CN103073660A - Magnesium halide carrier and application thereof, and olefin polymerization catalyst, olefin polymerization catalyst system, and olefin polymerization method - Google Patents
Magnesium halide carrier and application thereof, and olefin polymerization catalyst, olefin polymerization catalyst system, and olefin polymerization method Download PDFInfo
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Abstract
The invention provides a magnesium halide carrier and an application thereof, and an olefin polymerization catalyst, an olefin polymerization catalyst system, and an olefin polymerization method. The magnesium halide carrier provided by the invention comprises magnesium halide and crystal seed, wherein the crystal seed is one or more selected from montmorillonite, clay, kaolin, diatomite, bentonite, argil and alumina. The magnesium halide carrier provided by the invention has a high loading capacity, such that high active component load can be obtained. With the magnesium halide carrier provided by the invention, prepared olefin polymerization catalyst has high catalytic activity. When the catalyst is used in olefin polymerization, prepared polyolefin product has high bulk density. Also, the magnesium halide carrier provided by the invention has simple preparation process and low production cost.
Description
Technical field
The present invention relates to a kind of magnesium halide carrier and application thereof, the invention still further relates to a kind of olefin polymerization catalysis and olefin polymerization catalyst system, the invention further relates to a kind of olefine polymerizing process.
Background technology
Traditional Ziegler-natta catalyst comprises Primary Catalysts and promotor, and Primary Catalysts is generally the compound of the IVB family metallic element that contains in the periodic table of elements, and the most frequently used is titanium compound; Promotor is organo-aluminium compound normally, and promotor commonly used comprises Al (C
2H
5)
3, Al (C
2H
5)
2Cl, Al
2(C
2H
5)
3Cl
3Deng.
For the synthesis of the development of poly Ziegler-natta catalyst through several generations, performance is greatly improved, and the birth of supported catalyst has significantly improved the polymerization activity of Ziegler-natta catalyst.Active magnesium chloride is the most effective carrier of Ziegler-natta catalyst, and the more employing of prior art prepares the support of the catalyst with high reactivity and good particle form with active magnesium chloride load having the porous inert carrier of high-specific surface area (such as silicon-dioxide, aluminum oxide etc.); Also can directly adopt active magnesium chloride as carrier.
The start material for preparing active magnesium chloride includes Magnesium Chloride Anhydrous and other magnesium compound, prepares active magnesium chloride by physics or chemical means.For example, when adopting Magnesium Chloride Anhydrous to prepare active magnesium chloride as start material, can be with Magnesium Chloride Anhydrous and titanium tetrachloride mixed grinding, thus in the active magnesium chloride of formation the load titanium tetrachloride; Also can be with first Magnesium Chloride Anhydrous being prepared into alcohol adduct or hydrate, again with titanium tetrachloride reaction.
Result of study shows, the difference of the preparation process of active magnesium chloride can exert an influence to the chemical constitution of the olefin polymerization catalysis of final preparation, content and the distribution in active centre, and then so that the character of the polymkeric substance of preparation also has difference.In addition, await further to improve with the active centre content of existing active magnesium chloride as the Ziegler-natta catalyst of carrier preparation.
Summary of the invention
The purpose of this invention is to provide a kind of magnesium halide carrier and preparation method thereof, this magnesium halide carrier has the ability of high load active component, can effectively widen the charge capacity of active ingredient; And, carry out polymerization and the bulk density of the polyolefin products for preparing is high by the olefin polymerization catalysis catalyzed alkene of this magnesium halide carrier preparation, thereby can effectively improve the throughput of manufacture of polyolefins device, reduce production costs.
The present inventor finds in research process, in the presence of one or more crystal seeds in being selected from polynite, clay, kaolin, diatomite, wilkinite, carclazyte and aluminum oxide, MAGNESIUM METAL is contacted with halogenated alkane, and the magnesium halide carrier of preparation has the ability of very strong supported active composition; And when being used for olefinic polymerization, the bulk density of the polyolefin products of preparation is high by the olefin polymerization catalysis of this magnesium halide carrier preparation; In addition, the olefin polymerization catalysis by this magnesium halide carrier preparation also has higher catalytic efficiency.Finished thus the present invention.
