CN107880195A - 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
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- CN107880195A CN107880195A CN201610875802.6A CN201610875802A CN107880195A CN 107880195 A CN107880195 A CN 107880195A CN 201610875802 A CN201610875802 A CN 201610875802A CN 107880195 A CN107880195 A CN 107880195A
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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 acyl chloride 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) US3787384,
Disclosed in US4148754, US4173547, US4301029, US4508843, US4921920 and US5124296 using organic
Metal magnesium compound, chlorinating agent and transition metal titanium compound etc. prepare a variety of different types of catalyst, in these patents
During preparing catalyst, the problem of unmanageable forming step be present, and then have influence on the form of catalyst granules.Closely
The research of phase is found, in the dispersion that catalyst precarsor includes magnesium titanium compound, adds some things similar to emulsifying agent
Matter, it is allowed to form emulsion, then reaction precipitation goes out catalyst granules again, the particle shape of gained catalyst can be improved, in Europe
Disclose using PFPE, disclosed in Chinese patent CN1537118 using PFO in the patent EP0258089 of continent,
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
System, 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 acyl chloride compound；And component 5) be
At least one additive, described additive are 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, described acyl chloride compound formula is R in formula shown in (IV) RCOCl
It is C2-C20Alkyl.
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 mass content of polybutadiene in compound of birdsing of the same feather flock together is 3wt%-97wt%, more 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, more 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 acyl chloride compound is selected from formyl chloride, chloroacetic chloride, propionyl chloride, fourth
At least one of acyl chlorides, chlorobenzoyl chloride, phenyllacetyl chloride, phenylpropyl alcohol acyl chlorides and benzene butyl chloride, preferably formyl chloride, chloroacetic chloride, benzene first
At least one of acyl chlorides and phenyllacetyl chloride.
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, formed solution, then with acyl chloride compound
The clear solution mixing obtained with step 1), obtains mixed liquor；
3) in the mixed liquor for obtaining titanium-containing compound addition step 2), catalytic component is obtained.
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；Acyl chloride compound is 0.001-20 moles, preferably 0.01-10 moles；Additive is in reactant
Concentration in system is 0.001-100g/L, preferably 0.01-50g/L.
In the step 1), the reaction temperature of magnesium compound and hydroxyl class 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 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 acyl chloride compound and step 1) fills
Divide mixing, obtain mixed liquor.It is different according to the species of additive and property, the control of its solution allocation concentration 0.1-100 grams/
Rising, 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,
It is preferred that 0.01-50 g/l.Mixing temperature typically will be less than system boiling point, 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 DEG C -30 DEG C, preferably between -70 DEG C -0 DEG C, be then slowly added to titanium-containing compound,
Being sufficiently mixed in favor of various materials is generally sufficiently stirred during charging, charging rate generally selects bright not cause
Substantially heating is defined for aobvious reaction or system.After being sufficiently mixed, any of suitable method can be used to be heated up, it is such as slow
Slowly, progressively, rapidly or temperature programming, different temperature-rising methods can obtain the totally different catalyst of performance characteristics, in temperature-rise period
In, system can be changed into muddiness by clarification, separate out precipitation, in the precipitation reaction step, the reaction time of settling step should
It is long enough to obtain complete precipitation, the reaction time can last 1 minute to 10 hours, preferably -5 hours 3 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, -50 DEG C are cooled to, sequentially adds 0.4mL chlorobenzoyl chlorides and 0.35mL tetra-
Titanium chloride, after maintaining low-temp reaction half an hour, slowly heating naturally, after being warmed to room temperature, heating maintains 50 DEG C to react 2 hours.Will
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, washing
After the completion of, it is dry that brown solid mobility powder, its average grain diameter are 26.7 μm.
Elementary analysis (ICP)：Ti:8.14% (weight), Mg:14.75% (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 0.35mL titanium tetrachlorides in catalyst preparation process, be changed to 1mL titanium tetrachlorides, other conditions with embodiment 1,
The average grain diameter of catalytic component is 32.9 μm.
Elementary analysis (ICP)：Ti:12.07% (weight), Mg:20.14% (weight).
For the ethene slurry polymerization appreciation condition of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
0.4mL chlorobenzoyl chlorides in catalyst preparation process are changed to 0.4mL chloroacetic chlorides, other conditions are the same as embodiment 1, catalysis
The average grain diameter of agent component is 22.3 μm.
Elementary analysis (ICP)：Ti:9.26% (weight), Mg:15.95% (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 56.2 μm with embodiment 1, its average grain diameter, and particle diameter distribution is
Wider multi-modal.
Elementary analysis (ICP)：Ti:11.15% (weight), Mg:14.32% (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, Kraton FG1901 hexane solutions (10g/L) 3mL is added, is cooled to -50
DEG C, 0.2mL chlorobenzoyl chlorides and 0.35mL titanium tetrachlorides are then sequentially added, after maintaining low-temp reaction half an hour, is slowly risen naturally
Temperature, after being warmed to room temperature, heating maintains 50 DEG C to react 2 hours.Catalyst suspension temperature is down to room temperature, stood, sedimentation, with oneself
Alkane washs three times, and the dosage of each hexane is 50 milliliters, and after the completion of washing, dry brown solid mobility powder, it is average
Particle diameter is 12.4 μm.
Elementary analysis (ICP)：Ti:10.82% (weight), Mg:15.26% (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, obtained catalyst and polymer except particle shape
Good, narrow particle size distribution, the bulk density (BD) of polymer resin is higher, and the hydrogen response of catalyst is more preferable, and catalyst is comprehensive
Function admirable is closed, is easy to develop the resin new product of unique properties.
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 acyl chloride compound；And component 5) it is at least one additive, described additive is
Polybutadiene block polymethylmethacrylablock block is birdsed of the same feather flock together compound.
2. catalytic component according to claim 1, it is characterised in that the organo-magnesium compound 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 acyl chloride compound formula
For (IV) RCOCl, R is C in formula2-C20Alkyl；The acyl chloride compound is preferably selected from formyl chloride, chloroacetic chloride, propionyl chloride, fourth
At least one of acyl chlorides, chlorobenzoyl chloride, phenyllacetyl chloride, phenylpropyl alcohol acyl chlorides and benzene butyl chloride, more preferably formyl chloride, chloroacetic chloride, benzene
At least one of formyl chloride and phenyllacetyl chloride.
6. according to the catalytic component any one of claim 1-5, it is characterised in that the poly- first of polybutadiene block
Base methyl acrylate block compound of birdsing of the same feather flock together includes diblock and three block and its derivative, it is preferably linear, have side chain or
Star-shaped form, polybutadiene contains preferably in described polybutadiene block polymethylmethacrylablock block birdss of the same feather flock together compound
Measure as 3wt%-97wt%, preferably 10wt%-90wt%.
7. a kind of method for preparing the catalytic component any one of claim 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, formed solution, then with acyl chloride compound and step
The rapid clear solution mixing 1) obtained, obtains mixed liquor；
3) in the mixed liquor for obtaining titanium-containing compound addition step 2), catalytic component is obtained.
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；Acyl chlorides
Class compound is 0.001-20 moles, preferably 0.01-10 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 alkene is preferably alpha-olefin, more excellent
Elect at least one of ethene, propylene, butylene and octene as.
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| US3196137A (en) * | 1961-06-23 | 1965-07-20 | Firestone Tire & Rubber Co | Polymerization catalysts and process |
| CN102372803A (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 |
| CN102453171A (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 |
| CN105566524A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction, and catalyst thereof |
| CN105566523A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene homopolymerization or copolymerization reaction, and catalyst thereof |
-
2016
- 2016-09-30 CN CN201610875802.6A patent/CN107880195B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3196137A (en) * | 1961-06-23 | 1965-07-20 | Firestone Tire & Rubber Co | Polymerization catalysts and process |
| CN102372803A (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 |
| CN102453171A (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 |
| CN105566524A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene polymerization reaction, and catalyst thereof |
| CN105566523A (en) * | 2014-10-10 | 2016-05-11 | 中国石油化工股份有限公司 | Catalyst component used for ethylene homopolymerization or copolymerization reaction, and catalyst thereof |
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