KR100996844B1 - Polypropylene resin using Catalyst For Olefine Polymerization - Google Patents

Abstract

The present invention prepares a Ziegler-Natta catalyst for olefin polymerization, which is very suitable for polymerizing an olefin polymerization catalyst, especially propylene such as propylene with high activity and high stereoregularity, and is a block polypropylene having excellent bending strength. It relates to a resin composition. More specifically, a mixed solution is prepared using anhydrous magnesium chloride, dioxirane, a hydrocarbon, and an organophosphorus compound, followed by polymerization in a multistage reactor using a Ziegler-Natta catalyst for olefin polymerization prepared by adding titanium tetrachloride and an electron donor. And an organic or inorganic additive, which is a material which helps to nucleate the polypropylene resin, and provides a polypropylene resin which is prepared by the process, and contains a polypropylene homopolymer or an ethylene copolymer having an ethylene-propylene rubber content of 0.1 to 20% by weight. The present invention provides a method of preparing a resin having improved flexural strength by preparing a resin in which a grafted compatibilizer such as polyethylene wax and a lubricant is mixed.

Polypropylene, Ziegler-Natta catalyst, polypropylene copolymer, flexural modulus, nucleating agent

Description

Polypropylene Resin Using Catalyst For Olefine Polymerization

The present invention relates to a polypropylene resin composition having excellent flexural strength, and more particularly, to a resin composition comprising high rigidity block polypropylene and an inorganic material for forming a nucleus and polyethylene wax for improving moldability of a product. will be.

Polyolefin production methods typically include polymerizing olefin monomers with Ziegler-Natta catalysts, and catalysts for olefin polymerization called Ziegler-Natta catalysts include main catalysts composed mainly of transition metal compounds and cocatalysts of organometallic compounds, In addition, it refers to a catalyst system composed of a combination of electron donors, and has been extensively studied to improve basic elements such as polymerization activity, stereoregularity, and related technologies.

In the case of the Ziegler-Natta catalyst and the alpha olefin polymerization, the composition, structure, manufacturing method, etc. of the catalyst directly affect the properties and particle distribution of the resulting polyolefin. Therefore, in order to change the properties of the desired polyolefin, a catalyst composition, a carrier structure, a catalyst production method, or the like must be accompanied during the preparation of the catalyst. The activity of and the particle size, molecular weight and stereoregularity of the polymerized polymer should also be studied.

Ziegler-Natta catalysts consist of a solid catalyst component centered on titanium, magnesium and halogen compounds and an organoaluminum compound system as a promoter. Although many improvements have been made to improve catalyst activity and stereoregularity, which are fundamental elements in this system, due to the diversified use of polypropylene, various requirements such as high stereoregularity, high rigidity, uniform particle size and proper particle size distribution There is a demand for development of a catalyst corresponding to this.

Up to now, there have been known cases of improvement by the addition of an electron donor in the stereoregularity problem in U.S. Patent No. 4,544,717, and the U.S. Patent No. 4 for a high stereoregular catalyst having an isotactic value of 94 to 95 or more. 4,226,741 is known. In addition, the technology of solid Ziegler-Natta catalysts having high activity and high stereoregularity is known from European Patent No. 045,977, and is a solid catalyst compound as an internal electron donor of certain carboxylic acid ester compounds, preferably phthalate derivatives. The Ziegler-Natta catalyst can be prepared in conjunction with a titanium compound. In addition, a method of increasing polymerization activity and stereoregularity by alpha-olefin polymerization using an aluminum alkyl compound and a silicon compound having at least one silicon-ether bond as an external electron donor in these main catalysts has been proposed. However, in these preparation methods, there is a difficulty in controlling the size of the carrier particles and the molecular weight distribution of the polymer is often not good.

In addition, in order to make the particle size uniform, the catalytic process disclosed in U.S. Patent Nos. 4,946,816, 4,866,022, 4,988,656, 5,124,297 and the like first comprises (i) a solution comprising magnesium from magnesium carboxylate or magnesium alkylcarbonate. (Ii) precipitating a magnesium solution in the presence of a transition metal halide and an organosilane additive, and (iii) reacting the particles with a transition metal component and an electron donor compound to make a catalyst catalyst constant. However, these methods have many problems in the production of catalysts, complicated production processes, rapid decrease in catalyst activity during the polymerization process, and failure to meet current requirements in terms of stereoregularity and particle size.

In the case of the polypropylene produced by the catalyst, it is classified into a polypropylene homopolymer, a polypropylene random copolymer, and a polypropylene block copolymer according to the difference in composition of the polymerization method and the polymerized composition. Polypropylene homopolymers have excellent chemical resistance and pressure resistance, and polypropylene block copolymers have excellent impact strength, in particular, low temperature impact strength at 0 ° C or lower.

As a manufacturing method of a polypropylene block copolymer, the method of manufacturing a propylene block copolymer is generally performed by first forming a polypropylene homopolymer component, and then introducing an ethylene-propylene random copolymer component. According to this method, a polypropylene block copolymer resin is prepared by polymerizing monomers of propylene and ethylene in a gas phase or bulk slurry polymerization process without using a solvent in the presence of a solid complex titanium catalyst, an organoaluminum promoter and an external electron donor. In this case, the flexural strength and impact strength of the block copolymer are greatly influenced by the type of external electron donor used, and the eye affects the impact strength of the polypropylene homopolymer formed in the first step of preparing the block copolymer. The higher the soottic pentad fraction, the better the flexural strength characteristics. However, polypropylene block copolymers prepared according to such conventional methods have improved impact resistance compared to polypropylene homopolymers, while inferior in rigidity, hardness and heat resistance.

In order to improve the impact resistance of the polypropylene block copolymer resin composition, the content of the ethylene-propylene block copolymer may be increased. However, too much content of ethylene-propylene block copolymers lowers impact resistance and flexural modulus. Therefore, the optimal ethylene-propylene block copolymer content is important.

On the other hand, in the present invention, a special nucleating agent is used as an additive as a method of improving the rigidity without lowering the impact resistance of the polypropylene resin composition. The nucleating agent improves the flexural modulus by increasing the crystallization rate of the polypropylene resin and finely controlling the crystal structure. As the nucleating agent for this purpose, an organic nucleating agent or an inorganic nucleating agent may be used, and lubricating oil and other additives may also be used.

The present invention is to solve the above problems, to prepare a carrier using a precipitation aid and a shape control agent suitable for organic materials other than magnesium dichloride and alcohol, Ziegler-Natta catalyst by coordinating the ideal electron donor and active ingredient Through manufacturing, the purpose is to fundamentally modify the resin, and to produce a resin having a very high flexural strength through a post-treatment process using an inorganic or organic nucleation material.

In order to solve the above problems, according to a preferred embodiment of the present invention, an olefin prepared by preparing a mixed solution using anhydrous magnesium chloride, dioxirane, a hydrocarbon and an organophosphorus compound, and then adding titanium tetrachloride and an electron donor It provides a polypropylene resin composition prepared by polymerization in a multistage reactor using a Ziegler-Natta catalyst for polymerization and comprising a mixture of polypropylene homopolymer and ethylene copolymer having an ethylene-propylene rubber content of 0.1 to 20% by weight.

According to another suitable embodiment of the present invention, the polypropylene resin composition comprises 0.1 to 10 parts by weight of an organic nucleating agent or an inorganic nucleating agent, and 0.01 to 10 parts by weight of polyethylene wax based on 100 parts by weight of the polypropylene resin composition. do.

According to another suitable embodiment of the present invention, the organic nucleating agent is at least one selected from the group consisting of aluminum salts, calcium stearate and sodium benzoate of carboxylic acid, and the inorganic nucleating agent is talc, dibenzylidene sorbitol and substitution It is characterized in that at least one member selected from the group consisting of dibenzyl lidene sorbitol.

Polymerization of polypropylene using the Ziegler-Natta catalyst prepared according to the present invention, the content of ethylene-propylene rubber in the polypropylene is adjusted, and an organic or inorganic nucleating agent and polyethylene wax are added at an appropriate ratio to prepare a polypropylene resin. As a result, the bending strength can be improved. The polypropylene resin thus prepared can be effectively used as a molding material such as a plate, film or fiber.

The Ziegler-Natta catalyst system of the present invention is characterized in that it is formed of [A] transition metal compound, [B] organoaluminum compound as cocatalyst, and optionally [C] electron donor as subcatalyst.

The catalyst component [A] is of the general formula MR ⁺ _x , wherein M is a metal, R is halogen or hydrocarbyloxy and x is the oxidation number of the metal, preferably M is a group IVB or VB or VIB of the periodic table. And more preferably titanium. R is preferably chlorine, bromine, alkoxy or phenoxy and more preferably chlorine or ethoxy. In this case, a mixture of transition metal compounds may be used. In addition, catalysts are generally prepared in a form in which a catalyst component [A] is supported on a carrier to improve catalyst activity, and the carrier is a chemically inert solid component that does not cause a chemical reaction with the Ziegler-Natta catalyst component [A].

The cocatalyst component [B] is an organoaluminum compound, of the general formula R _n AlY _3-n (where R is 1-20 hydrocarbons, Y is halogen and ₀ ≦ _n ≦ ₃ ).

The subcatalyst component [C] may be classified into an internal electron donor present in the catalyst as an electron donor and an external electron donor provided together with the cocatalyst during polymerization.

The internal electron donor is added during the preparation of the catalyst, and a phthalate compound, a carboxylic acid ester compound or a diether compound is suitable. Specifically, the compounds of the phthalate family are monoethoxy phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, dinormal propyl phthalate, diisopropyl phthalate, dinormal butyl phthalate, diisobutyl phthalate, inomactyl phthalate, and dipentyl. Phthalates and the like or mixtures thereof. Carboxylic acid ester compounds include methyl acetate, ethyl acetate, phenyl acetate, ethyl propane, ethyl butyrate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate and diethyl Malonate etc. or a mixture thereof can be illustrated. Ether compounds include 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diasobutyl-1 in the form of 1,3-diether , 3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-enebutoxypropane, 2,2-diphenyl-1,3- Dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 1,3-diisobutoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane or their Mixtures and the like.

As the external electron donor, a compound having a structure of formula (1), in particular an organosilicon compound, is used.

Wherein R ¹ and R ³ are an alkoxy group or an arylalkyl group, such as methoxy, ethoxy, butoxy, and R ² is an alkyl group, an alkoxy group or an arylalkyl group, and methyl, ethyl, butyl, methoxy, ethoxy, butoxy And R ⁴ is an aromatic or cycloarylphatic group such as phenyl, anthracenyl, naphthalenyl, cyclopentyl, cyclohexyl, cyclooctyl and the like, X is carbon, silicon and the like.

Examples of the organosilicon compound include triethylmethoxy silane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, petylmethyldimethoxysilane, difetyldiethoxy Silane, Dicyclohexyldimethoxysilane Cyflohexylmethyldimethoxysilane, Cyflohexylmethyl diethoxysilane, Dicyclopentyldimethoxysilsane Dicyclopentyl diethoxy acid, Ethyltrimethoxysilane, Ethyltriethoxysilane , Vinyltrimethoxysilane and vinyltriethoxysilane, and preferably cyclohexylmethyldimethoxysilane and dicyclopentyl diethoxysilane are diphenyldimethoxysilane.

The external electron donor should be 0.001-50 mol%, preferably 0.01-20 mol%, more preferably 0.02-10 mol% per mole of promoter. If it is 0.001 mol% or less, the problem that the improvement of stereoregularity will not occur, and if it is 50 mol% or more, it will no longer affect stereoregularity.

In the present invention, the following method is used to prepare a catalyst having high activity, high stereoregularity, and producing a polymer having improved particle distribution and molecular weight distribution.

First, (i) dioxirane, preferably 0.1-20 mol of dimethyl oxirane, and (ii) hydrocarbon solvents in 1 mol of magnesium dichloride, decane, hexane, heptane, octane, decane, dodecane, cyclohexane, Xylene, toluene, benzene and the like can be used. Preferably, 0.01 to 30 moles of toluene are reacted with (iii) 0.01 to 4 moles of an organophosphorus compound at a temperature between 50 and 100 ° C.

The organophosphorus compounds used at this time include trimethylated phosphate, triethylated phosphate, tributylated phosphate, trimethylated phosphite, triethylated phosphite, tributylated phosphite, and the like, in particular tributylated phosphate and tripentylated phosphate. Is preferred.

Depending on the concentration of organophosphorus compound used, the size distribution of the particles is significantly affected. That is, since an organic phosphorus compound of too low concentration hardly forms a complex with the carrier, the carrier reacts at an excessively high rate by titanium tetrachloride added later, so that the size of the resulting carrier is small and there are almost no pores. The distribution of active points is uneven.

In addition, the average particle size of the catalyst and the particle distribution of the polymer are affected by the concentration of the organic material, hydrocarbon solvent and toluene used to dissolve the magnesium dichloride. As an organic substance used here, the compound of following General formula (2) is used.

delete

Wherein R ¹ and R ² are hydrogen or carbon atoms having 1 to 20 and are methyl, ethyl, propyl, butyl, isopropyl, isobutyl and the like.

As the organic compound, dioxirane compounds such as dimethoxydioxirane, ethylmethyldioxirane, methylpropyldioxirane, methylisopropyldioxirane, methylbutyldioxirane and methylisobutyldioxirane can be used. Especially dimethylbutyl dioxirane is preferable. When the concentrations of organic and toluene are low, magnesium can not be dissolved to interfere with the formation of magnesium particles, resulting in uneven particle formation of the catalyst, lowering of activity, and narrowing of particle distribution of the polymer. Conversely, when the concentration is increased, dissolution of magnesium becomes easy while precipitation of the carrier does not occur, resulting in a smaller size of the resulting carrier and an uneven distribution of active sites. The organic and hydrocarbon solvents added in an appropriate amount form a suitable environment when magnesium dichloride is produced as a carrier to form a carrier having a uniform particle size, and the obtained polymer has a wide particle distribution.

In addition, 0.01 to 10 mol, preferably 0.01 to 1.0 mol of a phthalic acid compound, which is a precipitation accelerator for controlling the production rate, is added to form a magnesium mixed solution.

Secondly, the resultant magnesium mixture solution is cooled to between -40 and 0 ° C., and then 5 to 20 moles of titanium tetrachloride is slowly added dropwise for 1 to 3 hours to form a carrier, followed by 0.5 to 5 ° C./min rate. The temperature is raised to. Temperature conditions then affect carrier uniformity. The precipitate is added with 0.05 to 2 mol of internal electron donor and reacted at 70 to 120 ° C. for 1 to 3 hours or more. Electron donors which can be preferably used in the present invention are monoethoxy phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, dinormal propyl phthalate, diisopropyl phthalate, dinomal butyl phthalate, diisobutyl phthalate, inomactyl Phthalates, dipentylphthalate and the like or mixtures thereof, most preferred of which is diisobutyl phthalate.

Third, after washing and filtering the reactant, and after adding titanium tetrachloride again and reacted at 60 ~ 100 ℃ for 1-5 hours, the solid component is filtered and the hydrocarbon component such as nucleic acid, heptane, octane, benzene, toluene It is washed until it is not detected to obtain a solid catalyst.

The polypropylene polymerization can be carried out in gas phase, liquid phase, or solution phase. When performing a polymerization reaction in a liquid phase, a hydrocarbon solvent may be used and olefin itself can also be used as a solvent. The gas phase process is preferable when preparing a block copolymer. The polymerization temperature is usually in the range of -50 to 350 ° C, preferably 20 to 100 ° C. If the temperature is less than 20 ° C., the activity of the catalyst is not good, and the particle shape does not grow properly at 100 ° C. or more, which is not good. The polymerization pressure is usually at atmospheric pressure of 250 kg / cm ² , preferably at atmospheric pressure of 200 kg / cm ² . If more than 250kg / cm ^{2 It} is not preferable in terms of industrial and economic.

In the present invention, the polypropylene obtained through the polymerization reaction means not only a propylene homopolymer but also a copolymer between propylene and at least one monomer. As the copolymerized monomer, for example, linear or branched alpha olefins containing 2 to 6 carbon atoms such as ethylene, 1-butene, 1-hexene, 1-octene, and 4-methylpentene-1 can be used. Do.

The polypropylene homopolymer used in the resin composition of the present invention is a high-stereoregular polypropylene having an isotactic pentad fraction, which is a stereoregularity index of nuclear magnetic resonance method, of 95% or more. If the isotactic pentad fraction of the polypropylene homopolymer is less than 95%, the flexural strength is lowered, which is not good.

The ethylene-propylene block copolymer used for the resin composition of this invention is 1.5-6.0 dl / g absolute viscosity measured at 135 degreeC. If the absolute viscosity is less than 1.5 dl / g, the flexural modulus decreases, while if it exceeds 6.0 dl / g, the dispersibility is poor.

It is preferable that the ethylene-propylene block copolymer used for the resin composition of this invention is 0.1-20 weight% of rubber content. If the rubber content is less than 0.1% by weight, the structure is similar to that of the homopolymer, and the impact resistance is lowered. If the rubber content is more than 20% by weight, the rigidity is lowered. The rubber content is too high. .

The resin composition of the present invention first polymerizes a polypropylene homopolymer having the above properties in a series of reactors, and then copolymerizes ethylene and propylene in the presence of the polypropylene homopolymer, thereby producing a polypropylene homopolymer and an ethylene-propylene block. A mixture of copolymers is obtained, followed by addition of an amount of organic or inorganic nucleating agent to the polymer mixture.

In the present invention, a commercially available inorganic nucleating agent or organic nucleating agent such as layered organic montmorillonite may be added to the polypropylene. This serves to facilitate the nucleation of the block polypropylene, it can be prepared in the form of extruding the polypropylene through an extruder in the presence of a reaction initiator.

The organonuclear agent may be an aluminum salt of carboxylic acid, calcium stearate, sodium benzoate, or the like, and the inorganic nucleus agent may be talc, dibenzylidene sorbitol, or substituted dibenzylidene sorbitol.

As for the usage-amount of the said organic and inorganic nucleating agent, 0.1-10 weight part is preferable with respect to 100 weight part of polypropylene resin compositions, More preferably, it is 0.1-5 weight part. If the amount of the organic and inorganic nucleating agents is less than 0.1% by weight, there is little effect of improving the mechanical properties desired in the present invention, whereas if it exceeds 10% by weight, it is difficult to obtain easy dispersibility and processability.

In parallel with this, a polyethylene wax or a lubricant may be added to the mixture to prepare an ethylene monomer, an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride, and a reactant in a reactor. It is preferable to use 0.01-10 weight part of polyethylene wax with respect to 100 weight part of polypropylene.

In addition to the components described above, the resin composition according to the present invention may further contain various additives usable for propylene polymers, such as stabilizers (eg, acid resistant, antioxidant or ultraviolet stabilizers) and processing aids. . The total content of these additives is generally 0.1 to 10 parts by weight or less, preferably 0.1 to 5 parts by weight or less based on 100 parts by weight of the polypropylene resin composition. In addition, the resin composition according to the present invention may contain a pigment. Generally, the content of the pigment does not exceed 3 parts by weight of the total composition, preferably 1 part by weight or less.

The resin of the present invention is prepared by weighing each component of the resin and the additive obtained by the above-described resin manufacturing method and uniformly mixing with a Henschel mixer, and then using a twinscrew extruder equipped with an eight-stage heating device. Pelletized by melt extrusion at temperature.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are provided to explain preferred embodiments of the present invention, and the scope of the present invention is not limited by the following examples.

In each Example and Comparative Example, the measurement method of physical properties is as follows.

The criteria shown below are methods for measuring the physical properties of polypropylene resins, and the physical properties of each resin were evaluated under standard conditions based on ASTM standards.

[Measurement of physical properties]

(1) Isotactic Index: 13C-NMR was used to measure the isotactic fraction as pentad units in the polypropylene molecular chain.

(2) Absolute viscosity of ethylene-propylene block copolymer: The copolymer was extracted with n-decane solution, and the extract was dissolved in 135 ° C decalin to measure the viscosity.

(3) Melt index (MFR): measured at 230 ° C. and 2.16 kg load according to ASTM D1238 method.

(4) Flexural Strength (FM): The flexural strength was measured after preparing the resin composition of the present invention in accordance with ASTM790.

Example 1

Catalyst preparation

Under a high-purity nitrogen atmosphere, 480 g of anhydrous magnesium dichloride, 5 mol of methylbutyl dioxirane, 9.5 l of toluene, and 1250 ml of tributylphosphate were added thereto, and the stirring was continued until a clear solution was produced at a temperature of 80 ° C. 140 g of phthalic anhydride was added thereto and stirring was continued for 2 hours to form a magnesium carrier mixed solution.

The mixed solution was slowly added dropwise to 2L of titanium tetrachloride whose temperature was lowered to -20 ° C, and the temperature was raised to 100 ° C. After adding 368 ml of diisobutyl phthalate at 100 ° C., the reaction was performed at 110 ° C. for 2 hours. After the reaction, the mixture was washed with toluene. Then, 6L of toluene and 4L of titanium tetrachloride were added thereto, and the mixture was reacted at 110 ° C. for 2 hours. After filtering the solid components, the mixture was washed with toluene and hexane to obtain a solid catalyst.

Propylene polymerization

The polymerization was carried out in a Hypol process consisting of a continuous reaction process consisting of a liquid phase reactor with two agitators and two gas phase reactors. During the polymerization, liquid propylene and hydrogen were added to the reactor, and triethylaluminum, dicyclopentyldimethoxysilane, and the catalyst prepared above were injected to carry out multistage polymerization.

Stabilizers and antioxidants were mixed in a powdery polymer mixture made through a continuous reaction process to prepare pellets in an extruder. The prepared resin composition was processed into an injection molding to measure various physical properties as in the above method.

[Example 2]

The catalyst was prepared under the same conditions as in Example 1 except for changing to dimethyldioxirane (5 mol) instead of methylbutyldioxane.

[Comparative Example 1]

The catalyst was prepared under the same conditions as in Example 1 except for changing to 2-ethylhexanol (5 mol) instead of methylbutyldioxirane.

Example 3

Prepared in the same manner as in Example 2, during the polymerization in a continuous reaction process (Hypol Process), the block copolymer was polymerized by further injection of ethylene in the last gas phase reactor. At this time, the content of ethylene-propylene rubber (Rubber) in the copolymer was adjusted to 13.4 parts by weight.

Comparative Example 2

A catalyst was prepared under the same conditions as in Comparative Example 1, and polymerized in the same manner as in Example 3.

Example 4

Prepared in the same manner as in Example 3, when 100 parts by weight of the total polyflophylene composition, 0.2 parts by weight of inorganic nucleating agent and 0.1 parts by weight of PE wax was added to prepare a pellet. Physical properties were measured and the results are shown in Table 1.

Example 5

Prepared in the same manner as in Example 4, pellets were prepared by adding 0.4 parts by weight of an inorganic nucleating agent and 0.2 parts by weight of a PE wax. Physical properties were measured and the results are shown in Table 1.

Example 6

Manufactured in the same manner as in Example 3, the content of ethylene propylene rubber (Rubber) in the copolymerization process was prepared to 7.3 parts by weight. Physical properties were measured and the results are shown in Table 1.

Example 7

Prepared in the same manner as in Example 6, pellets were prepared by adding 0.4 parts by weight of an inorganic nucleating agent and 0.2 parts by weight of a PE wax.

division content
(Parts by weight) Melt index
(g / 10 min) Ethyl propylene rubber content
(Parts by weight) Flexural strength
(kgf / cm ² ) Inorganic nucleating agent PE wax Example 1 0.25 - 18,150 Example 2 0.25 - 18,200 Comparative Example 1 0.25 - 17,950 Example 3 0.25 13.4 15,050 Comparative Example 2 0.25 13.4 14,200 Example 4 0.2 0.1 0.25 13.4 16,600 Example 5 0.4 0.2 0.25 13.4 17,100 Example 6 0.25 7.3 16,450 Example 7 0.4 0.2 0.25 7.3 19,850

As can be seen from the above table, the olefins are polymerized using the Ziegler-Natta catalyst prepared according to the present invention, and in addition to the ethylene-propylene rubber content, the flexural strength can be increased by using an inorganic nucleating agent and a PE wax at an appropriate ratio. Can be. The polypropylene produced by the present invention is effective for use as a molding material for plates, films, containers, and fibers.

Claims (3)

A mixed solution is prepared using anhydrous magnesium chloride, dioxirane, a hydrocarbon solvent, and an organophosphorus compound, and then polymerized in a multistage reactor using a Ziegler-Natta catalyst for olefin polymerization prepared by adding titanium tetrachloride and an electron donor. And a mixture of a polypropylene homopolymer and an ethylene-propylene block copolymer having an ethylene-propylene rubber content of 0.1 to 20% by weight. The polypropylene resin according to claim 1, wherein the polypropylene resin composition comprises 0.1 to 10 parts by weight of an organic nucleating agent or an inorganic nucleating agent and 0.01 to 10 parts by weight of polyethylene wax based on 100 parts by weight of the polypropylene resin composition. Composition. 3. The organic nucleating agent according to claim 2, wherein the organic nucleating agent is at least one selected from the group consisting of aluminum salts, calcium stearate, and sodium benzoate of carboxylic acid, and the inorganic nucleating agent is talc, dibenzylidene sorbitol, and substituted dibenzylidene sorbitol. Polypropylene resin composition, characterized in that at least one member selected from the group consisting of.