JP6750239B2 - Solid acid, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

The present invention relates to a solid acid, a catalyst for olefin polymerization using the solid acid, and a method for producing an olefin polymer. More specifically, it relates to a solid acid in which the amount of Lewis acid points having a specific strength is controlled, an olefin polymerization catalyst using the solid acid, and a method for producing an olefin polymer.

Solid acid is widely applied as a catalyst in petroleum refining and organic synthesis, and is used for isomerization, nuclear alkylation, disproportionation, polymerization, depolymerization, condensation, hydration, dehydration, esterification, acetalization, amination, cracking, etc. As a catalyst for various reactions, it is known that it is actually superior to conventional liquid acids not only in activity and selectivity but also in reaction operation and mechanism. Among them, solid acids such as clay minerals and ion-exchange layered silicates are used as catalyst components for olefin polymerization (see, for example, Patent Document 1), and the problem is to improve the catalytic activity, and various solid acids are used. Solution means have been proposed (see, for example, Patent Documents 2 to 4). For example, an olefin polymerization catalyst containing, as a catalyst component, a clay mineral that has been subjected to acid treatment, salt treatment, or chemical treatment in the coexistence of acid and salt is also known.

Also known is a method of obtaining high catalytic activity by using an ion-exchange layered silicate having a specific amount of acid points having a pKa of -8.2 or less as a catalyst component for olefin polymerization (for example, Patent Document 5). reference). However, in the above-mentioned conventional techniques, the activity of the catalyst component for olefin polymerization is not yet sufficient, and further technical improvement is desired.

JP-A-5-301917 JP, 7-309907, A JP-A-8-127613 JP, 10-168109, A JP 2002-053609 A

The object of the present invention is, in view of the situation and problems of the above-mentioned prior art , an ion-exchange layered silicate that is a solid acid that gives highly active performance, an olefin polymerization catalyst, and a method for producing an olefin polymer using the same. Is to provide.

The present inventors have arrived at the present invention as a result of earnestly studying the acid property of the ion-exchange layered silicate which is a solid acid. The transition metal of Groups 3 to 12 of the Periodic Table is required for the polymerization of olefins, and the ion-exchange layered silicate which is a solid acid is used as a means for activating the transition metal. The present invention provides a solid acid having a predetermined amount or more of a Lewis acid point having a specific acid strength or more, and by using an ion-exchange layered silicate that is this solid acid as a catalyst component, a highly active catalyst can be obtained. Is provided.

That is, the present invention has, as a main feature of the invention, the sum of the pore volumes of pores having a diameter of 2 to 10 nm calculated in the pore distribution curve calculated by the BJH analysis method using the adsorption isotherm by the nitrogen adsorption method. , Which is 60 to 100% of the total mesopore volume, is obtained by treatment with an organoaluminum compound, and the amount of Lewis acid points on which pyridine is adsorbed at 500° C. or higher is 45 μmol or more per 1 g of the ion-exchange layered silicate. An ion-exchange layered silicate that is a solid acid having is provided.
As an embodiment invention (each invention of dependent claims) accompanying the above-mentioned basic invention of the present invention, as a second invention, an ion-exchangeable layered silicate prepared by inorganic acid treatment or organic acid treatment is used. Provided is an ion-exchange layered silicate having a desorption ratio of aluminum , which is a main metal cation of a face sheet, of 10 to 65 mol %,
In addition, as the third to sixth inventions, the ion-exchange layered silicate is an ion-exchange layered silicate having a 2:1 layer structure or a smectite group silicate. salt, 2 are dioctahedral smectite ion-exchange layered silicate is an ion-exchange layered silicate and montmorillonite are silicates provided, seventh, as the invention of, obtained chemically treated ion A method of making an exchangeable layered silicate is provided.
An eighth invention is an olefin polymerization catalyst containing an ion-exchange layered silicate and a transition metal compound of Groups 3 to 12 of the periodic table, and a ninth invention is an ion-exchange layered silicate and the periodic table Third. As a tenth aspect of the present invention, there is provided a method for producing an olefin polymerization catalyst, which comprises bringing a transition metal compound of Group 12 into contact with an olefin, and an olefin polymer for homopolymerizing or copolymerizing an olefin using the olefin polymerization catalyst. A manufacturing method is provided.

A solid acid ion-exchange layered silicate The ion-exchange layered silicate is a solid acid having Louis scan acid sites of a specific acid strength greater than a predetermined amount of the present invention, the for olefin polymerization The solid acid By using it as a catalyst component, a transition metal compound can be efficiently activated and an olefin polymer can be produced with high activity.

Pyridine-TPD-IR/MS measurement results of chemically treated montmorillonite. Pyridine-TPD-IR/MS measurement results of organoaluminum-treated montmorillonite.

Hereinafter, the present invention will be described in detail for each item.

1. Solid acid [A]
The ion-exchange layered silicate which is a solid acid of the present invention has an amount of Lewis acid points which pyridine adsorbs at 500° C. or higher per 45 g of the ion-exchange layered silicate which is a solid acid. Here, the "Lewis acid point at which pyridine is adsorbed at 500°C or higher" is a Lewis acid point at which pyridine is adsorbed without desorption at a temperature of 500°C, and pyridine is desorbed at a temperature of 500°C or higher for the first time. It is the Lewis acid point.

1-1. Intensity and amount of Lewis acid point For measuring the Lewis acid point, the acid strength and the acid point of the acid point and the acid point of The amount (acid amount) can be calculated.

1-1-1. Thermal Desorption-Mass Spectrometry (TPD-MS)
The temperature programmed desorption-mass spectrometry (TPD-MS) used in the present invention is to continuously raise the temperature of the sample layer by adsorbing pyridine on the acid sites of the ion-exchange layered silicate which is a solid acid. This is a method of measuring the gas of pyridine released by the reaction. The amount of acid can be determined by measuring the amount of pyridine gas released. Further, since the pyridine adsorbed on the weak acid point is desorbed at a low temperature and the pyridine adsorbed on the strong acid point is desorbed at a high temperature, the acid strength distribution can be obtained. Before the measurement, a drying treatment may be carried out in order to remove excess water and the like in the solid acid. As a drying condition, the degree of vacuum is preferably 1.0 torr abs or less, and particularly preferably 0.5 torr abs or less. The drying temperature is preferably 0 to 1000°C, particularly preferably 0 to 600°C. The drying time is preferably 30 to 360 minutes, particularly preferably 30 to 240 minutes.

The adsorption of the ion-exchange layered silicate, which is a solid acid of pyridine, to the acid sites can be carried out by contacting pyridine with a gas. Further, the pyridine gas may contain an inert gas which does not adsorb to the acid sites, and the concentration of the pyridine gas is preferably 5 mol% or more, particularly preferably 50 mol% or more. When adsorbing liquid pyridine to the acid sites of the ion-exchange layered silicate, which is a solid acid , a measuring device including a liquid reservoir is used. By adding pyridine to the liquid reservoir and reducing the pressure in the system, pyridine vapor can be generated and brought into contact with the acid sites of the ion-exchange layered silicate which is a solid acid.
The longer the adsorption time, the better because the pyridine is adsorbed on all the acid points. Specifically, it is preferably 10 minutes or longer, and particularly preferably 30 minutes or longer. The adsorption temperature is preferably -100 to 500°C, particularly preferably 0 to 300°C.
In order to remove the pyridine physically adsorbed at the position other than the acid point of the ion-exchange layered silicate that is a solid acid , it is preferable to perform the removal by vacuum treatment. The vacuum degree of the vacuum treatment is preferably 1.0 torr abs or less, and particularly preferably 0.5 torr abs or less. The removal temperature is preferably 0 to 300°C, particularly preferably 0 to 200°C. The removal time is preferably 30 to 360 minutes, particularly preferably 30 to 240 minutes.
Even if not all the physical adsorption can be removed by the vacuum treatment, the pyridine used in the present invention has a small acid dissociation constant (pKa), and the physical adsorption force is much weaker than the adsorption force to the acid site. Therefore, the respective peaks of TPD-MS are observed at completely different positions, and it is easy to separate the peaks.

The measurement temperature is preferably −100 to 1000° C., particularly preferably 0 to 1000° C. The temperature rising rate is preferably 1 to 30°C/minute, particularly preferably 5 to 20°C/minute. The measurement atmosphere is preferably an inert gas such as helium, argon or nitrogen, and particularly preferably helium.

1-1-2. Infrared spectroscopy (IR)
There are two kinds of acid sites with different properties in the ion-exchange layered silicate which is a solid acid. One is a Bronsted acid point (B acid point) that gives a proton to a partner molecule, and the other is a Lewis acid point (L acid point) that accepts an electron pair from the partner molecule. Infrared spectroscopy (IR) used in the present invention is a method in which pyridine is adsorbed at each of the L acid point and the B acid point, and these acid points are distinguished by the difference in the position of the absorption band due to stretching vibration. Pyridine when adsorbed to B acid sites becomes pyridinium ion, absorption bands of C-N stretching vibration by IR is observed near 1500 cm ^-1 and 1540 cm ^-1. The pyridine is a coordination bond with pyridine to adsorb the L acid sites, the absorption band of the C-N stretching vibration by IR is observed near 1450 cm ^-1 and 1500 cm ^-1. The molar extinction coefficient (ε) of each absorption band is 1.73 (1450 cm ⁻¹ ) from the literature (A. Satsuma et al., Applied Catalysis A: General, 2012, 135, p.433-434.), 1.46 ^(1490cm -1), 1.23 is known as (1545 cm ^-1), it can be determined the ratio from the intensity ratio of B acid sites and L acid sites of the absorption band. Further, by changing the measurement temperature, the temperature dependence of the ratio of the B acid point and the L acid point can be obtained.

As the measurement of IR, a drying treatment may be performed before the measurement in order to remove excess water and the like in the ion-exchange layered silicate that is a solid acid. As a drying condition, the degree of vacuum is preferably 1.0 torr abs or less, and particularly preferably 0.5 torr abs or less. The drying temperature is preferably 10 to 1000°C, particularly preferably 10 to 600°C. The drying time is preferably 30 to 360 minutes, particularly preferably 30 to 240 minutes.

The adsorption of the ion-exchange layered silicate, which is a solid acid of pyridine, to the acid sites can be carried out by contacting pyridine with a gas. Further, the pyridine gas may contain an inert gas which does not adsorb to the acid sites, and the concentration of the pyridine gas is preferably 5 mol% or more, particularly preferably 50 mol% or more. Further, when adsorbing liquid pyridine to the acid sites of the ion-exchange layered silicate that is a solid acid , bubbling of pyridine with a circulating gas and contacting pyridine with the circulating gas can be performed. .. The circulating gas is preferably an inert gas such as helium, argon or nitrogen, and particularly preferably helium. The flow rate of the circulating gas is preferably 10 to 200 mL/min, and particularly preferably 20 to 150 mL/min.
The longer the contact time, the better because the pyridine is adsorbed on all the acid sites. Specifically, it is preferably 1 minute or longer, and particularly preferably 5 minutes or longer. The contact temperature is preferably 10 to 500°C, particularly preferably 10 to 300°C.

In order to remove the pyridine physically adsorbed at the position other than the acid point of the ion-exchange layered silicate that is a solid acid , it is preferable to perform the removal by vacuum treatment. The vacuum degree of the vacuum treatment is preferably 1.0 torr abs or less, and particularly preferably 0.5 torr abs or less. The removal temperature is preferably 10 to 300°C, and particularly preferably 10 to 200°C. The removal time is preferably 30 to 360 minutes, particularly preferably 30 to 240 minutes.

The measurement temperature is preferably 10 to 1000°C, particularly preferably 10 to 800°C. The temperature rising rate is preferably 1 to 30°C/minute, particularly preferably 5 to 20°C/minute. The holding time after the temperature rise is preferably 1 to 30 minutes, particularly preferably 5 to 20 minutes.

1-1-3. Combination of thermal desorption-mass spectrometry (TPD-MS) and infrared spectroscopy (IR) Acid strength and amount of Lewis acid points in the ion-exchange layered silicate that is a solid acid calculated according to the present invention Can be achieved by combining thermal desorption-mass spectrometry (TPD-MS) and infrared spectroscopy (IR). As described above, thermal desorption-mass spectrometry (TPD-MS) can determine the acid amount and acid strength distribution, and infrared spectroscopy (IR) can determine the ratio of Bronsted acid points and Lewis acid points. You can To calculate the amount and acid strength distribution of the Bronsted acid point and the Lewis acid point at each temperature by dividing the acid amount of TPD-MS for each temperature into the ratio of the Bronsted acid point and the Lewis acid point of IR. You can
Further, when there is a difference in measurement temperature between the measuring devices, it is possible to correct the temperature by regarding the times when the desorption rate of pyridine is the same as the same temperature.
The measurement of TPD-MS and IR may be performed continuously by the same device or separately.

The amount of Lewis acid points on which pyridine is adsorbed at 500° C. or higher measured by the above method is 45 μmol or more, preferably 50 μmol or more, and more preferably 50 μmol or more per 1 gram of the ion-exchange layered silicate that is a solid acid. The amount is 60 μmol or more, more preferably 70 μmol or more. The larger the amount of Lewis acid points adsorbed by pyridine at 500° C. or higher, the better, and the upper limit thereof is not limited, but actually it is 2000 μmol or less, preferably 1000 μmol or less.

The catalytic reaction of the ion-exchange layered silicate that is a solid acid involves the acid sites in the ion-exchange layered silicate that is a solid acid , and a particularly strong Lewis acid point may contribute to the reaction. Many. Therefore, the larger the amount, the higher the performance as a catalyst. Particularly in the catalyst for polyolefin polymerization, it is believed that the strong Lewis acid point contributes to the activation of the metallocene complex, and the larger the amount, the more the activation of the metallocene catalyst proceeds, and the higher polymerization activity is considered to be imparted. To be

Further, in the prior art, there is a method in which an ion-exchange layered silicate, which is a solid acid having a specific amount of acid points having a pKa of -8.2 or less, is used as a catalyst component for olefin polymerization (JP-A-2002-053609). It is known, but no distinction can be made regarding the type of acid. The “Lewis acid point at which pyridine is adsorbed at 500° C. or higher” of the present invention is an acid point which is much stronger than the acid point of pKa of the prior art of −8.2 and is a Lewis acid point.

1-2. Preparation of Solid Acid A solid acid having the above properties can be prepared by the following method.

The solid acid is a solid that exhibits the characteristics of a Breasted acid and/or a Lewis acid, and specific solid acids include zeolite, metal oxides, metal oxides having a plurality of metal elements, and the like. Examples thereof include inorganic oxides (composite oxides), metal sulfates, metal phosphates, solid phosphoric acid, cation exchange resins, heteropolyacids, clay minerals and the like.

More specifically, as the solid acid, Al ₂ O ₃ , Cr ₂ O ₃ , TiO ₂ , SiO ₂ —TiO ₂ , SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —ZrO ₂ , SiO ₂ —. _{BeO, SiO 2 -Y 2 O 3} , SiO 2 -La 2 O 3, SiO-WO 3, SiO 2 -V 2 O 5, SiO 2 -Ga 2 O 3, SiO 2 -MoO 3, Al 2 O 3 - _{ZrO 2, Al 2 O 3 -Bi} 2 O 3, Al 2 O 3 -MoO 3, Al 2 O 3 -V 2 O 5, Al 2 O 3 -WO 3, Cr 2 O 3 -Al 2 O 3, TiO _{2 -Al 2 O 3, TiO 2} -SiO 2, TiO 2 -ZrO 2, ZnO-Al 2 O 3, H-Y, La-Y, Ca-Y, heteropoly acid, ion-exchange layered silicate, zeolite , NiSO ₄ .H ₂ O, Al ₂ (SO ₄ ) ₃ .nH ₂ O, Fe ₂ (SO ₄ ) ₃ .nH ₂ O, BPO ₄ , FePO ₄ , TiO ₂ —B ₂ O ₃ , TiO ₂ —SnO. ₂ , ZnOSiO ₂ , ZnO-ZrO ₂ , WO ₃ -TiO ₂ , solid boric acid, solid sulfuric acid, solid phosphoric acid, and the like.
Among these, a combination ion-exchange layered silicate, _{zeolites, SiO 2 -Al 2 O 3,} SiO 2 and complex oxides in combination with other metals, _Al 2 _{O 3} and _Al 2 _{O 3} and another metal A complex oxide in which ZnO ₂ and another metal are combined is preferable. Among them, the ion-exchange layered silicate is particularly preferable.

1-2-1. Chemical Treatment of Solid Acids These solid acids may be chemically treated to form strong Lewis acid points.
The chemical treatment includes various treatments such as an acid treatment with an acid, an alkali treatment with an alkali, and a salt treatment with an inorganic salt.
The chemical treatment may be performed alone, in combination, or simultaneously. Preferably, other chemical treatment may be performed after the acid treatment with an acid. The solid acid of the present invention is preferably chemically treated with an acid, more preferably an inorganic acid among the acids.
The chemical treatment of these solid acids can change the structure or skeleton of the solid acids themselves, strengthen the strength of Lewis acid sites, and become a highly active catalyst component. Therefore, by carrying out the above chemical treatment, a solid acid of the present invention having a predetermined amount or more of Lewis acid points having a specific acid strength or more can be prepared.

1-2-2. Organoaluminum Treatment As the solid acid used in the present invention, a certain solid may be treated with an organoaluminum compound to form a strong Lewis acid point.
Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethylamide, diisobutyl aluminum hydride, diisobutyl aluminum chloride and the like.
Of these, triethylaluminum, triisobutylaluminum, and trinormaloctylaluminum are preferable.

As a condition for the organic aluminum treatment, the temperature is preferably 0 to 100°C, and preferably 10 to 80°C. More preferably, it is 15-60 degreeC. The amount of organoaluminum used is preferably 500 to 5000 μmol, and particularly preferably 1000 to 3000 μmol, per 1 g of the solid. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons and halides thereof. Further, the organoaluminum treatment can be performed in multiple times.

After performing the above-mentioned organoaluminum treatment, the reaction product or unreacted product remains in the reaction solution, which may lead to a decrease in activity. The cleaning rate is preferably 1/5 to 1/1000, 1/10 to 1/100. After washing, the slurry may be used as it is or may be dried. The drying is preferably carried out so as not to cause structural destruction of the ion-exchange layered silicate, and the drying temperature is generally 100 to 400°C, preferably 100 to 200°C. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. The drying method is not particularly limited, and various methods can be used.

When the solid (including the solid acid) is treated with an organoaluminum in this manner, it reacts with a functional group on the solid to form a structure exhibiting strong Lewis acidity, or the organoaluminum itself is supported by the solid to form a strong Lewis acid. It is acidic and can be a highly active catalyst component. Therefore, by carrying out the above-mentioned organoaluminum treatment, a solid acid of the present invention having a specific acid strength or more and a predetermined amount or more of Lewis acid points can be prepared.

1-2-3. Ion-exchange layered silicate As the solid acid used in the present invention, an ion-exchange layered silicate is particularly preferable. The raw material for the ion-exchange layered silicate is not limited to a natural product, and may be an artificial synthetic product. Specific examples of the ion-exchange layered silicate include those listed in the following Table 1 described in "Clay Handbook" (Clay Handbook of Japan, Gihodo Publishing, 2009, 3rd edition). To be

These may form a mixed layer. In addition, since many ion-exchange layered silicates are naturally produced as the main components of clay minerals, they often contain impurities (such as quartz and cristobalite). May be included.
The ion-exchange layered silicate of the present invention is preferably a layered silicate having a 2:1 type layer structure. The smectite group silicate is more preferable, the dioctahedral smectite group silicate is more preferable, and the montmorillonite is particularly preferable.

The ion-exchange layered silicate exhibiting the characteristics of the present invention can also be prepared by subjecting the ion-exchange layered silicate to a chemical treatment.

In the chemical treatment of the ion-exchange layered silicate, the acid treatment of treating with an acid will be described in detail below.
When the ion-exchange layered silicate is treated with an acid, impurities on the surface are washed with an acid, interlayer ions are eluted and exchanged with hydrogen cations, and then the cations forming the octahedral sheet. Will be eluted. In the course of this elution, properties such as acid points and pore structure change.
Therefore, the ion-exchange layered silicate of the present invention can be achieved by treating with an acid. The degree of elution varies depending on the concentration of acid, the treatment time, and the type of acid, but ion-exchange layered silicates containing a large amount of magnesium are generally large, followed by those containing a large amount of iron and those containing a large amount of aluminum. In addition, the higher the crystallinity and the larger the particles, the lower the elution property. This is related to the penetration of acid into the crystal layers and into the crystal structure.

As conditions for the acid treatment, the temperature is preferably 40 to 102°C, and preferably 50 to 100°C. More preferably, it is 60 to 95°C. If the temperature is lowered too much, the elution rate of cations will be extremely lowered, and the production efficiency will be lowered. On the other hand, if the temperature is raised too high, the operational safety will decrease.
The acid concentration during the acid treatment (weight percentage of acid relative to the total weight of the reaction system) is preferably 3 to 30% by weight, preferably 5 to 25% by weight, and more preferably 7 to 20% by weight. When the concentration is low, the elution rate of cations is low and the production efficiency is low.
The concentration of the ion-exchange layered silicate in the solvent can be adjusted to 3 to 50% by weight. It is preferably 5 to 30% by weight, more preferably 5 to 20% by weight. When the concentration becomes low, large facilities are required for industrial production. On the other hand, when the concentration is high, the viscosity of the slurry increases, making uniform stirring and mixing difficult, and the production efficiency also decreases.

The acid treatment can be performed in multiple times.
Examples of the acid compound used include inorganic acids and organic acids such as hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, benzoic acid, stearic acid, propionic acid, fumaric acid, maleic acid and phthalic acid. Among them, inorganic acids are preferable, and hydrochloric acid, nitric acid and sulfuric acid are preferable. Hydrochloric acid and sulfuric acid are more preferable, and sulfuric acid is particularly preferable.
It is preferable to elute the metal cations forming the octahedral sheet by 10 to 65% of the content before the chemical treatment by chemical treatment, particularly acid treatment, more preferably 15 to 60%, and further preferably The elution is 17-55%, particularly preferably 20-50%. When the elution ratio is small, a sufficient amount of pores cannot be secured and the surface area becomes small, so that the ion-exchange layered silicate of the present invention cannot be obtained.
Here, the ratio (mol %) of the metal cations to be eluted is represented by the following formula when the metal cations are aluminum.
[Aluminum/silicon before chemical treatment (molar ratio)-aluminum/silicon after chemical treatment (molar ratio)]/aluminum/silicon before chemical treatment (molar ratio)×100

After the chemical treatment is performed, the reaction product or unreacted product may remain in the reaction solution, which may lead to a decrease in activity. At this time, a liquid such as water or an organic solvent is generally used.
The cleaning rate is preferably 1/5 to 1/1000, 1/10 to 1/100. After washing and dehydration, drying is performed. The drying is preferably carried out so as not to cause structural destruction of the ion-exchange layered silicate, and generally, the drying temperature can be carried out at 100 to 800°C, preferably 150 to 600°C, and particularly preferable. Is 150 to 300° C., and the drying temperature is preferably 800° C. or lower so that the structural destruction of the ion-exchange layered silicate does not occur.
Since the characteristics of these ion-exchange layered silicates change depending on the drying temperature even if the structure is not destroyed, it is preferable to change the drying temperature depending on the application. The drying time is usually 1 minute to 24 hours, preferably 5 minutes to 4 hours, and the atmosphere is preferably dry air, dry nitrogen, dry argon, or under reduced pressure. The drying method is not particularly limited, and various methods can be used.

Further, the ion-exchange layered silicate generally contains adsorbed water and intercalation water. In the present invention, these adsorbed water and interlayer water are preferably removed before use.
Heat treatment is usually used to remove water. The method is not particularly limited, but it is preferable to select conditions under which adhered water and interlayer water do not remain and structural destruction does not occur.
The heating time is 0.1 hours or longer, preferably 0.2 hours or longer. At that time, the water content after removal is 3% by weight or less, preferably 1% by weight or less, when the water content when dehydrated for 2 hours at a temperature of 200° C. and a pressure of 1 mmHg is 0% by weight. Is preferred.

The ion-exchange layered silicate of the present invention has a total pore volume of pores having a diameter of 2 to 10 nm calculated in the pore distribution curve calculated by the BJH analysis method using the adsorption isotherm by the nitrogen adsorption method. It is preferably 60 to 100% of the total mesopore volume. Here, the BJH analysis method is a calculation method according to the model of Barrett, Joyner and Halenda, and is described in Journal of American Chemical Society, 1951, 73, p. 373. The method disclosed in.

Here, the method for measuring the pore diameter and the pore volume by the nitrogen adsorption method will be described below.
In the case where the amount of gas adsorbed on a solid is constant, if the solid and gas are determined, the potential for adsorption interaction can be considered to be almost constant, so the amount of adsorption is a function of pressure only. Is generally called an adsorption isotherm.
In the present invention, nitrogen, which is most commonly used when evaluating the pore size distribution, is used as the adsorption gas, and the relative pressure P/P0 (P0 is the atmospheric pressure) under liquid nitrogen temperature (temperature 77K). The adsorption isotherm was measured at 0.025 to 0.995.
The adsorption isotherm obtained when the relative pressure is increased is used to calculate the pore volume within the range defined by the present invention. The BJH analysis method is the most general method for calculating the pore distribution, and this method is used in the present invention.
In the present invention, the mesopores mean pores having a diameter of 2 to 50 nm according to the definition of IUPAC. Using the pore distribution curve, the total pore volume of the pores having a diameter of 2 to 10 nm and the pores having a diameter of 2 to 50 nm was obtained.

The ion-exchange layered silicate of the present invention is the sum of the pore volumes of pores having a diameter of 2 to 10 nm in the pore distribution curve calculated by the BJH analysis method using the adsorption isotherm by the nitrogen adsorption method (cc/ g) is preferably 60 to 100% with respect to the total pore volume (total mesopore volume) (cc/g) of pores having a diameter of 2 to 50 nm, that is, mesopores, and It is preferably 61 to 95%, more preferably 62 to 90%, particularly preferably 63 to 87%, and most preferably 63 to 85%.

The activity is considered to decrease when the total pore volume of pores having a diameter of 2 to 10 nm is less than 60% of the total mesopore volume. On the other hand, when only fine pores are present in the particles, the number of contact points between the ion-exchange layered silicates is higher than when there are large pores to some extent, and thus high particle strength is obtained. become. For example, it is desirable that the ion-exchange layered silicate used as a catalyst for polyolefin polymerization decomposes with the formation of a polymer in the polymerization of an olefin so that the polymerization proceeds with high activity and is uniformly dispersed in the polymer. At high particle strength, the activity of the polymer is lowered because it is unlikely to cause disintegration, and the polymer is nonuniformly present, resulting in deterioration of the powder properties of the polymer and defects in the processing/molding process.
Therefore, it is most preferable that the total pore volume of the pores having a diameter of 2 to 10 nm is 85% or less of the total mesopore volume.

It is considered that the strong Lewis acid sites are present in the pores having a pore diameter of 2 to 10 nm, and that the pores are present at the end faces in the ion-exchange layered silicate. The fact that the ratio of the volume of pores having a pore size of 2 to 10 nm is large relative to the total mesopore volume suggests that the end face portion is treated more uniformly by the chemical treatment. Therefore, the ion-exchange layered silicate having such a structure has many strong Lewis acid points and can be a highly active catalyst component.
The ion-exchange layered silicate having such a strong Lewis acid point is formed by a chemical treatment accompanied by elution of metal atoms of the ion-exchange layered silicate. This elution of metal atoms can also be achieved by using a raw material that proceeds uniformly from each layer constituting the ion-exchange layered silicate. Therefore, the sum of the pore volumes of the pores of 2 to 10 nm has a specific ratio with respect to the total mesopore volume, so that a solid acid having a specific acid strength or more of a Lewis acid point of a predetermined amount or more. Can be prepared.

Although the method for producing the solid acid [A] exhibiting the characteristics of the present invention has been described above, the method of producing the characteristics of the present invention is not limited to the above, and can be manufactured.

2. Olefin Polymerization Catalyst The olefin polymerization catalyst used in the present invention comprises the above solid acid [A] and component [B]. Each constituent is described in detail below.
2-1. Transition metal compound [B]
The component [B] used in the present invention is a transition metal compound of Groups 3 to 12 of the periodic table. Specifically, Group 3-10 transition metal halides, Group 3-6 transition metal metallocene compounds, Group 4 transition metal bisamides or bisalkoxide compounds, Group 8-10 transition metal bisimide compounds, Examples include phenoxyimine compounds of Group 3 to 11 transition metals.

Among these, metallocene compounds of Group 4 transition metals are preferable, and specifically, compounds represented by the following general formulas (I) to (VI) are used.

^{_{(C 5 H 5-a R}} 1 a) (C 5 H 5-b R 2 b) MXY ··· (I)
^{_{Q (C 5 H 4-c}} R 1 c) (C 5 H 4-d R 2 d) MXY ··· (II)
^{_{Q '(C 5 H 4-}} e R 3 e) ZMXY ··· (III)
^{_{(C 5 H 5-f R}} 3 f) ZMXY ··· (IV)
^{_{(C 5 H 5-f R}} 3 f) MXYW ··· (V)
^{_{Q "(C 5 H 5-}} g R 4 g) (C 5 H 5-h R 5 h) MXY ··· (VI)

Here, Q is a bonding group that bridges two conjugated five-membered ring ligands, Q'is a bonding group that bridges the conjugated five-membered ring ligand and a Z group, and Q″ is R ⁴ and R. ⁵ , M is a transition metal of Group 3 to 12 of the periodic table, X, Y, and W are each independently hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, and 1 carbon atom. To an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, Z is oxygen, A ligand containing sulfur, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms is shown.

