JPS62285905A - Production of stereoregular polyolefin - Google Patents

Abstract

PURPOSE:To obtain polymer particles of excellent powder properties in high activity and stereoregularity, by polymerizing an olefin in the presence of a specified catalyst system. CONSTITUTION:A catalyst system is obtained by combining a solid catalyst component (A) obtained by reacting a reaction product of at least one member selected from among metallic magnesium, a hydroxylated organic compound (e.g., methanol) and an oxygen-containing organic compound of Mg (e.g., magnesium methylate) with an oxygen-containing organic compound of titanium (e.g., titanium tetraethoxide), an organoaluminum compound (e.g., triethylaluminum) and an Si compound (e.g., hexamethyldisiloxane) with at least one catalyst component (B) selected from among the organometallic compounds of the metals of groups Ia, IIa, IIIb and IVb of the periodic table (e.g., n-butyllithium) and at least one catalyst component (C) selected from among the oxygen-containing organic compounds of Si (e.g., trimethyl-methoxysilane). At least one olefin is polymerized at 20-110 deg.C and a pressure of 2-50kg/cm<2> in the presence of this catalyst system.

Description

[Detailed Description of the Invention] - 3 Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for producing polyolefins comprising polymerizing at least one type of olein in the presence of a novel catalyst. In particular, the present invention relates to a production method suitable for producing highly stereoregular regular polymers with high catalytic activity in the polymerization of α-olefins having 3 or more carbon atoms.

[Conventional technology]

It is already known to use a catalyst system consisting of a transition metal compound and an organic synthetic compound for low-pressure polymerization of olefins. Further, as a highly active catalyst, a catalyst system containing as one component a reaction product of an inorganic or organic magnesium compound and a transition metal compound is also known. Furthermore, in the polymerization of α-olefins having 3 or more carbon atoms, the activity of the catalyst is only high, and it is necessary to maintain high stereoregularity of the resulting polyolefin. Addition of acid esters and the like has also been carried out to maintain high stereoregularity of polyolefins obtained.

Those 15! Most of the proposals use magnesium chloride or magnesium chloride that has been surface-treated by some method as a carrier, and titanium tetrachloride is supported on the surface of the carrier. However, the method for producing a catalyst component using titanium tetran oxide as a starting material as a transition metal compound has many drawbacks in terms of industrial handling. When titanium tetraquartide comes into contact with extremely small amounts of moisture or air, it decomposes and generates a large amount of hydrogen chloride, which causes significant corrosion of equipment and piping.In addition, the decomposition products cause hydroxylation of white crystals. It becomes a titanium-based or titanium oxide-based compound, causing problems such as clogging of pipes. This problem is serious, especially in the process of treating the cleaning solution after separation, because excessively used titanium tetrachloride is separated by washing during the production of catalyst components. The present inventors have already proposed a method for improving or eliminating the above drawbacks, such as in Japanese Patent Publication No. 52-15110.

There, a catalyst component (A) obtained by reacting magnesium metal with a hydroxide compound or an organic compound containing one element such as magnesium, an oxygen-containing wired compound of a transition metal, and an aluminum halide and a catalyst component of an organometallic compound. A relatively heavy and highly active catalyst system consisting of (8) is used.

However, in recent years, there has been a demand for the performance of good shape of the polymer particles obtained, and it has been found that polymer particles obtained in the presence of a catalyst disclosed in The resulting polymer particles had a small average particle diameter or a wide particle size distribution, and contained a large proportion of fine particles in the polymer particles, and were still unsatisfactory in terms of powder properties.

Therefore, the present inventors first proposed the
By using a silicon compound and/or a sterile aluminum compound in addition to the raw materials for the catalyst component (A) disclosed in ``3, etc., high activity and the powder characteristics of the polymer particles can be greatly improved. discovered a method for producing polyolefin, and published JP-A-56-155201 and JP-A-60-24.
No. 8705.

Japanese Patent Application Publication No. 60-262802, Patent Application No. 60-27513
proposed as a number.

[Problem that the invention seeks to solve]

However, in these proposals (113) it has been difficult to obtain polymer particles with excellent powder properties with high activity and good stereoregularity in the polymerization of α-olefins having 3 or more carbon atoms.

[Means for Solving the Problems] As a result of intensive studies by the present inventors on methods for solving the above problems, the inventors of the present invention have proposed the above-mentioned Japanese Patent Application Laid-Open No. 56-155205e, Japanese Patent Application Laid-Open No. 1987-155205,
JP 60-262802, patent application WE 60-275
Catalyst component (A) and catalyst component (B) shown in No. 13
In addition to this, the present invention was completed by using in combination a specific compound shown as the catalyst component (C) of the present invention.

That is, the present invention provides: (A) (i) at least one member selected from metallic magnesium and an organic hydroxide compound and an oxygen-containing organic compound of magnesium; (i) at least one oxygen-containing organic compound of titanium; (ii) ) A solid obtained by reacting at least one organoaluminum compound and/or (1) a reactant obtained by reacting at least one silicon compound, and (V) at least one aluminum halide compound. Catalyst component (A) and (B) lap 11! Table 1a, IIa, IIb, l1
lt) at least one catalyst component (8) selected from the group of organometallic compounds of group a and rVb metals, and (C)
In the presence of a catalyst system consisting of at least one catalyst component (C) selected from the group of oxygen-containing organic compounds of silicon,
A method for producing a stereoregular polyolefin, characterized by polymerizing at least one type of olefin.

[For production]

According to the present invention, a polymer with high activity and good particle shape can be produced with good stereoregularity.

