JP2001163909A - Catalyst component for olefin polymerization and catalyst using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst component for olefin polymerization that is highly active and capable of obtaining a polymer excellent in polymer properties at a low cost, and a catalyst for olefin polymerization using the same. SOLUTION: The catalyst component for olefin polymerization is characterized in using an ion-exchangeable layer silicate having following property [I]. [I] In a desorption isotherm in a nitrogen adsorption and desorption method the ratio of the remaining adsorption amount (b) at P/P0=0.85 to the adsorption amount (a) at the relative pressure of P/P0=1 satisfies the following formula: (b)/(a)>=0.8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst component for olefin polymerization and a catalyst for olefin polymerization using the catalyst component. More specifically, by using an ion-exchangeable layered silicate having a specific structure, the catalyst performance can be improved,
Particularly, the present invention provides a catalyst component which exhibits high activity in olefin polymerization and provides a polymer having good particle properties.

[0002]

2. Description of the Related Art As a method for producing an olefin polymer by polymerizing an olefin in the presence of a polymerization catalyst, a method using a catalyst system comprising a metallocene and an aluminoxane has already been proposed (Japanese Patent Application Laid-open No. 60-35
007, JP-B-4-12283, etc.). However, many of these catalyst systems are soluble in the polymerization reaction medium,
The particle shape of the obtained polymer is irregular, the bulk density is small, the amount of fine powder is large, the particle properties are not at a sufficient level,
When applied to slurry polymerization or gas phase polymerization, etc., there is a problem in the manufacturing process such as continuous stable operation becomes difficult, and the amount of expensive aluminoxane used for commercial production leaves many issues in the catalyst cost. I have.

On the other hand, in order to solve these problems, olefin polymerization is carried out using a catalyst system in which one or both of a transition metal compound and an organoaluminum are supported on an inorganic oxide or an organic substance such as silica or alumina. Methods have also been proposed (JP-A-61-108610, 60-108).
JP-A-135408, JP-A-61-296008, JP-A-3-74412, JP-A-3-74415 and the like. However, even in the polymers obtained by these methods, fine powders and coarse particles are still often found, and the bulk properties are low, and many of the particles have poor particle properties, and the polymerization activity per unit catalyst or cocatalyst is low. For example, low and insufficient levels for stable production of the polymer and production at commercially meaningful cost.

[0004]

SUMMARY OF THE INVENTION The present invention provides a catalyst component for olefin polymerization and a catalyst for olefin polymerization capable of obtaining a polymer having high activity and excellent polymer properties at low cost.

[0005]

As a result of various studies, the present inventors have found that when an inorganic silicate having a specific structure is used as a catalyst component for olefin polymerization, a powder having high activity and good particle properties is obtained. Has been found to exhibit excellent performance in production stability and economic efficiency of the polymer.

The present invention has been completed based on the above findings, and a first gist of the present invention is to provide an olefin polymerization characterized by using an ion-exchange layered silicate having the following property [I]. For the catalyst component. [I] In the desorption isotherm by nitrogen adsorption-desorption method, a relative pressure _{P / P 0 = 1 P /} P for adsorption (a) at ₀ =
The ratio of the residual adsorption amount (b) at 0.85 satisfies the following expression. (B) / (a) ≧ 0.8 The second point is that an olefin polymerization catalyst characterized by using an ion-exchangeable layered silicate having both the following properties [I] and [II]: In the ingredients. [I] In the desorption isotherm by nitrogen adsorption-desorption method, a relative pressure _{P / P 0 = 1 P /} P for adsorption (a) at ₀ =
The ratio of the residual adsorption amount (b) at 0.85 satisfies the following expression. (B) / (a) ≧ 0.8 [II] In the adsorption and desorption isotherms by the nitrogen adsorption / desorption method, the remaining adsorption amount (b) and the relative pressure of the desorption isotherm at the relative pressure P / P ₀ = 0.85 The difference in the adsorption amount (c) of the adsorption isotherm at P / P ₀ = 0.85 satisfies the following expression. (B)-(c)> 25 (cc / g) The third aspect is characterized by comprising the above-mentioned ion-exchangeable layered silicate and a transition metal compound of Groups 4 to 10 of the periodic table. It is present in olefin polymerization catalysts.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Olefin Polymerization Catalyst Component The olefin polymerization catalyst component of the present invention has the following property [I], preferably both of the following properties [I] and [I].
I] is used. [I] In the desorption isotherm by nitrogen adsorption-desorption method, a relative pressure _{P / P 0 = 1 P /} P for adsorption (a) at ₀ =
The ratio of the residual adsorption amount (b) at 0.85 satisfies the following expression. (B) / (a) ≧ 0.8 [II] In the adsorption and desorption isotherms by the nitrogen adsorption / desorption method, the remaining adsorption amount (b) and the relative pressure of the desorption isotherm at the relative pressure P / P ₀ = 0.85 The adsorption amount (c) of the adsorption isotherm at P / P ₀ = 0.85 satisfies the following expression. (B)-(c)> 25 (cc / g)

The measurement of the adsorption and desorption isotherms by the nitrogen adsorption / desorption method will be described below. The amount of gas adsorbed by a solid is constant when the temperature is constant.If the solid and gas are determined, the potential of the adsorption interaction can be considered to be almost constant. The curve shown is generally called the adsorption isotherm. In the present invention, the pressure is measured at a temperature of 77 K, and the pressure is a relative pressure P / P ₀ (P ₀
Is the atmospheric pressure. ), 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.

These adsorption isotherms vary in the shape of the curve depending on the type 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 referred to as adsorption hysteresis or adsorption hysteresis.
(steresis). Although there is no theory that can explain everything about this phenomenon, one idea is that the pore model `` ink bottle type '' has a narrower entrance than the inside,
(JH DeBoer: "The Structur").
e and Properties of Porous
Material "p. 68 (DH Evere)
ttet al ed Butterworths S
ci. Publications)). That is,
In ink bottle type pores, adsorption occurs from a wide radius portion of the pore and fills the pore, 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 difference will occur and hysteresis will appear.

In the present invention, the measurement was carried out according to a generally used nitrogen adsorption / desorption 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 affects the catalyst performance, particularly the catalyst activity. Was given. From such a viewpoint, the above-mentioned (b) // obtained from the adsorption / desorption isotherm by the nitrogen adsorption method.
It is necessary that the value of (a) is 0.8 or more, preferably 0.9 or more, and more preferably 0.95 or more.
Preferably, the value of (b)-(c) is selected to be 25 or more, preferably 30 or more, and more preferably 35 or more.

[0011] The measurement of pore size and pore distribution by adsorption generally involves measuring the equilibrium vapor pressure of a curved surface, such as the surface of a liquid in a capillary or pore, by the same liquid on a flat surface. The Kelvin equation relating to the equilibrium pressure is used. The ratio of the volume to the area in the pores is related to the shape of the pores, but is usually calculated assuming cylindrical pores. Also in the present invention, the pore diameter and the pore distribution were calculated according to the Kelvin equation assuming cylindrical pores.

In the silicate of the catalyst component of the present invention, the peak position of the pore size distribution by the nitrogen adsorption method is preferably 20
The structure is in the range of {over 1200}. Regarding the pore volume, a structure having a pore diameter of 500 ° or less and a structure of 0.15 cc / g or more and 2 cc / g or less is preferable. For surface area, general B
Analysis value by ET method is 50 m ² / g or more, 500 m ²
/ G or less is preferred.

The hysteresis and the pore distribution can be controlled by any method, for example, under the conditions of chemical treatment and granulation. The control of the chemical treatment conditions can be performed, for example, by selecting the type (acid, salt), amount, concentration, treatment temperature and time of the treatment agent.

In the present invention, an ion-exchangeable layered silicate used as a raw material (hereinafter simply referred to as silicate)
Refers to a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are bonded to each other and stacked in parallel, and the contained ions are exchangeable. Most silicates are naturally produced mainly as a main component of clay minerals, and therefore often contain impurities (quartz, cristobalite, etc.) other than ion-exchanged layered silicates. May be. In the present invention, the raw material refers to a silicate before the chemical treatment of the present invention described below. Further, the silicate used as a raw material in the present invention is not limited to naturally occurring one, and may be an artificially synthesized one. Specific examples of the silicate include, for example, the following layered silicates described in “Clay Mineralogy” written by Haruo Shimizu, Asakura Shoten (1995).

(1) A kaolin group such as dickite, nacrite, kaolinite, anoxite, metahaloisite, halloysite, which is a silicate having a 1: 1 type silicate as a main component, chrysotile, lizardite, antigolite (2) Smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite, and stavesite, whose main silicate is a silicate having a 2: 1 type structure, and vermiculite, etc. Vermiculite, mica, illite, sericite,
Mica tribes such as sea green stone, attapulgite, sepiolite,
Palygorskite, bentonite, pyrophyllite,
Talc, chlorite

The silicate used as a raw material in the present invention may be a mixture of the above (1) and (2) or a layered silicate having both a 1: 1 type structure and a 2: 1 type structure in the molecule. .
In the present invention, the silicate as the main component is preferably a silicate having a 2: 1 type structure, more preferably a smectite group, and particularly preferably montmorillonite. The kind of the interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easily and inexpensively available as an industrial raw material.

Chemical Treatment The silicate used as a catalyst component in the present invention can be used as it is for the above raw materials without any particular treatment, but is preferably subjected to a chemical treatment. Here, the chemical treatment can be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the structure of the clay.

Specifically, acid treatment, alkali treatment, salt treatment, organic substance treatment and the like can be mentioned. In the acid treatment, in addition to removing impurities on the surface, the surface area is increased by eluting cations such as Al, Fe, and Mg in the crystal structure. The alkali treatment destroys the crystal structure of the silicate,
Brings structural changes. In the salt treatment and the organic substance treatment, an ion complex, a molecular complex, an organic derivative, and the like are formed, and the surface area and the interlayer distance can be changed. If ion exchangeability is used to replace exchangeable ions between layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

The acid treating agent, alkali treating agent, salt treating agent and organic treating agent used in these chemical treatments may each be used in combination of two or more. Further, an acid treating agent and a salt treating agent, an alkali treating agent and a salt treating agent, an alkali treating agent and an organic treating agent may be used at the same time. These processing agents may be added at the start of the treatment or during the treatment. Further, the chemical treatment may be performed a plurality of times, and any combination of the same treatment or different treatments is possible.

The acid used in the acid treatment is preferably hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid, acetic acid, benzoic acid,
It is selected from stearic acid, propionic acid, acrylic acid, maleic acid, fumaric acid, phthalic acid.

The salts used in the salt treatment are listed in Periodic Table 1
At least one member selected from the group consisting of
A compound containing a cation containing an atom, preferably
Is a cation containing the group 1-14 atom, a halogen atom,
Selected from the group consisting of inorganic acid residues and organic acid residues
At least one kind of anion.
More preferably, a group consisting of atoms belonging to groups 2 to 14 of the periodic table
A cation containing at least one selected atom;
1, Br, I, F, PO_Four, SO_Four, NO_Three, CO_Three,
C_TwoO_Four, ClO_Four, OOCCH_Three, CH_ThreeCOCHC
OCH_Three, OCI _Two, O (NO_Three)_Two, O (ClO_Four)
_Two, O (SO_Four), OH, O_TwoCl_Two, OCI_Three, OO
CH, OOCCH_TwoCH_Three, C_TwoH_FourO_FourAnd C₆H_Five
O₇A shade containing at least one member selected from the group consisting of
And a compound consisting of

Specific salts include LiCl, Li_Two
SO_Four, Li_TwoC_TwoO_Four, LiNO _Three, Li_Three(C₆H
_FiveO₇), NaCl, Na_TwoSO_Four, Na_TwoC_TwoO_Four,
NaNO_Three, Na_Three(C₆H_FiveO₇), KCl, K_TwoS
O_Four, K_TwoC_TwoO_Four, KNO _Three, K_Three(C₆H
_FiveO₇), CaCl_Two, CaSO_Four, CaC_TwoO_Four, C
a (NO_Three)_Two, Ca_Three(C₆H_FiveO₇)_Two, MgCl
_Two, MgBr_Two, MgSO_Four, Mg_Three(PO_Four)_Two, M
g (ClO_Four)_Two, MgC_TwoO_Four, Mg (NO_Three)_Two,
Mg (OOCCH_Three)_Two, MgC_FourH_FourO_Four, Sc (O
OCCH_Three)_Two, Sc_Two(CO_Three)_Three, Sc_Two(C_TwoO
_Four)_Three, Sc (NO_Three)_Three, Sc_Two(SO_Four)_Three, Sc
F_Three, ScCl_Three, ScBr_Three, ScI_Three, Y (OOC
CH_Three)_Three, Y (CH_ThreeCOCHCOCH_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(SO_Four)_Three, YF
_Three, YCl_Three , La (OOCH_Three)_Three, La (CH_ThreeC
OCHCOCH_Three)_Three, La_Two(CO_Three)_Three, La (N
O_Three)_Three, La (ClO_Four)_Three, La_Two(C
_TwoO_Four)_Three, LaPO_Four, La_Two(SO_Four)_Three, LaF
_Three, LaCl_Three, LaBr_Three, LaI_Three, Sm (OOC
CH_Three)_Three, Sm (CH_ThreeCOCHCOCH_Three)_Three, S
m_Two(CO_Three)_Three, Sm (NO_Three)_Three, Sm (Cl
O_Four)_Three, Sm_Two(C_TwoO_Four)_Three, SmPO_Four, Sm_Two
(SO_Four)_Three, SmF_Three, SmCl_Three, SmBr_Three, S
mI_Three, Yb (OOCCH_Three)_Three, Yb (NO_Three)_Three,
Yb (ClO_Four)_Three, Yb_Two(C_TwoO_Four)_Three, Yb
_Two(SO_Four)_Three, YbF_Three, YbCl_Three, Ti (OOC
CH_Three)_Four, Ti (CO_Three)_Two, Ti (NO_Three)_Four, T
i (SO_Four)_Two, TiF_Four, TiCl_Four, TiBr_Four,
TiI_Four, Zr (OOCCH_Three)_Four, Zr (C
O_Three)_Two, Zr (NO_Three)_Four, Zr (SO_Four)_Two, Zr
F_Four, ZrCl_Four, ZrBr _Four, ZrI_Four, ZrOCl
_Two, ZrO (NO_Three)_Two, ZrO (ClO_Four)_Two, Zr
O (SO_Four), Hf (OOCCH)_Three)_Four, Hf (C
O_Three)_Two, Hf (NO_Three) _Four, Hf (SO_Four)_Two, Hf
OCI_Two, HfF_Four, HfCl_Four, HfBr_Four, HfI
_Four, V (CH_ThreeCOCHCOCH_Three)_Three, VOSO_Four,
VOCl_Three, VCl _Three, VCl_Four, VBr_Three, Nb (C
H_ThreeCOCHCOCH_Three)_Five, Nb_Two(CO _Three)_Five, N
b (NO_Three)_Five, Nb_Two(SO_Four)_Five, NbF_Five, Nb
Cl_Five, NbBr_Five, NbI_Five, Ta (OOCCH_Three)
_Five, Ta_Two(CO_Three)_Five, Ta (NO _Three)_Five, Ta
_Two(SO_Four)_Five, TaF_Five, TaCl_Five, TaBr_Five,
TaI_Five, 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_Two
Cl _Two, CrF_Three, CrCl_Three, CrBr_Three, Cr
I_Three, MoOCl_Four, MoCl_Three, MoCl_Four, MoC
l_Five, MoF₆, MoI_Two, WCl_Four, WCl₆, WF
₆, WBr_Five, Mn (OOCH_Three)_Two, Mn (CH_ThreeC
OCHCOCH_Three)_Three, MnCO_Three, Mn (N
O_Three)_Two, MnO, Mn (ClO_Four)_Two, MnF_Two, M
nCl_Two, MnBr_Two, MnI_Two, Fe (OOCH_Three)
_Two, Fe (CH_ThreeCOCHCOCH_Three)_Three, FeC
O_Three, Fe (NO_Three)_Three, Fe (ClO_Four)_Three, FeP
O _Four, FeSO_Four, Fe_Two(SO_Four)_Three, FeF_Three, F
eCl_Three, MnBr_Three, FeI_Two, FeC₆H_FiveO₇,
Co (OOCH_Three)_Two, Co (CH_ThreeCOCHCOCH
_Three)_Three, CoCO_Three, Co (NO_Three)_Two, CoC
_TwoO_Four, Co (ClO_Four) _Two, Co_Three(PO_Four)_Two, C
oSO_Four, CoF_Two, CoCl_Two, CoBr_Two, CoI
_Two, NiCO_Three, Ni (NO_Three)_Two, NiC_TwoO_Four, N
i (ClO_Four)_Two, NiSO_Four, NiCl_Two, NiBr
_Two, Pb (OOCCH_Three)_Four, Pb (OOCH_Three)_Two,
PbCO_Three, Pb (NO_Three)_Two, PbSO_Four, PbHP
O_Four, Pb (ClO_Four)_Two, PbF_Two, PbCl_Two, P
bBr_Two, PbI_Two, CuCl_Two, CuBr_Two, Cu
(NO_Three)_Two, CuC_TwoO_Four, Cu (ClO_Four)_Two, C
uSO_Four, Cu (OOCCH_Three)_Two, Zn (OOC
H_Three)_Two, Zn (CH_ThreeCOCHCOCH_Three)_Two, Zn
CO_Three, Zn (NO_Three)_Two, Zn (ClO_Four)_Two, Zn
_Three(PO_Four)_Two, ZnSO_Four, ZnF_Two, ZnCl_Two,
ZnBr_Two, ZnI_Two, Cd (OOCCH_Three)_Two, Cd
(CH_ThreeCOCHCOCH_Three)_Two, Cd (OCOCH_Two
CH_Three)_Two, Cd (NO_Three)_Two, Cd (ClO_Four)_Two,
CdSO_Four, CdF_Two, CdCl_Two, CdBr_Two, Cd
I_Two, AlF_Three, AlCl_Three, AlBr_Three, AlI_Three,
Al_Two(SO_Four)_Three, Al_Two(C_TwoO_Four)_Three, Al (C
H_ThreeCOCHCOCH_Three)_Three, Al (NO_Three)_Three, Al
PO_Four, GeCl_Four, GeBr_Four, GeI _Four, Sn (O
OCCH_Three)_Four, Sn (SO_Four)_Two, SnF_Four, SnC
l_Four, SnBr_Four, SnI_FourAnd the like.

The organic substance used for the organic substance treatment is as follows:
Compounds containing organic cations. Examples of preferred organic cations include trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, tridodecylammonium, N, N
-Dimethyloctadecyl ammonium, N, N-dimethylanilinium, N, N-diethylanilinium,
N-dimethyl-2,5-dimethylanilinium, N, N
-Dimethyl-pn-butylanilinium, N, N-dimethyl-p-trimethylsilylanilinium, N, N-
Dimethyl-2- (1-naphthyl) anilinium, N,
Ammonium ions such as N, 2-trimethylanilinium and 2,6-dimethylanilinium, pyridinium,
Nitrogen-containing aromatic compound cations such as 2,6-dimethylpyridinium, quinolinium, N-methylpiperidinium, 2,2,6,6-tetramethylpiperidinium, triphenylphosphonium, tri (o-tolyl) phosphonium And cations of phosphorus-containing compounds such as tri (p-tolyl) phosphonium and tri (mesityl) phosphonium, and oxonium ions such as dimethyloxonium, diethyloxonium, diphenyloxonium, furanium and oxolanium.

The anions constituting the organic treating agent include, for example, hexafluorophosphate, tetrafluoroborate, tetraphenylborate ion and the like in addition to the anions exemplified as the anions constituting the salt treating agent. However, the present invention is not limited to these.

The alkali used in the alkali treatment is preferably LiOH, NaOH, KOH, Mg (O
H) ₂ , Ca (OH) ₂ , Sr (OH) ₂ , Ba (O
H) _{2 and the} like.

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 include esters, ethers, ketones, aldehydes, furans, amines, dimethyl sulfoxide, dimethylformamide, carbon disulfide, nitrobenzene, pyridines, and halides thereof. Processing conditions are
Although not particularly limited, usually, the salt and acid concentrations are set at 0.1.
1 to 50% by weight, the treatment temperature is from room temperature to 150 ° C., and the treatment time is from 5 minutes to 24 hours, and the treatment is carried out under the condition that at least a part of the substance constituting the silicate is eluted. preferable.

According to the chemical treatment of the present invention, at least 40%, preferably at least 60%, of the exchangeable Group 1 or 2 metal cations contained in the silicate contained in the silicate before the chemical treatment,
It is preferable to perform ion exchange with a cation dissociated from the above-described acid treatment agent, salt treatment agent, organic substance treatment agent, or the like.

In the chemical treatment of the present invention, it is preferable to perform the above-mentioned acid treatment, the above-mentioned salt treatment, the above-mentioned organic material treatment or the treatment in which an acid and a salt coexist at least once.
Further, by these chemical treatments, in addition to removing surface impurities, a part of cations such as Al, Fe, and Mg having a crystal structure can be eluted, and the elution amount of each component element except silicon is preferably 90% or less, more preferably 85%
% Or less.

The silicate obtained by the chemical treatment according to the present invention includes, in addition to a layered silicate having an ion exchange property similar to the ion-exchangeable layered silicate as a raw material, physical and chemical Silicates whose properties have changed and ion exchangeability and layer structure have been lost are also included.

These silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to use the water after removing these adsorbed water and interlayer water. Here, the adsorbed water is water adsorbed on the surface of the silicate compound particles or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal. These adsorbed water and / or interlayer water can be removed by heat treatment.

The method of heat treatment of the silicate adsorbed water and interlayer water is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. . The temperature at the time of heating cannot be specified unconditionally depending on the type of silicate, but is selected to be 100 ° C. or higher, preferably 150 ° C. or higher, so that interlayer water does not remain. Conditions (depending on the heating time, for example, 800 ° C. or higher) are not preferable. In addition,
As long as no structural destruction occurs, the values of b / a and bc do not change by the drying operation. In the case of heat dehydration under a gas flow, an inert gas or air is usually used. The heating time is 1 minute or more, preferably 5 minutes or more. At this time, the water content of the silicate after the removal was 200 ° C. under a pressure of 1 m.
The water content after dehydration for 2 hours under the condition of
In terms of weight%, it is preferably 3% by weight or less, preferably 1% by weight or less.

As the silicate, it is preferable to use spherical particles having an average particle size of 5 μm or more. More preferably, spherical particles having an average particle size of 10 μm or more are used. More preferably, spherical particles having an average particle diameter of 10 μm or more and 100 μm or less are used. Here, the average particle size represents a median diameter measured by a particle size measuring device using laser scattering / diffraction.
The silicate may be a natural product or a commercial product as it is, as long as the particle shape is spherical, or granulation, sizing, and the like in which the shape and particle size of the particle are controlled by sorting or the like. Is also good.

In the present invention, shape control may be performed by pulverization, granulation, or the like before, during, or after the chemical treatment. Granulation method used here, for example, stirring granulation method, spray granulation method,
Rolling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, emulsion granulation, submerged granulation, compression molding granulation, etc. The method is not particularly limited as long as it can be granulated. Preferred examples of the granulation method include a stirring granulation method, a spray granulation method, a tumbling granulation method, and a fluidized granulation method, and particularly preferably include a stirring granulation method and a spray granulation method. 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 slurry.

In granulation, in order to obtain a carrier having a high particle strength, the silicate is finely divided as required. Silicates are
The miniaturization may be performed by any method. As a method of making fine, any of dry pulverization and wet pulverization can be used. Preferably, the wet pulverization is performed by using water as a dispersion medium and utilizing the swelling property of a silicate. For example, a method using forced stirring using a polytron or the like, a method using a Dyno mill, a pearl mill, or the like can be used. The particle diameter and the volume fraction of particles smaller than 1 μm are as follows: the average particle diameter is 0.01 to 5 μm and 1 μm.
m is 5% or more, preferably, the average particle diameter is 0.1 to 3 μm, and the particle fraction is less than 1 μm is 10%.
That is all.

In the spray granulation for obtaining spherical particles, the concentration of the silicate in the raw material slurry liquid is 0.1 to 70%, preferably 1 to 50%, particularly preferably 2 to 30%. The temperature of the inlet of the hot air during spray granulation varies depending on the dispersion medium, but when water is used as an example, the temperature is 80 to 260 ° C., preferably 100 ° C.
Perform at ~ 220 ° C. The spherical particles obtained as described above,
0.2M to suppress crushing and fine powder in the polymerization process
It preferably has a compressive breaking strength of Pa or more.

Catalyst for Olefin Polymerization The catalyst for olefin polymerization of the present invention comprises [A] Periodic Table 4 to
It comprises a Group 10 transition metal compound, [B] a predetermined ion-exchangeable layered silicate, and if necessary, [C] an organoaluminum compound.

The component [A] used in the present invention is a transition metal metallocene compound belonging to Groups 4 to 6 of the periodic table, or a compound having a heteroatom such as nitrogen, oxygen, sulfur or phosphorus which is a transition metal belonging to Groups 4 to 10 of the periodic table. A compound bonded to a metal.

The metallocene compound used in the present invention has a periodic table 4 to 6 having at least one conjugated five-membered ring ligand.
Group III transition metal compounds. Preferred as such transition metal compounds are the following general formulas (1), (2),
Compounds represented by (3) and (4).

[0039]

Embedded image

(Wherein A and A ′ each represent a conjugated five-membered ring ligand which may have a substituent (A and A ′ may be the same or different in the same compound); Represents a bonding group bridging the two conjugated five-membered ring ligands at an arbitrary position, Z represents a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom; 'Represents a bonding group bridging any position of the conjugated five-membered ligand and Z, M represents a metal atom selected from Groups 4 to 6 of the periodic table, and X and X' represent hydrogen. Atom, halogen atom, hydrocarbon group, alkoxy group, amino group, phosphorus-containing hydrocarbon group or silicon-containing hydrocarbon group (X and X ′ in the same compound)
May be the same or different). )

A and A ′ are conjugated five-membered ring ligands,
As described above, these may be the same or different in the same compound. This conjugated five-membered ring ligand (A
And A ′) include a conjugated carbon five-membered ring ligand,
That is, a cyclopentadienyl group can be mentioned. The cyclopentadienyl group may be a group having five hydrogen atoms [C ₅ H ₅ −], and derivatives thereof,
That is, some of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include a hydrocarbon group having 1 to 40, preferably 1 to 30 carbon atoms. Even if this hydrocarbon group is bonded to the cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the dienyl. As an example of the latter, two substituents are each ω-
The two adjacent groups in the cyclopentadienyl group
Those forming a fused six-membered ring by sharing a plurality of carbon atoms, i.e., an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and those forming a fused seven-membered ring, i.e., an azulenyl group, And an azulenyl group.

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, azulenyl group and the like. Among them, preferred is an azulenyl group. As the substituent on the cyclopentadienyl group, in addition to the above-mentioned hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, halogen atoms such as fluorine, chlorine and bromine, and alkoxy groups having 1 to 12 carbon atoms Groups such as -Si (R
^{1) (R 2) (R} 3 silicon-containing hydrocarbon group having 1 to 24 carbon atoms represented by), -P (R ¹⁾ (a phosphorus-containing hydrocarbon group having 1 to 18 carbon atoms represented by R ^2), Or -B (R ¹ )
Ageraru boron-containing hydrocarbon group having 1 to 18 carbon atoms represented by (R ^2). When there are a plurality of these substituents, each substituent may be the same or different. R described above
^{1 to} R ³ may be the same or different and each have 1 carbon atom;
And represents an alkyl group of -20.

Q represents an optional bond between two conjugated five-membered ring ligands.
Q 'is a conjugated five-membered ring ligand
Table 1 shows a bonding group that bridges any position of
You. Specific examples of Q and Q 'include (a) a methylene group,
Ethylene group, isopropylene group, phenylmethylmethyle
Group, diphenylmethylene group, cyclohexylene group, etc.
Alkylene group, (ii) dimethylsilylene group, diethyl
Silylene group, dipropylsilylene group, diphenylsilylene
Group, methylethylsilylene group, methylphenylsilylene
Group, methyl-t-butylsilylene group, disilylene group,
Silylene group such as tetramethyldisilylene group, (c) gel
Contains manium, phosphorus, nitrogen, boron or aluminum
Hydrocarbon groups, more specifically (CH_Three)_TwoGe,
(C₆H_Five)_TwoGe, (CH_Three) P, (C₆H_Five) P,
(C_FourH₉) N, (C₆H_Five) N, (C_FourH₉) B,
(C₆H _Five) B, (C₆H_Five) Al (C₆H_FiveO) Al
And the like. Preferred are alkylene groups
And silylene groups.

M is a metal transition metal selected from Groups 4 to 6 of the Periodic Table, preferably a Group 4 metal atom of the Periodic Table, specifically, titanium, zirconium, hafnium and the like.
Particularly, zirconium and hafnium are preferable.

