CN107880178A - Catalytic component and its preparation and application for olefinic polymerization - Google Patents
Catalytic component and its preparation and application for olefinic polymerization Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/651—Pretreating with non-metals or metal-free compounds
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/658—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657
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Abstract
The present invention relates to a kind of catalytic component for olefinic polymerization, and it is the reaction product for including at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl class compound, at least one chloride organo-aluminum compound and at least one additive；Wherein, the additive is that polystyrene block PEO is birdsed of the same feather flock together compound.Catalytic component provided by the invention, not only its catalytic activity is high, the hydrogen response of catalyst is good, resulting polymers bulk densities are high, and corresponding catalyst also has good particle shape and distribution, so as to be more beneficial for use of the catalyst on the polymerization technique device such as gas phase, slurry.
Description
Technical field
The invention belongs to catalytic component and its preparing technical field, and in particular to a kind of catalyst for olefinic polymerization
Component and its preparation and application.
Background technology
From after Efficient polyolefin catalyst development success the 1970s, there occurs great change for world's polyolefin industry.Closely
Over more than 20 years, with the development of olefin polymetiation process, the catalyst to match with polymerization technique has also got significant progress, its
Middle effective catalyst still occupies weight by its excellent polymerization and ripe application technology in polyolefin catalyst field
The status wanted.By exploratory development for many years, the preparation method of Mg-Ti systems effective catalyst is also by being co-mulled and made into method, Suspension
Method has developed into chemical reaction method.In chemical reaction method, many prior arts are related to using organic metal magnesium compound, chlorination
The chemical raw material such as agent and transition metal titanium compound, a variety of different types of catalyst are prepared with this kind of reactant.
In such Mg-Ti catalyst, have one it is fatal the shortcomings that be unmanageable forming step, so as to difficult
In the form of controlling prepared catalyst particle, recent development is the wind granular media for including magnesium titanium compound in catalyst precarsor
In system, some materials similar to emulsifying agent are added, are allowed to form emulsion, then reaction precipitation goes out catalyst granules, Ke Yigai again
Enter the particle shape of gained catalyst, still, these method forming steps are complicated, it is difficult to control, gained catalyst granules form
It is not easy to control, and used material price is high, it is difficult to obtain.
, will for preparing higher performance although having done substantial amounts of research work in Ziegler-Natta catalyst field
The ZN catalyst asked, it is still necessary to some new or improved methods.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided one kind is used for olefinic polymerization
Catalytic component and its preparation and application.The present inventor is in catalyst component for olefin polymerization and its preparation and application skill
The experimental study that art field has carried out extensively and profoundly is found, suitable property-modifying additive is selected, with regard to that can make process for synthetic catalyst
It is simple and easy, and it is preferable to obtain form, such as spherical, the catalyst granules of narrow size distribution, while have higher urge
Change activity and hydrogen response.
Therefore, first aspect present invention provides a kind of catalytic component for olefinic polymerization, it is to include at least one
Kind organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl class compound, at least one chloride organic calorize
The reaction product of compound and at least one additive；
Wherein, the chloride organo-aluminum compound is logical formula (IV) AlR4 pCl3-pShown compound, in logical formula (IV),
R4For C2-C20Alkyl or alkoxy, 0.5≤p ＜ 2.5；
The additive is that polystyrene block PEO is birdsed of the same feather flock together compound.
According to the present invention, the organo-magnesium compound is logical formula (I) MgR1 nCl2-nShown compound, in logical formula (I),
R1For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or closed chain C3-C20Alkyl, 0 ＜ n≤2.It is preferred that
The organo-magnesium compound includes dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and chlorination fourth
One or more in base magnesium.
According to the present invention, the titanium-containing compound is logical formula (II) Ti (OR2)mCl4-mShown compound, in logical formula (II)
In, R2For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or closed chain C3-C20Alkyl, 0≤m≤4；Cause
Generally it is in a liquid state at normal temperatures for tetravalent titanium compound, and it is also fine with the compatibility of some solvents.It is preferred that described contain titanizing
Compound includes the one or more in titanium tetrachloride, tetraethyl titanate and butyl titanate, more preferably titanium tetrachloride.
According to the present invention, the hydroxyl class compound is logical formula (III) HOR3Shown compound, in logical formula (III)
In, R3For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or closed chain C3-C20Alkyl.It is preferred that described contain
Hydroxy kind compound includes fatty alcohol and/or aromatic alcohol；More preferably described hydroxyl class compound include n-butanol, n-hexyl alcohol,
One or more in isooctanol, phenmethylol and benzyl carbinol.
