KR20070080086A - Butene-1 (co)polymer and the method for preparing the same - Google Patents

Abstract

Provided are a butane-1 (co)polymer having a tensile modulus of 4,400 kg/cm^2 or more and a tensile strength of 270 kg/cm^2 or more measured by ASTM D638 method, and a method for preparing the butane-1 (co)polymer. The butane-1 (co)polymer comprises 10 wt% or less of an alpha-olefin monomer of C2 to C8. The method comprises the steps of supplying an alpha-olefin in the presence of a solid catalyst component comprising a titanium (Ti) compound supported on MgCl2 and an internal electron donator and an alkyl aluminum to prepare a prepolymerized solid catalyst; and polymerizing butene-1 in liquid phase in the presence of the prepolymerized solid catalyst, an alkyl aluminum and an external electron donator. Preferably the titanium compound is TiCl4.

Description

Butene-1 (co) polymer and its preparation method {Butene-1 (co) polymer and the method for preparing the same}

FIELD OF THE INVENTION The present invention relates to butene-1 (co) polymers and methods for their preparation, more particularly comprising up to 10% by weight of α-olefin comonomers having 2 to 8 carbon atoms, according to the ASTM D638 method described herein. It relates to a butene-1 (co) polymer having a measured tensile strength of at least 270 kg / cm 2 and a tensile modulus of at least 4,400 kg / cm 2.

Commercialization of butene-1 (co) polymers began with the development of Mobil's liquid phase process, and research into the slurry and gas phase processes is ongoing. Butene-1 (co) polymers are in the spotlight, especially in pipe applications, despite their high cost of manufacture due to their unique properties different from other α-olefin (co) polymers.

However, as compared to ethylene or propylene polymerization using Ziegler-Natta catalyst systems, butene-1 (co) polymer polymerization has a low activity and low stereoregularity, resulting in deashing and removal of amorphous butene-1- (co) polymers. The process was needed. The problem of activity is that the development of TiCl ₄ supported on MgCl ₂ makes it possible to produce it without departing process, and WO2004 / 000895 eliminates the physical property unevenness between the polymerized product and the final processed product due to the high activity. In the case of international patent application publication WO05 / 021611, an inert gas is injected into the reactor to obtain about 15 kg to 20 kg of butene-1- (co) polymer per unit time per catalyst weight. Report that it was prepared.

In addition, the development of various external electron donors, in particular the development of di (cyclo) alkyldialkoxysilane compounds, enables the preparation of butene-1- (co) polymers having high stereoregularity, thus providing separate amorphous butene-1- (co) There is no need for removal of the polymer. For example, International Patent Application Publication No. WO99 / 045063 describes the preparation of at least 93 (mmmm)% butene-1- (co) polymer using diisopropyldimethoxysilane, and discloses international patent application publication. Publication WO05 / 021611 discloses the preparation of at least 96 (mmmm)% or more of butene-1- (co) polymer using diisobutyldimethoxysilane.

On the other hand, the pre-polymerization process in the α-olefin polymerization is generally employed to control the rapid initial activity of the catalyst to maintain a high activity during the residence time of the catalyst in the bulk density (Bulk Density, It is performed for the purpose of increasing BD) and uniformly controlling the appearance of the polymer, and the object of the process is slurry or gas phase process. However, no prepolymerization process has yet been introduced into the liquid phase production process of butene-1 (co) polymer.

It is an object of the present invention to provide butene-1 (co) polymers having higher stereoregularity and mechanical strength (tensile strength and tensile modulus) and methods for their preparation.

In order to achieve the above object of the present invention, the first aspect of the present invention comprises up to 10% by weight of α-olefin comonomer of 2 to 8 carbon atoms, the tensile strength measured according to the ASTM D638 method described herein is 270kg Butene-1 (co) polymer having at least / cm 2 and a tensile modulus of at least 4,400 kg / cm 2.

In order to achieve the above object of the present invention, the second aspect of the present invention is (a) i) in the presence of a solid catalyst component comprising a Ti compound and an internal electron donor supported on MgCl ₂ and ii) alkylaluminum, Preparing a prepolymerized solid catalyst by feeding olefins; And (b) polymerizing butene-1 in a liquid phase process in the presence of the prepolymerized solid catalyst prepared in step (a), alkylaluminum and an external electron donor. To provide.

Butene-1 (co) polymer according to the present invention can be improved stereoregularity and mechanical properties.

Hereinafter, the present invention will be described in more detail.

