CN102911299A - High-activity olefin polymerization catalyst, preparation method and application - Google Patents

High-activity olefin polymerization catalyst, preparation method and application Download PDF

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CN102911299A
CN102911299A CN2012104361368A CN201210436136A CN102911299A CN 102911299 A CN102911299 A CN 102911299A CN 2012104361368 A CN2012104361368 A CN 2012104361368A CN 201210436136 A CN201210436136 A CN 201210436136A CN 102911299 A CN102911299 A CN 102911299A
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alcohol
olefin polymerization
transition metal
warming
ortho
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CN102911299B (en
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黄启谷
刘伟
刘智
李凤娇
程璐
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention relates to a high-activity olefin polymerization catalyst, a preparation method and an application and belongs to the field of olefin polymerization. The high-activity olefin polymerization catalyst is composed of a main catalyst and a cocatalyst and characterized in that the main catalyst is composed of a magnesium halide carrier, a transition metal halide, alcohol which is smaller than C5, alcohol which is larger than C5, an organosilicon compound and an organic phosphorus compound; the mole ratio of the magnesium halide carrier, the transition metal halide, the alcohol which is smaller than C5, the alcohol which is larger than C5, the organosilicon compound and the organic phosphorus compound is 1: (1-40): (0.01-5): (0.01-10): (0.01-10): (0.05-5); and the cocatalyst is an organic aluminum compound. Particles of the catalyst are good in shape, spherical and free from adhering to the wall of a container; and the catalyst is high in activity, good in hydrogen regulation performance and applicable to a slurry polymerization process, a loop polymerization process, a gas phase polymerization process or a combined polymerization process, and a melt flow rate (MFR) of polyethylene can be regulated within a range of 0.1g/10min-600g/10min.

Description

Alkene catalyst structure and preparation method and application
Technical field
The invention belongs to alkene catalyst structure and field of olefin polymerisation, be specifically related to preparation method and application for catalyzer and the catalyzer of the equal polymerization of alkene or copolymerization.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology, development from olefin polymerization catalysis, sum up and mainly contain two aspects: (1) exploitation can prepare property or the more excellent polyolefin resin catalyzer of performance, such as metallocene catalyst and non-luxuriant late transition metal catalyst etc.; (2) for the production of general purpose polyolefin resin, on the basis of further improving catalyst performance, simplify catalyst preparation process, reduce the catalyzer cost, develop environment amenable technology, to increase the benefit, enhance the competitiveness.Before the eighties in 20th century, the emphasis of polyethylene catalysts research is to pursue catalyst efficiency, and through nearly 30 years effort, the catalytic efficiency of polyethylene catalysts is the order of magnitude and improves, thereby has simplified polyolefinic production technique, has reduced energy consumption and material consumption.
The Ziegler-Natta catalyst so far existing nearly 60 years history of coming out, although during occurred such as polyolefin catalysts such as metallocene and Nonmetallocenes, its industrial problems is more, such as the promotor costliness, the Primary Catalysts load also has difficulties etc.Therefore, just present industrial production and share of market, traditional Z-N catalyzer will be the leader of following for some time internal olefin polymerization field.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability and polymerization catalyzed activity also improve constantly.But still having deficiency aspect hydrogen response, control granules of catalyst regularity and the size distribution.Need develop in producing at present that preparation technology is simple, hydrogen response good, the uniform sphere of size distribution or class spherical catalyst.
Patent 96106647.4 X disclose a kind of olefin polymerization catalysis and preparation method thereof, with carrier MgCl 2Be dissolved in a kind of mixture of pure and mild alkane, form liquid MgCl 2Alcohol adducts, this liquid MgCl 2Alcohol adducts and TiCl 4Contact obtain olefin polymerization catalysis, but the hydrogen regulation performance of catalyzer is poor, and poly melting index MFR can only regulate in 0.1g/10min – 220g/10min.
Patent 200480008242.X discloses a kind of olefin polymerization catalysis and preparation method thereof, with carrier MgCl 2Directly be dissolved in ethanol and prepared solid MgCl 2Alcohol adducts is again with TiCl 4Load on solid MgCl 2Obtained olefin polymerization catalysis on the alcohol adducts.
Patent 201110382706.5 discloses a kind of olefin polymerization catalysis and preparation method thereof, with carrier MgCl 2Be dissolved in the organic solvent of isooctyl alcohol and ethanol and prepared solid MgCl 2Alcohol adduct is again with TiCl 4Load on solid MgCl 2Obtained olefin polymerization catalysis on the alcohol adduct, this catalyzer has good hydrogen to transfer effect.But catalyst activity is on the low side, and the Primary Catalysts particle easily sticks on the wall of container.
