JP2002053609A - Catalyst for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst of high activity for olefin polymerization by improving the physical properties of a cocatalyst to be combined with the transition metal compound. SOLUTION: The objective catalyst for olefin polymerization comprises the following components [A] and [B]: the component [A]: the ion-exchanging laminar silicate salt that includes >=0.05 mmol of 2,6-dimehylpyridine per 1 gram of the laminar silicate in order to neutralize the acid center with a pKa of <=-8.2 with 2,6-dimethylpyridine; the component [B] : a Group 3-Group 12 transition metal compound in the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization. More specifically, the present invention relates to a catalyst for olefin polymerization using a specific cocatalyst in which the strength and amount of acid sites are controlled.

[0002]

2. Description of the Related Art It is known to produce olefin polymers by polymerizing olefins in the presence of a catalyst utilizing clay or clay mineral as a catalyst component for olefin polymerization (Japanese Patent Application Laid-Open Nos. 5-295022 and 5-29522). −30191
7). Olefin polymerization catalysts containing, as a component, an ion-exchangeable layered compound which has been subjected to acid treatment or salt treatment are also known (JP-A-7-228621, JP-A-7-3).
09906, JP-A-7-309907, JP-A-7-22
8621, JP-A-8-127613, JP-A-10-16
8109).

Further, an olefin polymerization catalyst containing, as a component, an ion-exchangeable layered compound treated in the presence of an acid and a salt is also known (JP-A-10-16811).
0). However, these methods have a problem that the catalytic activity is not sufficient.

[0004]

SUMMARY OF THE INVENTION The present invention provides a highly active catalyst for olefin polymerization by controlling the physical properties of a co-catalyst, particularly an ion-exchangeable layered compound.

[0005]

Means for Solving the Problems The present inventors have noticed that certain clay minerals have a function as a solid acid,
As a result of intensive studies, the present invention has been achieved. Olefin polymerization requires a transition metal of Groups 3 to 12 of the periodic table, and one of the means for activating the transition metal is the use of an acid. The present invention provides a highly active catalyst by using, as a promoter component, an ion-exchangeable layered silicate having a specific acid strength in a predetermined amount with respect to an acid point.

That is, the present invention provides an olefin polymerization catalyst comprising the following components [A] and [B].

Component [A]: An amount of 0.05 mmol or more of 2,6 dimethylpyridine per 1 g of the ion-exchanged phyllosilicate to neutralize acid sites having a pKa of -8.2 or less. , Containing an ion-exchange layered silicate, Component [B]: a transition metal compound belonging to Groups 3 to 12 of the periodic table,

The present invention also provides a catalyst for olefin polymerization characterized by comprising the following components [A], [B] and [C].

Component [A]: An amount of 0.05 mmol or more of 2,6 dimethylpyridine per 1 g of ion-exchanged layered silicate to neutralize acid sites having a pKa of -8.2 or less. , An ion-exchange layered silicate contained therein, Component [B]: a transition metal compound belonging to Groups 3 to 12 of the periodic table, Component [C]: an organoaluminum compound,

Further, the present invention provides a catalyst for olefin polymerization, wherein the component [A] is a chemically treated smectite silicate, and a smectite group silicate wherein the component [A] is acid-treated. An object of the present invention is to provide an olefin polymerization catalyst.

Furthermore, the present invention provides a catalyst for olefin polymerization characterized by contacting the following components [A] and [B] with an olefin.

Component [A]: an amount of 0.05 mmol or more of 2,6 dimethylpyridine per 1 g of the ion-exchanged phyllosilicate to neutralize acid points having a pKa of -8.2 or less. , Containing an ion-exchange layered silicate, Component [B]: a transition metal compound belonging to Groups 3 to 12 of the periodic table,

[0013] The present invention also provides an olefin polymerization catalyst characterized by contacting the following components [A], [B] and [C] with an olefin.

Component [A]: an amount of 0.05 mmol or more of 2,6 dimethylpyridine per 1 g of ion-exchange layered silicate to neutralize acid sites having a pKa of -8.2 or less. , An ion-exchange layered silicate contained therein, Component [B]: a transition metal compound belonging to Groups 3 to 12 of the periodic table, Component [C]: an organoaluminum compound,

Further, the present invention provides a catalyst for olefin polymerization wherein the component [A] satisfies the following nitrogen adsorption / desorption property [I], and [I]: a relative pressure P in a desorption isotherm by a nitrogen adsorption / desorption method. P / P _{0 with} respect to the adsorption amount (a) at / P ₀ = 1
(B) / (a) ≧ 0.8 where P is a measured pressure and P ₀ is an atmospheric pressure. The present invention provides the above olefin polymerization catalyst, wherein the component [A] satisfies the following nitrogen adsorption / desorption property [II].

[II]: In the adsorption and desorption isotherms by the nitrogen adsorption / desorption method, the remaining adsorption amount (b) of the desorption isotherm at a relative pressure P / P ₀ = 0.85 and the relative pressure P / P ₀ = 0. 8
The difference in the adsorption amount (c) of the adsorption isotherm in No. 5 satisfies the following expression. (B)-(c)> 25 (cc / g)

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION <Component [A]> (1) Strength and Amount of Acid Site In the present invention, an acid site having a pKa of -8.2 or less is used for neutralizing the acid site. An ion-exchange phyllosilicate containing an amount of dimethylpyridine of 0.05 mmol or more per gram of the ion-exchange phyllosilicate is used.

Here, the acid is one of the categories of substance classification, and is defined as a substance that is a Bronsted acid or a Lewis acid. Further, the acid point is defined as a structural unit in which the substance exhibits properties as an acid, and the amount thereof is determined by an analytical means such as a titration method described below, which is required for neutralization per unit weight of 2,6. It is determined by the molar amount of dimethylpyridine. Acid sites having a pKa of -8.2 or less are called "strong acid sites".

When the ion exchangeable layered silicate of the catalyst component [A] of the present invention contains a specific strong acid site in a specific amount or more, the polymerization activity is remarkably improved.

The measurement of the acid point was carried out by using 2,6-
Dimethylpyridine is used, and anthraquinone is used as an indicator. A sample, anthraquinone and toluene were placed in a container, and 2,6-dimethylpyridine was added dropwise thereto, and the amount of 2,6-dimethylpyridine added until the yellow color, which was the acidic color of the indicator, disappeared. Have p
Ka is the amount of the strong acid point of -8.2 or less.

The term "disappearance of the yellow color, which is an acidic color" in the above description refers to the point in time when the color starts to change by adding the titrant and the color does not change when the titrant is further added. However, the color does not necessarily have to completely disappear. The term "yellow" refers to the color when the acid is colorless or white. When the sample originally has a color, it is not necessarily yellow, and in that case, it indicates the color generated by adding the indicator.

When the color does not change to yellow even when anthraquinone as an indicator is added, the amount of strong acid sites having a pKa of -8.2 or less is set to zero. The titration test needs to be performed in a purified inert gas, for example, a nitrogen or argon atmosphere in order to avoid the influence of oxygen and moisture. When the rate of addition of the titration reagent is extremely high or low, accurate measurement cannot be performed. Therefore, 2,6-dimethylpyridine is usually added in an amount of 0.5 to 5 per minute per 1 g of the ion-exchange layered silicate. It is necessary to add dropwise at a slow rate of micromol, preferably about 1 micromol. The measurement is performed at a temperature of 10 ° C.

The above method for measuring the amount of acid sites is described in O. John.
ref., J. Son. Phys. Chem. Vol5
9, 827 (1955). If the measurement cannot be performed by the above titration method in principle, other measurement methods, for example, a reverse titration method can be used instead.

The amount of acid sites is determined by the ion-exchange layered silicate 1
The amount of 2,6 dimethylpyridine required to neutralize the acid sites per gram is 0.05 mmol or more, preferably 0.07 mmol or more, more preferably 0.10 mmol or more, and even more preferably 0.12 mmol or more. The amount is at least millimol. The greater the amount of acid sites, the better, and the upper limit is not limited, but is practically 2 mmol or less, preferably 1 mmol or less.

As the ion-exchangeable layered silicate which is the component [A] of the present invention, those having the following characteristics [I] and [II] are preferably used.