According to the present invention, the chloride organo-aluminum compound is selected from ethyl aluminum dichloride, ethylaluminum sesquichloride, diethyl
At least one of base aluminium and dichloro aluminium isobutyl.
According to the present invention, the additive polystyrene block PEO (PS-b-POE) birds of the same feather flock together compound include it is two embedding
Section and three block and its derivative；It is preferred that the polystyrene block PEO is birdsed of the same feather flock together, the block type of compound is optionally line
Shape, band branch chain or star form.The content of polystyrene is in the polystyrene block PEO birdss of the same feather flock together compound
5wt%-95wt%, preferably 10wt%-90wt%.
Second aspect of the present invention provides a kind of preparation method of catalytic component as described in the first aspect of the invention, and it is wrapped
Include：
Step A, organo-magnesium compound and hydroxyl class compound are reacted, obtain clear solution；
Step B, additive is dispersed in C4-C20Alkane or C6-C20Aromatic solvent in, formed solution, then with step A
Obtained clear solution reaction, obtains mixed liquor；
Step C, chloride organo-aluminum compound and titanium-containing compound are added sequentially in the mixed liquor that step B is obtained, obtained
To catalytic component suspension, reclaim solid particle therein and obtain the catalytic component.
According to the inventive method, in terms of every mole of organo-magnesium compound, the titanium-containing compound is 0.01-10 moles, institute
Hydroxyl class compound is stated as 0.1-20 moles, the chloride organo-aluminum compound is 0.1-50 moles, and the additive is anti-
It is 0.001-100 grams/L to answer the concentration in system.It is preferred that the titanium-containing compound is 0.05-5 moles, the hydroxyl class chemical combination
Thing is 0.2-10 moles, and the chloride organo-aluminum compound is 0.5-20 moles, concentration of the additive in reaction system
For 0.01-50 grams/L.
According to the inventive method, in step, the reaction temperature of organo-magnesium compound and hydroxyl class compound is typically selected
Select and carry out at a higher temperature advantageously, preferably below the boiling temperature of reactant, temperature is normally no higher than 90 DEG C, and one
As be not higher than 70 DEG C.Reaction time depend on reactant property and operating condition, required time typically at 5 minutes to 2 hours,
It is preferred that 10 minutes to 1 hour.After organo-magnesium compound and the reaction of hydroxyl class compound, the solution of formation can be dilute with inertia
Release agent to be used in mixed way, inert diluent is generally selected from aliphatic hydrocarbon or aromatic hydrocarbon atent solvent, such as iso-butane, penta
Alkane, hexane, heptane, hexamethylene, benzene,toluene,xylene and its mixture, general hexane, heptane or toluene are proper
Atent solvent.
According to the inventive method, in stepb, additive is dispersed in C4-C20Alkane or aromatic solvent in, preferably divide
It is dispersed in hexane, heptane or toluene and its admixture solvent, forms solution, then is sufficiently mixed with the obtained clear solutions of step A,
Obtain mixed liquor.According to the species of additive and property difference, its C4-C20Alkane or arene solution configuration concentration control be
0.1-100 g/l, preferably 1-50 g/l, the amount of addition is so that concentration of the additive in reaction system is 0.001-100
G/l, preferably 0.01-50 g/l.Mixing temperature will typically be less than the boiling temperature of system, for convenience, be typically chosen
Between 0-90 DEG C, preferably between 10-50 DEG C.Both incorporation times are typically chosen 0.5 minute to 5 hours, preferably 10 points
Clock was to 1 hour.
According to the inventive method, in step C, the uniform mixing of all substances is quickly completed at a certain temperature, first
The solution system that first two steps are obtained is reduced to certain temperature, and solution still keeps clear at such a temperature, is unlikely to
Existing muddy or precipitation, temperature can be controlled between -90 to 30 DEG C, preferably between -70 to 0 DEG C, then by chloride organo-aluminium
Compound and titanium-containing compound are progressively slowly added to successively, are generally sufficiently stirred in favor of various materials during charging
Be sufficiently mixed, charging rate generally selects that substantially heating is defined not cause significant reaction or system., can be with after being sufficiently mixed
Heated up using any of suitable method, such as slowly, progressively, rapidly or temperature programming, different temperature-rising methods can
To obtain the totally different catalyst of performance characteristics.In temperature-rise period, system can be changed into muddiness by clarification, precipitation be separated out, at this
In precipitation reaction step, the reaction time of settling step should be long enough to obtain complete precipitation, and the reaction time can last 1 point
Clock was to 10 hours, preferably 3 minutes to 5 hours.
Experiment is found, after settling step, a period of time of reaction at a certain temperature carries out maturation process to catalyst
Particle shape than advantageous, it can improve the intensity of catalyst particle, be broken so as to reduce the particle of catalyst in the course of the polymerization process
Broken phenomenon.The final temperature of the temperature of maturation process generally greater than or equal to precipitation reaction, the time of slaking reaction can control
In 0.5-10 hours, preferably 1-5 hours.
After maturation process is carried out, typically to be washed, to remove shape in excessive reactant and preparation process
Into accessory substance, any atent solvent is used equally for this washing step, such as can select iso-butane, pentane, hexane, heptan
Alkane, hexamethylene, toluene or various aromatic hydrocarbons and its mixture etc., are generally selected after washing twice with toluene, then use hexane in experiment
Fully washing.After washing, it is dried under the protection of catalyst suspension nitrogen, to obtain catalyst fines.
Third aspect present invention provides a kind of catalyst for alkene homopolymerization or combined polymerization, and it is included such as the present invention
Catalytic component or the catalytic component of method preparation, and at least one as described in respect of the second aspect of the invention described in first aspect
Logical formula (V) AlR5 hX3-hShown organo-aluminum compound, in logical formula (V), R5For C that is identical or differing1-C8Alkyl, X is
Halogen, 1≤h≤3.It is preferred that the organo-aluminum compound includes triethyl aluminum (AlEt3), triisobutyl aluminium (Al (iso-Bu)3)、
Tri-n-hexyl aluminum (Al (n-C6H13)3), tri-n-octylaluminium (Al (n-C8H17)3) and diethylaluminum chloride (AlEt2Cl one kind in)
It is or a variety of.
Catalyst of the present invention can make according to the well-known way of this area olefinic polymerization Ziegler-Natta catalyst
With, such as it is used together with another co-catalyst or electron donor, can also be neat by the catalyst of the present invention and one or more
Ge Le-Natta catalyst or non-Ziegler-Natta catalyst are used in mixed way.
Fourth aspect present invention provides a kind of catalytic component as described in the first aspect of the invention, such as present invention second
Catalytic component prepared by aspect methods described or the catalyst as described in third aspect present invention are in alkene homopolymerization or copolymerization
Close the application in reaction.
Catalytic component and catalyst of the present invention are applied to the various any alkene that can carry out coordination poly-merization
Hydrocarbon, including a kind of homopolymerization of alkene or the combined polymerization of a variety of alkene.It is preferred that the alkene include the α such as ethene, propylene, butylene-
Alkene, or the mixture of ethene, propylene, butylene and one or more alpha-olefins.Preferable comonomer is C4-C10Alkene, such as
1- butylene, isobutene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene and 4-methyl-1-pentene, diene is such as
Butadiene, Isosorbide-5-Nitrae-hexadiene and 1,7- octadiene, cyclenes such as ENB, and their any mixture.
Catalyst of the present invention can be gathered in one or more polymer reactors using typical polymerization technology
Reaction is closed, 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, preferably 60-110 DEG C；Reactor pressure one
As in 0.2-8MPa, preferably 1-6MPa；Residence time is typically in 0.2-6 hours, preferably 0.5-3 hours.It is typically chosen boiling
Point uses in the aliphatic hydrocarbon of -70 to 100 DEG C of scopes as diluent；If desired, polymerisation can be at supercritical conditions
Carry out.
For Gas-phase reactor, reaction temperature is typically at 60-130 DEG C, preferably 70-110 DEG C；Reactor pressure typically exists
0.5-4MPa, preferably 1-3MPa；Residence time is typically in 0.5-10 hours, preferably 1-8 hours.If desired, selection is closed
Suitable aliphatic hydrocarbon is used as diluent, and polymerisation can be carried out under the conditions of frozen state.
Catalyst amount is generally dependent on property, type of reactor and the operating condition of catalyst and to polymerizate
The requirement of energy, can use conventional catalyst dosage.
The present invention is gathered in the preparation process for the catalytic component of olefinic polymerization using additive polystyrene block
Ethylene oxide polymer, it is preferable to obtain particle shape, almost spherical, narrower particle size distribution, and has higher catalysis
The catalytic component of activity and hydrogen response, polymerizate form can preferably replicate the particle shape of catalyst, i.e. institute
" print effect " of meaning, so as to which the control to the particle size and form of olefinic polymerization product is better achieved, therefore should
Catalyst has excellent combination property.
Embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment, these embodiments are only
Serve illustrative, it is not limited to application of the invention.