Patent CN85100997A, CN200810227369.0, CN200810227371.8, CN200810223088.8 disclose a kind of olefin polymerization catalysis and preparation method thereof, with MgCl 2Particle is dissolved in the system of organic epoxy compounds, organo phosphorous compounds and inert organic solvents, obtains MgCl 2Solution is again with TiCl 4Contact has prepared the Primary Catalysts of olefinic polymerization.The effect of described organo phosphorous compounds is to make MgCl 2A necessary component in the solvent system of grain dissolution.
This patent finds, in catalyst preparation process, add inert organic solvents, carbonatoms less than 5 alcohol, carbonatoms greater than 5 alcohol, MgCl 2Behind the grain dissolution, add again organo phosphorous compounds and silicoorganic compound, preparation liquid MgCl 2Alcohol adduct is again with TiCl 4With this liquid MgCl 2The alcohol adduct contact obtains the alkene catalyst structure, can improve the particle form of solid main catalyst, the hydrogen regulation performance of catalyst olefinic polymerization; This patent is found, after the magnesium halide carrier dissolving, adds organo phosphorous compounds again, can obviously improve catalyzer catalytic activity, can eliminate the static of solid main catalyst particle, the Primary Catalysts particle does not stick on the wall of container.The particle form of olefin polymerization catalysis provided by the present invention is good, and size distribution is even; The catalyzer hydrogen regulation performance is excellent, and poly melting index MFR can regulate in 0.1g/10min – 600g/10min; Catalyst loadings is high, and catalyst activity is high, and the solid main catalyst particle does not stick on the wall of container; Morphology is good, and tap density is high, and fine powder is few; Be applicable to slurry polymerization processes, endless tube polymerization technique, gas-phase polymerization process or polymerization mix technique; The preparation technology of Primary Catalysts is simple, and is low for equipment requirements, and energy consumption is little, and environmental pollution is little.
Summary of the invention
The object of the present invention is to provide a kind of catalyzer, the preparation method of catalyzer and application of catalyzer for olefinic polymerization or ethene (or propylene) and copolymerization monomer copolymerizable.
Olefinic polymerization provided by the present invention or ethene (or propylene) are comprised of Primary Catalysts and promotor with the spherical catalyst of copolymerization monomer copolymerizable; Described Primary Catalysts is by magnesium halide carrier, transition metal halide, form less than the alcohol of C5, alcohol, silicoorganic compound and organo phosphorous compounds greater than C5.Magnesium halide, transition metal halide, less than the alcohol of C5, the mol ratio of alcohol, silicoorganic compound and organo phosphorous compounds greater than C5 be: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10): (0.05-5).Primary Catalysts and promotor with magnitude relation be: the transition metal halide in the Primary Catalysts and the mol ratio of promotor are 1:(10-500).
Wherein, to be selected from general formula (1) as carrier be Mg (R) to described magnesium halide aX bCompound at least a, R is selected from C 1～C 20Aliphatic group, C 1～C 20Fatty alkoxyl group, C 3～C 20Alicyclic radical or C 6～C 20Aryl radical; X is selected from halogen; A=0,1 or 2, b=0,1 or 2, a+b=2.Specifically be selected from least a in magnesium dichloride, dibrominated magnesium, two magnesium iodides, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium, chlorination butoxy magnesium, chlorination phenoxy group magnesium, magnesium ethylate, isopropoxy magnesium, butoxy magnesium, chlorination isopropoxy magnesium, the butyl magnesium chloride etc., wherein, preferred magnesium dichloride.
Wherein, to be selected from general formula (2) be M (R to described transition metal halide 1) 4-mX mCompound at least a, in the formula, M is Ti, Zr, Hf, Fe, Co, Ni etc.; X is halogen atom, is selected from Cl, Br, F; M is 1 to 4 integer; R 1Be selected from C 1～C 20Aliphatic group, C 1～C 20Fatty alkoxyl group, C 1～C 20Cyclopentadienyl and derivative, C 1～C 20Aryl radical, COR` or COOR`, R` has C 1～C 10Fatty group or have C 1～C 10Aromatic base.R 1Specifically can be selected from: at least a in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, ortho-, meta-or p-aminomethyl phenyl, meta-aminomethyl phenyl, p-aminomethyl phenyl, ortho-, meta-or p-sulfonic group phenyl, formyl radical, the acetyl or benzoyl base etc.Described Ti, Zr, Hf, Fe, Co, the transition metal halides such as Ni specifically can be selected one or more the mixing in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, methoxyl group titanous chloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, four phenoxide titaniums, a chlorine triple phenoxyl titanium, two chlorodiphenyl oxygen base titaniums, trichlorine one phenoxide titanium.Wherein, preferred titanium tetrachloride.The mol ratio of transition metal halide and magnesium halide preferred (8-40): 1.
