pure complex compound.
Among the catalyst component A of the present invention, described magnesium dichloride and pure complex compound, wherein alcohol is C
1-C
4Low-carbon alcohol.
Among the catalyst component A of the present invention, the alcohol adduct of described magnesium dichloride is with C
1-C
4Low-carbon alcohol mix with magnesium dichloride, mole number in magnesium dichloride is 1, magnesium dichloride and pure mol ratio are 1: 2.0-3.6, through behind the heating and melting under high-speed stirring quick cooling, obtain containing the spheroidal particle carrier of 2.0-3.6 moles of alcohol per mole magnesium dichloride, magnesium chloride alcohol adduct preparation method is with reference to the document of patent publication No. CN1091748A.Magnesium Chloride Anhydrous and alcohol are generated magnesium chloride alcohol adduct melt by certain proportioning temperature reaction, after dispersion agent high speed dispersed with stirring, quick cooling forms the microspheroidal solid particulate of magnesium chloride alcohol adduct again, promptly obtains magnesium chloride alcohol adduct spheroidal particle after washing, drying.Dispersion agent employing varsol such as kerosene, paraffin oil, vaseline oil, white oil etc. also add some tensio-active agents or silicoorganic compound.
Olefinic polymerization or the copolymerization catalyst component of being used for of the present invention, wherein component A preparation method is as follows: with magnesium compound and mixing diluents, slurries are made in stirring, system is cooled to-80-0 ℃, preferably-60--20 ℃, the hexane solution that slowly adds aluminum alkyls, and reaction 2-6 hour under this temperature, filter out liquid, the solids that obtains with hexane wash, again this solids is made the solid slurry of toluene, O.5-6 hour at 30-100 ℃ of toluene solution that adds down late transition metal complex, reaction after stopping to stir leaches liquid, use toluene, the hexane wash solids obtains containing the catalyst component of late transition metal complex.
Wherein with after magnesium compound and the mixing diluents cooling, add the hexane solution of aluminum alkyls, described 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.Preferred triethyl aluminum.The weight content of aluminium in catalyzer is 0.O1-15%, preferred 0.2-10%.
The thinner of above-described magnesium compound is hexane, pentane, heptane, benzene, toluene.
Among the catalyst component A of the present invention, back transition catalyst component preparation method is as follows;
In the back transition Preparation of catalysts method that described magnesium compound is loaded with, late transition metal catalyst is meant the metal complexes shown in the general formula 1,
General formula 1
Wherein, R
1And R
7Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl, heterocyclic compound group.Wherein preferred C
6-C
30Aromatic hydrocarbon and substituted aroma hydrocarbon, as, phenyl, the 2-tolyl, the 3-tolyl, the 4-tolyl, 2, the 6-xylyl, 2,4, the 6-trimethylphenyl, the 2-ethylphenyl, the 3-ethylphenyl, the 4-ethylphenyl, 2,6-diethyl phenyl, 2,4, the 6-trimethylphenyl, the 2-isopropyl phenyl, the 3-isopropyl phenyl, the 4-isopropyl phenyl, 2, the 6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, the 2-tert-butyl-phenyl, the 3-tert-butyl-phenyl, the 4-tert-butyl-phenyl, 2, the 6-di-tert-butyl-phenyl, 2,4,6-tri-tert phenyl, 2-phenmethyl phenyl, 3-phenmethyl phenyl, 4-phenmethyl phenyl, 2,4-diphenyl-methyl phenyl, 2,4,6-trityl phenyl, the 1-naphthyl, the 2-naphthyl, the 2-phenyl, the 3-phenyl, the 4-phenyl, 2,4-phenylbenzene phenyl, 2,4,6-triphenyl phenyl, 2-(diphenyl-methyl) phenyl, 3-(diphenyl-methyl) phenyl, 4-(diphenyl-methyl) phenyl, 2,4-two (diphenyl-methyl) phenyl, 2,4,6-three (diphenyl-methyl) phenyl, 2-(trityl) phenyl, 3-(trityl) phenyl, 4-(trityl) phenyl, 2,4-two (trityl) phenyl, 2,4,6-three (trityl) phenyl etc.