The reason why the catalyst prepared and used in the present invention has excellent properties is not clear, but the reason is that a homogeneous solution (hereinafter referred to as Hg- Ti solution) is combined with organoaluminum compound (ii) and/or silicon compound (1
) will act as a nucleus for particle formation during the next reaction with aluminum halide compound (V) for the purpose of completing catalyst particle formation, and will change the particle shape. A good solid catalyst component (A) is obtained, and high activation and stereoregularity are achieved through the interaction of the solid catalyst component (A), catalyst component (B), and catalyst component (C). it is conceivable that.

In the present invention, the group consisting of metallic magnesium and a hydroxide organic compound as described in (1) above, which is a reactant used for preparing the solid catalyst component (A), includes the following.

Magnesium metal comes in various forms, namely powder 1.
Any shape such as particles, foil or ribbon can be used, and the hydroxylated organic compounds include alcohols,
Organic silanols and phenols are suitable.

As alcohols, linear or branched aliphatic alcohols, aliphatic alcohols or aromatic alcohols having 1 to 18 carbon atoms can be used. Examples include methanol, ethanol, n-propertool, i
-Propertool, n-butanol, i-butanol, n
-Amyl alcohol.

i-amyl alcohol, n-hexanol, 2-methylpentanol, 2-ethylhexanol.

Examples include n-octatool, i-octatool, 1-decanol, 1-dodecanol, n-stearyl alcohol, and ethylene glycol. Furthermore, the organic silanol has at least one hydroxyl group, and the zero base is 1 to 121 [! ] carbon atoms, preferably from 1 to 6 carbon atoms, selected from alkyl groups, cycloalkyl groups, arylalkyl groups, aryl groups, alkylaryl groups and aromatic groups. For example, we can give the following example. Trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol. Furthermore, examples of phenols include phenol, cresol, xylenol, and hydroquinone.

Among these, it is preferable to use alcohol. Of course, it is good to use alcohol alone, but in particular, 2 to 1
Direct aliphatic alcohols having 8 carbon atoms and 3 to 1
Preference is given to using a mixture with branched aliphatic alcohols having 8 carbon atoms. In that case, the quantitative ratio of straight chain fatty acid J]7i group alcohol to branched chain aliphatic alcohol is preferably in the range of 10:1 to 1:10, particularly preferably 3:1.
~1:3 range.

In addition, when obtaining the solid catalyst component (^) of the present invention using magnesium magnesium, in order to promote the reaction, it is necessary to use magnesium metal that may react with magnesium metal or form an addition compound. It is preferable to add one or more polar substances, such as iodine, mercuric chloride, alkyl halides, dioxylic acid esters, and organic acids.

Next, examples of compounds belonging to oxygen-containing organic compounds of magnesium include magnesium alkoxides, such as methylate, ethylate, isopropylate, decalate,
methoxyethylate and cyclohexalute, magnesium alkyl alkoxides such as ethyl ethylate, magnesium hydroalkoxides such as hydroxymethylate, magnesium phenoxides such as phenate, naphthinate, phenanthrenate and talezolate, magnesium carboxylates such as acetate, stearate.

Benzoate, phenylacetate, adipate.

Sebacates, phthalates, acrylates and oleates, oximates such as butyloximate, dimethylglyoximate and cyclohexyloximate, hydroxamates, hydroxylamine salts such as N-nitroso-N-phenyl-hydroxylamine derivatives, erulates, e.g. acetylacetonate,
Magnesium syralates, such as triphenylsilate, alkoxides of magnesium and Hakuno Kinkazu,
An example is Ma (A I (OC2day5))2. These oxygen-containing magnesium compounds may be used alone or as a mixture of two or more.

As the titanium oxygen-containing organic compound which is the reactant in (i) above, a compound represented by the general formula (T i O(OR2) b) m is used. However, in the general formula, R2 represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10, such as a straight chain or branched alkyl group, cycloalkyl group, arylalkyl group, aryl group, and alkylaryl group, a and b represent numbers that are compatible with the valence of titanium such that a≧O and b>o, and m represents an integer. In particular, it is desirable to use an oxygen-containing organic compound in which a is 0≦a≦1 and m is 1≦m≦6.

A specific example is titanium tetraethoxide.

Titanium tetra-n-propoxide, titanium tetra-1-
Examples thereof include propoxide, titanium tetra-n-butoxide, hexa-1-proboxydititanate, and the like. The use of oxygen-containing @-like compounds with several different hydrocarbon groups also falls within the scope of the invention. These oxygen-containing organic compounds of titanium may be used alone or as a mixture of two or more.

The organoaluminum compound which is the reactant in (i) above has the general formula R'I A I or R'AIY
The one represented by is used.

n 3-n However, in the general formula, R' is the same or different 1
represents an alkyl group having ~20, preferably 1 to 8 carbon atoms, Y is an alkoxy group, aryloxy group having 1 to 20, preferably 1 to 8 carbon atoms,
It represents a cycloalkoxy group or a halogen atom, and n represents a number of 1≦n<3.

The above organoaluminum compounds can be used alone or as a mixture of two or more.

Specific examples of organoaluminum compounds include triethylaluminum, tri-1-butylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, i-butylaluminum dichloride, diethylaluminum ethoxide, and the like.

As the silicon compound which is the reactant in (iV) above,
The following polysiloxanes and silanes are used.

As polysiloxane, the general formula % formula %) (wherein R3 and R4 are hydrocarbon groups such as alkyl groups having 1 to 12 carbon atoms, aryl groups, hydrogen, halogen, alkoxy groups having 1 to 12 carbon atoms, allyloxy represents an atom or residue that can be bonded to silicon such as a group, a fatty acid residue, etc., and R and R4 may be the same or different, and p is usually 2.
A siloxane polymer having a chain, cyclic or three-dimensional structure containing one or more repeating units (representing an integer from 10,000 to 10,000) in various ratios and distributions within the molecule. (However, cases where all R3 and R4 are hydrogen or halogen are excluded).

Specifically, the chain polysiloxane includes, for example, hexamethyldisiloxane, octamethyl 1-lysiloxane, dimethylborisioquinane, diethylborisiloxane,
Methyl ethyl polysiloxane.

Methylhydropolysiloxane, ethylhydropolysiloxane, butylhydropolysiloxane, hexaphenyldisiloxane, octaphenyltrisiloxane, diphenylpolysiloxane, phenylhydropolysiloxane, methylphenylpolysiloxane, 1,5-dichlorohexamethyltrisiloxane, 1 , 7-dichlorooctamethyltetrasiloxane, dimethoxypolysiloxane, jetoxypolysiloxane, diphenoxypolysiloxane, and the like.

Examples of the cyclic polysiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4.6-
Dolimethylcyclo1-lysiloxane, 2.4,6.8-
Examples include tetramethylcyclotetrasiloxane, triphenyltrimethylcyclotrisiloxane, tetraphenyltetramethylcyclotetrasiloxane, hexaphenylcyclotrisiloxane, and octaphenylcyclotetrasiloxane.

Examples of the polysiloxane having a three-dimensional structure include those obtained by heating the above-mentioned chain or cyclic polysiloxane to have a crosslinked structure.

It is desirable that these polysiloxanes be in a liquid state for handling, and the viscosity at 25° C. is preferably in the range of 1 to 10,000 centistokes, preferably 1 to 1,000 centistokes. There is no need to limit the amount of grease, and a solid material generally referred to as silicone grease may be used.

As the silanes, general formula 1-(S i rR5SX
t' (wherein R5 represents a hydrocarbon group such as an alkyl group having 1 to 12 carbon atoms or an aryl group, a group capable of bonding to silicon such as an alkoxy group having 1 to 12 carbon atoms, an allyloxy group, or a fatty acid residue) , each R5 may be different or the same, X represents a halogen different or the same, and q
, S and t are the above integers, r is a natural number, and Q+S+t=2r+2).

Specifically, for example, trimethylphenylsilane.

Silane hydrocarbons such as allyltrimethylsilane, linear and cyclic organic silanes such as hexamethyldisilane, and octaphenylcyclotetrasilane.

Organic silanes such as methylsilane, dimethylsilane and trimethylsilane, silicon halides such as silicon tetrachloride and silicon tetrabromide, dimethyl dichlorosilane, diethyl silane, etc.
Dichlorosilane, n-butyltrichlorosilane, diphenyl dichlorosilane.

alkyl and arylhalogenosilanes such as triethylfluorosilane, dimethyldibromosilane, alkoxysilanes such as trimethylmethoxysilane, dimethyljethoxysilane, tetramethoxysilane, diphenyljethoxysilane, tetramethyljethoxydisilane, dimethyltetraethoxydisilane; Dichlorojethoxysilane.

Examples include silane compounds containing fatty acid residues such as haloalkoxy and phenoxysilanes such as dichlorosifylsilane and tribromoethoxysilane, trimethylacetoxysilane, diethyldiacetoxysilane, and ethyltriacetoxysilane.

The above organosilicon compounds may be used alone, or two
It is also possible to use a mixture or reaction of more than one species.

The aluminum halide compound that is the reactant in (V) has the general formula R6△IX and Z
3Z Use as shown. However, in the general formula, represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and X represents a halogen atom,
Z represents a number of 0≦Z<3, preferably a number of O≦2≦2. Moreover, R6 is a straight chain or branched alkyl group,
cycloalkyl group.

Preferably, it is selected from arylalkyl, aryl and alkylaryl groups.

The above aluminum halide compounds can be used alone or in a mixture of two or more.

Specific examples of aluminum halide compounds include aluminum trichloride, diethylaluminum chloride, ethylaluminum dichloride, and i-butylaluminum dichloride.

Examples include a mixture of triethylaluminum and aluminum trichloride.

The solid catalyst component (A) used in the present invention is the above-mentioned reactant (
It can be prepared by reacting the reaction product obtained by reacting i> and (ii) with reactant (iii) and/or reactant (1v) and further with reactant (V).

These reactions are preferably carried out in a liquid medium. This should therefore be carried out in the presence of an inert organic solvent, especially if these reactants themselves are not liquid under the operating conditions, or if there is an insufficient amount of liquid reactant on the platform. As the inert organic solvent, any commonly used in the technical field can be used, including aliphatic, alicyclic or aromatic hydrocarbons, their halogen X and Q forms, or mixtures thereof, such as isobutane, hexane.

Heptane, cyclohexane, benzene, toluene.

Xylene, monochlorobenzene, etc. are preferably used.

Reactant (i>, (ii), (mountain) and/or i)
The reaction order of can be any order as long as it results in a chemical reaction. That is, for example, a method of adding a silicon compound to a mixture of a magnesium compound and a titanium compound, a method of adding an organoaluminum compound to a mixture of a magnesium compound and a titanium compound, and then adding a silicon compound, and a method of simultaneously mixing a magnesium compound, a titanium compound, and a silicon compound. Possible methods include adding a titanium compound to a magnesium compound and a silicon compound.

The method of adding an aluminum compound to a mixture of a magnesium compound and a titanium compound and then adding a silicon compound is preferable because the powder properties are excellent.