Wherein, described alcohol less than C5 is that carbonatoms is less than or equal to 5 Fatty Alcohol(C12-C14 and C12-C18), selects ethanol, methyl alcohol, propyl alcohol, butanols or amylalcohol, preferred alcohol.Mol ratio preferred (0.05 – 3.5) less than the alcohol of C5 and magnesium halide: 1.Adding can obviously improve the hydrogen regulation performance of catalyzer less than the alcohol of C5 especially ethanol.
Wherein, described alcohol greater than C5 is that carbonatoms is Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol or the aromatic alcohol of C6 – C20, preferred fat alcohol selects enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol or hexadecanol in the Fatty Alcohol(C12-C14 and C12-C18), preferred isooctyl alcohol.Mol ratio preferred (1 – 8) greater than the alcohol of C5 and magnesium halide: 1.
Wherein, described silicoorganic compound meet general formula R x 3R y 4Si (OR 5) zAnd general formula (R 6O) (R 7O) (R 8O) (R 9O) Si, wherein R 3And R 4Be respectively alkyl or halogen, R 5, R 6R 7R 8And R 9Alkyl or the cyclic hydrocarbon radical of C1 to C20,0≤x＜2,0≤y＜2, and 0＜z≤4, x+y+z=4.Silicoorganic compound are selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, the n-propyl triethoxyl silane, the n-propyl Trimethoxy silane, the decyl Trimethoxy silane, the decyl triethoxyl silane, cyclopentyl-trimethoxy-silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyltriethyloxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl triethoxy silane, cyclohexyltriethyloxysilane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyl three butoxy silanes, trimethyl phenoxysilane, methyl three allyloxy silane, vinyl nitrilotriacetic base silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dibutyl dimethoxy silane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, Cyclohexylmethyldimethoxysilane, the methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, the aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silanes, tolyl dimethoxy silane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, two cyclopentyl-methyl methoxy silane, cyclopentyl dimethyl methyl TMOS, diethoxy isopropoxy tert.-butoxy silane, three isopropoxy tert.-butoxy silane, diisopropoxy two tert.-butoxy silane, diethoxy cyclohexyloxy tert.-butoxy silane, diethoxy phenoxy group tert.-butoxy silane, one oxyethyl group diisopropoxy tert.-butoxy silane, oxyethyl group isopropoxy tert.-butoxy cyclohexyloxy silane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon, triethoxy hexyloxy silicon, in trimethoxy pentyloxy silicon or the triethoxy phenoxy group silicon etc. one or more.A kind of in preferred tetramethoxy-silicane, tetraethoxysilane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon or the triethoxy hexyloxy silicon.The mol ratio of silicoorganic compound and magnesium halide is (0. 5-8): 1.
Described organo phosphorous compounds is selected from least a in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid.Concrete as: at least a in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid three propyl ester, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or the phosphorous acid benzene methyl.Wherein, preferred ortho-phosphoric acid tri-n-butyl.The mol ratio of organo phosphorous compounds and magnesium halide is (0. 1-5): 1.The adding organo phosphorous compounds can obviously improve the catalytic activity of catalyzer.
One of feature of the present invention is the pure and mild alcohol greater than C5 that adds in the preparation process of solid main catalyst less than C5, described alcohol less than C5 is that carbonatoms is less than or equal to 5 Fatty Alcohol(C12-C14 and C12-C18), be selected from ethanol, methyl alcohol, propyl alcohol, butanols or amylalcohol, preferred alcohol is less than the mol ratio preferred (0.01 – 5) of the alcohol of C5 and magnesium halide: 1; Described alcohol greater than C5 is that carbonatoms is Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol or the aromatic alcohol of C6 – C20, preferred fat alcohol, select enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol, pentadecanol or hexadecanol in the Fatty Alcohol(C12-C14 and C12-C18), preferred isooctyl alcohol, described isooctyl alcohol is 2-ethyl-1-hexanol.Mol ratio preferred (0.01 – 10) greater than the alcohol of C5 and magnesium halide: 1.Adding can obviously improve the hydrogen regulation performance of catalyzer less than the alcohol of C5 especially ethanol.
One of feature of the present invention is to add organo phosphorous compounds in the preparation process of solid main catalyst, and described organo phosphorous compounds is selected from least a in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid.Concrete as: at least a in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid three propyl ester, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or the phosphorous acid benzene methyl, preferred ortho-phosphoric acid tri-n-butyl.The mol ratio of organo phosphorous compounds and magnesium halide preferred (0.05-5): 1.The adding organo phosphorous compounds can obviously improve the catalytic activity of catalyzer.
The preparation method of olefin polymerization catalysis provided by the present invention may further comprise the steps:
1) magnesium halide carrier is scattered in the inert organic solvents, adds the pure and mild alcohol greater than C5 less than C5, in 30 to 150 ℃ of lower stirring and dissolving 1 are to 5h, preferred 60 ℃ to 130 ℃.