[I]: In the desorption isotherm by the nitrogen adsorption / desorption method, the ratio of the residual adsorption amount (b) at P / P ₀ = 0.85 to the adsorption amount (a) at the relative pressure P / P ₀ = 1 (B) / (a) ≧ 0.8 where P is the measured pressure and P ₀ is the atmospheric pressure.

[0027] [II] nitrogen in the adsorption and desorption isotherm by adsorption and desorption, remaining adsorption amount of desorption isotherm at a relative pressure _{P / P 0 = 0.85 (b} ) and relative pressure P / P ₀ = 0.85
That the difference in the adsorption amount (c) of the adsorption isotherm satisfies the following equation. (B)-(c)> 25 (cc / g)

The measurement of the adsorption and desorption isotherms by the nitrogen adsorption method will be described below. The amount of gas absorbed by the solid is
When the temperature is constant, if the solid and the gas are determined, the potential of the adsorption interaction can be considered to be almost constant.Therefore, the adsorption amount is a function of only the pressure, and the curve showing the relationship between the two is generally expressed as an adsorption isotherm. Call. In the present invention,
The temperature is indicated by relative pressure P / P ₀ , and the curve when the relative pressure is increased is distinguished as an adsorption isotherm, and the curve when the relative pressure is decreased is distinguished as a desorption isotherm.

The shape of these adsorption isotherms changes depending on the kind of solid, and in the region where the relative pressure P / P ₀ is 0.3 or more, the desorption isotherm does not coincide with the adsorption isotherm and is irreversible. It is known that the desorption isotherm is above the adsorption isotherm in a certain relative pressure range. This is called the adsorption history phenomenon,
Alternatively, adsorption hysteresis (adsorption hysteresis)
(steresis). Although there is no theory that can explain everything about this phenomenon, one idea is to use a pore model “ink bottle type” with a narrower entrance than the inside.
ramer and McBain et al. (JH DeBoer: The Structure).
and Properties ofPorous
Material P68 (DH Everett)
et al ed Butterworths Sci.
Pulications)).

That is, in the ink bottle type pore, adsorption occurs from a wide radius portion in the pore and the pore is filled, whereas desorption occurs from the small radius entrance of the filled pore. The equilibrium pressure at the time of desorption is smaller than that at the time of adsorption, and the amount of adsorption at the entrance is smaller than the amount of adsorption in the pores. A pressure difference will occur and hysteresis will appear.

In the present invention, the measurement is carried out according to a generally used nitrogen adsorption method. The shape of the adsorption / desorption isotherm obtained from the ion-exchangeable layered silicate of the catalyst component of the present invention is such that the pore structure of the catalyst component tends to be an ink bottle type, and unexpectedly, the catalyst performance, particularly the catalyst activity, is unexpectedly increased. It was found that it had a significant effect. From such a viewpoint, the value of (b) / (a) obtained from the adsorption / desorption isotherm by the nitrogen adsorption method is preferably 0.8 or more, more preferably 0.9 or more, and particularly preferably 0.95 or more. It is suitable, and the value of (b)-(c) is more than 25, preferably 30 or more, and more preferably 35 or more.

(2) Ion-exchanged layered silicate The ion-exchanged layered silicate used in the present invention has a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with weak bonding force. A silicate compound whose contained ions are exchangeable. Most ion-exchanged phyllosilicates are naturally produced mainly as a main component of clay minerals, but these ion-exchanged phyllosilicates are not limited to natural ones, but are also artificially synthesized. There may be. Further, these ion-exchange layered silicates may be subjected to a chemical treatment described later.

In the present invention, if the ion-exchange property is present before the chemical treatment, the physical and chemical properties are changed by the treatment, and the ion-exchange property and the layer structure are lost. The acid salt is also treated as an ion-exchangeable layered silicate.

Specific examples of ion-exchangeable phyllosilicates include, for example, “Clay Mineralogy” written by Haruo Shimizu, Asakura Shoten (19)
1995) and the like, and a layered silicate having a 1: 1 type structure or a 2: 1 type structure. The 1: 1 type structure is basically based on a stack of a 1: 1 layer structure in which a one-layer tetrahedral sheet and a one-layer octahedral sheet are combined as described in the above “Clay Mineralogy” and the like. To indicate the structure
The 2: 1 type structure refers to a structure based on the stacking of a 2: 1 layer structure in which two layers of tetrahedral sheets sandwich one layer of octahedral sheets.

Specific examples of the ion-exchangeable layered silicate in which the 1: 1 layer is a main constituent layer include kaolin group silicates such as dickite, nacrite, kaolinite, metahaloisite, and halloysite, chrysotile, lizardite, and the like. Examples include serpentine group silicates such as antigorite.

Specific examples of the ion-exchange layered silicate in which the 2: 1 layer is a main constituent layer include montmorillonite,
Smectite silicates such as beidellite, nontronite, saponite, hectorite, stevensite, etc.
Vermiculite silicates such as vermiculite, mica, illite, sericite, mica silicates such as chlorite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite and the like. These may form a mixed layer.

Among these, those in which the main component is an ion-exchange layered silicate having a 2: 1 type structure are preferable. More preferably, the main component is a smectite group silicate, and even more preferably, the main component is montmorillonite.

The type of the interlayer cation (cation contained between the layers of the ion-exchange layered silicate) is not particularly limited, but the main components are alkali metals of Group 1 of the periodic table such as lithium and sodium; Alkaline earth metals of Group 2 of the periodic table such as calcium and magnesium, or transition metals such as iron, cobalt, copper, nickel, zinc, ruthenium, rhodium, palladium, silver, iridium, platinum and gold are industrial raw materials. Is preferred because it is relatively easily available.

The particle size of the ion-exchange layered silicate is preferably in the range of 0.02 to 2 μm as primary particles.

The ion-exchange layered silicate may be used in a dry state or in a slurry state in a liquid. The shape of the ion-exchange layered silicate is not particularly limited, and may be a naturally occurring shape, a shape at the time of artificial synthesis, or a shape obtained by operations such as pulverization, granulation, and classification. A processed ion-exchange layered silicate may be used. Of these, the use of a granulated ion-exchange layered silicate is particularly preferable because it gives good polymer particle properties when the ion-exchange layered silicate is used as a catalyst component.

The processing of the shape of the ion-exchanged layered silicate such as granulation, pulverization, classification, etc. may be performed before the chemical treatment (that is, the above-mentioned ion-exchanged layered silicate having a pre-processed shape is subjected to the above-mentioned chemical treatment). Treatment may be performed), or the shape may be processed after performing the chemical treatment.

Examples of the granulation method used here include stirring granulation, spray granulation, tumbling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, and emulsification. A granulation method, a submerged granulation method, a compression molding granulation method and the like are mentioned, but not particularly limited. Preferably, a stirring granulation method,
Spray granulation, tumbling granulation, and fluidized granulation are mentioned, and particularly preferred are stirring granulation and spray granulation.

When spray granulation is performed, water or methanol, ethanol,
Organic solvents such as chloroform, methylene chloride, pentane, hexane, heptane, toluene and xylene are used. Preferably, water is used as the dispersion medium. The concentration of the component [A] in the raw slurry liquid of the spray granulation for obtaining spherical particles is 0.1 to 70% by weight, preferably 1 to 50% by weight,
Particularly preferably, it is 5 to 30% by weight. The temperature at the inlet of the hot air for spray granulation from which spherical particles can be obtained varies depending on the dispersion medium.
Perform at 0-220 ° C.

Further, at the time of granulation, an organic substance, an inorganic solvent, an inorganic salt, and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcellulose, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein, Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel, gum arabic, sodium alginate and the like.

The spherical particles obtained as described above have a particle size of 0.2 to suppress crushing and fine powder generation in the polymerization step.
It preferably has a compressive breaking strength of not less than MPa. In the case of such a particle strength, the effect of improving the particle properties is effectively exhibited, particularly when prepolymerization is performed. The particle size of the granulated ion-exchange layered silicate is 0.1 to 1
000 μm, preferably in the range of 1 to 500 μm.
The pulverization method is not particularly limited, either dry pulverization or wet pulverization may be used.

(3) Chemical treatment of ion-exchange layered silicate It is desirable that the ion-exchanged layered silicate of the present invention is subjected to a chemical treatment. Contacting a treatment agent containing an alkali, an oxidizing agent, a reducing agent, or a compound capable of intercalating between layers of the ion-exchange layered silicate with the ion-exchange layered silicate. Intercalation refers to the introduction of another substance between layers of a layered substance, and the substance introduced is called a guest compound. Among these treatments, acid treatment or salt treatment is particularly preferred.

The common effect of the chemical treatment is to exchange interlayer cations. In addition, various chemical treatments have the following various effects. For example, according to the acid treatment with acids, impurities on the silicate surface are removed, and the surface area can be increased by eluting cations such as Al, Fe, and Mg in the crystal structure. This contributes to increasing the acid strength of the silicate and increasing the amount of acid sites per unit weight.

In the alkali treatment with alkalis, the crystal structure of the clay mineral is destroyed, resulting in a change in the structure of the clay mineral. In the case of intercalation or salt treatment, an ion complex, a molecular complex, an organic derivative, or the like is formed, and the surface area or the interlayer distance can be changed. By using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material in which the layers are expanded. That is, the bulky ions play a pillar-like role to support the layered structure, and are called pillars.

Hereinafter, specific examples of the treating agent will be shown. In the present invention, two or more selected from the group consisting of the following acids, salts, alkalis, oxidizing agents, reducing agents, and compounds capable of intercalating between layers of the ion-exchanged layered silicate are combined. Those may be used as a treatment agent.
In addition, these acids, salts, alkalis, oxidizing agents, reducing agents, and compounds capable of intercalating between the layers of the ion-exchange layered silicate may be a combination of two or more types. Among these, a combination of salt treatment and acid treatment is particularly preferred.

(A) Acids The acid treatment removes impurities on the surface, exchanges cations existing between layers, and partially removes cations such as Al, Fe, and Mg incorporated in the crystal structure. Alternatively, all can be eluted. Examples of the acid used in the acid treatment include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, benzoic acid, stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, and phthalic acid. Among them, inorganic acids are preferred.

(B) Salts Salts include cations selected from the group consisting of organic cations, inorganic cations and metal ions, organic anions,
Salts composed of inorganic anions and anions selected from the group consisting of halide ions are exemplified. For example, at least one selected from the group consisting of a cation containing at least one atom selected from Groups 1 to 14 of the periodic table and a halogen anion, an inorganic Bronsted acid and an organic Bronsted acid anion. Preferred examples include compounds composed of an anion. Particularly preferred is a compound whose anion comprises an inorganic Bronsted acid or halogen.

Specific examples of such salts include LiC
1, LiBr, Li_TwoSO_Four, Li_Three(PO_Four), LiNO
_Three, Li (OOCCH_Three), NaCl, NaBr, Na_Two
SO _Four, Na_Three(PO_Four), NaNO_Three, Na (OOCCH
_Three), KCl, KBr, K_TwoSO_Four, K_Three(PO_Four), KN
O_Three, K (OOCCH_Three), CaCl_Two, CaSO_Four, Ca
(NO_Three)_Two, Ca_Three(C₆H_FiveO₇)_Two, Sc (OOCC
H_Three)_Two, Sc_Two(CO_Three)_Three, Sc_Two(C_TwoO_Four)_Three, Sc
(NO_Three)_Three, Sc_Two(SO_Four)_Three, ScF_Three, ScCl_Three,
ScBr_Three, ScI_Three, Y (OOCCH_Three)_Three, Y (CH_Three
COCHCOCH_Three)_Three, Y_Two(CO_Three)_Three, Y_Two(C_TwoO_Four)
_Three, Y (NO_Three)_Three, Y (ClO_Four)_Three, YPO_Four, Y_Two(S
O_Four)_Three, YF_Three, YCl_Three, La (OOCH_Three)_Three, La
(CH_ThreeCOCHCOCH_Three)_Three, La_Two(CO_Three)_Three, La
(NO_Three)_Three, La (ClO_Four)_Three, La_Two(C _TwoO_Four)_Three, L
aPO_Four, La_Two(SO_Four)_Three, LaF_Three, LaCl_Three, La
Br_Three, LaI_Threeetc.

Sm (OOCCH ₃ ) ₃ , Sm (CH ₃ CO
CHCOCH ₃ ) ₃ , Sm ₂ (CO ₃ ) ₃ , Sm (N
O ₃ ) ₃ , Sm (ClO ₄ ) ₃ , Sm ₂ (C ₂ O ₄ ) ₃ , SmP
O ₄ , Sm ₂ (SO ₄ ) ₃ , SmF ₃ , SmCl ₃ , SmBr
₃ , SmI ₃ , Yb (OOCCH ₃ ) ₃ , Yb (N
O ₃ ) ₃ , Yb (ClO ₄ ) ₃ , Yb ₂ (C ₂ O ₄ ) ₃ , Yb ₂
(SO ₄ ) ₃ , YbF ₃ , YbCl ₃ , Ti (OOCC
H ₃ ) ₄ , Ti (CO ₃ ) ₂ , Ti (NO ₃ ) ₄ , Ti (SO
₄ ) ₂ , TiF ₄ , TiCl ₄ , TiBr ₄ , TiI ₄ , Zr
(OOCCH ₃ ) ₄ , Zr (CO ₃ ) ₂ , Zr (NO ₃ ) ₄ ,
Zr (SO ₄ ) ₂ , ZrF ₄ , ZrCl ₄ , ZrBr ₄ , Z
rI ₄ , ZrOCl ₂ , ZrO (NO ₃ ) ₂ , ZrO (Cl
O ₄ ) ₂ , ZrO (SO ₄ ), Hf (OOCCH ₃ ) ₄ , H
f (CO ₃ ) ₂ , Hf (NO ₃ ) ₄ , Hf (SO ₄ ) ₂ , Hf
_{OCl 2, HfF 4, HfCl 4} , HfBr 4, HfI 4,
V (CH ₃ COCHCOCH ₃ ) ₃ , VOSO ₄ , VOCl
₃ , VCl ₃ , VCl ₄ , VBr ₃ , Nb (CH ₃ COCH
COCH ₃ ) ₅ , Nb ₂ (CO ₃ ) ₅ , Nb (NO ₃ ) ₅ , N
b ₂ (SO ₄ ) ₅ , ZrF ₅ , ZrCl ₅ , NbBr ₅ , Nb
I ₅ , Ta (OOCCH ₃ ) ₅ , Ta ₂ (CO ₃ ) ₅ , Ta
(NO ₃ ) ₅ , Ta ₂ (SO ₄ ) ₅ , TaF ₅ , TaCl ₅ ,
TaBr ₅ , TaI _{5 and the} like.

Cr (OOCH_Three)_TwoOH, Cr (CH_ThreeC
OCHCOCH_Three)_Three, Cr (NO_Three) _Three, Cr (Cl
O_Four)_Three, CrPO_Four, Cr_Two(SO_Four)_Three, CrO_TwoCl_Three,
CrF_Three, CrCl_Three, CrBr_Three, CrI_Three, MoOCl
_Four, MoCl_Three, MoCl_Four, MoCl_Five, MoF₆, Mo
I_Two, WCl_Four, WCl₆, WF₆, WBr_Five, Mn (OO
CH_Three)_Two, Mn (CH_ThreeCOCHCOCH_Three)_Three, MnC
O_Three, Mn (NO_Three)_Two, MnO, Mn (ClO_Four)_Two, M
nF_Two, MnCl_Two, MnBr_Two, MnI_Two, Fe (OOC
H_Three)_Two, Fe (CH_ThreeCOCHCOCH_Three)_Three, FeC
O_Three, Fe (NO_Three)_Three, Fe (ClO_Four)_Three, FePO_Four,
FeSO_Four, Fe_Two(SO_Four)_Three, FeF_Three, FeCl_Three, M
nBr_Three, FeI_Three, FeC₆H_FiveO₇, Co (OOCH_Three)
_Two, Co (CH_ThreeCOCHCOCH_Three)_Three, CoCO_Three, C
o (NO_Three)_Two, CoC_TwoO_Four, Co (ClO_Four) _Two, Co_Three
(PO_Four)_Two, CoSO_Four, CoF_Two, CoCl_Two, CoB
r_Two, CoI_Two, NiCO_Three, Ni (NO_Three)_Two, NiC_TwoO
_Four, Ni (ClO_Four)_Two, NiSO_Four, NiCl_Two, NiB
r_Twoetc.

