CN104277146B - Catalyst component, its preparation method and application for olefinic polymerization - Google Patents
Catalyst component, its preparation method and application for olefinic polymerization Download PDFInfo
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Abstract
The present invention provides a kind of catalytic component for olefinic polymerization, and it is to include at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, at least one chloride organoboron compound and the product of at least one modifiers dispersants；Described chloride organoboron compound is such as formula (IV) BR4 pCl3‑pShown compound, R in formula (IV)4It is C2～C20Alkyl or alkoxyl, 0≤p 3；And described modifiers dispersants is polyisoprene blocks polyoxyethylene groups ether polymer.Used catalyst component of the present invention, not only its catalysis activity good, catalyst hydrogen response is good and resulting polymers bulk density height, and corresponding catalyst more preferably, thus can be more beneficial for catalyst use on the polymerization technique device such as gas phase, slurry to the particle shape of olefinic polymerization product and the control of granular size.
Description
Technical field
The present invention relates to a kind of for olefinic polymerization or the catalytic component of combined polymerization and catalyst, and this catalytic component
Preparation method and purposes.
Background technology
Over nearly more than 20 years, with the development of olefin polymetiation process, the catalyst matched with polymerization technique has also been got considerable
Progress, wherein effective catalyst by its excellent polymerization and ripe application technology in polyolefin catalyst field
Still occupy an important position.Through exploratory development for many years, the preparation method of Mg-Ti system effective catalyst at present more to be used
Chemical reaction method.
In chemical reaction method, many patents of invention relate to using organic metal magnesium compound, chlorinating agent and transition metal titanizing
The chemical raw materials such as compound, have prepared the catalyst of number of different types with this kind of reactant, and they are disclosed in Chinese patent
CN1158136, CN1299375, CN1795213 and United States Patent (USP) US3787384, US4148754, US4173547,
In US4508843 and 5124296.In such Mg-Ti catalyst, having a fatal shortcoming is to be difficult to control
Forming step processed, thus it is difficult to control to the form of prepared catalyst particle, recent development is to comprise magnesium at catalyst precarsor
In the wind prose style free from parallelism system of/titanium compound, adding the material of some similar emulsifying agents, be allowed to form emulsion, reaction precipitation goes out the most again
Catalyst granules, can improve the particle shape of gained catalyst, such as use in the EP-A-258089 of Montedison
PFPE, mentions employing PFO in Chinese patent CN1537118A, and these method forming step are complicated, is difficult to
Controlling, gained catalyst granules form is not easy to control, and the material price used is high, is difficult to obtain.
Although having done substantial amounts of research work in Ziegler-Natta catalyst field, preparation higher performance is required
ZN catalyst, it is still necessary to some methods that are new or that improve.
The present inventor, by repeatedly testing discovery, selects suitable modifiers dispersants, process for synthetic catalyst just can be made the easiest
OK, and it is obtained in that form is preferable, such as the catalyst granules of size distribution spherical, narrow, there is higher catalysis simultaneously and live
Property and hydrogen response.
Summary of the invention
Applicant of the present invention formerly provides (WO2012/022127) a kind of catalytic component for olefinic polymerization, its bag
Include at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, at least one contains
Chlorine organoboron compound and the product of at least one polybutadiene block PEO analog copolymer.Use this catalyst
Component and corresponding catalyst catalysis in olefine polymerization, can obtain the active and preferable hydrogen response of higher catalysis.Although this is urged
Agent component can bring preferable catalytic effect for olefinic polymerization, but inventor is also from cost of material and catalytic effect isogonism
Degree attempts to seek other different dispersing aiies, such as on the basis of existing polybutadiene block PEO analog copolymer
Consider to redesign its molecular structure, specifically, form new copolymer, change as being further added by one or more comonomers
Copolymer chain or branch lengths or Similarity Between Line Segments, partly or entirely replace the polybutadiene portion in copolymer with other comonomer
Dividing and/or polyethylene oxide portion, use halogen, alkyl or other hetero atom replace the hydrogen atom on main chain or side chain etc. side
Formula, makes this at least up to can gather with polybutadiene block when participating in olefinic polymerization catalysis as the new copolymer of dispersing aid
The catalytic effect that ethylene oxide copolymer is similar.
