CN107880170A - Catalytic component and its preparation and application for olefinic polymerization - Google Patents

Catalytic component and its preparation and application for olefinic polymerization Download PDF

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CN107880170A
CN107880170A CN201610873595.0A CN201610873595A CN107880170A CN 107880170 A CN107880170 A CN 107880170A CN 201610873595 A CN201610873595 A CN 201610873595A CN 107880170 A CN107880170 A CN 107880170A
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compound
catalytic component
catalyst
magnesium
boron
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CN107880170B (en
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王世波
周俊领
张磊
吕新平
黄廷杰
周歆
张长礼
邢宝泉
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • 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
    • C08F4/65—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
    • C08F4/6585—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 and aluminium or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Emergency Medicine (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to a kind of application for the catalytic component of olefinic polymerization, its preparation method and catalyst and the catalyst comprising the catalytic component.The catalytic component 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 organoboron compound and at least one additive；Wherein, the additive is that polystyrene block polyisobutene is birdsed of the same feather flock together compound.Not only its catalytic activity is high, the hydrogen response of catalyst is good for catalyst provided by the invention, 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

Catalytic component and its preparation and application for olefinic polymerization
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 by its excellent polymerization and ripe application technology in polyolefin catalyst field Consequence.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, suspending and soak Stain method develops into chemical reaction method.
In chemical reaction method, many patents of invention are related to using organic metal magnesium compound, chlorinating agent and transition metal The chemical raw materials such as titanium compound, a variety of different types of catalyst are prepared with this kind of reactant, they are disclosed in Chinese special Sharp CN1158136, CN1299375, CN1795213 and United States Patent (USP) US3787384, US4148754, US4173547, In US4301029, US4508843, US4921920 and US5124296.In such Mg-Ti catalyst, there is one The shortcomings that fatal is unmanageable forming step, so as to the form of unmanageable prepared catalyst particle.Recent development is In the dispersion that catalyst precarsor includes magnesium titanium compound, some materials similar to emulsifying agent are added, are allowed to form breast Liquid, then reaction precipitation goes out catalyst granules again, the particle shape of gained catalyst can be so improved, such as in Montedison EP 0258089A in the PFPE that uses, the PFO used in Chinese patent CN 1537118A.But these Method forming step is complicated, it is difficult to control, gained catalyst granules form is not easy to control, and used material price is high It 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 Ziegler-Natta catalyst asked, it is still desirable to some new or improved methods.Therefore, the problem of presently, there are is to be badly in need of Research and develop that a kind of preparation method is simple, and particle shape is preferable, and the catalyst with higher catalytic activity and hydrogen response.
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 Art field has carried out experimental study extensively and profoundly, sends out in the preparation process for the catalytic component for being currently used for olefinic polymerization and uses Additive polystyrene block polyisobutene is birdsed of the same feather flock together compound, and not only the particle of corresponding catalyst component is more uniform, and it is to alkene The control of the particle size and form of polymerization product can be more preferable, and the catalytic activity of corresponding catalyst and hydrogen response are high, The bulk density of polymer resin is high.
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 organoboration The reaction product of compound and at least one additive；
Wherein, the additive is that polystyrene block polyisobutene 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 or branched2-C20Alkyl or closed chain C3-C20Alkyl, 0 ＜ n≤2.It is preferred that institute Stating organo-magnesium compound includes di-n-butyl magnesium, 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 or branched2-C20Alkyl or closed chain C3-C20Alkyl, 0≤m≤4；It is excellent M=4 or m=0 is selected, because tetravalent titanium compound is generally in a liquid state at normal temperatures, and it is also fine with the compatibility of some solvents. It is preferred that the titanium-containing compound includes the one or more in titanium tetrachloride, tetraethyl titanate and butyl titanate；More preferably institute It is titanium tetrachloride to state titanium-containing compound.
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 or branched2-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 organoboron compound is logical formula (IV) BR4 pCl3-pShown compound, in formula (IV) in, R4For the C of straight or branched2-C20Alkyl or alkoxy；0≤p ＜ 3.It is preferred that the chloride organoboron compound bag Include dichloromethyl boron, Dichloroethyl boron, two chlorobutyl boron, dichloro methoxyl group boron, two chloroethoxy boron, boron chloride and two neoprenes One or more in epoxide boron.More preferably described chloride organoboron compound includes two chlorobutyl boron, dichloro methoxyl group boron, two One or more in chloroethoxy boron, boron chloride and dichloro butoxy boron.
According to the present invention, the additive polystyrene block polyisobutene (PS-b-PIB) compound of birdsing of the same feather flock together includes diblock With three block and its derivative；It is preferred that the polystyrene block polyisobutene is birdsed of the same feather flock together the block type of compound it is optionally linear, Band branch chain or star form.The band branch chain includes comb shape and Dendritic forms.The polystyrene block polyisobutene The content of polyisobutene in compound of birdsing of the same feather flock together is 10wt%-95wt%, preferably 20wt%-90wt%, more preferably 20wt%- 72wt%.
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 organoboron 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 organoboron 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 organoboron 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 Agent is released to be 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.
According to the inventive method, in stepb, additive is dispersed in C4-C20Alkane or C6-C20Aromatic solvent In, it is preferably dispersed in hexane, heptane or toluene and its admixture solvent, forms solution, then the clear solution obtained with step A It is sufficiently mixed, obtains mixed liquor.According to the species of additive and property difference, its C4-C20Alkane or C6-C20Arene solution Configuration concentration control be 0.1-100 g/l, preferably 1-50 g/l, the amount of addition so that additive in reaction system Concentration 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 side Just for the sake of, it is typically chosen between 0-90 DEG C, preferably between 10-50 DEG C.Both incorporation times are typically chosen 0.5 minute to 5 Hour, preferably 10 minutes 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 organic boron 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 includes the present invention the Catalytic component prepared by catalytic component or second aspect of the present invention methods described described in one side, and at least one formula (V)AlR5 hX3-hShown organo-aluminum compound, in logical formula (V), R5For C that is identical or differing1-C8Alkyl, X is halogen Element, 1≤h≤3.It is preferred that the organo-aluminum compound includes triethyl aluminum (AlEt3), triisobutyl aluminium (Al (iso-Bu)3), three N-hexyl aluminium (Al (n-C6H13)3), tri-n-octylaluminium (Al (n-C8H17)3) and diethylaluminum chloride (AlEt2Cl one kind in) or It is 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 C2-C12Alkene, It is preferred that C4-C10Alkene, such as 1- butylene, isobutene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene and 4- first Base -1- amylenes, diene such as butadiene, Isosorbide-5-Nitrae-hexadiene and 1,7- octadiene, cyclenes such as ENB, and any of theirs mix Compound.
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.
Catalyst of the present invention has higher catalytic activity and preferable hydrogen response, polymerizate form energy Enough particle shapes for preferably replicating catalyst, i.e., so-called " print effect ", the bulk density of polymer resin is high, therefore this is urged Agent 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) pattern of catalyst and polymer is measured using ESEM (SEM).
(4) melt index (MI2.16) determined using ASTM-D 1238.
(5) bulk density (BD) is determined using DIN-53194.
Embodiment
Embodiment 1
The preparation of catalytic component：Take successively 30mL hexanes, 3.15mL di-n-butyl magnesium hexane 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 the poly- isobutyl of polystyrene Hexane solution (10g/L) 3mL of alkene diblock copolymer (polyisobutene content is 72wt%), is cooled to -50 DEG C, sequentially adds The hexane solution (1M) and 0.35mL titanium tetrachlorides of 3.15mL boron chlorides, it is rapidly heated after adding material, in 10min to 50 DEG C, And maintenance reaction 2 hours.Catalyst suspension temperature is down to room temperature, stood, sedimentation, is washed three times with hexane, each hexane Dosage be 50mL, after the completion of washing, dry that brown solid mobility powder is catalytic component, measuring its average grain diameter is 37.7μm.Elementary analysis (ICP)：Ti:11.34wt%, Mg:16.74wt%.
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 adding in catalytic component preparation process " the 0.35mL titanium tetrachlorides " entered is changed to " 1mL titanium tetrachlorides ".Its average grain diameter is measured as 31.5 μm.Elementary analysis (ICP)： Ti:12.09wt%, Mg:14.12wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
The preparation method of catalytic component is with embodiment 1, and difference is, by catalytic component preparation process " 1.0mL isooctanol " is changed to " 0.6mL n-butanols ", will " (polyisobutene content is polystyrene polyisobutene diblock copolymer Hexane solution (10g/L) 3mL " 72wt%) is changed to that " (polyisobutene content is polystyrene polyisobutene diblock copolymer Hexane solution (10g/L) 10mL " 72wt%).Its average grain diameter is measured as 23.9 μm.Elementary analysis (ICP)：Ti: 9.86wt%, Mg:21.35wt%.
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 not added with the preparation process of catalytic component " hexane solution (10g/L) 3mL " of polystyrene block isobutylene-based polymer (polyisobutene content is 72wt%).Measure it Average grain diameter is 68.53 μm, and particle diameter distribution is wider multi-modal.Elementary analysis (ICP)：Ti:10.26wt%, Mg: 14.18wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 2
The preparation method of catalytic component is with embodiment 1, and difference is, by " polystyrene polyisobutene diblock Hexane solution (10g/L) 3mL " of copolymer (polyisobutene content is 72wt%) is changed to " Kraton FG1901 (polystyrene Polybutadiene triblock copolymer, wherein polybutadiene content are 70wt%) hexane solution (10g/L) 3mL ".It is average to measure it Particle diameter is 17.4 μm.Elementary analysis (ICP)：Ti:10.62wt%, Mg:14.73wt%.
For the ethene slurry polymerization appreciation condition 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 polyisobutene is birdsed of the same feather flock together compound additive, and obtained catalyst and the particle shape of polymer is good, vinyl polymerization Active high, the bulk density of polymer resin is higher, high melt index, 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. 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 class compound, the reaction product of at least one chloride organoboron compound and at least one additive；
Wherein, the additive is that polystyrene block polyisobutene 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 or branched2-C20Alkyl or The C of closed chain3-C20Alkyl, 0 ＜ n≤2；
It is preferred that the organo-magnesium compound includes di-n-butyl magnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, tonsilon One or more in magnesium and butyl magnesium chloride.
3. the catalytic component according to claim 1 or 2, 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 or branched2-C20Alkyl Or the C of closed chain3-C20Alkyl, 0≤m≤4；
It is preferred that the titanium-containing compound includes the one or more in titanium tetrachloride, tetraethyl titanate and butyl titanate.
4. according to the catalytic component described in any one in claim 1-3, it is characterised in that the hydroxyl class compound To lead to formula (III) HOR3Shown compound, in logical formula (III), R3For saturation or the C of undersaturated straight or branched2-C20 Alkyl or closed chain C3-C20Alkyl；
It is preferred that the hydroxyl class compound includes fatty alcohol and/or aromatic alcohol；More preferably described hydroxyl class compound includes One or more in n-butanol, n-hexyl alcohol, isooctanol, phenmethylol and benzyl carbinol.
5. according to the catalytic component described in any one in claim 1-4, it is characterised in that the chloride organic boron chemical combination Thing is logical formula (IV) BR4 pCl3-pShown compound, in logical formula (IV), R4For the C of straight or branched2-C20Alkyl or alkane Epoxide；0≤p ＜ 3；
It is preferred that the chloride organoboron compound includes dichloromethyl boron, Dichloroethyl boron, two chlorobutyl boron, dichloro methoxyl group One or more in boron, two chloroethoxy boron, boron chloride and dichloro butoxy boron.
6. according to the catalytic component described in any one in claim 1-5, it is characterised in that the polystyrene block gathers Isobutylene-based polymer includes diblock and three block and its derivative；It is preferred that the polystyrene block polyisobutene Type of Collective The block type of thing is optionally linear, band branch chain or star form；
It is preferred that the polystyrene block polyisobutene is birdsed of the same feather flock together, the content of polyisobutene is 10wt%-95wt% in compound, more excellent Elect 20wt%-90wt% as.
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 organoboron 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 organoboron 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 organoboron 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 includes urging described in any one in claim 1-6 Catalytic component prepared by agent component or the methods described of claim 7 or 8, and at least one 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.
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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CN115109189A (en) * 2022-06-15 2022-09-27 宁夏清研高分子新材料有限公司 Preparation method of cycloolefin copolymer material, catalyst system and application thereof

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WO2012007963A2 (en) * 2010-07-12 2012-01-19 Reliance Industries Limited Attrition resistant catalyst system for manufacture of polyolefins
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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CN115109189A (en) * 2022-06-15 2022-09-27 宁夏清研高分子新材料有限公司 Preparation method of cycloolefin copolymer material, catalyst system and application thereof
CN115109189B (en) * 2022-06-15 2024-01-30 宁夏清研高分子新材料有限公司 Preparation method of cycloolefin copolymer material, catalyst system and application thereof

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