Z is a nitrogen atom, an oxygen atom, a silicon atom,
Ligands containing phosphorus or sulfur atoms, hydrogen atoms,
Shows a halogen atom or a hydrocarbon group. Specific examples of preferred ones include an oxygen atom, a sulfur atom, and a carbon number of 1-2.
0, preferably 1 to 12 thioalkoxy group, 1 carbon atom
~ 40, preferably 1-18 silicon-containing hydrocarbon groups,
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; chlorine, bromine; It is a hydrogen group.

X and X 'each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, or diphenylphospho. A phosphorus-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms such as a fino group, or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms such as a trimethylsilyl group and a bis (trimethylsilyl) methyl group. It is a hydrogen group. X and X 'may be the same or different. Of these, halogen atoms and hydrocarbon groups, particularly those having 1 to 1 carbon atoms
8 and an amino group are preferred.

In the olefin polymerization catalyst of the present invention,
Among the compounds represented by the general formulas (1), (2), (3) or (4) as the component [A], particularly preferable ones have the following substituents. A, A ′ = cyclopentadienyl, n-butylcyclopentadienyl, indenyl, 2-methyl-indenyl,
2-methyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-
Methylbenzoindenyl, 2,4-dimethyl-4H-azulenyl, 2-methyl-4-phenyl-4H-azulenyl, 2-methyl-4- (2-naphthyl) -4H-azulenyl, 2-methyl-4- ( 4-t-butylphenyl)-
4H-azulenyl Q, Q '= ethylene, dimethylsilylene, isopropylidene Z = t-butylamide, phenylamide, cyclohexylamide, M = transition metal of Group 4, X, X' = chlorine, methyl, diethylamino.

The component [A] represented by the general formulas (1) to (4) may be used as a mixture of two or more compounds represented by the same general formula and / or compounds represented by different general formulas. it can.

Examples of the compound in which a heteroatom such as nitrogen, oxygen, sulfur, and phosphorus is bonded to a transition metal belonging to Groups 4 to 10 of the periodic table include, for example, bisamide compounds and bis (aryloxyimine) compounds of the periodic table And a Group 8 or Group 10 bisimine compound. Specific examples of these compounds are as follows.

[0050]

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[0051]

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Further, the above-mentioned component [A] is a metallocene compound of Groups 4 to 6 of the periodic table and a compound in which a hetero atom such as nitrogen, oxygen, sulfur or phosphorus is bonded to a transition metal of Groups 4 to 10 of the periodic table. It is also possible to use them together. Particularly preferred as component [A] of the present invention are metallocene compounds.

In the α-olefin polymerization catalyst of the present invention, a silane compound such as alkylsilane, alkylsilyl chloride, disilazane and polysilanol or an inorganic silicon compound such as silicon halide can be used as a co-catalyst. In the present invention, an organoaluminum compound as the optional component [C] is preferable, and one example thereof is
It is represented by the following general formula (5). AlR _a Y _3-a (5)

In the present invention, it goes without saying that the compound represented by the general formula (5) can be used alone, in combination of two or more kinds or in combination. In addition, this use can be used not only at the time of catalyst preparation but also at the time of prepolymerization or polymerization. In this formula, R represents a hydrocarbon group having 1 to 20 carbon atoms, and Y represents a halogen, hydrogen, an alkoxy group, an amino group or a siloxy group. a indicates a number greater than 0 and 3 or less. R is preferably an alkyl group, Y is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and 1 to 8 carbon atoms when it is an amino group. Is preferred. Therefore, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum,
Triisobutyl aluminum, tri normal hexyl aluminum, tri normal octyl aluminum, tri normal decyl aluminum, diethyl aluminum chloride, diethyl aluminum sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethyl amide, diisobutyl aluminum hydride, diisobutyl aluminum chloride, etc. Is mentioned. Of these, preferred are trialkylaluminum and dialkylaluminum hydride wherein a = 3. More preferably, R
Is a trialkylaluminum having 1 to 8 carbon atoms.

The catalyst according to the present invention can be formed by contacting the above-mentioned components outside or inside the polymerization tank, simultaneously or continuously, and once or a plurality of times. The contact of each component is usually performed in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. Although the contact temperature is not particularly limited, it is preferable to perform the contact between -20 ° C and 150 ° C. Any suitable combination of contact sequences is possible. Particularly preferred components are as follows. Usually, first, the component [B] is brought into contact with the component [A]. The addition of the component [C] to the component [B] can be added before, simultaneously with, or after the component [A], but is preferably a method of adding simultaneously or after. After contacting each component,
It is possible to wash with an aliphatic hydrocarbon or an aromatic hydrocarbon solvent.

The amounts of the components [A], [B] and [C] used in the present invention are arbitrary. For example, the amount of the component [A] used with respect to the component [B] is preferably 0.1 μmol to 1000 μmol, particularly preferably 0.5 μmol to 500 μmol per 1 g of the component [B].
The amount of the component [C] used relative to the component [B] is the same as that of the component [B].
Preferably, the amount of the transition metal is from 0.001 to 1 per gram.
00 μmol, particularly preferably 0.005 to 50 μmo
1 range. Therefore, the amount of the component [C] with respect to the component [A] is preferably a molar ratio of the transition metal, preferably 10 ^-5.
To 50, particularly preferably 10 ^{-4 to} 5.

The catalyst of the present invention can be, and preferably is, subjected to a prepolymerization treatment in which a polymerizable monomer is brought into contact with the catalyst and a small amount of the monomer is polymerized.
The stage of performing the prepolymerization is optional, and a method such as contacting the component [C] after contacting all the catalyst components of the present invention or after performing the prepolymerization is also possible. The polymerization conditions at that time are usually milder than those of the main polymerization. As the prepolymerized monomer, α-olefin can be used, and ethylene or propylene is preferable. The prepolymerization amount is usually from 0.01 to 100 g-PP / g-catalyst, preferably from 0.1 to 50 g-PP / g-catalyst.

At the time of or after the contact of each of the above components,
Polymers such as polyethylene and polypropylene, and solids of inorganic oxides such as silica and titania may coexist or may be brought into contact.

Use of Catalyst / Polymerization of Olefin As the polymerizable α-olefin, one having about 2 to 20 carbon atoms is preferable, and specifically, ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc. Is mentioned. In the case of copolymerization, the kind of the comonomer to be used may be selected from the above-mentioned α-olefins and selected from α-olefins other than the main component.

As the polymerization mode, any mode can be adopted as long as the catalyst component and each monomer are in efficient contact. Specifically, a slurry method using an inert solvent, a slurry method using propylene as a solvent without substantially using an inert solvent, a solution polymerization method, or a gas method for keeping each monomer in a gaseous state without substantially using a liquid solvent. The phase method can be adopted. Further, a method of performing continuous polymerization, batch polymerization, or preliminary polymerization is also applied.
In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used as a polymerization solvent. The polymerization temperature is from 0 ° C. to 200 ° C., and hydrogen can be used as an auxiliary as a molecular weight regulator. The polymerization pressure can be carried out in the range of 0 to 2000 kg / cm ² G.

[0061]

The following examples further illustrate the present invention, but the present invention is not limited by these examples without departing from the gist thereof. In the following Examples and Comparative Examples, evaluation of physical properties was performed as follows.

(1) Hysteresis and pore distribution: The conditions for measuring hysteresis and pore distribution by the nitrogen adsorption / desorption method are as follows. -Equipment: Autosorb 3 (manufactured by Cantachrome)-Measuring method: Gas adsorption method-Measuring conditions:-Pretreatment conditions: 200 ° C, 2 hours, in vacuum (10 ^-2 Torr)
・ Sample amount: about 0.2g ・ Gas type: Nitrogen ・ Gas liquefaction temperature: 77K ・ Measurement temperature: 77K

(2) Particle size: Laser micronizer (“LMS-24” manufactured by Seishin Enterprise Co., Ltd.) (3) MFR: Melt index according to JIS-K-6758 (4) Polymer BD: based on ASTM D1895-69 Polymer bulk density

<Example 1> [Chemical treatment of silicate] 1590 ml of ion-exchanged water and magnesium sulfate / 7 were placed in a glass flask equipped with a stirring blade.
Slowly add 318 g of hydrate, followed by 261 g of concentrated sulfuric acid (magnesium / sulfuric acid = 0.5 (molar ratio)), and further commercially available granulated montmorillonite (Bencray SL, manufactured by Mizusawa Chemical Co .; Al / Si = 0.28) , Mg / Si = 0.07
8, Fe / Si = 0.03, Na / Si = 0.090,
Average particle size = 27.1 μm, particle size distribution = 10 μm to 60 μm
m) 240 g were dispersed, the temperature was raised to 100 ° C. over 2 hours, the temperature was maintained for 2 hours, and then cooled to 50 ° C. in 1 hour. This slurry was filtered under reduced pressure to collect a cake. 4 L of distilled water was added to the cake to reslurry, and then filtered. This washing operation was repeated three times. The pH of the final washing solution (filtrate) was 3.20. The recovered cake was dried overnight at 110 ° C. under a nitrogen atmosphere. The weight after drying was 199 g.

The weight composition of this chemically treated montmorillonite was 7.4% Al, 1.7% Mg, and 2.0% Fe.
1% and 34.5% of Si were contained. The molar ratio of the constituent element to silicon as the main component is Al / Si = 0.2
2, Mg / Si = 0.057, Fe / Si = 0.031
Met. The adsorption / desorption isotherm according to the nitrogen adsorption method is shown in FIG. In the figure, the horizontal axis represents the value of the relative pressure P / P ₀ , and the vertical axis represents the value of the gas adsorption amount per unit amount of solid (unit is cc /
g). From the shape of the hysteresis loop, it is presumed to be an ink bottle type. The value of (b) / (a) is 0.9
8. The value of (b)-(c) was 41.5 cc / g. FIG. 2 shows the pore distribution by the desorption isotherm.
In the figure, the horizontal axis represents the pore diameter value (unit: μm), and the vertical axis represents the common logarithmic value (unit: cc / g) of the residual amount of absorption (differential). It showed a double-peaked pore distribution with peaks at diameters of about 40 μm and 55 μm. The pore volume was 0.32 cc / g.

[Preparation of catalyst] The following operations for catalyst preparation were carried out using a solvent and a monomer which had been deoxygenated and dehydrated under an inert gas. First, the ion-exchanged layered silicate granules obtained by the above chemical treatment were subjected to
Dried for 2 hours at ° C. 10 g of the dried product was introduced into a glass reactor having an inner volume of 1 L and equipped with a stirring blade, and toluene and further a solution of triethylaluminum in heptane (5 mmo) were introduced.
l) was added and stirred at room temperature. One hour later, it was washed with heptane (residual liquid ratio was less than 1%) to prepare a montmorillonite slurry (200 ml). Next, (r) -dimethylsilylenebis [2-methyl-4-] was added to a 100 ml flask.
(4-chlorophenyl) -4H-azulenyl] hafnium dichloride 0.2 mmol toluene slurry 65 m
l and 2.75 ml of a heptane solution of triisobutylaluminum (2 mmol) were added at room temperature and stirred to prepare a mixed solution.

Subsequently, propylene was sufficiently substituted.
Heptane 2 was added to a 1.0 L stirred autoclave.
35 ml were introduced and kept at 40 ° C. The montmorillonite slurry and the mixed solution of (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4H-azulenyl] hafnium dichloride and triisobutylaluminum were introduced there. Propylene was fed at a rate of 10 g / hour and the temperature was maintained. After 2 hours, the supply of propylene was stopped and maintained for another 2 hours. The prepolymerized catalyst slurry was recovered by siphon and dried at 40 ° C. under reduced pressure. By this operation, catalyst 1
A prepolymerized catalyst containing 1.75 g of polypropylene per g was obtained.

[Polymerization] Stirring type autoclave having an inner volume of 3 L
After sufficiently replacing the inside of the tube with propylene, 2.76 ml of triisobutylaluminum / n-heptane solution (2.0
2 mmol), and 15 g of ethylene and then 1500 ml of liquid propylene were introduced, and the internal temperature was maintained at 30 ° C. The prepolymerized catalyst prepared above was slurried in normal heptane, 30 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected, and the temperature was raised to 75 ° C. to start polymerization. The temperature in the tank was maintained at 75 ° C. One hour later, 5 ml of ethanol was added, and the remaining gas was purged to obtain a polymer.
Was dried. As a result, 294.9 g of a polymer was obtained. The catalyst activity was 9830 g-PP / g-catalyst · hr. Polymer BD = 0.46 (g / cc), MFR
= 0.15 (dg / min) and the ethylene content measured by IR was 1.48 wt%.

<Example 2> [Polymerization] Propylene homopolymerization without using ethylene,
It carried out similarly to Example 1 except using 50 mg of catalyst amounts. As a result, 126.7 g of a polymer was obtained. The catalyst activity was 2530 g-PP / g-catalyst.h. Polymer BD = 0.46 (g / cc), MFR =
0.18 (dg / min).

Comparative Example 1 [Chemical Treatment of Ion-Exchangeable Layered Silicate] A glass flask equipped with a stirring blade was charged with 5280 ml of distilled water and 868 sulfuric acid.
g, magnesium sulfate heptahydrate, and 1060 g of montmorillonite (Kunipia F manufactured by Kunimine Kogyo Co., Ltd., which is pulverized by a jet mill and used.)
(87 μm), dispersed in 800 g, reacted at 100 ° C. for 2 hours, and cooled to room temperature. This slurry was filtered under reduced pressure to collect a cake. The operation of reslurrying 7500 ml of distilled water with the cake and filtering was repeated three times. The pH of the final washing (filtrate) was 2.33. Filtration, unlike Example-1, required 3 hours or more.

[Granulation of ion-exchange layered silicate] Pure water was added to the above-mentioned chemically treated cake solid so as to have a concentration of 13 wt%, a slurry was prepared, and after stirring for 1 hour, a homogenizer treatment was performed for 10 minutes. did. The obtained montmorillonite slurry is spray-granulated by Okawara Kakoki Co., Ltd. (L
Spray granulation was performed using -8). Slurry physical properties and operating conditions are as follows. <Slurry physical properties: pH = 2.46, slurry viscosity = 1
9.4 CP, density = 1.090 g / cc; operating conditions: atomizer rotation speed 15000 rpm, supply amount = 0.7 L
/ H, inlet temperature = 199 ° C., outlet temperature = 130 ° C., cyclone differential pressure = 60 mmH ₂ O>

As a result, 211 g of granules were recovered.
The average particle size was 48.6 μm. The composition was analyzed by fluorescent X-ray. As a result, the molar ratio of the constituent elements to silicon as the main component was found to be Al / Si = 0.28, Mg / Si
= 0.072 and Fe / Si = 0.020. The adsorption / desorption isotherm by the nitrogen adsorption method is shown in FIG. The shape was different from the hysteresis loop of Example-1. (B) / (a) = 0.48, (b)-(c) = 1
2.2. FIG. 4 shows the pore distribution by the desorption isotherm. It shows a peak at a diameter of about 40 μm,
A pore distribution showing a broad distribution at μm or more was shown.

