CN101880342A - Olefin polymerization catalyst, preparation and application thereof - Google Patents

Olefin polymerization catalyst, preparation and application thereof Download PDF

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CN101880342A
CN101880342A CN 201010227114 CN201010227114A CN101880342A CN 101880342 A CN101880342 A CN 101880342A CN 201010227114 CN201010227114 CN 201010227114 CN 201010227114 A CN201010227114 A CN 201010227114A CN 101880342 A CN101880342 A CN 101880342A
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carrier
olefin polymerization
preparation
transition metal
polymerization catalysis
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CN101880342B (en
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义建军
黄启谷
李志飞
卢晓英
郑宏涛
汪红丽
陈商涛
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Petrochina Co Ltd
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Petrochina Co Ltd
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Abstract

The invention relates to an olefin polymerization catalyst and preparation and application thereof.A main catalyst consists of a carrier, transition metal halide, an organic alcohol compound and an organic siloxane compound; the molar ratio of the carrier, the transition metal halide, the organic alcohol compound and the organic siloxane compound is 1 to (0.01-20) to (0.1-6) to (0.01-5); the molar ratio of the cocatalyst to the transition metal halide in the main catalyst is (30-500) to 1; adding a precipitation aid in the preparation process, wherein the precipitation aid is alkane with the carbon atom number of 5-20 and cycloalkane with the carbon atom number of 5-20, and the weight ratio of the precipitation aid to the carrier is (5-100) to 1; the catalyst has high activity; is suitable for a slurry method, a gas-phase polymerization process or a combined polymerization process; the preparation method is simple, has low requirements on equipment and has little pollution to the environment.

Description

A kind of olefin polymerization catalysis and preparation thereof and application
Technical field
The present invention relates to a kind of catalyzer and preparation and application that is used for vinyl polymerization or copolymerization.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology, development from olefin polymerization catalysis, summarize and get up to mainly contain two aspects: (1) exploitation can prepare property or the more excellent polyolefin resin catalyzer of performance, 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 improves, and has simplified polyolefinic production technique, has reduced energy consumption and material consumption.
Patent CN85100997 once adds phthalic anhydride and makes precipitation additive when Preparation of Catalyst, the granules of catalyst form is improved.
Patent CN 1532211A, CN 1140722A, CN1552743 once add hexane and do precipitation additive when Preparation of Catalyst, and help catalyzer and become particulate state to separate out, but separation difficulty, the granules of catalyst form is bad.
Summary of the invention
The object of the present invention is to provide a kind of catalytic activity high catalyzer and preparation and the application that are used for vinyl polymerization or ethene and copolymerization monomer copolymerizable, in the Preparation of catalysts process, add precipitation additive several times.
Ethylene copolymerization catalyst provided by the present invention is made up of Primary Catalysts and promotor; Wherein, described Primary Catalysts is made up of carrier, transition metal halide, organic alcohol compound and organosilicone compounds.The mol ratio of carrier, transition metal halide, organic alcohol compound and organosilicone compounds is 1: (0.01-20): (0.1-6): (0.01-5); Described promotor is an organo-aluminium compound; The transition metal halide in the Primary Catalysts and the mol ratio of promotor are 1: (30-500).
Described carrier is meant the complex carrier of halide carrier or halide carrier and inorganic oxide carrier;
Wherein, described halide carrier be in the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol one of them or two halogen atoms by hydroxyl or halogen hydroxyl oxygen base institute metathetical derivative.Concrete compound is as at 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, dibutylmagnesium, the butyl magnesium chloride etc.Wherein, preferred magnesium dichloride, dibutylmagnesium or chlorobutyl magnesium;
Wherein, described inorganic oxide carrier is SiO 2, Al 2O 3Deng.
One of feature of the present invention is to add transition metal halide in the Primary Catalysts preparation process, and it is M (R that described transition metal halide is selected from general formula 1) 4-mX mCompound at least a, in the formula, M is Ti, Zr, Hf, Fe, Co, Ni etc.; X is a halogen atom, is selected from Cl, Br, F; M is 0 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: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, neighbour-aminomethyl phenyl ,-at least a in aminomethyl phenyl, right-aminomethyl phenyl, neighbour-sulfonic group phenyl, formyl radical, acetyl or benzoyl base etc.Described Ti, Zr, Hf, Fe, Co or Ni transition metal halide 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 for use.Wherein, preferred titanium tetrachloride.
The preferred 0.01-20 of the mol ratio of transition metal halide and carrier: 1.
One of feature of the present invention is to add the organosilicon oxygen compound in the Primary Catalysts preparation process, and described organosilicon oxygen compound is that general formula is R xSi (OR ') y, in the formula, R and R ' are the alkyl of C1-C15, the cycloalkyl of C1-C15, or the aryl of C1-C15; X is 1,2,3; Y is 1,2,3; X+y=4.The organosilicon oxygen compound is selected from: triethoxy isopropoxy silane, 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, 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, the cyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the isobutyl-triethoxyl silane, the cyclohexyl triethoxyl silane, 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, methylcyclohexyl dimethoxy silane, 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, in two cyclopentyl-methyl methoxy silane and the cyclopentyl dimethyl methyl TMOS etc. one or more.Preferred triethoxy isopropoxy silane, diethoxy isopropoxy tert.-butoxy silane, three isopropoxy tert.-butoxy silane, diisopropoxy two tert.-butoxy silane, diethoxy cyclohexyloxy tert.-butoxy silane or an oxyethyl group diisopropoxy tert.-butoxy silane or a tetraethoxysilane.
The preferred 0.01-5 of mol ratio of described organosilicon oxygen compound and carrier: 1.
One of feature of the present invention is to add precipitation additive in the preparation process of Primary Catalysts.Precipitation additive of the present invention is that carbonatoms is a 5-20 alkane, and carbonatoms is a 5-20 naphthenic hydrocarbon, preferred normal hexane, normal heptane or hexanaphthene.
One of feature of the present invention effect that precipitation additive adds several times in the preparation process of Primary Catalysts is better than once adding, and preferred 3 times, dissolve the back fully at carrier halogenide respectively and add, drip TiCl 4The back adds, and drips TiCl 4After add again more than being warming up to 50 degree.The amount of the precipitation additive that adds can equate at every turn, also can be unequal.
The weight ratio of described precipitation additive and carrier is 5-100: 1, and preferred 10-60: 1.
In the preparation process of Primary Catalysts or add organic epoxy compounds and make solubility promoter, it is the inner ether of 2-8 that described organic epoxy compounds is selected from the aliphatics alkene that carbonatoms is 2-8, the diolefine that carbonatoms is 2-8, the halogenated aliphatic alkene that carbonatoms is 2-8, the oxide compound that carbonatoms is the diolefine of 2-8, glycidyl ether or the carbonatoms that carbonatoms is 2-8.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane or methyl glycidyl ether.Wherein, preferred propylene oxide or epoxy chloropropane.
The preferred 0.5-10 of mol ratio of described organic epoxy compounds and magnesium halide: 1.
In the preparation process of Primary Catalysts or add organophosphate and make solubility promoter, described organophosphate is selected from the hydrocarbyl carbonate of ortho-phosphoric hydrocarbyl carbonate or phosphorous acid.Concrete as: 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 phosphorous acid benzene methyl.Wherein, preferred ortho-phosphoric acid tri-n-butyl.
The preferred 0.5-10 of the mol ratio of described organophosphate and magnesium halide: 1.
It is AlR that described promotor organo-aluminium compound is selected from general formula 5 nX 3-nCompound in one or both mixing, in the formula, R 5For hydrogen or carbonatoms are that the alkyl of 1-20 or alkoxyl group, X are halogen, n is the integer of 0＜n≤3, specifically can be selected from: the mixing of one or both in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-tert aluminium, trioctylaluminum, aluminium diethyl monochloride, ethyl aluminum dichloride, the sesquialter ethyl aluminum chloride etc.; Methylaluminoxane, ethyl aikyiaiurnirsoxan beta etc.Wherein, the mixing of one or both in preferred triethyl aluminum, triisobutyl aluminium or the methylaluminoxane.
As the preferred technical solution of the present invention, Primary Catalysts and promotor with magnitude relation be: the mol ratio of transition metal halide and promotor is 1: 30-500.
