JPH0782314A - Method of polymerizing olefin - Google Patents

Abstract

PURPOSE:To obtain a high-mol.wt. polyolefin and attain high catalytic activity in the polymerization by using a new catalyst system containing a palladium compound. CONSTITUTION:An olefin is polymerized in the presence of a catalyst comprising a palladium compound represented by the formula Pd(L<1>)n(L<2>)2 (wherein L<1> is a neutral ligand, L<2> is an anionic ligand, and n is 1, 2, 3, or 4) and an organoaluminumoxy compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for polymerizing olefins using a novel catalyst system.

[0002]

2. Description of the Related Art As an olefin polymerization catalyst system, a Ziegler-Natta catalyst comprising a combination of a transition metal compound of Groups IV to VI of the periodic table and an organic aluminum compound is known. Japanese Patent Application Laid-Open No. 4-13706 discloses a method for polymerizing ethylene using a Group VIII metal rhodium or ruthenium compound as a transition metal compound.

Palladium compounds belonging to Group VIII metals
With a combination of aluminium and an organoaluminum compound
For example, Makromol. Chem., Rapid Com
mun.11, 285 (1990), supported on magnesium chloride.
Touch composed of palladium chloride and triethylaluminum
Polymerization of ethylene using a medium system is disclosed. However
However, these catalyst systems have a polymerization activity of 0.5 kg · PE / 1 g.
・ There is a problem that it is only about Pd and its activity is low. Also,
J. Am. Chem. Soc.103, 4627 (1981), Tetraki
Su (acetonitrile) palladium Bis (tetrafluoro
Borate) Pd (CH₃CN)_Four(BF _Four)₂Ai
Is its tris (triphenylphosphine) complex Pd
(CH₃CN) (PPh₃)₃(BF_Four)₂For catalyst
Production of polystyrene was reported, but ethylene
When applied to polymerization, it should be noted that oligomers are formed.
It is listed.

[0004]

OBJECTS OF THE INVENTION The present invention provides a process for the polymerization and copolymerization of olefins which gives highly active and high molecular weight polyolefins using a novel catalyst system containing a palladium compound.

[0005]

[Technical Means for Solving Problems] The present invention is based on the formula (A) Pd (L ¹ ) _n (L ² ) ₂ (wherein L ¹ represents a neutral ligand and L ² is an anionic ligand). Represents a ligand, n is 1,
2, 3 or 4), and (B) an organoaluminum oxy compound component in the presence of a catalyst comprising a catalyst.

The component (A) of the catalyst of the present invention is represented by the formula Pd (L ¹ ) _n (L ² ) ₂ (wherein L ¹ represents a neutral ligand and L ² represents an anionic ligand). And n is
1, 2, 3 or 4).

L ¹ of the ligand of the palladium compound is a neutral ligand, and specific examples of the ligand include nitrile coordination such as acetonitrile (CH ₃ CN) and benzonitrile (PhCN). Child, triphenylphosphine (PP
h _3), trimethylphosphine (P (CH _{3) 3)} phosphine ligand, such as, P (OR) phosphite ligand represented by _3, hydrocarbyl amine ligand represented by R ₃ N, Examples thereof include linear or cyclic ether type ligands. Among them, acetonitrile and triphenylphosphine can be preferably used, and two or more kinds of the above ligands may be mixed and coordinated with palladium.

[0008] L ² ligands of the palladium compound are anionic ligands, specific examples of the ligand, tetrafluoroborate-containing anions ^(- BF _4), tetraphenyl boron anion ^(- B ( Ph) _4), tetrakis (pentafluorophenyl) boron anion ^(- B (C
₆ F ₅ ) ₄ ) and other boron-based ligands, fluorine anions (F ⁻ ), chlorine anions (Cl ⁻ ), bromine anions (B
r ^-) halogen-based ligands, acetate, such as (CH ₃ C
O ₂ ^-), a trifluoromethyl acetate (CF ₃ CO ₂ ^-) carboxylate-based ligand such as acetylacetonate (CH ₃ COCH ₂ COCH ₃ ^- enolate-based ligand such ^{_{as), CH 3 O -, CH}} 3 _{^{CH 2 O -, C 6 H}} 5 O -
And other hydrocarbyloxy ligands. Among them, tetrafluoroboron anion (B
F ₄ ^-) can be preferably used, ligands such above may be coordinated to palladium in a mixture of two or more kinds.