The method of testing used in the present invention is as follows：
(1) size distribution of carrier and catalyst uses MASTERSIZE particles distribution instruments, and n-hexane is surveyed as dispersant
It is 0.02-2000 μm to measure scope.
(2) relative weight percents of metal (mainly titanium, magnesium) use plasma emission spectrum in catalyst system
(ICP) measure.
(3) melt index (MI2.16) determined using ASTM-D 1238.
(4) bulk density (BD) is determined using DIN-53194.
Embodiment
Embodiment 1
The preparation of catalytic component：Take successively 30mL toluene, 3.15mL dibutylmagnesium toluene solution (1M) and 1.0mL
Isooctanol, 50 DEG C of maintenance stirring reaction half an hour are warming up to, obtain clear solution, then add polystyrene diblock polycyclic oxygen
Toluene solution (15g/L) 2mL of ethane copolymer A (polystyrene content 42wt%), is cooled to -50 DEG C, sequentially adds
The toluene solution (1M) and 0.35mL titanium tetrachlorides of 1.6mL ethyl aluminum dichlorides, after maintaining low-temp reaction half an hour, slowly rise naturally
Temperature, after being warmed to room temperature, heating maintains 50 DEG C, and reacts 2 hours at such a temperature.Catalyst suspension temperature is down to room temperature,
Standing, sedimentation, washed three times with hexane, the dosage of each hexane is 50mL, after the completion of washing, dry brown solid mobility
Powder is catalytic component, measures its average grain diameter as 11.7 μm.Elementary analysis (ICP)：Ti:10.21wt%, Mg:
14.46wt%.
Vinyl polymerization is evaluated：1L hexanes, 1mmol triethyl aluminums and a certain amount of catalytic component are added to 2L stainless steels
In stirred tank, temperature is then brought up to 85 DEG C, the disposable hydrogen for adding 0.18MPa, then with ethene by the stagnation pressure of system
Power maintains 1.03MPa and carries out polymerisation, after reacting 2 hours, stops adding ethene, cooling, pressure release, polyethylene powder claims
Weight, calculates the activity of catalyst, tests the bulk density of polyethylene powder and the melt index under 2.16Kg loads, as a result see
Table 1.
Embodiment 2
The preparation method of catalytic component is with embodiment 1, and difference is, by polystyrene diblock PEO
Toluene solution (15g/L) 2mL of copolymer A (polystyrene content 42wt%) is changed to polystyrene diblock PEO
Toluene solution (15g/L) 4mL of copolymer A (polystyrene content 42wt%).Its average grain diameter is measured as 6.8 μm.Element
Analyze (ICP)：Ti:9.93wt%, Mg:14.88wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
With embodiment 1, difference is the preparation method of catalytic component, will be to slowly warm up to room temperature naturally, then
50 DEG C are heated to be changed to be rapidly heated in 10 minutes to 50 DEG C.Its average grain diameter is measured as 7.5 μm.Elementary analysis (ICP)：Ti:
10.85wt%, Mg:16.78wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 1
With embodiment 1, difference is the preparation method of catalytic component, is added without in catalytic component preparation process
" polystyrene diblock polyethylene oxide copolymer A (polystyrene content 42wt%) toluene solution ".It is average to measure it
Particle diameter is 92.3 μm, and size distribution is very wide, with the presence of multiple peaks.Elementary analysis (ICP)：Ti:10.15wt%, Mg:
12.97wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 2：
The preparation of catalytic component:Take 30ml hexanes, 3.15ml dibutylmagnesium hexane solution (1M) and 1.0ml different successively
Octanol, 50 DEG C of maintenance stirring reaction half an hour are warming up to, obtain clear solution, then add Kraton FG1901 hexane solutions
(10g/L) 2ml, is cooled to -50 DEG C, sequentially adds hexane solution (2M) and the chlorinations of 0.35ml tetra- of 1.6 milliliters of ethyl aluminum dichlorides
Titanium, after maintaining low-temp reaction half an hour, slowly heating naturally, after being warmed to room temperature, heating maintains 50 DEG C to react 2 hours.Will catalysis
Agent suspension temperature is down to room temperature, stands, and sedimentation, is washed three times with hexane, and the dosage of each hexane is 50 milliliters, and washing is completed
Afterwards, it is dry that brown solid mobility powder, its average grain diameter are 15.6 microns.Elementary analysis (ICP)：Ti:11.04% (weight
Amount), Mg:12.64% (weight).
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Table 1
The experimental data of embodiment and comparative example can be seen that from table 1 uses in the preparation process of catalytic component
Polystyrene block PEO is birdsed of the same feather flock together compound additive, and obtained catalyst and the particle shape of polymer is good, and ethene gathers
It is high to close activity, the bulk density of polymer resin is higher, catalyst high comprehensive performance.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of catalytic component for olefinic polymerization, it is to include at least one organo-magnesium compound, at least one titaniferous
The reaction of compound, at least one hydroxyl class compound, at least one chloride organo-aluminum compound and at least one additive
Product；Wherein, the additive is that polystyrene block PEO is birdsed of the same feather flock together compound.
2. catalytic component according to claim 1, it is characterised in that the organo-magnesium compound is logical formula (I)
MgR1 nCl2-nShown compound, in logical formula (I), R1For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or
The C of closed chain3-C20Alkyl, 0 ＜ n≤2.
3. the catalytic component according to claim 1, it is characterised in that the titanium-containing compound is logical formula (II) Ti
(OR2)mCl4-mShown compound, in logical formula (II), R2For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl
Or the C of closed chain3-C20Alkyl, 0≤m≤4.
4. catalytic component according to claim 1, it is characterised in that the hydroxyl class compound is logical formula (III)
HOR3Shown compound, in logical formula (III), R3For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or ring
The C of shape chain3-C20Alkyl.
5. catalytic component according to claim 1, it is characterised in that the chloride organo-aluminum compound is logical formula (IV)
AlR4 pCl3-pShown compound, in logical formula (IV), R4For C2-C20Alkyl or alkoxy, 0.5≤p ＜ 2.5.
6. according to the catalytic component described in any one in claim 1-5, it is characterised in that the polystyrene block gathers
Ethylene oxide polymer includes diblock and three block and its derivative；It is preferred that the polystyrene block PEO class
The block type of polymer is optionally linear, band branch chain or star form；The polystyrene block PEO is birdsed of the same feather flock together
The content of polystyrene is 5wt%-95wt%, preferably 10wt%-90wt% in compound.
7. the preparation method of catalytic component as described in any one in a kind of 1-6 such as claim, it includes：
Step A, organo-magnesium compound and hydroxyl class compound are reacted, obtain clear solution；
Step B, additive is dispersed in C4-C20Alkane or C6-C20Aromatic solvent in, form solution, then obtained with step A
Clear solution reaction, obtain mixed liquor；
Step C, chloride organo-aluminum compound and titanium-containing compound are added sequentially in the mixed liquor that step B is obtained, urged
Agent ingredients suspension liquid, reclaim solid particle therein and obtain the catalytic component.
8. preparation method according to claim 7, it is characterised in that in terms of every mole of organo-magnesium compound, the titaniferous
Compound is 0.01-10 moles, and the hydroxyl class compound is 0.1-20 moles, and the chloride organo-aluminum compound is 0.1-
50 moles, concentration of the additive in reaction system is 0.001-100 grams/L；It is preferred that the titanium-containing compound is 0.05-5
Mole, the hydroxyl class compound is 0.2-10 moles, and the chloride organo-aluminum compound is 0.5-20 moles, the addition
Concentration of the agent in reaction system is 0.01-50 grams/L.
9. a kind of catalyst for alkene homopolymerization or combined polymerization, it is included as described in any one in claim 1-6
Catalytic component or the catalytic component such as the preparation of the methods described of claim 7 or 8, and at least one logical formula (V) AlR5 hX3-hInstitute
The organo-aluminum compound shown, in logical formula (V), R5For C that is identical or differing1-C8Alkyl, X is halogen, 1≤h≤3.
10. prepared by the catalytic component, such as methods described of claim 7 or 8 in a kind of 1-6 such as claim as described in any one
The application in alkene homopolymerization or copolymerization of catalytic component or catalyst as claimed in claim 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR78845E (en) * | 1957-07-20 | 1962-09-14 | Normande De Matieres Plastique | Improvements to ethylene polymerization processes |
| KR20070065506A (en) * | 2005-12-20 | 2007-06-25 | 삼성토탈 주식회사 | Catalyst for producing polyolefin having narrow molecular weight distribution and method for producing ethylene (c0)polymer using the same |
| CN102453170A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Components, preparation method and application of alkene polymerization catalyst |
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2016
- 2016-09-30 CN CN201610874918.8A patent/CN107880178B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR78845E (en) * | 1957-07-20 | 1962-09-14 | Normande De Matieres Plastique | Improvements to ethylene polymerization processes |
| KR20070065506A (en) * | 2005-12-20 | 2007-06-25 | 삼성토탈 주식회사 | Catalyst for producing polyolefin having narrow molecular weight distribution and method for producing ethylene (c0)polymer using the same |
| CN102453170A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Components, preparation method and application of alkene polymerization catalyst |
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