But, the present inventor in experimentation it was unexpectedly observed that use polyisoprene blocks polyoxyethylene ether birds of the same feather flock together
When compound substitutes former polybutadiene block PEO analog copolymer, not only catalysis activity and the hydrogen of corresponding catalyst is adjusted
Sensitiveness is without being decreased obviously；And the particle of corresponding catalyst component is more uniform, size distribution substantially narrows, it is to alkene
The particle size of polymerization product and the control of form can be more preferably.
Therefore, the present invention provides a kind of catalytic component for olefinic polymerization, its be include at least one organo-magnesium compound,
At least one titanium-containing compound, at least one hydroxyl compounds, at least one chloride organoboron compound and at least one
The product of modifiers dispersants；Described chloride organoboron compound is such as formula (IV) BR4 pCl3-pShown compound is logical
R in formula (IV)4It is C2～C20Alkyl or alkoxyl, 0≤p 3；And described modifiers dispersants is polyisoprene blocks
Polyoxyethylene groups ether polymer.
Catalytic component prepared by the present invention has good hydrogen regulation performance, the most also has good particle shape and distribution,
Thus it is more beneficial for its use on the polymerization technique device such as gas phase, slurry.
Described organo-magnesium compound such as formula (I) MgR1 nCl2-nShown in, R in formula1It is C2～C20Alkyl, permissible
It is saturated or undersaturated straight chain, side chain or closed chain, 0 ＜ n≤2.Concrete compound is as selected from dibutylmagnesium, two isobutyls
Base magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride etc..
Wherein said titanium-containing compound such as formula (II) Ti (OR2)mCl4-mShown in, R in formula2It is C2～C20Alkyl,
Can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4；M=4 or m=0 preferably wherein, because titanic
Compound is in a liquid state the most at normal temperatures, and the most fine with the compatibility of some solvents；Particular compound is selected from four chlorinations
At least one in titanium, tetraethyl titanate and butyl titanate, preferably titanium tetrachloride.
Wherein said hydroxyl compounds such as formula (III) HOR3Shown in, R in formula3It is C2～C20Alkyl, can
To be saturated or undersaturated straight chain, side chain or closed chain；Hydroxyl compounds is preferably fatty alcohol or aromatic alcohol, more excellent
Select at least one in n-butanol, n-hexyl alcohol, isooctanol, phenmethylol and benzyl carbinol.
In the present invention, concrete described chloride organoboron compound is selected from dichloromethyl boron, Dichloroethyl boron, two chlorobutyls
At least one in boron, dichloromethane epoxide boron, two chloroethoxy boron, boron chloride, dichloro butoxy boron.
Described modifiers dispersants polyisoprene blocks polyoxyethylene ether (PI-b-POE) base polymer includes diblock and three
Block (PI-b-POE-b-PI, POE-b-PI-b-POE) and derivative thereof；The block type of the most described polymer is optionally
Linear, band chain or star form.Polyisoprene in described polyisoprene blocks polyoxyethylene groups ether polymer
Content be 3～97wt%, preferably 10～90wt%.
The present invention also provides for the corresponding preparation method of above-mentioned catalytic component, comprises the steps,
A: organo-magnesium compound is reacted with hydroxyl compounds, obtains clear solution；
B: modifiers dispersants is dispersed in C4～C20In alkane or aromatic solvent, form solution, more saturating with what step a obtained
Bright solution reaction, obtains mixed liquor；
C: chloride organoboron compound and titanium-containing compound are added sequentially in the mixed liquor that step b obtains, obtain catalyst
Ingredients suspension liquid, reclaims solid particle therein and obtains described catalytic component.
Preferably in above-mentioned preparation method in terms of every mole of organo-magnesium compound, titanium-containing compound is 0.01～10 mole；Containing hydroxyl
Base class compound is 0.1～20 mole；Chloride organoboron compound is 0.1～50 mole；Modifiers dispersants is in reaction system
In concentration control at 0.001～100 grams per liters.Titanium-containing compound is 0.05～5 mole preferably wherein；Hydroxyl compounds
It it is 0.2～10 mole；Chloride organoboron compound is 0.5～20 mole；Modifiers dispersants concentration control in reaction system
System is at 0.01～50 grams per liters.
In step a, the reaction temperature of organo-magnesium compound and hydroxyl compounds is typically chosen in of a relatively high temperature
Under carry out advantageously, preferably below the boiling temperature of reactant, temperature is normally no higher than 90 DEG C, is generally not more than 70 DEG C.
The time of reaction depends on character and the operating condition of reactant, required time typically at 5 minutes to 2 hours, preferably 10
Minute to 1 hour.After organo-magnesium compound and hydroxyl compounds react, the solution of formation can be with inert diluent
Being used in mixed way, inert diluent is generally selected from aliphatic hydrocarbon, such as iso-butane, pentane, hexane, heptane or hexamethylene and
Its mixture, general hexane or heptane are proper atent solvents.
In stepb, modifiers dispersants is dispersed in C4～C20In alkane or aromatic solvent, it is preferably dispersed in hexane, heptan
In alkane or toluene and admixture solvent thereof, form the clear solution obtained in solution, with step a and be sufficiently mixed, according to modification
The kind of dispersant is different with character, its C4～C20The configuration concentration of alkane or arene solution controls at 0.1～100 grams per liters,
Preferably 1～50 grams per liters, the amount of addition is so that modifiers dispersants concentration in reaction system is 0.001～100 grams per liters, excellent
Select 0.01～50 grams per liters.The boiling temperature of mixing temperature system to be less than, for convenience, is typically chosen in 0～90 DEG C
Between, between preferably 10～50 DEG C.Both incorporation times are typically chosen 0.5 minute to 5 hours, and preferably 10 minutes to 1
Hour.
In step c, complete the uniform mixing of all substances, the solution system first first two steps obtained at a certain temperature
Being reduced to uniform temperature, solution still keeps clear at such a temperature, is unlikely to become turbid or precipitate, and temperature is permissible
Control between-90～30 DEG C, preferably between-70～0 DEG C, then by chloride organoboron compound and titanium-containing compound successively
Progressively being slowly added to, generally carry out being sufficiently stirred for being beneficial to being sufficiently mixed of various material during charging, charging rate is led to
Often select to be as the criterion not causing significant reaction or system substantially to heat up.After being sufficiently mixed, can use any of suitably
Method heats up, and as slowly, progressively, rapidly or temperature programming, it is totally different that different temperature-rising methods can obtain performance characteristics
Catalyst, in temperature-rise period, system can be changed into muddiness by clarification, separates out precipitation, in this precipitation reaction step,
The reaction time of settling step should be long enough to obtain precipitate completely, and the reaction time can last 1 minute to 10 hours,
Preferably 3 minutes～5 hours.
Experiment finds, after settling step, reaction a period of time carries out the maturation process grain to catalyst at a certain temperature
Shape ratio is advantageous, and it can improve the intensity of catalyst particle, thus it is existing to reduce catalyst particle fragmentation in the course of the polymerization process
As.The final temperature of the temperature of maturation process generally greater than or equal to precipitation reaction, the time of slaking reaction can control
0.5～10 hour, preferably 1～5 hour.
After carrying out maturation process, typically to wash, in order to remove formation in excessive reactant and preparation process
Accessory substance, any atent solvent is used equally to this washing step, such as can select iso-butane, pentane, hexane, heptane,
Hexamethylene, toluene or various aromatic hydrocarbons and mixture etc. thereof, be generally selected in experiment after washing twice with toluene, then fill with hexane
Divide washing.After washing, it is dried, to obtain catalyst fines under the protection of catalyst suspension nitrogen.
It addition, the invention still further relates to a kind of all polymerization or the catalyst of combined polymerization for alkene, it contains the above-mentioned present invention and urges
Agent component and the product of alkyl aluminum compound, the formula of alkyl aluminum compound wherein used is AlRhX3-hOrganic
Aluminium compound, in formula, R is hydrogen or alkyl that carbon number is 1～20, and X is halogen, 1 ＜ h≤3.Preferably AlEt3、
Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3、AlEt2Cl etc..
Catalytic component of the present invention can make according to the well-known way of this area olefinic polymerization Ziegler-Natta catalyst
With, as being used together with another kind of co-catalyst or electron donor, it is also possible to by the catalytic component of the present invention with a kind of or many
Plant Ziegler-Natta catalyst or non-Ziegler-Natta catalyst is used in mixed way.
The catalytic component that the present invention also provides for described catalytic component or described method prepares closes or altogether at ethylene homo
Application in polymerisation.
Catalytic component of the present invention is applicable to the various any alkene that can carry out coordination poly-merization, including a kind of alkene
All polymerization or the combined polymerization of multiple alkene of hydrocarbon, the alpha-olefin such as optimal ethylene, propylene, butylene in alkene, or ethene, propylene,
Butylene and the mixture of one or more alpha-olefins.Preferably comonomer is C2-C12 alkene, preferably C4-C10 alkene,
Such as 1-butylene, isobutene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4 methylpentenes 1,
Diene such as butadiene, Isosorbide-5-Nitrae-hexadiene and 1,7-octadiene, cyclenes such as ENB, and their any mixture.
It is anti-that catalyst of the present invention can use typical polymerization technology to carry out polymerization in one or more polymer reactors
Should, can be gas phase, slurry or bulk polymerization, polymerisation can be intermittently or serially polymerization process.
To slurry or bulk reaction device, reaction temperature is typically at 40-130 DEG C, and preferably 60-110 DEG C, reactor pressure typically exists
0.1-8MPa, preferably 0.3-6MPa, the time of staying typically at 0.2-6 hour, preferably 0.5-3 hour.It is typically chosen boiling point to exist
The aliphatic hydrocarbon of-70-100 DEG C of scope uses as diluent；If it is required, polymerisation can be carried out at supercritical conditions.
For Gas-phase reactor, reaction temperature is typically at 60-130 DEG C, and preferably 70-110 DEG C, reactor pressure typically exists
0.5-4MPa, preferably 1-3MPa, the time of staying typically at 0.5-10 hour, preferably 1-8 hour.If it is required, select to close
Suitable aliphatic hydrocarbon uses as diluent, and polymerisation can be carried out under the conditions of frozen state.
Catalyst amount is generally dependent on the character of catalyst, type of reactor and operating condition and to polymerizate performance
Requirement, it is possible to use conventional catalyst consumption.
Use catalyst of the present invention, the catalyst system and catalyzing with good form can be obtained, and catalyst has higher urging
Changing active and preferable hydrogen response, polymerizate form can preferably replicate the particle shape of catalyst, the most so-called
" print effect ", therefore this catalyst has excellent combination property.
Detailed description of the invention
The method of testing used in the present invention:
The size distribution of carrier and catalyst uses MASTERSIZE particles distribution instrument, and n-hexane, as dispersant, is measured
Scope 0.02～2000 μm；Wherein particle diameter breadth coefficient is by (d90-d10)/d50Being calculated, particle diameter breadth coefficient value is the least,
Illustrate that catalyst component particles size is the most uniform.
In catalyst system, the relative weight percents of metal (mainly titanium, magnesium) uses plasma emission spectrum (ICP)
Measure.The pattern of catalyst and polymer uses ESEM (SEM) to measure.Melt index uses ASTM-D1238
Measure.Bulk density uses DIN-53194 to measure.
Example given below illustrates that the present invention rather than limits the invention.
Embodiment 1
The preparation of catalytic component: take 310ml hexane, the dibutylmagnesium hexane solution (1M) of 31.5ml and 10.0ml successively
Isooctanol, is warming up to 50 DEG C and maintains stirring to react half an hour, obtain clear solution, be subsequently adding polyisoprene blocks polyoxy
The hexane solution (10g/L) of vinyl ether co-polymer (PI-b-POE linear copolymer, polyisoprene contents 48wt%)
100ml, is cooled to-20 DEG C, is sequentially added into boron chloride hexane solution (1M) and the 3.5ml titanium tetrachloride of 31.5 milliliters,
After adding material, it is to slowly warm up to 50 DEG C, and maintains reaction 2 hours.Catalyst suspension temperature is down to room temperature, stands,
Sedimentation, washs three times with hexane, and the consumption of each hexane is 300 milliliters, after having washed, is dried to obtain brown solid flowing
Property powder i.e. catalytic component, its average grain diameter is 12.7 microns；Particle diameter breadth coefficient is 0.81.Elementary analysis (ICP):
Ti:9.27%(weight), Mg:13.15%(weight).
Vinyl polymerization evaluates A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalytic component are joined 2L stainless
In steel stirred tank, then temperature bringing up to 80 DEG C, the disposable hydrogen adding 0.18MPa, then with ethene by system
Gross pressure maintains 0.73MPa and carries out polymerisation, after reacting 2 hours, stops adding ethene, cooling, pressure release, poly-second
Alkene powder material weighing, calculates the activity of catalyst, the bulk density of test polyethylene powder and the melted finger under 2.16Kg load
Number, result is as shown in table 1.
Vinyl polymerization evaluates B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalytic component are joined 2L stainless
In steel stirred tank, then temperature bringing up to 90 DEG C, the disposable hydrogen adding 0.4MPa, then with ethene by system
Gross pressure maintains 1.0MPa and carries out polymerisation, after reacting 2 hours, stops adding ethene, cooling, pressure release, poly-second
Alkene powder material weighing, calculates the activity of catalyst, the bulk density of test polyethylene powder and the melted finger under 2.16Kg load
Number, result is as shown in table 1.
Embodiment 2
" 3.5ml titanium tetrachloride " is adjusted to " 10ml titanium tetrachloride ", and other conditions of catalytic component preparation process are with real
Execute example 1.The average grain diameter of products obtained therefrom is 8.9 microns.Elementary analysis (ICP): Ti:13.48%(weight), Mg:10.14%
(weight).
The condition of ethene slurry polymerization evaluation A and B of catalyst is with embodiment 1, and polymerization result is shown in Table 1.
Embodiment 3
By " polyisoprene blocks polyoxyethylene groups ether copolymer (PI-b-POE linear copolymer, polyisoprene contents
Hexane solution (10g/L) 100ml 48wt%) " change " polyisoprene blocks polyoxyethylene groups ether copolymer into
Hexane solution (10g/L) 100ml of (PI-b-POE-b-PI linear copolymer, polyisoprene contents 72wt%) ", urge
Other conditions of agent component preparation process are with embodiment 1.The average grain diameter of products obtained therefrom is 5.2 microns.Elementary analysis
(ICP): Ti:11.26%(weight), Mg:14.58%(weight).
The condition of ethene slurry polymerization evaluation A and B of catalyst is with embodiment 1, and polymerization result is shown in Table 1.
Comparative example 1
By " (PI-b-POE linear copolymer, polyisoprene contains to add polyisoprene blocks polyoxyethylene groups ether copolymer
Amount 48wt%) hexane solution (10g/L) 100ml " step removes, i.e. and be added without modifiers dispersants, catalytic component
Other conditions of preparation process are with embodiment 1.The average grain diameter of products obtained therefrom is 65.72 microns；Its grain size distribution presents
Go out relatively wide multi-modal.Elementary analysis (ICP): Ti:10.24%(weight), Mg:12.36%(weight).
The condition of ethene slurry polymerization evaluation A and B of catalyst is with embodiment 1, and polymerization result is shown in Table 1.
Comparative example 2
The preparation of catalytic component: take 310ml hexane, the dibutylmagnesium hexane solution (1M) of 31.5ml and 10.0ml successively
Isooctanol, is warming up to 50 DEG C and maintains stirring to react half an hour, obtain clear solution, be subsequently adding polybutadiene block polycyclic oxygen
Hexane solution (10g/L) 100ml of ethane copolymer (polybutadiene content 75wt%), is cooled to-20 DEG C, is sequentially added into
The boron chloride hexane solution (1M) of 31.5 milliliters and 3.5ml titanium tetrachloride, after adding material, be to slowly warm up to 50 DEG C, and
Maintain reaction 2 hours.Catalyst suspension temperature is down to room temperature, stands, sedimentation, wash three times with hexane, every time own
The consumption of alkane is 300 milliliters, after having washed, is dried to obtain brown solid mobility powder, and its average grain diameter is 17.2 microns；
Particle diameter breadth coefficient is 0.96.Elementary analysis (ICP): Ti:9.16%(weight), Mg:15.20%(weight).
The condition of ethene slurry polymerization evaluation A and B of catalyst is with embodiment 1, and polymerization result is shown in Table 1.
Table 1
From the experimental data of table 1 embodiment and comparative example it can be seen that use PI-b-POE the preparation process of catalyst
Class modifiers dispersants, the catalytic component obtained and the particle shape of polymer are good, narrow particle size distribution, the accumulation of polymer resin
Density (BD) is higher, catalyst high comprehensive performance.Especially the embodiment of the present invention 1 and comparative example 2 use polybutadiene
Block polyethylene oxide copolymer is compared, and its activity and melt index are all suitable, and the bulk density of its polymer resin is higher；More
Making inventor feel surprised, the embodiment of the present invention 1, compared with comparative example 2, from the distribution of catalytic component particle diameter is at least
The size distribution of number and vinyl polymerization product it can be seen that technical scheme to the particle shape of vinyl polymerization product and
The control of granular size is more preferable.
Claims (13)
1., for the catalytic component of olefinic polymerization, it is to include at least one organo-magnesium compound, at least one titaniferous chemical combination
Thing, at least one hydroxyl compounds, at least one chloride organoboron compound and the reaction of at least one modifiers dispersants
Product；Described chloride organoboron compound is such as formula (IV) BR4 pCl3-pShown compound, R in formula (IV)4It is
C2～C20Alkyl or alkoxyl, 0≤p 3；And described modifiers dispersants is polyisoprene blocks polyoxyethylene groups ethers
Polymer.
Catalytic component the most according to claim 1, it is characterised in that described organo-magnesium compound such as formula (I)
MgR1 nCl2-nShown in, R in formula1It is C2～C20Alkyl, described alkyl is saturated or undersaturated straight chain, side chain or ring
Shape chain, 0 ＜ n≤2.
Catalytic component the most according to claim 1, it is characterised in that described titanium-containing compound such as formula (II)
Ti(OR2)mCl4-mShown in, R in formula2It is C2～C20Alkyl, described alkyl be saturated or undersaturated straight chain, side chain or
Closed chain, 0≤m≤4.
Catalytic component the most according to claim 1, it is characterised in that described hydroxyl compounds such as formula (III)
HOR3Shown in, R in formula3It is C2～C20Alkyl, described alkyl is saturated or undersaturated straight chain, side chain or closed chain.
5. according to the catalytic component described in any one in Claims 1 to 4, it is characterised in that described polyisoprene is embedding
Section polyoxyethylene groups ether polymer includes diblock and three blocks and derivative thereof.
Catalytic component the most according to claim 5, it is characterised in that described polyisoprene blocks polyoxyethylene groups
The block type of ether polymer is optionally linear, band chain or star form.
7. according to the catalytic component described in any one in Claims 1 to 4, it is characterised in that described polyisoprene is embedding
In section polyoxyethylene groups ether polymer, the content of polyisoprene is 3～97wt%.
Catalytic component the most according to claim 7, it is characterised in that described polyisoprene blocks polyoxyethylene groups
In ether polymer, the content of polyisoprene is 10～90wt%.
9., according to the preparation method of catalytic component described in any one in claim 1～8, comprise the steps,
A: organo-magnesium compound is reacted with hydroxyl compounds, obtains clear solution；
B: modifiers dispersants is dispersed in C4～C20In alkane or aromatic solvent, form solution, more saturating with what step a obtained
Bright solution reaction, obtains mixed liquor；
C: chloride organoboron compound and titanium-containing compound are added sequentially in the mixed liquor that step b obtains, obtain catalyst
Ingredients suspension liquid, reclaims solid particle therein and obtains described catalytic component.
Preparation method the most according to claim 9, it is characterised in that in terms of every mole of organo-magnesium compound, containing titanizing
Compound is 0.01～10 mole；Hydroxyl compounds is 0.1～20 mole；Chloride organoboron compound is 0.1～50 to rub
You；Modifiers dispersants concentration in reaction system controls at 0.001～100 grams per liters.
11. preparation methods according to claim 10, it is characterised in that in terms of every mole of organo-magnesium compound, titaniferous
Compound is 0.05～5 mole；Hydroxyl compounds is 0.2～10 mole；Chloride organoboron compound is 0.5～20 to rub
You；Modifiers dispersants concentration in reaction system controls at 0.01～50 grams per liters.
12. 1 kinds are all polymerized or the catalyst of combined polymerization for alkene, and it comprises catalysis described in any one in claim 1～8
The catalytic component that method described in agent component or claim 9 or 10 prepares, and at least one formula is AlRhX3-h
Organo-aluminum compound, in formula, R is hydrogen or alkyl that carbon number is 1～20, and X is halogen, 1 ＜ h≤3.
In 13. claims 1～8, method described in catalytic component described in any one or claim 9 or 10 prepares
Catalytic component application in ethylene homo conjunction or copolymerization.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148754A (en) * | 1975-11-27 | 1979-04-10 | Hoechst Aktiengesellschaft | Process for the preparation of a catalyst and catalyst used in olefin polymerization |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148754A (en) * | 1975-11-27 | 1979-04-10 | Hoechst Aktiengesellschaft | Process for the preparation of a catalyst and catalyst used in olefin polymerization |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
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