2) with 1) solution is cooled to 10 ℃ to 80 ℃, adds organo phosphorous compounds and silicoorganic compound, and reaction 0.5 is to 3h.
3) under-25 to 30 ℃, with step 2) system that obtains contacts with transition metal halide, and at-25 to 30 ℃ of lower reaction 0.5-5h, system is warming up to 20-150 ℃ again, preferred 50-120 ℃, reaction 0.5-5h, in temperature-rise period, solid particulate is separated out gradually, after reaction finishes, with toluene or normal hexane washed product 4-6 time, remove by filter unreacted reactant
Washed product contacts with transition metal halide, and at-25 to 30 ℃ of lower reaction 0.5-5h, system is warming up to 20-150 ℃ again, reaction 0.5-5h; Leave standstill, layering removes by filter unreacted reactant, adopts toluene or hexane washed product; This step repeats 0-4 time;
The mol ratio of transition metal halide and magnesium halide is: (1-40): 1;
Vacuum-drying obtains the pulverulent solids Primary Catalysts.The vacuum-drying temperature is 40 ℃ to 130 ℃, preferred 50 ℃ to 100 ℃; The vacuum-drying time is 0.5 hour to 5 hours, preferred 1 hour to 4 hours.
Described inert organic solvents is selected from C 5～C 15Stable hydrocarbon, C 5～C 10Alicyclic hydrocarbon or C 6～C 15Aromatic hydrocarbon, preferred decane, octane, dodecane, toluene, dimethylbenzene, hexane, heptane or hexanaphthene, or their mixed solvent.
Olefin polymerization catalysis provided by the present invention also needs to be comprised of promotor.Described promotor is for common are machine aluminium compound, preferred triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride, methylaluminoxane MAO etc.; The mol ratio of solid main catalyst and promotor is 1:(10-500).
The purposes of olefin polymerization catalysis provided by the present invention is: can be used as the copolymerization catalyst of vinyl polymerization or propylene polymerization or ethene (or propylene) and alpha-olefin, wherein, described alpha-olefin is selected from C 3～C 20Alkene, preferred propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentenes, 4-methyl-1-pentene, 1,3-butadiene, isoprene, vinylbenzene, vinyl toluene etc.
Olefin polymerization catalysis provided by the present invention has following beneficial effect:
The particle form of the alpha-olefinic copolymerization catalyzer that the purpose of this invention is to provide is good, spherical in shape, and granules of catalyst does not stick on the wall of container; The hydrogen regulation performance of catalyzer is excellent, and poly melting index MFR can regulate in 0.1g/10min – 600g/10min; Catalyst activity is high; Be applicable to slurry process, gas-phase polymerization process or polymerization mix technique; The preparation method is simple, and is low for equipment requirements, and environmental pollution is little.
Adopt GC to measure ethanol and other pure quality percentage composition in the Primary Catalysts, the results are shown in Table 1.
Adopt ICP to measure Mg in the Primary Catalysts, Ti, the quality percentage composition of Si and P.
The condition determination of the melting index of polyethylene and polyethylene and ethylene copolymers is that testing load is that 5kg, temperature are 190 ℃.
The condition determination of the melting index of isotatic polypropylene is that testing load is that 2.16kg, temperature are 230 ℃.
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited only to following embodiment.
Embodiment
Embodiment 1
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 0.2ml, isooctyl alcohol 6.5 ml stir and are warming up to 120 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 2.1 ml and tetraethoxysilane 0.15 ml, keeping temperature is 50 ℃ of reaction 2 h.System is down under-15 ℃, drips 30 ml titanium tetrachlorides, react 1 h, be warming up to 110 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, and four times (each 30 milliliters) of hexane washing in 70 ℃ of vacuum-dryings 2 hours, obtain good fluidity, non-stick container wall, size distribution pulverulent solids Primary Catalysts even, spherical in shape.
