KR20010112734A - A method for propylene polymerization or copolymerization - Google Patents

Abstract

The present invention relates to a propylene polymerization or copolymerization method, and more particularly, (1) (i) a mixture of a magnesium halide compound and a group IIIA compound of the periodic table is added to a mixed solvent of a cyclic ether, at least one alcohol, a phosphorus compound and an organosilane. Dissolving to prepare a magnesium compound solution, (ii) reacting the magnesium compound solution with a transition metal compound, a silicon compound, a tin compound or a mixture thereof to precipitate solid particles, and (i) depositing the precipitated solid particles as a titanium compound. And a solid titanium catalyst obtained by reaction with an internal electron donor, (2) an organometallic compound of Group I or Group III metals of the periodic table, and (3) a nitrogen compound located in an aromatic ring as an external electron donor. In the presence of a catalyst system consisting of unsaturated nitrogen compounds in the form of substituents with steric hindrance It relates to a propylene polymerization method. According to the method of the present invention, polypropylene having excellent elasticity and ductility can be produced in high yield.

Description

Polymerization or Copolymerization of Propylene {A METHOD FOR PROPYLENE POLYMERIZATION OR COPOLYMERIZATION}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymerization method, and to a polymerization or copolymerization method of propylene effective for producing polypropylene having an elasticity and ductility to the extent that it can replace soft polyvinyl chloride.

In order to improve the rigidity and heat resistance of polypropylene, many studies have been conducted on a polymerization catalyst capable of improving the stereoregularity of a polymer and a polymerization method using the same (Korean Patent Publication No. 92-2488, US Patent No. 4,990,479, European Patent No. 350,170A and Canadian Patent No. 1,040,379). However, these polymerization catalysts and polymers produced by the polymerization method using the same have excellent rigidity and heat resistance, but have a lot of restrictions in use due to their weak elasticity and ductility.

It is an object of the present invention to provide a propylene polymerization or copolymerization method for producing polypropylene which can replace soft polyvinylchloride by improving the weak elasticity and ductility while maintaining the rigidity and heat resistance of the existing polypropylene.

The present invention provides an effective steric hindrance on both sides of (1) a solid titanium catalyst, (2) an organometallic compound of group I or group III of the periodic table, and (3) a nitrogen compound located in an aromatic ring, as an external electron donor. The present invention relates to a propylene polymerization or copolymerization method capable of producing a high yield of polypropylene having excellent elasticity and ductility using an unsaturated nitrogen compound having a substituent.

The solid titanium catalyst (1) according to the present invention specifically comprises (i) dissolving a mixture of a magnesium halide compound having no reducibility and a Group IIIA compound of the periodic table in a mixed solvent of a cyclic ether, at least one alcohol, a phosphorus compound, and an organosilane. To prepare a magnesium compound solution, (ii) reacting the magnesium compound solution with a transition metal compound, a silicon compound, a tin compound or a mixture thereof to precipitate solid particles, and (i) precipitate the solid particles into a titanium compound and Reaction with the internal electron donor, followed by washing with a hydrocarbon solvent to produce a solid catalyst particle with controlled particle morphology is made in a simple and effective manufacturing process.

The preparation of the magnesium compound solution can be carried out in the presence or absence of a hydrocarbon solvent.

Non-reducing magnesium halide compounds used in the preparation of magnesium compound solutions include magnesium halides such as magnesium chloride, magnesium iodide, magnesium fluoride, and magnesium bromide; Halogenated alkylmagnesiums, such as methylmagnesium halide, ethylmagnesium halide, propylmagnesium halide, butylmagnesium halide, isobutylmagnesium halide, hexylmagnesium halide, amylmagnesium halide and the like are exemplified. The magnesium halide compound may be applied alone or as a mixture of two or more thereof, and is effective even when used in the form of a complex with another metal.