The butene-1 (co) polymers according to the present invention have excellent mechanical properties, specifically, tensile strength measured according to the ASTM D638 method described herein, 270 kg / cm 2 or more, tensile modulus of 4,400 kg / cm 2 or more, and also carbon number 2 to 8 of the α-olefin comonomer is included in 10% by weight or less. The α-olefin comonomer is preferably selected from the group consisting of ethylene, propylene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene and norbornene.

Also preferably the butene-1 (co) polymers according to the invention have an isotactic index (mmmm%) of 96 or more, as measured by ¹³ C-NMR analysis described herein.

The butene-1 (co) polymer having excellent mechanical properties and stereoregularity as described above may be prepared by polymerizing butene-1 in a liquid phase process under a prepolymerized solid catalyst.

In order to prepare a prepolymerized solid catalyst, first, prepolymerization is carried out by supplying α-olefin monomers in the presence of a solid catalyst component and alkylaluminum supported on MgCl ₂ including a Ti compound, which is the main component of the catalyst, and an internal electron donor compound. Carry out the reaction. The prepolymerization reaction is at a temperature of -20 to 80 ° C, preferably 0 to 60 ° C, most preferably 10 to 40 ° C, 0.1 to 500g, preferably 1 to 200g, most preferably 1 g of solid catalyst component. This is done by feeding a small amount of α-olefin monomer during the time that 1 to 50 g of polymer can be obtained. The prepolymerization reaction can be carried out in liquid phase, gas phase, or slurry.

Examples of compounds of Ti include TiCl ₃ , TiCl ₄ or Ti (OR) _n X _4-n ( _wherein R is C _1-18 alkyl, n is an integer from 0 to 3 and X is halogen) And preferably TiCl ₄ .

Compounds that can be used as internal electron donors include esters, ethers, amines or ketone compounds. The internal electron donor is preferably selected from alkyl, cycloalkyl or aryl esters of monocarboxylic acids such as benzoic acid or polycarboxylic acids (eg phthalic acid or malonic acid), wherein alkyl, cycloalkyl or The aryl group has 1 to 18 carbon atoms. Examples of the internal electron donor compound include methyl benzoate, ethyl benzoate, or diisobutyl phthalate. The amount of the internal electron donor used in the preparation of the solid catalyst component has a molar ratio (internal electron donor / MgCl ₂ ) to the injected MgCl ₂ of 0.01 to 10, preferably 0.01 to 1, more preferably 0.01 to 0.5.

Examples of alkylaluminum that may be used as a cocatalyst component include triethylaluminum (TEA), triisobutylaluminum (TIBA), tributylaluminum, trihexylaluminum, trioctylaluminum, or mixtures thereof, preferably tri Ethyl aluminum, triisobutylaluminum or mixtures thereof. The amount of cocatalyst used in the prepolymerization reaction is used such that the molar ratio of Al / Ti is 1 to 100, preferably 1 to 50, more preferably 5 to 20.

The external electron donor may be selectively injected into the prepolymerization reaction, which may be the same as or different from the internal electron donor. Examples of such external electron donors include silane compounds, ethers, 1,3-diethers, esters, amines, heterocyclic compounds, and the like, and preferably R1 _a R2 _b Si (OR3) _c (wherein R 1, R 2 and R 3 are each independently C _1-18 alkyl, C _1-18 cycloalkyl or C _1-18 allyl group, a and b are each independently an integer of 1 to 2, c is 1 to 3 Is an integer, and the sum of a, b, and c is 4), and more preferably R1 _a R2 _b Si (OR3) _c , wherein R1 and R2 are each independently C _1-18 alkyl, C ₁ A silane compound of _-18 cycloalkyl or a C _1-18 allyl group, R 3 is a methyl group, a and b are each 1, c is an integer of 2, and the sum of a, b, c is 4) And cyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane and the like. The amount of the external electron donor used in the prepolymerization reaction is used so that the molar ratio (external electron donor / Ti) with Ti in the catalyst component is 0 to 50, preferably 0 to 20, more preferably 0 to 10.

The α-olefin monomers that may be supplied to the prepolymerization reaction are ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 -Decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-ikocene, norbornene, norbonadiene, ethylidenenorbornene, vinylnorbornene, dicyclopentadiene, 1 , 4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene, preferably between 2 to 10 carbon atoms Α-olefin monomers, most preferably ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene and norbornene Selected from the group consisting of.

