JPH0693028A - Catalyst for polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE:To provide a catalyst composed of activated titanium trichloride, an organometallic compound and a specified organosilicon compound, excellent in polymerization activity and stereoregularity and capable of achieving a high yield without generating harmful substance. CONSTITUTION:This catalyst for polymerization of an alpha-olefin is composed of (A) activated titanium trichloride, (B) an organometallic compound and (C) an organosilicon compound represented by the formula (R<1> is a 1 to 10C hydrocarbon; R<2> is a 1 to 10C hydrocarbon, R<4>O, R<5>3Si, etc.; R<3> is methyl or ethyl x is 1 or 2; y is 0 or 1; z is 2 or 3; z is 2 or 3; x+y+z=4; R<4> is a 3 to 10C hydrocarbon; R<5> is a 4 to 10C hydrocarbon).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for .alpha.-olefin polymerization.

[0002]

2. Description of the Related Art An .alpha.-olefin polymerization catalyst composed of activated titanium trichloride and an organoaluminum compound has a property different from that of a so-called magnesium-supported catalyst in which a titanium compound is supported on a magnesium compound. It is characterized by being able to produce a polymer and having excellent resistance to poisoning. However, activated titanium trichloride has a problem that it has lower polymerization activity and slightly lower stereoregularity than a magnesium-supported catalyst. A catalyst in which a magnesium-supported catalyst and an organoaluminum compound are combined, further having a Si-O-C bond,
Alternatively, the general formula SiR ¹ R ² _n (OR ³ ) _3-n (n = 0 to
It is known that when the organosilicon compound represented by 2) is used, the stereoregularity of the resulting polymer is improved (for example, JP-A Nos. 54-94690 and 56-36203).
No. 57-63310, No. 58-83016, No. 62-11705, etc.).

On the other hand, a catalyst composed of activated titanium trichloride and an organoaluminum compound is further added with the general formula R ¹ _n Si.
A method for producing an α-olefin polymer having improved polymerization activity and stereoregularity by combining an organosilicon compound represented by (OR ² ) _4-n (0 ≦ n <4) has been proposed (special feature (Kaisho 63-238110). The improvement of stereoregularity and the polymerization activity depend on the type of the organosilicon compound. It is generally known that a silicon compound having an aromatic group exhibits good performance in the polymerization of α-olefins, but a silicon compound having an aromatic group may be harmful depending on the purpose of use of the polymer. .

[0004]

DISCLOSURE OF THE INVENTION The present invention is an organosilicon compound having no aromatic group, which is less harmful even if it is contained in a polymer, and is equivalent to the aromatic group-containing organosilicon compound. It is an object of the present invention to provide a catalyst for α-olefin polymerization, which comprises an organosilicon compound having higher performance as one component.

[0005]

Means for Solving the Problems The present inventors have conducted diligent research on an organosilicon compound to be combined with activated titanium trichloride and an organoaluminum compound, and as a result, the present invention has been achieved by using a specific organosilicon compound. The present invention has been completed by finding that the object of can be achieved. SUMMARY OF THE INVENTION That is, the gist of the present invention is (A) activated titanium trichloride, (B) an organometallic compound, and (C) a general formula.

[Chemical 2] [However, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O-, R ⁵ ₃ Si
- or R ^{6 ₃} SiO-, R ₃ is methyl or ethyl group, x is 1 or 2, y is 0 or 1, z is 2
Alternatively, 3 represents x + y + z = 4, and R ⁴ has 3 to 3 carbon atoms.
10 hydrocarbon groups, R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms. ] An α-olefin polymerization catalyst comprising an organosilicon compound represented by

Activated Titanium Trichloride Activated titanium trichloride used in the present invention (hereinafter referred to as component A)
Say. ) Is a β-titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound and further activated. Activation of β-type titanium trichloride is performed by converting the titanium trichloride into alcohol, ether, ester, lactone,
It is made by treating with an electron donating compound such as an amine, an acid halide and an acid anhydride. Further, activated titanium trichloride is used as a halogen-containing compound such as titanium tetrachloride, silicon tetrachloride, hydrogen halide, halogenated hydrocarbon, organoaluminum halide compound or an activator such as halogen element such as iodine or chlorine. It is also possible to process,
The treatment with the above-mentioned electron-donating compound can also be carried out in the presence of these activators. More detailed preparation method of the component A is described in, for example, JP-A-47-34478 and 50-7.
No. 4594, No. 50-74595, No. 50-1230.
No. 90, No. 50-123091, No. 52-10729
No. 4, No. 53-14192, No. 53-65286,
It is disclosed in Japanese Patent Laid-Open No. 53-65287.

That is, a method in which TiCl ₄ is reduced with an organoaluminum compound, the obtained solid (hereinafter referred to as a reduced solid) is treated with a complexing agent (electron-donating compound), and further reacted with TiCl ₄ ( JP-A-47-34478). A method in which the reduced solid is treated with a complexing agent, and further treated with a monoalkylaluminum dihalide (JP-A-50-7).
4594). A method in which the catalyst component obtained above is further treated with a complexing agent (JP-A-50-74595). A method in which the reduced solid is treated with a complexing agent and further treated with TiCl ₄ at a temperature of 40 ° C. or lower (JP-A-50-1).
23090). A method in which the catalyst component obtained above is further treated with carbon tetrachloride (JP-A-50-123091). A method of treating the reduced solid with a chlorinated hydrocarbon having 2 carbon atoms in the presence of a complexing agent (JP-A-52-107294).
issue). A method of treating the reduced solid with a chlorinated hydrocarbon having 3 or more carbon atoms in the presence of a complexing agent (JP-A-53-14192).
issue). A method in which the reduced solid is treated with a chlorinated hydrocarbon having 2 or more carbon atoms in the presence of a complexing agent and TiCl ₄ (Japanese Patent Laid-open No. Sho 53-53).
-65286). A method of treating the reduced solid with a chlorinated hydrocarbon having 2 or more carbon atoms in the presence of a complexing agent and AlCl ₃ -ether (JP-A-53-65287). The component A is prepared as described above, but the component A may be washed with an inert medium and further dried if necessary.

Further, the component A may further contain an olefin polymer produced in the component A by contacting with an olefin in the presence of an organoaluminum compound. The organoaluminum compound is selected from the organometallic compounds described below, which are one component of the catalyst of the present invention. As the olefin, α-olefins such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene can be used in addition to ethylene. The contact with the olefin is preferably carried out in the presence of an inert medium. The contact is usually performed at a temperature of 100 ° C or lower, preferably -10 to + 50 ° C. The amount of the olefin polymer contained in the component A is usually 0.01 to 100 g per 1 g of the component A. For the contact between the component A and the olefin, an electron donating compound may be present together with the organoaluminum compound. As the electron-donating compound, carboxylic acid esters, amines, phosphites, alkoxysilanes, and organic silicon compounds described later are particularly desirable. The component A contacted with the olefin can be washed with an inert medium if necessary, and can be further dried.

Organometallic Compound The organometallic compound (hereinafter referred to as component B) is an organic compound of a metal of group I to group III of the periodic table. As component B, organic compounds of lithium, magnesium, calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly preferable. Organoaluminum compounds that can be used include those represented by the general formula R _n A
1X _3-n (wherein R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group or a hydrogen atom, and n is any number in the range of 1 ≦ n ≦ 3). 1 to 1 carbon atoms such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide and dialkyl aluminum monohydride.
Particularly preferred are alkylaluminum compounds having 8 and preferably 2 to 6 carbon atoms or mixtures or complex compounds thereof. Specifically, such as trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, diisobutyl aluminum chloride, etc. Alkyl aluminum sesquihalides such as dialkyl aluminum monohalide, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, ethyl aluminum dibromide, ethyl aluminum diiodide, isobutyl aluminum dichloride, ethyl aluminum sesquichloride, etc. Dialkyl aluminum monoalkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl Examples include dialkyl aluminum hydrides such as aluminum hydride. Two or more of these compounds can be used in combination.

It is also possible to use an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include

[0011]

[Chemical 3] Etc. can be illustrated. Examples of organic compounds of metals other than aluminum metal include diethylmagnesium, ethylmagnesium chloride, diethylzinc, and other LiAl (C
Examples thereof include compounds such as ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Organosilicon Compound The organosilicon compound (hereinafter referred to as component C), which is one component of the catalyst of the present invention, is represented by the above general formula. In the formula, hydrocarbon groups of R ¹ and R ² and R ⁴ O—, R ⁵ ₃ S
The hydrocarbon group represented by R ⁴ , R ⁵ and R ⁶ in i-, R ⁶ ₃ SiO- is an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkadienyl group, an aryl group or an aralkyl group. Etc.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, s-butyl, t-butyl, amyl, i-amyl, t-amyl, hexyl, octyl, 2-ethylhexyl, As the alkenyl group such as a decyl group, vinyl, allyl, propenyl, isopropenyl, 1-butenyl, 1-pentenyl,
1-hexenyl, 1-octenyl, 1-decenyl, 1-
Methyl-1-pentynyl, 1-methyl-1-heptenyl and the like, cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl and methylcyclohexyl groups, and cycloalkenyl groups such as cyclopentenyl, cyclohexenyl and methylcyclohexenyl groups. Etc., the cycloalkadienyl groups include cyclopentadienyl, methylcyclopentadienyl, indenyl groups, etc., the aryl groups include phenyl, tolyl, xylyl groups, etc., and the aralkyl groups include benzyl, phenethyl group. , 3-phenylpropyl group and the like.

Specific examples of the component C are shown below. The smell below
, Me is methyl group, Et is ethyl group, Pr is propyl
Group, Bu represents a butyl group, and Ph represents a phenyl group.
You (Me-COO-) Si (OMe)₃, (Pr-C
OO-) Si (OMe)₃, (N-pentyl-COO
-) Si (OMe)₃, (Isopropenyl-COO-)
Si (OMe)₃, (Allyl-COO-) Si (OE
t)₃, (Cyclohexyl-COO-) Si (OMe)
₃, (Cyclopentenyl-COO-) Si (OM
e)₃, (Cyclopentadienyl-COO-) Si (O
Me)₃, (Ph-COO-) Si (OEt)₃,(I
Sopropenyl-COO-) Si (OMe)₂Me, (I
Sopropenyl-COO-) Si (OMe)₂Ph, (I
Sopropenyl-COO-) Si (OMe)₂(Oi-P
r), (Me-COO-) Si (OEt) ₂Me, (P
r-COO-) Si (OMe)₂i-Pr, (Cyclope
N-COO-) Si (OEt)₂(SiMe₃),
(Me-COO-) Si (OMe) ₂(OSiM
e₃), (Allyl-COO-) Si (OEt)₂(Ot
-Bu), (Me-COO-)₂Si (OEt)₂，
(2-butenyl-COO-)₂Si (OMe)₂、 (
Chlohexyl-COO-)₂Si (OMe)₂、 (Siku
Lopentenyl-COO-)₂Si (OMe)₂、 (Siku
Lopentadienyl-COO-) ₂Si (OEt)₂，
(Ph-COO-)₂Si (OEt)₂.

The catalyst of the present invention comprises component A, component B and component C, the proportions of which are such that component B is 0.5 to 100 gram moles per gram atom of titanium in component A,
Desirably 1 to 40 gram mol, component C is 0.001 to 10 mol, preferably 0.01 to
It is used so as to be 1.0 mol.

Polymerization of α-Olefin The catalyst of the present invention is a homopolymerization of α-olefin having 3 to 10 carbon atoms or another monoolefin or 3 to 10 carbon atoms.
Useful as a catalyst for the copolymerization with diolefins, especially α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene,
It exhibits extremely excellent performance as a catalyst for homopolymerization of 1-hexene or the like or for random and block copolymerization with the above α-olefins and / or ethylene.

The polymerization reaction may be carried out in a gas phase or a liquid phase. When the polymerization is carried out in a liquid phase, normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in inert hydrocarbons and in liquid monomers. The polymerization temperature is usually -80 ° C to +1.
It is in the range of 50 ° C, preferably 40 to 120 ° C. The polymerization pressure may be, for example, 1 to 60 atmospheres. Further, the molecular weight of the obtained polymer is controlled by the presence of hydrogen or other known molecular weight regulator. Further, the amount of the other olefin to be copolymerized with the α-olefin in the copolymerization is usually selected in the range of up to 30% by weight, particularly 0.3 to 15% by weight based on the α-olefin. The polymerization reaction by the catalyst system according to the present invention is carried out in a continuous or batch reaction,
The conditions may be those usually used. Further, the copolymerization reaction may be carried out in one step or in two or more steps.

[0018]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. The percentages (%) in the examples are by weight unless otherwise specified. The heptane-insoluble matter (hereinafter abbreviated as HI) showing the ratio of the crystalline polymer in the polymer is
6 with boiling n-heptane in a modified Soxhlet extractor
It is the remaining amount when time is extracted.

Example 1 Preparation of component A (activated titanium trichloride) A 2 liter flask equipped with a stirrer was placed in a constant temperature water bath kept at 0 ° C., and 700 ml of purified heptane and 250 ml of tetrachloride were placed in this flask. Titanium was added and mixed. Next, the temperature of the heptane solution of titanium tetrachloride is set to 0.
A mixture consisting of 315 ml of diethylaluminum chloride, 117 ml of ethylaluminum dichloride and 400 ml of purified heptane was added dropwise over 3 hours while maintaining the temperature at 0 ° C. After the completion of the dropping, the contents are heated with stirring, and 1 hour later, the temperature is raised to 65 ° C.
A reduced solid was obtained by stirring for a time. The reduced solid obtained is separated, washed with purified heptane and then at 65 ° C. under reduced pressure.
And dried for 30 minutes. Next, 25 g of this reduced solid is added to 100
A suspension dispersed in ml of purified heptane is prepared, and 100 ml of hexachloroethane corresponding to 1 gram mol of hexagram ethane per gram atom of titanium in the reduced solid are then prepared.
in the form of a solution containing 25 g of hexachloroethane in 1 liter, and further 0.6 per gram atom of titanium in the reduced solid.
An amount of dinormal butyl ether corresponding to gram mol was added and mixed with stirring. The mixture was then heated to 80 ° C. with stirring and stirred for 5 hours, then the solid obtained was washed 5 times with 100 ml of purified heptane and washed at 65 ° C. for 3 hours.
Component A was prepared by drying for 0 minutes.

Component A obtained above was placed in a 1.5-liter stainless steel autoclave equipped with a propylene polymerization stirrer under a nitrogen gas atmosphere.
40.8 mg, 2 ml of a solution containing 1 mol of diethylaluminum chloride (hereinafter referred to as DEAC) in 1 liter of n-heptane, and 0.2 mol of hexanoyloxytrimethoxysilane in 1 liter of n-heptane. What mixed 1 ml and hold | maintained for 5 minutes was put.
Then, 750 ml of hydrogen gas as a molecular weight controlling agent and 1 liter of liquid propylene were injected under pressure, and the reaction system was cooled to 70%.
The temperature was raised to 0 ° C., and propylene was polymerized for 1 hour. After completion of the polymerization, unreacted propylene was purged and HI 97.
2% white polypropylene powder was obtained. The polymerization activity of the catalyst was 4.8 kg / g · component A.

Example 2 Polymerization of propylene was carried out in the same manner as in Example 1 except that methacryloyloxyphenyldimethoxysilane was used instead of hexanoyloxytrimethoxysilane, and the results are shown in Table 1. .

Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the organosilicon compound, and the results are shown in Table 1.

[0023]

[Table 1]

Examples 3 to 4 Polymerization of propylene was carried out in the same manner as in Example 1 except that triethylaluminum was used as the organometallic compound instead of DEAC and the compounds shown in Table 2 were used as the organosilicon compound. The results are shown in Table 2.

Comparative Examples 2 to 3 Propylene was polymerized in the same manner as in Example 3 except that the organosilicon compounds shown in Table 2 were used, and the results are shown in Table 2.

[0026]

[Table 2]

[0027]

EFFECTS OF THE INVENTION When an organosilicon compound having an aromatic group is used, no harmful substance which is a problem is generated, and the polymerization activity is equal to or higher than that of the catalyst containing the silane compound having the aromatic group. It exhibits catalytic performance showing stereoregularity.

[Brief description of drawings]

FIG. 1 is a flowchart showing the steps for preparing a catalyst of the present invention.

Continuation of the front page (72) Inventor Yukiko Usui 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Corporation Research Institute (72) Inventor Takeshi Ishihara 1-3-3 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Tonen Co., Ltd. Research Institute

Claims (1)

[Claims] 1. (A) activated titanium trichloride, (B) an organometallic compound and (C) a general formula: [However, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, R ⁴ O-, R ⁵ ₃ Si
- or R ^{6 ₃} SiO-, R ₃ is methyl or ethyl group, x is 1 or 2, y is 0 or 1, z is 2
Alternatively, 3 represents x + y + z = 4, and R ⁴ has 3 to 3 carbon atoms.
10 hydrocarbon groups, R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms. ] The catalyst for alpha-olefin polymerization which consists of an organosilicon compound represented by these.