JP6136852B2 - Olefin polymerization catalyst component, catalyst component production method, olefin polymerization catalyst and olefin (co) polymer production method using the same - Google Patents

Description

  The present invention relates to a catalyst component for olefin polymerization, a method for producing the catalyst component, a catalyst for olefin polymerization, and a method for producing an olefin (co) polymer using the catalyst, and more specifically, an ion having a specific structure. The present invention relates to a catalyst component for olefin polymerization comprising an exchangeable layered silicate, a method for producing the catalyst component, a catalyst for olefin polymerization, and a method for producing an olefin (co) polymer using the catalyst.

  Olefin polymerization catalysts using clay, clay minerals or ion-exchange layered compounds as catalyst components are known (see, for example, Patent Documents 1 to 3). Further, in the technical field of olefin polymerization catalysts using clay, clay minerals or ion-exchange layered compounds as catalyst components, improvement of catalytic activity is an issue, and various means for solving them have been proposed (for example, Patent Documents 4 to 4). 6). For example, an olefin polymerization catalyst containing, as a catalyst component, clay, clay mineral, or ion-exchanged layered compound that has been subjected to acid treatment, salt treatment, or chemical treatment in the coexistence of acid and salt is also known.

  In addition, regarding the chemical composition of the ion-exchange layered silicate, a technique relating to the amount of desorption of metal mainly present in the octahedral layer and the pore structure has also been reported (for example, see Patent Documents 7 and 8). .) This technique focuses on improving the diffusion of substances and increasing the amount of acid by having large pores. However, the activity was not satisfactory.

On the other hand, another technique related to the chemical composition of the ion-exchange layered silicate is to improve the physical properties of the resulting olefin polymer. As a means for solving this problem, the molar ratio of aluminum atoms to magnesium atoms is low. From the idea that it is related to the formation of sex components, a technique is known in which the amount of aluminum atoms contained is defined relative to the amount of magnesium atoms (see Patent Document 9). However, this technology does not have the idea of increasing the active point.
As described above, in the conventional technology, the activity of the catalyst component for olefin polymerization is not yet sufficient, and further technical improvement is desired.

Japanese Patent Laid-Open No. 5-301917 JP 2000-103807 A JP 2000-103808 A JP-A-7-228621 JP-A-8-127613 JP 2001-31720 A JP 2001-163909 A JP 2002-53609 A JP 2001-354715 A

  An object of the present invention is to provide a highly active olefin polymerization catalyst component, an olefin polymerization catalyst, and a method for producing an olefin (co) polymer using the same, in view of the situation and problems of the prior art.

Regarding the chemical composition and structure of the ion-exchange layered silicate and the performance as a catalyst component for olefin polymerization, there are still many unclear points, and in order to obtain a more highly active catalyst component for polymerization, There was room for study regarding the chemical composition and structure of the salt.
Therefore, in order to achieve the above-mentioned object, the present inventors have made the metallocene transition metal compound stably present as active sites, and in order to increase the number of active sites, the ion-exchange layered silicate has As a result of diligent research on whether such a physical and chemical structure is necessary, the use of an ion-exchange layered silicate having a specific chemical composition and structure as a catalyst component for olefin polymerization enables catalytic activity. Has been found to be significantly improved. More specifically, the present inventors have found that the catalytic activity is remarkably improved by using an ion-exchange layered silicate having a specific isomorphous substitution rate as a catalyst component for olefin polymerization. The present invention has been completed based on these findings.

That is, according to the first invention of the present invention, there is provided an olefin polymerization catalyst component comprising an ion-exchange layered silicate having the following property 1.
According to a second aspect of the present invention, there is provided the catalyst component for olefin polymerization according to the first aspect, wherein the ion-exchange layered silicate further has the following characteristic 2. .
Characteristic 1: The isomorphous substitution rate is 22% or more.
Characteristic 2: The specific surface area is 150 m ² / g or more.

According to a third aspect of the present invention, there is provided the catalyst component for olefin polymerization according to the first or second aspect, wherein the ion-exchange layered silicate further has the following characteristic 3. .
Characteristic 3: The isomorphous substitution rate of the octahedral sheet constituting the ion-exchangeable layered silicate is 22% or more.
According to a fourth aspect of the present invention, there is provided the catalyst component for olefin polymerization according to any one of the first to third aspects, wherein the ion exchange layered silicate is montmorillonite.
Furthermore, according to a fifth invention of the present invention, in any one of the first to fourth inventions, the ion-exchange layered silicate contains a molar ratio (Mg / Al) of contained aluminum atoms to magnesium atoms. Is a catalyst component for olefin polymerization, characterized in that it is 0.28 to 3.5.

According to a sixth invention of the present invention, in any one of the first to fifth inventions, the ion-exchange layered silicate is acid-treated with an inorganic acid or an organic acid, and the acid treatment Provides an olefin polymerization catalyst component characterized in that 10 to 65 mol% of aluminum in the octahedral sheet constituting the ion-exchangeable layered silicate is eliminated .

According to a seventh invention of the present invention, there is provided a method for producing a catalyst component for olefin polymerization according to any one of the first to sixth inventions,
The aluminum of the octahedral sheet of ion-exchange layered silicate having a specific surface area of 0.1 to 140 m ² / g and a molar ratio of aluminum to magnesium (Mg / Al) of 0.285 to 3.5 is 10 to 10. There is provided a process for producing a catalyst component for olefin polymerization, which comprises a treatment step for desorption of 65 mol%.

According to an eighth aspect of the present invention, there is provided an olefin polymerization catalyst comprising the following component (a), component (b) and, if necessary, component (c).
Component (a): Metallocene compound of Group 4 transition metal of the periodic table Component (b): Catalyst component for olefin polymerization according to any one of inventions 1 to 6 Component (c): Organoaluminum compound

Moreover, according to the ninth invention of the present invention, an olefin (co) characterized by polymerizing or copolymerizing one or more olefins using the olefin polymerization catalyst according to the eighth invention. A method for producing a polymer is provided.

  By using the catalyst component for olefin polymerization of the present invention, the number of active sites is increased, and an olefin (co) polymer can be produced with high activity.

Hereinafter, the present invention will be described in detail.
1. Olefin Polymerization Catalyst Component For the olefin polymerization catalyst component of the present invention, an ion-exchange layered silicate having the following property 1 is used.
Characteristic 1: The isomorphous substitution rate is 22% or more.

The isomorphous substitution of the ion-exchange layered silicate means the following as described in the clay handbook (Japan Clay Society, Technical Hall Publishing, 2009, 3rd edition) P124.
Broad silicate mineral containing also ion-exchange layered silicate, O ^2-or OH cation (metal ion) ^- octahedral sheets can be coordinated, and O ² to the silicon ions (Si ⁴⁺⁾ It is composed of a tetrahedral sheet formed by coordination of ⁻ . Among the ion-exchange layered silicates, in the case of 2: 1 type mineral, the unit silicate layer is constituted by a structure in which two tetrahedral sheets sandwich both sides of one octahedral sheet. Moreover, in the 1: 1 type mineral, the unit silicate layer is constituted by a structure in which one side of the tetrahedral sheet and one side of the octahedral sheet are combined.
In the 2: 1 type mineral, when the cation of the tetrahedral sheet is only Si ^{4+ and} the cation of the octahedral sheet is only Al ³⁺ or Mg ²⁺ , it is electrically neutral and has no charge. However, in general, the number of coordinated O ²⁻ or OH ⁻ is unchanged, and the cation of the tetrahedral sheet or octahedral sheet is replaced with another cation having a different valence. Is called isomorphous replacement.

By isomorphous substitution, the silicate layer generates a positive or negative, mainly negative charge, which is referred to as a layer charge. As a typical ion-exchange layered silicate, Si ⁴⁺ is replaced with Al ³⁺ in a tetrahedral sheet, Al ³⁺ is replaced with Mg ²⁺ or Fe ²⁺ , or Mg ²⁺ is replaced with Li ⁺ in an octahedral sheet. (Clay handbook described above). In this case, it has a negative layer charge.
The present invention considers that this negative layer charge has the following actions and effects on the performance (activity) of the metallocene catalyst.
The active site precursor of the metallocene catalyst is a cation species of a metallocene transition metal compound (complex), and in order to make it exist stably as an active site, a counter ion having an appropriate negative charge called a counter anion is required. is necessary. When ion-exchangeable layered silicate is used as a catalyst component for olefin polymerization, it is assumed that the above-mentioned layer charge plays a role as this counter ion.
That is, in the ion-exchange layered silicate having a high isomorphous substitution rate, the layer charge is increased and the counter ion is increased. Then, the amount of cationic species that can exist as active sites increases, and the number of active sites increases. Therefore, high-activity polymerization, which has not been possible with conventional ion-exchange layered silicates, progresses. It becomes like this.

From the above viewpoint, in the ion-exchange layered silicate of the present invention, the lower limit of the isomorphous substitution rate is preferably 22% or more, more preferably 22.2% or more, still more preferably 22.5% or more, particularly preferably. Is 22.6% or more, most preferably 23% or more . On the other hand, the upper limit is preferably 78% or less, more preferably 72% or less, still more preferably 60% or less, particularly preferably 50% or less, still more preferably 45% or less, and most preferably 34% or less. . Examples of the lower limit and upper limit range of the isomorphous substitution rate include a range in which the preferred lower limit value and the preferred upper limit value are arbitrarily combined. For example, they are 22 to 78%, 22.2 to 72%, 22.2 to 60%, 22.5 to 50%, 22.6 to 45%, and 23 to 33%.
The isomorphous substitution rate indicates the ratio of this isomorphous substitution. The number of moles of the isomorphically substituted cation is represented by the number of moles of all cations constituting the sheet (number of moles of isomorphously substituted cation + isomorphous substitution). It is expressed as a percentage of the number of moles of cations). Specifically, the amount of cations can be obtained from a composition analysis in which a calibration curve is prepared by chemical analysis by JIS method and quantified by fluorescent X-ray measurement.

  The atoms constituting the tetrahedral sheet and octahedral sheet of the ion-exchange layered silicate can be determined from the chemical structural formula. The chemical structural formula is determined based on a quantitative determination of the contained atoms by a general chemical analysis method such as fluorescent X-ray analysis (XRF), ICP, or absorptiometry. The calculation method is generally performed by the method described in P272 to P274 of the clay handbook (Japan Clay Society, Technical Hall Publishing, 2009, 3rd edition). By obtaining the chemical structural formula by such a method, the cation of each sheet and the kind of cation that is isomorphously substituted for the cation are clarified.

As one of the calculation methods, a calculation method based on the number of negatively charged anions that is often used will be described below.
The number of cations is obtained by multiplying the molecular ratio of each atom obtained by chemical analysis by the number of charges of the cation contained in the oxide of the atom (for example, the charge is 4 for Si). Find the sum of.
Next, in order to obtain a coefficient for balancing the cation charge and the anion charge, the number of negative charges (O contained in the clay mineral) 22 in the structure is divided by the sum of the number of cations. By multiplying the coefficient thus obtained by the number of cations obtained for each atom previously obtained, the proportion of atoms contained in the structure can be calculated, and the structural formula can be completed. Thus, the cation which comprises each sheet | seat can be calculated | required.

Many ion-exchanged layered silicates have a tetrahedral sheet in which the cation silicon is replaced with aluminum (isomorphic substitution with aluminum), and in the octahedral sheet, when the cation is aluminum, magnesium and iron ( When the cation is magnesium, the negative layer charge is generated by substitution with lithium. These differ depending on the type of mineral. In montmorillonite, isomorphous substitution occurs mainly in octahedral sheets.
Further, when montmorillonite is examined in detail, the main cation constituting the octahedral sheet is aluminum, which is mainly isomorphously substituted with magnesium and a small amount of iron. The amount of isomorphous substitution can also be evaluated by the amount ratio of magnesium and aluminum.

The ion-exchangeable layered silicate used for the olefin polymerization catalyst component of the present invention preferably has the following property 3 in addition to the above property 1.
Characteristic 3: The isomorphous substitution rate of the octahedral sheet constituting the ion-exchangeable layered silicate is 22% or more.

  In the ion-exchange layered silicate of the present invention, the isomorphous substitution rate of the octahedral sheet constituting the ion-exchange layered silicate is preferably 22% or more. The isomorphous substitution rate is preferably 22 to 77%, more preferably 22.5 to 66%, further preferably 22.7 to 50%, and particularly preferably 22.8 to 44%. Furthermore, 23 to 37% is more preferable, and further 23 to 31% is particularly preferable.

The ion-exchange layered silicate used for the catalyst component for olefin polymerization of the present invention preferably has the following property 2 in addition to the above property 1.
As the characteristic 2, the ion-exchange layered silicate of the present invention preferably has a specific surface area of 150 m ² / g or more.

The specific surface area represents a necessary spatial area for the active site precursor to be supported on the ion-exchange layered silicate and the polymerization reaction proceeds as the active site, and a larger surface area is preferable. When the specific surface area is increased, the active site precursor is sufficiently supported, and a sufficient reaction surface for proceeding the polymerization reaction can be secured, thereby further improving the activity. On the other hand, if the specific surface area is too large, the particles become brittle and cannot maintain the shape, and the powder properties may be deteriorated. Further, if the catalyst is crushed or collapsed during the polymerization, generation of fine powders or lumps will occur. May lead to a decrease in the operational stability of the plant.
The lower limit of the specific surface area is preferably 150 m ² / g, more preferably 200 m ² / g, still more preferably 280 m ² / g, even more preferably 325 m ² / g, particularly preferably 330 m ² / g, most preferably 350 m. ² / g. The upper limit of the specific surface area is not particularly defined, but is preferably 600 m ² / g, more preferably 580 m ² / g, still more preferably 550 m ² / g, particularly preferably 500 m ² / g. Specific surface area can illustrate the range which combined the above-mentioned desirable lower limit and desirable upper limit arbitrarily as an upper limit and a minimum. For ^{example, 325~550m 2 / g, 330~500m 2} / g, 350~500m 2 / g, 200~600m 2 / g, 350~580m 2 / g, 280~550m 2 / g, 325~550m 2 / g It is.

The natural product of ion-exchange layered silicate has a specific surface area of 0.1 to 140 m ² / g, preferably about 0.1 to 90 m ² / g, and is relatively small, but is increased by chemical treatment described later. It is possible.
Here, the specific surface area was determined by a nitrogen adsorption method. The measurement method is shown below.
The amount of gas adsorbed to a solid is constant, and if the solid and gas are determined, the potential of the 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, most commonly used nitrogen is used as an adsorption gas, and the relative pressure P / P0 (P0 indicates atmospheric pressure) is 0.025 at a liquid nitrogen temperature (temperature 77K). The adsorption isotherm was measured in the range of 0.995. It calculated | required by implementing a BET multipoint method analysis using the obtained adsorption isotherm. In general, analysis was performed in a range where a good straight line was obtained around relative pressure P / P0 (P0 is atmospheric pressure) = 0.05 to 0.35, and the analysis range was determined while confirming the BET plot.

The ion-exchange layered silicate used for the catalyst component for olefin polymerization of the present invention preferably further has the following property 4.
In the ion-exchange layered silicate of the present invention, as the characteristic 4, the molar ratio (Mg / Al) between the amount of Mg and the amount of Al contained in the octahedral sheet of the ion-exchange layered silicate is 0.28 or more. Is preferred. 0.28 to 3.5 is more preferable, 0.285 to 2.5 is more preferable, 0.287 to 1.5 is still more preferable, 0.29 to 1 is particularly preferable, and 0.292 to 0.8. Is more particularly preferable, and 0.292 to 0.5 is most preferable.
As described above, when trivalent aluminum is substituted with divalent magnesium, it has a negative layer charge. Furthermore, this negative layer charge is used to stably present the cation species of the metallocene transition metal compound (complex), which is the active site precursor of the metallocene catalyst, as the active site with respect to the performance (activity) of the metallocene catalyst. The present inventors believe that it acts as a counter anion and has a high activation effect.

In the ion-exchange layered silicate of the present invention, as characteristic 5, the total (total) mesopore pore volume measured by the nitrogen adsorption method is preferably 0.30 cc / g or more, and 0.35 cc / g or more. Is more preferably 0.40 cc / g or more, and particularly preferably 0.45 cc / g or more. Further, the maximum amount is preferably 1 cc / g or less, more preferably 0.8 cc / g or less, and further preferably 0.6 cc / g or less.
The total pore volume of pores having a diameter in the range of 2 to 10 nm is preferably 0.15 cc / g or more, more preferably 0.20 cc / g or more, and 0.25 cc / g. More preferably, it is g or more. When the amount of pores is less than this, the activity may be lowered. On the other hand, the maximum amount is preferably 1 cc / g or less, more preferably 0.8 cc / g or less, further preferably 0.6 cc / g or less, and 0.5 cc / g or less. It is particularly preferred. When the amount of pores is more than this, there is a possibility of causing generation of fine powder and deterioration of powder properties.
The calculation of the pore volume within the range defined in the present invention uses an adsorption isotherm obtained when the relative pressure is increased. As a method for calculating the pore distribution, the BJH analysis method is the most common, and this method is adopted in the present invention. In the present invention, the mesopore pore refers to a pore having a pore diameter of 2 to 50 nm according to the definition of IUPAC. Using the pore distribution curve, the total pore volume was determined for pores having a diameter of 2 to 10 nm and pores having a diameter of 2 to 50 nm.

  The ion exchange layered silicate of the present invention preferably has an acid point as property 6. The lower limit of the amount of acid sites is preferably 30 μmol, more preferably 50 μmol, still more preferably 100 μmol, and particularly preferably 150 μmol of strong acid sites with a pKa <−8.2 or less per 1 g of ion-exchangeable layered silicate. The amount of acid sites is measured according to the method described in JP 2000-158707 A.

The ion-exchangeable layered silicate having the above characteristics can be produced by the following method.
The raw material of the ion-exchange layered silicate used in the present invention is not limited to a natural one but may be an artificial synthetic product. Specific examples of the silicate include the followings described in “Clay Mineralogy” (Haruo Hakusui, Asakura Shoten, 1995).
i) Serpentine-related minerals such as kaolins such as decaitite, nacrite, kaolinite, nacrite, serpentine groups such as chrysotile, lizardite, antigolite, amesite, Al lizardite, etc., whose 1: 1 layer is the main constituent layer etc.
ii) Smectite silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, etc., vermiculite silicates such as vermiculite, mica, illite, sericite, the main component layer of which is 2: 1. Mica group silicates such as sea chlorite, attapulgite, sepiolite, palygorskite, chlorite group, etc.

These may form a mixed layer. Many ion-exchange layered silicates are naturally produced as the main component of clay minerals, and therefore often contain impurities (such as quartz and cristobalite). You can leave.
The ion-exchangeable layered silicate of the present invention is preferably a layered silicate having a 2: 1 type structure. More preferred is a smectite silicate, and still more preferred is montmorillonite.

The ion-exchange layered silicate of the present invention is preferably layered silicic acid having a large layer charge due to a high isomorphous substitution amount. The isomorphous substitution of the ion-exchange layered silicate refers to the following as described in the clay handbook (Japan Clay Society, Technical Hall Publishing, 2009, 3rd edition) P124.
A broadly defined layered silicate mineral that also includes an ion-exchanged layered silicate includes an octahedral sheet formed by coordination of O ²⁻ or OH ⁻ with a metal ion (cation), and a silicon ion (Si ⁴⁺ ). , O ²⁻ is coordinated to form a tetrahedral sheet. As a kind of metal which comprises an octahedral sheet | seat, they are aluminum, magnesium, iron, titanium, etc., The content is 5-30 weight% with respect to the ion exchange layered silicate mineral whole quantity, for example.
Among the ion-exchange layered silicates, in the case of 2: 1 type mineral, the unit silicate layer is constituted by a structure in which two tetrahedral sheets sandwich both sides of one octahedral sheet. Moreover, in 1: 1 mineral, the unit silicate layer is comprised by the structure which the single side | surface of the tetrahedral sheet | seat and the single side | surface of the octahedral sheet | seat couple | bonded.
In the 2: 1 type mineral, when the cation of the tetrahedral sheet is only Si ^{4+ and} the cation of the octahedral sheet is only Al ³⁺ or Mg ²⁺ , each sheet is electrically neutral and has a charge. Does not have. However, the number of coordinated O ²⁻ or OH ⁻ is generally unchanged, and the cation of the tetrahedral sheet or octahedral sheet is generally replaced with another cation having a different valence, This is called isomorphous replacement.

  By this isomorphous substitution, the silicate layer generates a positive or mainly negative charge, which is referred to as a layer charge. Usually, in order to neutralize this layer charge, the ion-exchange layered silicate has exchangeable interlayer ions (ions contained between the layers of the ion-exchange layered silicate). Although not particularly limited, there are alkali metals of Group 1 of the periodic table such as lithium and sodium, and alkaline earth metals of Group 2 of the periodic table such as calcium and magnesium.

As described in the above-mentioned clay handbook (P125), the amount of isomorphous substitution of the ion-exchange layered silicate does not change once the mineral skeleton is formed, except in special cases. Therefore, it is preferable that the ion-exchange layered silicate of the present invention also has a high isomorphous substitution rate for the ion-exchange layered silicate used as a raw material.
It is preferable that the isomorphous substitution rate of the ion-exchange layered silicate which is the raw material of the ion-exchange layered silicate of the present invention is 22% or more. Moreover, 22-77% is preferable, 23-66% is more preferable, 23-60% is further more preferable, 24-50% is especially preferable, 24-44% is still more preferable, 24-40% is further especially preferable. Most preferred is 25-35%.
By using such an ion-exchange layered silicate as a raw material, an ion-exchange layered silicate satisfying the above-described property 1 can be obtained. As a raw material of the catalyst component for olefin polymerization, the isomorphous substitution rate of the layered silicate conventionally disclosed was 16 to 21%.

Examples of the ion-exchange layered silicate of the present invention include those in which Al ^{3+ of the} octahedral sheet is isomorphously substituted with Mg ²⁺ and Fe ²⁺ , and Mg ²⁺ is isomorphously substituted with Li ⁺ .
The ion-exchange layered silicate of the present invention is an octahedron sheet, a ratio in which Al ³⁺ is replaced with Mg ²⁺ , and a raw material having an aluminum / magnesium molar ratio of Mg / Al of 0.285 to 3.5. It is preferable to use it. The Mg / Al molar ratio is more preferably 0.29 to 3, further preferably 0.295 to 2, particularly preferably 0.3 to 1.5, and 0.31 to 1. It is highly preferred that Further, the Mg / Al molar ratio is more preferably 0.315 to 0.8, 0.32 to 0.65, or 0.325 to 0.55.

By using such an ion-exchange layered silicate as a raw material, an ion-exchange layered silicate satisfying the above-described properties 1, 3, and 4 can be obtained.
As a raw material of the catalyst component for olefin polymerization, the Mg / Al ratio of the layered silicate conventionally disclosed was about 0.25 to 0.27.

The ion-exchange layered silicate exhibiting the characteristics of the present invention can also be produced by subjecting the ion-exchange layered silicate to chemical treatment.
The chemical treatment includes various treatments such as an acid treatment for treating an ion-exchange layered silicate with acids, an alkali treatment for treatment with alkalis, and a salt treatment for treatment with inorganic salts.
The chemical treatment may be performed alone, in combination, or simultaneously. Preferably, other chemical treatments are performed after acid treatment with acids. The ion-exchange layered silicate of the present invention is preferably chemically treated with acids, and more preferably treated with inorganic acids among the acids.

In the chemical treatment of the ion-exchange layered silicate, the acid treatment treated with acids will be described in detail as follows.
When the ion-exchangeable layered silicate is treated with an acid, the surface impurities are washed with an acid, the interlayer ions are eluted and exchanged with hydrogen cations, and then the cations constituting the octahedral sheet are changed. It begins to elute. In the process of elution, characteristics such as acid point, pore structure and specific surface area change.
Therefore, the ion-exchangeable layered silicate of the present invention can be achieved by performing treatment with acids. The degree of elution varies depending on the acid concentration, treatment time, and type of acid, but those containing a large amount of magnesium are generally large, followed by those containing a lot of iron and those containing a lot of aluminum. In addition, the higher the degree of crystallinity and the larger the particle, the lower the elution property. This is related to the invasion of the acid into the crystal layer or the crystal structure.

As for elution, all the octahedral sheets of the crystal lattice have a uniform elution that has a microscopic void, and the silicic acid and layered silicic acid produced by the elution of metal cations at a specific site. A mechanism of heterogeneous elution, in which salt complexes are formed, is conceivable.
The ion-exchange layered silicate of the present invention uses a raw material having a high isomorphous substitution rate, so that in each sheet, in addition to the high negativeity of the layer charge, than the known ion-exchange layered silicate, We believe that uniform elution occurs between the sheets.

As conditions for the acid treatment, the temperature is preferably 40 to 102 ° C, and preferably 50 to 100 ° C. More preferably, it is 60-95 degreeC. When the temperature is lowered too much, the elution rate of the cation is extremely lowered, and the production efficiency is lowered. On the other hand, if the temperature is raised too much, operational safety is reduced.
Further, the acid concentration during acid treatment (the weight percentage of the acid relative to the total weight of the reaction system) is preferably 3 to 30% by weight, preferably 5 to 25% by weight, more preferably 7 to 20% by weight. When the concentration is lowered, the elution rate of the cation is lowered and the production efficiency is lowered.
Moreover, the density | concentration of an ion exchange layered silicate can be prepared in 3-50 weight%. Preferably it is 5 to 30 weight%, More preferably, it is 5 to 20 weight%. When the concentration is low, a large facility is required for industrial production. On the other hand, when the concentration is high, the viscosity of the slurry increases, and uniform stirring and mixing becomes difficult, and the production efficiency also decreases.

The acid treatment can be performed in a plurality of 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 these, inorganic acids are preferable, and hydrochloric acid, nitric acid, and sulfuric acid are preferable. More preferred are hydrochloric acid and sulfuric acid, and particularly preferred is sulfuric acid.
It is preferable to elute the metal cation constituting the octahedron sheet by chemical treatment, particularly acid treatment, with respect to the content before chemical treatment, 10 to 65%, more preferably 15 to 60%, and still more preferably 17%. It is eluted at ˜55%, particularly preferably 20-50%. When the elution ratio is small, a sufficient amount of pores cannot be secured, the surface area becomes small, and the ion-exchange layered silicate of the present invention cannot be obtained.
Here, the ratio (mol%) of the metal cation to be eluted is expressed by the following formula when the metal cation is aluminum, for example.
[Aluminum / Si (Molar ratio) before chemical treatment−Aluminum / Si (Molar ratio) after chemical treatment] ÷ Aluminum / Si (Molar ratio) before chemical treatment × 100

Since the reaction product or unreacted material in the reaction solution may remain after the chemical treatment is performed, the activity may be reduced. At this time, generally, a liquid such as water or an organic solvent is used.
The washing rate is preferably 1/5 to 1/1000, 1/10 to 1/100. Drying is performed after washing and dehydration. Drying is preferably performed so as not to cause structural destruction of the ion-exchange layered silicate. In general, the drying temperature can be 100 to 800 ° C, preferably 150 to 600 ° C, particularly preferably. It is preferable that the temperature is 150 to 300 ° C., the drying temperature is 800 ° C. or less, and that the structural breakdown of the ion-exchange layered silicate does not occur.
Since these ion-exchange layered silicates have different characteristics depending on the drying temperature even if they are not structurally 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. It does not specifically limit regarding a drying method, It can implement by various methods.

Further, in general, the ion-exchange layered silicate includes adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water before use. For the removal of water, heat treatment is usually used. The method is not particularly limited, but it is preferable to select conditions that do not cause adhesion water and interlayer water to remain and do not cause structural destruction.
The heating time is 0.1 hour or longer, preferably 0.2 hour or longer. At that time, the moisture content after removal is 3% by weight or less, preferably 1% by weight or less when the moisture content is 0% by weight when dehydrated for 2 hours under the conditions of a temperature of 200 ° C. and a pressure of 1 mmHg. It is preferable that
As mentioned above, although the manufacturing method of the ion exchange layered silicate which shows the characteristic of this invention has been described, the manufacturing method with which the characteristic of this invention is acquired is not restricted above, It can manufacture.
An embodiment of a preferred method for producing an ion-exchange layered silicate that is a catalyst component for olefin polymerization according to the present invention is described below. The specific surface area is 0.1 to 140 m ² / g, and the molar ratio of aluminum to magnesium (Mg / It is a method including a treatment step of desorbing 10 to 65 mol% of main metal cations of an octahedral sheet of ion-exchangeable layered silicate having Al) of 0.285 to 3.5.

The ion-exchange layered silicate of the present invention can be granulated, and is preferably granulated and used in a granulated body. The granulation method is not particularly limited, but preferred granulation production methods include stirring granulation method, spray granulation method, rolling granulation method, briquetting, compacting, extrusion granulation method, flow Examples thereof include layer granulation method, emulsion granulation method, submerged granulation method, and compression molding granulation method. More preferably, spray drying granulation, spray cooling granulation, fluidized bed granulation, spouted bed granulation, submerged granulation, emulsification granulation, etc. are mentioned, and spray drying granulation and spray cooling granulation are particularly preferable. Can be mentioned.
When spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, or xylene is used as a dispersion medium for the raw material slurry. Preferably, water is used as a dispersion medium.
During spray granulation, the concentration of the ion-exchangeable layered silicate in the raw slurry is 0.1 to 70% by weight, preferably 1 to 50% by weight, more preferably 4 to 45% by weight, and even more preferably 5%. A spherical granule is obtained by setting it to -40 wt%. When the upper limit of the concentration is exceeded, spherical particles cannot be obtained, and when the concentration is lower than the lower limit of the concentration, the average particle size of the granule becomes too small. The temperature at the inlet of hot air for spray granulation from which spherical particles are obtained varies depending on the dispersion medium, but when water is taken as an example, the temperature is 80 to 260 ° C, preferably 100 to 220 ° C.

  Moreover, you may use various binders, such as organic substance and an inorganic salt, in the case of granulation. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcelluloses, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch and casein. , Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, sodium alginate and the like.

The shape of the ion-exchange layered silicate before granulation is not particularly limited, and may be a naturally produced shape, a shape when artificially synthesized, or by operations such as grinding, granulation, and classification. You may use what processed the shape.
The particle size of the granulated ion-exchange layered silicate is 5 μm or more and 300 μm or less, and preferably spherical. More preferably, they are 5 micrometers or more and 250 micrometers or less, More preferably, they are 5 micrometers or more and 200 micrometers or less. If there are many fine particles of less than 5 μm, adhesion to the reactor is likely to occur, and depending on the aggregation of the polymers and the polymerization process, it may cause a short pass or long-term residence, which is not preferable. Coarse particles having a size of 300 μm or more are not preferable because problems such as blockage tend to occur. In order to obtain an average particle diameter that satisfies these conditions, or when particles that are extremely small or large with respect to the average particle diameter are present, the particle diameter may be controlled by classification, classification, or the like.

2. Olefin Polymerization Catalyst The ion-exchange layered silicate of the present invention is suitably used as a catalyst component for olefin polymerization. Examples of the olefin polymerization catalyst generally include a Ziegler-Natta catalyst and a metallocene catalyst.
In the present invention, the catalyst for olefin polymerization can be preferably prepared by contacting the component (a), the component (b) and, if necessary, the component (c).
Component (a): Metallocene compound of Group 4 transition metal of the periodic table Component (b): The above-described ion-exchange layered silicate Component (c): Organoaluminum compound

(1) Component (a)
The metallocene compound of Group 4 transition metal of the periodic table used in the present invention is a metallocene compound having at least one conjugated five-membered ring ligand. Preferred as such transition metal compounds are compounds represented by the following general formulas (1) to (4).

  In the above general formulas (1) to (4), A and A ′ are conjugated five-membered ring ligands which may have a substituent (in the same compound, A and A ′ may be the same or different. Q represents a bonding group that bridges two conjugated five-membered ring ligands at an arbitrary position, and Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom. Q ′ represents a binding group that bridges Z with an arbitrary position of the conjugated five-membered ring ligand, M represents a metal atom selected from Group 4 of the periodic table, and X and Y are A hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group, or a silicon-containing hydrocarbon group (in the same compound, X and X ′ may be the same or different).

Examples of A and A ′ include a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms [C ₅ H _5- ], or a derivative thereof, that is, one in which some of the hydrogen atoms are substituted with substituents. May be.
Examples of this substituent are hydrocarbon groups having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, and when there are a plurality of these, two of them are bonded at the other end (ω-end). A ring may be formed together with a part of cyclopentadienyl. As an example of the latter, two substituents are bonded to each other at the ω-end, and two adjacent carbon atoms in the cyclopentadienyl group are shared to form a condensed six-membered ring. That is, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and a group forming a condensed seven-membered ring, that is, an azulenyl group or a tetrahydroazurenyl group.
Preferable specific examples of the conjugated five-membered ring ligand represented by A and A ′ include a substituted or unsubstituted cyclopentadienyl group, indenyl group, fluorenyl group, or azulenyl group. Of these, a substituted or unsubstituted indenyl group or an azulenyl group is particularly preferable.

As the substituent on the cyclopentadienyl group, in addition to the hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, a halogen atom group such as fluorine, chlorine or bromine, or 1 to 12 carbon atoms. For example, a silicon-containing hydrocarbon group represented by -Si (R ¹ ) (R ² ) (R ³ ), a phosphorus-containing hydrocarbon group represented by -P (R ¹ ) (R ² ), or- Examples thereof include a boron-containing hydrocarbon group represented by B (R ¹ ) (R ² ). When there are a plurality of these substituents, each substituent may be the same or different. R ¹ , R ² and R ³ described above may be the same or different and each represents an alkyl group having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms.

Furthermore, you may have an at least 1 group 15-16 element (namely, hetero element) as a substituent on a cyclopentadienyl group. In this case, from the idea of improving the properties of the active site by allowing the hetero element itself to be present in the vicinity of the active site without bonding or coordination with the metal, a group 15-15 element and a conjugated five-membered ring are formed. A metallocene complex having 1 or less atoms bonding to the ligand is more preferable.
The position of the group 15 to 16 element on the ligand is not particularly limited, but is preferably on the 2-position substituent. More preferably, the 2-position substituent is monocyclic or polycyclic containing a heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom in a 5-membered or 6-membered ring. Preferably there is. Further, it is preferably a heteroaromatic group having 4 to 20 carbon atoms which may contain silicon or halogen, and the heteroaromatic group preferably has a 5-membered ring structure, and the heteroatom is an oxygen atom, a sulfur atom or a nitrogen atom. Preferably, an oxygen atom and a sulfur atom are more preferable, and an oxygen atom is more preferable.

Q is a bonding group that bridges between two conjugated five-membered ring ligands at an arbitrary position, and Q ′ is a bond that bridges an arbitrary position of the conjugated five-membered ring ligand with a group represented by Z. Represents a sex group.
Specific examples of Q and Q ′ include the following groups.
(I) Methylene group, ethylene group, isopropylene group, phenylmethylmethylene group, diphenylmethylene group, cyclohexylene group and other alkylene groups (b) dimethylsilylene group, diethylsilylene group, dipropylsilylene group, diphenylsilylene group, Silylene groups such as methylethylsilylene group, methylphenylsilylene group, methyl-t-butylsilylene group, disilylene group, tetramethyldisylylene group, etc. (c) Hydrocarbon groups containing germanium, phosphorus, nitrogen, boron or aluminum

More specifically, (CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ Ge, (CH ₃ ) P, (C ₆ H ₅ ) P, (C ₄ H ₉ ) N, (C ₆ H ₅ ) N, (C ₄ H ₉ ) B, (C ₆ H ₅ ) B, (C ₆ H ₅ ) Al, (C ₆ H ₅ O) Al and the like. Preference is given to alkylene groups and silylene groups.

M represents a metal atom transition metal atom selected from Group 4 of the periodic table, specifically titanium, zirconium, hafnium and the like. In particular, zirconium and hafnium are preferable.
Furthermore, Z represents a ligand, a hydrogen atom, a halogen atom or a hydrocarbon group containing a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom. Preferable specific examples include an oxygen atom, a sulfur atom, a thioalkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, a silicon-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, A nitrogen-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 18 carbon atoms, a hydrogen atom, a chlorine atom, a bromine atom, carbon It is a hydrocarbon group of number 1-20.

  X and Y are each a hydrogen atom, a halogen atom, a C1-C20, preferably a C1-C10 hydrocarbon group, a C1-C20, preferably a C1-C10 alkoxy group, an amino group, 1 to 20 carbon atoms such as a diphenylphosphino group, preferably a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms, or 1 to 20 carbon atoms such as a trimethylsilyl group or a bis (trimethylsilyl) methyl group, preferably 1 to 1 carbon atom. 12 silicon-containing hydrocarbon groups. X and Y may be the same or different. Of these, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, and an amino group having 1 to 12 carbon atoms are particularly preferable.

