CN107840910A - Catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application - Google Patents
Catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application Download PDFInfo
- Publication number
- CN107840910A CN107840910A CN201610829563.0A CN201610829563A CN107840910A CN 107840910 A CN107840910 A CN 107840910A CN 201610829563 A CN201610829563 A CN 201610829563A CN 107840910 A CN107840910 A CN 107840910A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- catalytic component
- ether
- compound
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a kind of catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application, the preparation method of the catalytic component and comprised the following steps：(1) magnesium compound, oxygen-containing titanium compound and ether compound are contacted, reaction forms clear solution；(2) clear solution that step (1) obtains is contacted with halide reagent, reaction obtains suspension；(3) suspension obtained step (2) carries out maturation process, quiet heavy, washing, dry the catalytic component；Magnesium compound is Mg (OR1)mCl2‑mShown, oxygen-containing titanium compound is Ti (OR2)nCl4‑nIt is shown, ether compound R3OR4Shown in OH, halide reagent R5 aMXbIt is shown.The catalyst of the present invention not only keeps higher polymerization activity, and hydrogen response is good, and the bulk density of resulting polymers powder is higher, and the following fine powder content of 200 mesh is few in polymer.
Description
Technical field
The present invention relates to the catalyst field for olefinic polymerization, is used for ethylene polymerization more particularly, to one kind
Catalytic component and preparation method thereof, the catalyst for ethylene polymerization and its application.
Background technology
At present, the research work of the Mg-Ti systems Ziegler-Natta catalyst composition to match with ethene polymerization process
Quite deep, person skilled in art possesses sufficiently high polymerization activity, good polymer particles particle shape making catalyst
State, good hydrogen mediation copolymerization performance etc. have done many work.Production is continuously run and improves for meet commercial plant
Rate, it is desirable to which resulting polymers possess that good particle shape and distribution, fine powder content are few, and polymer bulk density improves.
To control the particle shape of catalyst, a kind of preparation method of Z-N catalyst is by magnesium compound or magnesium compound
Complex compound dissolving after separate out again, control certain formation condition, prepare spherical Ti-MgCl2Catalyst, such as patent text
Offer in CN1463991, the catalyst is by the way that magnesium compound to be dissolved in the solvent of organic epoxy compound thing and organic phosphorus compound
In system, mixed after forming homogeneous solution with the halide of titanium, in the presence of precipitation additive, separate out the solids containing magnesium and titanium.
Shortcoming is that the catalyst preparation process is cumbersome, and condition is harsh, and cost is of a relatively high, to adapt to the complicated rear place of environmental requirement needs
Manage process matched therewith.
American documentation literature US3901863, US4617360, US4109071 disclose the preparation method of Z-N catalyst, first
Liquid solution is first prepared by oxygen-containing organo-magnesium compound and oxygen-containing titanium compound, then the solution connects with chloride organo-aluminum compound
Touch reaction and form precipitation, method for preparing catalyst is simple, activity compared with it is high, accessory substance is few, be adapted to the production of ethene slurry polymerization processes
Polyethylene product.But the broad particle distribution of catalyst, generally multi-modal obtained by this method.
American documentation literature US4363746 discloses a kind of much higher catalysis of activity polymerization catalysts many than ever
Agent, the metal halide of magnesium such as magnesium dihalide is reacted with tetraalkoxy titanium, then the solution and a kind of organic metal be also
Former agent reaction, obtains a kind of solids, then again the solids and a kind of halide ion exchanging source, as titanium tetrachloride is anti-
Should, although catalyst activity prepared by this method is higher, fine powder content is more in the application for the catalyst.
The content of the invention
The purpose of the present invention is that fine powder content is more in the application for the catalyst of greater activity for preparing for prior art
The problem of, there is provided a kind of catalytic component and catalyst for ethylene polymerization, make gained catalyst that there is higher polymerization
The following fine powder content of the mesh of resulting polymers 200 significantly reduces under active, same polymerizing condition, and catalyst preparation process is simply easy
Row, preparation cost are cheap, environmentally friendly.
To achieve these goals, the present invention provides a kind of catalytic component for ethylene polymerization, the catalyst
The preparation method of component comprises the following steps：
(1) magnesium compound, oxygen-containing titanium compound and ether compound are contacted, reaction forms the transparent molten of magnesium titanium complex
Liquid；
(2) clear solution that step (1) obtains is contacted with halide reagent, reaction obtains suspension；
(3) suspension obtained step (2) carries out maturation process, quiet heavy, washing, dry the catalytic component；
The magnesium compound is formula (I) Mg (OR1)mCl2-mIt is shown, wherein, R1For C2~C20Saturation is undersaturated straight
Chain or branched hydrocarbyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon radical, 0≤m≤2；
The oxygen-containing titanium compound is formula (II) Ti (OR2)nCl4-nIt is shown, wherein, R2For C2~C20Saturation or unsaturation
Straight or branched alkyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon radical, 0 ＜ n≤4；
The ether compound is formula (III) R3OR4Shown in OH, wherein, R3And R4It is identical or different, it is each independently
C2~C20Saturation or undersaturated straight or branched alkyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon radical；
The halide reagent is formula (IV) R5 aMXbIt is shown, wherein, M is third and fourth, five major elements or transition metal
Element, X are halogen, R5For C2~C20Saturation or undersaturated straight or branched alkyl, or be C3~C20Saturation or unsaturation
Cyclic hydrocarbon radical, a=0,1 or 2, b=1,2,3 or 4.
According to catalytic component provided by the invention, it is preferable that in formula (I), R1For C2~C10Alkyl；The magnesium
Compound is more preferably selected from alkoxyl magnesium and/or magnesium chloride, further preferably selected from diethoxy magnesium, dipropoxy magnesium, two fourth oxygen
At least one of base magnesium, two octyloxy magnesium and magnesium dichloride.
According to catalytic component provided by the invention, it is preferable that in formula (II), R2For C2~C10Alkyl；It is described to contain
Oxygen titanium compound is more preferably titanate esters；Further preferably selected from butyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate, metatitanic acid
At least one of four isopropyl esters and tetra-tert titanate esters.
According to catalytic component provided by the invention, it is preferable that in formula (III), R3For C2~C10Alkyl or C6~C10
Aryl, R4For C2~C10Alkyl；The ether compound is more preferably selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether, propane diols
Positive propyl ether, propane diols isopropyl ether, propylene glycol n-butyl ether, glycol tertiary butyl ether, propane diols phenylate, ethylene glycol ethyl ether, ethylene glycol third
Ether, glycol isopropyl ether, butyl glycol ether, the tertiary butyl ether of ethylene glycol, at least one of ethylene glycol phenyl ether and ethylene glycol monohexylether.
According to catalytic component provided by the invention, it is preferable that in formula (IV), R5For C2~C10Alkyl；The halogen
Change reagent and be more preferably selected from ethyl aluminum dichloride, aluminium diethyl monochloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, dichloro isopropyl
At least one of base aluminium, a chlorine diisopropyl aluminium, silicon tetrachloride and titanium tetrachloride.
According to catalytic component provided by the invention, it is preferable that in terms of every mole of magnesium in component (1), the dosage of component (2)
For 0.1~20 mole, the dosage of component (3) is 0.1~10 mole, and the dosage of component (4) is 0.5~50 mole.
According to catalytic component provided by the invention, it is preferable that the reaction temperature of step (1) is 30~140 DEG C；Step
(2) reaction temperature is -20~100 DEG C, more preferably -20~60 DEG C.
The present invention also provides a kind of preparation method of the catalytic component, and the preparation method comprises the following steps：
(1) magnesium compound, oxygen-containing titanium compound and ether compound are contacted, reaction forms the transparent molten of magnesium titanium complex
Liquid；
(2) clear solution that step (1) obtains is contacted with halide reagent, reaction obtains suspension；
(3) suspension obtained step (2) carries out maturation process, quiet heavy, washing, dry the catalytic component.
According to preparation method provided by the invention, in step (1), magnesium compound, oxygen-containing titanium compound and ether compound
Contacted with each other at 30-140 DEG C, reaction forms the clear solution of magnesium titanium complex, and higher temperature is beneficial to form the cooperation of magnesium titanium
The clear solution of thing；Reaction is carried out under agitation, and the reaction time depends on the property and operating condition of reactant, during reaction
Between require be enough to obtain clear solution, required time is typically at 1 to 20 hour, preferably 4 to 10 hours.It can add as needed suitable
The inert diluent of amount, inert diluent can not chemically react with dissolved component, and hydro carbons may be selected in inert diluent,
At least one of hexane, hexamethylene, pentane, heptane, iso-butane, isopentane, isooctane and toluene are preferably selected from, contributes to magnesium
The viscosity that is scattered and reducing solution of compound solution.
According to preparation method provided by the invention, step (2) is alternatively referred to as settling step, the magnesium titanium that step (1) is obtained
The clear solution of complex contacts with halide reagent, and reaction forms precipitation, obtains the suspension of catalytic component；In this step
The alkoxy in the chlorination reaction or chlorination reduction reaction of magnesium titanium complex, that is, chlorine element substitution magnesium titanium complex is completed,
Simultaneously different halide reagents can also revert to the valence state of titanium compound compared with lower valency, so that catalyst active center's base
Group's Precipitation from solution.The way of contact of the clear solution and halide reagent of magnesium titanium complex can use any of
Suitable method is carried out, can by the way of the clear solution of magnesium titanium complex is progressively added drop-wise in halide reagent solution,
Can also be by the way of halide reagent solution be progressively added drop-wise in the clear solution of magnesium titanium complex.Rate of addition generally selects
Select not cause the hot-spot of reaction to be defined, the steady progress in favor of reaction is generally stirred during dropwise addition.
In the settling step, reaction temperature can be controlled at -20-100 DEG C, preferably at -20~60 DEG C.The reaction time of settling step should
This is long enough to obtain complete precipitation, and the reaction time can be 1 minute to 10 hours, preferably 0.5~5 hour.
After settling step, gained reaction product is reacted into a period of time progress maturation process at a certain temperature, also can
Favorable influence is compared in the particle shape generation to catalyst to a certain extent, and it can make the size distribution narrow of catalyst, together
When can also improve the intensity of catalyst particle, show so as to reduce particle fragmentation of the catalyst during catalyzed ethylene polymerization
As.The temperature of the temperature of maturation process generally greater than or equal to precipitation reaction, the time of maturation process can be controlled 0.5~15
Hour, preferably 1~5 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
At least one of alkane, toluene and hexamethylene, preferably hexane.After wash, the suspension of catalytic component can pass through
It is dried under heating state with nitrogen purging, to obtain the powder of catalytic component.
The present invention also provides a kind of catalyst for ethylene polymerization, and it includes following components：
(a) catalytic component for being used for vinyl polymerization；
(b) formula is AlRnX3-nOrgano-aluminum compound, R is hydrogen or C in formula1~C20Alkyl, X is halogen, and n is 1 ＜
The integer of n≤3.
Component (b) is preferably alkyl aluminum, further preferably selected from AlEt3、Al(iso-Bu)3、Al(n-C6H13)3、Al(n-
C8H17)3And AlEt2At least one of Cl.
The present invention also provides a kind of application for the catalyst of ethylene polymerization in vinyl polymerization.
Catalyst of the present invention is applied to the homopolymerization of various ethene or the combined polymerization of ethene and other alpha-olefins, its
The one kind of middle alpha-olefin in propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 4- methylpentenes -1.
The beneficial effects of the present invention are：The catalyst of the present invention not only keeps higher polymerization activity, and hydrogen response is good,
And the bulk density of resulting polymers powder is higher, the following fine powder content of 200 mesh is few in ethene polymers；Catalyst preparation work
Skill is simple, cost is low, and accessory substance is few, environmentally friendly.
Embodiment
The preferred embodiment of the present invention will be more fully described by embodiment below.Although this is described in embodiment
The preferred embodiment of invention, however, it is to be appreciated that may be realized in various forms the reality of the invention without that should be illustrated here
The mode of applying is limited.
Method of testing：
Melt index：Determined according to ASTM D1238 standard methods.
Polymer sieves：Using Beijing original creation Science and Technology Ltd.'s standard inspection sieve (200 × 50GB6003.1-1997 of Φ)
Sieved.
Embodiment 1
(1) weigh magnesium dichloride 2.0g add band stir reactor in, it is possible to additionally incorporate 7.2ml butyl titanates,
2.76ml ethylene glycol monobutyl ethers and 60ml toluene, 100 DEG C of stirring reactions are warming up to, until forming clear solution；
(2) temperature for the clear solution for obtaining step (1) is down to 35 DEG C, is slowly dripped into reactor with constant pressure addition pipe
Add 50 milliliters of 1.8M Dichloroethyl aluminum solutions, after being added dropwise to complete, stirring reaction 1 hour at 45 DEG C, then heat to 65 DEG C
Stirring reaction 4 hours；
(3) press filtration removes supernatant after the reaction product quiescent settling for obtaining step (2), is washed with the hexane of clean dry
Wash four times, the dosage of each hexane is 80 milliliters, and reaction product is warming up into 68 DEG C after washing, is purged with high pure nitrogen dry
The dry powder for obtaining mobility ingredient of solid catalyst.
Evaluating catalyst：The catalytic component of 1L hexanes, 1mmol triethyl aluminums and 10mg is added to the stirring of 2L stainless steels
In kettle, temperature is then brought up to 90 DEG C, the disposable hydrogen for adding 0.4MPa, then maintained the gross pressure of system with ethene
Polymerisation is carried out in 1.0MPa, after reacting 2 hours, stops adding ethene, cooling, pressure release, polyethylene powder is weighed,
The activity of catalyst is calculated, tests the bulk density of polyethylene powder and the melt index under 2.16Kg loads, experimental result
As shown in table 1.
Embodiment 2
Method according to embodiment 1 prepares catalytic component, and difference is, in step (2), two chloroethenes will be added dropwise
Temperature of reaction kettle during base aluminum solutions maintains 45 DEG C.
With embodiment 1, polymerization results are shown in Table 1 for the evaluation of catalyst.
Embodiment 3
Method according to embodiment 1 prepares catalytic component, and difference is, in step (1), 2.76 milliliters of second two
Alcohol monobutyl ether is changed to 3.2 milliliters of propylene glycol monobutyl ethers.
With embodiment 1, polymerization results are shown in Table 1 for the evaluation of catalyst.
Embodiment 4
Method according to embodiment 1 prepares catalytic component, and difference is, in step (1), by 2.76 milliliters of second
Glycol monobutyl ether is changed to 2.5 milliliters of glycol propyl ethers；In step (2), by reaction kettle temperature during dropwise addition Dichloroethyl aluminum solutions
Degree maintains normal temperature.
With embodiment 1, polymerization results are shown in Table 1 for the evaluation of catalyst.
Embodiment 5
Method according to embodiment 1 prepares catalytic component, and difference is, in step (2), by 50 milliliters of 1.8M
Dichloroethyl aluminum solutions be changed to 25ml TiCl4, while temperature of reaction kettle when being added dropwise is maintained -5 DEG C.
With embodiment 1, polymerization results are shown in Table 1 for the evaluation of catalyst.
Comparative example 1
(1) 114 grams of diethoxy magnesium are weighed, add 340 milliliters of butyl titanates, in 140 DEG C of stirring and dissolvings until being formed
Clear solution, the temperature of gained clear solution is down to room temperature, it is standby to add 400 milliliters of dry hexane dilutions；
(2) clear solution that 9 milliliters of steps (1) obtain is weighed, 15 milliliters of 3M ethyl aluminum dichlorides are slowly added dropwise with buret
Hexane solution, after being added dropwise to complete, stirring reaction 4 hours at 60 DEG C, maturation process obtains the suspension of catalytic component；
(3) suspension temperature of catalytic component is down to room temperature, stood, sedimentation, washed three times with hexane, each hexane
Dosage be 50 milliliters, after the completion of washing, at 65 DEG C of bath temperature, with high pure nitrogen purge drying, obtain brown solid mobility powder
End.
With embodiment 1, polymerization results are shown in Table 1 for the evaluation of catalyst.
Comparative example 2
(1) 114 grams of diethoxy magnesium are weighed, add 340 milliliters of butyl titanates, in 140 DEG C of stirring and dissolvings until being formed
Clear solution, the temperature of gained clear solution is down to room temperature, it is standby to add 400 milliliters of dry hexane dilutions；
(2) clear solution for taking 9 milliliters of steps (1) to obtain, mix and place 12 small with 0.5 milliliter of ethyl benzoate
When.Its temperature is maintained 25 DEG C, the hexane solution of 15 milliliters of 3M ethyl aluminum dichlorides is slowly added dropwise with buret, is added dropwise to complete
Afterwards, stirring reaction 4 hours at 60 DEG C, the suspension of catalytic component is obtained after maturation process；
(3) suspension temperature of catalytic component is down to room temperature, stood, sedimentation, washed three times with hexane, each hexane
Dosage be 50 milliliters, after the completion of washing, at 65 DEG C of bath temperature, with high pure nitrogen purge drying, obtain brown solid mobility powder
End.
With embodiment 1, polymerization results are shown in Table 1 for the evaluation of catalyst.
Table 1
(wherein：BD --- bulk density)
Catalyst activity of the present invention is can be seen that from the experimental data of the embodiment of table 1 and comparative example and keeps higher level, together
When the obtained melt index of polymer significantly increase, illustrate that catalyst hydrogen response is good；In addition, resulting polymers powder of the present invention
The bulk density of material is higher, and the content of the following fine powder of 200 mesh is few in polymer, illustrates that carrying out ethene using catalyst of the present invention gathers
Close, resulting polymers fine powder content is obviously improved.
It is described above various embodiments of the present invention, described above is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
1. a kind of catalytic component for ethylene polymerization, it is characterised in that the preparation method of the catalytic component includes
Following steps：
(1) magnesium compound, oxygen-containing titanium compound and ether compound are contacted, reaction forms the clear solution of magnesium titanium complex；
(2) clear solution that step (1) obtains is contacted with halide reagent, reaction obtains suspension；
(3) suspension obtained step (2) carries out maturation process, quiet heavy, washing, dry the catalytic component；
The magnesium compound is formula (I) Mg (OR1)mCl2-mIt is shown, wherein, R1For C2~C20Saturation or undersaturated straight chain or
Branched hydrocarbyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon radical, 0≤m≤2；
The oxygen-containing titanium compound is formula (II) Ti (OR2)nCl4-nIt is shown, wherein, R2For C2~C20Saturation is undersaturated straight
Chain or branched hydrocarbyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon radical, 0 ＜ n≤4；
The ether compound is formula (III) R3OR4Shown in OH, wherein, R3And R4It is identical or different, it is each independently C2~
C20Saturation or undersaturated straight or branched alkyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon radical；
The halide reagent is formula (IV) R5 aMXbIt is shown, wherein, M is third and fourth, five major elements or transition metal,
X is halogen, R5For C2~C20Saturation or undersaturated straight or branched alkyl, or be C3~C20Saturation or undersaturated cyclic hydrocarbon
Base, a=0,1 or 2, b=1,2,3 or 4.
2. catalytic component according to claim 1, wherein, in formula (I), R1For C2~C10Alkyl；The magnesium chemical combination
Thing is preferably selected from alkoxyl magnesium and/or magnesium chloride, is more preferably selected from diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, two pungent
At least one of epoxide magnesium and magnesium dichloride.
3. catalytic component according to claim 1, wherein, in formula (II), R2For C2~C10Alkyl；It is described oxygen-containing
Titanium compound is preferably titanate esters；It is more preferably selected from butyl titanate, tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate
At least one of with tetra-tert titanate esters.
4. catalytic component according to claim 1, wherein, in formula (III), R3For C2~C10Alkyl or C6~C10's
Aryl, R4For C2~C10Alkyl；The ether compound is preferably selected from propylene glycol monomethyl ether, propylene-glycol ethyl ether, propane diols positive third
Ether, propane diols isopropyl ether, propylene glycol n-butyl ether, glycol tertiary butyl ether, propane diols phenylate, ethylene glycol ethyl ether, glycol propyl ether, second
Glycol isopropyl ether, butyl glycol ether, the tertiary butyl ether of ethylene glycol, at least one of ethylene glycol phenyl ether and ethylene glycol monohexylether.
5. catalytic component according to claim 1, wherein, in formula (IV), R5For C2~C10Alkyl；The halogenation
Reagent be preferably selected from ethyl aluminum dichloride, aluminium diethyl monochloride, dichloro aluminium isobutyl, a chloro-di-isobutyl aluminum, two chloro isopropyl aluminium,
At least one of one chlorine diisopropyl aluminium, silicon tetrachloride and titanium tetrachloride.
6. catalytic component according to claim 1, wherein, in terms of every mole of magnesium in component (1), the dosage of component (2)
For 0.1~20 mole, the dosage of component (3) is 0.1~10 mole, and the dosage of component (4) is 0.5~50 mole.
7. catalytic component according to claim 1, wherein, the reaction temperature of step (1) is 30~140 DEG C；Step (2)
Reaction temperature be -20~100 DEG C, be preferably -20~60 DEG C.
A kind of 8. preparation method of catalytic component as any one of claim 1-7, it is characterised in that the preparation side
Method comprises the following steps：
(1) magnesium compound, oxygen-containing titanium compound and ether compound are contacted, reaction forms the clear solution of magnesium titanium complex；
(2) clear solution that step (1) obtains is contacted with halide reagent, reaction obtains suspension；
(3) suspension obtained step (2) carries out maturation process, quiet heavy, washing, dry the catalytic component.
9. a kind of catalyst for ethylene polymerization, it includes following components：
(a) catalytic component for vinyl polymerization as described in claim 1-7；
(b) formula is AlRnX3-nOrgano-aluminum compound, R is hydrogen or C in formula1~C20Alkyl, X is halogen, and n is 1 ＜ n≤3
Integer.