Specific examples of the palladium compound used in the present invention include Pd (PPh ₃ ) ₂ (BF ₄ ) ₂ and Pd.
(CH ₃ CN) ₄ (BF ₄ ) ₂ , Pd (CH ₃ CN)
Mention may be made of a palladium divalent complex such as (PPh ₃ ) ₃ (BF ₄ ) ₂ . Above all, Pd (PPh ₃ )
₂ (BF ₄ ) ₂ can be preferably used.

The palladium compound of the present invention can be dissolved in an inert solvent and used as a homogeneous solution. Examples of the inert solvent include aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and aromatic hydrocarbons such as toluene and xylene.

The palladium compound of the present invention can be used as a supported catalyst by supporting it on an inorganic compound or an organic polymer compound. The inorganic compound carrier is preferably an inorganic oxide, an inorganic chloride or an inorganic hydroxide, and a carrier containing a small amount of a carbonate or a sulfate can also be used. Particularly preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia.

These inorganic oxide carriers have an average particle size of
Porous fine particles having a particle size of 5 to 150 μm and a specific surface area of ² to 800 m ² / g are preferable. Moreover, it is preferable to use after heat-treating at 100-800 degreeC. In particular, it is preferable to use silica or alumina heat-treated at 500 to 800 ° C.

The organic polymer compound carrier is preferably one having an aromatic ring, a substituted aromatic ring or a functional group such as a hydroxy group, a carboxyl group, an ester group or a halogen atom in its side chain. Specific examples include those having the functional group obtained by chemically modifying a homopolymer or copolymer of α-olefin such as ethylene, propylene and butene-1.
Mention may be made of homopolymers or copolymers of acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene and the like, as well as chemically modified products thereof. The shape of these organic polymer compound carriers is preferably spherical fine particles having an average particle diameter of 5 to 250 µ.

The method for supporting the palladium compound on the carrier is not particularly limited, and a conventional method such as a method of immersing the carrier in a solution of the palladium compound, a method of supporting the palladium compound on the carrier by a chemical bond, etc. Is mentioned.

The organoaluminum oxy compound, which is the component (B) of the catalyst in the present invention, has the general formula (--Al
(R) O-) _n is a linear or cyclic polymer, R is a hydrocarbon group having 1 to 10 carbon atoms, and a part of R is substituted with a halogen atom and / or an RO group. May be. n is the degree of polymerization and is usually 5 or more, preferably 10 or more.

As the method for producing the organoaluminum oxy compound, for example, a water-containing inert hydrocarbon solvent is reacted with an organoaluminum compound, and an inorganic compound containing crystal water is reacted with an organoaluminum compound in an inert hydrocarbon solvent. Or a method of simultaneously producing an organoaluminum oxy compound by introducing a hydrous olefin gas into an inert hydrocarbon solvent containing an organoaluminum compound during olefin polymerization.

The organoaluminum compound has the general formula A
lR _m X _3-m (wherein R is a hydrocarbon group having 1 to 10 carbon atoms,
X represents a halogen atom or a hydrogen atom, and m is 0 <m
≦ 3). For example, trialkylaluminum, dialkylhalogenoaluminum,
Examples thereof include sesquialkylhalogenoaluminum, alkenylaluminum, dialkylhydroaluminum and sesquialkylhydroaluminum.

In the present invention, the above organoaluminum compound can be used together with the organoaluminum oxy compound at the time of polymerization. In the present invention, the amount of the organoaluminum oxy compound used is such that the Pd atom of the palladium compound is Al of the organo aluminum oxy compound.
The atomic element ratio (Al / Pd) is preferably 20 to 10,000
Is.

As the polymerization method in the present invention, a slurry polymerization method using a non-polar solvent such as hexane or heptane, a high temperature solution method, a fluidized bed type or stirring type gas phase polymerization method in which a monomer is brought into contact with a catalyst in a gaseous state, Alternatively, a bulk polymerization method, a high pressure polymerization method or the like in which a monomer in a liquid state is used as a solvent for polymerization can be employed. Specific examples of the nonpolar solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane, and aromatic hydrocarbons such as toluene and xylene.

In the present invention, the slurry method in an inert hydrocarbon solvent or the stirred or fluidized bed gas phase polymerization method is usually at 20 to 120 ° C. for 10 to 300 minutes, and the polymerization pressure is 2 to 100 kg / cm 2. It can be performed under the conditions of ² . The high pressure polymerization method of the present invention is
Usually, it can be performed at 100 to 300 ° C. under a polymerization pressure condition of 130 kg / cm ² or more.

When the solid catalyst carrying the palladium component of the present invention is used in the gas phase polymerization method, the polymerization activity is improved, the catalyst is easily introduced into the polymerization reaction vessel, and the catalyst is prevented from adhering to the polymerization reaction vessel. For the purpose of, for example, improving the fluidity of the solid catalyst and the produced polymer in the gas-phase reaction vessel, an olefin preliminarily polymerized according to the above-mentioned various polymerization methods can be used as a catalyst in the main polymerization. The prepolymerization is, for example, in a slurry method in an inert hydrocarbon solvent, usually at 5 to 80 ° C. for 5 to 60 minutes, the atomic ratio of palladium to aluminum is 5 to 300, and the olefin polymer is added per 1 milligram atom of palladium. It can be performed under the condition that 1 to 100 g can be obtained.

Specific examples of the olefin polymerized by using the catalyst of the present invention include ethylene, propylene, butene-1,
Examples thereof include aliphatic monoolefins such as 4-methylpentene-1, hexene-1 and octene-1, and cyclic monoolefins such as cyclopentene, cyclohexene, 4-ethylcyclohexene and norbornene. These olefins can also be copolymerized. Alternatively, propylene may be homopolymerized, and then ethylene or a mixture of ethylene and propylene may be copolymerized in the presence of the homopolymer to produce a propylene block copolymer.

Further, in the above-mentioned olefin polymerization and copolymerization, dicyclopentadiene and 5-ethylidene are further added.
-2-norbornene, vinylcyclohexene, or 1,
Non-conjugated linear or cyclic diolefins such as 5-hexadiene and 1,5-cyclooctadiene can be copolymerized.

In the present invention, a chain transfer agent such as hydrogen can be used. Desired stereoregularity (H.
I. ) And the amount of hydrogen used for producing an olefin polymer having melt fluidity (MFR) can be appropriately determined depending on the polymerization method and the polymerization conditions.
Usually, the hydrogen partial pressure is in the range of 0.05 to 1.0.

[0025]

Industrial Applicability According to the method of the present invention, a highly active and high molecular weight polyolefin can be obtained using a novel catalyst system using a palladium compound.

[0026]

EXAMPLES In the examples, "polymerization activity" is the polymer yield (kg) per 1 g of palladium in the catalyst (A) component used in the polymerization reaction. The molecular weight distribution is the weight average molecular weight M determined from GPC using polystyrene as a standard substance.
_It was evaluated by the ratio M _W / M _{n of W} and the number average molecular weight M _n . The melting point in the copolymer was measured by DSC, and the comonomer content was measured by ¹ H-NMR.

Example 1 600 m of purified toluene was added to a 500 ml flask which had been sufficiently replaced with nitrogen.
After charging l, methylalumoxane (manufactured by Tosoh Akzo Co., Ltd.) corresponding to 10 mg atom in terms of aluminum atom was charged. After the temperature was raised to 40 ° C, Pd was used as the catalyst (A) component.
(PPh ₃ ) ₂ (BF ₄ ) ₂ was charged at 3.40 × 10 ⁻³ mmol and stirred for about 5 minutes to obtain a uniform solution. Then, ethylene gas was introduced at a rate of 1000 ml / min, the reaction was carried out for 1 hour, and then ethanol was added to terminate the polymerization. The polymer slurry solution was added to a large amount of ethanol solution to precipitate a polymer, which was separated by filtration and then dried under reduced pressure at 70 ° C. overnight. The polymer yield after drying was 1.24 g, and the polymerization activity was 3.42 Kg /
It was g.Pd.h. The M _n and M _w /
The _Mn was 200,000 and 2.7.

Comparative Example 1 In the method of Example 1, 9.0 in terms of aluminum atom
Polymerization was carried out in the same manner as in Example 1 except that methylalumoxane corresponding to mg atom was used and PdCl ₂ was 3.0 × 10 ⁻³ mmol as the catalyst (A) component. The polymer yield after drying was 0.0123 g, and the polymerization activity was 0.039 Kg / gP.
It was dh. In addition, this polymer exhibited a slight black coloration.

Example 2 1.6 L stainless steel autoclave with sufficient nitrogen substitution
After charging 600 ml of purified toluene into the
Methylalumoxane and catalyst corresponding to 11.3 mg atom
As the component (A), a catalyst Pd (PPh₃)₂(BF
_Four)₂1.13 x 10 ^-2mmol charged. Then the temperature is 40 ℃
After setting to, the total pressure is 2.7Kg / cm²To be ethylene
After introducing gas and reacting for 2 hours, add ethanol.
The polymerization was stopped by addition. Large amount of polymer slurry solution
Add to the ethanol solution to precipitate the polymer and separate by filtration
Then, it was dried under reduced pressure at 70 ° C. overnight. The polymer yield after drying is
 It was 2.97 g, and the polymerization activity was 1.23 Kg / g.Pd.h.
In addition, M of this polymer_nAnd M_W/ M_nIs 175,000
And 2.2.

Example 3 1.5 L stainless steel autoclave with sufficient nitrogen substitution
After charging 600 ml of purified toluene into the
Methylalumoxane and catalyst equivalent to 21.5 mg atom
As the component (A), a catalyst Pd (PPh₃)₂(BF
_Four)₂2.15 x 10 ^-2mmol charged. Then the temperature is 40 ℃
After setting to, the total pressure is 2.7Kg / cm²To be ethylene
Introduces mixed gas of butene (butene content 3.04 mol%)
After reacting for 2 hours, add ethanol to polymerize.
Stopped. Add a large amount of ethanol to the polymer slurry solution.
After adding to the solution and precipitating the polymer and separating by filtration, overnight at 70 ℃
It was dried under reduced pressure. Polymer yield after drying was 2.97 g.
The polymerization activity was 1.27 Kg / g.Pd.h. In addition, this
Polymer M_nAnd M_W/ M_nIs 205,000 and 2.6
It was. The butene content in the polymer was 0.62 mol%.
The melting point of the polymer was 128.5 ° C.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for preparing a solid catalyst for olefin polymerization of the present invention.

Front page continuation (72) Inventor Eiko Ogawa 8-1 Goi Minami Kaigan, Ichihara, Chiba Ube Industries Ltd. Chiba Research Institute (72) Inventor Nobuhiro Mitani 8-1 Goi Minami Kaigan, Ichihara-shi, Chiba Ube Ko Sanba Co., Ltd. Chiba Research Center

Claims (1)

[Claims] 1. A formula (A) Pd (L ¹ ) _n (L ² )
₂ (in the formula, L ¹ represents a neutral ligand, L ² represents an anionic ligand, and n is 1, 2, 3 or 4), and ( B) A method of polymerizing an olefin in the presence of a catalyst comprising an organoaluminum oxy compound component.