A first aspect of the present invention provides a kind of magnesium halide carrier, and this magnesium halide carrier contains magnesium halide and crystal seed, and described crystal seed is to be selected from polynite, clay, kaolin, diatomite, wilkinite, carclazyte and the aluminum oxide one or more.
A second aspect of the present invention provides the application of a kind of magnesium halide carrier according to the present invention in the preparation olefin polymerization catalysis.
A third aspect of the present invention provides a kind of olefin polymerization catalysis, and this catalyzer contains magnesium halide carrier and loads on titanium compound on the described magnesium halide carrier, and wherein, described magnesium halide carrier is magnesium halide carrier provided by the invention.
A fourth aspect of the present invention provides a kind of olefin polymerization catalyst system, this olefin polymerization catalyst system contains Primary Catalysts and promotor, described promotor is organo-aluminium compound, and wherein, described Primary Catalysts is olefin polymerization catalysis provided by the invention.
A fifth aspect of the present invention provides a kind of olefine polymerizing process, and the method is included under the olefinic polymerization condition, and one or more alkene are contacted with catalyst system provided by the invention.
Carrying capacity according to magnesium halide carrier of the present invention is strong, can obtain high activeconstituents charge capacity, thereby can effectively widen the scope of the charge capacity that loads on the activeconstituents on the described magnesium halide carrier, and then can prepare easily the catalyzer that satisfies multiple manufacturing condition requirement; And when being used for olefinic polymerization, the bulk density of the polyolefin products of preparation is high, thereby can effectively improve the throughput of manufacture of polyolefins device by the olefin polymerization catalysis of magnesium halide carrier according to the present invention preparation; Simultaneously, high by the catalytic activity of the olefin polymerization catalyst system of magnesium halide carrier provided by the invention preparation, can effectively enhance productivity; In addition, easy according to the preparation technology of magnesium halide carrier of the present invention, production cost is low.
Embodiment
A first aspect of the present invention provides a kind of magnesium halide carrier, and this magnesium halide carrier contains magnesium halide and crystal seed.
According to magnesium halide carrier of the present invention, described crystal seed is to be selected from polynite, clay, kaolin, diatomite, wilkinite, carclazyte and the aluminum oxide one or more.
According to magnesium halide carrier of the present invention, described magnesium halide can be this area various compounds that formed by magnesium elements and halogen (for example: fluorine, chlorine, bromine or iodine) commonly used, and preferably, described magnesium halide is magnesium chloride and/or magnesium bromide; More preferably, described magnesium halide is magnesium chloride.
According to magnesium halide carrier of the present invention, the content of described magnesium halide and described crystal seed can change within wide in range scope.Preferably, take the total amount of described magnesium halide carrier as benchmark, the content of described magnesium halide is the 30-90 % by weight, and the content of described crystal seed is the 10-70 % by weight.When the content of described magnesium halide and described crystal seed was within the above-mentioned scope, described magnesium halide carrier had higher carrying capacity, and the catalyzer that is prepared by this magnesium halide carrier has higher catalytic activity.More preferably, take the total amount of described magnesium halide carrier as benchmark, the content of described magnesium halide is the 30-70 % by weight, and the content of described crystal seed is the 30-70 % by weight.Further preferably, take the total amount of described magnesium halide carrier as benchmark, the content of described magnesium halide is the 40-60 % by weight, and the content of described crystal seed is the 40-60 % by weight.
According to magnesium halide carrier of the present invention, the average particulate diameter of described magnesium halide carrier can carry out appropriate selection according to the concrete application scenario of this magnesium halide carrier.Preferably, the average particulate diameter of described magnesium halide carrier is the 6-100 micron.More preferably, the average particulate diameter of described magnesium halide carrier is the 20-60 micron.
Among the present invention, described average particulate diameter is to adopt Malven Master Size 2000 particles distribution instruments to measure, and is the volume averaging particle diameter.
Preparation method according to magnesium halide carrier of the present invention can be included under the existence of crystal seed, MAGNESIUM METAL contacted with the halogenated alkane shown in the formula I, and with the formation magnesium halide,
R
1X
1(formula I),
Among the formula I, R
1Be C
3-C
12The straight or branched alkyl, X
1Be halogen (for example: fluorine, chlorine, bromine or iodine).
According to the present invention, among the formula I, R
1Be preferably C
3-C
6Alkyl; X
1Be preferably chlorine, bromine or iodine, more preferably chlorine or bromine, more preferably chlorine.
Among the present invention, described C
3-C
12The straight or branched alkyl example can for but be not limited to: n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, positive decyl and dodecyl.
According to the present invention, the example of described halogenated alkane can for but be not limited to: chloro n-propane, n-propyl bromide, chloroisopropane, bromo propane, n-propylcarbinyl chloride, bromination of n-butane, chloro-iso-butane, isobutane bromide, tert-butyl chloride, tert-bromo butane, chloro-n-pentane, bromo pentane, chloro normal hexane, bromo normal hexane, bromo heptane, n-octyl chloride and chloro n-decane.
According to the present invention, described MAGNESIUM METAL can be this area various forms of MAGNESIUM METAL commonly used.Preferably, described MAGNESIUM METAL is metal magnesium powder.
According to the present invention, the average particulate diameter of described crystal seed can carry out appropriate selection according to the average particulate diameter of the magnesium halide carrier of expecting.Preferably, the average particulate diameter of described crystal seed is the 5-50 micron.When the average particulate diameter of described crystal seed is within the above-mentioned scope, adopt the average particulate diameter of the magnesium halide carrier of method preparation of the present invention can be within the scope of 6-100 micron.More preferably, the average particulate diameter of described crystal seed is the 10-50 micron.Further preferably, the average particulate diameter of described crystal seed is the 15-40 micron.
According to the present invention, the relative proportion between described crystal seed and the described MAGNESIUM METAL is as the criterion with the content requirement of crystal seed in the magnesium halide carrier that can satisfy final preparation.Preferably, the weight ratio of described crystal seed and described MAGNESIUM METAL is 0.2-6: 1.More preferably, the weight ratio of described crystal seed and described MAGNESIUM METAL is 2.5-5.5: 1.
According to the present invention, the ratio between described MAGNESIUM METAL and the described halogenated alkane can be selected for the routine of this area.Preferably, the mol ratio of described MAGNESIUM METAL and described halogenated alkane is 1: 1-3.
According to the present invention, described MAGNESIUM METAL is carried out in the presence of solvent with contacting preferably of described halogenated alkane.The present invention is not particularly limited for the kind of described solvent, can select for the routine of this area.Preferably, described solvent is C
5-C
10Replacement or unsubstituted aliphatic hydrocarbon and C
6-C
12Replacement or in the unsubstituted aromatic hydrocarbons one or more.More preferably, described solvent is one or more in Skellysolve A, iso-pentane, normal hexane, octane, pentamethylene, hexanaphthene, benzene and 1, the 2-ethylene dichloride.
According to the present invention, the consumption of described solvent can be the conventional amount used of this area, and those skilled in the art can carry out appropriate selection according to the conventional knowledge of this area, do not repeat them here.
According to the present invention, the condition that MAGNESIUM METAL contacts with the halogenated alkane shown in the formula I can be selected for the routine of this area, can so that MAGNESIUM METAL and described halogenated alkane react, forming magnesium halide and be as the criterion.Usually, the condition of described contact comprises: the temperature of described contact can be 10-100 ℃, is preferably 20-80 ℃; The time of described contact can be 0.5-10 hour, is preferably 1-8 hour.
According to the present invention, MAGNESIUM METAL contacted with described halogenated alkane and after the mixture that obtains filters, can also wash with alkane, thereby obtain according to magnesium halide carrier of the present invention.
Can exist with the common various forms in this area according to magnesium halide carrier of the present invention, for example: described magnesium halide carrier can exist with solid form, described magnesium halide carrier can also be made the form of suspension.When described magnesium halide was made suspension, the solvent that is used to form described suspension can be generally used for the solvent that uses when magnesium halide contacted to prepare olefin polymerization catalysis with the activeconstituents with olefinic polymerization catalysis activity for this area.Preferably, described solvent is C
5-C
10Replacement or unsubstituted aliphatic hydrocarbon and C
6-C
12Replacement or in the unsubstituted aromatic hydrocarbons one or more.More preferably, described solvent is one or more in Skellysolve A, iso-pentane, normal hexane, octane, pentamethylene, hexanaphthene, benzene and 1, the 2-ethylene dichloride.
Magnesium halide carrier according to the present invention has stronger carrying capacity, is particularly suitable for preparing olefin polymerization catalysis.Thus, a second aspect of the present invention provides the application of a kind of magnesium halide carrier according to the present invention in the preparation olefin polymerization catalysis.
A third aspect of the present invention provides a kind of olefin polymerization catalysis, and this catalyzer contains magnesium halide carrier and loads on titanium compound on the described magnesium halide carrier, and wherein, described magnesium halide carrier is magnesium halide carrier provided by the invention.Described magnesium halide carrier is described in detail at preamble, does not repeat them here.
Olefin polymerization catalysis according to the present invention adopts magnesium halide provided by the invention to come load to have the titanium compound of olefinic polymerization catalysis effect as carrier, described magnesium halide carrier has stronger carrying capacity, therefore according in the olefin polymerization catalysis of the present invention, the amount of described titanium compound can change within wide in range scope.Usually, the mol ratio of the titanium in the magnesium in the described magnesium halide carrier and the described titanium compound can be in 1: within the scope of 0.2-5, even can be in 1: within the scope of 1-5.
Olefin polymerization catalysis according to the present invention is that the magnesium halide carrier that the application of the invention provides is realized purpose of the present invention, the present invention is not particularly limited for the kind of described titanium compound, can be this area titanium-containing compound with olefinic polymerization catalysis effect commonly used.Usually, described titanium compound is the titanium compound shown in the formula II,
Ti (OR
2)
nX
2 4-n(formula II),
Among the formula II, R
2Be C
1-C
10The straight or branched alkyl; X
2For halogen (for example: fluorine, chlorine, bromine or iodine), be preferably chlorine or bromine, more preferably chlorine; N be 0-4 integer (for example: 0,1,2,3 or 4).
Among the present invention, C
1-C
10The straight or branched alkyl example can for but be not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.
Among the present invention, the example of described titanium compound can for but be not limited to: one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, titanium isopropylate, tetrabutyl titanate, tetraethyl titanate, a chlorine triethoxy titanium, dichloro diethoxy titanium and trichlorine one ethanolato-titanium.
According to olefin polymerization catalysis of the present invention, concrete application scenario according to described olefin polymerization catalysis, described catalyzer can also contain the electron donor compound that loads on the described magnesium halide carrier, with catalytic activity and the hydrogen response of further raising catalyst according to the invention.
Olefin polymerization catalysis according to the present invention all is not particularly limited for kind and the content of described electron donor compound, can select for the routine of this area.Usually, take the total amount of described catalyzer as benchmark, the weight ratio of the magnesium in the described magnesium halide carrier and described electron donor compound is 1: 1-15.Preferably, the weight ratio 1 of the magnesium in the described magnesium halide carrier and described electron donor compound: 2-8.
Described electron donor compound can be selected for the routine of this area.Among the present invention, described electron donor compound for example can be in ether, ester, amine and the alcohol one or more.Particularly, described electron donor compound can be in tetrahydrofuran (THF), ethyl acetate, ethyl benzoate, tributyl phosphate, isopropylcarbinol, isooctyl alcohol and the DMF one or more.
A fourth aspect of the present invention provides a kind of olefin polymerization catalyst system, this olefin polymerization catalyst system contains Primary Catalysts and promotor, described promotor is organo-aluminium compound, and wherein, described Primary Catalysts is olefin polymerization catalysis provided by the invention.Described olefin polymerization catalysis is described in detail at preamble, does not repeat them here.
According to olefin polymerization catalyst system of the present invention, described organo-aluminium compound can be the field of olefin polymerisation various organo-aluminium compounds that can be used as the promotor of Ziegler-natta catalyst commonly used.Described organo-aluminium compound for example can trimethyl aluminium, in triethyl aluminum, triisobutyl aluminium, three hexyl aluminium, aluminium diethyl monochloride, trioctylaluminum and the three decyl aluminium one or more.Preferably, described aluminum alkyls is one or more in triethyl aluminum, aluminium diethyl monochloride, triisobutyl aluminium and the three hexyl aluminium.
