CN104418960A - Catalyst component applied to ethylene polymerization, preparation method of catalyst component and catalyst - Google Patents
Catalyst component applied to ethylene polymerization, preparation method of catalyst component and catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst component applied to ethylene polymerization. The catalyst component comprises a reaction product which is prepared from the following components: (1) a magnesium compound; (2) an oxygenous titanium compound; (3) a halohydrocarbon compound; and (4) a halogenating reagent. The catalyst component is uniform in particle size distribution; when the catalyst component is applied to the ethylene polymerization, a prepared polymer is low in content of fine powder; the catalyst component is relatively high in polymerization activity and high in hydrogen responsiveness; and the catalyst is simple in preparation process and few in side products, and is environmentally friendly.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polyreaction and catalyzer, more particularly, relate to a kind of Ziegler-Natta catalyst component for ethylene polymerization and preparation method thereof and catalyzer.
Background technology
In the Ziegler-Natta catalyst development process matched with ethene polymerization process, the research work of Mg-Ti system Ziegler-Natta catalyst composition is quite deep, the polymerization catalyst activity that one side person skilled in art is devoted to obtain is enough high, and catalyzer residual trying one's best in the polymer is lacked; Expect that the even particle distribution of resulting polymers, fine powder content are few on the other hand.
US Patent No. 3901863, US4617360, US4109071 disclose a kind of preparation method of Z-N catalyzer, first liquid solution is prepared by containing oxygen organo-magnesium compound with containing oxygen titanium compound, then this solution and chloride organo-aluminium compound contact reacts are formed and precipitate, method for preparing catalyst is simple, activity compared with high, by product is few, be applicable to ethene slurry polymerization processes produce polyethylene product.But the broad particle distribution of the method gained catalyzer, is generally multimodal distribution.
US Patent No. 4363746 discloses a kind of specific activity catalyzer that many polymerizing catalysts are much higher in the past, by the metal halide of magnesium as magnesium dihalide and four titan-alkoxides react, then this solution and a kind of organo-metallic reductive agent react, obtain a kind of solids, and then this solids and a kind of halide ion exchanging source, as titanium tetrachloride reaction, although catalyzer activity prepared by this method is higher, this catalyzer in the application fine powder content is more.
The object of the invention is the catalyzer prepared a kind of even particle size distribution, be applicable to ethene slurry polymerization, reduce the fine powder content in polymkeric substance, the present inventor is by repeatedly testing discovery, by preparation method of the present invention, prepared catalyzer not only polymerization activity improves, and hydrogen responsiveness is good simultaneously, narrow particle size distribution, resulting polymers size distribution is concentrated, and fine powder content is few, and catalyst preparation process is simple.
Summary of the invention
The invention provides a kind of catalyst component for ethylene polymerization and catalyzer, and the preparation method of this catalyst component, this catalyzer has the advantages such as higher polymerization activity, well hydrogen responsiveness, narrower size-grade distribution and fine polymer powder content are few.
Concrete technical scheme is as follows:
An object of the present invention is to provide a kind of catalyst component for ethylene polymerization, and this catalyst component comprises the reaction product of following component:
(1) magnesium compound;
(2) oxygen containing titanium compound;
(3) halogenated hydrocarbon compound;
(4) halide reagent;
Magnesium compound described in component (1) is by leading to formula I Mg(OR
1)
mcl
2-mshown in, wherein R
1c
2~ C
20alkyl, for saturated or undersaturated straight chain, side chain or closed chain, m is the integer of 0≤m≤2, and magnesium compound is selected from least one in alkoxyl magnesium and magnesium dichloride, and alkoxyl magnesium is selected from least one in diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium.
In component (2), oxygen containing titanium compound is by leading to formula II Ti (OR
2)
ncl
4-nshown in, R in formula
2c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, n be the integer of 0 < n≤4; Preferred use tetravalent titanium compound, because they are in a liquid state usually at normal temperatures, and also also fine with the consistency of some solvents under normal conditions.In logical formula II, preferred R
2for C
2~ C
10alkyl, n=4, wherein preferred tetrabutyl titanate.
Component (3) halogenated hydrocarbon compound can be selected from a halohydrocarbon, dihalo hydrocarbon or polyhalohydrocarbon, optional self-saturation halohydrocarbon, unsaturated or aromatic halohydrocarbon, can be selected from uncle halohydrocarbon, secondary halohydrocarbon and tertiary halohydrocarbon, chlorinated hydrocarbon compounds preferably in liquid state, specifically 1-chlorobutane can be selected from, Sec-Butyl Chloride, 1,4-dichlorobutane, 2-chloro-2-methyl propane, tetracol phenixin, 1,2-ethylene dichloride, 1,2-propylene dichloride, 2,2-propylene dichloride, chlorinated benzene, chloroform, trichlorotoluene zotrichloride, chlorotoluene, at least one in chlorocyclohexane.
Component (4) halide reagent, as logical formula III R
3 amX
bshown in, in formula, M is three, four, five main group element or transition metals, and X is halogen, R
3containing C
2~ C
20the alkyl of carbon atom, a=0,1 or 2, b=1,2,3 or 4; Halide reagent is selected from dichloro one aluminium triethyl, aluminium diethyl monochloride, ethylaluminum sesquichloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, two chloro isopropyl aluminium, a chlorine di-isopropyl aluminium, silicon tetrachloride, titanium tetrachloride, preferred dichloro one aluminium triethyl, ethylaluminum sesquichloride, dichloro aluminium isobutyl, two chloro isopropyl aluminium, silicon tetrachloride, titanium tetrachloride.
In the process of Kaolinite Preparation of Catalyst component, the feed molar ratio of various reactant, in every mole of magnesium in component (1), component (2) is 0.1 ~ 20 mole, component (3) is 0.1 ~ 20 mole, and component (4) is 0.5 ~ 50 mole, and preferred ingredient (2) is 0.5 ~ 10 mole, component (3) is 0.1 ~ 12 mole, and component (4) is 1.0 ~ 10 moles.
Second object of the present invention is to provide a kind of preparation method of the catalyst component for ethylene polymerization, and this preparation method comprises the steps:
(1) logical formula I magnesium compound and logical formula II are reacted formation magnesium titanium compound clear solution at a certain temperature containing oxygen titanium compound;
(2) step (1) is obtained product and general formula halogenated hydrocarbon compound reacts to obtain clear solution at-20 ~ 100 DEG C;
(3) solution step (2) obtained and logical formula III compound at a certain temperature contact reacts are formed and precipitate, and obtain the suspension of catalyst component;
(4) suspension that step (3) obtains is reacted certain hour at a certain temperature, then quiet heavy, washing, dry catalyst fines.Or suspension step (3) obtained is quiet heavy, removes a part of supernatant liquor, then adds a certain amount of thinner, then react certain hour at a certain temperature, quiet heavy, washing, drying obtain catalyst component.
In the step (1) of Kaolinite Preparation of Catalyst component, carry out under logical formula I magnesium compound and logical formula II are typically chosen in comparatively high temps containing the temperature that oxygen titanium compound contacts with each other, higher temperature is beneficial to and forms magnesium titanium compound clear solution, preferably below the decomposition temperature of reactant, general not higher than 200 DEG C, preferably less than 150 DEG C are carried out.Reaction carry out under agitation, the time of reaction depends on character and the operational condition of reactant, and reaction times requirement is enough to obtain transparent solution, required time generally at 1 to 20 hour, preferably 4 to 10 hours.Appropriate inert diluent can be added as required, inert diluent can not with by the component generation chemical reaction dissolved, inert diluent can select hydro carbons as normal hexane, hexanaphthene, pentane, heptane, Trimethylmethane, iso-pentane, octane-iso, toluene etc. and composition thereof, contributes to the dispersion of magnesium compound solution and reduces the viscosity of solution.
In the step (2) of Kaolinite Preparation of Catalyst component, the product obtain step (1) and halogenated hydrocarbon compound hybrid reaction obtain magnesium titanium complex clear solution; Mixing temperature will lower than the decomposition temperature of magnesium compound and halogenated hydrocarbon compound, general select-20 ~ 100 DEG C between, preferably between-20 ~ 60 DEG C.Mixing time generally selects 30 minutes to 6 hours.
The step (3) of Kaolinite Preparation of Catalyst component also can be described as settling step, complete chlorination reaction or the chlorination reduction reaction of magnesium titanium complex in this step, namely chlorine element replaces the alkoxyl group in magnesium titanium complex, the valence state of titanium compound also can be reverted to comparatively lower valency by different halide reagents simultaneously, thus makes catalyst active center's group Precipitation from solution.The contact method of magnesium titanium complex clear solution and halide reagent can adopt any known suitable method to carry out, the mode be progressively added drop-wise to by magnesium titanium complex solution in halide reagent solution can be adopted, also can adopt the mode be progressively added drop-wise to by halide reagent solution in magnesium titanium complex solution.The local superheating that rate of addition is selected not induce reaction usually is as the criterion, and usually carries out stirring being beneficial to steadily carrying out of reaction in dropping process.In this precipitin reaction step, temperature can control between-20 ~ 100 DEG C, preferably between-20 ~ 80 DEG C.The reaction times of settling step should be long enough to obtain to be precipitated completely, and the reaction times can last 1 minute to 10 hours, preferably 0.5 ~ 5 hour.
Experiment finds, after settling step, the a part of supernatant liquor of the quiet heavy rear extrusion of preferred suspension, then reacting for some time at a certain temperature, to carry out the particle shape of maturation process to catalyzer more favourable, it can make the size distribution narrow of catalyzer, also can improve the intensity of catalyst particle simultaneously, thus reduce the particle fragmentation phenomenon of catalyzer in catalyzed ethylene polymerization process.The temperature of maturation process is generally equal to or higher than the temperature of precipitin reaction, and curing temperature can control between 40 ~ 100 DEG C, preferably between 40 ~ 85 DEG C.The time of slaking reaction can control at 0.5 ~ 15 hour, preferably 1 ~ 5 hour.
After carrying out maturation process, generally to wash, to remove the by product formed in excessive reactant and preparation process, any inert solvent all can be used for this washing step, such as can select Trimethylmethane, pentane, normal hexane, heptane or hexanaphthene and composition thereof etc., in experiment, usually select normal hexane to be the inert solvent washed.After washing, catalyst suspension can by carrying out drying with nitrogen purging under heating state, to obtain the powder of catalyst component.
3rd object of the present invention is to provide a kind of catalyzer for ethylene polymerization, and it comprises the reaction product of following component:
The a catalyst component for ethylene polymerization that () is above-mentioned;
B () a kind of general formula is AlR
nx
3-norgano-aluminium compound, in formula, R is identical or not identical C
1-8alkyl, X is halogen, and n is the integer of 1 < n≤3.
Component (b) can select one or more aluminum alkyls used in combination, preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3, AlEt
2at least one in Cl.
The catalyzer that the present invention relates to is applicable to all polymerizations of various ethene or the copolymerization of ethene and other α-alkene, and wherein alpha-olefin adopts the one in propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methylpentene-1.This catalyzer is applicable to vapor phase process, slurry polymerization technique.
Catalyst component of the present invention and catalyzer thereof have following beneficial effect:
1. this catalyst component even particle size distribution, the fine polymer powder content for ethylene polymerization gained is few;
2. this catalyst component has higher polymerization activity, and hydrogen responsiveness is good simultaneously;
3. catalyst preparation process is simple, by product is few, environmentally friendly.
Embodiment
With embodiment, the present invention is described below, but not limits the scope of the invention.
Testing method:
Catalyst grain size distributes: measure on the MASTERSIZE2000 particles distribution instrument of Malvern company of Britain
Melt index: measure according to ASTM D1238 standard method
Embodiment 1
(1) take magnesium dichloride 14.9g, add 120ml tetrabutyl titanate, be warming up to 140 DEG C of stirring reactions until form clear solution, treat that solution temperature is cooled to close to room temperature, add toluene 100ml, be uniformly mixed, the solution obtained takes out for subsequent use.
(2) get the solution that 10 milliliter of (1) step obtains, add 30 milliliters of hexane dilutions, add 3.0ml1,4-dichlorobutane, stirring at room temperature reaction is spent the night.
(3) in second step reaction product, slowly drip the Dichloroethyl aluminum solutions of 12.5 milliliters of 3.0M under normal temperature with constant pressure addition pipe, after being added dropwise to complete, rise bath temperature to 45 DEG C of reactions 1 hour, then 60 DEG C of stirring reactions obtain catalyst component suspension in 4 hours.
(4) catalyst component suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 80 milliliters, after wash, when bathing temperature 65 DEG C, purging drying, obtain brown solid mobility powder with high pure nitrogen.
Evaluating catalyst: the catalyzer of 1L hexane, 1mmol triethyl aluminum and 10-20mg is joined in 2L stainless steel stirring tank, then temperature is brought up to 90 DEG C, the disposable hydrogen adding 0.4MPa, then with ethene, the total pressure of system is maintained 1.0MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, the test tap density of polyethylene powder and the melting index under 2.16Kg load, result is as shown in table 1.
