CN104829758B - Olefin polymerization catalysis and preparation method and application - Google Patents
Olefin polymerization catalysis and preparation method and application Download PDFInfo
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- 0 *[Si](c1ccccc1)(c1ccccc1)O[C@](BO[Si](c1ccccc1)(c1ccccc1)P=C)O[Si](c1ccccc1)(c1ccccc1)c1ccccc1 Chemical compound *[Si](c1ccccc1)(c1ccccc1)O[C@](BO[Si](c1ccccc1)(c1ccccc1)P=C)O[Si](c1ccccc1)(c1ccccc1)c1ccccc1 0.000 description 1
Abstract
Olefin polymerization catalysis and preparation method and application belong to field of olefin polymerisation.Olefin polymerization catalysis be made up of major catalyst and promoter it is characterised in that：By magnesium compound carrier, transition metal halide, carbon number, the alcohol being 2 to 15 and electron donor organosilicon boric acid ether compound form described major catalyst, and magnesium compound carrier, transition metal halide, carbon number are 2 to 15 alcohol and the mol ratio of organosilicon boric acid ether compound is：1：(1‑40)：(0.01–10)：(0.01–10)；Described promoter is organo-aluminum compound.The particle shape of catalyst of the present invention is good, and spherical in shape, catalyst granules is not adhere on chamber wall；Catalyst activity is high, and hydrogen regulation performance is good, and melt index MFR of polyethylene can adjust in 0.01g/10min 600g/10min it is adaptable to slurry polymerization technique, loop po lymerisation technique, gas phase polymerization technique or polymerization mix technique.
Description
Technical field
The invention belongs to alkene catalyst structure and field of olefin polymerisation, it is particularly used for alkene and is all polymerized or common
Polymerization catalyst, method for preparing catalyst and application.
Background technology
Olefin polymerization catalysis are the cores of polyolefin polymerization technology, from the point of view of the development of olefin polymerization catalysis, summarize
Get up mainly to have two aspects：(1) exploitation can prepare property or the more excellent vistanex catalyst of performance, such as cyclopentadienyl
Metallic catalyst and non-cyclopentadienyl late transition metal catalyst etc.；(2) for the production of general purpose polyolefin resin, changing further
On the basis of kind catalyst performance, simplify catalyst preparation process, reduce catalyst cost, develop environmentally friendly technology,
To increase the benefit, enhance the competitiveness.Before the eighties in 20th century, polyethylene catalysts research it is important that pursue catalyst effect
Rate, through the effort of nearly 30 years, the catalytic efficiency of polyethylene catalysts was in that the order of magnitude improves, thus simplifying polyolefinic production
Technique, reduces energy consumption and material consumption.
Ziegler-Natta catalyst comes out existing nearly 60 years history so far, although period occur in that as metallocene with non-
The polyolefin catalysts such as metallocene, but its industrial problems is more, and such as promoter is expensive, and major catalyst load also has difficulties
Deng.Therefore, with regard to, from the point of view of current commercial production and market share, traditional Z-N catalyst will be alkene in following a period of time
The leader in polymerized hydrocarbon field.In recent years, Z-N catalyst prod both domestic and external emerges in an endless stream, and catalyst stability is urged with being polymerized
Change activity also to improve constantly.But still there is deficiency in terms of hydrogen response, control catalyst granules regularity and particle diameter distribution.Mesh
Need to develop preparation process is simple, good, even particle size distribution the spherical or spherical catalyst of hydrogen response in front production.
Patent 96106647.4X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl2It is dissolved in one
Plant in alcohol and the mixture of alkane, form liquid MgCl2Alcohol adducts, this liquid MgCl2Alcohol adducts and TiCl4Contact, obtains
To olefin polymerization catalysis, but the hydrogen regulation performance of catalyst is poor, and melt index MFR of polyethylene can only be in 0.1g/10min
Adjust in 220g/10min.
Patent 200480008242.X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl2Directly
Connect and be dissolved in ethanol and be prepared for solid MgCl2Alcohol adducts, then by TiCl4It is supported on solid MgCl2Alkene has been obtained on alcohol adducts
Polymerization catalyst.
Patent 201110382706.5 discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl2Molten
It is prepared for solid MgCl in the organic solvent of isooctanol and ethanol2Alcohol adduct, then by TiCl4It is supported on solid MgCl2Alcohol adduct
On obtained olefin polymerization catalysis, this catalyst has good hydrogen to adjust effect.But catalyst activity is low, major catalyst
Grain is easily adhered on the wall.
Patent CN85100997A, CN200810227369.0, CN200810227371.8, CN200810223088.8 are public
A kind of olefin polymerization catalysis and preparation method thereof are opened, by MgCl2Granule is dissolved in organic epoxy compound thing, organic phosphorus compound
In the system of inert organic solvents, obtain MgCl2Solution, then with TiCl4Contact, is prepared for the major catalyst of olefinic polymerization.Institute
The effect of the organic phosphorus compound stated is to make MgCl2One of dicyandiamide solution of grain dissolution necessity component.
Patent 2013105985560 discloses in catalyst preparation process, adds inert organic solvents, carbon number little
The alcohol that monohydric alcohol in 5, carbon number are more than 5, after MgCl2 grain dissolution, adds organic phosphorus compound, organo-silicon compound
And organoboron compound, prepare liquid MgCl2 alcohol adduct, then TiCl4 is contacted with this liquid MgCl2 alcohol adduct, afterwards again
Add polyhydroxy solids, obtain olefin polymerization catalysis, particle shape, the catalyst of solid main catalyst can be improved
The hydrogen regulation performance of olefinic polymerization, polyolefinic bulk density.
Patent 201310034134 discloses in catalyst preparation process, adds inert organic solvents, carbon number little
The alcohol that alcohol in 5, carbon number are more than 5, after MgCl2 grain dissolution, adds organic phosphorus compound and organo-silicon compound, system
Standby liquid MgCl2 alcohol adduct, then TiCl4 is contacted with this liquid MgCl2 alcohol adduct, add polyhydroxy solids afterwards,
Obtain alkene catalyst structure, particle shape, the hydrogen of catalyst olefinic polymerization of solid main catalyst can be improved
Tonality energy.
Patent 201210436136.8 discloses in catalyst preparation process, adds inert organic solvents, carbon number
The alcohol that alcohol less than 5, carbon number are more than 5, after MgCl2 grain dissolution, adds organic phosphorus compound and organo-silicon compound,
Prepare liquid MgCl2 alcohol adduct, then TiCl4 is contacted with this liquid MgCl2 alcohol adduct, obtain the catalysis of alkene high-efficiency polymerization
Agent, can improve particle shape, the hydrogen regulation performance of catalyst olefinic polymerization of solid main catalyst；This patent finds,
After magnesium halide carrier dissolving, add organic phosphorus compound, the catalysis activity of catalyst can be significantly improved, solid can be eliminated
The electrostatic of primary catalyst particles, primary catalyst particles are not adhere on chamber wall.
This patent finds, in catalyst preparation process, adds the alcohol that inert organic solvents, carbon number are 2 to 15, magnesium
Compound carrier, adds electron donor organosilicon boric acid ether compound, prepares magnesium compound alcohol adduct, then by TiCl4With this magnesium
Compound alcohol adduct contacts, and obtains alkene catalyst structure, can improve the particle shape of solid main catalyst, catalyst is urged
Change the hydrogen regulation performance of olefinic polymerization；This patent finds, adds electron donor organosilicon boric acid ether compound can significantly improve and urges
The catalysis activity of agent, the electrostatic of solid main catalyst granule can be eliminated, primary catalyst particles are not adhere on chamber wall.This
The particle shape inventing provided olefin polymerization catalysis is good, and even particle size distribution；Catalyst hydrogen regulation performance is excellent, gathers
Melt index MFR of ethylene can be adjusted in 0.01g/10min 600g/10min；Catalyst loadings are high, catalyst activity
Height, solid main catalyst granule is not adhere on chamber wall；Morphology is good, and bulk density is high, and fine powder is few；It is applied to
Slurry polymerization processes, loop po lymerisation technique, gas-phase polymerization process or polymerization mix technique；The preparation process is simple of major catalyst,
Low for equipment requirements, energy consumption is little, and environmental pollution is little.
Content of the invention
It is an object of the invention to provide a kind of urged with copolymerization monomer copolymerizable for olefinic polymerization or ethylene (or propylene)
The application of the electron donor of agent, the preparation method of catalyst and catalyst.
The spheric catalyst of olefinic polymerization provided by the present invention or ethylene (or propylene) and copolymerization monomer copolymerizable is by leading
Catalyst and promoter composition；Described major catalyst by magnesium compound carrier, transition metal halide, carbon number be 2 to
15 alcohol and organosilicon boric acid ether compound composition.Magnesium compound carrier, transition metal halide, carbon number be 2 to 15 alcohol,
The mol ratio of organosilicon boric acid ether compound is：1：(1-40)：(0.01–10)：(0.01–10).Major catalyst and promoter
Use magnitude relation be：Transition metal halide in major catalyst is 1 with the mol ratio of promoter:(10-500).
Wherein, described magnesium compound is selected from formula (1) as carrier is Mg (R)aXbCompound at least one, R select
From C1～C20Aliphatic group, C1～C20Fatty alkoxyl, C3～C20Alcyl or C6～C20Aryl radical；X is selected from
Halogen；A=0,1 or 2；B=0,1 or 2, a+b=2.It is chosen in particular from magnesium dichloride, dibrominated magnesium, magnesium diiodide, chlorination methoxyl group
Magnesium, chlorination magnesium ethylate, chlorination propoxyl group magnesium, chlorination butoxy magnesium, chlorination phenoxy group magnesium, magnesium ethylate, isopropoxy magnesium, fourth
In epoxide magnesium, chlorination isopropoxy magnesium, butyl magnesium chloride, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium etc. at least one
Kind, wherein, preferably magnesium dichloride, diethoxy magnesium or dipropoxy magnesium etc..
