JPS60133010A - Preparation of titanium or vanadium component of carrier type for ethylene or alpha-olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the catalytic component having no coarse granules, providing a highly stereoregular polymer, by crushing an Mg halide and a liquid volatile additional matter, removing partially the liquid volatile additional matter, crushing them again to give a carrier, supporting Ti, etc. on the carrier. CONSTITUTION:A component consisting of (A) a magnesium halide, and (B) a liquid volatile addition agent (e.g., ethylene dichloride, etc.) is crushed by a ball mill, etc., the component B is at least partially removed out of the system before the crushing is over, they are subjected to crushing operation again to give a crushed material. A titanium compound (e.g., titanium trichloride, etc.) or a vanadium compound is supported on the crushed material, to give the desired component for a catalyst for ethylene or alpha-olefin polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a carrier-type titanium or vanadium component used in combination with an organoaluminum compound as a catalyst for ethylene or α-olefin polymerization, and more specifically, it relates to a method for producing a carrier-type titanium or vanadium component used in combination with an organoaluminum compound as a catalyst for ethylene or α-olefin polymerization. The present invention relates to a method for producing carrier-type titanium or vanadium components suitable for active polymerization.

Research continues into highly active catalysts using so-called supported titanium or vanadium components, in which titanium or vanadium compounds are supported on magnesium halide, as components of catalysts used in combination with organoaluminum compounds to polymerize ethylene or α-olefins. It is being

Among these, a method is known in which a carrier is prepared by adding and co-pulverizing an additive such as an electron donor to magnesium halide, and reacting the carrier with a titanium or vanadium compound to support the carrier.

Furthermore, for the purpose of improving this performance, a method has been proposed in Japanese Patent Application Laid-Open No. 106202, etc. in which liquid additives such as halogenated hydrocarbons and hydrocarbons are added during co-grinding.

Although the effects of these liquid additives are not clear, the addition of liquid additives significantly improves the activity of the catalyst and/or the stereoregularity of the produced polymer. However, while this advantage exists, it has also been recognized that if the amount of liquid additive added during pulverization is increased, the pulverized product becomes lumpy or has a large number of coarse particles, and this improvement has become necessary.

When the number of coarse particles in the pulverized carrier increases, the number of coarse particles also increases in the carrier-type titanium or vanadium component produced from the carrier.

The polymer obtained by polymerization becomes similar in size to the phase-type titanium or vanadium compound according to the amount of polymerization, so in order to obtain a polymer with fewer coarse particles, it is necessary to use a carrier-type titanium or vanadium compound with fewer coarse particles. .

As a result of a detailed study on the effect of adding this liquid additive, we found that by removing at least a portion of the liquid additive from the system during the relatively recovery period of grinding and continuing grinding, the effect of improving catalyst performance can be maintained. By contacting the carrier with a titanium or vanadium compound, a carrier-type titanium or vanadium component with less coarse particles can be obtained, and further, this carrier-type titanium or vanadium component can be obtained by contacting the carrier with a titanium or vanadium compound. By using it as a component of a catalyst for polymerization, it has become possible to produce polyolefins with fewer coarse particles.

As (1) magnesium halide used to prepare the carrier of the present invention, substantially anhydrous magnesium halide is used, and magnesium chloride and magnesium bromide are particularly preferred.

The liquid volatile component of (2) has a boiling point of 5 mm lI
A component having a boiling point lower than about 100°C under reduced pressure of Q is used. However, even if the boiling point falls within this range, compounds whose entire amount reacts or coordinates with the pulverized raw material such as magnesium halide during pulverization and change into components that are difficult to volatilize are excluded.

The compound used as the component (2) may be any compound having the above-mentioned boiling point, preferably hydrocarbons, halogenated hydrocarbons, liquid halogen compounds, etc. For example, pentane, hexane, heptane, benzene, toluene, etc. , chlorobenzene, methylene chloride, chloroform, carbon tetrachloride, methylene bromide, ethylene dichloride, ethyl bromide, n-butyl chloride, silicon tetrachloride, tin tetrachloride, and the like.