10. it is used for application of the catalyst of ethylene polymerization in vinyl polymerization as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610829563.0A CN107840910B (en) | 2016-09-18 | 2016-09-18 | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610829563.0A CN107840910B (en) | 2016-09-18 | 2016-09-18 | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107840910A true CN107840910A (en) | 2018-03-27 |
| CN107840910B CN107840910B (en) | 2020-06-09 |
Family
ID=61656874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610829563.0A Active CN107840910B (en) | 2016-09-18 | 2016-09-18 | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107840910B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759685A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof |
| CN116023541A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1862480A1 (en) * | 2006-05-31 | 2007-12-05 | Borealis Technology Oy | Process for preparing an olefin polymerisation catalyst component with improved high temperature activity |
| CN101857650A (en) * | 2010-06-02 | 2010-10-13 | 金发科技股份有限公司 | Preparation method of polyolefin catalyst spherical carrier |
| CN102558404A (en) * | 2011-12-15 | 2012-07-11 | 中国石油天然气股份有限公司 | Polyol ether polyolefin catalyst and preparation and application thereof |
| CN104418961A (en) * | 2013-09-03 | 2015-03-18 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction as well as preparation method of catalyst component and catalyst |
-
2016
- 2016-09-18 CN CN201610829563.0A patent/CN107840910B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1862480A1 (en) * | 2006-05-31 | 2007-12-05 | Borealis Technology Oy | Process for preparing an olefin polymerisation catalyst component with improved high temperature activity |
| CN101857650A (en) * | 2010-06-02 | 2010-10-13 | 金发科技股份有限公司 | Preparation method of polyolefin catalyst spherical carrier |
| CN102558404A (en) * | 2011-12-15 | 2012-07-11 | 中国石油天然气股份有限公司 | Polyol ether polyolefin catalyst and preparation and application thereof |
| CN104418961A (en) * | 2013-09-03 | 2015-03-18 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction as well as preparation method of catalyst component and catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759685A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof |
| CN112759685B (en) * | 2019-11-01 | 2023-02-28 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction, preparation method thereof, catalyst and application thereof |
| CN116023541A (en) * | 2021-10-27 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107840910B (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100509871C (en) | Method for the preparation of olefin polymerisation catalysts | |
| CN100471884C (en) | Method for the preparation of olefin polymerisation catalyst support and an olefin polymerisation catalyst | |
| CN1701081A (en) | Process for preparing an olefin polymerisation catalyst component with improved high temperature activity | |
| CN1518565A (en) | Preparation of olefin polymerisation catalyst component | |
| CN104903359B (en) | Generate the method and its purposes in olefin polymerization of the controlled polymerization catalyst of catalyst property | |
| CN1413222A (en) | Mixed ziegler/metallocene catalysts for production of bimodal polyolefins | |
| CN102039184A (en) | Supported non-metallocene catalyst as well as preparation method and application thereof | |
| CN102911299A (en) | High-activity olefin polymerization catalyst, preparation method and application | |
| CN101942049A (en) | Catalyst component for ethylene polymerization, preparation method and application | |
| CN107840910A (en) | Catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application | |
| CN102358761B (en) | Olefin polymerization catalyst and preparation method thereof | |
| CN102039187A (en) | Load type non-metallocene catalyst as well as preparation method and application thereof | |
| CN102875706A (en) | Catalyst component of ethylene polymerization reaction, and catalyst thereof | |
| CN102039191A (en) | Load type non-metallocene catalyst, preparation method and application thereof | |
| CN102059152A (en) | Loaded non-metallocene catalyst and preparation method and application thereof | |
| JP2006516954A (en) | Transition metal catalysts for (co) polymerization of olefinic monomers | |
| CN102059153A (en) | Loaded non-metallocene catalyst and preparation method and application thereof | |
| CN102059148B (en) | Loaded non-metallocene catalyst and preparation method and application thereof | |
| CN104418961B (en) | Catalyst component for ethylene polymerization reaction as well as catalyst and preparation method of catalyst component | |
| CN105085735B (en) | A kind of preparation method of catalytic component for olefinic polymerization | |
| CN107840911A (en) | Catalytic component for ethylene polymerization and preparation method thereof, catalyst and its application | |
| CN102399315B (en) | Supported non-metallocene catalyst and preparation method and use thereof | |
| CN104418960B (en) | A kind of catalytic component and catalyst and its preparation method for ethylene polymerization | |
| CN102039188A (en) | Supported non-metallocene catalyst, its preparation method and uses | |
| CN102059150B (en) | Loaded non-metallocene catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |