JPH11279216A - Production of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an olefin polymer by which the molecular weight of the olefin polymer is controlled when the production method of the olefin polymer by using an organic transition metal compound is applied to a polymerization reaction accompanying the formation of olefin polymer particles by carrying out the polymerization reaction in the presence of an organic zinc compound. SOLUTION: This method for producing an olefin polymer comprises carrying out the reaction in the presence of an organic zinc compound when carrying out the polymerization reaction accompanying the formation of olefin polymer particles by using an organic transition metal compound. A compound of the formula R<5> c ZnZ2-c [R<5> is a 1-8C hydrocarbon; Z is H and/or a halogen; 0<(c)<=2] is preferable as the organic zinc compound, and dimethylzinc and diethylzinc are especially preferable. The using amount is preferably 10-1,000 expressed in terms of molar ratio of the zinc atom in the organic zinc compound to the transition metal in the organic transition metal compound. The organic transition metal compound preferably has a cyclopentadiene-type anion skeleton- containing group. The polymerization reaction is preferably carried out by a slurry polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an olefin polymer which gives an olefin polymer having a controlled molecular weight. More specifically, the present invention is excellent in shape, particle properties, and molecular weight is controlled when an olefin polymerization catalyst using an organic transition metal compound such as metallocene is applied to a polymerization reaction involving formation of polymer particles. The present invention relates to a method for producing an olefin polymer that gives an olefin polymer.

[0002]

2. Description of the Related Art Many reports have been made on a method for producing an olefin polymer using an organic transition metal compound (for example, metallocene or nonmetallocene). For example, JP-A-58-19309 discloses a method for producing an olefin polymer using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane as an example using a metallocene-based organic transition metal compound. Japanese Patent Laid-Open Publication No. 1-502036 discloses a method for producing an olefin polymer using bis (pentamethylcyclopentadienyl) zirconium dimethyl and trinormalbutylammonium tetrakisphenylborate. Also, JP-A-5-178923 discloses the production of an olefin polymer using dimethylsilylenebis (2,4-dimethylcyclopentadienyl) zirconium dimethyl, dimethylaniliniumtetrakis (pentafluorophenyl) borate and triethylaluminum. A method is disclosed. An example using a nonmetallocene-based organic transition metal compound is also described in J. Amer. Chem.
Soc., 115, 8493 (1993)., Plastics Engineering, Ma.
r. 77 (1996). and WO 96/23010.

[0003] Catalysts using these organic transition metal compounds are usually soluble in the reaction system, and thus are formed when used in polymerization reactions involving the formation of polymer particles (eg, slurry polymerization, gas phase polymerization, etc.). The shape of the polymer is irregular, resulting in the formation of a coarse polymer, a bulk polymer, a fine powder polymer, etc., a decrease in the bulk density of the polymer, and the adhesion of the polymer to the polymerization reactor wall. And these contribute to
There have been problems in that heat transfer failure, heat removal failure, and the like occur in the reactor, and stable operation is difficult and productivity is reduced.

That is, in order to apply an organic transition metal compound to a polymerization reaction involving the formation of polymer particles (eg, slurry polymerization, gas phase polymerization, etc.), not only a sufficient polymerization activity is exhibited but also the shape and particle properties are increased. It is necessary to obtain an excellent polymer, and to solve the problem, a method of supporting an organic transition metal compound on a carrier has been proposed.

As one method, there has been reported a method of immobilizing and supporting all or a part of a catalyst component such as a metallocene complex or methylaluminoxane on an inorganic metal oxide carrier such as silica. For example, Japanese Unexamined Patent Publication (Kokai) No. 61-276805 discloses an olefin polymer using bis (cyclopentadienyl) zirconium dichloride and an organic aluminum component containing an inorganic oxide obtained by reacting a mixture of methylaluminoxane and trimethylaluminum with silica. A method for producing a coalescence is disclosed, and it is described that a method of adding hydrogen to the polymerization system and a method of adjusting the temperature can be used to adjust the molecular weight of the obtained olefin polymer.

[0006] As an improved loading method, a solid catalyst component in which all or a part of a catalyst component such as a metallocene complex or methylaluminoxane is immobilized on an inorganic metal oxide carrier such as silica and supported, and aluminoxane or organoaluminum are used. And a method using a prepolymerized catalyst that has undergone prepolymerization. For example, JP-A-63-51407 discloses a method for producing an olefin polymer using a solid catalyst component obtained by treating silica with methylaluminoxane and then bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. In this method, hydrogenation and temperature adjustment are described as methods for adjusting the molecular weight of the olefin polymer. JP-A-63-89
No. 505 discloses a method for producing an olefin polymer using triisobutylaluminum and a solid catalyst component obtained by treating silica with methylaluminoxane and then bis (cyclopentadienyl) zirconium dichloride, or the solid catalyst. A method for producing an olefin polymer using a solid catalyst component prepolymerized using the components and triisobutylaluminum is disclosed.However, as a method for adjusting the molecular weight of the olefin polymer, hydrogenation and Temperature regulation is described.

As a further improved and simplified method of the above-mentioned prior art, a method using no separately synthesized aluminoxane has been reported. As one method, a method of producing an aluminoxane by reacting organoaluminum with water in the presence of an inorganic metal oxide carrier such as silica to produce a solid catalyst component, and using the same to produce an olefin polymer has been reported. ing. For example, JP-A-61-31404 discloses a method for producing an olefin polymer by sequentially adding water, trimethylaluminum, and bis (cyclopentadienyl) zirconium dichloride to silica to use as a catalyst. It is described that the polymerization is carried out by supplying hydrogen to adjust the molecular weight of the polymer. JP-A-3-234710 discloses that a pre-polymerized solid catalyst is prepared by adding water, trimethylaluminum, and bis (methylcyclopentadienyl) zirconium dichloride to silica sequentially and further adding ethylene. A method for producing an olefin polymer using a catalyst and triisobutylaluminum is disclosed, and it is described that the molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in a polymerization system.

Recently, a method for producing an olefin polymerization catalyst by using an aluminum compound having a special group introduced therein instead of an aluminoxane with an organic transition metal compound, or further with an organic aluminum compound, and using the compound to produce an olefin polymerization catalyst. There have been reports of methods for producing coalescence. For example, JP-A-6-329713 discloses that
A method for producing an olefin polymer using an aluminum compound having an electron-withdrawing group and bis (cyclopentadienyl) titanium dichloride, which is obtained by reacting trimethylaluminum with pentafluorophenol, is disclosed. It is described that an aluminum compound having such a group introduced therein can be supported on an inorganic carrier or an organic carrier. In this catalyst system, as for the method of adjusting the molecular weight of the olefin polymer, there are descriptions such as the type of the catalyst component, the amount used, the selection of the polymerization temperature, and the polymerization in the presence of hydrogen. Nothing is described.