R
2-R
6Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl, heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2-R
6In two or more groups can be in ring.Preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the phenyl that nitro replaces, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, diphenyl-methyl, the tristane base, 2-phenyl-sec.-propyl, pyridyl, pyrryl, Azacyclyl, the oxa-cyclic group, the methyl-silicane base, dimetylsilyl, trimethyl silyl, the ethyl silicane base, the diethylsilane base, triethylsilyl, the diphenylmethylsilane base, the trityl group silyl, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, uncle's propoxy-, methylthio group, ethylmercapto group, phenoxy group, thiophenyl etc., wherein preferred hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, isohexyl, uncle's hexyl, phenyl, the tristane base, 2-phenyl-sec.-propyl, methoxyl group, oxyethyl group, uncle's propoxy-.
M is iron, the cobalt of the 8th family's metal, preferred iron;
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, is preferably a kind of in hydrogen atom, halogen, alkyl, allyl group, cyclopentadienyl, alkoxyl group, the fragrant-oxyl.Most preferably be chlorine, bromine, iodine, methoxyl group, oxyethyl group, isopropoxy, isobutoxy, butoxy, phenoxy group, oxy-o-cresyl, m-phenoxy, to phenoxy group, naphthyloxy.When n is 2 or when bigger, a plurality of X groups can be identical or different.
N is the integer that satisfies the M valence state.Synthetic method is with reference to patent documentation WO9827124, WO9830612.
The content of M in catalyzer is 0.01-10% (weight) after the load, preferred 0.1-5% (weight).
Catalyst A of the present invention, B component can directly apply to polymerization system, also can be used for polymerization system after the pre-earlier complex reaction.
The catalyzer that is used for vinyl polymerization or copolymerization of the present invention is applicable to slurry polymerization and vapour phase polymerization mode.
Catalyzer of the present invention can be used for the equal polymerization of ethene, also can be used for the copolymerization of ethene and other alpha-olefin, and comonomer can be propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene etc.
Polymerization or copolymerization that catalyzer of the present invention is used for ethene compared with prior art have following tangible advantage:
The present invention adopts the late transition metal complex catalyst of magnesium compound load to be used for vinyl polymerization or copolymerization has the catalytic activity height, and the polymer beads form is good, is spheroidal particle; Go for vapour phase polymerization and slurry polymerization processes; Polymkeric substance has the characteristics of bimodal or wide molecular weight distribution; Catalyst system of the present invention only adopts aluminum alkyls as promotor, has saved expensive methylaluminoxane, greatly reduces the catalyzer cost; In the ethene slurry polymerization processes, the hexane that need only use low toxicity is as solvent, for industrial application provides bright prospects.
Embodiment 1
(1) the magnesium chloride alcohol adduct is synthetic
Reflux exchanger, mechanical stirrer and thermometer are being housed, in 250 milliliters of glass reactors after nitrogen is fully replaced, add 37.8 milliliters of dehydrated alcohols, Magnesium Chloride Anhydrous 21.3 grams, stir down and heat up, treat that magnesium chloride all dissolves the back and adds 75 milliliters of white oils, 75 milliliters of silicone oil, keep 120 ℃ of temperature certain hours.In another volume is 500 milliliters the reaction flask that has high speed agitator, the silicone oil that adds 112.5 milliliters of white oils and equal volume in advance, be preheating to 120 ℃, the mixture of aforementioned preparation is pressed into rapidly in second reactor, keep under 120 ℃ of temperature, with 3500 rev/mins of high-speed stirring of rotating speed three minutes, stir down material to be transferred to and add 1600 milliliters of hexanes in advance and be cooled in-25 ℃ the 3rd reactor, finish until the material transfer, outlet temperature is no more than 0 ℃, suction filtration, use hexane wash, flush away silicone oil and white oil are through vacuum-drying, obtain spherical particle magnesium chloride alcohol adduct 43.5 gram, the analytical test carrier consist of MgCl
22.56C
2H
5OH, median size is 59.6 microns.
Synthesizing of two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyrrole heavy stone used as an anchor ferrous chloride of (2) 2,6-;
In bottle at the bottom of 250 milliliters of three mouthfuls of gardens, under the nitrogen protection, add 2 of 1.63 grams (10 mmole), 2 of 6-diacetyl pyridine, 3.1 milliliters (22 mmoles); 4, the 6-trimethylaniline adds 40 milliliters ethanol then; after the stirring and dissolving, add 2.0 milliliters Glacial acetic acid, temperature rising reflux 4 hours.Then decompression steams solvent, obtains yellowish brown oily matter, with the FeCl of 2.21 grams (11 mmole)
2.4H
2O is dissolved in 50 milliliters of propyl carbinols, slowly is added drop-wise in the oily matter, is heated to 90 ℃ of reactions one hour, stirred overnight at room temperature.Filter out solid, obtain 4.56 grams 2, two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyrrole heavy stone used as an anchor ferrous chloride of 6-.
