KR101115059B1 - Olefin prepolymerized catalyst, process for producing olefin by using the catalyst and polyolefin resin composition by the process - Google Patents

Abstract

The present invention is to prepare a crystalline polyolefin having high melt strength and high transparency by using a prepolymerization catalyst prepared by adding and polymerizing a diene compound and vinyl cycloalkane to the solid titanium catalyst for olefin polymerization. A method and a polyolefin produced thereby.

Ziegler-Natta catalysts, polyolefin polymerization, prepolymerization, diene compounds, vinyl ring saturated hydrocarbons

Description

Method for producing olefin prepolymerization catalyst and polyolefin polymerization method using olefin prepolymerization catalyst {OLEFIN PREPOLYMERIZED CATALYST, PROCESS FOR PRODUCING OLEFIN BY USING THE CATALYST AND POLYOLEFIN RESIN COMPOSITION BY THE PROCESS}

The present invention relates to a prepolymerization catalyst polymerization method for producing a long branched polyolefin having high melt strength and high transparency, and a polyolefin polymerized using the same.

In detail, a prepolymerization catalyst having a high molecular weight monomer encapsulated using a diene-based compound and vinyl cycloalkane (vinyl cycloalkane) around the optimum catalyst for alpha olefin polymerization, and polymerized using the The present invention relates to a crystalline ethylene-propylene random copolymer resin.

Since general polypropylene has a linear structure, the melt strength is very low compared to polyethylene, and thus, it is not suitable for process applications such as casting, thermoforming, extrusion coating, etc. which are processed in a molten state.

For this reason, the following two methods have been largely used to increase the melt tension of polypropylene.

The first is to introduce long chain branches into polyolefins to reduce the attractive force between the polymer chains in the processing process to give easy flow characteristics, and to ensure the dimensional stability of the molding process (especially large blows). In long-term use, long branches serve to increase melt tension through physical bridges between adjacent chains.

As a method of preparing a polyolefin having high melt strength by introducing such long branches, radicals are mainly formed on the polyolefins that have passed through the polymerization reactor through electron beam or reaction extrusion, and then reacted again to form long branches in the chain polyolefin. Was used.

The second is to physically blend polyethylene into polypropylene with a very low melt index. This method has a problem that the workability is lowered because the melt index. Polymerization method that directly polymerizes polyolefin having high melt strength useful as a molding material in the polymerization stage and further improves melt tension through blending with low density polyethylene. If a light blend method is developed, the use of polyolefin as a molding material can be expected to be expanded. There will be.

In addition, propylene is a general purpose plastic that is used for a wide range of applications because of its excellent formability and mechanical strength and low cost. However, according to the field of use, it is intended to improve the properties such as stiffness, transparency, and high cycle injection moldability in injection molding without impairing the inherent properties of the propylene polymer. It is known that these properties can be improved by increasing the crystallization rate of the propylene polymer.

Many substances and the like are already known as additives for increasing the crystallization rate of propylene polymers, and commercially available ones include aromatic carboxylic acid aluminum salts, dibenzylidene sorbitol, and substituted dibenzylidene sorbitol. By prescribing these additives (hereinafter referred to as nucleating agents), the crystallization degree is increased in the process of polypropylene being cooled from the molten state to the solid state due to the presence of the nucleating agent, thereby increasing the stiffness. When the crystals are formed in a spherical shape, the size of the crystals is refined, so that light scattering can be suppressed to improve transparency, glossiness, and shortening of the molding cycle. However, when these nucleating agents are used, care must be taken according to the use because shrinkage anisotropy may occur or nucleating agents may be attached to dies, dies, rolls, etc. depending on the molding conditions, resulting in warpage defects.

Therefore, in recent years, the technique which tries to improve the rigidity and transparency of polypropylene by displacing the prepolymerization process of a vinyl compound is proposed. The melting point of the vinyl cycloalkane polymer is about 370 ° C, which is much higher than that of general propylene (pure isotactic polypropylene has a melting point of 176 ° C). Has been.

For example, as a method of adding a nucleating agent, Japanese Laid-Open Patent Publication No. 60-139710 discloses a method of micropolymerization of vinyl cycloalkane before a propylene polymer. However, when the vinyl cyclic saturated hydrocarbon is polymerized alone, the particles are broken and the activity is deteriorated.