As described above, in the production of an olefin polymer using a carrier and an organic transition metal compound, particularly a metallocene-based organic transition metal compound, the most common method for adjusting the molecular weight of the olefin polymer is hydrogen. Is known. However, when hydrogen is used in polymerization using an olefin polymerization catalyst containing an organic transition metal compound, particularly a metallocene-based organic transition metal compound, it is presumed that the reactivity between the catalyst and hydrogen is extremely high. The amount of hydrogenation significantly reduces the molecular weight of the olefin polymer. Therefore, in order to adjust the molecular weight of the olefin polymer, there was a problem that the polymerization had to be carried out while controlling the hydrogenation amount in an extremely small and very small range.

[0010]

In view of such circumstances, the problem to be solved by the present invention, that is, the object of the present invention, is as follows.
When a method for producing an olefin polymer using an organic transition metal compound is applied to a polymerization reaction involving the formation of olefin polymer particles (eg, slurry polymerization, gas phase polymerization, etc.), an olefin polymer capable of controlling the molecular weight of the olefin polymer is obtained. An object of the present invention is to provide a method for producing a united product.

[0011]

Means for Solving the Problems In order to achieve the above object, the present inventors have developed a method for producing an olefin polymer using an organic transition metal compound, particularly an olefin polymer obtained by a polymerization reaction involving formation of polymer particles. We have been conducting intensive research on the manufacturing method of sapphire. As a result, they found a method for carrying out the polymerization reaction in the presence of an organozinc compound, and completed the present invention.

That is, the present invention relates to a method for producing an olefin polymer using an organic transition metal compound, wherein the polymerization reaction involving the formation of olefin polymer particles is carried out in the presence of an organic zinc compound. Things.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the organic zinc compound used in the present invention, a known organic zinc compound can be used. Preferably, the general formula (5) R ⁵ _c ZnZ _2-c (wherein, R ⁵ is a 1-8 hydrocarbon group carbon atoms, Zn represents zinc atom.
Z represents a hydrogen atom and / or a halogen atom, and c represents 0 <
represents a number satisfying c ≦ 2. ).

R ⁵ in the general formula (5) representing an organic zinc compound is preferably an alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group,
Examples include a normal butyl group, an isobutyl group, a normal hexyl group, a 2-methylhexyl group, a cyclohexyl group, a normal octyl group, and the like. Preferred are a methyl group, an ethyl group, a normal butyl group, and an isobutyl group. Specific examples of the case where Z is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

Specific examples of the organic zinc compound represented by the general formula (5) R ⁵ _c ZnZ _2-c include dimethyl zinc, diethyl zinc, dinormal propyl zinc, dinormal butyl zinc, diisobutyl zinc, dinormal hexyl Dialkyl zinc such as zinc, dicyclohexyl zinc and dinormal octyl zinc; alkyl zinc chloride such as methyl zinc chloride, ethyl zinc chloride, normal propyl zinc chloride, normal butyl zinc chloride, isobutyl zinc chloride, normal hexyl zinc chloride and cyclohexyl zinc chloride; Methyl zinc hydride, ethyl zinc hydride, normal propyl zinc hydride, normal butyl zinc hydride, isobutyl zinc hydride, normal hexyl zinc hydride, cyclohexyl Examples thereof include alkyl zinc hydrides such as sil zinc hydride. Of these, dialkyl zinc is preferred, dimethyl zinc, diethyl zinc, dinormal butyl zinc, diisobutyl zinc, or dinormal hexyl zinc is more preferred, and dimethyl zinc or diethyl zinc is particularly preferred. These organic zinc compounds may be used alone or in combination of two or more.

By using such an organic zinc compound, the molecular weight of the produced olefin polymer can be controlled, and as the amount of the organic zinc compound used increases, the molecular weight of the produced olefin polymer tends to decrease.

The amount of the organozinc compound used is usually 0.01 mol as the molar ratio (D) / (B) of the zinc atom in the organozinc compound (D) to the transition metal atom in the organic transition metal compound (B). It is appropriately selected from the range of from 100 to 100,000, more preferably from 0.1 to 50,000, and most preferably from 10 to 1,000.

The process for producing the olefin polymer of the present invention comprises the steps of:
It is based on a polymerization reaction involving formation of olefin polymer particles, and is suitably applied to slurry polymerization or gas phase polymerization, and more preferably applied to slurry polymerization.

The slurry polymerization may be performed according to a known slurry polymerization method and polymerization conditions, but is not limited thereto. As a preferred polymerization method in the slurry method, a continuous reactor in which a monomer (and a comonomer), a feed, a diluent and the like are continuously added as necessary, and a polymer product is continuously or at least periodically removed. included. Examples of the reactor include a method using a loop reactor, a plurality of stirred reactors having different reactors, and different reaction conditions in series or in parallel, or a combination thereof. The polymerization time is generally appropriately determined depending on the type of the intended olefin polymer and the reaction apparatus.
It can range from 1 minute to 20 hours.

As the diluent, for example, an inert diluent (medium) such as paraffin, cycloparaffin or aromatic hydrocarbon can be used. The temperature of the polymerization reactor or reaction zone can usually range from about 50C to about 100C, preferably from 60C to 80C. The pressure can usually be varied from about 0.1 MPa to about 10 MPa, preferably from 0.5 MPa to 5 MPa. The catalyst can be kept in suspension, the medium and at least some of the monomers and comonomers can be maintained in a liquid phase, and pressure can be applied to bring the monomers and comonomers into contact. Thus, the medium, temperature, and pressure may be selected so that the olefin polymer is produced as solid particles and recovered in that form. In addition, hydrogen may be added if necessary to assist in adjusting the molecular weight.

The components and monomers (and comonomers) used in the polymerization reaction can be added to the reactor or the reaction zone in any order by any known method. For example, a method of simultaneously adding each catalyst component and a monomer (and a comonomer) to the reaction zone, a method of sequentially adding the components, and the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere before contacting with the monomer (and comonomer).

The gas phase polymerization may be carried out according to known gas phase polymerization methods and polymerization conditions, but is not limited thereto. As the gas phase polymerization reactor, a fluidized bed type reaction vessel, preferably a fluidized bed type reaction vessel having an enlarged portion is used.
There is no problem even in a reactor in which a stirring blade is installed in the reaction tank. As a method of supplying each component used in the polymerization reaction to the polymerization tank, the components are supplied in a water-free state using an inert gas such as nitrogen or argon, hydrogen, ethylene, or the like, or dissolved or diluted in a solvent. Then, a method such as supplying in a solution or slurry state can be used.

As the polymerization conditions, the temperature is lower than the temperature at which the polymer melts, preferably from 20 ° C to 100 ° C, particularly preferably from 40 ° C to 90 ° C. Pressure is 0.1MPa ~
The range of 5MPa is preferable, more preferably 0.3MPa.
a to 4 MPa. Further, hydrogen may be added as a molecular weight modifier for the purpose of adjusting the melt fluidity of the final product. In addition, at the time of polymerization, an inert gas may coexist in the mixed gas.

The process for producing the olefin polymer of the present invention comprises:
The present invention relates to a method for producing an olefin polymer using an organic transition metal compound. As the organic transition metal compound, metallocene and non-metallocene are well known. As the organic transition metal compound, any organic transition metal compound capable of exhibiting olefin polymerization activity can be used. As the transition metal, a periodic table of elements (1993, IUP
Preferred are transition metals of the Group 4 AC or lanthanide series. More preferably, the organic transition metal compound is a metallocene-based organic transition metal compound, that is, an organic transition metal compound having at least one group having a cyclopentadiene-type anion skeleton.

The metallocene organic transition metal compound is, for example, a compound represented by the following general formula (3). The general formula ^{_{(3) ML a R 3 pa}} ( in the formula, M is the Periodic Table of the Elements (1993, IUPA
It is a transition metal atom of Group 4 or lanthanide series of C). L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and at least 1
One is a group having a cyclopentadiene-type anion skeleton. A plurality of L may be the same or different, and may be cross-linked to each other. R ³ is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. a is 0
<A ≦ p, p is the valence of the transition metal atom M. )

In the general formula (3) representing a metallocene-based organic transition metal compound, M represents a periodic table of elements (1993).
(IUPAC) is a transition metal atom belonging to the Group 4 or lanthanide series. Specific examples thereof include a titanium atom, a zirconium atom, and a hafnium atom as a transition metal atom of Group 4 of the periodic table, and a samarium atom as a lanthanide-based transition metal atom. Preferably, it is a titanium atom, a zirconium atom or a hafnium atom.

In the general formula (3) representing a metallocene-based organic transition metal compound, L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and at least one group is a group having a cyclopentadiene-type anion skeleton. It is. A plurality of L may be the same or different, and may be cross-linked to each other. Examples of the group having a cyclopentadiene-type anion skeleton include η ⁵ −
Examples thereof include a cyclopentadienyl group, an η ⁵ -substituted cyclopentadienyl group, and a polycyclic group having a cyclopentadiene-type anion skeleton. Examples of the substituent of the η ⁵ -substituted cyclopentadienyl group include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and a silyl group having 1 to 20 carbon atoms. And the like. As the polycyclic group having a cyclopentadiene type anion skeleton eta ⁵ - indenyl group and eta ⁵ - fluorenyl group and the like. The hetero atom in the group containing a hetero atom includes a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom and the like. Examples of such a group containing a hetero atom include a hydrocarbon amino group, a hydrocarbon phosphino group, a hydrocarbon oxy group, a hydrocarbon thio group, and the like, preferably an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group. A dialkylamino group, a diarylamino group, a dialkylphosphino group or a diarylphosphino group.

The eta ⁵ - Specific examples of the substituted cyclopentadienyl group, eta ⁵ - methylcyclopentadienyl group, eta ⁵
- ethyl cyclopentadienyl group, eta ⁵ - normal propyl cyclopentadienyl group, eta ⁵ - isopropyl cyclopentadienyl group, eta ⁵ - n-butylcyclopentadienyl group, eta ⁵ - isobutyl cyclopentadienyl group, η ⁵ -secondary butylcyclopentadienyl group, η ^5-
Tertiary butyl cyclopentadienyl group, eta ^5-1,2-
Dimethyl cyclopentadienyl group, eta ^{5-1,3-dimethyl-cyclopentadienyl} group, eta ^{5-1,2,3-trimethyl} cyclopentadienyl group, eta ^{5-1,2,4-tri-methylcyclopentadienyl} enyl, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ⁵ - trimethylsilyl cyclopentadienyl group and the like.

Specific examples of the polycyclic group having a cyclopentadiene-type anion skeleton include η ⁵ -indenyl group, η ⁵
-2-methylindenyl group, eta ^{5-4-methylindenyl} group, eta ^{5-4,5,6,7-tetrahydroindenyl} group, eta ⁵ - fluorenyl group and the like.

Specific examples of the group containing a hetero atom include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a thiomethoxy group, a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group and a diphenylamino group. Examples include an amino group, a pyrrolyl group, and a dimethylphosphino group.

Groups having a cyclopentadiene-type anion skeleton or groups having a cyclopentadienyl skeleton and a group containing a hetero atom may be cross-linked, in which case, an alkylene group such as an ethylene group or a propylene group,
Dimethylmethylene group, substituted alkylene group such as diphenylmethylene group, or silylene group, dimethylsilylene group,
A substituted silylene group such as a diphenylsilylene group or a tetramethyldisilylene group may be present.

R ³ in the general formula (3) representing a metallocene-based organic transition metal compound is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. a is 0 <a ≦ p
And p is the valence of the transition metal atom M.
Specific examples of R ³ include a fluorine atom as a halogen atom, a chlorine atom, a bromine atom, an iodine atom, 1 to carbon atoms
Examples of the 20 hydrocarbon groups include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a phenyl group, and a benzyl group. R ³ is preferably a chlorine atom, a methyl group or a benzyl group.

Among the metallocene-based organic transition metal compounds represented by the general formula (3), specific examples of the compound in which the transition metal atom M is a zirconium atom include bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl) zirconium dichloride. (Methylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) Zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) Ruconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) Enyl) (fluorenyl) zirconium dichloride,
Diphenylsilylene bis (indenyl) zirconium dichloride, (cyclopentadienyl) (dimethylamido) zirconium dichloride, (cyclopentadienyl) (phenoxy) zirconium dichloride, dimethylsilylene (tertiary butylamino) (tetramethylcyclopentadienyl) ) Zirconium dichloride, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium dimethyl, bis (4,5 6,7-tetrahydroindenyl) zirconium dimethyl, bis (fluorenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, dimethyl Silylene (tertiary-butylamino) (tetramethylcyclopentadienyl) zirconium dimethyl, and the like. Further, compounds in which zirconium is replaced with titanium or hafnium in the above zirconium compounds can also be exemplified. One of these metallocene-based organic transition metal compounds may be used alone, or two or more thereof may be used in combination.

