CN104277146A - Catalyst component for olefin polymerization and preparation method and application thereof - Google Patents
Catalyst component for olefin polymerization and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a catalyst component for olefin polymerization. The catalyst component is a reaction product comprising at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl-containing compound, at least one chlorine-containing organoboron compound and at least one modified dispersant; the chlorine-containing organoboron compound is a compound represented by a general formula (IV) of BR<4>[p]Cl[3-p], wherein in the general formula (IV), R<4> is C2-C20 alkyl or alkoxy, and 0<=p<3; the modified dispersant is a polyisoprene-block-polyoxyethylene ether polymer. The used catalyst component has good catalytic activity and good catalyst hydrogen-regulating sensitivity and allows an obtained polymer to have high packing density, a corresponding catalyst has better controllability on the particle morphology and the particle size of the olefin polymerization product, and thus the catalyst component is more favorable for the catalyst to be used in polymerization process devices of gaseous phase, slurry and the like.
Description
Technical field
The present invention relates to a kind of catalyst component for olefinic polymerization or copolymerization and catalyzer thereof, and the preparation method of this catalyst component and purposes.
Background technology
Over nearly more than 20 years, with the development of olefin polymetiation process, significant progress also got by the catalyzer matched with polymerization technique, and wherein effective catalyst relies on its excellent polymerization and ripe utilisation technology still to occupy an important position in polyolefin catalyst field.Through exploratory development for many years, the preparation method of Mg-Ti system effective catalyst at present more adopts chemical reaction method.
In chemical reaction method, many patents of invention relate to chemical feedstockss such as adopting organo-metallic magnesium compound, chlorizating agent and transition metal titanium compound, prepared the catalyzer of number of different types with this kind of reactant, they are disclosed in Chinese patent CN1158136, CN1299375, CN1795213 and US Patent No. 3787384, US4148754, US4173547, US4508843 and 5124296.In such Mg-Ti catalyzer, a fatal shortcoming is had to be difficult to control forming step, thus be difficult to the form controlling prepared catalyst particle, recent development comprises in the wind prose style free from parallelism system of magnesium/titanium compound at catalyst precursor, add the material of some similar emulsifying agents, make it to form emulsion, and then reaction precipitation goes out granules of catalyst, the particle form of gained catalyzer can be improved, as the PFPE adopted in the EP-A-258089 of Montedison, employing PFO is mentioned in Chinese patent CN1537118A, these method forming step are complicated, be difficult to control, gained granules of catalyst form is also wayward, and the material price adopted is high, be difficult to obtain.
Although done a large amount of research work in Ziegler-Natta catalyst field, for the ZN catalyzer preparing more high performance requirements, still need some methods that are new or that improve.
The present inventor is by repeatedly testing discovery, select suitable modifiers dispersants, process for synthetic catalyst just can be made simple, and it is better to obtain form, as the granules of catalyst of spherical, narrow size-grade distribution, there is higher catalytic activity and hydrogen response simultaneously.
Summary of the invention
Applicant of the present invention formerly provides (WO2012/022127) a kind of catalyst component for olefinic polymerization, and it comprises the reaction product of at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, the chloride organoboron compound of at least one and at least one polybutadiene block polyethylene oxide analog copolymer.Use this catalyst component and corresponding catalyst catalysis in olefine polymerization, higher catalytic activity and good hydrogen response can be obtained.Although this catalyst component can bring good catalytic effect for olefinic polymerization, but contriver also angularly attempts to seek other different dispersing auxiliaries from cost of material and catalytic effect, such as consider to redesign its molecular structure on existing polybutadiene block polyethylene oxide analog copolymer basis, particularly, new multipolymer is formed as increased one or more comonomers again, change copolymer chain or branch lengths or Similarity Between Line Segments, partly or entirely with the polybutadiene moieties in other comonomer replacement multipolymer and/or polyethylene oxide portion, use halogen, hydrogen atom on alkyl or other hybrid atom MCM-41 main chain or side chain etc. mode, this new multipolymer as dispersing auxiliary is made can at least to reach the catalytic effect similar with polybutadiene block polyethylene oxide analog copolymer when participating in olefinic polymerization catalysis.
But, the present inventor is surprised to find that in experimentation, when using polyisoprene blocks polyoxyethylene groups ether polymer to substitute former polybutadiene block polyethylene oxide analog copolymer, not only the catalytic activity of corresponding catalyst and hydrogen response are without obvious decline; And the particle of corresponding catalyst component is more even, size-grade distribution obviously narrows, it can be better to the control of the size of particles of olefinic polymerization product and form.
Therefore, the invention provides a kind of catalyst component for olefinic polymerization, it is the reaction product comprising at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, the chloride organoboron compound of at least one and at least one modifiers dispersants; Described chloride organoboron compound is as logical formula IV BR
4 pcl
3-pshown compound, R in logical formula IV
4c
2~ C
20alkyl or alkoxyl group, 0≤p ﹤ 3; And described modifiers dispersants is polyisoprene blocks polyoxyethylene groups ether polymer.
Catalyst component prepared by the present invention has good hydrogen regulation performance, also has good particle form and distribution simultaneously, thus is more conducive to its use on the polymerization technique such as gas phase, slurry device.
Described organo-magnesium compound is as logical formula I MgR
1 ncl
2-nshown in, R in formula
1c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0 < n≤2.Concrete compound is as being selected from dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride etc.
Wherein said titanium-containing compound is as logical formula II Ti (OR
2)
mcl
4-mshown in, R in formula
2c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4; Preferred wherein m=4 or m=0, because tetravalent titanium compound is in a liquid state usually at normal temperatures, and also also fine with the consistency of some solvents; Particular compound can be selected from least one in titanium tetrachloride, tetraethyl titanate and tetrabutyl titanate, preferred titanium tetrachloride.
Wherein said hydroxyl compounds is as logical formula III HOR
3shown in, R in formula
3c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain; Hydroxyl compounds is preferably fatty alcohol or aromatic alcohol, at least one more preferably in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and phenylethyl alcohol.
In the present invention, concrete described chloride organoboron compound is selected from least one in dichloromethyl boron, Dichloroethyl boron, two chlorobutyl boron, dichloro methoxyl group boron, two chloroethoxy boron, boron trichloride, dichloro butoxy boron.
Described modifiers dispersants polyisoprene blocks polyoxyethylene ether (PI-b-POE) base polymer comprises diblock and three blocks (PI-b-POE-b-PI, POE-b-PI-b-POE) and derivative thereof; The block type of preferred described polymkeric substance is optionally linear, band chain or star form.In described polyisoprene blocks polyoxyethylene groups ether polymer, the content of polyisoprene is 3 ~ 97wt%, preferably 10 ~ 90wt%.
The present invention also provides the corresponding preparation method of above-mentioned catalyst component, comprises the steps,
A: organo-magnesium compound and hydroxyl compounds are reacted, obtains clear solution;
B: modifiers dispersants is dispersed in C
4~ C
20in alkane or aromatic solvent, form solution, then react with the clear solution that step a obtains, obtain mixed solution;
C: chloride organoboron compound and titanium-containing compound are joined successively in the mixed solution that step b obtains, obtain catalyst component suspension, the solid particulate reclaimed wherein obtains described catalyst component.
Preferably in above-mentioned preparation method in every mole of organo-magnesium compound, titanium-containing compound is 0.01 ~ 10 mole; Hydroxyl compounds is 0.1 ~ 20 mole; Chloride organoboron compound is 0.1 ~ 50 mole; The concentration of modifiers dispersants in reaction system controls at 0.001 ~ 100 grams per liter.Preferably wherein titanium-containing compound is 0.05 ~ 5 mole; Hydroxyl compounds is 0.2 ~ 10 mole; Chloride organoboron compound is 0.5 ~ 20 mole; The concentration of modifiers dispersants in reaction system controls at 0.01 ~ 50 grams per liter.
In step a, carry out advantageously under the temperature of reaction of organo-magnesium compound and hydroxyl compounds is typically chosen in relatively high temperature, preferably below the boiling temperature of reactant, temperature usually not higher than 90 DEG C, generally not higher than 70 DEG C.The time of reaction depends on character and the operational condition of reactant, required time generally at 5 minutes to 2 hours, preferably 10 minutes to 1 hour.After organo-magnesium compound and the reaction of hydroxyl compounds, the solution formed can be used in combination with inert diluent, inert diluent is selected from aliphatic hydrocarbon usually, such as Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, general hexane or heptane are proper inert solvents.
In stepb, modifiers dispersants is dispersed in C
4~ C
20in alkane or aromatic solvent, be preferably dispersed in hexane, heptane or toluene and composition thereof solvent, form solution, fully mix with the clear solution obtained in step a, according to kind and the different in kind of modifiers dispersants, its C
4~ C
20the configuration concentration of alkane or arene solution controls at 0.1 ~ 100 grams per liter, preferably 1 ~ 50 grams per liter, and the amount added is 0.001 ~ 100 grams per liter to make the concentration of modifiers dispersants in reaction system, preferably 0.01 ~ 50 grams per liter.Mixing temperature generally will, lower than the boiling temperature of system, for simplicity, be typically chosen between 0 ~ 90 DEG C, preferably between 10 ~ 50 DEG C.Both mixing times generally select 0.5 minute to 5 hours, preferably 10 minutes to 1 hour.
In step c, complete the Homogeneous phase mixing of all substances at a certain temperature, first the solution system that first two steps obtain is reduced to certain temperature, solution still keeps clear at such a temperature, be unlikely to become turbid or precipitate, temperature can control between-90 ~ 30 DEG C, preferably between-70 ~ 0 DEG C, then chloride organoboron compound and titanium-containing compound are progressively slowly added successively, usually carry out fully stirring the abundant mixing being beneficial to various material in reinforced process, feed rate is usually selected not cause significant reaction or system obviously to heat up and is as the criterion.After abundant mixing, any known suitable method can be adopted to heat up, as slowly, progressively, rapidly or temperature programming, different temperature-rising methods can obtain the totally different catalyzer of performance characteristics, in temperature-rise period, system can change muddiness into by clarification, separate out precipitation, in this precipitin reaction step, the reaction times of settling step should be long enough to obtain to be precipitated completely, reaction times can last 1 minute to 10 hours, preferably 3 minutes ~ 5 hours.
Experiment finds, after settling step, reacting for some time at a certain temperature, to carry out the particle shape of maturation process to catalyzer more favourable, and it can improve the intensity of catalyst particle, thus reduces catalyzer particle fragmentation phenomenon in the course of the polymerization process.The temperature of maturation process is generally equal to or higher than the outlet temperature of precipitin reaction, and the time of slaking reaction can control at 0.5 ~ 10 hour, preferably 1 ~ 5 hour.
After carrying out maturation process, generally to wash, to remove the by product formed in excessive reactant and preparation process, any inert solvent all can be used for this washing step, such as can select Trimethylmethane, pentane, hexane, heptane, hexanaphthene, toluene or various aromatic hydrocarbons and composition thereof etc., usually select with after toluene wash twice in experiment, more fully wash with hexane.After washing, under catalyst suspension nitrogen protection, carry out drying, to obtain catalyst fines.
In addition, the invention still further relates to a kind of all polymerization for alkene or the catalyzer of copolymerization, it contains above-mentioned catalyst component of the present invention and the reaction product of alkylaluminium cpd, and the general formula of alkylaluminium cpd wherein used is AlR
hx
3-horgano-aluminium compound, in formula, R is hydrogen or carbonatoms is the alkyl of 1 ~ 20, and X is halogen, 1 < h≤3.Preferred AlEt
3, Al (iso-Bu)
3, Al (n-C
6h
13)
3, Al (n-C
8h
17)
3, AlEt
2cl etc.
Catalyst component of the present invention can use according to the well-known way of this area olefinic polymerization Ziegler-Natta catalyst, as used together with another kind of promotor or electron donor, can also by catalyst component of the present invention and one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalyst used in combination.
The application of the catalyst component that the present invention also provides described catalyst component or described method to prepare in ethylene homo conjunction or copolymerization.
Catalyst component of the present invention is applicable to various any alkene that can carry out coordination poly-merization, comprise a kind of copolymerization of all polymerization or multiple alkene of alkene, the alpha-olefin such as optimal ethylene, propylene, butylene in alkene, or the mixture of ethene, propylene, butylene and one or more alpha-olefins.Good comonomer is C2-C12 alkene, preferred C4-C10 alkene, as 1-butylene, iso-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 4-methylpentene-1, diene is as divinyl, Isosorbide-5-Nitrae-hexadiene and 1,7-octadiene, cyclenes is as norbornylene, and their any mixture.
Catalyzer of the present invention can adopt typical polymerization technology to carry out polyreaction in one or more polymerization reactor, can be gas phase, slurry or bulk polymerization, and polyreaction can be interval or continuous polymerization process.
To slurry or bulk reaction device, temperature of reaction generally at 40-130 DEG C, preferred 60-110 DEG C, reactor pressure generally at 0.1-8MPa, preferred 0.3-6MPa, the residence time generally at 0.2-6 hour, preferred 0.5-3 hour.General selection boiling point uses as thinner at the aliphatic hydrocarbon of-70-100 DEG C of scope; If needed, polyreaction can be carried out at supercritical conditions.
For Gas-phase reactor, temperature of reaction generally at 60-130 DEG C, preferred 70-110 DEG C, reactor pressure generally at 0.5-4MPa, preferred 1-3MPa, the residence time generally at 0.5-10 hour, preferred 1-8 hour.If needed, select suitable aliphatic hydrocarbon to use as thinner, polyreaction can be carried out under frozen state condition.
Catalyst levels generally depends on the character of catalyzer, type of reactor and operational condition and the requirement to polymerisate performance, can use conventional catalyst consumption.
Adopt catalyzer of the present invention, the catalyst system with good form can be obtained, and catalyzer has higher catalytic activity and good hydrogen response, polymerisate form can copy the particle form of catalyzer preferably, i.e. so-called " print effect ", therefore this catalyzer has excellent over-all properties.
Embodiment
The testing method used in the present invention:
The size-grade distribution of carrier and catalyzer uses MASTERSIZE particles distribution instrument, normal hexane as dispersion agent, useful range 0.02 ~ 2000 μm; Wherein size distribution coefficient is by (d
90-d
10)/d
50calculate, size distribution coefficient value is less, illustrates that catalyst component particles size is more even.
In catalyst system, the relative weight percents of metal (mainly titanium, magnesium) uses plasma emission spectrum (ICP) to measure.The pattern of catalyzer and polymkeric substance uses scanning electron microscope (SEM) to measure.Melting index uses ASTM-D1238 to measure.Tap density uses DIN-53194 to measure.
Embodiment given below is in order to the present invention is described, instead of limits the invention.
Embodiment 1
The preparation of catalyst component: get 310ml hexane, the dibutylmagnesium hexane solution (1M) of 31.5ml and 10.0ml isooctyl alcohol successively, be warming up to 50 DEG C and maintain stirring reaction half an hour, obtain clear solution, then polyisoprene blocks polyoxyethylene groups ether copolymer (PI-b-POE linear copolymer is added, polyisoprene contents 48wt%) hexane solution (10g/L) 100ml, be cooled to-20 DEG C, add boron trichloride hexane solution (1M) and the 3.5ml titanium tetrachloride of 31.5 milliliters successively, after adding material, slowly be warming up to 50 DEG C, and maintain reaction 2 hours.Catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 300 milliliters, after wash, dry must brown solid mobility powder and catalyst component, its median size is 12.7 microns; Size distribution coefficient is 0.81.Ultimate analysis (ICP): Ti:9.27%(weight), Mg:13.15%(weight).
Vinyl polymerization evaluates A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyst component are joined in 2L stainless steel stirring tank, then temperature is brought up to 80 DEG C, the disposable hydrogen adding 0.18MPa, then with ethene, the total pressure of system is maintained 0.73MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, the test tap density of polyethylene powder and the melting index under 2.16Kg load, result is as shown in table 1.
Vinyl polymerization evaluates B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyst component are joined in 2L stainless steel stirring tank, then temperature is brought up to 90 DEG C, the disposable hydrogen adding 0.4MPa, then with ethene, the total pressure of system is maintained 1.0MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, calculate the activity of catalyzer, the test tap density of polyethylene powder and the melting index under 2.16Kg load, result is as shown in table 1.
Embodiment 2
" 3.5ml titanium tetrachloride " is adjusted to " 10ml titanium tetrachloride ", and other conditions of catalyst component preparation process are with embodiment 1.The median size of products obtained therefrom is 8.9 microns.Ultimate analysis (ICP): Ti:13.48%(weight), Mg:10.14%(weight).
The ethene slurry polymerization of catalyzer evaluates the condition of A and B with embodiment 1, and polymerization result is in table 1.
Embodiment 3
" hexane solution (10g/L) 100ml of polyisoprene blocks polyoxyethylene groups ether copolymer (PI-b-POE linear copolymer; polyisoprene contents 48wt%) " changed into " hexane solution (10g/L) 100ml of polyisoprene blocks polyoxyethylene groups ether copolymer (PI-b-POE-b-PI linear copolymer; polyisoprene contents 72wt%) ", other conditions of catalyst component preparation process are with embodiment 1.The median size of products obtained therefrom is 5.2 microns.Ultimate analysis (ICP): Ti:11.26%(weight), Mg:14.58%(weight).
The ethene slurry polymerization of catalyzer evaluates the condition of A and B with embodiment 1, and polymerization result is in table 1.
Comparative example 1
Step is removed " will to add hexane solution (10g/L) 100ml of polyisoprene blocks polyoxyethylene groups ether copolymer (PI-b-POE linear copolymer; polyisoprene contents 48wt%) ", namely do not add modifiers dispersants, other conditions of catalyst component preparation process are with embodiment 1.The median size of products obtained therefrom is 65.72 microns; Its grain size distribution presents wider multimodal distribution.Ultimate analysis (ICP): Ti:10.24%(weight), Mg:12.36%(weight).
The ethene slurry polymerization of catalyzer evaluates the condition of A and B with embodiment 1, and polymerization result is in table 1.
Comparative example 2
The preparation of catalyst component: get 310ml hexane, the dibutylmagnesium hexane solution (1M) of 31.5ml and 10.0ml isooctyl alcohol successively, be warming up to 50 DEG C and maintain stirring reaction half an hour, obtain clear solution, then hexane solution (10g/L) 100ml of polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) is added, be cooled to-20 DEG C, add boron trichloride hexane solution (1M) and the 3.5ml titanium tetrachloride of 31.5 milliliters successively, after adding material, slowly be warming up to 50 DEG C, and maintain reaction 2 hours.Catalyst suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 300 milliliters, after wash, dry must brown solid mobility powder, its median size is 17.2 microns; Size distribution coefficient is 0.96.Ultimate analysis (ICP): Ti:9.16%(weight), Mg:15.20%(weight).
The ethene slurry polymerization of catalyzer evaluates the condition of A and B with embodiment 1, and polymerization result is in table 1.
Table 1
As can be seen from the experimental data of table 1 embodiment and comparative example, PI-b-POE class modifiers dispersants is used in the preparation process of catalyzer, the catalyst component obtained and the particle form of polymkeric substance good, narrow particle size distribution, the tap density (BD) of polymer resin is higher, catalyzer high comprehensive performance.Especially the embodiment of the present invention 1 is compared with use polybutadiene block polyethylene oxide copolymer in comparative example 2, and it is active and melting index is all suitable, and the tap density of its polymer resin is higher; What more make contriver feel surprised is, the embodiment of the present invention 1 is compared with comparative example 2, at least as can be seen from the size-grade distribution of catalyst component size distribution coefficient and vinyl polymerization product, technical scheme of the present invention to the particle shape of vinyl polymerization product and the control of granular size better.
Claims (10)
1., for the catalyst component of olefinic polymerization, it is the reaction product comprising at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl compounds, the chloride organoboron compound of at least one and at least one modifiers dispersants; Described chloride organoboron compound is as logical formula IV BR
4 pcl
3-pshown compound, R in logical formula IV
4c
2~ C
20alkyl or alkoxyl group, 0≤p ﹤ 3; And described modifiers dispersants is polyisoprene blocks polyoxyethylene groups ether polymer.
2. catalyst component according to claim 1, is characterized in that, described organo-magnesium compound is as logical formula I MgR
1 ncl
2-nshown in, R in formula
1c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0 < n≤2.
3. catalyst component according to claim 1, is characterized in that, described titanium-containing compound is as logical formula II Ti (OR
2)
mcl
4-mshown in, R in formula
2c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain, 0≤m≤4.
4. catalyst component according to claim 1, is characterized in that, described hydroxyl compounds is as logical formula III HOR
3shown in, R in formula
3c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain.
5. according to the catalyst component in Claims 1 to 4 described in any one, it is characterized in that, described polyisoprene blocks polyoxyethylene groups ether polymer comprises diblock and three blocks and derivative thereof; The block type of preferred described polymkeric substance is optionally linear, band chain or star form.
6. according to the catalyst component in Claims 1 to 4 described in any one, it is characterized in that, in described polyisoprene blocks polyoxyethylene groups ether polymer, the content of polyisoprene is 3 ~ 97wt%, preferably 10 ~ 90wt%.
7., according to the preparation method of catalyst component described in any one in claim 1 ~ 6, comprise the steps,
A: organo-magnesium compound and hydroxyl compounds are reacted, obtains clear solution;
B: modifiers dispersants is dispersed in C
4~ C
20in alkane or aromatic solvent, form solution, then react with the clear solution that step a obtains, obtain mixed solution;
C: chloride organoboron compound and titanium-containing compound are joined successively in the mixed solution that step b obtains, obtain catalyst component suspension, the solid particulate reclaimed wherein obtains described catalyst component.
8. preparation method according to claim 7, is characterized in that, in every mole of organo-magnesium compound, titanium-containing compound is 0.01 ~ 10 mole; Hydroxyl compounds is 0.1 ~ 20 mole; Chloride organoboron compound is 0.1 ~ 50 mole; The concentration of modifiers dispersants in reaction system controls at 0.001 ~ 100 grams per liter; Preferably wherein titanium-containing compound is 0.05 ~ 5 mole; Hydroxyl compounds is 0.2 ~ 10 mole; Chloride organoboron compound is 0.5 ~ 20 mole; The concentration of modifiers dispersants in reaction system controls at 0.01 ~ 50 grams per liter.
9. be all polymerized for alkene or the catalyzer of copolymerization, it comprises the catalyst component that described in catalyst component described in any one in claim 1 ~ 6 or claim 7 or 8, method prepares, and at least one general formula is AlR
hx
3-horgano-aluminium compound, in formula, R is hydrogen or carbonatoms is the alkyl of 1 ~ 20, and X is halogen, 1 < h≤3.
10. the catalyst component that in claim 1 ~ 6, described in catalyst component described in any one or claim 7 or 8, method prepares closes or application in copolymerization at ethylene homo.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880181A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148754A (en) * | 1975-11-27 | 1979-04-10 | Hoechst Aktiengesellschaft | Process for the preparation of a catalyst and catalyst used in olefin polymerization |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
-
2013
- 2013-07-01 CN CN201310271926.XA patent/CN104277146B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148754A (en) * | 1975-11-27 | 1979-04-10 | Hoechst Aktiengesellschaft | Process for the preparation of a catalyst and catalyst used in olefin polymerization |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst ingredient for olefin polymerization and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880181A (en) * | 2016-09-30 | 2018-04-06 | 中国石油化工股份有限公司 | Catalytic component and its preparation and application for olefinic polymerization |
| CN107880181B (en) * | 2016-09-30 | 2020-02-18 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation and application thereof |
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