Wherein, described transition metal halide is selected from formula (2) is M (R1)4-mXmCompound at least one, formula
In, M is Ti, Zr, Hf, Fe, Co, Ni etc.；X is halogen atom, selected from Cl, Br, F；M is 1 to 4 integer；R1Selected from C1～C20's
Aliphatic group, C1～C20Fatty alkoxyl, C1～C20Cyclopentadienyl group and its derivant, C1～C20Aryl radical, COR
` or COOR`, R` are with C1～C10Fatty group or there is C1～C10Aromatic radical.R1Specifically it is selected from：Methyl, ethyl,
Propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, isobutyl group, the tert-butyl group, isopentyl, tertiary pentyl, 2- ethyl hexyl
Base, phenyl, naphthyl, ortho-methyl phenyl, m- aminomethyl phenyl, p- aminomethyl phenyl, o- sulfonic group phenyl, formoxyl, acetyl group
Or at least one in benzoyl etc..Described Ti, the transition metal halide such as Zr, Hf, Fe, Co, Ni, specifically can be selected for four
Titanium chloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium,
Trichlorine one ethanolato-titanium, tetrabutyl titanate, isopropyl titanate, methoxytitanium trichloride, dibutoxy titanium chloride, three butoxy
One or more of titanium chloride, four phenoxide titaniums, a chlorine triple phenoxyl titanium, dichloro epoxide titanium, trichlorine one phenoxide titanium
Mixing.Wherein, preferred titanium tetrachloride.Transition metal halide is preferred (8-40) with the mol ratio of magnesium halide：1.
Wherein, described carbon number is 2 to 15 alcohol, selected from ethanol, methanol, propanol, butanol, amylalcohol, enanthol, different pungent
At least one in alcohol, capryl alcohol, nonyl alcohol, decanol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol or pentadecanol etc., preferred alcohol,
Isooctanol etc..Carbon number be the mol ratio of 2 to 15 alcohol and magnesium halide preferably (0.05 3.5)：1.
Wherein, it is B (OSiR that described organosilicon boric acid ether compound is selected from formula (3)2)3-n(OH)nIn at least one,
Wherein n is selected from 0,1,2 or 3；Wherein R2Selected from C1～C20Aliphatic group, C1～C20Alkoxyl, C3～C20Alcyl or C6
～C20Aryl radical.Organosilicon boric acid ether compound is chosen in particular from least one in following compound：
Wherein, described organosilicon boric acid ether compound selected from formula (4) is
In at least one, wherein q is 1 to 15 integer, wherein n be selected from 0,1,2 or 3.
Wherein R3It is H, halogen, the aliphatic group of C1～C15, C1～C15 alkoxyl, C3～C15 ring group or C6～C15 perfume alkyl.Have
Machine silicic-boric acid ether compound can be selected from least one in following compound：
Organosilicon boric acid ether compound is (0.01-10) with the mol ratio of magnesium compound carrier：1.Add organosilicon boric acid ether
Compound can significantly improve catalysis activity, hydrogen response and the copolymerized ability of catalyst.
One of feature of the present invention be solid main catalyst preparation process in add carbon number be 2 to 15 alcohol, its
In, described carbon number is 2 to 15 alcohol, selected from ethanol, methanol, propanol, butanol, amylalcohol, enanthol, isooctanol, capryl alcohol, nonyl
At least one in alcohol, decanol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol or pentadecanol etc., preferred alcohol, isooctanol etc..
Carbon number be the mol ratio of 2 to 15 alcohol and magnesium halide preferably (0.05 3.5)：1.The alcohol adding carbon number to be 2 to 15 can
To significantly improve the hydrogen regulation performance of catalyst.
One of feature of the present invention be solid main catalyst preparation process in add electron donor organosilicon boric acid etherificate
Compound.Wherein, it is B (OSiR that described organosilicon boric acid ether compound is selected from formula (3)2)3-n(OH)nIn at least one, its
Middle n is selected from 0,1,2 or 3；Wherein R2Selected from C1～C20Aliphatic group, C1～C20Alkoxyl, C3～C20Alcyl or C6~
C20Aryl radical.Organosilicon boric acid ether compound is chosen in particular from least one in following compound：
Wherein, described organosilicon boric acid ether compound selected from formula (4) can be
In at least one, wherein q is 1 to 15 integer, wherein n be selected from 0,1,2 or 3.
Wherein R3It is H, halogen, the aliphatic group of C1～C15, C1～C15 alkoxyl, C3～C15 ring group or C6～C15 perfume alkyl.Have
Machine silicic-boric acid ether compound can also be chosen in particular from least one in following compound：
Organosilicon boric acid ether compound is (0.01-5) with the mol ratio of magnesium halide：1.Add organosilicon boric acid ether compound
Catalysis activity, hydrogen response and the copolymerized ability of catalyst can be significantly improved.
The preparation method of olefin polymerization catalysis provided by the present invention comprises the following steps：
1) by magnesium compound support dispersion in inert organic solvents, add the alcohol that carbon number is 2 to 15, in 90 to 150
At DEG C, stirring and dissolving 1 is to 5h.
2) by 1) solution is cooled to 30 DEG C to 80 DEG C, adds organosilicon boric acid ether compound, reacts 0.5 to 3h.
3) at -25 to 30 DEG C, by step 2) system that obtains contacted with transition metal halide, and at -25 to 30 DEG C
Lower reaction 0.5-5h, then system is warming up to 50-120 DEG C, react 0.5-5h, in temperature-rise period, solid particle gradually separates out,
After reaction terminates, with toluene or normal hexane washed product 4-6 time, it is filtered to remove unreacted reactant,
Vacuum drying obtains pulverulent solids major catalyst.Vacuum drying temperature is 40 DEG C to 90 DEG C；Vacuum drying time
For 0.5 hour to 5 hours, preferably 1 hour to 4 hours.