The process for producing the olefin polymer of the present invention comprises the steps of:
The present invention relates to a polymerization reaction involving the formation of olefin polymer particles using an organic transition metal compound. As the olefin polymerization catalyst suitable for the polymerization reaction involving the formation of such olefin polymer particles, the following catalysts [1] to [1] 7]. [1] A catalyst obtained by contacting a carrier, an organic aluminum oxy compound, and an organic transition metal compound. [2] A catalyst comprising a solid catalyst component obtained by contacting a carrier with an organic aluminum oxy compound and then an organic transition metal compound, and an organic aluminum oxy compound or an organic aluminum compound. [3] A catalyst comprising a solid catalyst component obtained by contacting a carrier, moisture, and an organic aluminum compound and then contacting with an organic transition metal compound, and an organic aluminum oxy compound or an organic aluminum compound. [4] A catalyst obtained by contacting a support, a boron compound, and an organic transition metal compound, or further contacting an organic aluminum compound. [5] A catalyst comprising a solid catalyst component obtained by contacting a carrier, a boron compound, and an organic transition metal compound, or further contacting with an organic aluminum compound, and an organic aluminum oxy compound or an organic aluminum compound. [6] a solid catalyst component obtained by contacting ferrocene, concentrated sulfuric acid, and a clay mineral, an organoaluminum compound,
And an organic transition metal compound. [7] A solid obtained by contacting a carrier with an organoaluminum compound and then contacting a compound having an active hydrogen-containing functional group or an aprotic Lewis basic functional group and an electron-withdrawing group. A catalyst comprising a catalyst component, an organic aluminum compound, and an organic transition metal compound. The method for producing an olefin polymer using the organic transition metal compound of the present invention is preferably a method for producing an olefin polymer using any one of the above-mentioned catalysts [1] to [7].

As the carrier in the catalysts [1] to [7], a porous substance having a uniform particle size is preferable, and an inorganic substance or an organic polymer substance is suitably used.

Examples of the inorganic substance include inorganic oxides and mag
Nesium compounds, clay or clay minerals, etc.
They may be used as a mixture. Inorganic oxide
As a specific example, SiO 2_Two, Al_TwoO_Three, MgO, Zr
O_Two, TiO _Two, B_TwoO_Three, CaO, ZnO, BaO, Th
O_TwoAnd mixtures thereof, for example, SiO 2_Two-Mg
O, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two−
V_TwoO _Five, SiO_Two−Cr_TwoO_Three, SiO_Two-TiO_Two-Mg
O and the like can be exemplified. These inorganic oxides
Inside, SiO_TwoAnd / or Al_TwoO_ThreeIs preferred.
The inorganic oxide contains a small amount of Na_TwoCO_Three, K_TwoC
O_Three, CaCO_Three, MgCO_Three, Na_TwoSO_Four, Al_Two(SO
_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)_Two, Al (N
O_Three)_Three, Na_TwoO, K_TwoO, Li_TwoCarbonate such as O, sulfuric acid
It may contain salts, nitrates and oxide components.

Examples of the magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, and the like. Alkoxy magnesium halides; Allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium; phenoxy magnesium, dimethyl Allyloxymagnesium such as phenoxymagnesium; lau Magnesium phosphate, and the like can be exemplified carboxylates of magnesium such as magnesium stearate. Of these, magnesium halide or alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.

As the clay or clay mineral, kaolin,
Bentonite, kibushi clay, gairome clay, allophane,
Hisingelite, virophilite, talc, plum group,
Montmorillonite group, vermiculite, ryokudeite group, palygorskite, kaolinite, nacrite, dickite, halloysite and the like. Of these, smectite, montmorillonite, hectorite, laponite and saponite are preferred, and montmorillonite and hectorite are more preferred.

The average particle diameter of the inorganic substance is preferably
5 to 1000 μm, more preferably 10 to 500
μm, and more preferably 10 to 100 μm. The pore volume is preferably 0.1 ml / g or more, more preferably 0.3 ml / g or more. The specific surface area is preferably 10 to 1000 m ² / g, more preferably 100 m ² / g.
５００500 m ² / g.

As the organic polymer substance that can be used as the carrier, any organic polymer substance may be used.
Further, a plurality of kinds of organic polymer substances may be used as a mixture. The organic polymer substance is preferably an organic aluminum substance having a functional group capable of reacting with an organic aluminum oxy compound or an organic aluminum compound. Examples of such a functional group include a functional group having an active hydrogen and a non-proton donating Lewis basic functional group. Examples of the organic polymer substance that can be used as the carrier include a functional group having an active hydrogen and a non-active functional group. A polymer having a proton-donating Lewis basic functional group is preferred.

The functional group having active hydrogen is not particularly limited as long as it has active hydrogen, and specific examples include a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group. , Hydroxy group, hydroperoxy group, carboxyl group, formyl group, carbamoyl group, sulfonic acid group, sulfinic acid group, sulfenic acid group, thiol group, thioformyl group, pyrrolyl group, imidazolyl group,
Examples include a piperidyl group, an indazolyl group, and a carbazolyl group. Preferably, a primary amino group, a secondary amino group,
It is an imino group, an amide group, an imide group, a hydroxy group, a formyl group, a carboxyl group, a sulfonic acid group or a thiol group. Particularly preferred are a primary amino group, a secondary amino group, an amide group and a hydroxy group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The non-proton-donating Lewis basic functional group is not particularly limited as long as it is a functional group having a Lewis base portion having no active hydrogen atom. Specific examples thereof include a pyridyl group, an N-substituted imidazolyl group, N-substituted indazolyl group, nitrile group, azide group, N-substituted imino group, N,
N-substituted amino group, N, N-substituted aminooxy group, N,
N, N-substituted hydrazino, nitroso, nitro, nitrooxy, furyl, carbonyl, thiocarbonyl, alkoxy, alkyloxycarbonyl,
Examples include an N, N-substituted carbamoyl group, a thioalkoxy group, a substituted sulfinyl group, a substituted sulfonyl group, and a substituted sulfonic acid group. It is preferably a heterocyclic group, and more preferably an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring. Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazolyl group, and most preferred is a pyridyl group. These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

The amount of the functional group having an active hydrogen or the non-proton-donating Lewis basic functional group is not particularly limited, but is preferably 0.01 to 50 mmol as a molar amount of the functional group per gram of the polymer. / G,
More preferably, it is 0.1 to 20 mmol / g.

The polymer having such a functional group is, for example,
Obtained by copolymerizing a monomer having one or more unsaturated bonds with a functional group having an active hydrogen or a non-proton-donating Lewis basic functional group, and another monomer having one or more unsaturated bonds. be able to. At this time, it is preferable to further copolymerize together a crosslinkable polymerizable monomer having two or more unsaturated bonds.

Examples of such a monomer having an active hydrogen-containing functional group or a non-proton-donating Lewis basic functional group and one or more unsaturated bonds include the above-mentioned functional group having an active hydrogen and one or more unsaturated bonds. Examples include a monomer having a functional group, or a monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more unsaturated functional groups. Examples of such unsaturated functional groups include alkenyl groups such as vinyl group and allyl group,
An alkynyl group such as an ethyne group is exemplified. Examples of the monomer having an active hydrogen-containing functional group and one or more unsaturated bonds include a vinyl-containing primary amine, a vinyl-containing secondary amine, a vinyl-containing amide compound, and a vinyl-containing hydroxy compound. Can be. Specific examples include N- (1-ethenyl) amine, N- (2-propenyl) amine, N- (1-ethenyl) -N-methylamine, N- (2-propenyl) -N-methylamine,
1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-
(Propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-buten-1-ol and the like. Specific examples of the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and one or more unsaturated bonds include vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. be able to. Examples of the other monomer having one or more unsaturated bonds include ethylene and α-olefin, and specific examples thereof include ethylene, propylene, butene-1, hexene-1, 4-methyl-pentene-1, and styrene. And the like. Preferably it is ethylene or styrene. Two or more of these monomers may be used. Examples of the crosslinkable polymerizable monomer having two or more unsaturated bonds include a monomer having two or more unsaturated functional groups. Specific examples thereof include divinylbenzene.

The average particle size of the organic polymer substance is preferably 5 to 1000 μm, more preferably 10 to 1000 μm.
５００500 μm. Preferably, the pore volume is set to 0.1.
It is at least 1 ml / g, more preferably at least 0.3 ml / g. The specific surface area is preferably 10 to 1000 m ^2.
/ G, more preferably 50 to 500 m ² / g.

As the organoaluminum oxy compound in the above catalysts [1] to [7], a known compound (aluminoxane) can be used. For example, a compound obtained by reacting one kind of trialkylaluminum with water And those obtained by condensation of two or more kinds of trialkylaluminums with water. Specifically, methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, butyl aluminoxane,
Examples thereof include isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane. Particularly, methylaluminoxane, isobutylaluminoxane, or methylisobutylaluminoxane is preferably used. These organoaluminum oxy compounds are generally commercially available.

The organoaluminum compound in the catalysts [1] to [7] is preferably represented by the following general formula (1):
It is a compound represented by these. General formula (1) R ¹ _n AlX _3-n (wherein, Al is an aluminum atom, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R ¹
May be the same or different. X is a halogen atom or a hydrogen atom. n is a number satisfying 0 <n ≦ 3. )

Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, trinormalbutylaluminum, triisobutylaluminum, and trinormalhexylaluminum; dimethylaluminum chloride, diethylaluminum chloride, Dialkylaluminum halides such as dipropylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride, dinormalhexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, normalbutylaluminum dichloride, isobutylaluminumdichloride Alkyl aluminum dihalides such as chloride and normal hexyl aluminum dichloride; dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride and the like. . Preferably a trialkyl aluminum,
More preferred are trimethylaluminum, triethylaluminum, triisobutylaluminum, trinormalbutylaluminum, and trinormalhexylaluminum. Particularly preferred are trimethylaluminum, triethylaluminum and triisobutylaluminum.

The water content in the above catalyst [3] is as follows:
Water may be used as it is, or ice or steam may be used. Further, moisture may be used by a method of using a wet carrier without drying or a method of using a wet carrier. It may be used as water of crystallization.

As the boron compound in the catalyst [4] or [5], any of the following boron compounds (C1) to (C3) is preferable. (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (C3) a general formula (L −H) ⁺ (BQ ¹
Q ² Q ³ Q ^{4) -} In the boron compound represented by (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, A substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, G ⁺ is an inorganic or organic cation, L is a neutral Lewis base,
(LH) ⁺ is a Bronsted acid. )

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably Q ^{1 to} Q ⁴ are each at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl group.

Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. And Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (C1).
Is the same as

[0055] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

[0058] formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same as described above.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

A functional group having an active hydrogen or an aprotic Lewis basic functional group in the catalyst [7];
The functional group having active hydrogen or the aprotic Lewis basic functional group of the compound having the electron-withdrawing group usually reacts with the organoaluminum compound. The functional group having active hydrogen and the aprotic Lewis basic functional group are the same as those described above.

The compound has an electron-withdrawing group.
As an index of the electron-withdrawing group, a substituent constant σ of Hammett's rule or the like can be used, and a functional group having a positive substituent constant σ of Hammett's rule corresponds to the electron-withdrawing group. Specific examples of the electron-withdrawing group include a fluorine atom, a chlorine atom, a bromine atom,
Examples thereof include an iodine atom, a cyano group, a nitro group, a phenyl group, an acetyl group, a carbonyl group, a thionyl group, a sulfone group, and a carboxyl group.

The compound may have a plurality of types and / or a plurality of the above-described functional groups having active hydrogen or aprotic Lewis basic functional groups and electron-withdrawing groups.

Examples of such compounds include amines having electron-withdrawing groups, phosphines, alcohols, phenols, thiols, thiophenols, carboxylic acids, sulfonic acids and the like.

The compound is preferably a compound represented by the following general formula (2). Formula (2): R ² _m XH _xm (wherein, R ² represents an electron-withdrawing group or a group containing an electron-withdrawing group, X represents an atom of Group 15 or 16 of the periodic table, H represents a hydrogen atom, x is a valence of X and is 2 or 3, when x is 2, m is 1, x
Is 3 when m is 1 or 2. )

Examples of the group containing an electron-withdrawing group represented by R ² in the general formula (2) include an alkyl halide group, an aryl halide group, a cyanated aryl group, a nitrated aryl group, an ester group and the like. Can be

Specific examples of the halogenated alkyl group include:
Fluoromethyl group, chloromethyl group, bromomethyl group,
Iodomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, diiodomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, 2,2,2-trifluoroethyl group, 2, 2,2-trichloroethyl group, 2,2,2
-A tribromoethyl group, a 2,2,2-triiodoethyl group, a 2,2,3,3,3-pentafluoropropyl group,
2,2,3,3,3-pentachloropropyl group, 2,
2,3,3,3-pentabromopropyl group, 2,2
3,3,3-pentaiodopropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, 2,
2,2-trichloro-1-trichloromethylethyl group,
2,2,2-tribromo-1-tribromomethylethyl group, 2,2,2-triiodo-1-triiodomethylethyl group, 1,1,1,3,3,3-hexafluoro-2
A trifluoromethylpropyl group, 1,1,1,3,
3,3-hexachloro-2-trichloromethylpropyl group, 1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl group, 1,1,1,3,3,3-hexaiodo-2 -A triiodomethylpropyl group and the like.

