JPS5812885B2 - Polyolefin Inno Seizouhouhou - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel method for polymerizing olefins.

More specifically, the present invention provides (1) a substantially anhydrous magnesium halide and/or a manganese halide, (2) a halide of a metal selected from the group consisting of nickel, cobalt and iron, and (3) 4 Olefin is polymerized or copolymerized using a solid component obtained by co-pulverizing a titanium and/or vanadium compound with an organoaluminum compound and/or an organozinc compound as a catalyst, and the polymer yield per solid component and the titanium or The present invention relates to an olefin polymerization method characterized by increasing the polymer yield per vanadium, thereby eliminating the need for a step of removing catalyst residues from the polymer, and significantly increasing the molecular weight of the resulting polymer.

Conventionally, in this type of technical field, inorganic magnesium solids such as magnesium halides, magnesium oxides, and magnesium hydroxides are used as carriers, and organic aluminum compounds are combined with solid components that support transition metal compounds such as titanium or vanadium. Many catalysts are known.

(Japanese Patent Publication No. 43-13050, Publication No. 9548-1973, and others).

The polyolefin obtained using these carriers is
The ability to easily adjust the required molecular weight, or melt index, by adjusting the hydroxyl concentration, polymerization temperature, etc. is a great practical advantage, and the melt index can be adjusted in various fields such as injection molding, extrusion molding, and blow molding. It is widely used as a method to

On the other hand, a highly active catalyst that provides polyolefin with a sufficiently higher molecular weight than the above-mentioned catalyst using a magnesium compound as a carrier has been strongly desired from the standpoint of polymer design.

However, as a supported Ziegler catalyst that provides a high molecular weight, for example, a catalyst system in which titanium tetrachloride is supported on activated alumina (Japanese Patent Application Laid-Open No. 47-1096) is known, but it is still insufficient in terms of activity. there were.

As a result of intensive research to achieve the above-mentioned request, the present inventors have found that (1) substantially anhydrous magnesium halide and/or manganese halide (2) nickel, cobalt, and iron. Polymerization or copolymerization of olefins using a solid component obtained by co-pulverizing a metal halide, and (3) a compound of tetravalent titanium and/or vanadium, and an organoaluminium compound and/or an organozinc compound as a catalyst. or by copolymerizing olefins and diolefins, highly active polyolefins with a significantly lower melt index can be produced than when using catalysts without added halides of metals selected from the group consisting of nickel, cobalt, and iron. The present invention was completed based on the discovery that the present invention can be obtained using the following methods.

When an olefin is polymerized using a solid component obtained by milling compounds of magnesium halide and/or manganese halide, and titanium and/or vanadium and an organoaluminum compound and/or organozinc compound as a catalyst, a polyolefin with a relatively high melt index is produced. is obtained.

The present invention is produced by co-pulverizing a compound of magnesium halide, manganese halide, titanium and/or vanadium, and further adding a halide of a metal selected from the group consisting of nickel, cobalt and iron. We have discovered that when olefins are polymerized using solid components such as olefins and organoaluminum compounds and/or organozinc compounds as catalysts, the catalytic activity is further increased and a polyolefin with a significantly high molecular weight, that is, a significantly low melt index, can be obtained. be.

This fact is completely unexpected based on the conventional technical content and must be called surprising.

When the catalyst of the present invention is used, the polyolefin having a tart index of 0.001 or less can be produced even under polymerization conditions where a conventional catalyst using a solid carrier containing a magnesium compound yields a polyolefin having a melt index of about 5. It is surprising that the catalyst of the present invention can be produced in various polymer designs, for example, with a melt index of about 0.3, by combining the catalyst of the present invention with other catalysts. It is possible to control the molecular weight by producing not only a blow molding grade polyolefin but also a high molecular weight blow molding grade polyolefin with a melt index of 0.1 or less.

Another advantage of the present invention is that the required amount of reagents are co-pulverized using a ball mill or the like during catalyst production, so there is no need for a cleaning and removal process during the production process, and disposal of solutions containing transition metal compounds, which has become a problem in recent years. There's no need to worry about that.

As the magnesium halide used in the present invention, substantially anhydrous compounds such as magnesium chloride, magnesium fluoride, magnesium bromide, magnesium iodide, and mixtures thereof are used, and magnesium chloride is particularly preferably used.

As the manganese halide used in the present invention, manganese chloride is most preferably used.

Mixtures of magnesium halides and manganese halides are also preferably used in the present invention.

Examples of the nickel halide used in the present invention include nickel fluoride, nickel chloride, nickel bromide, and nickel iodide, but nickel chloride is particularly preferably used.

Examples of the cobalt halide used in the present invention include cobalt fluoride, cobalt chloride, cobalt bromide, and cobalt iodide, and cobalt chloride is particularly preferably used.

The iron halides used in the present invention include ferrous fluoride, ferric fluoride, ferrous chloride, ferric chloride, ferrous bromide, ferric bromide, and ferrous iodide. , ferric iodide.

Of course, these halides of nickel, cobalt, and iron can be suitably used not only individually but also as a mixture.

The tetravalent titanium compounds used in the present invention are not particularly limited, but include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, Examples include diisopropoxydichlorotitanium, reaction products of silicon tetrachloride and titanium alkoxide, and mixtures thereof.

The vanadium compound used in the present invention is not particularly limited, but examples include vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and the like.

Of course, there is no problem in using it in combination with the above-mentioned titanium compounds, and for example, titanium tetrachloride and vanadium tetrachloride are often used in combination.

(1) Magnesium halide and hydrogen in the present invention
Mata is a manganese halide, (2) a halide of a metal selected from the group consisting of nickel, cobalt and iron;
and (3) the order of co-pulverization of tetravalent titanium and/or vanadium compounds is not particularly limited, and it may be carried out while all the components are co-pulverized at the same time, or magnesium halide and/or halogenated Manganese and a halide of a metal selected from the group consisting of nickel, cobalt, and iron may be co-pulverized, and then a compound of tetravalent titanium and/or vanadium may be added thereto for further co-pulverization. A halide of a metal selected from the group consisting of cobalt and iron and a compound of tetravalent titanium and/or vanadium may be co-pulverized, and then magnesium halide and/or manganese halide may be added and further co-pulverized. and magnesium halide and/or manganese halide.
It may be co-milled with a compound of titanium and/or vanadium of valence, and then a halide of a metal selected from the group consisting of nickel, cobalt and iron may be added and further co-milled.

Of course, these operations should be carried out in an inert gas atmosphere, and moisture should be avoided as much as possible.

(1) Magnesium halide and/or manganese halide (2) The mixing ratio of halides of metals far from the group consisting of nickel, cobalt and iron can be varied over a wide range; for example, (2):(1) molar ratio but]:
A range of 100 to 100:1 can be achieved.

Since the melt index of the resulting polymer tends to decrease as the mixing ratio of component (2) increases, it is possible to adjust the polymer having a desired melt index by adjusting the content of component (2).

Of course, in all cases, it is natural that the melt index will be lower than when the component (2) is not present.

The amount of the tetravalent titanium and/or vanadium compound to be supported is preferably adjusted so that the titanium and/or vanadium contained in the produced solid is within the range of 0.05 to 20% by weight, and a well-balanced result is obtained. In order to obtain an activity per titanium and/or vanadium, and an activity per solid component, a range of 0.5 to 10% by weight is particularly desirable.

Of course, it is necessary to select the mixing ratio of each component such that a solid powder is finally obtained from the viewpoint of catalyst handling.

The equipment used for co-grinding is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and conditions such as mixing order, grinding time, grinding temperature, etc. depending on the grinding method are easily determined by those skilled in the art. It is determined.

The olefin polymerization reaction using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst.

In other words, all reactions are carried out in the absence of oxygen, water, etc.

The polymerization conditions for olefin are as follows: the temperature is 20 to 300°C, preferably 50 to 180°C, and the pressure is normal pressure (70 kg/cwt, preferably 2 to 60 kg/cwt).
It is ca.

The method of the present invention is applicable to the polymerization of all olefins that can be carried out using Ziegler's catalyst, such as the homopolymerization of ethylene, propylene, and 1-7" alpha-olefins, as well as the homopolymerization of ethylene and propylene, ethylene and 1-7" It is suitably used in the copolymerization of fluoropyrene and 1-butene, and when the purpose is to modify polyolefins, copolymerization with dienes, such as copolymerization of ethylene and butene, ethylene and 1,4 hexadiene, etc. is also preferable. It is done.

As the organometallic compound used in the present invention, organometallic compounds belonging to Groups 1 to 2 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but organoaluminum and organozinc compounds are particularly preferred.

Specific examples include general formulas R5Al, R2AIX, RA
IX2, R2AIOR. RAI(OR)X and R3
An organoaluminum compound of Al2X3 (wherein R is an alkyl group or an aryl group, X is a /.rogen atom, and R may be the same or different) or a general formula R2
Organozinc compounds of Zn (R is an alkyl group and may be the same or different) such as triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminium chloride, ethylaluminum Examples include sesquichloride, diethylzinc, and mixtures thereof.

In the present invention, the amount of these organometallic compounds to be used is not particularly limited, but is usually 0% relative to the transition metal/loginide.
．． 1 to 1000 mo can be used.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Preparation of catalyst Commercially available anhydrous magnesium chloride (HCI) at 350°C in a gas stream
treated for 16 hours) 3. OS', the best commercially available anhydrous nickel chloride (vacuum dried at 200°C for 4 hours) 6.5
Inner volume 4 containing 25 stainless steel balls with a diameter of 10 inches and 0.61 g of titanium tetrachloride.
The sample was placed in a 00ml stainless steel pot and ball milled for 16 hours at room temperature under a nitrogen atmosphere.

1 g of solid powder obtained after ball milling contains 1 titanium.
．． It contained 5.2m9.

(b) Polymerization A 2 liter stainless steel o-sheet crepe with an induction stirrer was purged with nitrogen, 1000 ml of hexane was added, 2 mmol of triethylaluminum, and 3 ml of the above solid.
g was added thereto, and the temperature was raised to 90°C while stirring.

The vapor pressure of hexane is 2 kg/cm2・G, but hydrogen is added until the total pressure reaches 6kg/cm2・G.
Then, ethylene was charged until the total pressure reached 10 kg/cm2·G to start polymerization.

Ethylene was continuously introduced so that the total pressure was 10 kg/cm2G, and polymerization was carried out for 1 hour.

The polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain 252 g of white polyethylene with a melt index of 0.001 or less.

Catalyst activity is 138000f polyethylene/gTi-h
r-C2H4 pressure, 2100g polyethylene/g solids/h
The r-C2H4 pressure was extremely high.

Comparative Example 1 10 g of magnesium chloride described in Example 1 and 0.91 g of titanium tetrachloride were placed in the Pall Mill pot described in Example 1.
Ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours to obtain a solid powder containing 22 μm of titanium per gram.

Using the above solid 30~, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain 150 g of white polyethylene with a melt index of 6.0.

Catalyst activity is 57900g polyethylene/gTi-hr-
C2H4 pressure, 1250f polyethylene/g solids hr.
At C2H4 pressure, the activity was lower than in Example 1, and the melt index was significantly higher.

Comparative Example 2 6.5 g of nickel chloride used in Example 1 and 0.6 g of titanium tetrachloride were added to the Pall mill pot described in Example 1.
Ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a solid powder containing 20.2 mg of titanium per gram.

Using 60 m of the above solid, 1
When time polymerization was performed, the melt index was 0.0.
A polyethylene of 0.01 or less was obtained.

Catalytic activity is 149 (l polyethylene/g Ti-hr-C
2H4 pressure, 30g polyethylene/g solid hr-C2H4
It was pressure.

Example 2 Into the Pall mill pot described in Example 1, 3.0 g of magnesium chloride and 20 g of anhydrous cobalt chloride used in Example 1 were added.
vacuum dried at 0°C for 3 hours) 6.52 and titanium tetrachloride 0. 6? 16 at room temperature under nitrogen atmosphere.
By performing ball milling for an hour, 17cm of titanium is produced in 1g.
A solid powder was obtained containing:

Using 30 mfl of the above solid, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was 0.
283 g of white polyethylene having a molecular weight of 0.001 or less was obtained.

Catalytic activity is 1 39001' polyethylene/gTi・h
r-C2H, pressure, 2360? Polyethylene/g'solid
The pressure was extremely high, hr-C2H4 pressure.

Example 3 Magnesium chloride 3.0? , anhydrous ferric chloride (200
6.5 g of titanium tetrachloride (vacuum dried at
A solid powder was obtained containing:

When the above solid 301n9 was used and polymerization was carried out for 1 hour in the same manner as in Example 1, the melt index was 0.
157 g of white polyethylene having a molecular weight of 0.001 or less was obtained.

Catalytic activity is 79500f polyethylene/gTi-h
The r=C2H4 pressure was extremely high, 1310f polyethylene/g solids/hr-C2H4 pressure.

Comparative Example 3 Magnesium chloride used in Example 1 in the Pall mill pot described in Example 1. Of, 6.5S' of commercially available anhydrous chromium trichloride (vacuum dried at 200°C for 3 hours) and 0.61% of titanium tetrachloride were ball-milled at room temperature under a nitrogen atmosphere for 16 hours to obtain titanium in 1g. 1
A solid powder containing 5.11n9 was obtained.

Using 30 volumes of the above solid, polymerization was carried out for 1 hour in the same manner as in Example 1, and 100 g of white polyethylene with a melt index of 2.7 was obtained.

Catalyst activity is 52200g polyethylene/fITi-hr
-C2H4 pressure, 840g polyethylene/g solid, hr-
The pressure was C2H4.

As described above, the melt index was significantly larger than that of Examples 1, 2, 3, etc.

Example 4 In the ball mill pot described in Example 1, 3.05' of magnesium chloride used in Example 1, 6.5 g of nickel chloride used in Example 1, and 0 titanium tetra n-butoxide were added.
．． 91 and 0.6 f of vanadium tetrachloride were added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a solid powder containing 12.3 to 1 g of titanium.

When polymerization was carried out for 1 hour in the same manner as in Example 1 using the above solid 30~, the melt index was 0.00.
208 g of white polyethylene with a weight of 1 or less was obtained.

Catalyst activity is 141,000g polyethylene/fTi-
The hr-C2H4 pressure was extremely high, 1730g polyethylene/g solid/hr-C2H4 pressure.

Example 5 6.51 of the magnesium chloride used in Example 1, 3.01 of the nickel chloride used in Example 1, and 0.61 of the titanium tetrachloride were placed in the Pall mill pot described in Example 1.
Ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours to obtain a solid powder containing 16.0 to 16.0% titanium per gram.

When polymerization was carried out for 1 hour using the above solid 30rn9 in the same manner as in Example 1, the melt index was 0.
238 g of 40 white polyethylene were obtained.

Catalyst activity is 124,000 g polyethylene/g Ti-hr
-C2H4 pressure, 1980g polyethylene/1 solid/hr
-C2H4 pressure was extremely high.

Example 6 7.5 g of magnesium chloride used in Example 1, 2.0 g of nickel chloride and 0.6 g of titanium tetrachloride used in Example 1 were placed in the Pall mill pot described in Example 1,
Ball milling was performed at room temperature in a nitrogen atmosphere for 16 hours to obtain a solid powder containing 16.3η of titanium in ly.

When polymerization was carried out for 1 hour in the same manner as in Example 1 using 30 ml of the above solid, the melt index was 0.9.
212 g of white polyethylene of No. 6 was obtained.

Catalyst activity is 108,000g polyethylene/Si'Ti
"hr" C2H4 pressure, 1760g polyethylene/
The pressure was extremely high, 3 solids/hr-C2H4 pressure.

Example 7 3.0 g of manganese chloride (a commercially available product vacuum-dried at 200°C for 5 hours) was placed in the Pall mill pot described in Example 1.
6.5 g of nickel chloride and 0.6 g of titanium tetrachloride used in Example 1 were added, and ball milling was performed at room temperature in a nitrogen atmosphere for 16 hours, resulting in a concentration of 15.5 to 15.5 g of titanium in 1 g.
A solid powder was obtained containing:

Using 30 mg of the above solid, 1
When time polymerization was performed, the melt index was 0.0.
124 g of white polyethylene of 0.01 or less was obtained.

Stem activity is 66500g polyethylene/gTi-hr-C
2H4 pressure, 1030P polyethylene/g solid, hr-C
The 2H4 pressure was extremely high.

Comparative Example 4 The manganese chloride lof used in Example 7 and 0.91 of titanium tetrachloride were placed in the Pall mill pot described in Example 1, and ball milling was performed at room temperature in a nitrogen atmosphere for 16 hours. A solid powder containing 20.8 mg of titanium was obtained.

Polymerization was carried out for 1 hour in the same manner as in Example 1 using the above solid 30 to obtain 70 g of white polyethylene with a melt index of 5.1.

Catalytic activity is 27900g polyethylene/CuTi-hr-
C2H4 pressure, 5801 polyethylene/g solids/hr-c
It was 2H4 pressure.

Example 8 Magnesium chloride 3.0? used in Example 1 in the Pall mill pot described in Example 1? , and titanium tetrachloride 0.
61 was added and ball milled for 16 hours at room temperature under a nitrogen atmosphere. Next, 6.5 g of nickel chloride used in Example 1 was added and ball milled for another 16 hours to obtain a solid containing 14.9 mg of titanium in 1 g. A powder was obtained.

When polymerization was carried out for 1 hour in the same manner as in Example 1 using 30 cm of the above solid, the melt index was 0.00.
250 g of white polyethylene of No. 2 was obtained.

Catalytic activity is 140000g polyethylene/gTj・hr
・C2H4 pressure, 2080g polyethylene/g solids・hr
・The C2H4 pressure was extremely high.

Example 9 Using 30 m9 of the solid obtained in Example 1, hexane, triethylaluminum, and a solid catalyst were added in the same manner as in Example 1, and the temperature was raised to 90°C.

Next, hydrogen was pressurized to a total pressure of 6 kg/cm2G, and then an ethylene-propylene mixed gas containing 2 mol% of propylene was supplied to increase the pressure of the autoclave to 10 k.
Polymerization was carried out for 1 hour while maintaining the temperature at g/cm2G, and a white polymer 2711 with a melt index of 0.028 and having 6.7 methyl groups per 1000 carbon atoms was obtained.
I got it.

Catalytic activity is 148,000g polyethylene/gTi・hr
・C2H4 pressure, 2250g polyethylene/g solids・hr
・C2H4 pressure and extremely high activity.

Claims (1)

[Scope of Claims] 1. A method of polymerizing or copolymerizing an olefin using a solid component containing a titanium and/or vanadium compound and an organoaluminum compound and/or an organozinc compound as a catalyst, in which the solid component (1) is substantially Anhydrous magnesium halide and/or magnesium halide is obtained by co-pulverizing a manganese halide (2) a halide of a metal selected from nickel and cobalt (3) a compound of tetravalent titanium and/or vanadium. A method for producing polyolefin.