R ^{1 to} R ⁵ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an aryloxy group, a silicon-containing hydrocarbon group, phosphorus. A hydrocarbon group containing, a hydrocarbon group containing nitrogen, or a hydrocarbon group containing boron is shown. In addition, two adjacent R ¹ , two R ² , two R ³ , two R ⁴ , or two R ⁵ are respectively bonded to form a ring having 4 to 10 carbon atoms. You may have. a, b, c, d, e, f, g, and h are 0≦a≦5, 0≦b≦5, 0≦c≦4, 0≦d≦4, 0≦e≦4, 0, respectively. It is an integer satisfying ≦f≦5, 0≦g≦5, and 0≦h≦5.

A bonding group Q that bridges between two conjugated five-membered ring ligands, a bonding group Q′ that bridges a conjugated five-membered ring ligand and a Z group, and bridges R ⁴ and R ⁵ . Specific examples of Q″ include the following: alkylene groups such as methylene group and ethylene group, ethylidene group, propylidene group, isopropylidene group, phenylmethylidene group and diphenylmethylidene group. Silicon such as alkylidene group, dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisilylene group Examples of the crosslinking group include a crosslinking group containing germanium, a crosslinking group containing germanium, an alkylphosphine, an amine, etc. Among them, an alkylene group, an alkylidene group, a crosslinking group containing silicon, and a crosslinking group containing germanium are particularly preferably used.

Specific Zr complexes represented by the above general formulas (I), (II), (III), (IV), (V) and (VI) are exemplified below, but Zr is replaced with Hf or Ti. Other compounds can be used as well. Further, the components [B] represented by the general formulas (I), (II), (III), (IV), (V) and (VI) are compounds represented by the same general formula or different general formulas. It can be used as a mixture of two or more kinds of the compounds shown.

General formula (I)
Biscyclopentadienyl zirconium dichloride, bis(2-methylindenyl)zirconium dichloride, bis(2-methyl-4,5-benzoindenyl)zirconium dichloride, bisfluorenylzirconium dichloride, bis(4H-azurenyl)zirconium dichloride , Bis(2-methyl-4H-azurenyl)zirconium dichloride, bis(2-methyl-4-phenyl-4H-azurenyl)zirconium dichloride, bis(2-methyl-4-(4-chlorophenyl)-4H-azurenyl)zirconium Dichloride.

General formula (II)
Dimethyl silylene bis(1,1'-cyclopentadienyl)zirconium dichloride, dimethyl silylene bis{1,1'-(2-methylindenyl)}zirconium dichloride, dimethyl silylene bis{1,1'-(2-methyl Indenyl)} zirconium dichloride, ethylene bis{1,1′-(2-methyl-4,5-benzoindenyl)} zirconium dichloride, dimethylsilylene bis{1,1′-(2-methyl-4-hydroazulenyl)} Zirconium dichloride, dimethylsilylene bis{1,1'-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride, dimethylsilylene bis[1,1'-{2-methyl-4-(4-chlorophenyl) -4-Hydroazurenyl}]zirconium dichloride, dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-4-hydroazurenyl)}zirconium dichloride, ethylenebis{1,1′-(2-methyl-4-) Hydroazulenyl)} zirconium dichloride.

General formula (III)
(Tertiary butyl amide)(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyl-zirconium dichloride, (methylamido)-(tetramethyl-η5-cyclopentadienyl)-1,2-ethanediyl-zirconium Dichloride, (Ethylamide)(tetramethyl-η5-cyclopentadienyl)-methylenezirconium dichloride, (tertiary butylamide) dimethyl-(tetramethyl-η5-cyclopentadienyl)silane zirconium dichloride, (tertiary butylamide) Dimethyl(tetramethyl-η5-cyclopentadienyl)silane zirconium dibenzyl, (benzylamido)dimethyl(tetramethyl-η5-cyclopentadienyl)silane zirconium dichloride, (phenylphosphide)dimethyl(tetramethyl-η5- Cyclopentadienyl)silane zirconium dibenzyl.

General formula (IV)
(Cyclopentadienyl)(phenoxy)zirconium dichloride, (2,3-dimethylcyclopentadienyl)(phenoxy)zirconium dichloride, (pentamethylcyclopentadienyl)(phenoxy)zirconium dichloride, (cyclopentadienyl)( 2,6-di-t-butylphenoxy)zirconium dichloride, (pentamethylcyclopentadienyl)(2,6-di-i-propylphenoxy)zirconium dichloride.

General formula (V)
(Cyclopentadienyl) zirconium trichloride, (2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) zirconium triisopropoxide, ( Pentamethylcyclopentadienyl) zirconium triisopropoxide.

General formula (VI)
Ethylene bis(7,7'-indenyl)zirconium dichloride, dimethylsilylene bis{7,7'-(1-methyl-3-phenylindenyl)}zirconium dichloride, dimethylsilylene bis[7,7'-{1-methyl -4-(1-Naphthyl)indenyl}]zirconium dichloride, dimethylsilylene bis{7,7′-(1-ethyl-3-phenylindenyl)}zirconium dichloride, dimethylsilylene bis{7,7′-(1- Isopropyl-3-(4-chlorophenyl)indenyl)}zirconium dichloride.

Further, as a specific example of the metallocene compound, JP-A-7-188335 and Journal of American Chemical Society, 1996, 118, p. 2291. It is also possible to use a transition metal compound having a ligand containing at least one element other than carbon in the 5-membered ring or the 6-membered ring disclosed in US Pat.

Suitable examples of the bisamide compound of Group 4 of the periodic table include Macromolecules, 1996, Vol. 29, p. 5241. And Journal of American Chemical Society, 1997, 119, p. 3830, Journal of American Chemical Society, 1999, 121 volumes, p. 5798. The cross-linked transition metal compound having a bulky substituent on the nitrogen atom disclosed in US Pat.

Further, as preferable examples of the bisalkoxide compound of Group 4 of the periodic table, transition metal compounds of Group 4 of the periodic table disclosed in WO 87/02370, preferably two aryloxy ligands are used. A cross-linking type transition metal compound which is bonded by a cross-linking group and more preferably the cross-linking group can coordinate to a transition metal can be mentioned.

Further, bisimide compounds of transition metals of Groups 8 to 10 of the periodic table are described in Journal of American Chemical Society, 1995, 117, p. 6414, WO 96/23010 and Journal of American Chemical Society, 1998, 120 volumes, p. Preferred examples thereof include a bridged transition metal bisimide compound having a bulky substituent at the nitrogen atom disclosed in 4049 and WO 98/27124.

In addition, as a preferable example of the phenoxyimine compound of a transition metal of Group 3 to 10 of the periodic table, a compound disclosed in JP-A No. 11-315109 can be mentioned.

Further, these components [B] can be used as a mixture of two or more kinds. Further, a plurality of kinds may be used in combination with the metallocene compound of Group 3 to 12 of the periodic table described above.

2-2. Olefin [C]
The olefin polymerization catalyst used in the present invention contains the above solid acid [A] and component [B], but the olefin [C] may be contacted by any method as necessary.
The olefin refers to a hydrocarbon containing at least one carbon-carbon double bond, and is exemplified by ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, etc. There is no limitation, and mixtures of these with other olefins may be used. An olefin having 3 or more carbon atoms is preferable.

2-3. Organoaluminum compound [D]
The olefin polymerization catalyst used in the present invention is composed of the above-mentioned components [A] and [B]. However, the organoaluminum compound [D] is used as an optional component within a range not impairing the effects of the present invention. You may contact by the method.
The component [D], the general formula organoaluminum compound represented by _{(AlR n X 3-n)} m is used. In the formula, R represents an alkyl group having 1 to 20 carbon atoms, X represents a halogen, hydrogen, an alkoxy group or an amino group, n represents an integer of 1 to 3 and m represents an integer of 1 to 2, respectively. The organoaluminum compounds can be used alone or in combination of two or more.

Specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, trinormalhexylaluminum, trinormaloctylaluminum, trinormaldecylaluminum, diethylaluminum chloride, diethylaluminum. Examples thereof include sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethylamide, diisobutyl aluminum hydride, diisobutyl aluminum chloride and the like. Of these, trialkyl aluminum and alkyl aluminum hydride with m=1 and n=3 are preferable. More preferably, R is trialkylaluminum having 1 to 8 carbon atoms.

2-4. Method for Preparing Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention contains the above solid acid [A], a transition metal compound [B] and, if necessary, an organoaluminum compound [D], and these are in a polymerization tank. Alternatively, the prepolymerization may be carried out in the presence of the olefin [C] by contacting the same with or outside the polymerization tank.

The amounts of the solid acid [A], the component [B], and the component [D] used are arbitrary, but the ratio of the transition metal in the component [B] to the aluminum in the component [D] is equal to that of the component [A]. It is preferable that the contact is performed at 0.1 to 1000 (μmol): 0 to 100000 (μmol) per 1 g.

The solid acid [A], the component [B], and the component [D] may be contacted in any order. Of these, two components may be contacted with each other and then the remaining one component may be contacted with each other, or three components may be contacted with each other. The components may be contacted simultaneously. A solvent may be used in order to make sufficient contact in these contacts. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons and their halides, and prepolymerized monomers.

The catalyst may be dried after the prepolymerization. The drying method is not particularly limited, and examples thereof include reduced pressure drying, heat drying, and drying by circulating a dry gas. These methods may be used alone or in combination of two or more. Good. In the drying step, the catalyst may be stirred, vibrated, fluidized or allowed to stand.

3. Olefin Polymerization Polymerization carried out using an olefin polymerization catalyst comprising the above solid acid [A], component [B], and optionally component [C] is carried out by mixing the olefin alone or with the other comonomer. It is performed by bringing them into contact. In the case of copolymerization, the amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio. It is also possible to change it. Further, one of the monomers may be added in divided portions in consideration of the copolymerization reaction ratio.

The polymerizable olefin preferably has about 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl-1,7. -Octadiene, cyclopentene, norbornene, ethylidene norbornene and the like. Preferred is an α-olefin having 2 to 8 carbon atoms. In the case of copolymerization, the type of comonomer used may be an olefin other than the main component selected from the above-mentioned olefins.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer are efficiently contacted with each other. Specifically, a slurry method using an inert solvent, a method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method or a gas phase in which each monomer is kept in a gaseous state without substantially using a liquid solvent. The law etc. can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or preliminary polymerization is also applied.

In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture as a polymerization solvent. The polymerization temperature is 0 to 150° C., and hydrogen can be supplementarily used as a molecular weight regulator. The polymerization pressure is 0 to 2000 kg/cm ² G, preferably 0 to 60 kg/cm ² G.

Next, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples without departing from the gist thereof.
The analytical instruments and measuring methods used for measuring the physical properties are as follows.

(1) Measurement of acid amount (pyridine-TPD-IR/MS):
<Thermal Desorption-Mass Spectrometry (TPD-MS)>
100 mg of the solid acid was weighed in a high-purity nitrogen glove box and filled in a cell. Then, the cell was taken out from the high-purity nitrogen glove box and installed in the TPD-MS measuring device. After depressurizing the inside of the cell to 5×10 ⁻² torr abs, the temperature was raised to 200° C. and kept for 1 hour to remove adsorbed water. The temperature was lowered to 150° C. under reduced pressure, pyridine vapor was introduced, and the mixture was kept for 1 hour to be adsorbed on the solid acid. The pressure was further reduced to 5×10 ⁻² torr abs at 150° C., and vacuum treatment was performed for 1 hour to remove the physically adsorbed pyridine. Then, the temperature was raised, the desorption behavior of pyridine was measured, and the acid amount and acid strength distribution were determined.
The measurement conditions are as follows.
Device: Nippon Bell Co., Ltd. Fully automatic thermal desorption spectroscopy device TPD-1-ATw
Measurement mode:
Temperature rising rate 10°C/min
Measurement temperature 150-810℃
Atmosphere: Helium flow (50 ml/min)
Capture MASS No. : 79
Adsorption species: pyridine

<Infrared spectroscopy (IR)>
The solid acid was filled in a sample cup for diffuse reflection IR in a high-purity nitrogen glove box, and the surface was abraded. The sample chamber was sealed with a lid equipped with a window material (CaF ₂ ). Then, the sample cup was taken out from the high-purity nitrogen glove box and placed in an IR measuring device. After depressurizing the sample chamber to 5×10 ⁻² torr abs, the temperature was raised to 200° C. and kept for 2 hours to remove the adsorbed water. The temperature was lowered to 150° C. under reduced pressure, and pyridine vapor was passed for 10 minutes under helium flow (50 ml/min) to adsorb it onto the solid acid. The pressure was further reduced to 5×10 ⁻² torr abs at 150° C., and vacuum treatment was performed for 1 hour to remove the physically adsorbed pyridine. Then, the temperature was raised to remove pyridine, and the ratio of the B acid point and the L acid point at each temperature was determined.
The measurement conditions are as follows.
Device: JASCO Corporation FT/IR-6200FV
Detector: MCT-M
Photometric method: Diffuse reflection method Wavelength range: 1000 to 4000 cm ^-1
Resolution: 4 times Number of measurements: 512 times Window material: CaF ₂
Atmosphere: Vacuum Background: Diamond powder measured at each temperature Adsorbed species: Pyridine Temperature: Every 50° C., until no peak is detected Molar extinction coefficient (ε): 1.73 (1450 cm ⁻¹ ),
1.46 (1490 cm ⁻¹ ),
1.23 (1545 cm ^-1 )

<Combination of TPD-MS and IR>
Considering the deviation of the measured temperatures of TPD-MS and IR, the analysis was performed assuming that the removal rates of the pyridines were the same and the temperatures were the same. The analysis temperature was unified with the temperature of TPD-MS. The total acid amount of TPD-MS was assigned to the L acid amount and the B acid amount based on the ratio determined by IR. By this method, the amount of strong Lewis acid that pyridine adsorbed at 500° C. or higher was calculated.

(2) Measurement of acid amount (titration using Hammett indicator (Hamett titration)):
2,6-Dimethylpyridine was used as a titration reagent with an acid amount of pKa of -8.2 or less, and anthraquinone was used as an indicator. The measurement was performed at 10°C. 20 mL of toluene was added to 0.40 g of a sample in an Erlenmeyer flask purged with nitrogen to form a slurry, and 2.0 mL of a 0.1 wt% toluene solution of anthraquinone as an indicator was added to change the color to yellow. 2,6-Dimethylpyridine (toluene solution, 0.01M) was added dropwise to this flask at a rate of 0.5 to 5 micromoles per minute per 1 g until the yellow color which was the acidic color of the indicator disappeared. The amount of 2,6-dimethylpyridine added was defined as the amount of acid points having a pKa of -8.2 or less.