Specific examples of the halogenated aryl group include:
2-fluorophenyl group, 3-fluorophenyl group, 4
-Fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4
-Iodophenyl group, 2,6-difluorophenyl group,
3,5-difluorophenyl group, 2,6-dichlorophenyl group, 3,5-dichlorophenyl group, 2,6-dibromophenyl group, 3,5-dibromophenyl group, 2,6-
Diiodophenyl group, 3,5-diiodophenyl group,
2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-triiodophenyl group, pentafluorophenyl group, pentachlorophenyl Group, pentabromophenyl group, pentaiodophenyl group, 2- (trifluoromethyl) phenyl group, 3- (trifluoromethyl)
A phenyl group, a 4- (trifluoromethyl) phenyl group,
2,6-di (trifluoromethyl) phenyl group, 3,5
-Di (trifluoromethyl) phenyl group, 2,4,6-
And a tri (trifluoromethyl) phenyl group.

Specific examples of the cyanated aryl group include 2
-Cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group and the like. Specific examples of the nitrated aryl group include a 2-nitrophenyl group, a 3-nitrophenyl group, a 4-nitrophenyl group, and the like.

Specific examples of the ester group include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propyloxycarbonyl group, an isopropyloxycarbonyl group, a phenoxycarbonyl group, a trifluoromethyloxycarbonyl group and a pentafluorophenyloxycarbonyl group. Can be

R ^{2 in the} general formula (2) is preferably a halogenated alkyl group or a halogenated aryl group,
More preferably, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,3-pentafluoropropyl group, a 2,2,2-triethyl group Fluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl group, 4-fluorophenyl group, 2,6-difluorophenyl group, 3.5 −
A difluorophenyl group, a 2,4,6-trifluorophenyl group or a pentafluorophenyl group, more preferably a trifluoromethyl group, a 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,
A 1,3,3,3-hexafluoro-2-trifluoromethylpropyl group or a pentafluorophenyl group.

X in the general formula (2) is the first in the periodic table.
H represents a group 5 or 16 atom, and H represents a hydrogen atom. Specific examples of X include a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom, and the like, preferably a nitrogen atom or an oxygen atom, and more preferably an oxygen atom.

X is the valence of X. For example, when X is a nitrogen atom or a phosphorus atom, x is 3, and when X is an oxygen atom or a sulfur atom, x is 2. When x is 2, m is 1; when x is 3, m is 1 or 2.

Specific examples of the compound include amines such as di (fluoromethyl) amine and di (chloromethyl) amine.
Amine, di (bromomethyl) amine, di (iodomethyl) amine, di (difluoromethyl) amine, di (dichloromethyl) amine, di (dibromomethyl) amine, di (diiodomethyl) amine, di (trifluoromethyl)
Amine, di (trichloromethyl) amine, di (tribromomethyl) amine, di (triiodomethyl) amine, di (2,2,2-trifluoroethyl) amine, di (2
2,2-trichloroethyl) amine, di (2,2,2-
Tribromoethyl) amine, di (2,2,2-triiodoethyl) amine, di (2,2,3,3,3-pentafluoropropyl) amine, di (2,2,3,3,3- Pentachloropropyl) amine, di (2,2,3,3,3)
-Pentabromopropyl) amine, di (2,2,3)
3,3-pentaiodopropyl) amine, di (2,2,
2-trifluoro-1-trifluoromethylethyl) amine, di (2,2,2-trichloro-1-trichloromethylethyl) amine, di (2,2,2-tribromo-1)
-Tribromomethylethyl) amine, di (2,2,2-
Triiodo-1-triiodomethylethyl) amine, di (1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl) amine, di (1,1,1,1
3,3,3-hexachloro-2-trichloromethylpropyl) amine, di (1,1,1,3,3,3-hexabromo-2-tribromomethylpropyl) amine, di (1,1,1,3 , 3,3-hexaiodo-2-triiodomethylpropyl) amine, di (2-fluorophenyl) amine, di (3-fluorophenyl) amine, di (4-fluorophenyl) amine, di (2-chlorophenyl) amine , Di (3-chlorophenyl) amine, di (4-chlorophenyl) amine, di (2-bromophenyl) amine, di (3-bromophenyl) amine, di (4
-Bromophenyl) amine, di (2-iodophenyl)
Amine, di (3-iodophenyl) amine, di (4-iodophenyl) amine, di (2,6-difluorophenyl) amine, di (3,5-difluorophenyl) amine, di (2,6-dichlorophenyl) Amine, di (3,
5-dichlorophenyl) amine, di (2,6-dibromophenyl) amine, di (3,5-dibromophenyl) amine, di (2,6-diiodophenyl) amine, di (3,5-diiodophenyl) Amine, di (2,4,6
-Trifluorophenyl) amine, di (2,4,6-trichlorophenyl) amine, di (2,4,6-tribromophenyl) amine, di (2,4,6-triiodophenyl) amine, di ( Pentafluorophenyl) amine,
Di (pentachlorophenyl) amine, di (pentabromophenyl) amine, di (pentaiodophenyl) amine, di (2- (trifluoromethyl) phenyl) amine, di (3- (trifluoromethyl) phenyl) amine, (4- (trifluoromethyl) phenyl) amine, di (2,6-di (trifluoromethyl) phenyl)
Amine, di (3,5-di (trifluoromethyl) phenyl) amine, di (2,4,6-tri (trifluoromethyl) phenyl) amine, di (2-cyanophenyl) amine, (3-cyanophenyl ) Amine, di (4-cyanophenyl) amine, di (2-nitrophenyl) amine, di (3-nitrophenyl) amine, di (4-nitrophenyl) amine and the like. A phosphine compound in which a nitrogen atom is substituted by a phosphorus atom can also be exemplified. These phosphine compounds are compounds represented by rewriting the amine in the above specific examples with phosphine.

Specific examples of the compound include alcohols such as fluoromethanol, chloromethanol, bromomethanol, iodomethanol, difluoromethanol, dichloromethanol, dibromomethanol, diiodmethanol, trifluoromethanol, trichloromethanol, and tribromomethanol. , Triiodomethanol, 2,2,2-trifluoroethanol, 2,2
2-trichloroethanol, 2,2,2-tribromoethanol, 2,2,2-triiodoethanol, 2,
2,3,3,3-pentafluoropropanol, 2,
2,3,3,3-pentachloropropanol, 2,2
3,3,3-pentabromopropanol, 2,2,3
3,3-pentaiodopropanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 2,
2,2-trichloro-1-trichloromethylethanol, 2,2,2-tribromo-1-tribromomethylethanol, 2,2,2-triiodo-1-triiodomethylethanol, 1,1,1,3, 3,3-hexafluoro-2-trifluoromethylpropanol, 1,1,
1,3,3,3-hexachloro-2-trichloromethylpropanol, 1,1,1,3,3,3-hexabromo-2-tribromomethylpropanol, 1,1,1,
3,3,3-hexaiodo-2-triiodomethylpropanol and the like. A thiol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiol compounds are compounds and the like which are represented by rewriting methanol to methanethiol, ethanol to ethanethiol, and propanol to propanethiol in the above specific examples.

Specific examples of the compound include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol,
3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,6-difluorophenol, 3,5 -Difluorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, 2,6-
Dibromophenol, 3,5-dibromophenol,
2,6-diiodophenol, 3,5-diiodophenol, 2,4,6-trifluorophenol, 2,4
6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol, pentafluorophenol, pentachlorophenol, pentabromophenol, pentaiodophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol,
3,5-di (trifluoromethyl) phenol, 2,
4,6-tri (trifluoromethyl) phenol, 2-
Examples include cyanophenol, 3-cyanophenol, 4-cyanophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol and the like. A thiophenol compound in which an oxygen atom is substituted by a sulfur atom can also be exemplified. These thiophenol compounds are compounds represented by rewriting phenol of the above-mentioned specific examples into thiophenol.

Specific examples of the compound include carboxylic acids such as 2-fluorobenzoic acid, 3-fluorobenzoic acid,
4-fluorobenzoic acid, 2,3-difluorobenzoic acid,
2,4-difluorobenzoic acid, 2,5-difluorobenzoic acid, 2,6-difluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2,3,5-trifluorobenzoic acid, 2,3 6-trifluorobenzoic acid, 2,4,5-
Trifluorobenzoic acid, 2,4,6-trifluorobenzoic acid, 2,3,4,5-tetrafluorobenzoic acid, 2,
3,4,6-tetrafluorobenzoic acid, pentafluorobenzoic acid, fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoroethylcarboxylic acid, heptafluoropropylcarboxylic acid, 1,1,1,3,3,3- Hexafluoro-2-propylcarboxylic acid and the like.

Specific examples of the compound include sulfonic acids such as fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1,1,3,3 , 3-Hexafluoro-2-
And propanesulfonic acid.

Preferably, the compound is di (trifluoromethyl) amine or di (2,2,2).
2-trifluoroethyl) amine, di (2,2,3)
3,3-pentafluoropropyl) amine, di (2,
2,2-trifluoro-1-trifluoromethylethyl) amine, di (1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropyl) amine, di (pentafluorophenyl) amine, Examples of alcohols include trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol, , 1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol,
As phenols, 2-fluorophenol, 3-phenol
Fluorophenol, 4-fluorophenol, 2,6
-Difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 2- (trifluoromethyl) phenol, 3- (trifluoromethyl) phenol, 4- (trifluoromethyl) Phenol, 2,6-di (trifluoromethyl) phenol, 3,5-di (trifluoromethyl) phenol, 2,4,6-tri (trifluoromethyl) phenol, carboxylic acids such as pentafluorobenzoic acid, Examples of trifluoroacetic acid and sulfonic acids include trifluoromethanesulfonic acid.

More preferably, the compound is di (trifluoromethyl) amine, di (pentafluorophenyl) amine, trifluoromethanol, 2,2,2-trifluoro-1-trifluoromethylethanol,
1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 4-fluorophenol, 2,
6-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol, 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, 2,4,6-tri (trifluoro Methyl) phenol, more preferably pentafluorophenol, or 1,1,1,3,3
3-hexafluoro-2-trifluoromethylpropanol (common name: perfluoro tertiary butanol).

The contact of the components in the above catalysts [1] to [7] is preferably carried out in an inert gas atmosphere. The treatment temperature is usually -80C to 200C, preferably -20C to 150C, and more preferably 0C to 100C. Processing time is usually 1 minute to 4 minutes.
8 hours, preferably 10 minutes to 24 hours.
Although it is preferable to use a solvent, the solvent to be used is preferably an aliphatic or aromatic hydrocarbon solvent which is inert to each component. Examples of the aliphatic hydrocarbon solvent include butane, pentane, hexane, heptane, and octane, and examples of the aromatic hydrocarbon solvent include benzene, toluene, and xylene. Alternatively, a mixture of these hydrocarbon solvents arbitrarily can be used.

The treatment after contacting in this manner includes a method of decanting the supernatant of the reaction solution, a method of washing the solid compound with an inert solvent after filtration,
After filtration, the solid compound is washed with an inert solvent and then dried under reduced pressure or flowing inert gas, and the solvent of the reaction solution is distilled off under reduced pressure or flowing inert gas. Alternatively, a treatment operation for isolating the obtained solid catalyst (component) may be omitted, and the obtained solid catalyst (component) is used in a polymerization reaction in a state of being suspended in an inert solvent in a reaction solution. May be.

Among the above catalysts [1] to [7], catalyst [7] can be most suitably applied to the present invention. In the catalyst [7], the amount of the organoaluminum compound (b) used with respect to the carrier (a) is determined based on the amount of the organoaluminum compound (b) contained in the solid obtained by contacting (a) with (b). The aluminum atom is 0.1 mmo as the number of moles of the aluminum atom contained in 1 g of the dried solid.
1 or more, preferably 0.5 mmol or more and 20
More preferably, the amount is not more than mmol. The amount of the compound (c) having a functional group having an active hydrogen or an aprotic Lewis basic functional group and an electron-withdrawing group is determined based on the amount of the compound (c) relative to the aluminum atom contained in 1 g of the solid in a dry state. ) Molar ratio (c) /
(B) is preferably from 0.01 to 100, more preferably from 0.05 to 5, and more preferably from 0.1 to
More preferably, it is 2.

In the catalyst [7], an organic transition metal compound
The amount of (B) used is usually 1 g of the solid catalyst component (A).
1 × 10^-8~ 1 × 10^-2mol, preferably 1 ×
10 ^-6~ 1 × 10^-Fourmol. Also organic aluminum
Of the organic compound (B)
Aluminum compound (C) for the transition metal atom of
As a molar ratio (C) / (B) of aluminum atoms of
It is preferably 0.01 to 10,000, and 0.1
More preferably 5,000 to 2,000.
Most preferably, it is 0.

In the present invention, the above catalysts [1] to
When any of [7] is used, the organozinc compound and each of the catalyst components in the catalysts [1] to [7] can be charged and used in an arbitrary order during the polymerization in the reactor, and any of them can be used. The components may be used in any combination by bringing the components into contact with each other in advance and then charging the reactor.

In the present invention, as the monomer used for polymerization, any of olefins and diolefins having 2 to 20 carbon atoms can be used, and two or more kinds of monomers can be used at the same time. Such monomers are exemplified below, but the present invention should not be limited to the following compounds. Specific examples of such olefins include ethylene, propylene, butene-1, pentene-
1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 4-methyl-1-pentene, 4-
Examples thereof include methyl-2-pentene and vinylcyclohexane. Examples of diolefin compounds include conjugated dienes and non-conjugated dienes of hydrocarbon compounds. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, and non-conjugated diene compounds.
1,4-pentadiene, 1,7-octadiene, 1,8
-Nonadiene, 1,9-decadiene, 4-methyl-1,
4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methyl-2- Examples include norbornene, norbornadiene, 5-methylene-2-norbornene, 1,5-cyclooctadiene, 5,8-endomethylenehexahydronaphthalene, and the like. Specific examples of the conjugated diene compound include 1,3-butadiene and isoprene. , 1,3-hexadiene, 1,3-octadiene,
Examples thereof include 1,3-cyclooctadiene and 1,3-cyclohexdiene.

Specific examples of the monomers constituting the copolymer include ethylene and propylene, ethylene and butene-1,
Combinations of ethylene and hexene-1 and propylene and butene-1 are exemplified, but the present invention should not be limited to the above compounds.

In the present invention, an aromatic vinyl compound can be used as a monomer. Specific examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene, and the like.

[0088]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The properties of the olefin polymer in the examples were measured by the following methods.

(1) Butene-1 content in the copolymer: The butene-1 content in the obtained polymer was determined from the infrared absorption spectrum. The measurement and calculation are described in the literature (Characterization of polyethylene by infrared absorption spectrum, written by Takayama, Usami et al., Or Die Makromolecular
e Chemie, 177, 461 (1976) McRae, MA, Madams, W.
According to the method described in F.), the measurement was performed using characteristic absorption derived from butene-1, for example, 1378 cm ^-1 and 1303 cm ^-1 . The infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).
The degree of short chain branching (SCB) was expressed as the number of short chain branches per 1000 carbons.

(2) Melting point of copolymer: Seiko SSC-
Using 5200, it was determined under the following conditions. Temperature rise: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 40 ° C (5 ° C / min), hold for 10 minutes Measurement: 40 ° C to 160 ° C (5 ° C / min)

(3) Intrinsic viscosity [η]: 100 mg of the obtained copolymer was dissolved in 50 ml of tetralin at 135 ° C., and an Ubbelohde viscometer set in a water bath maintained at 135 ° C. was used. And the falling speed of the tetralin solution in which the sample was dissolved.

(4) Molecular Weight and Molecular Weight Distribution: Gel Permeation Chromatograph (1 by Waters)
50, C) under the following conditions. Column: TSK gel GMH-HT Measurement temperature: 145 ° C Setting Measurement concentration: 10 mg / 10 ml-orthodichlorobenzene

(5) MFR: MFR was measured at 190 ° C. according to the method specified in JIS K6760.

Example 1 (1) Preparation of solid catalyst component 50 ml of 4 equipped with a stirrer, a dropping funnel and a thermometer
The one-necked flask was dried under reduced pressure and replaced with nitrogen. Silica (ES70X manufactured by Crossfield) 1.9 which was heat-treated in the flask at 300 ° C. for 5 hours under nitrogen flow.
g was collected. Thereto was added 10 ml of toluene to form a slurry, which was cooled to 5 ° C. using an ice bath.
3.8 ml of a toluene solution of trimethylaluminum adjusted to ol / ml was gradually added dropwise. At that time, gas generation was observed. After stirring at 5 ° C. for 30 minutes and at 80 ° C. for 2 hours, the supernatant was filtered, and the remaining solid compound was washed four times with 10 ml of toluene. Again, add toluene 1 to the flask
0 ml was added to make a slurry, and the concentration was 2 mmol / ml.
Then, 1.9 ml of a toluene solution of pentafluorophenol adjusted to the above was slowly added. At that time, gas generation was observed. After stirring at room temperature for 30 minutes and at 80 ° C. for 2 hours,
The supernatant was filtered, and the remaining solid compound was
1 × 4 times and hexane × 10 ml twice. afterwards,
The solid compound is dried under reduced pressure to obtain a solid compound A having fluidity.
2.4 g were obtained.

(2) Polymerization After drying under reduced pressure, the inside of a 400 ml-volume autoclave equipped with a stirrer and purged with argon was evacuated to remove butane to 95%.
g and butene-1 were charged in an amount of 5 g and heated to 70 ° C. Thereafter, ethylene was added so that the partial pressure became 0.59 MPa, the inside of the system was stabilized, and 0.25 ml of a triisobutylaluminum heptane solution adjusted to a concentration of 1 mmol / ml was introduced. Next, adjust the concentration to 2 μmol / ml.
Then, 0.5 ml of a toluene solution of ethylene bis (indenyl) zirconium dichloride adjusted was added. Next, 0.2 ml of a hexane solution of diethyl zinc adjusted to a concentration of 1 mmol / ml was added, and then 12.1 mg of the solid compound A obtained in the above (1) was added as a solid catalyst component. The polymerization was carried out at 70 ° C. for 30 minutes while feeding ethylene so as to keep the total pressure constant. 5.0 g of an olefin polymer was obtained. The polymerization activity per transition metal atom was 5.0 × 10 ⁷ g / molZr hours, and the polymerization activity per solid catalyst component was 820 g / g hours. Further, the obtained olefin polymer had SCB = 22.6,
Melting point: 103.4 ° C., [η] = 1.30.

(3) Change in polymerization conditions Polymerization was carried out in the same manner as in (2) above, except that the amounts of diethyl zinc and solid compound A were changed as shown in the following table (3-1, 3-2). 3-3). The results are also shown in the table below.

[Table 1]

[0097]

According to the present invention, a process for producing an olefin polymer using an organic transition metal compound is carried out by a polymerization reaction involving formation of polymer particles (eg, slurry polymerization, gas phase polymerization, etc.).
The present invention provides a method for producing an olefin polymer capable of controlling the molecular weight of the olefin polymer when applied to a olefin polymer, and its utility value is extremely large.

Claims (5)

[Claims] 1. A method for producing an olefin polymer using an organic transition metal compound, wherein a polymerization reaction involving formation of olefin polymer particles is carried out in the presence of an organic zinc compound. . 2. The method for producing an olefin polymer according to claim 1, wherein the organic zinc compound is a compound represented by the following general formula (5). Formula (5) R ⁵ _c ZnZ _2-c (wherein, R ⁵ represents a hydrocarbon group having 1 to 8 carbon atoms;
n represents a zinc atom. Z represents a hydrogen atom and / or a halogen atom, and c represents a number satisfying 0 <c ≦ 2. ) 3. The process for producing an olefin polymer according to claim 1, wherein the polymerization reaction involving formation of the olefin polymer particles is slurry polymerization or gas phase polymerization. 4. The process for producing an olefin polymer according to claim 1, wherein the organic transition metal compound is an organic transition metal compound having at least one group having a cyclopentadiene-type anion skeleton. 5. The process for producing an olefin polymer according to claim 1, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.