The preparation method of olefin polymerization catalysis provided by the present invention may further comprise the steps:
1) with carrier at 10-150 ℃, be scattered in the organic solvent, add organic alcohol compound and precipitation additive;
2) under-40-30 ℃, add transition metal halide in the solution that in step 1), obtains, dropwise the back and add organosilicone compounds, add precipitation additive for the second time.Be warming up to 40-110 ℃, add precipitation additive for the third time, reacted 0.5-24 hour, in temperature-rise period, particle is separated out and formed to solids gradually, after reaction finishes, adopt toluene or normal hexane washing 4-6 time, filter, remove unreacted reactant, solubility promoter, precipitation additive and solvent, vacuum is drained, and obtains main catalyst component.Solubility promoter, precipitation additive and solvent do not participate in chemical reaction in catalyst preparation process.
3) be 30-500 with Primary Catalysts and promotor by the mol ratio of transition metal halide in promotor and the Primary Catalysts: 1 mixes, and obtains olefin polymerization catalysis.
Described organic solvent is selected from toluene, dimethylbenzene, hexane, heptane, octane or decane, or their mixed solvent, preferred toluene, hexane, heptane or decane.
The purposes of ethylene rolymerization catalyst provided by the present invention is: can be used as the copolymerization catalyst of vinyl polymerization or ethene and alpha-olefin, wherein, the preferred propylene of described alpha-olefin, 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 ethylene copolymerization catalyst that the purpose of this invention is to provide is good, and is spherical in shape; The catalyst activity height; Be applicable to slurry process, gas-phase polymerization process or polymerization mix technology; The preparation method is simple, and is low for equipment requirements, and environmental pollution is little.
Embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is limited to following embodiment not to the utmost.
Embodiment 1
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 2g successively, epoxy chloropropane 3.5ml, tributyl phosphate 5.5ml, toluene 75ml, hexane 15ml, ethanol 3.2ml, be warming up to 70 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 8ml titanium tetrachloride, 3.5ml diethoxy isopropoxy tert.-butoxy silane is behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h, add hexane 15ml, be warming up to 60 ℃ of constant temperature, add hexane 10ml, reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds 1-octene 35mL, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa, constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 2
1) preparation Primary Catalysts: in the reactor of fully replacing through nitrogen, add magnesium dichloride 5g successively, epoxy chloropropane 7.5ml, tributyl phosphate 10.5ml, toluene 150ml, hexane 10ml, ethanol 6.2ml, stir down and be warming up to 60 ℃, solid dissolve fully form equal-solution after, constant temperature 1h; Then be cooled to-25 ℃, drip the 40ml titanium tetrachloride, dropwise the back and add the 2.5g tetraethoxysilane, 10 ℃ of constant temperature 1h add hexane 10ml, behind the reaction 1h, be warming up to 70 ℃ of constant temperature, hexane 10ml, reaction 2h, stop to stir, leave standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds 1-hexene 40mL, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into ethene to 0.3MPa, constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 3
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 5ml through nitrogen, tributyl phosphate 10.5ml, toluene 75ml, hexane 15ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 5g triethoxy uncle fourth oxosilane, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, add hexane 15ml, be warming up to 50 ℃ of perseverances, add hexane 20ml, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds 4-methyl-1-pentene 30mL, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 4
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 3g successively, epoxy chloropropane 3ml through nitrogen, tributyl phosphate 6.5ml, toluene 75ml, hexane 5ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride, dropwise the back and add 2mL triethoxy uncle's fourth oxosilane and 2mL diethoxy isopropoxy uncle fourth oxosilane, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h,-5 ℃ of constant temperature 1h add hexane 25ml, are warming up to 45 ℃ of perseverances, add hexane 20ml, temperature reaction 2h stops to stir, and leaves standstill suspension, layering, extract supernatant liquid, toluene wash twice, twice of hexane wash, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 5
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 3g successively, epoxy chloropropane 3ml through nitrogen, tributyl phosphate 6.5ml, toluene 75ml, octane 10ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 5mL diethoxy hexamethylene oxygen uncle fourth oxosilane, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 10 ℃ of constant temperature 1h, add octane 25ml, be warming up to 60 ℃ of perseverances, add octane 20ml, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 6
