TW555770B - Method of homo- or co-polymerization of alpha-olefin - Google Patents

Abstract

The present invention relates to a method of homo- or co-polymerization of alpha-olefin by means of using a catalyst system which comprises the following components: (1) a solid complex titanium catalyst produced by means of a production method comprising the following steps: (a) preparing a magnesium compound solution by dissolving a magnesium halide compound and a compound of group IIIA of the Periodical Table in a solvent of mixture of cyclic ester, one or more types of alcohol, a phosphorus compound, and an organic silane; (b) precipitating the solid particles by reacting said magnesium compound solution with a transitional metal compound, a silicon compound, a tin compound, or the mixture thereof; and (c) reacting said precipitated solid particles with a titanium compound and electron donors; (2) an organometallic compound of metal of group IIIA of the Periodical Table; and (3) external electron donors comprising three or more types of organo-silicon compounds, wherein the melt flow rates of the homopolymers obtained from polymerization by individually using said organo-silicon compounds under the same polymerization conditions are 5 or less, 5 to 20, and 20 or higher, respectively. According to the present invention, it has an advantage of obtaining polymers of broad molecular weight distribution with high hydrogen reactivity and melt flow rates while maintaining high stereoregularity and yields for olefin homo- or co-polymers during homo- or co-polymerization of alpha-olefin having three or more carbon atoms.

Description

555770 A7 B7 V. Description of the invention (1) Technical examples The present invention relates to a method of homo- or co-polymerization (hereinafter referred to as (co) polymerization) of avar · olefin, and more particularly to the control of the molecular weight distribution of polymers while Method for producing high stereoregular olefin (co) polymer in high yield. BACKGROUND OF THE INVENTION Generally, olefin polymers produced using MgCl2 supported catalysts have a narrow molecular weight distribution. Many efforts have been made to widen the molecular weight distribution to improve the fluidity of the products produced by these catalysts during processing. For this purpose, there is a method widely used in which polymers of different molecular weight distributions are first produced in different polymerization reactors and then mixed later, but the disadvantages are that more time and effort are required, and the product is often found to be very inefficient. Even. In a recent report from Mitsui Petrochemical of Japan, there is a method (Korean Patent Publication No. 10-1993-000665) in which two special electron donors are used to generate a broad molecular weight distribution For the olefin polymer, the homogeneous polyolefin having a melt flow rate (MFR) of 31.6 was polymerized under the same polymerization conditions using the electron donor. However, in this case, the catalyst activity is too low to be industrialized, not only its molecular weight is difficult to control, but also the hydrogen reactivity of controlling the molecular weight distribution of the polymer is very low, which places many restrictions on its handling. At the same time, many other prior art-techniques are known that use a solid titanium complex component as a titanium catalyst to (co) polymerize avar-olefins having more than 3 carbon atoms, the complex component comprising at least an electron donor Processed magnesium and 卣 and (, for example, Japanese Patent Publications Nos. 73-16986 and 73-16987, German Patent Publications Nos. 2,153,520, 2,230,672, and this paper standard apply to China National Standard (CNS) A4 Specification (210X297 mm) 555770 A7 B7 V. Invention Description (2) No. 2,230,728, No. 2,230,752 and No. 2,553,104). These references show the uses of particular catalyst mixture components and methods for forming these catalysts. As we are all familiar with, these solid titanium complex-containing catalysts have different combination methods and different combination conditions, which vary between different catalysts depending on the component mixture. Therefore, it is almost impossible to predict whether the catalysts used in a given set of combined conditions will produce similar results. Catalysts with extremely imperfect performance are usually produced. When suitable external electron donors are not used, these properties (such as polymer catalyst activity or stereoregularity) often prove to be inadequate, even if the catalyst is manufactured under suitable conditions. Solid titanium complex components containing at least magnesium, titanium and rhenium are no exception. In the presence of hydrogen and the use of a catalyst (co) polymerized with titanium and organometallic compounds belonging to metals of Groups I to IV of the Periodic Table to polymerize avalenic hydrocarbons containing not more than 3 carbon atoms, The tri-gasification catalyst obtained by reduction of tetrachloride with organic or organic compounds and the electron donor known to suppress the formation of amorphous (co) polymers, the effect varies depending on the electron donor used . The acceptable reason is that the electron donor is not only added, but is also combined with magnesium and titanium compounds electronically and in space to basically change the microstructure of the solid titanium complex catalyst. A new method of producing a highly stereoregular polymer from a certain silicone compound at a higher yield than existing methods has been requested from Dow Corning (US Patent No. 5,175,332 and European Patent Publication No. 602,922), Japan's Mitsui Petrochemical Corporation (Korean Patent Publication Nos. 10-1992-2488 and 10-1993-665; U.S. Patent No. 4,990,479; European Patent Patent Publication No. 350,170A; Canadian Patent No. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 555770 A7 B7 V. Invention Description (3) No. 1,040,379), Samsung General Chemicals of Korea 10-1998-082629) and other European companies we are familiar with. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing high organic stereo olefin homo- or copolymers with high yield and a catalyst system used in the method, which is used to produce olefin homo- with more than 3 carbon atoms. In the case of co- or copolymers, this method simultaneously controls the molecular weight distribution of the homo- or co-polymers of fluorene. Another object of the present invention is to provide a method for manufacturing a polypropylene or propylene copolymer. The polymer is suitable for manufacturing a film having sufficient heat-sealing, transparency and anti-sticking properties, and is also suitable for having excellent strength, impact resistance and Low-temperature heat-sealable injection molded product. Detailed description of the invention The avar-olefin (co) polymerization method includes the use of a catalyst system comprising the following components: (1) A solid titanium complex catalyst prepared by a manufacturing method including the following steps: (a) dissolving a magnesium halide and a compound of Group IIIA of the periodic table in a solvent of a mixture of a cyclic lipid, one or more alcohols, a rhenium compound, and an organic crusher to prepare a rhenium compound—a solution; (b) a solution of the magnesium compound Reacting with a transition metal compound, a silicon compound, a tin compound, or a mixture thereof to precipitate solid particles; and (c) reacting the precipitated solid particles with a titanium compound and an electron donor. -6- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 555770 A7 B7 V. Description of the invention (4) (2) — An organometallic compound of Group IIIA metal of the periodic table; and (3) Contains three or more electron donors other than organosilicon compounds, where homopolymer MFRs (melt flow rates) obtained when polymerized with a single organosilicon compound under the same polymerization conditions are 5 or less, 5 to 20, and 20 or more south. Regarding the catalyst system used for the (co) polymerization of the avatar-olefin method of the present invention, the method for manufacturing the solid titanium complex catalyst is the method described in Korean Patent Laid-Open No. 10-2000-009625, and the content thereof All are incorporated herein without special association. Compared with the conventional titanium catalyst, the solid titanium complex used in the homo- or co-polymerized Avar-olefin method of the present invention has excellent catalyst activity and can produce a high stereoregular polymer with a wide molecular weight distribution. . In step (a) of the method for generating a solid titanium complex catalyst, the magnesium compound may include a non-reducing liquid magnesium compound, for example, arsine, such as aerobium, magnesium bromide, magnesium iodide, and magnesium fluoride ; Magnesium alkoxylates, such as magnesium methoxylate, ethoxylate, isopropoxylate, butoxylate and octyloxylate; aryloxyhalides , Such as magnesium phenoxide and methylphenoxy, magnesium alkoxide, such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, and octyl magnesium; aryloxy magnesium , Such as phenoxymagnesium dimethylphenoxymagnesium; and magnesium double acid salts, such as magnesium laurate (laurylmagnesium) and magnesium stearate. The magnesium compound used in the present invention may be in the form of a compound compound or a mixture with other metals. Alternatively, a mixture of two or more magnesium compounds may be used as the magnesium compound. The preferred magnesium compound is magnesium hafnium, such as gasified magnesium, alkoxymagnesium chloride and aryloxymagnesium chloride, and more preferably CrC14 alkoxy. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297) (Centi) 555770 A7 _______B7 V. Description of the invention (5 ~) '' Burning oxyfluorene chloride and aryloxy magnesium vaporized, more preferably C5_c2〇 fused oxygen aryloxy gasification. The magnesium compounds listed above are generally represented by a simple chemical formula, but some compounds are difficult to express in this way depending on the manufacturing method. At this point they can be believed to be a mixture of these compounds. For example, compounds obtained by the following methods are all considered as a mixture of different compounds that depend on different reactants or different degrees of reactivity, and these compounds can also be used in the present invention. These methods are: The method of reacting magnesium metal with alcohol or phenol in the presence of thiosulfonium gas. 'The Grignard reagent pyrolysis method; borrows the degradation method that combines hydroxyl, ester, ether or similar groups. In the present invention, a non-reducing liquid magnesium compound or a solution in which a magnesium compound is dissolved in a hydrocarbon solvent is mainly used. To produce these compounds, the non-reducing magnesium compounds listed above can be reacted with at least one or more electron donors in the absence or presence of a hydrocarbon solvent capable of dissolving the magnesium compounds, the electron donors being selected from the group consisting of alcohols, organic carboxylic acids, aldehydes , Amines or mixtures thereof. Hydrocarbon solvents used for this purpose include, for example, aliphatic hydrocarbons such as pentylene, hexamethylene, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, fluorenylcyclopentane, Cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, dimethyl, ethylbenzene, cumene and methyl-isopropylbenzene; and selected from the group consisting of digas ethane, digas propane, dioxane Gas generation of ethylene, ~ three gas ethylene, four gasification carbon and chlorobenzene. _ In step ⑷ of the method for manufacturing the solid titanium complex catalyst as described above, the reaction of the functional magnesium compound and the alcohol is preferably performed in a hydrocarbon solvent. Depending on the type of compound and alcohol, the reaction is at room temperature or higher (for example, about 30-8-this paper size applies to China National Standard (CNS) A4 (210X 297 mm) 555770 A7 B7 five Description of the invention (6) ° C to 200 ° C, more preferably about 60 X: mig 150 ° C) for about 15 minutes to 5 hours (more preferably about 30 minutes to 3 hours). Electron donors that generate liquid magnesium compounds include compounds having at least 6 or preferably 6 to 20 carbon atoms, for example, aliphatic alcohols such as 2-methylpentanol, 2-ethylbutanol, n-heptanol, n- Octanol, 20 ethylhexanol, decanol, dodecanol, tetradecanol, undecenol, oleyl alcohol and stearyl alcohol; alicyclic alcohols, such as cyclohexanol and methylcyclohexanol; And aromatic alcohols, such as benzyl alcohol, methyl benzyl alcohol, isopropyl benzyl alcohol, α-methyl benzyl alcohol and α, α-dimethyl benzyl alcohol. For alcohols having 5 or less carbon atoms, methanol, ethanol, propanol, butanol, ethylene glycol, and methycarbitol can be used. Steps of the method for manufacturing the solid titanium complex catalyst as above ( In b), the magnesium compound in the liquid form produced as above is recrystallized by using silicon tetrahydroxide, alkyl halide, tin tetrafluoride, tin sulfide, tin hydrogen hydride, tetrakisperylene and the like. Spherical solid component. In step (c) of the method for manufacturing the solid titanium complex catalyst as described above, the liquid titanium compound to be reacted with the magnesium compound is preferably a tetravalent titanium compound of the general formula Ti (OR) mX4_m (where R is a hydrocarbon group, X Is a halogen atom, and m is a number of 0 < m < 4). R represents an alkyl group of 1 to 10 carbon atoms. Various titanium compounds can be used, for example, tetrahalides' such as TiCl4, TiBr4 and Til4, titanium alkoxides such as Ti (0CHl) Cl3, Ti (OC2H5) Cl3, Ti (OC4H9) Cl3, Ti (OC2H5) Br3 and Ti (0 (i-C2H5) Br3; titanium alkoxides such as Ti (OCH3) 2Cl2, Ti (OC2H5) 2Cl2, Ti (OC4H9) 2Cl2 and Ti (OC2H5) 2Br2; titanium alkoxides, Such as Ti (OCH3) 3Cl, Ti (OC2H5) 3Cl, Ti (OC4H9) 3Cl, and Ti (OC2H5) 3Br; and tetraalkoxy This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 555770 A7

Of these compounds, * Ti (〇CH3) 4'Ti (OC2H5) 4 and τCa ^ Among these compounds, ′ is preferably titanium tetraoxide, especially titanium tetragas. Examples of internal electron donors in step ⑷ for the production of solid titanium complex catalysts as described above are generally as follows: oxygen-containing electron donors, such as water%, aldehydes, carboxylic acids, esters, ethers, and amidines; and nitrogen-containing Electron donors, such as ammonia, amines, nitriles, and isocyanates; i Alcohols of 18 carbon atoms, such as methanol, ethanol, propanol, pentanol, hexanol, octanol, + dialkanol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, cumyl alcohol and isopropyl benzyl alcohol; Ketones; phenols that may contain lower alkyl groups and have 6 to 15 carbon atoms, such as phenol, cresol, dimethylphenol, ethylphenol, propylphenol, cumylphenol, and acetol; 2 to 15 Carbon atom pathways, such as acetaldehyde, propionaldehyde, octanal, benzaldehyde, toluene, and chloroform; organic acid esters with 2 to 18 carbon atoms, such as formate EI, ethyl formaldehyde, ethyl Therefore, ethyl acetate, ethyl acetate, propyl acetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexyl carboxylate, phenyl benzoate, ethyl benzoate, methyl methyl formate, toluene Ethyl formate, amyl toluate, ethyl ethyl benzoate, ethyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, α-benzene Pyranone, 2-phenylhydrazone [c] furanone, cyclohexyl acetate, ethyl propionate, methyl butyrate, methyl valerate, ethyl toluate, ethyl toluate, propyl benzoate Benzene Butyl acid, cyclohexyl benzoate, amyl toluate, ethyl carbonate and ethyl carbonate; halogenated halides with 2 to 15 carbon atoms, such as ethyl arsine gas, arsine base gas, toluene methyl arsine gas (Chlorotoluate) and chloroanisate; g amines; acids, such as ethyl ether, diethyl ether, isopropyl acid, butyl ether, pentyl ether, tetrahydrofuran, anisole, and benzoic acid; amines, such as methylamine 、 B-10- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Binding 555770 A7 B7 Five invention descriptions (, diethylamine, tributylamine, piperidine, trimethylamine, aniline, pyridine, rosin (pinoline), tetramethylethylenediamine; nitriles, such as acetonitrile, acetonitrile, and Tolyl ammonia; and aluminum, silicon, tin, and similar compounds having the above functional groups in the molecule. On the other hand, a catalyst that reacts with certain electron donors is used in the present invention to improve the regularity and higher yield of the carcass. Aval-olefin polymers are produced at a high rate. The internal electron donors used to generate catalysts in the present invention are especially monoethylene glycol (MEG), diethylene glycol (DEG), triethylene glycol (TEG), poly (ethylene glycol). Ester derivatives of ethylene glycol (PEG), monopropylene glycol (MPG) and dipropylene glycol (DpG), such as acetate, propionate, n- and iso-butyrate, benzoate, toluate Etc. As examples of the above electron donors, benzoates include early ethylene glycol monobenzoate, monoethylene glycol dibenzoate, diethylene glycol monobenzoate, or monoethylene glycol monobenzoate , Diethylene glycol monobenzoate, Monoethylene glycol monobenzoate, Triethylene glycol dibenzoate, Monopropylene dibenzoate Alcohol esters, dipropylene glycol monobenzoate, dimalonic acid dibenzoate, tripropylene glycol monobenzoate, and similar esters. The polymer obtained by slurry polymerization using the solid catalyst produced has a bulk density. Excellent and good particle size distribution of granular and spherical particles. The solid titanium complex catalyst may be used. It is useful for polymerizing olefins, such as ethylene, propidium and butin, or 4-methyl + pentyl, The catalyst is particularly useful for the polymerization of avalvanes having 3 or more carbon atoms, its copolymerization, avalvatones with 3 or more carbon atoms having less than 10 mole% acetam, copolymerization of hydrocarbons, and 3 & Copolymerization of multiple confined atomic avarene with polyunsaturated compounds (such as co-car or non-co-consumer difluorene).

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555770

The organometallic component (2) used this month includes, in particular, trisalyl aluminum, such as monoethylaluminum and dibutylaluminum, trienyl aluminum, such as triisoprenyl aluminum; partially alkoxylated alkyl groups Aluminum, such as aluminum dialkyl alkoxy, such as diethyl ethoxy and monobutyl butoxy; aluminum alkyl sesquialkane, such as ethyl sesquiethoxy, and butyl sesquiethyl Aluminium oxide; Alkyl dichloride, such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide; partially hydrogenated aluminum, such as aluminum hydride, such as diethyl aluminum hydride and dibutyl aluminum Aluminum hydride; dialkyl hydride inscriptions such as monobutyl weathering inscription; dioxinated and oxidized calcined inscriptions such as ethyl ethoxy aluminum vaporization, butyl butoxy aluminum vaporization and ethyl Aluminum ethoxylate. In the method for (co) polymerizing avar-olefins of the present invention, the organic regular compound is used as an external electron donor during the polymerization reaction to improve the stereoregularity of the polymer produced. The organic silicon compound used in the present invention includes ethyltriethoxysilane, n-propyltriethoxysilane, third butyldiethoxysilane, vinyltriethoxysilane, diphenyldimethoxy Silane, phenylmethyldimethoxysilane, bis (p-phenyl) dimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldisilane Methoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, etc .; cyclopentyl, cyclopentyl Organometallic dead compound or derivative thereof. As the external electron donor (3), dicyclopentyldimethoxysilane, cyclohexylfluorenyldimethoxysilane, and vinyltriethoxysilane are particularly preferably used. In this case, the molar ratio of dicyclopentyldimethoxysilane to the electron donor is in the range of 0.05 to 0.7; cyclohexylmethyldimethoxysilane is an electron donor-12- This paper is applicable to this paper China National Standard (CNS) A4 specification (210 X 297 mm) buckle 770 V. Description of the invention (The Molar ratio is in the range of 0 to 9; the Molar ratio of the donor of Erguangzi is 0 05 ~ 0 2 Ethyl lactate is better for electron donors. Dicyclopentylcyclohexylmethyldimethoxypyridine is for electron donors. Within the range, vinyl triethoxy Mole ratio is between 0.2 and 0.6. In the rural fan garden. Mole ratio for electron donors is in combination. When it is permanent, it is more suitable to use gas phase polymerization in liquid phase polymerization. It can be used in the liquid phase polymerization. Inactive solvents are used as reaction media, such as hexane, vanadium, heptane and kerosene, but olefins themselves can also be used as reaction media. If private: solid titanium complex catalyst in the polymerization system In terms of atomic weight, it is about 0 to $ millimoles per liter of solvent, more preferably about 0.001 to 0.5 millimoles. A:% — gross If the bucket is subjected to gas phase polymerization, the titanium atom: 10 'per: polymerization is about "· 001 ~ 5 millimoles, preferably about 00 millimoles ~ about 丨 · 0 耄 5 moles, more It is preferably about 0.01 to 0.5 millimolar. The proportion of organic = metal atoms in component ⑺ is about Moore per mole of titanium atom in solid catalyst ⑴, preferably about 5 to 500 Moore. The ratio of component ⑺ (Calculated as silicon atom) as component (2), about 0.001 to 10 mol per mole of organometallic atom, preferably about 0.001 to 2 mol ', more preferably about 0.05 to 1 Mo. Ear The polymerization method using the catalyst of the present invention is the same as the conventional method using a Ziegler-type catalyst. It should be noted that the reaction proceeds substantially in the absence of oxygen and underwater. It is better to use a temperature in the range of about 20 to 200 ° C (preferably in the range of about 50 to 180 ° C) at a pressure of about 1 atmosphere to 100 atmospheres. 13 · This paper size is suitable for financial standards (CNS) A4 (21G X 297) (Public love) 555770 A7 B7 V. Description of invention (11) range (preferably about 2 to 50 atmospheres). The reaction can be carried out batchwise, semi-batchwise or continuously, and different reactions can also be used. Two or more steps are performed under conditions. The present invention is further illustrated below by examples and comparative examples. However, these examples and comparative examples are for illustrative purposes only, and the present invention is not limited by its methods. Example 1 Manufacturing a solid titanium catalyst The catalyst used for component polymerization of avar-olefin was produced according to the method proposed in Example 1 of Korean Patent Laid-Open No. 10-2000-0009625. Regarding the catalyst production of polymerized avar-olefin used in the example, Korean Patent Laid-open No. 10 The description of -2000-0009625 is all incorporated in this article in a non-specific way. The particle size distribution of the carrier and catalyst was measured with a laser particle analyzer [Malvern Instrument, Mastersizer X Model]. The components of the carrier and catalyst were analyzed by ICP method, and the surface area was determined by BET method. The catalyst yield is determined by the final weight of the catalyst / the weight of MgCl2 initially placed in it. The resulting catalyst particles are 50 microns in size and include 3.1% by weight Ti, 18.8% by weight Mg, 250 ppm A1, and 230 ppm Si. The specific surface area is 241 m2 / g. The particle size distribution of the produced catalyst was respectively di0 = 33.6 microns 'd50 = 58.5 microns' and d50 = 97.1 microns. Here, shan, I50, and d90 refer to 10%, 50%, and 90% particles ~ Punch is less than 33.6 microns, 58.5 microns, and 97.1 microns. D50 is defined as the intermediate particle size. It undergoes prepolymerization and polymerization processes according to the following conditions After that, the catalyst activity generated by this method was tested: Pre-polymerization • 14- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 555770 A7 _ B7 V. Description of the invention (l2) Ml of n-hexane and 6 millimoles of triethyl were placed in a glass bottle containing 4 g of catalyst, and the catalyst was placed in an i-liter glass reactor maintained at 15.0. At 0.5 or lower atmospheric pressure to 100 cubic centimeters per minute while adding propylene, prepolymerize for 100 minutes with a stirring speed of 200 rpm. The prepolymer degree of the resulting prepolymer is 3 g polypropylene per gram catalyst. 40 ¾ g for polymerization Prepolymer, 7 mL of 1 mol / L triethylaluminum falling solution diluted in n-hexane (7 μmol, Al / Ti molar ratio M, οπ) and 7 mL of 0.1 mL diluted with n-hexane Electron donor solution (07 millimolar, Si / Ti molar ratio = 108) (cyclohexylmethyldimethoxysilane as an external electron donor 1. The molar ratios of monocyclopentyldimethoxysilane and vinyltriethoxysilane are 0.2, 0.4, and 0.4), respectively, and added to a 2 liter autoclave. The reactor is then adjusted to atmospheric pressure with nitrogen. After placing 1000 standard milliliters of hydrogen into the reactor, '1200 liters (600 grams) of liquid propylene was added. While stirring at 63 rpm, the temperature was raised to 70 X :. The temperature was maintained at 701 for 1 hour for polymerization. Then the stirring was stopped. When the temperature is reduced to room temperature, the inside of the reactor is replaced with nitrogen, which is the polymerization completion point. The structure of the polymer thus produced is analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc., and its structure Shown in Table 1. Example 2 · · ~ This example uses the same solid titanium catalyst as in Example 1. The polymerization was performed under the same conditions as in Example 1, but will contain 0.3, 0.35, and 0.35 corresponding mole ratio cyclohexyl 7 ml of fluorenyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxysilane as external electron donors mol / l -15-This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) 555770 A7 B7 Note (I3) Diluted n-hexane solution (0.7 millimolar, Si / Ti molar ratio = 1.08) is incorporated into the polymerization process. It is generated by analysis such as activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The polymer is shown in Table 1. Example 3 This example uses the same solid titanium catalyst as in Example 1. The polymerization was performed under the same conditions as in Example 1, but will contain 0.4, 0.3, and 0.3 corresponding mole ratio rings. Hexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxysilane as external electron donors 7 ml 0.1 mol / l n-hexane dilution solution (0.7 millimoles, Si / Ti molar ratio = 1.08) incorporated into the polymerization process 0 The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Example 4 This example uses the same solid titanium catalyst as Example 1. The polymerization was carried out under the same conditions as in Example 1, but will contain 0.5, 0.25, and 0.25 of the respective molar ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxysilane. As an external electron donor, 7 ml of a 0.1 mol / l n-hexane diluted solution (0.7 millimolar, Si / Ti molar ratio = 1.08) was incorporated into the polymerization process. • One The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Example 5 This example uses the same solid titanium catalyst as Example 1. Aggregation was carried out under the same conditions as in Example-16- This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 555770 A7 ___— _B7_ V. Description of the invention (l4) 1 but it will contain 〇6 , 0.2 and 0.2 correspond to 7 ml of 0.1 mol of the molar ratio of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and ethinotriethoxysilane as external electron donors. Ear / liter of n-hexane diluted solution (0.7 millimoles, Si / Ti mole ratio = 108) was incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table i. Example 6 This example uses the same solid titanium catalyst as Example 1. The polymerization was carried out under the same conditions as in Example 1, but will contain the corresponding molar ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and ethynyl groups of 0.7, 0.15, and 0.15. 