The product thus obtained is reacted with an aluminum halide compound to obtain a solid catalyst component (A).

In the present invention, the use of the reactant used for preparing the solid catalyst component (A) is not particularly limited, but examples include the duram atom of magnesium (h), the duram atom of titanium (Ti) in the titanium compound, an alkoxy group or an allyloxy group. When a silicon compound containing a group is used, the alkoxy group or allyloxy group in the silicon compound ff1 (S) and the halogen Durham atom (X) satisfy the following two formulas. It is preferable to select the ratio.

1/20≦H(]/Ti≦200. More preferably 2≦
Hg/Ti≦200 and 115≦P≦10<P=H(
J/Li+H (JXX/4 ・Ti+ 2-Hg+s)
More preferably, it is selected within the range of 1≦P≦10. The solid catalyst component (A) adjusted within this range is used as the catalyst component (B).
By combining with olefin and polymerizing olefin, it is possible to obtain a polymer with extremely high catalytic activity, moderate molecular weight distribution, and excellent powder properties. A very good product can be obtained. If h/Ti is too large outside this range, it becomes difficult to obtain a uniform Hg-Ti solution during catalyst preparation, and the activity of the catalyst during polymerization becomes low. On the other hand, if it is too small, the activity of the catalyst will decrease, causing problems such as coloring of the product and deterioration of the hue. Furthermore, if P is outside the range, the catalytic activity will be low, resulting in an undesirable improvement in powder properties.

Moreover, the moldability is poor, gels and fish eyes occur frequently, and the appearance of the film or seal of the product is deteriorated. It is also possible not to use the modified aluminum compound in (iii) above, but the powder properties may be changed to ri,
It is preferable to use it when viewing.

The aluminum compound R1, Δ1 or R'AIY
(In the formula, n is 1≦n<3)n
When using 3-n, the Durham atom of Δ1 (hereinafter referred to as
AI (iii)) multiplied by n (R'3 A
In the case of l, it is △1 Durham atom x 3) and the above (
The atomic ratio of the titanium compound of i) to the Durham atom of [i is as follows:
,5.

nxAl(iii) If Ti is too large outside this range, the catalytic activity will be low, and if it is too small, the improvement in powder properties will not be desired.

The atomic ratio of the gram atom of 3i in the diagonal compound of <:V> to the gram atom of Mg in the magnesium compound of (i>) is 1/20≦Hc+/Si≦100, preferably 115≦Hg/ It is preferable to select 111ω so that Si≦10.
If g/Si is too large, the improvement of powder properties will be insufficient. On the other hand, if it is too small, the activity of the catalyst will be low.

The amount of aluminum halide compound used in () above is:
P is chosen to be within the aforementioned range. Furthermore, when using the above (mountain) interrow aluminum compound, the above A1 is a mixture of 81 gram atoms (A1(ii)) in the aluminum compound (ii) and the aluminum halide compound (
The atomic ratio of the gram atom of A1 (hereinafter referred to as 81()) in V) is 1/20≦AI(…) /AI()≦10,
Preferably 1710. It is preferable to select Al(V) so that HAI(!n)<5. If the atomic ratio of 8l (ii>) deviates from this range formula 1 (■), the result is that the improvement in powder properties is not desired.

The reaction conditions at each step are not particularly critical, but -50 to 3
00'C1 preferably at a temperature in the range of 0 to 200°C,
The step is usually carried out under pressure in an inert gas atmosphere for 0.5 to 50 hours, preferably 1 to 6 hours.

The solid catalyst component (A) thus obtained may be used as is, but it is generally washed several times with an inert organic solvent after removing remaining unreacted substances and by-products by filtration or decanting. Afterwards, it is used by suspending it in an inert solvent. It can also be used which is isolated after washing and heated under normal pressure or reduced pressure to remove the inert organic solvent.

In the present invention, the first component of the periodic table, which is the catalyst component (B),
a, ffa, I[b, Ib, IVbfm Metal scrap metal compounds include lithium and magnesium.

Examples include individual metal compounds consisting of a metal such as zinc, tin or aluminum and an organic group. As the above-mentioned 1g, an alkyl group can be exemplified. This alkyl is also a straight chain or a branched chain with 1 carbon number.
~20 Al:1-nyl groups are used. This kind of love
Right having another group (metallic compounds include, for example, n-butyllithium, diethylmagnesium, diethylzinc,
Examples include trimethylaluminum, triethylaluminum, tri-1-butylaluminum, tri-n-butylaluminum, tri-n-decylaluminum, tetramethyltin, and tri-labdeltin.

Above all, it is preferable to use trialkylaluminum having a straight chain or (J-branched) alkyl group having 1 to 10 carbon atoms.

As component (B), hydrides of alkyl gold having an alkyl group having 1 to 20 carbon atoms can also be used. Specifically, such compounds include di-
Examples include mebutylaluminum hydride and trimethyltin hydride. or carbon number 1-20
Alkyl metal alkoxides having an alkyl group such as diethyl aluminum ethoxide can also be used.

The compound on the right obtained by the reaction of a trialkylaluminum or dialkylaluminum hydride having an argyl group having 1 to 20 carbon atoms and a diolefin having 4 to 20 carbon atoms is an aluminum compound, for example, a compound such as isoprenyl aluminum. You can also use

It is also possible to use aluminum-strength compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms, such as tetramethylaluminoxane and polymethylaluminoxane.

Examples of the silicon acid-containing silicon compound used in the present invention as the catalyst component (C) include compounds in which a hydrocarbon group having 1 to 12 carbon atoms is bonded to silicon via oxygen.

Specifically, for example, trimethylmethoxysilane, trimedylethoxysilane, dimethylethoxysilane, and trimethyl-1-propoxysilane.

Trimethyl-〇-propoxysilane, [・dimethyl-t
-butoxysilane, trimethyl-1-butoxysilane,
Trimethyl-n-butoxysilane, trimethyl-n-pentoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyldimethoxysilane, dimethyljethoxysilane, dimethyljethoxysilane.

diphenyljethoxysilane, methyldodecyljethoxysilane, methyloffdabcyljethoxysilane, methylphenyldiethoxysilane, methyljethoxysilane, dibenzyljethoxysilane, die 1-xysilane,
Dimethyldi-n-butoxysilane, dimethyldi-pentoxysilane.

Diethyldi-mi-pentoxysilane, di-mi-butyldi-mi-pentoxysilane, diphenyldi-1-pentoxysilane, diphenyl di-ro-octoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n
-Butyltrimethoxysilane, phenyltrimethoxysilane, vinyl 1-rimethoxysilane, chloromethyltrimethoxysilane, 3-chloropropyltrimethoxysilane.

4-chlorophenyltrimethoxysilane, trimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, n-butyltriethoxysilane,
Vinyltriethoxysilane, 3-aminopropyltriethoxysilane.

Triethoxysilane, ethyltri-i-propo-V disilane, vinyltri-1-propoxysilane, pentyltri-n-butoxysilane methyl-trimethylpentoxysilane, ethyl-1-pentoxysilane, methyltri-n-hexoxysilane, phenyltri-n-hexoxysilane mepentoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-1-propoxysilane, tetra-
n-propoxysilane, tetra-n-butoxysilane,
Alkoxysilane or aryloxysilane such as tetra-1'-pentoxysilane, tetra-n-hexoxysilane, tetra-raphenoxysilane, del-lamethyljethoxydisilane, dimethyltetraethoxydisilane, dichlorojethoxysilane, dichloro Examples include haloalkoxysilanes or haloaryloxysilanes such as diphenoxysilane and tribromoethoxysilane.

The above oxygen-containing organic compounds of silicon may be used alone, or two or more types may be mixed or reacted together.

In carrying out the present invention, the catalyst component (Δ) is preferably used in an amount corresponding to 0.001 to 2.5 millimoles (mm0 + ) of titanium atoms per reactor 11.

The organometallic compound of component (B) undergoes the reaction '/! ! 0.02 to 50 mmol, preferably 0.2 to 5 mm per liter
Use at a concentration of ol.

The silicon oxygen-containing organic compound of component (C) is
0.001 to 50 mmol, preferably 0.001 to 50 mmol per 1.
Use at 9 degrees from 01 to 511110+.

The mode of feeding the three components into the polymerization vessel in the present invention is not particularly limited, and for example, component (A), component (B
), a method in which each component (C) is separately fed into a polymerization machine, or a method in which component (△) and component (C) are brought into contact with each other, and then component (
A method of polymerizing by contacting with component (B) and component (C).
) may be brought into contact with component (A) for polymerization, or component (A), component <8), and component (C) may be brought into contact with each other in advance for polymerization. Polymerization of the olefin is carried out in the liquid phase or in the gas phase at a reaction temperature below the melting point of the combination.

When the polymerization is carried out in a liquid phase, the olefin itself may be used as the reaction medium, but an inert solvent can also be used as the reaction medium. The inert solvent can be any commonly used in the art, but especially alkanes containing 4 to 20 carbon atoms,
Cycloalkanes such as isobutane, benzene, hexane, cyclohexane and the like are suitable.

The olefin to be polymerized in the method for producing polyolefins of the present invention is an α-olefin of the general formula R-CH=CH2 (wherein R is a straight chain having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms). or a branched chain substituted/unsubstituted alkyl group). Specifically, propylene, 1-butene, 1-pentene, 4-methyl-1-
Penten.

1-octene etc. are abundant. These can be subjected to not only homopolymerization but also random copolymerization and block copolymerization. During copolymerization, two of the above α-olefins
More than one species or α-olefin and tsukudiene. Polymerization is performed using dienes such as isoprene. In particular, it is preferable to carry out the polymerization using propylene, propylene and ethylene, propylene and the above α-olefins other than propylene, propylene and dienes.

The reaction conditions in the present invention are not particularly limited as long as the reaction temperature is lower than the melting point of the polymer, but usually the reaction temperature is 20-20°C.
110'C, pressure 2-50 to 3/ci G.

The reactor used in each polymerization step can be appropriately used as long as it is commonly used in the technical field. For example, polymerization is carried out in a continuous manner using a stirred dump reactor or a circulating reactor.

It can be carried out either by a semi-batch method or a batch method.

Furthermore, it is also possible to carry out the polymerization in two or more stages with different reaction conditions.

〔Effect of the invention〕

The first effect of the present invention is that the powder properties of the polymer are remarkable. In other words, according to the present invention, it is possible to obtain a polymer with a low content of fine particles and a high degree of bulk with an appropriately large average particle diameter. It is also possible to produce 1q of polymers with extremely narrow particle size distribution. These things have extremely great industrial significance. In other words, in the polymerization process, the formation of deposits in the polymerization apparatus is prevented, and in the polymer separation and drying processes, separation and filtration of the polymer slurry is facilitated, and the polymer slurry is easily separated and filtered. Splashing outside is prevented. In addition, improved fluidity improves drying efficiency. In addition, in the transfer process,
No bridging occurs within the silo, eliminating transportation problems. Furthermore, it becomes possible to provide polymers with a certain quality.

The second effect of the present invention is that the catalytic activity is high, and in addition, the amount of polymer obtained per IQ vehicle base of the fixed catalyst component (A>) is significantly higher.

In addition, the activity per unit weight of Ti is extremely high; for example, in the case of propylene polymerization, the activity per hour per gram of titanium used and propylene partial pressure of 1 to 9/ci usually exceeds 1,000a in the most preferred case. , this value exceeds 10,000.

Therefore, problems such as deterioration and coloring can be avoided during polymer molding.

The third effect of the present invention is that the polymer has extremely high stereoregularity. Therefore, it is extremely advantageous for producing a polymer by a gas phase polymerization method that does not use a reaction medium.

The fourth effect of the present invention is that since titanium tetrahedride is not used in the production of the catalyst component, troubles in the catalyst production process and the catalyst cleaning liquid treatment process can be avoided. Titanium tetrahalide easily decomposes even when it comes into contact with even a small amount of air or moisture, producing large amounts of hydrogen chloride and solid deposits that are decomposition products, which can corrode equipment and piping.
This may cause problems such as clogging the pipes. By following the method of preparing the catalyst component according to the present invention, future problems caused by using titanium tetrahalide as a starting material can be improved or eliminated.

〔Example〕

The present invention will be illustrated below by examples, but the present invention is not limited in any way by these examples. In addition,
In the Examples and Comparative Examples, mel l~flow rate (
MFR (hereinafter abbreviated as MFR) was measured under ASTM D-1238 conditions.

The isotactic index (abbreviated as ■) indicates the proportion of the insoluble polymer after extraction with n-hebutane based on the total produced polymer in weight percentage.

Activity is the polymer production f per weight of solid catalyst component (A)
represents f1(cx). Ti activity is determined by the solid catalyst component (A
) represents the amount (g) of polymer produced per 1q of T1 inclusions. The breadth and narrowness of the particle size distribution of polymer particles can be determined by classifying the polymer particles using a sieve, plotting them on probability logarithm paper, and using a known method to determine the geometrical mark t? using an approximated straight line. ! The deviation was determined and expressed as its common logarithm (hereinafter referred to as σ). Further, the average particle size is a value obtained by reading the particle size corresponding to 50% of the heavy temperature cumulative field on the above-mentioned approximate straight line. The fine particle content is the proportion of fine particles with a particle size of 105 μm or less, expressed as an ffl hanging percentage.

Example Go (a) [Adjustment of solid catalyst component (A)] N-butanol 70a (0.94 mol) was placed in a No. 1,61 autoclave equipped with a stirring device, and 0.55q of iodine and a metal magnetic screw were added to the autoclave.・Kum powder 11q (0,4
5 mol>a and titanium te-1-rhabdoxide 61 g (0,
After adding 450 d of hexane to a colander, the mixture was heated to 80° C. and stirred for 1 hour under a nitrogen blanket while excluding generated hydrogen gas. Subsequently, the temperature was raised to 120°C and reaction was carried out for 1 hour to obtain a Hq-Ti solution.

Add 0.048 mol of Hg-Ti solution (calculated as H9) to a flask with an internal volume of 500 ml, raise the temperature to 45°C, and add 1 mol of a hexane solution of Treaty Butyl Aluminum (0,048 mol).
I added it over time. After everything was added, it was stirred at 60'C for 1 hour. Next, methylhydropolysiloxane was heated at 25°C.
2.8 ml (09048 gram atoms of silicon) (viscosity of about 30 centistokes) were added and allowed to react under reflux for 1 hour.

After cooling to 45° C., 90 d of a 50% hexane solution of 1-butylaluminum dichloride was added over a period of 2 hours.

That is, Hg/Ti is 2.5. P corresponds to 1.9. After all additions, stirring was carried out for 1 hour at 15.70'C. Hexane was added to the product and the product was washed 15 times by decanting. In this way, 1 g of slurry of the solid catalyst component (A) (containing 9.50% of the solid catalyst component (A)) which had been heated to 1 m in V-lean was prepared. A portion of it was collected, the supernatant liquid was removed, and it was dried in a nitrogen atmosphere or an ambient atmosphere. When elemental analysis was performed, the TI was 8.
It was 9wt%.

(b) Polymerization of propylene The interior of a stainless steel electromagnetic autoclave having an internal volume of 21 liters was sufficiently purged with nitrogen, and 0.57 g of triethylaluminum was added as the catalyst component (8).

Phenyltriethoxysilane as catalyst component (C) 0.
24g, and the solid catalyst component (△) in the head (a)
5 ml of slurry containing 30 m3 was added sequentially. Reduce the autoclave internal pressure to 0. 1 to 9/ciG, and after adding hydrogen at 0.2 K9/ai, 0.5 kg of liquid propylene was injected. At the same time as starting stirring, the temperature inside the autoclave was raised to 60°C, and at the same temperature 1.5
Polymerization of propylene was avoided between 11 and '+.

After the m-merization reaction was completed, stirring was stopped, and at the same time, unreacted propylene in the system was discharged, and the produced polymer was recovered.

As a result, the produced polymer was 230q, and the activity was 830
0Cl/g, T1 activity is 93Ktt/ai, :+i′]
I guess.

In addition, when various properties of the polymer particles were measured, MFR1
5q/10 minutes, Ir95.0%, bulk 'tU0.34g/
crj, average particle size 230 tl, σ 0.17°, and fine particle content 2.6%.

Examples 2-10. Comparative Examples 1 and 2 In the method of Example 1, an experiment was conducted by changing only the type d3 of component (C) and addition G as shown in Table 1. That is, the solid catalyst component prepared in Example 1 (
A > A-3 and triethylaluminum in Example 1
In Examples 2 and 3, the amount of phenyltriethoxysilane added was changed, and in Examples 4 to 8 rJ5 and Comparative Example 2, the type of catalyst component (C) was changed. Polymerization was carried out without using the catalyst component (C) and using the catalyst component (/\) i3 J: U (B) at a humidity of 10 m'j and 0.190, respectively.

The results [, are shown in Table 1 as U (.

Example 1] Using the same apparatus as in Example 1, n-butanol 37a (0.50 mol) and i-propatool 30 g were used as reactants.
(0.50 mol), iodine 0.55Q, metallic magnesium powder 11C1 (0.45 mol) and titanium tetrabutoxide 61C1 (0.18 mol), using V-san 450 mol, under the same conditions as in Example 1. Perform the reaction with )10
-Ti solution was obtained.

0.052 mol of this solution in terms of Hg was added to a 500 d flask, and the reaction with diethylaluminium chloride (0.10 mol) was carried out in the same manner as in Example 1 (a). At tU after the completion of the reaction, the mixture was cooled to room temperature, and hexane was added to the product to wash it three times using a decanting method. Subsequently, in the same manner as in Example 1 (a), methylhydropolysiloxane (silicon: 0.10 g atoms) was reacted with i-butylaluminum dichloride (0.28 mol) to form the solid catalyst component (A). 1 q of slurry. Hg/Ti is 2.5. P
is equivalent to 2,4, and ω including D is 9. It was OwtX.

Polymerization of propylene was carried out in the same manner as in Example 1 except that the obtained solid catalyst component (A>) was used.
4Q/10 minutes, Ir94.3%.

1υ of polypropylene with a bulk of 0.34Q10+f was prepared. Activity corresponds to 7700a/q. Also, the average particle size is 220μ, and σ is 0.17. The fines content was 3.0% by weight.

Example 12 32.2 c+ (0.42 mol) of n-butanol was added to a 1.6-inch volume W 1.6 crepe equipped with a stirrer, and 0.2 g of iodine and 4.0 g of metallic magnesium powder were added.
860 <0.20 mol) and titanium tetrabutoxide 2
After adding 7.2C1 (0.08E-L) and adding 200ml of hexane to a colander, the temperature was raised to 80°C, and the mixture was stirred for 1 hour under a nitrogen blanket while excluding generated hydrogen gas. Subsequently, the temperature was raised to 120'C and reaction was carried out for 1 hour.

Dimethylpolysiloxane (viscosity 50 centistokes at 25°C>153C) (silicon 0
．． 2 g atoms) was injected with nitrogen and heated to 1 at 120'C.
Allowed time to react.

Add 340 ml of hexane and lower the temperature to 45°C. 50% hexane solution of ethyl aluminum dichloride 3/18
Add rd over 31IY. After everything was added, the temperature was raised and stirred at 60'C for 1 hour. Hexane was added to the product, and the product was washed 15 times by decantation. Thus,
A slurry of solid catalyst component (A> containing solid catalyst component (A>380) suspended in hexane is 1!7. Collect a part of it, remove the supernatant liquid, and dry it under nitrogen atmosphere. When analyzed, the titanium content was found to be 9.3vtX.

Example 1 except that iq solid catalyst component (A) was used.
Polymerization of propylene was carried out in the same manner. The results are shown in Table 2.

Examples 13 to 15 The preparation of the solid catalyst component (A> and the polymerization of propylene were carried out in the same manner as in Example 2. However, the silicon compound (
As 1), various compounds were used in place of the dimethylpolysiloxane used in Example 12. That is, Example 13
In Example 14, methylphenylpolysiloxane (viscosity 500 centistokes at 25° C.) and diphenyl shed in Example 14.

In Example 15, tetramethoxysilane was used as xysilane.

Using each catalyst, propylene was polymerized in the same manner as in Example 1. The results are shown in Table 2.

Example 16 In a 1.6A autoclave equipped with a stirring device, n-butanol 37C) (0.50 mol) and 2-ethylhexanol 65Q (0.50 mol) were placed, and 0.55 g of iodine and metal Magnesium powder 11g (0,45
mol) and 15 g of titanium tetrabutoxide (0.04
ff with 450d of hexane added to the colander
The temperature was raised to 180°C, and the mixture was stirred for 1 hour under a nitrogen blanket while eliminating the generated hydrogen gas. Continue to 120'C
The reaction was carried out for 1 hour at a temperature of
is.

A Hg-Ti solution of H (I exchanged 0.048 mol) was added to a flask with a content of V'1500 rd, the temperature was raised to 45°C, and a hexane solution of diethylaluminium chloride (0,048 mol) was added over 1 hour. After all was added, it was heated for 1 hour at 60°C. 5.6 m (0.096 gram atom of silicon) of methylhydropolysiloxane (viscosity approximately 30 centistokes at 25°C) was then added and the mixture was heated under reflux. Cooled to 45°C for 1 hour.
A 50% hexane solution of i-butylaluminum dichloride (80%) was added over 2 hours. After everything was added, stirring was performed at 70°C. Add hexane to the product,
Washing was performed 15 times using the gradient method. In this way, a slurry of solid catalyst component (A> (containing solid catalyst component (△) 12.60) suspended in l\xane was obtained. A portion of it was collected,
The supernatant was removed and dried under a nitrogen atmosphere, and elemental analysis revealed that Ti was 3.6% by weight.

Example 1 except that the solid catalyst component (A) was used.
Polymerization of propylene was carried out in the same manner. The results are shown in Table 3.

Examples 17 to 20 The solid catalyst component (A> was adjusted and propylene was polymerized in the same manner as in Example 16. However, the solid catalyst component (△
) The type of reactant used in the production of the reactant and the method used for the reactant were varied. That is, in Example 7, 1-decanol <0.50'El) and j-propanol (0.50 mol), and in Example 18, 1-dodecanol (0.50 mol)
and 1-propatol (0.50 mol), and in Example 1, the use of titanium tetrabutoxide a was changed to 15q (0.044 mol). Also,
In Example 20, the alcohol was converted into n-octatool (0,
4. Use of titanium tetrabutoxide in 2-ethyl hekylinol (0.50 mol) and 2-ethylhexylnol (0.50 mol). CJ(0,
The solid catalyst component (A>) was prepared as 012 mol).

Polymerization of propylene was carried out in the same manner as in Example 1 using each of the solid catalyst components (Δ).

The results are shown in Table 3.

Example 21 Jetoxymagnesium 21.30 (0.2 mol) was placed in a No. 1,61 autoclave equipped with a stirrer, dithane tetrabutoxide 68Q (0.2 mol) was added thereto, and the mixture was heated to 120°C. t4 The mixture was heated and the reaction was carried out for 1 hour. Thereafter, at 120'C, dimethylpolysiloxane (25
153Q (viscosity approximately 50 centistokes at °C) was pumped with nitrogen and heated to 120 °C.
The reaction was carried out for 1 hour. After the reaction, 340 m of hexane was added, and after cooling to 45°C for 1 month, 186 g of i-butylaluminum dichloride diluted to 50 wt% with hexane (1,
2 mol) was added over 3 hours. 60 after adding everything
'C for 1 hour, and the solid catalyst component (A)
is. The 1i content of this solid catalyst component (A> is 12.4wt
%Met.

Using the obtained solid catalyst component (A), propylene was polymerized in the same manner as in Example 1. As a result, VFR2
2q/10 minutes, 1193.1%.

A polypropylene with high density ao and 32Q/cd was obtained.

The activity corresponds to 6700 g/g. Also, the average particle size is 2
50μ, fine particle content is 10% by weight, and σ is 0.3
It was 6.

Examples 22 and 23 Propylene was produced in the same manner as in Example 1, except that the solid catalyst component (A) of Example 1 was used and the source of hydrogen to be added was changed. The results are not shown in Table 4.

Example 24 Polymerization of propylene was carried out in the same manner as in Example 1, except that 0.290% of triethylaluminum and 0.300% of diethylaluminum chloride were used as the catalyst component (B).

As a result, MFR17Cl/10 minutes, 1188.7%,
Polypropylene with a bulk density of 0.34 g/ad was produced. The activity corresponds to 9300 g/C1. Also, the average particle size is 240μ, and σ is 0.17. Fine grain Senkin; h is 2.5
% by weight.

Fruit: Tsumema 25 Using the solid catalyst component (A) prepared in Example 1, polymerization was carried out in a gas phase. Made of stainless steel with an internal volume of 21.
Bulk density 0.34Q/ul in electromagnetic stirring autoclave
, 50 q of polypropylene powder with an MFR of 6 g/l and 0 minutes was prepared and dried in air at 70° C. for 2 hours. After the inside of the autoclave was sufficiently purged with nitrogen, the internal temperature was adjusted to 60°C. After that, triethylaluminum 0.57 as catalyst component (B)], phenyltriethoxysilane 0.24Q as component (C), and component (△) 30ta
g were added sequentially. After adjusting the reactor internal pressure to 9/ciG to 0.1, add 0.3 KS/c of hydrogen to bring the total pressure to 10/ciG.
Polymerization was carried out for 2 hours while continuously adding propylene to give 4K9/criG. MFR5q/
10 minutes, polypropylene 17 with bulk density 0.350/cm
5g was obtained.

Example 26 The inside of a stainless steel electromagnetic stirring autoclave with an internal volume of 2 was sufficiently replaced with nitrogen, 1.2 A of hexadiene was charged, and the internal temperature was adjusted to 60°C. .

Thereafter, 0.99 g of tri-1-butylaluminum was added as catalyst component (B). Phenyltriethoxysilane as catalyst component 0.24. The slurry containing solid catalyst components (A > 30) prepared in Example 3 and 5 was sequentially added. After adjusting the autoclave internal pressure to 0.1 Kg/cm, hydrogen was added to 0.2 to 9/cti. Then, polymerization was carried out for 1 hour while continuously adding propylene so that the internal pressure of the autoclave became 10.1 liter/ci G. After increasing the layer pressure to 0.1 to 9/crAG, hydrogen was added to 0.2
Kg/cm was added, and polymerization was carried out for 10 minutes while continuously adding ethylene so that the total pressure became 10.3 to 9/ciG, thereby converting propylene/ethylene block copolymer 140Q to 19.

Claims (1)

[Claims] (1) (A) (i) At least one member selected from magnesium metal and an organic hydroxide compound and an oxygen-containing organic compound of magnesium; (ii) at least one oxygen-containing organic compound of titanium; (iii) at least one A solid catalyst component (A ) and (B) Periodic Table Ia, IIa, IIb, IIIb and I
(C) at least one catalyst component (B) selected from the group of organometallic compounds of group Vb metals; and (C) at least one catalyst component (C) selected from the group of oxygen-containing organic compounds of silicon. A method for producing a stereoregular polyolefin, which comprises polymerizing at least one type of olefin in the presence of a catalyst system.