JP4567920B2 - Novel olefin polymerization catalyst and olefin polymerization method using the catalyst - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel olefin polymerization catalyst and an olefin polymerization method using the olefin polymerization catalyst.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
In general, polyolefins are used in various fields such as for various molded products because they are excellent in mechanical properties. However, in recent years, physical property requirements for polyolefins are diversified, and polyolefins having various properties are desired. Yes. Improvement of productivity is also desired.
[0003]
A so-called Kaminsky catalyst is well known as an olefin polymerization catalyst. This catalyst is characterized by extremely high polymerization activity and a polymer having a narrow molecular weight distribution. Examples of the transition metal compound used in such a Kaminsky catalyst include bis (cyclopentadienyl) zirconium chloride (see JP-A-58-19309), ethylene bis (4,5,6,7-tetrahydro). Indenyl) zirconium chloride (see JP-A No. 61-130314) is known. Recently, a transition metal compound having a ligand of diimine structure (see International Patent No. 9623010) has been proposed as a new catalyst for olefin polymerization.
[0004]
Further, as a new olefin polymerization catalyst, the present applicant has proposed a transition metal compound having a salicylaldoimine ligand as Japanese Patent Application No. 10-132706. In this case, when zirconium is used as the central metal, high polymerization catalyst activity is exhibited, but further improvement is desired in order to bring the activity to a practical level.
[0005]
[Object of the present invention]
An object of the present invention is to provide an olefin polymerization catalyst having excellent olefin polymerization activity. Furthermore, it aims at providing the polymerization method of the olefin using this olefin polymerization catalyst.
[0006]
SUMMARY OF THE INVENTION
  The olefin polymerization catalyst according to the present invention comprises:
(A) reacts with a transition metal compound represented by the following general formula (1) (chemical formula 4), (B) (B-2) an organoaluminum oxy compound, and (B-3) a transition metal compound (A). And at least one compound selected from compounds that form ion pairs.It is characterized by that.
[0010]
[Formula 4]
[0011]
(In the formula, M represents a zirconium atom, m represents an integer of 1 to 2, R¹Is2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl groupR²~ R^FiveMay be the same or different from each other and each represents a hydrocarbon group, a hydrogen atom, or a hydrocarbon-substituted silyl group, and R⁶Represents a hydrocarbon group or a hydrocarbon-substituted silyl group, n is a number satisfying the valence of M, and X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing Group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, heterocyclic compound residue, silicon-containing group, germanium-containing group, or tin-containing group, and when n is 2 or more, A plurality of groups shown may be the same as or different from each other, and a plurality of groups shown by X may be bonded to each other to form a ring. )
[0012]
The catalyst for olefin polymerization of the present invention is the transition metal compound (A) represented by the general formula (1), wherein m is 2, R¹Is an aromatic hydrocarbon group having 6 to 30 carbon atoms having one or more fluorine atoms, and n is preferably 2.
[0013]
The catalyst for olefin polymerization of the present invention is a transition metal compound (A) represented by the general formula (1), wherein R¹Is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms which is nucleus-substituted with any one or more selected from the group consisting of a fluorine atom and a hydrocarbon group substituted with a fluorine atom.
[0014]
The catalyst for olefin polymerization of the present invention is a transition metal compound (A) represented by the general formula (1), wherein R¹Is particularly preferably a pentafluorophenyl group or a 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl group.
[0015]
The olefin polymerization method of the present invention is characterized in that the olefin is polymerized in the presence of the olefin polymerization catalyst as described above.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the olefin polymerization catalyst and the olefin polymerization method using the catalyst in the present invention will be described in detail.
[0017]
In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. It may be used in the meaning that also includes coalescence.
[0018]
  Olefin polymerization catalyst according to the present invention(A)A transition metal compound represented by the following general formula (1) (chemical formula 5);(B) (B-2)It is formed from an organoaluminum oxy compound and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair.
[0019]
[(A) Transition metal compound]
The transition metal compound (A) used in the present invention is a compound represented by the following general formula (1) (chemical formula 5).
[0020]
[Chemical formula 5]
[0021]
(Note that N ... M generally indicates coordination, but may or may not be coordinated in the present invention.)
In general formula (1), M represents a zirconium atom.
[0022]
  m represents an integer of 1 to 2, and is preferably 2. R¹Is2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl groupR²~ R^FiveMay be the same or different from each other and each represents a hydrocarbon group, a hydrogen atom, or a hydrocarbon-substituted silyl group, and R⁶Represents a hydrocarbon group or a hydrocarbon-substituted silyl group. Also R¹~ R⁶May be the same or different from each other, and two or more of them may be bonded to each other to form a ring.
[0027]
R²~ R^FiveExamples of the hydrocarbon group include those having 1 to 30 carbon atoms.
Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably linear or A branched alkyl group; a linear or branched alkenyl group having 2 to 30, preferably 2 to 20 carbon atoms such as vinyl, allyl, and isopropenyl; and 2 to 30 carbon atoms such as ethynyl and propargyl; Preferably a linear or branched alkynyl group having 2 to 20; a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; C5-C30 cyclic unsaturated hydrocarbon group such as dienyl, indenyl, fluorenyl; phenyl, naphthyl, Aryl groups having 6 to 30, preferably 6 to 20 carbon atoms such as phenyl, terphenyl, phenanthryl, anthracenyl; alkyl substitution such as tolyl, isopropylphenyl, tert-butylphenyl, dimethylphenyl, di-tert-butylphenyl An aryl group etc. are mentioned.
[0028]
Moreover, the said hydrocarbon group may be substituted by other hydrocarbon groups, for example, aryl group substituted alkyl groups, such as benzyl and cumyl, etc. are mentioned.
[0029]
R²~ R^FiveExamples of the hydrocarbon-substituted silyl group include groups having 1 to 30 carbon atoms in total. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among these, methylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly preferred are trimethylsilyl, triethylsilyl, triphenylsilyl, dimethylphenylsilyl and the like.
[0030]
R⁶Examples of the hydrocarbon group include those having 1 to 30 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and the like have 1 to 30 carbon atoms, preferably 1 A linear or branched alkyl group of -20; a hydrocarbon group having an alicyclic skeleton having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl; phenyl, Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as naphthyl, biphenyl, triphenyl, fluorenyl, anthranyl, phenanthryl; and these groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms A group further substituted with a substituent such as an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, etc. Preferably exemplified, more preferably a tert- butyl group or a 1-adamantyl group or cumyl group.
[0031]
R⁶As the hydrocarbon-substituted silyl group of R,²~ R^FiveThe same thing is mentioned.
[0032]
n is a number satisfying the valence of M, specifically an integer of 2 to 4, more preferably 2.
[0033]
X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group, germanium-containing group, or A tin-containing group is shown. When n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring.
[0034]
Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, R²~ R^FiveThe thing similar to what was illustrated by (1) is mentioned. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl and phenanthryl However, it is not limited to these. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen.
[0035]
Heterocyclic compound residues include residues such as nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine, oxygen-containing compounds such as furan and pyran, sulfur-containing compounds such as thiophene, and heterocyclic groups thereof. Examples of the compound residue include a group further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20, carbon atoms.
[0036]
Specific examples of oxygen-containing groups include hydroxy groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy Acetoxy group; carbonyl group and the like, but not limited thereto.
[0037]
Specific examples of the sulfur-containing group include methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethyl benzene sulfonate, triisobutyl benzene sulfonate. Sulfonate groups such as sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate; methyl sulfinate, phenyl sulfinate, benzyl sulfinate, p-toluene sulfinate, trimethylbenzene sulfinate, penta Examples thereof include, but are not limited to, sulfinate groups such as fluorobenzenesulfinate; alkylthio groups; arylthio groups.
[0038]
Specific examples of nitrogen-containing groups include amino groups; alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. Arylamino groups or alkylarylamino groups such as, but not limited to.
[0039]
Specific examples of boron-containing groups include BR_Four(R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like).
[0040]
Specific examples of the phosphorus-containing group include triarylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tritolylphosphine; methyl phosphite, ethyl phosphite, and phenyl phosphite Examples thereof include, but are not limited to, phosphite groups (phosphide groups); phosphonic acid groups; phosphinic acid groups.
[0041]
Specific examples of silicon-containing groups include hydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl. Hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylsilylphenyl;
[0042]
Specific examples of the germanium-containing group include groups in which silicon in the silicon-containing group is replaced with germanium.
[0043]
Specific examples of the tin-containing group include groups in which silicon in the silicon-containing group is substituted with tin.
[0044]
Specific examples of halogen-containing groups include PF₆, BF_FourFluorine-containing groups such as ClO_Four, SbCl₆Chlorine-containing groups such as IO_FourExamples of the iodine-containing group include, but are not limited to.
Specifically, AlR as an aluminum-containing group_Four(R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, etc.), but is not limited thereto.
[0045]
  As the structure of the transition metal compound (A) used in the present invention, M in the general formula (1) is zirconium, m is 2,¹But2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl groupIt is desirable that n is 2.
[0046]
  MaR¹ 2, 3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl group, R⁶Is particularly preferably a t-butyl group.
[0047]
Specific examples of the transition metal compound represented by the general formula (1) are shown below, but are not limited thereto.
[0048]
[Chemical 6]
[0049]
The method for producing such a transition metal compound (A) is not particularly limited and can be produced, for example, as follows.
[0050]
First, the ligand constituting the transition metal compound (A) is a salicylaldehyde compound represented by the formula R¹-NH₂Primary amine compounds (R¹Is as defined above. ), For example, by reaction with an aniline compound or an alkylamine compound.
Specifically, both starting compounds are dissolved in a solvent. As the solvent, those commonly used in such a reaction can be used, and among them, alcohol solvents such as methanol and ethanol, and hydrocarbon solvents such as toluene solvent are preferable. The resulting solution is then stirred from room temperature under reflux conditions for about 1 to 48 hours to give the corresponding ligand in good yield. When synthesizing the ligand compound, an acid catalyst such as formic acid, acetic acid or toluenesulfonic acid may be used as a catalyst. Further, when molecular sieves, magnesium sulfate or sodium sulfate is used as a dehydrating agent, or dehydration is performed by Dean Stark, it is effective for the progress of the reaction.
[0051]
Next, the corresponding transition metal compound can be synthesized by reacting the thus obtained ligand with a transition metal M-containing compound. Specifically, the synthesized ligand is dissolved in a solvent, and a base is reacted as necessary to prepare a phenoxide salt, which is then mixed with a metal compound such as a transition metal halogen compound and a transition metal alkyl compound at a low temperature. The mixture is stirred for about 1 to 48 hours at -78 ° C to room temperature or under reflux conditions.
As the solvent, those generally used for such a reaction can be used, and among them, polar solvents such as ether and tetrahydrofuran, and hydrocarbon solvents such as toluene are preferably used. In addition, the base used in preparing the phenoxide salt is preferably a metal salt such as a lithium salt such as n-butyllithium, a sodium salt such as sodium hydride, or an organic base such as triethylamine or pyridine. is not.
[0052]
Further, depending on the properties of the compound, the transition metal compound (A) represented by the general formula (1) may be synthesized by directly reacting the ligand and the transition metal compound without going through phenoxide salt adjustment. it can. In addition, for example R¹~ R⁶When any of these is H, substituents other than H can be introduced at any stage of the synthesis.
[0053]
Moreover, the reaction solution of a ligand and a transition metal compound can also be used for polymerization as it is without isolating the transition metal compound represented by the general formula (1).
[0054]
The above transition metal compounds (A) are used singly or in combination of two or more.
[0055]
  [(B-1) Organometallic compound]
  In the present invention(B) may be used together with the compound(B-1) As an organometallic compoundDownThe organometallic compounds of Groups 1, 2 and 12, 13 of the periodic tableBe mentioned.
[0056]
(B-1a) General formula R^a _mAl (OR^b)_nH_pX_q
(Where R^aAnd R^bMay be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. )
An organoaluminum compound represented by
[0057]
(B-1b) General formula M²AlR^a _Four
(Where M²Indicates Li, Na, or K, and R^aRepresents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. )
The complex alkyl compound of the periodic table group 1 metal and aluminum which are represented by these.
[0058]
(B-1c) General formula R^aR^b M^Three
(Where R^aAnd R^bMay be the same or different from each other, and represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.^ThreeIs Mg, Zn or Cd. )
A dialkyl compound of a Group 2 or Group 12 metal represented by
[0059]
Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.
