CN109384870B - Ethylene polymerization main catalyst and preparation method thereof, ethylene polymerization catalyst and solution method copolymerization method of ethylene - Google Patents
Ethylene polymerization main catalyst and preparation method thereof, ethylene polymerization catalyst and solution method copolymerization method of ethylene Download PDFInfo
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Abstract
The invention provides an ethylene polymerization main catalyst for ethylene copolymerization by a solution method and a preparation method thereof. The invention also provides an ethylene polymerization catalyst containing the ethylene polymerization main catalyst and a solution method copolymerization method of ethylene. The catalyst system formed by the main catalyst can improve the copolymerization capability of ethylene in a solution method ethylene copolymerization process, and is suitable for preparing polyethylene resin with lower density.
Description
Technical Field
The invention relates to the field of ethylene copolymerization, in particular to an ethylene polymerization main catalyst for ethylene solution copolymerization, a preparation method thereof, an ethylene polymerization catalyst containing the main catalyst, and a solution method copolymerization method of ethylene.
Background
Polyethylene processes are divided into low pressure processes for the production of LLDPE and HDPE and high pressure processes, for a total of three production processes, including slurry, gas phase and solution processes. The polymer in the slurry process is in a suspended state and is insoluble in alkane diluents; in the gas phase process, the polymer exists in a solid particle state in a stirred bed or a fluidized bed; in the solution process, the polymer is dissolved in a solvent.
The greatest advantages of the solution process are short product switching times, low gel content in the film stock, the production of a full range of products (molecular weight distribution from narrow to broad) and lower density polyethylenes (i.e., VLDPEs, such as PE plastomers and elastomers), the copolymerization with higher alpha-olefins, and the excellent strength, toughness and sealability. In the production of lower density polyethylene products, it is desirable to increase the insertion rate of the alpha-olefin comonomer, and therefore, there is a need for a catalyst system which increases the copolymerization ability of ethylene and alpha-olefin, primarily for the production of lower density polyethylene resins.
CN1955198A discloses a main catalyst for ethylene polymerization and a preparation method thereof, an ethylene polymerization or copolymerization catalyst component and a preparation method thereof, which are prepared by reacting a carboxylic ester compound with a general formula of MgR in a liquid hydrocarbon solvent1R2A dialkyl magnesium compound, wherein R1、R2Is the same or different alkyl containing 1-20 carbon atoms, and the mixed solution reacts with a chlorine-containing compound to obtain a catalyst carrier; and (3) reacting the obtained catalyst carrier with a titanium-containing compound, washing and drying to obtain the titanium-containing catalyst component. However, the catalyst prepared by the method is only suitable for slurry method and gas phase method polymerization process, and is especially suitable for slurry method polymerization process.
Because the temperature of the polymerization reaction of ethylene by a slurry method and a gas phase method is 70-85 ℃, and the temperature of the polymerization reaction of ethylene by a solution method is about 200 ℃, the catalyst which is generally suitable for the polymerization process of ethylene by the slurry method and the gas phase method has low activity at the high temperature of about 200 ℃, and is not suitable for the polymerization reaction of ethylene by the solution method.
Currently, the solution-process ethylene polymerization process requires mainly a single-site catalyst for the production of lower density polyethylene. The use of a single-site catalyst requires modification of the original solution process and also requires large adjustment of polymerization process parameters, which increases production cost and difficulty. If the existing Ziegler-Natta catalyst system of the solution process is improved, the copolymerization capability of the catalyst system is improved, so that the capability of producing lower density polyethylene is achieved, and a feasible method is not lost.
Through repeated research, the inventor discovers a Ziegler-Natta catalytic system. The catalyst system can improve the copolymerization capability of ethylene and alpha-olefin in a solution polymerization process.
Disclosure of Invention
The invention aims to provide a main catalyst, a preparation method thereof, an ethylene polymerization catalyst containing the main catalyst and a solution method copolymerization method of ethylene, which can improve the copolymerization capability of ethylene in a solution method ethylene polymerization process and are suitable for preparing polyethylene resin with lower density.
Therefore, the invention provides an ethylene polymerization main catalyst, which is used for the solution-process copolymerization of ethylene and is prepared by reacting an alkyl magnesium compound, a chloralkane compound, a carboxylic ester compound, a silicon chloride compound and a titanium compound, wherein:
(1) the alkyl magnesium compound is represented by the general formula (I) MgR1 nCl2-nIn the formula, R1Same or different is C2～C20The hydrocarbon group of (1) is a saturated or unsaturated linear, branched or cyclic chain, 0<n≤2；
(2) Chloralkane compounds of the general formula (II) R2Cl, wherein R2Is C2～C20The hydrocarbon group of (a), which is a saturated or unsaturated linear, branched or cyclic chain;
(3) the carboxylic ester compounds are shown as general formula (III) R3(COOR4)mIn the formula, R3、R4Same or different, is an aromatic radical or C1～C20M is 1 or 2;
(4) silicon chloride compounds, e.g. of the formulaSi (OR) of the general formula (IV)5)nCl4-nIn the formula, R5Is C2～C20Is a saturated or unsaturated linear, branched or cyclic chain, 0. ltoreq. n<4；
(5) The titanium compound is represented by the general formula (V) Ti (OR)6)nCl4-nIn the formula, R6Is C2～C20Is a saturated or unsaturated linear, branched or cyclic chain, 0. ltoreq. n<4。
The ethylene polymerization main catalyst of the invention, wherein the temperature of the solution-process copolymerization of ethylene is preferably 180-220 ℃.
The ethylene polymerization procatalyst according to the present invention, wherein the alkyl magnesium compound is preferably at least one of diethylmagnesium, dibutylmagnesium, butyloctylmagnesium and butylmagnesium chloride.
The ethylene polymerization main catalyst is characterized in that the chloralkane compound is preferably at least one of methyl chloride, ethyl chloride, 1-chloropropane, 2-chloropropane, n-butyl chloride, isobutane chloride, tert-butyl chloride, cyclohexane chloride, chlorobenzene, p-methyl chlorobenzene and o-methyl chlorobenzene.
The ethylene polymerization main catalyst is characterized in that the carboxylic ester compound is preferably at least one of hydroxyethyl methacrylate, ethyl acrylate, ethyl acetate, ethyl benzoate, ethyl o-benzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate and diamyl phthalate.
The ethylene polymerization procatalyst of the present invention, wherein the silicon compound is preferably a mixture of products obtained by reacting an aliphatic alcohol with silicon tetrachloride. When silicon tetrachloride and aliphatic alcohol are used for reaction, the molar ratio of the aliphatic alcohol to the silicon tetrachloride is lower than 4.0, the reaction temperature is generally controlled between normal temperature and 50 ℃, and the reaction time is controlled between 0.5 and 5 hours.
The main catalyst for ethylene polymerization is characterized in that the titanium compound is preferably a mixture of products obtained by reacting aliphatic alcohol with titanium tetrachloride. When titanium tetrachloride and fatty alcohol are used for the reaction, the molar ratio of the fatty alcohol to the titanium tetrachloride is less than 4.0, the reaction temperature is generally controlled between normal temperature and 100 ℃, and the reaction time is controlled to be 0.5-5 hours.
The invention also provides a preparation method of the main catalyst for ethylene polymerization, which is the preparation method of the main catalyst for olefin polymerization and comprises the following steps:
(1) adding a compound shown in a general formula (II) into alkane solution containing the compound shown in the general formula (I) for mixing reaction;
(2) reacting the reactant in the step (1) with a compound shown in a general formula (III) and a compound shown in a general formula (IV);
(3) and (3) reacting the reactant in the step (2) with a compound shown as a general formula (V) to obtain the main catalyst.
In the preparation method of the main catalyst for ethylene polymerization, the compound represented by the general formula (II) is preferably controlled to be 1-10 mol, the compound represented by the general formula (III) is preferably controlled to be 0.05-2 mol, the compound represented by the general formula (IV) is preferably controlled to be 0.1-5 mol, and the compound represented by the general formula (V) is preferably controlled to be 0.1-5 mol per mol of the compound represented by the general formula (I).
In the preparation method of the main catalyst for ethylene polymerization, it is preferable that the compound represented by the general formula (II) is controlled to be 2 to 5 mol, the compound represented by the general formula (III) is controlled to be 0.1 to 1 mol, the compound represented by the general formula (IV) is controlled to be 0.2 to 2mol, and the compound represented by the general formula (V) is controlled to be 0.2 to 2mol per mol of the compound represented by the general formula (I).
In the preparation method of the main catalyst for ethylene polymerization, the alkane solution containing the compound represented by the general formula (I) preferably further contains aluminum alkyl.
The preparation method of the ethylene polymerization main catalyst provided by the invention has the advantages that the reaction temperature in the steps (1) and (2) is preferably 45-55 ℃, and the reaction temperature in the step (3) is preferably 85-115 ℃. The mixing time for the above step reaction is generally 0.5 to 20 minutes.
The invention also provides an ethylene polymerization catalyst, which is used for the solution method copolymerization of ethylene and is obtained by the reaction of the following components:
(a) the ethylene polymerization main catalyst or the ethylene polymerization main catalyst prepared by the preparation method;
(b) is shown as the general formula (VI) AlR'n(OR”)3-nAn organoaluminum compound represented by the formula, wherein R ' and R ' are the same or different and R ' are C1～C20Alkyl of 1<n≤3。
The ethylene polymerization catalyst of the present invention is preferably one wherein the organoaluminum compound is Al (OEt) Et2、Al(OEt)Et2、(EtO)Al(iso-Bu)2、(EtO)Al(n-C6H13)2And (EtO) Al (n-C)8H17)2Preferably, the molar ratio of the organoaluminum compound to titanium in the main catalyst is controlled to 1 to 500.
In order to make the final catalytic system have higher activity, the main catalyst can be aged for 2-30 minutes at 50-100 ℃ and then mixed with the organic aluminum component.
The invention also provides a solution method copolymerization method of ethylene, the catalyst of the method is the ethylene polymerization catalyst, the reaction monomer is ethylene and alpha-olefin, the alpha-olefin is at least one of butene, pentene, hexene, octene and 4-methylpentene-1, and the reaction temperature is 180-220 ℃.
The catalytic system is suitable for solution-process ethylene polymerization process, and can catalyze the copolymerization of ethylene and other alpha-olefins, wherein the alpha-olefins can be at least one of alkene, butene, pentene, hexene, octene and 4-methylpentene-1. Experiments show that when the catalytic system disclosed by the invention is used for catalyzing ethylene copolymerization, the insertion rate of a comonomer is high, and the density of the obtained polyethylene resin is lower.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
Example 1
(1) Preparation of the principal catalyst component
After 500mL of the autoclave was dried and sufficiently purged with nitrogen, 200mL of anhydrous cyclohexane, 5mL of dibutylmagnesium solution (a 1M hexane solution from Aldrich Co., Ltd., containing 12 mol% of triethylaluminum) and 1.1mL of anhydrous chlorot-butane were added to raise the temperature to 50 ℃, 0.07mL of ethyl benzoate and 0.05mL of silicon tetrachloride were added to react for 5 minutes, 0.1mL of titanium tetrachloride was added to raise the temperature to 100 ℃ and the mixture was stirred for 5 minutes for further use.
(2) Catalytic ethylene polymerization
In a 5L polymerizer, 3L of cyclohexane, 15mL of octene, and 2.3mL of ethyldiethoxyaluminum solution (which is prepared by reacting a triethylaluminum solution and ethanol at a molar ratio of 1:2 and has a concentration of 1M) were charged, followed by warming to 200 ℃. The main component of the catalyst prepared in the 500mL reaction kettle is transferred into a polymerization kettle, and ethylene is continuously introduced to carry out the polymerization reaction of ethylene. During polymerization, the system temperature is maintained at 200 ℃, the total pressure of the system is maintained at 1.0MPa by using ethylene, and after 1 hour of polymerization, the temperature is reduced, the pressure is released, and the material is discharged.
The polymeric resins were tested for relative molecular mass, melt index and density and the results are shown in table 1.
Example 2
The amount of ethyl benzoate 0.07mL in the preparation of the main catalyst component was adjusted to 0.10mL, and the other conditions were the same as in example 1.
Catalyzed ethylene polymerization the polymeric resins were tested for relative molecular mass, melt index and density as in example 1 and the results are shown in table 1.
Example 3
The amount of ethyl benzoate 0.07mL in the preparation of the main catalyst component was adjusted to 0.04mL, and the other conditions were the same as in example 1.
Catalyzed ethylene polymerization the polymeric resins were tested for relative molecular mass, melt index and density as in example 1 and the results are shown in table 1.
Example 4
The amount of ethyl benzoate 0.07mL in the preparation of the main catalyst component was adjusted to 0.05mL of ethyl acetate, and the other conditions were the same as in example 1.
Catalyzed ethylene polymerization the polymeric resins were tested for relative molecular mass, melt index and density as in example 1 and the results are shown in table 1.
Example 5
0.07mL of ethyl benzoate used in the preparation of the main catalyst component was adjusted to 0.10mL of di-n-butyl phthalate, and the other conditions were the same as in example 1.
Catalyzed ethylene polymerization the polymeric resins were tested for relative molecular mass, melt index and density as in example 1 and the results are shown in table 1.
Comparative example 1
The preparation of the main catalyst component is carried out with reference to the process disclosed in patent US 5492876. The specific preparation method is shown as follows.
(1) Preparation of the principal catalyst component
After 500mL of the autoclave was dried and sufficiently purged with nitrogen, 200mL of anhydrous cyclohexane, 0.2mL of titanium tetrachloride and 0.05mL of vanadium oxychloride were added, the temperature was controlled at 30 ℃ and then 3.4mL of a hexane solution of diethylaluminum monochloride (concentration: 1M) was added, and finally the temperature was raised to 100 ℃ and the reaction was stirred for 5 minutes to prepare a solution.
(2) Catalytic ethylene polymerization
In a 5L polymerizer, 3L of cyclohexane, 15mL of octene, and 5.5mL of ethyldiethoxyaluminum solution (which is prepared by reacting triethylaluminum solution and ethanol at a molar ratio of 1:2 and has a concentration of 1M) were charged, followed by warming to 200 ℃. The main component of the catalyst prepared in the 500mL reaction kettle is transferred into a polymerization kettle, and ethylene is continuously introduced to carry out the polymerization reaction of ethylene. During polymerization, the system temperature is maintained at 200 ℃, the total pressure of the system is maintained at 1.0MPa by using ethylene, and after 1 hour of polymerization, the temperature is reduced, the pressure is released, and the material is discharged.
The polymeric resins were tested for relative molecular mass, melt index and density and the results are shown in table 1.
Comparative example 2
The preparation of the main catalyst component is carried out with reference to the process disclosed in patent US 5519098. The specific preparation method is shown as follows.
(1) Preparation of the principal catalyst component
After 500mL of the autoclave was dried and sufficiently purged with nitrogen, 200mL of anhydrous cyclohexane, 5mL of a dibutylmagnesium solution (a 1M hexane solution from Aldrich Co., Ltd., containing 12 mol% of triethylaluminum), 1.3mL of anhydrous chlorot-butane and 0.1mL of titanium tetrachloride were sequentially added while maintaining the bath temperature at 30 ℃ and the temperature was raised to 130 ℃ to stir for 5 minutes for further use.
(2) Catalytic ethylene polymerization
In a 5L polymerizer, 3L of cyclohexane, 15mL of octene, and 2.3mL of ethyldiethoxyaluminum solution (which is prepared by reacting a triethylaluminum solution and ethanol at a molar ratio of 1:2 and has a concentration of 1M) were charged, followed by warming to 200 ℃. The main component of the catalyst prepared in the 500mL reaction kettle is transferred into a polymerization kettle, and ethylene is continuously introduced to carry out the polymerization reaction of ethylene. During polymerization, the system temperature is maintained at 200 ℃, the total pressure of the system is maintained at 1.0MPa by using ethylene, and after 1 hour of polymerization, the temperature is reduced, the pressure is released, and the material is discharged.
The polymeric resins were tested for relative molecular mass, melt index and density and the results are shown in table 1.
From the results in Table 1, it can be seen that, under the same polymerization conditions, the catalytic system of the invention, when it catalyzes the polymerization of ethylene, gives copolymers having a significantly lower density than the comparative examples.
Comparative example 3
The preparation of the main catalyst component is carried out according to the method disclosed in patent CN 1955198A. The specific preparation method is shown as follows.
(1) Preparation of the principal catalyst component
Drying a 500mL reaction kettle, fully replacing the reaction kettle with nitrogen, taking 150mL dibutyl magnesium solution (a product of Aldrich company, a hexane solution with the concentration of 1M), mixing the dibutyl magnesium solution with 75mmol of di-n-butyl phthalate at normal temperature, slowly dropwise adding the mixture into another reactor containing 86mL of silicon tetrachloride, heating the mixture to 36-40 ℃, stirring the mixture at the temperature for reaction for 10 hours, filtering the mixture, fully washing the mixture for 6 times with hexane, then adding 100mL of n-hexane, dropwise adding 33mL of titanium tetrachloride, stirring the mixture for reaction for 2 hours at 60 ℃ after the dropwise adding is finished, and then washing the mixture for 4 times with n-hexane to obtain a main catalyst suspension for later use.
(2) Catalytic ethylene polymerization
In a 5L polymerizer, 3L of cyclohexane, 15mL of octene, and 2.3mL of ethyldiethoxyaluminum solution (which is prepared by reacting a triethylaluminum solution and ethanol at a molar ratio of 1:2 and has a concentration of 1M) were charged, followed by warming to 200 ℃. Transferring a certain volume of the main component of the catalyst into a polymerization kettle, and continuously introducing ethylene to carry out the polymerization reaction of the ethylene. During polymerization, the system temperature is maintained at 200 ℃, the total pressure of the system is maintained at 1.0MPa by using ethylene, and after 1 hour of polymerization, the temperature is reduced, the pressure is released, and the material is discharged.
The polymeric resins were tested for relative molecular mass, melt index and density and the results are shown in table 1.
From the results in Table 1, it can be seen that, under the same polymerization conditions, the catalytic system of the invention, when it catalyzes the polymerization of ethylene, gives copolymers having a significantly lower density than the comparative examples.
Comparative example 4
The preparation of the main catalyst component is carried out according to the method disclosed in patent CN 101134790A. The specific preparation method is shown as follows.
(1) Preparation of the principal catalyst component
Under the protection of nitrogen, 8.0 g of thermally-annealed silica gel (model 2485, Grace, USA), 100mL of purified heptane and 13.4mL of dibutyl magnesium solution (concentration is 1M) are sequentially added into a dry reaction bottle with a stirrer, the reaction is stirred at 35 ℃ for 1 hour, 2.95mL of chloro-tert-butane is dropwise added, the reaction is carried out at 45 ℃ for 4 hours, 8.97mL of dibutyl magnesium solution (concentration is 1M) is dropwise added, the reaction is carried out at 50 ℃ for 1 hour, 0.8mL of silicon tetrachloride is dropwise added, the reaction is stirred for 4 hours, 2.0mL of titanium tetrachloride is dropwise added, and the mixture is washed with hexane for three times, so that a main catalyst suspension is obtained.
(2) Catalytic ethylene polymerization
In a 5L polymerizer, 3L of cyclohexane, 15mL of octene, and 2.3mL of ethyldiethoxyaluminum solution (which is prepared by reacting a triethylaluminum solution and ethanol at a molar ratio of 1:2 and has a concentration of 1M) were charged, followed by warming to 200 ℃. Transferring a certain volume of the main component of the catalyst into a polymerization kettle, and continuously introducing ethylene to carry out the polymerization reaction of the ethylene. During polymerization, the system temperature is maintained at 200 ℃, the total pressure of the system is maintained at 1.0MPa by using ethylene, and after 1 hour of polymerization, the temperature is reduced, the pressure is released, and the material is discharged.
The polymeric resins were tested for relative molecular mass, melt index and density and the results are shown in table 1.
TABLE 1
The catalyst system of the present invention has the characteristic of copolymerization capacity, and by using the catalyst system of the present invention, the insertion amount of octene is very high, and the catalyst in the comparative example has no copolymerization capacity to octene basically. From the results in Table 1, it can be seen that, under the same polymerization conditions, the catalytic system of the invention, when it catalyzes the polymerization of ethylene, gives copolymers having a significantly lower density than the comparative examples.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The main catalyst for ethylene polymerization is characterized by being used for solution copolymerization of ethylene and prepared by reacting an alkyl magnesium compound, a chloralkane compound, a carboxylic ester compound, a silicon chloride compound and a titanium compound, wherein:
(1) the alkyl magnesium compound is at least one of diethyl magnesium, dibutyl magnesium, butyl octyl magnesium and butyl magnesium chloride;
(2) chloralkane compounds of the general formula (II) R2Cl, wherein R2Is C2～C20The hydrocarbon group of (a), which is a saturated or unsaturated linear, branched or cyclic chain;
(3) the carboxylic ester compound is at least one of hydroxyethyl methacrylate, ethyl acrylate, ethyl acetate, ethyl benzoate, ethyl o-methylbenzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate and diamyl phthalate;
(4) the silicon chloride compound is silicon tetrachloride;
(5) the titanium compound is titanium tetrachloride;
wherein, based on each mole of the alkyl magnesium compound, the compound shown in the general formula (II) is controlled to be 1-10 moles, the carboxylic ester compound is controlled to be 0.05-2 moles, the silicon tetrachloride is controlled to be 0.1-5 moles, and the titanium tetrachloride is controlled to be 0.1-5 moles.
2. The main catalyst for ethylene polymerization as claimed in claim 1, wherein the temperature for the solution-process copolymerization of ethylene is 180-220 ℃.
3. The main catalyst for ethylene polymerization according to claim 1, wherein the chlorinated alkane compound is at least one of methyl chloride, ethyl chloride, 1-chloropropane, 2-chloropropane, n-butyl chloride, i-butyl chloride, t-butyl chloride, cyclohexane chloride, chlorobenzene, p-methyl chlorobenzene, and o-methyl chlorobenzene.
4. A method for preparing a procatalyst for polymerization of ethylene according to any one of claims 1 to 3, comprising the steps of:
(1) adding a compound shown in a general formula (II) into alkane solution containing an alkyl magnesium compound for mixing reaction;
(2) reacting the reactant in the step (1) with a carboxylic ester compound and silicon tetrachloride;
(3) and (3) reacting the reactant in the step (2) with titanium tetrachloride to obtain the main catalyst.
5. The method of claim 4, wherein the amount of the compound represented by the general formula (II) is 2 to 5 moles, the amount of the carboxylic acid ester compound is 0.1 to 1 mole, the amount of silicon tetrachloride is 0.2 to 2 moles, and the amount of titanium tetrachloride is 0.2 to 2 moles per mole of the alkyl magnesium compound.
6. The method of claim 4, wherein the alkane solution further comprises an aluminum alkyl.
7. The method for preparing a main catalyst for ethylene polymerization according to claim 4, wherein the reaction temperature in the step (1) and the step (2) is 45 to 55 ℃ and the reaction temperature in the step (3) is 85 to 115 ℃.
8. An ethylene polymerization catalyst, characterized in that the catalyst is used for the solution copolymerization of ethylene and is obtained by reacting the following components:
(a) the ethylene polymerization procatalyst according to any one of claims 1 to 3 or the ethylene polymerization procatalyst produced by the production process according to any one of claims 4 to 7;
(b) as shown in the general formula (
）AlR'n（OR''）3-nAn organoaluminum compound represented by the formula, wherein R ' and R ' ' are the same or different and R ' ' are C1～C20Alkyl of 1<n≤3。
9. The ethylene polymerization catalyst according to claim 8, wherein the organoaluminum compound is Al (OEt) Et２、Al(OEt)Et２、(EtO)Al(iso-Bu)2、(EtO)Al(n-C6H13)2And (EtO) Al (n-C)8H17)2Wherein the molar ratio of the organoaluminum compound to titanium in the main catalyst is controlled to 1 to 500.
10. A solution process for copolymerizing ethylene, wherein the catalyst is the ethylene polymerization catalyst as claimed in any one of claims 8 to 9, the reaction monomers are ethylene and α -olefin, the α -olefin is at least one selected from the group consisting of butene, pentene, hexene, octene and 4-methylpentene-1, and the reaction temperature is 180-220 ℃.
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| CN101134790A (en) * | 2006-09-01 | 2008-03-05 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction and catalyst |
| CN106459282A (en) * | 2014-06-13 | 2017-02-22 | 诺瓦化学品(国际)股份有限公司 | Short chain branching control on ehtylene-butene copolymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4229558A (en) * | 1976-12-13 | 1980-10-21 | Mitsubishi Chemical Industries Limited | Process for preparing polyolefin |
| EP0132288A1 (en) * | 1983-06-21 | 1985-01-30 | Asahi Kasei Kogyo Kabushiki Kaisha | A method of polymerizing an olefin |
| CN1069030A (en) * | 1991-07-25 | 1993-02-17 | Ecp埃尼化学有限公司 | The catalyzer that is used for olefinic polymerization |
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| CN101134790A (en) * | 2006-09-01 | 2008-03-05 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction and catalyst |
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