According to olefin polymerization catalyst system of the present invention, the consumption of described Primary Catalysts and described promotor can be selected for the routine of this area, is not particularly limited.Preferably, the mol ratio of the aluminium in the described promotor and the titanium in the described Primary Catalysts is 30-300: 1.More preferably, the mol ratio of the aluminium in the described promotor and the titanium in the described Primary Catalysts is 100-200: 1.
A fifth aspect of the present invention provides a kind of olefine polymerizing process, and the method is included under the olefinic polymerization condition, and one or more alkene are contacted with olefin polymerization catalyst system provided by the invention.Described olefin polymerization catalyst system is described in detail at preamble, does not repeat them here.
Can for the equal polymerization of alkene, also can be used for multiple alkene is carried out copolymerization according to olefine polymerizing process of the present invention.Described alkene can be ethene, C
3-C
10Aliphatics alpha-olefin and C
4-C
8Diolefin in one or more.The specific examples of described alkene can include but not limited to: ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and 4-methyl-1-pentene.Preferably, described alkene is ethene or ethene and C
3-C
8The aliphatics alpha-olefin.More preferably, described alkene is ethene or ethene and is selected from 1-butylene and the alpha-olefin of 1-hexene.
Can adopt this area various polymerization methodses commonly used to realize according to olefine polymerizing process of the present invention, for example: tank reactor or the successive polymerization still (for example: tubular reactor or tower reactor) that can commonly use in this area in the mode of mass polymerization or slurry polymerization in gas phase or liquid phase carry out.
According to olefine polymerizing process of the present invention, described olefinic polymerization condition can be the normal condition of this area.Usually, described olefinic polymerization condition comprises: temperature can be 50-110 ℃, and pressure can be 0.5-2MPa.According to olefine polymerizing process of the present invention, described olefinic polymerization condition can also be optimized according to concrete polymerization process.For example, when olefine polymerizing process according to the present invention carried out in slurry, described olefinic polymerization condition comprised: temperature can be 50-100 ℃, is preferably 60-90 ℃; Pressure can be 0.5-2MPa; When olefine polymerizing process according to the present invention carried out in gas phase, described olefinic polymerization condition comprised: temperature can be 70-110 ℃, is preferably 85-105 ℃; Pressure can be 1-2MPa.
According to olefine polymerizing process of the present invention, described one or more alkene carry out in the presence of hydrogen with contacting preferably of catalyst system provided by the invention, hydrogen can play the effect of molecular weight regulator like this, and the polyolefinic molecular weight of preparation is regulated.The method according to this invention is not particularly limited for the consumption of described hydrogen, can carry out appropriate selection according to the polyolefinic molecular weight (that is, melting index) of expection, and this paper repeats no more.
Describe the present invention in detail below in conjunction with embodiment.
In following examples, the method for employing chemistry titration is determined the composition of magnesium halide carrier and olefin polymerization catalysis.
In following examples, adopt the method for stipulating among the ASTM-D1895 to measure the polyolefinic bulk density of preparation.
In following examples, melting index is measured according to defined terms E among the ASTM-D1238, and wherein, temperature is 190 ℃, and load is 2.16kg.
Embodiment 1-10 is used for explanation according to magnesium halide carrier of the present invention and application and olefin polymerization catalysis, olefin polymerization catalyst system and olefine polymerizing process.
Embodiment 1
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 6g clay (is purchased from Zhejiang Feng Hong clay chemical industry company limited, average particulate diameter is 40 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL n-propylcarbinyl chloride is added dropwise in the reaction flask, time for adding is 2 hours, after dropwising, continues reaction 2 hours under 60 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.055g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 45 % by weight, and the content of clay is 55 % by weight, and the average particulate diameter of this magnesium halide carrier is 55 microns.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then slowly is added dropwise to 150mL in the suspension and contains 12g TiCl
4Hexane solution, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.99: 1.
(3) polymerization of ethene
Carry out slurry polymerization in the reactor of 2L, concrete operations are:
Olefin polymerization catalysis and triethyl aluminum with normal hexane, step (2) preparation adds in the aforesaid reaction vessel respectively, wherein, the amount of normal hexane is 1000mL, and the addition of triethyl aluminum and olefin polymerization catalysis is so that Al: Ti=100 (mol ratio).The temperature of reactor is increased to 70 ℃, then passes into hydrogen, then continue to pass into ethene, the total pressure of keeping in the reactor is 1.0MPa.The temperature of reactor is continued to be increased to 80 ℃, and under this temperature, keep reaction 2 hours.After polymerization is finished, stop to pass into ethene, reactor is cooled off and carry out exhaust.Reclaim the polyblend slurries, isolate polyethylene powders.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 2
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 6g polynite (is purchased from Zhejiang Feng Hong clay chemical industry company limited, average particulate diameter is 25 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL n-propylcarbinyl chloride is added drop-wise in the reaction flask, time for adding is 2 hours, after dropwising, continues reaction 3 hours under 60 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.052g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 53 % by weight, and the content of clay is 47 % by weight, and the average particulate diameter of this magnesium halide carrier is 35 microns.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then slowly drips 200mL in the suspension and contain 24g TiCl
4With the hexane solution of 4g isooctyl alcohol, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.50: 1, and the mol ratio of magnesium and isooctyl alcohol is 1: 0.5.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 2 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 3
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 6g kaolin (is purchased from Zhejiang Feng Hong clay chemical industry company limited, average particulate diameter is 30 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL n-propylcarbinyl chloride is added drop-wise in the reaction flask, time for adding is 4 hours, after dropwising, continues reaction 4 hours under 60 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.053g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 47 % by weight, and the content of clay is 53 % by weight, and the average particulate diameter of this magnesium halide carrier is 40 microns.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then slowly drips 300mL in the suspension and contain 48g TiCl
4With the hexane solution of 1.5g ethyl benzoate, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.25: 1, and the mol ratio of magnesium and ethyl benzoate is 1: 1.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 3 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 4
(1) preparation of magnesium halide carrier
Adopt the method identical with embodiment 2 to prepare magnesium halide carrier.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then slowly drips 200mL in the suspension and contain 24g TiCl
4With the hexane solution of 3g tetrahydrofuran (THF), dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.50: 1, and the mol ratio of magnesium and tetrahydrofuran (THF) is 1: 1.8.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 4 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 5
(1) preparation of magnesium halide carrier
Adopt the method identical with embodiment 2 to prepare magnesium halide carrier.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then in suspension, slowly drips the hexane solution that 150mL contains the 43g tetrabutyl titanate, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.5: 1.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 5 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 6
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 4g carclazyte (is purchased from Yushan County, Jiangxi Province wilkinite Industrial Co., Ltd., average particulate diameter is 20 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL n-propylcarbinyl chloride is added drop-wise in the reaction flask, time for adding is 2 hours, after dropwising, continues reaction 2 hours under 80 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.054g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 57 % by weight, and the content of clay is 43 % by weight, and the average particulate diameter of this magnesium halide carrier is 35 microns.
(2) preparation of olefin polymerization catalysis
Adopt the method identical with embodiment 2 to prepare olefin polymerization catalysis, different is the magnesium halide carrier that adopts embodiment 6 steps (1) to prepare.In this catalyzer, the mol ratio of magnesium and titanium is 0.49: 1, and the mol ratio of magnesium and isooctyl alcohol is 1: 0.5.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 6 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 7
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 8g wilkinite (is purchased from Yushan County, Jiangxi Province wilkinite Industrial Co., Ltd., average particulate diameter is 25 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL n-propylcarbinyl chloride is added drop-wise in the reaction flask, time for adding is 2 hours, after dropwising, continues reaction 3 hours under 60 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.058g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 43 % by weight, and the content of clay is 57 % by weight, and the average particulate diameter of this magnesium halide carrier is 42 microns.
(2) preparation of olefin polymerization catalysis
Adopt the method identical with embodiment 2 to prepare olefin polymerization catalysis, different is the magnesium halide carrier that adopts embodiment 7 steps (1) to prepare.In this catalyzer, the mol ratio of magnesium and titanium is 0.49: 1, and the mol ratio of magnesium and ethyl benzoate is 1: 0.5.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 7 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 8
(1) preparation of magnesium halide carrier
Adopt the method identical with embodiment 2 to prepare magnesium halide carrier.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then in suspension, slowly is added dropwise to the hexane solution that 150mL contains the 36g isopropyl titanate, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.50: 1.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that the step (2) of embodiment 8 prepares as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 9
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 6g diatomite (is purchased from Zhejiang Feng Hong clay chemical industry company limited, average particulate diameter is 15 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL n-propylcarbinyl chloride is added drop-wise in the reaction flask, time for adding is 2 hours, after dropwising, continues reaction 3 hours under 60 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.053g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 48 % by weight, and the content of clay is 52 % by weight, and the average particulate diameter of this magnesium halide carrier is 32 microns.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then slowly drips 20mL in the suspension and contain 24g TiCl
4With the hexane solution of 4g isooctyl alcohol, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.5: 1, and the mol ratio of magnesium and isooctyl alcohol is 1: 0.5.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 9 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Embodiment 10
(1) preparation of magnesium halide carrier
In the five mouthfuls of reaction flasks of 500mL that are equipped with agitator, condenser, dropping funnel and heating unit, adding 150mL normal hexane, 1.5g magnesium powder and 6g aluminum oxide (is purchased from Zhejiang Feng Hong clay chemical industry company limited, average particulate diameter is 38 microns, before using under 200 ℃ temperature dry 4 hours), under 60 ℃ temperature, the 14mL tert-butyl chloride is added drop-wise in the reaction flask, time for adding is 2 hours, after dropwising, continues reaction 3 hours under 60 ℃ temperature.After reaction is finished, reaction mixture is down to room temperature, after the filtration, with normal hexane washing 3 times, obtains the suspension (wherein, the concentration of magnesium halide carrier is 0.051g/mL) that 100mL contains with good grounds magnesium halide carrier of the present invention.Take the total amount of this magnesium halide carrier as benchmark, the content of magnesium halide is 55 % by weight, and the content of clay is 45 % by weight, and the average particulate diameter of this magnesium halide carrier is 45 microns.
(2) preparation of olefin polymerization catalysis
The magnesium halide carrier suspension of step (1) preparation is warmed up to 50 ℃ and stir under this temperature, then slowly drips 200mL in the suspension and contain 24g TiCl
4With the hexane solution of 4g isooctyl alcohol, dropwise rear continuation and keep reaction 3 hours.After reaction is finished, reaction mixture is cooled to room temperature, after the filtration, with normal hexane washing 3 times, solvent evaporated obtains according to olefin polymerization catalysis of the present invention.In this catalyzer, the mol ratio of magnesium and titanium is 0.5: 1, and the mol ratio of magnesium and isooctyl alcohol is 1: 0.5.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that embodiment 10 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Comparative Examples 1
(1) preparation of magnesium halide carrier
Adopt the method identical with embodiment 1 to prepare magnesium halide carrier, different is not use clay.
(2) preparation of olefin polymerization catalysis
Adopt the method identical with embodiment 1 to prepare olefin polymerization catalysis, different is the magnesium halide carrier that uses Comparative Examples 1 step (1) to prepare.In this catalyzer, the mol ratio of magnesium and titanium is 1.0: 1.
(3) polymerization of ethene
Adopt the method identical with embodiment 1 to carry out the polymerization of ethene, different is, uses catalyzer that Comparative Examples 1 step (2) prepares as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Comparative Examples 2
(1) preparation of magnesium halide carrier
Adopt the method identical with embodiment 3 to prepare magnesium halide carrier, different is not use kaolin.
(2) preparation of olefin polymerization catalysis
Adopt the method identical with embodiment 3 to prepare olefin polymerization catalysis, different is the magnesium halide carrier that uses Comparative Examples 1 step (1) to prepare.In this catalyzer, the mol ratio of magnesium and titanium is 1.0: 1.
(3) polymerization of ethene
Adopt the method identical with embodiment 3 to carry out the polymerization of ethene, different is, uses catalyzer that Comparative Examples 2 steps (2) prepare as Primary Catalysts.In the polymerization process, the amount of ethene and hydrogen and the result of polyreaction are shown in the table 1.