(3) Pore distribution measurement:
The pore distribution was measured by the nitrogen adsorption method. The adsorption isotherm was measured under liquid nitrogen temperature. Using the obtained adsorption isotherm, the sum of the pore volume and the mesopore distribution of pores having a diameter of 2 to 10 nm were obtained by BJH method analysis.
Device: Cantorchrome's Autosorb 3B
Measuring method: Nitrogen gas adsorption method Pretreatment condition: Sample heated at 200° C. under vacuum (1.3 MPa or less) for 2 hours under reduced pressure Sample amount: about 0.2 g
Gas liquefaction temperature: 77K

(4) Composition analysis of solid acid:
A calibration curve was prepared by chemical analysis according to the JIS method and quantified by fluorescent X-ray measurement.
The apparatus used was Rigaku Denki Kogyo Co., Ltd. ZSX-100e. The sample should be fired at 700° C. for 1 hour, then 0.5 g is divided and mixed with a flux (Li ₂ B ₄ O ₇ ) 4.5 g and a release agent (KBr) 0.03 g to prepare a glass bead. It was prepared in. The calibration curve range for each atom is as follows.
Si: 19.8 to 44.22%, Al: 2.01 to 19.4%.

(5) MFR (melt mass flow rate):
Using Takara's melt indexer, JIS K7210 "Plastics-Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics": 230°C, 2.16kg load And measured.

[Example 1]
1. Granulated montmorillonite As the ion-exchange layered silicate, "Ben clay KK" (main component is a smectite group montmorillonite having a 2:1 type layer structure) manufactured by Mizusawa Chemical Industry Co., Ltd., which is a granulated product of montmorillonite, was used. This granulated montmorillonite had an average particle size of 12.9 μm, a chemical composition (wt %):Al=9.57, Si=32.26, and a molar ratio of Al/Si=0.31. The main metal cation composing the octahedral sheet was aluminum.

2. Chemical Treatment 170 g of distilled water was put into a 0.3 L flask equipped with a stirring blade and a reflux device, and 50 g of sulfuric acid was added dropwise. The mixture was heated in an oil bath until the internal temperature reached 90° C., and when the target temperature was reached, 30 g of the granulated montmorillonite obtained above was further added and stirred.
Then, the mixture was reacted for 150 minutes while maintaining 90°C. The reaction was stopped by pouring the reaction solution into 0.3 L of distilled water, and the slurry was filtered by a device in which a nutator and an aspirator were connected to a suction bottle, and then washed with 0.7 L of distilled water three times. Then, 70 g of a cake-like solid was obtained. The obtained solid was pre-dried under a nitrogen stream at 100° C. for a whole day and night, coarse particles of 53 μm or larger were removed, and further dried under reduced pressure at 200° C. for 2 hours to obtain 19.5 g of chemically treated montmorillonite.
The composition (wt%) of the montmorillonite after the chemical treatment was Al=8.14 and Si=36.38, and the molar ratio was Al/Si=0.23. Al after sulfuric acid treatment was reduced by 25% (eluted) with respect to Al before sulfuric acid treatment. The pore volume PV _{2 to} 10 nm of the pores having a diameter of 2 to 10 nm is 0.209 cc/g, the mesopore volume PV is 0.339 cc/g, and the pore volume PV ₂ of the pores having a diameter of 2 to 10 nm is PV _{2. -10 nm} was 62% of the total mesopore volume PV.
The amount of acid having a pKa of -8.2 or less by the Hammett titration of the obtained chemically treated montmorillonite was 120 μmol per gram, and the amount of strong Lewis acid adsorbed by pyridine at 500° C. or higher was 8.6 μmol per gram. ..
FIG. 1 shows the measurement results of pyridine-TPD-IR/MS for determining the strength and amount of Lewis acid points.

3. Organoaluminum treatment After sufficiently replacing a 1 L flask with nitrogen, 10 g of the chemically treated montmorillonite obtained above was put, and heptane (66 mL) was added to make a slurry. Triisobutylaluminum (25 mmol: 34.0 mL of a heptane solution having a concentration of 143 mg/mL) was added thereto, and the mixture was stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100. Furthermore, organic aluminum-treated montmorillonite was obtained by drying under reduced pressure at 200° C. for 2 hours.
The amount of strong Lewis acid that pyridine of the obtained organoaluminum-treated montmorillonite adsorbed at 500° C. or higher was 63 μmol per gram. FIG. 2 shows the measurement results of pyridine-TPD-IR/MS for determining the strength and amount of Lewis acid points.

4. Preparation of catalyst After sufficiently replacing a 50 mL flask with nitrogen, 600 mg of the organoaluminum-treated montmorillonite obtained above was added, and heptane (10 mL) was added to form a slurry. Triisobutylaluminum (0.25 mmol: 0.34 mL of a heptane solution having a concentration of 143 mg/mL) was added thereto, and the mixture was further prepared in another 50 ml flask (r)-[1,1′-dimethylsilylenebis{2. -Methyl-4-(4-chlorophenyl)-4H-azurenyl}]zirconium dichloride (synthesis was carried out according to the example of JP-A-10-226712) 25 mg (35 μmol) of a toluene solution (11.6 mL). In addition, it stirred for 30 minutes at room temperature and prepared.

5. Propylene Polymerization After sufficiently replacing the inside of a stirring autoclave with an internal volume of 3 L with propylene, 2.8 ml (2.02 mmol) of a heptane solution of triisobutylaluminum was added, 750 g of liquid propylene was introduced, and the temperature was raised to 70°C. The temperature was maintained. 150 mg of the above-prepared catalyst heptane slurry was injected under pressure to initiate polymerization. Polymerization was continued for 1 hour while maintaining the internal temperature at 70°C. Then, 5 ml of ethanol was added to stop the polymerization reaction. The residual gas was purged to obtain a polymer. The obtained polymer was dried at 90° C. for 1 hour.
As a result, 400 g of polymer was obtained. The catalytic activity was 2,700 g-PP/g-catalyst/hr. The MFR was 2.5 g/10 minutes. The results are shown in Table 2.

[Example 2]
The same method as in Example 1 was repeated except that the chemical treatment time was 300 minutes.
The composition (wt%) of the chemically treated montmorillonite after the chemical treatment was Al=5.85 and Si=38.9, and the molar ratio was Al/Si=0.16. Al after the sulfuric acid treatment was reduced by 51% (eluted) with respect to Al before the sulfuric acid treatment. The pore volume PV2 to 10 nm of pores with a diameter of 2 to 10 nm is 0.32 cc/g, the mesopore volume PV is 0.49 cc/g, and the pore volume PV2 to 10 nm of pores with a diameter of 2 to 10 nm. Was 65% of the total mesopore volume PV. According to the Hammett measurement of the obtained chemically treated montmorillonite, the amount of acid having a pKa of −8.2 or less was 210 μmol per gram, and the amount of strong Lewis acid adsorbed by pyridine at 500° C. or higher was 7.3 μmol per gram. ..
The strong Lewis acid amount adsorbed by pyridine of the organoaluminum-treated montmorillonite obtained by the organoaluminum treatment at 500° C. or higher was 47 μmol per gram.
As a result, 310 g of polymer was obtained. The catalytic activity was 2070 g-PP/g-catalyst/hr. The MFR was 2.5 g/10 minutes. The results are shown in Table 2.

[Comparative Example 1]
In Example 1, it carried out by the same method except not performing "3. organoaluminum treatment."
As a result, 28 g of polymer was obtained. The catalytic activity was 200 g-PP/g-catalyst/hr. The MFR was 2.3/10 minutes. The results are shown in Table 3.

[Comparative Example 2]
Using the chemically treated montmorillonite that has been subjected to the same treatment as "(5-1) Chemical treatment of ion-exchange layered silicate of Example 5" of JP-A-2002-053609, "3. Organic of Example 1" is used. Aluminum treatment" and "5. Propylene polymerization" were performed. However, "Ben clay SL" manufactured by Mizusawa Chemical Co., Ltd. (main component is smectite group montmorillonite having a 2:1 type layer structure) has the following composition. The average particle size was 17.7 μm, the chemical composition (wt %): Al=8.87, Si=33.66, and the molar ratio was Al/Si=0.27. The main metal cation composing the octahedral sheet was aluminum.

The composition (wt %) of the chemically treated montmorillonite after the chemical treatment was Al=6.64 and Si=36.78, and the molar ratio was Al/Si=0.19. Al after sulfuric acid treatment was reduced by 37% (eluted) with respect to Al before sulfuric acid treatment. The pore volume PV _{2 to} 10 nm of pores having a diameter of 2 to 10 nm is 0.18 cc/g, the mesopore volume PV is 0.38 cc/g, and the pore volume PV ₂ of pores having a diameter of 2 to 10 nm is PV _{2. -10 nm} was 48% of the total mesopore volume PV. The amount of acid having a pKa of -8.2 or less by the Hammett titration of the obtained chemically treated montmorillonite was 110 μmol per gram, and the amount of strong Lewis acid adsorbed by pyridine at 500° C. or higher was 3.2 μmol per gram. ..
The strong Lewis acid amount adsorbed by pyridine of organoaluminum-treated montmorillonite obtained by the organoaluminum treatment at 500° C. or higher was 38 μmol per gram.
As a result, 217 g of polymer was obtained. The catalytic activity was 1,400 g-PP/g-catalyst/hr. The MFR was 2.5 g/10 minutes. The results are shown in Table 3.

[Comparative Example 3]
The same method as in Comparative Example 2 was performed except that "3. Organoaluminum treatment" was not performed.
As a result, 15 g of polymer was obtained. The catalyst activity was 100 g-PP/g-catalyst/hr. The MFR was 2.4 g/10 minutes. The results are shown in Table 3.

[Comparative Example 4]
In Example 2, the same method was used except that "Kunipia F" manufactured by Kunimine Industries Co., Ltd. was used as the granulated montmorillonite. "Kunipia F" manufactured by Kunimine Industries Co., Ltd. (the main component is a smectite group montmorillonite having a 2:1 type layer structure) has the following composition. The average particle size was 70.5 μm, the chemical composition (wt %): Al=12.2, Si=30.9, and the molar ratio was Al/Si=0.41. The main metal cation composing the octahedral sheet was aluminum.

The composition (wt %) of the chemically treated montmorillonite after the chemical treatment was Al=10.4 and Si=34.8, and the molar ratio was Al/Si=0.31. Al after sulfuric acid treatment was reduced by 24% (eluted) with respect to Al before sulfuric acid treatment. The pore volume PV2 to 10 nm of pores having a diameter of 2 to 10 nm is 0.16 cc/g, the mesopore volume PV is 0.29 cc/g, and the pore volume PV2 to 10 nm of pores having a diameter of 2 to 10 nm. Was 55% of the total mesopore volume PV. According to the Hammett measurement of the obtained chemically treated montmorillonite, the amount of acid having a pKa of −8.2 or less was 160 μmol per gram, and the amount of strong Lewis acid adsorbed by pyridine at 500° C. or higher was 6.5 μmol per gram. ..
The amount of strong Lewis acid adsorbed by pyridine of the organoaluminum-treated montmorillonite obtained by the organoaluminum treatment at 500° C. or higher was 17 μmol per gram.
As a result, 147 g of a polymer was obtained. The catalytic activity was 980 g-PP/g-catalyst/hr. The MFR was 2.3 g/10 minutes. The results are shown in Table 3.

[Comparative Example 5]
In Comparative Example 4, the same method was used except that "3. Organoaluminum treatment" was not performed. As a result, a polymer could not be obtained.

As is clear from Tables 2 and 3, when Examples 1 and 2 and Comparative Examples 1 to 5 are compared and examined, the solid acid of the present invention has high catalytic activity and is an excellent solid acid.
Specifically, by comparing Examples 1 and 2 with Comparative Examples 1, 3, and 5, the organoaluminum treatment increased the amount of strong Lewis acid adsorbed by pyridine at 500° C. or higher, and the polymerization activity was improved. I understand that That is, in Example 1, the strong Lewis acid amount adsorbing pyridine at 500° C. or higher was 63 μmol/g, and in Example 2, 47 μmol/g, whereas in Comparative Example 1, 8.6 μmol/g, In Example 3, it was 3.2 μmol/g, and in Comparative Example 5, it was 6.5 mol/g, showing a correlation between the amount of Lewis acid and the polymerization activity.
In addition, by comparing Example 1 with Comparative Examples 2 and 4, the chemically treated montmorillonite has an acid amount of pKa of -8.2 or less that is equal to or greater than that of the montmorillonite. The amount of strong Lewis acid adsorbed at 500° C. or higher is higher in Example 1, and it is understood that the catalytic activity is improved depending on the amount.
Therefore, as in the present example, the larger the amount of the strong Lewis acid that pyridine in the solid acid is adsorbed at 500° C. or higher, the higher the catalytic activity is, and the excellent result is obtained as compared with the comparative example. Can be said to be.

By using the olefin polymerization catalyst component consisting of the specific solid acid of the present invention, and the olefin polymerization catalyst using the same, the polymerization proceeds with high activity, which enables efficient production of polyolefin. , Industrially, high availability.

Claims (10)

The total pore volume of pores having a diameter of 2 to 10 nm calculated in the pore distribution curve calculated by the BJH analysis method using the adsorption isotherm by the nitrogen adsorption method is 60 to 100% of the total mesopore volume. There obtained is treated with an organic aluminum compound, ion-exchange layered silicate, characterized in that it comprises an amount of Lewis acid to adsorb pyridine at 500 ° C. or higher ion-exchange layered silicate 1g per 45μmol more .. The desorption ratio of aluminum which is a main metal cation of the octahedral sheet constituting the ion-exchange layered silicate by the inorganic acid treatment or the organic acid treatment is 10 to 65 mol%. 1. The ion-exchange layered silicate according to 1. The ion-exchange layered silicate is 2: Ion-exchange layered silicate according to claim 1 or 2, characterized by having a structure of one layer. The 2: Ion-exchange layered silicate of claim 3, ion-exchange layered silicate is characterized in that it is a smectite group silicate having the structure of one layer. The ion-exchange layered silicate according to claim 4 , wherein the smectite group silicate is a dioctahedral smectite group silicate. The ion-exchange layered silicate according to claim 5 , wherein the dioctahedral smectite group silicate is montmorillonite. The method for producing an ion-exchange layered silicate according to any one of claims 1 to 7 , which is obtained by chemical treatment. Claim 1 for olefin polymerization catalyst comprising the ion-exchange layered silicate and components according to any one of 6 [B].
Component [B]: Transition metal compound of Groups 3 to 12 of the periodic table A method for producing an olefin polymerization catalyst, which comprises bringing the ion-exchange layered silicate according to any one of claims 1 to 6 and the component [B] into contact with an olefin [C].
Component [B]: Transition metal compound of Groups 3 to 12 of the periodic table
A method for producing an olefin polymer, characterized in that an olefin is homopolymerized or copolymerized using the olefin polymerization catalyst according to claim 8 or the olefin polymerization catalyst obtained by the production method according to claim 9 .

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