In the presence of the prepolymerized solid catalyst, alkylaluminum and external electron donor prepared above, a reaction is carried out to polymerize the butene-1 (co) polymer in a liquid phase process. The polymerization reaction which consists of such a liquid process is 20-120 degreeC, Preferably it is 40-80 degreeC, Most preferably, the temperature of 50-80 degreeC so that the concentration of butene-1 (co) polymer may not exceed 45 weight%, Preferably 10 to 30% by weight, most preferably 20 to 30% by weight in consideration of the catalytic activity is selected, but 10 minutes to 20 hours, preferably 20 minutes to 10 hours, most preferably 30 minutes To 3 hours. In addition, the polymerization reaction is carried out under the pressure of its own vapor pressure to 1000 bar, preferably 5 to 100 bar, most preferably 5 to 50 bar in the reactor.

In the polymerization reaction, hydrogen may be used to control the molecular weight of the (co) polymer, or the molecular weight may be controlled by controlling the polymerization reaction temperature.

The alkylaluminum, which is an external electron donor and cocatalyst component added to the polymerization reaction, may be the same as or different from the case of the prepolymerization.

External electron donors used in the polymerization reaction include silane compounds, ethers, 1,3-diethers, esters, amines, heterocyclic compounds, and the like, preferably R1 _a R2 _b Si (OR3) _c ( Wherein R 1, R 2, and R 3 are each independently C _1-18 alkyl, C _1-18 cycloalkyl, or C _1-18 allyl group, a and b are each independently an integer from 1 to 2, c is 1 Is an integer of 3 to 3, and the sum of a, b, and c is 4), and more preferably R 1 _a R 2 _b Si (OR 3) _c , wherein R 1 and R 2 are each independently C _1-18 alkyl , A C _1-18 cycloalkyl or C _1-18 allyl group, R 3 is a methyl group, a and b are each 1, c is an integer of 2, and the sum of a, b, and c is 4). Examples thereof include cyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, and the like.

The amount of the external electron donor used in the polymerization reaction is used so that the molar ratio (external electron donor / Ti) to Ti in the catalyst component is 0.1 to 100, preferably 0.5 to 50, and more preferably 5 to 25.

In addition, examples of the alkyl aluminum which is a promoter component used in the polymerization reaction include triethyl aluminum (TEA), triisobutyl aluminum (TIBA), tributyl aluminum, trihexyl aluminum, trioctyl aluminum, or mixtures thereof. Preferably triethylaluminum, triisobutylaluminum, or mixtures thereof. The amount of cocatalyst used in the polymerization reaction is used so that the molar ratio of Al / Ti is 10 to 1000, preferably 50 to 500, and more preferably 100 to 400.

Small amounts of additional α-olefin comonomers can be injected into the polymerization reaction, such comonomers are ethylene, propylene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1 -Heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-ikocene, norbornene, norbornadiene, ethylidenenorbornene, vinylnorbornene, dicyclo Pentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene, preferably carbon number Α-olefin comonomers of 2 to 8, most preferably selected from the group consisting of ethylene, propylene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene and norbornene do. Such α-olepin comonomers should be contained in less than 10% by weight of the final butene-1 copolymer.

Stabilizers or additives may be added as needed to prevent deformation of the polyolefin due to the high temperature heat required to remove unreacted monomers. As such stabilizers or additives, phenol-based, phosphorus-based or sulfur-based antioxidants commonly used in polyolefin resins can be used.

The method according to the invention is not limited to the reactor form and can be applied regardless of the reactor type such as batch reactor, continuous batch reactor (CSTR), tubular reactor, other reactors.

Hereinafter, the present invention will be described in more detail using examples.

Analysis and measurement method

¹³ Measurement of stereoregularity (isotropic index, I.I.) (mmmm%) by C NMR

After preparing a 10 wt% butene-1- (co) polymer solution using C ₂ Cl ₄ D ₂ as a solvent, the pulse repetition time was 2 seconds at 120 ° C. using a Varian Unity Inova 500 (500 MHz NMR) equipment. The stereoregularity (mmmm%) was measured by 383000 scans and is described in "Carbon-13 NMR Spectral Assignment of Five Polyolefins Determined from the Chemical Shift Calculation and the Polymerization Mechanism", T. Asakura and others, Macromolecules 1991, 24 2334- 2340].

Melt Index Measurement

Melt index was measured according to ASTM D 1238 condition "E".

Breaking strength

Breaking strength was measured according to ASTM D 638.

Elongation at Break

Bankruptcy elongation was measured according to ASTM D 638.

