JPS5812282B2 - Olefuinno Jiyuugohouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for polymerizing olefins in the presence of a Ziegler type catalyst, which is characterized in that a novel solid catalyst component is used as a catalyst component.

In so-called Ziegler-type olefin polymerization catalysts consisting of transition metal halides and organometallic compounds, many efforts have been made to improve catalyst utilization efficiency with the aim of reducing product costs.

That is, many methods have been proposed in which a solid catalyst component is prepared by reacting a transition metal halide with various powdered solid substances, and this is combined with an organometallic compound to form an olefin polymerization catalyst.

As the powdered solid substance, a wide variety of substances can be used, such as organic polymer powders such as polyolefin, polyamide, and polyester, and inorganic oxide powders such as silica, alumina, titamore, zirconia, and thoria.

In particular, various powdered divalent metal compounds, such as divalent metal oxides, hydroxides, halides, sulfates, nitrates, phosphates, and silicates, are considered preferable because of their high catalytic activity. There is.

For example, magnesium hydroxychloride (Belgium Patent No. 650,679), magnesium oxide (Belgium Patent No. 705,220), magnesium sulfate (ibid.), magnesium hydroxide (Japanese Patent Publication No. 45-40295), etc. have been proposed as practically useful solid substances. has been done.

However, when polymers are produced with Ziegler-type catalysts prepared using these solid materials, it is necessary to remove the catalyst from the polymer in order to obtain a commercially valuable product; It is industrially extremely difficult to extract and remove solid catalyst components, and practically impossible.

On the other hand, it can be a particularly advantageous polymerization method if further processing is possible without removing the catalyst from the polymer.

However, this can only be achieved if high polymer yields are obtained per unit of catalyst.

Ziegler type catalysts prepared using the various powdered solid substances proposed above have higher catalytic activity than normal Ziegler type catalysts that do not use powdered solid substances, and have a higher catalytic activity per unit weight of transition metal halide. Polymer yields have increased significantly, but in many cases it is still not sufficient, and if the produced polymer is used unpurified, the transition metal halides remaining in the polymer will cause generation problems in processing machinery. Rust, discoloration, and deterioration of molded products may occur.

Furthermore, the low polymer yield per unit weight of the solid catalyst component results in a high ash content due to the powdery solid material in the polymer, resulting in so-called fish formation in molded articles made from these polymers. It has disadvantages that cause undesirable effects such as eye formation, thread breakage, and coloring.

The present inventors have developed a catalyst consisting of a solid catalyst component obtained by reacting a solid substance with a halide of a transitional metal represented by titanium and vanadium, and an organometallic compound represented by an organoaluminium compound and a dialkylzinc. The present invention was completed based on the discovery that an extremely highly active polymerization catalyst can be obtained by using a special solid catalyst component in a method for polymerizing olefins.

The purpose of the present invention is to obtain a polyolefin with an extremely high production rate per unit weight of transition metal halide and solid catalyst component, and another purpose is to obtain a polyolefin of sufficiently high quality without going through a post-polymerization catalyst removal step. There is a product to obtain polyolefin.

The olefin polymerization method of the present invention is carried out using the following general formula (I) R2N-M. 9-X ・・・・・・(I) (However, R
represents a hydrocarbon group, and X represents a halogen atom or an NR2 group, respectively.

) A solid catalyst component A that is insoluble in an inert hydrocarbon solvent obtained by reacting a nitrogen-containing organomagnesium compound represented by the formula with a liquid titanium or vanadium halide, and a catalyst component B that is an organoaluminum compound and/or dialkylzinc. It is characterized by bringing an olefin into contact with a catalyst consisting of.

The solid catalyst component A used in the present invention, namely:
The solid catalyst component obtained by reacting the nitrogen-containing organomagnesium compound represented by general 2R2N-M9-X with a transition metal halide has a particularly high The formation of a catalytically active catalyst is surprising, but the reason for this is currently unknown.