CuCl_Two, CuBr_Two, Cu (NO_Three)_Two,
CuC_TwoO_Four, Cu (ClO_Four)_Two, CuSO_Four, Cu (O
OCCH_Three)_Two, Zn (OOCH_Three)_Two, Zn (CH_ThreeCO
CHCOCH_Three)_Two, ZnCO_Three, Zn (NO_Three)_Two, Zn
(ClO_Four)_Two, Zn_Three(PO_Four)_Two, ZnSO_Four, Zn
F_Two, ZnCl_Two, ZnBr_Two, ZnI_Two, AlF_Three, Al
Cl_Three, AlBr_Three, AlI_Three, Al_Two(SO_Four)_Three, Al_Two
(C_TwoO_Four)_Three, Al (CH_ThreeCOCHCOCH_Three)_Three, Al
(NO_Three)_Three, AlPO_Four, GeCl_Four, Sn (OOCCH
_Three)_Four, Sn (SO_Four)_Two, SnF_Four, SnCl_FourEtc.
It is.

Examples of organic cations include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, dodecylammonium, N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4 , 5-pentamethylanilinium, N, N-dimethyloctadecyl ammonium, octadodecylammonium, N, N-2,4,
5-pentamethylanilinium, N, N-dimethyl-p
-N-butylanilinium, N, N-dimethyl-p-trimethylsilylanilinium, N, N-dimethyl-1-
Ammonium compounds such as naphthylanilinium, N, N, 2-trimethylanilinium and 2,6-dimethylanilinium, pyridinium, quinolinium, N-methylpiperidinium, 2,6-dimethylpyridinium,
Nitrogen-containing aromatic compounds such as 2,6,6-tetramethylpiperidinium, dimethyloxonium, diethyloxonium, diphenyloxonium, furanium, oxonium compounds such as oxolanium, triphenylphosphonium, tri-o-tolylphosphonium, Examples thereof include, but are not limited to, phosphonium compounds such as tri-p-tolylphosphonium and trimesitylphosphonium, and phosphorus-containing aromatic compounds such as phosphabenzonium and phosphanaphthalenium.

Examples of the anions include, in addition to the above-mentioned anions, anions composed of boron compounds and phosphorus compounds, such as hexafluorophosphate, tetrafluoroborate and tetraphenylborate. It is not limited to these.

These salts may be used alone or in combination of two or more. Further, it may be used in combination with an acid, an alkali, an oxidizing agent, a reducing agent, a compound intercalating between layers of the ion-exchange layered silicate, or the like. These combinations may be used in combination for the treatment agent added at the start of the treatment, or may be used in combination for the treatment agent added during the treatment.

(C) Alkali As the treating agent used in the alkali treatment, LiOH,
NaOH, KOH, Mg (OH) ₂ , Ca (OH) ₂ , S
r (OH) ₂ , Ba (OH) _{2 and the} like are exemplified. In addition,
Since the acid point loss of the ion-exchange layered silicate due to the alkali treatment can be considered, it is preferable to carry out the acid treatment after achieving the structural change of the clay mineral by the alkali treatment. Alternatively, even after the alkali treatment, the effect of the present invention is not impaired at all if the strength and amount of the acid point satisfy the above-mentioned range. Among these, LiO
H, NaOH, KOH and Mg (OH) ₂ are preferred.

(D) Oxidizing agents As oxidizing agents, HMnO ₄ , NaMnO ₄ , KMnO ₄
Permanganate acids such _{as, HNO 3, N 2 O 4} , N 2 O 3, N 2
O, Cu (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ , AgNO ₃ , K
Nitric acid compounds such as NO ₃ and NH ₄ NO ₃ , F ₂ , Cl ₂ , B
halogen such as r ₂ and I ₂ , H ₂ O ₂ , Na ₂ O ₂ , Ba
O ₂ , (C ₆ H ₅ CO) ₂ O ₂ , K ₂ S ₂ O ₈ , K ₂ SO ₅ , HC
O ₃ H, CH ₃ CO ₃ H, C ₆ H ₅ CO ₃ H, C ₆ H ₄ (COO
H) peroxides such as CO ₃ H, CF ₃ CO ₃ H, KIO,
KClO, KBrO, KClO ₃ , KBrO ₃ , KI
Oxygen acids such as O ₃ , HIO ₄ , Na ₃ H ₂ I ₆ , KIO ₄ ,
CeO ₂ , Ag ₂ O, CuO, HgO, PbO ₂ , Bi ₂ O
₃ , oxides such as OsO ₄ , RuO ₄ , SeO ₂ , MnO ₂ , As ₂ O ₅ , oxygens such as oxygen and ozone, hot concentrated sulfuric acid, a mixture of fuming sulfuric acid and concentrated nitric acid, nitrobenzene, iodoso compounds and the like. Can be

(E) Reducing agent H ₂ , HI, H ₂ S, LiAlH ₄ , N
hydrogen and hydrogen compounds such as aBH ₄ , sulfur compounds such as SO ₂ and Na ₂ S, alkali metals, alkaline earth metals,
Metals such as transition metals of Groups 3 to 10 of the periodic table or alloys thereof, Fe (II), Sn (II), Ti (II), Cr
Examples thereof include salts of metals in a low valence state such as (II), CO, and the like.

(F) Compound for Intercalation The guest compound used for intercalating between the layers of the ion-exchanged layered silicate is TiC
l ₄ , a cationic inorganic compound such as ZrCl ₄ , Ti (O
R) ₄ , Zr (OR) ₄ , PO (OR) ₃ , B (OR)
₃ Metal alcoholates such as [R is an alkyl group, an aryl group, etc.], [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH)
₁₄ ] ²⁺ , metal hydroxide ions such as [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ , ethylene glycol, glycerol, urea,
Organic compounds such as hydrazine, organic cations such as alkyl ammonium ion and the like can be mentioned.

When intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , Ge (OR)
Polymers obtained by hydrolyzing metal alcoholates such as _4, etc.,
Colloidal inorganic compounds such as SiO ₂ can also be present. Examples of pillars include oxides generated by intercalating the hydroxide ions between layers and then heating and dehydrating. As a method of using the guest compound, it may be used as it is, or may be used after newly adding and adsorbing water, or after heat dehydration treatment. Further, they may be used alone or as a mixture of two or more of the above solids.

The above-mentioned various treating agents may be dissolved in an appropriate solvent and used as a treating agent solution, or the treating agent itself may be used as a solvent. Solvents that can be used include
Water, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons,
Examples thereof include esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide, carbon disulfide, nitrobenzene, pyridines, and halides thereof. The concentration of the treating agent in the treating agent solution is preferably about 0.1 to 100% by weight, more preferably about 5 to 50% by weight. When the concentration of the treating agent is within this range, there is an advantage that the time required for the treatment is shortened and production can be efficiently performed.

(4) Chemical treatment step The treatment conditions are not particularly limited, but usually, the treatment temperature is selected from the room temperature to the boiling point of the treatment agent solution, and the treatment time is selected from 5 minutes to 24 hours. It is preferable to carry out the reaction under the condition that at least a part of the substance constituting the acid salt is removed or replaced. The ratio between the ion-exchange layered silicate and the treating agent in the chemical treatment step is not particularly limited, but is preferably ion-exchanged layered silicate [g]: treating agent [mol] = 1: 0.001 to 0.001. 1: about 0.1.

After the above chemical treatment, it is possible and preferable to remove excess treatment agent and ions eluted by the treatment. At this time, a liquid such as water or an organic solvent is generally used. After the dehydration, drying is performed. Generally, the drying temperature is 100 to 800 ° C., preferably 150 ° C.
It can be performed at 〜600 ° C. If the temperature is higher than 800 ° C., the silicate may be structurally broken, which is not preferable.

The properties of these ion-exchange layered silicates vary depending on the drying temperature even if the structure is not destroyed. Therefore, it is preferable to change the drying temperature according to 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 can be carried out by various methods.

When the chemically treated ion-exchange layered silicate is used as the component [A] of the present invention, the amount of acid sites is measured in the silicate after the chemical treatment. In the present invention, the acid sites having a pKa of -8.2 or less, and the amount of 2,6 dimethylpyridine required to neutralize the acid sites is 0.05 mmol or more per gram of the ion-exchange layered silicate. It is important that the ion-exchange layered silicate is appropriately combined with the above-mentioned various treatment methods so as to have a certain amount, preferably 0.07 mmol / g or more, and the strength and amount of acid sites are controlled. . The silicate has a guest compound,
Although various metals are contained in the form of pillars and the like, those containing aluminum in a state after chemical treatment are preferable.
/ Si atomic ratio of 0.05 to 0.4, preferably 0.05 to 0.25, more preferably 0.07 to 0.2
A range of 3 is preferred. The Al / Si atomic ratio is considered to be an index of the acid treatment of the clay portion.

<Component [B]> The component [B] used in the present invention is a transition metal compound belonging to 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
Examples thereof include bisimide compounds of transition metals of Groups 10 to 10, and phenoxyimine compounds of transition metals of Groups 3 to 11.

Among these, a metallocene compound of a Group 4 transition metal is preferable. Specifically, the following general formulas (I) to (I)
The compound represented by (VI) is used.

[0071] _{(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 bridging the two conjugated five-membered ring ligands, Q ′ is a bonding group bridging the conjugated five-membered ligand and the Z group, and Q ″ is R A bonding group bridging ⁴ and R ⁵ , M is a transition metal belonging to Groups 3 to 12 of the periodic table, X, Y and W are each independently hydrogen, halogen, or a carbon atom having 1 to 2 carbon atoms.
0 hydrocarbon group, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
A phosphorus-containing hydrocarbon group of 20 or a silicon-containing hydrocarbon group of 1 to 20 carbon atoms, Z is a ligand containing oxygen, sulfur, a silicon-containing hydrocarbon group of 1 to 40 carbon atoms, It indicates a nitrogen-containing hydrocarbon group or a phosphorus-containing hydrocarbon group having 1 to 40 carbon atoms. M is particularly preferably a Group 4 transition metal such as Ti, Zr or Hf.

R ^{1 to} R ⁵ are each independently a group having 1 to 1 carbon atoms.
20 hydrocarbon groups, halogen groups, halogen-containing hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups, aryloxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups or boron-containing hydrocarbons Represents a group. Also,
Two adjacent R ¹ , two R ² , two R ³ , two R ⁴ , or two R ⁵ are bonded to each other to form a C ⁴ to C 1
It may form zero rings. a, b, c, d, e,
And f are 0 ≦ a ≦ 5, 0 ≦ b ≦ 5, 0 ≦ c ≦
4, 0 ≦ d ≦ 4, 0 ≦ e ≦ 4, 0 ≦ f ≦ 5, 0 ≦ g ≦
5, an integer satisfying 0 ≦ h ≦ 5.

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

The above general formulas (I), (II) and (II)
Specific examples of the Zr complex represented by I), (IV), (V), and (VI) are shown below, but compounds in which Zr is replaced with Hf or Ti can also be used. 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 of the compounds shown.

Formula (I) biscyclopentadienyl zirconium dichloride, bis (2-methylindenyl) zirconium dichloride,
Bis (2-methyl-4,5benzoindenyl) zirconium dichloride, bisfluorenylzirconium dichloride, bis (4H-azulenyl) zirconium dichloride, bis (2-methyl-4H-azulenyl) cyclopentadienyl zirconium dichloride, bis (2-methyl-4-phenyl-4H-azulenyl) zirconium dichloride, bis (2-methyl-4- (4-chlorophenyl) -4H-azulenyl) zirconium dichloride.

Formula (II) Dimethylsilylenebis (1,1′-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-methylindenyl)} zirconium dichloride, dimethylsilylenebis} 1 , 1 '-(2-
Methylindenyl) {ethylenebis} 1,1 ′-(2-
Methyl-4,5 benzoindenyl) {zirconium dichloride, dimethylsilylenebis {1,1 '-(2-methyl-4-hydroazulenyl)} zirconium dichloride, dimethylsilylenebis {1,1'-(2-methyl-
4-phenyl-4-hydroazulenyl)} zirconium dichloride, dimethylsilylenebis [1,1 ′-{2-
Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride, dimethylsilylenebis {1,1 ′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride, ethylenebis {1,1 '-(2-Methyl-4-hydroazulenyl) zirconium dichloride.

Formula (III) (Tertiary butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide)-(tetramethyl-η
5-cyclopentadienyl) -1,2-ethanediyl-
Zirconium dichloride, (ethylamide) (tetramethyl-η5-cyclopentadienyl) -methylene zirconium dichloride, (tertiary butylamido) dimethyl- (tetramethyl-η5-cyclopentadienyl) silane zirconium dichloride, (tertiary butylamide) ) Dimethyl (tetramethyl-η5-cyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η5-cyclopentadienyl) silanezirconium dichloride, (phenylphosphido) dimethyl (tetramethyl-η5) -Cyclopentadienyl) silane zirconium dibenzyl.

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.

Formula (V) (cyclopentadienyl) zirconium trichloride,
(2,3-dimethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium trichloride, (cyclopentadienyl) zirconium triisopropoxide, (pentamethylcyclopentadienyl) zirconium triiso Propoxide.

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

Further, as specific examples of metallocene compounds, JP-A-7-188335 and Journal of
American Chemical Society
y, 1996, Vol. Transition metal compounds having a ligand containing at least one element other than carbon in the 5- or 6-membered ring disclosed in JP-A-118,2291 can also be used.

Preferable examples of the bisamide compound of Group 4 of the periodic table include Macromolecules, Vo
l. 29, 5241 (1996) and the Journal of
American Chemical Society
y, Vol. 119, No. 16, 3830 (199
7), Journal of American Che
medical Society, Vol. 121, No.
24, 5798 (1999), a crosslinked transition metal compound having a bulky substituent at the nitrogen atom.

Preferable examples of bisalkoxide compounds of Group 4 of the periodic table include transition metal compounds of Group 4 of the periodic table disclosed in WO 87/02370, and preferably include two aryloxy ligands. Are bonded by a cross-linking group, and more preferably, a cross-linkable transition metal compound in which the cross-linking group can coordinate to a transition metal.

Further, a bisimide compound of a transition metal belonging to Groups 8 to 10 of the periodic table is described in Jounalof America.
n Chemical Society, Vol. 11
7,6414, WO96 / 23010 and Chemica
l Communication 849, Jouna
l of American ChemicalSoc
iety, Vol. 120, 4049, WO 98/27
Preferable examples include a crosslinked transition metal bisimide compound having a bulky substituent on the nitrogen atom disclosed in No. 124.

In addition, as preferred examples of the phenoxyimine compound of a transition metal belonging to Groups 3 to 10 of the periodic table, the compounds disclosed in JP-A-11-315109 can be mentioned.

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

<Component [C]> As the component [C], 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, 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, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, trinormal decyl aluminum, and diethyl aluminum chloride. , Diethylaluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride,
Diisobutylaluminum chloride and the like.
Of these, preferred are trialkylaluminum and alkylaluminum hydride wherein m = 1 and n = 3. More preferably, R is a trialkyl aluminum having 1 to 8 carbon atoms.

<Olefin Polymerization Catalyst> In the present invention, an olefin polymerization catalyst can be prepared from the following components [A], [B] and, if necessary, component [C].

Component [A]: An ion-exchange layered silicate 1 for neutralizing an acid site having a pKa of -8.2 or less to neutralize the acid site
ion-exchangeable layered silicate containing 0.05 mmol or more of 2,6 dimethylpyridine per gram, component [B]: a transition metal compound belonging to Groups 3 to 12 of the periodic table, component [C]: organoaluminum Compound,

(1) Preparation of Catalyst, Prepolymerization The olefin polymerization catalyst of the present invention contains the above-mentioned component [A], component [B], and optionally component [C]. These may be brought into contact in a polymerization tank or outside the polymerization tank to carry out prepolymerization in the presence of an olefin. Olefins refer to hydrocarbons containing at least one carbon-carbon double bond, and include ethylene, propylene, 1-butene, 1-hexene, 3-methylbutene-1, styrene, divinylbenzene, and the like. There is no limitation, and a mixture of these with other olefins may be used. Preferably, an olefin having 3 or more carbon atoms is used.

The amounts of the components [A], [B], and [C] used are arbitrary, but the ratio of the transition metal in the component [B] to the aluminum in the component [C] is not limited. [A]
0.1 to 1000 (μmol): 0 to 10 per 1 g
It is preferable that the contact be made so as to be 0000 (μmol).

The order of contacting the component [A], the component [B], and the component [C] is arbitrary.
After contacting the three components, the remaining one component may be contacted, or the three components may be contacted simultaneously. In these contacts, a solvent may be used in order to perform the contact sufficiently. Examples of the solvent include aliphatic saturated hydrocarbons, aromatic hydrocarbons, aliphatic unsaturated hydrocarbons, halides thereof, and prepolymerized monomers.

After the prepolymerization, the catalyst may be dried. The drying method is not particularly limited, and examples thereof include reduced-pressure drying, heat drying, and drying by flowing a drying gas, and these methods may be used alone or in combination of two or more methods. Is also good. Stirring the catalyst in the drying step,
It may be vibrated, flowed, or allowed to stand still.

(2) Polymerization Polymerization using an olefin polymerization catalyst comprising the above-mentioned component [A], component [B], and optionally component [C] is carried out by olefin alone or another olefin. It is carried out by mixing and contacting with a comonomer. 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, or to change the mixing ratio of the supplied monomers over time. It is also possible to change it. Further, any of the monomers can be dividedly added in consideration of the copolymerization reaction ratio.

The polymerizable olefins include those having 2 carbon atoms.
About 20 are preferable, and specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene,
Examples include styrene, divinylbenzene, 7-methyl-1,7-octadiene, cyclopentene, norbornene, and ethylidene norbornene. Preferably 2 to 2 carbon atoms
8 α-olefin. In the case of copolymerization, the kind of the comonomer to be used can be selected from the olefins mentioned above and other than the main component.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer come into efficient contact 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 can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or preliminary polymerization is also applied.

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

[0100]

Next, the present invention will be described in detail with reference to examples. However, the present invention is not limited by these examples unless departing from the gist thereof.

The measuring method in the present example is as follows. (1) MFR: Melt index according to JIS-K-6758 (2) Measurement of acid point amount:

Amount of acid sites having a pKa of -8.2 or less: 2,6-dimethylpyridine was used as a titrant and anthraquinone was used as an indicator. The measurement was performed at 10 ° C. In a Erlenmeyer flask purged with nitrogen, silicate sample 0.1.
To 40 g, 20 mL of toluene was added 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, 0.01
M) was added dropwise at a rate of 0.5 to 5 micromoles per minute per 1 g, and the amount of 2,6-dimethylpyridine added until the yellow color, which is the acidic color of the indicator, disappeared was pKa
Was set to an amount of an acid point of -8.2 or less.

Example 1 (1-1) Chemical treatment of ion-exchangeable layered silicate Magnesium sulfate heptahydrate 66 in a separable flask
After adding 190 g of distilled water to the resulting solution to obtain a solution, 54 g of 96% sulfuric acid was added. Thereafter, 50 g of smectite group silicate (Benclay SL manufactured by Mizusawa Chemical Co., Ltd.) was added at 30 ° C. At this time, the concentration of sulfuric acid in the reaction system was 17% by weight. The slurry is heated at a rate of 1.2 ° C./min.
The temperature was raised to 100 ° C., and the reaction was performed at 100 ° C. for 120 minutes. The reaction slurry is cooled to room temperature for one hour, and the pH is adjusted with distilled water.
Washed until 3. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream to remove coarse particles of 53 μm or more.
By further drying under reduced pressure at 200 ° C. for 2 hours, 36.8 g of chemically treated smectite was obtained. The composition of this chemically treated smectite is Al: 6.6% by weight, Si: 38.0
Wt%, Mg: 1.4 wt%, Fe: 1.6 wt%, N
a <0.2% by weight, and Al / Si = 0.181 [m
ol / mol]. The amount of acid sites having a pKa of -8.2 or less in the obtained chemically treated smectite was 0.130 mmol per gram.

(1-2) Prepolymerization The inside of a three-necked flask having a volume of 1 L was replaced with dry nitrogen, 10 g of the chemically treated smectite obtained above was added, and 192 mL of heptane was further added to form a slurry. 5 mmol (8.4 mL as a heptane solution having a concentration of 68 mg / mL) was added, and the mixture was stirred for 1 hour, washed with heptane (washing ratio: 1/100), and the total volume was 2
Heptane was added to make up to 00 mL. This slurry was introduced into a 1 L autoclave.

In another flask (volume: 200 mL), toluene was added to (dimethylsilylenebis (2-methyl-
4- (p-chlorophenyl) dihydroazulenyl) hafnium dichloride (163 mg; 0.2 mmol) was added to make a slurry, and then triisobutylaluminum (2 mmol: 2.75 mL of a heptane solution having a concentration of 145 mg / mL) was added. The mixture was stirred at room temperature for 10 minutes to be reacted to obtain a uniform solution. This solution was introduced into a 1 L autoclave containing the chemically treated smectite reacted with the above-mentioned triethylaluminum. 235 mL of heptane was added to the autoclave. The slurry was stirred at 40 ° C. in an autoclave for 30 minutes.

Thereafter, 10 propylene was added to the autoclave.
Feeding was performed at a rate of g / hour, and prepolymerization was performed for 2 hours while maintaining the temperature at 40 ° C. Thereafter, the propylene feed was stopped, and polymerization was carried out for another 2 hours while maintaining the internal temperature at 40 ° C. The supernatant of the obtained catalyst slurry was removed by decantation, and triisobutylaluminum (8 mmol: concentration: 145 mg /
(11 mL of a heptane solution in mL) was added thereto, followed by stirring for 10 minutes. The solid was dried under reduced pressure at 40 ° C. for 3 hours to obtain 14.6 g of a dried prepolymerized catalyst. The pre-polymerization magnification (value obtained by dividing the amount of the pre-polymerized polymer by the amount of the solid catalyst) is 0.1.
46.

(1-3) Polymerization of Propylene In a 3 L autoclave at 30 ° C., 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL)
Was added, and after introducing 750 g of liquid propylene, 50 mg by weight of the above prepolymerized catalyst excluding the prepolymerized polymer was added.
Was pumped into the polymerization vessel with high pressure argon. After the temperature was raised to 75 ° C., polymerization was performed for 2 hours. The obtained polymer was 196.7.
g, MFR was 0.24 dg / min. Of this catalyst,
1 hour activity per weight excluding prepolymerized polymer
967 (g polymer / g catalyst · h), indicating high activity.

Example 2 (2-3) Copolymerization of Ethylene-Propylene In a 3 L autoclave at 30 ° C., 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL)
Was added, and 750 g of liquid propylene and 15 g of ethylene were introduced. Then, 30 mg by weight excluding the polymer of the prepolymerized catalyst obtained in Example 1-2 was pumped into the polymerization tank with high-pressure argon. After the temperature was raised to 75 ° C., polymerization was performed for 1 hour. The ethylene content of the obtained polymer was 1.6% by weight, MFR
Was 0.22 dg / min. The activity per unit weight of the catalyst excluding the prepolymerized polymer was 6767 (g polymer / g catalyst · h), indicating high activity.

Example 3 (3-1) Chemical treatment of ion-exchangeable layered silicate Smectite group silicate (Benkeley S manufactured by Mizusawa Chemical Co., Ltd.)
L) 100 g, magnesium sulfate heptahydrate 133 g, distilled water 660 g, sulfuric acid 109 g
Except that the sulfuric acid concentration in the reaction system was 12% by weight.
By performing the same operation as in Example 1-1, 80 g of chemically treated smectite was obtained. The composition of the obtained chemically treated smectite was as follows: Al: 7.8% by weight, Si: 36.7% by weight, Mg:
1.6 wt%, Fe: 2.1 wt%, Na <0.2 wt%, Al / Si = 0.221 [mol / mol]
Met. The amount of acid sites having a pKa of -8.2 or less in the obtained chemically treated smectite is 0.125 m per gram.
mol.

(3-2) Preliminary polymerization Preliminary polymerization was carried out in the same manner as in Example 1-2 except that the chemically treated smectite obtained by the above chemical treatment was used, to obtain 27.5 g of a dry preliminary polymerization catalyst. The prepolymerization magnification (value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.75.

(3-3) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1-3 except that the above-mentioned prepolymerized catalyst was used to obtain 253.3 g of a polymer. MFR was 0.18 dg / min. The activity of this catalyst per one hour per weight excluding the prepolymerized polymer was 2,533 (g polymer / g catalyst · h), indicating high activity.

[Example 4] (4-3) Ethylene-propylene copolymerization Using the prepolymerized catalyst obtained in Example 3-2, ethylene-propylene copolymerization was carried out in the same manner as in Example 2-3. Polymerization was performed. The ethylene content of the obtained polymer was 1.5% by weight, and the MFR was 0.15 dg / min. Of this catalyst,
The activity per weight excluding the prepolymerized polymer was 6933.
(G polymer / g catalyst · h), indicating high activity.

Example 5 (5-1) Chemical treatment of ion-exchangeable layered silicate Smectite group silicate (Benclay S manufactured by Mizusawa Chemical Co., Ltd.)
L) was 300 g, the amount of magnesium sulfate heptahydrate was zero, the amount of distilled water was 1130 g, the amount of sulfuric acid was 750 g, and the sulfuric acid concentration in the reaction system was 40% by weight.
The same operation as in Example 1-1 was performed except that the temperature was changed to 390 minutes, and 133 g of chemically treated smectite was obtained. The composition of the obtained chemically treated smectite was Al: 4.5% by weight,
Si: 40.7% by weight, Mg: 0.7% by weight, Fe:
1.3% by weight, Na <0.2% by weight, Al / Si
= 0.116 [mol / mol]. The amount of acid sites having a pKa of -8.2 or less in the obtained chemically treated smectite was 0.08 mmol per gram.

(5-2) Prepolymerization 20 g of the chemically treated smectite obtained by the above chemical treatment was placed in a three-necked flask (volume: 1 L) and heptane (183) was added.
mL) was added to form a slurry. Triethylaluminum (10 mmol: 16.8 mL of a 68 mg / mL concentration of heptane solution) was added to the slurry, and the mixture was stirred for 1 hour and washed with heptane to 1/100 to make the total volume 200 mL. Heptane was added as before.

In another flask (volume: 200 mL), heptane containing 3 wt% of toluene (87 mL)
Was added with (dimethylsilylenebis (2-methyl-4- (p-chlorophenyl) dihydroazulenyl) zirconium dichloride (0.3 mmol) to form a slurry.
Triisobutylaluminum (3 mmol: concentration 140
mg / mL of a heptane solution (4.26 mL).
The mixture was stirred at room temperature for 0 minutes to be reacted to obtain a uniform solution. This solution was added to the above 3 L flask (containing the chemically treated smectite reacted with triethylaluminum) and stirred at room temperature for 60 minutes. Then heptane was 213m
L was added, and the slurry was introduced into a 1 L autoclave.

After the internal temperature of the autoclave was adjusted to 40 ° C., propylene was fed at a rate of 20 g / hour, and prepolymerization was carried out at 40 ° C. for 2 hours. Thereafter, the propylene feed was stopped, the internal temperature was raised to 50 ° C., and residual polymerization was performed for another 2 hours. The supernatant of the obtained catalyst slurry was removed by decantation, and triisobutyl aluminum (12 mmol: concentration: 14
0 mg / mL of a heptane solution (17 mL).
Minutes. The solid was dried under reduced pressure for 3 hours to obtain 63.6 g of a dried prepolymerized catalyst. The prepolymerization magnification (value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) is 2.18.
Met.

(5-3) Polymerization of Propylene 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) was added to a 3 L autoclave.
After introducing 750 g of liquid propylene and 102 mL of hydrogen (volume in a standard state), the temperature was raised to 70 ° C. afterwards,
5 by weight excluding the prepolymerized polymer of the above prepolymerized catalyst
0 mg was pressure-fed to a polymerization tank with high pressure argon, and it polymerized at 70 degreeC for 1 hour. The obtained polymer was 163 g and the MFR was 3
It was 1.2 dg / min. The activity of this catalyst per weight excluding the prepolymerized polymer was 3260 (g polymer / g).
g catalyst · h), indicating high activity.

[Example 6] (6-3) Copolymerization of ethylene-propylene 2.86 mL of a heptane solution of triisobutylaluminum (140 mg / mL) was added to a 3 L autoclave.
After introducing 750 g of liquid propylene and 15 g of ethylene, the temperature was raised to 70 ° C. Thereafter, the weight of the prepolymerized catalyst obtained in Example 5-2, excluding the prepolymerized polymer, was 3% by weight.
0 mg was pressure-fed to a polymerization tank with high pressure argon, and it polymerized at 70 degreeC for 1 hour. The obtained polymer was 236 g, the ethylene content was 1.8% by weight, and the MFR was 1.8 dg / min. The activity per unit weight of the catalyst excluding the prepolymerized polymer was 7,870 (g polymer / g catalyst · h), indicating high activity.

Comparative Example 1 (Comparative 1-1) Chemical treatment of ion-exchanged layered silicate Magnesium sulfate heptahydrate 26 in a separable flask
After adding 7730 g of distilled water to 60 g to make a solution, 9
2180 g of 6% sulfuric acid was added, and then 2000 g of smectite group silicate (Kunimine F, manufactured by Kunimine Industries Co., Ltd.)
When added at 0 ° C., the sulfuric acid concentration in the reaction system was 17% by weight.
It became. This slurry was heated to 100 ° C. at 1.2 ° C./min over 1 hour, and reacted at 100 ° C. for 120 minutes.
The reaction slurry was cooled to room temperature in 1 hour and washed with distilled water to pH3. The obtained solid was granulated by turning it into a water slurry and performing spray drying. 20 more
By drying under reduced pressure at 0 ° C. for 2 hours, 1300 g of chemically treated smectite was obtained.

The composition of this chemically treated smectite was Al:
9.1 wt%, Si: 36.0 wt%, Mg: 2.0 wt%, Fe: 1.4 wt%, Na <0.2 wt%, Al / Si = 0.263 [mol / mol]. The pKa of the obtained chemically treated smectite is -8.
The amount of acid points of 2 or less is 0.036 mmol per gram
Met.

(Comparative 1-2) Prepolymerization Prepolymerization was carried out in the same manner as in Example 1-2, except that the chemically treated smectite obtained by the above chemical treatment was used, to obtain 29.2 g of a dry prepolymerized catalyst. . The prepolymerization magnification (value obtained by dividing the amount of the prepolymerized polymer by the amount of the solid catalyst) was 1.92.

(Ratio 1-3) Polymerization of Propylene Propylene was polymerized in the same manner as in Example 1-3 except that the above-mentioned prepolymerization catalyst was used, to obtain 70.4 g of a polymer. MFR was 0.25 dg / min. The activity of this catalyst per hour excluding the prepolymerized polymer was 704 (g polymer / g catalyst · h) per weight, which was low activity.

Comparative Example 2 (Comparative 2-3) Ethylene-propylene copolymerization Using the prepolymerized catalyst obtained in Comparative Example 1-2, copolymerization of ethylene-propylene was carried out in the same manner as in Example 2. went. The ethylene content of the obtained polymer is 1.6% by weight,
MFR was 0.09 dg / min. The activity of this catalyst per weight excluding the prepolymerized polymer was 1873 (g).
Polymer / g catalyst · h), and the activity was low.

[Comparative Example 3] (Comparative 3-1) Chemical treatment of ion-exchangeable layered silicate A glass lasco was charged with 150 mL of demineralized water and lithium sulfate.
25.7 g of monohydrate and 19.6 g of concentrated sulfuric acid were slowly added, and 40.8 g of commercially available mica (ME-100, manufactured by Corp Chemical) was dispersed.
The mixture was stirred for a period of time. Thereafter, the collected mica was sufficiently washed with deionized water and dried at 110 ° C. overnight.

The composition of the chemically treated mica is Al
/Si=0.002, Mg / Si = 0.66, Na / S
i = 0.026. The amount of the acid point having a pKa of -8.2 or less is the detection limit (0.005 m
mol / g). Nitrogen adsorption analysis results
The value of (b) / (a) was 0.49, and the value of (b)-(c) was 13.6.

(Comparative 3-2) The operation was carried out in the same manner as in Example 1 except that the above-mentioned chemically treated silicate was used. As a result, the catalytic activity was 125 g-PP / g-catalyst
R was 1.2.

[Comparative Example 4] (Comparative 4-1) Chemical treatment of ion-exchanged layered silicate To a glass flask, 300 mL of demineralized water and then 53.4 mL of titanium tetrachloride were slowly added, and further commercially available. 30 g of lithium hectorite (manufactured by Topy Industries) was dispersed and stirred at room temperature for 2 hours. Thereafter, the recovered hectorite was sufficiently washed with demineralized water and dried at 110 ° C. overnight.

This chemically treated hectorite has a pK
The amount of acid sites where a is -8.2 or less is below the detection limit (0.005 mmol / g) without color change of the indicator, and the result of nitrogen adsorption analysis shows that the value of (b) / (a) is 0. .64,
The value of (b)-(c) was 8.6.

(Comparative 4-2) Preparation of catalyst, prepolymerization, polymerization Except for using the above chemically treated hectorite,
It carried out similarly to Example 1. As a result, the catalytic activity was 5
7.2 g-PP / g-catalyst-hour.

Example 7 Prepolymerization (γ) -dimethylsilylenebis [2-methyl-4- (4
-Chlorophenyl) -4H-azulenyl] zirconium dichloride was used in the same manner as in Example 5 except for using prepolymerization. As a result, the preliminary polymerization magnification was 1.99.

Copolymerization of Ethylene-Propylene The prepolymerized catalyst obtained by the above method was carried out in the same manner as in Example 6 except that 15 mg by weight excluding the prepolymerized polymer and 34 mL of hydrogen were added. As a result, 168.
0 g of the polymer was obtained. The catalytic activity is 11200 g-
When the PP / g catalyst was used, the ethylene content was 1.57% by weight, and the MFR was 6.73.

Comparative Example 5 Preliminary Polymerization Preliminary polymerization was carried out in the same manner as in Example 7, except that the ion-exchange layered silicate used in Comparative Example 1 was used.

Ethylene-propylene copolymerization The same procedure as in Example 7 was carried out except that the prepolymerized catalyst obtained by the above method was used. As a result, the catalytic activity is 750
At 0 g-PP / g-catalyst, the ethylene content is 1.6
1% by weight, MFR was 7.05.

Example 8 Preliminary Polymerization Preliminary polymerization was carried out in the same manner as in Example 7, except that (γ) -dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was used. as a result,
The pre-polymerization rate was 1.86.

Copolymerization of Ethylene-Propylene The same procedure as in Example 7 was carried out except that the prepolymerized catalyst obtained by the above method was used. As a result, 117.5 g of a polymer was obtained. The catalytic activity is 7830 g-PP / g-
When the catalyst has an ethylene content of 1.65% by weight, MFR
Was 3.87.

Comparative Example 6 Preliminary Polymerization Preliminary polymerization was carried out in the same manner as in Example 8, except that the ion-exchange layered silicate used in Comparative Example 1 was used.

Copolymerization of Ethylene-Propylene The same procedure as in Example 8 was carried out except that the prepolymerized catalyst obtained by the above method was used. As a result, the catalytic activity is 320
At 0 g-PP / g-catalyst, the ethylene content is 1.6
5% by weight, MFR was 4.41.

Table 1 shows the results of Examples 1 to 8 and Comparative Examples 1 to 6.
To Table 3 below. Tables 1 and 2 show the raw materials of [Component A] and the results after the chemical treatment, and Table 3 shows the polymerization activity of the catalyst using the chemically treated [Component A].

[0139]

[Table 1]

[0140]

[Table 2]

[0141]

[Table 3]

As shown by the above results, in the case of propylene homopolymerization, the polymerization activity is improved from 2 times to about 40 times, and also in the ethylene-propylene copolymer, it is improved about 3 times.

[0143]

According to the method of the present invention, a highly active polyolefin polymerization catalyst can be produced and is effective as a catalyst for the polymerization and copolymerization of α-olefins such as ethylene, propylene, butene-1 and hexene-1.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Eiji Uchino 1 Toho-cho, Yokkaichi-shi, Mie Japan Inside the Process Development Center of Polychem Corporation (72) Inventor Hajime Takahashi 1-Tohocho, Yokkaichi-shi, Mie Japan Nippon Polychem Co., Ltd. F-term in the Company Process Development Center (reference) 4J028 AA01A AB00A AB01A AC01A AC08A AC10A AC26A AC28A BA00A BA01B BB00A BB01B BC15B BC16B BC19B BC24B BC27B CA30A EB02 EB04 EB05 EB08 EB09 EB17 FA04 FA07

Claims (9)

[Claims] An olefin polymerization catalyst comprising the following components [A] and [B]. Ingredient [A]: contains an acid point having a pKa of -8.2 or less in an amount required to neutralize the acid point of 2,6-dimethylpyridine of 0.05 mmol or more per 1 g of the ion-exchanged phyllosilicate. Ion-exchangeable layered silicate, component [B]: a transition metal compound belonging to Groups 3 to 12 of the periodic table, 2. An olefin polymerization catalyst comprising the following components [A], [B] and [C]. Component [A]: contains an acid point having a pKa of -8.2 or less, in an amount that requires 0.05 mmol or more of 2,6 dimethylpyridine per 1 g of the ion-exchanged phyllosilicate to neutralize the acid point. Ion-exchange layered silicate, Component [B]: transition metal compound of Groups 3 to 12 of the periodic table, Component [C]: Organoaluminum compound, 3. The catalyst for olefin polymerization according to claim 1, wherein the component [A] is a chemically treated smectite group silicate. 4. The olefin polymerization catalyst according to claim 1, wherein the component [A] is an acid-treated smectite silicate. 5. The composition according to claim 1, wherein the component [A] is an acid-treated smectite group silicate and has an atomic ratio of aluminum to silicon (Al
The catalyst for olefin polymerization according to any one of claims 1 to 4, wherein (/ Si) is from 0.05 to 0.4. 6. An olefin polymerization catalyst obtained by bringing the following components [A] and [B] into contact with an olefin. Ingredient [A]: contains an acid point having a pKa of -8.2 or less in an amount required to neutralize the acid point of 2,6-dimethylpyridine of 0.05 mmol or more per 1 g of the ion-exchanged phyllosilicate. Ion-exchange layered silicate, component [B]: transition metal compound of Groups 3 to 12 of the periodic table, 7. An olefin polymerization catalyst obtained by bringing the following components [A], [B] and [C] into contact with an olefin. Ingredient [A]: contains an acid point having a pKa of -8.2 or less in an amount required to neutralize the acid point of 2,6-dimethylpyridine of 0.05 mmol or more per 1 g of the ion-exchanged phyllosilicate. Ion-exchange layered silicate, Component [B]: transition metal compound of Groups 3 to 12 of the periodic table, Component [C]: Organoaluminum compound, 8. The catalyst for olefin polymerization according to claim 1, wherein the component [A] satisfies the following nitrogen adsorption / desorption property [I]. [I]: P / P _{0 with} respect to the adsorption amount (a) at a relative pressure P / P ₀ = 1 in the desorption isotherm by the nitrogen adsorption / desorption method.
(B) / (a) ≧ 0.8 where P is a measured pressure and P ₀ is an atmospheric pressure. 9. The component [A] has the following nitrogen adsorption / desorption property [II]:
The olefin polymerization catalyst according to any one of claims 1 to 8, which satisfies the following. [II]: in the adsorption and desorption isotherm by nitrogen adsorption-desorption, adsorption at a relative pressure of P / P remaining adsorption amount of desorption isotherm at ₀ = 0.85 (b) and relative pressure P / P ₀ = 0.85 The difference in the adsorption amount (c) of the isotherm satisfies the following equation.
(B)-(c)> 25 (cc / g)