Preparation Example: Preparation of Solid Catalyst Components

29.5 g of MgCl ₂ and 148.5 mL of 2-ethyl-hexanol were added to a 1 L glass reactor (Buchi) equipped with a magnetic stirrer. The total volume of the reactor was adjusted to 650 mL by adding hexane, and the temperature of the reactor was raised to 130 ° C. After stirring at 200 rpm for 3 hours. After the reactor temperature was lowered to 35 ° C., 178 mL of TiCl ₄ was injected for 4 hours, and then 4.5 mmol of diisobutyl phthalate was added thereto at the same temperature. Then, the temperature of the reactor was again increased to 110 ° C., followed by stirring at 250 rpm for 2 hours. . After cooling the temperature of the reactor to 35 ℃ to precipitate the solid component was filtered the supernatant and washed twice with hexane. After adding 150 mL of TiCl ₄ to the solid product thus obtained, the total volume of the reactor was changed to 500 mL with hexane, and then the reactor temperature was raised to 130 ° C. and stirred at 300 rpm for 2 hours. After lowering the reactor temperature to 80 ℃ and settled, the supernatant was filtered off, washed four times with hexane and dried under vacuum at 60 ℃.

The resulting solid catalyst component was 1.7 wt% Ti, 20.2 wt% Mg and 11.3 wt% internal electron donor.

Example 1

Prepolymerization

1 g of the solid catalyst component obtained in Preparation Example was placed in a 500 mL high pressure glass vessel reactor (Andrew glass) with a mechanical stirrer, and hexane was added so that the total reactor volume was 200 mL. Triethyl aluminum (TEA), a promoter, was added so that the Al / Ti ratio was 10, and the reactor temperature was adjusted to 15 ° C. Propylene was then introduced into the reactor at a rate of 60 mL / min through a mass flow controller (MFC). Allowed to inject and polymerized for 3 hours.

After the completion of the polymerization, the unreacted propylene was purged, the solid obtained was precipitated, the supernatant was filtered off, washed three times with 200 mL of hexane, and dried in vacuo at 30 ° C. The prepolymerized catalyst thus obtained produced 15.0 g of polypropylene per gram of solid catalyst component ( _{prepolymerization} of 15.0 g _{polypropylene} / g _{solid catalyst component} ).

polymerization

The total amount of Ti of the prepolymerized catalyst prepared in the prepolymerization step is about 7 to 8 μmol and the ratio of Al / Ti is 300, which is triisobutyl aluminum (TIBA) and Si / Ti 50 mL of diisopropyldimethoxysilane, which is an external electron donor compound, was added to the catalyst vessel so that the ratio was 10.

After fully purging the 3L stainless steel reactor with argon, 1700 mL of butene-1 was injected into the reactor, and hydrogen was injected such that the injected butene-1 and the weight ratio were 80 ppm. After the temperature of the reactor was raised to 60 ° C., the catalyst in the catalyst vessel was injected at high pressure, and the stirrer was stirred at 500 rpm to polymerize for 1 hour.

After the completion of the polymerization, 100 mL of a hexane solution containing 5 wt% of an antioxidant (Igarnox 1010, Ciba, Switzerland) was added thereto to terminate the polymerization reaction to obtain a butene-1 (co) polymer.

The polymerization activity of the butene-1 copolymer obtained from the above was 11.3 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 0.28 g / 10 min, and isotropic index II was 96.7 mm mm%. On the other hand, the butene-1 polymer obtained had a breaking strength of 291 Kg / cm 2, a tensile modulus of 4,566 Kg / cm 2, and an elongation at break of 439%.

Example 2

Prepolymerization

In the prepolymerization reaction, the same as in the prepolymerization reaction of Example 1, except that a prepolymerized catalyst of 7.0 g polypropylene per gram of catalyst was prepared by injecting 20 mL of propylene into the reactor via a mass flow controller (MFC). The method was carried out, and the prepolymerization degree of the resultant prepolymerized catalyst was 7.0 g _{polypropylene} / g _{solid catalyst component} .

polymerization

The polymerization was carried out in the same manner as in Example 1, whereby the polymerization activity of the resulting _butene-1 copolymer was 12.8 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 0.30 g / 10 min, isotropic Index II was 96.5 mm mm%. On the other hand, the butene-1 polymer obtained had a breaking strength of 297 Kg / cm 2, a tensile modulus of 4,412 Kg / cm 2, and an elongation at break of 464%.