Compounds of group IIIA of the periodic table used with magnesium halide compounds in the preparation of magnesium compound solutions include boron halides such as boron fluoride, boron chloride and boron bromide; And aluminum halides such as aluminum fluoride, aluminum bromide, aluminum chloride and aluminum iodide, of which aluminum halide is preferred, and aluminum chloride is most preferred. The molar ratio of the group IIIA compound of the periodic table to the magnesium compound is preferably 1: 0.25 or less, and more preferably 1: 0.15 or less.

The halogenated magnesium compound may be converted into a magnesium compound solution in the presence or absence of a hydrocarbon solvent as described above, and hydrocarbon solvents that may be used include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and kerosene; Alicyclic hydrocarbons such as cyclobenzene, methylcyclobenzene, cyclohexane, and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Examples are halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride, and chlorobenzene.

Examples of the cyclic ether used in the preparation of the magnesium compound solution include cyclic ethers having 2 to 15 carbon atoms, in particular tetrahydrofuran, 2-methyl tetrahydrofuran, and tetrahydropyran, and the most preferred cyclic ether is tetrahydrofuran.

One or more alcohols used to prepare the magnesium compound solution may be dissolved in part or all of the magnesium compound and added directly to the magnesium compound, or in a magnesium solution in which part or all of the magnesium compound is dissolved in one or more alcohols. Can be added. However, when the magnesium compound solution is reacted with the transition metal compound or the like in step (ii) to precipitate the solid particles, the total content of the at least one alcohol described above should be maintained. Alcohols that can be used include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, isopropylbenzyl alcohol, cumyl alcohol and Likewise, there are those having 1 to 20 carbon atoms, preferably alcohol having 1 to 12 carbon atoms. In more detail, it is preferable that the 1 or more types of alcohol used for manufacture of a magnesium compound solution consists of the alcohol which has a relatively small molecular weight 1-3 carbon number, and the alcohol which has a relatively large molecular weight 4-20 carbon number. . The molar ratio of the total alcohol and the alcohol having a relatively low molecular weight is 1: 0.01 to 1: 0.40, and preferably 1: 0.01 to 1: 0.25. Relatively low molecular weight alcohols are preferably methanol or ethanol, while relatively high molecular weight alcohols are preferably butanol, isoamyl alcohol or 2-ethyl hexanol.

The average particle size and particle distribution of the desired catalyst vary depending on the ratio of alcohol and cyclic ether, but in order to obtain a catalyst having a spherical particle size of about 50 microns, the total amount of alcohol and cyclic ether in the preparation of magnesium solution is at least per mole of magnesium. 0.5 mol-20 mol, preferably about 1.0 mol-20 mol, more preferably about 2.0 mol-10 mol. If it is less than 0.5 mol, it is difficult to produce magnesium solution, and if it is more than 20 mol, the size of the catalyst particles becomes small. And it is preferable that molar ratio of a cyclic ether and 1 or more types of alcohol is 1: 0.05-1: 0.95. If it is less than 1: 0.05, it is difficult to manufacture spherical catalyst, and if it is more than 1: 0.95, there is a problem that the catalytic activity is lowered.

The phosphorus compound used for preparation of a magnesium compound solution is represented by the following general formula.

PX_aR ^One _b(OR ² )_cOr POX_dR³ _e (OR ⁴ )_f

Here, X is a halogen atom, R ¹ , R ² , R ³ , R ⁴ is a hydrocarbon having 1 to 20 carbon atoms, alkyl, alkenyl, aryl and the like, may be the same or different. A + b + c = 3, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 0 ≦ c ≦ 3, d + e + f = 3, 0 ≦ d ≦ 3, 0 ≦ e ≦ 3, 0 ≤f≤3. Examples thereof include phosphorus trichloride, phosphorus tribromide, diethylchlorophosphite, diphenylchlorophosphite, diethylbromophosphite, diphenylbromophosphite, methyldichlorophosphite, phenylchlorophosphite, trimethylphosphite, tri Ethyl phosphite, trinormal butyl phosphite, trioctyl phosphite, tridecyl phosphite, triphenyl phosphite, oxychloride, triethyl phosphate, tri- normal butyl phosphate, triphenyl phosphate, etc. Other phosphorus compounds may also be used. As for these phosphorus compounds, 0.01 mol-0.25 mol per 1 mol of magnesium compounds are suitable, More preferably, they are 0.05 mol-0.2 mol per mol. If it is less than 0.01 mole, the polymerization activity of the catalyst is inferior and excellent ductility and elasticity cannot be obtained.

The organosilane used to prepare the magnesium compound solution is R _n SiR ' _4-n where R is hydrogen or alkyl having 1 to 10 carbon atoms, alkoxy, haloalkyl, aryl group or halosilane having 1 to 8 carbon atoms or halosilyl alkyl group. , R 'is OR or halogen, and has the general formula of n = 0-4. Examples include trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, tetraethoxysilane, tetrabutoxysilane and the like. In the present invention, the organosilane is used as a shape control agent, which is useful for controlling the particle distribution of the catalyst by inhibiting the production of fine catalyst particles or very large catalyst particles. The amount of organosilane used is preferably 0.01 mol to 0.25 mol per mole of magnesium compound, more preferably 0.05 mol to 0.2 mol. If it is less than 0.01 mole, the effect as a shape control agent is weak, and when it exceeds 0.25 mol, it is difficult to manufacture the catalyst of the shape desired by this invention.

In the preparation of the magnesium compound solution, the reaction of the mixed solvent of magnesium compound and cyclic ether with alcohol, phosphorus compound and organosilane is preferably carried out in a hydrocarbon medium, and the reaction temperature is a kind of cyclic ether with alcohol, phosphorus compound and organosilane and Depending on the amount, it is carried out for at least about -25 ° C, preferably at -10 ° C to 200 ° C, more preferably at about 0 ° C to 150 ° C for about 15 minutes to 5 hours, preferably about 30 minutes to 3 hours Good to do.

The magnesium compound solution prepared as described above is _a transition metal such as a titanium compound (R is a hydrocarbon group, X is a halogen atom, and a is 0 ≦ a ≦ ₄ ) of the general formula Ti (OR) _a X _{4-a in} the liquid state. Reaction with the compound precipitates solid particles with a constant particle shape, large size and narrow particle distribution. In said general formula, R is a C1-C10 alkyl group. Examples of the titanium compound satisfying the general formula include titanium tetrahalide such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , and Ti (O (iC ₄ H ₉ )) ₂ Cl ₂ , and Ti (OC ₂ H ₅ ) Dihalogenated alkoxytitanium such as ₂ Br ₂ ; Tetraalkoxytitaniums such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , and Ti (OC ₄ H ₉ ) ₄ are exemplified, and mixtures thereof may also be used in the present invention. Preferred titanium compounds are titanium compounds containing a halogen component, and more preferred titanium compounds are titanium tetrachloride.

In order to precipitate the solid component from the magnesium compound solution, those which may be used in addition to the transition metal compound include silicon compounds such as silicon tetrahalide and silicon alkyl halide; Tin compounds such as tin tetrahalide, tin alkyl halide and tin hydrohalide; And mixtures thereof; Or mixtures of these with titanium compounds. Even when these are used, solid components having a large average particle size and a narrow particle distribution can be precipitated.

The amount of titanium compound, silicon compound, tin compound, and mixtures thereof used to precipitate the magnesium compound solution is suitably 0.1 mol to 200 mol, preferably 0.1 mol to 100 mol, more preferably 0.1 mol per mol of the magnesium compound. Is 0.2 mol to 80 mol. The shape, size and particle distribution of the precipitated solid component (carrier) vary greatly by reaction conditions when the magnesium compound solution and the titanium compound, the silicon compound, the tin compound or a mixture thereof are reacted. Therefore, the reaction of the magnesium compound solution with the titanium compound, the silicon compound, the tin compound, or a mixture thereof is performed at a sufficiently low temperature so that the solid product is not immediately produced and the reaction product is heated so that the solid component is gradually produced. A solid component having a size and particle distribution can be obtained. Preferably, the contact reaction is preferably performed at -70 ° C to 70 ° C, and more preferably at -50 ° C to 50 ° C. After the contact reaction, the reaction temperature was gradually raised to fully react for 0.5 hours to 5 hours at 50 ° C to 150 ° C.

The resulting solid particles, ie magnesium support, are reacted with a titanium compound in the presence of a suitable internal electron donor to prepare a catalyst. This reaction typically involves reacting a magnesium carrier with a titanium compound or with a titanium compound and a suitable electron donor, separating the solid component and reacting the solid component once again with the titanium compound and the electron donor. The solid component is separated and dried in two steps to obtain a catalyst. Alternatively, the reaction may be carried out with a titanium compound in a presence or absence of a hydrocarbon or halogenated hydrocarbon solvent for a predetermined time, followed by an electron donor.

Titanium compounds which are beneficial for the reaction with the magnesium support obtained as precipitated solid particles are titanium halides and alkoxy halide titanium having 1 to 20 carbon atoms in the alkoxy functional group. In some cases, mixtures thereof may also be used. Of these, titanium halides and alkoxy halides having 1 to 8 carbon atoms of the alkoxy functional group are preferable, and titanium tetrahalide is more preferable.

Suitable types of internal electron donors used when the magnesium carrier is reacted with a titanium compound include compounds including oxygen, nitrogen, sulfur, and phosphorus. Examples of such compounds are organic acids, organic acid esters, alcohols, ethers, aldehydes, ketones, amines, amine oxides, amides, phosphate esters, and mixtures thereof. Internal electron donors which can preferably be used in the present invention are aromatic esters. More specifically, alkyl benzenes such as methyl benzoate, methyl bromo benzoate, ethyl benzoate, ethyl chloro benzoate, ethyl bromo benzoate, butyl benzoate, isobutyl benzoate, hexyl benzoate and cyclohexyl benzoate Esters and halobenzene acid esters are useful, and dialkyl phthalates having 2 to 10 carbon atoms such as diisobutyl phthalate, diethyl phthalate, ethyl butyl phthalate, dibutyl phthalate are suitable. These internal electron donors can be used in mixtures of two or more, and can be used in the form of adducts or complexes of other compounds. The amount of internal electron donor used may vary and is about 0.01 mol to 10 mol, preferably about 0.01 mol to 5 mol, more preferably 0.05 mol to 2 mol per mol of the magnesium compound.

Catalysts prepared according to the invention are advantageously used for propylene polymerization. In particular, these catalysts are copolymerized between olefins such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and their copolymers with polyunsaturated compounds such as conjugated or nonconjugated dienes. Can be used as appropriate.

The polymerization reaction of the present invention comprises (1) a solid titanium catalyst comprising magnesium, titanium, halogen, and an internal electron donor prepared as described above, and (2) a Group II and III organometallic compound of the periodic table as a cocatalyst, And (3) a catalyst system comprised of an external electron donor component comprising an unsaturated nitrogen compound.

The solid titanium catalyst component may be prepolymerized with an α-olefin before being used as a component in a polymerization reaction. Prepolymerization can be carried out in the presence or absence of an external electron donor such as an organoaluminum compound such as triethylaluminum or an unsaturated nitrogen compound at the sufficiently low temperature and α-olefin pressure conditions in the presence of a hydrocarbon solvent such as heptane. have. Prepolymerization helps to improve the shape of the polymer after polymerization by surrounding the catalyst particles with a polymer to maintain the catalyst shape. In addition, the activity of the catalyst may increase by prepolymerization. The weight ratio of polymer / catalyst after prepolymerization is usually from 0.1: 1 to 20: 1.

The organometallic compound beneficial in the present invention serves as a promoter and may be represented by the general formula of MR _n . Where M is a periodic table group II or IIIA metal component such as magnesium, calcium, zinc, boron, aluminum and gallium, and R represents an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl and decyl , n represents the valence of the metal component. Preferred organometallic compounds include trialkylaluminums having 1 to 6 carbon atoms, such as triethylaluminum and triisobutylaluminum, and mixtures thereof. In some cases, an organoaluminum compound having one or more halogen or hydride groups such as ethylaluminum dichloride, diethylaluminum chloride, ethylaluminum sesquichloride, diisobutylaluminum hydride may be used.

In general, in order to control the activity and stereoregularity of the catalyst in the polymerization of α-olefins, especially propylene, an external electron donor is frequently used. In the present invention, to improve the elasticity and ductility of the polymer by controlling the stereoregularity of the catalyst, an unsaturated nitrogen compound having a substituent attached to both sides of the nitrogen compound located in the aromatic ring is effectively used. . External electron donors that can be used in the present invention are specifically 2,3-dimethylquinoxaline, quinaldine, 2,6-lutidine, 2,4,6-collidine, tetramethylpyrazine, 2,4-dimethylquinoline, 2,6-dichloropyridine, 2-chloro-6-methoxypyridine, 2,3-dichloroquinoxaline, 2,4,6-trichloropyrimidine, 2,4,5,6-tetra-chloropyrimidine, Unsaturated nitrogen compounds such as 2-chlororepidine or 6-chloro-2-picoline are used.

The polymerization reaction is possible by gas phase or bulk polymerization in the absence of an organic solvent or by liquid phase slurry polymerization in the presence of an organic solvent. These polymerization methods are carried out in the absence of oxygen, water and other compounds that can act as catalyst poisons.

In the case of liquid phase slurry polymerization, the preferred concentration of the solid titanium catalyst (1) in the polymerization reaction system is about 0.001 to 5 mmol, preferably about 0.001 to 0.5 mmol, of titanium atoms of the catalyst with respect to 1 liter of solvent. Solvents include alkanes or cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethyl Alkylaromatics such as benzene, halogenated aromatics such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, and mixtures thereof are advantageous.

In the case of gas phase polymerization, the amount of the solid titanium catalyst (1) is preferably about 0.001 to 5 millimoles, preferably about 0.001 to 1.0 millimoles, more preferably about 0.01 to 0.5 millimoles of titanium atoms of the catalyst per 1 liter of the polymerization zone. .

The preferred concentration of the organometallic compound (2) is about 1 to 2000 moles per mole of titanium atoms in the catalyst (1), more preferably about 5 to 500 moles, calculated as organometallic atoms.

The preferred concentration of the unsaturated nitrogen compound external electron donor (3) is about 0.001 to 100 moles, more preferably about 0.05 to 60 moles per mole of organometallic atoms in the organometallic compound (2), calculated as nitrogen atoms.

The polymerization reaction is carried out at a sufficiently high temperature regardless of the polymerization process in order to obtain a high polymerization rate. Generally about 20-200 degreeC is suitable, More preferably, 20-95 degreeC is good. As for the pressure of the monomer at the time of superposition | polymerization, atmospheric pressure-100 atmospheres are suitable, More preferably, the pressure of 2-50 atmospheres is suitable.

When carrying out the polymerization reaction according to the method of the present invention, additives may be used in some cases to control the molecular weight of the resulting polymer. An exemplary additive is hydrogen, the use of which can be determined as commonly known.

Examples and Comparative Examples

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples.

Example 1

Preparation of Solid Titanium Catalyst (1)

Solid titanium catalyst component was prepared through the following three steps.

(i) step: preparation of magnesium compound solution

A mixture of 15 g of MgCl ₂ , 4.2 g of AlCl ₃ , and 550 ml of toluene was added to a 1.0 L reactor equipped with a mechanical stirrer, which was replaced with a nitrogen atmosphere, and stirred at 400 rpm. Then, 30 ml of tetrahydrofuran, 28 ml of butanol, 1.4 ml of ethanol, After adding 1.5 ml of silicon tetraethoxide and 3.0 ml of tributyl phosphate, the temperature was raised to 105 ° C. and reacted for 4 hours. The homogeneous solution obtained after the reaction was cooled to room temperature.

(Ii) step: preparation of a solid carrier

The magnesium compound solution was transferred to a 1.6 L reactor in which the temperature of the reactor was maintained at 13 ° C. After stirring was maintained at 350rpm, 15.5ml of TiCl ₄ was added thereto, and the temperature of the reactor was raised to 90 ° C. Solid carriers were produced during this process. After the reaction was conducted at 90 ° C. for 1 hour, stirring was stopped and the resulting solid support was allowed to settle. The supernatant was separated and the solid carrier was washed twice with 75 ml of toluene.

(Iii) Step: Preparation of Catalyst

100 mL of toluene and 100 mL of TiCl _{4 were} added to the solid carrier, and the temperature of the reactor was raised to 110 ° C., and then heated for 1 hour. After the stirring was stopped, the solid carrier was allowed to settle, the supernatant was separated, 100 ml of toluene and 100 ml of TiCl _{4 were} added, and 2.9 ml of diisobutyl phthalate was injected at 70 ° C. The temperature of the reactor was raised to 120 ° C. and stirred for 1 hour. After the stirring was stopped, the supernatant was separated, 100 ml of toluene was injected, and the temperature of the reactor was lowered to 70 ° C. and stirred for 30 minutes. After stopping the reactor agitation and separating the supernatant, 100 ml of TiCl ₄ was injected and stirred at 70 ° C. for 30 minutes. The catalyst thus prepared was washed five times with 75 ml of purified hexane. The catalyst was stored after drying in a nitrogen atmosphere.

The particle size distribution of the catalyst was measured using a laser particle analyzer (Mastersizer X, Malvern Instruments), and had a distribution of d ₁₀ = 26.2 μm, d ₅₀ = 48.1 μm, and d ₉₀ = 70.7 μm. This means that d ₁₀ , d ₅₀ , d _90, that is, 10, 50, 90 percent of the particles have particles smaller than 26.2 μm, 48.1 μm, and 70.7 μm, respectively, and d ₅₀ is defined as the median particle size. And the solid titanium catalyst (1) prepared contained 3.1 wt% titanium atoms.

polymerization

A 2 L high pressure reactor was washed with heptane, and then 27 mg of catalyst was placed in a glass vial and mounted in the reactor, and then purged sufficiently with nitrogen to make nitrogen. 1000 ml of heptane, 7 mmol of triethylaluminum and 2.59 mmol of 2,6-lutidine were injected into the reactor. Propylene pressure of 2 atm was added, and the catalyst vial was broken with a stirrer and prepolymerized at room temperature for 5 minutes while stirring at 650 rpm. After adding 100 Nml of hydrogen, the temperature was raised to 50 ° C., the propylene pressure was adjusted to 5 atm, and the polymerization was carried out for 1 hour. When the polymerization reaction was completed, the unreacted gas was discharged and the reactor was desorbed. The resulting polymer was collected separately and dried in a vacuum oven at 40 ° C. for at least 6 hours to obtain a white polymer.

The polymerization activity (kg-PP / g-catalyst) calculated as the weight (kg) ratio of polymer produced per weight (g) of catalyst used was 3.6 kg-PP / g-catalyst.

Polymer property measurement

The heat resistance of the polymer was determined by measuring the melting point by using a differential scanning calorimeter. In addition, 50 g of polymer, 0.5 g of Iganox 1010 and 0.25 g of calcium stearate were placed in a shaker mixer for 7 minutes at 170 ° C. to prepare specimens for measuring Shore D Hradness and Elongation Set. Blended. After cooling, compression molding was performed at 190 ° C. into a flat sheet of 3 mm thickness. The sheet was then cut into dumbbell-shaped tensile specimens. Thus prepared Shore D hardness was measured in accordance with ASTM D 2240, and the elongation set was measured according to ASTM D 412. The elongation set represents the extent to which the specimen is restored to its original state after being stretched 300%. Shore De Hardness is a measure of the polymer's stiffness and an elongation set is a measure of the polymer's elasticity.

The melting point of the polymer prepared in Example 1 was 155 ° C, Shore D hardness was 30, and the elongation set was 90%.

Example 2

The polymerization was carried out under the same conditions as in Example 1 except that the amount of 2,6-lutidine added was 1.93 mmol, and the results are shown in Table 1.

Example 3

The polymerization was carried out under the same conditions as in Example 1 except that the amount of 2,6-lutidine added was 1.35 mmol, and the results are shown in Table 1.

Example 4

The polymerization was carried out under the same conditions as in Example 1 except that the amount of 2,6-lutidine added was 0.77 mmol, and the results are shown in Table 1.

Example 5

The polymerization was carried out under the same conditions as in Example 1 except that the amount of 2,6-lutidine was 0.77 mmol and the amount of hydrogen was 50 Nml. The results are shown in Table 2.

Example 6

The polymerization was carried out under the same conditions as in Example 1 except that the amount of 2,6-lutidine was 0.77 mmol and the amount of hydrogen was 200 Nml. The results are shown in Table 2.

Example 7

The polymerization was carried out under the same conditions as in Example 1 except that 2,3-dimethylquinoxaline was used instead of 2,6-lutidine, and the results are shown in Table 3.

Example 8

The polymerization was carried out under the same conditions as in Example 1 except that quinaldine was used instead of 2,6-lutidine, and the results are shown in Table 3.

Example 9

The polymerization was carried out under the same conditions as in Example 1 except that 2,4,6-collidine was used instead of 2,6-lutidine, and the results are shown in Table 3.

Comparative Example 1

The polymerization was carried out under the same conditions as in Example 1 except that cyclohexylmethyldimethoxysilane was used instead of 2,6-lutidine as an external electron donor, and the results are shown in Table 1.

Comparative Example 2

The polymerization was carried out under the same conditions as in Example 1 except that dicyclopentyldimethoxysilane was used instead of 2,6-lutidine as an external electron donor, and the results are shown in Table 1.

Comparative Example 3

The polymerization was carried out under the same conditions as in Example 1 except that no external electron donor was used, and the results are shown in Table 1.

Comparative Example 4

A solid complex titanium catalyst was prepared and polymerized in the same manner as in Example 1 except that AlCl ₃ was not used to prepare a magnesium compound solution during the preparation of the solid complex titanium catalyst.

Polymerization activity was found to be 1.8 kg-PP / g-catalyst, melting point was 158 ° C, Shore Di hardness was 70 and elongation set was 200%.

Comparative Example 5

A solid complex titanium catalyst was prepared and polymerized in the same manner as in Example 1 except that silicon tetraethoxide was not used to prepare a magnesium compound solution during the preparation of the solid complex titanium catalyst.

The polymerization activity was found to be 1.5 kg-PP / g-catalyst, the melting point was 152 ° C, the Shore Di hardness was 60 and the elongation set was 210%.

Comparative Example 6

A solid complex titanium catalyst was prepared and polymerized in the same manner as in Example 1 except that tributylphosphate was not used to prepare a magnesium compound solution during the preparation of the solid complex titanium catalyst.

The polymerization activity was found to be 1.8 kg-PP / g-catalyst, melting point was 156 ° C, Shore Di hardness was 70, and elongation set was 230%.

With the propylene polymerization or copolymerization method according to the present invention, it is possible to prepare a propylene polymer or copolymer with excellent elasticity and ductility while maintaining excellent heat resistance of the existing polypropylene.

Claims (11)

(1) (i) a magnesium halide compound and a Group IIIA compound of the periodic table are dissolved in a mixed solvent of a cyclic ether, at least one alcohol, a phosphorus compound, and an organosilane to prepare a magnesium compound solution, and (ii) the magnesium compound solution is a transition metal. A solid titanium catalyst prepared by reacting a compound, a silicon compound, a tin compound, or a mixture thereof to precipitate solid particles, and (i) reacting the precipitated solid particles with a titanium compound and an internal electron donor, and (2) Propylene comprising using organometallic compounds of Group I or Group III metals and (3) unsaturated nitrogen compounds with substituents which give steric hindrance to both sides of the nitrogen compound located in the aromatic ring Polymerization or copolymerization method. The method of claim 1, wherein the Group IIIA compound of the periodic table in the production of the catalyst is aluminum halide, propylene polymerization or copolymerization method characterized in that it is used at less than 0.25 mol per mol of magnesium halide compound. The propylene polymerization or copolymerization method according to claim 1, wherein the cyclic ether is 2 to 15 carbon atoms, and the alcohol is 1 to 20 carbon atoms. The molar ratio of the total amount of the cyclic ether and the at least one alcohol to the magnesium compound in the preparation of the catalyst is 1: 0.5 to 1:20, and the molar ratio of the cyclic ether and the at least one alcohol is 1: 0.05 to Propylene polymerization or copolymerization process characterized in that 1: 1:95. The method of claim 1, wherein the phosphorus compound in the preparation of the catalyst is a general formula PX _a R ¹ _b (OR ² _{) c} or POX _d R ³ _e (OR ⁴ ) _f (where X is a halogen atom, R ¹ , R ² , R ³ , R ⁴ is a hydrocarbon having 1 to 20 carbon atoms, alkyl, alkenyl or aryl, each may be the same or different, a + b + c = 3, 0≤a≤3, 0≤b ≤ 3, 0 ≤ c ≤ 3, d + e + f = 3, 0 ≤ d ≤ 3, 0 ≤ e ≤ 3, 0 ≤ f ≤ 3) characterized in that the propylene polymerization or copolymerization method. The propylene polymerization or copolymerization method according to claim 1, wherein the phosphorus compound is used at 0.01 to 0.25 mol per mol of the magnesium compound. The method of claim 1, wherein the organosilane in the preparation of the catalyst is a general formula R _n SiR ' _4-n (where R is hydrogen or alkyl having 1 to 10 carbon atoms, alkoxy, haloalkyl, aryl group or halosilane having 1 to 8 carbon atoms) Or a halosilyl alkyl group, R 'is OR or halogen, and is an organosilane represented by an integer of n = 0 to 4). The propylene polymerization or copolymerization method according to claim 1, wherein the organosilane is used in the preparation of the catalyst in an amount of 0.01 to 0.25 mol per mol of the magnesium compound. The method of claim 1, wherein the organometallic compound is trialkylaluminum. The method of claim 1, wherein the external electron donor is 2,3-dimethylquinoxaline, quinaldine, 2,6-lutidine, 2,4,6-collidine, tetramethylpyrazine, 2,4-dimethylquinoline, 2, 6-dichloropyridine, 2-chloro-6-methoxypyridine, 2,3-dichloroquinoxaline, 2,4,6-trichloropyrimidine, 2,4,5,6-tetra-chloropyrimidine, 2- Propylene polymerization or copolymerization method, characterized in that chlororepidine or 6-chloro-2-picoline. The process for propylene polymerization or copolymerization according to claim 11, wherein the external electron donor is 2,3-dimethylquinoxaline, quinaldine, 2,6-lutidine, or 2,4,6-collidine.