[0060]
General formula R^a _mAl (OR^b)_3-m
(Where R^aAnd R^bMay be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably a number satisfying 1.5 ≦ m ≦ 3. )
An organoaluminum compound represented by
General formula R^a _mAlX_3-m
(Where R^aRepresents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably a number of 1.5 ≦ m ≦ 3. )
An organoaluminum compound represented by
General formula R^a _mAlH_3-m
(Where R^aRepresents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3. )
An organoaluminum compound represented by
General formula R^a _mAl (OR^b)_n X_q
(Where R^aAnd R^bMay be the same or different and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, and n is 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3. )
An organoaluminum compound represented by
[0061]
More specifically as an organoaluminum compound belonging to (B-1a)
Tri-n-alkylaluminums such as trimethylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum;
Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4 -Methylpentylaluminum, tri-2-methylhexylaluminum,
Tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
[0062]
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminums such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisobutylaluminum hydride; (i-C_FourH₉)_xAl_y(C_FiveH_Ten)_z  (Wherein x, y, z are positive numbers, z ≧ 2x) and the like, trialkenylaluminum such as triisoprenylaluminum;
[0063]
Alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum ethoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
[0064]
R^a _2.5Al (OR^b)_0.5A partially alkoxylated alkylaluminum having an average composition represented by:
Diethylaluminum phenoxide, diethylaluminum (2,6-di-tert-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide), diisobutylaluminum (2,6- Dialkylaluminum aryloxides such as di-tert-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-tert-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide;
[0065]
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.
[0066]
A compound similar to (B-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such compounds include (C₂H_Five)₂AlN (C₂H_Five) Al (C₂H_Five)₂And so on.
[0067]
Examples of the compound belonging to (B-1b) include LiAl (C₂H_Five)_Four, LiAl (C₇H₁₅)_FourAnd so on.
[0068]
In addition, (B-1) organometallic compounds include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium chloride, butyl magnesium. Bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.
[0069]
A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.
[0070]
(B-1) Among organometallic compounds, organoaluminum compounds are preferred.
[0071]
The (B-1) organometallic compounds as described above are used singly or in combination of two or more.
[0072]
[(B-2) Organoaluminum oxy compound]
The (B-2) aluminum oxy compound used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687. Good.
[0073]
A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.
[0074]
The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.
[0075]
Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a).
[0076]
Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
[0077]
The organoaluminum compounds as described above are used singly or in combination of two or more.
[0078]
Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.
The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred.
[0079]
As the organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula (2) (Chemical Formula 7) can also be exemplified.
[0080]
[Chemical 7]
[0081]
Where R⁷Represents a hydrocarbon group having 1 to 10 carbon atoms.
R⁸May be the same as or different from each other, and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.
[0082]
The organoaluminum oxy compound containing boron represented by the general formula (2) includes an alkyl boronic acid represented by the following general formula (3) and
[0083]
[Chemical 8]
[0084]
(Where R⁷Represents the same group as described above. )
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.
[0085]
Specific examples of the alkyl boronic acid represented by the general formula (3) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.
[0086]
Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a).
[0087]
Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.
[0088]
[(B-3) Compound that reacts with transition metal compound (A) to form an ion pair]
As a compound (B-3) that reacts with the transition metal compound (A) used in the present invention to form an ion pair (hereinafter referred to as “ionized ionic compound”), Japanese Patent Application Laid-Open No. 1-1501950, Lewis acids described in Kaihei 1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. , Ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
[0089]
Specifically, as Lewis acid, BR_Three(R is a phenyl group or fluorine which may have a substituent such as fluorine, methyl group or trifluoromethyl group), and examples thereof include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) ) Boron, tris (3,5-dimethylphenyl) boron and the like.
[0090]
Examples of the ionic compound include compounds represented by the following general formula (4) (Chemical Formula 9).
[0091]
[Chemical 9]
[0092]
Where R⁹⁺As H⁺, Carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptatrienyl cation, ferrocenium cation having a transition metal, and the like.
[0093]
R^Ten~ R¹³May be the same as or different from each other, and are an organic group, preferably an aryl group or a substituted aryl group.
[0094]
Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.
[0095]
Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tri (n-butyl) ammonium cation;
N, N-dialkylanilinium cations such as N, N-dimethylanilium cation, N, N-diethylanilium cation, N, N-2,4,6-pentamethylanilium cation; di (isopropyl) ammonium cation And dialkylammonium cations such as dicyclohexylammonium cation.
[0096]
Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
[0097]
R⁹For example, a carbonium cation and an ammonium cation are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.
[0098]
Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.
[0099]
Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m′-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.
[0100]
Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like.
[0101]
Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.
[0102]
Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl A cyclopentadienyl complex, a boron compound represented by the following formula (5) (Chemical Formula 10) or (6) (Chemical Formula 11) can also be exemplified.
[0103]
Embedded image
(In the formula, Et represents an ethyl group.)
[0104]
Embedded image
[0105]
Specifically as a borane compound, for example,
Decaborane (14);
Bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate Salts of anions such as bis [tri (n-butyl) ammonium] decachlorodecaborate and bis [tri (n-butyl) ammonium] dodecachlorododecaborate;
Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III) and bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.
[0106]
Specific examples of carborane compounds include:
4-carbanonaborane (14), 1,3-dicarbanonarborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1,3-dicarbanonarborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaunaborane (13), 2,7-dicarbaun Decaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecarborane, tri (n-butyl) ammonium 1- Carbadecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo 1-carbadodecaborate, tri ( n-Butyl) Monium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarboundeborate (12), tri ( n-Butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ) Ammonium undecahydride-8-butyl-7,9-dicarboundeborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbau Decaborate, salt anions, such as tri (n- butyl) ammonium undecalactone hydride-4,6-dibromo-7-Cal Bowne deca borate;
[0107]
Tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7 , 8-Dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaun) Carbolate) Ferrate (III), Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecarboxylate) chromate (III), Tri (n-butyl) ammonium Bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate ( III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7 -Carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelic acid (IV), and the like salts of metals carborane anions such.
[0108]
The heteropoly compound is composed of an atom selected from silicon, phosphorus, titanium, germanium, arsenic and tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germano-tungstovanadic acid, phosphomolybdo-tungstovanadic acid, germano-molybdo-tangostanodic acid, phosphomolybdotungstic acid , Phosphomolybdoniobic acid, and salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium etc Salts, and organic salts with triphenylmethyl salts, and the like can be used, not limited thereto.
[0109]
The (B-3) ionizable compounds as described above are used singly or in combination of two or more.
[0110]
When the transition metal compound according to the present invention is used as a catalyst, when it is used in combination with an organoaluminum oxy compound (B-2) such as methylaluminoxane as a cocatalyst, it exhibits a very high polymerization activity for olefinic compounds.
[0111]
  Olefin polymerization catalyst according to the present inventionIs (A)A transition metal compound represented by the general formula (1);(B) (B-2)Formed from an organoaluminum oxy compound and (B-3) a transition metal compound (A) and at least one compound selected from compounds that form ion pairs.ThisIn this case, these compounds are represented by the following general formula (7) (Chemical Formula 12) in the polymerization system.
[0112]
Embedded image
[0113]
(R in the formula¹~ R⁶, M, m, n, and X are the same as those in the general formula (1), and Y represents a so-called weakly coordinating anion. )
[0114]
In this formula, the bond between the metals M and Y may be covalently bonded or ionicly bonded. R in the formula¹~ R⁶, M, m, n, and X are the same as those in (1).
Chemical Review Journal Volume 88, 1405 (1988)
Chemical Review, Volume 93, 927 pages (1993)
WO 98/30162 Examples include weakly coordinating anions described on page 6, specifically,
AlR_Four ^-
(R may be one kind or two or more kinds, oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom or a substituent containing them, and aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic group. A hydrocarbon group which may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom or a halogen atom)
BR_Four ^-
(R may be one kind or two or more kinds, oxygen atom, nitrogen atom, phosphorus atom, hydrogen atom, halogen atom or a substituent containing them, and aliphatic hydrocarbon group, aromatic hydrocarbon group, alicyclic group. The hydrocarbon group may have a substituent containing an oxygen atom, a nitrogen atom, a phosphorus atom, a hydrogen atom, or a halogen atom.)
[0115]
  Moreover, the catalyst for olefin polymerization according to the present invention comprises the transition metal compound (A).And (B-2)A carrier (C) as described later can be used as necessary together with at least one compound (B) selected from an organoaluminum oxy compound and (B-3) an ionized ionic compound.
[0116]
[(C) Carrier]
The carrier (C) used in the present invention is an inorganic or organic compound and is a granular or particulate solid.
[0117]
Among these, as the inorganic compound, porous oxides, inorganic chlorides, clays, clay minerals or ion-exchangeable layered compounds are preferable.
[0118]
As a porous oxide, specifically, SiO₂, Al₂O_Three, MgO, ZrO, TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Or using composites or mixtures containing these, eg natural or synthetic zeolites, SiO₂-MgO, SiO₂-Al₂O_Three, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-MgO, SiO₂-Tio₂-MgO etc. can be used. Of these, SiO₂And / or Al₂O_ThreeThe main component is preferred.
[0119]
The inorganic oxide contains a small amount of Na.₂CO_Three  , K₂CO_Three, CaCO_Three, MgCO_Three, Na₂SO_Four, Al₂(SO_Four)_Three, BaSO_Four, KNO_Three, Mg (NO_Three)₂, Al (NO_Three)_Three, Na₂OK₂O, Li₂It may contain carbonates such as O, sulfates, nitrates and oxide components.
[0120]
Such porous oxides have different properties depending on the type and production method, but the carrier preferably used in the present invention has a particle size of 10 to 300 μm, preferably 20 to 200 μm, and a specific surface area of 50 to 1000 m.²/ G, preferably 100-700m²/ G and pore volume of 0.3-3.0 cm^Three/ G is desirable. Such a carrier is used after being calcined at 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.
[0121]
As inorganic chloride, MgCl₂, MgBr₂, MnCl₂, MnBr₂Etc. are used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. In addition, after dissolving the inorganic chloride in a solvent such as alcohol, these are precipitated into fine particles by a precipitant. It is also possible to use those.
[0122]
The clay used in the present invention is usually composed mainly of clay minerals. The ion-exchangeable layered compound used in the present invention is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with each other with a weak binding force, and the contained ions can be exchanged. . Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.
[0123]
Also, as clay, clay mineral or ionic layered compound, clay, clay mineral, hexagonal fine packing type, antimony type, CdCl₂Type, CdI₂Examples thereof include ionic crystalline compounds having a layered crystal structure such as a mold.
[0124]
Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysingelite, pyroferrite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, sikite, Examples of the ion-exchange layered compound include α-Zr (HAsO_Four)₂・ H₂O, α-Zr (HPO_Four)₂, Α-Zr (KPO_Four)₂・ 3H₂O, α-Ti (HPO_Four)₂. H₂O, α-Ti (HAsO_Four)₂・ H₂O, α-Sn (HPO_Four)₂・ H₂O, γ-Zr (HPO_Four)₂, Γ-Ti (HPO_Four)₂, Γ-Ti (NH_FourPO_Four)₂・ H₂Examples thereof include crystalline acid salts of polyvalent metals such as O.
[0125]
Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is determined by a mercury intrusion method using a mercury porosimeter.^FourMeasured over the range of cocoons.
[0126]
When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
[0127]
The clay and clay mineral used in the present invention are preferably subjected to chemical treatment. As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, causing a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, an organic derivative, or the like can be formed to change the surface area or the interlayer distance.
[0128]
The ion-exchangeable layered compound used in the present invention may be a layered compound in a state where the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchange property. . Such a bulky ion plays a role of a column supporting the layered structure and is usually called a pillar. Introducing another substance between layers of the layered compound in this way is called intercalation. As a guest compound to intercalate, TiCl_Four, ZrCl_FourCationic inorganic compounds such as Ti (OR)_Four, Zr (OR)_Four, PO (OR)_Three, B (OR)_ThreeMetal alkoxides (R is a hydrocarbon group, etc.), [Al₁₃O_Four(OH)_{twenty four}]⁷⁺, [Zr_Four(OH)₁₄]²⁺, [Fe_ThreeO (OCOCH_Three)₆]⁺And metal hydroxide ions. These compounds are used alone or in combination of two or more. In addition, when intercalating these compounds, Si (OR)_Four, Al (OR)_Three, Ge (OR)_FourPolymer obtained by hydrolyzing metal alkoxides such as R (hydrocarbon group, etc.), SiO₂Colloidal inorganic compounds such as can also be present together. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers.
[0129]
The clay, clay mineral, and ion-exchangeable layered compound used in the present invention may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.
[0130]
Of these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, teniolite and synthetic mica.
[0131]
Examples of the organic compound include granular or fine particle solids having a particle size in the range of 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers produced by the main component, and their modified products.
[0132]
  Moreover, the catalyst for olefin polymerization according to the present invention comprises the transition metal compound (A).And (B-2)Organic aluminum oxy compound, and (B-3) at least one compound (B) selected from ionized ionic compounds, together with carrier (C) as necessary, specific organic compound components as described later as necessary (D) can also be used.
[0133]
[(D) Organic compound component]
In the present invention, the organic compound component (D) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include, but are not limited to, alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.
As alcohols and phenolic compounds, usually R¹⁴-OH is used, where R¹⁴Represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms.
[0134]
For alcohols, R¹⁴Are preferably halogenated hydrocarbons. Moreover, as a phenolic compound, what substituted the o, o'-position of the hydroxyl group with the C1-C20 hydrocarbon is preferable.
[0135]
As carboxylic acid, usually R¹⁵The one represented by -COOH is used. R¹⁵Represents a hydrocarbon group having 1 to 50 carbon atoms or a halogenated hydrocarbon group having 1 to 50 carbon atoms, and a halogenated hydrocarbon group having 1 to 50 carbon atoms is particularly preferable.
[0136]
As the phosphorus compound, phosphoric acid having P—O—H bond, P—OR, phosphate having P═O bond, and phosphine oxide compound are preferably used.
[0137]
As the sulfonate, one represented by the following general formula (8) (Chemical Formula 13) is used.
[0138]
Embedded image
In the formula, M is an element of Groups 1 to 14 of the periodic table.
[0139]
R¹⁶Is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
X is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
m is an integer of 1 to 7, and n is 1 ≦ n ≦ 7 and m ≧ n.
[0140]
In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.
[0141]
(1) A method of adding the component (A) alone to the polymerization vessel.
(2) A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
(3) A method in which the catalyst component having component (A) supported on carrier (C) and component (B) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (B) supported on carrier (C) and component (A) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which the component (A) and the component (B) are supported on the carrier (C) is added to the polymerization vessel.
[0142]
In each of the above methods (2) to (5), at least two or more of the catalyst components may be contacted in advance.
[0143]
In the above methods (4) and (5) in which the component (B) is supported, the unsupported component (B) may be added in any order as necessary. In this case, the components (B) may be the same or different.
[0144]
The solid catalyst component in which the component (A) is supported on the carrier (C) and the solid catalyst component in which the component (A) and the component (B) are supported on the carrier (C) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.
[0145]
In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst as described above.
[0146]
In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
[0147]
Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Alicyclic hydrocarbons such as benzene, toluene, xylene and other aromatic hydrocarbons; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or mixtures thereof, and the olefin itself is used as a solvent. You can also
[0148]
When the olefin polymerization is carried out using the above olefin polymerization catalyst, the component (A) is usually 10 per liter of reaction volume.^-12-10^-3Moles, preferably 10^-Ten-10^-3It is used in such an amount that it becomes a mole.
[0149]
Component (B-1) has a molar ratio [(B-1) / M] of component (B-1) and transition metal atom (M) in component (A) of usually 0.01 to 100,000, Preferably it is used in an amount of 0.05 to 50000. Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) of usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) and transition metal atom (M) in component (A) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.
[0150]
When component (B) is component (B-1), component (D) has a molar ratio [(D) / (B-1)] of usually 0.01 to 10, preferably 0.1 to 0.1. 5 and the component (B) is the component (B-2), the molar ratio [(D) / (B-2)] is usually 0.001 to 2, preferably 0.8. When the component (B) is the component (B-3) in such an amount as 005 to 1, the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably The amount used is 0.1-5.
[0151]
Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C. The polymerization pressure is usually normal pressure to 100 kg / cm.², Preferably normal pressure to 50 kg / cm²The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions.
[0152]
The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust by the difference in the component (B) to be used.
[0153]
Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene. 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1 -Octadecene, 1-eicosene;
Cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydronaphthalene;
[0154]
Polar monomers, for example, α, such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic anhydride β-unsaturated carboxylic acids and their metal salts such as sodium, potassium, lithium, zinc, magnesium, calcium salts;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid α, β-unsaturated carboxylic acid esters such as n-propyl, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, stearic acid Vinyl esters such as vinyl and vinyl trifluoroacetate; unsaturated glycidyl esters such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate;
And halogenated olefins such as vinyl fluoride, vinyl chloride, vinyl bromide, and vinyl iodide.
[0155]
Moreover, vinylcyclohexane, diene, polyene, etc. can also be used as an olefin. As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having two or more double bonds is used. Specifically, butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1 , 3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene;
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene;
[0156]
Further, as olefins, aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, etc. Mono- or polyalkylstyrene;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene;
And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like. These olefins can be used alone or in combination of two or more.
[0157]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
The structure of the compound obtained in the synthesis example was determined using FD-mass spectrometry (JEOL SX-102A) or the like.
[0158]
Synthesis example 1
Into a 100 ml reactor thoroughly purged with nitrogen, 100 ml of toluene, 9.06 g (49.5 mmol) of pentafluoroaniline, 7.50 g of 3-t-butylsalicylaldehyde (purity 98%, 41.2 mmol) and a small amount as a catalyst p-Toluenesulfonic acid was added and stirred at reflux for 4 hours. After cooling to room temperature, the catalyst was removed by filtration, and the mixture was concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 13.98 g (yield 98%) of a yellow solid represented by the following formula (a) (Chemical Formula 14).
[0159]
Embedded image
[0160]
Synthesis example 2
Into a 50 ml reactor sufficiently purged with nitrogen was charged 1.043 g (purity 98.7%, 3.00 mmol) of compound (a) obtained in the above synthesis example and anhydrous diethyl ether, and cooled to -78 ° C. did. To this, 2.01 ml of n-butyllithium (n-hexane solution, 1.57 M, 3.15 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 2.5 hours, it was gradually added to a tetrahydrofuran slurry of 0.566 g (1.50 mmol) of zirconium tetrachloride · 2 tetrahydrofuran complex cooled to −78 ° C. After the addition, the temperature was slowly raised to room temperature, 20 ml of ether was added, the slurry was filtered, and the filtrate was concentrated. The residue was dissolved in 2 ml of ether, 30 ml of n-hexane was added, and the precipitated solid was collected and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 0.662 g (yield 52.1%) of a yellow compound represented by the following formula (9) (Chemical Formula 15). In addition, the result of FD-mass spectrometry of compound (9) is 846 (M⁺)Met.
[0161]
Embedded image
[0162]
Synthesis example 3
In a 100 ml reactor thoroughly purged with nitrogen, 50 ml of toluene, 2.98 g of 2,3,5,6-tetrafluoro-4- (trifluoromethyl) aniline (purity 95%, 12.1 mmol), 3-t-butyl 2.25 g of salicylaldehyde (purity 96%, 12.1 mmol) and a small amount of p-toluenesulfonic acid were added as a catalyst, and the mixture was heated and refluxed for 12 hours. The mixture was allowed to cool to room temperature and concentrated under reduced pressure. The residue was purified using a silica gel column to obtain 1.86 g (purity 95.9%, yield 37.5%) of a yellow solid represented by the following formula (b) (Chemical formula 16).
[0163]
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[0164]
Synthesis example 4
Sodium hydride 0.120 g (3.00 mmol as 60%) was placed in a 50 ml reactor sufficiently purged with argon, washed twice with 10 ml of hexane, and then suspended in 10 ml of anhydrous tetrahydrofuran. To this suspension, a solution prepared by dissolving 1.23 g (purity 95.9%, 3.00 mmol) of the compound (b) obtained in Synthesis Example 3 in 20 ml of anhydrous tetrahydrofuran was added dropwise at room temperature over 5 minutes. did.
After stirring for 2 hours after the completion of dropping, this solution was dropped into a tetrahydrofuran slurry of 0.566 g (1.50 mmol) of zirconium tetrachloride · 2 tetrahydrofuran complex at −78 ° C. over 10 minutes. After completion of the dropwise addition, the temperature was slowly raised to room temperature, and the solvent was distilled off. After adding 40 ml of methylene chloride and stirring, the precipitate was removed by filtration, and then the solvent was distilled off. 10 ml of diethyl ether was added for dissolution, 40 ml of n-hexane was added, and the precipitated solid was collected and washed with hexane. The solid was dried under reduced pressure to obtain 0.841 g (yield 59.2%) of a yellow solid represented by the following formula (10) (Chemical Formula 17). In addition, the result of FD-mass spectrometry of compound (10) is 946 (M⁺)Met.
[0165]
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[0166]
Synthesis example 5
A 1 l reactor purged with nitrogen was charged with 52.5 ml of ethylmagnesium bromide (ether solution, 3M, 157.5 mmol) and 50 ml of anhydrous tetrahydrofuran. Under ice cooling, a solution of 27.04 g (150 mmol) of 2-tert-butyl-4-methoxyphenol dissolved in 100 ml of anhydrous tetrahydrofuran was added dropwise over 15 minutes. After completion of dropping, the mixture was stirred at room temperature for 1 hour, 500 ml of toluene was added, 22.7 mlg (90%, 363 mmol) of paraformaldehyde and 29.9 ml (215 mmol) of triethylamine were added, and the mixture was heated and stirred at 70 to 90 ° C. for 5 hours did. After cooling to room temperature, 32 ml of concentrated hydrochloric acid and 250 ml of water were added. After liquid separation, the organic layer was washed with 150 ml of saturated aqueous sodium hydrogen carbonate solution and then with 150 ml of aqueous sodium chloride solution. After drying over anhydrous magnesium sulfate and concentrating under reduced pressure, the residue was purified using a silica gel column, and 2.55 g (purity 86.6% (GC)) of a yellow compound represented by the following formula (c) (chemical formula 18), Yield 6.6%).
[0167]
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[0168]
Synthesis Example 6
In a 100 ml reactor sufficiently purged with nitrogen, 3.26 g of the compound (c) obtained above (95.0% purity used, 15.0 mmol), 3.02 g (16.5 mmol) of pentafluoroaniline, 80 ml of toluene and a small amount of p-toluenesulfonic acid as a catalyst were charged, and the mixture was heated and refluxed for 2 and a half hours. After cooling to room temperature, the solvent was distilled off under reduced pressure. The residue was purified using a silica gel column, and 15 ml of methanol and 15 ml of water were added to the obtained solid and stirred. The precipitate was collected, washed with a small amount of methanol, and dried under reduced pressure to obtain 4.85 g (86.6%) of a dark yellow solid represented by the following formula (d) (Chemical formula 19).
[0169]
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[0170]
Synthesis example 7
Sodium hydride 0.160 g (4.00 mmol as 60%) was placed in a 100 ml reactor sufficiently purged with argon, and washed twice with 10 ml of hexane. Tetrahydrofuran (15 ml) was added for suspension, and a solution obtained by dissolving 1.49 g (4.00 mmol) of the compound (d) obtained above in 25 ml of tetrahydrofuran was added dropwise over 5 minutes. After stirring at room temperature for 2 hours, it was slowly added dropwise at −78 ° C. to a tetrahydrofuran slurry of 0.755 g (2.00 mmol) of zirconium tetrachloride · 2 tetrahydrofuran complex. After completion of dropping, the temperature was slowly raised to room temperature. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, 20 ml of anhydrous methylene chloride and 20 ml of anhydrous ether were added and stirred, and the precipitate was removed by filtration. The filtrate was concentrated, 15 ml of ether was added and dissolved, 20 ml of hexane was gradually added, and the mixture was stirred at room temperature for 20 minutes. The solid obtained by filtration was washed with hexane and dried under reduced pressure to obtain 0.331 g (yield 18.2%) of an orange solid represented by the following formula (11) (Chemical formula 20). In addition, the result of FD-mass spectrometry of compound (11) is 906 (M⁺)Met.
[0171]
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[0172]
Synthesis Example 8
A 200 ml reactor purged with nitrogen was charged with 16.2 ml of ethylmagnesium bromide (ether solution, 3M, 48.6 mmol) and 50 ml of anhydrous tetrahydrofuran. Under ice cooling, a solution of 11.2 g (46.2 mmol) of 2- (1-adamantyl) -4-methylphenol dissolved in 50 ml of anhydrous tetrahydrofuran was added dropwise over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature, 300 ml of toluene was added and the mixture was stirred with heating, and tetrahydrofuran and diethyl ether were distilled off. The mixture was cooled to room temperature, 3.80 g (127 mmol) of paraformaldehyde and 7.1 g (70.2 mmol) of triethylamine were added, and the mixture was heated and stirred at 80 to 90 ° C. for 20 minutes. The mixture was cooled to room temperature, and 200 ml of 10% hydrochloric acid was added while cooling with ice. 300 ml of diethyl ether was added for liquid separation, and the organic layer was washed twice with 200 ml of water and subsequently with an aqueous sodium hydrogen carbonate solution. After drying over anhydrous sodium sulfate, the crystals obtained by concentration under reduced pressure were dried under reduced pressure to obtain 10.5 g (yield 84%) of a yellow compound represented by the following formula (e) (Chemical Formula 21).
[0173]
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(Adm represents a 1-adamantyl group.)
[0174]
Synthesis Example 9
In a 100 ml reactor sufficiently purged with nitrogen, 80 ml of toluene, 2.75 g (15.0 mmol) of pentafluoroaniline, 4.07 g (purity 99.7%, 15.0 mmol) of the compound (e) obtained above and catalyst A small amount of p-toluenesulfonic acid was charged as follows, and stirring was continued for 5 and a half hours under reflux. After cooling to room temperature, the solvent was distilled off under reduced pressure. 50 ml of methanol was added and stirred, and the solid obtained by filtration was dried under reduced pressure to give 4.38 g of a yellow solid represented by the following formula (f) (Chemical Formula 22) (purity 97.2%, yield 67%). Obtained.
[0175]
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(Adm represents a 1-adamantyl group.)
[0176]
Synthesis Example 10
Sodium hydride 0.160 g (4.00 mmol as 60%) was placed in a 100 ml reactor sufficiently purged with argon, and washed twice with 10 ml of hexane. Tetrahydrofuran (15 ml) was added for suspension, and a solution obtained by dissolving 1.79 g (purity 97.2%, 4.00 mmol) of the compound (f) obtained above in 25 ml of tetrahydrofuran was added dropwise over 5 minutes. After stirring at room temperature, it was added dropwise to a tetrahydrofuran slurry of 0.755 g (2.00 mmol) of zirconium tetrachloride / 2 tetrahydrofuran complex at −78 ° C. over 10 minutes. After completion of dropping, the temperature was slowly raised to room temperature. After stirring at room temperature for 1 hour, the solvent was distilled off under reduced pressure, 30 ml of anhydrous methylene chloride was added and stirred, and the precipitate was removed by filtration. The filtrate was concentrated, 20 ml of ether was added and dissolved, 20 ml of hexane was gradually added, and the mixture was stirred at room temperature for 20 minutes. The solid obtained by filtration was washed with hexane and dried under reduced pressure to obtain 1.398 g of an orange solid (purity 94.1%, yield 63.8%). In addition, the result of FD-mass spectrometry of compound (12) (Chemical Formula 23) is 1030 (M⁺)Met.
[0177]
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(Adm represents a 1-adamantyl group.)
[0178]
Synthesis Example 11
A 500-ml reactor sufficiently purged with nitrogen was charged with 82.04 g (758.6 mmol) of p-cresol, 50 ml of toluene and 4.10 g of Amberlyst-15, and stirred at 75-80 ° C. for 2 hours. A solution prepared by dissolving 51.66 g (379.3 mmol) of 2-phenyl-2-propanol in 80 ml of toluene was added, and the mixture was heated and stirred at 75 to 80 ° C. for 10 and a half hours while distilling off the generated water. After cooling to room temperature, insoluble materials were removed by filtration, and the solvent was distilled off under reduced pressure. The residue was purified using a silica gel column to obtain 30.41 g (yield 35.4%) of a compound represented by the following formula (g) (Chemical Formula 24).
[0179]
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[0180]
Synthesis Example 12
A 1 liter reactor thoroughly purged with nitrogen was charged with 47.0 ml of ethylmagnesium bromide (ether solution, 3M, 141.0 mmol) and 70 ml of anhydrous tetrahydrofuran. Under ice cooling, a solution prepared by dissolving 30.40 g (134.3 mmol) of the compound (g) obtained above in 80 ml of anhydrous tetrahydrofuran was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, 500 ml of toluene was added and the mixture was stirred with heating, and tetrahydrofuran and diethyl ether were distilled off. After cooling to room temperature, 10.38 g (purity 94%, 325.1 mmol) of paraformaldehyde and 26.8 ml (192.1 mmol) of triethylamine were added, and the mixture was heated and stirred at 40 to 60 ° C. for 1 hour. The mixture was cooled to room temperature, and 200 ml of 10% hydrochloric acid was added while cooling with ice. The insoluble material was removed by filtration, followed by liquid separation. The organic layer was washed with 200 ml of a saturated aqueous sodium hydrogen carbonate solution and then with 200 ml of a saturated aqueous sodium sulfate solution. After drying with anhydrous magnesium sulfate, the residue obtained by concentration under reduced pressure was purified using a silica gel column, and 29.36 g (purity 93.8) of a yellow compound represented by the following formula (h) (Chemical Formula 25) was obtained. % (GC), yield 80.6%).
[0181]
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[0182]
Synthesis Example 13
In a 100 ml reactor thoroughly purged with nitrogen, 50 ml of toluene, 3.02 g (16.5 mmol) of pentafluoroaniline, 4.07 g (purity 93.8%, 15.0 mmol) of the compound (h) obtained above and catalyst Was charged with a small amount of p-toluenesulfonic acid and stirring was continued for 2 hours under reflux. After cooling to room temperature, the solvent was distilled off under reduced pressure. The residue was purified using a silica gel column to obtain 6.07 g (purity 94.5% (GC), yield 91%) of a yellow solid represented by the following formula (i) (Chemical Formula 26).
[0183]
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[0184]
Synthesis Example 14
A 50 ml reactor purged with nitrogen was charged with 1.33 g (purity 94.5%, 3.00 mmol) of the compound (i) obtained above and 20 ml of anhydrous diethyl ether, and cooled to -78 ° C. . To this, 1.89 ml of n-butyllithium (n-hexane solution, 1.59 M, 3.00 mmol) was added dropwise over 5 minutes, and then the temperature was slowly raised to room temperature. After stirring at room temperature for 3 hours, it was gradually added to a tetrahydrofuran slurry of 0.566 g (1.50 mmol) of zirconium tetrachloride · 2 tetrahydrofuran complex cooled to −78 ° C. After the addition, the temperature was slowly raised to room temperature, and the solvent was distilled off under reduced pressure. To the residue, 40 ml of methylene chloride was added and stirred, and the precipitated solid was removed by filtration. The filtrate was concentrated, and 5 ml of ether and 30 ml of n-hexane were added and stirred. The precipitated solid was collected and washed with a small amount of n-hexane. The solid obtained was dried under reduced pressure to obtain 0.493 g (yield 32.9%) of a yellow compound represented by the following formula (13) (Chemical Formula 27). In addition, the result of FD-mass spectrometry of compound (13) is 998 (M⁺)Met.
[0185]
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[0186]
  Reference example 1
  A glass autoclave with an internal volume of 500 ml that was sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with ethylene. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.00002 mmol of zirconium compound (9) were subsequently added to initiate polymerization. After reacting at 25 ° C. for 5 minutes under an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 1.44 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of zirconium was 863 kg.
[0187]
  Example1-3, Reference Examples 2-12
  Reference example 1The polymerization was carried out in the same manner except that the catalyst, catalyst amount, polymerization temperature, and polymerization time were changed as shown in Table 1.
[0188]
[Table 1]
[0189]
  Reference Example 13
  500 ml of heptane was charged into a SUS autoclave with an internal volume of 1 liter that had been sufficiently purged with nitrogen, and then ethylene was introduced to bring the total pressure to 8 kg / cm.²It was. Thereafter, methylaluminoxane was converted to aluminum atom equivalent to 1.25 mmol, followed by zirconium compound (90.00002 mmol was added to initiate polymerization. After reacting at 50 ° C. for 15 minutes, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 16.98 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of zirconium was 3396 kg.
[0190]
  Example4-5, Reference Examples 14-20
  Reference Example 13The polymerization was carried out in the same manner except that the catalyst, the catalyst amount, the polymerization temperature and the polymerization time were changed as shown in Table 2.
[0191]
[Table 2]
[0192]
  Reference Example 21
  A glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and a mixed gas of zirconium (50 l / h) and propylene (150 l / h) was circulated for 10 minutes with stirring. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.0001 mmol of zirconium compound (9) were subsequently added to initiate polymerization. After reacting at 50 ° C. for 10 minutes at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction solution was poured into methanol containing a small amount of hydrochloric acid to precipitate the whole amount of the polymer, and hydrochloric acid was added and filtered through a glass filter. After the polymer was dried under reduced pressure at 130 ° C. for 10 hours, 4.02 g of an ethylene / propylene copolymer (EBR) was obtained. The polymerization activity per 1 mmol of zirconium was 241 kg. The propylene content by IR measurement was 3.8 mol%.
[0193]
Reference Examples 22-30
  Reference Example 21The polymerization was carried out in the same manner except that the catalyst, catalyst amount, polymerization temperature and polymerization time were changed as shown in Table 3.
[0194]
[Table 3]
[0195]
Comparative Example 1
A glass autoclave with an internal volume of 500 ml that was sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently 0.00002 mmol of a zirconium compound represented by the following formula (14) (Chemical Formula 28) was added to initiate polymerization. After reacting at 25 ° C. for 5 minutes under an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 0.49 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of zirconium was 294 kg.
[0196]
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[0197]
Comparative Examples 2-6
Polymerization was conducted in the same manner as in Comparative Example 1 except that the polymerization temperature and the polymerization time were changed as shown in Table 4.
[0198]
[Table 4]
[0199]
Comparative Example 7
500 ml of heptane was charged into a SUS autoclave with an internal volume of 1 liter that had been sufficiently purged with nitrogen, and then ethylene was introduced to bring the total pressure to 8 kg / cm.²It was. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and subsequently, 0.00005 mmol of the zirconium compound (14) was added to initiate polymerization. After reacting at 50 ° C. for 15 minutes, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 14.90 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of zirconium was 1192 kg.
[0200]
Comparative Example 8
Polymerization was conducted in the same manner as in Comparative Example 7 except that the polymerization temperature was changed to 75 ° C. The obtained polyethylene (PE) was 2.61 g. The polymerization activity per 1 mmol of zirconium was 209 kg.
[0201]
Comparative Example 9
A glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen was charged with 250 ml of toluene, and a mixed gas of ethylene (50 l / h) and propylene (150 L / h) was circulated for 10 minutes with stirring. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and 0.0001 mmol of zirconium compound (14) were subsequently added to initiate polymerization. After reacting at 50 ° C. for 10 minutes at normal pressure, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction solution was poured into methanol containing a small amount of hydrochloric acid to precipitate the whole amount of the polymer, and hydrochloric acid was added and filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, 2.23 g of ethylene / propylene copolymer (EPR) was obtained. The polymerization activity per 1 mmol of zirconium was 134 kg. The propylene content by IR measurement was 1.3 mol%.
[0202]
Comparative Examples 10-11
Polymerization was conducted in the same manner as in Comparative Example 9 except that the catalyst amount was changed as shown in Table 5.
[0203]
[Table 5]
[0204]
Comparative Example 12
A glass autoclave with an internal volume of 500 ml that was sufficiently purged with nitrogen was charged with 250 ml of toluene, and the liquid phase and gas phase were saturated with ethylene. Thereafter, methylaluminoxane was added in an amount of 1.25 mmol in terms of aluminum atom, and then 0.0005 mmol of a titanium compound represented by the following formula (15) (Chemical Formula 29) was added to initiate polymerization. After reacting at 25 ° C. for 5 minutes under an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 1.02 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 24.5 kg.
[0205]
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[0206]
Comparative Examples 13-15
Polymerization was conducted in the same manner as in Comparative Example 12 except that the polymerization temperature was changed as shown in Table 6.
[0207]
[Table 6]
[0208]
Comparative Example 16
500 ml of heptane was charged into a SUS autoclave with an internal volume of 1 liter that had been sufficiently purged with nitrogen, and then ethylene was introduced to bring the total pressure to 8 kg / cm.²It was. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and then 0.0005 mmol of titanium compound (15) were added to initiate polymerization. After reacting at 50 ° C. for 15 minutes, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, hydrochloric acid was added to precipitate the entire amount of the polymer, hydrochloric acid was added, and the mixture was filtered through a glass filter. After the polymer was dried under reduced pressure at 80 ° C. for 10 hours, 6.72 g of polyethylene (PE) was obtained. The polymerization activity per 1 mmol of titanium was 53.8 kg.
[0209]
Comparative Example 17
Polymerization was conducted in the same manner as in Comparative Example 16 except that the polymerization temperature was changed to 75 ° C. The obtained polyethylene (PE) was 4.62 g. The polymerization activity per 1 mmol of titanium was 36.9 kg.
[0210]
Comparative Example 18
To a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, and a mixed gas of ethylene (50 l / h) and propylene (150 l / h) was circulated for 10 minutes with stirring. Thereafter, 1.25 mmol of methylaluminoxane in terms of aluminum atom and then 0.002 mmol of titanium compound (15) were added to initiate polymerization. After reacting at 50 ° C. for 10 minutes in an atmospheric pressure ethylene gas atmosphere, the polymerization was stopped by adding a small amount of isobutanol. After completion of the polymerization, the reaction solution was poured into methanol containing a small amount of hydrochloric acid to precipitate the whole amount of the polymer, and hydrochloric acid was added and filtered through a glass filter. After drying the polymer under reduced pressure at 130 ° C. for 10 hours, 0.80 g of ethylene / propylene copolymer (EPR) was obtained. The polymerization activity per 1 mmol of titanium was 2.41 kg. The propylene content by IR measurement was 11.1 mol%.
[0211]
【The invention's effect】
The olefin polymerization catalyst according to the present invention has high polymerization activity, and a high molecular weight polymer is obtained. The olefin polymerization method according to the present invention can produce a high molecular weight polymer with high polymerization activity.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (2)

(A) a transition metal compound represented by the following general formula (1) (chemical formula 2);
(B) (B-2) an organoaluminum oxy compound, and (B-3) at least one compound selected from compounds that react with the transition metal compound (A) to form an ion pair. An olefin polymerization catalyst.
(In the formula, M represents a zirconium atom, m represents an integer of 1 to 2, R ¹ represents a 2,3,5,6-tetrafluoro-4- (trifluoromethyl) phenyl group , R is ² to R ^5, may be the same or different and are each a hydrocarbon group, a hydrogen atom, a hydrocarbon-substituted silyl group, R ⁶ is a hydrocarbon group, a hydrocarbon-substituted silyl group, n represents, M X is a hydrogen atom, halogen atom, hydrocarbon group, oxygen-containing group, sulfur-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, A heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other; The plurality of groups shown may be bonded to each other to form a ring.) An olefin polymerization method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1 .