CN102875704B - Olefin polymerization catalyst as well as preparation method and application thereof - Google Patents
Olefin polymerization catalyst as well as preparation method and application thereof Download PDFInfo
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- CN102875704B CN102875704B CN201210326599.9A CN201210326599A CN102875704B CN 102875704 B CN102875704 B CN 102875704B CN 201210326599 A CN201210326599 A CN 201210326599A CN 102875704 B CN102875704 B CN 102875704B
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Abstract
The invention relates to an olefin polymerization catalyst as well as a preparation method and application of the olefin polymerization catalyst. The olefin polymerization catalyst comprises a primary catalyst and a promoter catalyst, wherein the primary catalyst comprises magnesium halide, transition metal halide, organic alcoholate, phosphate ester compound, epoxy haloalkane compound, organo-siloxane compound and organic alcohol ether compound; and the promoter catalyst comprises one or several kinds of the combination of organoaluminum compound. The preparation method of the olefin polymerization catalyst comprises the steps as follows: dispersing the magnesium halide into an organic solvent; sequentially adding the organic alcoholate, the phosphate ester compound and the epoxy haloalkane compound; heating and agitating to dissolve; then sequentially adding the organo-siloxane compound and the organic alcohol ether compound; and dropping the transition metal halide to obtain the primary catalyst, wherein the primary catalyst and the promoter catalyst are individually stored, and combined when in use. According to the olefin polymerization catalyst provided by the invention, the primary spherical catalyst and the promoter spherical catalyst are combined when in use, thus, high catalytic activity is achieved.
Description
Technical field
The present invention relates to a kind of olefin polymerization catalysis and preparation method thereof and application, belong to olefin polymerization catalysis and field of olefin polymerisation.
Background technology
The existing nearly 60 years history of Ziegler-Natta catalyst development, there is the polyolefin catalyst such as metallocene and Nonmetallocene in period, but its industrial problems is more, and such as promotor is expensive, load is difficult.Therefore current, with regard to industrial production and share of market, in following for some time, traditional Z-N catalyzer will be the absolute leader of field of olefin polymerisation.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability and catalytic activity also improve constantly.But catalyzer still has deficiency in granule regularizing and size distribution, gained polyolefin products tap density is low, fine powder content is high, and cause sticky still in production, hang still, block the problems such as pipeline, this greatly affects productivity effect.At present, be badly in need of in production developing that a kind of preparation technology is simple, the spherical catalyst of even particle size distribution.
Disclosed about preparing the technology of spherical catalyst at present, mainly concentrate on and adopt spherical carrier of catalyst aspect, the preparation method of ball type carrier is many, as reprecipitation method, recrystallization method and chemical reaction method etc.
Mostly conventional polyolefins spherical catalyst, be the method be shaped by physics, first prepares spherical magnesium chloride and add and thing carrier.Patent CN1718595A discloses a kind of spherical catalyst for olefinic polymerization, this spherical catalyst components comprises and to be carried on magnesium halide active carrier at least one titanium compound and optionally at least one electron donor compound, and wherein said magnesium halide active carrier is the solid particulate rotating dispersion by magnesium halide/alcohol adducts melt under super gravity field and obtain.
Patent CN1404416A discloses a kind of preparation method of magnesium dihalide ball type carrier, the method be by by the molten adduct emulsion dispersion of magnesium dihalide and Lewis base in liquid phase medium, then this emulsion is cooled fast, obtain form of spherical particles carrier adducts under certain condition.
Patent CN1397568A also discloses a kind of spherical polyolefin catalyst preparation method, that Magnesium Chloride Anhydrous and alcohol are obtained magnesium chloride alcohol adduct melt according to a certain ratio, after adding certain organic complexing agent again, stirring at low speed dispersion in methyl-silicone oil and whiteruss blending agent, then cooling forms MgCl2-alcohol-organic complexing agent mixture spheroidal particle rapidly.
Patent CN101712732A discloses a kind of preparation method of spherical catalyst for propylene polymerization.This patent first prepares ball type carrier: in reactor, adds white oil and silicone oil, drops into magnesium chloride and the ethanol of certain proportioning, melting; Move to after melting and add hexane in advance and be chilled in the reactor of-30 DEG C, outlet temperature is no more than 0 DEG C; Suction filtration, washing, obtained ball type carrier.
But the preparation of magnesium halide spherical adduct in these class methods, often need high melt temperature and low Formation temperature, and sometimes also need dealcoholation treatment, complicated process of preparation, energy consumption is large.
Along with going deep into of research, it is found that, by adding suitable precipitation agent, spherical carrier of catalyst can be prepared by the mode of crystallization of the dissolution and precipitation.Such as, patent CN101857650A, disclose a kind of preparation method of easy spherical polyolefin catalyst carrier, being specially and anhydrous magnesium halide is dissolved in tetrahydrofuran (THF) formation solution, take glycol ether as precipitation agent, glycol ether is slowly instilled in magnesium halide solution, keep high-speed stirring, gained system stratification, isolates bottom sediment and washs, after gained precipitation muriate or alkyl aluminum solutions are soaked after isolate precipitation again, and with alkane, spherical carrier of catalyst is obtained to its washing.
People also find, just can not prepare spherical catalyst with physical method, the object that equally also can reach with chemical reaction method.Compared to the physical method preparing magnesium halide ball type carrier, the advantage of chemical process is, preparation method is simple, and energy consumption is low.Such as, patent CN87102324A discloses the manufacture method of the spherical carrier of catalyst of used in alpha-olefines polymerization, the chlorine-containing organic compounds specifically associated with certain electron donor, react in the mixture that alkyl magnesium, aikyiaiurnirsoxan beta and/or aluminium are prefabricated for the electron donor of siloxanes and necessity, then obtain ball type carrier.
Patent CN102040683A discloses a kind of ball type carrier preparation method for olefin polymerization catalysis, this ball type carrier preparation method is, the magnesium chloride of certain proportioning, white oil and ethanol first react and form magnesium chloride alcohol and thing, then react with oxirane compound.Gained carrier granule form is good, and size is adjustable, narrow diameter distribution.
These chemical reaction methods are lower than physical method energy consumption, achieve progress, but they are all first prepare ball type carrier, then prepare spherical olefin polymerization catalysis by obtained ball type carrier, comprise two steps.If spherical catalyst can be obtained without the need to preparing ball type carrier, just energy Simplified flowsheet, a step-down less energy-consumption of going forward side by side.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of olefin polymerization catalysis, its Primary Catalysts has that particle form is spherical in shape, the advantage of even particle size distribution, and make the polymer bulk density for preparing high in conjunction with promotor, fine powder is few.
The present invention also aims to the preparation method that above-mentioned olefin polymerization catalysis is provided.This preparation technology is simple, and low for equipment requirements, energy consumption is little, and environmental pollution is little.
For reaching above-mentioned purpose, the invention provides a kind of olefin polymerization catalysis, it comprises Primary Catalysts and promotor;
Wherein, the raw material of described Primary Catalysts is made up of magnesium halide, transition metal halide, organic alcohol compound, phosphate compound, epoxy haloalkane compound, organosilicone compounds and Organic Alcohol ether compound;
The mol ratio of described magnesium halide, described transition metal halide, described organic alcohol compound, described phosphate compounds, described epoxy halo alkanes compound, described organosilicone compounds is 1: (1-30): (1-5): (0.1-10): (1-20): (0.001-0.4);
The mass ratio of described magnesium halide and described Organic Alcohol ether compound is 1: (0.001-0.2);
Described promotor includes the combination of one or more in machine aluminium compound;
The mol ratio of the transition metal halide in described promotor and described Primary Catalysts is (30-500): 1;
Described magnesium halide comprises formula M g (R
1)
ax
1 bthe combination of one or more in shown compound, in formula, R
1for C
1-C
20aliphatic group, C
1-C
20fatty alkoxyl group, C
3-C
20alicyclic radical or C
6-C
20aryl radical, X
1for halogen, a be 0 or 1, b be 1 or 2, a+b=2;
Described transition metal halide comprises formula M (R
2)
4-mx
2 mthe combination of one or more in shown compound, in formula, M is Ti, Zr, Hf, Fe, Co or Ni, X
2for Cl, Br or F, m is the integer of 1 to 4, R
2for C
1-C
20aliphatic group, C
1-C
20fatty alkoxyl group, C
5-C
20cyclopentadienyl and derivative, C
6-C
20aryl radical, COR ' or COOR ', wherein, R ' is C
1-C
10aliphatic group or C
6-C
10aryl radical;
Described phosphate compounds comprises general formula (R
3o)
3the combination of one or more in compound shown in PO, in formula, R
3for C
1-C
20aliphatic group, C
3-C
20alicyclic radical or C
6-C
20aryl radical;
Described epoxy halogen alkyl compound comprises general formula C
nh
(2n-1)oX
3the combination of one or more in shown compound, this compounds is straight-chain molecule, and an end group is epoxide group, and another end group is replaced by a halogen atom, and in formula, n is the integer of 3-20, X
3for halogen;
Described organosilicone compounds comprises general formula R
c 4x
d 4si (OR
5)
ethe combination of one or more in shown compound, in formula, R
4for alkyl, X
4for halogen, R
5for alkyl, c, d and e are integer, and 0≤c < 2,0≤d < 2, and 0 < e≤4, c+d+e=4;
Described Organic Alcohol ether compound comprises general formula HO (CH
2)
fo (CH
2)
gr
6the combination of one or more in shown compound, in formula, f is the integer of 1 to 20, and g is the integer of 1 to 10, R
6for aliphatic group, cycloalkyl or aryl radical, wherein, described aliphatic group is general formula C
hh
2h+1, C
hh
2h-1or C
hh
2h-3shown in one in group, 1≤h < 30 and h is integer, described cycloalkyl and described aryl radical are respectively general formula C
ih
2i-1, C
ih
2i-3, C
ih
2i-5or
ciH
2i-7shown in one in group, 3≤i < 30 and i is integer.
In above-mentioned olefin polymerization catalysis, preferably, described magnesium halide comprises the combination of one or more in magnesium dichloride, dibrominated magnesium, diiodinating magnesium, 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 and butyl magnesium chloride etc.More preferably, described magnesium halide is magnesium dichloride.
In above-mentioned olefin polymerization catalysis, preferably, the formula M (R of described transition metal halide
2)
4-mx
2 min R
2can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, o-aminomethyl phenyl, m-aminomethyl phenyl, p-aminomethyl phenyl, o-sulfonic group phenyl, formyl radical, acetyl or benzoyl base etc.
In above-mentioned olefin polymerization catalysis, preferably, described transition metal halide comprises the combination of one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, methoxytitanium trichloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, four phenoxide titaniums, a chlorine triple phenoxyl titanium, dichloro oxygen base titanium and trichlorine one phenoxide titanium etc.More preferably, described transition metal halide is titanium tetrachloride.
In above-mentioned olefin polymerization catalysis, described organic alcohol compound comprises C
1-C
15straight-chain alkyl alcohol, C
1-C
15branched alkyl alcohol, C
1-C
15cycloalkyl alcohol, C
1-C
15isomery alcohol and C
6-C
20aromatic alcohol in the combination of one or more.Preferably, described organic alcohol compound comprises ethanol, ethylene glycol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 1,3-PD, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, sorbyl alcohol, hexalin, methyl-cyclohexanol, benzylalcohol, xylyl alcohol and Isobutyl Benzyl Carbinol etc.More preferably, described organic alcohol compound is the combination of one or more in ethanol, butanols, 2-Ethylhexyl Alcohol and glycerol.
In above-mentioned olefin polymerization catalysis, preferably, described phosphate compound comprises the combination of one or more in tributyl phosphate, tri hexyl phosphate, trioctyl phosphate and TNPP tri n pentyl phosphate etc.More preferably, described phosphate compound is tributyl phosphate.
In above-mentioned olefin polymerization catalysis, preferably, described epoxy haloalkane compound comprises the combination of one or more in epoxy chloropropane, epoxy chlorobutane, epoxy chloropentane, Epiiodohydrin, epoxy butyl iodide, epoxy iodopentane, epoxy bromopropane and epoxy n-butyl bromide etc.More preferably, described epoxy haloalkane compound is epoxy chloropropane.
In above-mentioned olefin polymerization catalysis, preferably, described organosilicone compounds comprises 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, 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, cyclohexyltriethyloxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltrimethoxysilane, 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, vinyltributoxysilane, trimethyl phenoxysilane, methyl triolefin npropoxysilane, vinyl triacyloxysilanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dibutyldimethoxysilane, diisopropyl dimethoxy silane, diisopropyldiethoxysilane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, Cyclohexylmethyldimethoxysilane, methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, two o-tolyl dimethoxysilane, two o-tolyl diethoxy silane, tolyl dimethoxysilane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxysilane, biconjugate tolyl diethoxy silane, trimethylmethoxysilane, trimethylethoxysilane, three cyclopentylmethoxy silane, three cyclopentyl Ethoxysilanes, the combination of one or more in dicyclopentylmethyl methoxy silane and cyclopentyl dimethyl methoxy silane etc.More preferably, described organosilicone compounds is tetramethoxy-silicane and/or tetraethoxysilane.
In above-mentioned olefin polymerization catalysis, preferably, described Organic Alcohol ether compound comprises ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol propyl ether, dihydroxypropane single-ether, butyleneglycol list propyl ether, 2-(2-cyclopentyl oxyethyl group) ethanol, 3-(2-cyclohexylethoxy radical) propyl alcohol, 2-(5-phenylpentyloxy) ethanol, 4-(3-(naphthyl) propoxy-) butanols, 2-(3-epoxy ethyl propoxy-) ethanol, the combination of one or more in 2-(2-furyl oxyethyl group) ethanol and 3-(3-pyridyl propoxy-) propyl alcohol etc.Containing renovation agent Organic Alcohol ether compound in Primary Catalysts of the present invention, it can improve primary catalyst particles form and the size distribution situation of precipitation.
In above-mentioned olefin polymerization catalysis, described promotor is for common are machine aluminium compound, preferably, described promotor comprises the combination of one or more in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride and methylaluminoxane (MAO) etc.
The present invention also provides the preparation method of above-mentioned olefin polymerization catalysis, and it comprises the following steps:
Magnesium halide is scattered in organic solvent, adds organic alcohol compound, phosphate compounds and epoxy halogen alkyl compound successively, then stirring and dissolving at 30-100 DEG C, preferably, stirring and dissolving at 70-90 DEG C, afterwards isothermal reaction 1-5h;
Under 10-70 DEG C of agitation condition, add organosilicone compounds and Organic Alcohol ether compound successively, then isothermal reaction 0.5-3h;
Under-30 DEG C to 30 DEG C agitation conditions, drip metal halide compound with the speed of 15mL/h-40mlL/h, drip isothermal reaction 0.5-5h after finishing;
Be warming up to 20-100 DEG C, preferably, be warming up to 60-90 DEG C, then isothermal reaction 0.5-5h, in the process, solid particulate is separated out gradually;
With n-hexane product 4-6 time, cross and filter unreacted reactant, then vacuum-drying obtains Primary Catalysts;
Described promotor includes the combination of one or more in machine aluminium compound, and it can be obtained by ordinary method;
Described Primary Catalysts separates with described promotor to be deposited, and merges in use.
In above-mentioned preparation method, described organic solvent comprises C
5-C
15stable hydrocarbon, C
5-C
10alicyclic hydrocarbon, C
6-C
15aromatic hydrocarbon and C
2-C
10saturated heterocyclic hydrocarbon in the combination of one or more.Preferably, described organic solvent comprises the combination of one or more in toluene, dimethylbenzene, normal hexane, normal heptane, octane and n-decane etc.More preferably, described organic solvent is the combination of one or more in toluene, normal hexane, normal heptane and n-decane.
The present invention also provides above-mentioned olefin polymerization catalysis to be all polymerized as alkene or the application of catalyzer of ethene and copolymerization monomer copolymerizable.Preferably, described comonomer can be C
3-C
20alpha-olefin; More preferably, described comonomer comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 1,3-dibutene, isoprene, vinylbenzene, vinyl toluene and norbornylene etc.
In the present invention, in the preparation process of Primary Catalysts, in phosphate compound, epoxy alkyl halide compound, organic alcohol compound, magnesium halide, organosilicone compounds and organic solvent system, by adding Organic Alcohol ether compound, improve magnesium halide and separate out situation, thus obtain that particle form is spherical in shape, the Primary Catalysts of even particle size distribution.By adding promotor in use, making the activity of Primary Catalysts, stability increases.Catalyst loadings provided by the invention is high, and catalytic activity is high; The polymer bulk density obtained is high, and fine powder is few; Be applicable to slurry polymerization processes, gas-phase polymerization process or polymerization mix technique; And preparation technology is simple, and low for equipment requirements, energy consumption is little, and environmental pollution is little.
Accompanying drawing explanation
Fig. 1 is the grain size distribution of the Primary Catalysts of embodiment 1;
Fig. 2 is the grain size distribution of the Primary Catalysts of comparative example 1;
Fig. 3 is the scanning electron microscope diagram of the Primary Catalysts of embodiment 1;
Fig. 4 is the scanning electron microscope diagram of the Primary Catalysts of comparative example 1.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited only to following embodiment.
Embodiment 1
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 50 DEG C, add tetraethoxysilane 0.05mL successively, ethylene glycol monomethyl ether 0.02mL, isothermal reaction 2h.Be cooled to-5 DEG C, drip 15mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 2
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 40 DEG C, add tetraethoxysilane 0.02mL successively, ethylene glycol monoethyl ether 0.02mL, isothermal reaction 2h.Be cooled to-5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 3
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 1mL, tributyl phosphate 2.5mL, epoxy chloropropane 1.5mL, be warming up to 80 DEG C and stir simultaneously, afterwards isothermal reaction 2h.Be cooled to 60 DEG C, add tetraethoxysilane 0.01mL successively, ethylene glycol monobutyl ether 0.01mL, isothermal reaction 2h.Be cooled to-5 DEG C, drip 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 4
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 1.5mL, tributyl phosphate 1.5mL, epoxy chloropropane 1mL, be warming up to 85 DEG C and stir simultaneously, afterwards isothermal reaction 2h.Be cooled to 50 DEG C, add tetraethoxysilane 0.02mL successively, ethylene glycol propyl ether 0.04mL, isothermal reaction 2h.Be cooled to 0 DEG C, drip 30mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 85 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 5
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 3mL, tributyl phosphate 1.8mL, epoxy chloropropane 1.3mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 DEG C, add tetraethoxysilane 0.05mL successively, dihydroxypropane single-ether 0.02mL, isothermal reaction 2h.Be cooled to 0 DEG C, drip 30mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 6
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.7mL, tributyl phosphate 1mL, epoxy chloropropane 2mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 2h.Be cooled to 70 DEG C, add tetraethoxysilane 0.01mL successively, butyleneglycol list propyl ether 0.02mL, isothermal reaction 2h.Be cooled to 0 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 7
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.1mL, tributyl phosphate 2mL, epoxy chloropropane 1mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 45 DEG C, add tetraethoxysilane 0.03mL successively, 2-(2-cyclopentyl oxyethyl group) ethanol 0.05mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 8
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2mL, tributyl phosphate 2.5mL, epoxy chloropropane 1.6mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 65 DEG C, add tetraethoxysilane 0.05mL successively, 3-(2-cyclohexylethoxy radical) propyl alcohol 0.05mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 9
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 1.9mL, tributyl phosphate 3mL, epoxy chloropropane 2mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.02mL successively, 2-(5-phenylpentyloxy) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 80 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 10
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 1.5mL, tributyl phosphate 1mL, epoxy chloropropane 3mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 DEG C, add tetraethoxysilane 0.01mL successively, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 11
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.05mL successively, 2-(3-epoxy ethyl propoxy-) ethanol 0.02mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 12
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, Epiiodohydrin 4mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.01mL successively, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 13
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy bromopropane 1.7mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.03mL successively, 3-(3-pyridyl propoxy-) propyl alcohol 0.02mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 14
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, propyl alcohol 1.5mL, tributyl phosphate 2mL, Epiiodohydrin 4mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.01mL successively, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 15
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, butanols 1mL, tributyl phosphate 2mL, Epiiodohydrin 4mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.01mL successively, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 16
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, propylene glycol 1mL, tributyl phosphate 2mL, Epiiodohydrin 4mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 60 DEG C, add tetraethoxysilane 0.01mL successively, 2-(2-furyl oxyethyl group) ethanol 0.04mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 17
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, propyl alcohol 1mL, tributyl phosphate 1mL, epoxy chloropropane 3mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 DEG C, add tetraethoxysilane 0.01mL successively, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain mobility traitor, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 18
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, propylene glycol 1mL, tributyl phosphate 1mL, epoxy chloropropane 3mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 DEG C, add tetraethoxysilane 0.01mL successively, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Embodiment 19
Present embodiments provide a kind of olefin polymerization catalysis, it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, butanols 1mL, tributyl phosphate 1mL, epoxy chloropropane 3mL, be warming up to 90 DEG C and stir simultaneously, afterwards isothermal reaction 3h.Be cooled to 70 DEG C, add tetraethoxysilane 0.01mL successively, 4-(3-(naphthyl) propoxy-) butanols 0.06mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 25mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 90 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of the present embodiment, and the two merges in use.