In Japanese Patent Laid-Open No. 4-96907, prepolymerization of olefins is carried out in multiple stages in the presence of a titanium compound, an organoaluminum compound, and an organosilicon compound, and different organosilicon compounds are used in each prepolymerization step, and each prepolymerization step is performed. In at least one step, a prepolymerization method of olefins suitable for obtaining a polypropylene excellent in transparency by polymerizing vinyl cyclic saturated hydrocarbons and styrene compounds has also been proposed.

The present invention provides a long chain in the polymer chain and introduces a cyclic structure to prepare a polyolefin having high melt tension and high crystallinity in the polymerization step and post-processing. It is intended to prepare a prepolymerized catalyst.

In order to introduce long branches to increase the melt tension, the catalyst is modified by prepolymerization with a diene-based compound, and the polycyclic saturated hydrocarbon is used to produce polyolefins by increasing the crystallinity.

The present invention comprises the steps of: a) polymerizing a Ziegler-Natta catalyst with a diene compound; And

b) it provides a method for producing a catalyst for olefin polymerization comprising the step of polymerizing by adding a vinyl cyclic saturated hydrocarbon in step a).

In the step a), the diene compound may be added to a catalyst of 1 to 50 g / g based on the weight of the generated prepolymerization catalyst and polymerized with a 5 to 30 g / g catalyst.

In the step b), the vinyl cyclic saturated hydrocarbon compound may be introduced into a 10 to 50 g / g catalyst based on the weight of the generated prepolymerization catalyst and polymerized with a 15 to 30 g / g catalyst.

The diene compound is highly reactive with the Ziegler-Natta catalyst. However, when a small amount of diene compound is prepolymerized, especially when the cyclic saturated hydrocarbon compound is less than 2 g of diene compound, many branches due to the diene compound are not formed, so that no deformation strengthening phenomenon occurs. In addition, when the amount of the diene compound increases, the particles of the prepolymerization catalyst become too large, causing problems in the catalyst injection process.

In addition, the vinyl cyclic saturated hydrocarbon compound also has the greatest transparency in the range of 15 to 30 g / g catalyst, and when the prepolymerization proceeds to about 50 g / g catalyst, the particles of the catalyst are broken due to the large particle size of the vinyl cyclic saturated hydrocarbon. Or other physical properties are reduced.

The present invention also provides a catalyst for olefin polymerization prepared by the method for preparing a catalyst for olefin polymerization.

In addition, the present invention comprises the steps of A) prepolymerizing a Ziegler-Natta catalyst by the method for preparing a catalyst for olefin polymerization to prepare a prepolymerized Ziegler-Natta catalyst; And B) polymerizing the olefin using the Ziegler-Natta catalyst prepolymerized in step A).

In the step a), the diene compound may be added to a catalyst of 1 to 50 g / g based on the weight of the generated prepolymerization catalyst and polymerized with a 5 to 30 g / g catalyst.

In the step b), the vinyl cyclic saturated hydrocarbon compound may be introduced into a 10 to 50 g / g catalyst based on the weight of the generated prepolymerization catalyst and polymerized with a 15 to 30 g / g catalyst.

The present invention also provides a polyolefin produced by the olefin polymerization method.

Stepwise polymerization using a monomer of a diene compound and a vinyl ring-type saturated hydrocarbon to a Ziegler-Natta catalyst, and then polymerizing the olefin using the prepolymerized Ziegler-Natta catalyst in the olefin production method of the present invention According to the diene compound, the olefin has a long branch in molecular structure, and the vinyl ring-type saturated hydrocarbon has a cyclic structure. As a result, the production method of the present invention satisfies the structure of two conditions that reduce the crystallinity of the olefin, thereby producing a polyolefin having high melt strength and high transparency.

The method for preparing a catalyst for olefin polymerization of the present invention may include a step of polymerizing two or more olefins in a Ziegler-Natta catalyst.

In the above method for preparing the catalyst for olefin polymerization, when the Ziegler-Natta catalyst is polymerized stepwise with two or more types of olefins, the order of the olefin monomers is the crystallization temperature, stereoregularity, melt flow index, and melt of the resulting olefin polymer. It acts as a major factor that has a significant influence on tension and the like.

Specifically, as the olefin to be added stepwise to the Ziegler-Natta-based catalyst, a diene compound and a vinyl ring-type saturated hydrocarbon are preferable, and it is preferable to add them sequentially. The reason is that the polymer of the diene compound is coated on the surface of the catalyst by first polymerizing the diene compound on the catalyst particle, and the vinyl ring-type saturated hydrocarbon introduced later bonds with the polymer of the diene compound to break the catalyst particle. This is because the phenomenon can be prevented. Thus, the particles of the catalyst become more uniform, and the morphology of the polymer produced using such a catalyst also shows an improved result.

The composition of the diene compound and vinyl cyclic saturated hydrocarbon of the prepolymerization catalyst thus produced is 0.01 to 50 wt% of the diene compound and 10 to 99 wt% of the vinyl cyclic saturated hydrocarbon.

The diene compound used above is a diene compound having 4 to 14 carbon atoms having α, ω-diene structure, specifically 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9 -Decadiene 1,13- tetradecadiene, etc. are mentioned.

As the vinyl ring-type saturated hydrocarbon used above, a vinyl ring-type saturated hydrocarbon of 5 to 10 carbon atoms is preferable, and specifically, for example, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinyl-3-methylcyclopentane, Vinyl-2-methylcyclohexane, vinyl-3-methylcyclohexane, vinylnorbornene and the like, although vinylcyclohexane is preferred.

In addition, the catalyst for olefin polymerization of the present invention is characterized in that it is produced by the method for producing a catalyst for olefin polymerization.

In addition, the olefin polymerization method of the present invention comprises the steps of A) prepolymerizing the catalyst for olefin polymerization by the method for preparing the catalyst for olefin polymerization to prepare a pre-polymerized Ziegler-Natta catalyst; And B) polymerizing the olefin using the Ziegler-Natta catalyst prepolymerized in step A).

In the polymerization method of the olefin according to the present invention, a Ziegler-Natta catalyst is prepolymerized with a diene compound and a vinyl ring-type saturated hydrocarbon step by step, and then polymerized with an olefin using the prepolymerized catalyst, thereby producing a chain of polymer. Transparency can be improved by causing entanglement and increasing the crystallization temperature.

In the process according to the invention, 'polymerization' does not only mean homopolymerization of olefins, but also copolymerizes two or more olefins such as olefins, in particular propylene, such as ethylene, 1-butene, 1-hexene, A copolymerization process for producing the copolymer.

In the present invention, the Ziegler-Natta catalyst is dispersed into uniform particles in the polymerization process, and then the diene compound is polymerized on the catalyst surface. Such Ziegler-Natta catalysts may be used without particular limitation as long as they are generally used for olefin polymerization, but include transition metal compounds containing Group 4, Group 5 or Group 6 elements in the periodic table; And organometallic compounds comprising a Group 13 element in the periodic table.

The transition metal compound is preferably a solid titanium catalyst containing magnesium, titanium, a halogen element and an internal electron donor as the main catalyst in the Ziegler-Natta catalyst. Herein, the internal electron donor may be, for example, a diether compound, a phthalate compound, or a mixture thereof. Specifically, diisobutyl phthalate may be used.

The organometallic compound is preferably a co-catalyst in the Ziegler-Natta catalyst, and an organoaluminum compound is preferable. For example, there are trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride, alkyl aluminum sesquihalide, and the like, and one or more compounds can be selected and used from the group consisting of these.

Specifically, the organometallic compound may be Al (C ₂ H ₅ ) ₃ , Al (C ₂ H ₅ ) ₂ H, Al (C ₃ H ₇ ) ₃ , Al (C ₃ H ₇ ) ₂ H, Al (iC ₄ H ₉ ) ₂ H, Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₂ H ₂₅ ) ₃ , Al (C ₂ H ₅ ) (C ₁₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) (C ₁₂ H ₂₅ ) ₂ , Al (iC ₄ H ₉ ) ₂ H, Al (iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl, (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ and the like.

The organometallic compound may also be a mixture of organoaluminum compounds. At this time, the mixture may be a mixture of organometallic compounds belonging to Group 13 in the periodic table, it is preferable to use a mixture of different organoaluminum compounds. For example, the mixture of the organoaluminum compounds may be a mixture of Al (C ₂ H ₅ ) ₃ and Al (iC ₄ H ₉ ) ₃ ; A mixture of Al (C ₃ H ₇ ) ₃ , Al (C ₂ H ₅ ) ₃ and Al (C ₈ H ₁₇ ) ₃ ; A mixture of Al (C ₄ H ₉ ) ₂ H and Al (C ₈ H ₁₇ ) ₃ ; A mixture of Al (iC ₄ H ₉ ) ₃ and Al (C ₈ H ₁₇ ) ₃ ; A mixture of Al (C ₂ H ₅ ) ₃ and Al (C ₁₂ H ₂₅ ) ₃ ; A mixture of Al (iC ₄ H ₉ ) ₃ and Al (C ₁₂ H ₂₅ ) ₃ ; A mixture of Al (C ₂ H ₅ ) ₃ and Al (C ₁₆ H ₃₃ ) ₃ ; A mixture of Al (C ₃ H ₇ ) ₃ and Al (C ₁₈ H ₃₇ ) ₂ (iC ₄ H ₉ ), and the like, but is not limited thereto.

At this time, the molar ratio of the organometallic compound to the transition metal compound is preferably 5 to 50.

In the olefin polymerization method of the present invention, preferred nonpolar solvents for use in the prepolymerization step of step A) include saturated alicyclic hydrocarbons such as hexane, normal heptane, octane, nonane, and decane, cyclopentane and cyclohexane. Hydrocarbons, and the like, of which hexane is most preferred. These are preferably used after purification before use so as not to affect the catalytic activity.

B) of the olefin polymerization method of the present invention, an external electron donor may be further used in the step of polymerizing the olefin using a prepolymerized Ziegler-Natta catalyst.

Examples of the external electron donor include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 30 carbon atoms, and substituted or unsubstituted carbon atoms. It is preferred to include an organosilane compound comprising at least one or more groups selected from the group consisting of 1 to 20 alkoxy groups and comprising at least one oxygen atom.

Specifically, as the external electron donor, aromatic organic silane compounds such as diphenyldimethoxysilane, phenyltrimethoxysilane, phenylethyldimethoxysilane and phenylmethyldimethoxysilane, trimethylmethoxysilane, isobutyltrimethoxysilane, Aliphatic organic silane compounds such as diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane and dicyclohexyldimethoxysilane, Or mixtures thereof.

After the olefin is bonded to the Ziegler-Natta catalyst through the polymerization step as described above, the olefin polymerization step is performed by using the olefin polymerization step. The polymerization reaction of the olefin in the presence of the catalyst of the present invention is conventional Ziegler-Natta. It can proceed similarly to the polymerization method of the olefin using a system catalyst. However, the olefin polymerization reaction of the present invention is preferably carried out substantially in the absence of oxygen and water. At this time, the polymerization temperature of the olefin may preferably be carried out under a pressure of 1 to 100 atm, preferably about 2 to 50 atm at a temperature of about 20 to 200 ℃, more preferably about 50 to 180 ℃. .

Haze of the polyolefin is characterized in that it has a range of 1 to 50%.

In addition, the melt flow index of the polyolefin is characterized in that it has a range of 0.1 ~ 50g / 10 minutes.

In addition, when the polypropylene polymer having a long branch used in the present invention has a strain rate more than a certain value when measuring the stretching viscosity, strain hardening is expressed so that the stretching viscosity value is higher than that of the linear curve. It is characterized by a large increase, which may replace the value of the melt tension. Strain strengthening is indicative of an improvement in melt tension.

In addition, in the present invention, by having a cyclic structure, the degree of crystallinity is improved, and the crystal structure is reduced, thereby improving transparency and improving the Haze value.

Hereinafter, the present invention will be described in detail through embodiments of the present invention. However, embodiments of the present invention may be modified in various forms, the scope of the present invention should not be construed in a way that is limited by the embodiments described below. Embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Preparation Example 1 Preparation of Catalyst

Preparation of component a

25.25 g of magnesium compound (Mg (Cl ₂ -77C ₂ H ₅ OH)) and 150 ml of anhydrous heptane were added to a 500 ml glass reactor under a nitrogen atmosphere at 0 DEG C, stirred, and then 21.6 ml of diisobutyl phthalate, a phthalate compound, was added dropwise thereto. Then, 100 ml of 0 ° C. TiCl ₄ was added thereto, and the mixture was reacted at room temperature for 1 hour, and then 150 ml of TiCl ₄ was added dropwise, and the reaction mixture was heated to 100 ° C. for 2 hours, after which the supernatant was separated and TiCl ₄ was reacted. 200 ml was added dropwise and reacted for 2 hours at 120 ° C. After the reaction was completed, TiCl ₄ was removed, washed six times with heptane at 80 ° C., and then dried under vacuum at 40 ° C.

Example 1 Polymerization Process of Propylene

Stage A: Prepolymerization

After purging the reactor having a capacity of 0.5 L with argon at a high temperature, 2 g of the component a catalyst prepared above, 200 ml of hexane, triisobutylaluminum Al / Ti (= 10) and trimethyl methoxysilane were added to Si / Ti (= 2) was added and 20 g of 1,7-octadiene was added, and polymerization was performed at 20 ° C. for 1 hour. Thereafter, the catalyst was precipitated, washed three times with hexane, and 200 ml of hexane was added again. Triisobutylaluminum and trimethylmethoxy silane were added in the same amount as above, and 30 g of vinylcyclohexane was injected, followed by polymerization again for 3 hours. After washing three times with hexane, the hexane slurry was used for polymerization and the remainder was vacuum dried at room temperature for 2 hours. In the polymerization catalyst thus obtained, the amount of the high molecular weight monomer polymerized around the catalyst was set to 8 to 30 g per 1 g of the catalyst.

Step B: Polymerization

The autoclave reactor with a capacity of 2 L was vacuum dried for 1 hour and then purged sufficiently with nitrogen, 4 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane at room temperature, and the prepolymerized catalyst was added to titanium in the hexane slurry. The volume was adjusted to 5.0 ppm, and then charged into the reactor. Again, 3300ppm of hydrogen was added, followed by 1.2l of liquid propylene, and then the temperature was raised to 70 ° C while stirring the reactor to carry out polymerization for 1 hour. After the polymerization reaction was completed, the unreacted gas was discharged, and the reaction was terminated after cooling the temperature to room temperature. The resulting polymer was collected separately and dried in a vacuum oven at 70 ° C. for at least 1 hour to obtain a white polymer.

Step C: Injection and Evaluation

The resin prepared by the above method was melted through an injection machine after mixing 0.2 parts by weight of antioxidant with 3.9 g / 10 min according to ASTM D 1285 standard at 230 ° C. and 2.16 Kg under 100 parts by weight of polypropylene. Injection.

The ejected specimens were subjected to Haze and the drawn viscosity was measured. The measurement result of the drawing viscosity using ARES is shown in FIG.

Melt flow index and ethylene content measurement results of the polymer are summarized in Table 1 below.

Comparative Example 1

In Example 1, polymerization was carried out in the same manner as in Example 1, except that 10 mg of the prepared catalyst component A was used without prepolymerization and dicyclopentyldimethoxysilane was used as an external electron donor. A white polymer having a melt index of 4.3 g / 10 minutes was obtained.

Comparative Example 2

In the prepolymerization step of Example 1, the prepolymerization and polymerization were carried out in the same manner, except that 30 g of 1,7-octadiene was added without polymerization of vinylcyclohexane for 1 hour to carry out prepolymerization and polymerization. A white polymer having a value of 4.1 g / 10 min was obtained.

Comparative Example 3

Prepolymerization and polymerization were carried out under the same conditions except that 0.7 g of propylene was added per catalyst instead of 1,7-octadiene and polymerized vinylcyclohexane in the prepolymerization condition of Example 1, and the melt index was 4.1. A white polymer having a g / 10 min was obtained.

<Example 2>

A white polymer was obtained in the same manner as in Example B, except that 5000 ppm of hydrogen was added thereto and the melt index, which was C, was 6.2 g / 10 min.

The ejected specimens were subjected to Haze and the drawn viscosity was measured. The measurement result of the drawing viscosity using ARES is shown in FIG. Melt flow index and ethylene content measurement results of the polymer are summarized in Table 1 below.

<Comparative Example 4>

In the prepolymerization condition of Example 2, the prepolymerization and polymerization were carried out under the same conditions except that only 1,7-octadiene was added without vinylcyclohexane, and the melt index was 7.2 g / 10 min. A white polymer was obtained.

Comparative Example 5

Prepolymerization and polymerization were carried out under the same conditions, except that 0.7 g of propylene was added per catalyst instead of 1,7-octadiene in the prepolymerization condition of Example 2, and the melt index was 7.2 g / 10 min. A polymer was obtained.

The conditions and polymer evaluation results of Examples 1 to 2 and Comparative Examples 1 to 5 are summarized in Table 1 below.

Prepolymerization Monomer Melt Flow Index (g-PP / 10min) Ethylene Content (%) Deformation Strengthening
Haze
(%) Stage 1 Step 2 Example 1 1,7-octadiene Vinylcyclohexane 3.9 5.28 Expression 24.8 Comparative Example 1 - - 4.3 3.20 Not manifested 77.3 Comparative Example 2 1,7-octadiene - 4.1 4.38 Expression 76.2 Comparative Example 3 Propylene Vinylcyclohexane 4.1 4.16 Not manifested 21.0 Example 2 1,7-octadiene Vinylcyclohexane 6.2 4.78 Expression 30.5 Comparative Example 4 1,7-octadiene - 7.2 4.05 Expression 76.7 Comparative Example 5 Propylene Vinylcyclohexane 7.2 4.56 Not manifested 29.7

* Polymerization conditions: reaction time (1hr), reaction temperature (70 ℃)

1 is a value of the draw viscosity of the polymer of the melt flow index of 4.1 ± 0.2g / 10 components, Figure 2 is a measure of the draw viscosity of the polymer of the melt flow index of 6.7 ± 0.5g / 10 components.

As described above, when the polypropylene polymer having a long branch is introduced at a strain rate more than a certain value, strain hardening occurs and the stretch viscosity is larger than that of the linear curve. This may be substituted for the melt tension value.

In Example 1, Comparative Example 2, Example 2 and Comparative Example 4 containing 1,7-octadiene in the present invention was found that a long branch is introduced, the draw viscosity is very large compared to time. This means an improvement in melt strength.

In addition, in the case of Example 1 and Example 2, having a cyclic structure, the crystal structure becomes smaller, and the Haze value is lowered, thereby improving transparency. This structure has a characteristic that satisfies both characteristics of high melt strength and high transparency.

Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3 and Example 2, Comparative Example 4, Comparative Example 5 due to the difference in the amount of hydrogen put during the polymerization, the melt index was different. However, in Example 2 and Comparative Example 5 having a high melt index, it can be seen that the values of Haze are relatively higher than those of Example 1 and Comparative Example 3 having a low melt index. In the case of vinyl cyclic saturated hydrocarbon, the higher the molecular weight, that is, the lower the melt index, the greater the effect is shown to improve the transparency, that is, Haze.

Compared to Example 1, which has a low melt index, that is, a high molecular weight, and Example 2, which has a low molecular weight, in terms of strain hardening, the case of Example 1, which has a high molecular weight, results in long-term effects and the effect of molecular weight. The reinforcement phenomenon could be confirmed more clearly.

The properties of the polymer synthesized in Examples and Comparative Examples were measured through the following experimental method.

(1) Melt Flow Index

The melt flow index is measured using a weight of 2.16 kg at a temperature of 230 ° C. in accordance with ASTM D1238, expressed as weight (g) of the polymer melted for 10 minutes (g / 10 min).

(2) ethylene content

By FT-IR Bio Rad FTS 3000 used in the form of a film specimen IR absorption spectrum 4800 to the height (H) and the ethylene component in the 3500 cm ^-1 peak reflecting the sample thickness at the peak of 790-660 cm ^-1 peak The area (A) of was measured and calculated by the following equation.

Ethylene Content = 0.7321 X (A / H) + 0.3998

(3) Haze

The final copolymer was prepared by using a hydraulic injection machine (L / D: 18, injection temperature 220 ° C., mold temperature 50 ° C., 9 tons of clamping force) to prepare a 2 mm thick specimen and then measured by ASTM DF 1003.

(4) drawing viscosity

The draw viscosity was obtained by compressing the polymer to a thickness of 0.7 mm, a width of 10 mm, and a length of 11 mm, and measuring 30 seconds at a rate of 0.08 / second at a temperature of 170 ° C. using an ARES (Advanced Rheometric Expansion System).

1 is a measurement of the draw viscosity of the melt flow index of 4.1 ± 0.2g / 10 components polymer.

Figure 2 measures the draw viscosity of the melt flow index of 6.7 ± 0.5 g / 10 components polymer.

Claims (20)

a) first polymerizing a Ziegler-Natta catalyst with a diene compound; And b) a method of preparing a catalyst for olefin polymerization, comprising the step of secondary polymerization by adding a vinyl cyclic saturated hydrocarbon to the product of step a). The method for preparing an olefin polymerization catalyst according to claim 1, wherein the diene compound is added in an amount of 1 to 50 g / g based on the weight of the prepolymerization catalyst produced in step a). The method for preparing an olefin polymerization catalyst according to claim 1, wherein in the step b), the vinyl cyclic saturated hydrocarbon compound is introduced into a 10 to 50 g / g catalyst based on the weight of the generated prepolymerization catalyst. . The method for producing a catalyst for olefin polymerization according to claim 1, wherein the diene compound is a diene compound having 4 to 14 carbon atoms having α, ω-diene structures. The method of claim 1, wherein the vinyl cyclic saturated hydrocarbon is a vinyl cyclic saturated hydrocarbon having 5 to 10 carbon atoms. The method of claim 1, wherein the Ziegler-Natta catalyst is a transition metal compound containing a Group 4, 5 or 6 elements in the periodic table; And an organometallic compound comprising a Group 13 element in the periodic table, wherein the molar ratio of the organometallic compound to the transition metal compound is 1 to 50. The catalyst for olefin polymerization according to claim 6, wherein the transition metal compound is a solid titanium catalyst containing an internal electron donor of magnesium, titanium, halogen elements and diether-based compounds, phthalate-based compounds or mixtures thereof. Way. The organometallic compound of claim 6, wherein the organometallic compound is at least one organoaluminum compound selected from the group consisting of trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride and alkyl aluminum sesquihalide. Method for producing a catalyst for olefin polymerization, characterized in that. delete A) prepolymerizing the Ziegler-Natta catalyst by first polymerizing the Ziegler-Natta catalyst with the diene compound, followed by secondary polymerization with addition of vinyl ring-type saturated hydrocarbon; And B) polymerizing the olefin using a Ziegler-Natta catalyst pre-polymerized in step A). The polyolefin polymerization method according to claim 10, wherein the diene compound is added to 1-50 g / g catalyst based on the weight of the prepolymerization catalyst produced in step a). The polyolefin polymerization method according to claim 10, wherein in the step a), the vinyl cyclic saturated hydrocarbon is introduced into a 10 to 50 g / g catalyst based on the weight of the generated prepolymerization catalyst and subjected to secondary polymerization. The method of claim 10, wherein the Ziegler-Natta catalyst is a transition metal compound containing a Group 4, 5 or 6 elements in the periodic table; And an organometallic compound comprising a Group 13 element in the periodic table, wherein the molar ratio of the organometallic compound to the transition metal compound is 5 to 50. The polyolefin polymerization method according to claim 13, wherein the transition metal compound is a solid titanium catalyst containing an internal electron donor of magnesium, titanium, halogen elements and diether-based compounds, phthalate-based compounds or mixtures thereof. The organometallic compound according to claim 13, wherein the organometallic compound is at least one organoaluminum compound selected from the group consisting of trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride and alkyl aluminum sesquihalide. Polyolefin polymerization method. The polyolefin polymerization method according to claim 10, wherein the diene compound is a diene compound having 4 to 14 carbon atoms having α, ω-diene structures. The polyolefin polymerization method according to any one of claims 10 to 16, wherein the olefin is propylene. A polyolefin having a Haze of 1 to 50% of a polyolefin prepared by the method of claim 10. delete The polyolefin of claim 18, wherein the polyolefin has a melt flow index of 0.1 to 50 g / 10 minutes.

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