Embodiment 2
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 30 ml, ethanol 0.25 ml, isooctyl alcohol 7 ml stir and are warming up to 120 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add successively ortho-phosphoric acid tri-n-butyl 1.1 ml and tetraethoxysilane 0.5 ml, keeping temperature is 60 ℃ of reaction 2 h.System is down under-10 ℃, drips 40 ml titanium tetrachlorides, react 1 h, be warming up to 100 ℃ and react again 3 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 3
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 0.2 ml, isooctyl alcohol 8 ml stir and are warming up to 100 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 13 ml and tetraethoxysilane 2ml, be warming up to 80 ℃ of reaction 2 h.System is down under-15 ℃, drips 35 ml titanium tetrachlorides, react 1 h, be warming up to 65 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 4
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 2 ml, isooctyl alcohol 7 ml stir and are warming up to 90 ℃, react 4 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 0.5 ml and triethoxy methoxy silane 0.5 ml, be warming up to 100 ℃ of reaction 2 h.System is down under-15 ℃, drips 15 ml titanium tetrachlorides, react 1 h, be warming up to 120 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 80 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 5
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 0.1 ml, isooctyl alcohol 4 ml stir and are warming up to 80 ℃, react 5 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 40 ℃, add successively ortho-phosphoric acid triethyl 5ml and tetraethoxysilane 4ml, keeping temperature is 40 ℃ of reaction 2 h.System is down under-15 ℃, drips 25 ml titanium tetrachlorides, react 3 h, be warming up to 110 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 90 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 6
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 2.5 ml, isooctyl alcohol 3 ml stir and are warming up to 110 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively tributyl phosphate 3ml and tetraethoxysilane 8 ml, keeping temperature is 50 ℃ of reaction 3 h.System is down under-15 ℃, drips 40 ml titanium tetrachlorides, react 1 h, be warming up to 70 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 100 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 7
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, isooctyl alcohol 6.5 ml and ethanol 0.1 ml stir and are warming up to 60 ℃, react 4 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively ortho-phosphoric acid triphenylmethyl methacrylate 6ml and triethoxy cyclopentyloxy silane 3 ml and ethanol 0.2 ml, keeping temperature is 50 ℃ of reaction 4 h.System is down under-15 ℃, drips 35 ml titanium tetrachlorides, react 1 h, be warming up to 95 ℃ and react again 4 h.Stop to stir, leave standstill layering, filter twice of toluene wash (each 30 milliliters), four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 8
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, dodecane 20 ml, ethanol 0.3 ml, decyl alcohol 6 ml stir and are warming up to 110 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add successively ortho-phosphoric acid tri-n-butyl 6ml and diethoxy isopropoxy tert.-butoxy silane 5 ml, keeping temperature is 50 ℃ of reaction 3 h.System is down under-10 ℃, drips 30 ml titanium tetrachlorides, react 1 h, be warming up to 80 ℃ and react again 3 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 9
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, toluene 30 ml, propyl alcohol 3 ml, isooctyl alcohol 6.5 ml stir and are warming up to 50 ℃, react 5 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add ortho-phosphoric acid tri-n-butyl 6ml and tetraethoxysilane 6 ml, keeping temperature is 50 ℃ of reaction 2 h.System is down under 0 ℃, drips 15 ml titanium tetrachlorides, react 1 h, be warming up to 90 ℃ and react again 2 h.Stop to stir, leave standstill, hexane washed twice (each 30 milliliters) is filtered in layering.In reactor, add n-decane 20 ml at 0 ℃, be added dropwise to 25 ml titanium tetrachlorides, react 1 h, be warming up to 80 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 110 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 10
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, octane 30 ml, butanols 4 ml, isooctyl alcohol 6.5 ml stir and are warming up to 110 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add ortho-phosphoric acid tri-n-butyl 2ml and tetraethoxysilane 6 ml, keeping temperature is 50 ℃ of reaction 2 h.System is down under-5 ℃, drips 45 ml titanium tetrachlorides, react 1 h, be warming up to 90 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 120 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 11
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 15 ml, methyl alcohol 1.5 ml, lauryl alcohol 5 ml stir and are warming up to 110 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add ortho-phosphoric acid tri-n-butyl 4ml and tetraethoxysilane 6 ml, keeping temperature is 50 ℃ of reaction 2 h.System is cooled to 25 ℃, is added dropwise to again in the 25 ml titanium tetrachlorides that are in-10 ℃, at 0 ℃ of reaction 1 h, in 4 hours, be warming up to 110 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 12
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 40 ml, ethanol 0.5 ml, isooctyl alcohol 6.5 ml stir and are warming up to 120 ℃, react 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add ortho-phosphoric acid tri-n-butyl 3ml and tetraethoxysilane 6 ml, keeping temperature is 60 ℃ of reaction 2 h.System is cooled to 25 ℃, is added dropwise to again in the 25 ml titanium tetrachlorides that are in-15 ℃, at-5 ℃ of reaction 1 h, in 4 hours, be warming up to 100 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 3 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 13
