CN101880342B - Olefin polymerization catalyst and preparation and application thereof - Google Patents
Olefin polymerization catalyst and preparation and application thereof Download PDFInfo
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- CN101880342B CN101880342B CN201010227114A CN201010227114A CN101880342B CN 101880342 B CN101880342 B CN 101880342B CN 201010227114 A CN201010227114 A CN 201010227114A CN 201010227114 A CN201010227114 A CN 201010227114A CN 101880342 B CN101880342 B CN 101880342B
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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, a transition metal halide, an organic alcohol compound and an organosiloxane compound, wherein the molar ratio of the carrier to the transition metal halide to the organic alcohol compound to the organosiloxane compound is 1:(0.01-20):(0.1-6):(0.01-5); and the molar ratio of the transition metal halides in an assistant catalyst and the main catalyst is (30-500):1. In the preparation process, an assistant precipitation agent is added, wherein the assistant precipitation agent is alkane with the carbon atom number of 5 to 20 or cyclane with the carbon atom number of 5 to 20; and the mass ratio of the assistant precipitation agent to the carrier is (5-100):1. The olefin polymerization catalyst has the advantages of suitability for slurry process, gas-phase polymerization technology or combined polymerization technology, high catalyst activity, simple preparation method, low equipment requirement and less environmental pollution.
Description
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, like 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 water or alcohol of magnesium dihalide, magnesium dihalide one of them or two halogen atoms by hydroxyl or halogen hydroxyl oxygen base institute metathetical verivate.Concrete compound is like 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 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 characteristic of the present invention is to prepare at Primary Catalysts to add transition metal halide in the 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 moiety and verivate thereof, 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 characteristic of the present invention is to prepare at Primary Catalysts to add the organosilicon oxygen compound in the 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 naphthenic base 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 tert.-butoxy silane, an 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, n-propyl triethoxyl silane, n-propyl Trimethoxy silane, decyl Trimethoxy silane, decyl triethoxyl silane, cyclopentyl Trimethoxy silane, cyclopentyl triethoxyl silane, 2-methylcyclopentyl Trimethoxy silane, 2,3-dimethylcyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxyl silane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, isobutyl-triethoxyl silane, cyclohexyl triethoxyl silane, cyclohexyl trimethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, a chlorine Trimethoxy silane, a 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, di-isopropyl diethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, methylcyclohexyl dimethoxy silane, methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxy silane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxy silane, two o-tolyl dimethoxy silane, two o-tolyl diethoxy silane, two between tolyl dimethoxy silane, two between in tolyl diethoxy silane, biconjugate tolyl dimethoxy silane, biconjugate tolyl diethoxy silane, trimethylammonium methoxy silane, trimethylethoxysilane, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, two cyclopentyl-methyl methoxy silane and 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 characteristic of the present invention is in the preparation process of Primary Catalysts, to add precipitation additive.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 characteristic 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 of adding can equate at every turn, also can be unequal.
The weight ratio of said 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 alkyl or alkoxyl group, the X of 1-20 is halogen; N is the integer of 0＜n≤3, specifically can be selected from: the mixing of one or both in trimethylaluminium, 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.; MAO, ethyl aikyiaiurnirsoxan beta etc.Wherein, the mixing of one or both in preferred triethyl aluminum, triisobutyl aluminium or the MAO.
As optimal technical scheme of the present invention, the use magnitude relation of Primary Catalysts and promotor is: 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 are not participated 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, YLENE, 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 terminal olefin, wherein, the preferred propylene of described terminal olefin, 1-butylene; The 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; Catalyst activity is high; 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
Below in conjunction with embodiment the present invention is described further, 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 drum of fully replacing, add magnesium dichloride 2g successively, epoxy chloropropane 3.5ml through nitrogen; 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, are warming up to 60 ℃ of constant temperature, add hexane 10ml; Reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum of fully replacing, add magnesium dichloride 5g successively, epoxy chloropropane 7.5ml through nitrogen; 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-s, layering extracts supernatant liquid; Toluene wash twice, 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 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 drum 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 adds hexane 15ml, is warming up to 50 ℃ of perseverances, adds hexane 20ml; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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 dropwises the back and adds 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; Be warming up to 45 ℃ of perseverances, add hexane 20ml, temperature reaction 2h stops to stir; Leave standstill suspension-s, 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 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 drum 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, are warming up to 60 ℃ of perseverances, add octane 20ml; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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, are warming up to 50 ℃ of perseverances, add hexanaphthene 20ml; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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, are warming up to 60 ℃ of perseverances, add hexane 10mL; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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, successively in-10 ℃ of constant temperature 1h; 0 ℃ of constant temperature 1h adds hexane 10mL, is warming up to 40 ℃ of constant temperature 1h, is warming up to 50 ℃ of perseverances, adds hexane 10mL; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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, successively in-10 ℃ of constant temperature 1h; 0 ℃ of constant temperature 1h adds hexane 10mL, is warming up to 40 ℃ of constant temperature 1h, is warming up to 50 ℃ of perseverances, adds hexane 10mL; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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, successively in-10 ℃ of constant temperature 1h; 0 ℃ of constant temperature 1h adds hexane 10mL, is warming up to 40 ℃ of constant temperature 1h, is warming up to 50 ℃ of perseverances, adds hexane 10mL; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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, successively in-10 ℃ of constant temperature 1h; 0 ℃ of constant temperature 1h adds hexane 10mL, is warming up to 40 ℃ of constant temperature 1h, is warming up to 50 ℃ of perseverances, adds hexane 10mL; Temperature reaction 2h stops to stir, and leaves standstill suspension-s, and layering extracts supernatant liquid; Toluene wash twice, 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 drum 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-s, and layering extracts supernatant liquid; Toluene wash twice, 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 result sees table 1.
Table 1
Claims (2)
1. the preparation method of an olefin polymerization catalysis 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 titanium tetrachloride, 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, adopts toluene or normal hexane washing 4-6 time, filters; Remove unreacted reactant, solubility promoter, precipitation additive and solvent, vacuum is drained, and obtains main catalyst component; The mol ratio of carrier, titanium tetrachloride, organic alcohol compound and organosilicone compounds is 1: (0.01-20): (0.1-6): (0.01-5);
The mol ratio of 3) Primary Catalysts and promotor being pressed titanium tetrachloride 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 carrier is meant magnesium dihalide carrier or magnesium dihalide carrier and SiO
2, or Al
2O
3The complex carrier of carrier.
2. the preparation method of olefin polymerization catalysis according to claim 1, it is characterized in that: described precipitation additive is normal hexane, normal heptane or hexanaphthene.
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| CN101885791B (en) * | 2010-07-22 | 2012-05-30 | 中国石油天然气股份有限公司 | Broad/multimodal distributed polyolefin catalyst, preparation and application thereof |
| CN102432706B (en) * | 2011-09-15 | 2014-04-02 | 中国石油天然气股份有限公司 | Composite magnesium chloride spherical carrier, preparation and application |
| CN102492061B (en) * | 2011-11-26 | 2014-08-20 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
| CN104558280B (en) * | 2013-10-15 | 2017-02-15 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component as well as preparation method and catalyst thereof |
| CN104558264B (en) * | 2013-10-15 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of catalyst component for olefin and its catalyst and application |
| CN104558279B (en) * | 2013-10-15 | 2017-09-29 | 中国石油化工股份有限公司 | Catalyst component for olefin and its catalyst and application |
| JP6706582B2 (en) * | 2014-04-29 | 2020-06-10 | 中国石油化工股▲ふん▼有限公司 | Method for preparing catalyst component for olefin polymerization |
| CN104530272B (en) * | 2014-12-23 | 2017-04-19 | 中国科学院长春应用化学研究所 | Catalyst for polydiene synthesis and preparation method thereof |
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| CN101274967A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and components thereof |
| CN101891849A (en) * | 2010-06-25 | 2010-11-24 | 中国石油天然气股份有限公司 | Polyolefin catalyst, preparation thereof and application thereof |
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| CN101274967A (en) * | 2007-03-28 | 2008-10-01 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and components thereof |
| CN101891849A (en) * | 2010-06-25 | 2010-11-24 | 中国石油天然气股份有限公司 | Polyolefin catalyst, preparation thereof and application thereof |
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