Table 1
Embodiment 1 is compared and can find out with Comparative Examples 1, under the identical condition of the content of the titanium compound in olefin polymerization catalysis, employing has higher bulk density according to the olefin polymer of olefin polymerization catalyst system preparation of the present invention, and olefin polymerization catalyst system according to the present invention has higher catalytic efficiency.
Embodiment 3 is compared and can find out with Comparative Examples 2, under the identical condition of all the other conditions, can the more substantial titanium compound of load according to magnesium halide carrier of the present invention.
Claims (21)
1. magnesium halide carrier, this magnesium halide carrier contains magnesium halide and crystal seed, and described crystal seed is to be selected from polynite, clay, kaolin, diatomite, wilkinite, carclazyte and the aluminum oxide one or more.
2. magnesium halide carrier according to claim 1, wherein, take the total amount of this magnesium halide carrier as benchmark, the content of described magnesium halide is the 30-90 % by weight, the content of described crystal seed is the 10-70 % by weight.
3. magnesium halide carrier according to claim 1 and 2, wherein, the average particulate diameter of this magnesium halide carrier is the 6-100 micron.
4. magnesium halide carrier according to claim 1, wherein, the preparation method of this magnesium halide carrier is included under the existence of crystal seed, MAGNESIUM METAL is contacted with the halogenated alkane shown in the formula I, forming magnesium halide,
R
1X
1(formula I),
Among the formula I, R
1Be C
3-C
12The straight or branched alkyl, X
1Be halogen.
5. magnesium halide carrier according to claim 4, wherein, the weight ratio of described crystal seed and described MAGNESIUM METAL is 0.2-5: 1.
6. according to claim 1, the described magnesium halide carrier of any one in 2,4 and 5, wherein, the average particulate diameter of described crystal seed is the 5-50 micron.
7. magnesium halide carrier according to claim 4, wherein, the mol ratio of described MAGNESIUM METAL and described halogenated alkane is 1: 1-3.
8. magnesium halide carrier according to claim 4, wherein, described contact is carried out in the presence of solvent.
9. magnesium halide carrier according to claim 8, wherein, described solvent is C
5-C
10Replacement or unsubstituted aliphatic hydrocarbon and C
6-C
12Replacement or in the unsubstituted aromatic hydrocarbons one or more.
10. magnesium halide carrier according to claim 4, wherein, the temperature of described contact is 10-100 ℃, the time of described contact is 0.5-10 hour.
11. the application of the described magnesium halide carrier of any one in the preparation olefin polymerization catalysis among the claim 1-10.
12. an olefin polymerization catalysis, this catalyzer contain magnesium halide carrier and load on titanium compound on the described magnesium halide carrier, it is characterized in that described magnesium halide carrier is the described magnesium halide carrier of any one among the claim 1-10.
13. catalyzer according to claim 12, wherein, the mol ratio of the titanium in the magnesium in the described magnesium halide carrier and the described titanium compound is 1: 0.2-5.
14. according to claim 12 or 13 described catalyzer, wherein, this catalyzer also contains the electron donor compound that loads on the described magnesium halide carrier.
15. catalyzer according to claim 14, wherein, the weight ratio of the magnesium in the described magnesium halide carrier and described electron donor compound is 1: 1-15.
16. an olefin polymerization catalyst system, this olefin polymerization catalyst system contains Primary Catalysts and promotor, and described promotor is organo-aluminium compound, it is characterized in that, described Primary Catalysts is the described catalyzer of any one among the claim 12-15.
17. catalyst system according to claim 16, wherein, the mol ratio of the titanium in the aluminium in the described promotor and the described Primary Catalysts is 30-300: 1.
18. an olefine polymerizing process, the method are included under the olefinic polymerization condition, and one or more alkene are contacted with claim 16 or 17 described catalyst systems.
19. method according to claim 18, wherein, described alkene is ethene or ethene and C
3-C
8The aliphatics alpha-olefin.
20. method according to claim 18, wherein, described olefinic polymerization condition comprises: temperature is 50-110 ℃, and pressure is 0.5-2MPa.
21. method according to claim 18, wherein, described contact is carried out in the presence of hydrogen.
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