MS(EI)：523(M+)
Structure is as follows:
(3) preparation of magnesium chloride support Fe series catalysts A
Under nitrogen protection; join in 250 milliliters of glass reactors making spherical magnesium chloride alcohol adduct in 4.93 grams (1); add 40 milliliters of hexanes; slurries are made in stirring; be cooled to-60 ℃ with the low temperature bath; the triethyl aluminum hexane solution that slowly added 24 milliliter of 2 mol in one hour is kept-60 ℃ of reactions 4 hours.Press filtration goes out liquid then, and solid is with twice of 40 milliliters of hexane wash.Solid is stirred with 30 milliliters of toluene again and make slurries, under 20 ℃, slowly dripping 18.6 ml concns is 1.0 * 10
-5The Fe catalyzer toluene solution by gained in (2) of mol, stirring reaction 4 hours.Reaction is left standstill after finishing, and leaches liquid, with 40 milliliters of toluene wash twice, then, with twice of 40 milliliters of hexane wash, solid is dried up with nitrogen, obtain having magnesium chloride support Fe series catalysts A 4.01 grams of good flowability, its median size is 53.6 microns.
Ultimate analysis (ICP method): Fe:0.1wt.%; Al:2.26wt.%, Mg:6.26wt.%.
Embodiment 2
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then,, add all the other 800 milliliters of hexane solvents again still temperature rise to 70 ℃, adding along with hexane, the hexane solution of the triethyl aluminum of 0.5 milliliter of 2 mol is added, then add 38 milligrams of the magnesium chloride support Fe series catalysts A (the ferro-aluminum mol ratio is about 1470) that make among the embodiment 1, feed ethene, pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 143.3 grams, the efficient of catalyzer is 1886gPE/gcat, is 1.89 * 10
6GPE/gFeh also can be expressed as 1.06 * 10
8GPE/molFeh, bulk density (BD) is 0.30g/ml.Spherical in shape by the electron microscopic observation resin particle.Poly Mn:36200, Mw/Mn:12.1.
Embodiment 3
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents down at 35 ℃, simultaneously, add the triethyl aluminum hexane solution of 0.50 milliliter of 2 mol, add 41 milligrams of the magnesium chloride support Fe series catalysts A (the Al/Fe mol ratio is about 1370) that make among the embodiment 1, add the 20ml hexene, then, pour the hydrogen of 0.1MPa, in 3 minutes, after temperature risen to 70 ℃, add ethene, pressure is risen to and keep 1.0MPa, reacted 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 175.7 grams, catalyst efficiency can be expressed as 2143gPE/gcath, also can be expressed as 2.14 * 10
6GPE/gFeh also can be expressed as 1.20 * 10
8GPE/molFeh, bulk density (BD) is 0.27g/ml.Spherical in shape by the electron microscopic observation resin particle, fine powder (＜100 order):＜5wt%.Poly Mn:24500, Mw/Mn:12.
Embodiment 4
(1) the magnesium chloride alcohol adduct is synthetic with embodiment 1 (1);
(2) the Fe catalyzer is synthetic is 2 with embodiment 1 (2), two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride of 6-;
(3) preparation of magnesium chloride support Fe series catalysts A
Under nitrogen protection; join in 250 milliliters of glass reactors making spherical magnesium chloride alcohol adduct in 3.98 grams (1); add 40 milliliters of hexanes; slurries are made in stirring; be cooled to-60 ℃ with the low temperature bath; the triisobutyl aluminium hexane solution that slowly added 19 milliliter of 2 mol in one hour is kept-60 ℃ of reactions 4 hours.Press filtration goes out liquid then, and solid is with twice of 40 milliliters of hexane wash.Solid is stirred with 30 milliliters of toluene again and make slurries, under 20 ℃, slowly dripping 14.8 ml concns is 1.0 * 10
-5Mol by 2 of gained in (2), two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride toluene solutions of 6-, stirring reaction 4 hours.Reaction is left standstill after finishing, and leaches liquid, with 40 milliliters of toluene wash twice, then, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtains having magnesium chloride support Fe series catalysts A 2.40 grams of good flowability.
Ultimate analysis (ICP method): Fe:0.29wt.%; Al:2.65wt.%, Mg:15.53wt.%.
