KR100431457B1 - Methods for preparing of high activity catalysts for olefin polymerization, and methods for preparing polyolefin using the same - Google Patents

Abstract

The present invention relates to a method for preparing a high activity catalyst for olefin polymerization, and to a method for preparing polyolefin using the same, and in particular, a high density polyethylene copolymer or a linear low density polyethylene copolymer having excellent particle shape can be prepared by controlling molecular weight distribution. The present invention relates to a method for preparing an active catalyst. The present invention provides a method for preparing a high activity catalyst for olefin polymerization, comprising the steps of: a) contacting a solid anhydrous support with an alcohol represented by R ₁ -OH under a nonpolar solvent; b) contacting the mixture of a) with at least two alcohols represented by R ₂ -OH and R ₃ -OH; c) contacting the mixture of b) with a titanium compound represented by Ti (OR ₄ ) _L X _4-L , a vanadium compound represented by VO _m X ' _(n-2m) , or a mixture thereof; And d) contacting the mixture of c) with a vanadium compound represented by VO _m X ' _(n-2m) , a titanium compound represented by Ti (OR ₅ ) _m X'' _4-m , or a mixture thereof. It provides a method for producing a catalyst comprising a and a method for producing a polyethylene using the same (wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently or simultaneously an alkyl group having 1 to 10 carbon atoms; X, X 'and X''are each independently or simultaneously halogen elements; l is an integer of 1 to 4; m is an integer of 0 or 1; n is an integer of 2 to 5).

The catalyst according to the present invention is used in combination with an alkylated aluminum promoter to adjust the ratio of titanium and vanadium supported on a carrier or to further control the polymerization conditions or halides in the polymerization medium to further improve the molecular weight distribution of the ethylene polymer. By adjusting, a high density, medium density or linear low density polyethylene having a wide molecular weight distribution or a bimodal molecular weight distribution can be produced.

Description

METHODS FOR PREPARING OF HIGH ACTIVITY CATALYSTS FOR OLEFIN POLYMERIZATION, AND METHODS FOR PREPARING POLYOLEFIN USING THE SAME}

The present invention relates to a method for preparing a high activity catalyst for olefin polymerization, and to a method for preparing polyolefin using the same, and in particular, a high density polyethylene copolymer or a linear low density polyethylene copolymer having excellent particle shape can be prepared by controlling molecular weight distribution. The present invention relates to a method for preparing an active catalyst.

Since the development of the Ziegler catalyst in the 1950s that can polymerize ethylene and alpha-olefins using organometallic compounds as transition metals and cocatalysts, many advances have been made in this area. However, not only the copolymerization ability of the Ziegler catalyst, but also techniques for controlling particle morphology, molecular weight and molecular distribution remain the major challenges in developing a highly active supported catalyst.

The molecular weight distribution in high density polyethylene or linear low density polyethylene (hereinafter referred to as polyethylene) is one of the basic physical properties that determine the properties of polymers. Although it is difficult to define the influence of each property independently, it is known that molecular weight affects mechanical properties and molecular weight distribution greatly affects rheological properties. In general, the increase in molecular weight improves the physical properties of the resin, so there is a need for high molecular weight polyethylene. However, as the molecular weight increases, processing of the polymer becomes difficult, while the wider molecular weight distribution tends to improve fluidity at high shear rates during processing. Therefore, widening the molecular weight distribution can increase the processability of high molecular weight polyethylene having a low melt index during processing requiring relatively high die swell such as blow molding or extrusion.

The high molecular weight polyethylene having a wide molecular weight distribution serves to improve the processability in the region having a small molecular weight, the region having a large molecular weight improves the mechanical properties such as impact strength of a product such as a film, when processing polyethylene, More discharge can be obtained with relatively low energy. Initially, a wide molecular weight distribution could be obtained by mixing polyethylenes having different molecular weights in order to obtain the advantages of a wide molecular weight distribution, but was not as satisfactory as polyethylene formed through polymerization.

On the other hand, the production of a polyolefin having a bimodal or multimodal distribution has been described a method of polymerizing ethylene in two stages using a high activity catalyst known as a cascade process (US Patent No. 5,639,834). However, the ethylene polymer obtained by this process does not always exhibit suitable physical properties in various applications because its final properties are determined by the catalyst used. Therefore, there is a need for the development of a catalyst suitable for this need.

Until now, there is a catalyst containing vanadium to satisfy the above requirements, and when it is used, it is known to be suitable for producing a polyolefin having a wide molecular weight distribution. That is, a catalyst in which a titanium compound, an organoaluminum compound, and a vanadium compound are supported on silica gel is known (Alexander et al., European Patent No. 0057589), and the polyethylene produced by the catalyst has a considerably high melt index ratio (MFR). Indicates.

As another method, there is a method of preparing a polyolefin having a high molecular weight and a wide molecular weight distribution by using a catalyst component including titanium and vanadium, an alkylated aluminum promoter, and a catalyst system including a halide (Miro, U.S. Pat. 4,831,000, 4,972,033, and 5,075,271). The vanadium-containing catalyst component may be prepared by reacting an organoaluminum compound, a mixture of titanium and vanadium compounds, and an ether compound with an inert carrier, and may be activated using an organoaluminum compound containing a halogen and a halogenation reagent. . However, the activity of the catalyst system is not as satisfactory as the high activity catalysts currently used.

Batchelor reported in US Pat. No. 5,473,027 that ethylene or ethylene and C ₃ to C ₈ alpha olefins can be polymerized by applying a catalyst loaded with CrO ₃ / TiO ₂ to silica in a gas phase polymerization process.

However, although many similar techniques are known, the activity of these systems is not as satisfactory as the catalysts currently used, and the particle morphology of polymerized polyethylene is not described in detail in the literature. Therefore, the application of the preceding catalyst system to the actual gas phase or the commercial process of the slurry seems to cause serious problems.

From a technical point of view, there is a need to develop a high activity catalyst having a granular form of a suitable size so that the polymer produced in the polymerization step has good fluidity during granulation.

In general, recent polyethylene production-related technologies place importance on the high activity of the catalyst, the control of the polymer properties, and the control of the molecular weight and molecular weight distribution as well as the copolymerization capacity.

In other words, in order to produce polyethylene polymers suitable for high-strength high-molecular weight films or B / M products, it is known to be possible through special processes such as cascade technology using specially designed multi-site catalysts. Bimodal molecular weight distribution in polymers with narrow molecular weight distribution or polymers with unimodal molecular weight distribution by changing the copolymer when the specially designed multi-site catalyst is applied in a multistage process It can produce a polymer having. The combination of these catalysts and processes is also expected to produce polymers that can be applied to all film and B / M products.

Therefore, there is a need for the development of highly active catalysts having good particle morphology to be available in practical commercial processes. In general, the trend of the current development of polyethylene catalyst technology is to develop a catalyst which is not only capable of copolymerizing a catalyst but also highly active, having a good particle form, and which is easy to control molecular weight and molecular weight distribution. From this general knowledge it can be concluded that the production of highly rigid catalysts with high molecular weight and blow molded products requires the use of specially designed catalysts in addition to process technologies such as cascade processes. The well-designed catalyst for multistage processes not only copolymerizes other alpha olefins with ethylene but also makes it easier to control the molecular weight distribution. Therefore, the development of a catalyst capable of producing various kinds of polyethylene having excellent properties for film and blow molding by appropriately using a high activity catalyst and a multistage process satisfying the above conditions is required.