In this case, it is essential to separate and use only the solid component from the product obtained by reacting the nitrogen-containing organomagnesium compound and the transition metal halide, and the catalyst structure of the present invention Simply mixing the three components results in extremely low catalytic activity.

For example, Japanese Patent Publication No. 46-35847 describes a titanium, vanadium or zirconium halide, b alkyl aluminum dihalide, and C a bond between a magnesium atom and a nitrogen atom or a bond between a zinc atom and a nitrogen atom.
An olefin polymerization catalyst has been proposed that uses a mixture of three components of nitrogen-containing organometallic compounds containing one or more nitrogen-containing organometallic compounds, but its catalytic activity is extremely low compared to the catalyst of the present invention.
The amount of catalyst normally used in the present invention exhibits substantially no catalytic activity.

The nitrogen-containing organomagnesium compound used in the present invention is represented by the general formula R2N-Mg-X as described above, and specific examples thereof include N,N-diethylaminemagnesium chloride, N,N-di-n-butylamino Magnesium chloride, N,N-di-n-butylaminomagnesium bromide, N,N-diphenylaminomagnesium chloride, N,N-diphenylaminomagnesium iodide, bis(N,N-dimethylamino)magnesium, bis(N-diphenylaminomagnesium iodide) , N-di-n-butylamino)magnesium, piperidinomagnesium chloride, and the like.

These nitrogen-containing organomagnesium compounds can be obtained by known production methods; for example, di-n-butylaminomagnesium chloride can be easily obtained by reacting di-n-butylamine and n-butylmagnesium chloride.

Various known methods can be used to produce the solid catalyst component A by reacting these nitrogen-containing organomagnesium compounds with a transition metal halide.

For example, a transition metal halide is added little by little at room temperature to a nitrogen-containing organomagnesium compound diluted with any inert hydrocarbon solvent in the absence of moisture and oxygen, and after the entire amount is added, the reaction is heated at room temperature to 150°C. is common, but a reaction temperature below room temperature may be preferable in some cases.

A reaction time of 5-240 minutes is generally sufficient.

Although it depends on conditions such as the presence or absence of a diluent, in the case of a relatively high reaction temperature of 100°C or higher, a short time is sufficient; if the reaction time is too long, not only will the performance of the catalyst not be improved at all, but the In some cases, it may even deteriorate.

After the reaction is completed, the solid components produced are separated and free transition metal halides are washed away with an inert solvent such as hexane, heptane, kerosene, etc.

Next, the washing liquid is volatilized under a stream of dry inert gas or under reduced pressure, thus obtaining solid catalyst component A.

Of course, it is also possible to use the product directly dispersed in a solvent without removing the solvent after removing the free transition metal halide from the product.

Although the quantitative ratio of the nitrogen-containing organomagnesium compound to the transition metal halide does not need to be particularly limited, the molar ratio of the transition metal halide to the nitrogen-containing organomagnesium compound is generally selected from 0.1 to 50. The transition metal halide used in the production of is a titanium or vanadium halide.

That is, as a titanium halide, the general formula T i
Xn (OR') 4 - n (in the formula, X is a halogen atom, R' is a hydrocarbon residue having 1 to 18 carbon atoms, n is 1,2
, 3 or 4); for example, T i
C 14T iBr4 ,T t (OC2 H5 )
C 13 , T i (OC3 H7) CI+TI(O
C4H9)Cl37Tt(OC2H5)2Ct, ,
Ti(QC3H7)2C12tTi(OC4Ho)2C
Examples of vanadium halides include ■C14 and ■OC13.

The content of the transition metal in the solid catalyst component A obtained by such a method can be adjusted appropriately by changing the reaction conditions (quantity ratio, temperature, time, presence or absence of a solvent, etc.) between the nitrogen-containing organomagnesium compound and the transition metal halide. adjusted to.

Generally, per gram of solid catalyst component, 1-. The amount is preferably 200 mg, and the solid catalyst component A obtained by adjusting the transition metal atomic weight within this range exhibits extremely high catalytic activity.