Comparative example 1
This comparative example provides a kind of olefin polymerization catalysis, and it is prepared by following steps:
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 40mL, ethanol 2.5mL, tributyl phosphate 2mL, epoxy chloropropane 1.7mL.Be warming up to 85 DEG C to stir, afterwards isothermal reaction 3h simultaneously.Be cooled to 60 DEG C, add tetraethoxysilane 0.05mL, isothermal reaction 2h.Be cooled to 5 DEG C, drip 20mL titanium tetrachloride, then isothermal reaction 1h.Be warming up to 100 DEG C, isothermal reaction 2h.Stop stirring, leave standstill, layering, filter, n-hexane four times (each 30 milliliters), dry, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.Promotor is the AlEt of 2mmol/mL
3hexane solution, itself and above-mentioned Primary Catalysts form the olefin polymerization catalysis of this comparative example, and the two merges in use.
Application examples 1
Should use-case provide above-described embodiment 1-19 and the olefin polymerization catalysis catalyzed ethylene polymerization prepared by comparative example 1 reaction method and result.This ethylene polymerization comprises the following steps: by 2 liters of stainless steel autoclaves after nitrogen is fully replaced, and adds the Primary Catalysts 20mg of embodiment 1-19 and comparative example 1 successively in still, dehydration normal hexane 1000mL, promotor AlEt
3hexane solution 1.2mL (2mmol/mL), after being warming up to 80 DEG C, be filled with hydrogen 0.28MPa, be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.After completion of the reaction, weighed by the polymkeric substance prepared, calculate catalytic efficiency, catalytic efficiency represents divided by Primary Catalysts consumption (g) with polymer weight (kg); ICP is adopted to detect Primary Catalysts titanium content a; The tap density of polymkeric substance is according to ASTM D 1,895 2003 standard testing; The detection method of polyethylene fine powder content is method of sieving, and be less than 200 object polyethylene fine powders as detected object, experimental result is as shown in table 1.
Application examples 2
Above-described embodiment 1-19 and the olefin polymerization catalysis catalyzed ethylene prepared by comparative example 1 and 1-hervene copolymer should be provided close the method and result of reacting by use-case.This copolymerization comprises the following steps: by 2 liters of stainless steel autoclaves after nitrogen is fully replaced, and adds the Primary Catalysts 20mg of embodiment 1-19 and comparative example 1 successively in still, dehydration normal hexane 1000mL, promotor AlEt
3hexane solution 1.2mL (2mmol/mL), add 30mL 1-hexene.After being warming up to 80 DEG C, be filled with hydrogen 0.28MPa, be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.The method of calculation of catalytic efficiency are with application examples 1, and experimental result is as shown in table 1.
As shown in table 1, the catalyzer that the charge capacity of the catalyzer that embodiment provides and catalytic activity provide higher than comparative example 1; Polyethylene tap density obtained by the catalyzer that embodiment provides is high, and fine powder is few, and the polymer bulk density obtained by catalyzer that comparative example 1 provides is low, and fine powder is more.As depicted in figs. 1 and 2, the size distribution of Primary Catalysts that provides of embodiment 1 is more even compared to the Primary Catalysts of comparative example 1; As shown in Figure 3 and Figure 4, the particle form of the Primary Catalysts that embodiment 1 provides is spherical in shape, and the particle form of the Primary Catalysts of comparative example 1 is irregular.It can thus be appreciated that embodiment, by adding Organic Alcohol ether compound, can be improved magnesium halide and separate out situation, thus obtain that particle form is spherical in shape, the Primary Catalysts of even particle size distribution; Add promotor in use, make the activity of Primary Catalysts, stability increases.
Table 1
Claims (6)
1. an olefin polymerization catalysis, it comprises Primary Catalysts and promotor;
Wherein, the raw material of described Primary Catalysts is made up of magnesium halide, transition metal halide, organic alcohol compound, phosphate compounds, epoxy halogen alkyl compound, organosilicone compounds and Organic Alcohol ether compound;
The mol ratio of described magnesium halide, described transition metal halide, described organic alcohol compound, described phosphate compounds, described epoxy halogen alkyl compound, described organosilicone compounds is 1:(1-30): (1-5): (0.1-10): (1-20): (0.001-0.4);
The mass ratio of described magnesium halide and described Organic Alcohol ether compound is 1:(0.001-0.2);
Described promotor includes the combination of one or more in machine aluminium compound;
The mol ratio of the transition metal halide in described promotor and described Primary Catalysts is (30-500): 1;
Described olefin polymerization catalysis prepares by the following method:
Magnesium halide is scattered in organic solvent, adds organic alcohol compound, phosphate compounds and epoxy halogen alkyl compound successively, then stirring and dissolving at 30-100 DEG C, afterwards isothermal reaction 1-5h;
Under 10-70 DEG C of agitation condition, add organosilicone compounds and Organic Alcohol ether compound successively, then isothermal reaction 0.5-3h;
Under-30 DEG C to 30 DEG C agitation conditions, drip metal halide compound, drip isothermal reaction 0.5-5h after finishing;
Be warming up to 20-100 DEG C, then isothermal reaction 0.5-5h, in the process, solid particulate is separated out gradually;
With n-hexane product 4-6 time, cross and filter unreacted reactant, then vacuum-drying obtains Primary Catalysts;
Described promotor comprises the combination of one or more in triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride and methylaluminoxane;
Described Primary Catalysts separates with described promotor to be deposited, and merges in use;
Wherein, described magnesium halide comprises the combination of one or more in magnesium dichloride, dibrominated magnesium, diiodinating magnesium, chlorination magnesium methylate, chlorination magnesium ethylate, chlorination propoxy-magnesium, chlorination butoxy magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium and butyl magnesium chloride;
Described transition metal halide comprises the combination of one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium, trichlorine one ethanolato-titanium, methoxytitanium trichloride, dibutoxy titanium dichloride, three butoxy titanium chlorides, a chlorine triple phenoxyl titanium, dichloro oxygen base titanium and trichlorine one phenoxide titanium;
Described organic alcohol compound comprises the combination of one or more in ethanol, ethylene glycol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 1,3-PD, glycerol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, sorbyl alcohol, hexalin, methyl-cyclohexanol, benzylalcohol, xylyl alcohol and Isobutyl Benzyl Carbinol;
Described phosphate compound comprises the combination of one or more in tributyl phosphate, tri hexyl phosphate, trioctyl phosphate and TNPP tri n pentyl phosphate;
Described epoxy halogen alkyl compound comprises the combination of one or more in epoxy chloropropane, epoxy chlorobutane, epoxy chloropentane, Epiiodohydrin, epoxy butyl iodide, epoxy iodopentane, epoxy bromopropane and epoxy n-butyl bromide;
Described organosilicone compounds comprises 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, 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, cyclohexyltriethyloxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltrimethoxysilane, ne-butyltriethoxysilaneand, isobutyl triethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, one chlorine Trimethoxy silane, one chlorine triethoxyl silane, ethyl three isopropoxy silane, vinyltributoxysilane, trimethyl phenoxysilane, methyl triolefin npropoxysilane, vinyl triacyloxysilanes, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dibutyldimethoxysilane, diisopropyl dimethoxy silane, diisopropyldiethoxysilane, tertbutyl methyl dimethoxysilane, tertbutyl methyl diethoxy silane, tert-pentyl methyldiethoxysilane, dicyclopentyl dimethoxyl silane, bicyclopentyl diethoxy silane, Cyclohexylmethyldimethoxysilane, methylcyclopentyl diethoxy silane, methylcyclopentyl dimethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, aminomethyl phenyl diethoxy silane, aminomethyl phenyl dimethoxysilane, two o-tolyl dimethoxysilane, two o-tolyl diethoxy silane, tolyl dimethoxysilane between two, tolyl diethoxy silane between two, biconjugate tolyl dimethoxysilane, biconjugate tolyl diethoxy silane, trimethylmethoxysilane, trimethylethoxysilane, three cyclopentylmethoxy silane, three cyclopentyl Ethoxysilanes, the combination of one or more in dicyclopentylmethyl methoxy silane and cyclopentyl dimethyl methoxy silane,
Described Organic Alcohol ether compound comprises ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol propyl ether, dihydroxypropane single-ether, butyleneglycol list propyl ether, 2-(2-cyclopentyl oxyethyl group) ethanol, 3-(2-cyclohexylethoxy radical) propyl alcohol, 2-(5-phenylpentyloxy) ethanol, 4-(3-(naphthyl) propoxy-) butanols, 2-(3-epoxy ethyl propoxy-) ethanol, the combination of one or more in 2-(2-furyl oxyethyl group) ethanol and 3-(3-pyridyl propoxy-) propyl alcohol.
2. the preparation method of olefin polymerization catalysis according to claim 1, it comprises the following steps:
Magnesium halide is scattered in organic solvent, adds organic alcohol compound, phosphate compounds and epoxy halogen alkyl compound successively, then stirring and dissolving at 30-100 DEG C, afterwards isothermal reaction 1-5h;
Under 10-70 DEG C of agitation condition, add organosilicone compounds and Organic Alcohol ether compound successively, then isothermal reaction 0.5-3h;
Under-30 DEG C to 30 DEG C agitation conditions, drip metal halide compound, drip isothermal reaction 0.5-5h after finishing;
Be warming up to 20-100 DEG C, then isothermal reaction 0.5-5h, in the process, solid particulate is separated out gradually;
With n-hexane product 4-6 time, cross and filter unreacted reactant, then vacuum-drying obtains Primary Catalysts;
Described promotor includes the combination of one or more in machine aluminium compound;
Described Primary Catalysts separates with described promotor to be deposited, and merges in use.
3. preparation method according to claim 2, wherein, described organic solvent comprises C
5-C
15stable hydrocarbon, C
5-C
10alicyclic hydrocarbon, C
6-C
15aromatic hydrocarbon and C
2-C
10saturated heterocyclic hydrocarbon in the combination of one or more.
4. olefin polymerization catalysis according to claim 1 is all polymerized as alkene or the application of catalyzer of ethene and copolymerization monomer copolymerizable.
5. application according to claim 4, wherein, described comonomer is C
3-C
20alpha-olefin.
6. application according to claim 4, wherein, described comonomer comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene, 1,3-dibutene, isoprene, vinylbenzene, vinyl toluene and norbornylene.
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| CN103183754A (en) * | 2013-03-13 | 2013-07-03 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst and preparation method thereof |
| CN104231140B (en) * | 2013-06-21 | 2016-12-07 | 中国石油天然气集团公司 | A kind of ethene-alpha-olefin catalyst for copolymerization and preparation thereof and application |
| CN104558276B (en) * | 2013-10-10 | 2017-08-25 | 中国石油化工股份有限公司 | Catalyst for olefines polymerizing and its preparation method and application |
| CN104558277B (en) * | 2013-10-10 | 2017-04-26 | 中国石油化工股份有限公司 | A catalyst used for olefin polymerization, a preparing method thereof and an olefin polymerization method |
| FR3019064B1 (en) * | 2014-03-25 | 2020-02-28 | IFP Energies Nouvelles | NOVEL CATALYTIC COMPOSITION AND PROCESS FOR THE OLIGOMERIZATION OF ETHYLENE TO HEXENE-1 |
| CN105085734B (en) * | 2014-04-29 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of preparation method of catalytic component for olefinic polymerization |
| CN105440178B (en) * | 2014-09-28 | 2018-03-02 | 中国石油化工股份有限公司 | A kind of olefin polymerization catalysis and preparation method thereof and the method for olefinic 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 |
| CN106519084B (en) * | 2015-09-15 | 2019-02-15 | 中国石油天然气股份有限公司 | Olefin polymerization catalysis major catalyst and preparation method thereof and olefin polymerization catalysis |
| CN108864346A (en) * | 2017-05-12 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of ethylene and end alkenyl silanes/siloxanes copolymerization process |
| RU2648079C1 (en) * | 2017-05-24 | 2018-03-22 | Общество с ограниченной ответственностью "МИРРИКО" | Method for obtaining a reagent to reduce the hydrodynamic resistance of a turbulent flow of liquid hydrocarbons in pipelines |
| CN109694424B (en) * | 2017-10-24 | 2021-08-03 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization |
| WO2019094216A1 (en) * | 2017-11-13 | 2019-05-16 | W.R. Grace & Co.-Conn. | Catalyst components for propylene polymerization |
| CN108129591B (en) * | 2017-12-27 | 2021-05-28 | 杨翠 | External electron donor composition, olefin polymerization catalyst system and application of external electron donor composition and olefin polymerization catalyst system |
Citations (2)
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| CN102492061A (en) * | 2011-11-26 | 2012-06-13 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
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| CN102492061A (en) * | 2011-11-26 | 2012-06-13 | 北京化工大学 | Alkene polymerization catalyst, preparation method thereof, and application thereof |
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