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 0.1 ml, isooctyl alcohol 6.5 ml stir and are warming up to 110 ℃, react 3 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add ortho-phosphoric acid tri-n-butyl 1ml and tetraethoxysilane 2 ml, reaction 2 h under 50 ℃ of temperature.System is down under 0 ℃, drips 15 ml titanium tetrachlorides, react 1 h, be warming up to 90 ℃ of reaction 2 h.Stop to stir, leave standstill, hexane washed twice (each 30 milliliters) is filtered in layering.In reactor, add n-decane 20 ml at 0 ℃, be added dropwise to 25 ml titanium tetrachlorides, react 1 h, be warming up to 80 ℃ and react again 3 h.Stop to stir, leave standstill, hexane washed twice (each 30 milliliters) is filtered in layering.In reactor, add n-decane 20 ml at 0 ℃ again, be added dropwise to 25 ml titanium tetrachlorides, react 2 h, be warming up to 80 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 14
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, toluene 10ml, ethanol 1 ml, isooctyl alcohol 6.5 ml stir and are warming up to 100 ℃, react 4 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 40 ℃, add ortho-phosphoric acid tri-n-butyl 3ml, be warming up to 70 ℃ of reaction 2 h.System is down under-15 ℃, drips 15 ml titanium tetrachlorides, react 1 h, be warming up to 90 ℃ of reaction 2 h.Stop to stir, leave standstill, hexane washed twice (each 30 milliliters) is filtered in layering.In reactor, add n-decane 20 ml at 0 ℃, be added dropwise to 25 ml titanium tetrachlorides, react 1 h, be warming up to 80 ℃ and react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 15
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 0.4 ml, isooctyl alcohol 6.5 ml stir and are warming up to 120 ℃, react 0.5 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add ortho-phosphoric acid tri-n-butyl 3ml and succinate 10 ml, keeping temperature is 50 ℃ of reaction 3 h.System is down under-15 ℃, drips 15 ml titanium tetrachlorides, react 1 h, be warming up to 90 ℃ and react again 2 h.Stop to stir, leave standstill layering, filter, hexane washed twice (each 30 milliliters) adds n-decane 20 ml at 0 ℃ in 60 ℃ of vacuum-dryings after 2 hours in reactor, be added dropwise to 25 ml titanium tetrachlorides, react 1 h, be warming up to 80 ℃ and react again 2 h and stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 60 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Comparative Examples 1
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, decane 20 ml, isooctyl alcohol 16 ml, ethanol 0.4 ml stirs and is warming up to 110 ℃, reacts 2 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 5 ml, keeping temperature is 50 ℃ of reaction 2 h.System is down under-15 ℃, drips 35 ml titanium tetrachlorides, react 1 h, be warming up to 100 ℃ of reaction 2 h.Stop to stir, leave standstill, layering is filtered, and four times (each 30 milliliters) of hexane washing in 80 ℃ of vacuum-dryings 2 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape, and the Primary Catalysts particle easily adheres on the wall of container.
Comparative Examples 2
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, decane 20 ml, isooctyl alcohol 16 ml, ethanol 0.4 ml stirs and is warming up to 120 ℃, reacts 3 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 50 ℃, add tetraethoxysilane 5 ml, keeping temperature is 50 ℃ of reaction 2 h.System is down under-15 ℃, drips 15 ml titanium tetrachlorides, react 1 h, be warming up to 90 ℃ of reaction 2 h.Stop to stir, leave standstill, hexane washed twice (each 30 milliliters) is filtered in layering.Be added dropwise to again 25 ml titanium tetrachlorides at 0 ℃, react 1 h, be warming up to 80 ℃ of reaction 2 h.Stop to stir, leave standstill, hexane washed twice (each 30 milliliters) is filtered in layering.Stop to stir, leave standstill, layering is filtered, and four times (each 30 milliliters) of hexane washing in 60 ℃ of vacuum-dryings 2 hours, obtain the pulverulent solids Primary Catalysts, and the Primary Catalysts particle easily adheres on the wall of container.
Application mode one
Vinyl polymerization: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 1.17 ml (2 mmol/ml) are filled with hydrogen 0.28 MPa after being warming up to 75 ℃, are filled with ethene to 0.73 MPa, constant voltage isothermal reaction 2 h again.
Application mode two
Ethylene copolymerization: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component 10 mg successively in still, dehydration hexane 1000 ml, AlEt 3Solution 1.17 ml (2mmol/ml) add 30 ml 1-hexenes.After being warming up to 75 ℃, be filled with hydrogen 0.28 MPa, be filled with again ethene to 0.73 MPa, constant voltage isothermal reaction 2 h.
Application mode three
Propylene polymerization: 2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component 10 mg successively in still, dehydration hexane 1000 ml, AlEt 3Solution 1.17 ml (2mmol/ml) add external electron donor triethoxy cyclopentyloxy silicon 4 ml (0.18M hexane solution), be warming up to 80 ℃ after, be filled with hydrogen 0.1 MPa, be filled with again propylene to 3 MPa, constant voltage isothermal reaction 2 h.Polyacrylic melting index MFR=111 g/10min.
Olefinic polymerization the results are shown in Table 2.
Embodiment 16
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 1.5 ml, isooctyl alcohol 6.5 ml stir and are warming up to 120 ℃, react 3 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tributyl phosphate 2ml and tetraethoxysilane 0.2 ml, keeping temperature is 60 ℃ of reaction 2 h.System is down under-5 ℃, drips 35 ml titanium tetrachlorides, react 1 h; In 4 hours, be warming up to 110 ℃, react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 5 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 0.6 ml (2 mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1 h again.