Example 3

Prepolymerization

In the prepolymerization reaction, the same as in the prepolymerization reaction of Example 1, except that a prepolymerized catalyst of 7.0 g polypropylene per gram of catalyst was prepared by injecting 20 mL of propylene into the reactor via a mass flow controller (MFC). The method was carried out, and the prepolymerization degree of the resultant prepolymerized catalyst was 7.0 g _{polypropylene} / g _{solid catalyst component} .

polymerization

The polymerization was carried out in the same manner as in Example 1 except that propylene was used as the comonomer in addition to butene-1, and the polymerization activity of the resulting _{butene-1 copolymer} was 14.7Kg _{butene-1 copolymer} / g _{solid. It was a catalyst component} , MI _2.16 was 0.34 g / 10min, and the isotropic index II was 96.3 mmmm%. On the other hand, the butene-1 copolymer obtained had a break strength of 287 Kg / cm 2, a tensile modulus of 4,402 Kg / cm 2, and an elongation at break of 474%.

Example 4

In the prepolymerization reaction, an external electron donor diisobutyldimethoxysilane was used so that the Si / Ti ratio was 2, The same procedure as in Example 1 was carried out except that propylene was injected into the reactor at 50 mL / min for 1 hour through a mass flow controller (MFC), and the total polymerization degree of the resulting prepolymerized catalyst was 5.7 g _{poly. Propylene} / g _{solid catalyst component} .

The polymerization was carried out in the same manner as in Example 1, whereby the polymerization activity of the resulting butene-1 copolymer was 13.0 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 0.38 g / 10 min, isotropic Index II was 96.6 mmmm%. On the other hand, the butene-1 polymer obtained had a breaking strength of 315 Kg / cm 2, a tensile modulus of 4,859 Kg / cm 2, and an elongation at break of 506%.

Example 5

The same method as in Example 1 was carried out except that 6 g of 4-methyl-1-pentene (4M1P) was used in the prepolymerization reaction, and the total polymerization degree of the obtained _{prepolymerized} catalyst was 4.5 g _poly-4M1P / g _It was a _{solid catalyst component} .

The polymerization was carried out in the same manner as in Example 1, whereby the polymerization activity of the resulting _{butene-1 polymer} was 10.5 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 0.28 g / 10 min, and isotropic index II was 96.8 mmmm%. On the other hand, the butene-1 copolymer obtained had a breaking strength of 295 Kg / cm 2, a tensile modulus of 4,446 Kg / cm 2, and an elongation at break of 462%.

Example 6

The same method as in Example 1 was carried out except that 6 g of 3-methyl-1-butene (3M1B) was used in the prepolymerization reaction, and the total polymerization degree of the obtained prepolymerized catalyst was 2.0 g _poly-3M1B / g _It was a _{solid catalyst component} .

The polymerization was carried out in the same manner as in Example 1, whereby the polymerization activity of the resulting _{butene-1 polymer} was 9.8 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 0.33 g / 10 min, and isotropic index II was 96.9 mm mm%. On the other hand, the butene-1 copolymer obtained had a break strength of 271 Kg / cm 2, a tensile modulus of 4,680 Kg / cm 2, and an elongation at break of 458%.

Comparative Example 1

The solid catalyst component obtained in the preparation example was used in the polymerization reaction without performing the prepolymerization reaction, and the polymerization method was carried out in the same manner as in the polymerization reaction of Example 1. The resulting butene-1 polymer had a polymerization activity of 14.0 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 0.36 g / 10 min, and isotropic index II was 94.9 mm mm%. On the other hand, the butene-1 copolymer obtained had a break strength of 266 Kg / cm 2, a tensile modulus of 4,278 Kg / cm 2, and an elongation at break of 429%.

Comparative Example 2

The solid catalyst component obtained in the preparation example was used for the polymerization reaction without performing the prepolymerization reaction, and the polymerization method was carried out at a polymerization temperature of 80 ° C., an Al / Ti ratio of 100, and a Si / Ti ratio of 5 The polymerization reaction was carried out in the same manner as in Example 1 except for the above. The resulting butene-1 polymer had a polymerization activity of 7.1 Kg _{butene-1 polymer} / g _{solid catalyst component} , MI _2.16 was 2.32 g / 10 min and the isotropic index II was 85.0 mm mm%. On the other hand, the butene-1 copolymer obtained had a break strength of 267 Kg / cm 2, a tensile modulus of 4,284 Kg / cm 2, and an elongation at break of 486%.

