CN103130924B - Catalyst carrier used for olefin polymerization and preparation method thereof - Google Patents
Catalyst carrier used for olefin polymerization and preparation method thereof Download PDFInfo
- Publication number
- CN103130924B CN103130924B CN201110386502.9A CN201110386502A CN103130924B CN 103130924 B CN103130924 B CN 103130924B CN 201110386502 A CN201110386502 A CN 201110386502A CN 103130924 B CN103130924 B CN 103130924B
- Authority
- CN
- China
- Prior art keywords
- boron
- support
- catalyst
- magnesium
- carrier
- 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.)
- Active
Links
Abstract
The invention provides a catalyst carrier used for olefin polymerization. The catalyst carrier used for the olefin polymerization comprises at least one organo-magnesium compound, at least one compound containing hydroxyl, at least one organboron compound containing chlorine and at least one reaction product formed by a modified precipitation agent, wherein the modified precipitation agent is a copolymer of polybutadiene block polyethylene oxide (PB-b-POE). Correspondingly, the invention further provides a preparation method of the catalyst carrier used for the olefin polymerization. The catalyst carrier prepared with the method has the advantages of being good in particle morphology and distribution, and capable of being used on polymerization process devices such as a gaseous phase polymerization process device and a slurry polymerization process device.
Description
Technical field
The present invention relates to a kind of all polymerization for alkene or the support of the catalyst of copolymerization and the preparation method of this support of the catalyst and purposes.
Background technology
After 20 century 70 Efficient polyolefin catalyst development successes, world's polyolefin industry there occurs great change.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 is also by common polishing, and Suspension method has developed into pre-forming carrier and then adopted chemical reaction method.
Pre-forming carrier Kaolinite Preparation of Catalyst has a lot of apparent advantage, as granules of catalyst form is good, size distribution is narrow, but the over-all properties of pre-forming carrier directly affects and determines the performance of gained catalyzer, the carrier therefore preparing good over-all properties just becomes the developing important ring of catalyst technology.
Early stage support of the catalyst selects magnesium compound milled processed to obtain, but the carrier obtained so directly causes the granules of catalyst form that obtains bad and size distribution is very wide, produces bring a lot of difficulty to polyolefin device.
Many patent disclosure are had again to adopt various method to prepare High-efficiency catalyst carrier subsequently, and improve the performances such as granules of catalyst form, catalytic efficiency and resulting polymers form thereof to a certain extent, be applied in polyolefin industry is produced, but the sphericity of this kind of carrier gained catalyzer is poor, not globulate, its representational patent is the US4952649 of Mitsui petro-chemical corporation and the US4784983 of Sinopec Beijing Chemical Research Institute.
As far back as middle 1970s Italy's Meng Ai house journal US4111835 announcement spray method obtain magnesium chloride alcohol adduct carrier, but spray method to produce qualified carrier yield too low, and gained catalyst efficiency is lower.Another patent US4399054 of the said firm announces and adopts magnesium chloride alcohol adduct melt in the ejection of dispersion medium mesohigh or high-speed stirring dispersion subsequently, then shapingly in cryostat ball type carrier is obtained, obtain spherical catalyst with this carrier again, but the efficiency of catalyzer and orientation property are all poor.UCC house journal of U.S. US4293673 discloses a kind of catalyzer adopting silica gel and magnesium chloride complex carrier to prepare, this catalyst application has greater activity in gas phase polymerization technique, prepared ethene polymers has good particle form, but the most preparation technology of this kind of catalyzer is more loaded down with trivial details.
The object of the invention is to overcome deficiency of the prior art, adopt more simple and practical preparation method, obtain the spherical carrier of catalyst that can be used for olefinic polymerization.The present inventor is by repeatedly testing discovery, select suitable chemical reaction system, support of the catalyst synthetic method just can be made simple, and the catalyst carrier particle of spherical, narrow size-grade distribution can be obtained, and with the catalyzer that this carrier prepares, there is higher catalytic activity and good hydrogen response.
Summary of the invention
The invention provides a kind of support of the catalyst for olefinic polymerization, it comprises the reaction product formed by least one organo-magnesium compound, at least one hydroxyl compounds, the chloride organoboron compound of at least one and at least one modification precipitation agent; Wherein, described organo-magnesium compound is as general 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; Described hydroxyl compounds is as general formula (II) HOR
2shown in, R in formula
2c
2~ C
20alkyl, can be saturated or undersaturated straight chain, side chain or closed chain; Described chloride organoboron compound is as general formula (III) BR
3 qcl
3-qshown in, R in its Chinese style
3c
2~ C
20alkyl or alkoxyl group, 0≤q < 3; Described modification precipitation agent is polybutadiene block polyethylene oxide (PB-b-POE) analog copolymer.
In preferred organo-magnesium compound general formula (I) of the present invention, R
1c
2~ C
20alkyl.More preferably described organo-magnesium compound is selected from least one in dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride.
Preferred hydroxyl compounds of the present invention is fatty alcohol or aromatic alcohol, at least one more preferably in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and phenylethyl alcohol.
Preferred chloride organoboron compound of the present invention is selected from least one in dichloromethyl boron, Dichloroethyl boron, two chlorobutyl boron, dichloro methoxyl group boron, two chloroethoxy boron, boron trichloride and dichloro butoxy boron.More preferably at least one in two chlorobutyl boron, dichloro methoxyl group boron, two chloroethoxy boron, boron trichloride and dichloro butoxy boron.
Preferred polybutadiene block polyethylene oxide analog copolymer of the present invention comprises diblock and three blocks (PB-b-POE-b-PB, POE-b-PB-b-POE) and derivative thereof, and block type is optionally linear, band chain or a star form; In described polybutadiene block polyethylene oxide analog copolymer, the content of polyhutadiene is 3-97wt%, is more preferably 10-90wt%.
The present invention also provides a kind of preparation method of the support of the catalyst for olefinic polymerization, comprises the steps, a: described organo-magnesium compound and the reaction of described hydroxyl compounds are formed clear solution; B: described modification precipitation agent is dispersed in C
4~ C
20alkane is or/and be mixed to get mixed solution with the clear solution that step a obtains in aromatic solvent; C: described chloride organoboron compound is mixed under the low temperature of-70 ~ 30 DEG C with the mixed solution that step b obtains, then temperature reaction forms the suspension containing solid particulate; And d: described in separated and collected, solid particulate is support of the catalyst.
Preferably in preparation method of the present invention, in every mole of organo-magnesium compound, hydroxyl compounds is 0.1 ~ 20 mole, more preferably 0.2 ~ 10 mole; Chloride organoboron compound is 0.1 ~ 50 mole, more preferably 0.5 ~ 20 mole; The concentration of modification precipitation agent in reaction system controls at 0.001 ~ 100 grams per liter, more preferably 0.01 ~ 50 grams per liter.
In the step a of Kaolinite Preparation of Catalyst carrier, magnesium compound and alcohols material react advantageously at a relatively high temperature, but preferably below the boiling temperature of reactant, namely temperature is not usually higher than 90 DEG C, preferably not higher than 70 DEG C.The time of reaction depends on reactant character and operational condition, generally at 5 minutes to 2 hours, and preferably 10 minutes to 1 hour.The clear solution that magnesium compound and alcohols material reaction are formed can be used in combination with inert diluent, and inert diluent is selected from aliphatic hydrocarbon usually, such as Trimethylmethane, pentane, hexane, heptane or hexanaphthene and composition thereof, preferred hexane or heptane.
In the step b of Kaolinite Preparation of Catalyst carrier, fully mix dissolving modification precipitation agent solution in a solvent with the clear solution obtained in step a, described solvent be preferably in hexane, heptane and toluene one or more.According to kind and the different in kind of modification precipitation agent, its concentration in a solvent controls at 0.1 ~ 100 grams per liter, preferably 1 ~ 50 grams per liter; The add-on of modification precipitation agent solution controls at 0.001 ~ 100 grams per liter to make the concentration of modification precipitation agent in reaction system, preferably 0.01 ~ 50 grams per liter.The mixing temperature of this step generally lower than the boiling temperature of system, for simplicity, will be typically chosen in 0 ~ 90 DEG C, preferably 10 ~ 50 DEG C.The mixing time of two kinds of solution is typically chosen in 0.5 minute to 5 hours, preferably 10 minutes to 1 hour.
In the step c of catalyst support preparation, first the mixed solution that step b obtains is reduced to certain temperature, solution still keeps clear at such a temperature, be unlikely to become turbid or precipitate, temperature can control between-70 ~ 30 DEG C, preferably between-40 ~ 0 DEG C, is then progressively slowly added by compound general formula (III) Suo Shi, in reinforced process, usually carry out stirring be beneficial to abundant mixing, feed rate usually obviously heats up with do not induce reaction obviously aggravation or system and is as the criterion.After abundant mixing, any known suitable method can be adopted to heat up, heating up as being rapidly heated, slowly, progressively heating up or the temperature programming of gradual change, different temperature-rising methods can obtain the totally different support of the catalyst of performance characteristics, in temperature-rise period, system can become muddiness from clarification, separates out solid particulate and precipitates.In formation settling step, its reaction times should sufficiently long to make precipitation completely, specifically can be 1 minute ~ 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 support of the catalyst more favourable, and it can improve the intensity of carrier particle, thus reduces the particle fragmentation phenomenon in catalyst cupport and olefin 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, first carry out solid-liquid separation, such as can select and filter or the conventional means such as centrifugal, and generally need to wash solid particulate, 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, the suspension of carrier in above-mentioned inert solvent carries out drying under nitrogen protection, to obtain support powder.
Use the carrier granule for preparing of the inventive method to be spherical, it has controlled globule size and distribution, median size at 0.1-200 μm, preferred 1-100 μm.The support of the catalyst that the present invention prepares has good particle form and distribution, thus is more conducive to the use of catalyzer on the polymerization technique such as gas phase, slurry device.
The supported mode that the support of the catalyst that the present invention relates to can be known according to this area olefinic polymerization Ziegler-Natta catalyst and single site catalysts uses, as used together with transistion metal compound or electron donor, described carrier can also be used for one or more Ziegler-Natta catalysts or non-Ziegler-Natta catalyst mixed load.
The catalyzer that carrier component of the present invention obtains 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, hexene and octene 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.
The catalyzer that carrier of the present invention prepares 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 0.2-8MPa, preferred 1-6MPa, 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.
Adopt carrier of the present invention and preparation method thereof, the catalyzer with good particle form can be obtained, and catalyzer has higher catalytic activity and good hydrogen response; The polymerisate form that this catalyst olefinic polyreaction obtains can the particle form of replicating vector preferably; Therefore carrier of the present invention has excellent over-all properties.
Embodiment
The size-grade distribution of carrier and catalyzer: adopt MASTERSIZE particles distribution instrument, normal hexane as dispersion agent, useful range 0.02 ~ 2000 μm.
The relative weight percents of metal (mainly titanium, magnesium) in carrier and catalyzer: adopt plasma emission spectrum (ICP).
The pattern of catalyzer and polymkeric substance: adopt scanning electron microscope (SEM).
The mensuration of melting index: ASTM-D1238.
The mensuration of tap density: DIN-53194.
The embodiment below provided only in order to the present invention is described, instead of limits the invention; Protection scope of the present invention is as the criterion with claims.
Embodiment 1
Get 30ml hexane, the dibutylmagnesium hexane solution (1M) of 3.15ml and 1.0ml isooctyl alcohol successively, be warming up to 50 DEG C and maintain stirring reaction half an hour, obtain clear solution, then polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 3ml is added, be cooled to-30 DEG C, add the boron trichloride hexane solution (1M) of 3.15 milliliters, naturally slowly heat up, after rising to room temperature, heating maintenance 50 DEG C reaction 2 hours.Suspension temperature is down to room temperature, leaves standstill, sedimentation, with hexanes wash three times, the consumption of each hexane is 50 milliliters, after wash, dry must pale solid mobility powder, its particle form is good, and its median size is 23.6 microns.
Ultimate analysis: Mg:24.35% (weight), Cl:31.20% (weight).
Embodiment 2
Under nitrogen protection; spherical carrier particle embodiment 1 obtained 4.76 grams joins in 250 milliliters of glass reactors; add 50 ml n-hexanes; slurries are made in stirring; 0 DEG C is cooled to low temperature bath; the hexane solution (containing titanium tetrachloride 2.0ml) of slow dropping 20.0 milliliters of titanium tetrachlorides, stirring reaction 1 hour, is then slowly warming up to 50 DEG C and maintains stirring reaction 2 hours.After reaction terminates, leave standstill, leach liquid, with 40 milliliters of hexanes wash filter cakes twice, dried up by solid nitrogen, obtain the magnesium chloride supported catalyst 4.24 grams with good mobility, its median size is 23.2 microns.
Ultimate analysis (ICP): Ti:3.79% (weight), Mg:21.50% (weight).
The ethene slurry polymerization appreciation condition of catalyzer is as follows:
Vinyl polymerization evaluates A: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in 2L stainless steel stirring tank, then temperature is brought up to 85 DEG C, the disposable hydrogen adding 0.5MPa, then with ethene, the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, calculate the active 6.1kg polymkeric substance/g cat of catalyzer, the tap density of test polyethylene powder is 0.33g/ml, and the melting index under 2.16Kg load is 20.4g/10min.
Vinyl polymerization evaluates B: 1L hexane, 1mmol triethyl aluminum and a certain amount of catalyzer are joined in 2L stainless steel stirring tank, then temperature is brought up to 85 DEG C, the disposable hydrogen adding 0.18MPa, then with ethene, the total pressure of system is maintained 1.03MPa and carry out polyreaction, react after 2 hours, stop adding ethene, cooling, pressure release, polyethylene powder is weighed, calculate the active 16.9kg polymkeric substance/g cat of catalyzer, the tap density of test polyethylene powder is 0.35g/ml, and the melting index under 2.16Kg load is 1.13g/10min.
Ultimate analysis (ICP): Ti:2.61% (weight), Mg:19.52% (weight).
Embodiment 3
The method preparing carrier is basic identical with embodiment 1, but " will add polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 3ml " and change into " adding polybutadiene block polyethylene oxide copolymer (polybutadiene content 75wt%) hexane solution (10g/L) 1ml ".Gained carrier median size is 58.2 microns.
Ultimate analysis: Mg:26.34% (weight), Cl:29.88% (weight).
Embodiment 4
The method preparing carrier is basic identical with embodiment 1, but is changed into " adding the boron trichloride hexane solution (1M) of 6.3 milliliters " " adding the boron trichloride hexane solution (1M) of 3.15 milliliters ".Gained carrier median size is 25.8 microns.
Ultimate analysis: Mg:27.16% (weight), Cl:39.25% (weight).
Embodiment 5
The method preparing carrier is basic identical with embodiment 1, but " 1.0ml isooctyl alcohol " is changed into " 0.6ml propyl carbinol ".Gained carrier median size is 18.7 microns.
Ultimate analysis: Mg:22.32% (weight), Cl:37.84% (weight).
The particle form of gained carrier of the present invention is good as can be seen from the above embodiments, particle is little and narrow diameter distribution, and during for load catalyst for olefines polymerizing, the activity of gained catalyzer is higher and hydrogen response is better.And those skilled in the art known be, if do not add modification precipitation agent of the present invention or the modification precipitation agent that adds and improper in carrier preparation process, the product grain size then prepared is uneven, and form is irregular, within median size is also difficult to reach micro scale; This product generally can not be used as carrier supported catalyst.
Claims (16)
1., for a support of the catalyst for olefinic polymerization, it comprises the reaction product formed by least one organo-magnesium compound, at least one hydroxyl compounds, the chloride organoboron compound of at least one and at least one modification precipitation agent;
Described organo-magnesium compound is as logical formula I MgR
1 ncl
2-nshown in, R in formula
1c
2~ C
20alkyl, 0 < n≤2;
Described hydroxyl compounds is as logical formula II HOR
2shown in, R in formula
2c
2~ C
20alkyl;
Described chloride organoboron compound is as logical formula III BR
3 qcl
3-qshown in, R in its Chinese style
3c
2~ C
20alkyl or alkoxyl group, 0≤q ﹤ 3;
Described modification precipitation agent is polybutadiene block polyethylene oxide analog copolymer.
2. support of the catalyst according to claim 1, wherein said organo-magnesium compound leads in formula I, R
1c
2~ C
20alkyl; Described hydroxyl compounds is fatty alcohol or aromatic alcohol.
3. support of the catalyst according to claim 2, described organo-magnesium compound is selected from least one in dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride, butyl magnesium chloride; Described hydroxyl compounds is selected from least one in propyl carbinol, n-hexyl alcohol, isooctyl alcohol, phenylcarbinol and phenylethyl alcohol.
4. support of the catalyst according to claim 1, 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 and dichloro butoxy boron.
5. support of the catalyst according to claim 4, described chloride organoboron compound is selected from least one in two chlorobutyl boron, dichloro methoxyl group boron, two chloroethoxy boron, boron trichloride and dichloro butoxy boron.
6. support of the catalyst according to claim 1, described polybutadiene block polyethylene oxide analog copolymer comprises diblock and three blocks and derivative thereof, and block type is optionally linear, band chain or a star form.
7. support of the catalyst according to claim 1, in described polybutadiene block polyethylene oxide analog copolymer, the content of polyhutadiene is 3-97wt%.
8. support of the catalyst according to claim 7, in described polybutadiene block polyethylene oxide analog copolymer, the content of polyhutadiene is 10-90wt%.
9. a preparation method for the support of the catalyst for olefinic polymerization as described in one of claim 1-8, comprises the steps:
A: described organo-magnesium compound and the reaction of described hydroxyl compounds are formed clear solution;
B: described modification precipitation agent is dispersed in C
4~ C
20alkane is or/and be mixed to get mixed solution with the clear solution that step a obtains in aromatic solvent;
C: described chloride organoboron compound is mixed under the low temperature of-70 ~ 30 DEG C with the mixed solution that step b obtains, then temperature reaction forms the suspension containing solid particulate;
D: described in separated and collected, solid particulate is support of the catalyst.
10. preparation method according to claim 9, is characterized in that, the low temperature in described step c is-40 ~ 0 DEG C; Described heating mode is be rapidly heated, slowly heat up, progressively heat up or the temperature programming of gradual change.
11. preparation methods according to claim 9, is characterized in that, in every mole of organo-magnesium compound, hydroxyl compounds is 0.1 ~ 20 mole; Chloride organoboron compound is 0.1 ~ 50 mole; The concentration of modification precipitation agent in reaction system controls at 0.001 ~ 100 grams per liter.
12. preparation methods according to claim 11, is characterized in that, in every mole of organo-magnesium compound, hydroxyl compounds is 0.2 ~ 10 mole; Chloride organoboron compound is 0.5 ~ 20 mole; The concentration of modification precipitation agent in reaction system controls at 0.01 ~ 50 grams per liter.
13. preparation methods according to claim 9, in described step b solvent be selected from hexane, heptane and toluene one or more.
14. 1 kinds as carrier as described in any one in claim 1 ~ 8 or the carrier for preparing as any one preparation method in claim 9 ~ 13, it is characterized in that, carrier granule is spherical, and it has controlled globule size and distribution, and median size is at 0.1-200 μm.
15. carriers according to claim 14, it is characterized in that, median size is at 1-100 μm.
16. 1 kinds are all polymerized or application in copolymerization at alkene as carrier as described in any one in claim 1 ~ 8 or the carrier for preparing as any one preparation method in claim 9 ~ 13, and wherein said alkene is ethene, propylene, butylene, hexene and octene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110386502.9A CN103130924B (en) | 2011-11-29 | 2011-11-29 | Catalyst carrier used for olefin polymerization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110386502.9A CN103130924B (en) | 2011-11-29 | 2011-11-29 | Catalyst carrier used for olefin polymerization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103130924A CN103130924A (en) | 2013-06-05 |
| CN103130924B true CN103130924B (en) | 2015-06-17 |
Family
ID=48491420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110386502.9A Active CN103130924B (en) | 2011-11-29 | 2011-11-29 | Catalyst carrier used for olefin polymerization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103130924B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880182B (en) * | 2016-09-30 | 2021-02-05 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof and catalyst |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030845A (en) * | 2009-09-29 | 2011-04-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
-
2011
- 2011-11-29 CN CN201110386502.9A patent/CN103130924B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030845A (en) * | 2009-09-29 | 2011-04-27 | 中国石油化工股份有限公司 | Catalyst component used for vinyl polymerization reaction and catalyst thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103130924A (en) | 2013-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102453132B (en) | Catalyst component for olefin polymerization, and preparation method thereof | |
| CN102372798B (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| CN102453169B (en) | Catalyst ingredient for olefin polymerization and preparation method thereof | |
| CN102372802A (en) | Catalyst ingredient for olefin polymerization and preparation method thereof | |
| CN102453170B (en) | Components, preparation method and application of alkene polymerization catalyst | |
| CN102372801B (en) | Catalyst component for olefin polymerization and preparation method for catalyst component | |
| CN102372800B (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| CN102453171A (en) | Catalyst component for olefin polymerization and preparation method thereof | |
| CN102372799B (en) | Catalyst ingredient used for alkene polymerization and preparation method thereof | |
| CN102372803A (en) | Catalyst component for olefin polymerization, and preparation method thereof | |
| CN102453126B (en) | Catalyst component for olefin polymerization, preparation method and application thereof | |
| CN103130924B (en) | Catalyst carrier used for olefin polymerization and preparation method thereof | |
| CN103130926B (en) | A kind of support of the catalyst for olefinic polymerization and preparation method thereof | |
| CN103130923B (en) | Catalyst carrier for olefin polymerization and preparation method thereof | |
| CN103130928B (en) | Catalyst carrier for olefin polymerization and preparation method thereof | |
| CN103130930B (en) | A kind of support of the catalyst for olefinic polymerization and preparation method thereof | |
| CN103130925B (en) | Catalyst carrier for olefin polymerization and preparation method thereof | |
| CN103130922B (en) | Catalyst carrier used for olefin polymerization and preparation method thereof | |
| CN103130929B (en) | Catalyst carrier for olefin polymerization and preparation method thereof | |
| CN103130921B (en) | Catalyst carrier for olefin polymerization and preparation method thereof | |
| CN104277145A (en) | Catalyst component for olefin polymerization and preparation method and application thereof | |
| CN103130920B (en) | Catalyst carrier for olefin polymerization and preparation method thereof | |
| CN104277156B (en) | For the catalyst component of olefinic polymerization, its preparation method and application | |
| CN104277151B (en) | For the catalyst component of olefinic polymerization, its preparation method and application | |
| CN102453131B (en) | Catalyst ingredient for olefin polymerization and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |