CN104829760A - Olefin polymerization catalyst, and preparation method and application thereof - Google Patents
Olefin polymerization catalyst, and preparation method and application thereof Download PDFInfo
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- CN104829760A CN104829760A CN201510219001.XA CN201510219001A CN104829760A CN 104829760 A CN104829760 A CN 104829760A CN 201510219001 A CN201510219001 A CN 201510219001A CN 104829760 A CN104829760 A CN 104829760A
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Abstract
The invention provides an olefin polymerization catalyst. The catalyst is composed of a main catalyst and a cocatalyst, and the main catalyst is composed of a magnesium halide carrier, transition metal halide, C2-15 alcohol, an organo silicon compound and an alkyloxy organic phosphoric acid ether compound according to a molar ratio of 1:(1-40):(0.01-5):(0.01-10):(0.01-10); and the cocatalyst is an organic aluminum compound. The catalyst has the advantages of good particle form, high catalysis activity and good hydrogen regulation performance. The invention also provides a preparation method and an application of the olefin polymerization catalyst.
Description
Technical field
The invention belongs to alkene catalyst structure and field of olefin polymerisation, be specifically related to all to be polymerized for alkene or the catalyzer of copolymerization and the preparation method of catalyzer and application.
Background technology
Olefin polymerization catalysis is the core of polyolefin polymerization technology, from the development of olefin polymerization catalysis, sum up and mainly contain two aspects: (1) exploitation can prepare property or the more excellent polyolefin resin catalyzer of performance, as metallocene catalyst and non-luxuriant late transition metal catalyst etc.; (2) for the production of general purpose polyolefin resin, improving on the basis of catalyst performance further, simplifying catalyst preparation process, reducing 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 pursues catalyst efficiency, and through the effort of nearly 30 years, the catalytic efficiency of polyethylene catalysts was that the order of magnitude improves, thus simplifies polyolefinic production technique, reduces energy consumption and material consumption.
Ziegler-Natta catalyst comes out and has nearly 60 years history so far, although period has occurred that, as the polyolefin catalyst such as metallocene and Nonmetallocene, its industrial problems is more, as promotor is expensive, Primary Catalysts load also has difficulties.Therefore, just current industrial production and share of market, traditional Z-N catalyzer will be the leader of following for some time internal olefin polymerization field.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability and polymerization catalytic activity also improve constantly.But at hydrogen response, control to still have deficiency in granules of catalyst regularity and size distribution.Need in current production to develop that preparation technology is simple, hydrogen response good, the spherical or class spherical catalyst of even particle size distribution.
Patent 96106647.4X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl
2be dissolved in the mixture of a kind of alcohol and alkane, form liquid MgCl
2alcohol adducts, this liquid MgCl
2alcohol adducts and TiCl
4contact, obtain olefin polymerization catalysis, but the hydrogen regulation performance of catalyzer is poor, poly melting index MFR can only regulate in 0.1g/10min – 220g/10min.
Patent 200480008242.X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl
2directly be dissolved in ethanol and prepare solid MgCl
2alcohol adducts, then by TiCl
4load is at solid MgCl
2alcohol adducts obtains olefin polymerization catalysis.
Patent 201110382706.5 discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl
2be dissolved in the organic solvent of isooctyl alcohol and ethanol and prepared solid MgCl
2alcohol adduct, then by TiCl
4load is at solid MgCl
2alcohol adduct obtains olefin polymerization catalysis, and this catalyzer has good hydrogen to adjust effect.But catalyst activity is on the low side, primary catalyst particles easily adheres on the wall.
Patent CN85100997A, CN200810227369.0, CN200810227371.8, CN200810223088.8 disclose a kind of olefin polymerization catalysis and preparation method thereof, by MgCl
2particle is dissolved in the system of organic epoxy compound thing, organo phosphorous compounds and inert organic solvents, obtains MgCl
2solution, then with TiCl
4contact, has prepared the Primary Catalysts of olefinic polymerization.The effect of described organo phosphorous compounds makes MgCl
2a necessary component in the solvent system of grain dissolution.
Patent 2013105985560 discloses in catalyst preparation process, add inert organic solvents, alcohol that monohydroxy-alcohol, carbonatoms that carbonatoms is less than 5 are greater than 5, after MgCl2 grain dissolution, add organo phosphorous compounds, silicoorganic compound and organoboron compound again, prepare liquid MgCl2 alcohol adduct, again TiCl4 is contacted with this liquid MgCl2 alcohol adduct, add poly-hydroxy solids more afterwards, obtain olefin polymerization catalysis, the particle form of solid main catalyst, the hydrogen regulation performance of catalyst olefinic polymerization, polyolefinic tap density can be improved.
Patent 201310034134 discloses in catalyst preparation process, add inert organic solvents, alcohol that alcohol, carbonatoms that carbonatoms is less than 5 are greater than 5, after MgCl2 grain dissolution, add organo phosphorous compounds and silicoorganic compound again, prepare liquid MgCl2 alcohol adduct, again TiCl4 is contacted with this liquid MgCl2 alcohol adduct, add poly-hydroxy solids more afterwards, obtain alkene catalyst structure, the hydrogen regulation performance of the particle form of solid main catalyst, catalyst olefinic polymerization can be improved.
Patent 201210436136.8 discloses in catalyst preparation process, add inert organic solvents, alcohol that alcohol, carbonatoms that carbonatoms is less than 5 are greater than 5, after MgCl2 grain dissolution, add organo phosphorous compounds and silicoorganic compound again, prepare liquid MgCl2 alcohol adduct, again TiCl4 is contacted with this liquid MgCl2 alcohol adduct, obtain alkene catalyst structure, the hydrogen regulation performance of the particle form of solid main catalyst, catalyst olefinic polymerization can be improved; This patent finds, after magnesium halide carrier dissolves, then add organo phosphorous compounds, can significantly improve the catalytic activity of catalyzer, can eliminate the electrostatic of solid main catalyst particle, primary catalyst particles does not adhere on the wall.
This patent finds, in catalyst preparation process, adds inert organic solvents, carbonatoms is the alcohol of 2 to 15, MgCl
2after grain dissolution, then add alkoxyl group organic phosphoric acid ether compound and silicoorganic compound, prepare liquid MgCl
2alcohol adduct, then by TiCl
4with this liquid MgCl
2alcohol adduct contacts, and obtains alkene catalyst structure, can improve the hydrogen regulation performance of the particle form of solid main catalyst, catalyst olefinic polymerization; This patent finds, after magnesium halide carrier dissolves, then add alkoxyl group organic phosphoric acid ether compound and can significantly improve the catalytic activity of catalyzer, can eliminate the electrostatic of solid main catalyst particle, primary catalyst particles does not adhere on the wall.The particle form of olefin polymerization catalysis provided by the present invention is good, and even particle size distribution; Catalyzer hydrogen regulation performance is excellent, and poly melting index MFR can regulate in 0.01g/10min – 600g/10min; Catalyst loadings is high, and catalyst activity is high, and solid main catalyst particle does not adhere on the wall; Morphology is good, and tap density is high, and fine powder is few; Be applicable to slurry polymerization processes, loop po lymerisation technique, gas-phase polymerization process or polymerization mix technique; The preparation technology of Primary Catalysts is simple, and low for equipment requirements, energy consumption is little, and environmental pollution is little.
Summary of the invention
The object of the present invention is to provide a kind of for the application with the catalyzer of copolymerization monomer copolymerizable, the preparation method of catalyzer and catalyzer of olefinic polymerization or ethene (or propylene).
Olefinic polymerization provided by the present invention or ethene (or propylene) are made up of Primary Catalysts and promotor with the spherical catalyst of copolymerization monomer copolymerizable; Alcohol, silicoorganic compound and alkoxyl group organic phosphoric acid ether compound that described Primary Catalysts is 2 to 15 by magnesium halide carrier, transition metal halide, carbonatoms form.Magnesium halide, transition metal halide, carbonatoms are the alcohol of 2 to 15, the mol ratio of silicoorganic compound and alkoxyl group organic phosphoric acid ether compound is: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10).Primary Catalysts and promotor with magnitude relation be: the transition metal halide in Primary Catalysts and the mol ratio of promotor are 1:(10-500).
Of the present invention in one of them, described magnesium halide, as carrier, is selected from general formula (1) Mg (R)
ax
bcompound at least one, R is selected from C
1~ C
20aliphatic group, C
1~ C
20fatty alkoxyl group, C
3~ C
20alicyclic radical or C
6~ C
20aryl radical; X is selected from halogen; A=0 or 1, b=1 or 2, a+b=2.Specifically be selected from least one 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, butyl magnesium chloride etc., wherein, preferred magnesium dichloride.
Of the present invention in one of them, described transition metal halide is selected from general formula (2) M (R
1)
4-mx
mcompound at least one, in formula, M is Ti, Zr, Hf, Fe, Co, Ni etc.; X is halogen atom, is selected from Cl, Br, F; M is the integer of 1 to 4; R
1be selected from C
1~ C
20aliphatic group, C
1~ C
20fatty alkoxyl group, C
1~ C
20cyclopentadienyl and derivative, C
1~ C
20aryl radical, COR` or COOR`, R` there is C
1~ C
10fatty group or there is C
1~ C
10aromatic base.R
1specifically can be selected from: at least one in methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl-, the tertiary butyl, isopentyl, tert-pentyl, 2-ethylhexyl, phenyl, naphthyl, o-aminomethyl phenyl, m-aminomethyl phenyl, p-aminomethyl phenyl, o-sulfonic group phenyl, formyl radical, acetyl or benzoyl base etc.Described Ti, Zr, Hf, Fe, Co, the transition metal halides such as Ni, specifically can select the mixing 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, trichlorine one phenoxide titanium.Wherein, preferred titanium tetrachloride.Of the present invention in one of them, the mol ratio of described transition metal halide and described magnesium halide carrier is preferably (8-40): 1.
Of the present invention in one of them, described carbonatoms be 2 to 15 alcohol be fatty alcohol or alicyclic ring alcohol or aromatic alcohol, preferably be selected from least one in ethanol, methyl alcohol, propyl alcohol, butanols, amylalcohol, enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol or pentadecanol etc., more preferably ethanol, isooctyl alcohol etc.Carbonatoms is that the alcohol of 2 to 15 and the mol ratio of described magnesium halide carrier are preferably (0.05 – 3.5): 1.
Wherein, described silicoorganic compound are selected from general formula (3) R
x 3r
y 4si (OR
5)
zor general formula (4) (R
6o) (R
7o) (R
8o) (R
9at least one in the compound of O) Si, wherein R
3and R
4be respectively alkyl or halogen, R
5, R
6, R
7, R
8and R
9alkyl or the cyclic hydrocarbon radical of C1 to C20,0≤x < 2,0≤y < 2, and 0 < z≤4, x+y+z=4.Silicoorganic compound are selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (2-ethyl hexyl oxy) silane, ethyl trimethoxy silane, ethyl triethoxysilane, methyltrimethoxy silane, Union carbide A-162, 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, dicyclopentylmethyl methoxy silane, cyclopentyl dimethyl methoxy silane, diethoxy isopropoxy tert-butoxy silane, three isopropoxy tert-butoxy silane, diisopropoxy two tert-butoxy silane, diethoxy cyclohexyloxy tert-butoxy silane, diethoxy phenoxy group tert-butoxy silane, one oxyethyl group diisopropoxy tert-butoxy silane, oxyethyl group isopropoxy tert.-butoxy cyclohexyloxy silane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon, triethoxy hexyloxy silicon, trimethoxy pentyloxy silicon or triethoxy phenoxy group silicon, one or more in silica gel etc.Described silicoorganic compound be preferably in tetramethoxy-silicane, tetraethoxysilane, triethoxy methoxyl group silicon, triethoxy pentyloxy silicon, silica gel or triethoxy hexyloxy silicon one or more.Preferably, the mol ratio of described silicoorganic compound and magnesium halide carrier is (0.5-8): 1.
Of the present invention in one of them, described alkoxyl group organic phosphoric acid ether compound is selected from general formula (5) O=P (OSiR
10)
3-n(OH)
nat least one in compound, wherein n is selected from 0,1,2 or 3; Wherein R
10be selected from C
1~ C
20aliphatic group, C
1~ C
20alkoxyl group, C
3~ C
20alicyclic radical or C
6~ C
20aryl radical.Preferably, described alkoxyl group organic phosphoric acid ether compound is selected from least one in following compound:
In one aspect of the invention, described alkoxyl group organic phosphoric acid ether compound also optional self-drifting (6)
compound at least one, wherein q is the integer of 1 to 15, and wherein n is selected from 0,1,2 or 3.Wherein R
11h, halogen, the aliphatic group of C1 ~ C15, C1 ~ C15 alkoxyl group, C3 ~ C15 cyclic group or C6 ~ C15 aryl radical.Preferably, described alkoxyl group organic phosphoric acid ether compound can be selected from least one in following compound:
Of the present invention in one of them, the mol ratio of described alkoxyl group organic phosphoric acid ether compound and magnesium halide is (0.01-5): 1.Add alkoxyl group organic phosphoric acid ether compound and can significantly improve the catalytic activity of catalyzer, hydrogen response and copolymerized ability.
One of feature of the present invention adds the alcohol that carbonatoms is 2 to 15 in the preparation process of solid main catalyst, wherein, described carbonatoms be 2 to 15 alcohol be fatty alcohol or alicyclic ring alcohol or aromatic alcohol, be preferably selected from least one in ethanol, methyl alcohol, propyl alcohol, butanols, amylalcohol, enanthol, isooctyl alcohol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alcohol or pentadecanol etc., more preferably ethanol, isooctyl alcohol etc.Carbonatoms is the alcohol of 2 to 15 and the mol ratio preferred (0.05 – 3.5) of magnesium halide: 1.Add carbonatoms be 2 to 15 alcohol can significantly improve the hydrogen regulation performance of catalyzer.
Present invention also offers the preparation method of foregoing olefin polymerization catalysis.The preparation method of olefin polymerization catalysis provided by the present invention comprises the following steps:
1) described magnesium halide carrier is scattered in inert organic solvents, adds the alcohol that described carbonatoms is 2 to 15, stirring and dissolving 1 to 5h at 30 to 150 DEG C, preferably 60 DEG C to 130 DEG C;
2) by 1) solution is cooled to 10 DEG C to 80 DEG C, adds described alkoxyl group organic phosphoric acid ether compound and described silicoorganic compound, at 30 to 150 DEG C, stir 1 to 5h;
3) at-25 to 30 DEG C, by step 2) system that obtains contacts with described transition metal halide, and react 0.5-5h at-25 to 30 DEG C, then system is warming up to 20-150 DEG C, preferred 50-120 DEG C, reaction 0.5-5h, in temperature-rise period, solid particulate is separated out gradually, after reaction terminates, with toluene or n-hexane product 4-6 time, cross and filter unreacted reactant, vacuum-drying obtains pulverulent solids Primary Catalysts.
Of the present invention in one of them, vacuum-drying temperature is 40 DEG C to 130 DEG C, preferably 50 DEG C to 100 DEG C; The vacuum-drying time is 0.5 little of 5 hours, and preferably 1 is little of 4 hours.
Of the present invention in one of them, described inert organic solvents is selected from C
5~ C
15stable hydrocarbon, C
5~ C
10alicyclic hydrocarbon or C
6~ C
15aromatic hydrocarbon, preferred decane, octane, dodecane, toluene, dimethylbenzene, hexane, heptane or hexanaphthene, or their mixed solvent.
Olefin polymerization catalysis provided by the present invention also comprises promotor.Described promotor for common are machine aluminium compound, preferred triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride, methylaluminoxane MAO etc.; The mol ratio of solid main catalyst and promotor is 1:(10-500).
The purposes of olefin polymerization catalysis provided by the present invention is: the copolymerization catalyst that can be used as vinyl polymerization or propylene polymerization or ethene (or propylene) and alpha-olefin, wherein, described alpha-olefin is selected from C
3~ C
20alkene, preferred propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, cyclopentenes, 4-methyl-1-pentene, 1,3-butadiene, isoprene, vinylbenzene, vinyl toluene etc.
Olefin polymerization catalysis provided by the present invention has following beneficial effect:
The particle form of the alpha-olefinic copolymerization catalyzer that the object of this invention is to provide is good, and spherical in shape, granules of catalyst does not adhere on the wall; The hydrogen regulation performance of catalyzer is excellent, and poly melting index MFR can regulate in 0.01g/10min – 600g/10min; Catalyst activity is high; Be applicable to slurry process, gas-phase polymerization process or polymerization mix technique; Preparation method is simple, and low for equipment requirements, environmental pollution is little.
ICP is adopted to measure the mass percentage of Mg, Ti, Si and P in Primary Catalysts.
The condition determination of the melting index of polyethylene and polyethylene and ethylene copolymers is testing load is 5kg, temperature is 190 DEG C.
The condition determination of the melting index of isotatic polypropylene is testing load is 2.16kg, temperature is 230 DEG C.
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
Embodiment 1
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, isooctyl alcohol 6.5ml, stir and be warming up to 120 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (1) 2.1ml and tetraethoxysilane 0.15ml, keep temperature to be 50 DEG C of reaction 2h.At system being down to-15 DEG C, drip 30ml titanium tetrachloride, reaction 1h, is warming up to 110 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 70 DEG C of vacuum-dryings 2 hours, obtains good fluidity, non-stick container wall, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 2
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 30ml, ethanol 0.25ml, isooctyl alcohol 7ml, stir and be warming up to 120 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 60 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (2) 1.1ml and tetraethoxysilane 0.5ml, keep temperature to be 60 DEG C of reaction 2h.At system being down to-10 DEG C, drip 40ml titanium tetrachloride, reaction 1h, is warming up to 100 DEG C and reacts 3h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 60 DEG C of vacuum-dryings 3 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 3
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, isooctyl alcohol 8ml, stir and be warming up to 100 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (3) 13ml and tetraethoxysilane 2ml, be warming up to 80 DEG C of reaction 2h.At system being down to-15 DEG C, drip 35ml titanium tetrachloride, reaction 1h, is warming up to 65 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 50 DEG C of vacuum-dryings 4 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 4
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 2ml, isooctyl alcohol 7ml, stir and be warming up to 90 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (4) 0.5ml and triethoxy methoxy silane 0.5ml, be warming up to 100 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, is warming up to 120 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 80 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 5
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.1ml, isooctyl alcohol 4ml, stir and be warming up to 80 DEG C, reaction 5h, solid dissolves form homogeneous solution completely.At being cooled to 40 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (5) 5ml and tetraethoxysilane 4ml, keep temperature to be 40 DEG C of reaction 2h.At system being down to-15 DEG C, drip 25ml titanium tetrachloride, reaction 3h, is warming up to 110 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 90 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 6
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 2.5ml, isooctyl alcohol 3ml, stir and be warming up to 110 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (6) 3ml and tetraethoxysilane 8ml, keep temperature to be 50 DEG C of reaction 3h.At system being down to-15 DEG C, drip 40ml titanium tetrachloride, reaction 1h, is warming up to 70 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 100 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 7
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, isooctyl alcohol 6.5ml and ethanol 0.1ml, stir and be warming up to 60 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (7) 6ml and triethoxy cyclopentyloxy silane 3ml and ethanol 0.2ml, keep temperature to be 50 DEG C of reaction 4h.At system being down to-15 DEG C, drip 35ml titanium tetrachloride, reaction 1h, is warming up to 95 DEG C and reacts 4h again.Stop stirring, leave standstill, layering, filter, toluene wash twice (each 30 milliliters), hexanes wash four times (each 30 milliliters), in 60 DEG C of vacuum-dryings 3 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 8
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, dodecane 20ml, ethanol 0.3ml, decyl alcohol 6ml, stir and be warming up to 110 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding successively and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (8) 6ml and diethoxy isopropoxy tert-butoxy silane 5ml, keep temperature to be 50 DEG C of reaction 3h.At system being down to-10 DEG C, drip 30ml titanium tetrachloride, reaction 1h, is warming up to 80 DEG C and reacts 3h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 60 DEG C of vacuum-dryings 4 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 9
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, toluene 30ml, propyl alcohol 3ml, isooctyl alcohol 6.5ml, stir and be warming up to 50 DEG C, reaction 5h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (9) 6ml and tetraethoxysilane 6ml, keep temperature to be 50 DEG C of reaction 2h.At system being down to 0 DEG C, drip 15ml titanium tetrachloride, reaction 1h, is warming up to 90 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 110 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 10
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, octane 30ml, butanols 4ml, isooctyl alcohol 6.5ml, stir and be warming up to 110 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (10) 2ml and tetraethoxysilane 6ml, keep temperature to be 50 DEG C of reaction 2h.At system being down to-5 DEG C, drip 45ml titanium tetrachloride, reaction 1h, is warming up to 90 DEG C and reacts 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 120 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 11
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 15ml, methyl alcohol 5ml, stir and be warming up to 110 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (11) 4ml and tetraethoxysilane 6ml, keep temperature to be 50 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise to and is in the 25ml titanium tetrachloride of-10 DEG C, at 0 DEG C of reaction 1h, in 4 hours, be warming up to 110 DEG C react 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 50 DEG C of vacuum-dryings 3 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 12
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 40ml, ethanol 1.5ml, stir and be warming up to 120 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 60 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (12) 3ml and tetraethoxysilane 6ml, keep temperature to be 60 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise to and is in the 25ml titanium tetrachloride of-15 DEG C, at-5 DEG C of reaction 1h, in 4 hours, be warming up to 100 DEG C react 2h again.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 50 DEG C of vacuum-dryings 3 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 13
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, isooctyl alcohol 6.5ml, stir and be warming up to 110 DEG C, reaction 3h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (15) 1ml and tetraethoxysilane 2ml, at 50 DEG C of temperature, react 2h.At system being down to 0 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 50 DEG C of vacuum-dryings 4 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 14
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, ethanol 1ml, isooctyl alcohol 6.5ml, stir and be warming up to 100 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 40 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (16) 3ml and silica gel 0.15g, be warming up to 70 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 15
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.4ml, isooctyl alcohol 6.5ml, stir and be warming up to 120 DEG C, reaction 0.5h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, adding and meet general formula (6) alkoxyl group organic phosphoric acid ether compound (17) 3ml and succinate 10ml, keep temperature to be 50 DEG C of reaction 3h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, is warming up to 90 DEG C and reacts 2h again, in 60 DEG C of vacuum-dryings 2 hours, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 16
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, ethanol 1ml, isooctyl alcohol 6.5ml, stir and be warming up to 100 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 40 DEG C, adding and meet general formula (6) alkoxyl group organic phosphoric acid ether compound (18) 3ml and tetraethoxysilane 0.25ml, be warming up to 70 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 17
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, ethanol 1ml, isooctyl alcohol 6.5ml, stir and be warming up to 100 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 40 DEG C, adding and meet general formula (6) alkoxyl group organic phosphoric acid ether compound (19) 3ml and tetraethoxysilane 0.25ml, be warming up to 70 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 18
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, ethanol 1ml, isooctyl alcohol 6.5ml, stir and be warming up to 100 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 40 DEG C, adding and meet general formula (6) alkoxyl group organic phosphoric acid ether compound (20) 3ml and tetraethoxysilane 0.25ml, be warming up to 70 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Embodiment 19
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, ethanol 1ml, isooctyl alcohol 6.5ml, stir and be warming up to 100 DEG C, reaction 4h, solid dissolves form homogeneous solution completely.At being cooled to 40 DEG C, adding and meet general formula (6) alkoxyl group organic phosphoric acid ether compound (23) 3ml and tetraethoxysilane 0.25ml, be warming up to 70 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Comparative example 1
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, ethanol 0.4ml, stir and be warming up to 110 DEG C, reaction 2h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, add tetraethoxysilane 3ml, keep temperature to be 50 DEG C of reaction 2h.At system being down to-15 DEG C, drip 35ml titanium tetrachloride, reaction 1h, be warming up to 100 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 80 DEG C of vacuum-dryings 2 hours, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape, primary catalyst particles easily adheres on wall of container.
Comparative example 2
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, ethanol 0.4ml, stir and be warming up to 120 DEG C, reaction 3h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, add tributyl phosphate 3ml and tetraethoxysilane 3ml, keep temperature to be 50 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts, primary catalyst particles easily adheres on wall of container.
Comparative example 3
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, decane 20ml, isooctyl alcohol 16ml, ethanol 0.4ml, stir and be warming up to 120 DEG C, reaction 3h, solid dissolves form homogeneous solution completely.At being cooled to 50 DEG C, add tributyl phosphate 3ml, keep temperature to be 50 DEG C of reaction 2h.At system being down to-15 DEG C, drip 15ml titanium tetrachloride, reaction 1h, be warming up to 90 DEG C of reaction 2h.Stop stirring, leave standstill, layering, filter, hexanes wash twice (each 30 milliliters), in 60 DEG C of vacuum-dryings 2 hours, obtain pulverulent solids Primary Catalysts, primary catalyst particles easily adheres on wall of container.
Application mode one
Vinyl polymerization: by 2 liters of stainless steel autoclaves after nitrogen is fully replaced, add main catalyst component component 10mg successively in still, dehydration hexane 1000ml, promotor AlEt
3solution 1.17ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 75 DEG C, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode two
Ethylene copolymerization: by 2 liters of stainless steel autoclaves after nitrogen is fully replaced, add main catalyst component 10mg successively in still, dehydration hexane 1000ml, AlEt
3solution 1.17ml (2mmol/ml), adds 30ml1-hexene.After being warming up to 75 DEG C, be filled with hydrogen 0.28MPa, then be filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode three
Propylene polymerization: by 2 liters of stainless steel autoclaves after nitrogen is fully replaced, add main catalyst component 10mg successively in still, dehydration hexane 1000ml, AlEt
3solution 1.17ml (2mmol/ml), adds external electron donor triethoxy cyclopentyloxy silicon 4ml (0.18M hexane solution), after being warming up to 80 DEG C, is filled with hydrogen 0.1MPa, then is filled with propylene to 3MPa, constant voltage isothermal reaction 2h.Polyacrylic melting index MFR=111g/10min.
Olefinic polymerization the results are shown in Table 1.
Embodiment 20
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 1.5ml, isooctyl alcohol 6.5ml, stir and be warming up to 120 DEG C, reaction 3h, solid dissolves form homogeneous solution completely.At being cooled to 60 DEG C, adding and meet general formula (5) alkoxyl group organic phosphoric acid ether compound (3) 2ml and tetraethoxysilane 0.2ml, keep temperature to be 60 DEG C of reaction 2h.At system being down to-5 DEG C, drip 35ml titanium tetrachloride, reaction 1h; In 4 hours, be warming up to 110 DEG C, then react 2h.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 50 DEG C of vacuum-dryings 4 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
Vinyl polymerization
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 5mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 0.6ml (2mmol/ml), is filled with hydrogen 0.1MPa after being warming up to 70 DEG C, then is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 253.2 grams, tap density BD=0.32, melting index MFR=0.6g/10min.
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 10mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 0.6ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 70 DEG C, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 350.5 grams, tap density BD=0.33, melting index MFR=3.6g/10min.
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 25mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 3.0ml (2mmol/ml), is filled with hydrogen 0.73MPa after being warming up to 70 DEG C, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 243.6 grams, tap density BD=0.35, melting index MFR=520g/10min.
Embodiment 21
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, ethanol 0.4ml, isooctyl alcohol 6.5ml, stir and be warming up to 120 DEG C, reaction 3h, solid dissolves form homogeneous solution completely.At being cooled to 60 DEG C, adding and meet general formula (6) alkoxyl group organic phosphoric acid ether compound (21) 2.5ml and tetraethoxysilane 0.2ml, keep temperature to be 60 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise to and is in the 25ml titanium tetrachloride of-15 DEG C, at 0 DEG C of reaction 1h; In 4 hours, be warming up to 110 DEG C, then react 2h.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 50 DEG C of vacuum-dryings 4 hours, obtains good fluidity, even particle size distribution, non-stick container wall, pulverulent solids Primary Catalysts spherical in shape.
The molecular formula of alkoxyl group organic phosphoric acid ether compound (1)-(21) in embodiment is as follows;
Vinyl polymerization
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 5mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 0.6ml (2mmol/ml), is filled with hydrogen 0.1MPa after being warming up to 70 DEG C, then is filled with ethene to 0.6MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 265.3 grams, tap density BD=0.31, melting index MFR=0.88g/10min.
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 10mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 0.6ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 70 DEG C, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 368.3 grams, tap density BD=0.32, melting index MFR=3.6g/10min.
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 25mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 3.0ml (2mmol/ml), is filled with hydrogen 0.73MPa after being warming up to 70 DEG C, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 248.1 grams, tap density BD=0.34, melting index MFR=490g/10min.
Comparative example 3
In the reactor that nitrogen is fully transposed, add 1g magnesium dichloride, n-decane 20ml, isooctyl alcohol 6.5ml and ethanol 0.4ml, stir and be warming up to 120 DEG C, reaction 3h, solid dissolves form homogeneous solution completely.At being cooled to 60 DEG C, add tetraethoxysilane 2ml, keep temperature to be 60 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise to and is in the 25ml titanium tetrachloride of-15 DEG C, at 0 DEG C of reaction 1h; In 4 hours, be warming up to 110 DEG C, then react 2h.Stop stirring, leave standstill, layering, filter, hexanes wash four times (each 30 milliliters), in 50 DEG C of vacuum-dryings 4 hours, obtain good fluidity, even particle size distribution, pulverulent solids Primary Catalysts spherical in shape, primary catalyst particles easily adheres on wall of container.
Vinyl polymerization
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 10mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 0.6ml (2mmol/ml), is filled with hydrogen 0.1MPa after being warming up to 70 DEG C, then is filled with ethene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 235.3 grams, tap density BD=0.30, melting index MFR=0.3g/10min.
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 10mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 0.6ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 70 DEG C, then is filled with ethene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain polyethylene 188.3 grams, tap density BD=0.28, melting index MFR=3.1g/10min.
By 2 liters of stainless steel autoclaves after nitrogen is fully replaced, in still, add main catalyst component component 50mg successively, dehydration hexane 1000ml, promotor AlEt
3solution 3.0ml (2mmol/ml), is filled with hydrogen 0.73MPa after being warming up to 70 DEG C, then is filled with ethene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain polyethylene 172.1 grams, tap density BD=0.26, melting index MFR=126g/10min.
Table 1 olefinic polymerization result
Claims (8)
1. olefin polymerization catalysis, it is made up of Primary Catalysts and promotor, it is characterized in that: described Primary Catalysts is by magnesium halide carrier, transition metal halide, carbonatoms is the alcohol of 2 to 15, silicoorganic compound and alkoxyl group organic phosphoric acid ether compound composition, and magnesium halide carrier, transition metal halide, carbonatoms is the alcohol of 2 to 15, the mol ratio of silicoorganic compound and alkoxyl group organic phosphoric acid ether compound is: 1:(1-40): (0.01 – 5): (0.01 – 10): (0.01-10), described promotor is organo-aluminium compound, transition metal halide in Primary Catalysts and the mol ratio of promotor are 1:10-500.
2. olefin polymerization catalysis according to claim 1, is characterized in that: described magnesium halide carrier is selected from general formula (1) Mg (R)
ax
bcompound at least one, wherein R is selected from C
1~ C
20aliphatic group, C
1~ C
20fatty alkoxyl group, C
3~ C
20alicyclic radical or C
6~ C
20aryl radical; X is selected from halogen; A=0 or 1, b=1 or 2, and a+b=2.
3. olefin polymerization catalysis according to claim 1, is characterized in that: described transition metal halide is selected from general formula (2) M (R
1)
4-mx
mcompound at least one, wherein M is Ti, Zr, Hf, Fe, Co or Ni; X is halogen atom, is selected from Cl, Br, F; M is the integer of 1 to 4; R
1be selected from C
1~ C
20aliphatic group, C
1~ C
20fatty alkoxyl group, C
1~ C
20cyclopentadienyl and derivative, C
1~ C
20aryl radical, COR` or COOR`, R` be C
1~ C
10fatty group or C
1~ C
10aromatic base; Preferably, the mol ratio of described transition metal halide and magnesium halide carrier is (8-40): 1.
4. olefin polymerization catalysis according to claim 1, it is characterized in that: described carbonatoms be 2 to 15 alcohol be fatty alcohol or alicyclic ring alcohol or aromatic alcohol, preferably, described carbonatoms is the alcohol of 2 to 15 and the mol ratio of magnesium halide carrier is (0.05 – 10): 1.
5. olefin polymerization catalysis according to claim 1, is characterized in that: described silicoorganic compound meet general formula R
x 3r
y 4si (OR
5)
zor general formula (R
6o) (R
7o) (R
8o) (R
9o) Si, wherein R
3and R
4be respectively alkyl or halogen, R
5, R
6, R
7, R
8and R
9alkyl or the cyclic hydrocarbon radical of C1 to C20,0≤x≤2,0≤y≤2, and 0 < z≤4, x+y+z=4; Preferably, the mol ratio of described silicoorganic compound and magnesium halide carrier is (0.5-8): 1.
6. olefin polymerization catalysis according to claim 1, is characterized in that described alkoxyl group organic phosphoric acid ether compound is selected from:
(a) general formula (5) O=P (OSiR
10)
3-n(OH)
ncompound at least one, wherein n is selected from 0,1,2 or 3; Wherein R
10be selected from C
1~ C
20aliphatic group, C
1~ C
20alkoxyl group, C
3~ C
20alicyclic radical or C
6~ C
20aryl radical;
Or
(b) general formula (6)
compound at least one, wherein q is the integer of 1 to 15, and wherein n is selected from 0,1,2 or 3, wherein R
11h, halogen, the aliphatic group of C1 ~ C15, C1 ~ C15 alkoxyl group, C3 ~ C15 cyclic group or C6 ~ C15 aryl radical,
Preferably, the mol ratio of described alkoxyl group organic phosphoric acid ether compound and magnesium halide carrier is (0.01-5): 1.
7. the preparation method of olefin polymerization catalysis according to claim 1, is characterized in that comprising the following steps:
1) described magnesium halide carrier is scattered in inert organic solvents, adds the alcohol that described carbonatoms is 2 to 15, stirring and dissolving 1 to 5h at 30 to 150 DEG C, preferably 60 DEG C to 130 DEG C;
2) by 1) mixed solution that obtains lowers the temperature 10 DEG C to 80 DEG C, and add described alkoxyl group organic phosphoric acid ether compound and described silicoorganic compound, at 30 to 150 DEG C, stir 1 to 5h;
3) by 2) mixed solution that obtains is cooled to-20 DEG C to 30 DEG C, contact with transition metal halide, and 0.5-5h is reacted at-20 to 30 DEG C, again system is warming up to 20-150 DEG C, reaction 0.5-5h, after reaction terminates, with toluene or n-hexane product, vacuum-drying obtains pulverulent solids Primary Catalysts;
Preferably, the mol ratio of described magnesium halide carrier, transition metal halide and alkoxyl group organic phosphoric acid ether compound is: 1:(1-40): (0.01 – 5),
Preferably, described inert organic solvents is selected from C
5~ C
15stable hydrocarbon, C
5~ C
10alicyclic hydrocarbon or C
6~ C
15aromatic hydrocarbon or their mixed solvent.
8. the application of olefin polymerization catalysis according to claim 1, it is characterized in that: described olefin polymerization catalysis is the catalyzer of the copolymerization of vinyl polymerization, propylene polymerization, ethene and alpha-olefin or the copolymerization of propylene and alpha-olefin, wherein, described alpha-olefin is selected from C
3~ C
20alkene.
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| CN112088456B (en) * | 2018-04-27 | 2024-04-19 | 大金工业株式会社 | Electrolyte, electrochemical device, lithium ion secondary battery and assembly |
| CN112119528A (en) * | 2018-05-14 | 2020-12-22 | 大金工业株式会社 | Electrolyte solution, electrochemical device, lithium ion secondary battery, and assembly |
| CN112119528B (en) * | 2018-05-14 | 2024-04-05 | 大金工业株式会社 | Electrolyte, electrochemical device, lithium ion secondary battery and assembly |
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