Embodiment 5
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then,, add all the other 800 milliliters of hexane solvents again still temperature rise to 70 ℃, adding along with hexane, the triethyl aluminum of 0.50 milliliter of 2 mol is added, then add 21 milligrams of the magnesium chloride support Fe series catalysts A (the Al/Fe mol ratio is about 919) that make among the embodiment 6, feed ethene, pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 229.32 grams, catalyst efficiency can be expressed as 5460gPE/gcath, also can be expressed as 1.88 * 10
6GPE/gFeh also can be expressed as 1.05 * 10
8GPE/molFeh, bulk density (BD) is 0.25g/ml.Spherical in shape by the electron microscopic observation resin particle.Poly Mn:35700, Mw/Mn:15.4.
Embodiment 6
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents down at 35 ℃, simultaneously, add the triethyl aluminum hexane solution of 0.50 milliliter of 2 mol, add 25 milligrams of the magnesium chloride support Fe series catalysts A (the Al/Fe mol ratio is about 770) that make among the embodiment 4, add the 20ml hexene, then, pour the hydrogen of 0.1MPa, in 3 minutes, after temperature risen to 50 ℃, add ethene, pressure is risen to and keep 1.0MPa, reacted 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 143.6 grams, catalyst efficiency can be expressed as 2992gPE/gcath, also can be expressed as 1.0 * 10
6GPE/gFeh also can be expressed as 5.58 * 10
7GPE/molFeh, bulk density (BD) is 0.25g/ml.Spherical in shape by the electron microscopic observation resin particle, poly Mn:31800, Mw/Mn:16.0.
Embodiment 7
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then,, add all the other 800 milliliters of hexane solvents again still temperature rise to 70 ℃, adding along with hexane, the triethyl aluminum of 2 milliliter of 2 mol is added, then add 36 milligrams of the magnesium chloride support Fe series catalysts A (the Al/Fe mol ratio is about 2150) that make among the embodiment 4, feed ethene, pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 193.40 grams, catalyst efficiency can be expressed as 2686gPE/gcath, also can be expressed as 8.95 * 10
5GPE/gFeh also can be expressed as 5.01 * 10
7GPE/molFeh, bulk density (BD) is 0.21g/ml.Spherical in shape by the electron microscopic observation resin particle.Poly Mn:22600, Mw/Mn:19.4.
Embodiment 8
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then,, add all the other 800 milliliters of hexane solvents again still temperature rise to 70 ℃, adding along with hexane, the triethyl aluminum of 4 milliliter of 2 mol is added, then add 42 milligrams of the magnesium chloride support Fe series catalysts A (the Al/Fe mol ratio is about 3680) that make among the embodiment 4, feed ethene, pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 180.2 grams, catalyst efficiency can be expressed as 2145gPE/gcath, also can be expressed as 7.15 * 10
5GPE/gFeh also can be expressed as 4.00 * 10
7GPE/molFeh, bulk density (BD) is 0.20g/ml.Spherical in shape by the electron microscopic observation resin particle.Poly Mn:30300, Mw/Mn:11.8.
Embodiment 9
(1) the magnesium chloride alcohol adduct is synthetic with embodiment 1 (1).
(2) the Fe catalyzer is synthetic is 2 with embodiment 1 (2), two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride of 6-.
(3) preparation of magnesium chloride support Fe series catalysts A
Under nitrogen protection; join in 250 milliliters of glass reactors making spherical magnesium chloride alcohol adduct in 3.04 grams (1); add 40 milliliters of hexanes; slurries are made in stirring; be cooled to-60 ℃ with the low temperature bath; the triethyl aluminum hexane solution that slowly added 18 milliliter of 2 mol in one hour is kept-60 ℃ of reactions 4 hours.Press filtration goes out liquid then, and solid is with twice of 40 milliliters of hexane wash.Solid is stirred with 30 milliliters of toluene again and make slurries, under 20 ℃, slowly dripping 80 ml concns is 1.0 * 10
-5Mol by 2 of gained in (2), two [1-(2,4,6-Three methyl Benzene imines) ethyl] the pyridine ferrous chloride toluene solutions of 6-, stirring reaction 4 hours.Reaction is left standstill after finishing, and leaches liquid, directly solid is dried up with nitrogen, obtains having magnesium chloride support Fe series catalysts A 2.48 grams of good flowability.
Ultimate analysis (ICP): Fe:1.51wt.-%; Al:3.33wt.-%, Mg:14.71wt.-%.
