JPS61126111A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin in a high catalytic activity, by (co)polymer izing an olefin in the presence of a catalyst comprising a specified vanadium catalyst component and a modified organoaluminum catalyst component. CONSTITUTION:A catalyst is obtained by combining a vanadium catalyst compo nent obtained by reacting VCl4 with an ester (e.g., ethyl acetate) or an ether (e.g., diethyl ether) at a molar ratio of 0.1-100 with a modified organoaluminum compound obtained by reacting an ether, an ester or a ketone (e.g, acetone) with an organoaluminum compound selected from among an alkylaluminum of formula I (wherein R<5> is a 1-10C alkyl, X is a halogen and n is 1-3) and an alkoxyaluminum of formula II (wherein R<6-7> are each R<5> and m is 0-2) or aluminoxane at a molar ratio of 0.1-50. An olefin is (co)polymerized at -50-200 deg.C and a pressure of normal-100kg/cm<2>G in the presence of the cata lyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefins. BACKGROUND ART Conventionally, it has been known to use a vanadicum-based catalyst consisting of a combination of a panadicum compound and an organoaluminum in producing polyolefins by polymerizing olefins. Although this vanadicum-based catalyst has a high initial activity and good copolymerizability of olefins, the sustainability of the activity is poor, and various attempts have been made to improve this activity. For example, a method is known in which the activity of a vanadicum compound is improved by treating it with ether (Japanese Patent Laid-Open No. 53-9
8382).

However, even in this case, the improvement in catalytic activity cannot be said to be sufficient.

Therefore, the present inventors conducted further studies on vanadium-based catalysts in order to solve the above-mentioned conventional drawbacks, and found that a reaction product of vanadium tetrachloride and an ether or an ester was used as the vanadium catalyst component, and an organic aluminum compound was used as an ether or an ether. It was discovered that a highly active and highly durable catalyst could be obtained by combining this with a catalyst modified with an ester or ketone, and based on this knowledge, the present invention was completed.

That is, the present invention provides a method for producing a polyolefin by polymerizing or copolymerizing an olefin using a catalyst consisting of a vanadium catalyst component and an organoaluminium catalyst component, and in which vanadium tetrachloride and an ether or an ester are used as the vanadium catalyst component. The present invention provides a method for producing a polyolefin, which is characterized in that the reaction product of the present invention is used as the organoaluminum catalyst component, and a metal organoaluminide modified with an ether, an ester, or a ketone is used as the organoaluminum catalyst component.

In the present invention, the olefin used for polymerization is not particularly limited, but ethylene is particularly preferred.

It is also possible to copolymerize ethylene with an α-olefin such as propylene or butene-1.

In producing polyolefins by polymerizing or copolymerizing the above-mentioned olefins, a catalyst consisting of a vanadium catalyst component and an organoaluminium catalyst component is used. Use the reaction product.

Here, the ether usually has the general formula Rl -o -R2
(In the formula, Hz R2 is an alkyl group having 1 to 20 carbon atoms.

Cycloalkyl group, aryl group, vinyl group, aralkyl group, alkenyl group or alkoxyalkyl group.

R1 and R2 may be the same, or
may be different. ), and
Specifically, diethyl ether, diisoamyl ether,
Examples include diimpropyl ether, n-butyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, dicyclohexyl ether, diphenyl ether, dibenzyl ether, anisole, and ethylene glycol dibutyl ether.

Furthermore, examples of the ethers include cyclic ethers and trioxane.

In particular, as the ether used in the reaction with vanadium tetrachloride as a vanadium catalyst component, cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane are preferred.

Furthermore, as a vanadium catalyst component, a reaction product of vanadium tetrachloride and an ester can also be used. Here, the ester is expressed by the general formula % (wherein, R' and R' are alkyl groups having 1 to 20 carbon atoms. .

It represents a cycloalkyl group, an aryl group, a vinyl group, an aralkyl group, or an alkenyl group, and R3 and R4 may be the same or different. ). Specifically ethyl acetate.

Vinegar Ml n-propyl, 1-propyl acetate, n-butyl acetate, hexyl acetate, 2-ethylhexyl acetate.

Acetate esters such as phenyl acetate and benzyl acetate, ethyl propionate, and n-propyl propionate.

1-propyl propionate, n-butyl propionate,
Propionate esters such as hexyl propionate, 2-ethylhexyl glopionate, phenyl propionate, benzyl propionate, methyl butyrate, ethyl valerate,
Ethyl acrylate, methyl methacrylate, ethyl benzoate, n-propyl benzoate, 1-propyl benzoate, n-butyl benzoate, hexyl benzoate, octyl benzoate.

Benzoic acid esters such as phenyl benzoate and benzyl benzoate, ethyl toluate, euflovir toluate,
1-7'lovir toluate, @n-butyl toluate,
Examples include toluic acid esters such as hexyl toluate, octyl toluate, phenyl toluate, and benzyl toluate, chloroacetic esters such as methyl chloroacetate and ethyl dichloroacetate, and malemonoesters such as dimethyl maleate. can. The above ester is preferably a benzoic acid ester such as ethyl benzoate.

The above ether or ester is O01 to 100 (molar ratio) to vanadium tetrachloride, preferably 0.5 to 50.
(Molar ratio) In addition, the reaction product obtained by performing the reaction is used as a vanadium catalyst component. Here, the reaction temperature is -20~
The temperature is 200°C, preferably 0 to 150°C.

Next, in the present invention, an organoaluminum compound modified with an ether, ester or ketone is used as the organoaluminum catalyst component.

Here, the organoaluminum compound modified with ether, ester or ketone has the general formula % (wherein, R6 is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom, and n is a real number of 1 to 3). Alkyl aluminum represented by ].

Examples include alkoxy aluminum or aluminoxane represented by the general formula % formula %: 1 (wherein Re and 7 represent an alkyl group having 1 to 10 carbon atoms, and m represents a real number of 0 to 2).

Here, specific examples of the alkyl aluminum represented by the above general formula CI) include trimethylaluminum, triethylaluminum, triisopropylaluminium,
Triisobutylaluminum.

Trialkylaluminium compounds such as trioctylaluminum, diethylaluminum lac chloride, diethylaluminum heptanopromide, didiethylaluminum monoiodide, diisopropylaluminum monochloride, diisobutylaluminum monochloride,
Dialkyl aluminum monohalides such as dioctyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride.

Alkylaluminum sesquihalides such as ethylaluminum heptaskipromide and butylaluminum sesquichloride are preferred, and mixtures thereof are also preferred.

Further, examples of the alkoxyaluminum represented by the above general formula [II] include diethylaluminum ethoxide and diethylaluminium isopropoxide.

Mention may be made of alkyl aluminum alkoxides such as diimbutyl aluminum ethoxide.

Furthermore, as the aluminoxane, it is also possible to use an aluminoxane containing an alkyl group produced by the reaction of an alkyl aluminum and water.

As these organoaluminum compounds, triethylaluminum, triisobutylaluminum, diethylaluminium monochloride, etc. are preferably used.

The ether used for modifying the organoaluminum compound is as described above, and may be the same as that used for modifying the vanadium catalyst component, or may be a different one (but preferably di-n-butyl ether, di-n-butyl ether, Jupropyl ether.

Diisopropyl ether, diethyl ether, tetrahydrofuran, dioxane, etc. are used.

Furthermore, esters can also be used to modify the organoaluminum compound. This ester is as described above, and may be the same as that used for modifying the vanadium catalyst component, or may be different. However, benzyl benzoate.

Benzoic acid esters such as octyl benzoate and acetic acid esters such as butyl acetate are preferably used.

Furthermore, in the present invention, a ketone can also be used to modify the organoaluminum compound. Here, the ketone is represented by the general formula % (wherein R' and R'' are alkyl groups having 1 to 20 carbon atoms.

It represents a cycloalkyl group, an aryl group, a vinyl group, an aralkyl group, or an alkenyl group, and R8 and Ro may be the same or different. ) or cyclic ketones such as cyclopentanone and cyclohexanone are used. The above-mentioned ketones include in particular acetone, methyl ethyl ketone, methyl imbutyl ketone, and acetophuninone.

Carbon number 3-150 such as benzophenone and benzoquinono
Ketones are preferably used.

By adding 0.1 to 50 (mole ratio), preferably 0.2 to 20 (mole ratio) of the above ether, ester, or ketone to the organoaluminum compound, the organoaluminum compound is modified to form an organoaluminum catalyst component. do. There are no particular restrictions on the denaturation conditions, but usually O
The reaction may be carried out at a temperature of ~100°C for 1 to 60 minutes.

In the present invention, an olefin is polymerized or copolymerized using a catalyst comprising a vanadium catalyst component and an organoaluminum catalyst component as described above. Here, the catalyst composition is 0.0% aluminum to vanadium as metal atoms.
The ratio may be 1 to 1000 (molar ratio), preferably 1 to 500 (molar ratio).

Polyolefins are produced by polymerizing or copolymerizing olefins using the catalysts described above.

The polymerization reaction is carried out using a polymerization solvent such as an aliphatic hydrocarbon, an aromatic hydrocarbon, a cyclic hydrocarbon, or a halogenated hydrocarbon. The polymerization conditions are a reaction temperature of -50 to 2
00°C, preferably -30 to 100°C, and the reaction pressure is normal pressure to 100 kg/art"G, preferably normal pressure to
30 m”G, more preferably normal pressure to 10 kg/c
m''G. Molecular weight adjustment during polymerization may be carried out using hydrogen-alkylzinc or the like.

The present invention uses a catalyst in which the reaction product of vanadium tetrachloride and ether or ester is combined with an organoaluminium compound modified with ether, ester or ketone, so the activity of the catalyst is significantly improved. However, the polymerization activity, especially the ethylene polymerization activity, can be improved.

Furthermore, in the present invention, the step of removing the catalyst in the polyolefin product (deashing step) can be omitted, and the polyolefin can be efficiently produced.

Therefore, the present invention can be effectively used for producing polyolefins, particularly polyethylene and ethylene copolymers.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 1) Preparation of vanadium catalyst component In a 30ON four-necked flask purged with argon, 150 g of heptane and 2.8 f3 rt of tetrahydrofluff were added.
tl (35.5 mmol) was added thereto, and a hebutane solution of vanadium tetrachloride bo, 75aj (7.1 mmol) was added dropwise over 20 minutes at 25°C. After 3 hours of reaction, the reddish-purple solid was filtered and washed to obtain a vanadium catalyst component.

(2) Preparation of organoaluminium catalyst component Into a 100 mmol reaction vessel purged with argon, 50 m of hexane and 920 mmol of diethyl aluminum were gradually added.
A modified organoaluminum catalyst component was obtained by reacting at 0°C for (capital) minutes (3) Polymerization of ethylene Reaction vessel K, 500 m long, purged with argon, Hexa 730
After adding 0.5 mmol of the organoaluminum catalyst component prepared in (2) above, the temperature was raised to 50° C., ethylene was introduced, and the mixture was stirred until 1 kg/cWL-S-G-teethylene was saturated. Furthermore, after dropping 0.0025 mlJ mol of the vanadium catalyst component prepared in (1) above, ethylene was continuously introduced to maintain 2 kg/cru"G, and polymerization was carried out for 2 hours while stirring. The reaction was carried out.Next, inglobanol was added to stop the polymerization, and the polyethylene was recovered and dried under reduced pressure for 2 hours.As a result, polyethylene 36.0S was obtained, and the catalyst activity was 28.
It was 3 kg/9.vanadium.

Example 2 In Example 1, the amount of vanadium catalyst component used was 0.
Ethylene polymerization was carried out in the same manner as in Example 1 except that the amount was 0.1 mmol. As a result, the yield of polyethylene was 57.6 fi, and the catalyst activity was 113.1 k.
g/9・vanadium〇Comparative Example 1 Except that in Example 2, 5 mmol of unmodified triethylaluminum O was used instead of triethylaluminum modified with di-n-butyl ether as an organoaluminum catalyst component during ethylene polymerization. Polymerization of ethylene was carried out in the same manner as in Example 1. As a result, the yield of polyethylene was 3.7 g, and the catalytic activity was 7.
．． It was 3 kg/11.vanadium.

Example 3 Example 2 except that 0.5 mmol of diisopropyl ether was used instead of di-n-butyl ether as a modifier for triethylaluminum.
Polymerization of ethylene was carried out in the same manner. As a result, the yield of polyethylene was 43°1,9, and the catalytic activity was 8.
It was 4.4 kg/17.vanadium.

Example 4 Ethylene polymerization was carried out in the same manner as in Example 2 except that 0.5 mmol of diethyl ether was used instead of di-n-butyl ether as a modifier for triethylaluminum. As a result, the yield of polyethylene was 40.9.9, and the catalyst activity was 80.1.
kg/l・vanadium.

Example 5 In Example 1, the amount of vanadium catalyst component used was o,
o O5 Mi! Polymerization of ethylene was carried out in the same manner as in Example 1, except that 0.5 mmol of benzyl benzoate was used instead of di-n-butyl ether as the modified IJ of triethylaluminum. As a result, the yield of polyethylene was 36.5. F, and the catalytic activity is 143.3 kg/I!・It was vanadium.

Example 6 In Example 5, 0.5 miI of butyl acetate was used instead of benzyl benzoate as a modifier for triethylaluminum.
Ethylene polymerization was carried out in the same manner as in Example 5 except that J mol was used. As a result, the yield of polyethylene was 12.9 F, and the catalytic activity was 50.6 kli'/F.
9.Vanadium@Example 7 Ethylene polymerization was carried out in the same manner as in Example 5, except that diphenyl ketone was used instead of benzyl benzoate as the female agent for triethylaluminum. As a result, the yield of polyethylene was 4.91, and the catalyst activity was 19.2h7g·vanadium.

Example 8 Ethylene polymerization was carried out in the same manner as in Example 1, except that a reaction product of 0.5 mmol of triisobutylaluminum and 0.5 mmol of di-n-butyl ether was used as the organoaluminum catalyst component. Ta. As a result, the yield of polyethylene was 6.6 p, and the catalyst activity was 51.8 kf/g.vanadium.

Comparative Example 2 The same procedure as in Example 8 was carried out, except that 0.5 mmol of unmodified triisobutylaluminum was used in place of the triimbutylaluminum modified with di-n-butyl ether as the organoaluminum catalyst component. Polymerization of ethylene was carried out. As a result, the yield of polyethylene was 0.89, and the catalyst activity was 6.3 kg.
/9, vanadium.

Example 9 In Example 2, the polymerization of ethylene was carried out in the same manner as in Example 2 except that a reaction product of 0.5 mmol of diethylaluminum monochloride and 0.1 mmol of di-n-butyl ether was used as the organoaluminum catalyst component. As a result, the yield of polyethylene was s o,
o y, and the catalytic activity is 98 kg/9.vanadium
Met.

Example 10 In Example 1, 7.1 mmol of vanadium tetrachloride and 35.0 mmol of tetrahydropyran were used as vanadium catalyst components.
o, o as the reaction product with 5 mmol of vanadium
Ethylene polymerization was carried out in the same manner as in Example 1 except that os mmol was used. As a result, the yield of polyethylene was 21.4,9, and the catalyst activity was 84.0ki9.
/p vanadium Example 11 Except that in Example I, 0.01 mmol of vanadium was used as a reaction product of 7.1 mmol of vanadium tetrachloride and 35.5 mmol of dioxane as a vanadium catalyst component. Polymerization of ethylene was carried out in the same manner as in Example 1. As a result, the yield of polyethylene was 17.7
, li', and the catalyst activity was 34.7 kll/9·vanadium.

Example 12 In Example 1, 7.1 mmol of vanadium tetrachloride and 35.5 mmol of ethyl benzoate were used as vanadium catalyst components.
Ethylene polymerization was carried out in the same manner as in Example 1, except that the reaction product with J mole was 0.01 mmol of vanadium. As a result, the yield of polyethylene is 2
4.69, and the catalyst activity was 48.3 kg/p-vanadium.

Example 13 In a 500M reaction vessel purged with argon, 30% hexane was added.
0.5) C by introducing propylene into it.
! 9/α2G, propylene was saturated with hexane, and then the organoaluminum catalyst component obtained in Example 1 (2) was added to o, s! Added j moles. Next, ethylene was introduced into this so that the total pressure was 2 U/crIL2G, and Example 1 (
After adding 0.005 mmol of the vanadium catalyst component prepared in 1), the reaction was carried out for 2 hours with stirring. After treatment with alcohol and drying under reduced pressure, 29.7 g of ethylene-propylene copolymer was obtained. Catalytic activity is 116.6 kg/
The propylene content in this copolymer was 2.8 mol%.

Claims (3)

[Claims] (1) When producing a polyolefin by polymerizing or copolymerizing an olefin using a catalyst consisting of a vanadium catalyst component and an organoaluminium catalyst component, a reaction product of vanadium tetrachloride and an ether or ester is used as the vanadium catalyst component. and using an organoaluminum compound modified with an ether, ester or ketone as the organoaluminum catalyst component. (2) Claim 1 in which the olefin is ethylene
Manufacturing method described in section. (3) The organoaluminum compound has the general formula R^5_nAlX_8_-_n (in the formula, R^5 is an alkyl group having 1 to 10 carbon atoms, X is a halogen atom, and n is a real number of 1 to 3). Alkylaluminium represented by the general formula R^6_m(R^7O)_8_-_mAl (wherein, R^6 and R^7 represent an alkyl group having 1 to 10 carbon atoms, and m represents a real number of 0 to 2. .) The manufacturing method according to claim 1, wherein the alkoxyaluminum or aluminoxane is represented by: