CN107880175A - Catalytic component for olefinic polymerization and preparation method thereof and catalyst - Google Patents

Catalytic component for olefinic polymerization and preparation method thereof and catalyst Download PDF

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Publication number
CN107880175A
CN107880175A CN201610874235.2A CN201610874235A CN107880175A CN 107880175 A CN107880175 A CN 107880175A CN 201610874235 A CN201610874235 A CN 201610874235A CN 107880175 A CN107880175 A CN 107880175A
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compound
catalyst
magnesium
formula
silane
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CN107880175B (en
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王世波
周俊领
宋阳
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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—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
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
    • 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
    • C08F4/651—Pretreating with non-metals or metal-free compounds
    • 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

Abstract

The invention provides a kind of catalytic component for olefinic polymerization and preparation method thereof and catalyst.The catalytic component includes the reaction product of at least one organo-magnesium compound, at least one liquid titanium-containing compound, at least one hydroxy-containing compounds, at least one chlorine-and-silicon-contained compound and at least one additive, is birdsed of the same feather flock together compound wherein described additive is polystyrene block polymethylmethacrylablock block.Catalyst provided by the invention not only has good hydrogen regulation performance, while 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 for olefinic polymerization and preparation method thereof and catalyst
Technical field
The invention belongs to catalyst for olefines polymerizing field, is related to a kind of catalytic component and its system for olefinic polymerization Preparation Method and catalyst.
Background technology
Over nearly more than 20 years, along with the development of olefin polymetiation process, the catalyst to match with olefinic polymerization also achieves Significant progress, wherein, effective catalyst is by its excellent catalytic performance and ripe application technology in field of olefin polymerisation Occupy an important position.By exploratory development for many years, the preparation method of Mg-Ti systems effective catalyst is by being co-mulled and made into method, suspending Infusion process has developed into chemical reaction method.Chinese patent CN158136, CN1795213 and United States Patent (USP) US4508843, Disclose in US4921920 and US5124296 and made using organic metal magnesium compound, chlorinating agent and transition metal titanium compound etc. For a variety of different types of catalyst are gone out, during these patent systems are for catalyst, unmanageable forming step be present The problem of, and then have influence on the form of catalyst granules.Recent study is found, magnesium titanium compound is included in catalyst precarsor Dispersion in, add some materials similar to emulsifying agent, be allowed to form emulsion, then reaction precipitation goes out catalyst particles again Grain, the particle shape of gained catalyst can be improved, is disclosed in European patent EP 0258089 using PFPE, in Disclosed in state patent CN1537118 using PFO, but the method forming step disclosed in these patents is complicated, it is difficult to Control, the form of obtained catalyst granules is not easy to control, and the material price used is high, and cost is high.
, 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
Inventor selects suitable additive by testing discovery repeatedly, it becomes possible to makes the building-up process of catalyst simple It is easy, and the catalyst granules of preferable, the narrow size distribution of form can be obtained, while catalyst has higher catalytic activity And hydrogen response.
First purpose of the present invention is to provide a kind of catalytic component for olefinic polymerization.
Include component 1 provided by the present invention for the catalytic component of olefinic polymerization), reaction 2), 3), 4) He 5) production Thing, wherein component 1) it is at least one organo-magnesium compound；Component 2) it is that the preferred liquid of at least one titanium-containing compound contains titanizing Compound；Component 3) it is at least one hydroxy-containing compounds；Component 4) it is at least one chlorine-and-silicon-contained compound；And component 5) be At least one additive, described additive are that polystyrene block polymethylmethacrylablock block is birdsed of the same feather flock together compound (PS-b- PMMA)。
According to the preferred embodiment of the present invention, described organo-magnesium compound formula is (I) MgR1 nCl2-n, R in formula1For C2-C20Alkyl, 0 ＜ n≤2.
According to the preferred embodiment of the present invention, described titanium-containing compound formula is (II) Ti (OR2)nCl4-nIt is shown, formula Middle R2For C2-C20Alkyl, 0≤m≤4.
According to the preferred embodiment of the present invention, described hydroxy-containing compounds formula is (III) HOR3, R in formula3For C2- C20Alkyl.
According to the preferred embodiment of the present invention, described chlorine-and-silicon-contained compound formula is (IV) SiR4 pCl4-p, in formula R4For C2-C20Alkyl or C2-C20Alkoxy, 0≤p ＜ 4.
According to the preferred embodiment of the present invention, described polystyrene block polymethylmethacrylablock block Type of Collective Thing is selected from diblock, three block and its derivative, can be linear, have side chain etc. other block class forms, have side chain It can include star-shaped, comb shape, dendritic etc..Preferably, the polystyrene block polymethylmethacrylablock block The matter content of polystyrene in compound of birdsing of the same feather flock together is 5wt%-95wt%, preferably 10wt%-90wt%.
According to the present invention, the alkyl includes alkyl, alkenyl and alkynyl, can be straight chain, side chain or ring-type.Institute State C2-C20The example of alkyl include C2-C20Straight chained alkyl, C3-C20Branched alkyl, C3-C20Cycloalkyl, C2-C20Straight-chain alkenyl, C3-C20Branched-chain alkenyl, C3-C20Cycloalkenyl group, C2-C20Straight-chain alkynyl, C3-C20Branch alkynyl etc..
According to the preferred embodiment of the present invention, in the organo-magnesium compound, R1For C2-C20Alkyl, specific chemical combination Thing such as MgCl2、MgEtCl、MgBu2.Preferably, the organo-magnesium compound is selected from dibutylmagnesium, diisobutyl magnesium, dioctyl At least one of magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and butyl magnesium chloride.
According to the preferred embodiment of the present invention, the titanium-containing compound is tetravalent titanium compound, because usual titanic Compound is liquid at normal temperatures, good with the compatibility of solvent.Preferably, the titanium-containing compound is titanium tetrachloride, metatitanic acid four At least one of ethyl ester and butyl titanate, more preferably titanium tetrachloride.
According to the preferred embodiment of the present invention, described hydroxy-containing compounds are fatty alcohol or aromatic alcohol, preferably just At least one of butanol, n-hexyl alcohol, isooctanol, phenmethylol and benzyl carbinol.
According to the preferred embodiment of the present invention, the chlorine-and-silicon-contained compound is selected from trichlorophenyl silane, trichloromethyl Silane, trichloroethyl silane, trichlorine octyl group silane, trichloromethoxy silane, tri-chloroethoxy base silane, trichlorine butoxy silane, At least one of dichloro dimethoxysilane, dichlorodiethyl TMOS and silicon tetrachloride, preferably trichloromethyl silane, three At least one of chloroethylsilane, trichloromethoxy silane, tri-chloroethoxy base silane and silicon tetrachloride.
Second object of the present invention is to provide a kind of method for preparing the catalytic component, comprises the following steps：
1) organo-magnesium compound is reacted with hydroxy-containing compounds, obtains clear solution；
2) additive is dispersed in C4-C20Alkane or C6-C20In aromatic solvent, solution is formed, then obtained with step 1) Clear solution mixes, and obtains mixed liquor；
3) chlorine-and-silicon-contained compound and titanium-containing compound are added in the mixed liquor that step 2) obtains successively, heating is urged Agent component.
Preferably, in the preparation process of the catalytic component, the ratio of each component is, with every mole of organic-magnesium Compound meter, titanium-containing compound are 0.01-10 moles, preferably 0.05-5 moles；Hydroxy-containing compounds are 0.1-20 moles, preferably For 0.2-10 moles；Chlorine-and-silicon-contained compound is 0.05-50 moles, preferably 0.1-20 moles；Additive is in reaction system Concentration be 0.001-100g/L, preferably 0.01-50g/L.
In the step 1), the reaction temperature of organo-magnesium compound and alcohols material is typically chosen in of a relatively high temperature 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 for lower progress. The time of reaction depends on the property and operating condition of reactant, and required time is typically at 5 minutes to 2 hours, preferably 10 minutes To 1 hour.After organo-magnesium compound and alcohols material reaction, the solution of formation can be used in mixed way with inert diluent, lazy Property diluent is generally selected from alkanes, such as iso-butane, pentane, toluene, heptane or hexamethylene and its mixture, general toluene or Heptane is proper atent solvent.
In the step 2), the reaction solution that will obtain in a certain amount of additive toluene solution prepared in advance and step 1) It is sufficiently mixed, different with property according to the species of additive, its toluene solution configuration concentration is controlled at 0.1-100 g/l, preferably 1-50 g/l, the concentration of the amount of addition in order to additive in reaction system is controlled at 0.001-100 g/l, preferably 0.01-50 g/l.Mixing temperature typically will be less than system boiling temperature, for convenience, be typically chosen in 0-90 DEG C it Between, preferably between 10-50 DEG C.Both incorporation times are typically chosen 0.5 minute to 5 hours, preferably 10 minutes to 1 hour.
In the step 3), the uniform mixing of all substances is quickly completed at a certain temperature, first obtains first two steps Solution system be reduced to certain temperature, solution still keeps clear at such a temperature, is unlikely to become turbid or precipitates, Temperature can be controlled between -90-30 DEG C, preferably between -70-0 DEG C, then by chlorine-and-silicon-contained compound and titanium-containing compound Progressively it is slowly added to successively, being sufficiently mixed in favor of various materials, charging speed is generally sufficiently stirred during charging Degree is generally selected not cause significant reaction or system substantially to heat up and be defined.After being sufficiently mixed, any of conjunction can be used Suitable method is heated up, and such as slowly, progressively, rapidly or temperature programming, it is widely different that different temperature-rising methods can obtain performance characteristics Different catalyst, in temperature-rise period, system can be changed into muddiness by clarification, separate out precipitation, in the precipitation reaction step, be sunk The reaction time of shallow lake step should be long enough to obtain complete precipitation, and the reaction time can last 1 minute to 10 hours, preferably 3 - 5 hours minutes.
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 At -10 hours 0.5 hour, preferably -5 hours 1 hour.
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.
The catalyst prepared by the method for the present invention, which removes, has good hydrogen regulation performance, while also has well 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.
Third object of the present invention is to provide a kind of catalyst for olefinic polymerization, and it includes the reaction of following components Product：
A) catalytic component of the present invention；
B) formula is AlR5 qCl3-qAt least one of organo-aluminum compound, in formula, R5For identical or different C1-C8 Alkyl, 0 ＜ q≤3.
The embodiment of catalyst according to the invention, one or more kinds of alkyl aluminums can be selected to be used in mixed way, It is preferred that AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-C8H17)3Or AlEt2At least one of Cl.
The catalyst using this area Ziegler-Natta catalyst well-known way use, such as with another co-catalysis Agent or electron donor are used together, can also be by the catalyst and one or more Ziegler-Natta catalysts or non homogeneity lattice Le-Natta catalyst is used in mixed way.
Fourth object of the present invention is to provide application of the catalyst in olefinic polyreaction.
Catalyst provided by the invention is applied to the various alkene that can carry out coordination poly-merization, including a kind of alkene Homopolymerization or the combined polymerization of a variety of alkene, the alpha-olefin such as optimal ethylene, propylene, butylene in alkene, or ethene, propylene, butylene with The mixture of one or more alpha-olefins.Preferable comonomer is C2-C12Alkene, preferably C4-C10Alkene, such as 1- butylene, different Butylene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene and 4-methyl-1-pentene, diene such as butadiene, 1, 4- hexadienes and 1,7- octadiene, cyclenes such as ENB, and their any mixture.
Catalyst of the present invention one or more polymer reactors using typical polymerization technology suitable for being gathered Close reaction, including gas phase, slurry and bulk polymerization, polymerisation can be intermittently or serially polymerization process.
To slurry or bulk reaction device, reaction temperature is 40-130 DEG C, preferably 60-110 DEG C；Reactor pressure is 0.2- 8MPa, preferably 1-6MPa；Residence time is typically in 0.2-6 hours, preferably 0.5-3 hours.Boiling point is typically chosen at -70-100 DEG C The aliphatic hydrocarbon of scope is used as diluent, if it is desired, polymerisation can be carried out at supercritical conditions.
For Gas-phase reactor, reaction temperature is 60-130 DEG C, preferably 70-110 DEG C；Reactor pressure is typically in 0.5- 4MPa, preferably 1-3MPa；Residence time is 0.5-10 hours, preferably 1-8 hours.If desired, suitable aliphatic hydrocarbon is selected to make Used for diluent, 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, typically selects conventional catalyst dosage.
Using catalyst of the present invention, the catalyst system and catalyzing with good form can be obtained, and catalyst is with higher Catalytic activity and preferable hydrogen response, polymerizate form can preferably replicate the particle shape of catalyst, i.e. institute " print effect " of meaning, therefore the catalyst has excellent combination property.
Embodiment
Method of testing：
1st, the size distribution of carrier and catalyst：MASTERSIZE particles distribution instruments, n-hexane measure model as dispersant Enclose 0.02 μm -2000 μm.
2nd, the relative weight percents of metal in catalyst system (mainly titanium, magnesium)：Plasma emission spectrum (ICP).
3rd, melt index MI2.16Measure：ASTM-D 1238.
4th, bulk density BD measure：DIN-53194.
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
Embodiment 1
Take successively 30mL toluene, 3.15mL dibutylmagnesium toluene solution (1M) and 1.0mL isooctanol, be warming up to 50 DEG C Stirring reaction half an hour is maintained, obtains clear solution, it is (poly- then to add styrene methyl methacrylate diblock copolymer A Styrene-content 48wt%) toluene solution (10g/L) 2mL, be cooled to -10 DEG C, sequentially add 0.36 milliliter of silicon tetrachloride and 0.35mL titanium tetrachlorides, after adding material, it is rapidly heated in 10 minutes to 50 DEG C, and maintenance reaction 2 hours.By catalyst suspension Temperature is down to room temperature, stands, and sedimentation, is washed three times with toluene, and the dosage of each toluene is 50 milliliters, then washs two with hexane Secondary, the dosage of each hexane is 50 milliliters, dry that brown solid mobility powder, its average grain diameter are after the completion of washing 25.9 microns.
Elementary analysis (ICP)：Ti:4.93% (weight), Mg:21.18% (weight).
Vinyl polymerization is evaluated：1L hexanes, 1mmol triethyl aluminums and a certain amount of catalyst are added to the stirring of 2L stainless steels In kettle, temperature is then brought up to 85 DEG C, the disposable hydrogen for adding 0.18MPa, then tieed up the gross pressure of system with ethene Hold and carry out polymerisation in 1.03MPa, after reacting 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, and is counted The activity of catalyst is calculated, the bulk density of polyethylene powder and the melt index under 2.16Kg loads are tested, as a result such as the institute of table 1 Show.
Embodiment 2
Toluene solution (10g/L) 2mL of addition A in catalyst preparation process is changed to add to A toluene solution (10g/ L) 4mL, for other conditions with embodiment 1, its average grain diameter is 19.7 microns.
Elementary analysis (ICP)：Ti:4.55% (weight), Mg:21.97% (weight).
For the ethene slurry polymerization appreciation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
" slowly heating naturally, after being warmed to room temperature, heating maintains 50 DEG C to react 2 hours " in catalyst preparation process is changed 50 DEG C were warming up to for 10 minutes, heating maintains 50 DEG C to react 2 hours, and for other conditions with embodiment 1, its average grain diameter is 22.3 micro- Rice.
Elementary analysis (ICP)：Ti:4.05% (weight), Mg:18.47% (weight).
For the ethene slurry polymerization appreciation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 1
By the addition styrene methyl methacrylate diblock copolymer A in catalyst preparation process, (polystyrene contains 48%) toluene solution (10g/L) 2mL removes amount, and other conditions are with embodiment 1, and its average grain diameter is 67.7 microns, size distribution It is very wide, with the presence of multiple peaks.
Elementary analysis (ICP)：Ti:3.86% (weight), Mg:19.62% (weight).
For the ethene slurry polymerization appreciation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 2
30mL hexanes, 3.15mL dibutylmagnesium hexane solution (1M) and 1.0mL isooctanol are taken successively, are warming up to 50 DEG C of dimensions Stirring reaction half an hour is held, obtains clear solution, then adds Kraton FG1901 hexane solutions (10g/L) 1mL, cooling To -10 DEG C, sequentially add 0.36 milliliter of silicon tetrachloride and 0.35mL titanium tetrachlorides, after adding material, be rapidly heated in 10 minutes 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, every time The dosage of hexane is 50 milliliters, dry that brown solid mobility powder, its average grain diameter are 56.2 microns after the completion of washing.
Elementary analysis (ICP)：Ti:9.48% (weight), Mg:20.84% (weight).
For the ethene slurry polymerization appreciation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Table 1
It can be seen that from the experimental data of the embodiment of table 1 and comparative example and polyphenyl second used in the preparation process of catalyst Alkene block polymethylmethacrylablock block analog copolymer, obtained catalyst and the particle shape of polymer is good, size distribution Narrow, the bulk density (BD) of polymer resin is higher, catalyst high comprehensive performance.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair The restriction of embodiments of the present invention, for those of ordinary skill in the field, may be used also on the basis of the above description To make other changes in different forms, all embodiments can not be exhaustive here, it is every to belong to this hair Row of the obvious changes or variations that bright technical scheme is extended out still in protection scope of the present invention.

Claims (10)

1. a kind of catalytic component for olefinic polymerization, it includes component 1), reaction product 2), 3), 4) He 5), wherein group Point 1) it is at least one organo-magnesium compound；Component 2) it is at least one titanium-containing compound；Component 3) it is at least one hydroxyl Compound；Component 4) it is at least one chlorine-and-silicon-contained compound；And component 5) it is at least one additive, described additive Birdsed of the same feather flock together compound for polystyrene block polymethylmethacrylablock block.
2. catalytic component according to claim 1, it is characterised in that the organo-magnesium compound formula is (I) MgR1 nCl2-n, R in formula1For C2-C20Alkyl, preferably C2-C20Alkyl, 0 ＜ n≤2；The organo-magnesium compound is preferably selected from two At least one of dibutyl magnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and butyl magnesium chloride.
3. catalytic component according to claim 1 or 2, it is characterised in that the titanium-containing compound formula is (II) Ti (OR2)mCl4-mIt is shown, R in formula2For C2-C20Alkyl, 0≤m≤4；The titanium-containing compound is preferably tetravalent titanium compound, more excellent Elect at least one of titanium tetrachloride, tetraethyl titanate and butyl titanate as.
4. according to the catalytic component any one of claim 1-3, it is characterised in that the hydroxy-containing compounds formula For (III) HOR3, R in formula3For C2-C20Alkyl；The hydroxy-containing compounds are preferably selected from n-butanol, n-hexyl alcohol, isooctanol, benzene first At least one of alcohol and benzyl carbinol.
5. according to the catalytic component any one of claim 1-4, it is characterised in that the chlorine-and-silicon-contained compound is led to Formula is (IV) SiR4 pCl4-p, R in formula4For C2-C20Alkyl or C2-C20Alkoxy, 0≤p ＜ 4；The chlorine-and-silicon-contained compound is excellent Choosing is selected from trichlorophenyl silane, trichloromethyl silane, trichloroethyl silane, trichlorine octyl group silane, trichloromethoxy silane, trichlorine In Ethoxysilane, trichlorine butoxy silane, dichloro dimethoxysilane, dichlorodiethyl TMOS and silicon tetrachloride at least One kind, more preferably trichloromethyl silane, trichloroethyl silane, trichloromethoxy silane, tri-chloroethoxy base silane and four chlorinations At least one of silicon.
6. according to the catalytic component any one of claim 1-5, it is characterised in that the poly- first of polystyrene block Base methyl acrylate block compound of birdsing of the same feather flock together includes diblock and three block and its derivative, elects linear, have a side chain or star as The form of shape, the content of polystyrene preferably in described polystyrene block polymethylmethacrylablock block birdss of the same feather flock together compound For 5wt%-95wt%, more preferably 10wt%-90wt%.
7. a kind of preparation method for preparing the catalytic component any one of claim 1-6, comprises the following steps：
1) organo-magnesium compound is reacted with hydroxy-containing compounds, obtains clear solution；
2) additive is dispersed in C4-C20Alkane or C6-C20In aromatic solvent, solution is formed, then is obtained with step 1) transparent Solution mixes, and obtains mixed liquor；
3) chlorine-and-silicon-contained compound and titanium-containing compound are added in the mixed liquor that step 2) obtains successively, obtains catalyst group Point.
8. according to the method for claim 7, it is characterised in that in terms of every mole of organo-magnesium compound, titanium-containing compound is 0.01-10 moles, preferably 0.05-5 moles；Hydroxy-containing compounds are 0.1-20 moles, preferably 0.2-10 moles；It is chloride to contain Silicon compound is 0.05-50 moles, preferably 0.1-20 moles；Concentration of the additive in reaction system is 0.001-100g/ L, preferably 0.01-50g/L.
9. a kind of catalyst for olefinic polyreaction, it includes the reaction product of following components：
A) catalytic component any one of claim 1-6 or the preparation method according to claim 7 or 8 obtain Catalytic component；
B) at least one formula is AlR5 qCl3-qOrgano-aluminum compound, in formula, R5For identical or different C1-C8Alkyl, 0 ＜ q ≤3。
10. application of the catalyst described in claim 9 in olefinic polyreaction, the alkene is preferably alpha-olefin, more excellent Elect at least one of ethene, propylene, butylene and octene as.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426600A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Preparation method of solid catalyst for olefin polymerization

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372798A (en) * 2010-08-19 2012-03-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method thereof
CN102372801A (en) * 2010-08-19 2012-03-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method for catalyst component
CN102372802A (en) * 2010-08-19 2012-03-14 中国石油化工股份有限公司 Catalyst ingredient for olefin polymerization and preparation method thereof
CN104277148A (en) * 2013-07-01 2015-01-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102372798A (en) * 2010-08-19 2012-03-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method thereof
CN102372801A (en) * 2010-08-19 2012-03-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method for catalyst component
CN102372802A (en) * 2010-08-19 2012-03-14 中国石油化工股份有限公司 Catalyst ingredient for olefin polymerization and preparation method thereof
CN104277148A (en) * 2013-07-01 2015-01-14 中国石油化工股份有限公司 Catalyst component for olefin polymerization and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114426600A (en) * 2020-10-15 2022-05-03 中国石油化工股份有限公司 Preparation method of solid catalyst for olefin polymerization
CN114426600B (en) * 2020-10-15 2024-03-26 中国石油化工股份有限公司 Preparation method of solid catalyst for olefin polymerization

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