CN106632755B - Catalyst system for ethylene polymerization and application thereof - Google Patents
Catalyst system for ethylene polymerization and application thereof Download PDFInfo
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- CN106632755B CN106632755B CN201510717141.XA CN201510717141A CN106632755B CN 106632755 B CN106632755 B CN 106632755B CN 201510717141 A CN201510717141 A CN 201510717141A CN 106632755 B CN106632755 B CN 106632755B
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Abstract
The application discloses a catalyst system for ethylene polymerization, which comprises the following components: component a titanium-containing solid catalyst component prepared by: dissolving magnesium halide in a solvent system containing an organic alcohol compound to form a solution, adding an organic silicon compound without active hydrogen to obtain a mixed solution, then carrying out a titanium carrying process by contacting and reacting the mixed solution with a titanium compound, optionally adding or not adding the organic silicon compound without active hydrogen for reaction, stirring and washing; component B an organoaluminum compound, and component C a halogenated metal compound. The application also discloses the use of the catalyst system in ethylene polymerization. When the catalyst system is used for ethylene polymerization, the ethylene polymerization activity can be improved, and the apparent density of the polymer is improved.
Description
Technical Field
The invention relates to a catalyst system for olefin polymerization, in particular to ethylene polymerization, and a preparation method and application of the catalyst system.
Background
As is well known, polyethylene resin with wide molecular weight distribution has comprehensive excellent physical and mechanical properties and processability, and is widely used for film materials, pipes, hollow products, cable materials and the like. The polymerization process for producing polyethylene with wide molecular weight distribution mainly adopts a polymerization mode of a serial multistage hydrogenation reactor. Commonly known are dual reactor series polymerization processes, including liquid-liquid phase processes, gas-gas phase processes, and liquid-gas phase processes. In the double reactor polymerization process, the polyethylene produced in different reactors has different molecular weights mainly by adjusting the hydrogen concentration and the polymerization conditions in the two reactors, thereby realizing the bimodal or broad distribution of the molecular weight of the final polymerization product. The multistage reactor polymerization process requires a catalyst having good hydrogen response, especially at high hydrogen concentrations and high polymerization activity. At the same time, the polymers are also required to have good particle morphology. In the prior art catalyst technology, the catalysts used in the two reactor polymerization process are primarily Z-N catalysts. To obtain the low molecular weight fraction (high melt index) of bimodal resins, high hydrogen concentrations are used in the first reactor, resulting in low catalyst activity, increased catalyst loading, and, in addition, the polymer particle shape also affects the continuous stability of the operation.
Japanese document discloses a method for ethylene polymerization and copolymerization with a Z/N type catalyst, wherein an alkane compound is used as a solvent, an alcohol compound is in contact reaction with a magnesium compound, and due to the large polarity difference between the alcohol and the alkane solvent, magnesium halide cannot be completely dissolved to form a homogeneous solution, but a fine-particle colloidal suspension or a swelled magnesium halide slurry is generated. This results in some disadvantages associated with the lamellar crystalline nature of magnesium halides, such as: the prepared polymer has low apparent density, poor particle shape and distribution and the like. There is disclosed a catalyst obtained by dissolving a magnesium halide in isooctanol to form a transparent solution, and reacting the solution with a halide of a transition metal titanium or a derivative thereof, and combining the solution with an organoaluminum compound at the time of polymerization. During the preparation of the catalyst, magnesium chloride is dissolved to form a uniform and transparent solution, and the obtained catalyst has good particle morphology, shows higher activity when used for ethylene polymerization, has higher apparent density, but has poor sensitivity to hydrogen.
Disclosure of Invention
Aiming at the defects of the catalyst system in the prior art, the inventor of the invention finds that the introduction of the halogenated metal compound into the catalyst system can improve the catalytic activity of ethylene polymerization, and the apparent density of the polymer is improved.
According to one aspect of the present invention, there is provided a catalyst system for ethylene polymerization comprising the following components: component a titanium-containing solid catalyst component prepared by: dissolving magnesium halide in a solvent system containing an organic alcohol compound to form a solution, adding an organic silicon compound without active hydrogen to obtain a mixed solution, then carrying out a titanium carrying process by contacting and reacting the mixed solution with a titanium compound, optionally adding or not adding the organic silicon compound without active hydrogen for reaction, stirring and washing; component B an organoaluminum compound, and component C a halogenated metal compound.
The introduction of the halogenated metal compound into the catalyst system can improve the ethylene polymerization activity of the catalyst and simultaneously improve the apparent density of the polyethylene. According to the catalyst system provided by the invention, due to the interaction among the components, the obtained catalyst system is used for ethylene polymerization, the catalytic activity and the hydrogen regulation sensitivity are improved, the molecular weight distribution can be broadened, and the melt index can be improved.
According to a preferred embodiment of the present invention, the halogenated metal compound includes at least one of germanium tetrachloride, germanium tetrabromide, antimony tetrachloride, tellurium tetrabromide, tin tetrachloride, tin tetrabromide, diethyl germanium dichloride, dimethyl germanium dichloride, diethyl tellurium dichloride, dimethyl tellurium dichloride, diphenyl germanium dichloride, triethyl germanium chloride, trimethyl germanium chloride and triphenyl germanium chloride. According to a specific embodiment of the present invention, the molar ratio of the component C to the component a is 200:1 to 0.01:1, such as 50:1 to 0.05:1, preferably 50:1 to 0.5:1, based on the molar ratio of the halogenated metal compound to titanium.
According to a particular embodiment of the invention, said component B is an alkylaluminum compound. Specific alkylaluminum compounds are known in the art, and all alkylaluminum compounds useful in this field can be used in the present invention. And will not be described in detail herein. In a specific example, the molar ratio of component B to component A, calculated as aluminum/titanium, is from 100:1 to 0.001:1, preferably from 10:1 to 0.01:1, more preferably from 1:1 to 0.1: 1.
According to the present invention, a magnesium halide is dissolved in a solvent system containing an organic alcohol compound to form a homogeneous solution, optionally with or without the use of an inert diluent in the solvent system.
According to the present invention, the magnesium halide includes at least one of magnesium dihalide, a complex of magnesium dihalide with water or alcohol, and a derivative of magnesium dihalide in which one halogen atom is replaced by hydrocarbyloxy group or halohydrocarbyloxy group in the molecular formula. The magnesium dihalide is specifically at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide. Among them, magnesium dichloride is particularly preferable. The magnesium halide used preferably has a particle size which is easily dissolved by stirring, and the dissolution temperature is-10 ℃ to 150 ℃, preferably 50 ℃ to 140 ℃.
According to the invention, an inert diluent is optionally added during dissolution. The inert diluent includes aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, etc.; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and the like; aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as 1, 2-dichloroethane, chlorobenzene, etc. Among them, decane is preferable.
According to the invention, the organic alcohol comprises C1-C20Linear or isomeric alcohols. Including at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, glycerol, pentanol, decanol, dodecanol, octadecanol, benzyl alcohol, and phenethyl alcohol, etc. 2-ethylhexanol is particularly preferred. The organic alcohol is used in an amount capable of dissolving the magnesium halide. In a specific example, the amount of the organic alcohol is from 0.005 to 25 moles, preferably from 0.05 to 10 moles, per mole of the magnesium halide.
According to the present invention, the magnesium halide solution obtained in the above step is added with an organosilicon compound having no active hydrogen, and then contacted with a titanium compound (preferably at a low temperature). The low temperatures mentioned here are temperatures of-35 to 60 ℃ and preferably-30 to 10 ℃.
In a specific embodiment, magnesium halide is dissolved in a solvent system formed by organic alcohol or organic alcohol and inert solvent under stirring to form a uniform solution, and an organosilicon compound without active hydrogen is added to obtain a mixed solution. The titanium compound is dropped into the mixed solution preferably at a temperature of-35 to 60 c, preferably-30 to 10 c, or conversely, the titanium supporting process is carried out by a contact reaction of both. Then, optionally, an organosilicon compound free of active hydrogen is added or not added at-30 to 120 ℃ (e.g., -30 to 110 ℃). Thereafter, stirring is carried out (preferably at a temperature of 80-120 ℃ C. for 1 minute to 10 hours), then the mother liquor is filtered, removed and the solid is washed with an inert diluent (e.g., toluene, such as hexane). When the method of dropping the mixed solution into the titanium compound is employed, the dropping time is preferably controlled within 5 hours, and when the temperature is gradually raised, the temperature is preferably raised at a rate of 4 to 100 ℃ per hour.
According to a specific embodiment of the present invention, the titanium compound is a compound commonly used in the art, such as at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, and trichloromonoethoxytitanium. The amount of the titanium compound is 0.2 to 200mol, preferably 3 to 100mol, per mol of the magnesium halide. In another specific example, the amount of the titanium compound is 0.2mol to 20 mol.
According to another embodiment of the present invention, the organosilicon compound free of active hydrogen has the formula R1 XR2 YSi(OR3)ZWherein x is 0. ltoreq.2, y is 0. ltoreq.2, z is 0. ltoreq.4, and x + y + z is 4, R2Is halogen, R1And R3Are each a hydrocarbyl group, preferably independently C1-C4A hydrocarbon group of (1). Preferably, the organosilicon compound is at least one selected from tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. The amount of the silicon compound is such that the amount of the silicon compound is 0.05 to 5mol, preferably 0.05 to 1mol, per mol of the magnesium compound.
By means of the component A according to the invention, it is possible to use it in the form of a solid or a suspension.
According to another aspect of the present invention, there is also provided the use of the above catalyst system in the polymerization of ethylene.
The polymerization in the present invention includes homopolymerization of ethylene and copolymerization of ethylene and alpha-olefin. The comonomer alpha-olefins may be propylene, butene, pentene, hexene, octene and/or 4-methyl-1-pentene.
According to one embodiment of the use according to the invention, component C is added during the preparation of component A. In a preferred embodiment, the component C is added after the titanium loading process is completed. Then, before or during the polymerization, it is mixed with component B.
According to another embodiment of the use of the present invention, any two of the component A, the component B and the component C are premixed and then mixed with the other component. For example, among others: (1) pre-mixing the component A with the component C, and then mixing with the component B; (2) component C is premixed with component B and then with component a and so on. The mixing after the premixing may be conducted before the polymerization or at the time of the polymerization. When component C is premixed with component B, the halogenated metal compound of component C is preferably added dropwise to component B at a temperature of from-10 to 60 ℃, preferably from 0 to 60 ℃. Among them, the dropping rate is preferably 0.1 to 0.5 ml/min. Preferably component C is diluted before addition.
According to another embodiment of the use according to the invention, the component A, the component B and the component C are added simultaneously at the time of use. The component A, the component B and the component C can be added simultaneously for complexation before polymerization and then used for polymerization. Or during the polymerization, the component A, the component B and the component C are added simultaneously for ethylene polymerization.
In the above application mode, the components A, B and C in the catalyst system are respectively added into the reaction system; and adding the components A, B and C into the reaction system after pre-complexing.
According to the present invention, the polymerization may be carried out by liquid phase polymerization or gas phase polymerization. In the liquid phase polymerization, an inert solvent such as a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc. may be used as a reaction medium, and a prepolymerization may be carried out before the polymerization. The polymerization may be carried out in a batch, semi-continuous or continuous manner. The polymerization temperature is preferably from room temperature to 150 ℃ and more preferably from 50 ℃ to 100 ℃. In order to regulate the molecular weight of the polymer, hydrogen is used as a molecular weight regulator. In a specific example, the polymerization is a slurry polymerization.
According to the invention, the component A in the catalyst system, the organic aluminum compound and the halogenated metal compound act together, and when the catalyst system is used for ethylene homopolymerization or copolymerization, the catalyst system not only embodies higher ethylene polymerization catalytic activity, but also improves the apparent density of the polymer.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Example 1:
preparation of component A:
in the presence of high purity N2To the fully displaced reactor, 4.0g of anhydrous MgCl was added in sequence228mL of decane and 24mL of 2-ethylhexanol, and the mixture was heated to 130 ℃ with stirring and maintained for 3 hours, cooled to 50 ℃, and then 3mL of tetraethoxysilane was added and stirred for 2 hours to obtain a mixed solution. The mixed solution was cooled to room temperature. In another by high purity N2100ml of titanium tetrachloride is added into a reactor which is fully replaced, the titanium tetrachloride is cooled to-5 ℃ under stirring, the prepared mixed solution is slowly dripped into titanium tetrachloride liquid, the temperature is slowly raised to 110 ℃ after dripping, and the reaction is carried out for 2 hours at the temperature. The mother liquor was removed, and the solid was washed with hexane several times to obtain a solid catalyst component A.
Ethylene polymerization
Stainless steel kettle vessel H with volume of 2 liters2After sufficient displacement, 1000mL of hexane, a metered amount of the above-prepared solid catalyst component containing 0.5mmol of Ti, 1.0mmol of triethylaluminum, and germanium tetrachloride were added theretoThe molar ratio to Ti in the solid catalyst component was 3.6. The temperature is raised to 70 ℃, hydrogenation is carried out for 0.26MPa (gauge pressure), ethylene is introduced to ensure that the pressure in the kettle is 0.72MPa (gauge pressure), and polymerization is carried out for 2 hours at 80 ℃.
Example 2
Component A As in example 1, the molar ratio of germanium tetrachloride to Ti in the solid catalyst component was changed to 9 by merely adding germanium tetrachloride during the polymerization.
Example 3
Component A As in example 1, the molar ratio of germanium tetrachloride to Ti in the solid catalyst component was changed to 18 by adding only germanium tetrachloride during the polymerization.
Example 4
Component A germanium tetrachloride was added to the polymerization as in example 1 and the molar ratio to Ti in the solid catalyst component was changed to 27.
Example 5
Component A germanium tetrachloride was added to the polymerization as in example 1 and the molar ratio to Ti in the solid catalyst component was changed to 36.
Example 6
Component A germanium tetrachloride was added to the polymerization as in example 1 and made to be 45 moles with respect to Ti in the solid catalyst component.
Example 7
Preparation of components:
in the presence of high purity N2To the fully displaced reactor, 4.0g of anhydrous MgCl was added in sequence228mL of decane and 24mL of 2-ethylhexanol, and the mixture was heated to 130 ℃ with stirring and maintained for 3 hours, cooled to 50 ℃, and then 3mL of tetraethoxysilane was added and stirred for 2 hours to obtain a mixed solution. The mixed solution was cooled to room temperature. In another by high purity N2100ml of titanium tetrachloride was added to the fully-replaced reactor, and the mixture was cooled to-5 ℃ with stirring, and the prepared mixed solution was slowly added dropwise to the titanium tetrachloride liquid, and after completion of the addition, 5ml of germanium tetrachloride (molar ratio of germanium tetrachloride to magnesium: 1) was added, and the temperature was slowly raised to 110 ℃ over 3 hours, and the reaction was continued at that temperature for 2 hours. The mother liquor was removed and the solid was washed several times with hexane to give a solid.
Ethylene polymerization:
stainless steel with a volume of 2 litersKettle warp H2After sufficient displacement, 1000mL of hexane, a metered amount of the solid prepared above containing 0.5mmol of Ti, and 1.0mmol of triethylaluminum were added thereto. The temperature is raised to 70 ℃, hydrogenation is carried out for 0.26MPa (gauge pressure), ethylene is introduced to ensure that the pressure in the kettle is 0.72MPa (gauge pressure), and polymerization is carried out for 2 hours at 85 ℃.
Comparative example 1:
catalyst component synthesis component a was the same as example 1.
Ethylene polymerization 1: stainless steel kettle vessel H with volume of 2 liters2After sufficient displacement, 1000mL of hexane, a metered amount of the above-prepared solid catalyst component containing 0.5mmol of Ti, and 1.0mmol of triethylaluminum were added thereto. The temperature is raised to 70 ℃, hydrogenation is carried out for 0.26MPa (gauge pressure), ethylene is introduced to ensure that the pressure in the kettle is 0.72MPa (gauge pressure), and polymerization is carried out for 2 hours at 80 ℃. The results are shown in Table 1.
TABLE 1 polymerization results
As can be seen from the data in Table 1, the catalyst system of the present invention can improve the catalytic activity and the apparent density of the polymer when used for ethylene polymerization.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (18)
1. A catalyst system for the polymerization of ethylene, consisting of: component a titanium-containing solid catalyst component prepared by: dissolving magnesium halide in a solvent system containing an organic alcohol compound to form a solution, adding an organic silicon compound without active hydrogen to obtain a mixed solution, then carrying out a titanium carrying process by contacting and reacting the mixed solution with a titanium compound, optionally adding or not adding the organic silicon compound without active hydrogen for reaction, stirring and washing; component B an organoaluminum compound and component C a halogenated metal compound; the halogenated metal compound is germanium tetrachloride;
the molar ratio of the component C to the component A is 200:1-0.01:1 in terms of the molar ratio of the halogenated metal compound to titanium; and/or the molar ratio of the component B to the component A is 100:1 to 0.001:1 in terms of aluminum/titanium.
2. The catalyst system of claim 1, wherein the molar ratio of component C to component a is 50:1 to 0.5:1, based on the molar ratio of the halogenated metal compound to titanium; and/or the molar ratio of the component B to the component A is 10:1-0.01:1 in terms of aluminum/titanium.
3. The catalyst system of claim 2 wherein the molar ratio of component B to component a is from 1:1 to 0.1:1 on an aluminum/titanium basis.
4. A catalyst system as claimed in any one of claims 1 to 3 wherein the organosilicon compound free of active hydrogen is of the formula R1 XR2 YSi(OR3)ZWherein x is 0. ltoreq.2, y is 0. ltoreq.2, z is 0. ltoreq.4, and x + y + z is 4, R2Is halogen, R1And R3Are all hydrocarbyl groups; and/or
The magnesium halide compound comprises at least one of magnesium dihalide, a water or alcohol complex of magnesium dihalide, and a derivative of magnesium dihalide in which one halogen atom is replaced by hydrocarbyloxy or halohydrocarbyloxy; and/or
The titanium compound is at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium; and/or
The organic alcohol comprises C1-C20Linear or isomeric alcohols.
5. The catalyst system of claim 4 wherein the organosilicon compound free of active hydrogen is independently C1-C4A hydrocarbon group of (a); and/or
The organic alcohol comprises at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, glycerol, pentanol, decanol, dodecanol, octadecanol, benzyl alcohol and phenethyl alcohol.
6. The catalyst system according to claim 5, wherein the organosilicon compound is at least one member selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
7. The catalyst system according to any one of claims 1 to 3, characterized in that the titanium compound is used in an amount of 0.2 to 200mol per mol of magnesium compound; and/or the silicon compound is used in an amount of 0.05mol to 5 mol; and/or the organic alcohol is used in an amount of 0.005mol to 25 mol.
8. The catalyst system according to claim 7, wherein the titanium compound is used in an amount of 3 to 100mol per mol of the magnesium compound; and/or the silicon compound is used in an amount of 0.05mol to 1 mol; and/or the organic alcohol is used in an amount of 0.05mol to 10 mol.
9. The catalyst system according to any one of claims 1 to 3, wherein the mixed solution is contacted with a titanium compound to react at-30 to 60 ℃; and/or the stirring is carried out at 80 to 120 ℃ for 1 minute to 10 hours.
10. The catalyst system according to claim 9, wherein the contacting reaction of the mixed solution with the titanium compound is carried out at-30 to 10 ℃.
11. Use of a catalyst system according to any one of claims 1 to 10 in the polymerisation of ethylene.
12. Use according to claim 11, wherein component C is added during the preparation of component a.
13. Use according to claim 12, wherein component C is added after the titanium loading process is completed.
14. Use according to claim 11, wherein any two of component a, component B and component C are premixed and then mixed with the other component.
15. Use according to claim 14, wherein the halogenated metal compound of component C is brought to a temperature of-10 to 60 ℃ when component C is premixed with component B.
16. Use according to claim 15, characterized in that it is added dropwise to component B at a temperature of 0-60 ℃.
17. Use according to claim 16, wherein the dropping rate is 0.1-0.5 ml/min.
18. Use according to claim 11, wherein, in use, component a, component B and component C are added simultaneously.
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| CN1958620A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst components in use for polymerizing ethylene, and catalyst |
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| CN102295716A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst used for vinyl polymerization and preparation method as well as application thereof |
| CN102977233A (en) * | 2011-09-02 | 2013-03-20 | 中国石油化工股份有限公司 | Catalyst system for ethylene polymerization |
| CN103087226A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction or ethylene copolymerization reaction, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1958620A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst components in use for polymerizing ethylene, and catalyst |
| CN101939342A (en) * | 2008-02-07 | 2011-01-05 | 巴塞尔聚烯烃意大利有限责任公司 | Catalyst for the polymerization of olefins |
| CN102295716A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst used for vinyl polymerization and preparation method as well as application thereof |
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