CN105330770A - Catalyst used for ethylene slurry polymerization and application thereof - Google Patents
Catalyst used for ethylene slurry polymerization and application thereof Download PDFInfo
- Publication number
- CN105330770A CN105330770A CN201410273530.3A CN201410273530A CN105330770A CN 105330770 A CN105330770 A CN 105330770A CN 201410273530 A CN201410273530 A CN 201410273530A CN 105330770 A CN105330770 A CN 105330770A
- Authority
- CN
- China
- Prior art keywords
- component
- compound
- catalyzer
- slurry polymerization
- polymerization according
- 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
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a carrier catalyst used for ethylene slurry polymerization, catalyst composition and a preparation method thereof. The catalyst is composed of a component A, a component B and a component C. The component A is characterized in that magnesium halide is dissolved in an organic epoxy compound, an organic phosphorous compound and an electron donor compound to form an uniform solution, TiCl4 is slowly reacted with the magnesium halide uniform solution under low temperature, catalyst crystal is precipitated, a heating reaction is strictly controlled to obtain the catalyst component A; the component B is an organic aluminum compound, the component C is a halogenated hydrocarbon compound, the component C provides two usage modes, 1) the component C and the component B are mixed, then a mixture is added in an ethylene polymerization system, and 2) the component A, the component B and the component C are respectively added while polymerization is carried out. The catalyst has good mechanical property for ethylene slurry polymerization to obtain polyethylene, and the polymerization activity of the catalyst can be increased.
Description
Technical field
The present invention relates to a kind of catalyzer for olefinic polymerization particularly ethene slurry polymerization, and the preparation method of this catalyzer and application.
Background technology
Traditional Z-N catalyzer, by the titanium-Al catalysts of classics, has developed into by the stage of the compound activatings such as magnesium chloride, other various organic compound modifications; And by simple raising catalyst activity, develop into the performance by regulating catalyzer to improve polymeric articles.
Since the seventies, it take magnesium chloride as the Ti-Mg high-effective carrier catalyst of carrier that the companies such as Mitsui petrochemical industry Co., Ltd. succeed in developing multiple, world's slurry process production polyolefin industry is obtained and develops fast.
The method of vinyl polymerization and copolymerization disclosed in Japanese Patent JP49-51378, this catalyzer is Ti/Mg high-effective carrier catalyst.This catalyst preparation process is simple, and reaction conditions is not harsh, and operation is easier to.But because this catalyzer adopts the larger alcohols of different polarities and alkane solvents to dissolve magnesium halide, making magnesium halide can not be generated homogeneous phase solution by dissolving completely, is only generate a kind of particulate soliquid or swelling magnesium halide slurries.Serve the shortcoming relevant with magnesium halide stratiform crystallization property so to prepared catalyst strips, the polymkeric substance apparent density as prepared is lower, particle form and distribute bad etc.
CN1229092A proposes and a kind ofly to close or the catalyzer of copolymerization and the preparation method of this catalyzer for ethylene homo, wherein catalyzer is dissolved in organic epoxy compound thing, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, obtain with the halogenide or derivatives thereof effect of at least one precipitation additive and transition metals Ti again, be combined with organo-aluminium compound during polymerization.This catalyst preparation process is simple, shows very high activity for vinyl polymerization, and the particle form of resulting polymers is better simultaneously, and apparent density is higher, but catalyzer is good not to the susceptibility of hydrogen.
Halohydrocarbon is used successfully to vanadium series catalyst as the accelerative activator of catalyzer, and has been successfully applied to gas-phase polyethylene industrial production.Vanadium series catalyst activity can be made to improve 4-10 doubly owing to adding promotor.Chinese patent CN1189505A is open, and traditional titanium Z/N type catalyzer is when for ethene gas-phase polymerization, and when using suitable halohydrocarbon and titanium mol ratio, catalyst activity improves 80-200%.
The present invention introduces halogenated hydrocarbon compound in special catalyst system, is found by lot of experiments, halohydrocarbon add the activity that not only can improve catalyzer, and poly mechanical property can be improved its tensile yield strength is improved.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system for slurry olefin polymerization, halogenated hydrocarbon compound is introduced in catalyst system, not only can improve the activity of catalyzer, and poly mechanical property can be improved its tensile yield strength is improved.
A kind of catalyst system for slurry olefin polymerization of the present invention, comprises following component:
(A) ingredient of solid catalyst of titaniferous, it is dissolved in organic epoxy compound thing, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, the halogenide or derivatives thereof of transition metals Ti is slowly added in above-mentioned homogeneous solution, with inert diluent washing, obtain ingredient of solid catalyst;
(B) organo-aluminium compound;
(C) halogenated hydrocarbon compound.
Described halogenated hydrocarbon compound and the mol ratio of titanium are 0.01 ~ 50, with 0.1 ~ 10 as well.
The general formula of described halogenated hydrocarbon compound is R
1r
2x
4-b, R in formula
1c
1~ C
20alkyl or aromatic base, R
2c
1~ C
20alkyl, b is 1,2 or 3, X is F, Cl, Br.Particular compound comprises monochlorethane, a chloropropane, a chlorobutane, a chloropentane, a chlorohexane, 1,2-ethylene dichloride, 1,3-propylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, 1, one or more in 5-dichloropentane, 1,6-dichloro hexane, trichloromethane, mono chloro benzene, dichlorobenzene.
Described halogenated hydrocarbon compound can have following several method when using: first organo-aluminium compound and halogenated hydrocarbon compound are obtained by reacting mixture in advance during (1) polymerization, its preparation method be by dilution after halohydrocarbon at-10 ~ 10 DEG C, under being top condition with 0 ~ 60 DEG C, slowly be added drop-wise in organo-aluminium compound, rate of addition is 0.1 ~ 0.5ml/min; (2) during polymerization, organo-aluminium compound and halogenated hydrocarbon compound are added paradigmatic system respectively.
Magnesium halide described in component (A) comprise one of them halogen atom in complex compound, the magnesium dihalide molecular formula such as water or alcohol of magnesium dihalide, magnesium dihalide by-oxyl or halogen-oxyl the derivative of replacing, above-mentioned magnesium dihalide is specially magnesium dichloride, dibrominated magnesium, diiodinating magnesium.Wherein, be best with magnesium dichloride.
The magnesium halide granularity used is to stir lower easy dissolving as well, and solvent temperature is-10 DEG C ~ 150 DEG C, with 20 DEG C ~ 130 DEG C as well.Can add during dissolving or not with inert diluent as benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound.Wherein, benzene,toluene,xylene is good, and toluene, dimethylbenzene are best.
Organic epoxy compound thing described in component (A) comprises carbonatoms at the aliphatics alkene of 2 ~ 8, the compound such as oxide compound, glycidyl ether, inner ether of diolefine halogenated aliphatic alkene or diolefine.Particular compound is as oxyethane, propylene oxide, butylene oxide ring, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.Wherein, being preferably oxyethane, propylene oxide, epoxy chloropropane, tetrahydrofuran (THF), is best with tetrahydrofuran (THF), epoxy chloropropane.
Organo phosphorous compounds described in component (A) comprises hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, triphenyl phosphite, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, triphenyl phosphite, phosphorous acid benzene methyl etc.Wherein, be preferably ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl and ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid tri-n-butyl is best.
Electron donor described in component (A) can be selected from C
1~ C
20alcohol or isomery alcohol, such as: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-Ethylhexyl Alcohol, n-Octanol, lauryl alcohol, glycerol, amylalcohol, decyl alcohol, dodecanol, Stearyl alcohol, Bian alcohol, phenylethyl alcohol, with C
1~ C
8straight chain alcohol be best.
Magnesium halide described in component (A) also can add alkyl metal cpd as zinc alkyl(s) and or aluminum alkyls in the process of dissolving formation homogeneous solution.
Can also add silicoorganic compound in component (A), the general formula of silicoorganic compound is R
1 xr
2 ysi (OR
3)
z, wherein R
1and R
2be respectively alkyl or halogen, R
3for alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.Particular compound comprises: tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride etc.
Mol ratio in component (A) between each component in every mole of magnesium halide, organic epoxy compound thing 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Organo phosphorous compounds 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Electron donor 0.005 ~ 15 mole, with 0.05 ~ 10 mole as well; Alkyl metal cpd 0 ~ 2 mole, with 0 ~ 0.5 mole as well; The halogenide of transition metals Ti or 0.2 ~ 20 mole, derivative; Silicoorganic compound are 0.05 ~ 1 mole.In component (A), titaniferous amount is 1wt% ~ 8wt%.
The preparation method of component A: under agitation magnesium halide is dissolved in organic epoxy compound thing and organo phosphorous compounds and adds electron donor again, form homogeneous transparent solution, add or do not add alkyl metal cpd, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, by the halogenide of transition metals Ti or derivative instillation magnesium halide homogeneous solution, silicoorganic compound can be added at-30 ~ 110 DEG C, filter, wash, obtain component A solids.
Described component (B) organo-aluminium compound is alkylaluminium cpd.Wherein the molar ratio computing of aluminium and titanium is 100 ~ 0.001, preferably 10 ~ 0.01, be preferably 1 ~ 0.1.
Catalyst A of the present invention, B, component C can directly apply to polymerization system, also can be applied to polymerization system after first pre-complexing.
Catalyzer of the present invention can be used for all polymerizations of ethene, also can be used for the copolymerization of ethene and alpha-olefin, and comonomer can adopt propylene, butylene, amylene, hexene, octene, 4-methyl 1-amylene.
Polymerization process comprises the following steps: the preparation of (1) component A: be under agitation dissolved in organic epoxy compound thing and organo phosphorous compounds by magnesium halide and add electron donor again, form homogeneous transparent solution, add or do not add alkyl metal cpd, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, by the halogenide of transition metals Ti or derivative instillation magnesium halide homogeneous solution, silicoorganic compound can be added at-30 ~ 110 DEG C, filter, wash, obtain component A solids; (2) in reaction unit, B component organo-aluminium compound, component C halogenated hydrocarbon compound mix with component A, carry out vinyl polymerization.
B component organo-aluminium compound in step (2) and component C halogenated hydrocarbon compound can also be obtained by reacting mixture in advance, and then mix with component A, carry out vinyl polymerization.
When adopting the method dripping halogenated titanium, time for adding preferably controls within 5 hours, and when heating up gradually, heat-up rate with intensification per hour 4 ~ 100 DEG C as well.
Through above-mentioned steps, obtained (A) component of invention catalyst system, this component can the form of solids or suspension use.
Can liquid polymerization be adopted during polymerization, also can adopt vapour phase polymerization.When carrying out liquid polymerization, propane, hexane, heptane, hexanaphthene, Trimethylmethane, iso-pentane, petroleum naphtha can be used, raffinate oil, the inert solvent such as aliphatic saturated hydrocarbon or aromatic hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene makes reaction medium, before polymerization, first can carry out prepolymerization.Polymerization methods can adopt intermittent type, semi continuous or continous way.Polymerization temperature is room temperature ~ 150 DEG C, with 50 DEG C ~ 100 DEG C as well.In order to the molecular weight of telomerized polymer, hydrogen is adopted to make molecular weight regulator.
Due to component A and organo-aluminium compound and halogenated hydrocarbon compound acting in conjunction in catalyst system, when catalyst system of the present invention is used for slurry polymerization, not only embody higher catalytic activity, and the polymkeric substance obtained has higher tensile yield strength.
Embodiment
Following examples describe the present invention's citing specifically, but the present invention is not limited to these embodiments.
Embodiment 1
The preparation of catalyst component (A): through high-purity N
2in the reactor of abundant displacement, add the anhydrous MgCl of 4.0g successively
2, 50mL toluene, 2.0mL epoxy chloropropane, 3.0mL tributyl phosphate, 50 DEG C are warmed up under stirring, and maintain 15 minutes, add 6.0mL ethanol, continue reaction 15 minutes, this solution is cooled to-5 ~ 0 DEG C, again 30mL titanium tetrachloride is added dropwise in above-mentioned magnesium chloride homogeneous solution, add 5ml tetraethoxy-silicane again, by solution warms to 80 DEG C, removing mother liquor.With hexanes wash 4 times, vacuum-drying, obtains ingredient of solid catalyst A.
Vinyl polymerization 1: volume be the stainless steel still of 2 liters after H2 fully replaces, add hexane 1000mL wherein, metering containing 0.5mmolTi above-mentioned prepared ingredient of solid catalyst A, triethyl aluminum 1.0mmol.Adding 1,2-ethylene dichloride makes itself and catalyzer Ti mol ratio be 1.5, is warming up to 70 DEG C of hydrogenation 0.26MPa, then passes into ethene and make to reach 0.73MPa (gauge pressure) in still, at 85 DEG C, is polymerized 2 hours.
Vinyl polymerization 2: volume is that the stainless steel still of 2 liters is after ethene is fully replaced, add hexane 1000mL wherein, catalyzer (B) component triethyl aluminum 2.0mL, that measures contains the above-mentioned prepared ingredient of solid catalyst A of 0.5mmolTi, adds 1,2-ethylene dichloride and makes itself and catalyzer Ti mol ratio be 1.5, be warming up to 70 DEG C of hydrogenation 0.15MPa (gauge pressure), pass into ethene again to make in still, to reach 0.25MPa (gauge pressure), at 85 DEG C, be polymerized 2 hours.
Embodiment 2
Catalyst component (A), with embodiment 1, only will add 1,2-ethylene dichloride in polymerization 1 and 2 and make the mol ratio of Ti in itself and catalyzer change 1.0 into.
Embodiment 3
Catalyst component (A), with embodiment 1, only will add 1,2-ethylene dichloride in polymerization 1 and 2 and make the mol ratio of Ti in itself and catalyzer change 2.0 into.
Embodiment 4
Catalyst component (A), with embodiment 1, will add trichloromethane in polymerization 1 and 2 and makes the mol ratio of Ti in itself and catalyzer be 1.0.
Embodiment 5
Catalyst component (A), with embodiment 1, will add trichloromethane in polymerization 1 and 2 and make the mol ratio of Ti in itself and catalyzer change 1.5 into.
Embodiment 6
Catalyzer (A) component, with embodiment 1, will add trichloromethane in polymerization 1 and 2 and make the mol ratio of Ti in itself and catalyzer change 2.0 into.
Embodiment 7
Catalyzer (A) component is with embodiment 1, and will add trichloromethane in polymerization 1 and 2 and make itself and catalyzer Ti, mol ratio changes 2.5 into.
Embodiment 8
Catalyzer (A) component, with embodiment 1, will add trichloromethane in polymerization 1 and 2 and make the mol ratio of Ti in itself and catalyzer change 3.0 into.
Embodiment 9
Catalyzer (A) component, with embodiment 1, will add 1-chlorobenzene in polymerization 1 and 2 and make the mol ratio of Ti in itself and catalyzer change 2.0 into.
Comparative example: catalyzer synthesizes with embodiment 1 (A) component,
Vinyl polymerization 1: volume be the stainless steel still of 2 liters after H2 fully replaces, add hexane 1000mL wherein, metering containing the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, triethyl aluminum 1.0mmol.Be warming up to 70 DEG C of hydrogenation 0.26MPa (gauge pressure), then pass into ethene and make in still, to reach 0.73MPa (gauge pressure), at 85 DEG C, be polymerized 2 hours.
Vinyl polymerization 2: volume is that the stainless steel still of 2 liters is after ethene is fully replaced, add hexane 1000mL wherein, catalyzer (B) component 2.0mL, that measures contains the above-mentioned prepared ingredient of solid catalyst of 0.5mmolTi, be warming up to 70 DEG C of hydrogenation 0.15MPa (gauge pressure), pass into ethene again to make in still, to reach 0.25MPa (gauge pressure), at 85 DEG C, be polymerized 2 hours.
Test poly tensile yield strength: by polymerization 1 powder 53%, the ratio of being polymerized 2 powders 47% takes polyethylene powder, carries out Mechanics Performance Testing after Homogeneous phase mixing.
Experimental result is in table 1
Table 1 polymerization result 1
Table 2 polymerization result 2
As can be seen from the data of table 1 and table 2, when catalyst system of the present invention is used for slurry polymerization, not only embody higher catalytic activity, and the polymkeric substance obtained has higher tensile yield strength.
Claims (15)
1. the catalyzer for ethene slurry polymerization, comprise following component: the ingredient of solid catalyst of (A) titaniferous, it is dissolved in organic epoxy compound thing, organo phosphorous compounds by magnesium halide to add electron donor formation homogeneous solution again, the halogenide or derivatives thereof of transition metals Ti is slowly added in above-mentioned homogeneous solution, with inert diluent washing, obtain the ingredient of solid catalyst of titaniferous; (B) organo-aluminium compound; (C) halogenated hydrocarbon compound, its general formula is R
1r
2x
4-b, R in formula
1c
1~ C
20alkyl or aromatic base, R
2c
1~ C
20alkyl, b is 1,2 or 3, X is F, Cl, Br.
2. a kind of catalyzer for ethene slurry polymerization according to claim 1, it is characterized in that described halogenated hydrocarbon compound is selected from monochlorethane, a chloropropane, a chlorobutane, a chloropentane, a chlorohexane, 1,2-ethylene dichloride, 1,3-propylene dichloride, 1,4-dichlorobutane, 1, at least one in 5-dichloropentane, 1,6-dichloro hexane, trichloromethane, mono chloro benzene, dichlorobenzene.
3. a kind of catalyzer for ethene slurry polymerization according to claim 1, is characterized in that the mol ratio of described halogenated hydrocarbon compound and titanium is 0.01 ~ 50, the consumption of B component with the molar ratio computing of aluminium and titanium for 100 ~ 0.001.
4. a kind of catalyzer for ethene slurry polymerization according to claim 1, is characterized in that the mol ratio of described halogenated hydrocarbon compound and titanium is 0.1 ~ 10, the consumption of B component with the molar ratio computing of aluminium and titanium for 1 ~ 0.1.
5. a kind of catalyzer for ethene slurry polymerization according to claim 1, it is characterized in that described component (A) comprises general formula is R
1 xr
2 ysi (OR
3)
zsilicoorganic compound, wherein R
1and R
2be respectively alkyl or halogen, R
3for alkyl, 0≤x≤2,0≤y≤2 and 0≤z≤4, and x+y+z=4.
6. a kind of catalyzer for ethene slurry polymerization according to claim 5, is characterized in that described silicoorganic compound are selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silicon, silicon tetrachloride.
7. a kind of catalyzer for ethene slurry polymerization according to claim 1, it is characterized in that described magnesium halide comprise one of them halogen atom in complex compound, the magnesium dihalide molecular formula such as water or alcohol of magnesium dihalide, magnesium dihalide by-oxyl or halogen-oxyl the derivative of replacing.
8. a kind of catalyzer for ethene slurry polymerization according to claim 1, is characterized in that described organic epoxy compound thing comprises carbonatoms at the aliphatics alkene of 2 ~ 8, the compound such as oxide compound, glycidyl ether, inner ether of diolefine halogenated aliphatic alkene or diolefine.
9. a kind of catalyzer for ethene slurry polymerization according to claim 1, is characterized in that described organo phosphorous compounds comprises hydrocarbyl carbonate or the halogenation hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.
10. a kind of catalyzer for ethene slurry polymerization according to claim 1, is characterized in that also comprising alkyl metal cpd in described component (A).
11. a kind of catalyzer for ethene slurry polymerization according to claim 1, is characterized in that in every mole of magnesium halide, organic epoxy compound thing 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Organo phosphorous compounds 0.01 ~ 10 mole, with 0.02 ~ 4 mole as well; Electron donor 0.005 ~ 15 mole, with 0.05 ~ 10 mole as well; The halogenide of transition metals Ti or 0.2 ~ 20 mole, derivative.
12. a kind of catalyzer for ethene slurry polymerization according to claim 1, it is characterized in that the halogenated hydrocarbon compound after by dilution is under-10 ~ 10 DEG C of conditions, slowly be added drop-wise in organo-aluminium compound, rate of addition is 0.1 ~ 0.5ml/min, and then with component A contact reacts.
13. a kind of catalyzer for ethene slurry polymerization according to claim 1, it is characterized in that by organo-aluminium compound and halogenated hydrocarbon compound respectively with component A contact reacts.
14. application of the catalyzer for ethene slurry polymerization according to claim 1 in slurry polymerization, comprise the following steps: the preparation of (1) component A: under agitation magnesium halide is dissolved in organic epoxy compound thing and organo phosphorous compounds and adds electron donor again, form homogeneous transparent solution, add or do not add alkyl metal cpd, at-35 ~ 60 DEG C of temperature, best-30 ~ 10 DEG C, by the halogenide of transition metals Ti or derivative instillation magnesium halide homogeneous solution, silicoorganic compound can be added at-30 ~ 110 DEG C, filter, washing, obtain component A solids, (2) in reaction unit, B component organo-aluminium compound, component C halogenated hydrocarbon compound mix with component A, carry out vinyl polymerization.
15. application of the catalyzer for ethene slurry polymerization according to claim 14 in slurry polymerization, it is characterized in that B component organo-aluminium compound in step (2) and component C halogenated hydrocarbon compound are obtained by reacting mixture in advance, and then mix with component A, carry out vinyl polymerization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273530.3A CN105330770B (en) | 2014-06-18 | 2014-06-18 | A kind of catalyst and its application for ethylene slurry polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273530.3A CN105330770B (en) | 2014-06-18 | 2014-06-18 | A kind of catalyst and its application for ethylene slurry polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105330770A true CN105330770A (en) | 2016-02-17 |
| CN105330770B CN105330770B (en) | 2018-11-30 |
Family
ID=55281553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410273530.3A Active CN105330770B (en) | 2014-06-18 | 2014-06-18 | A kind of catalyst and its application for ethylene slurry polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105330770B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690153A (en) * | 2018-04-13 | 2018-10-23 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN112759683A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189505A (en) * | 1997-01-31 | 1998-08-05 | 台湾聚合化学品股份有限公司 | Ti family catalyst system capable of polymerizing olefines |
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst for ethylene polymerization or copolymerization and preparation method thereof |
| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
| CN102977232A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization |
| CN102977235A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component for ethylene polymerization and catalyst system composed of the titanium-containing solid catalyst component |
| CN103772543A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylene polymerization catalyst and production method thereof |
| CN103772550A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and catalyst thereof |
-
2014
- 2014-06-18 CN CN201410273530.3A patent/CN105330770B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189505A (en) * | 1997-01-31 | 1998-08-05 | 台湾聚合化学品股份有限公司 | Ti family catalyst system capable of polymerizing olefines |
| CN1229092A (en) * | 1998-03-17 | 1999-09-22 | 中国石油化工集团公司 | Catalyst for ethylene polymerization or copolymerization and preparation method thereof |
| CN101139407A (en) * | 2006-09-07 | 2008-03-12 | 北京金鼎科化工科技有限公司 | Catalyst active component for ethylene polymerization or copolymerization and catalyst precursor comprising the active component and preparation method thereof |
| CN102977232A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization |
| CN102977235A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Titanium-containing solid catalyst component for ethylene polymerization and catalyst system composed of the titanium-containing solid catalyst component |
| CN103772543A (en) * | 2012-10-19 | 2014-05-07 | 中国石油化工股份有限公司 | Ethylene polymerization catalyst and production method thereof |
| CN103772550A (en) * | 2012-10-23 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst ingredient used for ethylene polymerization, and catalyst thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690153A (en) * | 2018-04-13 | 2018-10-23 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN108690153B (en) * | 2018-04-13 | 2021-03-30 | 中国石油天然气股份有限公司 | Olefin polymerization catalyst, preparation method and application thereof |
| CN112759683A (en) * | 2019-11-04 | 2021-05-07 | 中国石油化工股份有限公司 | Olefin polymerization catalyst and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105330770B (en) | 2018-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100406476C (en) | Prepolymerized catalyst components for polymerization of olefins | |
| CN101173014B (en) | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same | |
| CN101942050B (en) | Catalyst component for ethylene polymerization in slurry process and preparation method thereof | |
| CN102039187B (en) | Load type non-metallocene catalyst as well as preparation method and application thereof | |
| CN103772543A (en) | Ethylene polymerization catalyst and production method thereof | |
| CN102295716B (en) | Catalyst used for vinyl polymerization and preparation method as well as application thereof | |
| CN102977232B (en) | A kind of catalyst system for vinyl polymerization | |
| CN105330770A (en) | Catalyst used for ethylene slurry polymerization and application thereof | |
| CN102977233B (en) | Catalyst system for ethylene polymerization | |
| CN103772553A (en) | Catalyst for ethylene polymerization and its preparation method | |
| CN102059153B (en) | Loaded non-metallocene catalyst and preparation method and application thereof | |
| CN105175587A (en) | Catalyst used for ethylene polymerization, and application thereof | |
| CN101565476B (en) | Catalyst for ethylene polymerization or copolymerization through slurry method and preparation method and application thereof | |
| CN106008759B (en) | A kind of electron donor of Ziegler Natta catalyst and its application in ethylene polymerization | |
| CN102977235B (en) | Catalyst component for ethylene polymerization and catalyst | |
| CN102977231B (en) | Catalyst system for ethylene polymerization | |
| CN102039188A (en) | Supported non-metallocene catalyst, its preparation method and uses | |
| CN102059150B (en) | Loaded non-metallocene catalyst and preparation method and application thereof | |
| CN102532357B (en) | Catalyst applied to vinyl polymerization and preparation method and application thereof | |
| CN102321206B (en) | Ethylene polymerization catalyst, preparation and application thereof | |
| CN105732851B (en) | Preparation method and application of ethylene polymerization catalyst with magnesium ethoxide spherical carrier | |
| CN111057169B (en) | Catalyst for olefin polymerization and preparation method and application thereof | |
| CN105199022A (en) | Catalyst for ethylene homopolymerization or copolymerization and application thereof | |
| CN105199023A (en) | Catalyst for ethylene homopolymerization or copolymerization and application thereof | |
| CN102964490A (en) | Supported non-metallocene catalyst, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |