JPS61264009A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having high quality, using only a small amount of transition metal compound, by using a catalyst obtained by reacting a sulfur-containing Mg compound with a Ti compound, etc., and adding a halogen-containing alkyl-Al compound to the obtained transition metal compound component. CONSTITUTION:The objective polymer can be produced by (co)polymerizing an olefin using a catalyst composed of (A) a transition metal compound component produced by reacting (i) a sulfur-containing magnesium compound of formula Mg(SR<1>)2 (R<1> is 1-20C alkyl, cycloalkyl, aryl, etc.) with (ii) a Ti compound of a V compound at an atomic ratio of <0.5 based on the Mg atom and (B) an organometallic compound component composed of a halogen-containing alkylaluminum compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing polyolefins, and more specifically, a method for producing polyolefins using a catalyst having high olefin polymerization activity despite the use of a small amount of transition metal compound. The present invention relates to a method for efficiently producing polyolefin.

[Prior Art and Problems to be Solved by the Invention] Various heavy metal catalysts have been used in the production of polyolefins. As these polymerization catalysts, those consisting of a combination of a transition metal compound and an organometallic compound are widely used. Here, a compound of titanium or vanadium is added to a phase such as magnesium chloride or magnesium alkogide as a transition metal compound component. What it carried is known.

However, the conventional polymerization catalysts mentioned above require the use of multi-lobed titanium compounds and vanadium compounds during their preparation, which not only increases the consumption of titanium and vanadium when producing polyolefins, but also increases the catalyst preparation process. There is a problem in that it is expensive to dispose of surplus titanium compounds and surplus vanadium compounds discharged after the wave or polymerization reaction. In addition, there have been problems such as the need for washing and separation operations in order to improve the polymerization activity of the catalyst. Furthermore, in the conventional method, a large amount of highly halogenated titanium such as titanium tetrachloride is used, resulting in a high halogen content in the resulting polyolefin, resulting in a decrease in the quality of polyolefin products and corrosion of molding equipment. There was a problem.

The present inventors have conducted intensive research in order to solve the problems of the prior art described in 2 and to develop a method for producing high-quality polyolefin using a catalyst in which the transition metal base h1 exhibits at least high activity. I slept 1.

[Means for solving problems]

As a result, a reaction product of a specific sulfur-containing magnesium compound and a titanium compound or a vanadium compound was used as a transition metal compound component, which is a component of the catalyst, and a rogen-containing alkyl aluminum compound was used as an organometallic compound component. I found that I could achieve my purpose by using K. The present invention was completed based on this knowledge.

That is, the present invention provides (A) a transition metal compound component and
Per K for producing a polyolefin by polymerizing or copolymerizing an olefin using a catalyst containing an organometallic compound component as a main component, (A) as a transition metal compound component, (a>
-, general formula Mg (stt')s [wherein R1 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group].

Indicates an aryl group or an aralkyl group. ] Using a reaction product obtained by reacting a sulfur-containing magnesium compound represented by (b) with a titanium compound or a vanadium compound at a ratio of 1 to less than 0.5 (original ratio) to magnesium atoms, The present invention provides a method for producing a polyolefin, characterized in that a halogen-containing alkyl aluminum compound is used as an organometallic compound component.

The catalyst used in the method of the present invention has the above-mentioned (A) and CB) components as main components, and the transition metal compound component (4) is a compound of the above-mentioned (aL(b)). The sulfur-containing magnesium compound, which is a reaction product, is the compound (a) having the general formula Mg(SR').

[In the formula, R1 is the same as above. ], specifically di(methylthio)magnesium, di(ethylthio)magnesium, di(propylthio)magnesium, di(butylthio)magnesium, di(amylthio)magnesium, di(hexylthio)magnesium, di(octylthio) magnesium.

Examples include di(dodecylthio)magnesium. Among them, di(hexylthio)magnesium.

Di(octylthio)magnesium, di(dodecylthio)
Magnesium is cited as a preferred material.

This sulfur-containing magnesium compound can be obtained by various methods, but usually has the general formula MgR', [wherein R4 is an alkyl group having 1 to 10 carbon atoms, ', chloroalkyl group, aryl group, or aralkyl group] Indicates the group.

] Organomagnesium represented by □General formula'
SR [wherein R1 is the same as above. ] by the following reaction.

MgR', + 2 R"8H→Mg(81'L'),
+ 2R'H Various compounds can be used as the compound (b), that is, the titanium compound or vanadium compound, to be reacted with the sulfur-containing magnesium compound that is the compound (a) above. For example, the titanium compound has the general formula T1(OR2)mx'4-m [wherein R2 represents an alkyl group, aryl group, aralkyl group, or acyl group having 1 to 20 carbon atoms, and X1 represents a halogen atom.