Accordingly, an object of the present invention is to provide a method of producing a high activity catalyst having high activity, easy shape control of polymer particles, and good sensitivity to hydrogen, in view of the problems of the prior art.

It is another object of the present invention to provide a method for producing a high activity catalyst for producing high density polyethylene or linear low density polyethylene, which is suitable for the production of high-strength polymer films and L-drum blow molding resins.

Another object of the present invention is to provide a high activity catalyst for olefin polymerization prepared by the above described method.

Another object of the present invention is to polymerize 1-olefins such as ethylene by using the high activity catalyst together with an organometallic promoter to obtain a high density or linear low density polyethylene having excellent processability and physical properties with a considerably wide molecular weight distribution or bimodal molecular distribution. It is to provide a method for producing the same polyolefin.

The present invention to achieve the above object,

In the method for producing a high activity catalyst for olefin polymerization,

a) a solid anhydrous carrier in a non-polar solvent;

Contacting with the alcohol;

b) two or more alcohols represented by the following Chemical Formulas 2 and 3

Contacting the ol;

c) a titanium compound represented by the following formula (4),

Contact with the vanadium compound represented by the formula (5), or a mixture thereof

step; And

d) the vanadium compound represented by the following Formula 5 to the mixture of c),

Contact with a titanium compound represented by the formula (6), or a mixture thereof

Steps

It provides a method for producing a catalyst comprising:

[Formula 1]

R ₁ -OH

In Formula 1, R ₁ is an alkyl group having 1 to 10 carbon atoms,

[Formula 2]

R ₂ -OH

[Formula 3]

R ₃ -OH

In the formula 2 and 3,

R ₂ and R ₃ are each independently or simultaneously an alkyl group having 1 to 10 carbon atoms,

[Formula 4]

Ti (OR ₄ ) _ℓ X _4-ℓ

[Formula 5]

VO _m X ' _(n-2m)

In the formulas (4) and (5),

R ₄ is an alkyl group having 1 to 10 carbon atoms; X and X 'are each independently or simultaneously halogen atoms; l is an integer from 1 to 4; m is 0 or 1; n is an integer from 2 to 5,

[Formula 5]

VO _m X ' _(n-2m)

[Formula 6]

Ti (OR ₅ ) _m X '' _4-m

In the formulas 5 and 6,

R ₅ is an alkyl group having 1 to 10 carbon atoms; X 'and X''are each independently or simultaneously a halogen element; m is 0 or 1; n is an integer of 2-5.

The present invention also provides a high activity catalyst for olefin polymerization prepared by the above described method.

In addition, the present invention is a method for producing a polyolefin,

One or more olefins

a) a promoter represented by the following formula (7); And

b) a high activity catalyst prepared by the method of preparation of the substrate

It provides a production method comprising the step of polymerizing under a catalyst system comprising:

[Formula 7]

(R ₆ ) _y MX '' _(3-y)

In Formula 7, R ₆ is an alkyl group of C ₁ to C ₁₀ ; M is selected from the group consisting of elements of groups IB, IIA, IIIB, and IVB on the periodic table; X '' is halogen; And y is an integer of 1 to 3.

Hereinafter, the present invention will be described in detail.

The present invention provides a method for producing a high activity catalyst that can control the molecular weight distribution of fine particles by controlling the ratio of titanium and vanadium using magnesium chloride as a carrier or by changing the polymerization conditions. The present invention also provides a process for the preparation of high density or linear low density polyethylene in which molecular weight distribution is controlled through polymerization of olefins, preferably alpha-olefins, using the catalyst in combination with a promoter (catalyst activator). The high activity catalyst according to the present invention has high activity, is easy to control the shape of the polymer particles, and has good sensitivity to hydrogen, so that it is used in combination with a promoter (catalyst activator), preferably an organoaluminum compound, such as ethylene. When applied to the polymerization of -olefins, high density polyethylene (HDPE) or linear low density polyethylene (LLDPE) can be prepared with a fairly wide molecular weight distribution (MWD) and excellent processability and physical properties.

In the high activity catalyst according to the present invention, a solid anhydride carrier is reacted with an alcohol, followed by reaction with two or more other alcohols, and then the reaction mixture is primarily reacted with a titanium compound, a vanadium compound, or a mixture thereof. It is prepared by second reaction with a titanium compound, a vanadium compound, or a mixture of the same or different from the titanium compound.

The high activity catalyst can produce a high density polyethylene or linear low density polyethylene having a narrow or medium molecular weight distribution when the halide is not used in the reactor during olefin polymerization, and when the halide is used, a polyethylene having a wide molecular weight distribution It can be manufactured. The molecular weight distribution of the ethylene polymer can be controlled by controlling the molar ratio of titanium and vanadium supported on the support, or by varying the amount of halides added to the polymerization medium or other polymerization conditions.

The catalyst can be combined to form a high density or linear low density polyethylene having a broad molecular weight distribution, such as a promoter known as a catalytically active material, for example aluminum alkyl.

Referring to the production method of a high-activity catalyst for olefin polymerization of the present invention in more detail as follows.

The present invention includes the step of contacting the solid anhydride support with an alcohol compound represented by the following formula (1).

[Formula 1]

R ₁ -OH

In Formula 1, R ₁ is a C ₁ to C ₁₀ alkyl group, preferably a C ₂ to C ₈ alkyl group, more preferably an aliphatic alcohol component.

Specific examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, 1-pentanol, isopentanol, n-hexanol, 1-octanol, and 2-ethyl-1-hexane At least one selected from the group consisting of ol, the most preferred alcohol compound is 2-ethyl-1-hexanol. Mixtures of these alcohol components can also be used in this process. The amount of the alcohol is used in a molar ratio of magnesium chloride and alcohol, which is a carrier, from 1: 1 to 10, preferably from 1: 1.5 to 8, more preferably from 2 to 6.

The solid anhydrous support is preferably a porous material which does not contain water as a solid inorganic material. Specific examples of such solid anhydrous carriers may use magnesium oxide, magnesium chloride, silica, silica-alumina, silica-magnesia, silica-titania, alumina, zirconia, soria, titania, magnesia, or mixtures thereof. The particle size of the solid anhydrous carrier is 0.1 to 200 μm, preferably 10 to 150 μm. The shape of the carrier is in the form of spherical fine particles, preferably anhydrous magnesium chloride having a water content of less than 1.0% is used.

Preferred method of the reaction of the alcohol is to directly add a solution of the alcohol represented by the formula (1) or the alcohol represented by the formula (1) to the slurry of the non-polar solvent and the carrier and the slurry at a temperature of about 100 ~ 150 ℃ Allow enough time for reaction until a clear solution is obtained.

In addition, the present invention includes the step of cooling the compound formed above to room temperature and contacting (contavt) with two or more alcohol mixtures represented by the following formulas (2) and (3).

[Formula 2] [Formula 3]

R ₂ -OH R ₃ -OH

In Formulas 2 and 3, R ₂ and R ₃ are each independently or simultaneously an alkyl group of C ₁ to C ₁₀ .

At this time, the alcohol of the formula (2) and formula (3) can be used to produce a polyethylene resin having a wider molecular weight distribution using a different type of alcohol, respectively. Preferably the alcohol is an aliphatic alcohol and specific examples of such aliphatic alcohols are from the group consisting of methanol, ethanol, 1-propanol, isopropanol, n-butanol, isobutanol, pentanol, isopentanol, and n-hexanol At least one is selected, preferably methanol, ethanol, isopropanol, n-butanol. The amount of alcohol is used so that the molar ratio of magnesium chloride and alcohol, which is a carrier, is about 1: 0.1 to 10, preferably 1: 0.25 to 8, more preferably 1: 0.4 to 6.

Thereafter, the present invention is slowly added to the reaction mixture by adding the alcohol mixture represented by Formula 2 and 3 or the mixture of alcohol represented by Formula 2 and 3 and a non-polar solvent in the form of droplets. At this time, the reaction mixture is stirred at room temperature or about 30-80 ° C. for a sufficient time, preferably overnight, for the alcohol compound to react completely with the carrier or the product of the first process.

Next, the present invention includes the step of first contacting the resulting mixture with a titanium compound represented by the following formula (4), a vanadium compound represented by the following formula (5), or a mixture thereof.

[Formula 4]

Ti (OR ₄ ) _ℓ X _4-ℓ

[Formula 5]

VO _m X ' _(n-2m)

In Formulas 4 and 5, R ₄ is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms; X and X 'are each halogen, preferably Br or Cl, more preferably Cl; l is an integer from 1 to 4; m is 0 or 1, preferably 1; n is an integer from 2 to 5, preferably 5.

Preferred titanium compound of formula (4) in the present invention is titanium tetrachloride, and vanadium compound of formula (5) in the present invention is vanadium oxytrichloride.

The present invention may further include the above process in some cases.

The titanium compound represented by the formula (4) and the vanadium compound represented by the formula (5) may be added to the slurry as such, but are preferably added in a dissolved state in a suitable solvent such as a nonpolar solvent to form a slurry of the carrier. That is, the titanium compound represented by the formula (4), the vanadium compound represented by the formula (5), or a mixture thereof is dissolved in a nonpolar solvent, homogenized, and then added to the reaction mixture at 30 to 100 ° C, preferably 40 to 80 ° C. React for a sufficient time. The amount of the titanium compound represented by the formula (4), the vanadium compound represented by the formula (5), or a mixture thereof may be about 1: 0.1 to 10, preferably 1: 0.2 to 8, with a molar ratio between the carrier and these compounds. use. The number of moles of titanium atoms per unit weight in the titanium compound represented by the formula (4) is 0.05 to 0.7 mmol Ti / g, preferably 0.1 to 0.7 mmol Ti / g.

In addition, the present invention includes a step of finally reacting the product produced from the reaction with one or more transition metal compounds to finally prepare a catalyst. In this case, at least one vanadium compound should be used, and the vanadium compound may be a compound represented by Formula 5, a titanium compound represented by Formula 6, or a mixture thereof.

[Formula 6]

Ti (OR ₅ ) _n X '' _4-n

In Chemical Formula 6, R ₅ is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms; X '' is halogen, preferably Br or Cl, more preferably Cl; n is an integer of 1-4.

Preferred titanium compounds of formula 6 are titanium tetrachloride or chlorinated vanadium oxide. The titanium compound of Chemical Formula 6 may be added directly into a slurry or mixed with a suitable solvent such as a nonpolar solvent. Other transition metal compounds may be used instead of the titanium compounds, and mixtures thereof may also be used.

In the present invention, a mixture of the titanium compounds represented by Chemical Formula 6 may also be used, and in this case, it is preferable to add the titanium compounds to the mixture formed in the fourth process after mixing uniformly using a single or nonpolar solvent.

The present invention is homogeneous by dissolving the titanium compound represented by the formula (6), the vanadium compound represented by the formula (5), or a mixture thereof in a non-polar solvent and homogenized, and 30 to 100 ℃, preferably 40 to 80 ℃ The reaction is carried out for a sufficient time at. As mentioned above, the amount of the titanium compound represented by the formula (6), the vanadium compound represented by the formula (5), or a mixture thereof is about 1: 0.1 to 10, preferably in a molar ratio of the carrier and these compounds. It is used so that it may be 1: 0.2-8.

The present invention removes the unreacted titanium or vanadium compound by blowing the solvent of the resultant obtained above or by using a nonpolar solvent to prepare a solid supported catalyst precursor, and then slurry with a nonpolar solvent to polymerize ethylene. use.

The present invention utilizes nonpolar solvents such as hexane in all the catalyst preparations mentioned above, and other types of nonpolar solvents are also possible and entail chemical reactions with the compounds and reactants used in the catalyst synthesis, even when polar. You can also use it if you don't.

In addition, the compound of Formulas 1 to 6 should be a liquid or a substance soluble in a nonpolar solvent, at least partially soluble and liquid at the temperature used for catalytic synthesis. Preferred examples of the nonpolar solvent include alkanes selected from nonpolar isobutane, pentane, hexane, n-heptane, octane, nonane, and decane; Cyclohexanes such as cyclohexane; And aromatic compounds selected from benzene, toluene, and ethylbenzene. More preferred nonpolar solvent is hexane. The nonpolar solvent should be purified in a suitable manner to remove substances that affect the catalytic activity, such as water, oxygen, polar compounds.

On the other hand, the present invention is prepared by using the catalyst obtained in the above-described method to prepare a polyolefin, preferably polyethylene by combining with a cocatalyst known as a catalyst activation material, for example, one or more alkylated aluminum by the following process do. That is, the present invention provides a method for producing a polyolefin comprising polymerizing one or more olefins under a catalyst system including a cocatalyst represented by the following Chemical Formula 7, and a high activity catalyst prepared by the method of preparing the substrate. .

The present invention uses the catalyst in a suitable process to produce polyolefins by polymerization of olefins, preferably alpha-olefins. The polymerization is possible in all of the slurry, liquid phase, gas phase, preferably using a slurry polymerization.

The present invention includes the step of introducing a promoter into a reactor filled with a nonpolar solvent. The promoter used for the olefin polymerization includes at least one selected from the group consisting of elements of groups IB, IIA, IIIB, and IVB on the periodic table, and a promoter represented by the following formula (6) is used.

[Formula 7]

(R ₆ ) _y MX ''' _(3-y)

In Formula 7, R ₆ is an alkyl group of C ₁ to C ₁₀ ; M is selected from the group consisting of elements of groups IB, IIA, IIIB, and IVB on the periodic table; X '''is halogen, preferably Br or Cl, more preferably Cl; And y is an integer of 1 to 3.

In Chemical Formula 7, when M is aluminum, R ₆ is preferably an alkyl group of C ₁ to C ₆ , more preferably an alkyl group of C ₂ to C ₄ . Preferred examples of the aluminum compound include methyl aluminum dichloride or methyl aluminum dibromide, dimethyl aluminum chloride or dimethyl aluminum bromide, propyl aluminum dichloride or propyl aluminum dibromide, butyl aluminum dichloride or butyl aluminum dibromide, dibutyl aluminum chloride, Dibutylaluminum bromide, isobutylaluminum dichloride or isobutyl bromide, diisobutylaluminum chloride or diisobutylaluminum chloride, hexylaluminum dichloride or hexyl bromide, dihexyl aluminum or dihexyl aluminum bromide, dichloride Octyl aluminum fluoride, or butyl aluminum bromide, dioctyl aluminum chloride or dioctyl aluminum bromide.

In addition, the organoaluminum co-catalyst is an aluminum alkyl halide or diethyl aluminum used in the present invention, the carbon number of the alkyl group is a C ₁ ~ C _20. Preferred promoters are trialkylaluminums having alkyl groups of 1 to 6 carbon atoms, more preferably triethylaluminum.

The promoter has a great influence on the polymerization activity using the solid supported catalyst of the present invention, and the amount of the promoter used is at least 3: 1, preferably 10: 1, 25: 1, in the molar ratio of aluminum of the promoter and titanium in the catalyst. , 100: 1, 200: 1, or larger molar ratios. The catalyst can be activated by adding a promoter and a catalyst, respectively, to the polymerization medium. In addition, the catalyst and the cocatalyst may be mixed and put into the polymerization reactor before being put into the polymerization reactor. Preferably each is added to the polymerization reaction medium.

In the present invention, a high density polyethylene (HDPE) or a linear low density polyethylene (LLDPE) resin having a narrow or fairly wide molecular weight distribution may be prepared by polymerizing alpha-olefins under mild conditions without adding halides to the polymerization reactor. The molecular weight distribution area of the polyethylene can be adjusted by changing the polymerization conditions such as the concentration of the catalyst added, the polymerization temperature, and the Al / Ti ratio.

In addition, the present invention may further synthesize a high density polyethylene (HDPE) or a linear low density polyethylene (LLDPE) resin having a broader molecular weight distribution by further including a halide represented by the following formula (8). In this case, the melt index ratio (hereinafter referred to as 'MFR') is increased and the molecular weight distribution of the resin is widened.

[Formula 8]

MH _q X _(pq)

In Formula 8, M is silicon, carbon, germanium, or tin, preferably silicon or carbon, more preferably carbon; X is halogen, preferably Cl or Br, more preferably Cl; p is the oxidation state of M; And q is an integer of 0-4.

Specific examples of the halide are selected from the group consisting of carbon dichloride, carbon trichloride, carbon tetrachloride, silicon dichloride, silicon trichloride, and silicon tetrachloride. In this case, when M is carbon, the halide is a halogenated hydrocarbon having 1 to 6 carbon atoms such as Frcon 11, 12 or Frcon 114, and most preferably carbon trichloride.

When the concentration ratio between the halide represented by the formula (8) and the aluminum compound represented by the formula (7) is 0.1: 100 to 3: 100, the MFR is 25 to 80, preferably intermediate having a value of 45 to 70 A polymer having a molecular weight distribution of a degree is obtained. If the concentration ratio of the halide represented by the formula (8) and the aluminum compound represented by the formula (7) is adjusted to 3: 100 to 20: 100, the MFR ranges from 80 to 120, preferably from 80 to 110. It is possible to obtain a polymer having a. The values are calculated from the halide content in the total solution during slurry polymerization. The halide represented by the formula (8) is added before mixing the compound having the same molecular formula as the compound represented by the formula (5) in the nonpolar solvent and adding the slurry of TEA or solid catalyst component to the polymerization reactor.

In addition, the present invention includes the step of removing the gas in the reactor and the solvent in the reactant in the form of a slurry until the atmospheric pressure after the reaction.

In the present invention, the molecular weight of the polymer is preferably adjusted using hydrogen, and the temperature at the time of polymerization is 30-105 degreeC. The molecular weight can be confirmed by measuring the melt index (I ₂ ) of the polymer.

The high density polyethylene (HDPE) uses a small amount of alpha olefins such as n-butene, n-hexene, or n-octene together with ethylene during polymerization, wherein the mole number of the alpha olefin is about 0.020 to 0.050 with respect to ethylene. . In the case of the linear low density polyethylene (LLDPE), the number of moles of the alpha olefin is about 0.130 to 0.250 relative to ethylene.

The molecular weight distribution of the high density polyethylene (HDPE) or linear low density polyethylene (LLDPE) is dependent on the catalyst synthesis conditions and polymerization conditions, wherein the MFR of the measured polymer has a value of about 25 to 50. In the case of the high density polyethylene (HDPE), the measured polymer density is 0.940 to 0.965 and the melt index (I ₂ ) is about 0.1 to 100. In general, a high MFR value means a broad molecular weight distribution, and the application of these catalysts in multistage reaction processes yields resins with superior toughness, stiffness, and tensile strength compared to linear low density polyethylene. have.

In contrast, the linear low density polyethylene (LLDPE) has excellent tear strength and puncture resistance. The density of the linear low density polyethylene (LLDPE) is 0.900 to 0.935, the melt index (I ₂ ) has a value of about 0.20 to 100. The polymer is useful for the production of highly rigid films and injection molded articles. Copolymers prepared using the catalyst of the present invention may have two or more repeating units, such as ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / 4-methyl-1pentene And a copolymer composed of three monomers such as ethylene / 1-butene / 1-hexene, ethylene / propylene / 1-hexene, and ethylene / propylene / 1-butene.

In this case, the MFR represents the ratio of I _21.6 and I ₂ as follows.

MFR = I _21.6 / I ₂

As described above, the catalyst of the present invention has a very high activity and has an activity of at least 4,000 g / g catalyst / 100 psi / hr or 200,000 g / g Ti / 100 psi / hr. That is, in general, catalysts conventionally used are vanadium, vanadium-titanium supported catalysts or chromium catalysts, and the activity is mostly less than 1000 g / g catalyst / 100 psi / hr, whereas the catalyst according to the present invention has a very high activity and a particle shape. Excellent and excellent molecular weight distribution control and copolymerization ability.

Hereinafter, the present invention will be described with reference to specific examples as follows, but the present invention is not limited thereto.

Example 1

Catalytic synthesis

In a 250 ml flask substituted with nitrogen, 2.5 g of anhydrous magnesium chloride (more than 99%, less than 1% of water) was added, and 90 ml of purified hexane having a water content of less than 0.5 ppm was added thereto. 12.3 ml of anhydrous 2-ethyl-1-hexanol were added with stirring. The reaction mixture was stirred for about 2 hours until a homogeneous solution at a temperature of 130 ℃.

When all of the mixture was dissolved, it was cooled to room temperature, 4.8 ml of butanol and 4.6 ml of ethanol were slowly added dropwise while stirring and stirring was continued at room temperature for one night to allow the reaction to occur completely.

Then, 10 ml of TiCl ₄ was first diluted in 40 ml of hexane, and then slowly added to the reaction mixture with stirring for 1.5 hours, followed by further stirring for 1 hour. After the reaction, the reactant was precipitated and the liquid part except the solid component was removed. The solid component was washed with 200 ml of hexane and then 70 ml of purified hexane was added.

Secondly 5 ml of TiCl ₄ was diluted in 30 ml of hexane, then added with stirring for 1 hour and further stirred for 1 hour. The reaction mixture was further stirred at 80 ° C. for 1 hour. After stirring was stopped, the solid component was precipitated, the liquid portion was removed and washed with 150 ml of purified hexane (5 times with 150 ml). At the end of the procedure, purified hexane was added so that the total volume was 200 ml. The titanium concentration at this time became 10-20 mmol / L.

The catalyst thus prepared was stored in a vessel substituted with nitrogen in the form of a hexane slurry. In addition, the conditions for the number of moles of the reactant and the reaction temperature with respect to 1 mol of the magnesium chloride carrier and the analysis results of the prepared solid catalyst are shown in Table 1 below.

EXAMPLES 2-4

Catalytic synthesis

A catalyst was prepared in a similar manner to Example 1, except that the catalyst was prepared at a reaction temperature, an amount of titanium, and an amount of alcohol used in Example 1. Table 1 shows the catalyst synthesis conditions of each example and the analysis results are also shown in Table 1.

Comparative Example 1

Catalytic synthesis

To prepare a catalyst in the same manner as in Example 1, only 6.9 ml of ethanol was used in the second step, and 15 ml and 7.5 ml of TiCl ₄ were used respectively.

The amount of titanium supported in the solid catalyst was 8.3% w / w. Detailed amounts of the reagents used and the analysis results of the solid catalysts are shown in Table 1 below.

Table 1

division Catalytic Synthesis Conditions Catalyst component ratio (%) EtOH (mole) BuOH (mole) TiCl ₄ TiCl ₄ Ti Mg Cl mole T (℃) ¹⁾ mole T (℃) ¹⁾ Example 1 3.0 2.0 3.5 r.t. 1.75 r.t./80 10.0 12.7 54.3 Example 2 4.5 1.0 5.2 50/50 2.6 50/60 6.2 17.5 64.5 Example 3 4.5 0.5 5.2 50/50 2.6 50/85 10.9 13.9 59.1 Example 4 4.5 1.0 5.2 50/50 2.6 50/85 10.9 15.5 58.8 Comparative Example 1 4.5 - 5.2 50/50 2.6 50/85 8.3 14.8 58.5 1) Temperature of TiCl ₄ dropping / reaction temperature

As can be seen in Table 1, the amount of titanium supported is particularly affected by the reagent used and the reaction temperature. Examples 2 and 4 were prepared under similar synthetic conditions, but the loading of titanium was greater than that of Example 2, which had a higher temperature of 85 ° C. when the catalyst was prepared, and had a lower temperature of 60 ° C. Therefore, the amount of titanium supported can be easily controlled by catalyst synthesis conditions such as temperature.

[Examples 5-11]

Catalytic synthesis

Prepared in the same manner as in Example 1, a catalyst was prepared using VOCl ₃ instead of TiCl ₄ added secondary.

In addition, the catalysts of Examples 5 to 11 were prepared by varying the conditions as shown in Tables 2 and 3 below in order to know the effects of reaction temperature, the number of titanium treatments, the properties of the reactants, and the like on the catalyst.

TABLE 2

division EtOH (mole) BuOH (mole) TiCl ₄ (1) TiCl ₄ (2) VOCl ₃ mole T (℃) ¹⁾ mole T (℃) ¹⁾ mole T (℃) Example 5 4.5 1.0 5.2 50/50 - - 2.0 50/80 Example 6 4.5 1.0 5.2 50/50 - - 2.0 50/70 Example 7 ²⁾ 4.5 1.0 5.2 50/50 - - 2.0 50/85-90 Example 8 4.5 1.0 5.2 50/50 - - 2.0 50/85-90 Example 9 4.5 1.0 3.5 50/50 1.75 60/90 2.0 r.t./r.t. Example 10 4.5 1.0 4.4 50/50 1.75 60/90 2.0 r.t./50 Example 11 4.5 1.0 4.4 50/50 1.75 60/90 2.0 80/80 1) TiCl ₄ enemy temperature of the visible / reaction temperature 2) TiCl ₄ is discarded, and then added dropwise to the filtrate was added dropwise ₃ VOVl

TABLE 3

division Ti (%) V (%) Cl (%) Mg (%) Molar ratio of Ti / V Example 5 4.02 5.35 58.84 14.91 0.80 Example 6 4.53 1.75 59.57 17.21 2.75 Example 7 4.54 1.39 62.82 19.17 3.48 Example 8 3.35 5.70 57.91 15.27 0.63 Example 9 4.34 0.48 61.18 17.75 9.62 Example 10 5.12 1.86 62.32 16.72 2.93 Example 11 4.38 2.78 60.78 15.91 1.68

Example 12

Ethylene Polymerization of the Catalyst of Example 1

1 L of purified hexane was added to a 2 L stainless autoclave sufficiently substituted with nitrogen, heated to 65 ° C., and 4 mmol of triethylaluminum was added as a promoter. The temperature of the reactor was raised to 75 ° C. and 0.02 mmol of the catalyst prepared in Example 1 was added. The temperature of the reactor was raised to 80 ° C. and hydrogen was added to 50 psi in the reactor. The polymerization was then carried out by adding ethylene for 2 hours while maintaining the total reactor pressure at 130 psi. At the end of the polymerization, the reactor temperature was lowered moderately and the gas in the reactor was removed until the reactor pressure was at atmospheric pressure. The reactant in the form of a slurry was filtered and then removed from hexane, and dried sufficiently in a vacuum dryer at 60 ℃. As a result, the total dried polymer was 135 g, yielding 70.5 kg PE / (g Ti-hr) and 7.1 kg PE / (g cat-hr). Melt index (I ₂ ) of the polymer was 1.382 g / 10 min, D 50 was 179 μm, and the fine particles less than 106 μm were 21.0%. Table 4 shows the polymerization conditions and the results.

[Examples 13-15]

Ethylene Polymerization of Examples 2-4

The polymerization was carried out in the same manner as in Example 12, and instead of the catalyst of Example 1, the ethylene polymerization of Examples 13 to 15 was performed using the catalysts of Examples 2 to 4, respectively. Detailed polymerization conditions and results are shown in Table 4 below.

Comparative Example 2

Comparative Example 1 Ethylene Polymerization of Catalyst

In the same manner as in Example 5, ethylene polymerization was carried out using the catalyst of Comparative Example 1. The result was 52.4 kg PE / (g Ti-hr) and 4.8 kg PE / (g cat-hr) .The melt index of polymer I ₂ was 1.370 g / 10 min, MFR was 30.2, D50 was 251 μm, 106 The microparticles smaller than 20 mu m were 20%. Table 4 shows the polymerization conditions and the results.

Table 4

division catalyst activation BD (g / ml) MFR D50 (㎛) Particle size distribution (%) Kg PE / g Ti Kg PE / g cat <106 µm 106 to 500㎛ > 500㎛ Example 12 Example 1 140.9 14.1 0.27 33.3 179 0.21 0.65 0.14 Example 13 Example 2 292.3 18.1 0.37 31.5 260 0.22 0.62 0.16 Example 14 Example 3 187.9 20.5 0.22 30.9 361 0.06 0.62 0.32 Example 15 Example 4 177.5 19.3 0.31 31.3 ＞ 500 0.07 0.41 0.52 Comparative Example 2 Comparative Example 1 114.8 9.5 0.31 30.2 251 0.20 0.64 0.16

In Table 4, it can be seen that the catalysts described in the present invention have a very high activity, excellent particle shape and BD, and a wide molecular weight distribution as can be seen in the MFR value compared to Comparative Example 2.

Comparative Example 3

Catalytic synthesis

To prepare a catalyst in the same manner as in Example 1, instead of VOCl _{3 to be} added secondly, diluted 5 ml of TiCl ₄ in 30 ml of hexane, stirred at 50 ℃ and added for 1 hour and stirred for 1 hour at 85 ℃ to prepare a catalyst It was. The titanium content in the solid catalyst thus prepared was 10.9 wt%.

[Comparative Example 4]

Ethylene Polymerization Using Catalyst of Comparative Example 3

Ethylene polymerization was carried out in the same manner as in Example 8, except that 4.0 mL of a 1M TEA solution diluted in hexane was added, 0.02 mmol of the catalyst prepared in Comparative Example 1 was added, and ethylene was changed only under a condition that the hydrogen partial pressure in the reactor was 50 psi. The polymerization was carried out to obtain 180 g of the result. This yield is 94 kg PE / (g Ti-hr), 9.1 kg PE / (g cat-hr), polymer melt index (I ₂ ) is 2.924 g / 10 min, MFR is 30.9, D50 is 361 μm, Microparticles less than 106 μm were 6%.

As in the case of Comparative Example 4, the activity of the vanadium or vanadium / titanium supported catalyst using silica as a general carrier was less than 1000 g PE / (g cat-100psi-hr).

[Examples 16 to 18]

Ethylene Polymerization of the Example 2 Catalyst by Changing the Hydrogen Pressure

The polymerization was carried out in a similar manner as in Example 12. In order to understand the effect of hydrogen pressure on the polymerization, the hydrogen pressure was changed to use the Example 2 catalyst instead of the catalyst of Example 1. Detailed polymerization conditions and results are shown in Table 5 below.

Table 5

division [Ti] × 10 ^-5 M P _H2 / P _C2 activation BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) Kg PE / g Ti Kg PE / g cat <106 µm 106 to 500㎛ > 500㎛ Example 16 1.0 0.118 ¹⁾ 605 37.5 0.38 0.1455 37.5 291 0.21 0.51 0.28 17 1.0 0.295 ¹⁾ 522 32.4 0.37 1.006 33.5 246 0.25 0.56 0.19 18 2.0 0.538 ²⁾ 146 9.1 0.37 4.967 31.5 260 0.22 0.62 0.16

[Examples 19-20]

Ethylene Polymerization of Example 2 Catalyst Stored for 6 Months at Different Hydrogen Pressures

The polymerization was carried out in a similar manner as in Example 12. The catalyst was used as the catalyst of Example 2, the catalyst was stored in a nitrogen-substituted container for 6 months at room temperature, the effect of the storage time of the catalyst on the polymerization, the effect of hydrogen pressure on the polymerization by varying the hydrogen pressure I figured out. Detailed polymerization conditions and results are shown in Table 6 below.

Table 6

division [Ti] × 10 ^-5 M P _H2 / P _C2 activation BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) Kg PE / g Ti Kg PE / g cat <106 µm 106 to 500㎛ > 500㎛ Example 19 1.0 0.118 ¹⁾ 595.0 36.9 0.35 0.2083 50.2 295 15.9 58.2 25.9 20 1.0 0.230 ¹⁾ 358.0 22.2 0.35 0.3896 46.0 339 11.9 54.2 33.9

In Table 6 above, the catalyst of the present invention shows excellent stability with little change in activity, particle morphology and MFR despite long term preservation.

[Examples 21 to 22]

Preparation of Linear Low Density Polyethylene Using the Catalyst of Example 2

The polymerization was carried out in the same manner as in Example 12, except that a linear low density polyethylene was prepared by using the catalyst of Example 2 and adding a certain amount of butene, and detailed polymerization conditions and results are shown in Table 7 below.

TABLE 7

division Butene (g) [Ti] × 10 ^-5 M activation BD (g / ml) MI _2.16 MFR D50 (㎛) Particle size distribution (%) density Kg PE / g Ti Kg PE / g cat <106 µm 106 to 500㎛ > 500㎛ Example 21 15.7 1.0 542.8 33.7 0.23 0.5552 36.7 ＞ 500 4.2 43.1 52.8 0.9319 22 29.3 1.0 365.3 22.7 - 6.998 30.5 - - - - 0.9209

As can be seen in Table 7, the catalyst of the present invention can be used to prepare a linear low density polyethylene copolymer having excellent copolymerization capability with alpha olefins.

Example 23

Ethylene Polymerization Using the Catalyst of Example 5

The catalyst precursor prepared in Example 5 was placed in a 2L autoclave reactor filled with hexane. Triethylaluminum was used as cocatalyst (catalyst activator) and all catalyst and cocatalyst were added using a syringe.

The reactor sufficiently substituted with nitrogen was evacuated for 30 minutes to completely remove nitrogen, followed by addition of 0.8 L of purified hexane, heated to 65 DEG C, and 2.0 mL of a 1M TEA solution diluted in hexane. Then, the temperature of the reactor was raised to 75 ° C and 0.01 mmol of the catalyst prepared in Example 1 was added. The temperature of the reactor was raised to 80 ° C. and the hydrogen partial pressure in the reactor was 35 psi. The total reactor pressure was then maintained at 130 psi and ethylene was added for 2 hours to polymerize. At the end of the polymerization, the reactor temperature was lowered moderately and the gas in the reactor was removed until the reactor pressure was at atmospheric pressure. The reactant in the form of a slurry was filtered to remove hexane and then dried sufficiently in a vacuum dryer at 60 ℃. As a result, an ethylene polymer of 250 kg PE / (g Ti-hr) and 14.5 kg PE / (g cat-hr) was obtained. Melt index I ₂ of the polymer was 0.3476 g / 10 min, D 50 was 414 μm, and the fine particles smaller than 106 μm were 9.6%. Table 8-1 and 8-2 to show the detailed polymerization conditions and results.

[Examples 24 to 34]

Ethylene Polymerization of Catalysts of Examples 5-11

The polymerization was carried out in the same manner as in Example 23, but the catalysts prepared in Examples 5 to 11 were used as catalysts. Titanium concentration, hydrogen partial pressure, and reaction time in each reactor were adjusted, and their detailed polymerization results are shown in Tables 8-1 and 8-2.

Table 8-1

division catalyst Polymerization condition activation [Ti] × 10 ^-5 (M) H ₂ (Psi) Time (min) Kg PE / gTi Kg PE / gCat · h Example 23 Example 5 1.0 35 120 250.5 14.5 24 Example 5 2.0 50 120 112.2 6.5 25 Example 6 2.0 50 120 125.3 6.2 26 Example 7 1.0 50 120 88.8 4.6 27 Example 7 2.0 50 120 66.9 3.5 28 Example 8 2.0 50 60 67.8 3.5 29 Example 8 2.0 50 120 88.8 4.6 30 Example 9 2.0 50 120 151.4 6.2 32 Example 10 2.0 50 60 240.1 13.0 33 Example 10 1.0 35 120 344.5 18.6 34 Example 11 2.0 35 120 172.3 8.2

Table 8-2

division BD (g / ml) MI _2.16 MFR D50 Particle size distribution (%) <106 μm 106 to 500 μm > 500 μm Example 23 0.30 0.3476 32.8 414 9.6 48.7 41.7 24 0.35 2.342 33.5 211 34.6 51.2 14.2 25 0.29 2.625 31.8 235 22.3 57.9 19.8 26 0.33 0.4063 34.5 305 11.4 80.8 7.8 27 0.34 0.9561 32.4 248 15.7 80.6 3.7 28 0.22 0.8786 32.5 405 3.6 58.0 38.4 29 0.29 2.281 32.5 359 10.0 55.4 34.6 30 0.32 5.692 31.4 147 43.4 51.8 4.8 31 0.36 9.721 30.4 159 43.3 47.4 9.3 32 0.34 1.141 33.6 243 23.7 56.4 19.9 33 0.32 1.362 32.8 266 23.6 52.1 24.3

[Examples 34 to 49]

Polymerization of Ethylene Using the Catalyst of Example 5 and Chloroform

The polymerization was carried out in the same manner as in Example 23, but the polymerization was carried out under the conditions of the following Tables 9-1 and 9-2 using the catalyst precursor of Example 5 together with chloroform.

Table 9-1

division CHCl ₃ / Al [Ti] × 10 ^-5 M P _H2 activation Kg PE / g Ti Kg PE / g cat Example 34 0 1.0 25 308.0 17.9 35 1/64 1.0 25 210.6 12.2 36 1/32 1.0 25 167.0 9.7 37 1/8 1.0 25 88.8 5.2 38 0 1.0 30 245.3 14.3 39 1/61/644 1.0 30 187.9 10.9 40 1/32 1.0 30 142.0 8.3 41 1/40 1.0 35 130.5 7.6 42 1/20 1.0 35 101.3 5.9 43 0 2.0 25 201.5 11.7 44 1/64 2.0 25 187.9 10.9 45 1/32 2.0 25 133.1 7.7 46 1/16 2.0 25 94.0 5.5 47 0 2.0 30 164.4 9.6 48 1/64 2.0 30 154.5 9.0 49 1/32 2.0 30 109.6 6.4

Table 9-2

division BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) <106 μm 106 to 500 μm > 500 μm Example 34 0.32 0.0641 43.4 251 13.2 70.7 16.1 35 0.31 0.0285 55.7 229 13.3 73.2 13.5 36 0.31 0.0574 55.2 198 17.5 71.7 10.8 37 0.29 0.0769 57.9 172 22.8 70.2 7.0 38 0.31 0.1855 31.0 228 15.1 72.8 12.1 39 0.31 0.2169 36.7 216 17.7 70.2 12.1 40 0.29 0.1103 40.0 215 11.6 72.8 10.1 41 0.27 0.2149 41.4 225 16.1 70.9 13.0 42 0.29 0.2043 43.9 191 30.2 58.6 11.2 43 0.34 0.1125 37.8 217 19.4 68.7 11.9 44 0.34 0.3010 38.2 206 20.6 67.5 11.9 45 0.31 0.1220 50.0 198 21.4 66.8 11.8 46 0.30 0.1094 49.5 185 23.1 66.8 10.1 47 0.34 0.3576 33.5 194 22.2 69.0 8.8 48 0.34 0.4659 36.7 203 20.4 69.5 10.1 49 0.32 0.2164 42.7 182 23.7 66.6 9.7

[Examples 50-66]

Ethylene Polymerization Using Catalyst and Example 11 Chloroform

The polymerization was carried out in the same manner as in Examples 34 to 49, except that the catalyst component of Example 11 was used. Detailed polymerization conditions and results of titanium concentration, chloroform concentration, hydrogen partial pressure, reaction time, and the like in each reactor are shown in Tables 10-1 and 10-2.

Table 10-1

division CHCl ₃ / Al [Ti] × 10 ^-5 M P _H2 activation Kg PE / g Ti Kg PE / g cat Example 50 1/4 0.5 20 135.7 6.5 51 1/2 0.5 15 156.6 7.5 52 0 1.0 25 381.0 18.1 53 1/32 1.0 25 281.9 13.4 54 1/16 1.0 25 187.9 8.9 55 1/8 1.0 25 146.2 7.0 56 0 2.0 35 172.3 8.2 57 1/160 1.0 35 360.2 17.1 58 0 2.0 25 214.0 10.2 59 1/64 2.0 25 214.0 10.2 60 1/32 2.0 25 146.4 7.0 61 1/16 2.0 25 135.7 6.5 62 1/8 2.0 25 101.8 4.9 63 1/4 2.0 25 83.5 4.0 64 0 2.0 50 151.4 7.2 65 1/160 2.0 50 174.9 8.3

Table 10-2

division BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) <106 μm 106 to 500 μm > 500 μm Example 50 0.27 - 16.7 ¹⁾ 272 19.5 58.2 22.3 51 0.29 - 24.6 ¹⁾ 283 23.4 52.0 24.6 52 0.34 0.2297 35.6 274 19.4 55.3 25.3 53 0.34 0.2055 39.9 252 22.4 55.7 21.9 54 0.30 0.1118 47.0 249 17.2 63.7 19.1 55 0.31 0.093 48.9 218 24.6 58.6 16.8 56 0.32 1.362 32.8 266 23.6 52.1 24.3 57 0.31 1.658 33.1 286 17.4 55.7 26.9 58 0.33 0.4441 34.4 249 24.4 55.3 20.3 59 0.31 0.5499 36.6 266 25.0 52.1 22.9 60 0.32 0.2094 41.2 266 21.1 55.3 23.6 61 0.31 0.2104 43.1 251 20.9 59.5 19.6 62 0.31 0.1511 46.4 241 22.6 59.4 18.0 63 0.31 0.1388 53.8 235 25.0 60.3 14.7 64 0.35 5.121 31.1 233 24.4 57.8 17.8 65 0.35 11.47 30.2 249 22.5 56.9 20.6

[Examples 66-73]

Ethylene Polymerization at Different Al / Ti Ratios Using the Catalyst of Example 5

The polymerization was carried out in the same manner as in Example 24, but the polymerization was performed by controlling the aluminum / titanium ratio, hydrogen partial pressure, and reaction time in the reactor using the catalyst component of Example 5. Detailed polymerization conditions and results are shown in Tables 11-1 and 11-2.

Table 11-1

division Al / Ti [Ti] × 10 ^-5 M P _H2 activation Kg PE / g Ti Kg PE / g cat Example 66 25 2.0 30 53.2 3.1 67 25 3.0 30 111.3 6.5 68 25 4.0 30 94.5 5.5 69 50 1.0 30 93.9 5.5 70 50 2.0 30 154.5 9.0 71 100 1.0 30 224.5 13.0 72 200 1.0 30 245.3 14.3 73 400 1.0 30 261.0 15.2

Table 11-2

division BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) <106 μm 106 to 500 μm > 500 μm Example 66 0.30 0.0806 51.6 136 30.8 66.0 3.2 67 0.34 0.3798 46.6 165 25.7 68.8 5.5 68 0.34 0.4912 42.4 160 28.0 66.8 5.2 69 0.30 0.0873 44.6 167 22.5 71.3 6.2 70 0.31 0.2701 36.6 188 20.2 72.8 7.0 71 0.28 0.1110 37.3 243 11.3 76.2 12.5 72 0.31 0.1855 37.0 228 15.1 72.8 12.1 73 0.34 0.1433 36.7 219 17.8 70.8 11.4

[Examples 74 to 78]

Ethylene Polymerization at Different Temperatures Using the Catalyst of Example 5

The polymerization was carried out in the same manner as in Example 24, except that the polymerization was carried out by controlling the titanium concentration, hydrogen partial pressure, and reaction time in the reactor using the catalyst component of Example 5. Detailed polymerization conditions and results are shown in Tables 12-1 and 12-2.

Table 12-1

division Temperature (℃) [Ti] × 10 ^-5 M P _H2 activation Kg PE / g Ti Kg PE / g cat Example 74 70 1.0 30 219.2 12.7 75 76 1.0 30 241.2 14.0 76 80 1.0 30 245.3 14.3 77 84 1.0 30 205.5 14.6 78 80 1.0 30 164.4 9.6

Table 12-2

division BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) <106 μm 106 to 500 μm > 500 μm Example 74 0.30 0.0336 46.9 222 16.0 73.8 10.2 75 0.30 0.0647 42.4 234 13.5 76.1 10.4 76 0.31 0.1855 31.0 228 15.1 72.8 12.1 77 0.31 0.2989 35.5 230 13.3 76.1 10.6 78 0.34 0.3576 33.5 194 22.2 69.0 8.8

[Examples 78 to 82]

Linear Low Density Polyethylene (LLDPE) Synthesis Using the Catalyst of Example 5

The polymerization was carried out in the same manner as in Example 23, but the catalyst precursor of Example 5 was charged into a 2L autoclave reactor filled with hexane and a halide, and polymerized using butene. Each polymerization condition and the results are shown in Tables 13-1 and 13-2.

Table 13-1

division Butene (g) [Ti] × 10 ^-5 M P _H2 activation Kg PE / g Ti Kg PE / g cat Example 79 14.8 1.0 - 365.3 21.2 80 15.4 1.0 32 219.2 12.7 81 30.3 2.0 - 192.1 11.1 82 27.6 2.0 32 160.8 9.32

Table 13-2

division BD (g / ml) MI _2.16 MFR D50 (μm) Particle size distribution (%) Density (g / ml) <106 μm 106 to 500 μm > 500 μm Example 79 0.33 0.2075 39.7 191 20.8 72.2 7.0 0.9363 80 0.26 0.0760 63.5 165 24.1 71.2 4.7 0.9355 81 - 1.863 33.1 - - - - 0.9284 82 - 1.320 41.7 - - - - 0.9303

As described above, the high activity catalyst of the present invention exhibits high activity under all conditions, has good catalytic activity, easy control of polymer particle shape and molecular weight distribution, and excellent copolymerization characteristics. Therefore, by using the high activity catalyst of the present invention, it is possible to control the shape of polyethylene and to obtain polyethylene having a fine particle content of less than 20%. That is, the catalyst of the present invention can control the particle size distribution of polyethylene by adjusting the ratio of titanium and vanadium supported on the carrier, or by changing polymerization conditions such as temperature, Al / Ti ratio, catalyst concentration, and halide addition. have. Another advantage of the catalyst described in the present invention is that changing the partial pressure of hydrogen results in a wider molecular weight distribution. This property is suitable for the production of films and blow molded articles requiring a wide molecular weight distribution.

As described above, the catalyst according to the present invention, in combination with an alkylated aluminum cocatalyst, controls the ratio of titanium and vanadium supported on a carrier when applied to polyethylene production, or further comprises a halide in the polymerization conditions or the control of polymerization conditions. By controlling the molecular weight distribution of the ethylene polymer, high density, medium density or linear low density polyethylene having a wide molecular weight distribution or a bimodal molecular weight distribution can be produced.

Claims (12)

a) contacting the solid anhydrous support with an alcohol represented by the following Chemical Formula 1 in a nonpolar solvent to generate a homogeneous solution; b) contacting the mixed solution of a) with two or more alcohols represented by the following Chemical Formulas 2 and 3; c) contacting the mixture of b) with a titanium compound represented by Formula 4, a vanadium compound represented by Formula 5, or a mixture thereof; And d) contacting the mixture of c) with a vanadium compound represented by Formula 5, a titanium compound represented by Formula 6, or a mixture thereof Method for producing a catalyst for olefin polymerization, the activity of which comprises a maximum of 200,000 g polymer / g catalyst / hr: [Formula 1] R ₁ -OH [Formula 2] R ₂ -OH [Formula 3] R ₃ -OH [Formula 4] Ti (OR ₄ ) _ℓ X _4-ℓ [Formula 5] VO _m X ' _(n-2m) [Formula 6] Ti (OR ₅ ) _m X '' _4-m In the above formula, R ₁ is an alkyl group having 1 to 10 carbon atoms, R ₂ and R ₃ are each independently or simultaneously an alkyl group having 1 to 10 carbon atoms, R ₄ is an alkyl group having 1 to 10 carbon atoms; X and X 'are each independently or simultaneously halogen atoms; l is an integer from 1 to 4; m is 0 or 1; n is an integer from 2 to 5, R ₅ is an alkyl group having 1 to 10 carbon atoms; X 'and X''are each independently or simultaneously a halogen element; m is 0 or 1; n is an integer of 2-5. The method of claim 1, wherein the molar ratio of the solid anhydrous support and alcohol in step a) is 1: 1 to 10. The method of claim 1, wherein the solid anhydrous support of step a) is at least one selected from the group consisting of magnesium oxide, magnesium chloride, silica, silica-alumina, silica-magnesia, silica-titania, alumina, zirconia, titania, and magnesia. Method for preparing the catalyst selected. The method according to claim 1, wherein the molar ratio of the alcohols represented by the formulas (2) and (3) of step b) is 1: 1 to 10, respectively, with respect to the solid anhydrous carrier. The method of claim 1, wherein the molar ratio of the titanium compound represented by the formula (4), the vanadium compound represented by the formula (5), or a mixture thereof is 1: 1 to 10, respectively, based on the solid anhydrous carrier. . The method of claim 1, wherein the molar ratio of the vanadium compound represented by the formula (5), the titanium compound represented by the formula (6), or a mixture thereof is 1: 1 to 10 with respect to the solid anhydrous carrier, respectively. . The high activity catalyst for olefin polymerization which has the maximum activity of 200,000 g polymer / g catalyst / hr manufactured by the method of any one of Claims 1-6. In the method for producing a polyolefin, One or more olefins a) a promoter represented by the following formula (7); And b) a highly active catalyst prepared by the process of claim 1 Process for producing comprising the step of polymerization under a catalyst system comprising: [Formula 7] (R ₆ ) _y AlX '' _(3-y) In Chemical Formula 7, R ₆ is an alkyl group of C ₁ to C ₁₀ ; X '' is halogen; y is an integer of 1 to 3. The method for producing a polyolefin according to claim 8, wherein R ₆ of the cocatalyst represented by Chemical Formula 7 of a) is C ₁ to C ₆ . The method of claim 8, wherein the polymerization is further performed by further including a halide represented by the following formula (8). [Formula 8] MH _q X _(pq) In Formula 8, M is silicon, carbon, germanium, or tin; p is the oxidation state of M; q is an integer of 0-4. The process for producing a polyolefin according to claim 10, wherein said halide is a halogenated silicone or hydrocarbyl halide. The method for producing a polyolefin according to claim 8, wherein the polymerization is carried out at 30 to 105 캜.