[Preparation of Catalyst / Preliminary Polymerization] Preparation of catalyst and preliminary polymerization were carried out in the same manner as in Example 1 except that the above-mentioned chemically treated and granulated ion-exchange layered silicate was used. As a result, 1.88 polypropylene / g catalyst
g of the prepolymerized catalyst was obtained.

[Polymerization] The same procedure as in Example 1 was carried out except that the above-mentioned prepolymerized catalyst was used. As a result, 118.
5 g of polymer were obtained and the catalytic activity was 3950 g-P
P / g-catalyst · hour and activity were low. MFR =
0.44 (dg / min) and the ethylene content was 1.6 wt%.

<Comparative Example 2> [Polymerization] The polymerization was carried out in the same manner as in Example 2 except that 50 mg of the catalyst synthesized in Comparative Example 1 was used. As a result, 7
2.5 g of polymer were obtained. The catalytic activity is 1250
g-PP / g-catalyst, MFR = 0.48 (dg /
Min).

Example 3 [Preparation of Catalyst] The complex to be used was (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4
[H-azulenyl] zirconium dichloride was used, except that it was used. As a result, catalyst 1
A prepolymerized catalyst containing 0.37 g of polypropylene per g was obtained.

[Polymerization] The polymerization was carried out in the same manner as in Example 1 except that the above prepolymerized catalyst was used. As a result, 406 g
Was obtained. The catalytic activity is 13500 g-P
At the time of P / g-catalyst, the MFR was 1.95 (dg / min) and the ethylene content was 1.68 wt%.

Comparative Example 3 [Preparation of Catalyst] The complex used was (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4
[H-azulenyl] zirconium dichloride, except that the reaction was carried out in the same manner as in Comparative Example 1. As a result, catalyst 1
A prepolymerized catalyst containing 1.24 g of polypropylene per gram was obtained.

[Polymerization] The polymerization was carried out in the same manner as in Example 1 except that the above prepolymerized catalyst was used. As a result, 186 g
Was obtained. The catalytic activity is 6200 g-PP
/ G-catalyst / hr, MFR was 1.96 (dg / min).

<Example 4> [Chemical treatment of silicate] As in Example 1, except that lithium sulfate monohydrate was used as the coexisting salt (lithium / sulfuric acid = 1.0 (molar ratio)). It was carried out. As a result of the analysis by the nitrogen adsorption method, the value of (b) / (a) was 0.96, (b)
-The value of (c) was 61.9. The shape of the pores is assumed to be an ink bottle type as in Example-1. As for the pore distribution, a two-peak distribution was shown in the same manner as in Example-1.
The average pore diameter is 45.2 μm and the pore volume is 0.34 cc /
g.

[Preparation of Catalyst] In a 100 ml flask, 200 mg of the chemically treated silicate obtained above and 0.8 ml of a toluene solution of triethylaluminum (concentration:
(0.5 mol-aluminum / L) and stirred at room temperature for 1 hour. Then, it was washed with toluene. In a 50 ml flask, 3 ml of the above slurry (100 parts as a solid component)
mg), and a toluene solution of (r) -dimethylsilylenebis [2-ethyl-4- (4-chlorophenyl) -4H-azulenyl] hafnium dichloride (1.0 μm
ol / ml) was added. Then, a toluene solution of triisobutylaluminum (0.01 mmol /
3 ml), and contacted at room temperature for 5 minutes to obtain a catalyst component.

[Polymerization] All the above catalyst components were added to a 2 L autoclave, 100 ml of liquefied propylene was introduced, and preliminary polymerization was carried out at room temperature for 5 minutes with stirring. Then, a toluene solution of triisobutylaluminum (0.5 mm
ol / ml), and liquefied propylene was added to 1200 ml.
Then, polymerization was carried out at 75 ° C. for 1 hour. Thereafter, unreacted propylene was purged to terminate the polymerization. The obtained propylene polymer was 350 g. The catalyst activity was 7,000 g-PP / g-catalyst-hour.

<Example-5> [Chemical treatment of silicate] 38 ml of ion-exchanged water and then 5 g of concentrated sulfuric acid were slowly added to a glass flask, and commercially available granulated montmorillonite (Benclay SL manufactured by Mizusawa Chemical Co., Ltd.) was added. 5) was dispersed and stirred under reflux for 2 hours. Thereafter, the collected montmorillonite was sufficiently washed with demineralized water, and dried at 110 ° C. overnight. The analysis result of the obtained montmorillonite by the nitrogen adsorption method is (b) /
The value of (a) is 0.97, and the value of (b)-(c) is 3
5.8. As for the pore distribution, a two-peak distribution was shown in the same manner as in Example-1. The average pore diameter was 41.0 μm, and the pore volume was 0.38 cc / g.

[Preparation / Polymerization of Catalyst] Using the above chemically treated silicate, using (r) -dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4H-azulenyl] hafnium dichloride, It carried out like Example 4 except having made polymerization time into 23 minutes. As a result, the catalyst activity was 9340 g-PP / g-catalyst · hr.

Example 6 [Preparation of catalyst] The same procedure as in Example 1 was carried out except that (r) -dimethylsilylenebis [2-methyl-4-phenyl-4H-azulenyl] zirconium dichloride was used. did. As a result, 0.3 g of polypropylene per 1 g of catalyst was used.
A prepolymerized catalyst containing 3 g was obtained.

[Polymerization] The polymerization was carried out in the same manner as in Example 1 except that the above-mentioned prepolymerized catalyst was used and the polymerization temperature was 70 ° C. The catalyst activity was 11,100 g-PP / g-catalyst. MFR = 1.77 (dg / min), and the ethylene content measured by IR was 1.70 wt%.

<Comparative Example 4> [Chemical treatment of silicate] Montmorillonite to be used was the same as Kunipine F manufactured by Kunimine Industries Co., Ltd.
It carried out similarly to Example-5. The composition of this chemically treated montmorillonite is Al / Si = 0.34, Mg / S
i = 0.071 and Fe / Si = 0.020. The analysis results by the nitrogen adsorption method show that the value of (b) / (a) is
0.74, and the value of (b)-(c) was 28.2.

[Preparation of Catalyst / Polymerization] Using the above chemically treated silicate and (r) -dimethylsilylenebis (2-methyl-4-phenyl-4H-azulenyl) zirconium dichloride, the polymerization temperature was set to 80. Except at ℃
It carried out similarly to Example-4. As a result, the catalytic activity is
1000 g-PP / g-catalyst-hour.

<Example-7> [Chemical treatment of silicate] The same procedure as in Example-1 was carried out except that the temperature of the chemical treatment was 90 ° C and the treatment time was 8 hours. The composition of this chemically treated silicate is Al / Si =
0.15, Mg / Si = 0.035, Fe / Si = 0.
025. Analysis results by nitrogen adsorption method
The value of (b) / (a) was 0.97, and the value of (b)-(c) was 34.8. The pore volume was 0.32 cc / g

[Preparation of catalyst] Using the above chemically treated silicate, (r) -dimethylsilylenebis [2-methyl-
4- (4-Chlorophenyl) -4H-azulenyl] zirconium dichloride was used, except that it was used. As a result, a prepolymerized catalyst containing 0.76 g of polypropylene per 1 g of the catalyst was obtained.