The organometallic compound which is the catalyst component B combined with the solid catalyst component A has the general formula A I R2n X3 −
n (in the formula, R2 is a hydrocarbon residue having 1 to 18 carbon atoms, X is a halogen atom, a hydrogen atom, or an alkoxy group, and n is 1
, 3/2, 2 or 3 respectively.

) and/or an organoaluminum compound represented by the general formula ZnR32 (wherein R3 represents an alkyl group having 1 to 18 carbon atoms).

) can be used.

Preferred examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, triprobylaluminium, tributylaluminum, diethylaluminum chloride, dibutylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, dibutylaluminum hydride, diethylaluminum ethoxide, and the like. Can be mentioned.

Furthermore, examples of organic zinc compounds include diethylzinc, dibutylzinc, and the like.

In order to polymerize olefin with a catalyst obtained from the solid catalyst component A and the organometallic compound component B that constitute these catalysts, each component is generally charged into a polymerization reactor separately to form a catalyst, or both components are inorganized in advance. A method is used in which a catalyst suspension obtained by reacting in an active solvent is supplied to a polymerization reactor.

The ratio of solid catalyst component A and organometallic compound component B constituting the catalyst used for polymerization of olefin is 1 to 1000 mol of aluminum and/or zinc atoms per 1 mol of transition metal atom.

The amount of the catalyst to be used is that the solid catalyst component A has a concentration of 0.001 to 1 g per 1 liter of solvent or 14 reaction volumes, and the catalyst component B, which is an organometallic compound, has a concentration of 0.1 to 1 g per 1 liter of solvent or 1 liter of reaction volume. 5ommoL especially 0. 2 ~
Used at a concentration of 10 mmol.

The olefins applied to the process of the invention include, for example, alpha-olefins such as ethylene, propylene, butene-1,4-methylpentene-1, in particular ethylene alone or ethylene and small amounts of other alpha-olefins or diolefins, such as Examples include mixtures with propylene, butene-1-butadiene, and the like.

In order to polymerize olefins using the catalyst of the present invention, a method similar to the polymerization of olefins using ordinary Ziegler type catalysts is used.

For example, the catalyst is added and dispersed in a suitable inert hydrocarbon solvent such as hexane, heptane, kerosene, etc., and the olefin is introduced into the solvent to initiate polymerization.

The polymerization temperature is usually 30 to 200°C, preferably 60 to 10°C.
The temperature is 0° C., and the pressure is generally selected from normal pressure to 50 kg/cm 2 .

Molecular weight adjustment when polymerizing olefins in the method of the present invention is possible to some extent by changing polymerization conditions such as polymerization temperature and catalyst component charging ratio, but it can be done effectively by adding hydrogen to the polymerization system. It will be done.

As mentioned above, the advantage of the method of the present invention is that the activity of the catalyst used is extremely high, so that the amount of residual catalyst contained in the resulting polymer is extremely small.

As a result, there are almost no adverse effects caused by the residual catalyst seen in conventional methods, and molded products with excellent color tone and strength can be obtained by processing as is, without taking any special measures to remove the catalyst.

Furthermore, there is almost no corrosive effect on processing machines.

In addition, according to the method of the present invention, the activity of the catalyst changes little during polymerization, and the initial high polymerization activity is maintained for a long time, so stable continuous polymerization is possible, and it is sensitive to molecular weight regulators such as hydrogen. By using a small amount of a molecular weight modifier, the molecular weight of the resulting polymer can be changed over a wide range, making it possible to produce a wide variety of grades.

Examples will be shown below, but the technical scope of the present invention is not limited thereby.

Example 1 (a) Preparation of solid catalyst component A G-n-butylamine 1 dissolved in 150 ml of toluene
0 0 mmol, n at room temperature and nitrogen atmosphere
- 40 ml of tetrahydrofuran solution of butylmagnesium chloride (n-butylmagnesium chloride 1
0. This corresponds to 9 mmol.

) was added little by little and reacted to obtain a homogeneous solution.

Next, 90% of the liquid phase was distilled off under reduced pressure to remove a large amount of tetrahydrofuran and toluene.

The thus obtained di-n-butylaminomagnesium chloride was re-diluted by adding 100 ml of toluene, and then 100 ml of titanium tetrachloride was added little by little without stirring.

The temperature was maintained below 30° C. during the addition of titanium tetrachloride.

Then, the temperature was raised and heated at 70°C for 1 hour.

Immediately after the reaction, the same phase portion produced was separated and washed with n-hexane until no chlorine ions were observed in the washing solution.

When the solid catalyst component A thus obtained was analyzed, it was found that it contained 50.0 to 50.0 titanium per gram of solid catalyst component A.

(1) Ethylene polymerization A 1.2L stainless steel autoclave whose interior was replaced with nitrogen was charged with n-hexane 600, followed by 1.0 mmol of triisobutylaluminum and the above (a).
Solid catalyst component A8 prepared in A suspension of solid catalyst component A in n-hexane corresponding to 2 m9 was successively added.

Next, 3 kg/cm2 of hydrogen was injected, the temperature was raised to 85°C, and then ethylene was continuously introduced for 1 hour while maintaining the total pressure at 9 kg/crtt.

After cooling, the pressure was removed and the polymer slurry was taken out.

The produced polymer was directly separated from the solvent and dried.

157 g of white powdered polyethylene was obtained.

This polyethylene has a tart index MI2 (ASTM-D1238) at 190°C under a 2.16ky load.
D ) measured by the method of -65T was 1.45, and the density was 0.9618 g/cm3.

In this case, the catalyst activity is 384,000 gPE/gTi.
hr and 19,200,9PE/. 9c a t-
Corresponds to h r.

In addition, gPE/,9Ti・hr is the polyethylene yield per 1 g of titanium and 1 hour of polymerization time, and 9PB/gc
a t-hr represents the polyethylene yield per solid catalyst component Ai per hour of polymerization time.

Comparative Example 1 Triisobutylaluminum, di-n-butylaminomagnesium chloride, and titanium tetrachloride were sequentially charged into a polymerization vessel as catalyst components to polymerize ethylene.

That is, the amounts of aluminum and titanium catalyst components were the same as in Example 1 (1.0 mmol and 8.0 mmol, respectively).
This corresponds to 5×10−3 mmol.

), and further, ethylene was polymerized using the same molar amount of magnesium catalyst component with respect to the amount of titanium catalyst component and the other conditions being the same as in Example 1.

Substantially no polyethylene formation was observed.

Comparative Example 2 Ethylaluminum dichloride as organoaluminum compound2. Ethylene was polymerized in the same manner as in Comparative Example 1 except that 5 mm o l and equimolar amount of the magnesium catalyst component were used.

No ethylene absorption was observed and no polymerization activity was observed.

Example 2 (a) Preparation of solid catalyst component A A solid catalyst component was prepared in the same manner as in Example 1, except that diethylaminomagnesium chloride was used as the nitrogen-containing organomagnesium compound and the reaction with titanium tetrachloride was carried out at 90°C for 1 hour. A was prepared.

As a result of analysis, the obtained solid catalyst component A was found to have a concentration of 72 to 1 g.
of titanium.

(1) Polymerization of ethylene Ethylene polymerization was carried out under the same conditions as in Example 1 except that 10 to 10 times of the solid catalyst component A prepared in (a) above was used.

175 g of polyethylene was obtained. ? M1 of the polyethylene was 1.93.

The catalyst activity is 243,000. @PE/gTi・hr
and 17,500,9PE/,9c a t-h
Corresponds to r.

Example 3 (a) Preparation of solid catalyst component A A solid was prepared in the same manner as in Example 1 except that diphenylamine magnesium chloride was used as the nitrogen-containing organomagnesium compound and the reaction with titanium tetrachloride was carried out at 90°C for 2 hours. Catalyst component A was prepared.

As a result of analysis, the obtained solid catalyst component A was found to have a concentration of 136 per gram.
It contained ~ titanium.

(1) Polymerization of ethylene Ethylene polymerization was carried out under the same conditions as in Example 1, except that 48 mg of the solid catalyst component A prepared in (a) above was used.

66g of polyethylene was obtained, and the M■
2 was 0.60.

In addition, the catalyst activity in this case is 10.10051PE/gT
i-hr and 1,3709PE/gc at.
It is hr.

Example 4 (a) Preparation of solid catalyst component A Same as (a) of Example 1 (a) Copolymerization of ethylene and butene-1, except that 3,0g of butene-1 was introduced before the injection of ethylene. When polymerization was carried out under exactly the same conditions as in Example 1, 140 g of powdered polyethylene was obtained.

The M■2 of this polyethylene is 211, which is 0.9 5
It had a density of 30 g/cm3.

In addition, as a result of measurement using infrared absorption spectroscopy, the number of methyl groups with less than 1,000 carbon atoms in the molecular chain was 4.2.
It was confirmed that it is a copolymer of ethylene and butene-1.

The catalyst activity in this case is 3 4 2.0 0 0 g
PE/gTi-hr and 17,100 gPE
/gcat・hr.

Example 5 (a) Preparation of solid catalyst component A 50 ml of vanadium oxytrichloride instead of titanium tetrachloride
Solid catalyst component A was prepared in the same manner as in Example 1.

When the obtained solid catalyst component A was analyzed, it was found that 7
It contained 4Tn9 vanadium.

(1) Polymerization of ethylene Ethylene was polymerized in the same manner as in Example 1, except that the solid catalyst component A16 obtained in (a) above and 1.5 mmol of triisobutylaluminum were used and the amount of hydrogen added was 1 kg/cm2.

66 g of polyethylene of M120.75 was obtained.

Catalytic activity is 55,400gPE/. 9V・hr and 4
, 100iPE/gcat-hr.

Example 6 (1) Polymerization of propylene n-hexane 600 r/ll 1 tri-butylaluminum 2. 0 mmol and 50 mg of the solid catalyst component A produced in Example 1 were sequentially charged into an autoclave.

Next, polymerization was carried out at 65° C. for 1 hour while continuously introducing propylene so that the total pressure was 9 kg/d.

After the polymerization was completed, the pressure was removed, and the reaction product containing polypropylene was poured into a large amount of methanol and stirred.

The solid polymer was then filtered and dried under reduced pressure to obtain 93 g of polypropylene.

The catalyst activity in this case is 37,200.9PP/7Ti
-hr and 1,860gPP/. ! 17cat-hr
corresponds to

In addition,. FPP/gTi・hr is the polypropylene yield per 1 g of titanium and 1 hour of polymerization time, and gPPl
9cat-hr is solid catalyst component A1! ! Each represents the polypropylene yield per hour of polymerization time.

Example 7 (a) Preparation of solid catalyst component A Bis(N,N-di-n-butylamine)magnesium was used as the nitrogen-containing organic magnesium compound, and titanium tetrachloride was reacted in the same manner as in Example 1. .

The solid phase portion produced after the reaction was washed several times with 300 ml of toluene to bring the total volume to 100 ml.

Next, 100 ml of titanium tetrachloride was added, and after reacting at 90° C. for 1 hour, the same post-treatment as in Example 1 was performed to obtain solid catalyst component A.

This component A contained 411n9 titanium per gram.

(Example) Polymerization of ethylene Ethylene was polymerized using 10% of the above solid catalyst component A and using the same conditions as in Example 1 except for the above.

198 g of polyethylene was obtained, and M2 was 1.60.

Claims (1)

[Claims] 1 The following general formula (I) R2N-Mg-X (I) (wherein R represents a hydrocarbon group and X represents a halogen atom or NR2 group, respectively). A solid catalyst component A insoluble in an inert hydrocarbon solvent obtained by reacting the nitrogen-containing organomagnesium compound represented by the above with a liquid titanium or vanadium halide, and a catalyst component B which is an organoaluminium compound and/or dialkylzinc. A method for polymerizing olefin, which comprises bringing olefin into contact with a catalyst.