Obtain polyethylene 253.2 grams, tap density BD=0.32, melting index MFR=0.8g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 0.6 ml (2 mmol/ml) is filled with hydrogen 0.28 MPa after being warming up to 70 ℃, is filled with ethene to 0.73 MPa, constant voltage isothermal reaction 2 h again.
Obtain polyethylene 350.5 grams, tap density BD=0.33, melting index MFR=3.1g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 25 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 3.0 ml (2 mmol/ml) are filled with hydrogen 0.73 MPa after being warming up to 70 ℃, are filled with ethene to 1.0 MPa, constant voltage isothermal reaction 1 h again.
Obtain polyethylene 243.6 grams, tap density BD=0.35, melting index MFR=510g/10min.
Embodiment 17
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, ethanol 0.4 ml, isooctyl alcohol 6.5 ml stir and are warming up to 120 ℃, react 3 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tributyl phosphate 2.5ml and tetraethoxysilane 0.2 ml, keeping temperature is 60 ℃ of reaction 2 h.System is cooled to 25 ℃, is added dropwise to again in the 25 ml titanium tetrachlorides that are in-15 ℃, at 0 ℃ of reaction 1 h; In 4 hours, be warming up to 110 ℃, react again 2 h.Stop to stir, leave standstill, layering is filtered, four times (each 30 milliliters) of hexane washing, in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution evenly, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 5 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 0.6 ml (2 mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1 h again.
Obtain polyethylene 265.3 grams, tap density BD=0.31, melting index MFR=0.88g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 0.6 ml (2 mmol/ml) is filled with hydrogen 0.28 MPa after being warming up to 70 ℃, is filled with ethene to 0.73 MPa, constant voltage isothermal reaction 2 h again.
Obtain polyethylene 368.3 grams, tap density BD=0.32, melting index MFR=3.9g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 25 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 3.0 ml (2 mmol/ml) are filled with hydrogen 0.73 MPa after being warming up to 70 ℃, are filled with ethene to 1.0 MPa, constant voltage isothermal reaction 1 h again.
Obtain polyethylene 248.1 grams, tap density BD=0.34, melting index MFR=530g/10min.
Comparative Examples 3
In the reactor of fully replacing through nitrogen, add 1 g magnesium dichloride, n-decane 20 ml, isooctyl alcohol 6.5 ml and ethanol 0.4ml stir and are warming up to 120 ℃, react 3 h, and solid dissolves the solution that forms homogeneous fully.Be cooled under 60 ℃, add tetraethoxysilane 2 ml, keeping temperature is 60 ℃ of reaction 2 h.System is cooled to 25 ℃, is added dropwise to again in the 25 ml titanium tetrachlorides that are in-15 ℃, at 0 ℃ of reaction 1 h; In 4 hours, be warming up to 110 ℃, react again 2 h.Stop to stir, leave standstill, layering is filtered, and four times (each 30 milliliters) of hexane washing in 50 ℃ of vacuum-dryings 4 hours, obtain good fluidity, size distribution pulverulent solids Primary Catalysts even, spherical in shape, and the Primary Catalysts particle easily adheres on the wall of container.
Vinyl polymerization
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 0.6 ml (2 mmol/ml) is filled with hydrogen 0.1MPa after being warming up to 70 ℃, is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1 h again.
Obtain polyethylene 235.3 grams, tap density BD=0.30, melting index MFR=1.1g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 10 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 0.6 ml (2 mmol/ml) is filled with hydrogen 0.28 MPa after being warming up to 70 ℃, is filled with ethene to 0.73 MPa, constant voltage isothermal reaction 2 h again.
Obtain polyethylene 188.3 grams, tap density BD=0.28, melting index MFR=4.0g/10min.
2 liters of stainless steel autoclaves after nitrogen is fully replaced, are added main catalyst component component 50 mg successively in still, dehydration hexane 1000 ml, promotor AlEt 3Solution 3.0 ml (2 mmol/ml) are filled with hydrogen 0.73 MPa after being warming up to 70 ℃, are filled with ethene to 1.0 MPa, constant voltage isothermal reaction 1 h again.
Obtain polyethylene 172.1 grams, tap density BD=0.26, melting index MFR=446g/10min.
Mg, Si in table 1 Primary Catalysts, phosphorus, less than the quality percentage composition of the pure and mild alcohol greater than C5 of C5
Figure BDA0000235933971
Table 2 olefinic polymerization result
Figure BDA0000235933972

Claims (10)

1. olefin polymerization catalysis is comprised of Primary Catalysts and promotor, it is characterized in that: described Primary Catalysts by magnesium halide, transition metal halide, be less than or equal to the alcohol of C5, alcohol, silicoorganic compound and organo phosphorous compounds greater than C5 forms; Magnesium halide, transition metal halide, less than the alcohol of C5, the mol ratio of alcohol, silicoorganic compound and organo phosphorous compounds greater than C5 be: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10): (0.05-5); Described promotor is organo-aluminium compound; Transition metal halide in the Primary Catalysts and the mol ratio of promotor are 1:10-500.
2. olefin polymerization catalysis according to claim 1, it is characterized in that: it is Mg (R) that described magnesium halide carrier is selected from general formula (1) aX bCompound at least a, R is selected from C 1～C 20Aliphatic group, C 1～C 20Fatty alkoxyl group, C 3～C 20Alicyclic radical or C 6～C 20Aryl radical; X is selected from halogen; A=0,1 or 2, b=1 or 2, and a+b=2.
3. olefin polymerization catalysis according to claim 1, it is characterized in that: it is M (R that transition metal halide is selected from general formula (2) 1) 4-mX mCompound at least a, in the formula, M is Ti, Zr, Hf, Fe, Co or Ni; X is halogen atom, is selected from Cl, Br, F; M is 1 to 4 integer; R 1Be selected from C 1～C 20Aliphatic group, C 1～C 20Fatty alkoxyl group, C 1～C 20Cyclopentadienyl and derivative, C 1～C 20Aryl radical, COR` or COOR`, R` is C 1～C 10Fatty group or C 1～C 10Aromatic base; The mol ratio of transition metal halide and magnesium halide (8-40): 1.
4. olefin polymerization catalysis according to claim 1, it is characterized in that: the alcohol of the described C5 of being less than or equal to is that carbonatoms is less than or equal to 5 Fatty Alcohol(C12-C14 and C12-C18) or alicyclic ring alcohol, is less than or equal to the alcohol of C5 and the mol ratio of magnesium halide and is (0.05 – 3.5): 1.
5. olefin polymerization catalysis according to claim 1, it is characterized in that: described alcohol greater than C5 is that carbonatoms is Fatty Alcohol(C12-C14 and C12-C18), alicyclic ring alcohol or the aromatic alcohol of C6 – C20, is (1 – 8) greater than the alcohol of C5 and the mol ratio of magnesium halide: 1.
6. olefin polymerization catalysis according to claim 1, it is characterized in that: described silicoorganic compound meet general formula R x 3R y 4Si (OR 5) zAnd general formula (R 6O) (R 7O) (R 8O) (R 9O) Si, wherein R 3And R 4Be respectively alkyl or halogen, R 5, R 6R 7R 8And R 9Alkyl or the cyclic hydrocarbon radical of C1 to C20,0≤x≤2,0≤y≤2, and 0＜z≤4, x+y+z=4; The mol ratio of silicoorganic compound and magnesium halide is (0.5-8): 1.
7. olefin polymerization catalysis according to claim 1 is characterized in that described organo phosphorous compounds is selected from least a in the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid; The mol ratio of organo phosphorous compounds and magnesium halide (0.1-5): 1.
8. organo phosphorous compounds according to claim 7 is characterized in that described organo phosphorous compounds specifically is selected from least a in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid three propyl ester, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate or the phosphorous acid benzene methyl.
9. the preparation method of olefin polymerization catalysis according to claim 1 is characterized in that: may further comprise the steps:
1) magnesium halide carrier is scattered in the inert organic solvents, adds the pure and mild alcohol greater than C5 be less than or equal to C5, in 50 ℃ to 150 ℃ lower stirring and dissolving 1 to 5h;
2) with 1) solution is cooled to 10 ℃ to 80 ℃, adds organo phosphorous compounds and silicoorganic compound, and reaction 0.5 is to 3h;
3) under-25 to 30 ℃, with step 2) system that obtains contacts with transition metal halide, and at-25 to 30 ℃ of lower reaction 0.5-5h, system is warming up to 20-150 ℃ again, reaction 0.5-5h; Leave standstill, layering removes by filter unreacted reactant, adopts toluene or hexane washed product; Washed product contacts with transition metal halide, and at-25 to 30 ℃ of lower reaction 0.5-5h, system is warming up to 20-150 ℃ again, reaction 0.5-5h; Leave standstill, layering removes by filter unreacted reactant, adopts toluene or hexane washed product; This step repeats 0-4 time;
The mol ratio of transition metal halide and magnesium halide is: (1-40): 1;
Vacuum-drying obtains the pulverulent solids Primary Catalysts;
Wherein, described inert organic solvents is selected from C 5～C 15Stable hydrocarbon, C 5～C 10Alicyclic hydrocarbon or C 6～C 15Aromatic hydrocarbon or their mixed solvent.
10. the application of olefin polymerization catalysis according to claim 1, it is characterized in that: described olefin polymerization catalysis is the catalyzer of the copolymerization of the copolymerization of vinyl polymerization, propylene polymerization, ethene and alpha-olefin or propylene and alpha-olefin, wherein, described alpha-olefin is selected from C 3～C 20Alkene.
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