As the compound represented by the general formula (1), for example,
(1) bis (methylcyclopentadienyl) zirconium dichloride,
(2) bis (n-butylcyclopentadienyl) zirconium dichloride,
(3) bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
(4) bis (1-n-butyl-3-methylcyclopentadienyl) zirconium dichloride,
(5) bis (1-methyl-3-trifluoromethylcyclopentadienyl) zirconium dichloride,
(6) bis (1-methyl-3-trimethylsilylcyclopentadienyl) zirconium dichloride,
(7) bis (1-methyl-3-phenylcyclopentadienyl) zirconium dichloride,
(8) bis (indenyl) zirconium dichloride,
(9) bis (tetrahydroindenyl) zirconium dichloride,
(10) Bis (2-methyl-tetrahydroindenyl) zirconium dichloride,
Etc.

Examples of the compound represented by the general formula (2) include:
(1) Dimethylsilylenebis {1- (2-methyl-4-isopropyl-4H-azurenyl)} zirconium dichloride,
(2) Dimethylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(3) Dimethylsilylenebis [1- {2-methyl-4- (4-fluorophenyl) -4H-azulenyl}] zirconium dichloride,
(4) Dimethylsilylenebis [1- {2-methyl-4- (2,6-dimethylphenyl) -4H-azulenyl}] zirconium dichloride,
(5) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropyl-4H-azurenyl)} zirconium dichloride,
(6) Diphenylsilylenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(7) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(8) ethylenebis {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(9) Dimethylsilylenebis {1- [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium dichloride,
(10) Dimethylsilylenebis {1- [2-methyl-4- (2 ′, 6′-dimethyl-4-biphenylyl) -4H-azulenyl]} zirconium dichloride,
(11) Dimethylsilylene {1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} {1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium dichloride,
(12) Dimethylsilylene {1- (2-ethyl-4-phenyl-4H-azulenyl)} {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(13) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoro-4H-azurenyl)} zirconium dichloride,
(14) Dimethylsilylenebis {1- (2-ethyl-4-indolyl-4H-azurenyl)} zirconium dichloride,
(15) Dimethylsilylenebis [1- {2-ethyl-4- (3,5-bistrifluoromethylphenyl) -4H-azurenyl}] zirconium dichloride,
(16) Dimethylsilylene bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium bis (trifluoromethanesulfonic acid),
(17) Dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(18) Dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
(19) Dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl) indenyl}] zirconium dichloride,
(20) Dimethylsilylenebis {1- (2-methyl-4,6-diisopropylindenyl)} zirconium dichloride,

(21) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(22) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(23) ethylene-1,2-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(24) isopropylidenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(25) ethylene-1,2-bis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(26) isopropylidenebis {1- (2-methyl-4-phenyl-4H-azurenyl)} zirconium dichloride,
(27) Dimethylgermylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
(28) Dimethylgermylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(29) phenylphosphinobis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
(30) Dimethylsilylenebis [3- (2-furyl) -2,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(31) Dimethylsilylenebis [2- (2-furyl) -3,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(32) Dimethylsilylenebis [2- (2-furyl) -indenyl] zirconium dichloride,
(33) Dimethylsilylenebis [2- (2- (5-methyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(34) Dimethylsilylenebis [2- (2- (5-trimethylsilyl) furyl) -4,5-dimethyl-cyclopentadienyl] zirconium dichloride,
(35) Dimethylsilylenebis [2- (2-thienyl) -indenyl] zirconium dichloride,
(36) Dimethylsilylene [2- (2- (5-methyl) furyl) -4-phenylindenyl] [2-methyl-4-phenylindenyl] zirconium dichloride,
(37) Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
(38) Dimethylsilylenebis (2,3-dimethyl-5-ethylcyclopentadienyl) zirconium dichloride,
(39) Dimethylsilylenebis (2,5-dimethyl-3-phenylcyclopentadienyl) zirconium dichloride,
Etc.

Examples of the compound represented by the general formula (3) include:
(1) (tetramethylcyclopentadienyl) titanium (bis t-butylamide) dichloride,
(2) (tetramethylcyclopentadienyl) titanium (bisisopropylamide) dichloride,
(3) (tetramethylcyclopentadienyl) titanium (biscyclododecylamide) dichloride,
(4) (Tetramethylcyclopentadienyl) titanium {bis (trimethylsilyl) amide)} dichloride,
(5) (2-Methyl-4-phenyl-4H-azurenyl) titanium {bis (trimethylsilyl) amide} dichloride,
(6) (2-methylindenyl) titanium (bis t-butylamide) dichloride,
(7) (fluorenyl) titanium (bis t-butylamide) dichloride,
(8) (3,6-diisopropylfluorenyl) titanium (bis t-butylamide) dichloride,
(9) (Tetramethylcyclopentadienyl) titanium (phenoxide) dichloride,
(10) (tetramethylcyclopentadienyl) titanium (2,6-diisopropylphenoxide) dichloride,
Etc.

Examples of the compound represented by the general formula (4) include:
(1) Dimethylsilanediyl (tetramethylcyclopentadienyl) (t-butylamido) titanium dichloride,
(2) Dimethylsilanediyl (tetramethylcyclopentadienyl) (cyclododecylamide) titanium dichloride,
(3) Dimethylsilanediyl (2-methylindenyl) (t-butylamido) titanium dichloride,
(4) Dimethylsilanediyl (fluorenyl) (t-butylamido) titanium dichloride, and the like.
The compounds in which the dichlorides of these exemplified compounds are replaced with dibromide, difluoride, dimethyl, diphenyl, dibenzyl, bisdimethylamide, bisdiethylamide and the like are also exemplified. Further, compounds in which zirconium in the exemplified compound is replaced with hafnium or titanium, and titanium is replaced with hafnium or zirconium are also exemplified.

As the transition metal compound used in the present invention, a compound represented by the general formula (2) is preferable, and a compound having a condensed seven-membered ring as a substituent, that is, a compound having an azulenyl group or a tetrahydroazurenyl group. Is particularly preferred.
In addition, a metallocene compound can be used alone or in combination of two or more.
When two or more types are used in combination, two or more types can be selected from the compound group included in any one of the general formulas (1) to (4). It is also possible to select one or two or more selected from the group of compounds included in the above and one or two or more selected from the group of compounds included in other general formulas.
For example, it is a metallocene compound that forms a polymerization catalyst for producing an olefin macromer, and a metallocene compound that forms a polymerization catalyst for producing an olefin macromer is a terminal vinyl ratio when propylene homopolymerization is carried out at 70 ° C. A combination of the metallocene compound (a-1) forming a propylene homopolymer satisfying 0.5 or more and the metallocene compound (a-2) represented by the general formula (4) can be given. The molar ratio (a-1) / (a-2) of the component (a-2) to the component (a-1) can be 1.0 to 99.0.

(2) Component (c)
Component (c) is an organoaluminum compound.
As the organoaluminum compound used as the component (c) in the present invention, an organoaluminum compound represented by the general formula: (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 atom, a hydrogen atom, an alkoxy group or an amino group, n represents an integer of 1 to 3, and m represents 1 or 2. Represent. The organoaluminum compounds can be used alone or in combination.

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

(3) Preparation of Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention is made by contacting component (a), component (b) and, if necessary, component (c).
Although the contact method is not specifically limited, Contact can be made in the following order. This contact may be performed in the absence of the monomer or in the presence of the monomer. In these contacts, a solvent may be used for sufficient contact. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers.
(I) The component (a) is contacted with the component (b).
(Ii) After contacting the component (a) and the component (b), the component (c) is contacted.
(Iii) After contacting the component (b) and the component (c), the component (a) is contacted.
(Iv) After contacting the component (a) and the component (c), the component (b) is contacted.
(V) contacting the three components simultaneously.

  A preferred contact method is to contact the component (b) with the component (c), then remove the unreacted component (c) by washing or the like, and then convert the necessary minimum component (c) to the component (b) again. It is the method of making it contact, and making a component (a) contact after that. In this case, the Al / transition metal molar ratio is in the range of 0.1 to 1,000, preferably 2 to 100, and more preferably 4 to 50.

The temperature at which the component (b) and the component (c) are brought into contact (in which case the component (a) may be present) is preferably 0 ° C to 100 ° C, more preferably 20 to 80 ° C, and particularly preferably 30-60 ° C. When it is lower than this range, the reaction is slow, and when it is high, there is a disadvantage that a side reaction proceeds.
Moreover, when a component (a) and a component (c) are made to contact (in that case component (b) may exist), it is preferable to make an organic solvent exist as a solvent. In this case, the concentration of component (a) in the organic solvent is preferably higher. The lower limit of the concentration of the component (a) in the organic solvent is preferably 3 mmol / L, more preferably 4 mmol / L, still more preferably 6 mmol / L. If it is less than the lower limit, the reaction is slow and the reaction may not proceed sufficiently.
Component (a) is in the range of 0.001 to 10 mmol, preferably 0.001 to 1 mmol per 1 g of component (b).

In addition, the catalyst of the present invention is preferably subjected to a prepolymerization treatment in which a small amount of polymer is brought into contact with an olefin in advance to improve particle properties. The olefin to be used is not particularly limited, but ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene and the like can be used. It is possible to use, and it is particularly preferable to use propylene.
The olefin can be supplied by any method, such as a supply method for maintaining the olefin at a constant speed or in a constant pressure state, a combination thereof, or a stepwise change.

The prepolymerization time is not particularly limited, but is preferably in the range of 5 minutes to 24 hours. The amount of prepolymerization is preferably 0.01 to 100 g, more preferably 0.1 to 50 g, based on 1 g of the component (b).
The prepolymerization temperature is not particularly limited, but is preferably 0 ° C to 100 ° C, more preferably 10 to 70 ° C, particularly preferably 20 to 60 ° C, and further preferably 30 to 50 ° C. Below this range, there is a possibility that the reaction rate decreases or the activation reaction does not proceed. On the other hand, when it exceeds the above range, the prepolymerized polymer dissolves or the prepolymerization rate is too high, and the particle properties May be adversely affected or the active site may be deactivated due to side reactions.

The preliminary polymerization can be carried out in a liquid such as an organic solvent, and this is preferable. Although there is no restriction | limiting in particular in the density | concentration of the catalyst at the time of prepolymerization, Preferably it is 30 g / L or more, More preferably, it is 40 g / L or more, Most preferably, it is 45 g / L or more. The higher the concentration, the more active the metallocene and the higher the activity of the catalyst.
Furthermore, a polymer such as polyethylene, polypropylene, or polystyrene, or an inorganic oxide solid such as silica or titania can be allowed to coexist during or after the contact of the above components.

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

3. Production method of olefin (co) polymer Polymerization carried out using an olefin polymerization catalyst comprising the component (a), the component (b), and the component (c) used as necessary is performed by polymerizing one kind of olefin. Or by copolymerizing two or more olefins.
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 possible to supply each monomer at a constant mixing ratio. It is also possible to change with time. Also, any of the monomers can be added in portions in consideration of the copolymerization reaction ratio.

  As the olefin that can be polymerized, those having about 2 to 20 carbon atoms are preferred, and specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, styrene, divinylbenzene, 7-methyl. Examples include -1,7-octadiene, cyclopentene, norbornene, and ethylidene norbornene. Preferably it is a C2-C8 alpha olefin, More preferably, they are ethylene and propylene. In the case of copolymerization, the type of comonomer used can be selected from one or two or more olefins other than the main component from those listed as the olefin. Preferably, the main component is propylene.

As the polymerization mode, any mode can be adopted as long as the catalyst and the monomer are in efficient contact. 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 method for maintaining a monomer in a gaseous state without using a liquid solvent. Etc. can be adopted. Moreover, the method of performing continuous polymerization and batch type polymerization is also applied.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, toluene, or the like is used alone or as a polymerization solvent. The polymerization temperature is 0 to 150 ° C., and hydrogen can be used as an auxiliary molecular weight regulator. The polymerization pressure is suitably 0 to 2000 kg / cm ² G, preferably 0 to 60 kg / cm ² G.
Although it does not specifically limit as an olefin (co) polymer obtained by the manufacturing method of this invention, If an example is given to the following, an ethylene homopolymer, a propylene homopolymer, a propylene-ethylene block copolymer, propylene -An ethylene random copolymer, a propylene / ethylene-alpha-olefin type copolymer, etc. are mentioned.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.
The analytical instruments and measurement methods used for measuring physical properties are as follows.

(Various physical property measurement methods)
(1) Composition analysis of ion-exchange layered silicate:
A calibration curve was prepared by chemical analysis by the JIS method and quantified by fluorescent X-ray measurement.
(2) Pore measurement and specific surface area measurement:
The pore distribution and specific surface area by nitrogen adsorption method were measured. The adsorption isotherm was measured under liquid nitrogen temperature. BET multipoint analysis was performed using the obtained adsorption isotherm to determine the specific surface area.
In addition, using the adsorption isotherm, the total pore volume and mesopore distribution of pores having diameters of 2 to 10 nm were determined by BJH method analysis.
Equipment: Autosorb 3B manufactured by Canterchrome
Measurement method: Nitrogen gas adsorption method Pretreatment condition: Sample is heated under reduced pressure at 200 ° C. under vacuum (1.3 MPa or less) for 2 hours.
Gas liquefaction temperature: 77K

(3) Measurement of particle size:
Using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by HORIBA, Ltd., the dispersion solvent was measured under the conditions of ethanol, refractive index 1.3, and shape factor 1.0.
(4) MFR (melt mass flow rate):
Using Takara's melt indexer, JIS K7210 "Plastics-Testing methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics": compliant with 230 ° C, 2.16 kg load And measured.

[Example 1]
1. Granulated montmorillonite As the ion-exchanged layered silicate, “Ben clay KK” (main component is a smectite 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 has an average particle size of 11.4 μm, chemical composition (% by weight): Al = 9.72, Si = 1.72, Fe = 1.65, Mg = 3.11, Na = 3.48 there were. The molar ratios were Al / Si = 0.319, Mg / Si = 0.113, Fe / Si = 0.026, and Mg / Al = 0.355. The specific surface area was 65 m ² / g. Moreover, the main metal cation which comprises an octahedral sheet | seat was aluminum.

2. Chemical treatment of ion-exchange layered silicate Into a 0.5 L flask equipped with a stirring blade and a reflux apparatus, 397.7 g of distilled water was added, and 117.2 g of 96% sulfuric acid was added dropwise. The mixture was heated in an oil bath until the internal temperature reached 90 ° C. When the target temperature was reached, 70 g of the granulated montmorillonite of 1 was added and stirred.
Thereafter, the reaction was carried out for 210 minutes while maintaining 90 ° C. The reaction is stopped by pouring the reaction solution into 0.2 L of pure water, and the slurry is filtered through a device in which an aspirator is connected to Nutsche and a suction bottle, and then washed three times with 0.7 L of pure water. did.
In this chemical treatment, the structure of montmorillonite remained unchanged with a 2: 1 type layer structure. The isomorphous substitution rate of the processed montmorillonite is 23%, the composition (% by weight) is Al = 6.67, Si = 37.9, Mg = 1.83, and Na is a numerical value below the detection lower limit. The ratios were Al / Si = 0.183 and Mg / Al = 0.304. 42.6% of Al after sulfuric acid treatment was eluted with respect to Al before sulfuric acid treatment. The specific surface area was 376 m ² / g.
The recovered cake was dried at 120 ° C. overnight, and 55 g was weighed and used in the next step. This montmorillonite was added to an aqueous solution in which 25 g of lithium sulfate hydrate was dissolved in 347 ml of pure water in a 1 L plastic beaker and reacted at 61 ° C. for 2 hours. This slurry was filtered with a device in which an aspirator was connected to Nutsche and a suction bottle, washed with 0.5 L of pure water three times, and the recovered cake was dried at 120 ° C. overnight.
As a result, 44.9 g of chemically treated montmorillonite was obtained. Since this chemically treated montmorillonite has a Li content of 0.42% by weight and contains Li between the layers, it can be confirmed that the ion-exchangeability is maintained even after the acid and salt treatment. It was. Other compositions and specific surface areas did not change before and after this chemical treatment.
The chemically treated montmorillonite thus obtained was sieved with a sieve having an opening of 53 μm to remove coarse particles, and 42.7 g of particles having an average particle diameter of 13.9 μm were obtained as a sieve passage.

3. Catalyst preparation The following operations were carried out under inert gas using deoxygenated and dehydrated solvents and monomers.
The chemically treated montmorillonite prepared above was placed in a 200 ml volume flask and dried under reduced pressure at 200 ° C. for about 3 hours (more than 2 hours after bumping had subsided). Next, 10 g of the dried montmorillonite was weighed into a 1 L flask, and 65 ml of heptane and 35 ml of heptane solution of triisobutylaluminum (TiBA) (25.3 mmol, concentration 143.4 g / l) were added, followed by stirring at room temperature for 1 hour. did. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. To this, 85 ml of heptane and 1.53 ml of heptane solution of tri-normal octyl aluminum (TnOA) (concentration 143.6 mg / ml, 599 μmol) were added and stirred at room temperature for 15 minutes.
Here, (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride (synthesis) prepared in another flask (volume: 200 ml) Was carried out according to the example of JP-A-10-110136.) A solution of 125 mg (153.8 μmol) of heptane (30 mL) was added and stirred at 60 ° C. for 60 minutes. After completion of the reaction, heptane was added to prepare 333 ml.
The montmorillonite / metallocene complex prepared above was introduced into a stirring autoclave having an internal volume of 1 L subjected to nitrogen substitution. When the temperature in the autoclave was stabilized at 40 ° C., propylene was supplied at a rate of 5 g / hour to maintain the temperature at 40 ° C. After 4 hours, the supply of propylene was stopped and maintained for another 1 hour for prepolymerization.
After the prepolymerization, the remaining propylene was purged, and the prepolymerized catalyst slurry was recovered from the autoclave. The recovered prepolymerized catalyst slurry was allowed to stand, and 150 ml of the supernatant was extracted. Subsequently, 4.14 ml (2.96 mmol) of a heptane solution of TiBA was added at room temperature, and then dried under reduced pressure at 40 ° C. for 1 hour. As a result, 31.48 g of a prepolymerized catalyst containing 2.11 g of polypropylene per 1 g of catalyst was obtained.

4). Propylene / ethylene copolymer After thoroughly replacing the inside of the stirred autoclave with an internal volume of 3 L with propylene, 2.8 ml (2.02 mmol) of a heptane solution of TiBA was added, and 16.5 g of ethylene, 45 ml of hydrogen, and 750 ml of liquid propylene were introduced. The temperature was raised to 70 ° C. and the temperature was maintained. The prepolymerized catalyst was slurried with heptane, and 15 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. While maintaining the internal temperature at 70 ° C., polymerization was continued for 1 hour. Thereafter, 5 ml of ethanol was added to stop the polymerization reaction. The residual gas was purged to obtain a polymer. The resulting polymer was dried at 90 ° C. for 1 hour.
As a result, 349.6 g of polymer was obtained. The catalytic activity was 23,300 g-PP / g-catalyst / hr. The MFR was 0.35 g / 10 min. The results are shown in Table 1.

[Example 2]
1. Chemical treatment of ion-exchange layered silicate The sulfuric acid treatment was performed in the same manner as in Example 1 except that the granulated montmorillonite used in Example 1 was used and reacted with sulfuric acid for 150 minutes.
The chemically treated montmorillonite obtained here had an isomorphous substitution rate of 24%, and the composition (% by weight) was Al = 7.79, Si = 36.51, Mg = 2.20, Li = 0.50, The ratios were Al / Si = 0.222 and Mg / Al = 0.313. Al was eluted 30.4% before and after the sulfuric acid treatment. The specific surface area was 348 m ² / g.
In the same manner as in Example 1, a lithium sulfate hydrate treatment was performed. The surface area and pore distribution were not changed before and after the lithium sulfate hydrate treatment. In the subsequent catalyst preparation, in the same manner as in Example 1, sieving was performed with a sieve having an opening of 53 μm to remove coarse particles, and the portion passing through the sieve was used.

2. Catalyst preparation 10 g of the chemically treated montmorillonite prepared above, 126 mg (155 μmol) of (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride The same operation as in Example 1 was performed except that.
As a result, 31.90 g of a prepolymerized catalyst containing 2.15 g of polypropylene per 1 g of catalyst was obtained.

3. Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 20,600 g-PP / g-catalyst / hr. The MFR was 0.40 g / 10 min. The results are shown in Table 1.

[Example 3]
1. Chemical treatment of ion-exchange layered silicate The sulfuric acid treatment was performed in the same manner as in Example 1 except that the granulated montmorillonite used in Example 1 was used and reacted with sulfuric acid for 300 minutes.
The chemically treated montmorillonite obtained from this had an isomorphous substitution rate of 23%, the composition (% by weight) was Al = 4.94, Si = 40.45, Mg = 1.30, Li = 0.28. The ratios were Al / Si = 0.127 and Mg / Al = 0.292, and 60.2% of Al was eluted before and after the sulfuric acid treatment. The specific surface area was 406 m ² / g.
In the same manner as in Example 1, a lithium sulfate hydrate treatment was performed. The surface area and pore distribution did not change before and after the lithium sulfate hydrate treatment. In the subsequent catalyst preparation, as in Example 1, the coarse particles were removed by sieving with a sieve having a mesh opening of 53 μm, and the amount passed through the sieve was used.

2. Catalyst Preparation 10 g of the chemically treated montmorillonite prepared above and 120 mg (147. [r, 1]-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride). The same operation as in Example 1 was performed except that the amount was 6 μmol).
As a result, 31.98 g of a prepolymerized catalyst containing 2.16 g of polypropylene per 1 g of catalyst was obtained.

3. Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 20,900 g-PP / g-catalyst / hr. The MFR was 0.45 g / 10 minutes. The results are shown in Table 1.

[Comparative Example 1]
1. Granulated montmorillonite As the ion-exchangeable layered silicate, “Ben clay SL” (main component is a smectite montmorillonite having a 2: 1 type layer structure) manufactured by Mizusawa Chemical Industry, which is a granulated product of montmorillonite, was used.
This granulated montmorillonite has an average particle size of 17.5 μm, composition (% by weight): Al = 8.87, Si = 33.66, Fe = 11.99, Mg = 2.04, Na = 2.55. In the molar ratio, Al / Si = 0.274, Mg / Si = 0.070, and Mg / Al = 0.255. The specific surface area was 93 m ² / g. Moreover, the main metal cation which comprises an octahedral sheet | seat was aluminum.

2. Chemical treatment of ion-exchange layered silicate Similar to Example 1 except that 226.4 g of distilled water, 66.7 g of sulfuric acid and 40.1 g of the granulated montmorillonite were used and reacted with sulfuric acid for 60 minutes. Sulfuric acid treatment was performed. The chemically treated montmorillonite obtained from this has an isomorphous substitution rate of 15%, composition (% by weight) of Al = 8.18, Si = 36.78, Mg = 1.30. Si = 0.232, Mg / Al = 0.176, and Al was eluted by 15.3% before and after the sulfuric acid treatment. The specific surface area was 214 m ² / g.
In the same manner as in Example 1, a lithium sulfate hydrate treatment was performed. The surface area and pore distribution were not changed before and after the lithium sulfate hydrate treatment. In the subsequent catalyst preparation, as in Example 1, the coarse particles were removed by sieving with a sieve having a mesh opening of 53 μm, and the amount passed through the sieve was used.

3. Catalyst preparation 10 g of the chemically treated montmorillonite prepared above, 122 mg (150 μmol) of (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride The same operation as in Example 1 was performed except that.
As a result, 29.05 g of a prepolymerized catalyst containing 1.87 g of polypropylene per 1 g of catalyst was obtained.

4). Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 8,000 g-PP / g-catalyst / hr. The MFR was 0.92 g / 10 min. The results are shown in Table 1.

[Comparative Example 2]
1. Chemical treatment of ion-exchange layered silicate The same sulfuric acid treatment was performed using the same granulated montmorillonite as in Comparative Example 1 except that the reaction was carried out with sulfuric acid for 240 minutes. The chemically processed montmorillonite obtained from this has an isomorphous substitution rate of 14%, a composition (% by weight) of Al = 6.60, Si = 38.89, Mg = 0.98. Si = 0.177 and Mg / Al = 0.165. Al was eluted 35.4% before and after the sulfuric acid treatment. The specific surface area was 259 m ² / g.
In the same manner as in Example 1, a lithium sulfate hydrate treatment was performed. The surface area and pore distribution were not changed before and after the lithium sulfate hydrate treatment. In the subsequent catalyst preparation, as in Example 1, the coarse particles were removed by sieving with a sieve having a mesh opening of 53 μm, and the amount passed through the sieve was used.

2. Catalyst Preparation 10 g of the chemically treated montmorillonite prepared above and 123 mg (151. 1) of (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride. The same operation as in Example 1 was performed except that the amount was 3 μmol).
As a result, 32.19 g of a prepolymerized catalyst containing 2.18 g of polypropylene per 1 g of catalyst was obtained.

3. Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 15,000 g-PP / g-catalyst / hr. The MFR was 0.42 g / 10 min. The results are shown in Table 1.

[Comparative Example 3]
1. Chemical treatment of ion-exchange layered silicate 660 g of distilled water, 109 g of sulfuric acid, and 133 g of magnesium sulfate heptahydrate were added, 100 g of granulated montmorillonite used in Comparative Example 1, reaction temperature of 90 ° C., 23. The sulfuric acid treatment was the same as in Comparative Example 1 except that the reaction was performed for 5 hours.
The chemically processed montmorillonite obtained from this has an isomorphous substitution rate of 18%, the composition (% by weight) is Al = 3.50, Si = 39.60, Mg = 0.70, and the molar ratio is Al / Si. = 0.092 and Mg / Al = 0.222. Al was eluted by 66.4% before and after the sulfuric acid treatment. The specific surface area was 353 m ² / g. Thereafter, the treatment with lithium sulfate hydrate was not carried out, and sieving was carried out with a sieve having an opening of 53 μm to remove coarse particles, and the portion passing through the sieve was used.

2. Catalyst Preparation 10.2 g of the chemically treated montmorillonite prepared above and 122 mg of (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium dichloride ( The same operation as in Example 1 was performed except that the amount was 150.2 μmol).
As a result, 22.40 g of a prepolymerized catalyst containing 1.17 g of polypropylene per 1 g of catalyst was obtained.

3. Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 10,000 g-PP / g-catalyst / hr. The MFR was 0.45 g / 10 minutes. The results are shown in Table 1.

[Comparative Example 4]
1. Chemical treatment of ion-exchange layered silicate The same sulfuric acid treatment as in Comparative Example 3 was carried out except that 67 g of magnesium sulfate heptahydrate and 55 g of sulfuric acid were used to change the treatment concentration. The isomorphous substitution rate of the chemically treated montmorillonite obtained here was 21%, the composition (% by weight) was Al = 6.50, Si = 34.50, Mg = 1.60, and the molar ratio was Al / Si = It was 0.196 and Mg / Al = 0.273. Al was eluted 28.5% before and after the sulfuric acid treatment. The specific surface area was 301 m ² / g. Thereafter, the treatment with lithium sulfate hydrate was not carried out, and sieving was carried out with a sieve having an opening of 53 μm to remove coarse particles, and the portion passing through the sieve was used.

2. Catalyst Preparation 10 g of the chemically treated montmorillonite prepared above and 123 mg (151. 1) of (r)-[1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium dichloride. The same operation as in Example 1 was performed except that the amount was 3 μmol).
As a result, 15.15 g of a prepolymerized catalyst containing 0.50 g of polypropylene per 1 g of catalyst was obtained.

3. Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 18,000 g-PP / g-catalyst / hr. The MFR was 0.50 g / 10 min. The results are shown in Table 1.

[Comparative Example 5]
1. Granulated montmorillonite As the ion-exchangeable layered silicate, “Ben clay SL” (main component is a smectite montmorillonite having a 2: 1 type layer structure) manufactured by Mizusawa Chemical Industry, which is a granulated product of montmorillonite, was used.
This granulated montmorillonite has an average particle size: 14.4 μm, composition (% by weight): Al = 8.83, Si = 33.07, Fe = 2.11, Mg = 2.12, Na = 2.38. In the molar ratio, Al / Si = 0.278, Mg / Si = 0.704, and Mg / Al = 0.266. The specific surface area was 113 m ² / g. The main metal cation constituting the octahedron sheet was aluminum.

2. Chemical treatment of ion-exchange layered silicate Example 1 described in JP-A No. 2001-354715 was traced while changing the scale.
A sulfuric acid aqueous solution of magnesium sulfate prepared with 306 g of distilled water, 25.8 g of magnesium sulfate, and 41.8 g of sulfuric acid is heated to 90 ° C., 40 g of the above-mentioned commercially available granulated montmorillonite is added, and the reaction is continued at 90 ° C. for 420 minutes. It was. After filtering and washing this with demineralized water, the obtained solid cake was dried at 110 ° C. for 10 hours. Lumps in the obtained dried montmorillonite were removed with a sieve having an opening of 75 μm, and 23 g of particles that passed through the sieve were obtained.
Next, 110 g of a commercially available sulfuric acid aqueous solution of titanium sulfate (30% titanium sulfate (IV) solution, containing 13% sulfuric acid) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 156 g of pure water. Then, 23 g of magnesium salt-treated montmorillonite particles were dispersed and reacted at 90 ° C. for 180 minutes. This was filtered and washed to pH 3 with demineralized water, and the obtained water-containing solid cake was pre-dried at 110 ° C. for 10 hours to obtain 22.4 g of particulate titanium salt-treated montmorillonite having good flowability. This chemically treated montmorillonite has an isomorphous substitution rate of 16%, a composition (% by weight) of Al = 6.48, Mg = 1.08, and a molar ratio of Mg / Al = 0.185. Al was eluted by 26.6%. The specific surface area was 263 m ² / g.

3. Catalyst preparation The same operation as in Example 1 was performed except that the chemically treated montmorillonite prepared above was used.
As a result, a prepolymerized catalyst containing 2.18 g of polypropylene per 1 g of catalyst was obtained.

3. Propylene / ethylene copolymer The same operation as in Example 1 was performed except that the above catalyst was used.
As a result, the catalytic activity was 18,000 g-PP / g-catalyst / hr. The MFR was 0.40 g / 10 min. The results are shown in Table 1.

[Example 4]
1. Preparation of chemically treated ion-exchange layered silicate Chemically treated montmorillonite was obtained in the same manner as in Example 1.

2. Catalyst preparation In a three-necked flask (volume: 1 L), 10 g of the chemically treated montmorillonite prepared above was added, and heptane (66 mL) was added to form a slurry. (34.0 mL) was added and the mixture was stirred for 1 hour, and then washed with heptane until the residual liquid ratio became 1/100 to make the total volume 50 mL.
In another flask (volume: 200 mL), rac-dichloro [1,1′-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4- i-propylphenyl) indenyl}] hafnium (105 μmol) is dissolved in toluene (21 mL) (solution 1), and in another flask (volume 200 mL), rac-dichloro [1] is used as the catalyst component (a-2). , 1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium (45 μmol) was dissolved in toluene (9 mL) (solution 2).
After adding triisobutylaluminum (0.42 mmol: 0.6 mL of a heptane solution with a concentration of 143 mg / mL) to the 1 L flask containing the chemically treated montmorillonite, the above solution 1 (21 mL) was added and stirred for 20 minutes at room temperature. did.
Thereafter, triisobutylaluminum (0.18 mmol: 0.25 mL of a heptane solution having a concentration of 143 mg / mL) was added, and then the above solution 2 was added, followed by stirring for 1 hour at room temperature.
Thereafter, 170 mL of heptane was added, and this slurry was introduced into a 1 L autoclave.
After the internal temperature of the autoclave was set to 40 ° C., propylene was fed at a rate of 5 g / hour, and prepolymerization was performed while maintaining the temperature at 40 ° C. for 4 hours. Thereafter, propylene feed was stopped and residual polymerization was carried out for 1 hour. After removing the supernatant of the obtained catalyst slurry by decantation, triisobutylaluminum (6 mmol: 8.5 mL of a heptane solution having a concentration of 143 mg / mL) was added to the remaining portion and stirred for 5 minutes.
This solid was dried under reduced pressure for 1 hour to obtain 31.0 g of a dry prepolymerized catalyst. The prepolymerization ratio (a value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 2.10.

3. Propylene homopolymerization After the 3L internal stirring autoclave was sufficiently replaced with propylene, 2.8ml (2.02mmol) of TiBA heptane solution was added, 95ml of hydrogen and 750ml of liquid propylene were introduced, and the temperature was raised to 70 ° C. Maintained its temperature. The prepolymerized catalyst was slurried with heptane, and 50 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate the polymerization. While maintaining the internal temperature at 70 ° C., polymerization was continued for 1 hour. Thereafter, 5 ml of ethanol was added to stop the polymerization reaction. The residual gas was purged to obtain a polymer. The resulting polymer was dried at 90 ° C. for 1 hour.
As a result, 260 g of polymer was obtained. The catalytic activity was 5,200 g-PP / g-catalyst / hr. The MFR was 1.2 g / 10 minutes. The results are shown in Table 1.

[Comparative Example 6]
Catalyst preparation and propylene homopolymerization were carried out in the same manner as in Example 4 except that the prepared chemically treated montmorillonite was used in the same manner as in Comparative Example 1. As a result, 130 g of polymer was obtained. The catalytic activity was 2,600 g-PP / g-catalyst / hr. The MFR was 3.0 g / 10 minutes. The results are shown in Table 1.

  From Table 1, in the catalysts of Examples 1 to 3, the catalyst component composed of the ion-exchange layered silicate contained in the catalyst has an isomorphous substitution rate of 22% or more and an isomorphous substitution rate of less than 22%. It can be seen that the catalytic activity is high as compared with the catalysts of Comparative Examples 1 to 5 in which the porous silicate is a catalyst component. Similarly, in the catalyst of Example 4, the catalyst component composed of the ion-exchange layered silicate contained in the catalyst has an ion-exchange rate of 22% or more, and the ion-exchange rate layered silicic acid having an isoform-change rate of less than 22%. It can be seen that propylene homopolymerization has higher catalytic activity than the catalyst of Comparative Example 6 using a salt as a catalyst component.

  By using the catalyst component for olefin polymerization comprising the specific ion-exchange layered silicate of the present invention and the catalyst for olefin polymerization using the same, the polymerization proceeds with high activity, so that polyolefin is efficiently produced. It is possible to use it, and the industrial applicability is high.

Claims (9)

A catalyst component for olefin polymerization comprising an ion-exchange layered silicate having the following property 1.
Characteristic 1: The isomorphous substitution rate is 22% or more. The olefin polymerization catalyst component according to claim 1, wherein the ion-exchange layered silicate further has the following property 2.
Characteristic 2: The specific surface area is 150 m ² / g or more. The olefin polymerization catalyst component according to claim 1 or 2, wherein the ion-exchange layered silicate further comprises an ion-exchange layered silicate having the following property 3.
Characteristic 3: The isomorphous substitution rate of the octahedral sheet constituting the ion-exchangeable layered silicate is 22% or more.   The olefin polymerization catalyst component according to claim 1, wherein the ion-exchange layered silicate is montmorillonite.   The ion-exchange layered silicate has a molar ratio (Mg / Al) of aluminum atoms to magnesium atoms of 0.28 to 3.5. The catalyst component for olefin polymerization as described. The ion-exchange layered silicate is acid-treated with an inorganic acid or an organic acid, and 10 to 65 mol% of aluminum in the octahedron sheet constituting the ion-exchange layered silicate is desorbed by the acid treatment. The catalyst component for olefin polymerization according to any one of claims 1 to 5, wherein It is a manufacturing method of the catalyst component for olefin polymerization in any one of Claims 1-6 ,
The aluminum of the octahedral sheet of ion-exchange layered silicate having a specific surface area of 0.1 to 140 m ² / g and a molar ratio of aluminum to magnesium (Mg / Al) of 0.285 to 3.5 is 10 to 10. A process for producing a catalyst component for olefin polymerization, comprising a treatment step of desorbing 65 mol%. A catalyst for olefin polymerization comprising the following component (a), component (b) and, if necessary, component (c).
Component (a): Metallocene compound of group 4 transition metal of periodic table component (b): Catalyst component for olefin polymerization according to any one of claims 1 to 6 Component (c): Organoaluminum compound A method for producing an olefin (co) polymer, wherein one or two or more olefins are polymerized or copolymerized using the olefin polymerization catalyst according to claim 8 .