JP3237246B2 - Ionic compounds and catalysts for olefin polymerization using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ionic compound and a catalyst for olefin polymerization using the same. More specifically, the present invention relates to an ionic compound comprising a non-coordinating anion and a substituted triarylcarbenium, and an olefin, an acetylene, a vinyl, which is used alone or in combination with a transition metal compound. The present invention relates to an olefin polymerization catalyst useful for polymerization of an aromatic compound or the like.

[0002]

2. Description of the Prior Art Ziegler
It is known that the catalyst is produced using a catalyst system based on a Natta catalyst. In recent years, in particular, in recent years, there have been many production methods using a transition metal compound and an aluminoxane as a cocatalyst as a soluble catalyst. However, this aluminoxane, particularly highly active methylaluminoxane, is expensive in the raw material trimethylaluminum, and involves a risk in the production process, resulting in an expensive compound.Moreover, in a system using the methylaluminoxane as a cocatalyst, Since a large amount of aluminoxane is required for the transition metal compound, there is a drawback that the production cost of the polymer cannot be avoided.

In such an olefin polymerization catalyst system which does not use an expensive aluminoxane, a metallocene cation complex formed by bringing a neutral metallocene into contact with an ionic compound containing an iron (III) cation is converted to an ethylene or the like. It has been reported that the olefin has a polymerization ability [J. Am. Chem. Soc., No. 10, "Journal of the American Chemical Society."
8, 7410 (1987)]. The iron (II
I) In a system in which an ionic compound containing a cation is used as a metallocene ionizing agent, a ligand is extracted by utilizing the oxidation / reduction ability of an iron (III) cation to form a metallocene cation complex. This reaction can be exemplified as shown below.

[0004]

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[Wherein, R represents an alkyl group, Cp represents a cyclopentadienyl group, M represents a metal, and A represents an anion. When the above reaction is carried out under polymerization conditions, after the polymerization, a compound derived from the iron (III) cation remains in the resulting resin. This causes coloring of the resin or the like, and may impair the properties inherent to the resin. As a method of ionizing metallocene, a protonation method is disclosed (European Patent No. 2).
No. 77004). This is a method of producing a metallocene cation by reacting a metallocene having a group capable of reacting with a proton with an ammonium salt having an active proton. An example of this reaction is as follows.

[0006]

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Wherein R, Cp, M and A are the same as above. In this reaction, a Lewis base (an amine such as R ₃ N) is generated as a by-product. The Lewis base can coordinate to the metallocene cation, reducing catalytic activity. In addition, the catalyst and the resins made with this catalyst contain toxic residual amines. further,
A method for producing a metallocene cation by contacting an ionized ionic compound with a neutral metallocene is disclosed (European Patent No. 426637). The ionized ionic compound shown here is an ionic compound containing a cation having no active proton, such as a triphenylcarbenium cation. In this reaction, a ligand is extracted from the metallocene by a carbenium ion as exemplified in the following formula, and a metallocene cation is generated.

[0008]

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Wherein R, Cp, M and A are the same as above, and Ph represents a phenyl group. 〕However,
Conventional carbenium compounds have high solubility in small solvents used in the production of polymers and have low reactivity with chain transfer agents typified by organoaluminum,
Therefore, sufficient activity cannot be obtained.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ionic compound comprising a novel carbenium compound having low or no reactivity with an organoaluminum compound and having high solubility in a solvent having low polarity. Is to provide. Another object of the present invention is to produce an olefin polymer that does not contain heavy metals such as iron or highly toxic amines in the produced resin without using expensive aluminoxane, and it is also possible to produce amines and the like. An object of the present invention is to provide an olefin polymerization catalyst which does not cause a decrease in activity due to the by-product of a Lewis base.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that an ionic compound comprising a non-coordinating anion and a substituted triarylcarbenium, It has been found that the olefin polymerization catalyst used can be adapted to the purpose. The present invention has been completed based on such findings. That is, the present invention provides an ionic compound comprising a non-coordinating anion and a substituted triarylcarbenium. The present invention also provides an olefin polymerization catalyst comprising the ionic compound.

The ionic compound of the present invention comprises a non-coordinating anion and a substituted triarylcarbenium. Examples of the non-coordinating anion include those represented by the following general formula (I) (M ¹ X ¹ X ^{2 ··· X n) (nm)} - ··· (I) [wherein, M ¹ is a metal selected from group 5 to 15 of the periodic table, X ¹ to X ⁿ are each a hydrogen atom, dialkylamino Group, alkoxy group, aryloxy group, carbon number 1-20
Represents an alkyl group, an aryl group having 6 to 20 carbon atoms (including a halogen-substituted aryl group), an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group or a halogen atom, and m is a valence of M ¹ An integer of 1 to 7, and n is an integer of 2 to 8. ] Can be cited.

M¹Specific examples of B, Al, Si,
There are P, As, Sb, and the like. Also, X ¹~ XⁿExamples of
As, for example, dimethyl as a dialkylamino group
Amino group: diethylamino group, alkoxy group
Xy group; ethoxy group; n-butoxy group, aryloxy
A phenoxy group as a group; 2,6-dimethylphenoxy
A group; a naphthyloxy group, an alkyl group having 1 to 20 carbon atoms;
Methyl group; ethyl group; n-propyl group;
Pill group; n-butyl group; n-octyl group;
Xyl group, aryl group or alkyl ant having 6 to 20 carbon atoms
A phenyl group as a phenyl group or an arylalkyl group;
p-tolyl group; benzyl group; mono-penta (fluoro)
Phenyl group; 3,5-di (trifluoromethyl) phenyl
4-tert-butylphenyl group; 2,6-di
Methylphenyl group; 3,5-dimethylphenyl group; 2,
4-dimethylphenyl group; 1,2-dimethylphenyl
Group, halogen as F, Cl, Br, I, organic metalloy
Pentamethylantimony group as tridosil; trimethylsilyl
Group; trimethylgermyl group; diphenylarsine group; di
Cyclohexylantimony; diphenylboron, etc.
No. And as a specific example of this anion,
B (C₆F_Five)_Four ^-, B (C₆HF _Four)_Four ^-, B (C₆
H_TwoF_Three)_Four ^-, B (C₆H_ThreeF_Two)_Four ^-, B (C₆H
_FourF)_Four ^-, BF_Four ^-, PF₆ ^-, P (C
₆F_Five)₆ ^-, Al (C₆F_Five)_Four ^-Etc.
You.

A compound generally called a carborane is also a non-coordinating anion. On the other hand, examples of the substituted triarylcarbenium include those represented by the general formula (II) [CR ¹ R ² R ³ ] ⁺ ... (II). R ¹ , R ² and R ³ in the general formula (II) are aryl groups such as a phenyl group, a substituted phenyl group, a naphthyl group, an anthracenyl group, and they are different even if they are the same. At least one of them may be a substituted phenyl group, a naphthyl group or an anthracenyl group. The substituted phenyl group can be represented for example by the general formula _{(III) C 6 H 5-} k R 4 k ··· (III). R ⁴ in the general formula (III) is
And represents a hydrocarbyl group, an alkoxy group, an aryloxy group, a thioalkoxy group, a thioaryloxy group, an amino group, an amide group, a carboxyl group, or a halogen atom having 1 to 10 carbon atoms, and k is an integer of 1 to 5. When k is 2 or more, a plurality of R ⁴ may be the same or different.

Specific examples of the non-coordinating anion represented by the general formula (I) include tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate,
Tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (trifluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentane Fluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, and tridecahydride-7,8-dicarboundecaborate. In the present invention, non-coordinating ani
The following general formula as an on ^{(I ') (BX 1 X} 2 X 3 X 4) - ··· (I') ^{wherein, X 1, X 2, X} 3, X 4 are each a hydrogen atom, dialkyl
Killamino group, alkoxy group, aryloxy group, carbon
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms
(Including halogen-substituted aryl groups), alkylaryl
Group, arylalkyl group, substituted alkyl group, organic metallo
Represents an id group or a halogen atom. Non-coordination represented by
Targets anions.

On the other hand, specific examples of the substituted triarylcarbenium represented by the general formula (II) include tri (tolyl) carbenium, tri (methoxyphenyl) carbenium, tri (chlorophenyl) carbenium, and tri (fluorophenyl) carbenium. Carbenium, tri (xylyl)
Carbenium, [di (toluyl), phenyl] carbenium, [di (methoxyphenyl), phenyl] carbenium, [di (chlorophenyl), phenyl] carbenium, [toluyl, di (phenyl)] carbenium, [methoxyphenyl, di (phenyl) )] Carbenium, [chlorophenyl, di (phenyl)] carbenium and the like. In the present invention, a substituted triarylcarbenium and
The following general formula (II ′) [CR ⁵ R ⁶ R ⁷ ] ⁺ ... (II ′) wherein R ⁵ , R ⁶ and R ⁷ are each a phenyl group,
Or a substituted phenyl group represented by C ₆ H _5-k R ⁸ ;
They may be the same or different
But at least one of them is a substituted phenyl group
You. R ⁸ is a hydrocarbyl group having 1 to 10 carbon atoms,
A koxy group, an aryloxy group or a halogen atom;
It is an integer of 1 to 5. when k is 2 or more, plural R ⁸ is
They may be the same or different. ]
Substituted triarylcarbenium.

As the ionic compound of the present invention, there can be mentioned, for example, compounds in which any one of the above-mentioned non-coordinating anions and substituted triarylcarbeniums is selected and combined. The catalyst for olefin polymerization of the present invention uses the ionic compound obtained as described above, and may be the ionic compound alone, or may be a mixture of the ionic compound and a transition metal compound. It may be one mixed by contact. As the transition metal compound, a compound of a metal of Groups 3 to 6 of the periodic table and a lanthanoid metal compound can be used. In particular the general formula _{^{(IV) M 2 R 5 a}} R 6 b R 7 c R 8 p- (a + b + c) L q ···
The Group 4 and lanthanoid metal compounds represented by (IV) exhibit high performance.

In the above general formula (IV), M ² represents a Group 4 metal such as titanium, zirconium, hafnium and a lanthanoid metal. R ⁵ , R ⁶ , R ⁷ and R
⁸ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (specifically, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, 2-ethylhexyl group, etc.) An alkoxy group having 1 to 20 carbon atoms (specifically, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an amyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, etc.);
20 thioalkoxy groups (specifically, thiomethoxy group and the like), C6-C20 aryl groups (specifically, phenyl group, tolyl group, xylyl group, benzyl group and the like), and C6-C20 aryloxy group (Specifically, a phenoxy group, a benzyloxy group and the like), a thioaryloxy group having 6 to 20 carbon atoms (specifically, a thiophenoxy group and the like), a cyclopentadienyl group, and a substituted cyclopentadienyl group (specifically, Represents a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, etc.), an indenyl group, a substituted indenyl group, a fluorenyl group, a substituted fluorenyl group or a halogen atom (specifically, Chlorine, bromine, iodine, fluorine). R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different, and may be mutually cross-linked. L represents a neutral Lewis base, a, b and c each are an integer of 0 to p, p valence of M ^2, q represents 0 or 1.

Among the transition metal compounds represented by the above general formula (IV), specific examples of compounds not containing a group having a cyclopentadienyl skeleton include titanium tetraethoxide, tetrabenzyl zirconium, 2,2,2 '-Thiobis (4-methyl-6-t-butylphenyl) titanium dipropyl and the like. Specific examples of the compound having one group having a cyclopentadienyl skeleton include cyclopentadienyltitanium trimethoxide. Pentamethylcyclopentadienyl titanium trimethyl, pentamethylcyclopentadienyl titanium trimethoxide,
Pentamethylcyclopentadienyl zirconium trimethyl, pentamethylcyclopentadienyl hafnium trimethoxide and the like can be mentioned.

Specific examples of the compound having two groups having a cyclopentadienyl skeleton include bis (cyclopentadienyl) titanium dibenzyl, bis (cyclopentadienyl) zirconium dimethyl and bis (pentamethylcyclo). (Pentadienyl) hafnium dimethyl, dimethylsilylenebis (cyclopentadienyl) titanium dimethyl, dimethylsilylenebis (cyclopentadienyl) zirconium dimethyl, ethylidenebis (indenyl) zirconium dimethyl, ethylidenebis (tetrahydroindenyl) zirconium dimethyl, ethylidene Bis (tetrahydroindenyl) hafnium dimethyl, isopropylidene (fluorenyl) (cyclopentadienyl) zirconium dimethyl and the like can be mentioned.

Examples of the olefin monomer to which the catalyst for olefin polymerization of the present invention is applicable include ethylene propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; 4
-Phenylbutene-1; 6-phenylhexene-1; 3
-Methylbutene-1; 4-methylpentene-1; 3-methylpentene-1; 3-methylhexene-1; 4-methylhexene-1; 5-methylhexene-1; 3,3-dimethylpentene-1; 3 , 4-dimethylpentene-1;
4,4-dimethylpentene-1; vinylcyclohexane; α-olefin such as vinylcyclohexene, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; Ethylene; halogen-substituted α-olefins such as 3,4-dichlorobutene-1, cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene 7-methylnorbornene; 5,5,6-trimethylnorbornene;
5-phenylnorbornene; 5-benzylnorbornene; 5-ethylidene norbornene; cyclic olefins such as 5-vinylnorbornene, styrene; p-methylstyrene; o-methylstyrene; m-methylstyrene;
4-dimethylstyrene; 2,5-dimethylstyrene;
3,4-dimethylstyrene; 3,5-dimethylstyrene; pt-butylstyrene; p-chlorostyrene; m
-Chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; o-bromostyrene; p
-Fluorostyrene; m-fluorostyrene; o-fluorostyrene; o-methyl-p-fluorostyrene;
Vinyl aromatic compounds such as -vinyl biphenyl; 3-vinyl biphenyl; 2-vinyl biphenyl, and acetyls. These olefin monomers may be used alone or in a combination of two or more.

Using the olefin polymerization catalyst of the present invention,
When the above olefin is polymerized, an organoaluminum compound, hydrogen, and the like can coexist. Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trit-butylaluminum, dimethylaluminum chloride, diethyl Aluminum chloride, di-n-propylaluminum chloride,
Dialkylaluminum halides such as diisopropylaluminum chloride, din-butylaluminum chloride, diisobutylaluminum chloride, dit-butylaluminum chloride, dialkylaluminum alkoxides such as dimethylaluminum methoxide and dimethylaluminum ethoxide, dimethylaluminum hydride, diethylaluminum hydride; Examples thereof include dialkylaluminum hydrides such as diisobutylaluminum hydride. Of these, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferable.

The polymerization method is not particularly limited, and a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like can be used, and any of a continuous method and a discontinuous method can be employed. it can. Examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane;
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane can be used. The polymerization temperature is usually selected in the range of -80 to 252 ° C, preferably 20 to 200 ° C, and the polymerization pressure is usually normal pressure to 30 kg / cm ² · G.
Is selected in the range.

[0024]

Next, the present invention will be described in more detail with reference to examples. Example 1 (1) Production of Ionic Compound Under dry nitrogen, 5.0 g of 4,4 ′, 4 ″ -trimethoxytrityl alcohol was dissolved in 10 ml of dry toluene, and 2.0 ml of thionyl chloride was added dropwise under ice cooling. Thereafter, the temperature was raised and the reaction was carried out for 6 hours under reflux.
The mixture was allowed to cool and at 40 ° C., 20 ml of hexane was added to precipitate 4,4 ′, 4 ″ -trimethoxytrityl chloride. The crude crystals were re-used from a mixed solvent of toluene / hexane (weight ratio 1/2). Crystallized and purified 4,4 ', 4 "-
4.8 g of trimethoxytrityl chloride were obtained.

Under dry nitrogen, 4,4 ', 4 "-trimeth
4.5 mmol of xithrityl chloride in dry methylene chloride
Dissolve in 30 ml and add lithium tetrakis (pen
Methylene chloride containing 4.0 g of (tafluorophenyl) borate
Was dropped into 60 ml. After stirring for 1 hour at room temperature,
Filter through a glass filter under dry nitrogen.
It was concentrated to a liter. 450 ml of dry hexane
4,4 ',
4 "-trimethoxyphenylcarbenium tetrakis
(Pentafluorophenyl) borate as dark red solid
I got it. The cationic carbon of this thing¹³C-nuclear magnetic resonance
The chemical shift of the spectrum is 192.5 ppm (solvent
(Δ value when the formol was 77.00 ppm). FIG.
To ¹1 shows an H-nuclear magnetic resonance spectrum. This compound
When dissolved in Ruen, a solution of 20 mmol / L
The liquid was a red homogeneous solution.

(2) Preparation of polymerization catalyst 0.3 g of 4,4 ', 4 "-trimethoxyphenylcarbeniumtetrakis (pentafluorophenyl) borate was dissolved in 30 ml of toluene. (Pentamethylcyclopentadienyl) titanium 10 ml of a 10 mmol / l toluene solution of trimethyl and 2
M / liter of 1 ml of a toluene solution of triisobutylaluminum was previously brought into contact with 29 ml of toluene, and then 4,4 ′, 4 ″ -trimethoxyphenylcarbenium tetrakis (pentafluorophenyl) borate was dissolved in the above toluene solution. A catalyst was prepared by contacting 10 ml.

(3) Polymerization 400 ml of dry toluene was placed in a 1 liter SUS autoclave, heated to 70 ° C., and 15 ml of the above-mentioned catalyst solution was added under a nitrogen stream, and ethylene was separated at a partial pressure of 4 kg / cm. ² was introduced so as to be constant, 1
Polymerization was carried out for 5 minutes. By this polymerization reaction, 5.7 g of polyethylene was obtained.

Reference Example 1 Triphenylcarbenium tetrakis (pentafluoro
92 mg (0.1 mmol) of phenyl) borate
Red oily substance when added in 5 ml
Separation and sedimentation did not give a homogeneous solution. Example 2 In Example 1- (1), 4,4 ′, 4 ″ -trimeth
4,4'-dimethoxy instead of xithrityl chloride
Except that trityl chloride was used, Examples 1- (1) and
[(4,4'-dimethoxyphenyl),
Enyl] carbenium tetrakis (pentafluorophe
Nyl) borate was obtained as a dark red solid. Of this one
Cationic carbon¹³Chemical shift of C-nuclear magnetic resonance spectrum
Is 195.2 ppm (solvent chloroform is 77.00p
δ value in pm). In FIG. ¹H-nuclear magnetic resonance
Indicates a vector. This [(4,4'-dimethoxyphenyl)
Phenyl) carbenium tetrakis (pentaflu
Orophenyl) borate in heavy benzene solution
Isobutyl aluminum was added, but at room temperature,¹H-
No change was observed in the nuclear magnetic resonance spectrum.

Reference Example 2 When an equal amount of triisobutylaluminum was added to a heavy benzene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate, the ¹ H-nuclear magnetic resonance spectrum rapidly changed at room temperature. A spectrum of the decomposition product of carbenium tetrakis (pentafluorophenyl) borate was observed.

Example 3 In Example 1- (1), 4,4 ', 4 "-trimethoate was used.
4,4 ', 4 "instead of using xithrityl chloride
Example except that trichlorotrityl chloride was used
4,4 ', 4 "-Trichloro by the same operation as 1- (1)
Phenylcarbenium tetrakis (pentafluorophen
Nyl) borate was obtained as a yellow solid. Click here
On-carbon¹³The chemical shift of the C-nuclear magnetic resonance spectrum is
 203.3 ppm (solvent chloroform 70.00 ppm
Δ value). In FIG. ¹H-nuclear magnetic resonance spec
Indicates a torr.

[0031]

According to the present invention, it is possible to obtain an ionic compound comprising a novel carbenium compound having low or no reactivity with an organoaluminum compound and having high solubility in a solvent having low polarity. . The catalyst for olefin polymerization using the ionic compound can easily give an olefin polymer which does not contain heavy metals such as iron and highly toxic amines in the formed resin, and furthermore, it is possible to give a Lewis base such as amine by-product. Does not result in a lively loss of activity.

[0032]

[Brief description of the drawings]

FIG. 1 is a ¹ H-nuclear magnetic resonance spectrum of 4,4 ′, 4 ″ -trimethoxyphenylcarbenium tetrakis (pentafluorophenyl) borate.

FIG. 2 is a ¹ H-nuclear magnetic resonance spectrum of [(4,4′-dimethoxyphenyl), phenyl] carbenium tetrakis (pentafluorophenyl) borate.

FIG. 3 shows the results of 4,4 ′, 4 ″ -trichlorophenylcarbenium tetrakis (pentafluorophenyl) borate
^{It is a} < ¹ > H- nuclear magnetic resonance spectrum figure.

Claims (2)

(57) [Claims] 1. A (A) the general formula ^{(I ') (BX 1 X} 2 X 3 X 4) - ··· (I') ^{wherein, X 1, X 2, X} 3, X 4 each hydrogen Atom, dial
Killamino group, alkoxy group, aryloxy group, carbon
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms
(Including halogen-substituted aryl groups), alkylaryl
Group, arylalkyl group, substituted alkyl group, organic metallo
Represents an id group or a halogen atom. ] Non-coordinating anion and represented by (B) the general formula (II ') [CR ⁵ R ⁶ R ^{7] +} ··· (II') wherein, R ^5, R ⁶ and R ^7, A phenyl group,
Or a substituted phenyl group represented by C ₆ H _5-k R ⁸ ;
They may be the same or different
But at least one of them is a substituted phenyl group
You. R ⁸ is a hydrocarbyl group having 1 to 10 carbon atoms,
A koxy group, an aryloxy group or a halogen atom;
It is an integer of 1 to 5. when k is 2 or more, plural R ⁸ is
They may be the same or different. ]
And a substituted triarylcarbenium. 2. An olefin polymerization catalyst comprising the ionic compound according to claim 1.