To summarize the results performed in the above Examples and Comparative Examples are shown in Tables 1 and 2.

division Prepolymer monomer Total degree of polymerization (g _polymer / g _{solid catalyst component} ) Polymerization Activity (Kg _{Butene-1 (Co) polymer} / g _{Solid Catalyst Component} ) MI _2.16 (g / 10min) I.I. (mmmm%) Example 1 Propylene 15.0 11.3 0.28 95.7 Example 2 Propylene 7.0 12.8 0.30 96.5 Example 3 Propylene 7.0 14.7 0.34 96.3 Example 4 Propylene 5.7 13.0 0.38 96.6 Example 5 4MIP 4.5 10.5 0.28 96.8 Example 6 3MIB 2.0 9.8 0.33 96.9 Comparative Example 1 - - 14.0 0.36 94.9 Comparative Example 2 - - 7.1 2.32 85.0

division Breaking Strength (Kg / ㎠) Tensile Modulus (Kg / ㎠) Elongation at Break (%) Example 1 291 4566 439 Example 2 297 4412 464 Example 3 287 4902 474 Example 4 315 4859 506 Example 5 295 4446 462 Example 6 271 4680 458 Comparative Example 1 266 4278 429 Comparative Example 2 267 4284 486

The present invention is applied to the liquid phase process of the butene-1 (co) polymer manufacturing process by applying the prepolymerization catalyst system, while maintaining high activity as compared to the butene-1 (co) polymer that does not use the prepolymerization catalyst system is higher Not only were the properties obtained but also the preparation of butene-1- (co) polymers with higher breaking strength and tensile modulus was achieved.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

Claims (16)

Butene-1 containing up to 10% by weight of α-olefin comonomers having 2 to 8 carbon atoms, having a tensile strength of at least 270 kg / cm 2 and a tensile modulus of at least 4,400 kg / cm 2, measured according to the ASTM D638 method described herein; Co) polymers. The method of claim 1 wherein the α-olefin comonomer is selected from the group consisting of ethylene, propylene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene and norbornene. Butene-1 (co) polymer. The butene-1 (co) polymer of claim 1, having an isotactic index (mmmm%) of at least 96 as measured by ¹³ C-NMR analysis described herein. (a) preparing a prepolymerized solid catalyst by feeding α-olefin in the presence of i) a solid catalyst component comprising a Ti compound and an internal electron donor supported on MgCl ₂ and ii) alkylaluminum; And (b) polymerizing butene-1 in a liquid phase process in the presence of the prepolymerized solid catalyst prepared in step (a), alkylaluminum and an external electron donor. . The method of claim 4, wherein step (a) is carried out at a temperature of 10 to 40 ° C. The method of claim 4, wherein step (b) is carried out at a temperature of 50 to 80 ° C. The compound of claim 4, wherein the Ti compound of step (a) is TiCl ₃ , TiCl ₄ or Ti (OR) _n X _4-n , wherein R is C _1-18 alkyl, n is an integer from 0 to 3 , X is halogen). 8. The method of claim 7, wherein the Ti compound is TiCl ₄ . 5. The method of claim 4, wherein the internal electron donor is selected from the group consisting of esters, ethers, amines and ketones. 10. The method of claim 9, wherein the internal electron donor is selected from the group consisting of C _1-18 alkyl, C _1-18 cycloalkyl and C _1-18 aryl esters of benzoic acid or polycarboxylic acid. The method of claim 4, wherein the alkylaluminum of steps (a) and (b) is each independently selected from the group consisting of triethylaluminum, triisobutylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum and mixtures thereof. Characterized in that the method. The method of claim 4, wherein the external electron donor is selected from the group consisting of silane compounds, ether compounds, 1,3-diether compounds, ester compounds, amine compounds, and heterocyclic compounds. The method of claim 12, wherein the external electron donor is R 1 _a R 2 _b Si (OR 3) _c , wherein R 1, R 2 and R 3 are each independently C _1-18 alkyl, C _1-18 cycloalkyl or C _1-18 allyl group And a and b are each independently an integer of 1 to 2, c is an integer of 1 to 3, and the sum of a, b and c is 4). 5. The method of claim 4, further comprising injecting an external electron donor in step (a). 5. The method of claim 4, further comprising injecting an α-olefin comonomer having 2 to 8 carbon atoms into the liquid phase process of step (b). The method of claim 15 wherein the α-olefin comonomer is selected from the group consisting of ethylene, propylene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene and norbornene. How to.