Described inert organic solvents are selected from C5～C15Saturated hydrocarbons, C5～C10Alicyclic or C6～C15Aromatic hydrocarbon,
Preferably decane, octane, dodecane, toluene, dimethylbenzene, hexane, heptane or hexamethylene, or their mixed solvent.
Olefin polymerization catalysis provided by the present invention also need cocatalyst to form.Described promoter is common
Organo-aluminum compound, preferably triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, aluminium diethyl monochloride, MAO MAO etc.；
Solid main catalyst is 1 with the mol ratio of promoter:(10-500).
The purposes of olefin polymerization catalysis provided by the present invention is：Can be used as vinyl polymerization or propylene polymerization or ethylene
The copolymerization catalyst of (or propylene) and alpha-olefin, wherein, described alpha-olefin is selected from C3～C20Alkene, preferably propylene, 1-
Butylene, 1- hexene, 1- octene, 1-decene, 3-methyl-1-butene, cyclopentenes, 4-methyl-1-pentene, 1,3-butadiene, isoamyl
Diene, styrene, methyl styrene etc..
Olefin polymerization catalysis provided by the present invention have the advantages that：
It is an object of the invention to provide alpha-olefinic copolymerization catalyst particle shape good, spherical in shape, catalyst granules
It is not adhere on chamber wall；The hydrogen regulation performance of catalyst is excellent, and melt index MFR of polyethylene can be in 0.01g/10min
Adjust in 600g/10min；Catalyst activity is high；It is applied to slurry process, gas-phase polymerization process or polymerization mix technique；Preparation side
Method is simple, and low for equipment requirements, environmental pollution is little.
Mg in major catalyst, the weight/mass percentage composition of Ti and Si are measured using ICP.
The condition determination of the melt index of polyethylene and polyethylene and ethylene copolymers be testing load be 5kg, temperature be 190 DEG C.
The condition determination of the melt index of isotactic polypropylene be testing load be 2.16kg, temperature be 230 DEG C.
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention is not limited only to down
State embodiment.
Specific embodiment
Embodiment 1
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, different
Capryl alcohol 6.5ml, stirring is warming up to 120 DEG C, reacts 2h.It is cooled at 50 DEG C, sequentially add and meet formula (3) organosilicon boric acid ether
Compound (1) 2.5g, keeping temperature is 50 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 30ml titanium tetrachloride, react 1h,
It is warming up to 110 DEG C and react 2h again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), true in 70 DEG C
Empty dry 2 hours, obtain good fluidity, non-stick container wall, even particle size distribution, pulverulent solids major catalyst spherical in shape.
Embodiment 2
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 30ml, ethanol 0.25ml,
Isooctanol 7ml, stirring is warming up to 120 DEG C, reacts 2h.It is cooled at 60 DEG C, sequentially add and meet formula (3) organosilicon boric acid ether
Compound (2) 1.5g, keeping temperature is 60 DEG C of reaction 2h.At system is down to -10 DEG C, Deca 40ml titanium tetrachloride, react 1h,
It is warming up to 100 DEG C and react 3h again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), true in 60 DEG C
Empty dry 3 hours, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 3
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 0.2ml, different
Capryl alcohol 8ml, stirring is warming up to 100 DEG C, reacts 2h.It is cooled at 50 DEG C, sequentially add and meet formula (3) organosilicon boric acid etherificate
Compound (3) 13g, is warming up to 80 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 35ml titanium tetrachloride, reacts 1h, is warming up to
65 DEG C are reacted 2h again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), be vacuum dried 4 in 50 DEG C
Hour, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 4
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 2ml, different pungent
Alcohol 7ml, stirring is warming up to 110 DEG C, reacts 4h.It is cooled at 50 DEG C, sequentially add and meet the etherificate conjunction of formula (3) organosilicon boric acid
Thing (4) 0.5g, is warming up to 100 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, is warming up to
120 DEG C are reacted 2h again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), be vacuum dried in 80 DEG C
2 hours, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 5
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 0.1ml, different
Capryl alcohol 4ml, stirring is warming up to 100 DEG C, reacts 5h.It is cooled at 40 DEG C, sequentially add and meet formula (3) organosilicon boric acid etherificate
Compound (5) 5g, keeping temperature is 40 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 25ml titanium tetrachloride, reacts 3h, heats up
React 2h to 110 DEG C again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), do in 90 DEG C of vacuum
Dry 2 hours, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 6
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 2.5ml, different
Capryl alcohol 3ml, stirring is warming up to 110 DEG C, reacts 2h.It is cooled at 50 DEG C, sequentially add and meet formula (3) organosilicon boric acid etherificate
Compound (6) 3g and tetraethoxysilane 8ml, keeping temperature is 50 DEG C of reaction 3h.At system is down to -15 DEG C, Deca 40ml tetra-
Titanium chloride, reacts 1h, is warming up to 70 DEG C and reacts 2h again.Stop stirring, standing, layering, filter, hexane washs four times (every time 30
Milliliter), it is vacuum dried 2 hours in 100 DEG C, obtain good fluidity, even particle size distribution, non-stick container wall, powder spherical in shape
Shape solid main catalyst.
Embodiment 7
In the reactor being sufficiently displaced from through nitrogen, add 1g diethoxy magnesium, normal heptane 30ml, and ethanol
0.2ml, stirring is warming up to 110 DEG C, reacts 4h.It is cooled at 50 DEG C, add and meet formula (3) organosilicon boric acid ether compound
(7) 6g and ethanol 0.2ml, keeping temperature is 50 DEG C of reaction 4h.At system is down to -15 DEG C, Deca 35ml titanium tetrachloride, reaction
1h, is warming up to 95 DEG C and reacts 4h again.Stop stirring, standing, layering, filter, toluene washes twice (30 milliliters every time), and hexane is washed
Wash four times (30 milliliters every time), in 60 DEG C be vacuum dried 3 hours, obtain good fluidity, even particle size distribution, non-stick container wall,
Pulverulent solids major catalyst spherical in shape.
Embodiment 8
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, dodecane 20ml, ethanol 0.3ml, the last of the ten Heavenly stems
Alcohol 6ml, stirring is warming up to 110 DEG C, reacts 2h.It is cooled at 50 DEG C, sequentially add and meet the etherificate conjunction of formula (3) organosilicon boric acid
Thing (8) 6g, keeping temperature is 50 DEG C of reaction 3h.At system is down to -10 DEG C, Deca 30ml titanium tetrachloride, reacts 1h, is warming up to
80 DEG C are reacted 3h again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), be vacuum dried 4 in 60 DEG C
Hour, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 9
In the reactor being sufficiently displaced from through nitrogen, add 1g dipropoxy magnesium, toluene 30ml, propanol 0.5ml, stir
Mix and be warming up to 110 DEG C, react 5h.It is cooled at 50 DEG C, adds and meet formula (3) organosilicon boric acid ether compound (9) 6g, keep
Temperature is 50 DEG C of reaction 2h.System is down at 0 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, be warming up to 90 DEG C and react 2h again.
Stop stirring, standing, layering, filter, hexane washes twice (30 milliliters every time), be vacuum dried 2 hours in 110 DEG C, flowed
Dynamic property is good, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 10
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, normal octane 30ml, butanol 4ml, different pungent
Alcohol 6.5ml, stirring is warming up to 110 DEG C, reacts 2h.It is cooled at 50 DEG C, add and meet formula (3) organosilicon boric acid ether compound
(10) 2g, keeping temperature is 50 DEG C of reaction 2h.At system is down to -5 DEG C, Deca 45ml titanium tetrachloride, reacts 1h, is warming up to 90
DEG C react 2h again.Stop stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), be vacuum dried 2 in 120 DEG C
Hour, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 11
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, n-decane 15ml, ethanol 5ml, stirring
It is warming up to 110 DEG C, react 2h.It is cooled at 50 DEG C, adds and meet formula (3) organosilicon boric acid ether compound (11) 4g, keep
Temperature is 50 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise in the 25ml titanium tetrachloride being in -10 DEG C, react at 0 DEG C
1h, was warming up to 110 DEG C in 4 hours and reacts 2h again.Stop stirring, standing, layering, filter, hexane washs four (30 millis every time
Rise), it is vacuum dried 3 hours in 50 DEG C, obtain good fluidity, even particle size distribution, non-stick container wall, powder spherical in shape admittedly
Body major catalyst.
Embodiment 12
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, n-decane 40ml, ethanol 1.5ml, stir
Mix and be warming up to 120 DEG C, react 2h.It is cooled at 60 DEG C, add and meet formula (3) organosilicon boric acid ether compound (12) 3g and four
Ethoxysilane 6ml, keeping temperature is 60 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise to the 25ml tetra- being in -15 DEG C
In titanium chloride, react 1h at -5 DEG C, be warming up to 100 DEG C in 4 hours and react 2h again.Stop stirring, standing, layering, filter, oneself
Alkane washs four times (30 milliliters every time), is vacuum dried 3 hours in 50 DEG C, obtains good fluidity, even particle size distribution, non-stick container
Wall, pulverulent solids major catalyst spherical in shape.
Embodiment 13
In the reactor being sufficiently displaced from through nitrogen, addition 1g diethoxy magnesium, n-decane 20ml, isooctanol 3ml,
Stirring is warming up to 110 DEG C, reacts 3h.It is cooled at 50 DEG C, add and meet formula (3) organosilicon boric acid ether compound (15) 1g,
2h is reacted at a temperature of 50 DEG C.System is down at 0 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, be warming up to 90 DEG C of reaction 2h.
Stop stirring, standing, layering, filter, hexane washes twice (30 milliliters every time), be vacuum dried 4 hours in 50 DEG C, flowed
Property is good, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 14
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, second
Alcohol 1ml, isooctanol 6.5ml, stirring is warming up to 100 DEG C, reacts 4h.It is cooled at 40 DEG C, add and meet formula (3) organic silicon-boron
Sour ether compound (16) 3g and silica gel 0.15g, is warming up to 70 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 15ml tetra- chlorination
Titanium, reacts 1h, is warming up to 90 DEG C of reaction 2h.Stop stirring, standing, layering, filter, hexane washes twice (30 milliliters every time),
It is vacuum dried 2 hours in 60 DEG C, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids master spherical in shape
Catalyst.
Embodiment 15
In the reactor being sufficiently displaced from through nitrogen, add 1g diethoxy magnesium, n-decane 20ml, isooctanol
6.5ml, stirring is warming up to 120 DEG C, reacts 0.5h.It is cooled at 50 DEG C, add and meet formula (4) organosilicon boric acid ether compound
(17) 8g and succinate 10ml, keeping temperature is 50 DEG C of reaction 3h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride,
Reaction 1h, is warming up to 90 DEG C and reacts 2h again, is vacuum dried 2 hours in 60 DEG C, obtains good fluidity, even particle size distribution, do not glue
Chamber wall, pulverulent solids major catalyst spherical in shape.
Embodiment 16
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, second
Alcohol 1ml, isooctanol 6.5ml, stirring is warming up to 100 DEG C, reacts 4h.It is cooled at 40 DEG C, add and meet formula (4) organic silicon-boron
Sour ether compound (18) 6g, is warming up to 70 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride, react 1h,
It is warming up to 90 DEG C of reaction 2h.Stop stirring, standing, layering, filter, hexane washes twice (30 milliliters every time), in 60 DEG C of vacuum
It is dried 2 hours, obtain good fluidity, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 17
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, n-decane 20ml, toluene 10ml, second
Alcohol 1ml, isooctanol 6.5ml, stirring is warming up to 100 DEG C, reacts 4h.It is cooled at 40 DEG C, add and meet formula (4) organic silicon-boron
Sour ether compound (19) 5g and tetraethoxysilane 0.25ml, is warming up to 70 DEG C of reaction 2h.At system is down to -15 DEG C, Deca
15ml titanium tetrachloride, reacts 1h, is warming up to 90 DEG C of reaction 2h.Stop stirring, standing, layering, filter, hexane washes twice (every
Secondary 30 milliliters), it is vacuum dried 2 hours in 60 DEG C, obtain good fluidity, even particle size distribution, non-stick container wall, powder spherical in shape
Last shape solid main catalyst.
Embodiment 18
In the reactor being sufficiently displaced from through nitrogen, add 1g diethoxy magnesium, normal hexane 30ml, stirring is warming up to
100 DEG C, react 4h.It is cooled at 40 DEG C, add and meet formula (4) organosilicon boric acid ether compound (20) 3g, be warming up to 70 DEG C
Reaction 2h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, is warming up to 90 DEG C of reaction 2h.Stop stirring, quiet
Put, layering, filter, hexane washes twice (30 milliliters every time), be vacuum dried 2 hours in 60 DEG C, obtain good fluidity, particle diameter divides
Cloth is uniform, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Embodiment 19
In the reactor being sufficiently displaced from through nitrogen, addition 1g diethoxy magnesium, n-decane 20ml, ethanol 20ml,
Stirring is warming up to 100 DEG C, reacts 4h.It is cooled at 40 DEG C, add and meet formula (4) organosilicon boric acid ether compound (23) 3g,
It is warming up to 70 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, is warming up to 90 DEG C of reaction 2h.
Stop stirring, standing, layering, filter, hexane washes twice (30 milliliters every time), be vacuum dried 2 hours in 60 DEG C, flowed
Property is good, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Comparative example 1
In the reactor being sufficiently displaced from through nitrogen, addition 1g diethoxy magnesium, decane 20ml, isooctanol 16ml,
Ethanol 0.4ml, stirring is warming up to 110 DEG C, reacts 2h.It is cooled at 50 DEG C, adds tetraethoxysilane 3ml, keeping temperature is
50 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 35ml titanium tetrachloride, reacts 1h, is warming up to 100 DEG C of reaction 2h.Stopping is stirred
Mix, standing, layering, filter, hexane wash four times (30 milliliters every time), in 80 DEG C be vacuum dried 2 hours, obtain good fluidity,
Even particle size distribution, pulverulent solids major catalyst spherical in shape, primary catalyst particles are easily adhered on chamber wall.
Comparative example 2
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctanol 16ml, second
Alcohol 0.4ml, stirring is warming up to 120 DEG C, reacts 3h.It is cooled at 50 DEG C, add tributyl phosphate 3ml and tetraethoxysilane
3ml, keeping temperature is 50 DEG C of reaction 2h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, is warming up to 90 DEG C
Reaction 2h.Stop stirring, standing, layering, filter, hexane washes twice (30 milliliters every time), be vacuum dried 2 hours in 60 DEG C,
Obtain pulverulent solids major catalyst, primary catalyst particles are easily adhered on chamber wall.
Comparative example 3
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, decane 20ml, isooctanol 16ml, second
Alcohol 0.4ml, stirring is warming up to 120 DEG C, reacts 3h.It is cooled at 50 DEG C, adds tributyl phosphate 3ml, keeping temperature is 50 DEG C
Reaction 2h.At system is down to -15 DEG C, Deca 15ml titanium tetrachloride, reacts 1h, is warming up to 90 DEG C of reaction 2h.Stop stirring, quiet
Put, layering, filter, hexane washes twice (30 milliliters every time), be vacuum dried 2 hours in 60 DEG C, obtain pulverulent solids and sponsor
Agent, primary catalyst particles are easily adhered on chamber wall.
Application mode one
Vinyl polymerization：After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component successively in kettle
Component 10mg, is dehydrated hexane 1000ml, promoter AlEt3Solution 1.17ml (2mmol/ml), is filled with hydrogen after being warming up to 75 DEG C
Gas 0.28MPa, is re-filled with ethylene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode two
Ethylene copolymerization：After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add major catalyst group successively in kettle
Divide 10mg, be dehydrated hexane 1000ml, AlEt3Solution 1.17ml (2mmol/ml), adds 30ml 1- hexene.After being warming up to 75 DEG C,
It is filled with hydrogen 0.28MPa, be re-filled with ethylene to 0.73MPa, constant voltage isothermal reaction 2h.
Application mode three
Propylene polymerization：After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component successively in kettle
10mg, is dehydrated hexane 1000ml, AlEt3Solution 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, is re-filled with propylene to 3MPa, constant voltage constant temperature is anti-
Answer 2h.Polyacrylic melt index MFR=111g/10min.
Olefinic polymerization the results are shown in Table 1.
Embodiment 20
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 1.5ml, different
Capryl alcohol 6.5ml, stirring is warming up to 120 DEG C, reacts 3h.It is cooled at 60 DEG C, add and meet formula (5) alkoxyl organic phosphoric acid ether
Compound (3) 3g and tetraethoxysilane 0.2ml, keeping temperature is 60 DEG C of reaction 2h.At system is down to -5 DEG C, Deca 35ml
Titanium tetrachloride, reacts 1h；It is warming up to 110 DEG C in 4 hours, then react 2h.Stop stirring, standing, layering, filter, hexane is washed
Wash four times (30 milliliters every time), in 50 DEG C be vacuum dried 4 hours, obtain good fluidity, even particle size distribution, non-stick container wall,
Pulverulent solids major catalyst spherical in shape.
Vinyl polymerization
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 5mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 0.6ml (2mmol/ml), is filled with hydrogen 0.1MPa after being warming up to 70 DEG C, then
It is filled with ethylene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain 375.2 grams of polyethylene, bulk density BD=0.34, melt index MFR=0.1g/10min.
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 10mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 0.6ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 70 DEG C,
It is re-filled with ethylene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain 355.5 grams of polyethylene, bulk density BD=0.34, melt index MFR=1.6g/10min.
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 25mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 3.0ml (2mmol/ml), is filled with hydrogen 0.73MPa after being warming up to 70 DEG C,
It is re-filled with ethylene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain 263.6 grams of polyethylene, bulk density BD=0.35, melt index MFR=480g/10min.
Embodiment 21
In the reactor being sufficiently displaced from through nitrogen, addition 1g magnesium dichloride, n-decane 20ml, ethanol 0.4ml, different
Capryl alcohol 6.5ml, stirring is warming up to 120 DEG C, reacts 3h.It is cooled at 60 DEG C, add and meet formula (6) alkoxyl organic phosphoric acid ether
Compound (21) 2.5g and tetraethoxysilane 0.2ml, keeping temperature is 60 DEG C of reaction 2h.System is cooled to 25 DEG C, then drips
Add in the 25ml titanium tetrachloride being in -15 DEG C, react 1h at 0 DEG C；It is warming up to 110 DEG C in 4 hours, then react 2h.Stop
Stirring, standing, layering, filter, hexane washs four times (30 milliliters every time), be vacuum dried 4 hours in 50 DEG C, obtain mobility
Well, even particle size distribution, non-stick container wall, pulverulent solids major catalyst spherical in shape.
Vinyl polymerization
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 5mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 0.6ml (2mmol/ml), is filled with hydrogen 0.1MPa after being warming up to 70 DEG C, then
It is filled with ethylene to 0.6MPa, constant voltage isothermal reaction 1h.
Obtain 285.3 grams of polyethylene, bulk density BD=0.33, melt index MFR=0.18g/10min.
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 10mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 0.6ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 70 DEG C,
It is re-filled with ethylene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain 361.3 grams of polyethylene, bulk density BD=0.33, melt index MFR=1.7g/10min.
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 25mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 3.0ml (2mmol/ml), is filled with hydrogen 0.73MPa after being warming up to 70 DEG C,
It is re-filled with ethylene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain 258.1 grams of polyethylene, bulk density BD=0.34, melt index MFR=490g/10min.
Comparative example 3
In the reactor being sufficiently displaced from through nitrogen, add 1g magnesium dichloride, n-decane 20ml, isooctanol 6.5ml
With ethanol 0.4ml, stir and be warming up to 120 DEG C, react 3h.It is cooled at 60 DEG C, add tetraethoxysilane 2ml, keeping temperature
For 60 DEG C of reaction 2h.System is cooled to 25 DEG C, then is added dropwise in the 25ml titanium tetrachloride being in -15 DEG C, react 1h at 0 DEG C；
It is warming up to 110 DEG C in 4 hours, then react 2h.Stop stirring, standing, layering, filter, hexane washs four (30 millis every time
Rise), it is vacuum dried 4 hours in 50 DEG C, obtain good fluidity, even particle size distribution, pulverulent solids major catalyst spherical in shape,
Primary catalyst particles are easily adhered on chamber wall.
Vinyl polymerization
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 10mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 0.6ml (2mmol/ml), is filled with hydrogen 0.1MPa after being warming up to 70 DEG C, then
It is filled with ethylene to 0.8MPa, constant voltage isothermal reaction 1h.
Obtain 235.3 grams of polyethylene, bulk density BD=0.30, melt index MFR=0.3g/10min.
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 10mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 0.6ml (2mmol/ml), is filled with hydrogen 0.28MPa after being warming up to 70 DEG C,
It is re-filled with ethylene to 0.73MPa, constant voltage isothermal reaction 2h.
Obtain 188.3 grams of polyethylene, bulk density BD=0.28, melt index MFR=3.1g/10min.
After 2 liters of stainless steel autoclaves are sufficiently displaced from through nitrogen, add main catalyst component component 50mg in kettle successively,
Dehydration hexane 1000ml, promoter AlEt3Solution 3.0ml (2mmol/ml), is filled with hydrogen 0.73MPa after being warming up to 70 DEG C,
It is re-filled with ethylene to 1.0MPa, constant voltage isothermal reaction 1h.
Obtain 172.1 grams of polyethylene, bulk density BD=0.26, melt index MFR=126g/10min.
Table 1 olefinic polymerization result
Claims (5)
1. olefin polymerization catalysis, be made up of major catalyst and promoter it is characterised in that：Described major catalyst is by magnesium
Thing carrier, transition metal halide, carbon number are 2 to 15 alcohol and electron donor organosilicon boric acid ether compound composition, magnesium
Compound carrier, transition metal halide, carbon number are 2 to 15 alcohol and the mol ratio of organosilicon boric acid ether compound is：1：
(1-40)：(0.01–10)：(0.01–10)；Described promoter is organo-aluminum compound；Major catalyst and promoter
With magnitude relation it is：Transition metal halide in major catalyst is 1 with the mol ratio of promoter:(10-500)；
It is B (OSiR that described electron donor organosilicon boric acid ether compound is selected from formula (3)2 3)3-n(OH)nIn at least one,
Wherein n is selected from 0,1,2 or 3；Wherein R2Selected from C1～C20Aliphatic group, C1～C20Alkoxyl, C3～C20Alcyl or C6
～C20Aryl radical；
According to following steps preparation：
1) by magnesium compound support dispersion in inert organic solvents, add the alcohol that carbon number is 2 to 15, at 90 to 150 DEG C
Stirring 1 to 5h；
2) by 1) mixed system is cooled to 30 DEG C -80 DEG C, adds electron donor organosilicon boric acid ether compound, reacts 1-5h；
3) by 2) mixed system is cooled to -20 DEG C to 30 DEG C, mixed system is contacted with transition metal halide, and -20 to
React 0.5-5h at 30 DEG C, then system is warming up to 50-120 DEG C, react 0.5-5h, after reaction terminates, with toluene or normal hexane
Washed product, is filtered to remove unreacted reactant；Vacuum drying obtains pulverulent solids major catalyst；Vacuum drying temperature is for 40 DEG C extremely
90℃；Vacuum drying time is 0.5 hour to 5 hours；
Wherein, described inert organic solvents are selected from C5～C15Saturated hydrocarbons, C5～C10Alicyclic or C6～C15Aromatic hydrocarbon
Or their mixed solvent.
2. olefin polymerization catalysis according to claim 1 it is characterised in that：Described magnesium compound is selected from logical as carrier
Formula (1) is Mg (R)aXbCompound at least one, R be selected from C1～C20Aliphatic group, C1～C20Fatty alkoxyl,
C3～C20Alcyl or C6～C20Aryl radical；X is selected from halogen；A=0,1 or 2；B=0,1 or 2, a+b=2.
3. olefin polymerization catalysis according to claim 1 it is characterised in that：Described transition metal halide is selected from logical
Formula (2) is M (R1)4-mXmCompound at least one, in formula, M is Ti, Zr, Hf, Fe, Co or Ni；X is halogen atom, is selected from
Cl,Br,F；M is 1 to 4 integer；R1Selected from C1～C20Aliphatic group, C1～C20Fatty alkoxyl, C5～C20Ring penta
Dialkylene and its derivant, C6～C20Aryl radical, COR` or COOR`, R` is with C1～C10Fatty group or have
C6～C10Aromatic radical；Transition metal halide is (8-40) with the mol ratio of magnesium compound carrier：1.
4. olefin polymerization catalysis according to claim 1 are it is characterised in that described carbon number is 2 to 15 alcohol,
Selected from ethanol, propanol, butanol, amylalcohol, enanthol, isooctanol, capryl alcohol, nonyl alcohol, decanol, undecyl alcohol, lauryl alcohol, tridecanol, 14
At least one in alcohol or pentadecanol；Carbon number is 2 to 15 alcohol is (0.05 3.5) with the mol ratio of magnesium compound carrier：1.
5. olefin polymerization catalysis according to claim 1 application it is characterised in that：Described olefin polymerization catalysis
It is the catalyst of the combined polymerization of the combined polymerization of vinyl polymerization, ethylene and alpha-olefin or propylene and alpha-olefin, wherein, described α-
Alkene is selected from C3～C20Alkene.
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