JPH0317843B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for polymerizing olefins, particularly ethylene or ethylene and other 1-olefins. Specifically, it is a novel and active catalyst characterized by using a solid catalyst component obtained by reacting a hydrocarbon-soluble component obtained from a specific organomagnesium complex compound, an alcohol and a transition metal alkoxide, and a specific halogenated organoaluminum compound. The present invention relates to an olefin polymerization method with high olefin polymerization.

(Prior Art) In the polymerization of olefins, particularly ethylene or ethylene and other 1-olefins, a catalyst system consisting of a solid catalyst component containing magnesium, halogen, and titanium and an organoaluminum compound has traditionally been used with high activity. is known to show. There are many proposals for synthesizing this magnesium-containing solid catalyst component, such as synthesis from inorganic magnesium chloride and organic magnesium. Publication, U.S. Patent No.
In specification No. 4526943, specification No. 4544647, etc.,
Certain organic magnesium solutions and alcohol etc.
A method has been published in which a homogeneous solution is prepared from an OH group-containing organic compound and a transition metal alkoxide, and this is halogenated with organoaluminum halide to synthesize a solid catalyst component.

For example, the catalyst obtained by the technique described in JP-A No. 61-25004 has extremely high activity and does not require removal of the catalyst from the polymer, and the obtained polymer has a relatively wide molecular weight. It is possible to produce a polymer having a wide molecular weight distribution suitable for extrusion molding or blow molding by a method such as combining with a multi-stage polymerization method.

(Problems to be Solved by the Invention) However, in producing a catalyst using this method, a large amount of organoaluminum compound is required to make a homogeneous solution when synthesizing a specific hydrocarbon-soluble magnesium-containing component, and on the other hand, it is necessary to For safety reasons, the total organometallic concentration cannot be increased, and as a result, the magnesium concentration is diluted and reduced, resulting in a low amount of catalyst produced per unit volume of the reactor.

(Means for Solving the Problems) As a result of repeated research in order to solve the above problems, the present inventors have found that a specific number of carbon atoms is The present invention was achieved by discovering that by using a primary n-alcohol, the amount of organoaluminum compound required to be used can be reduced. That is, the present invention provides (A) (i) (a) General formula MgAlαR ¹ _p R ² _q (OR ³ ) _r (where α is 0<α≦2, p and q are numbers greater than 0, r is 0 or a number greater than 0, and p
+q+r=2+3α, R ¹ , R ²
( ^b ) n-butyl alcohol (c) an alkoxide of a transition metal selected from titanium, zirconium, and vanadium;
,
A hydrocarbon-soluble component obtained by mixing and reacting in the order of (c), (ii) general formula AlR ⁴ _3-o X _o (wherein R ⁴ is a hydrocarbon group, X is a halogen, , and n is 1≦
An olefin characterized by using a catalyst comprising a solid catalyst component (A) obtained by reacting a halogenated organoaluminum compound represented by n≦2) and (B) an organometallic compound. This relates to a polymerization method.

The present invention will be explained in detail below.

The hydrocarbon-soluble organomagnesium complex compound used in the present invention (A)(i)(a) has the general formula MgAlαR ¹ _p R ² _q (OR ³ ) _r (where α is 0<α≦
2, p and q are numbers greater than 0, r is 0 or a number greater than 0, and have the relationship p+q+r=2+3α, R ¹ and R ² are the same or different alkyl groups having 1 to 8 carbon atoms; , R ³ represents a primary hydrocarbon group having 4 carbon atoms), and α preferably satisfies 0.2≦α≦1, particularly preferably 0.3≦α≦0.6. Ru. These hydrocarbon-soluble organomagnesium complex compounds may be synthesized according to, for example, the following publications, gazettes, documents, etc., although there are no particular limitations on the production method. In other words, for α > 0,
Publication No. 139885, Japanese Unexamined Patent Application Publication No. 18235-1987, Publication No. 18235, Publication No.
Publication No. 47-24009, Annarenderhiemi 605
Volume 93-97 (1957), Japanese Patent Application Laid-Open No. 154388-1988,
It may be synthesized from the corresponding organomagnesium and organoaluminum with reference to JP-A-50-157490 and JP-A-53-40696. Additionally, certain magnesium compounds known to be hydrocarbon soluble, such as n-butylethylmagnesium, n-butyl sec-butylmagnesium, n-
Butyl isopropylmagnesium, etc. [For their synthesis, see JP-A-54-12327, JP-A-56-26893, U.S. Patent Nos. 4127507, 33646231, and 3766280. Specification, Journal of Organic Chemistry Vol. 34, pp. 1116-1121 (1969), Vol. 64, pp. 25-1969
40 (1974) using the corresponding Grignard compound or alkyllithium compound], it is also possible to synthesize from this and the corresponding organoaluminum,
and give favorable results. Hydrocarbon-soluble organomagnesium complex compounds obtained by these synthesis methods include, for example, di-(n-butyl)magnesium/1/5 triethylaluminum, n-butyl
sec-Butylmagnesium/1/2 triisobutylaluminum, butyl ethylmagnesium/1/2 triisobutylaluminum, butyl ethylmagnesium/1/3 triisobutylaluminum, butyl ethylmagnesium/1/4 triisobutylaluminum, butyloctylmagnesium/1 /2 triisobutylaluminum, dihexylmagnesium/1/2 triisobutylaluminum, butylethylmagnesium/triethylaluminum,
Examples include n-butyl sec-butylmagnesium and 1/3 triisobutylaluminum.

In the present invention (A)(i)(b), n-butyl alcohol is used.

Examples of the transition metal alkoxide selected from titanium, zirconium, and vanadium used in the present invention (A)(i)(c) include tetraisopropoxytitanium, tetra-n-butoxytitanium, and tetra(2-ethylhexoxy)titanium. , Tetler n-
Examples include butoxyzirconium, tri-n-butoxyvanadate, and the like. Particularly preferred are titanium alkoxides, examples of which include tetraisopropoxytitanium and tetra-n-butoxytitanium.

The halogenated organoaluminum compound used in the present invention (ii) has the general formula AlR ⁴ _3-o X _o (wherein,
R ⁴ is a hydrocarbon group, X is a halogen,
and n is a value of 1≦n≦2), and preferable examples include ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum chloride, and the like. Particularly preferably, ethylaluminum dichloride is used.

Next, the organometallic compound used in the present invention (B) will be explained.

Examples of the organometallic compound used in the present invention (B) include organoaluminum compounds, organoboron compounds, organozinc compounds, organolithium compounds, hydrocarbon-soluble organomagnesium compounds or complex compounds, but organoaluminum compounds are preferable. Particularly preferred are trialkyl aluminum or dialkyl aluminum hydrides. For example, triethylaluminum, triisobutylaluminum, trin-
Mention may be made of hexylaluminum, tridecylaluminum, diethylaluminum hydride, isoprenylaluminum and mixtures thereof.

Next, the synthesis of the solid catalyst component (A) will be explained.

First, (A) (i) the hydrocarbon-soluble organomagnesium complex compound of (a), (b) n-butyl alcohol, and (c) a transition metal alkoxide are combined into (a), (b), (c), or (b). ),
The following describes how to mix (a) and (c) in the order and react to obtain a hydrocarbon soluble component.

The reaction is carried out in an atmosphere sufficiently excluded from moisture and oxygen in an inert hydrocarbon medium such as aliphatic hydrocarbons such as hexane, heptane, benzene,
The reaction can be carried out in an aromatic hydrocarbon such as toluene or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or a mixed medium thereof. From the viewpoint of catalytic performance, an aliphatic hydrocarbon medium is preferably used. The reaction temperature is not particularly limited, and can be carried out at a commonly used temperature, for example, between room temperature and 100°C. There is no particular restriction on the reaction ratio of each component, but preferably,
The amount of alcohol in (b) is
0.5 to 1.5 mol, and the amount of transition metal alkoxide (c) is such that the ratio of transition metal atoms to the number of Mg atoms in the hydrocarbon-soluble organomagnesium complex compound (a) is 0.02 to 0.2, particularly preferably is 0.05~
0.1 is recommended.

Next, the hydrocarbon soluble component (i) obtained by the above reaction and the halogenated organoaluminum compound (ii)
A method for obtaining the solid catalyst component (A) by reacting with the solid catalyst component (A) will be explained.

The reaction is carried out in an atmosphere sufficiently excluded from moisture and oxygen in an inert hydrocarbon medium such as aliphatic hydrocarbons such as hexane, heptane, benzene,
The reaction can be carried out in an aromatic hydrocarbon such as toluene or xylene, or an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or a mixed medium thereof. From the viewpoint of catalytic performance, an aliphatic hydrocarbon medium is preferably used. The reaction temperature is not particularly limited and can be carried out at a commonly used temperature, for example between room temperature and 100°C, but is preferably carried out at a temperature of 20 to 60°C in view of the progress of the reaction. There is no particular restriction on the reaction ratio of the two components, but preferably the reaction ratio is based on the number of Mg atoms in the hydrocarbon-soluble component.
A ratio of Cl atoms of 6 to 20, particularly preferably 8 to 12, is recommended. Regarding the reaction method, there is a simultaneous addition method in which the two types of catalyst components are simultaneously introduced into the reaction zone and reacted, or a method in which the first type of catalyst component is charged into the reaction zone in advance, and then the remaining catalyst components are introduced into the reaction zone. Any of the so-called forward (reverse) addition methods, in which the reaction is carried out while reacting, is possible and gives preferable results.

Next, a method of combining the solid catalyst component (A) obtained by the above reaction with the organometallic compound (B) will be explained.

The solid catalyst component (A) and the organometallic compound (B) are:
They may be added to the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. It is also possible to use a method in which the solid catalyst component is previously treated with the organometallic compound and then combined with the organometallic compound and fed into the polymerization system. The ratio of both components to be combined is (organometallic)/
A molar ratio of Ti in the range of 0.01 to 3000 is recommended.

Next, a method for polymerizing olefin using the catalyst of the present invention will be explained.

Olefins that can be polymerized using the catalysts of the invention are alpha-olefins, especially ethylene. Furthermore, the catalyst of the present invention can also be used for copolymerization of ethylene with monoolefins such as propylene, butene-1, hexene-1, etc., or for polymerization in the coexistence of dienes such as butadiene, isoprene, etc.

By carrying out copolymerization using the catalyst of the present invention, it is possible to produce polymers with a density in the range of 0.91 to 0.97 g/cm ³ .

As the polymerization method, usual suspension polymerization, solution polymerization, and gas phase polymerization are possible. In the case of suspension polymerization or solution polymerization, the catalyst is a polymerization solvent such as propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into the reactor under an inert atmosphere. By pressurizing ethylene at 1 to 200 kg/cm ² to the bottom, polymerization can be carried out at a temperature of room temperature to 320°C. It is also possible to apply a so-called high-pressure polymerization method in which polymerization is carried out using a tubular reactor, an autoclave reactor, an autoclave to a tubular reactor, etc. at a pressure of 200 to 2000 Kg/cm ² and a temperature of 150 to 300°C. It is.

On the other hand, in gas phase polymerization, ethylene is heated at a pressure of 1 to 50 kg/cm ² at a temperature of room temperature to 120°C, using a fluidized bed, moving bed, etc. to ensure good contact between ethylene and the catalyst.
Alternatively, polymerization can be carried out by mixing by stirring or the like.

The polymerization may be carried out in a conventional one-stage polymerization using one reaction zone, or using multiple reaction zones.
It may also be carried out by so-called multi-stage polymerization. The catalyst of the present invention is highly active, and the step of removing catalyst residue from the produced polymer can naturally be omitted. Furthermore, the polymer polymerized using the catalyst of the present invention can be
Even stage polymerization has a relatively wide molecular weight distribution, and in particular, by applying multistage polymerization in which polymerization is performed under two or more different reaction conditions, it is possible to produce polymers with an even wider molecular weight distribution, making it suitable for blow molding and extrusion molding applications. It is extremely suitable for

In order to adjust the molecular weight of the polymer, it is of course possible to use known techniques such as adjusting the polymerization temperature, adding hydrogen to the polymerization system, or adding an organometallic compound that tends to cause chain transfer. Furthermore, it is also possible to perform polymerization by combining methods such as adding a titanate ester to control density and molecular weight.

(Effect of the invention) In catalyst production, when synthesizing a specific titanium-containing hydrocarbon-soluble magnesium component homogeneous solution,
Using the method of the present invention, the amount of organoaluminum compound used can be reduced. That is, according to the conventional technique disclosed in JP-A-61-250004, for example, when n-propyl alcohol is used as the alcohol, α=Al/Mg=0.5.
is a practical limit, and as is clear from the comparative examples described below, when α=Al/Mg=0.33, a homogeneous solution of the titanium-containing hydrocarbon-soluble magnesium component cannot be obtained. On the other hand, if the method of the present invention is used, that is, n-butyl alcohol is used as the specific alcohol species, α=Al/Mg=0.33 as shown in the example below.
Even if the amount of organoaluminum compounds is reduced to
A homogeneous titanium-containing hydrocarbon-soluble magnesium component solution can be obtained.

Certain alcohols, i.e. n-
The fact that the amount of organoaluminum compound used can be reduced by selecting butyl alcohol as described above is not disclosed at all in the above-mentioned JP-A-61-250004, and is a surprising discovery. According to this selective invention, the amount of organoaluminum compound used can be reduced, and as a result, a decrease in the magnesium concentration due to dilution is prevented, so that the amount of catalyst produced per unit capacity of the reactor can be increased. This has great industrial advantages, such as reduction in catalyst production costs and miniaturization of catalyst synthesis equipment.

(Examples) Examples of the present invention will be shown below, but the present invention is not limited to these Examples in any way.

In addition, catalyst activity in the examples refers to monomer pressure.
At 10Kg/cm ² , it represents the amount of polymer produced (g) per 1g of catalyst solid component per hour. Also, MI
represents melt index, ASTM D-
1238, measured at a temperature of 190°C and a load of 2.16 kg. FR has a temperature of 190℃ and a load of 21.6Kg.
It is the quotient obtained by dividing the value measured by MI by MI, and is known to those skilled in the art as an index representing the breadth of molecular weight distribution.

[Example 1] 1 Synthesis of titanium-containing hydrocarbon-soluble component (1-1) Synthesis of raw material solution 0.64 mol/butylethylmagnesium
390.6 ml (250 mmol) and 83.3 ml of a hexane solution of 1.0 mol/triisobutylaluminum
(83.3 mmol) (Al/Mg=0.33). This solution was concentrated to a (Mg+Al) concentration of 1 mol/min to obtain a raw material solution.

(1-2) Synthesis of titanium-containing hydrocarbon-soluble component The above (1-2) containing 30 mmol of magnesium
8.2 ml (90 mmol) of n-butyl alcohol and 8.2 ml of hexane were added to 40 ml of the raw material solution synthesized in 1) so as to maintain the temperature at 35°C, and the mixture was heated at 50°C for 1 hour. Furthermore, 3 ml (3 mmol) of 1 mol/tetra n-butoxytitanium was added dropwise.

The resulting solution was a homogeneous, colorless and transparent hydrocarbon solution. The magnesium concentration in the solution at this time was 0.5 mol/.

2 Synthesis of solid catalyst component 70.6 ml (120 mmol) of 1.7 mol/ethyl aluminum dichloride was added dropwise to the titanium-containing hydrocarbon soluble component obtained in (1-2) at about 25°C, and further aged at 50°C for 2 hours. A brown slurry was obtained.

The obtained brown slurry was decanted to sufficiently remove the Al component in the liquid phase to obtain a solid catalyst component (A). The amount of Ti in this solid catalyst is
It was 3.4wt%.

3 Polymerization A slurry containing 2 mg of the solid catalyst component (A) synthesized in 2 and 0.20 mmol of triisobutylaluminum as the organometallic compound (B) were mixed with 0.8 of hexane obtained by dehydrating and deoxygenating the inside of the slurry, which was vacuum degassed and replaced with nitrogen. was placed in an autoclave.
Keep the internal temperature of the autoclave at 80℃ and add hydrogen to
Add Kg/cm ² and add ethylene to bring the total pressure to 10Kg/cm ²
And so. The total pressure is increased by replenishing ethylene.
Polymerization was carried out for 1 hour while maintaining the temperature at 10Kg/cm ² and 100g
of polymer was obtained. Catalytic activity is 50000g/g-
The solid catalyst hr and MI were 0.66 and FR42.

[Comparative example]

Raw material solution 40 synthesized in (1-1) of Example-1
ml (α=Al/Mg=0.33, 30 as magnesium
mmol) to 6.7 ml (90 mmol) of n-propyl alcohol.
mmol) was added together with 9.7 ml of hexane to maintain the temperature at 35°C, and the mixture was aged at 50°C for 1 hour. Furthermore,
3 ml of 1 mol/tetra n-butoxy titanium (3
mmol) was added dropwise.

In the resulting reaction mixture, a jelly-like substance precipitated and a homogeneous solution could not be obtained, and the subsequent solid catalyst component (A)
It could not be used for the synthesis of

[Example 2] In Example-1, when synthesizing the raw material solution of (1-1), 34.5 g of di-n-butylmagnesium
(250 mmol) and triethylaluminum 9.5 g
(83.3 mmol) and added hexane to make the total volume 333.3 ml (α=Al/Mg=0.33), (Mg+
Synthesis and polymerization were carried out in the same manner as in Example 1 except that the Al) concentration was set to 1 mol/mol.

Polymer yield is 110g, catalyst activity 55000g/g-
The solid catalyst was hr, MI0.85, and FR41.

[Example 3] In Example-1, the n-
Synthesis and polymerization were carried out in the same manner as in Example 1, except that the amount of butyl alcohol was changed to 6.6 ml (72 mmol).

Polymer yield was 90 g, catalyst activity 45000 g/g-solid catalyst/hr, MI 0.96, FR 40.

[Brief explanation of the drawing]

FIG. 1 is a schematic flowchart illustrating aspects of the present invention.

Claims (1)

[Claims] 1 (A) (i) (a) General formula MgAl〓R ¹ _p R ² _q (OR ³ ) _r
(In the formula, α is 0<α≦2, p and q are numbers larger than 0, r is 0 or a number larger than 0, and has the relationship p+q+r=2+3α,
R ¹ and R ² are the same or different alkyl groups having 1 to 8 carbon atoms, R ³ is 4 carbon atoms
(b) n-butyl alcohol (c) an alkoxide of a transition metal selected from titanium, zirconium and vanadium (a), (b) ), (c) to (a), (b), (c) or (b),
A hydrocarbon soluble component obtained by mixing and reacting in the order of (a) and (c), and (ii) general formula AlR ⁴ _3-o Xn (where R ⁴ is a hydrocarbon group and X is is a halogen, and n is 1≦n
Polymerization of olefin characterized by using a catalyst consisting of a solid catalyst component (A) obtained by reacting a halogenated organoaluminum compound represented by a value of ≦2) and (B) an organometallic compound. Method. 2. The polymerization method according to claim 1, wherein the transition metal alkoxide of component (c) is a titanium alkoxide. 3. The polymerization method according to claim 1 or 2, wherein the organometallic compound (B) is an organoaluminum compound.