[Polymerization] Stirring type autoclave having an inner volume of 3 L
After sufficiently replacing the inside of the tube with propylene, 2.76 ml of triisobutylaluminum / n-heptane solution (2.0
2 mmol), 15 g of ethylene, 35 ml of hydrogen,
Subsequently, 1500 ml of liquid propylene was introduced, and the internal temperature was maintained at 70 ° C. The above prepolymerized catalyst was slurried in normal heptane, and 15 mg of the catalyst (excluding the weight of the prepolymerized polymer) was injected to initiate polymerization. The temperature in the tank was maintained at 70 ° C. One hour later, 5 ml of ethanol was added, the residual gas was purged, and the obtained polymer was dried.
As a result, 201.2 g of a polymer was obtained. The catalyst activity was 13400 g-PP / g-catalyst · h. M
FR = 2.79 (dg / min), ethylene content measured by IR was 1.76 wt%.

<Example-8> [Chemical treatment of silicate] The same operation as in Example-1 was carried out except that the temperature of the chemical treatment was 90 ° C and the treatment time was 23.5 hours. The composition of this chemically treated silicate is Al / Si
= 0.092, Mg / Si = 0.020, Fe / Si =
It was 0.014. Analysis results by nitrogen adsorption method
The value of (b) / (a) was 0.98, and the value of (b)-(c) was 49.0. The pore volume was 0.55 cc / g

[Preparation / Polymerization of Catalyst] The same procedure as in Example 7 was carried out except that the above chemically treated silicate was used. As a result, 1.18 polypropylene / g catalyst
g of the prepolymerized catalyst was obtained. Polymerization was carried out in the same manner as in Example 7 using this catalyst, and as a result, 167.5 was obtained.
g of polymer were obtained. The catalytic activity is 11200 g-
PP / g-catalyst-hr. MFR = 4.23 (dg
/ Min), the ethylene content measured by IR is 1.84 w
t%.

<Comparative Example-5> [Preparation / polymerization of catalyst] The same operation as in Example-8 was carried out except that the silicate synthesized in Comparative Example-1 was used. As a result, a prepolymerized catalyst containing 2.28 g of polypropylene per 1 g of the catalyst was obtained. Polymerization was carried out in the same manner as in Example 8 using this catalyst, and as a result, 81.0 g of a polymer was obtained.
was gotten. The catalyst activity was 5400 g-PP / g-catalyst · h. MFR = 12.58 (dg / min), IR
Was 1.91% by weight.

<Comparative Example-6> [Chemical treatment of silicate] 50 ml of demineralized water was placed in a glass flask.
Then, 8.57 g of lithium sulfate monohydrate and 6.54 g of concentrated sulfuric acid were slowly added, and 13.6 g of commercially available mica (ME-100, manufactured by Coop Chemical Co., Ltd.) was dispersed. The mixture was stirred for an hour. Thereafter, the collected mica was sufficiently washed with demineralized water, and dried at 110 ° C. overnight. The composition of this chemically treated mica is Al / Si =
0.002, Mg / Si = 0.66, Na / Si = 0.
026. The analysis result by the nitrogen adsorption method is (b)
The value of / (a) is 0.49 and the value of (b)-(c) is 1
3.6.

[Preparation / Polymerization of Catalyst] The procedure of Example 1 was repeated except that the above chemically treated silicate was used and (r) -dimethylsilylenebis [2-methyl-4-phenyl-4H-azulenyl] zirconium dichloride was used. -4. As a result, the catalytic activity was 1500 g-PP / g-
It was a catalyst.

<Comparative Example-7> [Chemical treatment of silicate] Demineralized water 10 was placed in a glass flask.
0 ml and subsequently 17.8 ml of titanium tetrachloride were slowly added, and 10 g of commercially available lithium hectorite (manufactured by Topy Industries) was dispersed, followed by stirring at room temperature for 2 hours. Thereafter, the recovered hectorite was sufficiently washed with demineralized water, and dried at 110 ° C. overnight. As a result of analyzing the obtained hectorite by the nitrogen adsorption method, the value of (b) / (a) was 0.64, and the value of (b)-(c) was 8.6.

[Preparation / Polymerization of Catalyst] The procedure of Example 1 was repeated except that the above chemically treated silicate was used and (r) -dimethylsilylenebis [2-methyl-4-phenyl-4H-azulenyl] zirconium dichloride was used. -4. As a result, the catalyst activity was 990 g-PP / g-catalyst · hr.

[0099]

According to the present invention, a powder having high activity and good particle properties can be obtained, and the polymer exhibits excellent performance in production stability and economy.

[Brief description of the drawings]

FIG. 1 Adsorption / desorption isotherm by nitrogen adsorption method (Example 1)

FIG. 2 Pore distribution by desorption isotherm (Example 1)

FIG. 3 Adsorption / desorption isotherm by nitrogen adsorption method (Comparative Example 1)

FIG. 4 Pore distribution by desorption isotherm (Comparative Example 1)

Continuing from the front page (72) Inventor Hiroyuki Nakano 1 Tohocho, Yokkaichi-shi, Mie, Japan Process Development Center (72) Inventor Yoichi Uchimura 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Chemical Inside the Tsukuba Research Laboratories Co., Ltd. (72) Inventor Kazuhiro Yamamoto 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Co., Ltd. F-term in the Company Technology Development Center (reference) 4J015 EA00 4J028 AA01A AB00A AB01A AC01A AC08A AC10A AC26A AC28A BA00A BA00B BA01B BB00A BB00B BB01B BC15B BC16B BC17B BC19B BC24B BC27B CA30B CA30C DA01 EB01 FA01 EB01 DA03 FA04 4J100 AA02P AA03P AA04P AA16P AA19P CA01 CA04 FA10

Claims (6)

[Claims] 1. An olefin polymerization catalyst component comprising an ion-exchange layered silicate having the following property [I]. [I] In the desorption isotherm by nitrogen adsorption-desorption method, a relative pressure _{P / P 0 = 1 P /} P for adsorption (a) at ₀ =
The ratio of the residual adsorption amount (b) at 0.85 satisfies the following expression. (B) / (a) ≧ 0.8 2. A catalyst component for olefin polymerization, comprising using an ion-exchangeable layered silicate having both the following properties [I] and [II]. [I] In the desorption isotherm by nitrogen adsorption-desorption method, a relative pressure _{P / P 0 = 1 P /} P for adsorption (a) at ₀ =
The ratio of the residual adsorption amount (b) at 0.85 satisfies the following expression. (B) / (a) ≧ 0.8 [II] In the adsorption and desorption isotherms by the nitrogen adsorption / desorption method, the relative pressure P / P ₀ = 0.85
Adsorption amount (b) and relative pressure P / P ₀ of the desorption isotherm at
= 0.85, the difference of the adsorption amount (c) of the adsorption isotherm is
Satisfy the following formula. (B)-(c)> 25 (cc / g) 3. The catalyst component for olefin polymerization according to claim 1, wherein the ion-exchange layered silicate is chemically treated. 4. The catalyst component for olefin polymerization according to claim 1, wherein the ion-exchangeable layered silicate is a smectite group. 5. The catalyst component for olefin polymerization according to claim 1, wherein the ion-exchangeable layered silicate is montmorillonite. 6. [A] a transition metal compound belonging to Groups 4 to 10 of the periodic table, [B] the catalyst component according to any one of claims 1 to 5, and [C] an organoaluminum as required. An olefin polymerization catalyst comprising a compound.