Embodiment 2
By the 3.0ml1 in catalyst preparation step (2), 4-dichlorobutane changes 6.0 milliliters into, and other conditions are with embodiment 1.The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Embodiment 3
Change 3.0 milliliters of Isosorbide-5-Nitrae-dichlorobutane in catalyst preparation step (2) into 2.0 milliliters of 2-chloro-2-methyl propane, other conditions are with embodiment 1.The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Embodiment 4
Change the Dichloroethyl aluminum solutions of 12.5 milliliters of 3.0M in catalyst preparation step (3) into 10ml titanium tetrachloride, other conditions are with embodiment 1.The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Comparative example 1
(1) take 114 grams of diethoxy magnesium, add 340 milliliters of tetrabutyl titanates, 140 DEG C of stirring and dissolving until form clear solution, solution temperature is down to room temperature, adds 400 milliliters of dry hexane diluted for use.
(2) get the solution that 9 milliliter of (1) step obtains, slowly drip the hexane solution of 15 milliliters of 3M ethyl aluminum dichlorides with drop-burette, after being added dropwise to complete, the slaking in 4 hours of 60 DEG C of stirring reactions obtains catalyst suspension.
(3) catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 50 milliliters, after wash, when bathing temperature 65 DEG C, purging drying, obtain brown solid mobility powder with high pure nitrogen.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Comparative example 2
(1) take 114 grams of diethoxy magnesium, add 340 milliliters of tetrabutyl titanates, 140 DEG C of stirring and dissolving until form clear solution, solution temperature is down to room temperature, adds 400 milliliters of dry hexane diluted for use.
(2) get the solution that 9 milliliter of (1) step obtains, mix with 0.5 milliliter of ethyl benzoate and place and spend the night.Its temperature is maintained 35 DEG C, slowly drips the hexane solution of 15 milliliters of 3M ethyl aluminum dichlorides with drop-burette, after being added dropwise to complete, the slaking in 4 hours of 60 DEG C of stirring reactions obtains catalyst suspension.
(3) catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 50 milliliters, after wash, when bathing temperature 65 DEG C, purging drying, obtain brown solid mobility powder with high pure nitrogen.
The slurry polymerization appreciation condition of catalyzer is with embodiment 1, and polymerization result is in table 1.
Table 1 analytical results
As can be seen from the experimental data of table 1 embodiment and comparative example, catalyst activity of the present invention keeps higher level, and the melting index of the polymkeric substance obtained obviously increases, and illustrates that catalyzer hydrogen responsiveness is good.The narrower particle size distribution of gained catalyzer of the present invention, the tap density of resulting polymers improves.
Claims (14)
1., for a catalyst component for ethylene polymerization, comprise the reaction product of following component:
(1) magnesium compound
(2) oxygen containing titanium compound
(3) halogenated hydrocarbon compound
(4) halide reagent
Described magnesium compound is by leading to formula I Mg(0R
1)
mcl
2-mshown in, wherein R
1c
2~ C
20alkyl, be saturated or undersaturated straight chain, side chain or closed chain, m is the integer of 0≤m≤2;
Described oxygen containing titanium compound is by leading to formula II Ti (OR
2)
ncl
4-nshown in, R in formula
2c
2~ C
20saturated or undersaturated straight chain, side chain or closed chain alkyl, n is the integer of 0 < n≤4;
Described halogenated hydrocarbon compound is selected from least one in a halohydrocarbon, dihalo hydrocarbon, polyhalohydrocarbon, saturated halogenated hydrocarbon, unsaturated halohydrocarbon, aromatic halohydrocarbon, uncle halohydrocarbon, secondary halohydrocarbon and tertiary halohydrocarbon; Described halide reagent is by leading to formula III R
3 amX
bshown in, in formula, M is three, four, five main group element or transition metals, and X is halogen, R
3containing C
2~ C
20alkyl, a=0,1 or 2, b=1,2,3 or 4.
2. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that described halogenated hydrocarbon compound is the chlorinated hydrocarbon compounds in liquid state.
3. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that this catalyst component is prepared from by following steps: (1) will lead to formula I magnesium compound and logical formula II forms magnesium titanium compound clear solution containing the reaction of oxygen titanium compound; (2) step (1) is obtained product and halogenated hydrocarbon compound reacts to obtain clear solution at-20 ~ 100 DEG C; (3) solution step (2) obtained and logical formula III compound contact reacts are formed and precipitate, and obtain the suspension of catalyst component; (4) suspension that step (3) obtains is reacted certain hour at a certain temperature, quiet heavy, washing, dry catalyst fines, or suspension step (3) obtained is quiet heavy, remove a part of supernatant liquor, add thinner again, react certain hour at a certain temperature, quiet heavy, washing, drying obtain catalyst component.
4. according to a kind of catalyst component for ethylene polymerization one of claim 1-3 Suo Shu, it is characterized in that the material ratio of various component is in every mole of magnesium in component (1), component (2) is 0.1 ~ 20 mole, component (3) is 0.1 ~ 20 mole, and component (4) is 0.5 ~ 50 mole.
5. a kind of catalyst component for ethylene polymerization according to claim 4, it is characterized in that the material ratio of various component is in every mole of magnesium in component (1), component (2) is 0.5 ~ 10 mole, and component (3) is 0.1 ~ 12 mole, and component (4) is 1.0 ~ 10 moles.
6. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that halogenated hydrocarbon compound is selected from 1-chlorobutane, Sec-Butyl Chloride, Isosorbide-5-Nitrae-dichlorobutane, 2-chloro-2-methyl propane, tetracol phenixin, 1,2-ethylene dichloride, 1,2-propylene dichloride, 2,2-propylene dichloride, chlorinated benzene, chloroform, trichlorotoluene zotrichloride, chlorotoluene, at least one in chlorocyclohexane, preferred Isosorbide-5-Nitrae-dichlorobutane, 2-chloro-2-methyl propane, 1,2-ethylene dichloride, 1,2-propylene dichloride, 2,2-propylene dichloride, chlorocyclohexane.
7. a kind of catalyst component for ethylene polymerization according to claim 1, it is characterized in that halide reagent is selected from dichloro one aluminium triethyl, aluminium diethyl monochloride, ethylaluminum sesquichloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, two chloro isopropyl aluminium, a chlorine di-isopropyl aluminium, silicon tetrachloride, titanium tetrachloride, preferred dichloro one aluminium triethyl, ethylaluminum sesquichloride, dichloro aluminium isobutyl, two chloro isopropyl aluminium, silicon tetrachloride, titanium tetrachloride.
8. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that R in the general formula containing oxygen titanium compound
2for C
2~ C
10alkyl, n=4, preferred tetrabutyl titanate.
9. a kind of catalyst component for ethylene polymerization according to claim 1, is characterized in that magnesium compound is selected from least one in alkoxyl magnesium and magnesium dichloride.
10. a kind of catalyst component for ethylene polymerization according to claim 9, is characterized in that alkoxyl magnesium is selected from least one in diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and two octyloxy magnesium.
The preparation method of the catalyst component for ethylene polymerization that one of 11. claim 1-10 are described, comprises the following steps: (1) will lead to formula I magnesium compound and logical formula II forms magnesium titanium compound clear solution containing the reaction of oxygen titanium compound; (2) step (1) is obtained product and halogenated hydrocarbon compound reacts to obtain clear solution at-20 ~ 100 DEG C; (3) solution step (2) obtained and logical formula III compound contact reacts are formed and precipitate, and obtain the suspension of catalyst component; (4) suspension that step (3) obtains is reacted certain hour at a certain temperature, quiet heavy, washing, dry catalyst fines, or suspension step (3) obtained is quiet heavy, remove a part of supernatant liquor, add thinner again, react certain hour at a certain temperature, quiet heavy, washing, drying obtain catalyst component.
The preparation method of 12. catalyst components for ethylene polymerization according to claim 11, it is characterized in that the temperature of reaction of step (1) is less than 200 DEG C, reaction times is 1 to 20 hour, the reaction times of step (2) is 30 minutes to 6 hours, the temperature of reaction of step (3) is-20 ~ 100 DEG C, reaction times is 1 minute to 10 hours, and the temperature of reaction of step (4) is 40 ~ 100 DEG C, and the reaction times is being 0.5 ~ 15 hour.
13. 1 kinds of catalyzer for ethylene polymerization, comprise the catalyst component for ethylene polymerization that one of component (a) claim 1-10 is described; A kind of general formula of component (b) is AlR
nx
3-norgano-aluminium compound, in formula, R is identical or not identical C
1-8alkyl, X is halogen, and n is the integer of 1 < n≤3.
14. application of catalyzer according to claim 13 in ethylene polymerization.
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| CN109422827A (en) * | 2017-08-22 | 2019-03-05 | 中国石油天然气股份有限公司 | Main catalyst component for solution-process ethylene polymerization, preparation method thereof and catalyst system |
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