Embodiment 10
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then,, add all the other 800 milliliters of hexane solvents again still temperature rise to 70 ℃, adding along with hexane, the triethyl aluminum of 2 milliliter of 2 mol is added, then add 40 milligrams of the magnesium chloride support Fe series catalysts A (the Al/Fe mol ratio is about 370) that make among the embodiment 9, feed ethene, pressure is risen to and keeps 1.0MPa, 70 ℃ of reactions 1 hour.After polyreaction finishes, collect the polyethylene particle powder, weigh 386.5 grams, catalyst efficiency can be expressed as 9663gPE/gcath, also can be expressed as 6.40 * 10
5GPE/gFeh also can be expressed as 3.58 * 10
7GPE/molFeh, bulk density (BD) is 0.31g/ml.Spherical in shape by the electron microscopic observation resin particle.Poly Mn:31200, Mw/Mn:11.0.
Embodiment 11
(1) the magnesium chloride alcohol adduct is synthetic with embodiment 1 (1).
Synthesizing of two [1-(2,6-diisopropyl benzene imines) ethyl] the pyridine ferrous chloride of (2) 2,6-;
Method is similar with (2) among the embodiment 1, and just with 2, the 6-diisopropyl aniline replaces 2, obtains 2, two [1-(2,6-diisopropyl benzene imines) ethyl] pyridine ferrous chloride 5.13 grams of 6-.
MS(EI)：606(M+)
Structure is as follows:
(3) preparation of magnesium chloride support Fe series catalysts A
Under nitrogen protection; join in 250 milliliters of glass reactors making spherical magnesium chloride alcohol adduct in 2.70 grams (1); add 40 milliliters of hexanes; slurries are made in stirring; be cooled to-60 ℃ with the low temperature bath; the triethyl aluminum hexane solution that slowly added 13 milliliter of 2 mol in one hour is kept-60 ℃ of reactions 4 hours.Press filtration goes out liquid then, and solid is with twice of 40 milliliters of hexane wash.Solid is stirred with 20 milliliters of toluene again and make slurries, under 20-25 ℃, slowly dripping 10 ml concns is 1.0 * 10
-5Mol by 2 of gained in (2), two [1-(2,6-diisopropyl benzene imines) ethyl] the pyridine ferrous chloride toluene solutions of 6-, stirring reaction 4 hours.Reaction is left standstill after finishing, and leaches liquid, with 40 milliliters of toluene wash twice, then, with 40 milliliters of hexane wash twice, solid is dried up with nitrogen, obtains having magnesium chloride support Fe series catalysts A 1.54 grams of good flowability.
Ultimate analysis (ICP method): Fe:0.35wt.-%; Al:4.72wt.-%, Mg:15.03wt.-%.
Embodiment 12
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 1000 milliliters of hexane solvents down at 35 ℃, simultaneously, the triethyl aluminum hexane solution that adds 0.50 milliliter of 2 mol adds, 44 milligrams of the magnesium chloride support Fe series catalysts A that makes among the adding embodiment 7, add the 10ml hexene, then, pour the hydrogen of 0.1MPa, in 3 minutes, after temperature risen to 70 ℃, add ethene, pressure is risen to and keep 1.0MPa, reacted 2 hours.After polyreaction finishes, collect the polyethylene particle powder, weigh 92.0 grams, catalyst efficiency can be expressed as 1046gPE/g cath, also can be expressed as 3.0 * 10
5GPE/g Feh also can be expressed as 1.67 * 10
7GPE/mol Feh, bulk density (BD) is 0.25g/ml.Spherical in shape by the electron microscopic observation resin particle.Poly Mn:63000, Mw/Mn:5.49.
Comparative example 1
In 2 liters stainless steel polymermaking autoclave, respectively replace three times with nitrogen and ethene, add 200 milliliters of hexane solvents then, with still temperature rise to 25 ℃, add all the other 800 milliliters of hexane solvents again, along with the adding of hexane,, then add the toluene solution (concentration 1.0 * 10 of the Fe catalyzer that makes among the embodiment 1 (2) with the aluminum alkyls hexane solution adding of 1 milliliter of 2 mol
-2Mol) 0.40 milliliter, feed ethene, pressure is risen to and keeps 1.0MPa, 25 ℃ of reactions 0.5 hour.After polyreaction finishes, collect polyethylene powder, weigh 99.70 grams, catalytic activity is 8.90 * 10
5GPE/gFeh also can be expressed as 4.99 * 10
7GPE/molFeh.Poly Mn:24990, Mw/Mn:10.12, polymer morphology is bad.
Claims (15)
1, a kind of vinyl polymerization or copolymerization catalyst of being used for is characterized in that, comprises following component:
A) a kind of late transition metal complex by magnesium compound load, its structure is shown in general formula 1 formula:
General formula 1
Wherein, R
1And R
7Be selected from hydrogen, halogen, C respectively
1-C
30Alkyl, substituted hydrocarbon radical, assorted alkyl, substituted heterohydrocarbyl or heterocyclic compound group; R
2-R
6Be respectively hydrogen atom, chlorine atom, C
1-C
20Alkyl or heterocyclic compound group, contain the organic group of oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom and R
2-R
6In two or more groups can be in ring, M is iron or cobalt;
X is selected from a kind of in hydrogen, halogen, alkyl, substituted hydrocarbon radical,-oxyl, fragrant-oxyl, acid group, the amido, when n is 2 or when bigger, a plurality of X groups can be identical or different;
N is the integer that satisfies the M valence state; The content of M in catalyzer is 0.01-10% weight;
B) alkylaluminium cpd, it 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 or ethyl aluminum dichloride;
Amount ratio is 100-5000 with the Al/M molar ratio computing between B component and the component A.
2, vinyl polymerization or the copolymerization catalyst of being used for according to claim 1 is characterized in that, among the component A, the content of M in catalyzer is 0.1-5% weight.
3, vinyl polymerization or the copolymerization catalyst of being used for according to claim 1, it is characterized in that, magnesium compound among the described component A is a magnesium dihalide, the complex compound of the water of magnesium dihalide or alcohol, a kind of by in the derivative that alkyl or-oxyl replaced of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.
4, vinyl polymerization or the copolymerization catalyst of being used for according to claim 1 is characterized in that, in the described A component, magnesium compound is magnesium dichloride and pure complex compound.
5, vinyl polymerization or the copolymerization catalyst of being used for according to claim 4 is characterized in that wherein said alcohol is C
1-C
4Low-carbon alcohol.
6, vinyl polymerization or the copolymerization catalyst of being used for according to claim 4 is characterized in that in the described A component, the alcohol adduct of magnesium dichloride is with C
1-C
4Low-carbon alcohol mix with magnesium dichloride, mole number in magnesium dichloride is 1, magnesium dichloride is 1 with the mol ratio of alcohol: 2.0-3.6, through behind the heating and melting under high-speed stirring quick cooling, obtain containing the spheroidal particle carrier of 2.0-3.6 moles of alcohol per mole magnesium dichloride.
7, vinyl polymerization or the copolymerization catalyst of being used for according to claim 1 is characterized in that wherein said M is an iron.
8, vinyl polymerization or the copolymerization catalyst of being used for according to claim 1 is characterized in that, described B component alkylaluminium cpd is triethyl aluminum or three hexyl aluminium.
9, vinyl polymerization or the copolymerization catalyst of being used for according to claim 1 is characterized in that amount ratio is 150-2000 with the Al/M molar ratio computing between B component and the component A.
10, any one described vinyl polymerization or copolymerization catalyst of being used among the claim 1-9, wherein the preparation method of component A is: with magnesium compound and mixing diluents, slurries are made in stirring, system is cooled to-80-0 ℃, the hexane solution that slowly adds aluminum alkyls, and reaction 2-6 hour under this temperature, filter out liquid, the solids that obtains with hexane wash, again this solids is made the solid slurry of toluene, at 30-100 ℃ of toluene solution that adds late transition metal complex down, reacted 0.5-6 hour, after stopping to stir liquid is leached, use toluene, the hexane wash solids obtains containing the catalyst component of late transition metal complex.
11, vinyl polymerization or the copolymerization catalyst of being used for according to claim 10 is characterized in that, among the component A preparation method, system cooling scope is-and 60--20 ℃.
12, vinyl polymerization or the copolymerization catalyst of being used for according to claim 10, it is characterized in that, among the component A preparation method, after magnesium compound and mixing diluents cooling, add the hexane solution of 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 or ethyl aluminum dichloride.
13, vinyl polymerization or the copolymerization catalyst of being used for according to claim 12 is characterized in that, among the component A preparation method, after magnesium compound and mixing diluents cooling, adds the hexane solution of aluminum alkyls, and wherein said aluminum alkyls is a triethyl aluminum.
14, vinyl polymerization or the copolymerization catalyst of being used for according to claim 10 is characterized in that, among the component A preparation method, the weight content of aluminium in catalyzer is 0.1-15%.
15, vinyl polymerization or the copolymerization catalyst of being used for according to claim 10 is characterized in that, among the component A preparation method, used thinner is hexane, pentane, heptane, benzene or toluene.
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