JP3213373B2 - Solid catalyst for olefin polymerization and method for producing polyolefin using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an olefin polymerization catalyst and a method for producing a polyolefin using the same. More specifically, the present invention relates to a method for producing a polyolefin with high activity by using an olefin polymerization catalyst in which a specific compound is combined.

[0002]

2. Description of the Related Art As an olefin polymerization catalyst, a combination of a metallocene compound having a conjugated π electron, particularly cyclopentadiene or a derivative thereof as a ligand, and an alkylaluminoxane obtained by reacting a trialkylaluminum with water. It has been known. For example, JP-A-58-19309 discloses a method for polymerizing olefins using biscyclopentadienyl zirconium dichloride and methylaluminoxane as catalysts. Also JP-A-61-13031
4, JP-A-61-264010, JP-A-1-301704 and JP-A-2-301
41303 discloses a method for producing isotactic poly-α-olefin or syndiotactic poly-α-olefin and a polymerization catalyst for producing these stereoregular poly-α-olefins. All of the catalyst systems used use aluminoxane as a cocatalyst.

[0003] On the other hand, studies have been made on a homogeneous Ziegler-Natta catalyst which does not use aluminoxane.
A catalyst system mainly comprising a metallocene compound and an alkylaluminum compound has been studied. Although this catalyst system has low activity, it is already known to have polymerization activity for olefins. It is believed that the active species of this catalyst is a cationic metallocene compound or an ion-pair metallocene complex.

[0004] Recently, it has been reported that an isolated cationic metallocene compound having cyclopentadiene or a derivative thereof as a ligand has polymerization activity for olefins alone without the coexistence of methylaluminoxane as a cocatalyst. Have been. For example, RFJORDAN et al. In J. Am. Chem. Soc., 1986, 108: 7410-7411, zirconium cation having tetraphenylborane as an anion and having two cyclopentadienyl groups and a methyl group as ligands. The complex was isolated by using a donor such as tetrahydrofuran as a ligand, and it was reported that the isolated complex had ethylene polymerization activity in methylene chloride.

Also, Turner et al., J. Am. Chem. Soc., 1989
Volume 111, pages 2728-2729 and Tokiohei 1-501950, Tokiohei 1-5020
A transition metal compound capable of reacting with at least one proton having a cyclopentadienyl group or a derivative thereof having a substituent at 36 as a ligand, and a compound providing a stable anion having a cation capable of providing a proton It has been reported that an ion-pair type metallocene complex formed from has olefin polymerization activity. Also JP-A-3-179005, JP-A-3-17906, JP-A-3-207703,
JP-A-3-207704 also discloses a method for polymerizing an olefin without using an aluminoxane.

Further, Zambelli et al., Macromolecules, 1989.
Vol. 22, pp. 2186-2189 shows that isotactic polypropylene can be obtained by polymerizing propylene using a zirconium compound having a cyclopentadienyl group derivative as a ligand and a catalyst combining trimethylaluminum and fluorodimethylaluminum. It has been reported that the active species is also a metallocene compound in an ion-pair form.

[0007]

An olefin polymerization method using a combination catalyst of a metallocene compound and an alkylaluminoxane is characterized by high polymerization activity per transition metal. However, the high polymerization activity per metallocene compound unit in these methods is due to the use of a large amount of expensive aluminoxane as a cocatalyst, and the activity per aluminoxane unit is not very high. Therefore, there is a problem that the production cost of the polymer increases, and further, it is very difficult to remove the aluminoxane from the polymer produced after the polymerization, and there is a problem that a large amount of catalyst residue remains in the polymer.

[0008] On the other hand, the above-mentioned problems relating to alkylaluminoxane are eliminated by the method using a cationic zirconium complex as a catalyst without using alkylaluminoxane, but these catalyst systems are more effective in reducing olefins than catalyst systems using alkylaluminoxane. Has very low polymerization activity. Furthermore, in these methods, it is necessary to use a dimethyl complex obtained by alkylating the dichloro complex with an expensive alkylating reagent such as methyllithium or methyl Grignard reagent, and there is a problem in the alkylation yield. Therefore, there was a problem that the production cost of the catalyst was increased. Furthermore, many of these alkylated metallocene compounds are unstable,
In particular, in a solution dissolved in a hydrocarbon solvent or the like, impurities such as a very small amount of moisture or oxygen or light are easily decomposed, so that impurities contained in the monomer or the solvent during polymerization must be minimized.

In the case of polymerizing an olefin using a Ziegler catalyst, it is possible to remove impurities contained in the olefin by treating the monomer and / or solvent with an organometallic compound, particularly an alkylaluminum compound. . This method can be applied to the case where these ion pair catalysts are used, and the use of a monomer and / or a solvent treated with an alkylaluminum can improve the polymerization activity for olefins to some extent even with these catalysts. JP-A-3-179005, JP-A-3-3-905
207704. However, even such a method is inferior in activity as compared to a combined catalyst system using an alkylaluminoxane as a cocatalyst. In addition, most of the catalysts known as ion-pair catalysts which do not use alkylaluminoxane so far use metallocene compounds having at least one cyclopentadienyl derivative as a ligand, and are relatively stable and inexpensive. It has been desired that a transition metal compound having a transition metal-hetero atom bond, which is easily available and can be easily synthesized, can be used as it is, and olefin polymerization can be highly active.

[0010]

Means for Solving the Problems The present inventors have solved the above-mentioned problems and have intensively studied a method for producing a polyolefin with high activity using a transition metal compound other than a metallocene compound, and completed the present invention.

That is, the present invention relates to a fine solid component having Lewis acidity represented by the following general formula (3) or (4):
A and B are bonded to M by the general formula OR '(wherein R'
Is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or
Some of which are substituted with heteroatoms)
That are the same or different ligands each other, A 'and B' are different same or crosslinked with R, is bonded to M
General formula OR ′ (wherein R ′ is hydrogen or C 1-20)
Hydrocarbons or some of them are heteroatoms
A ligand containing a nitrogen atom, oxygen atom, phosphorus atom or sulfur atom represented by
A residue containing an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom, or a straight-chain saturated hydrocarbon residue which may have a side chain, or a part or all of the straight-chain carbon atoms of which are a silicon atom or a germanium atom Or a residue substituted with a tin atom, M represents a metal atom selected from Group 4 of the periodic table, and X represents a halogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom bonded to M. A solid catalyst component supporting a transition metal compound represented by an atom or a ligand containing a sulfur atom).

[0012]

Embedded image

[0013]

Embedded image After treatment with an organometallic compound of a metal belonging to Group 1, 2, 12, or 13 of the periodic table , a contact reaction with a compound that reacts with a reaction product of the solid catalyst component and the organometallic compound to become a stable anion is performed. The present invention also relates to a method for producing a polyolefin using the above catalyst.

In the present invention, the transition metal compound includes
A transition metal compound represented by the following general formula [Formula 3] or [Formula 4] can be exemplified.

The ligand represented by A or B is OR '
(R 'Some of number of 1 hydrogen or carbon hydrocarbons or their 20 residue substituted with heteroatoms) Ru ligand der bonded to the transition metal atom M represented by . These may be the same or different.

The ligand represented by A 'or B'
OR '(R' is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or
Residues in which some of them have been replaced by heteroatoms)
Ligand bound to the transition metal atom M represented byIn
You. These may be the same or different. here
Has a structure in which R 'of A' and B 'is cross-linked by R.
Is what you do.

The divalent group represented by R includes -O-, -S-
, -SS-, -SO-, -SO _2- , -CO-, -NR "-, -PR"-, -PO
R "-, -OSiR" ₂ O- or a methylene group represented by the following formula [Formula 5] or a silylene in which part or all of carbon atoms of the methylene group are substituted with a silicon atom, a germanium atom, or a tin atom Groups, germylene groups, and stannylene groups are exemplified.

[0018]

## STR5 ##-(R " ₂ C) n-(R" ₂ Si) m- (R " ₂ Ge) p- (R" ₂ Sn) q- (wherein R "is a hydrogen atom or a carbon atom having 1 carbon atom. And two R ″ s may be the same or different, and n, m, p and q are integers of 0 to 4 and the following formula 1 ≦
represents an integer satisfying n + m + p + q ≦ 4. X is a halogen atom such as fluorine, chlorine, bromine or iodine or a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, a boron atom or a sulfur atom coordinated to M, and NR '" ₂ ,
OR '", OCR'" ₂ , OSiR '" ₃ , SiR'" ₃ , GeR '" ₃ , PR'" ₂ , PO
_{R '"2,SR'"} , SOR '", SO 2 R'", BR '"3(R'" some hydrocarbons or of their 20 number of 1 hydrogen or carbon is replaced with a heteroatom Residue). Xs may be cross-linked to each other, and chelating ligands are also exemplified.

The compound which becomes a stable anion by reacting with a reaction product of the solid catalyst component and the organometallic compound is an ionic compound formed from an ion pair of a cation and an anion or an electrophilic compound. It reacts with the reactant of the component and the organometallic compound to form a polymerization active species. Among them, the ionic compound is represented by the following formula [Formula 6].

[0020]

[Omitted] [Q] m [Y] m -

Q is a cation component of the ionic compound, and is a carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation, phosphonium cation, transition metal cation, ferrocenium cation, indenium Cations and the like. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, triphenyl Examples include cations such as sulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver, and ferrocenium.

Y is an anionic component of an ionic compound, and examples thereof include a boron compound anion, an aluminum compound anion, and a gallium compound anion. Specifically, tetraphenylboron, tetrakis (pentafluorophenyl) boron, tetrakis (3,4,5-trifluorophenyl) boron, tetraphenylaluminum,
Tetrakis (pentafluorophenyl) aluminum,
Examples include anions such as tetrakis (3,5-bistrifluorophenyl) aluminum, tetraphenylgallium, and tetrakis (pentafluorophenyl) gallium.

The finely divided solid component having Lewis acidity used in the present invention includes various metal halide compounds and metal oxides known as solid acids. Specific examples include magnesium halide, manganese halide, silica, oxides such as alumina, magnesium silicate, talc, smectite, and the like.
Here, a finely divided solid component having no Lewis acidity can be used, but in that case, the transition metal compound is not easily supported, and the transition metal compound component is easily released during the polymerization.

These finely divided solid components preferably have a large surface area, and those having a small surface area are further pulverized or synthesized by a method of once dissolving and then reprecipitating to obtain a specific surface area of 5 m ² / g. It is preferable to use a compound of an inorganic oxide of from 1 to 1000 m ² / g or less.

In the present invention, the organometallic compound to be reacted with the solid catalyst component supporting the transition metal compound is Group 1 of the periodic table,
Group 2, Group 12 and Group 13 metal atoms, preferably aluminum, boron, gallium, zinc or magnesium, include halogen, oxygen or hydrogen or alkyl, alkoxy, aryl and the like. When a residue is coordinated and a plurality of ligands are present, they may be the same or different, and examples thereof include those in which at least one is an alkyl group. For example, an alkyl metal compound in which one or two or more alkyl residues having 1 to 12 carbon atoms are coordinated, an alkyl metal halide in which the above-described alkyl residue is coordinated with another atom or residue, an alkyl metal alkoxide, and the like. Is exemplified. Among them, an alkyl boron compound or an alkyl aluminum compound in which at least one alkyl residue having 2 or more carbon atoms is coordinated is preferably used.

Preferred examples of the organometallic compound in which the metal atom is aluminum include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum. ,
Triheptyl aluminum, trioctyl aluminum, tridecyl aluminum, isoprenyl aluminum, diethyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride, diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, diethyl aluminum Ethoxide, diisopropyl aluminum isopropoxide, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, isobutyl aluminum sesquichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, isobutyl aluminum dichloride, ethyl acetate Mini Umm diisopropoxide, and the like.

The method of treating the solid catalyst component supporting the transition metal compound with the organometallic compound is not particularly limited, and it is sufficient to simply mix both. Usually, it is preferable to treat in a hydrocarbon solvent. As the hydrocarbon solvent,
For example, saturated hydrocarbon compounds such as propane, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, cycloheptane, and methylcyclohexane; and aromatic hydrocarbon compounds such as benzene, toluene, and xylene. Is exemplified.

The use ratio of the organometallic compound to the transition metal compound is from 1 to 100,000 times, usually from 1 to 5000 times. The treatment temperature is not particularly limited, but is usually -20.
It is preferably carried out at a temperature of 100100 ° C. These mixtures can be stored in this state, and the temperature at which they are stored is not particularly limited. Similarly, it is preferable to store the mixture at a temperature of -20 to 100 ° C. The processing time does not need to be particularly limited. Of course, as described above, the processing time can be stored as it is until it is used, and used as needed.

The amount of the compound forming a stable anion is 0.1 to 0.1 with respect to the transition metal compound used in the catalyst.
It is 100,000 mole times, usually 0.5-10000 mole times.

An important point in the present invention is that a solid catalyst component supporting a transition metal compound is first reacted with an organometallic compound, and thereafter, a compound that forms these stable ions is brought into contact. If the order is different, the olefin will not polymerize at all, or the activity will be very low even if it is polymerized, resulting in poor reproducibility of polymerization.

It is a preferred embodiment of the present invention that the solid catalyst component supporting the transition metal compound is treated with the organometallic compound and then brought into contact with the olefin before the stable anion is brought into contact with the compound. By using a catalyst system that has been brought into contact with an olefin and then with a compound that will become a stable anion, the polymerization proceeds smoothly and the polymerization activity is improved.

Further, when a solid catalyst component carrying a transition metal compound is treated with an organometallic compound and reacted, a reactant obtained from the solid catalyst component is brought into contact with a compound to be a stable anion.
Instead of adding the whole amount of the compound to be a stable anion all at once, it is also possible to add it in at least two or more portions. That is, one part of the compound that becomes a stable anion is added before starting the polymerization to start the polymerization, and the remaining amount is further added at appropriate intervals during the reaction, or added continuously. That is. This makes it possible to carry out the polymerization stably for a long time.

In the present invention, hydrogen used in a Ziegler catalyst can be used to adjust the molecular weight of the resulting polyolefin. Furthermore, the molecular weight of the produced polyolefin can be controlled by the presence of an internal olefin during the polymerization of the olefin.

Specific examples of the internal olefin include 2-
Linear internal olefins such as butene, 2-pentene and 2-hexene, cycloolefins such as cyclopentene, cyclohexene, cycloheptene and norbornene, 5-methylene-2-
Dienes such as norbornene and 5-ethylidene norbornene are exemplified.

The solvent used in the preparation, polymerization or treatment of the catalyst using the catalyst component in the present invention includes, for example, propane, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane, Saturated hydrocarbon compounds such as cycloheptane and methylcyclohexane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, and halogenated hydrocarbon compounds such as methylene chloride and chlorobenzene can also be used. In addition, ethers, nitriles, ester compounds, and the like can be used as long as the solvent itself does not bind to the generated transition metal cation compound or strongly coordinate to inactivate the polymerization activity. The polymerization conditions of the olefin using this catalyst component are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, and a gas phase polymerization method can be used.

Examples of the olefin used in the polymerization include olefins having 2 to 25 carbon atoms, and specific examples thereof include ethylene, propylene, butene-1, pentene-1, and hexene-.
1, heptene-1, octene-1, nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene
-1, pentadecene-1, hexadecene-1, octadecene-1
In addition to linear olefins such as 3-methylbutene-1, 4-methylpentene-1, branched olefins such as 4,4-dimethylpentene-1 and cyclopentene, cyclooctene, and cyclic olefins such as norbornene are exemplified. An olefin can be homopolymerized or a copolymer of olefins can be copolymerized with each other. If necessary, a diene can be copolymerized. Further, in this polymerization system, an aromatic olefin such as styrene can be polymerized, and aromatic olefin alone or copolymerization with the above olefin can be performed.

As the polymerization temperature and the polymerization pressure, general conditions used in a known method are used. The polymerization temperature is -20 to 150 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ^2. .

[0038]

The present invention will be further described with reference to examples.

Example 1 A 500 ml four-necked flask purged with nitrogen was placed under reduced pressure at 600 ° C.
10 g of .gamma.-alumina heat-treated for 6 hours was added, and 100 ml of toluene was added, and 250 ml of a toluene solution containing 1 g of tetrabutoxytitanium as a transition metal compound was added dropwise with stirring. After stirring at room temperature for 8 hours, the solvent was removed, and the mixture was further washed three times with 50 ml of pentane and dried under reduced pressure. The titanium component was almost quantitatively supported in the obtained solid catalyst component.

After suspending 100 mg of the above solid catalyst component in 20 ml of toluene, 0.33 g of triisobutylaluminum was added and reacted. Into a 2 liter autoclave, 1 liter of toluene was charged, and then ethylene was added at a pressure of 3 kg.
/ cm ² · G, and the operation of depressurizing was repeated three times to replace toluene with ethylene. The solid catalyst component was charged into an autoclave, and ethylene was added at 20 ° C. to 8 kg.
/ cm ² · G and then press-fit a solution prepared by dissolving 30 mg of triphenylmethanetetra (pentafluorophenyl) boron in 20 ml of toluene at 20 ° C and 8 kg / cm ² · G while introducing ethylene. Polymerized for 1 hour. After polymerization, propylene is purged, and the content is filtered and dried to obtain 32 g of polymer.
I got

Comparative Example 1 Example 1 without using triisobutylaluminum
Polymerization of ethylene was carried out in the same manner as described above, but no polymer was obtained.

Example 2 A solid catalyst was synthesized in the same manner as in Example 1 except that tetraisopropoxytitanium was used instead of tetrabutoxytitanium, and ethylene was polymerized to obtain 38 g of a polymer.

Comparative Example 2 Example 2 without using triisobutylaluminum
Polymerization of ethylene was carried out in the same manner as described above, but no polymer was obtained.

Example 3 A solid catalyst was synthesized in the same manner as in Example 1 except that 2,2'-thiobis (4-methyl-6-t-butylphenoxy) titanium propoxide was used instead of tetrabutoxytitanium. Then, ethylene was polymerized to obtain 250 g of a polymer.

Example 4 Polymerization pressure was 3 kg using propylene instead of ethylene.
Polymerization of propylene was carried out in the same manner as in Example 1 except that the amount was changed to / cm ² · G to obtain 120 g of a polymer.

Example 5 Triphenylmethanetetra (pentafluorophenyl)
When ethylene was polymerized in the same manner as in Example 3 except that triphenylmethanetetra (pentafluorophenyl) aluminum was used instead of boron, 130 g of a polymer was obtained.

[0047]

By carrying out the method of the present invention, a polyolefin can be obtained with high activity per catalyst using an inexpensive catalyst, which is industrially valuable.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention.

Continuation of front page (56) References JP-A-5-230133 (JP, A) JP-A-52-96685 (JP, A) JP-A-4-309508 (JP, A) JP-A-4-249504 (JP) , A) WO 92/1723 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] A microparticulate solid component having Lewis acidity is represented by the following general formula (1) or (2), wherein A and B are bonded to M, wherein R ′ is hydrogen or carbon. number
From 1 to 20 hydrocarbons or some of them
The same or different ligands represented by the following formula: OR '(the same or different, bridged by R, and bonded to M ) In the formula
R 'is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or
Some of which are substituted with heteroatoms)
The ligand is, R represents a divalent nitrogen atom, oxygen atom, silicon atom, phosphorus atom or residue or side chain may also be straight-chain saturated comprises hydrocarbon residue or linear containing a sulfur atom A residue in which some or all of the carbon atoms in the chain are substituted with silicon atoms, germanium atoms or tin atoms, M is a metal atom selected from Group 4 of the periodic table, and X is a halogen bonded to M A solid catalyst component supporting a transition metal compound represented by an atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom). Embedded image After treatment with an organometallic compound of a metal belonging to Group 1, 2, 12, or 13 of the periodic table , a contact reaction with a compound that reacts with a reaction product of the solid catalyst component and the organometallic compound to become a stable anion is performed. A solid catalyst for the polymerization of olefins. 2. A method for producing a polyolefin, comprising polymerizing an olefin using the solid catalyst for polymerization according to claim 1.