(2) The amount of component used is 1 part of magnesium halide (
0.01 to 0.5 part based on weight), preferably 0.0
5~('1.3 parts) In the present invention, in addition to (1) and (2), a component that is difficult to volatilize,
Or magnesium halide, or a compound that reacts or coordinates with other additives and changes into a component that is difficult to volatilize (
3) may be co-pulverized. A representative example of such a compound is an electron-donating compound.

Examples of electron-donating compounds include O, N, P, S, S, etc., such as etheno-1 ketone, aldehyde, amine, amide, nitrile, thioester,
Examples include thioethers and orthocarboxylic acid esters of esters.

Examples of specific compounds include methyl formate, n-butyl formate, ethinoacetate, allyl acetate, 2-ethylhexyl butyrate, ethyl valerate-methyl acrylate, n-butyl crotonate, methyl chloroacetate, ethyl dichloroacetate, and benzoic acid. Methyl, ethyl benzoate, n- or leupropyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, styryl benzoate, ethyl salicylate, methyl p-oxybenzoate, cyclohexyl p-oxybenzoate, anisic acid Methyl, anisic acid -=-
Butyl, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, p-)phenyl toluate, ethyl p-aminobenzoate, dimethyl terephthalate, methyl cyclohexanecarboxylate, methylcyclohexanecarboxylate, trimethyl phosphite,
Triphenyl phosphite, diphenylethyl phosphite, diethyl benzyl phosphite, dipropyl sulfate, isoaminobenzene sulfite, isoamyl nitrite, phenyl silicate, ethyl silicate, methyl ethyl ether, diethyl ether, siphthyl ether, diisoamyl ether, diphenyl ether, ditri ether, acetone, methyl ethyl ether, acetaldehyde, isobutyraldehyde, ethylamine, n-propylamine, aniline,
N-methylaniline, 2.2.6.6-titramethylpiperazine, ethanenitrile, pentanedinitrile, propylamine, pentanediamide, allylbenzylsulfite, methyl orthobenzoate, ethyl orthobenzoate, methyl orthotoluate , methyl orthoanisate,
Examples include methyl orthonaphthoate, methyl orthoformate, and ethyl orthoacetate.

These electron-donating compounds can be used alone or in combination of two or more.

Even so-called electron-donating compounds can be used as a type of liquid volatile additive used in the present invention if they have a low boiling point and do not coordinate with magnesium halide under pulverization conditions.

In the method of the present invention, co-pulverization of (1), (2) and, if necessary, (3) is first performed. The pulverizer used for this pulverization may be a conventional pulverizer used for pulverizing powder, such as a ball mill or a vibration mill. The grinding operation must be carried out in a vacuum or in an inert gas atmosphere, with moisture, oxygen, etc. almost completely removed.

There are no particular restrictions on the pulverization conditions, but the temperature is generally in the range of about 0°C to 100°C, and the pulverization time varies depending on the type of pulverizer, but is usually about 2 to 100 hours.

The ratio of volatile additive (2) to magnesium halide (1) during pulverization is 100% magnesium halide.
The amount is about 0.5 to 50 parts.

After pulverization, a part of the volatile additive is removed (operation is carried out. This operation is not particularly limited, but the pulverization may be stopped while the pulverization is being carried out, or the powder may be removed from the pulverizer and the pulverized material may be heated. Generally, the method is to reduce the pressure, to pass an inert gas, or to use a combination of these methods.

The rate at which volatile additives are removed varies depending on the amount of volatile additives initially added, but it is generally preferable to remove 5% or more, preferably 10% or more.

After removing the volatile additives, grinding is carried out again.

The grinding process is carried out for more than one hour using the equipment and method described above.

A carrier with few coarse particles is prepared by the above operations, and then a titanium or vanadium compound is supported.

The titanium compound is supported on the carrier by a commonly known method. Typical methods include (a) a method of pulverizing the carrier and the titanium or vanadium compound; and (b) a method of bringing the carrier and the titanium or vanadium compound into contact under conditions other than pulverization.

In method (a), the carrier and the titanium or vanadium compound are pulverized in the same manner as the method of pulverizing the carrier.

In the method (b), the carrier prepared as described above is brought into contact with a titanium or vanadium compound.

In this treatment, the support is suspended in a titanium or vanadium compound, or an inert solution thereof, and brought into contact at a temperature of 0°C to 200°C, preferably 50 to 135°C. If necessary, the solid material may be separated and dried or washed with an inert solvent to remove free titanium halides.

The titanium or vanadium compound used in this cooperating operation includes titanium tetrachloride, titanium tetrabromide, n-nipoxytrichlorotitanium, vanadium tetrachloride, vanadyl oxychloride, titanium trichloride, and the like. The inert solvent used during washing is an aliphatic, alicyclic, or aromatic hydrocarbon, or a halogen derivative thereof, or a mixture thereof.

The carrier-type titanium or vanadium component prepared as described above can be used in the polymerization and copolymerization of ethylene or α-olefin in combination with an organoaluminum compound, or in combination with an organoaluminum compound and an electron donor.

The organoaluminum compound has the general formula A l RmX3-m
(However, R is an alkyl group or aryl group having 1 to 12 carbon atoms, X is hydrogen, halogen, or an alkoxy group, m is 1 (m
(3), for example, trimethylaluminum 1. triethylaluminum, )IJ −
11-furobylaluminum, tri-i, r-loafylaluminum,) IJ-n-hexylaluminum,
Diethyl aluminum monochloride, G-L-1er
- One or two types of butylaluminium Σ chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, diethylaluminum monochloride, diethylaluminum monoiodide, diethylaluminium monofluoride, diethylaluminium hydride, diethylaluminum ethoxide, etc. Use the above mixture.

The type of organoaluminum compound used in combination can be varied over a wide range, but it is generally preferred that the mole ratio of the carrier type titanium or vanadium component to titanium or vanadylram is in the range of 1 to 500.

As the electron carrier compound added if necessary during polymerization, the same compound as that used in preparing the carrier is used, and organic acid esters are particularly preferably used.

Examples of the organic acid ester include methyl benzoate, ethyl benzoate, methyl p-)ruylate, ethyl p-1-ruylate, methyl anisate, and ethyl anisate. The amount used is 5 mol or less, preferably 1.5 mol or less per 1 mol of organoaluminum compound.

When polymerizing an α-olefin to form a stereoregular polymer, it is preferable to add an electron-donating compound during the polymerization.

The organoaluminum compound and electron donor in the polymerization reaction may be added at the beginning of the polymerization, or both or one of the components may be added during the polymerization. Further, when the polymerization reaction is carried out continuously in multiple tanks, it is also possible to freely add both or one of the components to the multiple tanks.

A polymerization reaction method using a catalyst prepared by the method of the present invention in combination with a carrier-type titanium or vanadium component, an organoaluminum compound, and, if necessary, an electron-donating compound will be described.

The polymerization reaction is carried out using ethylene or the general formula R1'-CH=CH2 (
However, R1 represents an alkyl group having 1 to 10 carbon atoms), such as propylene, butene-1
, hexeno-1,4-methyl-pentene-1, etc., and random or block copolymerization of the above α-olefins or ethylene.

As for random or block copolymerization, all known polymerization methods conventionally carried out using Ziegler and Natsuta catalysts can be used.

For the polymerization reaction using the catalyst component prepared by the method of the present invention, methods and conditions commonly used in the prior art can be employed. The polymerization temperature at that time is 20 to 100°C1
Preferably, the temperature is in the range of 40 to 90°C, and the polymerization pressure is usually 1 to 100 to 9ΔJabs, preferably 1 to 5 ('1 k
g/εrIabs. In the polymerization reaction, aliphatic, alicyclic, aromatic hydrocarbons or mixtures thereof can generally be used as a solvent, such as propane, butane, pentane, hexane, hebutane, cyclohexane, benzene, etc., and mixtures thereof. In addition, bulk polymerization methods that use the liquid monomer itself as a solvent, so-called gas phase polymerization methods that contact the gaseous monomer with a catalyst, and furthermore, Polymerization can also be carried out in a combination of polymerization methods.

Furthermore, polymerization can be carried out freely by treating the catalyst system with a small amount of olefin, by changing the polymerization temperature or /' and conditions, or by changing the hydrogen concentration during the polymerization.

In the polymerization reaction, the molecular weight of the produced polymer varies depending on the reaction mode, catalyst system, and polymerization conditions, but can be controlled by adding hydrogen, alkyl halide, dialkylzinc, etc., if necessary.

The catalyst prepared by the method of the present invention, in which a carrier-type titanium or vanadium component is added to an organoaluminum compound and, if necessary, Denshi 4, can obtain a highly active polymer with few coarse particles, and in the production process, it is possible to obtain a polymer with a small amount of coarse particles. Various troubles caused by coarse particles due to movement etc. are eliminated.

Example 1 (1) Preparation of carrier A vibratory mill equipped with a grinding pot having an internal volume of 600 m1 and containing 80 steel balls with a diameter of 12 mm is prepared.

Anhydrous magnesium chloride 4 was added to this pot in a nitrogen atmosphere.
(1. Add 1 (l) of ethylene dichloride and heat at 30℃ for 20 minutes.
Time crushed. (This is considered as a pulverized product.) The carrier raw material was taken out from the pot and heated at 5,000 °C for 1
heated for an hour. The analytical values of ethylene dichloride before and after heating are shown below.

Ethylene dichloride content (wt%) before heating 19.
5 After heating 4.0 After heating 8 of ethylene dichloride which is a liquid volatile component
3.5% were excluded. Next, the heated carrier raw material was put back into the pot and pulverized for 2 hours. (This is used as a treated carrier) (2) Following preparation of carrier-type titanium component (1), the composition of titanium trichloride (TLC4 reduced and ground with metal aluminum is rTLc13.] -klc11.) 2.91' Add tg to the treated carrier and add 3
The powder was ground at 0'C for 3 hours to obtain a carrier-type titanium component. This titanium content was 1.61 wt%.

(3) Polymerization of ethylene 11 n-hebutane in a 21 autoclave made of 5O8-32
The carrier type titanium component prepared in (2) is 0.1.0! ;2,
) IJ-L, atp-butylaluminum n, 5ml
was added in a nitrogen stream. After evacuating the nitrogen in the autoclave with a vacuum pump, hydrogen was added at a gas phase partial pressure of 4,5 k.
gArl was charged, and then ethylene was charged to set the pressure in the gas phase to 6.5 kg/'cJ gauge.

After heating the autoclave, the internal temperature reaches 90° after 15 minutes.
The temperature was raised to 90°C and the polymerization pressure was 9.5 kgAr.
While charging ethylene to maintain the A gauge, the polymerization was
It lasted for hours.

After the autoclave was cooled, unreacted ethylene was purged and the contents were taken out and filtered to obtain 505 g of white powdery polyethylene.

The bulk specific gravity of this polyethylene was n, 4oq7; nξ intrinsic viscosity was ], 10 dA/9 (measured at 135° C. with a tetralin solution, below U).

The polymerization activity of the catalyst in this polymerization was 2525 r/'r-ca.
t・hr (cat indicates carrier-type titanium or vanadium component +. The same applies hereinafter), the amount of polyethylene obtained is 50509
/' Ku Cat, 304 kg/9-T #.

In addition, the particle size distribution of the obtained polyethylene was measured, and found that coarse particles of 10 m1 iL or more were 0.0%, 10 to 2 Q m<
The coarse particles of il- were 1.8%.

Comparative Example 1 2.812 kg of titanium trichloride used in Example 1 was added to a treated carrier obtained by omitting the heat treatment at 50°C in a nitrogen stream in the method for preparing the carrier in (1) of Example. 30
'C It was ground for 3 hours to obtain a carrier-type titanium component. When this phase-type titanium component was taken out, lumps (titanium content: 1.61 w, t%) were found on the wall of the pot.

Using the obtained carrier-type titanium component, polymerization was carried out in exactly the same manner and under the same conditions as in Example 1, and polyethylene 3039 was obtained. The bulk specific gravity of this polyethylene is O.4297nl, the intrinsic viscosity number is 1.10.10m,
a, 10.5% of coarse particles of iJ or more, 10-20 m-e:
Coarse particles of il 20.3%, polymerization activity] 5159/
'9-cat・h'', acquisition amount 3030!7./'7-C
at, 1881c9//ri-Tb)).

Comparing this with the results in Example 1, the polymerization activity was low and the resulting polyethylene had a very large number of coarse particles (the effect of the volatile component removal step of the present invention was obvious).

Comparative Example 2 In the method of Example 1, the addition of ethylene dichloride was omitted, and 40 g of anhydrous magnesium chloride and 2.88 g of titanium trichloride were co-pulverized at 30°C for 25 hours, and the Tb content was 1.
A 61 wt % carrier-type titanium component was prepared, and polymerization was carried out using the same method and conditions as in Example 1. The polymerization results are shown in Table 1.

Comparative Example 3 In accordance with the composition of the treated carrier of Example 1, 40 g of anhydrous magnesium chloride and 1,67 g of ethylene dichloride were ground for 22 hours, and then 2.88 g of titanium trichloride was added and ground for 3 hours to obtain a carrier-type titanium component. Obtained.

Table 1 shows the results of polymerization carried out using this carrier-type titanium component according to the method and conditions of Example 1.

Comparing Example 1 with Comparative Examples 1 to 3, it was found that the polymerization activity was high and the method of the present invention was effective in reducing the amount of coarse particles in the produced polymer.

Example 2 (1) Preparation of carrier type titanium component According to the method of Example 1, anhydrous magnesium chloride 4n9,
4.2 g of ethyl benzoate, 4.69 g of carbon tetrachloride, and 6.8 g of diphenyl ether were placed in a pot and pulverized for 20 hours. The crushed material had a reddish-purple color.

Take out the pulverized material into an eggplant-shaped flask and add it to a size of 50 mm at room temperature.
The mixture was dried under reduced pressure for 2 hours. The content of carbon tetrachloride in the powder before and after drying is shown below.

Carbon tetrachloride content (wt%) Before drying: 4.0 After drying: 0.2 After drying, the powder was put back into the pot and ground for 5 hours to obtain a treated carrier.

300 - The above treated carrier 1 was placed in a round bottom flask under a nitrogen atmosphere.
09, n-hebutane l Q Qi , titanium tetrachloride 1.
The mixture was stirred at 80°C for 2 hours, and the supernatant liquid was removed by decantation. Next, n-hebutane 200-
After stirring at room temperature for 30 minutes, the supernatant was removed by decantation, and this operation was repeated 5 times. Furthermore n-
Hebutane was added to obtain a slurry of carrier-type titanium component. A part of this was sampled, n-hebutane was evaporated and analyzed, and the carrier-type titanium component was 1.20 w.
It contained t7tlD titanium.

(2) Polymerization of propylene 5US-32 21 autoclave with n-hebutane IC
Support type titanium component (1,11 (0.0375 m9 aityyh as Ti atom) prepared in (L), triyl 4σ-butylaluminum O04i (1,59mM
) Ethyl benzoate 0.10d (n, 0.7mM),
Diethylaluminium monochloride n, 12i (0,
97 mM) in a nitrogen atmosphere. After evacuating the nitrogen in the autoclave with a vacuum pump, hydrogen was charged at a partial pressure in the gas phase (9/'rrl in 1 and 3, then propylene was charged, and the pressure in the gas phase was increased to 2 to 9Ar!). I used it as a gauge.

The contents of the autoclave were heated, and after 5 minutes the internal temperature was raised to 70°C, and the polymerization pressure was increased to 5kg/2J at 70'C.
Polymerization was carried out for 2 hours while charging propylene to maintain the gauge.
It lasted for hours.

After cooling the autoclave, unreacted propylene was purged and the contents were taken out and filtered to obtain polypropylene 510 in the form of a white powder.

The proportion of the boiling n-hebutane extraction residual polymer (crystalline polypropylene) in this powdered polypropylene (hereinafter abbreviated as Powder II) is 9R, 3wt%, and the bulk specific gravity is 0.4.
4q~, intrinsic viscosity number 1.65 dA'/ri, 10 mcil
The coarse grains of AN ('1.1%, 10-20 m) were as low as 2% of the coarse grains of I.

On the other hand, 5 g of n-hebutane soluble polymer (amorphous polymer) was obtained by concentrating the filtrate.

Polymerization activity in this polymerization reaction was 1717 ri/! 7~cat・h
r Obtained amount 3433g/'9<at, 286 to 9/'
The ratio of n-hebutane extraction residual polymer to the total produced polymer (hereinafter abbreviated as total) is 9.
It was 7.3%.

Comparative Example 4 The results are shown in which the drying operation under reduced pressure, which is the removal step of the liquid volatile additive of the present invention, was omitted in the method of Example 2, and the catalyst was prepared and polymerized using the same method and conditions as in Example 2. Shown in 2. (Titanium content of carrier type titanium component: 1.
Comparing this result with the result of Example 2, it is clear that the produced polymer had many coarse particles, and the volatile additive removal process of the present invention is effective in reducing coarse particles. .

Comparative Example 5 A carrier was prepared by grinding for 25 hours according to the method of Example 2, omitting the addition of carbon tetrachloride during co-pulverization.

The carrier was white and had a different color from the co-pulverized product of Example 2. TLC using this co-pulverized product as it is or as a carrier.
II4 in the same manner as in Example 2 to prepare a carrier-type titanium component (titanium content: 1.03 wt%), and polymerization was performed using this.

The polymerization results are shown in Table 2.

If carbon tetrachloride is not added during co-pulverization, the color of the carrier is completely different, and the resulting polymer has fewer coarse particles, but the polymerization activity and
The total TI etc. were very low compared to Example 2.

Example 3 According to the method of Example 1, anhydrous magnesium chloride 409,
Orunethyl acetate 3.6g, ethylene dichloride 12
The material was ground in a closed crusher system (N2 atmosphere) at a temperature of 30°C for 20 hours.

Next, the pulverization temperature was raised to 60° C., and the mixture was pulverized for 5 hours while passing N2 into the pot to remove volatile components, thereby obtaining a carrier. Ethylene dichloride contained in this carrier was 2 wt%.

30 - The above treated carrier 10 is placed in a round bottom flask under a nitrogen atmosphere.
9. 50 i of titanium tetrachloride was taken and stirred at 80°C for 2 hours, and the supernatant liquid was removed by decantation.

Next, 2 ootnl of n-hebutane was added, the mixture was stirred at room temperature for 30 minutes, and the supernatant liquid was removed by decantation, which was repeated 7 times. Furthermore, n-hebutane was added to obtain a slurry of carrier-type titanium component.

A portion of this was sampled, n-hebutane was evaporated, and analysis revealed that the carrier-type titanium component contained 1.9 wt% titanium.

Polymerization was carried out in the same manner and under the same conditions as in Example 2 using the obtained carrier-type titanium component.

375g of white powder polypropylene in 2 hours of polymerization,
7.6 ml of n-hebutane soluble polymer was obtained from the filtrate.

Powdered polypropylene para f-if 97.0wt
%, Bulk specific gravity 0038 4ζ Intrinsic viscosity number 1.57 dl
/ri, 1゜mzzjJLan, coarse particles 0%, 10-20-
The coarse particles of nbii were 8.5%.

The polymerization activity in this polymerization reaction is 12759/G cat-h
r acquisition amount 2550gΔ-cat, total 1. L95.1wt
%Met.

Comparative Examples 6 to 7 The results of the case where the carrier was prepared without adding ethylene dichloride in Example 3 are shown in Comparative Example 6, and the volatile matter removal operation step is performed in a closed system using the method of Example 3, and the volatile matter is removed from the system. The results of pulverization conducted under conditions that do not meet the above conditions are shown in Table 3 as Comparative Example 7 together with the results of Example 3.

Examples 4 to 6 In the method of Example 2, various compounds were used in the same manner and under the same conditions as the electron-donating compound ethyl benzoate and/or the volatile additive carbon tetrachloride. The results of the preparation and polymerization are shown below.

The coarse particle content of the produced polymer when the volatile additive removal step was omitted is shown in the table for comparison.

Claims (1)

[Claims] A co-pulverized product consisting of at least (1) magnesium halide (2) a liquid volatile additive,
Ethylene or α with titanium or vanadium compound supported
- In a method for producing a carrier-type titanium or vanadium component for an olefin polymerization catalyst, before completing this co-pulverization, at least a part of the liquid volatile additive is removed from the system, and then the pulverization is performed again. 1. A method for producing a carrier-type titanium or vanadium component for an ethylene or α-olefin polymerization catalyst, the method comprising using a co-pulverized product obtained by subjecting the catalyst to co-pulverization.