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 4g successively, epoxy chloropropane 3ml through nitrogen, tributyl phosphate 6.5ml, toluene 75ml, hexanaphthene 10ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 8g diethoxy isopropoxy benzene TMOS, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 40 ℃ of constant temperature 1h, add hexanaphthene 25ml, be warming up to 50 ℃ of perseverances, add hexanaphthene 20ml, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 7
1) preparation Primary Catalysts: in the reactor of fully replacing, add dibutylmagnesium 3g successively through nitrogen, toluene 75ml, Butyryl Chloride 10ml, hexane 10mL, isooctyl alcohol 3.2ml is warming up to 60 ℃, constant temperature 1h under stirring; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 5mL diethoxy hexamethylene oxygen uncle fourth oxosilane, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 10 ℃ of constant temperature 1h, add hexane 10mL, be warming up to 60 ℃ of perseverances, add hexane 10mL, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 8
1) preparation Primary Catalysts: in the reactor of fully replacing, add a chlorobutyl magnesium 3g successively through nitrogen, toluene 75ml, benzyl chloride 10ml adds hexane 10mL, and isooctyl alcohol 2.2ml is warming up to 60 ℃, constant temperature 1h under stirring; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 8g diethoxy isopropoxy benzene TMOS, behind the reaction 1h, in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h adds hexane 10mL successively, be warming up to 40 ℃ of constant temperature 1h, be warming up to 50 ℃ of perseverances, add hexane 10mL, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 9
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium chloride 3g successively through nitrogen, epoxy chloropropane 3ml, tributyl phosphate 6.5ml, toluene 75ml adds hexane 10mL, and p-methyl phenol 2g is warming up to 60 ℃, constant temperature 1h under stirring; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 8g diethoxy isopropoxy benzene TMOS, behind the reaction 1h, in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h adds hexane 10mL successively, be warming up to 40 ℃ of constant temperature 1h, be warming up to 50 ℃ of perseverances, add hexane 10mL, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 10
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium chloride 3g successively through nitrogen, toluene 75ml, epoxy chloropropane 3ml, tributyl phosphate 6.5ml adds hexane 10mL, and phenol 2g is warming up to 60 ℃, constant temperature 1h under stirring; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 8g diethoxy isopropoxy benzene TMOS, behind the reaction 1h, in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h adds hexane 10mL successively, be warming up to 40 ℃ of constant temperature 1h, be warming up to 50 ℃ of perseverances, add hexane 10mL, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Embodiment 11
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium chloride 3g successively through nitrogen, toluene 75ml, epoxy chloropropane 3ml, tributyl phosphate 6.5ml, ethanol 3.2mL adds hexane 10mL, and phenol 2g is warming up to 60 ℃, constant temperature 1h under stirring; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride dropwises the back and adds 8g diethoxy isopropoxy benzene TMOS, behind the reaction 1h, in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h adds hexane 10mL successively, be warming up to 40 ℃ of constant temperature 1h, be warming up to 50 ℃ of perseverances, add hexane 10mL, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.5ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds the own 30mL of 1-, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
Comparative Examples 1
1) preparation Primary Catalysts: in the reactor of fully replacing, add magnesium dichloride 3g successively, ethanol 3.2mL through nitrogen, epoxy chloropropane 3ml, tributyl phosphate 6.5ml, ethanol toluene 75ml, be warming up to 60 ℃ under stirring, after solid dissolves the solution that forms homogeneous fully, constant temperature 1h; Then be cooled to-25 ℃, Dropwise 5 0ml titanium tetrachloride drips hexane 10ml, dropwises the back and adds the 4mL tetraethoxysilane, behind the reaction 1h, successively in-10 ℃ of constant temperature 1h, 0 ℃ of constant temperature 1h, 20 ℃ of constant temperature 1h are warming up to 60 ℃ of perseverances, drip hexane 10ml, temperature reaction 2h stops to stir, and leaves standstill suspension, layering extracts supernatant liquid, twice of toluene wash, hexane wash twice, nitrogen dries up, and obtains the main catalyst component of good fluidity, narrow diameter distribution;
2) ethylene copolymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into hydrogen to 0.28MPa after being warming up to 80 ℃, charges into ethene again to 0.73MPa, adds 1-hexene 30mL, constant voltage isothermal reaction 2h.
3) vinyl polymerization: 0.5 liter of stainless steel autoclave after nitrogen is fully replaced, is added main catalyst component 20mg successively in still, dehydration hexane 200ml, AlEt 3Solution 1.2ml (2mmol/ml) charges into ethene to 0.3MPa constant voltage isothermal reaction 2h after being warming up to 80 ℃.
The results are shown in Table 1.
Table 1
Figure BSA00000191902000151

Claims (9)

1. an olefin polymerization catalysis is made up of Primary Catalysts and promotor; Wherein, described promotor is an organo-aluminium compound; It is characterized in that: described Primary Catalysts is made up of carrier, transition metal halide, organic alcohol compound and organosilicone compounds; The mol ratio of carrier, transition metal halide, organic alcohol compound and organosilicone compounds is 1: (0.01-20): (0.1-6): (0.01-5); The mol ratio of transition metal halide is (30-500) in promotor and the Primary Catalysts: 1;
Described carrier is meant the complex carrier of halide carrier or halide carrier and inorganic oxide carrier.
2. olefin polymerization catalysis according to claim 1 is characterized in that: it is M (R that described transition metal halide is selected from general formula 1) 4-mX mCompound at least a, in the formula, M is Ti, Zr, Hf, Fe, Co or Ni; X is a halogen atom, is selected from Cl, Br or F; M is 0 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.
3. olefin polymerization catalysis according to claim 1 is characterized in that: described organosilicon oxygen compound is that general formula is: R xSi (OR ') y, in the formula, R and R ' are the alkyl of C1-C15, the cycloalkyl of C1-C15, or the aryl of C1-C15; X takes from 0,1, and 2 or 3; Y takes from 1,2, and 3 or 4; X+y=4.
4. olefin polymerization catalysis according to claim 1 is characterized in that: described organic alcohol compound is selected from least a in the isomery alcohol that straight chain alcohol that carbonatoms is 1-15, branched alkyl alcohol that carbonatoms is 1-15, cycloalkyl alcohol that carbonatoms is 1-15 or carbonatoms be 1-15.
5. the preparation method of the described olefin polymerization catalysis of claim 1 is characterized in that:
1) carrier is scattered in the organic solvent at 10-150 ℃, adds organic alcohol compound and precipitation additive;
2) under-40-30 ℃, in the solution that step 1) obtains, add transition metal halide, dropwise the back and add organosilicone compounds, for the second time add precipitation additive, be warming up to 40-110 ℃, add precipitation additive for the third time, reacted 0.5-24 hour, in temperature-rise period, particle is separated out and formed to solids gradually, after reaction finishes, adopt toluene or normal hexane washing 4-6 time, filter, remove unreacted reactant, solubility promoter, precipitation additive and solvent, vacuum is drained, and obtains main catalyst component;
3) mol ratio of Primary Catalysts and promotor being pressed transition metal halide in promotor and the Primary Catalysts is (30-500): 1 mixes, and obtains olefin polymerization catalysis.
Described precipitation additive is that carbonatoms is a 5-20 alkane, and carbonatoms is a 5-20 naphthenic hydrocarbon, and the weight ratio of precipitation additive and carrier is (5-100): 1;
Described solubility promoter is organic epoxy compounds or organophosphate, the mol ratio of organic epoxy compounds or organophosphate and magnesium halide (0.5-10): 1.
6. the preparation method of olefin polymerization catalysis according to claim 5, it is characterized in that: described precipitation additive is normal hexane, normal heptane or hexanaphthene.
7. the preparation method of olefin polymerization catalysis according to claim 5, it is characterized in that: described organic epoxy compounds is propylene oxide or epoxy chloropropane.
8. the preparation method of olefin polymerization catalysis according to claim 5, it is characterized in that: described organophosphate is the ortho-phosphoric acid tri-n-butyl.
9. the application of the described olefin polymerization catalysis of claim 1 is characterized in that: be used for that ethylene homo closes or the copolymerization of ethene and Alpha-alkene.
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