7 ml of a mol / l n-hexane diluted solution (0.7 mmol, Si / Ti molar ratio = 108) of triethoxysilane as an external electron donor was incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Example 7 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, but will include the respective mole ratios of cyclohexylmethyldimethoxysilane, tri-1, pentamyldimethoxysilane and 0.8, 0.1, and 0.1. 7 ml of a 0.1 mol / l di-hexane burned dilute solution of vinyltriethoxysilane as an external electron donor (0.7 millimolar, Si / Ti molar ratio = 108) is incorporated into the polymerization process. , Melt Flow Rate (MFR), NMR, RDS, DSC, etc. -17- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) m-binding

k 555770 A7 _____ B7 V. Description of the invention (I5) The polymer thus produced was analyzed. The results are shown in Table 1. Example 8 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, but it would contain the corresponding molar ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and vinyltriethoxy. 7 ml of a 0.1 mol / l n-hexane diluted solution of silane as an external electron donor (0.7 millimolar, Si / Ti molar ratio = 108) was incorporated into the polymerization process, and then 500 standard milliliter of hydrogen was added. The polymer thus obtained was analyzed by activity, melt flow rate (MFR), NMR, 'RDS, DSC, etc., and the results are shown in Table 1. Example 9 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, except that 0, 0, 15 and 0,15 corresponding mole ratios of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and vinyldi 7 ml of a 0.01 ml mol / l dioxane-diluted solution (0.7 mmol, Si / Ti mole ratio = 108) of ethoxylithium as an external electron donor was incorporated into the polymerization process, and then added to 2000 Standard ml of hydrogen. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table i. The following provides comparative examples of the properties of polymers obtained by cross-linking units or binary external electron donors with polymers obtained using ternary external electron donors in the examples. Comparative Example 1 This comparative example uses the same solid'catalyst as in Example 1. Converge on

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It was performed under the same conditions as in the example, except that 7 ml of a mol / l n-hexane solution (0.7 mmol, Si) containing cyclohexylmethyldimethoxyfluorene alone as an external electron donor was used. / Ti molar ratio = 108) is incorporated into the polymerization process. The polymer thus produced was analyzed by activity, body flow rate (R), NMR, RDs, dsc and the like, and the results are shown in Table i. Comparative Example 2 This comparative example uses and examples! Same solid titanium catalyst. The polymerization was carried out under the same conditions as in the example, but it will contain a single dicyclopentyldimethoxysilane: 7 ml of 0 mol, a dilute solution of n-hexane (0.7 mol) , Si / Ti molar ratio = 108) is incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, dsc, etc. The results are shown in Table i. Comparative Example 3 This comparative example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, except that 7 ml of a G1 mole / liter di-hexane-diluted solution (0.7¾ mole, Si / Ti mole) containing vinyl triethoxy stone sinter alone as an external electron donor was used. Ear ratio = 108) incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Comparative Example 4 This example uses the same solid titanium catalyst as in Example 1. The polymerization was carried out under the same conditions as in Example 1, but using 7 and 5 corresponding molar ratios of dicyclopentyl-methoxybenzoate and ethoxytriethoxylate as the external electron donors. Milliliter of 0.1 mol / L n-hexane diluted solution (07 millimoles, Si / Ti -19- This paper size applies to China National Standard (CNS) A4 specifications (210X 297 mm) 555770 A7 B7 V. Description of the invention (Γ7) Molar ratio = 108) was incorporated into the polymerization process, and then 500 standard milliliter of hydrogen was added. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Comparative Example 5 This example uses the same solid titanium catalyst as in Example 1. Polymerization was carried out under the same conditions as in Example 1, but using 7 ml of 0.1 mol / l containing 0.5 and 0.5 corresponding mole ratios of dicyclopentyldimethoxysilane and vinyltriethoxysilane as external electron donors. One liter of n-hexane diluted solution (0.7 millimolar, Si / Ti molar ratio = 108) was incorporated into the polymerization process. The polymer thus produced was analyzed by activity, melt flow rate (MFR), NMR, RDS, DSC, etc. The results are shown in Table 1. Comparative Example 6 This example uses the same solid titanium catalyst as in Example 1. Polymerization was carried out under the same conditions as in Example 1, but using 7 ml of 0.1 mol / l containing 0.5 and 0.5 corresponding mole ratios of dicyclopentyldimethoxysilane and vinyltriethoxysilane as external electron donors. Liter of n-hexane diluted solution (0.7 millimolar, Si / Ti molar ratio = 108) is incorporated into the polymerization process, and then 2000 standard milliliter hydrogen is added 0 -20- This paper size applies to China National Standard (CNS) A4 specifications (210X297) (Centi) 555770 A7 B7 V. Description of the invention (20) * In the table above, the activity is expressed in kg-polypropionamine / g catalyst / hour, and the solution flow rate is expressed in grams / 10 minutes. In addition, the following initial letters are used in the table: Comp: Compound, E: Example, CE: Comparative Example, MR: Mole ratio, DCPDMS: Dicyclopentyldimethoxysilane, CHMDMS: Cyclohexylmethyldimethyl Oxysilane, VTES: vinyltriethoxysilane, and MWD ·· Molecular weight distribution. * Polymerization conditions: bulk polymerization, 40 mg prepolymerization catalyst (prepolymerization degree: 3 g polypropylene / g catalyst), 600 g liquid propidium, 7 millimoles triethylaluminum, 0.7 millimoles external electron donor Body, 70. ° C, and polymerized for 1 hour. The formula provided according to the present invention has the advantages of obtaining a polymer with a wide molecular weight distribution with high hydrogen reactivity and melting point flow rate, and at the same time during the copolymerization (polymerization) of avalan-hydrocarbons having three or more carbon atoms, Or the co-polymer maintains high stereoregularity and yield. -23- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

Fixed replacement @m i8797 Patent Application Shenkou 7 Please replace the patent fan garden (April 1992)-Application scope 1. A method for homo-or co-polymerization of avar-pyrene using a catalyst system, the catalyst The system includes the following components: (1) A solid titanium catalyst prepared by a manufacturing method including the following steps: (a) Dissolving a magnesium halide compound and a compound of Group mA of the periodic table in a mounting ether, one or more alcohols A solvent of a mixture of a phosphorus compound and an organosilane to prepare a magnesium compound solution; (b) reacting the magnesium compound with a transition metal compound, a silicon compound, a tin compound, or a mixture thereof to precipitate solid particles; and (c) using All Shen Dian solid particles react with the compound and the electron donor. (2) an organometallic compound of a Group I ΠA metal of the periodic table; and (3) an electron donor other than three or more organosilicon compounds, wherein by using these three or more organosilicon compounds alone One kind of homopolymer obtained by polymerization under the same polymerization conditions has a flow rate of 5 or less, 5 to 20, and 20 or more, respectively. 2. A method for homo- or co-polymerizing avar-fluorene according to item 1 of the scope of the patent application, wherein the organometallic compound is a trialkylaluminum. 3. The homo- or co-polymerized avatar-associated hydrocarbon method according to item 1 of the scope of the patent application, wherein the avatar-olefin is propylene, and the external electron donor is dicyclopentyl-methoxylithium. Amylmethyldimethoxylithium and ethylene triethoxysilane. 4. A method of homogeneous or co-polymerizing avatars according to item 3 of the scope of the patent application, wherein the external electron donor includes dicyclopentyl in a ratio of 0.05 to 0.7 mol ratio compared to all external electron donors Dimethoxy crushing, to the size of this paper applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) " ~ β ~~ '-AB CD 555770 6. Apply for a patent range of 0.9 Morrbi ring Hexylmethyldimethoxysilane and ethynyltriethoxysilane from 0.05 to 0.7 mol. 5. A method of homo- or co-polymerizing avar-olefin according to item 3 of the scope of the patent application, wherein the external electron donor includes dicyclopentyldi, 0.05 to 0.5 mole ratio compared to all external electron donors Methoxysilane, 0.2 to 0.6 mole ratio of cyclohexylmethyldimethoxysilane, and 0.05 to 0.5 mole ratio of vinyltriethoxysilane. -2- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)