Further, m is a real number between 0 and 4. ], specifically Ti014, Ti
Tetrahalogenated titanium such as Br4, TiI<,'11+(r)OHI)0/1,'l! 1
(OC@H6) C/8°TI (0-rr-041io
) CIB, trihalogenated monoalkoxytitanium such as 1(0('+gli5)Brl), Ti(OOI
J@) 10/, .

Ti(00(,IIB,)20/2, Tl(0”
111-04TI) golsl.

Dihalogenated dialkoxytitanium such as Ti(0011H5)QBrs, Tj(0011a)aot)
Tl (OOi+Ha) sol tT1(('
) ・n-04Hs)anl+ Ti(OCsHa)
Monohalosaponified trialkoxytitanium such as aBr, T
j((”long)4゜Tj((101H5)4.T
i(00sHy)4+'l'1(0-n-04)1s
+) 4 and other tetraalkoxy titanium, Ti(00QH
s)s(OCQIIg) +Ti(OOJ(o)a(0
0("1osH7) s'ri(008H,), (
Onoo, H8).

ri'] (00QH6)g (OOOOOHll)g
, 'I' i ((106H7) @ (00
001tH@s)@tT1 (009H5)
(OOOOH@) 6, T i (OOQ■I
6) (0flO011TI?) @tT x
(008H7) (000011'17) a,
T i (00aH7) (000017I(15) a
HT+(006Hta)((')OOolyHae)
Alkoxycarboxytitanium such as a, 'l! j
(0OOOTI Hatake) 4, 'ri(OanO,H
,)Q.

Tj, ((10008117)4, Ti(000
0alf+a)4+ Ti(OOOOstkiss)4
Examples include tetracarboquine titanium.

Also, various vanadium compounds can be considered, such as VC/4. Vanadium chloride i such as VC78 VflOl♂, vanadium chloride A such as V(10/g; V(Q・n-04Ho)4+
V(1(00i+Hs)syvO(0・n−04H*
) 8 and other vanadium alkoxides; cyclopentadienyl vanadium derivatives such as dicyclopentadienyl vanadium chloride; V(acac)a + VO(
vanadium acetylacetonate compounds such as acac)Q can be mentioned. In addition, here a Ca
C represents an acetylacetonate group, that is, an acetylacetone ion.

The component (d) of the catalyst used in the method of the present invention is the above-mentioned (d).
It is a reaction product of the compound (t) and (t). Buddha)
When reacting the sulfur-containing magnesium compound (b) with the titanium compound or vanadium compound (b), the reaction conditions are not particularly limited and may be determined as appropriate depending on various situations. Usually, the titanium compound or vanadium compound of (b) is used so that its titanium atom or vanadium atom is "C" (i.e., 'I'l/λfg or v/Mg ) less than 0.5 (atomic ratio), preferably
(1,005 to (1,4 (atomic ratio)) (
Mix the open compounds of δ) and (b) and react.
, r, i. If the amount of the titanium compound or vanadium compound (b) used is too large, the consumption of titanium or vanadium during olefin polymerization will increase, and the process of cleaning and removing the surplus or wasteful titanium compound or vanadium compound will be required. This is not desirable both economically and industrially. Moreover, even if the titanium compound or vanadium compound is used in an amount exceeding the above-mentioned ratio, there is little improvement in the activity of the resulting catalyst, but rather a tendency for the activity to decrease. Note that this reaction is usually carried out in an inert hydrocarbon solvent such as pentane, hexane, heptane, etc. at a temperature of 0 to 20
0°C, preferably 30-150°C, reaction time 5 minutes-10
The reaction time is preferably 30 minutes to 5 hours. .

Phosphine, phosphoramide, ester, thioether, thioester, acid anhydride, acid halide.

It is also effective to obtain a reaction product by adding and reacting an electronic compound such as an aldehyde or an organic acid, and to use this reaction product as the (A) transition metal compound component of the olefin polymerization catalyst.

Furthermore, the reaction product of the above-mentioned (aL (b) compounds) or the reaction product obtained by reacting these (aL (b) compounds with an electron-stretching compound)... What was reacted with,
It is also effective to use CALM as a transfer metal compound component. The halogen-containing alkyl aluminum compound used here may be the same as or different from the halogen-containing alkyl aluminum compound as the organometallic compound component (0).

According to the method of the present invention, - the above reaction product is used as a transition gold maple compound component as component (A), and the halogen-containing alkyl aluminum compound is used as an organometallic compound component as component (B) (^) , (B) are used as main components to polymerize an olefin to produce a polyolefin.

There are various types of alkylaluminum compounds containing nitrogen used as component (B), but they usually have the general formula R"nhtx",..., r, where R" 47 has 1 to 1 carbon atoms.
10 alkyl groups are shown, and x2 represents a halogen IQ atom.

Further, n is a real number satisfying 0 < n < 3. ] This is a compound represented by

Specifically, diethylaluminum monochloride.

Dialkylaluminum monohalides such as diimpropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride; monoalkylaluminum civalides such as ethylaluminum dichloride, isopropylaluminum dichloride, and inbutylaluminum dichloride; methylaluminum sesquichloride, ethylaluminum Alkylaluminium sesquihalides such as sesquichloride, ethylaluminum sesquipromide, and mixtures thereof, as well as triethylaluminum.

Mixtures with trialkylaluminum compounds such as triisopropylaluminum, triisobutylaluminum, trioctylaluminum, etc. are preferred.

In the method of the present invention, when 1 lyolefin is polymerized, 1 B is added to the reaction system as component (A). (a), (b)
) Reaction products of compounds, 1. Components i and (B), i.e., the alkyl aluminum compounds containing nitrogen, and further an electron-donating compound if desired, are added, and then (7) is added.
The raw material olefin is introduced into the system.

The polymerization method and conditions are not particularly limited, and any of solution polymerization, suspension polymerization, gas phase polymerization, etc. is possible, and both continuous polymerization and discontinuous polymerization are possible. For example, in the case of solution polymerization or suspension polymerization with the addition of a catalyst component, the amount of component (A) in terms of titanium atoms or vanadium atoms is 0.001 to 5.0 mmol/e, preferably ( 1,002 to 1.0 mmol/l, (
The ratio of component B) to the titanium or vanadium atoms in component (A) is 1 to 5,000 (molar ratio), preferably 5 to 1ooO (molar ratio).

The pressure of the reaction system is preferably normal pressure to 50 kg/clIL'', and the reaction temperature is 0 to 150°C, preferably 40 to 1
The temperature shall be 20°C. The molecules during polymerization can be controlled by known means, such as hydrogen. The reaction time may be appropriately selected from 5 minutes to 10 hours, preferably from 30 minutes to 5 hours. Note that the polymerization solvent is an aliphatic hydrocarbon or an alicyclic hydrocarbon.

There are aromatic hydrocarbons, logenated hydrocarbons, etc. Specifically, hexane, heptane, and benzene.

Al with toluene, xylene, etc.

In the method of the present invention, polyolefins are produced by polymerizing olefins, and it is particularly suitable for use in the polymerization of ethylene and copolymerization of ethylene and other α-olefins. Examples of α-olefins used in this case include linear monoolefins such as propylene, butene-1, hexene-1, and octene-1, as well as branched monoolefins such as 4-methyl-pentene-1. can. Furthermore, the method of the present invention can be effectively applied to the homopolymerization of these α-olefins.

〔Effect of the invention〕

According to the method of the present invention, the consumption 1' of titanium compounds and vanadium compounds during the preparation of the catalyst used is small, and □ There is no need for washing or separation operations to improve the catalytic activity, and the titanium compounds used are Almost all of the vanadium compounds are used as catalysts, so there is no need for treatment equipment for waste titanium compounds or waste vanadium compounds. Moreover, since the catalyst activity is extremely high, there is no need for a deashing process (catalyst removal □ process), and as a result,
The production of polyolefins is extremely efficient.

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

Example 1 (Preparation of titanium catalyst component) Alumina was substituted, and a 200 txl flask was prepared.
50 ml of n-heptane and 20 ml of dodecyl mercaptan
Add 10 mmol of ethylbutylmagnesium to this.
30 d of millimolar hebutane solution was added dropwise over 20 minutes at room temperature. Then, the temperature was raised and n-hebutane was refluxed for 3
Allowed time to react. Next, the reaction product was heated to 40" (L), 1 ml of titanium tetrachloride was added to it, the temperature was raised to 1-++, and the reaction product was refluxed with n-hebutane for 3 hours. A titanium catalyst component was obtained.

(2) One-time argon substitution of ethylene [also in an autoclave with contents f*11,
n-hexane 400ml1. 2 mmol of triethylaluminum, 2 mmol of diethylaluminum chloride, and 0.01 mmol of the titanium catalyst component obtained in 11) above as titanium atoms were added, and after raising the temperature to 80°, the hydrogen partial pressure was 3 kg/cm2a. Hydrogen was supplied so that Then, ethylene was continuously supplied so that the partial pressure of ethylene was 5 kL/cIn"G, and the combination reaction was carried out for 1 hour. As a result, polyethylene 100.!i+ was obtained. Catalytic activity was 209 kg/fl・Titanium, time, polyethylene 190″C;.

Melt index at a load of 2.16 kg (Ml2
．． ．． 6) was 2.2 g 710 minutes.

Example 2 Only 2 mmol of diethylaluminium chloride was used as the aluminum catalyst component (see (2) of Example 1).
The same operation was performed. The yield of polyethylene is 619
．． The catalyst activity is 127 kg/9・titanium・hour,
Melt index (λ112.□6) is 1.7971
It was 0 minutes.

Example 3 +11 Preparation of titanium catalyst component Hexyl mercaptan 2 instead of dodecyl mercaptan
A titanium catalyst component was obtained by carrying out the same operation as in Example 1 (1) except that 0 mmol was used.

(2) Polymerization of ethylene The same operation as in (2) of Example 1 was performed except that the titanium catalyst component obtained in (1) above was used as the titanium catalyst component. The yield of polyethylene was 74.9, and the catalytic activity was 154 kg/! ?・Titanium・Time. Also, the melt index (Ml2.□6) is 1.8
．． ! i'/10 minutes.

Example 4 (1) Preparation of titanium catalyst component 1 mmol of tetraethoxytitanium was used in place of titanium tetrachloride as the titanium compound in Example 1 (11).
A titanium catalyst component was obtained by performing the same operation as above.

(2) Ethylene polymerization The same operation as in Example 1 (2) was performed except that the titanium catalyst component obtained in step +11 above was used as the titanium catalyst component. The yield of polyethylene was 78 g, and the catalyst activity was x6aky/1 titanium.hour. Also, the melt index (Ml20.6) is 2.9 g7
It was 10 minutes.

Example 5 +11 Preparation of titanium catalyst component The titanium catalyst component obtained in Example 1 (1) was reacted with an equimolar amount of diethylaluminium chloride at 40° C. for 3 hours to obtain a new titanium catalyst component.

(2) Polymerization of ethylene The same operation as in (2) of Example 1 was performed except that the titanium catalyst component obtained in the above Ni; tl) was used as the titanium catalyst component. The yield of polyethylene was 168y, and the catalyst activity was 351 kg/g titanium hour. Also, melt index (Ml2..6) &t
It was 2.39/10 minutes.

Comparative Example 1 10 Preparation of titanium catalyst component Same as Example 1 except that 5 mmol of titanium tetrachloride was used.
The same operation as in 11 was carried out to obtain a titanium catalyst component having an atomic ratio of 0.5 i/Mg.

(2) Polymerization of ethylene The same operation as in (2) of Example 1 was performed except that the titanium catalyst component obtained in (1) above was used as the titanium catalyst component. The yield of polyethylene was 35 g, and the catalyst activity was 74 kg/g titanium hour.

Furthermore, the melt index (M
l,,6) was 1.29710 minutes.

Comparative Example 2 (1) Preparation of titanium catalyst component Titanium tetrachloride was used for 10 mmol (except for
A titanium catalyst component was obtained.

(2) Polymerization of ethylene The same operation as in (2) of Example 1 was performed except that the titanium catalyst component obtained in (1) above was used as the titanium catalyst component. The yield of polyethylene was 12 g, and the catalyst activity was 25 kf17 g titanium hour.

Furthermore, the melt index (h
1■21.6) was 0.75 g/l 0 minutes.

Claims (3)

[Claims] (1) When producing a polyolefin by polymerizing or copolymerizing an olefin using a catalyst whose main components are (A) a transition metal compound component and (B) an organometallic compound component, as (A) a transition metal compound component, (a) General formula M
g(SR^1)_2 [In the formula, R^1 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms. ] Using a reaction product obtained by reacting a sulfur-containing magnesium compound represented by (b) with a titanium compound or a vanadium compound at a ratio of less than 0.5 (atomic ratio) to magnesium atoms, (B) A method for producing a polyolefin, characterized in that a halogen-containing alkyl aluminum compound is used as an organometallic compound component. (2) (A) (b) The titanium compound has the general formula Ti(OR
^2)_mX^1_4_-_m [In the formula, R^2 represents an alkyl group, aryl group, aralkyl group, or acyl group having 1 to 20 carbon atoms, and X^1 represents a halogen atom. Moreover, m is a real number of 0 or more and 4 or less. ] The manufacturing method according to claim 1, which is a compound represented by: (3) (B) The halogen-containing alkyl aluminum compound has the general formula R^3_nAlX^2_3_-_n [in the formula,
R^3 represents an alkyl group having 1 to 10 carbon atoms, and X^2 represents a halogen atom. Further, n is a real number satisfying 0<n<3. ] The manufacturing method according to claim 1, which is a compound represented by: