CN107880187A - 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 PDFInfo
- Publication number
- CN107880187A CN107880187A CN201610875804.5A CN201610875804A CN107880187A CN 107880187 A CN107880187 A CN 107880187A CN 201610875804 A CN201610875804 A CN 201610875804A CN 107880187 A CN107880187 A CN 107880187A
- Authority
- CN
- China
- Prior art keywords
- compound
- catalyst
- magnesium
- phosphorus
- 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
- 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
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 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 titanium-containing compound, at least one hydroxyl class compound, at least one chloride phosphorus-containing compound and at least one additive, is birdsed of the same feather flock together compound wherein described additive is polybutadiene 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
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 hydroxyl class compound；Component 4) it is at least one chloride phosphorus-containing compound；And component 5)
For at least one additive, described additive is that polybutadiene block polymethylmethacrylablock block is birdsed of the same feather flock together compound (PB-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)mCl4-mIt is shown, formula
Middle R2For C2-C20Alkyl, 0≤m≤4.
According to the preferred embodiment of the present invention, described hydroxyl class compound formula is (III) HOR3, R in formula3For
C2-C20Alkyl.
According to the preferred embodiment of the present invention, the chloride phosphorus-containing compound is PCl5Or by formula (IV)
OpPR4 qCl3-qShown compound, R in formula4It is C2-C20Alkyl or C2-C20Alkoxy, 0≤q ＜ 3, p=0 or 1.
According to the preferred embodiment of the present invention, described polybutadiene 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 polybutadiene block polymethylmethacrylablock block
The matter content of polybutadiene in compound of birdsing of the same feather flock together is 3wt%-97wt%, preferably 10wt%-95wt%.
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.Preferably, it is described
Organo-magnesium compound is selected from dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and butyl magnesium chloride
At least one of.
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 or butyl titanate, preferably titanium tetrachloride.
According to the preferred embodiment of the present invention, described hydroxyl class compound is fatty alcohol or aromatic alcohol, is preferably
At least one of n-butanol, n-hexyl alcohol, isooctanol, phenmethylol and benzyl carbinol.
According to the preferred embodiment of the present invention, the chloride phosphorus-containing compound be selected from dichloromethyl phosphorus, Dichloroethyl phosphorus,
Two chlorobutyl phosphorus, phosphorus trichloride, phosphorus pentachloride, POCl3, dichloro methyl orthophosphoric acid, dichloro etherophosphoric acid and dichloro butylphosphoric acid ester
At least one of, it is preferably selected from least one of phosphorus trichloride, phosphorus pentachloride and POCl3.
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 and hydroxyl class compound are reacted, 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) chloride phosphorus-containing compound and titanium-containing compound are added in the mixed liquor that step 2) obtains successively, obtains catalyst
Component.
Preferably, in the preparation process of described 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；Hydroxyl class compound is 0.1-20 moles,
Preferably 0.2-10 moles；Chloride phosphorus-containing compound is 0.1-50 moles, preferably 0.5-20 moles；Additive is in reaction system
In concentration be 0.001-100g/L, preferably 0.01-50g/L.
In the step 1), the reaction temperature of organo-magnesium compound and hydroxyl class material is typically chosen in of a relatively high
At a temperature of carry out advantageously, preferably below the boiling temperature of reactant, temperature is normally no higher than 90 DEG C, is generally not more than 70
℃.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 points
Clock was to 1 hour.After organo-magnesium compound and hydroxyl class substance reaction, the solution of formation can mix with inert diluent to be made
With inert diluent is generally selected from alkanes, such as iso-butane, pentane, hexane, heptane or hexamethylene and its mixture, typically
Hexane or heptane are proper atent solvents.
In the step 2), additive is dispersed in C4-C20Alkane or C6-C20In aromatic solvent, be preferably dispersed in hexane,
In heptane or toluene and its admixture solvent, solution is formed, then the clear solution obtained with step 1) is sufficiently mixed, and is mixed
Liquid.Different with property according to the species of additive, its solution allocation concentration is controlled at 0.1-100 g/l, preferably 1-50 g/l,
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 will typically be less than the boiling point of system, for convenience, be typically chosen between 0-90 DEG C, preferably between 10-50 DEG C.
Both incorporation times are typically chosen 0.5 minute to 5 hours, preferably 10 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 chloride phosphorus-containing 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) at least one formula is AlR " '3Organo-aluminum compound, R " ' is C that is identical or differing in formula1-C8Alkane
Base, wherein one or two alkyl can be substituted by chlorine.
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 AlEt2One or more in 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, the pattern of catalyst and polymer：ESEM (SEM).
4th, 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
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 polybutadiene block polymethyl methacrylate copolymer (poly- fourth
Diene content 33wt%) hexane solution (10g/L) 2mL, be cooled to -50 DEG C, sequentially add 0.6 milliliter phosphorus trichloride 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 hexane, and the dosage of each hexane is 50 milliliters, after the completion of washing, dries
Brown solid mobility powder is obtained, its average grain diameter is 26.8 microns.
Elementary analysis (ICP)：Ti:8.33% (weight), Mg:16.10% (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
By the addition polybutadiene block polymethyl methacrylate copolymer in catalyst preparation process, (polybutadiene contains
Measure 33wt%) hexane solution (10g/L) 2mL, it is changed to add polybutadiene block polymethyl methacrylate copolymer (polybutadiene
Alkene content 33wt%) hexane solution (10g/L) 4mL, while 0.6 milliliter of phosphorus trichloride is changed to 0.6 milliliter of POCl3,
For other conditions with embodiment 1, the average grain diameter of catalytic component is 15.3 microns.
Elementary analysis (ICP)：Ti:8.98% (weight), Mg:16.21% (weight).
For the ethene slurry polymerization appreciation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
1.0mL isooctanol in catalyst preparation process is changed to 3.0mL isooctanol, will be rapidly heated in 10 minutes to 50
DEG C, it is changed to nature and is to slowly warm up to room temperature, is then heated to 50 DEG C, other conditions are the same as embodiment 1, the average grain of catalytic component
Footpath is 20.4 microns.
Elementary analysis (ICP)：Ti:10.51% (weight), Mg:17.29% (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 polybutadiene block polymethyl methacrylate copolymer in catalyst preparation process, (polybutadiene contains
Amount 33wt%) hexane solution (10g/L) removes, and other conditions are with embodiment 1, and its average grain diameter is 64.76 microns, particle diameter distribution
It is wider multi-modal.
Elementary analysis (ICP)：Ti:10.07% (weight), Mg:13.16% (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) 3mL, cooling
To -50 DEG C, sequentially add 0.6 milliliter of phosphorus trichloride 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 17.6 microns after the completion of washing.
Elementary analysis (ICP)：Ti:9.86% (weight), Mg:12.69% (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 polybutadiene used in the preparation process of catalyst
Alkene block polymethylmethacrylablock block is birdsed of the same feather flock together compound additive, and obtained catalyst and the particle shape of polymer is good, is gathered
The bulk density (BD) of resin is higher, and melt index is high under equal polymerizing condition, illustrates that catalyst has well
Hydrogen regulation performance.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 chloride phosphorus-containing compound；And component 5) it is at least one additive, described additive
Birdsed of the same feather flock together compound for polybutadiene 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 hydroxyl class compound is led to
Formula is (III) HOR3, R in formula3For C2-C20Alkyl；The hydroxyl class compound be preferably selected from n-butanol, n-hexyl alcohol, isooctanol,
At least one of phenmethylol and benzyl carbinol.
5. according to the catalytic component any one of claim 1-4, it is characterised in that the chloride phosphorus-containing compound is
PCl5Or by formula (IV) OpPR4 qCl3-qShown compound, R in formula4It is C2-C20Alkyl or C2-C20Alkoxy, 0≤q
＜ 3, p=0 or 1；The chloride phosphorus-containing compound is preferably selected from dichloromethyl phosphorus, Dichloroethyl phosphorus, two chlorobutyl phosphorus, tri-chlorination
At least one of phosphorus, phosphorus pentachloride, POCl3, dichloro methyl orthophosphoric acid, dichloro etherophosphoric acid and dichloro butylphosphoric acid ester, more preferably
For at least one of phosphorus trichloride, phosphorus pentachloride and POCl3.
6. catalytic component according to claim 1 or 5, it is characterised in that the polybutadiene block polymethyl
Sour methyl esters block compound of birdsing of the same feather flock together includes diblock and three block and its derivative, preferably linear, having side chain or star-shaped
Form, preferably the content of polybutadiene is in described polybutadiene block polymethylmethacrylablock block birdss of the same feather flock together compound
3wt%-97wt%, preferably 10wt%-95wt%.
7. a kind of method for preparing the catalytic component described in claim any one of 1-6, comprises the following steps：
1) organo-magnesium compound and hydroxyl class compound are reacted, 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) chloride phosphorus-containing 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；Hydroxyl class compound is 0.1-20 moles, preferably 0.2-10 moles；It is chloride
Phosphorus-containing compound is 0.1-50 moles, preferably 0.5-20 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) catalysis that catalytic component any one of claim 1-6 or the method according to claim 7 or 8 obtain
Agent component；
B) at least one formula is AlR " '3Organo-aluminum compound, R " ' is C that is identical or differing in formula1-C8Alkyl, its
One or both of alkyl can be substituted by chlorine.
10. application of the catalyst described in claim 9 in olefinic polyreaction, the catalyst described in claim 9 is in alkene
Application in polymerized hydrocarbon reaction, the alkene is preferably alpha-olefin, more preferably in ethene, propylene, butylene and octene at least
It is a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610875804.5A CN107880187B (en) | 2016-09-30 | 2016-09-30 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610875804.5A CN107880187B (en) | 2016-09-30 | 2016-09-30 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107880187A true CN107880187A (en) | 2018-04-06 |
| CN107880187B CN107880187B (en) | 2020-12-18 |
Family
ID=61770124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610875804.5A Active CN107880187B (en) | 2016-09-30 | 2016-09-30 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107880187B (en) |
Citations (3)
| 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 |
| CN102453132A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method thereof |
| CN104277156A (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 |
-
2016
- 2016-09-30 CN CN201610875804.5A patent/CN107880187B/en active Active
Patent Citations (3)
| 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 |
| CN102453132A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, and preparation method thereof |
| CN104277156A (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107880187B (en) | 2020-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453132B (en) | Catalyst component for olefin polymerization, and preparation method thereof | |
| CN107880175A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880187A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880180A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880182A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880170A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN107880189A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN107880184A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880171A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880179A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN104277156B (en) | For the catalyst component of olefinic polymerization, its preparation method and application | |
| CN107880174A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN104277148B (en) | For catalyst component, its preparation method and the application of olefinic polymerization | |
| CN104277146B (en) | Catalyst component, its preparation method and application for olefinic polymerization | |
| CN107880195A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880194A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880177A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN104277149B (en) | For the catalyst component of olefinic polymerization, its preparation method and application | |
| CN107880166A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN107880173A (en) | Catalytic component for olefinic polymerization and preparation method thereof and catalyst | |
| CN107880162A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN107880185A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN104277152B (en) | For the catalyst component of olefinic polymerization, its preparation method and application | |
| CN107880178A (en) | Catalytic component and its preparation and application for olefinic polymerization | |
| CN104277150B (en) | For catalyst component, its preparation method and the application of olefinic polymerization |
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 |